Fluorine-containing ethylene / vinyl alcohol copolymer resin composition, and mixture and blend thereof

Abstract

To obtain a fluorine-containing ethylene / vinyl alcohol copolymer resin composition and its mixture and blend.SOLUTION: The present disclosure relates to a fluorine-containing ethylene-vinylalcoholcopolymer (EVOH) composition, and a mixture and a blend thereof, wherein the fluorine-containing EVOH composition comprises an EVOH and fluorine-containing particles, wherein a total fluoride ion content of the fluorine-containing EVOH composition is from 45ppm to 41000ppm. The present invention can reduce the adhesion of EVOH to the inside of the extruder, thereby effectively reducing the occurrence of gel or gelation in the subsequent finished product.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) The claims of this application are based on the patent application filed on December 30, 2019, entitled "Ethylene Vinyl Alcohol-Based Polymerization of Polymerizable Compounds." U.S. Patent Application No. 16 / 729,984 entitled "Alcohol Pellets and Films Thereof" Priority is claimed, and the present application is a continuation-in-part of the above application, the entire contents of which are incorporated herein by reference. This application was filed on May 19, 2020. Claiming priority to U.S. Patent Application Nos. 16 / 877,555 and 16 / 877,570 No. 6,239,999, the entire contents of which are incorporated herein by reference.

[0002] (Technical field) The present invention relates to a fluorine-containing ethylene-vinyl alcohol copolymer (ethylene-viny The present invention relates to a fluorine-containing ethylene vinyl alcohol (EVOH) resin composition. The polyol copolymer resin composition contains particles, particularly fluorine-containing particles. The total fluorine ion content in the fluorine-containing EVOH resin composition is 45 ppm to 41,000 The present invention further relates to a fluorine-containing ethylene-vinyl alcohol copolymer resin composition.

[0003] Disclosed are mixtures and blends comprising: [Background technology]

[0003] EVOH resins are widely used in multi-layered products and are used to preserve perishable goods. For example, EVOH resins and multilayers are commonly used in the food packaging industry, medical equipment and accessories industry, and other industries. EVOH resins are used in the pharmaceutical, electronics, and agricultural chemical industries. is commonly added as a separate layer in multilayers and used as an oxygen barrier layer. .

[0004] Die buildup is a common occurrence in extrusion processes using EVOH. Another common problem in extrusion processes using EVOH is sticking to the screw. These problems are caused by the undesirable phenomenon of EVOH forming This can cause deterioration in the appearance and mechanical strength of the film. has not yet been adequately addressed or resolved.

[0005] For example, in the conventional method, boron was added to remove the particles that had adhered to the inside of machinery and equipment. However, if the boron ion concentration becomes too high, the current and pressure of the extruder will increase. If the boron ions are not uniformly distributed, the subsequently formed The film becomes excessively gel-rich, resulting in poor appearance. It occurs.

[0006] This provides better film properties and allows for cost-effective manufacturing processes. There is a continuing need for EVOH resins that can achieve this. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention relates to a fluorine-containing ethylene vinyl alcohol copolymer (EVOH) resin composition. It has particles, particularly fluorine-containing particles, and is a fluorine-containing ethylene vinyl alcohol. The total fluorine ion content in the coal copolymer resin composition is 45 ppm to 41,000 ppm. The fluorine-containing EVOH resin composition can be used to prepare a film or a multilayer structure. Since EVOH and fluoropolymers are immiscible, their combination is For example, the immiscibility of EVOH and fluorinated polymers can lead to the formation of This can be expected to have a negative impact on the appearance and mechanical properties of the resulting film. [Means for solving the problem]

[0008] Due to the problems caused by immiscibility, EVOH and fluoropolymers (fluoropoly) have traditionally been mixed together. The present invention avoids the use of fluoropolymers. When the EVOH resin composition is prepared using the fluoropolymer, the partial miscibility of the fluoropolymer is The inventors have also discovered that this improves the flow rate and reduces the problem of screw sticking. The fluorine-containing EVOH resin composition of the present invention can reduce adhesion of EVOH to the inside of the extruder. effectively reduces the occurrence of gels or gelled products in the subsequent finished product, and It can also improve film appearance and transparency, and reduce extruder torque and melt pressure. I also discovered that.

[0009] The above-mentioned fluorine-containing EVOH resin composition usually contains an ethylene vinyl alcohol copolymer and a small amount of The total fluorine contained in the fluorine-containing EVOH resin composition contains at least one fluorine-containing microparticle. The ion content may be 45 ppm to 41,000 ppm. The fluorine ion content at the surface is preferably between 1 and 126 ppm. The fluorine ion content and the total fluorine ion content on the surface of the fluorine-containing EVOH resin composition are preferably The ratio of the content of fluorine may be 0.0015 to 0.03. The fluorine-containing EVOH resin composition further has a boron content of 50 to 250 ppm. can be done.

[0010] The fluorine-containing EVOH resin composition preferably has at least two melting points. In other words, it has at least a first melting point temperature and a second melting point temperature. The first melting point temperature is about 100 The second melting point temperature may be between about 150°C and about 195°C.

[0011] Ethylene vinyl alcohol in the fluorine-containing EVOH resin composition according to at least one embodiment The copolymer has an ethylene content and a degree of saponification, of which the ethylene content is about 24%. ~ about 48 mole %, the degree of saponification is 99.5 mole % or more, and fluorine-containing The microparticles include a fluorinated polymer.

[0012] The above-mentioned fluorine-containing EVOH resin composition can be used to prepare a mixture or blend, i.e., A blend having a fluorine-containing EVOH resin composition or a blend having a fluorine-containing EVOH resin composition It is possible to manufacture

[0013] The mixture containing the fluorine-containing EVOH resin composition comprises the fluorine-containing EVOH resin composition and a first It contains ethylene vinyl alcohol copolymer, and when calculated based on 20g of the mixture, The total fluorine ion content contained therein is 100 ppm to 11,000 ppm. The ethylene content of the EVOH resin composition and the ethylene content of the first ethylene-vinyl alcohol copolymer The fluorine ion content at the surface of the mixture may be 2 to 5. The fluoride ion content at the surface of the mixture and the total fluoride content are preferably between 0.5 ppm and 1.5 ppm. The ratio of the ion content is preferably 0.0019 to 0.04.

[0014] The blend containing the fluorine-containing EVOH resin composition comprises the fluorine-containing EVOH resin composition, the first an ethylene vinyl alcohol copolymer and a second ethylene vinyl alcohol copolymer; The ethylene content of the first ethylene vinyl alcohol copolymer and the second ethylene vinyl alcohol The ethylene content of the copolymers varies, and the calculation for a 20g blend is The total fluoride ion content is 200 ppm to 2000 ppm. The ratio of the fluorine ion content on the surface of the fluoride to the total fluorine ion content is 0.0013 to 0. Preferably it is .045. [Brief explanation of the drawings]

[0015] Practice of the techniques of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0016] [Figure 1] FIG. 1 is a cross-sectional view of an exemplary EVOH pellet of the present invention. [Figure 2] FIG. 1 is a diagram of two melting point temperatures of exemplary EVOH pellets of the present invention. [Figure 3] FIG. 1 is a cross-sectional view of EVOH pellets of the present invention melted and flowing through an extruder.

[0017] It should be understood that the various aspects of the present invention are not limited to the arrangements, instrumentalities and features shown in the accompanying drawings. sea ​​bream. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention relates to a fluorine-containing ethylene vinyl alcohol copolymer (EVOH) resin composition. The fluorine-containing EVOH resin composition contains dispersed particles, particularly fluorine-containing particles. The fluorine-containing EVOH resin composition is used to prepare a film or a multilayer structure. It is possible.

[0019] In one aspect, the present invention provides a fluorine-containing EVOH resin composition. The resin composition may be in the form of pellets, films, fibers, etc. The fluorine-containing EVOH pellets are one or more pellets formed by granulating a fluorine-containing EVOH resin composition. As used herein, the term "pellet" refers to one or more pellets formed via granulation. Although the above describes a fluorine-containing EVOH resin composition in the form of fluorine-containing EVOH pellets, The fluorine EVOH resin composition is processed into the form of beads, cubes, chips, shavings, etc. The fluorine-containing EVOH resin composition of the present invention is usually an ethylene-vinyl alcohol copolymer. The particle size of the fluorine-containing particle is 20 μm or less. do.

[0020] FIG. 1 depicts a cross-sectional view of an exemplary fluorinated EVOH pellet 100 of the present invention. The fluorine-containing EVOH pellets 100 are formed from EVOH, and the EVOH contains ethylene. For example, the ethylene content of EVOH is about 24 to about 48 mole %. about 20 to about 50 mole%, about 25 to about 45 mole%, about 28 to about 42 mole%, or The fluorine-containing EVOH resin composition 100 may contain different ethylene groups. It can be formed from two or more types of EVOH having different amine contents. The ethylene content of one type of EVOH may be in the range of about 20 to about 35 mole %, e.g. For example, about 24 to about 35 mole%, about 28 to about 35 mole%, about 20 to about 32 mole% , about 24 to about 32 mole%, about 28 to about 32 mole%, about 20 to about 30 mole% The content of EVOH is about 24 to about 30 mole %. The olefin content may be in the range of about 36 to about 50 mole %, for example about 40 to about 50 mole %. e%, about 44 to about 50 mole%, about 36 to about 45 mole%, or about 40 to about 45 mole% However, in some preferred embodiments, the EVOH resin composition 100 contains It is formed from a single EVOH having an ethylene content of about 24 to about 48 mole %.

