KR20180001248A - Copolymer, polymer resin composition and polymer film for inner liner using the same - Google Patents

Abstract

The present invention relates to: a copolymer having an excellent thermal shock resistance, a low modulus characteristic and improved durability; a polymer resin composition, capable of providing an inner liner film which can realize an excellent airtightness even with a thin thickness and improve the fuel efficiency of a vehicle by reducing the weight of a tire and having excellent moldability and mechanical properties; and a polymer film for an inner liner provided from the polymer resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymer, a polymer resin composition using the polymer resin composition, and a polymer film for an inner liner,

The present invention relates to a copolymer, a polymer resin composition using the same, and a polymer film for an inner liner. More specifically, the present invention provides a copolymer having an excellent heat-resistant impact strength, a low modulus characteristic, and improved durability, and an excellent air-tightness even at a thin thickness, A polymeric resin composition capable of providing an inner liner film having mechanical properties, and a polymer film for an inner liner provided from the polymeric resin composition.

The tire supports the load of the vehicle, mitigates the impact from the road surface, and transmits the driving force or braking force of the vehicle to the ground. Generally, a tire is a composite of a fiber / steel / rubber and has a structure as shown in Fig.

Tread (1): It is a part that comes into contact with the road surface, it should provide friction force necessary for braking and driving, good abrasion resistance, able to withstand external impact, and low heat generation.

Body Ply (or Carcass) (6): It is a coil layer inside the tire. It should support the load and resist the impact.

Belt (5): It is located between the body fly, and it is made of steel wire in most cases, it alleviates the external impact and keeps the ground surface of the tread wide to improve the running stability.

Side Wall (3): A rubber layer between the lower portion of the shoulder (2) and the bead (9), and protects the inner body ply (6).

Inner Liner (7): Located inside the tire instead of the tube, it prevents leakage of air to enable pneumatic tires.

BEAD (9): A square or hexagonal wire bundle with rubber coated wire to seat and fix the tire on the rim.

CAP PLY (4): It is a special cloth paper placed on the belt of the radial tires for some passenger cars, minimizing the movement of the belt when driving.

APEX (8): It is a triangular rubber filling material used to minimize the dispersion of beads, protect the beads by mitigating external impact, and prevent the inflow of air during molding.

In recent years, tube-less tires having high-pressure air of about 30 to 40 psi have been generally used without using a tube. In order to prevent the inner air from leaking to the outside during the operation of the vehicle An inner liner having high airtightness is disposed on the inner layer of the carcass.

Previously, an inner liner having rubber components such as butyl rubber or halobutyl rubber, which is relatively low in air permeability, was used. In this inner liner, the rubber content or the thickness of the inner liner had to be increased in order to obtain sufficient airtightness. However, when the content of the rubber component and the tire thickness are increased, the total weight of the tire is increased and the fuel economy of the automobile is lowered.

In addition, the rubber components have relatively low heat resistance, and air pockets are formed between the inner rubber of the carcass layer and the inner liner during the vulcanization process of the tire or the running of the vehicle in which repeated deformation occurs at high temperature, There is a problem that the shape and physical properties are changed. In order to bond the rubber components to the carcass layer of the tire, a vulcanizing agent or a vulcanization process has to be applied.

Accordingly, various methods have been proposed to reduce the thickness and weight of the inner liner to reduce fuel consumption, and to reduce changes in the form and physical properties of the inner liner that occur during the molding or running of the tire. However, any previously known method has had a limitation in maintaining excellent air permeability and moldability of the tire while sufficiently reducing the thickness and weight of the inner liner. In addition, the inner liner obtained by the previously known method has a problem in that the properties of the inner liner itself deteriorate in the manufacturing process of the tire in which the high temperature repetitive molding is performed or the repeated process of deformation, There were many problems.

The present invention is to provide a copolymer having excellent heat shock resistance, low modulus property, and improved durability.

It is another object of the present invention to provide a polymer resin composition capable of providing an inner liner film which can realize excellent airtightness even with a thin thickness and can reduce weight of a tire, improve automobile fuel economy, and have excellent moldability and mechanical properties.

Further, the present invention is to provide a polymer film for inner liner which realizes excellent airtightness even with a thin thickness, can reduce the weight of the tire, improve automobile fuel economy, and has excellent moldability and mechanical properties.

In the present specification, a branched repeating unit containing three or more ether-based functional groups; An aliphatic copolyether repeating unit containing two or more polyoxyalkylene repeating units; And a copolymer comprising a polyamide-based repeating unit.

The present invention also provides a polymer resin composition comprising the copolymer.

The present invention also provides a polymer film for an inner liner comprising a base film layer containing a melt extrudate of the polymer resin composition.

BEST MODE FOR CARRYING OUT THE INVENTION A copolymer according to a specific embodiment of the present invention, a polymer resin composition using the same, and a polymer film for an inner liner will now be described in detail.

According to one embodiment of the present invention, there is provided an organic electroluminescent device comprising: a branched repeating unit containing three or more ether-based functional groups; An aliphatic copolyether repeating unit containing two or more polyoxyalkylene repeating units; And a copolymer containing a polyamide-based repeating unit can be provided.

The present inventors have found that the above-mentioned specific copolymer contains a copolyether repeating unit in which two or more polyoxyalkylene repeating units are copolymerized as an aliphatic polyether repeating unit constituting a soft segment in the copolymer, And the durability can be improved. The present invention has been accomplished on the basis of these findings.

The aliphatic copolyether repeating units containing two or more kinds of polyoxyalkylene repeating units may allow the copolymer to have low modulus characteristics or to reduce the load generated during stretching, and even after a specific heat treatment process, The structure change due to the crystallization of the inner liner film or the like can be suppressed and the durability against tire deformation can be improved.

