WO2021124951A1 - アイオノマー樹脂、樹脂シートおよび合わせガラス - Google Patents

アイオノマー樹脂、樹脂シートおよび合わせガラス Download PDF

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Publication number
WO2021124951A1
WO2021124951A1 PCT/JP2020/045450 JP2020045450W WO2021124951A1 WO 2021124951 A1 WO2021124951 A1 WO 2021124951A1 JP 2020045450 W JP2020045450 W JP 2020045450W WO 2021124951 A1 WO2021124951 A1 WO 2021124951A1
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Prior art keywords
ionomer resin
meth
unit
resin
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/045450
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English (en)
French (fr)
Japanese (ja)
Inventor
智香 城内
憲太 竹本
卓郎 新村
淳裕 中原
芳聡 淺沼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to EP20902361.3A priority Critical patent/EP4079699A4/en
Priority to CN202080041719.3A priority patent/CN113993909B/zh
Priority to US17/786,568 priority patent/US20230025550A1/en
Priority to KR1020217032472A priority patent/KR102353434B1/ko
Priority to JP2021513490A priority patent/JP6913264B1/ja
Publication of WO2021124951A1 publication Critical patent/WO2021124951A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10935—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08F210/02—Ethene
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/1009—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using vacuum and fluid pressure
    • 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
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0876—Salts thereof, i.e. ionomers

Definitions

  • the present invention relates to an ionomer resin, a resin sheet having one or more layers containing the ionomer resin, a laminated glass interlayer film made of the resin sheet, and a laminated glass having the laminated glass interlayer film.
  • Ionomer which is a neutralized product of an ethylene-unsaturated carboxylic acid copolymer, is used as an interlayer film of laminated glass because of its excellent transparency and adhesiveness to glass (for example, Patent Document 1).
  • Patent Document 1 the required performance for laminated glass has increased, and even for ionomer resins, high transparency is maintained regardless of the manufacturing conditions of laminated glass, high elastic modulus is maintained even at high temperatures, and the strength of laminated glass is reduced. There has been a demand for not allowing it to occur, and for having less coloring and an excellent appearance.
  • Patent Document 2 describes a copolymerization unit of ethylene, a copolymerization unit of first ⁇ and ⁇ -unsaturated carboxylic acid having 3 to 10 carbon atoms, and a second ⁇ having 3 to 10 carbon atoms.
  • Ionomer a neutralized product of an ethylenic acid copolymer containing a copolymerization unit of a ⁇ -unsaturated carboxylic acid derivative, is described.
  • Patent Document 2 describes that the ionomer described in the document exhibits improved optical characteristics (haze) as compared with the conventional ionomer.
  • the ionomer described in Patent Document 2 is easily thermally decomposed during the molding process, and the obtained interlayer film is likely to have defects such as black foreign matter.
  • an object of the present invention is to provide an ionomer resin having high transparency and high thermostable decomposition property.
  • the present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention provides the following suitable forms.
  • (Meta) Acrylic acid unit (A), (Meta) Acrylic acid neutralized product unit (B), and ethylene unit (C) Ionomer resin including
  • the total content of the unit (A) and the unit (B) is 6 to 10 mol% based on all the monomer units constituting the ionomer resin, and is composed of a strong acid and a strong base in the ionomer resin.
  • Ionomer resin having a salt content of 1 to 400 mg / kg.
  • the ionomer resin further contains a (meth) acrylic acid ester unit (D), and the total content of the unit (A), the unit (B) and the unit (D) constitutes the ionomer resin.
  • the salt composed of the strong acid and the strong base is at least one cation selected from the group consisting of sodium ion and potassium ion, and at least one selected from the group consisting of halogen ion, nitrate ion, and sulfate ion.
  • [5] A resin sheet having one or more layers containing the ionomer resin according to any one of [1] to [4].
  • [6] A laminated glass interlayer film made of the resin sheet according to [5].
  • [7] A laminated glass having two glass plates and a laminated glass interlayer film according to [6] arranged between the two glass plates.
  • the ionomer resin of the present invention contains a (meth) acrylic acid unit (A), a (meth) acrylic acid neutralized product unit (B), and an ethylene unit (C), and the unit (A) and the unit (B).
  • the total content of the ionomer resin is 6 to 10 mol% based on all the monomer units constituting the ionomer resin.
  • the "unit” means a "constituent unit of origin", and for example, the (meth) acrylic acid unit indicates a structural unit derived from (meth) acrylic acid, and is (meth) acrylic.
  • the acid neutralized product unit indicates a structural unit derived from a (meth) acrylic acid neutralized product
  • the ethylene unit indicates a structural unit derived from ethylene.
  • (meth) acrylic acid means methacrylic acid or acrylic acid.
  • the total content exceeds the above upper limit value, it is difficult to suppress an increase in the melt viscosity during the molding process of the ionomer resin, and as a result, the molding processability of the ionomer resin tends to decrease. Further, when the total content is less than the above lower limit, the transparency of the ionomer resin, particularly the transparency when the ionomer resin is slowly cooled to promote the crystallization of the ionomer resin (hereinafter, also referred to as the transparency during slow cooling). ) Is likely to decrease.
  • the total content is 6 mol% or more, preferably 6.5 mol% or more, from the viewpoint of easily improving the transparency of the ionomer resin (particularly the transparency during slow cooling) and the adhesiveness to a substrate such as glass. It is more preferably 7.0 mol% or more, still more preferably 7.5 mol% or more, and from the viewpoint of easily improving the molding processability, it is 10 mol% or less, preferably 9.9 mol% or less, more preferably. Is 9.5 mol% or less.
  • the total content of the unit (A) and the unit (B) can be adjusted by the method for producing the ionomer resin. More specifically, when an ionomer resin is produced by using an ethylene- (meth) acrylic acid ester copolymer as a raw material and a method including a saponification reaction step of the copolymer, the ethylene- (meth) acrylic acid ester Each reaction that converts (meth) acrylic acid ester units in the copolymer into (meth) acrylic acid units (A) and (meth) acrylic acid neutralized product units (B) by the saponification reaction and demetallization reaction. It can be adjusted by the degree of reaction (conversion rate) of.
  • (meth) acrylic acid unit (A) examples include acrylic acid and methacrylic acid, and methacrylic acid is preferable from the viewpoint of heat resistance and adhesiveness to a substrate. These (meth) acrylic acid units may be used alone or in combination of two.
  • the content of the (meth) acrylic acid unit (A) in the ionomer resin is such that the total content of the unit (A) and the unit (B) is 6 to 6 based on all the monomer units constituting the ionomer resin. There is no particular limitation as long as it is within the range of 10 mol%. In one embodiment of the present invention, the content of the (meth) acrylic acid unit (A) in the ionomer resin is preferably 4.5 mol% or more, based on all the monomer units constituting the ionomer resin.
  • It is preferably 5.0 mol% or more, more preferably 5.5 mol% or more, particularly preferably 5.8 mol% or more, and preferably 9.0 mol% or less, more preferably 8.5 mol% or more. Below, it is more preferably 8.0 mol% or less, and particularly preferably 7.5 mol% or less.
  • the content of the unit (A) is at least the above lower limit value, the transparency of the ionomer resin and the adhesiveness to the substrate are likely to be improved. Further, when it is not more than the above upper limit value, the molding processability is likely to be improved.
  • the (meth) acrylic acid neutralized product unit (B) is preferable.
  • the (meth) acrylic acid neutralized product is obtained by replacing the hydrogen ion of (meth) acrylic acid with a metal ion.
  • the metal ions include ions of monovalent metals such as lithium, sodium and potassium, and ions of polyvalent metals such as magnesium, calcium, zinc, aluminum and titanium. Such metal ions may be used alone or in combination of two or more. For example, it may be a combination of one or more kinds of monovalent metal ions and one or more kinds of divalent metal ions.
  • the content of the (meth) acrylic acid neutralized substance unit (B) in the ionomer resin is such that the total content of the unit (A) and the unit (B) is the total monomer unit constituting the ionomer resin.
  • the content of the (meth) acrylic acid neutralized product unit (B) is preferably 0.65 mol% or more, more preferably 0.65 mol% or more, based on all the monomer units constituting the ionomer resin.
  • Each content of the unit (A) and the unit (B) is made from an ethylene- (meth) acrylic acid ester copolymer as a raw material, and is an ionomer by a method including a saponification reaction step and a metal removal reaction step of the copolymer.
  • the (meth) acrylic acid ester unit in the ethylene- (meth) acrylic acid ester copolymer is subjected to the saponification reaction and the demetallization reaction to form the (meth) acrylic acid unit (A) and (meth). It can be adjusted by the degree of reaction in each reaction to be converted into the acrylic acid neutralized product unit (B).
  • the content of the ethylene unit (C) is preferably 80 mol% or more, more preferably 85 mol% or more, based on all the monomer units constituting the ionomer resin, from the viewpoint of easily increasing the impact resistance of the ionomer resin. It is more preferably 88 mol% or more, and preferably 94 mol% or less, more preferably 91 mol% or less, from the viewpoint of easily increasing the transparency of the ionomer resin (particularly the transparency at the time of slow cooling).
  • the content of the ethylene unit (C) is at least the above lower limit value, the mechanical strength and molding processability are likely to be improved, and when it is at least the above upper limit value, the transparency is likely to be improved.
  • the ionomer resin of the present invention can easily obtain higher transparency. Further, it is preferable to contain the (meth) acrylic acid ester unit (D).
  • the ionomer resin contains a (meth) acrylic acid ester unit (D)
  • the total content of the unit (A), the unit (B) and the unit (D) is transparent (particularly transparency during slow cooling). ) Is easily improved, and it is preferably 6 to 10 mol% based on all the monomer units constituting the ionomer resin. That is, in a preferred embodiment of the present invention, the ionomer resin of the present invention comprises (meth) acrylic acid unit (A), (meth) acrylic acid neutralized unit (B), ethylene unit (C), and (meth).
