WO2016136460A1 - Particule de résine composite, particule expansible, particule expansée et moulage de celle-ci - Google Patents

Particule de résine composite, particule expansible, particule expansée et moulage de celle-ci Download PDF

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WO2016136460A1
WO2016136460A1 PCT/JP2016/053795 JP2016053795W WO2016136460A1 WO 2016136460 A1 WO2016136460 A1 WO 2016136460A1 JP 2016053795 W JP2016053795 W JP 2016053795W WO 2016136460 A1 WO2016136460 A1 WO 2016136460A1
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particles
mass
composite resin
resin
vinyl acetate
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PCT/JP2016/053795
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English (en)
Japanese (ja)
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慎悟 寺崎
直也 森島
誠一 森本
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積水化成品工業株式会社
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Priority to CN201680012358.3A priority Critical patent/CN107250184B/zh
Priority to KR1020177023504A priority patent/KR101996231B1/ko
Priority to JP2017502046A priority patent/JP6453995B2/ja
Publication of WO2016136460A1 publication Critical patent/WO2016136460A1/fr

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    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
    • C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
    • C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Definitions

  • the present invention relates to a polystyrene-based composite resin particle and its expandable particle, expanded particle, and expanded molded article.
  • a polystyrene-based composite resin particle capable of giving a foamed molded article excellent in impact resistance and slow flame retardancy without adding a flame retardant, and its foamable particles, foamed particles and foamed molded article. can do.
  • Foamed molded articles made of polystyrene resin are widely used as packaging materials and heat insulating materials because they have excellent buffering properties and heat insulating properties and are easy to mold.
  • the impact resistance and flexibility are insufficient, there is a problem that cracks and chips are likely to occur, and it is not suitable, for example, for packaging precision instrument products.
  • a foam-molded article made of polyolefin resin is excellent in impact resistance and flexibility, but requires a large facility for molding. Also, due to the nature of the resin, it must be transported from the raw material manufacturer to the molding processing manufacturer in the form of expanded particles. Therefore, bulky expanded particles are transported, and there is a problem that the manufacturing cost increases.
  • Patent Document 1 discloses a composite resin containing 20 to 50% by mass of an olefin resin (A) and 50 to 80% by mass of a styrene resin (B) (however, In the composite resin foamed particles including the olefin resin (A) and the styrene resin (B) as a base resin and containing a brominated flame retardant, the styrene resin (B)
  • the copolymer component includes one or more (meth) acrylic acid ester components (b1) selected from methacrylic acid alkyl ester components having 1 to 10 carbon atoms and acrylic acid alkyl esters components having 1 to 10 carbon atoms.
  • the content of the (meth) acrylic acid ester component (b1) in 100% by mass of the styrene resin (B) is 2 to 12% by mass, and the glass transition of the styrene resin (B).
  • Temperature (Tg) of a is 100 ⁇ 104 ° C.
  • the composite resin foamed particles is disclosed a 50% decomposition temperature of the brominated flame retardant is a 260 ⁇ 340 ° C.
  • the composite resin foamed particles have excellent mechanical properties without inhibiting the inherent heat resistance of the composite resin, while using the composite resin that is difficult to be flame retardant as the base resin. However, it is said that it can exhibit high flame retardancy.
  • Patent Document 2 JP-A-2014-237747 discloses a linear low-density polyethylene resin (A) and a polystyrene resin (B) obtained by impregnating and polymerizing the resin (A) with a styrene monomer.
  • the composite resin foam particles having a composite resin as a base resin contains 20 to 50% by mass of the resin (A) and 50 to 80% by mass of the resin (B) (provided that the resin (A) ) And the resin (B) are 100% by mass), the resin (A) forms a dispersed phase, and the resin (B) forms a continuous phase, the bulk density is 5 to 15 kg / m 3 , Composite resin foam particles having a closed cell ratio of 90% or more are disclosed.
  • Patent Document 1 describes that the composite resin foam particles preferably have an apparent density of 10 to 500 kg / m 3 , but in actuality, only the case where the expansion ratio is about 20 times is verified. It has only been done. Further, Patent Document 1 describes that the base resin of the composite resin contains 20 to 50% by mass of the olefin resin (A) and 50 to 80% by mass of the styrene resin (B). Actually, only when the mass ratio of resin (A) / resin (B) is 30/70 has been verified.
