WO2014104630A1 - Film pour revêtement intérieur et son procédé de fabrication - Google Patents

Film pour revêtement intérieur et son procédé de fabrication Download PDF

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Publication number
WO2014104630A1
WO2014104630A1 PCT/KR2013/011626 KR2013011626W WO2014104630A1 WO 2014104630 A1 WO2014104630 A1 WO 2014104630A1 KR 2013011626 W KR2013011626 W KR 2013011626W WO 2014104630 A1 WO2014104630 A1 WO 2014104630A1
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WO
WIPO (PCT)
Prior art keywords
film
base film
polyamide
innerliner
inner liner
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Application number
PCT/KR2013/011626
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English (en)
Korean (ko)
Inventor
정영한
권소연
남궁현
김성훈
Original Assignee
코오롱인더스트리 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020130154636A external-priority patent/KR20140088008A/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to US14/654,337 priority Critical patent/US20150329744A1/en
Priority to CN201380069034.XA priority patent/CN104884560A/zh
Publication of WO2014104630A1 publication Critical patent/WO2014104630A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2477/00—Presence of polyamide
    • C09J2477/006—Presence of polyamide in the substrate

Definitions

  • the present invention relates to an innerliner film and a method for producing the same. More specifically, it is possible to lighten tires and improve fuel efficiency by implementing excellent airtightness even at a thin thickness, and to provide an inner liner film and an inner liner film having mechanical properties such as high durability and fatigue resistance with excellent formability. It relates to a manufacturing method.
  • the tires support the load on the car. To mitigate the impact from the road. It acts to transfer the driving force or braking force of the vehicle to the ground.
  • tires are also a composite of fiber / steel / rubber. It is common to have a structure like 1 ' .
  • Body Ply (or Carcass) (6): This is a layer of cord inside the tire, which must support load, withstand stratification and have strong fatigue resistance to flexing during driving.
  • Side Wall (3) It refers to the rubber layer between the lower part of the shoulder (2) and the bead (9), and serves to protect the inner body ply (6).
  • Inner Liner (7) Replace with tube . It is located on the inside of the ear to prevent air leakage and enables pneumatic tires.
  • Wire-It is a rubber-coated square or hexagonal wire bundle that rests and fixes the tire to the rim.
  • CAP PLY (4) A special Koh H magazine located on the belt of some passenger car radial tires to minimize belt movement when driving.
  • APEX (8) A triangular rubber filling used to minimize the dispersion of beads, to mitigate external impacts, to protect the beads, and to prevent the ingress of air during molding. . .
  • Tubeless tires with high pressure air injected in the range of about 40 to psi are commonly used .
  • a highly airtight inner liner is arranged in the carcass inner layer.
  • an innerliner was used mainly composed of rubber components such as butyl rubber or halo butyl rubber having relatively low air permeability.
  • the content of the rubber or the thickness of the innerliner had to be increased to obtain sufficient airtightness.
  • the content of ⁇ eu and the tire thickness of the rubber component increases, there is a problem that the tire is the total weight of the fuel efficiency degradation increases.
  • the rubber component are relatively "gajyeoseo a low heat resistance, in the vulcanizing process of the tire of a car or the operation process is repeated deformation in high-temperature conditions that occur in the air between the inner surface of the carcass layer and the inner liner rubber.
  • the innerliner obtained by the previously known method is a phenomenon in which the physical properties of itself or cracks in the film occur during the manufacturing process of tires in which repeated molding of silver is formed or in the process of driving a car which is repeatedly deformed and generates high heat. Appeared.
  • the present invention implements excellent airtightness even at a thin thickness to reduce the weight of the tire and improve the fuel economy of the car, and with excellent formability, high durability and It is to provide an inner liner film having mechanical properties such as fatigue resistance. Moreover, this invention is providing the washing
  • the present invention is a polyamide resin (a), polyamide (poly-amide)
  • a copolymer (b) comprising a segment and a polyether ether segment, and a polymer crystallization retardant (c) . And an adhesive layer formed on at least one surface of the substrate film layer, wherein the adhesive layer comprises a resorcinol-formalin-latex (RFL) adhesive agent; and the content of the polyether segment of the copolymer.
  • RTL resorcinol-formalin-latex
  • an innerliner film having a weight of 2 to 3 ⁇ 4 to 40% by weight based on the total weight of the base film pack.
  • this invention is a plyamide-type resin (a). Melting a mixture comprising a copolymer (b) comprising a polyamide-based segment and a polyether-based segment, and a polymer crystallization retarder (c); at 230 to 300 ° C And extruding to form a base film layer, and forming an adhesive worm including a resorcinol-formalin-latex (RFL) -based adhesive on at least one surface of the base film layer.
  • RTL resorcinol-formalin-latex
  • Inner film for the inner liner and the inner liner according to a specific embodiment of the present invention .
  • the manufacturing method of a film is demonstrated in more detail.
  • An adhesive layer comprising a resorcinol-formalin—latex (RFL) -based adhesive, wherein the content of the polyether-based segment of the copolymer is from 2% by weight to 40% by weight relative to the total weight of the base film charge.
  • An inner liner film may be provided.
  • the copolymer including the polyether-based segment in a specific content the base film layer formed by using the polyamide-based resin and the polymer crystallization retarder together. Excellent airtightness even with a thin thickness can make the tire lighter and improve the fuel economy of the car. It has been confirmed that an innerliner film having high heat resistance and exhibiting mechanical properties such as high durability and fatigue resistance with excellent moldability can be provided. ⁇
  • the base film filler contains a polymer crystallization retardant.
  • the innerliner film may have a low modulus property with sufficient strength, and the crystallinity of the base film layer is not so large even through the forming process or stretching process of 100 ° C. or higher, and thus the modulus property / elasticity or elastic recovery rate It is possible to ensure excellent moldability since the back is not greatly reduced.