  • Acrylic acid ester unit (D) is included, and the total content of the unit (A), the unit (B), and the unit (D) is 6 to 6 based on all the monomer units constituting the ionomer resin. It is 10 mol%.
  • the ionomer resin contains a (meth) acrylic acid ester unit (D)
  • the ionomer resin It is easy to suppress an increase in melt viscosity during molding, and thereby it is easy to improve the molding processability of the ionomer resin.
  • the total content is at least the lower limit value
  • the transparency of the ionomer resin tends to be enhanced.
  • the ionomer resin contains a (meth) acrylic acid ester unit (D)
  • the total content of the unit (A), the unit (B) and the unit (D) is transparent (particularly during slow cooling).
  • the content is 6 mol% or more, preferably 6.5 mol% or more, more preferably 7.0 mol% or more, still more preferably 7.5 mol% or more.
  • it is 10 mol% or less, preferably 9.9 mol% or less, and more preferably 9.5 mol% or less.
  • the total content of the unit (A), the unit (B) and the unit (D) can be adjusted by the raw material of the ionomer resin. More specifically, when an ionomer resin is produced by using an ethylene- (meth) acrylic acid ester copolymer as a raw material and a method including a saponomerization reaction step of the copolymer, ethylene-, which is a raw material of the ionomer resin, is produced. It can be adjusted by the amount of (meth) acrylic acid ester modification of the (meth) acrylic acid ester copolymer. Further, as described in US Pat. No.
  • Examples of the monomer constituting the (meth) acrylic acid ester unit (D) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate.
  • preferable monomers from the viewpoint of transparency or heat resistance are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and ( N-Butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, and more preferred monomers are methyl (meth) acrylate, ( Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and more preferred monomers are (meth).
  • Methyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and a particularly preferred monomer is methyl (meth) acrylate.
  • These (meth) acrylic acid esters may be used alone or in combination of two or more.
  • the content of the (meth) acrylic acid ester unit (D) in the ionomer resin is not particularly limited.
  • the content of the (meth) acrylic acid ester unit (D) in the ionomer resin is preferably more than 0 mol%, more preferably more than 0 mol%, based on all the monomer units constituting the ionomer resin. Is 0.01 mol% or more, more preferably 0.05 mol% or more, particularly preferably 0.08 mol% or more, and preferably 1.0 mol% or less, more preferably 0.7 mol% or less. , More preferably 0.5 mol% or less.
  • the content of the unit (D) is at least the above lower limit value and at least the above upper limit value, the transparency of the ionomer resin is likely to be improved.
  • the content of the unit (D) is a step of saponification reaction of the copolymer using an ethylene- (meth) acrylic acid ester copolymer as a raw material.
  • the ionomer resin is produced by a method including a demetallization reaction step, the (meth) acrylic acid ester unit (D) in the ethylene- (meth) acrylic acid ester copolymer is replaced with the (meth) acrylic acid unit (A). It can be adjusted by the degree of reaction of the saponification reaction to be converted into.
  • the ionomer resin of the present invention comprises a (meth) acrylic acid unit (A), a (meth) acrylic acid neutralized unit (B), and an ethylene unit (C), and optionally a (meth) acrylic acid ester unit (meth). It may contain other monomer units other than D). Examples of other monomer units include a carboxylic acid unit (A2) other than the (meth) acrylic acid unit (A) and a carboxylic acid neutralized product unit (B) other than the (meth) acrylic acid neutralized unit (B). B2) and the like can be mentioned.
  • Examples of the monomer constituting the carboxylic acid unit (A2) include itaconic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and the like, and monomethyl maleate and monoethyl maleate are preferable.
  • Examples of the monomer constituting the carboxylic acid neutralized product unit (B2) include the neutralized product unit of the carboxylic acid unit (A2).
  • the carboxylic acid neutralized product is obtained by replacing the hydrogen ion of the carboxylic acid with a metal ion.
  • Examples of the metal ion include the same as the metal ion in the above-mentioned (meth) acrylic acid neutralized product unit (B), and the metal ion may be one kind alone or a combination of two or more kinds. These other monomer units may be used alone or in combination of two or more.
  • the total content thereof for example, the total contents of (A2) and (B2) may be appropriately selected within a range that does not impair the effects of the present invention, for example.
  • the monomer units constituting the ionomer resin it is preferably 5 mol% or less, more preferably 3 mol% or less, further preferably 1 mol% or less, and preferably 0.01 mol% or more. More preferably, it is 0.1 mol% or more.
  • NMR nuclear magnetic resonance spectroscopy
  • the ionomer resin of the present invention contains 1 to 400 mg / kg of a salt composed of a strong acid and a strong base (hereinafter, also simply referred to as “salt”).
  • salt a salt composed of a strong acid and a strong base
  • the present inventors have found that when the ionomer resin contains 1 to 400 mg / kg of salt, the thermostable decomposition property can be improved while maintaining the high transparency of the ionomer resin (particularly the transparency at the time of water absorption). Therefore, the ionomer resin of the present invention can achieve both high transparency and high thermodegradability.
  • the ionomer resin of the present invention is excellent in thermostable decomposition property by containing a salt within the above range is not clear, but due to the interaction between the salt and the (meth) acrylic acid unit (A) in the ionomer resin, the ionomer It is considered that this is because the (meth) acrylic acid unit (A) in the resin can be suppressed from being desorbed by heat.
  • the salt content exceeds the above upper limit value, the transparency of the ionomer resin tends to decrease, and if it is less than the above lower limit value, the thermostable decomposition property decreases, and for example, during molding processing, the ionomer tends to decrease.
  • the resin is easily thermally decomposed.
  • the content of the salt is 1 mg / kg or more, preferably 3 mg / kg or more, and more preferably 5 mg / kg or more from the viewpoint of easily improving the thermostable decomposition property. Further, from the viewpoint of easily improving the transparency (particularly the transparency at the time of water absorption), it is 400 mg / kg or less, preferably 300 mg / kg or less, and more preferably 200 mg / kg or less.
  • the salt content in the ionomer resin can be appropriately selected depending on the method for adding the salt to the ionomer resin as described later.
  • the salt content in the ionomer resin can be measured by using an ion chromatograph, for example, by the method described in Examples.
  • the salt composed of a strong acid and a strong base is not particularly limited, and examples thereof include a metal salt of an alkali metal and / or an alkaline earth metal composed of a strong acid and a strong base. These salts may be used alone or in combination of two or more.
  • alkali metal salts include lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt and the like.
  • the preferred alkali metal salt is a lithium salt, a sodium salt, a potassium salt, more preferably a sodium salt or a potassium salt, and further preferably a sodium salt.
  • alkaline earth metal salts examples include beryllium salt, magnesium salt, calcium salt, strontium salt, barium salt and the like. From the viewpoint of easily enhancing the heat-resistant decomposition property of the ionomer resin, preferable alkaline earth metal salts are magnesium salts and calcium salts.
  • more preferable salts are at least one cation selected from the group consisting of sodium ion, potassium ion, magnesium ion and calcium ion, and halogen ion, sulfate ion and nitrate ion.
  • a salt consisting of at least one anion selected from the group consisting of nitrate ions are at least one anion selected from the group consisting of sodium ion, potassium ion, magnesium ion and calcium ion, and halogen ion, sulfate ion and nitrate ion.
  • Specific preferred salt examples include sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, p-toluenesulfonic acid.
  • Examples thereof include sodium, potassium p-toluenesulfonate, magnesium p-toluenesulfonate, and calcium p-toluenesulfonate.
  • more preferable salts are sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, and more preferably sodium chloride, sodium sulfate, and sodium nitrate.
  • the method of containing the salt in the ionomer resin is not particularly limited, and for example, (I) a method of producing and containing a salt in the process of producing the ionomer resin, (II) a method of attaching a salt in the process of producing the ionomer resin, and the like. (III) A method of producing an ionomer resin containing no salt and then adding a salt to the resin can be mentioned. Among these methods, from the viewpoint that the salt can be easily dispersed uniformly in the ionomer resin, thereby improving the transparency and the thermostable decomposition property, the salt is generated and contained in the ionomer resin manufacturing process (the above method). I) is preferable.
  • the method for adjusting the content of the salt consisting of a strong acid and a strong base in the ionomer resin can be appropriately selected according to the above-mentioned salt content method.
  • the salt when the salt is contained by the method (I), it can be adjusted by the degree of cleaning of the obtained resin. More specifically, the salt content in the ionomer resin can be adjusted by the number of washings in the step of washing the obtained resin with the washing liquid.
  • the cleaning solution include solvents that are good solvents for salts and poor solvents for resins, such as water, alcohols such as methanol, ketones such as acetone, and mixed solvents thereof.
  • the content of the salt in the ionomer resin can be adjusted by the amount of the attached salt and the amount of the salt to be added later.
  • the dispersed state of the salt composed of a strong acid and a strong base in the ionomer resin is not particularly limited, but it is preferable that the salt is uniformly dispersed in the ionomer resin from the viewpoint of easily improving transparency and thermostable decomposition.
  • the degree of branching per 1000 carbons of the ionomer resin of the present invention is not particularly limited, and is preferably 5 to 30, more preferably 6 to 20.
  • the degree of branching is adjusted by the temperature at which the ionomer resin is polymerized, for example, when the ionomer resin is synthesized by the EMMA saponification method, the polymerization temperature at the time of synthesizing ethylene- (meth) acrylic acid ester (X). it can.
  • the degree of branching per 1000 carbons can be measured by the DDMAS method using solid-state NMR.
  • the melting point of the ionomer resin of the present invention is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 80 ° C. or higher, from the viewpoint of heat resistance and heat-degradability.
