• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1456379 Laminates SUMITOMO BAKELITE CO Ltd 21 Dec 1973 [27 Dec 1972 (4)] 59501/73 Heading B5N [Also in Division C3] Composite materials comprising (1) a thermoplastic resin comprising 2 to 50 parts by weight of chlorinated polyethylene having a specific gravity of 1À00 to 1À35, a chlorine content of 5 to 50 weight per cent and a molecular weight of 20,000 to 200,000 and 100 parts by weight of polyvinyl chloride having a mean degree of polymerization of 300 to 2500 and (2) an olefinic polymer may be prepared by pressing the thermoplastic resin and olefinic polymer together at elevated temperature. In examples (1) sheets of polyvinyl chloride (PVC) or vinyl chloride/vinyl acetate copolymer and chlorinated polyethylene (CPE) are heat bonded to the polyethylene surfaces of polyethylene/polyethylene terephthalate film laminates, (2) PVC/CPE compositions and polyethylene are coextruded to form composite film, (3) PVC/CPE sheets are heat bonded to films of polyethylene, ethylene/vinyl acetate copolymer and ethylene/ sodium acrylate ionomer, and (4) a laminate of sheets of compositions of PVC or vinyl chloride/ vinyl acetate copolymer with CPE is heat bonded to polyethylene sheet.
    公开号:SU912047A3
    申请号:SU731988581
    申请日:1973-12-26
    公开日:1982-03-07
    发明作者:Исии Ко；Есида Тадамаса
    申请人:Сумитомо Бейклайт Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    I
    The invention relates to methods of gluing polymers of polyolefin and polyvinyl chloride with each other or, with other materials, at elevated temperature and pressure using 5 glue of adhesives.
    It is known that a large number of adhesives, each of which has specific properties, and is used for specific purposes. Polyvinyl chloride and olefin polymer, for example., Polyethylene, polypropylene, etc., are used in large quantities because of their good Properties and low cost .15
    Olefin polymer and polyvinyl chloride can be glued together with one or several adhesives, but it is almost impossible to heat them together, since olefin polymers have a weak polarity of JQ, while polyvinyl chloride is a polar material with poor crystallinity. Usually, the olefin polymer and polyvinyl chloride are glued together with adhesive substances after activation.
    vanishing their surface with organic peroxide, irradiating with ionizing radiation, treating with an oxidizing gas, etc. Heat bonding of olefinic polymers and polyvinylchloride is achieved only after a certain treatment and using a third material. .
    The closest to the invention in its technical essence is the method of gluing polyolefin polymers to polyvinyl chloride with other thermoplastic materials at elevated temperature and pressure. The method involves the use of an intermediate layer of a polymer film comprising the links of both of the combined polymers C 1
    A disadvantage of the known method is that in order to ensure sufficient adhesion strength between the materials being joined, it is necessary in each particular case to prepare a copolymer for an intermediate layer film.
    39
    The purpose of the invention is to increase the bonding strength of dissimilar thermoplastic materials.
    This goal is achieved by the fact that when gluing polymers of olefin and polyvinyl chloride with each other or with other materials at elevated temperature and pressure using glue, a composition comprising 2-50 parts by weight is used as glue. chlorinated polyethylene having a specific gravity of 1.00-1.35, with a chlorine content of 550% and an average molecular weight of 20,000-200,000, and 100 parts by weight. polyvinyl chloride having an average degree of polymerization of 300-2500.
    Moreover, the adhesive can be used in the form of a film, sheet or solution in an organic solvent.
    When using such glue, you can glue polyvinyl chloride and olefin polymer by thermal bonding without prior surface treatment. Simultaneous extrusion method, extrusion method, and other known methods can be used for thermal bonding. During simultaneous extrusion, the extrusion temperature should not be higher and the temperature of the die should not be higher.
    In the manufacture of laminates with extrusion, it is desirable that the olefin polymer is extruded and laminated simultaneously. When using the extrusion method, the temperature is not higher, the polyvinyl chloride thermally decomposes at higher temperatures and a decrease in productivity is possible.
    When using glue in the form of a solution, solvents can also be used as aromatic hydrocarbons, for example benzene, toluene, chlorinated organic compounds such as carbon tetrachloride, trichlorethylene, tetrachlorethylene, tetrachloroethane, chlorobenzene, in addition, tetrahydrofuran, methyl ethyl ketone, di-hexane and mixtures of solvents.
