Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a vinyl alcohol copolymer, a resin composition containing the same, and a resin molding.
• a vinyl alcohol polymer (hereinafter sometimes abbreviated as "PVA") is one of the few hydrophilic polymers with crystallinity. Utilizing its excellent water solubility and film properties (strength, oil resistance, film-forming properties, oxygen gas barrier properties, etc.), PVA is used as an emulsifier, suspending agent, surfactant, fiber processing agent, various binders, and paper processing. It is widely used in agents, adhesives, films, etc.
• PVA has poor moldability due to its high crystallinity.
• PVA with reduced crystallinity is known to improve moldability, and for example, PVA with reduced crystallinity by lowering the degree of saponification is manufactured and sold.
• PVA with a reduced degree of saponification is degraded in its original features such as oxygen gas barrier properties, mechanical properties, and thermal stability. For the reasons described above, it is difficult to achieve both moldability and performance at the same time.
• Patent Document 1 describes a PVA containing 2 to 19 mol% of ethylene, and the PVA has excellent thermal stability, water resistance, gas barrier properties, water vapor barrier properties, and low-temperature storage stability of an aqueous solution. It is stated that there are
• Patent Document 2 describes a PVA containing an olefin having 3 or 4 carbon atoms
• Patent Document 3 describes a PVA containing an olefin having 4 or less carbon atoms, and these PVA can be melt-molded. is described.
• the PVA described in Patent Document 1 has low secondary workability.
• the secondary processability of the PVA described in Patent Documents 2 and 3 is not sufficient, and there is no disclosure of the relationship between the secondary processability and the production method. Specifically, even if these PVA's are formed into films by melt molding, their secondary workability, for example, their heat-sealing properties, are not sufficient, and their actual use may be difficult.
• An object of the present invention is to solve the above problems, and a vinyl alcohol copolymer having excellent secondary workability while maintaining the mechanical properties of PVA, and a resin composition containing the same, and an object of the present invention is to provide a resin molding.
• the present invention includes the following inventions.
• U1 is the molecular weight MU1 calculated from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer
• the molecular weight MU1 defined by the following formula. is the value of the peak intensity of the chromatogram obtained from the ultraviolet absorption detector at .
• Log 10 MU1 Log 10 (Mn) + 0.5 R1 is defined by the following formula, where Mn is calculated from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer. 4 is the peak intensity value of the chromatogram obtained from the refractive index detector at molecular weight MR1.
• Log 10 MU2 Log 10 (Mn) - 0.5 R2 is defined by the following formula, where Mn is calculated from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer. 2 is the peak intensity value of the chromatogram obtained from the refractive index detector at molecular weight MR2.
• Log 10 MR2 Log 10 (Mn) - 0.5 Mn is the number average molecular weight of the copolymer obtained by acetylating the vinyl alcohol copolymer calculated from the chromatogram obtained from the refractive index detector.
• the olefin constituent unit is a propylene unit, 1-butene unit, cis-2-butene unit, trans-2-butene unit, 2-methylpropylene unit, 1-pentene unit, cis-2-pentene unit, trans -2-pentene unit, 2-methyl-1-butene unit, 2-methyl-2-butene unit, 3-methyl-1-butene unit, 1-hexene unit, 1-heptene unit, 1-octene unit, 1-
• the vinyl alcohol copolymer according to [2] which is at least one structural unit selected from the group consisting of nonene units, 2-methyl-1-octene units, and 7-methyl-1-octene units.
• the olefin structural unit is at least one structural unit selected from the group consisting of propylene units, 1-butene units, cis-2-butene units, trans-2-butene units, and 2-methylpropylene units.
• the resin composition according to [13] which contains at least one polymer selected from the group consisting of polyvinyl butyral, starch, starch derivatives, cellulose, and cellulose derivatives having a degree of saponification of %.
• the resin molding according to [15] which is a film.
• a method for producing a vinyl alcohol copolymer that satisfies at least one of the following: polymerizing an olefin and vinyl acetate under conditions where the pressure of the olefin varies to obtain a crude copolymer; A production method comprising a step of saponifying the crude copolymer.
