WO2024143460A1 - 樹脂組成物、フィルム、積層体、合わせガラス用中間膜および合わせガラス - Google Patents

樹脂組成物、フィルム、積層体、合わせガラス用中間膜および合わせガラス Download PDF

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Publication number
WO2024143460A1
WO2024143460A1 PCT/JP2023/046896 JP2023046896W WO2024143460A1 WO 2024143460 A1 WO2024143460 A1 WO 2024143460A1 JP 2023046896 W JP2023046896 W JP 2023046896W WO 2024143460 A1 WO2024143460 A1 WO 2024143460A1
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Prior art keywords
mass
resin composition
multilayered
particles
film
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PCT/JP2023/046896
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English (en)
French (fr)
Japanese (ja)
Inventor
洵一郎 倉橋
展史 川北
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2024567925A priority Critical patent/JPWO2024143460A1/ja
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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
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters

Definitions

  • (meth)acrylic acid ester refers to either or both of a methacrylic acid ester and an acrylic acid ester. The same applies to "(meth)acrylate” and "(meth)acrylic resin”.
  • the average acetalization degree is more preferably 60 to 85 mol%, and from the viewpoint of water resistance, it is further preferably 65 to 80 mol%, and particularly preferably 67 to 75 mol%.
  • the above average acetalization degree is a value based on the vinyl acetal component in the polyvinyl acetal described below.
  • the reaction temperature of the acetalization reaction can be appropriately selected and is not particularly limited. However, in order to improve the corrosion resistance of the film obtained using this resin composition, from the viewpoint of producing a porous polyvinyl acetal that is easy to wash after the reaction, it is preferable to carry out the reaction at a relatively low temperature of 0 to 40°C until polyvinyl acetal particles are precipitated during the reaction, and more preferably at 5 to 20°C. If the reaction temperature is 40°C or lower, it is easy to prevent the polyvinyl acetal from fusing, and it is easy to produce a porous polyvinyl acetal. If the reaction temperature is 0°C or higher, it is preferable because the reaction system is easy to handle. In addition, after carrying out the reaction at a relatively low temperature of 0 to 40°C, the reaction temperature is preferably set to 50 to 80°C, and more preferably to 65 to 75°C, in order to drive the reaction and increase productivity.
  • the multilayered particles may be, for example, the following: two-layered polymer particles having a core (inner layer) of a crosslinked rubber polymer (I) and a shell (outermost layer) of a thermoplastic polymer (II); three-layered polymer particles having a core (inner layer) of a polymer (III) and a shell (outermost layer) of a crosslinked rubber polymer (I) and a thermoplastic polymer (II); four-layered polymer particles having a core (inner layer) of a crosslinked rubber polymer (I) and a first shell (inner layer) of a polymer (III) and a second shell (inner layer) of a crosslinked rubber polymer (I) and a shell (outermost layer) of a thermoplastic polymer (II).
  • particles having various laminated structures can be used as the multilayered particles, but among these, it is preferable to use a three-layered polymer particle as the multilayered particles from the viewpoint of impact resistance.
  • the crosslinked rubber polymer (I) preferably contains 2 to 30 mass %, more preferably 10 to 25 mass %, and even more preferably 15 to 20 mass % of structural units derived from a vinyl monomer (e.g., an aromatic vinyl monomer) relative to the total mass of the crosslinked rubber polymer (I).
  • a vinyl monomer e.g., an aromatic vinyl monomer
  • the method for producing the multilayered particles is not particularly limited, and can be a known method. However, from the viewpoint of particle size control, it is preferable to use an emulsion polymerization method. Specifically, a seed particle is obtained by emulsion polymerization of the monomers that make up the core (inner layer), and then, in the presence of this seed particle, the monomers that make up each layer are added successively, and polymerization is performed up to the outermost layer, thereby obtaining the multilayered particles.
  • the average number of repeating units of ethylene oxide units in the exemplary compounds of nonionic emulsifiers and nonionic and anionic emulsifiers is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less, in order to maintain the appropriate foaming properties of the emulsifiers.
  • the separation and acquisition of multilayered particles from the polymer latex obtained by emulsion polymerization can be performed by known methods such as salting-out coagulation, freeze-coagulation, and spray drying.
  • the salting-out coagulation and freeze-coagulation methods are preferred, and the freeze-coagulation method is more preferred, since impurities contained in the multilayered particles can be easily removed by washing with water.
  • the freeze-coagulation method does not use a flocculant, so a film with excellent water resistance is easily obtained.
  • the multilayered particles As aggregated particles of 1,000 ⁇ m or less, and more preferably as aggregated particles of 500 ⁇ m or less.
