JPH07507582A - Fluorination treatment of polyolefin 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] Fluorination treatment of polyolefin films Field of the invention The present invention relates generally to thermoplastic films, and more particularly to various applications. The present invention relates to fluorinated thermoplastic films suitable for use.

Background of the invention One type of polyolefin film is a stretch/cling film. Luminaires are useful in a wide range of applications, including bundling and packaging food and other items. be.

Applications of particular relevance to the invention include large rolls of carpets, textiles etc. for shipping. Wrapping of items for transportation and storage, such as wrapping. The importance of these packaging applications The most common parts are the wrapping and unit division of pallet loading. such uses In some cases, the film is attached to prevent the film from being removed from the pallet. It is desirable that the material has adhesive properties. Stretching on a stretched film also causes the film to break. This may be the reason why it is more likely to be damaged or torn. Good elongation, tensile and tear resistance It is essential for polyolefin films to have breakage and tear resistance properties as a whole. desirable. Thermal stability of the various film components is influenced by the different film manufacturing processes. This is important for recycling scraps and film waste.

To provide or improve the adhesion properties of a particular film. The well-known tackifying additives have been used. Regular tackifying additive Additives include polybutene, terpene resin, alkali metal stearate, and hydrogenated Includes rosin and ester gum. However, the use of tackifying additives is not recommended. Not. Tackifying additives tend to accumulate on stretch packaging equipment and are often Requires periodic cleaning and maintenance. Tackifying additives can also be packaged or This may cause damage to the product, and there may be a large amount of material in the film. It even migrates into the layer film, resulting in stickiness on both sides. loading operation In some cases, the film may adhere to adjacent pallets, causing the package to be torn or destroyed. damage or cause other damage or compromise the integrity of the separated shipment. Ru.

For this reason, stretch/stick films are used to prevent sticking to pallets. It is desirable that the "outside" of the film has slip or "anti-stick properties." The slippage is Defined by the coefficient of friction. In other words, the "outside" of the film is It is desirable to have a low coefficient of friction in contact with materials such as films. stomach. Contains silica, silicates, diatomaceous earth and various lubricants while having adhesive properties Using a variety of well-known slip agents, anti-stick additives and/or anti-stick additives. By using it, slippage is imparted to the film and improved.

In addition to traditional anti-adhesion additives, film adhesion properties can be improved by exposure to corona discharge. It can be changed depending on. The reactivity of the discharge particles can change the surface chemistry of the film. and, as a result, change its physical properties. The effect of such exposure is that the film Observed by changes in surface energy.

Recently, multilayer films are often used. Multilayer film provides adhesion properties on one side It is possible to obtain a stretched/adhered packaging material with one side and sliding properties on the other side (e.g. See, e.g., U.S. Pat. No. 4,518,654).

Other multilayer films containing layers of various of the above-described stretchable/adhesive materials are disclosed in U.S. Pat. No. 508.944, No. 3.817.821, No. 4.022.646, No. 4.082 ．． No. 877, No. 4.147.827, No. 4, No. 189.420, No. 4.194.03 No. 9, No. 4.303.710, No. 4.399.180, No. 4.364.981, 4, 4+8.11.4, 4.425.268, 4.436.788, 4. 504.434, 4.588.650 and 4,671. , No. 987, British Special Patent Application No. 2.123.747, French Patent No. 2.031.801 and European Patent No. 2.031.801 It is disclosed in patent application no. 0.198.091. Those multilayer films are The general Manufactured according to

However, many multilayer films still suffer from drawbacks inherent to their individual layers. is recieving. For example, most still use adhesives to give the film slip properties. Requires the use of additives. Others, especially in highly stretched conditions, , does not have the desired slip properties. Other factors include elongation, tensile strength, tear resistance, and fracture resistance. Does not have the desired combination of resistance and thermal stability.

It is known to treat various polymer surfaces with fluorination. polytetra Materials such as fluoroethylene (PTFE) are widely used and have very low polarity. Has surface energy. An alternative to relatively expensive fluorinated polymers such as PTFE Alternatively, localized fluorination at the surface of the polymer can be used to save costs. has been used.