  • the adhesive agent containing a resorcinol formalin- latex (RFL) type adhesive agent is formed on the said base film layer. It has been found that it can be firmly bonded to the tire without applying additional vulcanization processes or significantly increasing the thickness of the adhesive layer.
  • the polymer crystallization retardant is included in the base film layer . Can lower the crystallinity.
  • the polymer crystallization retardant may be a compound including at least one reactive functional group selected from the group consisting of a hydroxyl group and a carboxyl group.
  • a polymer used or synthesized in the manufacturing process of the base film layer for example, a polyamide-based resin (a) and a polyamide-based segment and a polyether (poly- (b) more crosslinking reactions can occur between each or each other. Accordingly, the crystallinity of the base film layer may be lowered.
  • the inner liner film may increase durability against external lamination or self deformation, and may prevent the film itself from breaking or tearing during the storage process or tire manufacturing process of the film.
  • the orientation of the base film pack is lowered and the modulus is reduced to some extent to provide an inner liner film having high elasticity and durability.
  • the polymer crystallization retardant is used.
  • the physicochemical properties of the film layer can also be optimized for the innerliner film.
  • the polymer crystallization retardant is aromatic polycarboxylic acid.
  • Aromatic polycarboxylic acid esters may include one or more compounds selected from the group consisting of aromatic polycarboxylic anhydrides and polyols.
  • the aromatic carboxylic acid has 6 to 6 carbon atoms substituted with two or more carboxyl groups
  • aromatic ring compounds may include 20 aromatic ring compounds. More specifically, it may be benzene tricarboxylic acid, benzene tetracarboxylic acid or a combination thereof. Examples of the benzene tricarboxylic acid include trimesic acid or trimellitic acid. Further, examples of the benzene tetracarboxylic acid include benzene-1.2,4.5-tetracarboxylic acid.
  • the aromatic polycarboxylic acid ester may be a compound in which hydrogen of the carboxyl group of the aromatic carboxylic acid is substituted with a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the aromatic polycarboxylic anhydride means a compound in which two carboxyl groups of the aromatic carboxylic acid react to form anhydride functional group.
  • the polyol is a compound containing two or more hydroxy groups, specific examples of which include pentaerythritol and dipentaerythr itol. Tripentaerythr itol, trimethylolethane, trimethyl propane !; ⁇ ! ⁇ ⁇ ⁇ , trimethylolbutane, glycerol. 1,3, 5-tris (2—hydroxyethyl) isocyanurate (1.3,5-tns (2—hydroxyethyl) isocyaiuirate) or a combination of two or more thereof.
  • the base film layer may include 0.01 to 8% by weight of a polymer crystallization retardant. If the content of the polymer crystallization and the retardant is too small, the degree of crosslinking between the polymers included in the base film filling is not sufficient and the crystallinity cannot be sufficiently lowered. When the content of the polymer crystallization retardant is too high, the compatibility with other components included in the base film is low, so that the physical properties of the innerliner film is lowered. Unnecessarily many crosslinking may arise in a base film.
  • the base film layer may further include a heat resistant agent.
  • the degree of crystallinity of the polymer may be significantly lowered. Accordingly, even in a high temperature environment, even when left for a long time or exposed, the physical properties of the polymer may not be significantly reduced. I.e., as the heat-resistant agent is added to the base film charge. In the process of forming tires, the phenomenon of base film filling crystallization or hardening to a high level can be significantly reduced. It is possible to prevent the occurrence of cracks or breakages in the innerliner even in the driving point of the car which is repeatedly subjected to repeated deformation and high temperature.
  • the base film layer ⁇ may include a heat resistant agent 50 to 5,000ppmw.
  • a heat resistant agent 50 to 5,000ppmw When the content of the heat resistant agent is too small, the effect of improving heat resistance may be insignificant. Also. If the heat-resistant agent content is too large may decrease the physical properties of the base film layer. There is virtually no effect of improving the heat resistance according to the content used, which can unnecessarily increase the price of the final product.
  • heat resistant agents include.
  • An aromatic amine compound, a hindered phenol compound, a phosphorus compound, an inorganic compound, a polyamide compound, a polyether compound, or a mixture of two or more thereof can be used.
  • the heat-resistant agent may be applied in the production method to be described later to the powder (powder) form or in liquid form and the like.
  • hindered phenolic compound N. ⁇ '-nuclear methylene bis (3.5-diethyl-4-hydroxy-hydrocinamide) or pentaerythri to tetrakis 3- (3,5-di-t-butyl- 4-hydroxyphenyl) propion Eight [Pentaerythritol Tetrakis (3- (3, 5-d l-te t ⁇ bu ty 1 -4-hydr oxypheny 1) i * oi ona te), ⁇ ) version 1 rganox 1010]
  • the examples of the hindered phenol compound that can be used as the heat resistant agent are not limited thereto.
  • aromatic amine compound examples include 2,2,4-trimethyl-1,2-dihydroquinoline or polymers thereof.
  • the phosphorus-based compound examples include triphenyl phosphate (PPP), triaryl phosphate, aromatic phosphate esters, 2-ethylethylsilyl diphenyl phosphate, triethylene phosphate, tricresyl phosphate (TCP), cresyl phenyl phosphate, and chlorethyl phosphate.
  • PPP triphenyl phosphate
  • triaryl phosphate aromatic phosphate esters
  • 2-ethylethylsilyl diphenyl phosphate triethylene phosphate
  • TCP tricresyl phosphate
  • cresyl phenyl phosphate cresyl phenyl phosphate
  • chlorethyl phosphate Tris- ⁇ -chlorpropyl phosphate
  • Tris dichlorpro 3 ⁇ 4 phosphate Tris dichlorpro 3 ⁇ 4 phosphate,. Halogen-containing condensed phosphate esters and aromatic condensed phosphate esters. Although polyphosphate, red phosphorus, or two or more combinations thereof are mentioned, The example of the phosphorus compound which can be used as said heat resistant agent is not limited to this.
