(19)
(11)EP 3 219 484 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
02.12.2020 Bulletin 2020/49

(21)Application number: 15858815.2

(22)Date of filing:  17.10.2015
(51)Int. Cl.: 
B32B 7/12  (2006.01)
B32B 27/12  (2006.01)
B29D 7/01  (2006.01)
B32B 27/32  (2006.01)
B32B 7/10  (2006.01)
B29C 69/02  (2006.01)
B32B 7/00  (2019.01)
(86)International application number:
PCT/CN2015/092142
(87)International publication number:
WO 2016/074552 (19.05.2016 Gazette  2016/20)

(54)

METHOD FOR IMPROVING TEAR RESISTANCE OF STRETCHING FILM

VERFAHREN ZUR VERBESSERUNG DER REISSFESTIGKEIT EINER DEHNFOLIE

PROCÉDÉ POUR AMÉLIORER LA RÉSISTANCE À LA DÉCHIRURE D'UN FILM À ÉTIREMENT


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 11.11.2014 CN 201410631681

(43)Date of publication of application:
20.09.2017 Bulletin 2017/38

(73)Proprietor: Molecon (Suzhou) Novel Materials Co., Ltd.
Suzhou City, Jiangsu 215121 (CN)

(72)Inventors:
  • HUANG, Bin
    Fremont City, California 94539 (US)
  • SUN, Kun
    Suzhou, Jiangsu 215121 (CN)

(74)Representative: Franks & Co Limited 
15 Jessops Riverside Brightside Lane
Sheffield S9 2RX
Sheffield S9 2RX (GB)


(56)References cited: : 
WO-A1-02/102592
CN-A- 101 117 034
CN-Y- 201 109 217
CN-A- 101 117 034
CN-Y- 201 109 217
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Field of the Invention



    [0001] The present invention is related to a method for improving tear resistance of a composite film and pertains to the field of material processing techniques

    Background



    [0002] Stretch films are thermoplastic plastic films that are stretched and oriented during their fabrication and thermally shrink during the use. Usually, a flat film is first made by extrusion blow molding or extrusion casting and is then either stretched along both its longitudinal and transverse directions or along only one of the direction and not at all in the other directions, at a temperature above its softening point and below its melting point, where the film becomes highly elastic. Stretch films fabricated by the former approach are known as biaxially stretched films, whilst those by the latter approach are called uniaxially stretched films.

    [0003] Due to their advantages such as being thin, highly transparent, tough, cold-resistant, heat-resistant, pressure-resistant, dust-resistant and waterproof, stretch films have been found wide use in the packaging of food, medicines, electronic devices and other products. However, as macromolecular chains in stretch films are highly oriented along their stretch direction(s), they suffer from low tear resistance along this/these direction(s). In particular, the commonly-used biaxially stretched films are inferior in tear resistance due to orientation of their macromolecular chains along both the stretch directions. This greatly limits the application of stretch films. Therefore, there is an imperative need for improving the tear resistance of stretch films.

    [0004] Conventional methods for addressing the low tear resistance problem for stretch films can be categorized into chemical methods and physical methods. For example, Chinese Patent Application CN201280003595.5 discloses a tear-resistant film made of a film material including an SEEPS elastomeric block copolymer having a Tm ranging from about 10 °C to 20 °C. Chinese Patent Application CN101117034 A discloses a multi-directionally tension-resistant, tear-resistant composite film fabricated by flattening a tubular film and stretching it in one direction at a temperature that is higher than its glass transition point and lower than its viscous flow temperature to allow orientation of its macromolecules. It is then inflated to again form a tubular film, and the tubular film is spirally cut along a direction with an angle of 15-75° from the stretch direction and unfolded into a flat film in which the macromolecular orientation is inclined at an angle of 15-75° with respect to the film edges. After that, at least two such unfolded flat films are bonded together in such a manner that their macromolecular orientations cross each other, thereby forming the composite film. WO 02/102592 A1 discloses a laminate comprising a monofilm-formed or multifilm-formed ply (B) both mainly consisting of thermoplastic polymer material, whereby at least A consists of cold-orientable material in which A has a waved fluted configuration while B is not waved, and B on a first side is adhesively bonded in bonding zones to crests on a first side of A. Chinese patent application CN 201109217 Y discloses a multi-directionally tension-resistant, tear resistant composite film fabricated with at least two flat films formed by cutting a tubular flat film at an oblique angle of 15-75° to the edge of the film. These methods are both subject to limitations in use and cannot be universally used for improving the production of stretch films from various existing materials and processes.