  • the temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 150 ° C. or lower.
  • the melting point can be measured based on JIS K7121: 2012.
  • DSC differential scanning calorimeter
  • the heat of fusion of the ionomer resin of the present invention is preferably 0 J / g or more and 25 J / g or less.
  • the heat of fusion can be measured based on JIS K7122: 2012. Specifically, it is measured using a differential scanning calorimeter (DSC) under the conditions of a cooling rate of -10 ° C / min and a temperature rise rate of 10 ° C / min, and is calculated from the area of the melting peak at the time of the second temperature rise. can do.
  • DSC differential scanning calorimeter
  • the melt flow rate (MFR) of the ionomer resin of the present invention measured under the conditions of 190 ° C. and 2.16 kg according to JIS K7210-1: 2014 is preferably 0.1 g / g. 10 minutes or more, more preferably 0.3 g / 10 minutes or more, still more preferably 0.7 g / 10 minutes or more, even more preferably 1.0 g / 10 minutes or more, particularly preferably 1.5 g / 10 minutes or more. It is preferably 50 g / 10 minutes or less, more preferably 30 g / 10 minutes or less, and particularly preferably 10 g / 10 minutes or less.
  • the MFR of the ionomer resin is not less than the above lower limit value and not more than the upper limit value, it is easy to perform molding processing suppressing deterioration due to heat, and it is easy to obtain a resin sheet having excellent penetration resistance.
  • the melting point, heat of fusion and MFR of the ionomer resin are the molecular weight of the ionomer resin, and the (meth) acrylic acid unit (A), the (meth) acrylic acid neutralized unit (B), and the ethylene unit (C) of the ionomer resin. It can also be adjusted by the content of the (meth) acrylic acid ester unit (D), which is optionally included.
  • the storage elastic modulus (E') at 50 ° C. measured by the dynamic viscoelasticity measurement of the ionomer resin of the present invention is good independence (that is, high elastic modulus), particularly high temperature. From the viewpoint of independence in an environment (high elastic modulus in a high temperature environment), it is preferably 20 MPa or more, more preferably 30 MPa or more, still more preferably 40 MPa or more, and particularly preferably 50 MPa or more.
  • the upper limit of the storage elastic modulus (E') is not particularly limited and may be 1000 MPa.
  • the storage modulus includes the molecular weight of the ionomer resin, as well as the (meth) acrylic acid unit (A), the (meth) acrylic acid neutralized unit (B), and the ethylene unit (C), and optionally (meth). It can be adjusted by the content of the acrylic acid ester unit (D).
  • the ionomer resin of the present invention contains 1 to 400 mg / kg of salt as described above, it can have high heat-resistant decomposability.
  • the 1% weight loss temperature (Td1) of the ionomer resin of the present invention at a temperature rise of 10 ° C./min under a nitrogen atmosphere is preferably 330 ° C. or higher, more preferably 350 ° C. or higher. More preferably, it is 360 ° C. or higher, particularly preferably 370 ° C. or higher, and usually 450 ° C. or lower.
  • the 1% weight loss temperature of the ionomer resin is equal to or higher than the above lower limit value, it is easy to reduce foaming and / or thermal decomposition during melt molding of the ionomer resin, and black foreign matter and the like generated by thermal decomposition of air bubbles and / or the resin are generated. It is easy to obtain an interlayer film that has no defects.
  • the 1% weight loss temperature represents the temperature at which the weight loss rate becomes 1% based on the weight at 200 ° C.
  • the 1% weight loss temperature can be measured according to JIS K7120: 1987, and can be measured, for example, by the method described in Examples.
  • the ionomer resin of the present invention has high transparency, and in a preferred embodiment of the present invention, the haze of the ionomer resin of the present invention at a sheet thickness of 0.8 mm is preferably 2.0% or less, more preferably 2.0% or less. Is 1.5% or less, more preferably 1.0% or less.
  • the haze of the ionomer resin is measured using a haze meter in accordance with JIS K7136: 2000.
  • the present inventors tend to improve the thermal degradability of the ionomer resin when the ionomer resin contains a salt composed of a strong acid and a strong base, while when the salt content is too large, the transparency of the ionomer resin, particularly the ionomer resin It was found that the transparency (transparency at the time of water absorption) in the state of water absorption is reduced. Therefore, as a result of further studies, the present inventors have found that if the salt content of the ionomer resin is 400 mg / kg or less, the transparency of the ionomer resin in a water-absorbed state can be enhanced.
  • the ionomer resin of the present invention having a salt content of 1 to 400 mg / kg has high transparency even when it absorbs water.
  • the haze (water absorption haze) at a sheet thickness of 0.8 mm in a state where the ionomer resin of the present invention has absorbed water is preferably 9.0% or less, more preferably 5.0% or less. More preferably, it is 3.0% or less.
  • the lower limit is not particularly limited and may be, for example, 0.01%.
  • the ionomer resin was kept immersed in ion-exchanged water at 23 ° C. for 300 hours, removed from the ion-exchanged water, and the ionomer resin from which the water adhering to the surface was wiped off was used as a test piece and a haze meter was used.
  • JIS K7136 2000, and can be measured, for example, by the method described in Examples.
  • the ionomer resin if the crystallinity of the ionomer resin is too high, the ionomer resin tends to whiten. Therefore, the ionomer resin is slowly cooled to be transparent in a state where the crystallization of the resin is promoted. The property (transparency during slow cooling) tends to decrease.
  • the ionomer resin obtained by the present invention is difficult to crystallize because the total content of the (meth) acrylic acid unit (A) and the (meth) acrylic acid neutralized product unit (B) in the resin is 6 mol% or more. Therefore, it has high transparency even during slow cooling.
  • the haze (slow cooling haze) in a state in which the crystallization of the ionomer resin of the present invention is promoted by slow cooling is preferably 5.0% or less, more preferably 4. It is 5% or less, more preferably 4.0% or less, even more preferably 3.0% or less, and particularly preferably 2.5% or less.
  • an ionomer resin having a sheet thickness of 0.8 mm is placed between two glass plates to prepare a laminated glass, and the laminated glass is heated to 140 ° C. and then 140 ° C. to 0.1 ° C./min. It is obtained by measuring the haze after slowly cooling to 23 ° C. with a haze meter in accordance with JIS K7136: 2000.
  • the ionomer resin of the present invention has a low degree of coloring and is preferably colorless.
  • the yellowness (YI) of the ionomer resin of the present invention at a sheet thickness of 0.8 mm is preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.5 or less, from the viewpoint of low colorability. Particularly preferably, it is 1.0 or less.
  • the yellowness (YI) can be measured in accordance with JIS Z8722: 2009 using a color difference meter.
  • the method for producing the ionomer resin of the present invention is not particularly limited.
  • the ionomer resin is produced by producing a salt in the production process. Even if (II) it is produced by attaching a salt in the production process of the ionomer resin, (III) it is produced by first producing an ionomer resin containing no salt and then adding a salt to the resin. You may.
  • a salt composed of a strong acid and a strong base can be easily dispersed uniformly in the ionomer resin, thereby easily improving transparency and thermostable decomposition. Therefore, a salt is generated during the manufacturing process of the ionomer resin.
  • the method (I) described above is preferable. Hereinafter, the method (I) will be described in detail.
  • ethylene- (meth) acrylic acid ester copolymer (X) is used as a raw material, and all or a part of the (meth) acrylic acid ester unit in the copolymer is (meth) acrylic acid.
  • Converted to units and (meth) acrylic acid neutralized units (meth) acrylic acid unit (A), (meth) acrylic acid neutralized product unit (B), ethylene unit (C) and optionally (meth)
  • a crude ionomer resin containing an acrylic acid ester unit (D) was produced (step i), a poor solvent was added to the obtained crude ionomer resin solution to precipitate a granular resin (step ii), and then the precipitated granular resin was precipitated.
  • Step iii can be mentioned.
  • Step i> As a method of converting all or part of the (meth) acrylic acid ester unit in the ethylene- (meth) acrylic acid ester copolymer (X) into (meth) acrylic acid unit and (meth) acrylic acid neutralized product unit. Converts all or part of the (meth) acrylic acid ester unit to the (meth) acrylic acid neutralized product unit by saponifying the ethylene- (meth) acrylic acid ester copolymer (X) with a strong base. Then, an ethylene- (meth) acrylic acid ester- (meth) acrylic acid neutralized product copolymer was obtained, and then a part of the (meth) acrylic acid neutralized product unit in the obtained copolymer was strongly acidified.
  • a method (hereinafter, also referred to as method (1)) of demetallizing and converting to (meth) acrylic acid unit can be mentioned.
  • the (meth) acrylic acid neutralization in the ethylene- (meth) acrylic acid ester- (meth) acrylic acid neutralizer copolymer obtained by saponification in the above method (1) All the physical units are demetallized with a strong acid and converted into (meth) acrylic acid units to obtain an ethylene- (meth) acrylic acid copolymer, and then the (meth) acrylic acid units in the obtained copolymer.
  • a method of neutralizing a part of the above with metal ions hereinafter, also referred to as method (2)) can be mentioned.
  • a salt composed of a strong acid and a strong base is produced by a neutralization reaction between a strong base used for the saponification reaction and a strong acid used for demetallization, and is composed of the strong acid and the strong base.
  • a crude ionomer resin containing a salt can be obtained.
  • Examples of the monomers constituting the (meth) acrylic acid ester unit of the ethylene- (meth) acrylic acid ester copolymer (X) include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and (meth).
  • N-propyl acrylate N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) ) Amyl acrylate, Isoamyl (meth) acrylate, n-hexyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentadecyl (meth) acrylate, dodecyl (meth) acrylate , (Meta) isobornyl acrylate, (meth) phenyl acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-meth
  • preferred monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, more preferred monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n (meth) acrylate.