[0021] The fluorine content of the above-mentioned fluorine-containing EVOH resin composition 100 varies depending on the amount of one or more fluorines added. It is related to fluorinated polymers (also referred to herein as "fluoropolymers"), and The mer can form fluorine-containing fine particles 110 dispersed in the EVOH pellets 100. For example, the one or more fluoropolymers mentioned above may be polyvinylidene fluoride (poly vinylidene fluoride, PVDF), polytetrafluoroethylene ( polytetrafluoroethylene), polyhexafluoropropylene ( polyhexafluoropropylene), polychlorotrifluoroethylene (polychlorotrifluoroethylene, PCTFE), 2-chloro 2-chloropentafluropropene oropropene, dichlorodifluoroethylene roethylene), 1,1-dichlorofluoroethylene (1,1-dichlor fluoroethylene) and combinations thereof Additionally / or alternatively, the fluoropolymer may be vinylidene fluoride. fluoride, VDF), hexafluoropropylene (hexafluoropropane) ethylene, HFP) and tetrafluoroethylene It may contain a copolymer derived from at least two of the following: In some embodiments, the fluoropolymer may be selected from the group consisting of VDF, HFP, and TFE. The EVOH resin composition may contain a copolymer derived from two or more types of EVOH. 00 is a copolymer derived from VDF and HFP, a copolymer derived from TFE and HFP Polymers, copolymers derived from VDF and TFE and / or VDF, HFP and TF Without being limited to any particular theory, the copolymer may include copolymers derived from E. The inventors have demonstrated that by reducing the crystal size of certain fluoropolymers, EVOH pellets can be produced. We believe that it is possible to lower the melting point of at least one of the compounds described above.

[0022] The fluorine-containing EVOH resin composition 100 has fluorine-containing particles 110, and the particles are in the form of fine particles. According to the International Union of Pure and Applied Chemistry (IUPAC), the definition of a fine particle is 10 -7 ~1 0 -4 The particle size of the microparticles in the present invention is measured in terms of diameter or cross-sectional area. The length of the main axis is 0.5 to about 19 μm, 1.0 to about 19 μm, or 1.2 to about 16 μm. The size of the fluorine-containing particles is preferably determined by the type or kind of fluoropolymer, It can be controlled by adjusting the amount of mer and the ethylene content of EVOH. When the fluorine-containing particles are spherical, whether or not the fluorine-containing particles have a desired particle size depends on the particle size. Determined by the diameter of the cross section. If the fluorine-containing particles are not spherical and / or the cross section of the fluorine-containing particles If the surface shape is not circular (for example, oval or blocky), the fluorine-containing particles may not be the desired particle. Whether or not a particle has a diameter is determined by the length of the main axis of the cross section of the fluorine-containing particle. In some embodiments, the fluorine-containing EVOH resin composition is 100 The particle diameter of all the fluorine-containing particles 110 evaluated on the cross section is 20 μm or less. , for example, 19 μm or less, 18 μm or less, 16 μm or less, 14 μm or less, or 12 μm or less In other words, in some embodiments, the particle size of the fluorine-containing particles 110 is 20 μm or less. not exceeding, for example, 19 μm, 18 μm, 16 μm, 14 μm or 12 μm The particle size of the fluorine-containing particles 110 is 0.1 μm or more, 0.3 μm or more, or 0.5 μm or more. For example, the fluorine-containing EVOH resin composition 100 may have a particle size of 1. The fluorine-containing particles 110 may be 0 to about 19 μm or 1.2 to about 16 μm. In some examples, all of the samples evaluated on a cross section of the fluorine-containing EVOH resin composition 100 were All of the fluorine-containing particles 110 are within the desired particle size range described herein. However, in some examples, the results were evaluated on a cross section of the fluorine-containing EVOH resin composition 100. The majority of the fluorine-containing particles 110 are within the desired particle size range. Exemplary factors that influence whether or not a polymer is fluoropolymer-based include (a) the amount of fluoropolymer, (b) the ethylene content of the EVOH, and (c) fluoropolymer type, (d) temperature in the extruder, and (e) screw The rotational speed of the rotor may be included.

[0023] As shown in FIG. 2, the fluorine-containing EVOH resin composition 100 has at least two melting points. In some embodiments, the fluorine-containing EVOH resin composition 100 may have One melting point temperature (for example, the first melting point temperature) is about 100°C to about 140°C, for example. For example, about 105°C to about 135°C, about 110°C to about 135°C, or about 120°C to about 130°C. The first melting point temperature is derived from the fluorine-containing particles. The melting point temperature (for example, the second melting point temperature) is about 150°C to about 195°C, for example, about 158°C. The second melting point is about 190°C or about 164°C to about 187°C, In some embodiments, the fluorine-containing EVOH resin composition is derived from a fluorine-containing EVOH copolymer. In another embodiment, the product 100 has at least three different melting point temperatures. The VOH resin composition 100 may comprise at least four, at least five, or at least six different The fluorine-containing EVOH resin composition 100 has a melting point temperature of 90°C or more. 0.8 mole% or more, preferably 95 mole% or more, preferably 97 mole% or more, It is over 99.5 mole%.

[0024] The above-mentioned fluorine-containing EVOH resin composition 100 does not contain polyalkylene oxide or For example, the fluorine-containing EVOH resin composition 100 may contain less than 5 wt % of less than 4 wt. %, less than 3 wt. %, Less than 2 wt%, less than 1 wt%, or less than 0.5 wt%.

[0025] The above-mentioned fluorine-containing EVOH resin composition 100 is an EVOH film formed therefrom. For example, the fluorine-containing EVOH resin composition 100 is useful for more efficiently preparing E In the VOH film manufacturing process, improve deposition on the die and solve the problem of adhesion to the screw. The suitable method and equipment for preparing the fluorine-containing EVOH film can reduce the The invention may include methods and equipment that are readily apparent to those skilled in the art. A fluorine-containing particle 110 is used, which is compatible (and partially immiscible) with a fluorine-containing polymer. By preparing a fluorine-containing EVOH resin composition 100 containing It is believed that the mers separate on the inner surface of the extruder, forming a coating layer 120. FIG. 3 shows the state where a part of the fluoropolymer of the fluorine-containing EVOH pellets of the present invention is extruded. The figure shows a coating layer 120 formed on the inner surface of the extruder. The coated fluoropolymer layer protects the EVOH resin as it flows through the extruder. Even if the extrusion process of raw EVOH pellets is carried out at high temperatures, the EVOH film does not discolor. This is advantageous in making them feel more comfortable.

[0026] In another embodiment, the fluorine-containing EVOH resin composition of the present invention is It may include one or more characteristics, attributes or properties of OH resins and / or pellets. Addition of fluorine can contribute to the screw processing of the EVOH resin composition. The polymer adheres to the inner wall of the screw extruder, and the EVOH resin composition is The flow resistance during passage through the extruder is reduced. According to one preferred embodiment, the present invention The total fluorine ion content / concentration of the provided fluorine-containing EVOH resin composition is 45ppm The total fluorine ion content is 1000 ppm to 41,000 ppm for the fluorine-containing EVOH resin composition. The total fluorine ion content in the fluorine-containing EVOH resin composition is calculated as follows: 45~41000ppm, 45~38000ppm, 45~35000ppm, 45 ~33000ppm、45~30000ppm、45~28000ppm、45~250 00ppm、45~23000ppm、45~20000ppm、45~18000pp m、45~15000ppm、45~13000ppm、45~10000ppm、45 ~8000ppm、45~5000ppm、45~3000ppm、45~1000pp m、45~800ppm、45~500ppm、45~300ppm、45~100pp m、100~41000ppm、100~38000ppm、100~35000ppm 、100~33000ppm、100~30000ppm、100~28000ppm、 100~25000ppm、100~23000ppm、100~20000ppm、1 00~18000ppm、100~15000ppm、100~13000ppm、10 0~10000ppm、100~8000ppm、100~5000ppm、100~3 000ppm、100~1000ppm、100~800ppm、100~500ppm 、100~300ppm、1000~41000ppm、1000~38000ppm、 1000~35000ppm、1000~33000ppm、1000~30000pp m、1000~28000ppm、1000~25000ppm、1000~23000 ppm、1000~20000ppm、1000~18000ppm、1000~150 00ppm、1000~13000ppm、1000~10000ppm、1000~8 000ppm、1000~5000ppm、1000~3000ppm、10000~4 1000ppm、10000~38000ppm、10000~35000ppm、10 000~33000ppm, 10000~30000ppm, 10000~28000p pm, 10000~25000ppm, 10000~23000ppm, 10000~2 0000ppm, 10000~18000ppm, 10000~15000ppm, 10 000~13000ppm, 20000~41000ppm, 20000~38000p pm, 20000~35000ppm, 20000~33000ppm, 20000~3 0000ppm, 20000~28000ppm, 20000~25000ppm, 20 000~23000ppm, 30000~41000ppm, 30000~38000p pm, 30,000 to 35,000 ppm or 30,000 to 33,000 ppm is acceptable. Surprisingly, the total fluorine ion content of the fluorine-containing EVOH resin composition is 45 to 4100 If the fluorine is within the range of 0 ppm, it can act as a lubricant and anti-adhesion agent. This reduces adhesion to the die or screw during processing, improving processability. In the present invention, the fluorine-containing EVOH resin composition containing the fluorine-containing particles 110 If the total fluorine ion content of the product 100 is within the desired range, the fluorine ions generated during the formation of the EVOH film can be The fisheyes are reduced, and the mechanical properties and film appearance can be improved. The total fluorine content depends on the type of fluoropolymer added, the amount of fluoropolymer, and the amount of EVOH. The amount of ethylene contained, the mixing method, the amount of boron contained, etc. are related to the The total fluorine ion content of the fluorine-containing EVOH resin composition 100 is controlled within a desired range. It is possible.