• the resin molded article of the present invention it is possible to obtain a resin molded article having both good mechanical properties and excellent secondary workability. Due to these properties, the resin molded article of the present invention can be used in various applications such as films, fibers, and water-soluble substrates.
• the vinyl alcohol copolymer of the present invention contains vinyl alcohol constitutional units and olefin constitutional units.
• a vinyl alcohol structural unit is one type of repeating unit, and can be obtained, for example, by polymerizing and saponifying a vinyl ester.
• Vinyl esters are not particularly limited, but examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl stearate, vinyl benzoate, vinyl trifluoroacetate, vinyl formate, vinyl isobutyrate, and vinyl isovalerate.
• Vinyl acetate is preferred because of its versatility and availability.
• the content of the vinyl alcohol structural unit in the vinyl alcohol copolymer of the present invention is preferably 40 mol % to 99.9 mol %, more preferably 75 mol % to 99 mol %, still more preferably 80 mol % to 95 mol %. If the content of the vinyl alcohol structural unit is less than 40 mol%, the strength may decrease. may decrease.
• the olefin structural unit is a unit that can be formed by polymerization of any olefin such as ⁇ -olefin and ⁇ -olefin, and is composed of 3 to 30 carbon atoms, more preferably 3 to 9 carbon atoms, and still more preferably 3 to 5 carbon atoms. .
• the olefin structural unit that may be contained in the vinyl alcohol copolymer of the present invention is preferably a structural unit derived from an ethylenically unsaturated monomer.
• olefin structural units derived from ethylenically unsaturated monomers include propylene, 1-butene, cis-2-butene, trans-2-butene, 2-methylpropylene (2-methylpropene), 1-pentene , cis-2-pentene, trans-2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl 1-butene, 1-octene, 1-decene, 1-dodecene, 1 -tetradecene, 1-hexadecene, 1-octadecene, etc., and combinations thereof.
• Olefin constituent units are derived from propylene, 1-butene, cis-2-butene, trans-2-butene, and 2-methylpropylene, especially for the reason that separation from other monomers after copolymerization is good.
• Structural units and combinations thereof are preferable, and structural units derived from propylene are more preferable from the viewpoint of facilitating purification and separation after the polymerization reaction.
• 2-methylpropylene is preferable from the viewpoint that the obtained vinyl alcohol copolymer is excellent in secondary workability such as heat sealability.
• the content of the olefin structural unit in the vinyl alcohol copolymer of the present invention is preferably 0.1 mol % to 60 mol %, more preferably 1 mol % to 30 mol %, still more preferably 3 mol % to 20 mol %. mol %, most preferably 5 mol % to 15 mol %. If the content of the olefin constitutional unit is less than 0.1 mol %, secondary workability such as heat sealability may deteriorate. When the content of the olefin constitutional unit exceeds 60 mol %, the molecular weight may decrease and the strength may decrease.
• the vinyl alcohol copolymer of the present invention is a structural unit containing a hydroxyl group other than the vinyl alcohol structural unit, which is copolymerizable with the vinyl alcohol structural unit and the olefin structural unit within a range in which the effects of the present invention are not impaired.
• the functional group that can be derivatized to a hydroxyl group is not particularly limited, but examples thereof include an ester group, an amide group, an ether group, an acetal group, and the like. is preferred.
• Examples of structural units containing hydroxyl groups other than vinyl alcohol structural units include 1,3-diacetoxy-2-methylenepropane (DAMP), 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyl Ronyloxy-2-methylenepropane, 1,3-dihydroxy-2-methylenepropane, allyl alcohol, 3-acetoxy-1-propene, 3,4-dihydroxy-1-butene, 3,4-diacetoxy-1-butene, 4 -hydroxy-2-methyl-1-butene, 4-acetoxy-2-methyl-1-butene, methallyl alcohol, methallyl acetate, etc., and combinations thereof. Structural units derived from DAMP are preferred because polymerization using these structural units is
• the content of structural units containing hydroxyl groups other than vinyl alcohol structural units is preferably 0.1 mol % to 40 mol %, more preferably 1 mol % to 20 mol %. , and even more preferably 5 mol % to 15 mol %. If the content of hydroxyl group-containing structural units other than vinyl alcohol structural units is less than 0.1 mol %, the resulting vinyl alcohol copolymer may have reduced water solubility. When the content of structural units containing hydroxyl groups exceeds 40 mol %, the resulting vinyl alcohol copolymer may have a low molecular weight and a low strength.