  • ethylene- (meth) acrylic acid ester copolymer (X) examples include an ethylene-methyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl methacrylate copolymer, and an ethylene-methacryl copolymer.
  • Ethyl acetate copolymer n-propyl copolymer of ethylene-acrylate, n-propyl copolymer of ethylene-methacrylate, isopropyl copolymer of ethylene-isopropylate, isopropyl copolymer of ethylene-isopropylacrylate, ethylene-acrylic acid
  • examples thereof include an n-butyl copolymer, an ethylene-n-butyl methacrylate copolymer, a sec-butyl copolymer of ethylene-acrylate, a sec-butyl copolymer of ethylene-methacrylate and the like.
  • copolymers As these copolymers, commercially available products may be used, or those synthesized by the high-temperature and high-pressure radical polymerization method described in US2013 / 0274424, JP-A-2006-23309 or JP-A-2007-84743 may be used.
  • Examples of the commercially available product include "Aklift” (registered trademark) WD301F manufactured by Sumitomo Chemical Co., Ltd., "Lexpearl” (registered trademark) A4250 manufactured by Japan Polyethylene Corporation, and the like.
  • the content of the (meth) acrylic acid ester unit in the ethylene- (meth) acrylic acid ester copolymer (X) is preferably 6 mol% or more, more preferably 6.5 mol% or more, still more preferably 7 mol. % Or more, particularly preferably 7.5 mol% or more, preferably 10 mol% or less, more preferably 9.9 mol% or less, still more preferably 9.5 mol% or less.
  • the content of the (meth) acrylic acid ester unit in the copolymer (X) is the (meth) acrylic acid unit (A) and the (meth) acrylic acid neutralized product unit in the obtained crude ionomer resin and ionomer resin.
  • the content of the (meth) acrylic acid ester unit in the copolymer (X) is the above lower limit.
  • the transparency of the obtained ionomer resin particularly the transparency at the time of slow cooling, can be easily increased, and when the content is not more than the above upper limit value, the molding processability of the obtained ionomer resin is improved.
  • the content of the (meth) acrylic acid ester unit in the copolymer (X) can be adjusted by the copolymerization ratio of ethylene and the (meth) acrylic acid ester.
  • the content includes the (meth) acrylic acid unit (A), the (meth) acrylic acid neutralized product unit (B), and the ethylene unit (C) in the above-mentioned ionomer resin, and when contained (meth).
  • the melt flow rate (MFR) of an ethylene- (meth) acrylic acid ester copolymer (X) measured at 190 ° C. and 2.16 kg in accordance with JIS K7210-1: 2014. ) Is preferably 5 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, further preferably 50 g / 10 minutes or more, still more preferably 100 g / 10 minutes or more, preferably 400 g / 10 minutes or less, and more. It is preferably 350 g / 10 minutes or less, more preferably 300 g / 10 minutes or less, and even more preferably 250 g / 10 minutes or less.
  • the MFR of the ethylene- (meth) acrylic acid ester copolymer (X) is not less than the above lower limit value and not more than the above upper limit value, the moldability and strength of the obtained ionomer resin can be easily improved.
  • the MFR of the ethylene- (meth) acrylic acid ester copolymer (X) can be adjusted by the degree of polymerization and the content of the (meth) acrylic acid ester unit.
  • the MFR can be measured, for example, by the method described in Examples.
  • the weight average molecular weight of the ethylene- (meth) acrylic acid ester copolymer (X) is preferably 15,000 g / mol or more, more preferably 20 from the viewpoint of easily improving the moldability and strength of the obtained ionomer resin. It is 000 g / mol or more, more preferably 30,000 g / mol or more, preferably 200,000 g / mol or less, and more preferably 100,000 g / mol or less. From the same viewpoint, the number average molecular weight of the ethylene- (meth) acrylic acid ester copolymer (X) is preferably 5,000 g / mol or more, more preferably 10,000 g / mol or more, still more preferably 15.
  • the weight average molecular weight and the number average molecular weight can be adjusted by the amount of the polymerization initiator and / or the chain transfer agent at the time of polymerization.
  • the molecular weights (weight average molecular weight and number average molecular weight) of these ethylene- (meth) acrylic acid ester copolymers (X) are column ( three series of TSKgel GMH HR- H (20) HT) and 1,2, It can be measured in terms of polystyrene using a 4-trichlorobenzene solvent at a column temperature of 140 ° C.
  • the degree of branching of the ethylene- (meth) acrylic acid ester copolymer (X) per 1000 carbons is not particularly limited, and is preferably 5 to 30, more preferably 6 to 20.
  • the degree of bifurcation can be adjusted by the polymerization temperature when the copolymer (X) is polymerized.
  • the degree of branching can be measured by the inverse gate decoupling method of 13 C-NMR in which the ethylene- (meth) acrylic acid ester copolymer (X) is dissolved in deuterated orthodichlorobenzene.
  • Examples of the alkali used for the saponification reaction in the above methods (1) and (2) include strong bases such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and the solubility in the solvent used for the saponification reaction and From the viewpoint of economy, sodium hydroxide and potassium hydroxide are preferable.
  • Examples of the solvent used in the saponification reaction include ethers such as tetrahydrofuran and dioxane; halogen-containing solvents such as chloroform and dichlorobenzene; ketones having 6 or more carbon atoms such as methylbutyl ketone; hydrocarbon compounds and methanol, ethanol, etc.
  • Examples thereof include a mixed solvent with alcohols such as 1-propanol, 2-propanol and 1-butanol; an aromatic compound such as benzene, toluene, xylene and ethylbenzene; and a mixed solvent between an aromatic compound and alcohols. These solvents may be used alone or in combination of two or more.
  • preferable solvents are mixed solvents of hydrocarbon compounds and alcohols, mixed solvents of aromatic compounds and alcohols, and more preferable solvents are toluene and the like. It is a mixed solvent of an aromatic compound and alcohols such as methanol.
  • the ratio of the hydrocarbon compound or aromatic compound to the alcohol in the mixed solvent may be appropriately selected according to the type of each solvent used. For example, the mass ratio of the hydrocarbon compound or aromatic compound to the alcohol (carbonation). Hydrocarbon compounds or aromatic compounds / alcohols) may be 50/50 to 90/10.
  • the temperature at which the saponification reaction is carried out is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and further, from the viewpoint of its reactivity and solubility of the ethylene- (meth) acrylic acid ester copolymer (X). It is preferably 70 ° C. or higher, particularly preferably 80 ° C. or higher.
  • the upper limit of the temperature is not particularly limited as long as it is lower than the temperature at which the ethylene- (meth) acrylic acid ester copolymer (X) is decomposed, and is, for example, 300 ° C. or lower.
  • the saponification reaction may be carried out in air or in an inert gas such as nitrogen gas or argon gas. Further, the saponification reaction may be carried out under normal pressure, pressure, or reduced pressure, and is preferably carried out under pressure.
  • Examples of the acid used for demetallization in the above methods (1) and (2) include strong acids such as hydrochloric acid, nitric acid, sulfuric acid, and toluenesulfonic acid. From the viewpoint of easily removing salts from the ionomer resin after demetallization, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid are preferable.
  • the solvent used for the demetallization the same solvent as the solvent used for the saponification reaction can be selected.
  • the temperature at the time of demetallizing is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 40 ° C. or higher, and preferably 100 ° C. or lower, from the viewpoint of easily lowering the viscosity of the reaction solution. It is more preferably 80 ° C. or lower, still more preferably 60 ° C. or lower.
  • the demetallization may be performed in air or in an inert gas such as nitrogen gas or argon gas. Further, the saponification reaction may be carried out under normal pressure, pressure, or reduced pressure, and is preferably carried out under pressure.
  • the neutralizing agent used when a part of the (meth) acrylic acid unit is neutralized and converted into the (meth) acrylic acid neutralized product unit is an ionic compound containing a metal ion.
  • the metal ions include alkali metal ions such as lithium, potassium and sodium, alkaline earth metal ions such as magnesium and calcium, transition metal ions such as zinc, nickel, iron and titanium, and aluminum ions.
  • the neutralizing agent include sodium hydroxide and the like.
  • the crude ionomer resin obtained in step i contains (meth) acrylic acid unit (A), (meth) acrylic acid neutralized product unit (B) and ethylene unit (C), and the unit (A) and the unit ( The total content of B) is 6 to 10 mol% based on all the monomer units constituting the crude ionomer resin.
  • the crude ionomer resin preferably contains a (meth) acrylic acid ester unit (D) in addition to the unit (A), the unit (B) and the unit (C), and the crude ionomer resin preferably contains the crude ionomer resin.
  • the total content of the unit (A), the unit (B) and the unit (D) is the total monomer unit constituting the crude ionomer resin. As a reference, it is preferably 6 to 10 mol%.
  • the crude ionomer resin further comprises a carboxylic acid other than the (meth) acrylic acid unit. It may contain other monomer units such as a carboxylic acid neutralized product unit (B2) other than the acid unit (A2) and the (meth) acrylic acid neutralized product unit.
  • Examples of the unit (A) and the unit (B) in the crude ionomer resin, and the unit (D) which may be contained in some cases, and other monomer units (A2) and (B2) are as follows.
  • the unit (A), unit (B), unit (D), unit (A2) and unit (B2) contained in the ionomer resin of the present invention include the same units as those described above, and preferred forms are also the above-mentioned ionomer. Similar to resin.
  • the total content of the unit (D) is the same as for the ionomer resin of the present invention, including the above-mentioned content and the preferable form.
  • the crude ionomer resin solution can be prepared by dissolving the crude ionomer resin obtained in step i in a solvent, and the reaction solution of the crude ionomer resin obtained in step i may be used as the crude ionomer resin solution.