    98-70% w / w or preferably 95-80% w / w solvent in a liquid adhesive is typically used. Chlorinated polyethylene does not always completely dissolve in organic solvents; therefore, glue can be used in the form of a uniform gel or in a swollen state.
    74
    The adhesive may additionally contain materials commonly used to improve the properties and processability of polyvinyl chloride, such as plasticizers, fillers, antioxidants in small quantities.
    Example 1. Polyvinyl chloride having a degree of polymerization of 400,
    and non-crystalline chlorinated polyethylene with an average molecular weight of about 40,000 and containing 30% chlorine is dissolved in different ratios in solvents,
    listed in table. one.
    Each of these adhesives is applied t-using an applicator to aluminum foil with a thickness of 25 μm and dried. This foil with a layer of glue is then glued to a low-density polyethylene film with a thickness of 80 microns when heated. In this case, the metal uncoated surface comes into contact with the hot plate of the heat treatment machine.
    glueing and C1 bonding are made in the following conditions:
    Hot pl150 temperatures
    YOU,
    Pressure, kg / cm
    2 Duration of gluing, с1,0 The surface of the applied polyethylene film is not treated.
    When testing the samples for delamination by the ASTM-D1876-6IT method, it was established that the delamination strength of samples 1-6 is 0 respectively; 0.08; 0.36; 0.60; 0.68 and 0.60 kg / cm.
    Example 2. After applying the glue, as described in example 1, onto aluminum foil and subsequent drying, the foil is glued together with a 200 μm thick film of solid polyvinyl chloride when heated. Heat bonding is performed under the following conditions:
    Hot plate temperature, c160
    Pressure, kg / cm 4 Duration of gluing, c2
    When testing the obtained samples as described in example 1, it was found that the peel strength of samples 1.-6 was 1.80; 1.88; 2.20; 2.32; 1.72 and 1.20 kg / cm, respectively. Example 3. Polyvinyl chloride, containing 5% vinyl acetate and having an average degree of polymerization of 400, and non-crystalline chlorinated polyethylene, having an average molecular weight of about 40,000 and a chlorine content of 35%, are dissolved in the solvents listed in Table 2. After applying the applicator with prepared adhesive onto a film of solid polyvinyl chloride with a thickness of 250 microns and drying it is glued with a method of thermal gluing, a film of low density polyethylene with a thickness of 80 microns whose surface was not subjected to any pretreatment, under the following conditions: Hot plate temperature, C .150 pressure, kg / cm 2 Duration of thermal bonding, s 2 Samples of the obtained film are tested for delamination by the ASTM-D method. 1876-6IT, whereby it was found that the peel strength of samples 7-12 was 0; 0.12; 0.48; 0.72; Oh, 64. and 0.52 kg / cm, respectively. Example 4. After applying the adhesive, as described in example 3, on a 6-nylon film with a thickness of 80 microns, the surface of which was not subjected to any treatment, and after drying, a 250-micron thick solid polyvinyl chloride film and 250-micron polyethylene film are glued to this film when heated. in the following conditions: The temperature is hot. plates, C220 Applied pressure, Duration, thermal bonding, 2 When testing samples for delamination, as described in Example 3, the results are given in Table 5. Example: On a 0.45-meter calender, prepare two films 50 μm thick each, Apply two types of compositions listed in Table. 4. Each film is placed between a film of 6-nylon with a thickness of 80 microns, the surface of which is not treated, and a polyvinyl chloride film with a thickness of 100 microns 47. 6 and the entire assembly is subjected to thermal gluing under the following conditions: Hot plate temperature, ° С220 Applied pressure, kg / cm 2 Duration of thermal bonding, s 2 When testing the delamination between the 6-nylon film and the polyvinyl chloride film using the А5ТМ-Д-1876-6IT method, the delamination strength for samples 13 and 14 was 0.68 and About kg / cm, respectively. Consequently, the film consisting of a mixture of additionally chlorinated polyethylene and polyvinyl chloride is an effective adhesive for the thermal welding of a 6-nylon film and a film of polyvinyl chloride. EXAMPLE 6. The application of the film-forming adhesive of Example 5 produces heat-bonding under the conditions specified in Example 5. The films glued together when using the film-forming adhesive are listed in Table. where the results of testing the delamination of samples are also given. Example 7. Four different copolymers of vinyl chloride and noncrystalline chlorinated polyethylene with a molecular weight of about 30,000 and a chlorine content BL / J are dissolved in a solvent, the composition of which is given in table. 