WO2020158064A1 - Additif pour pmma et composition de résine de pmma - Google Patents

Additif pour pmma et composition de résine de pmma Download PDF

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Publication number
WO2020158064A1
WO2020158064A1 PCT/JP2019/041089 JP2019041089W WO2020158064A1 WO 2020158064 A1 WO2020158064 A1 WO 2020158064A1 JP 2019041089 W JP2019041089 W JP 2019041089W WO 2020158064 A1 WO2020158064 A1 WO 2020158064A1
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pmma
particles
additive
synthetic
resin composition
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PCT/JP2019/041089
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English (en)
Japanese (ja)
Inventor
将志 中村
林田　浩一
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神島化学工業株式会社
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Publication of WO2020158064A1 publication Critical patent/WO2020158064A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/26—Mordenite type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/50—Zeolites wherein inorganic bases or salts occlude channels in the lattice framework, e.g. sodalite, cancrinite, nosean, hauynite
    • C01B39/52—Sodalites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the present invention relates to an additive for PMMA containing, as a main component, synthetic analcime particles composed of synthetic analcime and/or its anhydride, and a PMMA resin composition containing the additive.
  • PMMA Polymethylmethacrylate
  • PMMA is a highly transparent plastic, is easy to polish, cut, and cut, and is a resin that does not easily deteriorate, so it is used in various applications that take advantage of its transparency.
  • the surface hardness is not sufficient as compared with glass or the like, and in applications such as automobile tail lamp covers, scratches due to car washing and the like pose a problem, which is a factor limiting applications.
  • an inorganic filler is often used, but depending on the chemical composition of the inorganic filler, the shape of the fine particles, and the agglomerated structure, the effect of improving the surface hardness and strength is not sufficient. There is a problem that it becomes sufficient, and transparency and durability are impaired.
  • the synthetic analcime particles themselves are known as described in Patent Documents 1 and 2, and for example, silica, caustic alkali, and aluminum hydroxide or aluminate are hydrothermally mixed at a ratio commensurate with the composition of the analcime. It is known that it can be produced by reacting (see Patent Document 1).
  • Patent Document 1 describes an antiblocking agent for films and the like
  • Patent Document 2 describes that it can be used as an antiblocking agent for various resin films.
  • synthetic analcime particles can be used as an additive, especially for PMMA.
  • an object of the present invention is to provide an additive for PMMA and a PMMA resin composition which, when added to PMMA, can sufficiently obtain the effect of improving the surface hardness and hardly impair transparency and durability.
  • the present inventor has used the synthetic analcime particles as an additive for PMMA, whereby the surface hardness of the obtained resin composition is sufficiently improved, and the transparency and durability are less likely to be impaired. This has led to the completion of the present invention.
  • the additive for PMMA of the present invention is an additive for PMMA used by being added to polymethylmethacrylate (PMMA), and contains synthetic analcime particles and/or synthetic analcime particles composed of an anhydride thereof as a main component. It is characterized by
  • the additive for PMMA of the present invention since it contains synthetic analcime particles composed of synthetic analcime and/or its anhydride as a main component, when used as an additive for PMMA, the refractive index of the particles is close to that of a resin. It is thought that transparency and durability are less likely to be impaired because of its high chemical stability. Further, it is considered that the particle shape and the agglomerated structure of the synthetic analcime particles also contribute to the improvement of the surface hardness and the maintenance of the transparency of the obtained resin composition.
  • the synthetic analcime particles have a volume-based cumulative 50% diameter (D50) of 1 to 200 ⁇ m in the particle size distribution obtained by a laser diffraction type particle size distribution analyzer.
  • the synthetic analcime particles have a particle size distribution index (D10) obtained by a ratio of a cumulative 10% diameter (D10) and a cumulative 50% diameter (D50) on a volume basis in a particle size distribution obtained by a laser diffraction type particle size distribution meter.
  • D10 particle size distribution index
  • D50 cumulative 50% diameter
  • the synthetic analcime particles are composed of primary particles of a dodecahedron.
  • the PMMA resin composition of the present invention is characterized by containing the above-mentioned PMMA additive and polymethylmethacrylate (PMMA).