  • inorganic compound Mg (0H) 2 , AK0H) 2, Sb 2 0 3 , guadidine salt.
  • Sb 2 0 5 zinc borate, molybdenum compound, zinc stannate, Cul .
  • iodide compounds such as KI, or two or more mismatches thereof.
  • the mixture of Cul and KI When the mixture of Cul and KI is used as the heat resistant agent, it can be used as 50 ⁇ ⁇ to l, 000ppw compared to the paper film. And ⁇ the content of copper ( ⁇ in the mixture of Cul and 1 (1) may be 5 to 10 weight? 3 ⁇ 4.
  • the gong-group heat resistance can be greatly improved while hardly affecting other physical properties of the base film layer.
  • the innerliner film may have a relatively low crystallinity and may have a lower modulus property and a higher elasticity or elasticity stiffness rate, so that the innerliner may be subjected to continuous deformation and vehicle driving under external pressure. The film may be prevented from being broken or torn, thereby ensuring higher durability.
  • the base film is a polyamide-based.
  • a copolymer containing a specific amount of polyether-based segments that impart elastomeric properties to the resin It can have a relatively low modulus with good airtightness.
  • the polyamide-based resin included in the base film pack exhibits excellent airtightness due to its inherent molecular chain properties, for example, about 10 to 20 times higher than that of butyl rubber generally used in tires at the same thickness. The modulus is not so high compared to other resins. And.
  • the polyether-based segment of the copolymer may be present in a bonded or dispersed state between polyamide-based segments or polyamide-based resins, thereby lowering the modulus of the base film layer, and The increase in the rigidity can be suppressed and the crystallization at a high temperature can be prevented.
  • the base film layer has a role of having a low air permeability while having a thin thickness.
  • the polyamide-based resin exhibits modulus that is not relatively high as compared with other resins, the polyamide-based resin and the copolymer containing the specific content of the polyether-based segment. Even when applied together, the film for innerliner exhibiting relatively low modulus characteristics can be obtained, thereby improving the moldability of the tire.
  • the polyamide-based resin since the polyamide-based resin has sufficient heat resistance and chemical stability, the inner liner film may be prevented from being deformed or modified when exposed to chemical substances such as high silver conditions or additives applied during tire manufacturing.
  • the polyamide-based resin may have a relative viscosity (96% solution of sulfuric acid) of 3.0 to 3.5, preferably 3.2 to 3.4. If the viscosity of polyamide-based resin is less than 3.0, sufficient elongation may not be secured due to lowered toughness, which may cause damage during tire manufacturing or driving a car. It may be difficult to secure physical properties such as airtightness or moldability that the base film layer should have as the innerliner film. In addition, when the viscosity of the polyamide-based resin exceeds 3.5, the modulus or viscosity of the base film layer to be produced may be unnecessarily high, and the innerliner may be less likely to have proper moldability or elasticity.
  • Relative viscosity of the polyamide-based resin means a relative viscosity measured using a 963 ⁇ 4 sulfuric acid solution at room temperature. Specifically, specimens of a certain polyamide-based resin (eg, 0.025 g of specimen) were added to 96% sulfuric acid solution at different concentrations. After dissolving two or more measurement solutions (for example, polyamide-based resin specimens were dissolved in 96% sulfuric acid so as to have a concentration of 0.25 g ⁇ 1L, 0.10g / dL, and 0.05 g ⁇ 1L to prepare three measurement solutions). ), Relative of the measurement solution using a viscosity tube at 25 0 C. The viscosity (for example, the ratio of the average passage time of the measurement solution to the viscosity tube passage time of 96% sulfuric acid solution) can be obtained. '
  • group which can be used for the said base film layer.
  • Resin include a polyamide resin, such as nylon 6, nylon 66, nylon 46, nylon 11, nylon 12.
  • the polyamide-based resin may be included in the base film layer by preparing a base film layer using not only a method of using the resin itself but also a monomer of the polyamide-based resin or a precursor of the polyamide-based resin. ... ' .
  • the polyamide-based resin may be included in the base film layer in the remaining amount excluding the copolymer (b) and the polymer crystallization retardant (c).
  • the copolymer comprising a polyamide amide segment and a polyether segment is present in a bonded or dispersed state between the plyamide resins. It is possible to lower the modulus of the base film layer, to suppress the increase in the rigidity of the base film layer, and to prevent the crystallization at a high temperature.
  • the film for innerliner As such a copolymer is included in the base film layer, the film for innerliner. It can achieve high elasticity or elastic recovery rate while securing mechanical properties such as excellent durability, heat resistance and fatigue resistance. Accordingly, the inner liner film may exhibit excellent moldability, and the tire to which the inner liner film is applied is repeatedly deformed. In the course of driving a car where high heat is continuously generated, it may not be physically damaged or its properties or performance may be degraded.
  • the content of the polyether segment of the copolymer was a whole When the weight is 2% to 40% by weight, preferably 3% to 34% by weight, more preferably 4 to 30% by weight, the thinner liner film may exhibit more excellent physical properties and performance. .
  • the content of the polyether-based segment exceeds 40% by weight of the entire film, an inner liner is required _ gas barrier performance is not good because the tire performance may be reduced.