U.S. Patent No. 3.740.325 to Maulon includes: Materials and methods for making surface fluorinated materials are disclosed. Fluorine treated compounds The quality has greater water resistance, corrosion resistance and dirty water resistance, rather close to PTFE. It is said that

U.S. Patent No. 3.647.61 granted to Scotland No. 3 covers surfaces used in the manufacture of containers suitable for storing hydrocarbons. A fluorine treated high density polyethylene is disclosed. 0.01 to 3 per d The HDPE surface with a fluorine concentration of 0 micrograms has a low permeability to gasoline. It is said to improve sex.

U.S. Pat. No. 4,880,675 discloses that the inner layer is treated with a reactive fluorine source. A plastic container consists of an outer polypropylene layer and an inner coextruded polyethylene layer. Disclosed. Such treatment allows the lining of the container to release flavor and aroma compounds. It is said to prevent the absorption of

U.S. Patent No. 4.743 to Bierschcnk ．． No. 419 discloses that the polymer film is continuously hooked while it is being extruded. An online method for clarification is disclosed.

U.S. Patent No. 4.264.750 and No. No. 4.404.256 describes the use of ions or ions of fluorinated species in cold plasmas. A method of producing fluorinated low energy polymer surfaces by exposure to has a virtually fully fluorinated, low surface energy surface that is free of oxygen A polymer is disclosed.

Surface fluorine of high density and low density polyethylene films at 40°C to 100°C Macromolecular Chcmie, Macromolccul ar Symposium, volume 25, pages 243-248 (1X89) described by Volkmann et al. The reaction is Increased degree of fluorination with greater F28 degrees in fluorinated gas mixtures It is stated that the spread is controlled.

The method of surface fluorination of polymer films achieves complete surface fluorination. Oxygen is introduced to the surface as a reaction by-product when the reaction time is less than the time required for was observed to enter. Anard et al. Atmospheric oxygen or states that this is due to post-reactions caused by oxygen impurities. In any case, this phenomenon It is generally not found after complete surface fluorination.

The presence of oxygen after partial fluorination of the polymer surface causes the surface energy to , the polar component increases, making the surface more adhesive. Milker and "5 surface Pretreatment of Koch" "Polymer webs by Means of Fluorine" and “Fluorine” by Milker and Koch llakes Plastics Flexible” has good adhesive properties. A fluorination method is described for producing polymeric films said to have the following properties.

The method alters the surface on a more or less durable basis so as to increase the polar character of the material. It is stated that.

Summary of the invention After partial fluorination of one or both outer surfaces of the film, the polyolefin filament The invention resides in part in the discovery that the properties of lume are unexpectedly enhanced. . Broadly speaking, the process involves coating one or both sides of the film with a carrier of fluorinated species. - gaseous diluted mixture for less than the time required to achieve complete surface fluorination. exposure time to expose the partially fluorinated film surface to oxygen. include.

In one aspect, the present invention provides superior adhesion properties without the use of tackifying additives. The present invention provides a thermoplastic film having properties. In fact, in one embodiment, the deposited layer essentially It is desirable in the present invention to eliminate the use of tackifying additives so that there is no tackifying agent present. Delicious.

Additionally, the present invention provides enhanced wettability, printability and/or inkability. The present invention provides a film having the following properties:

The invention further has excellent adhesion properties on one side, even in highly stretched states. , provides a multilayer stretched/adhered film with excellent sliding properties on its opposite side.

Still further, the present invention as a whole provides the desired elongation, tensile strength, fracture resistance, tear resistance. A multilayer stretched/deposited film with anti- and thermal stability properties is provided.

Finally, the present invention provides a method for producing such polyolefin films. Partially fluorinated on one or both sides of the coextruded layer of the film to increase properties . Fluorination reactions catalyze oxygenation side reactions upon exposure to air.

The surface to be treated can be exposed to e.g. fluorine-containing plasma, fluorine-containing gas mixtures, solvents, etc. A suitable reactive fluorine such as fluorine dissolved in a UV-activated fluorine gas mixture, etc. Exposure to the source. For example, described in the literature of Wolfmann or Milker and Kotsuho. Any apparatus and method system for fluoridation that has been described can be used. preferred foot The oxidation method is a direct fluorination method using a gas mixture of molecular fluorine in an inert carrier gas. It is fluorinated.