Specifically, the aliphatic copolyether repeating unit containing two or more kinds of polyoxyalkylene repeating units contains two or more different polyoxyalkylene repeating units in the repeating unit, and one kind of polyoxyalkylene repeating unit , The modulus reduction effect is excellent and the mechanical strength can be improved by reducing the impact strength before and after the heat treatment.

Further, the branched type repeating unit containing three or more ether-type functional groups contained in the copolymer of one embodiment improves the degree of crosslinking of one or more repeating units, polymers, or compounds in the copolymer , The copolymer can have low modulus properties with high heat resistance and mechanical properties, and durability can be improved.

As a result, the copolymer can overcome the limitations of previously used rubber components such as butyl rubber or halobutyl rubber, and it has excellent mechanical properties such as high elasticity and low modulus at low temperature and high temperature as well as room temperature Lt; / RTI >

Since the copolymer does not require an additional additive or a rubber component for improving the physical properties of the inner liner as in the prior art, it is possible to simplify the manufacturing process and reduce the tire manufacturing cost.

In the copolymer, the aliphatic copolyether-based repeating unit containing the polyamide-based repeating unit and the two or more polyoxyalkylene repeating units is preferably a repeating unit derived from the branched repeating unit containing three or more ether-based functional groups It is possible to form a crosslinked structure which is bonded to the inner liner. By virtue of this chemical structural property, when the inner liner is manufactured using the copolymer, high airtightness, excellent moldability and elasticity, high mechanical properties and durability have.

At this time, the polyamide-based repeating units have an excellent airtightness due to their inherent molecular chain characteristics, for example, they show airtightness of 5 to 50 times as much as those of butyl rubber generally used for tires at the same thickness, It can exhibit non-high modulus properties.

Specifically, the copolymer may include an aliphatic copolyether-based repeating unit containing two or more polyoxyalkylene repeating units. The aliphatic copolyether-based repeating unit can inhibit the growth of large crystals, lower the modulus of the copolymer, and prevent the molded article produced from the copolymer from being easily broken.

The aliphatic copolyether-based repeating units are used to make the copolymer have low modulus characteristics or to reduce the load generated during stretching and to prevent the properties of the film from significantly changing even after a specific heat treatment process, The structural change due to crystallization and the like can be suppressed and the durability against tire deformation can be improved.

The aliphatic copolyether-based repeating unit may mean the aliphatic copolyether repeating unit itself or may include a repeating unit containing a functional group grafted to the main chain while injecting the aliphatic copolyether repeating unit. The specific examples of the grafted functional groups are not limited, and various functional groups widely known in the related art can be used without limitation.

It is also possible to include all repeating units other than aliphatic copolyether repeating units included in the main chain while containing an aliphatic copolyether repeating unit in the main chain. The specific examples of the above other repeating units are not limited, and various repeating units widely known in the related art can be used without limitation.

Specifically, the aliphatic copolyether-based repeating unit may include two or more polyoxyalkylene repeating units. The polyoxyalkylene repeating unit includes an ether bond (-O-) in the repeating unit structure, and more specifically, may include a polyoxyalkylene repeating unit having 1 to 10 carbon atoms.

The polyoxyalkylene repeating unit having 1 to 10 carbon atoms has a structure in which an alkylene group having 1 to 10 carbon atoms is bonded to an ether functional group and the alkylene group means a divalent functional group derived from an alkane, A straight chain, branched or cyclic alkylene group having 1 to 10 carbon atoms such as methylene, ethylene, propylene, tetramethylene, isopropylene, isobutylene, sec-butylene, , A hexylene group, and the like.

Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, An aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amido group, a carbonyl group, A carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

The term "substituted" means that another functional group is bonded in place of a hydrogen atom in the compound, and the position to be substituted is not limited as far as the position where the hydrogen atom is substituted, that is, The substituents may be the same or different from each other.

The aliphatic copolyether-based repeating unit may include at least two kinds of polyoxyalkylene repeating units of different kinds within the repeating unit structure, wherein the term " type " means an alkyl group in the polyoxyalkylene repeating unit It can be distinguished by lengi. For example, the aliphatic copolyether-based repeating unit may include two polyoxyalkyl repeating units composed of polyoxytetramethylene repeating units containing tetramethylene groups as alkylene groups and polyoxypropylene repeating units containing propylene groups as alkylene groups Lt; / RTI > repeat unit.

More specifically, the aliphatic copolyether-based repeating unit contained in the copolymer may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

R ₁ and R ₂ are the same or different and each independently represents a linear or branched alkylene group having 1 to 10 carbon atoms; n and m are each independently an integer of 1 to 100; and R ₃ and R ₄ may be the same or different and are each independently a direct bond, -O-, -NH-, -COO- or -CONH-. The term "direct bond" means that no atom or atomic group exists at the corresponding position and is connected to the bond line.

More specifically, in Formula 1, R ₁ is a straight chain alkylene group having 3 to 10 carbon atoms such as a propylene group, a tetramethylene group, an isopropylene group, an isobutylene group, a sec-butylene group, a tert- , Pentylene group, hexylene group, and the like, R ₂ represents a branched alkylene group having 1 to 7 carbon atoms such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an isopropylene group, A sec-butylene group, a tert-butylene group and the like.

In Formula 1, the ratio of n: m (molar ratio) may be 8: 2 to 6: 4. If the value of n is excessively increased relative to the value of m in the above formula (1), durability may be deteriorated due to an increase in modulus of the finally produced polymer film. If the value of m is excessively increased relative to the value of n, Mechanical properties such as tensile strength, elongation, and elastic modulus may be deteriorated.

In addition, the copolymer may contain a branched repeating unit containing three or more ether-based functional groups. The branched repeating unit containing three or more ether functional groups improves the degree of crosslinking of one or more repeating units, polymers, or compounds in the copolymer through three or more ether functional groups, It is possible to maintain the durability and the mechanical properties of the inner liner while maintaining a relatively low modulus value, thereby realizing the physical properties suitable for the inner liner production.