  • the "reactivity is reduced, the adhesive inner liner that can be difficult to easily adhere to the carcass layer, then it may not be easy to form a uniform film by the elasticity of the base film layer is increased eu
  • 'Reugye segment to the emitter poly, or is combined with the amide-based replicon segments, may be present in a dispersed state between the polyamide resin, based on the operation process of the tire manufacturing process or vehicle. It is possible to suppress the growth of large crystals in the film layer or to prevent the base film layer from being easily broken. ⁇ Also, such polyether-based segments can lower the modulus of the film for the innerliner. This makes it possible to easily mold the tire by allowing it to be minified-or deformed-according to the shape of the tire, even if a small force is applied during the tire forming.
  • the polyether-based segment can suppress the rise of the rigidity of the film at a low temperature, can prevent the crystallization at a high temperature, and can damage the inner liner film damage or tear due to repeated deformation, etc., By improving the resilience against the deformation of the inner liner, it is possible to suppress the occurrence of wrinkles of the film due to permanent deformation, thereby improving the durability of the tire or the inner liner.
  • the polyamide-based segment may serve to allow the copolymer to have a certain level or more of mechanical properties but not to significantly increase modulus properties. together .
  • Base film filling As the polyamide-based segment is applied. Base film filling . It has a thin thickness and low air permeability. It can be sufficient in heat resistance and chemical stability.
  • Polyamide-based segment of the copolymer is represented by the formula It may include a repeating unit of formula (2).
  • a straight chain or branched chain alkylene group having 1 to 20 carbon atoms in Formula 1 .
  • R 2 is an alkylene group of a straight-chain or branched-chain having 1 to 20 carbon atoms, an alkylene group, a linear or branched chain having 1 to 20 carbon atoms.
  • polyether segment of the copolymer may include a repeating unit represented by the following Formula 3.
  • 3 ⁇ 4 is a straight or branched chain alkylene group having 1 to 10 carbon atoms
  • n is an integer of 1 to 100
  • R 6 and R 7 may be the same or different from each other, a direct bond, -0-, -NH-,- CO or -C0NH-.
  • the weight average molecular weight of the copolymer including the polyamar-based segment and the polyether-based segment may be 50,000 to 500,000, preferably 80,000 to 300.000. If the increase average molecular weight of the copolymer is too small, the base film layer to be produced may not secure sufficient mechanical properties for use in the film for the inner liner, the film for the inner liner to ensure sufficient gas barrier (Gas barrier) It can be difficult. In addition, if the absolute weight average molecular weight of the copolymer is too large. When heating at high temperature, the modulus or crystallinity of the base film layer is excessively increased to secure the elasticity or elastic recovery rate to have as the innerliner film. It can be difficult. ⁇
  • the co-polymer is.
  • the polyether based segment may be a polyamide based segment and a polyether based segment in a range of 2% to 40% by weight based on the total weight of the film. To 3: It may be preferably included in the weight bar of 5: 5 to 4: 6.
  • the modulus of the base film filler or the innerliner film may be increased, thereby reducing the moldability of the tire, or greatly reducing the physical properties due to repeated deformation. Also, on the poly . If the content of the territorial segment is too three. The airtightness of the film for the inner liner may be lowered. It may be difficult for the innerliner to easily adhere to the carcass layer due to the decrease in reactivity to the adhesive, and the elasticity of the base film layer may be increased to make it difficult to produce a uniform film.
  • the polyamide-based resin and the co-polymer described above may be included in a weight ratio of 6: 4 to 3 :, preferably 5: 5 to 4: 6. If the content of the polyamide-based resin is too small, the density or airtightness of the base film layer may be lowered. In addition, when the content of the polyamide-based resin is too large, the modulus of the base film layer may be excessively high or the moldability of the tire may be deteriorated. The resin may crystallize, and cracks may occur due to repeated deformation.
  • the base film filling may be an unstretched film.
  • the base film layer is in the form of an unstretched film, it has a low modulus and a high strain rate and can be suitably applied to a tire forming process in which high expansion occurs. Also. Because uncrystallized film hardly occurs crystallization phenomenon. Repeated deformation can also prevent damage such as cracks.
  • an inner liner having uniform physical properties can be obtained.
  • the said base material as shown to the manufacturing method of the film for innerliners mentioned later. '' Method of suppressing the orientation of the film layer as much as possible.
  • the base film layer can be produced as an unoriented or unoriented film by changing a die die standard or adjusting a winding speed. New non-drawn base film by additive charging. Applying a filter ⁇ , a film for the inner liner in the tire building "process can be easily produced in a cylindrical shape or a sheet shape. In particular, when an unstretched sheet-like layer is applied to the base film layer. It is not necessary to build a separate film ' manufacturing facility for each tire size, and it is desirable to minimize impact and wrinkles on the film during transport and storage. In addition, when the base film layer is manufactured in a sheet form, the process of adding an adhesive layer to be described later may be performed more easily. It is possible to prevent damage or dents caused by manufacturing process increase due to the difference between the molding drum and the standard.
  • the resorcinol-formalin adhesive eu is charged to the latex comprises a (RFL) adhesive.
  • the substrate film layer and the tire carcass layer also have excellent adhesion and adhesion retention performance, and thus, the inner liner film and the carcass interfacial interface generated by heat or repetitive deformation generated during the tire manufacturing process or driving process, etc. It is possible to prevent break so that the innerliner film has sufficient fatigue resistance.
  • the main properties of the above-described adhesive layer appear to be due to the inclusion of certain resorcinol formalin-latex (RFL) based adhesives having a specific composition.
  • RTL resorcinol formalin-latex
  • As an adhesive for the transfer of the inner liner was used include "tie gum of a rubber type. This required an additional vulcanization process.
  • the adhesive includes a resorcinol-formalin-latex (RFL) -based adhesive of a specific composition, and has high reaction properties and adhesion to the base film layer, as well as high temperature heating conditions without increasing the thickness thereof. By pressing at the base film layer and the tire carcass layer can be firmly bonded.