  • PMMA resin composition of the present invention since it contains synthetic analcime particles as the main component, the refractive index of the particles is close to that of the resin and the chemical stability is high, so that it is difficult to impair transparency and durability. Conceivable. Further, it is considered that the particle shape and the agglomeration structure of the synthetic analcime particles also contribute to the improvement of the surface hardness of the obtained resin composition.
  • the molded product of the present invention is characterized by being formed by molding the above PMMA resin composition. According to the molded product of the present invention, the effect of improving the surface hardness is sufficiently obtained, and the transparency and durability are less likely to be impaired.
  • Example 1 is an SEM photograph of synthetic analcime particles obtained in Example 1 of the present invention.
  • 3 is a SEM photograph of synthetic analcime particles obtained in Example 2 of the present invention.
  • 3 is a powder X-ray diffraction pattern of the synthetic analcime particles obtained in Example 1 of the present invention.
  • the PMMA additive of the present invention is used by being added to polymethylmethacrylate (PMMA).
  • PMMA polymethylmethacrylate
  • the additive can be used for improving surface hardness, strength, and design. That is, the additive can be used as a surface hardness improving agent, a reinforcing material, a design improving agent, or the like.
  • the resin is whitened by the additive, it becomes difficult to obtain a design property such as deep natural stone. Therefore, it is desirable that the transparency is maintained in order to improve the design property.
  • the additive for PMMA of the present invention contains, as a main component, synthetic analcime particles and/or synthetic analcime particles composed of an anhydride thereof.
  • "Containing as a main component” means that it is usually contained in the additive in an amount of 80% by mass or more, preferably 90% by mass or more in the additive, and most preferably 100% by mass. ..
  • Other components include surface treatment agents for synthetic analcime particles, and other additives for resins.
  • “synthetic analcime particle” refers to a particle composed of synthetic analcime and/or an anhydride thereof, and the synthetic analcime is typically represented by a composition formula of NaAlSi 2 O 6 ⁇ H 2 O.
  • Synthetic analcime anhydrides are typically represented by the composition formula of NaAlSi 2 O 6 .
  • the synthetic analcime has a cubic crystal system, and the anhydrous synthetic analcime has a cubic crystal system.
  • the synthetic analcime particles are primary particles that are a tetrahedron, or the corners of a tetrahedron are It is preferably composed of curved primary particles.
  • the typical chemical composition of the synthetic analcime particles is as follows: SiO 2 49 to 59% by mass, Al 2 O 3 21 to 25% by mass, Na 2 O 12 to 14% by mass, H 2 O 7 to 10% by mass. % Is exemplified.
  • the cumulative 50% diameter (D50) on a volume basis in the particle size distribution obtained by a laser diffraction type particle size distribution analyzer for synthetic analcime particles has a sufficient effect of improving the surface hardness when added to PMMA, and improves transparency and durability.
  • the thickness is preferably 1 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, and further preferably 20 to 100 ⁇ m.
  • the cumulative 50% diameter (D50) is 20 to 100 ⁇ m.
  • Synthetic analcim particles have a cumulative 10% diameter (D10) from the viewpoint of improving the design and surface hardness of a molded article by reducing the particle aggregation while having a narrower particle size distribution by making the particle size distribution narrower.
  • the particle size distribution index (D10/D50) determined by the ratio with the cumulative 50% diameter (D50) is preferably 1.0 to 1.5, more preferably 1.0 to 1.4, It is more preferably 1.0 to 1.3.
  • the refractive index of synthetic analcim particles is usually 1.48 to 1.49, and PMMA resin (refractive index 1.49) has a similar refractive index, so transparency is maintained by mixing with such resin. It is possible to improve the design of the molded product.
  • the synthetic analcime particles may contain impurities depending on the production method and the like.
  • impurities such as iron, copper, manganese, chromium, cobalt, nickel and vanadium.
  • the content of these impurities is preferably 0.5 mass% or less in terms of metal.
  • the synthetic analcime particles in the present invention can be produced by a known method. For example, it can be produced by mixing a silica raw material, a caustic alkali, and an aluminum raw material in a ratio corresponding to the composition of analcime, and hydrothermally reacting them.