    Summary of the Invention



    [0005] In view of the shortcomings of the prior art discussed above, it is an object of the present invention to provide a method for improving the tear resistance of composite films, which is suitable for extensive use in improving tear resistance of composite films fabricated from various existing materials and processes.

    [0006] To achieve the above object, the subject matter of the present invention is as follows:
    a method for improving tear resistance of a composite film, the composite film comprising two stretched films bonded together with an adhesive by hot rolling or UV curing, each of the stretched films comprising a primary stretch direction with a primary stretch ratio and a secondary stretch direction with a secondary stretch ratio, wherein the ratio of the primary stretch ratio to the secondary stretch ratio in each of the stretch films is in the range between 1.4:1 and 3.5:1, said method comprising arranging the two stretched films such that their primary stretch directions cross each other.

    [0007] In a preferred embodiment, the primary stretch directions of the two stretched films form an angle of 30-150°.

    [0008] In a more preferred embodiment, the primary stretch directions of the two stretched films form an angle of 60-120°.

    [0009] In an even more preferred embodiment, the primary stretch directions of the two stretched films form an angle of 90°.

    [0010] In a preferred embodiment, each of the stretched films is selected from a asymmetrically biaxially stretched film and a uniaxially stretched film.

    [0011] In a more preferred embodiment, the asymmetrically stretched films are produced using a flat-film method.

    [0012] As used herein, the term "asymmetric stretching" refers to a biaxial stretching process performed in such a manner that a stretch ratio in one direction (longitudinal or transverse) is greater than a stretch ratio in the other direction. An extreme scenario of asymmetric stretching is uniaxial stretching, i.e., orientation in only one of the directions and not at all in the other direction. In asymmetric stretching, the direction with the greater stretch ratio is known as a primary stretch direction, while the direction with the lesser stretch ratio is known as a secondary stretch direction. Accordingly, in uniaxial stretching, the direction in which stretching is performed is the primary stretch direction, while that in which stretching is not performed is the secondary stretch direction.

    [0013] As described herein, the flat film method refers to a process involving: casting a thick sheet using a T-die from pellets produced by an extruder; quickly cooling the sheet and heating it on hot rollers to a temperature for stretching; and performing synchronous or successive stretching as well as a final finish. Here, the synchronous stretching means stretching in both the longitudinal and transverse directions at the same time, while the successive stretching means stretching in one of the directions followed by stretching in the other direction. The present invention is limited neither to stretch films resulting from synchronous stretching or those from successive stretching nor to specific thicknesses of the individual stretch films, and designing according to specific applications is allowed.

    [0014] According to the present invention, the adhesive used in the bonding by hot rolling or UV curing is an existing adhesive for film bonding that contains a solvent or not, with a two-component polyurethane adhesive not containing a solvent being preferred.

    [0015] The present invention provides significant advances over the prior art as follows:
    1. 1. Composite films resulting from the invention possess significantly improved slit tear strength and tear resistance over biaxially stretched films with the same thicknesses.
    2. 2. It is widely applicable without being limited to specific film materials or stretching processes, and is easily extendible to the existing stretch film production.
    3. 3. It allows simple operations and is readily applicable to mass production.

    Brief Description of the Drawings



    [0016] The subject matter of the present invention will be described in further detail below with reference to several embodiment examples so that it can be fully understood.

    [0017] In the examples, each stretch film sample was prepared using a flat-film method including: making a cast sheet with a thickness of about 140-560 mm from a plastic material or a resin (a commercially available PET resin was used in the examples) using a multi-layer extruder (manufactured by Nanjing Chuangbo Machinery Co., Ltd.); placing the cast sheet on a film stretcher (manufactured by Brückner Maschinenbau GmbH and used at Beijing Research Institute of Chemical Industry (BRICI)), clamping it with clips and stretching it according to a preset program (stretch ratios and stretching temperatures); and finishing the resulting film by rapid cooling in the air.

    [0018] In the examples, tear resistance related tests were carried out using a CH-9002A-20 multi-functional tensile tester (manufactured by Suzhou Baoyuntong Testing Equipment Co., Ltd.). In each test, an approximately 20-mm-long slit was made in the film sample along a tear direction under test, and both ends of the slit were then clamped with clips. Afterward, the test was initiated under the control of an automatic program, followed by data collection.