  • the adhesive layer may exhibit high fatigue resistance against physical / chemical deformations that may be applied during tire manufacturing or driving, the adhesive force or other physical properties during the manufacturing process under high temperature conditions or during driving of a vehicle in which mechanical deformation is applied for a long time. Can minimize the degradation.
  • the resorcinol ⁇ formalin-latex (RFL) -based adhesives are capable of crosslinking between latex and rubber, resulting in adhesive performance.
  • Physically latex Since it is a polymer, it has a low degree of hardening and may have a flexible property such as rubber, and a chemical bond between the end group and the base film layer of the methi of the resorcinol-formalin copolymer is possible. Accordingly, the resorcinol to the base film layer, when the PORT 1 eu dried latex (RFL) system, to apply the adhesive agent i. Sufficient adhesion can be achieved.
  • the resorcinol ⁇ formalin-latex (RFL) -based adhesive is . 2 to 32 weight 3 ⁇ 4, preferably 10 to 20 weight% and latex 68 to 98 weight% of condensates of resorcinol and formaldehyde. Preferably 80 to 90% by weight.
  • the condensation of the resorcinol and formaldehyde is 1: 0.3 to 1: 3.0 of the resorcinol and formaldehyde. Preferably it may be obtained by mixing in a molar ratio of 1: 0.5 to 1: 2.5 and then condensation reaction. Also.
  • the condensate of resorcinol and formaldehyde may be included in an amount of 2% by weight or more based on the total amount of the adhesive layer in terms of chemical reaction for excellent adhesion, and may be included in an amount of 32% by weight or less to secure proper fatigue resistance.
  • the latex had a natural rubber latex, styrene / butadiene rubber latex. Acrylonitrile / butadiene. Rubber latex.
  • the chloroprene rubber latex and styrene / butadiene / vinylpyridine rubber latex may be one or two or more mixtures selected from the group consisting of.
  • the latex may be included in 6S% by weight or more based on the total amount of the adhesive layer for the flexibility of the material and the effective crosslinking reaction with the rubber, and included in an amount of 98 wt.3 ⁇ 4 or less for chemical reaction with the base film and rigidity of the adhesive.
  • the adhesive is 0.1 to 20 ni. Preferably it may have a thickness of 0.1 to 10, more preferably 0.2 to 7, even more preferably 0.3 to 5, it may be formed on one surface or both surfaces of the film for the inner liner.
  • the thickness of the adhesive layer is too thin, the adhesive layer itself may be thinner when the tire is inflated, the crosslinking adhesive force between the carcass layer and the base film may be lowered, and the stress may be concentrated on a part of the adhesive, thereby reducing the fatigue characteristics. Also. If the adhesive is too thick, interfacial separation may occur in the adhesive, resulting in poor fatigue characteristics. And.
  • a method for producing an innerliner film which includes forming an adhesive layer including an (RFL) -based adhesive, may be provided.
  • the mixture between the copolymer (b) and the polymer crystallization and the delaying agent (C) may be melted and extruded to form a substrate, a film charge, and an adhesive layer may be formed on at least one surface of the substrate film layer to provide an inner liner film. .
  • the inner liner film manufactured as described above has excellent airtightness even at a thin thickness, thereby making the tire lighter and improving the fuel efficiency of the car.
  • a film for innerliner having high heat resistance and high mechanical properties such as high durability and fatigue resistance with excellent moldability can be provided . It was confirmed that it can.
  • the innerliner film may have low modulus properties with sufficient strength.
  • the crystallinity of the base film layer is not so large even through the molding process or the thinning process of 100 ° C. or higher, and thus the moldability, elasticity, or elastic recovery rate is not significantly reduced, thereby ensuring excellent moldability.
  • the polyamide-based resin may have a relative viscosity (96% solution of sulfuric acid) of 3.0 to 3.5, preferably 3.2 to 3.4.
  • the content of the polyether segment of the co-polymer is 2 wt% based on the total weight of the base film filling. 3 ⁇ 4 to 40% by weight, preferably 3 to 35% by weight, more preferably 4 to 30% by weight.
  • a copolymer comprising the polyamide-based resin and the polyamide-based segment and the polyether-based segment.
  • the specific information about the polymer crystallization retarder includes the above-described content with respect to the film for the innerliner of one embodiment of the invention.
  • the polymer crystallization retarder (c) is the polyamide resin (a) and Can be mixed with the co-polymer (b) sequentially or simultaneously to be melted and extruded . It was. Also. Wherein the polymer crystallization retardant (c) may be heunhap above the polyamide resin (a) and copolymers (b) at branding method of simple mixing mix or 240 ° C to about 300 o C in the compounding method.
  • the copolymer and the polyamide-based resin In order to extrude the film having a more uniform thickness, the copolymer and the polyamide-based resin have a uniform size . I can regulate it. As such, as the size of the copolymer and the polyamide-based resin are adjusted, in the step of mixing them, staying in the raw material supply unit maintained at a constant temperature, or melting and extruding. The said copolymer and the polyamide resin can be made more uniform heunhap 'and. The co-polymer and the polyamide-based resin may be prevented from increasing in size by being aggregated with each other or with each other, and thus a base film layer having a more uniform thickness may be formed.
  • the copolymer and the polyamide resin have a similar size. . Future mixtures. In the melting or extrusion step, it is possible to minimize a phenomenon in which raw material chips agglomerate with each other or a phenomenon in which a non-uniform shape or region appears, thereby forming a base film layer having a uniform thickness over the entire film area.
  • the size of the copolymer and the polyamide-based resin that can be used in the production method is not particularly limited. ,
  • the method for producing the film for the inner liner may further comprise the step of mixing the polyamide-based resin and the co- polymer at a weight ratio of 6: 4 to 3: 7 ⁇ content of the polyamide-based resin Too small.