  • Mixing can be performed by, for example, a method of mixing the remaining raw materials with a caustic aqueous solution, or a method of previously mixing a silica raw material dissolved in a caustic aqueous solution and an aluminum raw material dissolved in a caustic aqueous solution. it can.
  • silica raw materials include amorphous silica powder, crystalline silica powder, colloidal silica, fumed silica, sodium silicate, phosphosilicate stone, cristobalite and colloidal silica.
  • caustic alkali examples include caustic soda (NaOH) and caustic potash (KOH).
  • concentration of caustic alkali in the caustic aqueous solution is preferably 0.1 M (mol/L) or more, more preferably 1 to 10 M, further preferably 2 to 5 M.
  • metal aluminum aluminum, aluminum oxide, aluminum hydroxide, aluminate, etc. may be mentioned.
  • the molar ratio adjusted during mixing is such that Na 2 O/SiO 2 is, for example, 0.5 to 5.0, preferably 0.7 to 3.0, and SiO 2 /Al 2 O 3 is, for example, 2 to 50. , Preferably 3 to 20, and H 2 O/Na 2 O is, for example, 20 to 500, preferably 50 to 200.
  • the molar ratio SiO 2 /Al 2 O 3 is preferably from 1 to 10, and more preferably from 3 to 6, in order to obtain synthetic analcime particles having a narrow particle size distribution.
  • each raw material is mixed to form a gel of alkali aluminosilicate, and the gel is homogenized by stirring and mixing, and then heated under normal pressure or hydrothermal conditions. By crystallizing under conditions, synthetic analcime particles can be obtained.
  • the hydrothermal treatment temperature is preferably 100 to 300°C, more preferably 150 to 250°C.
  • the hydrothermal treatment time depends on the hydrothermal treatment temperature, but is preferably 1 to 100 hours, more preferably 3 to 50 hours.
  • the hydrothermal treatment method is not particularly limited, but is usually performed in a heat resistant container such as an autoclave.
  • the pressure inside the container during the hydrothermal treatment is not particularly limited, but is preferably 0.1 to 5.0 MPa, more preferably 0.2 to 4.0 MPa. When the hydrothermal treatment pressure is within this range, crystal growth and average particle size can be controlled within an appropriate range.
  • the slurry obtained by the hydrothermal treatment is vacuum-filtered to separate into a solid (cake) containing the synthetic analcime particles and a filtrate, and sufficiently washed with 20 times or more of the solid content of water.
  • a solid (cake) containing the synthetic analcime particles and a filtrate
  • the solid matter after washing with water may be dried in an oven or the like at 100 to 150° C. for 1 to 24 hours, and if necessary, the solid matter after drying may be dry pulverized or classified to obtain desired synthetic analcime particles. it can.
  • the surface of the synthetic analcime particles can be subjected to a surface treatment if necessary, and for example, metal soap, resin acid soap, various resins or waxes, silane-based or titanium-based coupling agents, silica coating, etc. are used. Can be surface treated.
  • a known dry method or wet method can be applied to the surface treatment of the synthetic analcime particles using such a surface treatment agent.
  • the surface treatment agent may be added in a liquid, emulsion or solid state under stirring with a mixer such as a Henschel mixer, and the powder of the synthetic analcime particles may be sufficiently mixed with or without heating.
  • a powder of synthetic analcime particles is added to a non-aqueous solvent slurry with a surface treatment agent in a solution state or an emulsion state, and the mixture is mechanically mixed at a temperature of, for example, about 1 to 100° C., and thereafter dried by a non-aqueous method. The solvent may be removed.
  • the amount of the surface treatment agent added can be appropriately selected, but is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the synthetic analcime particles.
  • the surface treatment level tends to be non-uniform as compared with the wet method, so it is better to use a slightly larger amount than the wet method.
  • the surface-treated synthetic analcime particles can be washed with water, dehydrated, granulated, dried, crushed, and classified, if necessary.
  • the resin composition of the present invention contains the additive for PMMA described above and polymethylmethacrylate (PMMA).
  • the PMMA may be a homopolymer of methyl methacrylate or a copolymer obtained by copolymerizing methyl methacrylate with another monomer.