  • the solvent in the solution of the crude ionomer resin is not particularly limited as long as it is a solvent capable of dissolving the crude ionomer resin, and examples thereof include the same solvent as the solvent used in the saponification reaction. Among them, a mixed solvent of an aromatic compound such as toluene and an alcohol such as methanol is preferable from the viewpoint of solubility of the crude ionomer resin.
  • the ratio of the aromatic compound to the alcohols in the mixed solvent may be appropriately selected according to the type of each solvent used. For example, the mass ratio of the aromatic compound to the alcohols (aromatic compound / alcohols) may be selected. , 50/50 to 90/10, preferably 65/35 to 85/15.
  • the concentration of the solution of the crude ionomer resin it is easy to obtain a granular resin having a small particle size, and as a result, it is easy to adjust the salt content in the ionomer resin within the range of 1 to 400 mg / kg, and the heat-resistant decomposition of the ionomer resin is easy. From the viewpoint of easily improving the properties, it is preferably 30% by mass or less, more preferably 15% by mass or less, and preferably 1% by mass or more, more preferably 5% by mass or more.
  • the temperature of the solution of the crude ionomer resin makes it easy to suppress the aggregation or sticking of the precipitated granular resin, the salt content in the ionomer resin can be easily adjusted within the range of 1 to 400 mg / kg, and the thermal degradability of the ionomer resin.
  • the temperature is preferably equal to or lower than the melting point of the ionomer resin, more preferably 60 ° C. or lower, still more preferably 50 ° C. or lower.
  • the temperature is more preferably 25 ° C. or higher, still more preferably 30 ° C. or higher.
  • the poor solvent to be added to the crude ionomer resin solution is not particularly limited as long as it is a solvent that is mixed with the crude ionomer resin solution and does not dissolve the ionomer resin.
  • methanol, ethanol, 1-propanol, 2-propanol, etc. Alcohols such as 1-butanol; water; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; hydrocarbons such as n-hexane, cyclohexane and heptane. Examples include compounds.
  • the poor solvent is preferably methanol, 2-propanol or the like from the viewpoint that the ionomer resin is easily dried because of its low boiling point and the salt in the granular resin is easily removed because the salt can be dissolved.
  • the amount of the poor solvent added may be appropriately selected according to the concentration of the crude ionomer resin solution.
  • the amount of the poor solvent added is preferably 30 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 100 parts by mass or more, based on 100 parts by mass of the solution of the crude ionomer resin.
  • the upper limit of the amount of the poor solvent added is not particularly limited, and is usually 1000 parts by mass or less with respect to 100 parts by mass of the solution of the crude ionomer resin.
  • the method of adding the poor solvent to the solution of the crude ionomer resin is not particularly limited.
  • the poor solvent may be added to the solution of the crude ionomer resin at one time, or may be added in a plurality of times by dropping or the like.
  • Good From the viewpoint that the particle size of the granular resin tends to be small, thereby improving the removability of salts in the granular resin, and as a result, the transparency of the ionomer resin tends to be improved, the addition of the poor solvent is relatively short. It is preferable to carry out with, and it is more preferable to add at once. When the poor solvent is added in a plurality of times, it is preferable to complete the addition of the poor solvent within 1 hour, more preferably within 30 minutes, and even more preferably within 10 minutes.
  • the stirring speed is not particularly limited, but the faster the stirring speed, the easier it is to obtain a granular resin having a small particle size.
  • the stirring time is not particularly limited, and for example, the mixture may be stirred until the granular resin is precipitated and the mixed solution of the crude ionomer resin solution and the poor solvent becomes a slurry. Specifically, it is preferably 1 second or longer. It is 3 hours or less, more preferably 10 seconds or more and 1 hour or less, and further preferably 1 minute or more and 30 minutes or less.
  • the peak top particle size of the granular resin deposited by adding a poor solvent to the solution of the crude ionomer resin makes it easier to reduce the salt content in the granular resin by increasing the specific surface area of the granular resin, and as a result.
  • the salt content can be easily adjusted within the range of 1 to 400 mg / kg and the thermal decomposition property of the ionomer resin can be easily improved, 700 ⁇ m or less, preferably 650 ⁇ m or less, more preferably 600 ⁇ m or less, still more preferably. It is 550 ⁇ m or less.
  • it is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, and preferably 80 ⁇ m or more.
  • the peak top particle size of the granular resin precipitated by adding a poor solvent to the crude ionomer resin solution can be adjusted by adjusting the concentration and temperature of the crude ionomer resin solution. Specifically, lowering the concentration and / or temperature of the crude ionomer resin solution can reduce the peak top particle size of the precipitated granular resin, and increasing the concentration and / or temperature of the crude ionomer resin solution causes precipitation.
  • the peak top particle size of the granular resin can be increased.
  • the peak top particle size of the granular resin can also be adjusted by the method of adding the poor solvent and the stirring speed of the mixed solution of the crude ionomer resin solution and the poor solvent.
  • the cleaning liquid in step iii is not particularly limited as long as it is a solvent in which the ionomer resin is insoluble and the salt can be dissolved.
  • Examples of preferable cleaning solutions include alcohols such as methanol, ethanol, 1-propanol and 2-isopropanol; water; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; dimethyl ether, diethyl ether, tetrahydrofuran and the like. Ethers can be mentioned. These may be used alone or in combination of two or more.
  • alcohols, water, and a mixed solution thereof are preferable from the viewpoint of high salt solubility and easy removal of salts contained in the granular resin.
  • a more preferable cleaning solution is a mixed solution of water and alcohols.
  • Preferred alcohols are methanol, ethanol, and more preferably methanol because they are easy to dry and have high compatibility with water.
  • the ratio of water to alcohols (water / alcohols (mass%)) in the mixed solution of water and alcohols is preferably 20/80 to 8/20, more preferably 30/70 to 70/30. ..
  • a method of filtering the granular resin from the granular resin dispersion liquid in which the granular resin is precipitated in step ii, mixing the collected granular resin with the cleaning liquid, and then removing the liquid can be mentioned. More specifically, after mixing the granular resin collected from the granular resin dispersion and the cleaning liquid, the granular resin is collected from the cleaning liquid (hereinafter, also referred to as cleaning step (a)), and then the collected granules.
  • a method of cleaning by mixing the resin with a new cleaning liquid and then filtering out the granular resin from the cleaning liquid (hereinafter, also referred to as a cleaning step (b)) can be mentioned.
  • the cleaning of the granular resin is performed from the viewpoint that the content of the salt contained in the granular resin can be easily adjusted within the range of 1 to 400 mg / kg, the heat-resistant decomposition property of the ionomer resin can be easily improved, and the production efficiency of the ionomer resin is improved.
  • the amount of the cleaning liquid used per cleaning step may be appropriately selected according to the amount of granular resin to be cleaned.
  • the amount of the cleaning liquid used per cleaning step is preferably 100 parts by mass to 2000 parts by mass, more preferably 200 parts by mass to 1000 parts by mass, still more preferably, with respect to 100 parts by mass of the granular resin at the time of drying. Is 300 parts by mass to 700 parts by mass.
  • the ionomer resin obtained in step iii may be dried if necessary.
  • the drying temperature may be preferably lower than the melting point of the ionomer resin, more preferably 80 ° C or lower.
  • an additive may be added to the ionomer resin of the present invention to obtain a resin composition.
  • the resin composition of the present invention comprises the ionomer resin of the present invention and an additive.
  • additives that may be optionally added include UV absorbers, anti-aging agents, antioxidants, thermal deterioration inhibitors, light stabilizers, anti-sticking agents, lubricants, mold release agents, polymer processing aids, etc.
  • examples thereof include antistatic agents, flame retardant agents, dyes and pigments, organic pigments, matting agents, phosphors and the like.
  • ultraviolet absorbers ultraviolet absorbers, antioxidants, antioxidants, thermal deterioration inhibitors, light stabilizers, anti-sticking agents, lubricants, mold release agents, polymer processing aids, and organic dyes are preferable.
  • the additive When added, the additive may be used alone or in combination of two or more.
  • the ultraviolet absorber is a compound that has the ability to absorb ultraviolet rays, and is said to have the function of mainly converting light energy into heat energy.
  • Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These may be one kind alone or a combination of two or more kinds.
  • Benzotriazoles are preferable as UV absorbers because they have a high effect of suppressing deterioration of optical properties such as coloring due to UV exposure.
  • Examples of preferred benzotriazoles include 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name: TINUVIN329), 2 -(2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name: TINUVIN234), 2,2'-methylenebis [6- (2H) -Benzotriazole-2-yl) -4-t-octylphenol] (manufactured by ADEKA Co., Ltd .; trade name: Adecastab LA-31), 2- (5-octylthio-2H-benzotriazole-2-yl) -6- Examples thereof include
  • triazine UV absorbers examples include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA Co., Ltd .; trade name). : Adecastab LA-F70) and its relatives, hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; trade names: TINUVIN477 and TINUVIN460), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxy) Phenyl) -1,3,5-triazine and the like can be mentioned. These may be one kind alone or a combination of two or more kinds.
  • anti-aging agents examples include known materials. Specific examples of anti-aging agents include hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylphenol, 2,6-di (t-butyl) -4-methylphenol, mono (or di, or tri).
  • Phenolic compounds such as ( ⁇ -methylbenzyl) phenol; 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), Bisphenol compounds such as 4,4'-thiobis (3-methyl-6-t-butylphenol); benzimidazole compounds such as 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole; 6-ethoxy-1,2- Dihydro-2,2,4-trimethylquinolin, a reaction product of diphenylamine and acetone, amine-ketone compounds such as 2,2,4-trimethyl-1,2-dihydroquinolin polymer; N-phenyl-1-naphthylamine, Fragrances such as alkylated diphenylamine, octylated diphenylamine, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, p- (p- (
  • the antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen.