• the vinyl alcohol copolymer of the present invention may also contain an ethylene structural unit copolymerizable with the vinyl alcohol structural unit and the olefin structural unit as long as the effects of the present invention are not impaired.
• the content of the ethylene structural unit in the vinyl alcohol copolymer of the present invention is preferably 0.1 mol % to 60 mol %, more preferably 1 mol % to 50 mol %, still more preferably 5 mol % to 40 mol %. mol %, most preferably 7 to 20 mol %.
• the content of the ethylene structural unit is less than 0.1 mol %, the viscosity stability of the aqueous solution may deteriorate.
• the strength of the obtained vinyl alcohol copolymer may decrease.
• the vinyl alcohol copolymer of the present invention may contain constitutional units other than those described above as long as the effects of the present invention are not impaired.
• Other structural units are not particularly limited, but examples include acrylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t acrylate -Unsaturated monomers having acrylic esters such as butyl, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i- methacrylate propyl, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl me
• the content of other structural units in the vinyl alcohol copolymer of the present invention is preferably 40 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less. If the content of structural units containing hydroxyl groups exceeds 40 mol %, the strength may decrease.
• the vinyl alcohol copolymer of the present invention has a difference between the melting point and the minimum heat-sealing temperature of 45°C or more, preferably 50°C or more, more preferably 60°C or more, or the minimum heat-sealing temperature of 80°C or less, It is preferably 75° C. or lower, more preferably 70° C. or lower.
• minimum heat sealing temperature used in this specification means that the upper crimped portion (10 mm), the lower crimped portion (10 mm), And under the conditions of a pressing force of about 0.6 MPa and 1 second, two humidity-conditioned films are heat-sealed, and the breaking strength or peel strength of the obtained heat-sealed portion is measured by T peel (180 degree peel test) at a width of 15 mm. It is measured at a test speed of 300 mm/min and refers to the lowest temperature value when the strength exceeds 5 N/15 mm.
• the difference between the melting point and the minimum heat-sealing temperature is less than 45°C, there are concerns that the obtained vinyl alcohol copolymer (resin) will melt and the heat-sealing strength of the film obtained from the copolymer will be insufficient. can cause Although the lower limit of the lowest heat sealing temperature is not limited, if it is lower than 40°C, films obtained from the vinyl alcohol copolymer may adhere to each other during storage.
• the vinyl alcohol copolymer of the present invention was measured by gel permeation chromatography of the copolymer obtained by acetylating the vinyl alcohol copolymer. Satisfy any of the household formulas.
• U1 is the molecular weight MU1 calculated from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer
• the molecular weight MU1 defined by the following formula. is the value of the peak intensity of the chromatogram obtained from the ultraviolet absorption detector at .
• Log 10 MU1 Log 10 (Mn) + 0.5 R1 is defined by the following formula, where Mn is calculated from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer. 4 is the peak intensity value of the chromatogram obtained from the refractive index detector at molecular weight MR1.
• the upper limit value in the above formula (a) is preferably 0.985 or less, more preferably 0.980 or less, 0.975 or less, 0.970 or less, 0.950 or less, or 0.930, Most preferably, it is 0.910 or less.
• the lower limit in the above formula (b) is preferably 1.013 or more, more preferably 1.018 or more, 1.025 or more, 1.030 or more, or 1.050 or more, or 1.070 or more, Most preferably it is 1.100 or more.
• the vinyl alcohol copolymer of the present invention can provide good heat sealability to the film obtained by satisfying the above range for formula (a) or (b).