Methods for fluorinating film materials on one or both sides in batch or continuous operations Are known. In a continuous process, the film is reacted continuously without escaping gas. Typically, specific locks (1ocks) are placed at either end to allow passage into the chamber. Introduce the film into the reaction chamber containing the film. The lock is typically operated by a vacuum pump. With low pressure seal provided. Generally pressurized with diluent gas, higher filling pressure Fluorine is metered and dispensed from a compressed cylinder. I want to leave the reaction chamber The body is compressed, combined with make-up gas, and recirculated to maintain a stable gas flow rate in the reaction chamber. do.

Absorbents are used to remove HF byproduct gas from the recycle stream. very pure Provide nitrogen as a flood and dilution gas. Excess fluorine is catalyzed into fluorine. converted to hydrogen hydroxide, which is then absorbed by absorbents such as calcium hydroxide. .

Desirable increase in properties such as adhesion, slippage, printability, ink retention and wettability The duration of exposure to F2 and air required to obtain and characteristics, F2 concentration, etc. Completes the fluorination reaction, i.e. on the carbon backbone It is important not to displace most of the available bonded hydrogen atoms.

The available Fluorination is essentially complete when most of the surface hydrogen atoms are replaced with fluorine atoms. Ru. Partial fluorination reduces the polar surface energy when complete surface fluorination is achieved. Unlike surface energies higher than indicated by a highly dispersive surface energy.

Generally, F2 exposure times of 1 to 30 minutes are suitable. the film that follows Surface oxygenation allows for complete oxygenation without adverse effects on desired film properties. Exposure to oxygen can be extended to ensure that when exposed to air is instantaneous.

The amount of F2 to ensure the properties is relatively small. For X-ray electron spectroscopy (XPS) The surface stoichiometry of fluorine:carbon is as low as 0.001 when measured from Adhesion and blocking are improved when But fluorine: If the carbon surface stoichiometry is too high, the surface becomes less active for reaction with oxygen. This results in a less polar surface, which adversely affects adhesion. Fluorine: carbon table Surface stoichiometry is preferably about 0.001 to about 3.0, more preferably about 0.0 1 to 1.0, more preferably about 0.01 to about 0.15. activated surface The amount of oxygen bonds formed depends on the surface F/C stoichiometry and support material. Ru. For polyethylene, a suitable O/C stoichiometry is about 10% or greater. prescribed support The degree of surface activity towards the carrier material (expressed by the subsequent O/C ratio) is shown in Table 1. is believed to be maximum at a certain degree of surface fluorination (i.e., F/C ratio). ing.

Without wishing to be bound to any particular theory, fluorination is due to the abstraction of hydrogen. It is thought that the process proceeds through a radical mechanism. some radicals generated To the extent that the fluorine does not react during fluorination, no subsequent reactivity with oxygen occurs.

Oxygenation increases polar surface energy, which is a measure of hydrophilicity. Radicals too reacts with carbons in adjacent chains resulting in a degree of surface cross-linking. Crosslinking is caused by boundary diffusion [ That is, the tendency for "blocking" is reduced.

Thermoplastic stretched/adhesive film The thermoplastic film produced according to the present invention has excellent adhesion properties in the adhesion layer. and has sliding properties in the non-adhesive layer. In a preferred embodiment, partially fluorinated Tackifying additives due to the excellent adhesion properties of adhesion layer polymers to non-adhesive surfaces can be avoided. However, increasing the adhesive properties of the stretched/adhered film On the other hand, the treatment does not substantially increase the tendency to stick and generally reduces the stickiness substantially. A reduction is found. It is preferable whether the non-adherent layer is treated, but which side is treated may be done. The thermoplastic film of the invention as a whole additionally has the desired elongation, Has tensile, fracture and tear resistance properties. Furthermore, it can be used for adhesion and non-adhesion layers. The thermoplastic material used has excellent thermal stability and makes the scrap layer an important material for film properties. It can be processed without major loss. The combination of properties makes the thermoplastic film of the present invention The film is particularly well suited for use as a stretch/adhesive packaging material.

The thermoplastic film preferably includes an adhesive layer and a non-adhesive layer, one or both of the outer surfaces partially fluorinated. In the adhesive layer, the first monomer is ethylene and the second monomer is ethylene. Monomers include polymers of two or more monomers that are acrylates. acrylic refers to both single acrylates and combinations of different acrylates . The polymer is commonly called ethylene-acrylate (or EA) polymer. cormorant.