6, and get four glue. The following wikyl chloride copolymers are used: Glue 15. A copolymer of vinyl chloride, having an apparent average degree of polymerization of about 400 and containing 1% ethylene. Glue 16. A vinyl chloride copolymer having a mean polymerization degree of about 450 and containing 10% acrylic acid. Glue 17. A grafted copolymer of ethylene, vinyl acetate and vinyl chloride, having an average degree of polymerization of about 800 (the trade name is Sumigraft CB from Sumitomo Chemicals Company). Glue 18o Chlorinated podinyl chloride, having an apparent average polymerization degree of about 700 and containing 65% chlorine. After each applicator applied the film on a 6-6 nylon film with a thickness of 50 µm, which surface was not treated, and dried, a film of hard polyvinyl chloride 250 µm thick was glued to this tape, using glue 15, a polypropyl film on a thickness of 100 µm, using adhesive 16, ethylene-acrylic acid copolymer film 50 acm thick, direct adhesive 17, and ethylene methacrylate ionomer film with 50 µm toogacin, use adhesive 18. Thermal bonding is performed under the following conditions: The temperature of the hot plate. Applied pressure, kg / cm 2 Duration of thermal bonding, s 2 Then the peel strength is determined, which is 0.32; 0.20; 0.56 and 0., 28 kg / cm for samples 15-18, respectively Example 8. Eight different films, each 40 microns thick, are prepared on a calender. A layer of glue is placed between specific films and, after thermal gluing, the peel strength of all samples is determined. Glue 19. Vinyl chloride copolymer having an apparent polymerization degree of about 750 and containing 1% ethylene. Glue 20. Vinyl chloride copolymer, having an apparent average degree of polymerization of about 800 and containing 10% acrylic acid. Glue 21. Grafted copolymer of ethyl, vinyl acetate and vinyl chloride, which has an apparent average degree of polymerization of about 1000, the trade name Sumigraft of Sumitomo Chemical Company,. Glue 22. Chlorinated polyvinyl chloride, having an apparent average polymerization degree of about 700 and containing 65% chlorine. Specific films are films of a mixture of 15% polyethylene and 85% polypropylene with a thickness of 150 microns (A); a mixture of 10% copolymer, 90% ethylene and 10% vinyl acetate and 90% polyethylene with a thickness of 100 microns (polybutylene film 100 microns (in); 6-10-nail film on a thickness of 50 microns (G) polyvinyl chloride film with a thickness of 250 microns ( d),, 1 stitched chlorinated polyvinyl chloride with a thickness of 250 microns (k) and a mixture film of 97% polyvinyl chloride and 3% polypropylene with a thickness of 250 μm (g). The compositions of the adhesives and the results are shown in Table 7. 8, is used to make films with an alternating calender return shaft of b - type. The prepared film is glued by thermal gluing to a laminated film consisting of a polyethylene terephthalate film 25 μm thick and a high-pressure polyethylene film 60 μm thick, under the following conditions: Hot plate temperature, C220 Applied pressure., kg / cm 2 Duration of thermal gluing c 2 Then the samples of all the films are tested for delamination by the AS-TM-fl1876-61T method, as a result of which it was established that the peel strength of the samples of "Experiments 1-5 is 0; 0.12; 0.72; 0.88 and 1.0 kg / cm, respectively. Consequently, polyvinyl chloride mixed with chlorinated polyethylene; nom, can be glued together with polyethylene film when heated. Properties of resin compositions are shown in Table. 9. Therefore, polyvinyl chloride compositions containing 2-50 parts by weight. chlorinated polyethylene, have the properties of polyvinyl chloride and can be glued together when heat is applied to polyethylene. . Example 10. The apparatus used to form a bilayer extruded film consists of an extruder 1 with an internal diameter of 90 mm and an extruder II with an internal diameter of 50 mm. The melts removed from the extruders are joined and melted in the same die. Low pressure polyethylene, having a melting index of 1.0, is extruded through an extruder II and a film with a thickness of about 100 microns is obtained, and the polyvinyl chloride composition indicated in Table 2. 7 and 8, extruder I is melt extruded from the melt and a film is made of thickness
    9
    about 500 microns; thus, a two-layer film is made.
    The compositions are given in table. ten,
    After chilling, the adhesion of the layered film is measured; The complex film of experiment b is easily separated into two layers, while the layers of the film of experiment 7 are difficult to separate from each other.
    On the polyethylene side of the two-layer film, 1 cuts are made with a depth greater than the thickness of the polyethylene film, 2 mm apart from each other. An adhesive tape is pressed on the surface of the incised layer, pressed by hand, and then removed by hand. The notched layers are not removed with adhesive tape, which proves that the two layers after thermal gluing of the double layer film of experiment 7 have sufficient adhesion.