[0027] According to one preferred embodiment, the fluorine-containing EVOH resin composition provided by the present invention is useful. The fluoride ion content / concentration on the surface is between 1 and 126 ppm. The fluorine ion content is calculated for the fluorine-containing EVOH resin composition. The fluorine ion content on the surface of the fluorine-containing EVOH resin composition is 1 to 126 ppm. , 1~115ppm, 1~100ppm, 1~90ppm, 1~80ppm, 1~70p pm, 1~60ppm, 1~50ppm, 1~40ppm, 1~30ppm, 1~20p pm, 1~10ppm, 5~126ppm, 5~115ppm, 5~100ppm, 5~ 90ppm, 5~80ppm, 5~70ppm, 5~60ppm, 5~50ppm, 5~ 40ppm, 5~30ppm, 5~20ppm, 5~10ppm, 15~126ppm, 15~115ppm, 15~100ppm, 15~90ppm, 15~80ppm, 15 ~70ppm, 15~60ppm, 15~50ppm, 15~40ppm, 15~30p pm, 15~20ppm, 25~126ppm, 25~115ppm, 25~100ppm m, 25~90ppm, 25~80ppm, 25~70ppm, 25~60ppm, 25 ~50ppm, 25~40ppm, 25~30ppm, 35~126ppm, 35~11 5ppm, 35~100ppm, 35~90ppm, 35~80ppm, 35~70ppm m, 35~60ppm, 35~50ppm, 35~40ppm1~126ppm, 45~ 115ppm, 45~100ppm, 45~90ppm, 45~80ppm, 45~70 ppm, 45~60ppm, 45~50ppm, 55~126ppm, 55~115ppm m, 55~100ppm, 55~90ppm, 55~80ppm, 55~70ppm, 5 5~60ppm, 65~126ppm, 65~115ppm, 65~100ppm, 65 ~90ppm, 65~80ppm, 65~70ppm, 75~126ppm, 75~11 5ppm, 75~100ppm, 75~90ppm, 75~80ppm, 85~126p pm, 85~115ppm, 85~100ppm, 85~90ppm, 95~126ppm m, 95~115ppm, 95~100ppm, 105~126ppm, 105~115 ppm or 120-126 ppm. is a fluorine compound contained in EVOH resin, which exists near the surface of the EVOH resin pellet. It means the amount of fluorine compounds contained in the EVOH resin pellets. The fluoride ion content on the surface is measured by ion chromatography (M etrohm 930 Compact IC Flex / Ses / PP / Deg ) and the test method used was the NIEA W415.54B water anion detection method. In the pretreatment, 0.5 g of sample pellets was first placed in 5 cc of methanol and After transferring to a 200°C environment and stirring for 4 hours, the mixture was filtered to remove the pellets, and 0.5 c. of the liquid was added. c., and burn the liquid with an oxygen cylinder, then extract it with water and perform chemical analysis. By dissolving EVOH in a methanol solution, in which it is hardly soluble, fluorine ions on the surface was precipitated.

[0028] The content of fluorine ions on the surface depends on the type of fluoropolymer, The amount of additive, ethylene content, and boron content are all affected by the overall effect of the surface fluorine. The actual amount of fluorine-containing polymer that is added is mainly affected by the amount of fluorine-containing polymer added. The difference in ethylene content also leads to different reaction levels between EVOH and fluoropolymers, resulting in different EVOH / fluoropolymer ratios. In addition to having different ratios of fluorine concentration present on the OH surface and in the EVOH pellet, The iodine content not only affects the viscosity of the EVOH, which in turn affects the reaction time, but also There is a certain competitive action with fluorine particles, and some reaction with EVOH occurs, resulting in a concentration of surface fluorine. Therefore, the fluorine content of the surface of the present invention may be The type of fluoropolymer, the amount of fluoropolymer added, the ethylene content, the boron content, etc. The results are obtained by synthesizing and testing the effects of the present invention. Adjust the above variables according to routine testing to obtain the desired surface fluorine concentration. It is possible.

[0029] Further, in one preferred embodiment, the present invention provides a fluorine-containing EVOH resin composition. The composition has a ratio of the surface fluorine ion content to the total fluorine ion content of 0.0015 The fluorine ion content and total fluorine ion content on the surface of the fluorine-containing EVOH resin composition are The ratio of fluoride ion content is 0.0015~0.03, 0.0015~0.028, 0 .0015~0.026, 0.0015~0.024, 0.0015~0.022, 0. 0.0015~0.02, 0.0015~0.018, 0.0015~0.016, 0.00 15~0.014, 0.0015~0.012, 0.0015~0.01, 0.0015 ~0.007, 0.0015~0.005, 0.0015~0.003, 0.0015~ 0.0025, 0.0015~0.002, 0.0015~0.0017, 0.003~ 0.03, 0.003 to 0.028, 0.003 to 0.026, 0.003 to 0.024 , 0.003~0.022, 0.003~0.02, 0.003~0.018, 0.00 3~0.016、0.003~0.014、0.003~0.012、0.003~0. 01、0.003~0.007、0.003~0.005、0.005~0.03、0. 005~0.028、0.005~0.026、0.005~0.024、0.005~ 0.022、0.005~0.02、0.005~0.018、0.005~0.016 、0.005~0.014、0.005~0.012、0.005~0.01、0.00 5~0.007、0.007~0.03、0.007~0.028、0.007~0.0 26、0.007~0.024、0.007~0.022、0.007~0.02、0. 007~0.018、0.007~0.016、0.007~0.014、0.007~ 0.012、0.007~0.01、0.009~0.03、0.009~0.028、 0.009~0.026、0.009~0.024、0.009~0.022、0.00 9~0.02、0.009~0.018、0.009~0.016、0.009~0.0 14、0.009~0.012、0.009~0.01、0.011~0.03、0.0 11~0.028、0.011~0.026、0.011~0.024、0.011~0 .022、0.011~0.02、0.011~0.018、0.011~0.016、 0.011~0.014、0.011~0.012、0.015~0.03、0.015 ~0.028、0.015~0.026、0.015~0.024、0.015~0.0 22、0.015~0.02、0.015~0.018、0.015~0.016、0. 02~0.03、0.02~0.028、0.02~0.026、0.02~0.024 , 0.02 to 0.022, 0.025 to 0.03, 0.025 to 0.028 or 0.02 According to one embodiment of the present invention, the total fluorine ion content may be in the range of 0.5 to 0.026. If the fluorine ion content is high and the surface fluorine ion content is low, the fluorine ion is released relatively late and affects the transmittance, but the content of fluorine ions on the surface is If the EVOH has a constant level, there is no need to wait for the EVOH to melt or disintegrate, and the fluorine ions The fluoride ions are released relatively quickly, reducing deposition. However, if there are too many fluoride ions on the surface, The fluoride ion content at the surface and the total fluoride ion concentration are important factors in determining the gel behavior during film formation. By controlling the content ratio within a specific range, the transmittance effect can be improved. This can be done.

[0030] The fluorine-containing EVOH resin composition may contain, under certain circumstances, a boron compound and / or boric acid. and / or cinnamic acid and / or alkali metal and / or conjugated polyene and / or lubricant and The above-mentioned materials may be used in EVOH resin compositions to provide better EVOH properties. Properties can be imparted.

[0031] Further / or according to another aspect of the present invention, the fluorine-containing EVOH resin composition comprises a fluorine-containing The boron content of the particles may be 50 to 250 ppm. The calculations are based on a fluorine-containing EVOH resin composition. Although it is not specified, the inventors have reported that a boron compound is added to an EVOH resin composition having fluorine-containing particles. By adding this and adjusting the boron content of EVOH to 50 to 250 ppm, The sticking of the EVOH resin composition during the extrusion process is reduced or eliminated, and the film thickness is We believe that this will result in improved uniformity and plasticity. The EVOH resin composition stuck to the inner surface of the screw extruder during the extrusion process. The VOH resin may be removed or at least partially removed to clean the screw extruder.

[0032] A typical fluorine-containing EVOH resin composition is an ethylene vinyl alcohol copolymer. The composition may contain at least one fluorine-containing particle and a boron compound, among which ethylene vinyl The boron content of the alcohol copolymer resin composition is 50 to 250 ppm. In this situation, the boron content of the fluorine-containing EVOH resin composition is Based on the total weight of the composition, about 50 to 250 ppm, about 50 to about 225 ppm, about 50 to about 2 00ppm, about 50 to about 175ppm, about 50 to about 150ppm, about 50 to about 125ppm m, about 50 to about 100ppm, about 75 to 250ppm, about 75 to about 225ppm, about 75 ~approx. 200 ppm, ~approx. 75 to ~approx. 175 ppm, ~approx. 75 to ~approx. 150 ppm, ~approx. 75 to ~approx. 12 5ppm, about 75 to about 100ppm, about 100 to 250ppm, about 100 to about 225ppm m, about 100 to about 200ppm, about 100 to about 175ppm, about 100 to about 150ppm , about 100 to about 125ppm, about 150 to 250ppm, about 150 to about 225ppm, about 150 to about 200 ppm, about 150 to about 175 ppm, about 200 to 250 ppm, or about 2 The boron content of the fluorine-containing EVOH resin composition may be within a certain range. When the viscosity of the fluorine-containing EVOH resin composition is increased, Reduces the chance of product sticking to the screw or removes EVOH from the screw This allows the material to self-clean, further improving film thickness uniformity. In some circumstances, boron content of 50-250 ppm can be In addition, the fluorine-containing EVOH resin composition may further contain cinnamic acid, alkali metal, conjugated polyene , lubricants, alkaline earth metals, salts thereof and / or mixtures thereof. The substance is generally a substance that is commonly present in EVOH resin compositions and has better properties. The content of the compound having a conjugated polyene structure per unit weight of the EVOH resin composition When the content is 1 to 30,000 ppm, heat discoloration is more suppressed and thermal stability is better. The amount of alkali metal per unit weight of the fluorine-containing EVOH resin composition can be The content of compounds containing alkaline earth metals or compounds containing alkaline earth metals is 1 to 1000 ppm in terms of metal. In this case, the long-run moldability can be improved. When the content of the lubricant per unit weight in the composition is 1 to 300 ppm, the processability is improved. It can be excellent.