  • the density or airtightness of the base film layer may be lowered.
  • the modulus of the base film layer may be excessively high or the moldability of the tire may be reduced, and the polyamide-based resin in a high environment that occurs during tire manufacturing or driving of a vehicle May crystallize and cracks may occur due to repeated deformation.
  • any device or method known to be used for mixing the polymer resin can be used without particular limitation.
  • the copolymer may include a polyamide-based segment and a polyether ether segment in a weight ratio of 6: 4 to 3: 7. .
  • the mixture of the polyamide-based resin and the copolymer has a specific temperature. For example 50 to 100 ° C. It can be supplied to the extrusion die through the raw material supply unit maintained at a temperature. As the feeder is maintained at a temperature of 50 to 100 o C.
  • the mixture of the amide-based resin and the copolymer has a proper viscosity, etc., and can be easily moved to another part of the extrusion die or the extruder, and-the mixture is caused by agglomeration.
  • the raw material supply part as a part that serves to supply the raw material injected from the extruder to the extrusion die or other parts.
  • the configuration is not particularly limited and may be a conventional feeder included in an extruder for producing a polymer resin.
  • the mixture supplied to the extrusion die through the raw material supply at 230 to 300 ° C, it is possible to form a base film layer.
  • Silver degree of melting the mixture is 230 to 300 ° C.
  • it may be 240 to 280 ° C.
  • the melting temperature should be higher than the melting point of the polyamide-based compound hajimin ⁇ , too high may cause carbonization or decomposition to inhibit the physical properties of the film. Bonding between the polyether-based resins may occur, or orientation may occur in the fiber array direction, which may be disadvantageous in manufacturing an unstretched film.
  • the extrusion die can be used without any limitation as long as it is known that it can be used for extrusion of the polymer resin.
  • a T-type daa In order to make the thickness of the said base film filling more uniform, or to prevent orientation generate
  • the step of forming the base film layer is a thickness of the mixture of the copolymer comprising the polyamide-based resin, polyamide-based segments and polyether-based segments of 30 to 300 It may comprise the step of extruding into a film of.
  • the roughness of the thickness of the film produced is extrusion conditions. For example, by adjusting the extruder discharge amount or the gap of the extrusion die, or by changing the winding speed of the extruded or recovered process.
  • the die gap of the extrusion die may be adjusted to 0.3 to 1.5 mm.
  • the die gap Gap is too small.
  • the die shear pressure of the melt extrusion process is too high and the shear force is high, so that the uniform shape of the extruded film may be difficult and the productivity may be deteriorated .
  • the melt "increased over the stretching of the film is extruded is oriented occur: it is possible, it can increase the difference between the species of the base film layer to be produced and transverse direction physical properties.
  • the lip gap adjustment blit of the T die A film having a more uniform thickness can be obtained by reducing the variation of the base film pack produced by adjusting. It is also possible to configure automated process steps by using an automated system, such as an Auto Die system, to control the film thickness-feedback—extrusion die.
  • the formed base film worm may further comprise the step of solidifying at the angled portion is maintained at a silver of 5 to 40 o C, preferably 10 to 30 o C
  • the base film filling formed by melting and extruding may be provided in a film having a more uniform thickness by being solidified in a cooling unit maintained at a silver of 5 to .40 o C.
  • the base film layer obtained by melting and extruding may be grounded or adhered to the cooling unit maintained at the appropriate temperature so that stretching may not occur substantially.
  • the base film charge may be provided as an unstretched film.
  • the solidifying step may be performed by using an air knife, an air nozzle, an electrostatic charge device (Pinning device), or a combination thereof to maintain the base film charge formed by melting and extruding at a temperature of 5 to 40 ° C. And evenly adhering to each roll . have.
  • the base film layer formed by melting and extruding the substrate film layer formed by using an air knife, an air nozzle, an electrostatic pinning device or a combination thereof in close contact with the cooling is brought into the air after extrusion.
  • Phenomena such as flying or partially unevenness in the middle of the film can be prevented, and thus a film having a more uniform thickness can be formed, and a portion of the film having a relatively thicker or thinner area than the surrounding part is substantially May not be formed, .
  • the melt extruded under the specified die gap condition has a horizontal distance of 10 to 150 mm from the die outlet.
  • the cooling installed at 20 to 12 kPa is attached to or " grounded .” Operation and orientation can be ruled out.
  • the horizontal distance from the die outlet to the cooling is the distance between the die outlet and the point at which the discharged melt grounds the relief angle. If the linear distance between the outlet of the die and the attachment point of the molten film is too small, the film may be unevenly cooled by disturbing the uniform flow of the molten extruded resin, and if the distance is too large, It is not possible to achieve stretching effect suppression.
  • the "extrusion processing conditions of the film that are commonly used in the manufacture of polymers and is loaded with the exception of steps and conditions of the above-described specific.
  • screw diameter screw rotation speed.
  • line speed etc. can be selected suitably and used. .
  • the forming of the base film charge may further include adding a heat resistant agent to the mixture.
  • the heat resistant agent may be mixed with the polyamide-based resin (a), the copolymer (b) and the polymer crystallization retardant (C) sequentially or simultaneously to be melted and extruded.
  • the heat-resistant agent is a simple 'mixing and blending branding method ' or compounding at 240 o C to 300 o C. method. It may be mixed with the polyamide-based resin ( a ), co-polymer (b) and polymer crystallization retardant (c). :
  • the heat resistant agent of the prepared base film may be 50 to 5,000ppmw.
  • the heat resistant agent may include one or more compounds selected from the group consisting of aromatic amine compounds, hindered phenol compounds, phosphorus compounds, inorganic compounds, plyamide compounds, and polyether compounds.