    Consequently, by the co-extrusion method, such a complex film of polyvinyl chloride and olefin polymer can be obtained with a thermal gluing process that cannot be prepared using conventional methods.
    Example 11. From each composition of polyvinyl chloride (average degree of polymerization 700), shown in Table. : 8, films with a thickness of 250 microns are made using a calender roll.
    The composition is given in table. AND.
    Then when ekstUDUdirovaniya. 50 μm thick films are prepared from the following olefin polymers: polyethylene: a mixture of 90% polyethylene and 10% copolymer of ethylene and vinyl acetate, ethylene ion meter, and sodium acrylate.
    047. 10
    Each prepared film and film of experience 8--, nlc9 is passed through a pressure roll to form two-layer films, S The layers of the two-layer film of experiment 9 are easily separated after cooling, while the layers of film of experiment 8 are not. even when using adhesive tape, as described
    0 in example 10.
    Example 12, From each KOMnoci tion, whose composition is shown in. Tabl, 12, produces a film of a thickness of 500 μm using a calender film.
    roll.
    The films are made of a multilayer material measuring just 10 mm. on which a new film with a thickness of I mm is laid, and the following conditions are pressed;
    Temperature is hot
    plates, C
    180
    Applied pressure, 5 kg / cm
    sho
    Duration
    ten
    pressing, min
    The layered product has dimensions of I K 1 m. After cooling this multilayer material, the polyethylene layer is easily separated from the polyvinyl chloride layer in experiments 10 and 12, while the polyethylene layer cannot be separated manually from the polyvinyl chloride layer in experiments P to 13,
    five
    The material manufactured in accordance with the proposed method can be used for various purposes, for example for packaging food products, medicines, and their products, etc.
    I
    t a
    faces
    Polivi nilchloride
    Chlorinated polyethylene
    Ca-Zn Soap
    Methyl ethyl ketone
    Tetrahydrofuran
    ABOUT
    ten
    50
    100
    Polyvinyl chloride containing 5% vinyl acetate
    6-nylon chlorinated (Polyvinyl chloride) O0.04 0.32 6-nylon (polyethylene)
    Composition
    Polyvinyl chloride (average
    degree of polymerization 800)
    Chlorinated ethylene (average molecular weight about 45,000, chlorine content 30%)
    Qa-Zrf soap
    Stearic acid (grease)
    Epoxidized Soy
    butter
    ABOUT
    ten
    100 90 0.04 0.12
    T a 6 l and / c a 4
    Content, parts
    14
    13 1,08 1,16 1,20 0,44 0,60 0,72
    13
    Films
    Hard plasticine (thickness 100 microns) Low density polyethylene (thickness 80 microns)
    Rigid polyvinyl chloride (100 micron thickness) aluminum foil (thickness 25 micron).
    Low density polyethylene (thickness 80 microns)
    Aluminum foil (thickness 25 microns)
    6-nylon (thickness 80 microns) low density polyethylene (thickness 80 microns)
    Vinyl copolymer 100 100. 100 100 100 chloride
    Chlorinated polyethylene (average molecular weight about 30,000, chlorine content 34%)
    91204714
    . -f
    G al b l n c a 5
    The strength of delamination, kg / cm
    14
    13
    100 100 100
    20, About
    20
    20 o
    15
    Ca-Zn Soap
    Stearic acid (grease)
    Epoxidized Soybean Oil
    Specific
    Polyvinyl chloride (cf. degree of polymerization 700)
    Copolymer of 5% vinyl acetate and vinyl chloride (average degree of polymerization 650)
    Chlorinated polyethylene (average molecular weight about 38,000, chlorine content 40%)
    Ca-Zn soap (stabilizer)
    Epoxidized Soybean Oil
    Stearic acid (grease)
    9120A7
    16 Continued table. 7
    T a b | I C and 8
    100 100 100 O
    100
    too oh
    Polyvinyl chloride (average degree of polymerization 700),.