[0033] In one embodiment of the present invention, the boron content is adjusted to a specific range in the presence of a fluoropolymer. This not only improves the plasticity and processing properties of EVOH, but also Moreover, the appearance of the product can be further improved.

[0034] In some circumstances, the boron compound may include boric acid or a metal salt thereof. Examples of metal salts include: Calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate) etc.), aluminum potassium borate, ammonium borate (ammonium metaborate , ammonium tetraborate, ammonium pentaborate, ammonium octaborate, etc.), boric acid Cadmium (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate ( Potassium octaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, octaboric acid potassium, etc.), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate , copper metaborate, copper tetraborate, etc.), sodium borate (sodium metaborate, diboric acid Sodium borate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate sodium borate, etc.), lead borate (lead metaborate, lead hexaborate, etc.), nickel borate ( nickel tetraborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), Barium borate (barium orthoborate, barium metaborate, barium diborate, barium tetraborate) barium borate, bismuth borate, magnesium borate (magnesium orthoborate) , magnesium diborate, magnesium metaborate, trimagnesium tetraborate, tetraboric acid manganese borate (manganese borate, manganese metaborate, tetramagnesium borate, etc.), manganese borate (manganese borate, manganese metaborate, tetramagnesium borate, manganese ... manganese borate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, lithium phosphate, etc.), salts thereof or combinations thereof. For example, borax, kernite, inyoite, cottite, suanite and borate minerals such as szaibelyite. Borax, boric acid and sodium borate (sodium metaborate, sodium diborate) , sodium tetraborate, sodium pentaborate, sodium hexaborate and sodium octaborate It is preferable to use a

[0035] In another aspect, the present invention provides a mixture having a fluorine-containing EVOH resin composition. It contains a fluorine-containing EVOH resin composition and a first ethylene vinyl alcohol copolymer. When calculated based on a 20g mixture, the total fluoride ion content is 1 00 ppm to 11000 ppm, and the total fluorine ion content is 100 to 110 00ppm, 100~10000ppm, 100~8500ppm, 200~8500p pm, 200~7500ppm, 200~6500ppm, 500~5000ppm, 5 00~4000ppm, 500~3000ppm, 800~3000ppm, 800~2 000ppm, 800~1500ppm, 800, 800~1250ppm, 800~1 000ppm, 1100~2000ppm, 1100~1750ppm, 1100~15 00ppm, 1100~1250ppm, 1400~2000ppm, 1400~175 The range may be 0 ppm, 1400-1500 ppm, or 1700-2000 ppm. The fluorine ion content on the surface of the compound is 2 to 55 ppm, 2 to 50 ppm, 2 to 45 ppm. ppm, 2~40ppm, 2~35ppm, 2~30ppm, 2~25ppm, 2~20 ppm, 2~15ppm, 2~10ppm, 5~55ppm, 5~50ppm, 5~45 ppm, 5~40ppm, 5~35ppm, 5~30ppm, 5~25ppm, 5~20 ppm, 5~15ppm, 5~10ppm, 15~55ppm, 15~50ppm, 15 ~45ppm, 15~40ppm, 15~35ppm, 15~30ppm, 15~25p pm, 15~20ppm, 30~55ppm, 30~50ppm, 30~45ppm, 3 Within the range of 0-40 ppm, 30-35 ppm, 45-55 ppm or 45-50 ppm The ratio of the fluoride ion content at the surface of the mixture to the total fluoride ion content is 0.0 For example, the ratio range is preferably 0.0019 to 0.04. 0.0019~0.035, 0.0019~0.03, 0.0019~0.025, 0. 0.0019~0.02, 0.0019~0.015, 0.0019~0.01, 0.001 9~0.005, 0.0019~0.004, 0.0019~0.003, 0.0025 ~0.04, 0.0025~0.035, 0.0025~0.03, 0.0025~0. 025, 0.0025~0.02, 0.0025~0.015, 0.0025~0.01 , 0.0025~0.005, 0.0025~0.004, 0.005~0.04, 0. 0.005~0.035, 0.005~0.03, 0.005~0.025, 0.005~0 .02, 0.005~0.015, 0.005~0.01, 0.0075~0.04, 0 .0075~0.035, 0.0075~0.03, 0.0075~0.025, 0.0 0.075~0.02, 0.0075~0.015, 0.0075~0.01, 0.01~0 .04, 0.01-0.035, 0.01-0.03, 0.01-0.025, 0.01 ~0.02, 0.0125~0.04, 0.0125~0.035, 0.0125~0. 03, 0.0125~0.025, 0.0125~0.02, 0.015~0.04, 0 0.015~0.035, 0.015~0.03, 0.015~0.025, 0.015~ 0.02, 0.0175~0.04, 0.0175~0.035, 0.0175~0.0 3, 0.0175~0.025, 0.02~0.04, 0.02~0.035, 0.02 ~0.03, 0.02~0.025, 0.0225~0.04, 0.0225~0.03 5, 0.0225~0.03, 0.025~0.04, 0.025~0.035 or 0. 0.03~0.04.

[0036] Ethylene content of fluorine-containing EVOH resin composition and first ethylene vinyl alcohol copolymerization The ethylene content of the cells may be the same or different. The invention provides a mixture having a fluorine-containing EVOH resin composition, which is a fluorine-containing EVOH resin. The resin composition contains 20g of a first ethylene vinyl alcohol copolymer. When calculated as a compound, the total fluoride ion content is 100 ppm to 11,000 ppm. pm. Among them, the ethylene content of the fluorine-containing EVOH resin composition and the first ethylene vinyl acetate The ethylene content of the vinyl alcohol copolymer may be the same. A blend of H resin compositions (also referred to herein as general-purpose resins) is a single ethylene content EVOH, which can be selected according to various gas barrier properties, flexibility, and permeability. In general, it can be used as a food packaging film or the like. For example, the present invention provides a mixture having a fluorine-containing EVOH resin composition, which is The EVOH resin composition and the first ethylene vinyl alcohol copolymer, When calculated based on 0g of the mixture, the total fluoride ion content is 100ppm~11 000 ppm of which the ethylene content of the fluorine-containing EVOH resin composition and the first ethylene content of the fluorine-containing EVOH resin composition are The ethylene content of the ethylene vinyl alcohol copolymer may vary. The fluorine-containing EVOH resin composition mixture (also referred to herein as thermoforming resin) is It is an EVOH with a low content of ethylene, and has a high hydrogen bond ratio, so it has good gas barrier properties. EVOH with a high ethylene content has good elasticity, so two types of EVOH with different ethylene contents were By mixing OH, it is possible to achieve both gas barrier properties and elasticity at the same time, making it suitable for food use. It is often used for molded containers and packaging such as containers for containers and cosmetics. The mixture of fat compositions may or may not contain boron.

[0037] According to one embodiment of the present invention, the present invention provides a blend having a fluorine-containing EVOH resin composition. The present invention provides a polymerizable composition comprising a fluorine-containing EVOH resin composition, a first ethylene vinyl alcohol The first ethylene vinyl alcohol copolymer and the second ethylene vinyl alcohol copolymer. The ethylene content of the ethylene-vinyl alcohol copolymer and the ethylene content of the second ethylene-vinyl alcohol copolymer The amount is different, and the ethylene content of the fluorine-containing EVOH resin composition is the first ethylene vinyl Ethylene content of alcohol copolymer and second ethylene vinyl alcohol copolymer and its Each of these ingredients is the same or different. When calculated based on a 20g blend, The total fluorine ion content is 200 ppm to 2000 ppm. The content is 200-2000 ppm, 200-1750 ppm, 200-1500 ppm , 200~1250ppm, 200~1000ppm, 200~750ppm, 200~ 500ppm, 500~2000ppm, 500~1750ppm, 500~1500p pm, ppm, 500~1000ppm, 500~750ppm, 800~2000pp m, 800~1750ppm, 800~1500ppm, 800~1250ppm, 80 0~1000ppm, 1100~2000ppm, 1100~1750ppm, 1100 ~1500ppm, 1100~1250ppm, 1400~2000ppm, 1400~ 1750 ppm, 1400-1500 ppm, or 1700-2000 ppm. The ratio of the fluorine ion content at the surface of the blend to the total fluorine ion content is 0.0 For example, the ratio ranges from 0.0013 to 0.045, 0.00 13~0.035, 0.0013~0.025, 0.0013~0.015, 0.001 3~0.0095, 0.0013~0.0085, 0.0013~0.0075, 0.0 013~0.0065, 0.0013~0.0055, 0.0013~0.0045, 0 .0013~0.0035, 0.0013~0.0025, 0.002~0.045, 0 0.002~0.035, 0.002~0.025, 0.002~0.015, 0.002 ~0.0095, 0.002~0.0085, 0.002~0.0075, 0.002~ 0.0065, 0.002 to 0.0055, 0.002 to 0.0045, 0.002 to 0 0.0035, 0.004~0.045, 0.004~0.035, 0.004~0.02 5, 0.004~0.015, 0.004~0.0095, 0.004~0.0085, 0.004~0.0075, 0.004~0.0065, 0.004~0.0055, 0 0.006~0.045, 0.006~0.035, 0.006~0.025, 0.006 ~0.015, 0.006~0.0095, 0.006~0.0085, 0.006~0 0.0075, 0.008~0.045, 0.008~0.035, 0.008~0.02 5, 0.008~0.015, 0.008~0.0095, 0.01~0.045, 0. 01~0.035, 0.01~0.025, 0.01~0.015, 0.015~0.0 45, 0.015~0.035, 0.015~0.025, 0.02~0.045 or 0 It is .02 to 0.035.