  • the heat resistant agent may comprise a mixture of copper iodide and potassium iodide.
  • a mixture of Cur and KI as the heat-resistant agent, it can be used as 50ppmw to lOOOOppw of the base film prepared above.
  • the content of copper (Cu) in the mixture of Cul and KI may be 5 to 10% by weight.
  • Specific content of the heat-resistant agent includes the above-mentioned information in the content of the film for the innerliner of one embodiment of the Xing-based invention.
  • the method for producing the innerliner film includes a resorcinol-formalin latex (RFL) adhesive on at least one surface of the base film layer. Forming an adhesive layer may be included.
  • RTL resorcinol-formalin latex
  • the resorcinol eu formalin - the adhesive latex (RFL), ⁇ an adhesive layer, including, the resorcinol-formalin- may be formed by coating on one surface of the latex (RFL) system wherein the adhesive base material film layer, resorcinol,
  • An adhesive film comprising a synol-formalin-latex (RFL) -based adhesive may also be formed by laminating one surface of the base film layer.
  • the step of forming such an adhesive layer is resorcinol-form .
  • the dried latex (RFL) -based adhesive may be coated on one or both surfaces of the formed base film filling and then dried.
  • the formed adhesive layer may have a thickness of 0.1 to 20, preferably 1 to 10.
  • the resorcinol ⁇ formalin ⁇ latex (RFL) -based adhesive may include 2 to 32% by weight of condensate of resorcinol and formaldehyde and 68 to 98% by weight of latex, preferably 80 to 90% by weight. '
  • the coating or coating method or apparatus that is commonly used for the application of the adhesive can be used without any particular limitation, knife coating method. Bar coating , gravure coating or spraying or dipping can be used. Knife coating method. Uniform application and coating of adhesives using gravure coating or bar coating. It is preferable in terms of.
  • the drying and the adhesive reaction may be simultaneously performed, but after the drying step is considered in consideration of the reactivity of the adhesive, the heat treatment reaction step may be divided. And. In order to apply the thickness or adhesive of the adhesive layer, the adhesive layer forming, drying and reaction steps may be applied several times. In addition, after the adhesive is applied to the base film layer, the heat treatment may be performed by a method of solidifying and reacting under heat treatment conditions for about 30 seconds to 3 minutes at 10CKL50 0 C.
  • additives such as a heat resistant antioxidant or a heat stabilizer may be further added.
  • the provided innerliner film may have a low modulus property with sufficient strength, and the crystallinity of the base film layer is not so large even through a high temperature molding process or a stretching process of 100 or more. Elasticity or elastic recovery rate is not significantly reduced, it is possible to ensure excellent moldability.
  • FIG. 1 schematically shows the structure of a tire.
  • Figure 3 shows the FT-IR of the inner liner film of Comparative Example 1.
  • Polyamide-based resin (nylon 6) having a relative viscosity (96% solution of sulfuric acid) 3.3 and a copolymer resin having an absolute weight average molecular weight of 145,000 (including 60 weights of polyamide repeat units and 3 ⁇ 4 and 40 weight percent polyether repeat units) Mixed at a weight ratio of 5: 5, to which a polymer crystallization retardant (benzene tricarboxylic acid) and a heat resistant agent [content of copper (Cu) in the mixture-complex of copper iodide and potassium iodide 7 wt 3 ⁇ 4] are added thereto To prepare a mixture for producing a base film. . The content of the polymer crystallization retardant in the mixture was 1% by weight, and the heat resistant agent lOOppmw was included.
  • the mixture is extruded at 260 ° C through a T-type die (Die Gap] -1.0 mm) while maintaining a uniform melt flow, and cooling is controlled to 25 ° C using an air knife on the surface.
  • the molten resin into a film of uniform thickness Cooling solidified.
  • an unstretched base film layer having a thickness of 100 ⁇ m was obtained without passing through the stretching and heat treatment sections at a speed of 15 m / min.
  • Resorcinol and formaldehyde were mixed in a molar ratio of 1: 2 and condensation reaction was carried out to obtain a condensation mixture of resorcinol and formaldehyde.
  • 12% by weight of the condensate of resorcinol and formaldehyde and 88% by weight of styrene / butadiene-1,3 / vinylpyridine latex were mixed to obtain a resorcinol-formalin-latex (RFL) adhesive having a concentration of 20%.
  • RTL resorcinol-formalin-latex
  • the resorcinol-formalin-latex (3 ⁇ 4L) -based adhesive was coated on the base film layer at a thickness of 1 uiii using a gravure coater, and dried and reacted at 150 ° C. for 1 minute to form an adhesive layer.
  • polyamide-based resin nylon 6 having a relative viscosity (96% solution of sulfuric acid) 3.3 and a copolymer resin (60% by weight of polyamide-based repeating unit and polyether-based repeating unit) with an absolute weight average molecular weight of 145, 000 60 wt%), including 40 wt% each, were combined.
  • the specific measuring method is as follows.
  • Oxygen Permeability The method of ASTM D 3895 was measured using an Oxygen Permeation Analyzer (Model 8000, manufactured by Illinois Instruments ⁇ ) at 25 ° C. 60 RH% 5 atmosphere.