Particularly, since the branched repeating unit contained in the copolymer contains three or more ether functional groups, the number of the repeating units, the polymer, or the compound capable of reacting with one or more kinds of repeating units, The cross-linking structure of the three-dimensional network structure can be formed more easily.

Specifically, for example, the copolymer includes a copolymer in which the polyamide-based repeating unit and the aliphatic copolyether-based repeating unit are bonded via a branched repeating unit containing three or more ether-based functional groups .

The ether-based functional group is a functional group containing an ether bond (-O-) in the functional group, and may specifically include a polyoxyalkylene repeating unit having 1 to 10 carbon atoms. That is, the ether-based functional group may mean a polyether-based functional group, and the polyoxyalkylene repeating unit contains an ether bond (-O-) in the repeating unit structure, and more specifically, has 1 to 10 carbon atoms And may include polyoxyalkylene repeating units.

The polyoxyalkylene repeating unit having 1 to 10 carbon atoms has a structure in which an alkylene group having 1 to 10 carbon atoms is bonded to an ether functional group and the alkylene group means a divalent functional group derived from an alkane, A straight chain, branched or cyclic alkylene group having 1 to 10 carbon atoms such as methylene, ethylene, propylene, tetramethylene, isopropylene, isobutylene, sec-butylene, , A hexylene group, and the like.

Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, An aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amido group, a carbonyl group, A carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

The branched repeating unit may include an intermediate functional group containing at least one central element selected from the group consisting of carbon, nitrogen, phosphorus, sulfur, oxygen and silicon, and at least three ether functional groups respectively bonded to the intermediate functional group .

The intermediate functional group means a functional group capable of mediating the bonding of the three or more ether functional groups, and the intermediate functional group includes at least one central element selected from the group consisting of carbon, nitrogen, phosphorus, sulfur, oxygen and silicon can do. That is, the three or more ether-based functional groups may form a bond through the central element, and more specifically, three or more ether-based functional groups may be simultaneously bonded to the central element.

In addition, in the branched type repeating unit, one end of the ether-based functional group may be bonded to the central element, and the other end of the ether-based functional group may be one or two or more kinds of repeating units contained in the copolymer, , Or a compound or the like.

Specifically, the branched repeating unit may include a trivalent repeating unit in which three ether-based functional groups are bonded through nitrogen. The term " trivalence "means that the number of functional groups bonded to the central atom is 3, and the trivalent repeating unit having three ether-based functional groups bonded through the nitrogen includes repeating units represented by the following formula (2) can do.

(2)

In the above formula (2), R ₈ to R ₁₀ may be the same or different from each other, and each independently represents an alkylene group having 1 to 10 carbon atoms, and x, y, and z are each independently an integer of 1 to 50. In the above formula (2), * denotes a bonding point or a reaction point.

In Formula 2, x, y, and z mean the number of moles of repeating units contained in the ether-based functional group. Specifically, for example, in Formula 2, x represents the number of moles of the polyoxyalkylene repeating unit represented by -R ₈ -O-, y represents the number of polyoxyalkylene repeating units represented by -R ₉ -O- Unit, and z represents the number of moles of the polyoxyalkylene repeating unit represented by -R < ₁₀ > -O-.

The alkylene group means a divalent functional group derived from an alkane, and includes, for example, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group , Isobutylene group, sec-butylene group, tert-butylene group, pentylene group, hexylene group and the like.

The branched repeating unit may include a trivalent repeating unit having three ether-based functional groups bonded through carbon. The trivalent repeating unit to which the three ether-based functional groups are bonded through the carbon atom may include a repeating unit represented by the following formula (3).

(3)

In the above formula (3), R ₁₁ to R ₁₃ may be the same or different from each other and each independently represent an alkylene group having 1 to 10 carbon atoms, R ₁₄ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, n ₁ , n ₂ and n ₃ are each independently an integer of 1 to 50. In the above formula (3), * denotes a bonding point or a reaction point.

In Formula 3, n ₁ , n ₂ , and n ₃ represent the number of moles of the polyoxyalkylene repeating unit contained in the ether-based functional group. Specifically, for example, in Formula 3, n ₁ represents the number of moles of the polyoxyalkylene repeating unit represented by -R ₁₁ -O-, and n ₂ represents the number of moles of the polyoxyalkylene represented by -R ₁₂ -O- Means the number of moles of the repeating unit of phenylene, and n ₃ means the number of moles of the polyoxyalkylene repeating unit represented by -R ₁₃ -O-.

The alkylene group means a divalent functional group derived from an alkane, and includes, for example, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group , Isobutylene group, sec-butylene group, tert-butylene group, pentylene group, hexylene group and the like.

The alkyl group is a monovalent functional group derived from an alkane, for example, a straight chain, branched or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, isobutyl, sec- , Pentyl, hexyl, and the like. At least one hydrogen atom of the alkyl group may be substituted with the same substituent as the alkylene group.

The aryl group is a monovalent functional group derived from arene, for example, monocyclic or polycyclic. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like. Examples of the polycyclic aryl group include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, klycenyl, At least one of the hydrogen atoms of the aryl group may be substituted with the same substituent as the alkylene group.

The content of the branched repeating unit containing at least three ether functional groups contained in the copolymer may be from 0.1% by weight to 20% by weight, or from 1% by weight to 10% by weight, or from 2% by weight to 5% by weight have. When the content of the branched repeating units is excessively increased, the degree of crosslinking of the copolymer is excessively increased, the modulus of the copolymer is not sufficiently lowered, flexibility may be decreased, and heat resistance and compatibility may also be reduced. In addition, the thermosetting property is increased due to the high crosslinking effect, and the problem of increased gas permeability may arise.

On the other hand, if the content of the branched repeating unit is too small, the effect of improving the durability of the copolymer may not be sufficiently realized, the reactivity of the copolymer may be difficult to control, and the physical properties may not be improved sufficiently .