• the number average molecular weight (Mn) of the copolymer obtained by acetylating the vinyl alcohol copolymer of the present invention is preferably 400 to 200,000, more preferably 10,000 to 150,000, even more preferably 15,000 to 100,000, and most preferably 20,000 to 50,000. If the Mn of the copolymer obtained by acetylating the vinyl alcohol copolymer is less than 400, sufficient strength may not be obtained, for example, when formed into a film. When the Mn of the vinyl alcohol copolymer exceeds 200,000, the industrial production of the vinyl alcohol copolymer itself may become difficult, and the workability of the film may deteriorate. Mn is calculated by, for example, high performance liquid chromatography (HPLC).
• HPLC high performance liquid chromatography
• the degree of saponification of the vinyl alcohol copolymer of the present invention is not particularly limited, it is preferably 50 to 100 mol %. If the degree of saponification is less than 50 mol %, the resin molding obtained using the copolymer may not have sufficient water vapor barrier properties.
• the degree of saponification is more preferably 70 mol% or more, more preferably 80 mol% or more.
• the degree of saponification is preferably 99.99 mol% or less, more preferably 99.95 mol% or less, even more preferably 99.90 mol% or less.
• the degree of saponification is defined by DS shown in the following formula (S 1 ), and specifically calculated from the measurement result of 1 H-NMR.
• D is the number of moles of hydroxyl groups in the vinyl alcohol copolymer
• E is the number of moles of hydroxyl groups in the vinyl alcohol copolymer and is the total number of moles of ester groups in
• the vinyl alcohol copolymer of the present invention is, but not necessarily limited to, a vinyl ester monomer, an olefin monomer, and/or other monomers under conditions where the pressure of the olefin monomer fluctuates. It can be produced by polymerizing with In the following, as a method for producing a vinyl alcohol copolymer of the present invention, a vinyl ester monomer, an olefin monomer, and/or other monomers are mixed under conditions where the pressure of the olefin monomer fluctuates. A case of polymerization will be described.
• Polymerization of vinyl ester monomers, olefinic monomers, and/or other monomers may be carried out using any of batch, semi-batch, continuous, or semi-continuous polymerization regimes. However, it is preferable to carry out the polymerization under conditions where the pressure of the olefin monomer fluctuates, for example, in a batch polymerization.
• the average fluctuation speed of the pressure of the olefin structural unit is 1.0 ⁇ 10 ⁇ 5 Pa/min or more, preferably 10.0 ⁇ 10 ⁇ 5 Pa/min or more, more preferably 20.0 ⁇ 10 ⁇ 5 Pa/min. / min or more.
• the average fluctuation speed is the absolute value of the pressure change speed (represented by a positive value when the pressure increases and a negative value when the pressure decreases).
• the average value of the absolute values of the respective pressure change speeds is taken as the average fluctuation speed.
• polymerization method known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be employed.
• the solvent used in the solution polymerization method is not particularly limited, but alcohols are preferably used, and lower alcohols such as methanol, ethanol and propanol are more preferably used.
• the amount of the solvent used in the polymerization reaction solution can be selected in consideration of the viscosity average degree of polymerization of the desired vinyl alcohol copolymer and the chain transfer of the solvent.
• the mass ratio (solvent/total monomers) is preferably selected in the range of 0.01-10, more preferably in the range of 0.05-3.
• a known polymerization initiator can be used for copolymerizing the vinyl ester monomer and the olefin monomer.
• the type of polymerization initiator to be used can be appropriately selected according to the polymerization method. Examples of such polymerization initiators include azo initiators, peroxide initiators, and redox initiators.
• azo initiators examples include 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(4-methoxy-2,4-dimethyl valeronitrile).
• peroxide-based initiators include peroxydicarbonate-based compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, perester compounds such as ⁇ -cumyl peroxyneodecanate and acetyl peroxide; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate and the like.
• potassium persulfate, ammonium persulfate, hydrogen peroxide, and the like may be used in combination with the above initiators.