  • the copolymerization ratio of methyl methacrylate is preferably 50 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%.
  • the content of the methyl methacrylate homopolymer or copolymer is preferably 50% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass in the total resin.
  • alkyl methacrylate other than methyl methacrylate, alkyl acrylate, ester of methacrylic acid and phenol, ester of methacrylic acid and aromatic alcohol, aromatic vinyl monomer, vinyl cyanide
  • system monomers and conjugated diene monomers include system monomers and conjugated diene monomers.
  • polymers to be blended include, for example, acrylic resins, ABS (acrylonitrile-butadiene-styrene copolymer) resins, polyethylene resins (linear polyethylene, low density polyethylene, high density polyethylene), polypropylene resins.
  • Resin (homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, copolymer of propylene and other small amount of ⁇ -olefin), ethylene- ⁇ -olefin copolymer, ethylene-vinyl acetate copolymer
  • examples thereof include polymers, polystyrene resins, polybutadiene resins, isoprene resins, polyolefins such as ethylene-propylene rubber and ethylene-propylene rubber.
  • acrylic resins and the like are preferable from the viewpoint of compatibility with PMMA.
  • the content of synthetic analcime particles is adjusted according to the function as an additive.
  • the synthetic analcime particles are added in an amount of 0.1 to 200 parts by mass per 100 parts by mass of the resin. It is preferably contained, more preferably 1 to 150 parts by mass, further preferably 5 to 100 parts by mass.
  • additives may be added to the above resin composition in addition to the above components as long as the effects of the present invention are not impaired.
  • additives include antioxidants, antistatic agents, pigments, foaming agents, plasticizers, fillers, reinforcing agents, flame retardants, crosslinking agents, light stabilizers, ultraviolet absorbers, lubricants, lubricants, Antiaging agents, weathering agents, coloring agents, curing accelerators and the like can be mentioned. You may mix
  • the amount of the other additives to be added is not particularly limited from the viewpoint that the effects of the present invention are not impaired, but it is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin.
  • the mixing and filling of the synthetic anal-sime particles and the resin and the like can be obtained by a known kneading method or filling method. , Orbital rotation type kneader, etc. It is also possible to carry out kneading while removing bubbles in the resin composition by using a device having a defoaming effect.
  • the molded body contains the resin composition.
  • a molded article can be obtained by a known molding method after blending a predetermined amount of synthetic analcime particles and the like with a resin to form a resin composition.
  • a molding method an extrusion molding machine, an injection molding machine, a blow molding machine, a press molding machine, a calender molding machine, etc., a lamination molding, a doctor blade method and the like can be used.
  • the molded product of this embodiment can be used in various forms such as a film form, a sheet form, a plate form, a lump form, and a special form according to various applications.
  • the molded product is formed of a resin composition containing synthetic analcime particles, it can be suitably applied to applications requiring surface hardness, transparency, heat resistance, water resistance and the like.
  • the use of the molded product is not particularly limited, and examples thereof include bathtubs, washbasins, sinks, decorative boards, decorative plates, decorative films, automobile lamp covers, automobile lamp lenses, and the like.
  • FIG. 1 shows a SEM photograph of the analcime particles obtained in Example 1
  • FIG. 2 shows a SEM photograph of the analcime particles obtained in Example 2.
  • PMMA polymethylmethacrylate resin
  • Labo Plastomill manufactured by Toyo Seiki
  • the kneaded product obtained by melt-kneading at 220° C. for 5 minutes was put in a mold having a space of 125 mm in length ⁇ 13 mm in width ⁇ 3 mm in thickness and press-molded at 220° C. to obtain a molded body of 125 mm in length ⁇ 13 mm in width ⁇ 3 mm in thickness. Created.
  • a molded body prepared in the same manner without containing particles was also evaluated.
  • the pencil hardness was measured by the method according to JIS K5400. At that time, a pencil was set at 45 degrees on the wheeled block, and measurement was performed with a tip load of 750 g.
  • Bending strength was measured based on JIS K7171 using a test piece punched from this molded body into a strip shape (13 mm x 120 mm).