In addition, the copolymer may include a polyamide-based repeating unit. The polyamide-based repeating unit may serve to prevent the modulus of the copolymer from significantly increasing while allowing the copolymer to have mechanical properties of a certain level or higher. In addition, as the polyamide-based repeating unit is applied, sufficient heat resistance and chemical stability can be ensured.

Specifically, the polyamide-based repeating unit has an airtightness of about 5 to 50 times as much as that of a butyl rubber generally used in a tire at the same thickness, for example, at the same thickness due to its inherent molecular chain characteristics, It can exhibit modulus characteristics not so high.

The polyamide-based repeating unit of the copolymer may include a repeating unit represented by the following formula (4) or (5).

[Chemical Formula 4]

In Formula 4, R ₅ is a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a linear or branched alkylene group having 7 to 20 carbon atoms.

[Chemical Formula 5]

Wherein R ₆ is a linear or branched alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, R ₇ is a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 6 to 20 carbon atoms Or a linear or branched alkylene group having 7 to 20 carbon atoms.

The arylene group may be a bivalent group derived from arene and may be, for example, a phenylene group, a biphenylene group, a terphenylene group, a stilbene group, a naphthylenyl group, and the like, but is not limited thereto.

The weight average molecular weight of the copolymer may be from 30,000 to 500,000, or from 40,000 to 300,000, or from 50,000 to 150,000, or from 60,000 to 120,000. As a result, the polymerization reaction of the copolymer can proceed stably and sufficient mechanical properties can be ensured. If the weight average molecular weight of the copolymer is less than 30,000, it may be difficult to secure sufficient mechanical properties and airtightness of the inner liner film prepared by mixing with other components. If the absolute weight average molecular weight of the copolymer exceeds 500,000, The modulus or crystallinity of the coalescence may excessively increase and it may be difficult to secure a desired elasticity or elastic recovery rate.

In the present specification, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a detector such as a known analyzer and a refractive index detector, and an analyzing column can be used. Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30, a chloroform solvent (Chloroform), and a flow rate of 1 mL / min.

The weight ratio of the polyamide-based repeating unit to the aliphatic copolyether-based repeating unit containing the two or more polyoxyalkylene repeating units in the copolymer is not particularly limited, but may be a mixture of the copolymer alone or in combination with other components In order for the inner liner film to be produced to have better physical properties, the copolymer preferably contains the polyamide-based repeating unit and the aliphatic copolyether-based repeating unit in a weight ratio of 100: 1 to 1: 100, or 50: 1 to 1: 50, or a weight ratio of 9: 1 to 1: 9, or a weight ratio of 6: 4 to 3: 7.

If the content of the aliphatic copolyether repeating unit containing two or more polyoxyalkylene repeating units in the copolymer is too small, the formability of the inner liner film produced by mixing the copolymer alone or in combination with other components Degradation of the inner liner film due to repeated or deformation of the inner liner film may occur. If the content of the aliphatic copolyether repeating unit in the copolymer is too large, the airtightness of the inner liner film produced by mixing the copolymer alone or with other components may be deteriorated, and the elasticity of the inner liner film It may not be easy to bond the tire to the tire with a uniform thickness.

The copolymer may further include an additive such as a heat resistant agent that can be used in the production process. Accordingly, it is possible to prevent chain breakage of the polymer due to heat generated during the production of the copolymer, to inhibit radical generation due to thermal decomposition, and accordingly, even when exposed to a high temperature for a long time or exposed, The physical properties are not significantly deteriorated.

The content of the heat resisting agent contained in the copolymer may be 0.005 wt% to 2.50 wt%, or 0.01 wt% to 1.00 wt%. If the content of the heat resistant agent is too small, the effect of improving heat resistance may be insignificant. Also, if the content of the heat resistant agent is too large, the physical properties of the copolymer may be deteriorated, and the effect of improving the heat resistance according to the amount of use may not be substantially increased, thereby unnecessarily raising the price of the final product.

Specific examples of such heat resisting agents include aromatic amine compounds, hindered phenol compounds, phosphorus compounds, inorganic compounds, polyamide compounds, polyether compounds, or a mixture of two or more thereof. Such a heat resisting agent may be applied in the form of a powder or a liquid in the manufacturing method described later.

According to another embodiment of the present invention, a polymer resin composition comprising the copolymer of the above embodiment may be provided.

The content of the copolymer is described above with respect to the copolymer of one embodiment of the invention described above.

The polymer resin composition may further comprise a polyamide resin having a relative viscosity (sulfuric acid: 96% solution) of 2.5 to 4.0. By using a polyamide resin together with the above-mentioned copolymer, it is possible to realize excellent airtightness even with a thin thickness, to lighten the weight of the tire, to improve the fuel economy of automobile, and to provide a tire having high heat resistance, It is possible to provide an inner liner film showing mechanical properties such as fatigue resistance and the like.

In addition, in general, the polymer liner film used for the inner liner film has viscoelasticity or elastic recovery property is not so high, while the inner liner film produced using the polymer resin composition exhibits excellent elastic behavior or shape recovery property . Accordingly, the inner liner film produced by using the polymer resin composition not only has high durability and excellent shape stability against deformation occurring during running of the automobile, but also has an excellent elasticity It is possible to minimize problems that can be exhibited, for example, a phenomenon in which wrinkles or cracks are generated on the film, deterioration of physical properties or adhesive strength, and the like. Specifically, the feature of the above-mentioned inner liner film is that the copolymer is used in combination with the polyamide resin.

The polyamide based resin may have a relative viscosity (96% solution of sulfuric acid) of 2.5 to 4.0, or 3.0 to 3.5, or 3.2 to 3.4. If the viscosity of the polyamide based resin is less than 2.5, a sufficient elongation can not be secured due to a reduction in toughness, so that the inner liner film may be damaged during tire production or automobile operation. In addition, It may be difficult to secure the physical properties such as < / RTI > When the viscosity of the polyamide resin exceeds 4.0, the viscosity of the inner liner film to be produced may be unnecessarily high, and it may be difficult for the inner liner to have appropriate moldability or elasticity.