[0038] According to one preferred embodiment, the present invention provides a blend having a fluorine-containing EVOH resin composition. The present invention provides a polymerizable composition comprising a fluorine-containing EVOH resin composition, a first ethylene vinyl alcohol a first ethylene vinyl alcohol copolymer and a second ethylene vinyl alcohol copolymer; The ethylene content of the ethylene-vinyl alcohol copolymer and the ethylene content of the second ethylene-vinyl alcohol copolymer The amounts vary. Calculating the total fluorine content of a 20g blend, The ion content is 200 ppm to 2000 ppm, and the fluorine-containing EVOH resin composition The blend may contain boron or may be completely boron-free. The blends of OH resin compositions (also referred to herein as specialty resins) are generally in line with thermoforming resin specifications. The properties of the molding material have been more comprehensively balanced, and the subsequent development of automobile tires The present invention can be applied in the form of an inner liner or oil reservoir pipe. The "mixture" and "blend" mentioned above are both the fluorine-containing EVOH resin composition of the present invention and the fluorine-containing EVOH resin composition of the present invention. It refers to a mixture of fluorine-free EVOH (pure EVOH) and general-purpose EVOH. To distinguish between resins, thermoforming resins, and specialty resins, the term "mixture" in this specification refers to the The fluorine-containing EVOH resin composition of the present invention is a fluorine-free EVOH (pure EVOH) H), but the ethylene content of pure EVOH and the content of the present invention The ethylene content of the fluorine EVOH resin composition may be the same or different, and the mixture may contain Other necessary additives may also be added, and are not limited thereto. The term "bond" means that the fluorine-containing EVOH resin composition of the present invention is a fluorine-containing EVOH resin having at least two kinds of ethylene content. and those formed by mixing only with EVOH (pure EVOH) that does not contain fluorine and has different As defined, other necessary additives may be added and are not limited herein. [Example]

[0039] The non-limiting examples of each aspect of the present invention provided below are primarily intended to illustrate each aspect of the present invention and the methods therefor. The purpose is to clarify the effects that can be achieved by [Example]

[0040] Four types of fluoropolymers were prepared according to the present invention (Example fluoropolymers A to D). ) Then, using the fluoropolymers A to D of the examples, the fluorine-containing ethylene vinyl copolymers of the present invention were An alcohol copolymer (hereinafter referred to as "EVOH") resin composition is prepared. Example fluoropolymers A to D are prepared based on the specific methods described above. Fluoropolymers can also be used to add to the EVOH.

[0041] Example Fluoropolymer A An autoclave was used as a batch reactor to prepare Example Fluoropolymer A. The autoclave has an internal volume of approximately 20 L and is equipped with an electromagnetic induction stirrer. The tube was fully filled with nitrogen gas (N2) and then filled with reduced pressure nitrogen gas five times.

[0042] At the same time as reducing the pressure inside the autoclave, 6,960g of deoxygenated pure water and 3,204g of 1,1,2-trichloro-1,2,2-trifluoroethane and 3.5 g of methylcellulose The viscosity of the methyl cellulose was 50 cp, and the suspension stabilizer The mixture was stirred at 450 rpm into the composition in the autoclave. The composition was placed at 52°C.

[0043] 25.3wt% vinylidene fluoride (VDF), 68.6wt% hexafluoropropane A model composed of pyrene (HFP) and 6.1 wt% tetrafluoroethylene (TFE) Nomer was mixed into the batch as a fill gas at 10 kg / cm 2 Then, Approximately 90 wt% of 1,1,2-trichloro-1,2,2-trifluoroethane and 10 wt 45.6 g of a solution containing 100% diisopropyl peroxydicarbonate was added as a catalyst. The polymerization reaction was initiated by adding diisopropyl peroxydicarbonate. The pressure drops during the polymerization reaction, so the pressure is 44.7 A mixed monofilament having 32.5 wt% VDF, 32.5 wt% HFP and 22.8 wt% TFE. Add a grease and apply a pressure of 10 kg / cm 2 After the polymerization reaction was completed, the remaining mixed mono The mercury was removed, and the resulting suspension was dehydrated in a centrifuge, washed with deionized water, and then The mixture was dried in a vacuum at 00°C to obtain 7.5 kg of Example Fluoropolymer A.

[0044] Example Fluoropolymer B A similar autoclave was used to prepare Example Fluoropolymer B, and Example Fluoropolymer B. The autoclave was set up in the same manner as Polymer A. The autoclave was also filled with nitrogen gas under reduced pressure. The filling was repeated five times.

[0045] At the same time as reducing the pressure inside the autoclave, 7,200g of deoxygenated pure water and 3,250g of 1,1,2-trichloro-1,2,2-trifluoroethane and 4 g of methylcellulose The viscosity of methyl cellulose was 50 cp, and it was used as a suspension stabilizer. The mixture was stirred at 500 rpm into the batch in the autoclave. The chips were placed at 52°C.

[0046] Monomer composed of 25wt% VDF, 55wt% HFP and 20wt% TFE - as the filling gas, 20kg / cm 2 After that, about 85 wt% of 1,1, 2-trichloro-1,2,2-trifluoroethane and 15 wt% diisopropyl perfluoroethane 40 g of a solution containing oxydicarbonate was added as a catalyst to initiate the polymerization reaction. Diisopropyl peroxydicarbonate is used as an initiator to start the polymerization reaction. Since the pressure drops during the polymerization reaction, a mixture of 40 wt% VDF and 35 wt% H A mixed monomer containing FP and 25 wt% TFE was added, and the pressure was increased to 20 kg / cm. 2 After the polymerization reaction was completed, the remaining mixed monomers were removed, and the resulting suspension was centrifuged. Dehydrate in a separator, wash with deionized water, and then vacuum dry at 100°C. Fluoropolymer B was obtained.

[0047] Example Fluoropolymer C The same autoclave and induction stirrer as those used in the preparation of Example Fluoropolymer A were used. Example Fluoropolymer C was prepared using the above. The autoclave was fully filled with nitrogen gas. The mixture was mixed with 3 L of a composition containing deoxygenated pure water and 30 g of ethanol as an emulsifier. The composition in the autoclave is heated for 6 hours. It was heated to 0°C and stirred at 380 rpm.

[0048] After that, the internal pressure of the autoclave was 20 kg / cm 2 until it reaches about 70 wt% A mixed gas containing VDF and approximately 30 wt% HFP was filled into the autoclave. , about 80 wt% 1,1,2-trichloro-1,2,2-trifluoroethane and 20 wt Autoclave 40 g of a solution containing t% diisopropyl peroxydicarbonate. Nitrogen gas was added to the mixture. Diisopropyl peroxydicarbonate was used in the polymerization reaction. was used as an initiator to initiate the reaction.

[0049] During the polymerization reaction, a mixed gas of VDF (62 wt%) and HFP (38 wt%) was continuously The internal pressure of the autoclave was increased to 20 kg / cm 2 The polymerization rate was maintained at 100%. The concentration of 1,1 was approximately 80 wt% after 3 hours from the start of the polymerization reaction. ,2-trichloro-1,2,2-trifluoroethane and 20 wt% diisopropyl ether 30 g of a solution containing hydroxydicarbonate was added to the autoclave using nitrogen gas. After the monomer was polymerized for an additional 3 hours, the resulting suspension was dewatered in a centrifuge and After washing with deionized water and drying under vacuum at 100°C, 7.2 kg of the example fluoropolymer was -C was obtained.

[0050] Example Fluoropolymer D An autoclave with a volume of about 3 L was used as a batch reactor, and Example Fluoropolymer D was The autoclave was equipped with an electromagnetic stirrer. 936 g of deionized water, 0 0.36g methylcellulose, 360g VDF, 0.3g t-butylperoxypyridine tert-butyl peroxypivalate, 0.36g of H. pylori sodium acid pyrophosphate, 0.36 g sodium acid pyrophosphate and 1.8 g diethyl carbonate The batch was added to an autoclave and stirred at 10°C for 30 minutes, then heated at 45°C for 14 minutes. Heated for 0 minutes.

[0051] The maximum pressure inside the autoclave was 6 MPa. When the temperature dropped to 100 Pa, the polymerization reaction of the monomer was completed. After the polymerization reaction was completed, the polymer slurry was taken out and dehydrated. After washing with ethanol and dehydrating, it was dried at 80°C for 24 hours to reach an inherent viscosity of 2.0. Polyvinylidene fluoride (Example: Fluoropolyvinylidene fluoride) with a bulk density of 0.5 dl / g and a bulk density of 0.225 g / ml The compound (D) was obtained in a yield of 55%. [Example]

[0052] Hereinafter, the fluorine-containing EVOH pellets formed from the fluorine-containing EVOH resin composition will be described. Non-limiting preparation methods are provided. Fluorine particles can be prepared by a method similar to that disclosed below. Sixteen non-limiting example EVOH resin compositions (Examples EVOH 1 to 16) were prepared. Four types of EVOH resin compositions for Examples and Comparative Examples (Comparative EVOH 1 to 4) were prepared. The specific method for preparing EVOH 1 to 16 and Comparative Example EVOH 1 to 4 is usually one or more This method differs from the method disclosed below in this respect.

[0053] Ethylene vinyl acetate copolymer (ethylene-) with an ethylene content of 29 mole percent vinyl acetate copolymer (hereinafter referred to as "EVAC") The EVOH polymer was then saponified to a degree of 99.5%. The EVO solution was dissolved in a solution containing ethanol and water (ratio 70:30). The solid content of H was 41 wt %, and the solution was placed at 60°C.

[0054] Underwater pelletization The above-mentioned solution of methanol, water and EVOH was granulated. The above-mentioned solution of methanol, water and EVOH was sent to the supply pipe at a flow rate of 120 L / min, and then The mixture was then fed into a suction pipe with a diameter of 2.8 mm and cut at 1500 rpm using a rotating knife. Water at 0.5°C was added to cool the EVOH pellets. Then, the EVOH pellets were centrifuged. The EVOH particles were separated by washing with water and then placed in a boric acid solution. The boric acid solution concentration was determined based on the final fluorine-containing EVOH resin composition. The boron content was adjusted and then dried to obtain EVOH pellets (boron-added In some cases, the drying process is carried out as is.