    Chlorinated polyethylene (average molecular weight about 30000i chlorine content 30%)
    Octyl Tin Stabilizer
    Epoxidized Soybean Oil
    Antioxidant type alkylphenol
    Stearic acid
    (grease)
    Stearyic Acid Butyl Ester
    100
    20
    3.5
    4.0
    0.4
    2.0
    0.1
    Components
    Polyvinyl chloride
    Chlorinated polyethylene (average molecular weight about 30,000, chlorine content 30%)
    Ca-Zn 2 Stabilizer
    Epoxidized Soybean Oil
    Stearic acid
    Components
    Polyvinyl chloride (average polymerization degree is about 1000)
    Vinyl chloride copolymer containing 5% vinyl acetate (average polymerization degree of about 800)
    Chlorinated polyethylene (average molecular weight about 30,000, chlorine content about 35%)
    Phthalic acid plasticizer
    Stabilizer type .PB
    权利要求:
    Claims (2)
    [1]
    Stearic acid (lubricant) Claim 1. Gluing polymers of olefin and polyvinyl chloride with each other or with other materials at elevated temperature and pressure using glue, characterized in that, in order to increase the bonding strength,
    Composition, parts by weight
    100
    About 2
    3
    3
    2
    mv
    Table 12
    Composition, parts by weight
    11 12
    ten
    13
    100 100 O
    About 100
    100
    30 o
    thirty
    10 10
    10 3 3 3 an adhesive composition was used, comprising 2-50 parts by weight. chlorinated polyethylene having ud. 1.00-1.35, with a chlorine content of 5-50% and an average molecular weight of 20,000,200,000, and 100 parts by weight polyvinyl chloride having an average degree of polymerization of 300-2500.
    2191204722
    [2]
    2. The method according to p. 1, distinction-sources of information
    Yu and with the fact that, the glue used in consideration in the examination is in the form of a film, sheet or growth I, USSR Author's Certificate
    thief in an organic solvent. No. 468794, cl. From 09 J 5/10, 1972.
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    同族专利:
    公开号 | 公开日
    DE2364806B2|1979-03-15|
    DE2365851C2|1982-08-05|
    AU475475B2|1976-08-26|
    FR2212409A1|1974-07-26|
    GB1456379A|1976-11-24|
    DE2365851A1|1976-07-29|
    AU6385873A|1975-06-26|
    FR2212409B1|1976-10-08|
    IT1000788B|1976-04-10|
    CA1028110A|1978-03-21|
    DE2364806A1|1974-07-11|
    DE2364806C3|1984-11-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2543218C2|2009-08-26|2015-02-27|Хенкель Аг Унд Ко. Кгаа|Two-component water-based adhesive|BE599711A|1960-02-01|
    US3134496A|1961-09-11|1964-05-26|Continental Can Co|Closure member gasket compositions|
    FR1374521A|1962-08-31|1964-10-09|Allied Chem|Compositions and ground covers made from these compositions|
    US3459591A|1964-11-17|1969-08-05|Daicel Ltd|Process for coating polyolefinic films to make them heat-sealable and gas and water-vapor impermeable|
    US3423231A|1965-05-20|1969-01-21|Ethyl Corp|Multilayer polymeric film|US4156749A|1978-01-18|1979-05-29|Union Carbide Corporation|Elastic multilayer packaging film containing plasticized polyvinyl chloride|
    DE2914463A1|1979-04-10|1980-10-23|Hoechst Ag|MEDICAL DEVICES FOR PARENTERAL LIQUIDS|
    IT1194942B|1980-05-09|1988-09-28|Gaspare Puleo|METHOD AND EQUIPMENT FOR THE PRODUCTION THROUGH THE BLOWN EXTRUSION SYSTEM OF COEXTRUDED PVC FILMS OR OTHER THERMOPLASTIC MATERIALS WITH TWO OR MORE LAYERS, IN THE FORM OF AN EXTENSIBLE FILM OR SUCH AS THREADED OR MONO-ORIENTED, WHICH IS MONO-POINTED, WHICH IS MONO-POINTED, WHICH IS MONO-POINTED, WHICH IS MONO-POINTED, WHICH IS MONO-POINTED, WHICH IS MONO-POINTED, WHICH IS SINGLE POINTED, WHICH IS MONO-POINTED, WHICH IS SINGLE POINTED, WHICH IS SINGLE POINTED, WHICH IS SINGLE POINTED, WHICH IS SINGLE POINTED, WHICH IS DETERMINED.|
    JPH0454712B2|1983-12-21|1992-09-01|Mitsui Petrochemical Ind|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP12998972A|JPS4997047A|1972-12-27|1972-12-27|
    JP12999072A|JPS5143508B2|1972-12-27|1972-12-27|
    JP12999272A|JPS5143512B2|1972-12-27|1972-12-27|
    JP47129991A|JPS5229775B2|1972-12-27|1972-12-27|
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