The relative viscosity of the polyamide resin refers to the relative viscosity measured using a 96% solution of sulfuric acid at room temperature. Specifically, after dissolving a sample of a certain polyamide resin (for example, 0.025 g of a test piece) in 96% sulfuric acid solution at different concentrations to prepare two or more measuring solutions (for example, a polyamide based resin sample The solution for measurement was prepared by dissolving in 96% sulfuric acid to have a concentration of 0.25 g / dL, 0.10 g / dL and 0.05 g / dL), 25, the relative viscosity (for example, The ratio of the average passage time of the measuring solution to the viscosity tube passing time of the 96% solution of sulfuric acid).

Specific examples of the polyamide based resin include copolymers of nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 6/66/610 copolymers, nylon MXD6 , Nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer and nylon 66 / PPS copolymer; Or N-alkoxyalkylates thereof, such as methoxymethylated 6-nylon, methoxymethylated 6,610-nylon or methoxymethylated 612-nylon. Nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610 or nylon 612 are preferably used as the polyamide resin for ensuring proper physical properties as an inner liner.

The polyamide resin may be a monomer of the polyamide resin or a precursor of the polyamide resin as well as a method of using the resin itself.

The polyamide-based resin and the copolymer may be contained in a weight ratio of 2: 8 to 8: 2. If the content of the polyamide resin is too small, the density and airtightness of the polymer resin composition may be lowered. If the content of the polyamide resin is too large, the modulus of the polymer resin composition may become too high or the moldability may be deteriorated.

Wherein the weight ratio of the aliphatic copolyether repeating unit containing the branched repeating unit containing at least three ether functional groups and at least two polyoxyalkylene repeating units to the total weight of the polymeric resin composition is from 2 to 50% , Or 2 to 40 wt%, 3 wt% to 35 wt%, or 4 wt% to 30 wt%, or 10 to 30 wt%. That is, even in the polymer resin composition containing the copolymer or the copolymer and the mixture of the polyamide-based resin, the aliphatic copoly- mer containing the branched repeating unit containing three or more ether-based functional groups and the polyoxyalkylene repeating unit Ether repeating units may be 2 to 50 wt%, or 2 to 40 wt%, 3 wt% to 35 wt%, or 4 wt% to 30 wt%, or 10 to 30 wt%.

When the combined weight of the branched type repeating unit containing three or more ether functional groups and the aliphatic copolyether repeating unit containing two or more polyoxyalkylene repeating units is reduced to less than 2% by weight of the total polymer resin composition, The modulus reduction effect due to the aliphatic copolyether repeating unit containing the branched repeating unit containing at least three ether functional groups and at least two polyoxyalkylene repeating units may not be sufficiently realized.

On the other hand, the combined weight of the aliphatic copolyether repeating units containing the branched repeating units containing at least three ether functional groups and at least two polyoxyalkylene repeating units is increased to more than 50% by weight in the entire polymer resin composition , The polymeric resin composition exhibits thermosetting property and has a high modulus value, resulting in deterioration of moldability, deterioration of properties due to repeated deformation, and flexibility of the polymeric resin composition may be reduced.

The polymer resin composition may further comprise a second copolymer comprising an aliphatic copolyether repeating unit containing two or more polyoxyalkylene repeating units and a polyamide repeating unit. The second copolymer is a copolymer which is distinguished from the copolymer of one embodiment, and may be composed of an aliphatic copolyether repeating unit containing at least two polyoxyalkylene repeating units and a polyamide repeating unit. The content of the aliphatic copolyether-based repeating unit and the polyamide-based repeating unit containing the two or more polyoxyalkylene repeating units includes the above-mentioned contents in the above embodiment.

Meanwhile, the polymer resin composition may further include an olefin-based polymer compound. The olefin-based polymer compound serves to improve the softness of the polymer resin composition and to improve the ability to absorb external impacts. The olefin polymer compound can also greatly reduce the modulus of the polymer resin composition, It is possible to prevent the phenomenon that the internal structure of the compound or the polymer contained in the polymer is changed to crystallize.

The polymer resin composition may include 3 to 35% by weight, or 10 to 30% by weight of the olefin-based polymer compound. If the content of the olefin-based polymer compound is too small, the degree of action and effect of the olefin-based polymer compound may be insignificant. If the content of the olefin-based polymer compound is too large, the physical properties and effects expressed by the polymer resin composition can be reduced. By applying the polymer resin composition of one embodiment, the physical properties .

The olefin-based polymer compound may include an olefin-based polymer or copolymer grafted with an olefin-based polymer, an olefin-based copolymer, a dicarboxylic acid or an acid anhydride thereof, or a mixture of two or more thereof.

The olefin-based polymer may include polyethylene, polypropylene or a mixture thereof.

The olefin-based copolymer may be an ethylene-propylene copolymer or an ethylene-acrylic ester-maleic anhydride terpolymer, an acrylic ester-maleic anhydride copolymer, maleic anhydride functionalized polyolefin, ethylene-butyl acrylate-glycidyl methacrylate (GMA) terpolymer of ethylene, butylacrylate (BA) and glycidylmethacrylate (GMA).

As described above, the olefin-based polymer compound may include an olefin-based polymer or copolymer grafted with a dicarboxylic acid or an acid anhydride thereof. The dicarboxylic acid may be selected from the group consisting of maleic acid, phthalic acid, itaconic acid, , Alkenyl succinic acid, cis-1,2,3,6 tetrahydrophthalic acid, 4-methyl-1,2,3,6 tetrahydrophthalic acid, or a mixture of two or more thereof, and the dicarboxylic acid May be a dicarboxylic acid dianhydride of the above-mentioned examples.

The content of the grafted dicarboxylic acid or its acid anhydride in the olefinic polymer or copolymer grafted with the dicarboxylic acid or an acid anhydride thereof may be 0.3 wt% or more, or 0.5 wt% to 3.0 wt% .