    Example 1



    [0019] An adhesive (e.g., an TS9002A, TS9002B or TS9002C adhesive manufactured by Yantai) was uniformly applied to one side of a stretch film, and another stretch film was then bonded thereto after evaporation of a solvent contained in the adhesive such that a primary stretch direction (with a greater stretch ratio) of the second stretch film crossed that of the first stretch film at angles of 90°). The composite film was then subjected to hot rolling performed on a 60-85°C roller (the hot rolling temperature might depend on the adhesive used) and then placed at room temperature until it completely cured.

    [0020] Table 1 shows a tear resistance comparison among composite films formed from respective stretch films with different ratios of primary stretch ratio to secondary stretch ratio using the method according to this Example.
    Table 1
    Sample   Slit Tear Resistance
    Primary Stretch ratioSecondary Stretch ratioSingle Layer Thickness (µm)Sample Thickness (µm)Tearing Force (kg)Tear Strength (N/mm)
    3.9 3.8 100 100 0.07 7.18
    3.6 3.1 150 150 0.30 19.86
    4 1 75 150 1.03 67.49
    3.5 1 50 100 3.00 294.00
    2.7 1 50 100 3.44 337.27
    4 2.8 70 140 3.47 242.94


    [0021] As can be seen from Table 1, the composite stretch films obtained from the inventive method all had significantly increased tear strength over those of the biaxially stretched single-layer films having the same thicknesses. Although tear strength increased with sample thickness, compared to the 150-pm-thick biaxially stretched single-layer film whose tear strength was only 19.86 N/mm, the tear strength of the inventive 100-µm-thick composite film (with a ratio of primary stretch ratio to secondary stretch ratio of 2.7) was up to 337.27 N/mm. That is, a significant increase in tear resistance was obtained. In addition, the higher the asymmetry, the greater the slit tear strength. Ratios of primary stretch ratio to secondary stretch ratio of (1.4:1)-(3.5:1) corresponded to slit tear strength of 240-340 N/mm. However, at a ratio of primary stretch ratio to secondary stretch ratio of 4, tear strength tended to decrease even when the thickness was increased to 150µm.

    Example 2



    [0022] An adhesive (e.g., an 6062Aor 7725B adhesive produced by Henkel) was uniformly applied to one side of a stretch film, and another stretch film was then bonded thereto such that a primary stretch direction (with a greater stretch ratio) of the second stretch film crossed that of the first stretch film at angles of 90°). The composite film was subjected to hot rolling performed on a 60-85°C roller (the hot rolling temperature might depend on the adhesive used) and then placed at room temperature until it completely cured.

    [0023] Table 2 shows a tear resistance comparison among composite films formed from respective stretch films with different ratios of primary stretch ratio to secondary stretch ratio using the method according to this Example.
    Table 2
    SampleSlit Tear Resistance
    Primary Stretch ratioSecondary Stretch ratioSingle Layer Thickness (µm)Sample Thickness (µm)Tearing Force (kg)Tear Strength (N/mm)
    3.9 3.8 100 100 0.07 7.18
    3.6 3.1 150 150 0.30 19.86
    4 1 75 150 1.48 96.45
    3.5 1 50 100 6.22 609.79
    4 2 50 140 3.57 349.86


    [0024] As can be seen from Table 2, the composite stretch films obtained from the inventive method all had significantly increased tear strength over that of the biaxially stretched single-layer films having the same thicknesses. Although tear strength increased with sample thickness, compared to the 150-µm-thick biaxially stretched single-layer film whose tear strength was only 19.86 N/mm, the tear strength of the inventive 100-µm-thick composite stretch film (with a ratio of primary stretch ratio to secondary stretch ratio of 3.5) was up to 609.79 N/mm. That is, a significant increase in tear resistance was obtained. In addition, the higher the asymmetry, the greater the slit tear strength. Ratios of primary stretch ratio to secondary stretch ratio of (2:1)-(3.5:1) corresponded to slit tear strength of 340-610 N/mm. However, at a ratio of primary stretch ratio to secondary stretch ratio of 4, tear strength tended to decrease even when the thickness was increased to 150µm.

    [0025] It is revealed from a comparison between Tables 1 and 2 that when an adhesive containing a solvent is used in the bonding by hot rolling, the solvent may cause loose molecular orientation in the stretch films and hence lower tear strength.

    Example 3



    [0026] With reference to Example 2, a tear resistance comparison was made between a composite film resulting from asymmetrically biaxially stretched films obtained by simultaneous stretching and a composite film resulting from asymmetrically biaxially stretched films obtained by successive stretching. The test results are presented in Table 3.
    Table 3
    SampleSlit Tear Resistance
    Pri mar y Stre tch ratioSecondar y Stretch ratioSingle Layer Thickness (µm)Sample Thickne ss (µm)Tearin 9 Force (kg)Tear Streng th (N/mm )
    4 2.8 70 (simultane ous stretching) 140 0.78 54.81
    4 2.8 70 (successiv e stretching) 140 0.61 42.95


    [0027] As can be seen from the results in Table 3,the slit tear strength of the composite film made from the simultaneously biaxially stretched films was slightly higher than that of the composite film made from the successively biaxially stretched films, although the difference was significant.