  • phosphorus-based antioxidants, hindered phenol-based antioxidants, thioether-based antioxidants and the like can be mentioned. These antioxidants may be used alone or in combination of two or more. Among them, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and a combination of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable, from the viewpoint of the effect of preventing deterioration of optical properties due to coloring. ..
  • the amount of the phosphorus-based antioxidant used is preferably 1: 5 to 2 in terms of mass ratio. 1, more preferably 1: 2 to 1: 1.
  • Examples of preferable phosphorus-based antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (manufactured by ADEKA Corporation; trade name: ADEKA STAB HP-10), Tris (2).
  • antioxidants examples include pentaerythrityl-tetrax [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name: IRGANOX1010). Examples thereof include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name: IRGANOX1076). These may be one kind alone or a combination of two or more kinds.
  • the heat deterioration inhibitor can prevent the heat deterioration of the resin by capturing the polymer radicals generated when exposed to high heat under a substantially oxygen-free state.
  • a preferable heat deterioration inhibitor 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name) : Smilizer GM), 2,4-di-t-amyl-6- (3', 5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl) phenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; Product name: Sumilyzer GS) and the like. These may be one kind alone or a combination of two or more kinds.
  • the light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light.
  • preferred light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. These may be one kind alone or a combination of two or more kinds.
  • anti-sticking agents include fatty acid salts or esters, polyhydric alcohol esters, inorganic salts, inorganic oxides, and particulate resins.
  • preferable anti-adhesion agents include calcium stearate, calcium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, silicon dioxide (manufactured by Evonik; trade name: Aerosil), particulate acrylic resin and the like. These may be one kind alone or a combination of two or more kinds.
  • lubricants include stearic acid, behenic acid, stearoamic acid, methylene bisstearoamide, hydroxystearic triglyceride, paraffin wax, ketone wax, octyl alcohol, hydrogenated oil and the like. These may be one kind alone or a combination of two or more kinds.
  • the release agent examples include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride. These may be one kind alone or a combination of two or more kinds.
  • polymer particles having a particle size of 0.05 to 0.5 ⁇ m which can be produced by an emulsion polymerization method, are usually used.
  • the polymer particles may be single-layer particles composed of polymers having a single composition ratio and a single extreme viscosity, or may be multilayer particles composed of two or more kinds of polymers having different composition ratios or ultimate viscosities. Good. These may be one kind alone or a combination of two or more kinds. Among these, particles having a two-layer structure having a polymer layer having a low ultimate viscosity in the inner layer and a polymer layer having a high ultimate viscosity of 5 dl / g or more in the outer layer are preferable.
  • the ultimate viscosity of the polymer processing aid is preferably 3 to 6 dl / g. If the ultimate viscosity is too small, the effect of improving moldability tends to be low, and if the ultimate viscosity is too large, the moldability of the copolymer tends to be deteriorated.
  • an organic dye a compound having a function of converting ultraviolet rays into visible light is preferably used.
  • the organic dye may be used alone or in combination of two or more.
  • fluorescent materials include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, fluorescent bleaching agents, and the like. These may be one kind alone or a combination of two or more kinds.
  • the contents of the various additives can be appropriately selected as long as the effects of the present invention are not impaired, and the total content of the various additives is preferable with respect to the total mass of the resin composition. Is 7% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less.
  • additives may be added at the time of producing the ionomer resin, may be added after the production of the ionomer resin, or may be added at the time of producing the resin sheet described later.
  • the ionomer resin of the present invention and the resin composition of the present invention may be in the form of pellets or the like in order to enhance convenience during storage, transportation, or molding.
  • the ionomer resin and the resin composition are pelletized, they can be obtained, for example, by cutting the strands obtained by the melt extrusion method.
  • the temperature of the resin or the resin composition at the time of melt extrusion in the case of pelleting by the melt extrusion method is preferably 150 ° C. or higher, more preferably 170 ° C. or higher from the viewpoint of easily stabilizing the discharge from the extruder. Further, the temperature is preferably 250 ° C. or lower, more preferably 230 ° C.
  • the ionomer resin of the present invention and the resin composition of the present invention have high heat-resistant decomposition properties, problems such as thermal decomposition of the ionomer resin to generate black foreign matter are unlikely to occur when pelletizing by the melt extrusion method in this way. ..
  • the present invention also includes a resin sheet having one or more layers containing the ionomer resin of the present invention.
  • the resin sheet of the present invention has one or more layers containing the ionomer resin of the present invention (hereinafter, also referred to as layer (x)).
  • the layer (x) is a layer containing the ionomer resin of the present invention and optionally additives.
  • the resin sheet of the present invention may be composed of only the layer (x), or may be a laminate containing at least one layer (x).
  • the laminate is not particularly limited, and examples thereof include a laminate containing two or more layers (x), a laminate including one or more layers (x), and one or more other layers. Be done.
  • the layer (x) or the other layer is a plurality of layers, the resin or the resin composition constituting each layer may be the same or different.
  • Examples of the other layer include a layer containing a known resin.
  • the resin include polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, and polyphenylensulfide among polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polytetrafluoroethylene, acrylic resin, polyamide, polyacetal, polycarbonate, and polyester.
  • Polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, liquid crystal polymer, polyimide, thermoplastic elastomer and the like can be used.
  • additives may also contain the above-mentioned additives, as well as plasticizers, anti-blocking agents, pigments, dyes, and heat-shielding materials (for example, inorganic heat-shielding fine particles or organic heat-shielding materials having infrared absorbing ability).
  • plasticizers for example, acrylic wax, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate,
  • the resin sheet of the present invention has a concavo-convex structure on the surface by a conventionally known method such as melt fracture or embossing. It is preferable to have.
  • a conventionally known method such as melt fracture or embossing.
  • melt fracture or embossing it is preferable to have.
  • shape of the melt fracture and the embossing conventionally known shapes may be appropriately selected.
  • the thickness of the layer (x) 1 layer in the resin sheet of the present invention is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, and particularly preferably 0.4 mm or more. Further, it is preferably 5 mm or less, more preferably 4 mm or less, still more preferably 2 mm or less, and particularly preferably 1 mm or less.
  • the layers (x) in the resin sheet are a plurality of layers, the thicknesses of the plurality of layers (x) in the resin sheet may be the same or different.
  • the thickness of the resin sheet of the present invention is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, still more preferably 0.4 mm or more, and particularly preferably 0.5 mm or more. Especially more preferably 0.6 mm or more, particularly more preferably 0.7 mm or more, particularly preferably 0.75 mm or more, and preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less, still more preferably. Is 5 mm or less, particularly preferably 4 mm or less, particularly more preferably 2 mm or less, and particularly preferably 1 mm or less.
  • the thickness of the resin sheet is measured using a conventionally known method, for example, a contact type or non-contact type thickness gauge.
  • the resin sheet may be rolled up in a roll shape or may be in a single-wafered state one by one.
  • the resin sheet of the present invention may have the same haze, water absorption haze, slow cooling haze, storage modulus and yellowness as the ionomer resin of the present invention.
  • the resin sheet of the present invention preferably has a low water content from the viewpoint of being difficult to foam when manufacturing laminated glass.
  • the water content of the resin sheet is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.02% by mass or less, and particularly preferably 0.01% by mass or less.
  • the content can be measured by a coulometric titration method.
  • the method for producing the resin sheet of the present invention is not particularly limited.
  • the layer (x) is formed by a known film forming method such as an extrusion method, a calendar method, a press method, a solution casting method, a melt casting method, or an inflation method. Can be manufactured.
  • the layer (x) may be used alone as a resin sheet. Further, if necessary, two or more layers (x) or one or more layers (x) and one or more other layers may be laminated by press molding or the like to form a laminated resin sheet.
  • Two or more layers (x), or one or more layers (x) and one or more other layers may be molded by a coextrusion method to form a laminated resin sheet.
  • the layer (x) or the other layer is a plurality of layers, the resin or the resin composition constituting each layer may be the same or different.
  • the resin temperature at the time of extrusion is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, from the viewpoint of easily stabilizing the discharge of the resin from the extruder and easily reducing mechanical troubles.
  • the resin temperature at the time of extrusion is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, from the viewpoint of easily reducing the decomposition of the resin and the deterioration of the resin due to the decomposition.
  • the resin sheet of the present invention can be suitably used as a laminated glass interlayer film (also simply referred to as an interlayer film). Therefore, the present invention includes a laminated glass interlayer film made of the resin sheet of the present invention.
  • the present invention also includes a laminated glass having two glass plates and a laminated glass interlayer film of the present invention arranged between the two glass plates. Since the laminated glass of the present invention has a laminated glass interlayer film made of the resin sheet, it can have excellent transparency.
  • Examples of the glass plate to be laminated with the interlayer film of the present invention include inorganic glass such as float plate glass, polished plate glass, template glass, meshed plate glass, and heat ray absorbing plate glass, as well as conventionally known organic materials such as polymethyl methacrylate and polycarbonate. Glass or the like can be used. These may be either colorless or colored. One of these may be used, or two or more thereof may be used in combination. Further, the thickness of one glass plate is preferably 100 mm or less, and the thickness of the two glass plates may be the same or different.
  • the laminated glass formed by sandwiching the resin sheet of the present invention between two sheets of glass can be produced by a conventionally known method.
  • a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, a method using a nip roll, and the like can be mentioned.
  • Laminated glass can be manufactured by laminating (layers, etc.).
  • a method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, which is a glass plate at 100 to 160 ° C. under a pressure of about 2 ⁇ 10 ⁇ 2 to 3 ⁇ 10 ⁇ 2 MPa.
  • Laminated glass can be produced by laminating an interlayer film and any layer.