Acrylates useful in the present invention have the general formula: (wherein R is hydrogen or Hydrocarbon radicals having up to 22 carbon atoms, preferably alkyl, aryl, aromatic , olefin, etc., and R- is the same or different hydrocarbon group (selected from the group).

Preferred acrylates are those in which R is selected from hydrogen or an alkyl group, and R- is selected from such The alkyl group is the same as or different from the alkyl group. preferred acrylic Specific examples of acrylates include methyl acrylate, ethyl acrylate, and propyl acrylate. Acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate Includes tacrylate, n-butyl methacrylate, and the like. Among these, methyl Acrylates are particularly preferred.

In a preferred embodiment, the EA polymer contains about 2% to about 2% by weight of the EA polymer. about 40% by weight, more preferably about 10% to about 35% by weight, most preferably from about 20% to about 30% by weight and especially from about 24% to about 28% by weight. What is the acrylate content? EA polymers have a wide range of melt index (Ml ), generally about 0.1 to about 30 dg/min, more preferably about 1 to about 10 dg/min. g/min (ASTM D-1238, Condition E).

EA polymers may include one or more free radically polymerizable termonomers. limited to that Suitable examples include vinyl esters, acrylic acids (i.e. methacrylic acids), but suitable examples include (acrylic acid and ethacrylic acid), other acrylates, carbon oxides, etc. this Additional termonomers such as Less than about 10% by weight.

Optionally, tackifying additives are added during the polymerization reaction to improve the adhesion properties of the film. It may be added to the EA polymer or blended subsequently. wide range of viscosity Plating additives are well known in the art and include, for example, polybutene, actinic additives, etc. Tsuku polypropylene, terpene resin, hydrogenated rosin, ester gum and hydrocarbon Others such as tackifying resins are included. However, the above EA polymer Produces films with sufficient adhesion such that the use of coloring additives is not required do. Although the present invention contemplates the use of tackifying additives, its use is not necessarily I also don't like it. In a preferred embodiment, the EA polymer is essentially free of tackifying additives. Not included.

The adherent layer is preferably about 5% to about 95% of the combined thickness of the adherent and non-adherent layers. more preferably about 5% to about 35%, most preferably about 10% to about 20% of %.

The second layer of the multilayer stretched film includes a non-adherent layer opposite the adhesive layer. The non-adherent layer is , suitable polyolefins or polyolefins such as polyethylene, polypropylene copolymers of ethylene and polyolefins and small amounts of other olefins, esp. from ethylene and/or propylene copolymerized with C4-C12 olefins, including combinations of resulting polymers. Particularly preferred is medium density polyethylene. (MDPE), polypropylene and linear low density polyethylene (LLDP) E), i.e., ethylene and up to about 20% by weight of C4-C1o olefin; It is a copolymer of Particularly preferred olefin comonomers include 1-butene, 1 -hexene, 1-octene and 4-methylpentene-1.

Suitable MDPEs include about 0.92 to about 0.95 g/cc and a wide range of mel. index, generally less than about 30 dg/min, preferably from about 0.5 to about 10 Includes those having a melt index of % by weight.

Suitable LLDPEs include greater than about 0.900 g/cc, more preferably about It has a density of 0.900 to about 0.940 g/cc. LLDPE has a wide range of Melt index of generally less than about 30 dynes, preferably from about 0.5 to Included are those having a melt index of about 10 dg/min.

Suitable polypropylenes are usually solid and isotactic, i.e. 90% Larger amount of butane insoluble matter to heat, with a wide range of solubility from about 0.1 to about 300 dg/min. It has a melting amount. As is known, such polypropylene is Typical density range for cutic polypropylene is 0.89 to about 0.91 g/cc It is crystalline with . The use of polypropylene in the anti-stick layer It has the added benefit of providing wear resistance.

The anti-adhesion layer preferably accounts for about 5% to about 95% of the combined adhesion/non-adhesion layer thickness. , more preferably about 65% to about 95%, most preferably about 80% to about 90% It is.

Wettable, printable, inkable films According to other embodiments of the present invention, wettable, printable, inkable films A printable and/or inkable polyolefin film is provided.