  • the form of the aggregated particles is not particularly limited, and may be, for example, a pellet-like state in which the outermost layers are fused together, or a powder or granular powder.
  • the dispersant used in the present resin composition is not particularly limited as long as it has the effect of suppressing the aggregation of multilayer structure particles.
  • examples of dispersants include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionomers; styrene-based resins such as polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; (meth)acrylic acid ester-based polymers such as polymethacrylate, polyacrylate, (meth)acrylate copolymer, and methyl methacrylate-styrene copolymer; polyethylene terephthalate, poly
  • the rubber include polyester resins such as butylene terephthalate; polyamides such as nylon 6, nylon 66,
  • a dispersant a polymer that has a solubility parameter close to that of the other components contained in the resin composition, i.e., polyvinyl acetal and multilayer structure particles, and a refractive index close to that of the other components (e.g., 1.45 to 1.55).
  • a polymer that can produce a film with excellent transparency and break resistance can be obtained.
  • the refractive index of polyvinyl butyral is 1.49.
  • polymers having such a refractive index include (meth)acrylic acid ester polymers such as polymethacrylate, polyacrylate, and (meth)acrylate copolymers.
  • the amount of the (meth)acrylic acid ester polymer in the resin composition can be appropriately set, but from the viewpoint of improving break resistance, it is preferable to contain 10 to 100 parts by mass of the (meth)acrylic acid ester polymer relative to 100 parts by mass of the multilayer structure particles.
  • an acrylic acid ester-methacrylic acid ester copolymer is particularly preferred.
  • the content of the acrylic acid ester unit in the copolymer is preferably 1% by mass or more and 20% by mass or less.
  • the content of the acrylic acid ester unit is more preferably 3% by mass or more and 15% by mass or less, and even more preferably 5% by mass or more and 10% by mass or less.
  • the number average molecular weight of the dispersant is preferably 10,000 to 500,000, more preferably 15,000 to 400,000, even more preferably 20,000 to 200,000, and particularly preferably 25,000 to 100,000. By having the number average molecular weight of the dispersant within the above range, suitable dispersibility can be easily achieved.
  • the form of the dispersant is not particularly limited, but from the viewpoint of mixing with the multilayer structure, it is preferably in the form of particles. More specifically, a particulate dispersant (e.g., acrylic dispersant copolymer particles) is mixed with multilayer structure particles (e.g., core-shell rubber (CS rubber)), and then kneaded with polyvinyl acetal, so that a resin composition with better dispersibility, low haze, and few defects can be easily obtained.
  • the average particle size of the dispersant is preferably 0.05 to 1 ⁇ m, more preferably 0.07 to 0.5 ⁇ m, and further preferably 0.1 to 0.3 ⁇ m. When a dispersant having an average particle size within such range is used, the dispersibility of the multilayer structure particles is further improved.
  • the method for producing the dispersant is not particularly limited and can be any known method, but emulsion polymerization is preferred, and for example, the same production method as for the multilayered particles can be used.
  • the present resin composition may contain various additives other than the above-mentioned components, such as polymer processing aids, ultraviolet absorbers, antioxidants, heat stabilizers, lubricants, antistatic agents, colorants, impact resistance aids, etc., as necessary, within the scope of the present disclosure. From the viewpoint of the mechanical properties and surface hardness of a film produced using the present resin composition, it is preferable that the amount of foaming agent, filler, matting agent, light diffusing agent, softener, and plasticizer added to the present resin composition is small (for example, 0.1 to 10% by mass in the resin composition).
  • composition of Resin Composition the blending ratio (mass ratio) of the polyvinyl acetal, the multilayered particles, and the dispersant is not particularly limited and can be appropriately set within a range that does not impair the properties of the polyvinyl acetal itself.
  • the preferred content ratio of each component please refer to the above explanation.
  • the method for preparing the resin composition is not particularly limited, and a known method can be appropriately used, but a method of melt-kneading and mixing each component is preferred.
  • the mixing operation can be performed using a known mixing or kneading device such as a kneader-ruder, an extruder, a mixing roll, or a Banbury mixer.
  • a twin-screw extruder it is preferable to use a twin-screw extruder.
  • the shear rate during melt-kneading is preferably 10 to 1,000/sec.
  • the temperature during mixing and kneading is usually 150 to 320°C, preferably 200 to 300°C.
  • the resin composition can be obtained, for example, in the form of pellets.
  • the mixture of multilayered particles and dispersant can be prepared by isolating the dispersions (emulsions) of the multilayered particles and dispersant separately by known separation and acquisition methods such as salting out coagulation, freeze coagulation, spray drying, etc., and then mixing them, or by mixing emulsions of the multilayered particles and dispersant together and then separating them by known separation and acquisition methods such as the above method.