  • the designability was evaluated by confirming the transparency using the molded bodies having different particle contents. To check the transparency, place the molded object on the paper on which the characters (line thickness 0.5 mm, size 5 mm x 5 mm) are printed, and if the characters below can be identified, the character can be seen. When the distinction was difficult, it was marked with ⁇ , and when it was not visible at all, it was marked with x. In the case of ⁇ , it was judged that there was a design property.
  • the container is left to cool to room temperature, the semi-solid slurry obtained after the reaction is taken out, vacuum filtered with a Nutsche, and sufficiently washed with 20 times or more the volume of water relative to the solid content, and 120° C. And dried in a dryer for 10 hours to obtain analcime particles.
  • Example 2 (Analsime medium particle size product)
  • colloidal silica Snowtex O manufactured by Nissan Kagaku Co., Ltd.
  • This particle has a cumulative 50% diameter (D50) of 68.5 ⁇ m and a particle size distribution index (D10/D50) of 1.3, and as shown in FIG. The particles were of uniform shape.
  • Example 3 (Analsime large particle size product)
  • 5.0 g of crystalline silica manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent
  • 5.0 g of amorphous silica in terms of solid content the charge molar ratio was SiO.sub.2).
  • 2 /Al 2 O 3 3.1
  • analcime particles were obtained under the same conditions as in Example 1.
  • These particles have a cumulative 50% diameter (D50) of 122.3 ⁇ m and a particle size distribution index (D10/D50) of 1.4, and, as in Example 1, are particles of uniform shape composed of primary particles of a dodecahedron. Met.
  • the container is allowed to cool to room temperature, the semi-solid slurry obtained after the reaction is taken out, vacuum filtered with a Nutsche, and sufficiently washed with 20 times or more the volume of water relative to the solid content, and at 120°C. It was dried in a dryer for 10 hours to obtain Thaichite particles having a cumulative 50% diameter (D50) of 3.2 ⁇ m.
  • Table 1 shows the results of the above-mentioned evaluations using the particles obtained in the above Examples and Comparative Examples.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne : un additif pour PMMA qui n'est pas sujet à compromettre la transparence ou la durabilité, et qui produit une amélioration adéquate de la dureté de surface lorsqu'il est ajouté au PMMA ; et une composition de résine de PMMA.　La présente invention concerne : un additif pour polyméthacrylate de méthyle (PMMA), utilisé en étant ajouté au polyméthacrylate de méthyle, l'additif pour PMMA contenant, en tant que composant principal, des particules d'analcime synthétiques comprenant un analcime synthétique et/ou un anhydride de celui-ci ; une composition de résine de PMMA contenant l'additif et le polyméthacrylate de méthyle (PMMA) ; et un article moulé obtenu par moulage de la composition de résine de PMMA.
PCT/JP2019/041089 2019-01-29 2019-10-18 Additif pour pmma et composition de résine de pmma WO2020158064A1 (fr)

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JP2019-013249 2019-01-29
JP2019013249A JP7155029B2 (ja) 2019-01-29 2019-01-29 Ｐｍｍａ用添加剤、及びｐｍｍａ樹脂組成物

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5090343A (fr) * 1973-12-10 1975-07-19
JP2512324B2 (ja) * 1988-11-24 1996-07-03 株式会社ジーシーデンタルプロダクツ 歯科用樹脂組成物
JP2014031409A (ja) * 2012-08-02 2014-02-20 Sharp Corp 熱可塑性樹脂組成物およびその成形体
CN109111672A (zh) * 2018-06-27 2019-01-01 武汉工程大学 一种丙烯酸酯接枝改性沸石耐高温复合材料及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE511897C2 (sv) * 1998-04-23 1999-12-13 Erik Danielsson Bjälklagselement

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5090343A (fr) * 1973-12-10 1975-07-19
JP2512324B2 (ja) * 1988-11-24 1996-07-03 株式会社ジーシーデンタルプロダクツ 歯科用樹脂組成物
JP2014031409A (ja) * 2012-08-02 2014-02-20 Sharp Corp 熱可塑性樹脂組成物およびその成形体
CN109111672A (zh) * 2018-06-27 2019-01-01 武汉工程大学 一种丙烯酸酯接枝改性沸石耐高温复合材料及其制备方法

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