The grafting ratio of the dicarboxylic acid or its acid anhydride can be determined from the results obtained by acid-base titration of the olefinic polymer. For example, about 1 g of the olefin-based polymer compound is placed in 150 ml of xylene saturated with water and refluxed for about 2 hours. A small amount of a 1% by weight thymol blue-dimethylformamide solution is added, and a 0.05 N sodium hydroxide-ethyl alcohol solution To obtain a solution of a dark blue solution. The resulting solution was again in a 0.05N hydrochloric acid / isopropyl alcohol solution until the solution turned yellow to determine its acid value. From this, the dicarboxylic acid grafted to the olefinic polymer compound The amount of acid can be calculated.

The olefin-based polymer compound may have a density of 0.77 g / cm 3 to 0.95 g / cm 3, or 0.80 g / cm 3 to 0.93 g / cm 3.

The polymer resin composition can be used for manufacturing an inner liner film of a tire.

According to another embodiment of the present invention, there can be provided a polymer film for an inner liner comprising a substrate film layer containing a melt extrudate of the polymer resin composition of another embodiment.

The content of the polymer resin composition includes the above-mentioned contents in relation to the other embodiments.

The polymer film may be used as an inner liner of a pneumatic tinner. Since the polymer film can realize excellent airtightness even with a thin thickness, the pneumatic tire can be lightened as compared with a pneumatic tire known in the prior art, so that the fuel efficiency of the automobile can be improved. In addition, since the polymer film exhibits low modulus and low crystallinity, the film itself is crystallized or cracks or the like are damaged even in a tire manufacturing process in which a large deformation is performed under a high temperature condition or in an automobile traveling process in which repetitive deformation is continuously applied. Can be prevented.

The base film layer may include a melt extrudate of the polymer resin composition. Examples of a specific method of melting and extruding the polymeric resin composition are not limited, and various methods used in the prior art relating to the molding of a polymeric resin can be used without limitation. For example, a melt extruder Can be used.

The base film layer may have a thickness of 10 to 300 mu m, or 50 to 200 mu m. Thus, the base film layer may have a lower air permeability, for example, an oxygen permeability of 200 cm 3 / (m 2 24 hr 揃 atm) or less, while being thinner than previously known.

The polymer film may be an unoriented film. When the polymer film is in the form of an unstretched film, it can be suitably applied to a tire forming process in which high expansion occurs due to low modulus and high strain. Further, since the crystallization phenomenon hardly occurs in the unstretched film, damage such as cracks can be prevented even by repeated deformation. In addition, since the unoriented film does not have a large deviation in orientation and physical properties in a specific direction, an inner liner having uniform physical properties can be obtained. A method of suppressing the orientation of the polymer film as much as possible, for example, by adjusting the viscosity through optimization of the melt extrusion temperature, changing the size of the spinneret, or adjusting the winding speed, the polymer film is made into an unoriented or unstretched film can do.

Meanwhile, the polymer film may further include an adhesive layer formed on at least one side of the base film layer and including a resorcinol-formalin-latex (RFL) -based adhesive.

The resorcinol-formalin-latex (RFL) based adhesive comprises 2 to 32 wt%, or 10 to 20 wt%, and 68 to 98 wt%, or 80 to 90 wt% of a condensate of resorcinol and formaldehyde, .

The condensate of resorcinol and formaldehyde may be obtained by mixing resorcinol and formaldehyde in a molar ratio of 1: 0.3 to 1: 3.0, or 1: 0.5 to 1: 2.5, followed by condensation reaction. In addition, the condensate of resorcinol and formaldehyde may be contained 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 contained in an amount of 32% by weight or less have.

The latex may be one or a mixture of two or more selected from natural rubber latex, styrene / butadiene rubber latex, acrylonitrile / butadiene rubber latex, chloroprene rubber latex and styrene / butadiene / vinylpyridine rubber latex. The latex may be contained in an amount of not less than 68% by weight based on the total amount of the adhesive layer for the flexibility of the material and an effective crosslinking reaction with the rubber, and not more than 98% by weight for the chemical reaction with the base film and the rigidity of the adhesive layer.

The adhesive layer may have a thickness of 0.1 to 20 占 퐉, or 0.1 to 10 占 퐉, or 0.2 to 7 占 퐉, or 0.3 to 5 占 퐉, and may be formed on one surface or both surfaces of the base film layer.

If the thickness of the adhesive layer is too thin, the adhesive layer itself may become 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 concentrate on a part of the adhesive layer. In addition, if the adhesive layer is too thick, the interface separation in the adhesive layer may occur and the fatigue characteristics may be deteriorated. In order to adhere the inner liner film to the carcass layer of the tire, an adhesive layer is generally formed on one surface of the base film layer. However, in the case of applying the inner liner film of a multilayer structure or when the inner liner film surrounds the bead portion, It is preferable to form an adhesive layer on both sides of the base film layer when adhesion with rubber is required on both sides according to the method and structure design.

The polymer film for an inner liner may have a tensile strength at 25% stretching of 20 MPa or less, or 10 MPa to 20 MPa, as measured by ASTM D882 after heat treatment at 170 캜 for 1 hour. Accordingly, the polymer film for inner liner can have excellent heat resistance and high moldability through low modulus.

Specifically, after the polymer film was heat-treated at 170 ° C. for 1 hour, the tensile strength at 25% elongation was measured by hanging one end of the polymer film in a hot air oven at 170 ° C., leaving it standing for 30 minutes (Model 4204, Instron) immediately after completion of the heat treatment, and the measurement was carried out in accordance with ASTM D882.

Also, the inner-liner polymer film may have an impact strength of 1200 KJ / g or more, or 1200 KJ / g to 4000 KJ / g, as measured by ASTM D6110 after heat treatment at 170 ° C for 1 hour. Accordingly, the polymer film for inner liner can have excellent heat resistance and high impact resistance.