  • a foamed molded product of polyethylene resin particles obtained by modifying low density polyethylene resin (LDPE) with styrene is excellent in light weight, but has insufficient impact resistance and retarded flame retardancy, particularly retarded flame retardancy. Improvement of the property is desired. Therefore, the present invention provides a polystyrene-based composite resin particle capable of giving a foamed molded article excellent in impact resistance and retarding flame resistance without adding a flame retardant, and its foamable particles, foamed particles and foamed molded article. The task is to do.
  • LDPE low density polyethylene resin
  • LDPE low-density polyethylene resin
  • EVA ethylene-vinyl acetate copolymer
  • the polyethylene resin and the polystyrene resin are contained in a range of 50 to 20% by mass and 50 to 80% by mass, respectively, based on the total of these, and the polyethylene resin has a density of 910 to 930 kg. / M 3 low density polyethylene resin and ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 30% by mass in the range of 45 to 85% by mass and 15 to 55% by mass, respectively.
  • a composite resin particle that contains and is substantially free of brominated flame retardants.
  • grains containing said composite resin particle and a volatile foaming agent are provided. Furthermore, according to the present invention, there are provided expanded particles obtained by pre-expanding the expandable particles. Moreover, according to this invention, the foaming molding obtained by carrying out foam molding of said foaming particle is provided.
  • a polystyrene-based composite resin particle capable of giving a foamed molded article excellent in impact resistance and slow flame retardancy without adding a flame retardant, and its foamable particles, foamed particles and foamed molded article. can do.
  • Composite resin particles obtained by modifying low density polyethylene resin with styrene tend to be less combustible due to the molecular structure of polyethylene than composite resin particles obtained by modifying linear low density polyethylene resin with styrene.
  • the composite resin particles can satisfy the slow flame retardancy without adding a brominated flame retardant, and moreover, the foamed molded article has a foaming ratio of less than 49 kg / m 3 and a foaming ratio exceeding 20.4 times. Is also possible.
  • the composite resin particles of the present invention are (1) The polyethylene resin contains 3 to 10% by mass of vinyl acetate. (2) When about 1 g of the composite resin particles is treated with 100 ml of toluene at a temperature of 130 ° C., the gel fraction insoluble in toluene is 15 to 35% by mass. (3) The composite resin particles have an average particle diameter of 1.0 to 2.0 mm. The above excellent effect is further exhibited when at least one of the above conditions is satisfied. Furthermore, when the foamed molded product of the present invention has a density of less than 49 kg / m 3 , the above excellent effect is further exhibited.
  • Composite resin particles comprise a polyethylene resin and a polystyrene resin in the range of 50 to 20% by mass and 50 to 80% by mass, respectively, based on the total of these, However, a low-density polyethylene resin having a density of 910 to 930 kg / m 3 and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 30% by mass with respect to the total of 45 to 85% by mass and 15 to It is characterized by being contained in the range of 55% by mass and substantially not containing a brominated flame retardant.
  • substantially free of a brominated flame retardant means that no flame retardant, particularly a brominated flame retardant, is actively added in the production process of composite resin particles. However, flame retardant components derived from resin raw materials are excluded.
  • the conventional composite resin particles have a co-continuous structure region in which an amorphous polystyrene resin is dispersed in a polyethylene resin ( 1)
  • the composite resin particles of the present invention include a sea-island structure region in which polystyrene resin particles are dispersed in a polyethylene resin, and a co-continuous structure region in which amorphous polystyrene resin is dispersed in a polyethylene resin. Are mixed (see FIGS. 2 and 3).
  • the polystyrene resin constituting the composite resin particle of the present invention is not particularly limited as long as it is a resin mainly composed of a styrene monomer, and examples thereof include styrene or a styrene derivative alone or a copolymer.
  • examples of the styrene derivative include ⁇ -methylstyrene, vinyl toluene, chlorostyrene, ethyl styrene, isopropyl styrene, dimethyl styrene, bromostyrene, and the like. These styrenic monomers may be used alone or in combination.
  • the polystyrene resin may be a combination of a vinyl monomer copolymerizable with a styrene monomer.