• redox initiators include combinations of the above peroxide initiators and reducing agents such as sodium hydrogensulfite, sodium hydrogencarbonate, tartaric acid, L-ascorbic acid, and Rongalite.
• the amount of polymerization initiator used is not necessarily limited because it varies depending on the type of polymerization catalyst used in combination, but the amount can be arbitrarily adjusted by those skilled in the art according to, for example, the polymerization rate.
• the amount of polymerization initiator used is preferably 0.01 to 0.2 mol %, more preferably 0.02 to 0.15 mol %, relative to the vinyl ester monomer. Copolymerization of the vinyl ester monomer and the olefin monomer can be carried out more efficiently by using the polymerization initiator in an amount within this range with respect to the vinyl ester monomer. obtain.
• the polymerization temperature is not particularly limited, for example, room temperature to about 150° C. is appropriate, and a temperature of 40° C. or higher and the boiling point or lower of the solvent used can be preferably selected.
• the polymerization may be carried out in the presence of a chain transfer agent to the extent that the effects of the present invention are not impaired.
• chain transfer agents examples include aldehydes such as acetaldehyde and propynaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; phosphinates such as sodium phosphinate monohydrate. mentioned.
• the amount of the chain transfer agent to be added to the polymerization reaction solution can be determined according to the chain transfer coefficient of the chain transfer agent and the degree of polymerization of the desired vinyl alcohol copolymer. 0.1 to 10 parts by mass is preferable.
• a crude copolymer can be produced by the above polymerization.
• the crude copolymer obtained above may be saponified.
• all or part of the vinyl ester units derived from the vinyl ester monomer in the copolymer are converted to vinyl alcohol units.
• a single saponification reaction may simultaneously hydrolyze different types of ester groups.
• a known method can be adopted as such a saponification method.
• Saponification is usually carried out in an alcoholic or hydroalcoholic solution.
• Alcohols preferably used at this time are, for example, lower alcohols such as methanol and ethanol, preferably methanol.
• the alcohol or hydroalcohol used for saponification may contain other solvents such as acetone, methyl acetate, ethyl acetate, benzene, etc. up to 40% by weight of the alcohol.
• Catalysts used for saponification include, for example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkali catalysts such as sodium methylate, and acid catalysts such as mineral acids.
• a temperature of, for example, 20 to 120° C. is set during the saponification. When a gel-like product precipitates as the saponification progresses, washing and drying may be performed after pulverizing the product.
• the vinyl alcohol copolymer of the present invention can be produced.
• the vinyl alcohol copolymer of the present invention can be used alone, or can be used as a resin composition by blending other copolymers and/or additives.
• Examples of other copolymers include polyvinyl alcohol and ethylene-vinyl alcohol copolymers that do not contain structural units containing hydroxyl groups other than the vinyl alcohol structural units described above. More specific examples of other copolymers include polyvinyl alcohol with a degree of saponification of 40-100%, modified polyvinyl alcohol with a degree of saponification of 40-100%, ethylene- Vinyl alcohol copolymers, polyvinyl butyral with a degree of saponification of 40-100%, starches, starch derivatives, cellulose and cellulose derivatives, and combinations thereof.
• additives examples include inorganic salts, organic salts, crosslinkers, solvents, UV absorbers, antioxidants, antistatic agents, plasticizers, fungicides, and preservatives, and combinations thereof. .
• the contents of other copolymers and other additives are not particularly limited, and suitable amounts can be selected by those skilled in the art.
• the resin molded article of the present invention is obtained from the resin composition containing the vinyl alcohol copolymer.
• the resin composition utilizes the excellent gas barrier properties (e.g., oxygen gas barrier properties and water vapor barrier properties) and maintainability of the vinyl alcohol copolymer, and can be used for packaging materials such as heat seals (e.g., It can be molded into forms such as films (including polarizing films), (binder) fibers, polarizing films, and water-soluble substrates.
• the resin molded article of the present invention may have the form of a film for heating.
• the size and thickness are not particularly limited, and can be arbitrarily set by those skilled in the art according to the purpose of use. If necessary, the heat-sealing film of the present invention may be laminated with another thermoplastic resin film as a base layer.