  • the present resin composition can be prepared using a mixture prepared by either method, but the latter is more preferable.
  • the present resin composition it is preferable to include a step of melt-kneading the present resin composition, extruding it in a molten state from a T-die, and contacting both sides of the composition with a mirror-finished roll surface or a mirror-finished belt surface to mold it.
  • the present film produced using the present resin composition is excellent in transparency, load-bearing property, weather resistance, impact resistance, and corrosion resistance. Taking advantage of these excellent properties, the present film may be used alone or as each layer (inner layer or outermost layer) constituting the laminate or as a part of those layers.
  • the laminate according to the present disclosure (hereinafter also referred to as the present laminate) may include the present film, and its shape, configuration, use, etc. are not particularly limited.
  • the present laminate preferably has a thermoplastic resin layer together with the present film.
  • thermoplastic resin constituting the thermoplastic resin layer examples include polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, (meth)acrylic resin, ABS resin, ethylene-vinyl alcohol resin, polyvinyl butyral resin, polyvinyl acetal resin, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, and acrylic thermoplastic elastomer.
  • the resin composition can also be suitably used as an interlayer film for laminated glass.
  • an interlayer film for laminated glass can be produced by inserting and laminating a film made using the resin composition between two or more pieces of glass made of inorganic glass or organic glass.
  • Such an interlayer film for laminated glass can be suitably used for laminated glass in which at least a portion of the film is in contact with a functional material.
  • the functional material preferably contains a metal.
  • functional materials include heat sensors, light sensors, pressure sensors, thin-film capacitance sensors, liquid crystal display films, electrochromic functional films, heat-shielding materials, electroluminescent functional films, light-emitting diodes, cameras, IC tags, antennas, and electrodes and wiring for connecting them.
  • the film obtained in each example was cut into a size of 50 mm x 50 mm to prepare a test piece, and the haze (%) was measured at a temperature of 23°C by a method in accordance with JIS K 7136.
  • the haze value is preferably 5% or less.
  • Example 1 (Preparation of multi-layered particles) In a reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a monomer inlet tube and a reflux condenser, 1050 parts by mass of ion-exchanged water, 0.3 parts by mass of sodium polyoxyethylene tridecyl ether acetate and 0.7 parts by mass of sodium carbonate were charged, and the inside of the reactor was fully replaced with nitrogen gas. Then, the inside temperature was set to 80°C. 0.25 parts by mass of potassium persulfate was added thereto and stirred for 5 minutes.
  • the obtained latexes (A) and (B) were mixed to prepare a dispersion, which was then frozen and solidified. The mixture was then washed with water and dried to separate and obtain a mixed powder containing multilayered particles and copolymer particles.
  • the mixing ratio was 67 parts by mass of multilayered particles and 33 parts by mass of copolymer particles (dispersant).
  • the average particle size of the multilayered particles was 0.23 ⁇ m, and the average particle size of the copolymer particles was 0.13 ⁇ m.
  • the values were measured by the following method. That is, the films obtained in Examples 1 to 3 were placed in an impact tester (manufactured by Yasuda Seiki Seisakusho, product name: No. 181 Film Impact Tester) and the energy required to break the film was measured. The energy (J) was then divided by the film thickness (mm) to obtain the impact resistance performance (J/mm).
  • an impact tester manufactured by Yasuda Seiki Seisakusho, product name: No. 181 Film Impact Tester
  • a resin composition using polyvinyl acetal that can impart superior break resistance while maintaining the inherent transparency of the resin. Furthermore, it is possible to provide a film, a laminate, an interlayer film for laminated glass, and laminated glass that use the resin composition and have these properties.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Joining Of Glass To Other Materials (AREA)
PCT/JP2023/046896 2022-12-28 2023-12-27 樹脂組成物、フィルム、積層体、合わせガラス用中間膜および合わせガラス Ceased WO2024143460A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003040654A (ja) * 2001-07-30 2003-02-13 Kanegafuchi Chem Ind Co Ltd 合わせガラス用樹脂組成物
JP2009513725A (ja) * 2003-06-24 2009-04-02 ポリマーズ オーストラリア プロプライアタリー リミティド ナノ複合材料におけるアクリル系分散剤
JP2017165630A (ja) * 2016-03-17 2017-09-21 藤倉化成株式会社 セラミックグリーンシート成形用樹脂組成物およびセラミックグリーンシート成形用材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003040654A (ja) * 2001-07-30 2003-02-13 Kanegafuchi Chem Ind Co Ltd 合わせガラス用樹脂組成物
JP2009513725A (ja) * 2003-06-24 2009-04-02 ポリマーズ オーストラリア プロプライアタリー リミティド ナノ複合材料におけるアクリル系分散剤
JP2017165630A (ja) * 2016-03-17 2017-09-21 藤倉化成株式会社 セラミックグリーンシート成形用樹脂組成物およびセラミックグリーンシート成形用材料

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