  • the vinyl monomer include divinylbenzene such as o-divinylbenzene, m-divinylbenzene and p-divinylbenzene, alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate.
  • polyfunctional monomers such as (meth) acrylate; (meth) acrylonitrile, methyl (meth) acrylate, butyl (meth) acrylate and the like.
  • polyfunctional monomers are preferable, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 4 to 16 ethylene units, and divinylbenzene are more preferable, and divinylbenzene, ethylene glycol di ( Particularly preferred is (meth) acrylate.
  • the content is set so that it may become the quantity (for example, 50 mass% or more) which a styrene-type monomer becomes a main component.
  • “(meth) acryl” means “acryl” or “methacryl”.
  • the low density polyethylene resin constituting the composite resin particle of the present invention is not particularly limited as long as it is a polyethylene resin having a density of 910 to 930 kg / m 3 , and specifically, a commercial product as used in the examples. Is mentioned.
  • the LDPE used in the present invention refers to a polyethylene-based resin defined by a high pressure method low density polyethylene, a branched low density polyethylene, a long chain branched low density polyethylene, a radical polymerization polyethylene, and an ethylene low density polymer.
  • the linear low density polyethylene (LLDPE) not used in the present invention is a medium-low pressure method low density polyethylene, a linear low density polyethylene, a short chain branched low density polyethylene, an ion polymerization method polyethylene, an ethylene / ⁇ -olefin copolymer. It refers to a polyethylene-based resin defined as a polymer.
  • the ethylene-vinyl acetate copolymer constituting the composite resin particle of the present invention is not particularly limited as long as it is a copolymer of ethylene and vinyl acetate having a vinyl acetate content of 10 to 30% by mass. Is a commercially available product as used in the examples.
  • the vinyl acetate content is less than 10% by mass, when the vinyl acetate content of the final polyethylene resin (seed particles) is constant, the proportion of the ethylene-vinyl acetate copolymer kneaded with the low density polyethylene resin is large. turn into.
  • the heat resistance of the obtained foamed molded product may be lowered.
  • the vinyl acetate content exceeds 30% by mass
  • the vinyl acetate content of the final polyethylene resin (seed particles) is constant
  • the ethylene-vinyl acetate copolymer kneaded with the low density polyethylene resin The ratio will decrease. For this reason, the dispersibility of vinyl acetate in the final polyethylene resin (seed particles) is low, and the slow flame retardancy may be lowered.
  • the vinyl acetate content (% by mass) is, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30.
  • a preferable vinyl acetate content in the ethylene-vinyl acetate copolymer is 15 to 25% by mass.
  • the composite resin particles of the present invention contain a polyethylene resin and a polystyrene resin in the range of 50 to 20% by mass and 50 to 80% by mass, respectively, based on the total of these. If the polystyrene resin is less than 50% by mass in the mass ratio of the polyethylene resin and the polystyrene resin, foamability and moldability may be insufficient. On the other hand, if the polystyrene resin exceeds 80% by mass, the impact resistance and flexibility may be insufficient.
  • the mass ratio (mass%) of the polystyrene resin is, for example, 50, 55, 60, 62.5, 65, 67.5, 70, 72.5, 75, 80.
  • Preferred mass ratios of polyethylene resin and polystyrene resin are in the range of 40 to 25 mass% and 60 to 75 mass%.
  • the polyethylene resin of the composite resin particle of the present invention contains a low density polyethylene resin and an ethylene-vinyl acetate copolymer in a range of 45 to 85% by mass and 15 to 55% by mass, respectively, based on the total of these.
  • a low density polyethylene resin and an ethylene-vinyl acetate copolymer in a range of 45 to 85% by mass and 15 to 55% by mass, respectively, based on the total of these.
  • the mass ratio of the low density polyethylene resin and the ethylene-vinyl acetate copolymer when the ethylene-vinyl acetate copolymer is less than 15% by mass, the dispersibility of vinyl acetate in the final polyethylene resin (seed particles) is low, Delayed flammability may be reduced.
  • the mass ratio (% by mass) of the ethylene-vinyl acetate copolymer is, for example, 15, 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, 40, 42.5, 45, 47.5, 50, and 55.