  • a glass plate, an interlayer film and an arbitrary layer are laminated, degassed by a roll at a temperature equal to or lower than the flow start temperature of the interlayer film, and then pressure-bonded at a temperature closer to the flow start temperature.
  • a method of heating to 30 to 70 ° C. with an infrared heater or the like, degassing with a roll, further heating to 50 to 120 ° C., and then crimping with a roll can be mentioned.
  • the operating conditions of the autoclave process are appropriately selected depending on the thickness and composition of the laminated glass, and the pressure is, for example, 0.5 to 1.5 MPa. Underneath, it is preferable to treat at 100 to 160 ° C. for 0.5 to 3 hours.
  • the laminated glass of the present invention has excellent transparency.
  • the haze of the laminated glass when the sheet thickness of the interlayer film is 0.8 mm is preferably 1.0% or less, more preferably 0.8% or less, still more preferably 0.5. % Or less.
  • the haze of the laminated glass is measured using a haze meter in accordance with JIS K7136: 2000.
  • the laminated glass of the present invention is excellent in transparency even after being heated to 140 ° C. and then slowly cooled from 140 ° C. to 23 ° C. at a rate of 0.1 ° C./min.
  • a haze (slow cooling haze) after heating a laminated glass having a sheet thickness of 0.8 mm as an interlayer film to 140 ° C. and then slowly cooling from 140 ° C. to 23 ° C. at a rate of 0.1 ° C./min is preferable. Is 5.0% or less, more preferably 4.5% or less, still more preferably 4.0% or less, and particularly preferably 3.0% or less.
  • the smaller the haze the higher the transparency of the laminated glass. Therefore, the lower limit is not particularly limited and may be, for example, 0.01%.
  • the slow cooling haze is also measured using a haze meter in accordance with JIS K7136: 2000.
  • the laminated glass of the present invention is less colored and is preferably colorless as much as possible.
  • the yellowness (YI) of the laminated glass of the present invention is preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.5 or less, when the sheet thickness of the interlayer film is 0.8 mm. Particularly preferably, it is 1.0 or less.
  • the yellowness (YI) is measured according to JIS Z8722: 2009 using a color difference meter.
  • the adhesive strength between the laminated glass and the interlayer film of the present invention is measured by, for example, the compression shear strength test described in WO1999-058334.
  • the compressive shear strength is preferably 15 MPa or more, more preferably 20 MPa or more, and particularly preferably 25 MPa or more, from the viewpoint of easily increasing the adhesive force. Further, the compressive shear strength may be 50 MPa or less from the viewpoint of easily increasing the penetration resistance of the laminated glass.
  • the resin sheet having one or more layers containing the ionomer resin of the present invention is useful as a laminated glass interlayer film.
  • the laminated glass interlayer film is particularly preferable as an interlayer film for laminated glass for structural materials (for façade) because it is excellent in adhesiveness, transparency, and self-supporting property to a base material such as glass.
  • the laminated glass of the present invention is not limited to the interlayer film of the laminated glass for structural materials, and the laminated glass of the present invention is used for automobile front glass, automobile side glass, automobile sun roof, automobile rear glass, head-up display glass, outer wall and roof. It can be suitably used for laminated glass, panels, doors, windows, walls, roofs, sun roofs, sound insulation walls, display windows, balconies, handrail walls and other building materials, conference room partition glass members, solar panels and the like.
  • the ionomer resins obtained in Examples and Comparative Examples are each dissolved in a mixed solvent of dehydrated toluene / dehydrated acrylic acid (75/25% by mass), reacted at 100 ° C. for 2 hours, and then acetone / water (80/20).
  • the (meth) acrylic acid neutralized product unit (B) was converted to the (meth) acrylic acid unit (A) by reprecipitation in a mixed solvent of (% by mass).
  • the obtained resin was sufficiently washed with water, dried, and the following (1) to (3) were performed on the dried resin.
  • the components of the monomer units constituting the resin were analyzed by thermal decomposition GC-MS.
  • the acid value of the resin was measured according to JIS K0070: 1992.
  • Chloride ion or sulfate ion was quantified based on the peak area obtained by the measurement, and the amount of the chloride ion or sulfate ion was converted into the amount of sodium salt to determine the amount of residual inorganic salt.
  • Eluent A mixed solution of an aqueous sodium carbonate solution (0.6 mmol / L) and an aqueous sodium hydrogen carbonate solution (12 mmol / L); Flow velocity: 1.0 mL / min; Column temperature: 40 ° C; Column: IC-SA2 (250L x 4.0)
  • melt flow rates of the raw material resins used in Examples and Comparative Examples and the ionomer resins obtained in Examples and Comparative Examples were measured. Specifically, each resin is melted in a cylinder and extruded from a die having a nominal hole diameter of 2.095 mm installed at the bottom of the cylinder under a load condition of 190 ° C. and 2.16 kg, and the amount of resin extruded per 10 minutes. (G / 10 minutes) was measured.
  • thermostable decomposability of the ionomer resins obtained in Examples and Comparative Examples was evaluated according to JIS K7120: 1987. Specifically, using a differential thermogravimetric simultaneous measuring device TG-DTA7200 (manufactured by Hitachi High-Tech Science Co., Ltd.), each resin was heated at 20 ° C. under a nitrogen atmosphere with a heating rate of 10 ° C./min and a flow rate of 50 mL / min. The weight loss rate when heated to ⁇ 550 ° C. was measured. The 1% weight loss temperature (Td1), which is the temperature at which the weight loss rate becomes 1% based on the weight at 200 ° C., was used as an index of thermodegradability.
  • Td1 The 1% weight loss temperature
  • the haze of the water-absorbing sample is measured using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136: 2000. did.
  • the laminated glass obtained by the above method was heated to 140 ° C. and then slowly cooled to 23 ° C. at a rate of 0.1 ° C./min.
  • the haze of the laminated glass after the slow cooling operation was measured using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136: 2000.
  • Example 1 100 parts by mass of EMMA2 in Table 1 was introduced into a pressure-resistant container made of SUS, 233 parts by mass of toluene was added thereto, and the mixture was stirred at 60 ° C. under 0.02 MPa pressurization to dissolve EMMA2.
  • 96 parts by mass of a methanol solution of sodium hydroxide (20% by mass) was added, and the mixture was stirred at 100 ° C. for 4 hours to saponify EMMA2 to convert a part of methyl methacrylate into sodium methacrylate units. Converted. Then, after cooling this solution to 50 ° C., 83 parts by mass of hydrochloric acid (20% by mass) was added, and the mixture was stirred at 50 ° C.
  • a resin solution was obtained.
  • a mixed solvent of toluene / methanol (75/25% by mass) was added to the obtained crude ionomer resin solution so that the crude ionomer resin concentration was 10% by mass to dilute the solution.
  • the diluted solution of the obtained crude ionomer resin was adjusted to 34 ° C., and then 430 parts by mass of methanol at 34 ° C. was added to the diluted solution to 100 parts by mass of the crude ionomer resin solution to precipitate the granular resin. It was.
  • Example 2 Ionomer resin 2 was obtained in the same manner as in Example 1 except that EMMA3 was used instead of EMMA2 and the temperature of the diluted solution of crude ionomer resin and methanol was changed from 34 ° C. to 37 ° C. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 2.
  • Example 3 Ionomer resin 3 was obtained in the same manner as in Example 1 except that EMMA3 was used instead of EMMA2 and the temperature of the diluted solution of crude ionomer resin and methanol was changed from 34 ° C. to 40 ° C. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 3.
  • Example 4 The ionomer resin 4 was obtained in the same manner as in Example 3 except that 220 parts by mass of sulfuric acid (30% by mass) was added instead of hydrochloric acid. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 4.
  • Example 5 Example 1 except that EEA1 was used instead of EMMA2, the concentration of the diluted solution of crude ionomer resin was changed from 10% by mass to 6% by mass, and the temperature of the diluted solution of crude ionomer resin and methanol was changed from 34 ° C to 41 ° C.
  • the ionomer resin 5 was obtained in the same manner as in the above.
  • Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 5.
  • Example 6 Using EMMA1 instead of EMMA2, the amount of sodium hydroxide solution added in methanol (20% by mass) was changed from 96 parts by mass to 73 parts by mass, and the amount of hydrochloric acid (20% by mass) was changed from 83 parts by mass to 63 parts by mass.
  • the ionomer resin 6 was obtained in the same manner as in Example 1 except that the temperature of the diluted solution of the crude ionomer resin and the methanol was changed from 34 ° C. to 37 ° C. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 6.
  • Example 7 After obtaining the ionomer resin 3 in the same manner as in Example 3, 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethyl) with respect to 100 mass of the ionomer resin 3 Ionomer resin 7 was obtained by adding 0.1 parts by mass of butyl) phenol (manufactured by BASF; trade name: TINUVIN329) and melt-kneading. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 7.
  • Example 1 The ionomer resin 8 was obtained in the same manner as in Example 1 except that the temperature of the diluted solution of the crude ionomer resin and the methanol was changed from 34 ° C. to 43 ° C. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 8.
  • Example 2 The ionomer resin 9 was obtained in the same manner as in Example 1 except that the temperature of the diluted solution of the crude ionomer resin and the methanol was changed from 34 ° C. to 46 ° C. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 9.
  • Example 3 The ionomer resin 10 was prepared in the same manner as in Example 1 except that 220 parts by mass of sulfuric acid (30% by mass) was added instead of hydrochloric acid to change the temperature of the diluted solution of the crude ionomer resin and methanol from 34 ° C to 50 ° C. Obtained.
  • Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 10.