Specifically, after the polymer film was heat-treated at 170 ° C for 1 hour, the impact strength was measured by hanging one end of the polymer film in a hot air oven at 170 ° C and leaving it standing for 1 hour in a no-load and no- ), A test piece having a size of 30 mm in width and 70 mm in length can be measured according to ASTM D6110 using an impact tester (Zwick / Roell Co., Ltd. HIT5.5P).

The oxygen permeability of the inner liner polymer film measured by ASTM D1434 for 24 hours at a temperature of 23 캜 and a relative humidity of 55 RH% may be 500 cc / (m 2 · 24 hr · atm) or less.

According to the present invention, it is possible to provide a copolymer having improved heat resistance and mechanical properties, a low modulus characteristic and an improved durability, and an excellent airtightness even at a thin thickness to lighten the tire and improve automobile fuel economy, A polymer resin composition capable of providing an inner liner film having physical properties and a polymer film for an inner liner provided from the polymer resin composition may be provided.

Fig. 1 schematically shows the structure of a tire.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Examples 1 to 2: Preparation of Copolymer >

Example 1

After charging 1.5 kg of? -Caprolactam, 500 g of polyoxytetramethylene / polyoxypropylenediamine, 40 g of polyoxypropylenetriamine (weight average molecular weight: 3000 g / mol) and 4 g of phenol-based antioxidant, 70 g of water Mixed together and stirred at 130 rpm for 2 hours at 60 rpm. Thereafter, the temperature of the reactor was raised to 240 캜, and the reaction was carried out at 60 rpm for 1 hour while maintaining a pressure of 14 kg / cm 2.

The pressure of the reactor was gradually lowered for 1 hour to make atmospheric pressure. After the pressure was reduced to 0.3 kg / cm 2 for 30 minutes, the reaction was continued for 210 minutes. After the polymerization was completed, the polymerization was carried out at a pressure of 2 kg / And dried in a chip shape at 95 ° C for 24 hours to remove unreacted materials and vacuum dried at 100 ° C for 20 hours to obtain a copolymer.

Example 2

A copolymer was prepared in the same manner as in Example 1 except that 100 g of the polyoxypropylene triamine was used.

≪ Comparative Examples 1 to 3: Production of Copolymer >

Comparative Example 1

A copolymer was prepared in the same manner as in Example 1 except that polyoxytetramethylene diamine was used instead of polyoxytetramethylene / polyoxypropylene diamine.

Comparative Example 2

A copolymer was prepared in the same manner as in Example 1 except that polyoxypropylene diamine was used instead of polyoxytetramethylene / polyoxypropylene diamine.

Comparative Example 3

A copolymer was prepared in the same manner as in Example 1 except that 500 g of polyoxytetramethylenediamine was used without using both polyoxytetramethylene / polyoxypropylenediamine and polyoxypropylenetriamine.

≪ Experimental Example: Measurement of physical properties of copolymer obtained in Examples and Comparative Examples >

The copolymers obtained in the above Examples and Comparative Examples were extruded at a temperature of 250 DEG C by a melt extruder and formed into a film having a thickness of 120 mu m and then physical properties were measured by the following methods. The results are shown in Tables 1 to 2 .

Experimental Example 1: Tensile properties

One end of the film was suspended in a hot air oven at 170 占 폚 for a film produced from the copolymer of the examples and comparative examples, and left to stand (heat-treated) for 30 minutes in a no-load and no-contact state. Then, according to ASTM D882, 25% tensile strength at tensile strain, 25% tensile strain at break, and tensile stress at break were measured before and after the heat treatment And the results are shown in Table 1 below. The specific measurement method is as follows.

(1) Measuring instrument: universal material testing machine (Model 4204, Instron)

(2) Measurement conditions:

    i) Head speed 50 mm / min,

    ii) Grip Distance 50 mm,

    iii) Sample Width 15 mm,

(3) five times each, and an average value of the obtained results was obtained.

Tensile property measurement results of Examples and Comparative Examples division thickness
(탆) 25% Tensile strength at stretching (MPa) Tensile modulus at break (%) Tensile strength at break (MPa) Example 1 Before heat treatment 100 13.14 488 33.18 After heat treatment 100 19.82 378 31.45 Example 2 Before heat treatment 100 14.32 470 34.88 After heat treatment 100 19.97 367 29.85 Comparative Example 1 Before heat treatment 100 13.12 507 33.75 After heat treatment 100 21.82 345 25.77 Comparative Example 2 Before heat treatment 100 16.40 462 31.41 After heat treatment 100 21.98 319 19.98 Comparative Example 3 Before heat treatment 100 13.33 455 31.07 After heat treatment 100 24.12 320 18.76

As shown in Table 1, the tensile strength (modulus) of the copolymers of Examples 1 and 2 was lowered to 20 MPa or less at 25% elongation after heat treatment, whereas the elongation at break of Comparative Examples 1 to 3 was 21.82 MPa or more It can be confirmed that the measured value is high. As a result, it was confirmed that the 25% elongation modulus after heat resistance was improved in the above example.

Comparing the tensile strength at break in Table 1, the tensile strength change after heat treatment in Examples 1 and 2 was less than 6 MPa, while in Comparative Examples 1 to 3, the tensile strength value after heat treatment was greatly reduced Respectively. As a result, it was confirmed that the heat resistant strength retention ratio was improved in the case of the above embodiment.

Experimental Example 2: Impact Strength Characteristics

One end of the film was suspended in a hot air oven at 170 占 폚 for a film produced from the copolymer of the examples and the comparative examples, and the film was allowed to stand (heat treatment) for 1 hour in a no-load and no-contact state. Then, the specimens of 30 mm in width and 70 mm in length were measured for impact strength before and after the heat treatment using an impact tester (Zwick / Roell Co., Ltd. HIT5.5P) according to ASTM D6110, The impact strength retention after the time heat treatment was determined by the following formula (1), and is shown in the following Table 2.