[0055] EVOH pellets and fluoropolymers such as those in Example 1 were mixed in a certain ratio, and then the mixture was subjected to a biaxial spindle. As shown in Table 1, the extruder was fed into 13 sections (sections 1 to 4) of the twin-screw extruder. After mixing, strand cut at 25°C. cutting) and then cutting particles having fluorine elements (also referred to as "fluorine particles" in this specification). In Table 1, "EV27" means an EVOH containing 27% ethylene. "EV29" refers to EVOH with an ethylene content of 29 mole%. "EV32" refers to EVOH with an ethylene content of 32 mole%. "EV38" refers to EVOH with an ethylene content of 38 mole%, and is the same as "EV44". refers to EVOH with an ethylene content of 44 mole%.

[0056] [Table 1] [Example]

[0057] Based on the following method, films were formed using Example EVOH pellets 1 to 16. The EVOH pellets 1 to 16 of the examples and the EVOH pellets 1 to 4 of the comparative examples were mixed in a single layer T-da The mixture was fed to a cast film extruder (optical control system MEV4) to prepare a film. Each of the pellets formed from Example EVOH pellets 1 to 16 and Comparative Example EVOH pellets 1 to 4 The thickness of each film was 20 μm. The temperature of the extruder was set at 220° C., and the die (i.e. The temperature of the T-die was set to 230°C. The screw rotation speed was 7 rpm (rotation ns / minutes). [Example]

[0058] Example EVOH pellets 1 to 16 and Comparative Example EVOH pellets 1 to 4 were evaluated. The properties of these EVOH pellets and the films formed therefrom were evaluated. EVOH pellets 1 to 16 were prepared according to a method similar to that described in Example 2. However, the preparation method of EVOH pellets 1 to 16 was different depending on the EVOH pellets to be prepared. Regarding different ethylene contents, different fluoropolymers, different total fluorine ion contents, Surface fluoride ion content, and surface fluoride ion content and total fluoride ion content The EVOH pellets 1 to 4 of the comparative example are different in that they have a ratio of the ethylene content. It was prepared according to a method similar to that described in Example 2.

[0059] According to the same method as described in Example 3, Examples EVOH 1 to 16 and Comparative Example EVO Films were formed using each of H1 to H4. The films were evaluated to determine their appearance, density, and other properties. The state of deposition on the film and the transmittance of the film were determined.

[0060] Table 2 below shows the results of Example EVOH pellets 1 to 16 and Comparative Example EVOH pellets 1 to 4. Several attributes, namely the ethylene content of the EVAC and the specific fluorine content in the fluorine-containing particles Table 3 below summarizes the polymer and fluoropolymer content of the example EVOH. The total fluorine content of the EVOH pellets in pellets 1 to 16 and comparative EVOH pellets 1 to 4 was fluoride ion content, surface fluoride ion content and surface fluoride ion content and the ratio of the total fluorine ion content, and the ratio of Example EVOH pellets 1 to 16 to Comparative Example EVOH pellets 1 is a summary of the properties of films formed with H pellets 1 to 4.

[0061] [Table 2]

[0062] [Table 3]

[0063] Total fluorine ions of EVOH pellets 1 to 16 of Examples and EVOH pellets 1 to 4 of Comparative Examples To evaluate the content, an ion chromatograph (Metrohm 930 Compaq Analysis is performed using IC Flex / Ses / PP / Deg), and the testing method is NIE A W415.54B method for detecting negative ions in water was used. After burning 20g of the sample, it was extracted with water and then chemically analyzed. The samples were collected and analyzed 10 times, and the average value of the 10 tests was calculated.

[0064] The surface of the EVOH pellets 1 to 16 of the examples and the EVOH pellets 1 to 4 of the comparative examples To evaluate the fluorine ion content, an ion chromatograph (Metrohm 930 C Analysis was performed using compact IC (Flex / Ses / PP / Deg), and the test method was N The IEA W415.54B method for detecting anions in water was used. The sample pellet was placed in 5 cc of methanol, transferred to a 60°C environment, and stirred for 4 hours. After that, filter it, remove the pellets, take 0.5cc of the liquid, and refrigerate it with an oxygen tank. After burning the liquid, it was extracted with water and then subjected to chemical analysis. The samples were analyzed 10 times, and the average value of the 10 tests was calculated.

[0065] The boron content of each EVOH resin composition (0.1 g each) was measured in a microwave oven. The sample solution for the examples and comparative examples was prepared by decomposing the sample with concentrated nitric acid. The concentration was adjusted to 0.75 mg / ml. Thermo iCAP 7000 analyzer and an inductively coupled plasma optical emission spectrometer lasma optical emission spectrometer,ICP- The boron content in the prepared solution was measured using an OES. This corresponds to the amount of boron derived from the boron compound used.

[0066] The melting points of the examples and comparative examples were determined according to the method of ISO 11357-3 (2011). TA-Q200 Differential Scanning Calorimeter The measurements were performed using a differential scanning calorimeter (DSC, manufactured by TA Instruments). The first and second melting point temperatures obtained in the first thermal scan of the calorimeter were used.

[0067] The appearance of the films formed from Examples EVOH 1 to 16 and Comparative Examples EVOH 1 to 4 Regarding this, 1m 2 The number of fish eyes larger than 200 μm in size is less than 5 If it is less than 1m, it is represented by "O" and 2 Within the range, the size of the filter is larger than 200 μm. If the number of Shuai is 5 to 10, it is expressed as "Δ" and 1m 2 Within 200 μm If the number of fisheyes larger than 10 is greater than 10, it is represented by an "X". The test for the number of wires is performed using a charge coupled device (CCD). FSA-1, designed with a CCD sensor and FSA-100 V.8 software 00 was used.

[0068] Evaluation of processing performance Extruder system ME-25 / 5800V4 purchased from OCS, film thickness measuring instrument Visual inspection was performed using the FTM-200. If there was no adhesion on the die or screw, the mark was "O". If there was adhesion on the die or screw, it was indicated by "X".

[0069] The transmittance can be evaluated by the method of ASTM D1003, and the thickness of the film is 25 μm. Films were taken for measurements and analyzed using an OCS-EVOHM Gamma 12 instrument. Based on the above-mentioned transmittance measurement method, if the transmittance of the EVOH film is 90% or more, If it is less than 90% and more than 85%, it is expressed as "Δ", and if it is less than 85%, it is expressed as "X". " is expressed as

[0070] The films of Examples EVOH 1 to 16 did not adhere to the die, and 2 Within The number of fish eyes larger than 200 μm was 5 or less, and Examples EVOH1 to 16 were formed. All of the films exhibited excellent appearance and processing performance, but the comparative examples EVOH1 to EVOH4 Surprisingly, the films formed by the fluorine-containing When the total fluorine ion content of the EVOH resin composition is within the range of 45 to 41,000 ppm, In this case, fish eyes that occur during EVOH film formation are reduced, and the mechanical properties and film appearance are improved. As shown in Table 2, Comparative Examples 1 and 2 were found to be able to improve the properties of the composition described in this specification. The total fluoride ion content is higher than the desired range, and the number of fish eyes is excessive. In addition, in the present invention, the total amount of the fluorine-containing EVOH resin composition containing the fluorine-containing particles is If the fluoride ion content is within the desired range (between 45 and 41,000 ppm), The fluoropolymer in the formula reduces adhesion to the die and screw during the processing, For example, the total fluorine ion content of Comparative Examples EVOH 3 and 4 is Although the amount is lower than the desired range described herein, the result is adhesion to the die and screw. This shows that...

[0071] For the fluorine-containing EVOH resin composition that satisfies the above total fluorine ion content, Further investigation of the ratio of the fluoride ion content in the permeable membrane to the total fluoride ion content will The fluorine content in the surface of the present invention is Type of fluoropolymer, amount of fluoropolymer added, ethylene content, boron content, etc. The results were obtained by combining and testing the effects of the fluoride ion content and total fluoride on the surface. Controlling the ratio of the ion content within a certain range can improve the transmittance effect. This can be done. [Example]

[0072] The mixture containing the fluorine-containing EVOH resin composition was prepared in a manner similar to that described in Example 2. Based on this method, Example EVOH 17 to 38 and Comparative Example EVOH 5 to 16 were prepared. However, the main differences are as follows: First, a fluorine-containing EVOH resin composition is prepared, and then it is dried. In the step, a first ethylene vinyl alcohol copolymer (1 st EVOH) The mixture was mixed and mixed using a conical screw mixer (Kyoiki Kikai Kogyo Co., Ltd., model number: CM-2). The amount of material added was 500 kg, and the operation time was 20 minutes, and the mixture was thoroughly mixed until it was homogeneous. The ethylene content of the ethylene vinyl alcohol copolymer in the EVOH resin composition and the primary ethylene content of the ethylene vinyl alcohol copolymer in the EVOH resin composition The ethylene content of the ethylene vinyl alcohol copolymer is the same, and the first ethylene vinyl alcohol The alcohol copolymer is prepared by kneading a fluoropolymer into a fluorine-containing EVOH resin composition. The EVOH manufacturing process before the addition is as shown in Table 4. The ethylene content is set as shown in Table 4. The boron content was adjusted according to the ethylene content of the first ethylene vinyl alcohol copolymer. , and calculated for the first ethylene vinyl alcohol copolymer, but the ethylene content is 2 When the ethylene content is 32mole, the boron content is 120ppm. When the ethylene content is 38 mol %, the boron content is 100 ppm. e%, the boron content is 90 ppm and the ethylene content is 44 mole%. In some cases, the boron content is 70 ppm. Both the fluorine EVOH resin composition and the first ethylene vinyl alcohol copolymer contain boron. Since this is an example that does not include boric acid, the step of immersing in a boric acid solution is not performed.