  • Granular resin is obtained by using EMMA3 instead of EMMA2 and reprecipitating the crude ionomer resin solution in a mixed solvent of 500 parts by mass of acetone / water (80/20% by mass) with respect to 100 parts by mass of the crude ionomer resin. Further, the ionomer resin 11 was obtained in the same manner as in Example 1 except that the obtained granular resin was washed three times with a mixed solvent of acetone / water (20/80 mass%). Table 2 shows the analysis results and evaluation results of the obtained ionomer resin 11.
  • the ionomer resins obtained in Examples 1 to 7 have a high 1% weight loss temperature (Td1), low water absorption haze and slow cooling haze, and high transparency. confirmed.
  • Td1 1% weight loss temperature
  • Comparative Examples 1 to 5 at least one of the 1% weight loss temperature, the water absorption haze and the slow cooling haze gave a poor result.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
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US17/786,568 US20230025550A1 (en) 2019-12-19 2020-12-07 Ionomer resin, resin sheet, and laminated glass
KR1020217032472A KR102353434B1 (ko) 2019-12-19 2020-12-07 아이오노머 수지, 수지 시트 및 접합 유리
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022071065A1 (https=) * 2020-09-29 2022-04-07
WO2022270545A1 (ja) * 2021-06-23 2022-12-29 株式会社クラレ アイオノマー樹脂組成物、樹脂シートおよび合わせガラス
WO2022270540A1 (ja) * 2021-06-23 2022-12-29 株式会社クラレ アイオノマー樹脂組成物を含んでなる層を有する樹脂シートおよび合わせガラス
WO2023008485A1 (ja) * 2021-07-28 2023-02-02 株式会社クラレ アイオノマー樹脂粒状物の製造方法
US12617885B2 (en) 2020-09-29 2026-05-05 Kuraray Europe Gmbh Ionomer resin, resin sheet, and laminated glass

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024094995A (ja) * 2022-12-28 2024-07-10 クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツング アイオノマー樹脂組成物、樹脂シートおよび合わせガラス
CN118772320A (zh) * 2023-04-07 2024-10-15 宁德时代新能源科技股份有限公司 无氟聚合物、其制备方法及应用、绝缘涂层及其制备方法、电池及用电装置
CN120137083A (zh) * 2025-04-15 2025-06-13 安徽亿年半导体有限公司 一种用于夹层玻璃的抗水解型EMAA-Na+共聚物的改性方法

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49121891A (https=) * 1973-03-28 1974-11-21
JPS6079015A (ja) * 1983-09-14 1985-05-04 Nippon Petrochem Co Ltd 変性エチレン共重合体の製造法
US4638034A (en) * 1985-06-24 1987-01-20 National Distillers And Chemical Corporation Preparation of ethylene-acrylic acid copolymer or salt thereof
JPS62195005A (ja) * 1985-11-21 1987-08-27 エ−・ツエ−・エルデ−ルヘミイ・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング アイオノマ−改質ポリエチレン、製造法及びフイルム材料としての使用
JPH02185504A (ja) * 1988-11-25 1990-07-19 Minnesota Mining & Mfg Co <3M> 写真材料
WO1999058334A2 (en) 1998-05-14 1999-11-18 E.I. Du Pont De Nemours And Company Glass laminates for threat resistant window systems
JP2000072879A (ja) * 1998-08-27 2000-03-07 Du Pont Mitsui Polychem Co Ltd 水性分散液及びその用途
US6432522B1 (en) 1999-02-20 2002-08-13 Saint-Gobain Vitrage Transparent acoustical and mechanical barrier
EP1235683B1 (de) 1999-10-25 2003-08-20 Ht Troplast Ag Verfahren und folie zur herstellung von verbundsicherheitsscheiben
JP2006233059A (ja) 2005-02-25 2006-09-07 Sumitomo Chemical Co Ltd エチレン共重合体樹脂の高圧重合方法
JP2007084743A (ja) 2005-09-26 2007-04-05 Sumitomo Chemical Co Ltd エチレン系重合体樹脂の高圧重合方法
JP2009518464A (ja) * 2005-11-30 2009-05-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 積層安全ガラスでの使用に適した熱可塑性樹脂組成物
US8399096B2 (en) 2008-10-31 2013-03-19 E I Du Pont De Nemours And Company High-clarity ionomer compositions and articles comprising the same
US20130274424A1 (en) 2010-12-22 2013-10-17 Basell Polyolefine Gmbh Process for monitoring the polymerization of ethylene or ethylene and comonomers in a tubular-reactor at high-pressures
JP2017519083A (ja) 2014-06-26 2017-07-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ エチレン酸コポリマー、それらのイオノマー、並びに包装用フィルムおよび射出成形品におけるそれらの使用
JP6542492B1 (ja) * 2018-11-13 2019-07-10 住友精化株式会社 高分子組成物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8871335B2 (en) * 2005-08-31 2014-10-28 Kuraray America Inc. Solar control laminate
JP2009541523A (ja) * 2006-06-20 2009-11-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 透明積層体での使用に適した熱可塑性樹脂組成物
EP2221322A4 (en) * 2007-12-07 2010-11-24 Mitsui Du Pont Polychemical IONOMER, THE IONOMIC RESIN COMPOSITION, UNCOVERED FILM, PLATE OR FORM BODY COMPOSITION AND LAMINATE WITH A LAYER OF THE UNCOVERED FOIL
US20090151772A1 (en) * 2007-12-14 2009-06-18 E.I. Du Pont De Nemours And Company Terionomer Films or Sheets and Solar Cell Modules Comprising the Same
WO2010053097A1 (ja) * 2008-11-05 2010-05-14 株式会社クラレ 成形品
KR101546874B1 (ko) * 2011-05-27 2015-08-24 듀폰-미츠이 폴리케미칼 가부시키가이샤 메타크릴계 수지 조성물 및 성형체
JP6079015B2 (ja) * 2012-07-11 2017-02-15 セイコーエプソン株式会社 印刷装置および印刷方法
CN107075005B (zh) * 2014-10-15 2020-07-10 日本聚乙烯株式会社 乙烯系离聚物的制造方法和乙烯系离聚物
US10427384B2 (en) * 2014-11-10 2019-10-01 Kuraray Co., Ltd. Interlayer film for laminated glass and laminated glass
EP3442794A1 (en) * 2016-04-16 2019-02-20 Kuraray Europe GmbH Method for improving manufacture of laminated glass
US10736212B2 (en) * 2016-05-20 2020-08-04 Ares Materials Inc. Substrates for stretchable electronics and method of manufacture

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49121891A (https=) * 1973-03-28 1974-11-21
JPS6079015A (ja) * 1983-09-14 1985-05-04 Nippon Petrochem Co Ltd 変性エチレン共重合体の製造法
US4638034A (en) * 1985-06-24 1987-01-20 National Distillers And Chemical Corporation Preparation of ethylene-acrylic acid copolymer or salt thereof
JPS62195005A (ja) * 1985-11-21 1987-08-27 エ−・ツエ−・エルデ−ルヘミイ・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング アイオノマ−改質ポリエチレン、製造法及びフイルム材料としての使用
JPH02185504A (ja) * 1988-11-25 1990-07-19 Minnesota Mining & Mfg Co <3M> 写真材料
WO1999058334A2 (en) 1998-05-14 1999-11-18 E.I. Du Pont De Nemours And Company Glass laminates for threat resistant window systems
JP2000072879A (ja) * 1998-08-27 2000-03-07 Du Pont Mitsui Polychem Co Ltd 水性分散液及びその用途
US6432522B1 (en) 1999-02-20 2002-08-13 Saint-Gobain Vitrage Transparent acoustical and mechanical barrier
EP1235683B1 (de) 1999-10-25 2003-08-20 Ht Troplast Ag Verfahren und folie zur herstellung von verbundsicherheitsscheiben
JP2006233059A (ja) 2005-02-25 2006-09-07 Sumitomo Chemical Co Ltd エチレン共重合体樹脂の高圧重合方法
JP2007084743A (ja) 2005-09-26 2007-04-05 Sumitomo Chemical Co Ltd エチレン系重合体樹脂の高圧重合方法
JP2009518464A (ja) * 2005-11-30 2009-05-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 積層安全ガラスでの使用に適した熱可塑性樹脂組成物
US8399096B2 (en) 2008-10-31 2013-03-19 E I Du Pont De Nemours And Company High-clarity ionomer compositions and articles comprising the same
US20130274424A1 (en) 2010-12-22 2013-10-17 Basell Polyolefine Gmbh Process for monitoring the polymerization of ethylene or ethylene and comonomers in a tubular-reactor at high-pressures
JP2017519083A (ja) 2014-06-26 2017-07-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ エチレン酸コポリマー、それらのイオノマー、並びに包装用フィルムおよび射出成形品におけるそれらの使用
JP6542492B1 (ja) * 2018-11-13 2019-07-10 住友精化株式会社 高分子組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4079699A4

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022071065A1 (https=) * 2020-09-29 2022-04-07
WO2022071065A1 (ja) * 2020-09-29 2022-04-07 株式会社クラレ アイオノマー樹脂、樹脂シートおよび合わせガラス
JP7186329B2 (ja) 2020-09-29 2022-12-08 株式会社クラレ アイオノマー樹脂、樹脂シートおよび合わせガラス
US12617885B2 (en) 2020-09-29 2026-05-05 Kuraray Europe Gmbh Ionomer resin, resin sheet, and laminated glass
WO2022270545A1 (ja) * 2021-06-23 2022-12-29 株式会社クラレ アイオノマー樹脂組成物、樹脂シートおよび合わせガラス
WO2022270540A1 (ja) * 2021-06-23 2022-12-29 株式会社クラレ アイオノマー樹脂組成物を含んでなる層を有する樹脂シートおよび合わせガラス
WO2023008485A1 (ja) * 2021-07-28 2023-02-02 株式会社クラレ アイオノマー樹脂粒状物の製造方法

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