Single- or multilayer films as described above, or homopolyethylene or copolyethylene , homopolypropylene or copolypropylene, ethylene, vinyl acetate etc. Other polyolefin films can be partially fluorinated to improve wettability, printability and/or increases ink spreadability.

Wettability is determined when the adhesive is brought into contact with the adherend and the intermolecular forces across the interface are maximum. The idea is that maximum interfacial adhesive bond strength is achieved. The partially fluorinated fluorinated film when compared to non-fluorinated film. wettability was increased . Wettability is measured using a camphor treatment solution well known in the art (AST M D257g-94). This specification refers to ASTM D2578-94. Incorporate into. Wettability is typically determined by, for example, Detsuka, which is incorporated herein by reference. Polymer Interface and ・Adhesion (Polymer Interface and Adhes) Polar surface energy measured by the geometric mean formula shown on page 103 of ion) reported in terms of ghee. In essence, partially fluorinated films are Inks, dyes, pigments, adhesives, tackifiers, hot melt adhesives and stronger bonds. more sensitive to those that cause oxidation. partially fluorinated film The wettability of the film is substantially improved when compared to non-fluorinated films. preferred In some embodiments, the partially primed film has at least about 10 dyes. per country, preferably at least about 15 dynes/cm, more preferably less than Both have a polarity of about 20 dynes/cm, and preferably at least about 30 dynes/σ. Has surface energy.

Therefore, the present invention is suitable for use in multiple applications such as tapes and labels. A partially fluorinated film having an adhesive composition coated thereon is contemplated. Ru. Suitable adhesives include hot melt compositions, pressure sensitive adhesive compositions, tactile adhesive compositions. Contains products, etc. Examples include EVA hot melt, polyurethane, and polyurethane. Contains acrylates.

The present invention is a non-adhesive product used in various applications such as packaging, bags, containers, etc. Also partially fluorinated films are contemplated.

Similarly, partially fluorinated films also contain Tsuksin (c I 42510 ), Calcocid Greens (CI 440 90) Titanium dioxide, colloidal carbon, graphite, ceramics, clay Inks, dyes and other markings known to those skilled in the art, including phosphorus particles, metal particles, etc. More sensitive to printing agents or colorants.

These agents can be administered by any of several methods known in the art. Can be applied. For example, the pigment may be made of nitrocellulose or polyamide. resin and a solvent such as ethyl acrylate or n-propyl alcohol. are combined to produce a printing fluid that is subsequently applied to the support. Rotogravure and and fluorescence fluorography are examples.

Various films can be modified to provide structural support, e.g. to change the physical property balance, to use recycled offcuts and scraps, or to use oxygen or other for any of several well-known purposes to provide a shielding layer for gases of For this purpose, one or more interlayers may be included between the layers. As shown, this middle layer It may contain circulating offcuts and debris or may contain other suitable polymers.

However, that intermediate layer is preferred but optional and should be considered a limitation on the invention. isn't it.

The film layers of the present invention optionally contain one or more antioxidants, UV absorbers, antistatic agents, etc. Well-known additives such as inhibitors, release agents, pigments, colorants, etc. may also be included.

In addition, there is no waste from film production methods or from properly recovered and recycled film. Ordinary scraps and debris are recycled into the core structural layer of the layer, preferably the three-layer film. obtain.

Preferred EA polymers for use in stretch-attached films include, for example, completely Incorporated by reference for all purposes as if set forth in Some well-known patents, such as those described in U.S. Pat. can be produced by one of the following methods. Generally, for making EA copolymers ethylene and any comonomers such as acrylates and others if desired Some well-known free radicals are suitable for preparing monomers of EA polymers. Metered into a high pressure autoclave reactor along with one of the polymerization initiators (catalysts) do.

Particularly preferred catalysts include, for example, lauroyl peroxide, di-tert-petite, Organic peroxides such as luperoxide and various azo compounds are included. typical The catalyst is dissolved in any suitable liquid such as benzene, mineral oil, etc. usually , the catalyst is about 50 to about 20,000 ppm based on the weight of monomer, and more. Preferably, an amount of about 100 to about 250 ppm is used.

MDPE, LLDPE and polypropylene can be used in various forms including gas phase, slurry, solution etc. It can be produced by the known Ziegler catalytic process and is readily commercially available.