  • Experimental Example 2 Air Pressure Holding Performance Measurement
  • the tire was manufactured by applying the inner liner films of the above examples and comparative examples to 205R / 65R1 & specification. In addition, the manufactured tires were evaluated by comparing the internal pressure retention (IPR Internal Pressure Retention) for 90 days according to the following formula (2) under 101.3 kPa pressure at 21 0 C using ASTM F1112-06 method. :
  • Tires were manufactured by applying the inner liner films of Examples and Comparative Examples to 205R / 65R16. During the tire manufacturing process, the manufacturing ease and appearance were evaluated after the production of green tires, and the final appearance of the tires after vulcanization was examined. At this time, if the tire after the green tire or vulcanization is not crushed and the standard deviation of the diameter of the ⁇ is less than 5% was evaluated as 'good'. If the tire is not properly manufactured due to crushing of the tire after green tire or vulcanization, or if the inner liner inside the tire is melted or torn or damaged, or if the standard deviation of the diameter is more than 5%, the shape is defective. Rated ⁇
  • the innerliner films prepared in Examples and Comparative Examples were analyzed using the ATR method of Digilab FTS-40 FT-IR. Specimens used in the analysis are prepared by cutting the width * length 2 ⁇ * 2 ⁇ size . The pressure is applied using a torque wrench. The analysis was carried out after setting the same torque always applied to the specimen with a torque of 70 cN-m.
  • FT—IR results of the innerliner films prepared in Examples and Comparative Examples are shown in Table 2 below.
  • FT ⁇ IR measurement results of the innerliner films prepared in Example 1 and Comparative Example 1 are shown in FIGS. 2 and 3, respectively.
  • Ic. Is the peak value in the kayser of the portion having a crystallinity in the FT-IR of the prepared inner liner film, I_a. Has an amorphous in the FT ⁇ IR of the manufactured inner liner film It is the peak value in the kaser of the part.
  • the innerliner film of the example was I— c (1202) / I ′ a. It was confirmed that the ratio of (1170) was relatively small compared with the film for innerliners of the comparative example, and the crystallinity was not so high.
  • the kaiser (kayser, [Ic] of the portion having crystallinity with respect to the peak in the kaiser (kayser, [Ia. About 1170 cm 1 ]) of the portion having an amorphous in the FT-IR film of the inner liner of the above embodiment
  • the ratio of the peak value at about 1202 cm 1 ] was 1.0102
  • the film for the innerliner of the comparative example was found to be 1.0345 or 1.0406.
  • the peak [1202 (cm—) for the portion having crystallinity is relatively low in the FT-IR spectrum of the innerliner film of Example .1, while Comparative Example 1 In the FT—IR spectrum of the inner liner film, the peak of the crystallinity was relatively high, ie, the ' crystallization of the polymer included in the base film layer by using the polymer crystallization retardant.
  • the innerliner film of the embodiment may have low stiffness: low modulus property with strength, and the crystallinity of the base film layer is not so large even through the forming process or stretching process of 100 ° C. or higher. Modulus properties, elasticity or elastic recovery rate are not greatly reduced, and excellent moldability can be ensured.
  • the tire of the 205R / 75R15 standard was manufactured and evaluated with the innerliner film of the said Example and a comparative example. At this time, 1300De72ply HMLS tire cord was applied as the cord included in the body fly, Steel Cord was used as the belt, and N66 840De72ply was applied as the cap fly.
  • the prepared inner liner film was wrapped on a tire forming drum, and in order to fix the inner liner film, a length of 3 cm was overlapped and the folding portion was fixed with a linm thick tie gum. Then, a sheet thickness of 2% thicker reinforcement rubber was attached to one part of the liner corresponding to the position where the crimp was to be formed from 9cni to 14cm from the center of the drum with 5cm width.
  • Green tires were prepared by sequentially forming a rubber layer for forming a shoulder portion and a sidewall portion.
  • the green tire thus prepared was put in a mold to produce a tire through vulcanization for 160 degrees 30 minutes.
  • the durability of the produced tires was experimentally evaluated using the US FMVSS139 tire durability measurement method. These endurance measures increase the load step by step. Two methods were used: Step Load Endurance Test and High Speed Test to increase the speed step by step. The result was special in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Tyre Moulding (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne un film pour un revêtement intérieur et son procédé de fabrication, le film comprenant : une couche de film de base comprenant une résine à base de polyamide, un copolymère spécifique et un retardant de cristallisation de polymère ; et une couche d'adhésion.
PCT/KR2013/011626 2012-12-31 2013-12-16 Film pour revêtement intérieur et son procédé de fabrication WO2014104630A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/654,337 US20150329744A1 (en) 2012-12-31 2013-12-16 Film for tire inner liner and method for manufacturing the same
CN201380069034.XA CN104884560A (zh) 2012-12-31 2013-12-16 用于轮胎内衬层的膜及其制造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2012-0158573 2012-12-31
KR20120158573 2012-12-31
KR1020130154636A KR20140088008A (ko) 2012-12-31 2013-12-12 이너라이너용 필름 및 이의 제조 방법
KR10-2013-0154636 2013-12-12

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080319119A1 (en) * 2005-12-16 2008-12-25 Exxonmobil Chemical Patents Inc. Processing Aids for Elastomeric Compositions
US20100260991A1 (en) * 2007-11-14 2010-10-14 Dow Global Technologies Inc. Articles and methods of making the same
KR20110110023A (ko) * 2010-03-31 2011-10-06 코오롱인더스트리 주식회사 타이어 이너라이너용 필름 및 이의 제조 방법
KR20120002495A (ko) * 2010-06-30 2012-01-05 코오롱인더스트리 주식회사 타이어 이너라이너용 필름 및 그의 제조 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080319119A1 (en) * 2005-12-16 2008-12-25 Exxonmobil Chemical Patents Inc. Processing Aids for Elastomeric Compositions
US20100260991A1 (en) * 2007-11-14 2010-10-14 Dow Global Technologies Inc. Articles and methods of making the same
KR20110110023A (ko) * 2010-03-31 2011-10-06 코오롱인더스트리 주식회사 타이어 이너라이너용 필름 및 이의 제조 방법
KR20120002495A (ko) * 2010-06-30 2012-01-05 코오롱인더스트리 주식회사 타이어 이너라이너용 필름 및 그의 제조 방법

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