    Claims

    1. A method for improving tear resistance of a composite film, the composite film comprising two stretched films bonded together with an adhesive by hot rolling or UV curing, each of the stretched films comprising a primary stretch direction with a primary stretch ratio and a secondary stretch direction with a secondary stretch ratio, wherein the ratio of the primary stretch ratio to the secondary stretch ratio in each of the stretch films is in the range between 1.4:1 and 3.5:1, said method comprising arranging the two stretched films such that their primary stretch directions cross each other.
     
    2. The method of claim 1, wherein the primary stretch directions of the two stretched films form an angle of 30-150°.
     
    3. The method of claim 2, wherein the primary stretch directions of the two stretched films form an angle of 60-120°.
     
    4. The method of claim 3, wherein the primary stretch directions of the two stretched films form an angle of 90°.
     
    5. The method of claim 1, wherein the two stretched films comprise one uniaxially stretched film and one asymmetrically biaxially stretched film.
     
    6. The method of claim 1, wherein each of the stretched films is selected from a uniaxially stretched film and an asymmetrically biaxially stretched film.
     


    Ansprüche

    1. Verfahren zur Verbesserung der Reißfestigkeit einer Verbundfolie, wobei die Verbundfolie zwei Streckfolien umfasst, die mit einem Klebstoff durch Warmwalzen oder UV-Härten miteinander verklebt werden, wobei jede der Streckfolien eine primäre Streckrichtung mit einem primären Streckverhältnis und eine sekundäre Streckrichtung mit einem sekundären Streckverhältnis umfasst, wobei das Verhältnis des primären Streckverhältnisses zu dem sekundären Streckverhältnis in jeder der Streckfolien im Bereich zwischen 1,4:1 und 3,5:1 liegt, wobei man bei dem Verfahren die zwei Streckfolien so anordnet, dass sich ihre primären Streckrichtungen kreuzen.
     
    2. Verfahren nach Anspruch 1, wobei die primären Streckrichtungen der zwei Streckfolien einen Winkel von 30-150° bilden.
     
    3. Verfahren nach Anspruch 2, wobei die primären Streckrichtungen der zwei Streckfolien einen Winkel von 60-120° bilden.
     
    4. Verfahren nach Anspruch 3, wobei die primären Streckrichtungen der zwei Streckfolien einen Winkel von 90° bilden.
     
    5. Verfahren nach Anspruch 1, wobei die zwei Streckfolien eine monoaxial verstreckte Folie und eine asymmetrisch biaxial verstreckte Folie umfassen.
     
    6. Verfahren nach Anspruch 1, wobei jede der Streckfolien aus einer monoaxial verstreckten Folie und einer asymmetrisch biaxial verstreckten Folie ausgewählt ist.
     


    Revendications

    1. Procédé pour l'amélioration de la résistance à la déchirure d'un film composite, le film composite comprenant deux films étirés liés l'un à l'autre avec un adhésif par laminage à chaud ou par durcissement aux UV, chacun des films étirés comprenant une direction d'étirement primaire dotée d'un rapport d'étirement primaire et une direction d'étirement secondaire dotée d'un rapport d'étirement secondaire, le rapport du rapport d'étirement primaire sur le rapport d'étirement secondaire dans chacun des films étirés se situant dans la plage entre 1,4:1 et 3,5:1, ledit procédé comprenant l'agencement des deux films étirés de sorte que leurs directions d'étirement primaire se croisent.
     
    2. Procédé selon la revendication 1, les directions d'étirement primaire des deux films étirés formant un angle de 30 à 150°.
     
    3. Procédé selon la revendication 2, les directions d'étirement primaire des deux films étirés formant un angle de 60 à 120°.
     
    4. Procédé selon la revendication 3, les directions d'étirement primaire des deux films étirés formant un angle de 90°.
     
    5. Procédé selon la revendication 1, les deux films étirés comprenant un film étiré de manière uniaxiale et un film étiré asymétriquement de manière biaxiale.
     
    6. Procédé selon la revendication 1, chacun des films étirés étant choisi parmi un film étiré de manière uniaxiale et un film étiré asymétriquement de manière biaxiale.
     




    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description