In producing the thermoplastic film of the present invention, the previously incorporated literature Some well-known extruded or coextruded multilayer films as shown ) techniques may be used. As a preferred example, The blow or chill roll casting process shown and described is suitable for making thermoplastic fibres, according to the present invention. Suitable for use in manufacturing lums.

As previously mentioned, the thermoplastic film of the present invention is particularly suitable for stretch/adhesive films. This use is considered a limitation of the present invention. It shouldn't be. For example, this film is one of several into other forms such as tape by known cutting, slitting and/or rewinding operations. can do. Including, but limited to, tensile strength, tear strength and elongation physical properties to meet the requirements for a given packaging, bundling or tape application. A wide range of adjustments can be made by varying the resin type and specification suitable for the material.

In bundling, packaging and unitization applications, the thermoplastic films of the present invention can be used in any of several ways. to any well-known process (as disclosed in the incorporated literature above). so that the adhesive layer faces inwards (toward the article) and the non-adhesive layer faces outwards. stretch-wrapping (away from the article) around the article or articles; heat of the invention Typical articles suitable for bundling, packaging and unitizing with plastic films include: , various foods (canned or fresh), carpet rolls, liquid containers and shipping , normally containerized and/or palletized for storage and/or display. These include, but are not limited to, items such as: A further aspect of the present invention The general description is given by way of illustration of the above invention and by way of non-limiting example to the following specific examples. A further example will be given.

Example In the examples below, we specifically discuss the dazzling required to peel two strips of film. Report I10 adhesion as force on the ram. Upward facing outer (0) surface (not attached) Glue the first strip to a 30 degree inclined plane with a 30° slope. downwards The second 1 inch above the first strip with the inside facing (1) surface (adhesion) ×8 inch strips were placed. Apply pressure to the strips and separate the two strips. Glued it. If evaluation of adhesion under stretching conditions is desired, both films are The strip was stretched and relaxed. At the base of the inclined plane A clip and string are attached to the end of the second strip to exert strain at a constant speed. (Instron 1130). Next, the string above is Crop the two strips at a rate of 10 cm/min until they are parallel to the bottom of the inclined plane. Pull away at speed. The force at this point is reported as adhesion.

154°F for the inner surface (deposition) of the second film sample for a specified time. Pressurized at 200 ps i (1.378 MPa at 103.3°C) Adhesiveness as 180 degree peel strength of the first film sample outer surface (non-adhesive) Report (block).

Prevents sticking, sticking or slipping of multicomponent multilayer films on rolls or on packaging pallets. properties that a film has when it comes into physical contact with itself. like that Properties are commonly quoted by noting the location of the surfaces or layers contacted.

Examples 1 and 2 and Comparative Examples 1 to 6 Melt toy produced in gas phase reactor M　D　P　E fi... produced rum. The film was fluorinated using two different degrees of fluorination. . One film has a high fluorine concentration at the surface and the other film has a low fluorine concentration. I had it. Film table regarding O/C and F/'C measured by X-ray electron spectroscopy The surface stoichiometry is shown in Table ■.

Molecular fluorine in pure nitrogen carrier gas for a set time in a reaction vessel. Consider using conventional batch equipment to expose the film support to a gas mixture of Fluorination was performed by a commercially available facility.

To illustrate the effect of fluorination treatment on adhesion tendency, the above film interface is The surface of the adhesive layer containing the 24%E M A film and the non-adhesive layer containing the above fluorinated MDPE The interface of the film was produced by applying pressure to the surface of the adhesive layer. The pressurization conditions are 2 00 psi pressure and 158°F temperature (105.5°C at 1,378 MPa) Met. Adhesive tendency was measured by the peel force required to separate the film. . As seen in Table H, fields made using both low and high fluorinated MDPE The surface has much less peel force compared to a film interface that does not have a fluorinated surface. Or didn't need it. Furthermore, the interface between the low-fluorinated film and the high-fluorinated film The adhesive resistance was almost the same as that of the interface.