• thermoplastic resin films include, for example, polyolefin films (such as polyethylene films and polypropylene films), polyester films (such as polyethylene terephthalate films), nylon, polyacrylonitrile, polyvinyl chloride and polyvinylidene chloride (PVDC), and combinations thereof.
• the size and thickness of the other thermoplastic resin film are not particularly limited, and can be arbitrarily set by those skilled in the art according to the purpose of use.
• the vinyl alcohol copolymer and/or resin composition of the present invention includes, for example, surfactants; dispersion stabilizers for organic and inorganic pigments such as paints and adhesives; vinyl chloride, vinylidene chloride, styrene, (meth)acrylate, Dispersion stabilizers and dispersion aids for suspension polymerization of various vinyl compounds such as vinyl acetate; adhesives; various binders; additives for cement and mortar; Modifiers; sizing agents; textile processing agents; leather finishing agents; paints; anti-fogging agents; flocculants for suspended and dissolved substances in water; metal flocculants; fibers, sheets, pipes, tubes, leak-proof films, water-soluble fibers for chemical laces; sponges; water-soluble films; polarizing films; barrier films; , post-reaction applications with high-molecular-weight organic compounds or inorganic compounds; adhesives for wood, paper, aluminum foil and inorganic substances; non-woven fabric binders; warp sizing agents
• Acetone was added to the collected solids so that the total weight was 5 g, and the solids were dissolved by heating to 50°C.
• the solution was again added to a beaker containing 100 g of water to precipitate a copolymer, and the solid was recovered and dried under reduced pressure to obtain an acetylated copolymer.
• Mn number average molecular weight
• Mn Log 10
• U1 is the molecular weight MU1 calculated from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer
• the molecular weight MU1 defined by the following formula. is the value of the peak intensity of the chromatogram obtained from the ultraviolet absorption detector at .
• Log 10 MU1 Log 10 (Mn) + 0.5 R1 is defined by the following formula, where Mn is calculated from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer.
• Log 10 MR1 Log 10 (Mn) + 0.5 U2 is defined by the following formula by calculating Mn from the chromatogram obtained from the refractive index detector in the gel permeation chromatography measurement of the copolymer obtained by acetylating the vinyl alcohol copolymer. It is the value of the peak intensity of the chromatogram obtained from the ultraviolet absorption detector at the molecular weight MU2.
• D is the number of moles of hydroxyl groups in the vinyl alcohol copolymer
• E is the number of moles of hydroxyl groups in the vinyl alcohol copolymer and is the total number of moles of ester groups in
• Aqueous vinyl alcohol copolymer solutions obtained in Examples and Comparative Examples having a concentration of 10% by mass were prepared, filtered and centrifuged to remove foreign matter and air bubbles.
• the copolymer was insoluble in water, it was dissolved in a mixed solution containing 2-propanol until it became soluble (the concentration of the polymer at that time was 10% by mass).
• the aqueous solution was poured onto a PET film and dried in an atmosphere of 23° C. and 50% RH for 1 week to obtain a film with a thickness of about 100 ⁇ m. This film was conditioned at 20° C. and 40% RH for one week, and the stress at the maximum point was measured under the following conditions.
• Apparatus Autograph AG-X plus (manufactured by Shimadzu Corporation) Distance between chucks: 70mm
• Tensile speed 500 mm/min
• Sample shape Dumbbell shape (width 10 mm, thickness about 0.1 mm)
• Test environment 23°C, 50% RH
• the tensile strength is 5 kgf/mm 2 or more, the practically necessary strength can be ensured.
• Crystal melting enthalpy, glass transition temperature and melting point Crystal melting enthalpy, glass transition temperature and melting point were measured under the following conditions. Apparatus: Differential scanning calorimeter (DSC25 manufactured by TA instruments) Temperature profile: After raising the temperature from room temperature to 250°C, the temperature was lowered to -30°C, and then raised to 250°C again. Crystal melting enthalpy, glass transition temperature, and melting point were measured from the final heating profile. Temperature increase/decrease rate: 10°C/min Sample amount: about 3 mg (using an aluminum pan)
• the pressure represents gauge pressure unless otherwise specified.