[0073] First, a fluorine-containing EVOH resin composition was prepared. ethylene-vinyl acetate copolymer lymer (hereinafter referred to as "EVAC") was saponified to obtain EVOH at a saponification degree of 99.5%. The polymer was then prepared by dissolving EVOH in a mixture of methanol and water (ratio 70:30). After that, the solid content of EVOH in the solution became 41 wt%. The liquid was placed at 60°C.

[0074] The above-mentioned solution of methanol, water and EVOH was granulated by underwater pelletization. Specifically, the above-mentioned solution of methanol, water, and EVOH was pumped at a flow rate of 120 L / min into the supply pipe, then into the suction pipe with a diameter of 2.8 mm, and The cut was performed at 500 rpm. Water at 5°C was added to cool the EVOH pellets. The EVOH pellets were centrifuged to separate the EVOH particles. The EVOH particles were immersed in a boric acid solution and stirred. The boric acid solution concentration was the same as that of the EVOH particles mentioned above. The ethylene content was adjusted according to various ethylene contents and the final fluorine-containing EVOH resin composition was The boron content was adjusted according to the boron content to be added, and then dried to obtain EVOH pellets (boron-containing In examples where no additives are added, the drying process is carried out as is.

[0075] EVOH pellets and fluoropolymers such as those in Example 1 were mixed in a certain ratio, and then the mixture was subjected to a biaxial spindle. The mixture was fed into a twin screw (or single screw, melt-stirring) extruder. The 13 zones (zones 1 to 13) of the extruder have different temperatures. After mixing, Fluorine particle-containing EVOH was prepared by strand cutting or underwater granulation.

[0076] Next, a drying step is carried out, and after the drying step, the first ethylene vinyl alcohol copolymer (1 st EVOH) was mixed and added. A mixture was prepared.

[0077] Finally, based on the method described in Example 3, Examples EVOH17 to EVOH38 and Comparative Example EVO Films were prepared using H5 to H16, respectively.

[0078] Table 4 below shows the ethylene content of the mixture of fluorine-containing EVOH resin compositions and the first ethylene vinyl acetate copolymer. The ethylene content of the ethylene alcohol copolymer is the same (i.e., Examples EVOH 17 to 38 and Some attributes of the comparative EVOHs (5-16), namely, ethylene content, fluorine-containing EVOH Specific fluoropolymers and fluoropolymer content contained in the fluoropolymers, fluorinated EVOH The total fluorine ion content of the mixture containing the resin composition, the fluorine ion content on the surface, and and the ratio of surface fluoride ion content to total fluoride ion content. In addition, Examples EVOH17 to EVOH38 and Comparative Example EVOH were prepared according to the method described in Example 3. Evaluate H5~16 films and analyze film appearance (number of fish eyes), die or This is an overview of the evaluation of several properties such as adhesion to the screw and transmittance. These were measured according to the methods described in Examples 2 to 4.

[0079] [Table 4] JPEG2026012247000006.jpg245163JPEG2026012247000007.jpg247163JPEG20260122470 00008.jpg244162JPEG2026012247000009.jpg240161JPEG2026012247000010.jpg186161

[0080] Surprisingly, the total fluorine ion content of the mixture of the fluorine-containing EVOH resin composition of the present invention When the concentration is between 100 ppm and 11,000 ppm, the film does not adhere to the die. , and 1m 2 It was found that there were five or fewer fisheyes larger than 200 μm. As shown above, none of Examples EVOH 17 to 38 had any adhesion on the die. 1m 2 There were five or fewer fish eyes larger than 200 μm in size.

[0081] In addition, the fluorine ion-containing EVOH resin composition of the present invention is preferably present on the surface of the mixture. When the ratio of the amount of fluoride ions to the total fluoride ion content is 0.0019 to 0.04, the film The transmittance was 90% or more in all cases. As shown above, the blending of the fluorine-containing EVOH resin composition The ratio of the fluorine ion content on the surface of the compound to the total fluorine ion content is 0.0019 When the value was 0.04, the transmittance was 90% or more.

[0082] In Comparative Examples EVOH 5 to 16, in which the total fluorine ion content was above the desired range, Adhesion occurs to 1m 2 There were five or more fish eyes larger than 200 μm in size. The ratio of the surface fluorine ion content to the total fluorine ion content exceeded the desired range. In the case of a mixture of EVOH and fluorine-containing EVOH resin composition, the film transmittance is 90%. As described above, the total fluorine ion content of the fluorine-containing particles was within a specific range. Under the condition of having a large amount of EVOH, the flow behavior of EVOH in the screw extruder becomes smoother. Smooth and provides fluoropolymer protection to the inner wall of the screw extruder , reducing deposits on the die and improving film appearance.

[0083] Regarding the total fluorine ion content present in the mixture of fluorine-containing EVOH resin compositions, Above the desired range, the EVOH resin composition blend may have an undesirable film appearance. However, this may result in poor processability.

[0084] The mixture of fluorine-containing EVOH resin compositions obtained in this example (i.e., general-purpose resin) is a single EVOH with ethylene content of 100%, according to various gas barrier properties, flexibility and permeability It can be selected and used as a food packaging film, etc. [Example]

[0085] The mixture containing the fluorine-containing EVOH resin composition of this example was similar to that described in Example 5. Based on a similar method, Examples EVOH 39 to 43 and Comparative Example EVOH 17 were prepared. However, the main differences are as follows: First, a fluorine-containing EVOH resin composition is prepared, and then it is dried. In the step, a first ethylene vinyl alcohol copolymer (1 st EVOH) The mixture was mixed and mixed using a conical screw mixer (Kyoiki Kikai Kogyo Co., Ltd., model number: CM-2). The amount of material added was 500 kg, and the operation time was 20 minutes, and the mixture was thoroughly mixed until it was homogeneous. The ethylene content of the ethylene vinyl alcohol copolymer in the EVOH resin composition and the primary ethylene content of the ethylene vinyl alcohol copolymer in the EVOH resin composition The ethylene content of ethylene vinyl alcohol copolymer is different, the first ethylene vinyl The alcohol copolymer is prepared by mixing a fluorine-containing EVOH resin composition with a fluoropolymer. The ethylene content is set according to the values ​​in Table 5. The boron content was adjusted according to the ethylene content as described above. Regarding the fluorine-containing EVOH resin composition and the first ethylene vinyl alcohol copolymer, Since none of these examples contain boron, the step of immersion in a boric acid solution is not performed.

[0086] Based on the method described in Example 3, Examples EVOH39 to 43 and Comparative Example EVOH17 and Films were prepared using each method.

[0087] Table 5 below shows the ethylene content of the mixture of fluorine-containing EVOH resin compositions and the first ethylene vinyl acetate copolymer. The ethylene content of the ethylene alcohol copolymer is different (i.e., Examples EVOH 39 to 43 and Comparative Example EVOH 17), namely, ethylene content, fluorine-containing EVOH pellets. Specific fluoropolymers and fluoropolymer content contained in the product, fluorine-containing EVOH resin The total fluoride ion content of the mixture containing the oil composition, the fluoride ion content on the surface, and The ratio of surface fluoride ion content to total fluoride ion content is also summarized. Example EVOHs 39 to 43 and Comparative Example EVOHs prepared according to the method described in Example 3 Seventeen films were evaluated to determine the appearance of the film (number of fisheyes), the die or screen. This is an overview of the determination of several properties, such as adhesion to the Ryu and transmittance. Measurement was carried out according to the method described in Examples 2 to 4.

[0088] [Table 5] JPEG2026012247000012.jpg238161JPEG2026012247000013.jpg54161

[0089] Surprisingly, the total fluorine ion content of the mixture of the fluorine-containing EVOH resin composition of the present invention When the concentration is between 100 ppm and 11,000 ppm, the film does not adhere to the die. , and 1m 2 It was found that there were five or fewer fisheyes larger than 200 μm in the sample. As shown above, all of Examples EVOH 39 to 43 did not adhere to the die. Not yet, 1m 2 There were five or fewer fish eyes larger than 200 μm in size. .

[0090] In addition, the fluorine ion-containing EVOH resin composition of the present invention is preferably present on the surface of the mixture. When the ratio of the amount of fluoride ions to the total fluoride ion content is 0.0019 to 0.04, the film The transmittance was 90% or more in all cases. The transmittance of each film was over 90%.

[0091] Total fluoride ion content, surface fluoride ion content and total fluoride ion content In the comparative example EVOH17, the ratio of which is above the desired range, the transmittance is 85% to 90%. There was only a short time.

[0092] The fluorine-containing EVOH resin composition mixture (i.e., thermoforming resin) obtained in this example was It is an EVOH with a low content of ethylene and has a high ratio of hydrogen bonds, making it excellent in gas barrier properties and ethylene. EVOH with a high ethylene content has good elasticity, so two types with different ethylene contents are By mixing EVOH, it is possible to achieve both gas barrier properties and elasticity at the same time. Therefore, it will be used in the form of molded containers and packaging such as food containers and cosmetic containers. It is possible. [Example]

[0093] The blend containing the fluorine-containing EVOH resin composition was prepared in a manner similar to that described in Example 5. Based on this, Examples EVOH 44 to 49 and Comparative Examples EVOH 18 to 26 were prepared. The main differences are as follows: First, a fluorine-containing EVOH resin composition is prepared, and then a drying process is carried out. In the process, a first ethylene vinyl alcohol copolymer and a second ethylene vinyl alcohol copolymer are further Coal copolymer (1 st EVOH+ 2 nd EVOH) is mixed and added, and a cone-shaped screen is A feed mixer (manufactured by Kyoki Machinery Industry Co., Ltd., model number: CM-2) was used, and the input volume was 500 kg. The mixture was thoroughly mixed for 20 minutes until it was homogeneous. The ethylene content of the copolymer and the ethylene content of the second ethylene vinyl alcohol copolymer are The first method for preparing ethylene vinyl alcohol copolymer is different from the first method for preparing fluorine-containing EVOH. This is the same as the EVOH manufacturing process before the fluoropolymer is mixed into the resin composition. The content is set according to the values ​​in Table 6, and the boron content is adjusted according to the ethylene content as described above. The second ethylene vinyl alcohol copolymer was prepared by the method of preparing a fluorine-containing EVOH resin composition. This is the EVOH manufacturing process before the fluoropolymer is mixed into the product, and the ethylene content was set according to the values ​​in Table 6, and the boron content was adjusted according to the ethylene content as described above. .