table! surface stoichiometry Surface Surface stoichiometry Surface energy 0/CF/C dispersibility polarity Example L MDPE 0117 0.021 10.1 34.8 Comparative Example IM DPE O, 0610, 93834, 30, 1 table ■ Adhesion test results Film surface Pressure time Peeling force Adhesive layer Non-adhesive layer min 8 lb/inch Example 2 Untreated EMA Example 1 30 0.08 (24% MA) Comparative Example 2 Untreated EMA Comparative Example 1 30 0.01 (24% M A) Comparative Example 3 Untreated EMA Untreated MDPE 30 0.25 (24% MA) Comparative Example 4 Untreated E MA Untreated MDPE 5 0.28 (24% MA) Comparative Example 5 Untreated EMA Untreated MDPE 60 0.37 (24% MA) Comparative Example 6 Non-treatment F1. EMA Untreated MDPE 120 0.53 (24% MA ) a: 200 ps i / 158°F pressurization condition (at 1,378M P a 105.5°C) Example 3 and Comparative Examples 7 and 8 0 for the film interface produced in the same manner as Examples 1 and 2 and Comparative Examples 1 to 6. % stretch adhesion was measured. The results were compared to a similar fibril without surface fluorination at the interface. compared to Lum. As seen in Table ■, the film with low fluorine treated surface The interface (Example 3) showed increased adhesion. Fiber with high fluorine treated surface The lum interface (comparative example 7) had very little adhesion as expected. Ta.

Table■ Adhesion test results Film interface adhesion (g/inch) Adhesive layer Non-adhesive layer Maximum average Example 3 Untreated EMA Example 1 358 28g (24% MA) Comparative Example 7 Untreated EMA Comparative Example 1 70 63 (24% MA) Comparative Example 8 Untreated HMA Untreated MDr'E 284 241 (24% MA) The foregoing description of the invention is given for illustrative purposes. Many variations and modifications will be apparent to those skilled in the art in view of the foregoing description. Claims All such variations and modifications in scope or spirit are hereby encompassed. It is intended that

Copy and translation of amendment) Submission (Article 184-8 of the Patent Law) October 31, 1994

Claims (20)

[Claims] 1. at least one partially exposed film to substantially increase the wettability of the film. Films containing one, two or multiple layers of polyolefin films with a textured surface Mu. 2. the film has a surface polar energy of at least about 15 dynes per cm , The film according to claim 1. 3. Exposure to fluorine and oxygen forms a partially fluorinated surface, The film according to claim 1. 4. A film according to claim 1 having an adhesive coated thereon. 5. having one or more inks, dyes, pigments or mixtures thereof applied thereon , The film according to claim 1. 6. 2. The film of claim 1 further having ink printed thereon. 7. 6. A film according to claim 5, wherein the pigment is titanium dioxide. 8. The fluorinated surface is between about 0.001 and about 3.0, as determined by X-ray electron spectroscopy. 2. The film of claim 1, having a fluorine:carbon surface stoichiometry. 9. 9. The fluorine:chlorine stoichiometry of claim 8, wherein the fluorine:chlorine stoichiometry is from about 0.01 to about 1.0. film. 10. The film according to claim 1, further comprising a core layer. 11. The core layer is made of linear low-density polyethylene, recycled polyolefin, or polypropylene. 10. The film of claim 9, selected from the group consisting of pyrene or mixtures thereof. . 12. At least one layer is high density polyethylene, medium density polyethylene, low density polyethylene Polyethylene, linear low density polyethylene, polypropylene or blend thereof The thermoplastic film according to claim 1, wherein the thermoplastic film is selected from the group consisting of: 13. exposing one or more surfaces of the polyolefin film to fibers and oxygen. Therefore, it is possible to partially fluorinate single, double or multilayer polyolefin films. A method of producing a thermoplastic film having substantially increased wettability, comprising: 14. The film has a polar surface energy of at least about 15 dynes per cm. 14. The method according to claim 13. 15. 14. The method of claim 13, wherein the film is exposed to oxygen in the form of air. 16. Partially fluorinated film is coated with inks, dyes, pigments or colorants. 14. The method of claim 13, comprising: 17. The partially fluorinated film is further coated with an adhesive composition. 14. The method of claim 13, comprising: 18. The fluorinated surface has an X-ray electron spectroscopy range of about 0.001 to about 3.0 14. The method of claim 13, having a fluorine:carbon stoichiometry determined by: 19. further comprising a partially fluorinated printing ink on the film; 14. The method according to claim 13. 20. Claim further comprising coextruding the film with a second polyolefin. The method according to item 13.