[Equation 1]

(%) = [Thermal shock resistance after heat treatment at 170 占 폚 for 1 hour / thermal shock resistance before heat treatment - thermal shock resistance after heat treatment at 170 占 폚 for 1 hour] X 100.

The impact strength measurement results of the examples and comparative examples division Impact strength (KJ / g) Before heat treatment After heat treatment Retention rate (%) Example 1 2312 1370 59 Example 2 2217 1388 62 Comparative Example 1 2357 871 37 Comparative Example 2 2845 1148 40 Comparative Example 3 2432 805 33

In Examples 1 and 2, the impact strength retention ratio before and after heat treatment was as high as 50% or more. On the other hand, in the case of Comparative Examples 1 to 3, it was confirmed that the impact strength retention ratio before and after the heat treatment was measured as low as 40% or less.

Claims (25)

Branched repeating units containing three or more ether-based functional groups; An aliphatic copolyether repeating unit containing two or more polyoxyalkylene repeating units; And a polyamide-based repeating unit.
The method according to claim 1,
Wherein the aliphatic copolyether repeating unit containing two or more polyoxyalkylene repeating units comprises a repeating unit represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ are different from each other and each independently represents a straight or branched alkylene group having 1 to 10 carbon atoms, n and m are each independently an integer of 1 to 100,
R ₃ and R ₄ may be the same or different and are each independently a direct bond, -O-, -NH-, -COO- or -CONH-.
3. The method of claim 2,
In the above formula (1), the ratio of n: m is from 8: 2 to 6: 4.
3. The method of claim 2,
Wherein R ₁ is a linear or branched alkylene group having 4 to 10 carbon atoms.
3. The method of claim 2,
Wherein R ₂ is a linear or branched alkylene group having 1 to 3 carbon atoms.
The method according to claim 1,
Wherein the branched repeating unit comprises an intermediate group containing at least one central element selected from the group consisting of carbon, nitrogen, phosphorus, sulfur, oxygen and silicon, and at least three ether- coalescence.
The method according to claim 1,
Wherein the ether-based functional group comprises a polyoxyalkylene repeating unit having 1 to 10 carbon atoms.
The method according to claim 1,
Wherein the content of the branched repeating unit containing the three or more ether-based functional groups contained in the copolymer is 0.1 wt% to 20 wt%.
The method according to claim 1,
Wherein the branched repeating unit comprises at least one selected from the group consisting of a trivalent repeating unit having three ether functional groups bonded to each other through nitrogen and a trivalent repeating unit having three ether functional groups bonded to each other through carbon, Copolymer.
The method according to claim 1,
Wherein the branched type repeating unit comprises at least one selected from the group consisting of repeating units of the following formula (2) and repeating units of the following formula (3):
(2)

In Formula 2,
R ₈ to R ₁₀ may be the same or different and are each independently an alkylene group having 1 to 10 carbon atoms,
x, y and z each independently represents an integer of 1 to 50,
(3)

In Formula 3,
R ₁₁ to R ₁₃ may be the same or different and are each independently an alkylene group having 1 to 10 carbon atoms, R ₁₄ is an alkyl group having 1 to 10 carbon atoms,
n ₁ , n ₂ , and n ₃ are each independently an integer of 1 to 50.
The method according to claim 1,
Wherein the copolymer has a weight average molecular weight of 30,000 g / mol to 500,000 g / mol.
The method according to claim 1,
Wherein the polyamide-based repeating unit comprises a repeating unit represented by the following formula (4) or (5):
[Chemical Formula 4]

In Formula 4, R ₅ is a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a linear or branched alkylene group having 7 to 20 carbon atoms,
[Chemical Formula 5]

Wherein R ₆ is a linear or branched alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, R ₇ is a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 6 to 20 carbon atoms Or a linear or branched alkylene group having 7 to 20 carbon atoms.
A polymeric resin composition comprising the copolymer of claim 1.
14. The method of claim 13,
Further comprising a polyamide resin having a relative viscosity (sulfuric acid: 96% solution) of 2.5 to 4.0.
15. The method of claim 14,
Wherein the polyamide resin and the copolymer are contained in a weight ratio of 8: 2 to 2: 8.
14. The method of claim 13,
Wherein the weight ratio of the aliphatic copolyether repeating unit containing a branch type repeating unit containing at least three ether functional groups contained in the copolymer and two or more polyoxyalkylene repeating units contained in the polymer resin composition is 2 wt% To 50% by weight of the polymeric resin composition.
14. The method of claim 13,
A second copolymer comprising an aliphatic copolyether repeating unit containing at least two polyoxyalkylene repeating units and a polyamide repeating unit.
14. The method of claim 13,
Wherein the polymer resin composition further comprises an olefin-based polymer compound.
19. The method of claim 18,
Wherein the olefinic polymer compound comprises at least one compound selected from the group consisting of an olefinic polymer, an olefinic copolymer, and an olefinic polymer or copolymer in which a dicarboxylic acid or an acid anhydride thereof is grafted.
14. The method of claim 13,
The polymer resin composition is used for producing an inner liner film of a tire.
A polymer film for an inner liner comprising a base film layer containing a melt extrudate of the polymer resin composition of claim 13.
22. The method of claim 21,
Further comprising an adhesive layer formed on at least one side of the base film layer and including a resorcinol-formalin-latex (RFL) -based adhesive.
23. The method of claim 22,
Wherein the base film layer has a thickness of 10 mu m to 300 mu m and the adhesive layer has a thickness of 0.1 mu m to 20 mu m.
22. The method of claim 21,
And a tensile strength at 25% stretching of 20 MPa or less as measured by ASTM D882 after heat treatment at 170 占 폚 for 1 hour.
22. The method of claim 21,
A polymer film for an inner liner having an impact strength of 1200 KJ / g or more as measured by ASTM D6110 after heat treatment at 170 占 폚 for 1 hour.

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