• an initiator solution was prepared by dissolving 2.0 g of 2,2-azobis(isobutyronitrile) (AIBN) as a radical polymerization initiator in 56 g of methanol, and the solution was bubbled with nitrogen gas to replace with nitrogen.
• AIBN 2,2-azobis(isobutyronitrile)
• propylene was introduced into the pressurized reactor so that the reactor pressure was 0.500 MPa. After the introduction, the gas was removed over 30 minutes until the reactor pressure reached 0.100 MPa. This operation of introducing propylene and degassing was carried out a total of three times to replace the inside of the reaction vessel with propylene. After raising the internal temperature of the reactor from 0.100 MPa to 60° C., propylene was introduced until the reactor pressure reached 0.700 MPa. From the state of the reactor at 60° C. and 0.700 MPa, the above initiator solution was added at a rate of 15 mL/min.
• the internal temperature of the reactor was maintained at 60° C., and the polymerization was allowed to proceed while gradually decreasing the reactor pressure at a rate of 8.01 ⁇ 10 ⁇ 5 MPa/min.
• the polymerization inhibitor solution (2,2,6,6-tetramethylpiperidine 1 - a mixed solution of 4 g of oxyl free radicals and 10 g of methanol) was added to stop the polymerization.
• modified PVAc modified vinyl acetate copolymer
• This resin was pulverized, washed five times with 720 parts by mass of 2-propanol, and dried under reduced pressure at 40° C. for 3 days to obtain a copolymer.
• the gelled system was pulverized with a pulverizer and allowed to stand at 40° C. for 1 hour to promote saponification, after which 1000 g of methyl acetate was added to neutralize the remaining alkali.
• a mixed solvent of 900 g of methanol and 100 g of water was added to the white solid saponified product obtained by filtration, and the mixture was allowed to stand at room temperature for 3 hours and washed.
• the saponified product obtained by centrifugal deliquoring was allowed to stand in a dryer at 70° C. for 2 days to obtain a dried vinyl alcohol copolymer.
• the materials and conditions employed are listed in Tables 1 and 2, and the evaluation results are shown in Tables 3 and 4.
• Examples 2-14, Comparative Examples 1-6 and Reference Examples 1-2: Production of vinyl alcohol copolymer A vinyl alcohol copolymer was produced in the same manner as in Example 1, except that the materials and reaction conditions employed in Example 1 were changed as shown in Tables 1 and 2. Evaluation results are shown in Tables 3 and 4.
• Example 6 DAMP (1,3-diacetoxy-2-methylenepropane) as a comonomer was charged in the amount shown in Table 1 at the same time as vinyl acetate. The additional portion was gradually added in the form of a methanol solution from immediately after addition of the polymerization initiator until immediately before addition of the terminator.
• Example 7 Furthermore, in Example 7 and Comparative Example 4, the amount of the sodium hydroxide methanol solution was changed to 2.3 parts by weight.
• the copolymer obtained by polymerizing with decreasing olefin pressure has the lowest heat sealability than the copolymer obtained by polymerizing with constant olefin pressure.
• the temperature was decreasing (eg, compare Examples 1-3 with Comparative Example 1; see Compare Example 5 with Comparative Example 2).
• the copolymer obtained by polymerizing while increasing the olefin pressure has a lower heat-sealable temperature than the copolymer obtained by copolymerizing with a constant olefin pressure. (eg, compare Examples 8-10 with Comparative Example 1; see Compare Example 11 with Comparative Example 2).
• the tensile strength of the copolymer obtained by polymerization while decreasing the olefin pressure tended to be superior to that of the copolymer obtained by polymerization under a constant olefin pressure.
• ethylene is used as the olefin
• the resin composition of the present invention is useful, for example, in technical fields such as food and beverage fields, pet food fields, fats and oils industry fields, pharmaceutical fields, and electrical and electronic fields.

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• 2022
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