[0094] Based on the method described in Example 3, Examples EVOH44 to 49 and Comparative Examples EVOH18 to 26 films were prepared using each of the methods.

[0095] The following Table 6 shows the blends of fluorine-containing EVOH resin compositions (i.e., Examples EVOH 44 to 49). and comparative examples EVOH 18-26), namely, ethylene content, fluorine-containing EVOH Specific fluoropolymers and fluoropolymer content contained in H pellets, fluorine-containing EV The total fluorine ion content of the blend containing the OH resin composition, the fluorine ion content on the surface The outline of the amount of fluoride ions and the ratio of the surface fluoride ion content to the total fluoride ion content Examples EVOH 44 to 49 and Comparative Example EVOH 45 prepared according to the method described in Example 3 are also included. Evaluate EVOH 18~26 film and analyze film appearance (number of fisheyes) This is a summary of the evaluation of several properties, such as adhesion to the die or screw, and transmittance. However, they were measured according to the methods described in Examples 2 to 4.

[0096] [Table 6] JPEG2026012247000015.jpg245165JPEG2026012247000016.jpg244166JPEG2026012247000017.jpg244166JPEG2026012247000018.jpg153166

[0097] The inventors have found that the total fluorine ion content of the blend of the fluorine-containing EVOH resin composition of the present invention is When the concentration is 200 ppm to 2000 ppm, the film does not stick on the die, and 1m 2 We found that there were no more than five fisheyes larger than 200 μm in size. As shown above, none of Examples EVOH 44 to 49 had any adhesion on the die. 1m 2 There were five or fewer fish eyes larger than 200 μm in size.

[0098] In addition, the fluorine ion content on the surface of the blend of the fluorine-containing EVOH resin composition of the present invention is If the ratio of the fluoride ion content to the total fluoride ion content is 0.0013 to 0.045, the filter As shown above, the transmittance of each of the films was 90% or more. The transmittance of each film was 90% or more.

[0099] In Comparative Examples EVOH 18 to 26, in which the total fluorine ion content was above the desired range, Adhesion occurs on top, 1m 2 There are five or more fish eyes larger than 200 μm in size. The ratio of the surface fluorine ion content to the total fluorine ion content was above the desired range. In the comparative examples EVOH18 to 26, the transmittance of the film was 90% or less.

[0100] The blend of fluorine-containing EVOH resin compositions obtained in this example (i.e., special resin) was thermally cured. The concept of molding resin standards has been inherited, and the properties of molding materials have been more comprehensively averaged. It can be applied in such aspects as inner liners of automobile tires or oil reservoir pipes.

[0101] In summary, the EVOH resin composition or a mixture or blend containing the same is a fluorine-containing particle. and a specific range of total fluorine ion content, The flow behavior of EVOH in the machine is smoother, and the inner wall of the screw extruder is It provides protection for the polymer, reducing deposition on the die and improving the appearance of the film. If the total fluorine ion content exceeds the desired range, the EVOH resin composition This can result in undesirable film appearance and poor processability.

[0102] All ranges provided herein are inclusive of each specific range and percentage within the assigned range. This means that combinations of subranges between assigned ranges are included. Unless otherwise stated, all ranges provided herein are inclusive of the endpoints of the range. The range 1 to 5 specifically includes 1, 2, 3, 4, and 5, as well as 2 to 5, 3 to 5, 2 to 3, Includes secondary ranges such as 2-4 and 1-4.

[0103] All publications and patent applications referenced herein are hereby incorporated by reference. and for any and all purposes, each and every publication or patent application is hereby incorporated by reference. All such disclosures are expressly and individually indicated to be incorporated herein by reference. In the event of a conflict between any publication or patent application incorporated herein, , as per the present specification.

[0104] As used herein, the terms "including," "having," and "including" are used in an open, The terms "a," "an," and "the" are understood to include the plural and the singular. The term "one or more" refers to "at least one" and therefore not a single It may include a property or a mixture / combination of properties.

[0105] Except in the operating examples or where otherwise indicated, all references to quantities of ingredients and / or reaction conditions All figures can be modified in all instances by the term "about"; This means that the value is within ±5% of the indicated value. The terms "free" or "substantially free" mean less than about 2% of a particular characteristic. Any element or feature explicitly described in this specification may be omitted from the claims. can be quantitatively excluded. [Explanation of symbols]

[0106] 100 EVOH pellets 110 Fluorine-containing fine particles 120 coating layers

Claims

1. A fluorine-containing ethylene-vinyl alcohol copolymer resin composition, comprising an ethylene-vinyl alcohol copolymer and at least one fluorine-containing particle; the fluorine-containing particles contain a fluorinated polymer; wherein the total fluorine ion content in the fluorine-containing ethylene-vinyl alcohol copolymer resin composition is more than 45 ppm and less than 41,000 ppm; The total fluorine ion content is measured in accordance with NIEA W415.54B method for detecting anions in water, by combusting 20 g of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition in an oxygen cylinder as a pretreatment, extracting the composition with water, and then analyzing the extracted product by ion chromatography (Metrohm 930 Compact IC Flex / Ses / PP / Deg), A fluorine-containing ethylene-vinyl alcohol copolymer resin composition further comprising at least two melting point temperatures, the first melting point temperature being between 100°C and 140°C and the second melting point temperature being between 150°C and 195°C, and further having a boron content of 50 to 250 ppm.

2. the fluorine ion content on the surface of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition is between 1 and 126 ppm; 2. The fluorine-containing ethylene-vinyl alcohol copolymer resin composition according to claim 1, wherein the surface fluorine ion content is measured according to NIEA W415.54B method for detection of anions in water by adding 0.5 g of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition to 5 cc of methanol, stirring at 60°C for 4 hours, filtering to obtain a liquid from which the fluorine-containing ethylene-vinyl alcohol copolymer resin composition has been removed, combusting 0.5 cc of the liquid in an oxygen cylinder, extracting with water, and analyzing by ion chromatography (Metrohm 930 Compact IC Flex / Ses / PP / Deg).

3. 3. The fluorine-containing ethylene-vinyl alcohol copolymer resin composition according to claim 1, wherein a ratio of the fluorine ion content at the surface of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition to the total fluorine ion content is 0.0015 to 0.

03.

4. 4. The fluorine-containing ethylene-vinyl alcohol copolymer resin composition according to claim 1, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 24 to 48 mole %.

5. 5. The fluorine-containing ethylene-vinyl alcohol copolymer resin composition according to claim 1, wherein the ethylene-vinyl alcohol copolymer has a degree of saponification of more than 99.5 mole %.

6. A fluorine-containing ethylene-vinyl alcohol copolymer resin composition, comprising an ethylene-vinyl alcohol copolymer and at least one fluorine-containing particle; the fluorine-containing particles contain a fluorinated polymer; wherein the ratio of the fluorine ion content on the surface of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition to the total fluorine ion content is 0.0015 to 0.03; The total fluorine ion content is measured in accordance with NIEA W415.54B method for detecting anions in water, by combusting 20 g of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition in an oxygen cylinder as a pretreatment, extracting the composition with water, and then analyzing the extracted product by ion chromatography (Metrohm 930 Compact IC Flex / Ses / PP / Deg), The fluorine ion content on the surface is measured according to NIEA W415.54B method for detecting anions in water by adding 0.5 g of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition to 5 cc of methanol, stirring at 60°C for 4 hours, and then filtering to obtain a liquid from which the fluorine-containing ethylene-vinyl alcohol copolymer resin composition has been removed. 0.5 cc of the liquid is combusted in an oxygen cylinder, extracted with water, and then analyzed by ion chromatography (Metrohm 930 Compact IC Flex / Ses / PP / Deg). A fluorine-containing ethylene-vinyl alcohol copolymer resin composition further comprising at least two melting point temperatures, the first melting point temperature being between 100°C and 140°C and the second melting point temperature being between 150°C and 195°C, and further having a boron content of 50 to 250 ppm.

7. A mixture containing a fluorine-containing ethylene-vinyl alcohol copolymer resin composition, The fluorine-containing ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 6, a first ethylene vinyl alcohol copolymer; The mixture has a total fluoride ion content of 100 ppm to 11,000 ppm when calculated based on 20 g of the mixture.

8. 8. The mixture of claim 7, wherein the fluoride ion content at the surface of the mixture is between 2 and 55 ppm.

9. 9. The mixture according to claim 8, wherein the ratio of the fluorine ion content at the surface of the mixture to the total fluorine ion content is 0.0019 to 0.

04.

10. 10. The mixture according to claim 7, wherein the ethylene content of the fluorine-containing ethylene-vinyl alcohol copolymer resin composition is the same as or different from the ethylene content of the first ethylene-vinyl alcohol copolymer.

11. A blend having a fluorine-containing ethylene-vinyl alcohol copolymer resin composition, The fluorine-containing ethylene-vinyl alcohol copolymer resin composition according to any one of claims 1 to 6, a first ethylene vinyl alcohol copolymer; a second ethylene vinyl alcohol copolymer; the ethylene content of the first ethylene-vinyl alcohol copolymer is different from the ethylene content of the second ethylene-vinyl alcohol copolymer; When calculated based on 20 g of the blend, the total fluorine ion content contained therein is 200 ppm to 2000 ppm.

12. 12. The blend of claim 11, wherein the ratio of the surface fluoride ion content of the blend to the total fluoride ion content is from 0.0013 to 0.045.

Images