  • Preferred mass ratios of the low density polyethylene resin and the ethylene-vinyl acetate copolymer are in the range of 50 to 80% by mass and 20 to 50% by mass.
  • the polyethylene resin preferably has a vinyl acetate content of 3 to 10% by mass.
  • the vinyl acetate content is less than 3% by mass, the obtained foamed molded article may have insufficient impact resistance and slow flame retardancy.
  • the vinyl acetate content exceeds 10% by mass, the obtained foamed molded article may have insufficient heat resistance.
  • the vinyl acetate content (% by mass) is, for example, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 and 10.
  • the preferable vinyl acetate content in the polyethylene resin is 4 to 8% by mass.
  • the composite resin particle of the present invention has a gel fraction insoluble in toluene boiling at 130 ° C. of 15 to 35% by mass. More specifically, about 1 g of the composite resin particle is added with 100 ml of 130 ° C. toluene. When treated, the gel fraction insoluble in toluene is preferably 15-35% by weight. Thereby, the impact resistance of the foaming molding shape
  • the gel fraction is, for example, 15, 16, 17, 18, 19, 20, 20.5, 21, 2, 1.5, 22, 22.5, 23, 23.5, 24, 24.5. 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 31, 32, 33, 34, 35.
  • a more preferable gel fraction is in the range of 20 to 30% by mass, and further preferably in the range of 25 to 30% by mass. The method for measuring the gel fraction will be described in detail in Examples.
  • the composite resin particles of the present invention preferably have an average particle size of 1.0 to 2.0 mm. If the average particle diameter of the composite resin particles is less than 1.0 mm, high foamability may not be obtained. On the other hand, when the average particle diameter of the composite resin particles exceeds 2.0 mm, the filling property of the foamed particles during molding may be insufficient.
  • the average particle diameter (mm) of the composite resin particles is, for example, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0. More preferably, the average particle diameter of the composite resin particles is 1.2 to 1.6 mm.
  • the composite resin particles of the present invention have a Z average molecular weight: Mz of about 600,000 to 1,000,000.
  • the Z average molecular weight ( ⁇ 10 3 ) of the composite resin particles is, for example, 600, 650, 700, 750, 800, 850, 900, 950, 1000.
  • the composite resin particles of the present invention have a weight average molecular weight: Mw of about 250,000 to 450,000.
  • the weight average molecular weight ( ⁇ 10 3 ) of the composite resin particles is, for example, 250, 300, 350, 400, 450.
  • the composite resin particles of the present invention are not particularly limited, but can be produced, for example, by a seed polymerization method (seed polymerization).
  • seed polymerization the composite resin particles can be generally obtained by allowing the seed particles to absorb the monomer and polymerizing the monomer after or while absorbing the monomer.
  • the foamed particles can be obtained by impregnating the composite resin particles with a foaming agent after polymerization or while polymerizing.
  • seed particles composed of the above-mentioned polyethylene-based resin are allowed to absorb the styrene-based monomer, and after the absorption or absorption, the styrene-based monomer is polymerized.
  • the styrenic monomer does not need to be supplied to the aqueous medium at the same time, and all or part of the monomer may be supplied to the aqueous medium at different timings.
  • the additive may be added to the styrene monomer or the aqueous medium, or may be included in the seed particles. The amount of monomer and resin is almost the same.
  • the polymerization of the styrene monomer can be carried out, for example, by heating at 60 to 150 ° C. for 2 to 40 hours. In the polymerization step, it is preferable to hold at the polymerization temperature for a long time, that is, to anneal. In the previous steps up to the annealing step, the styrene monomer and polymerization initiator absorbed in the seed particles have not completely completed the reaction, and there are not a few unreacted substances in the composite resin particles. is doing.
  • the mechanical properties and heat resistance of the foamed molded product are degraded due to the influence of low molecular weight unreacted materials such as styrene monomers. And odor caused by volatile unreacted materials becomes a problem. Therefore, by introducing an annealing step, it is possible to secure a time for the unreacted material to undergo a polymerization reaction, and to remove the remaining unreacted material so as not to affect the physical properties of the foam molded article.
  • the styrenic monomer include those exemplified in the section of composite resin particles, and the amount used is in the range described in the section of composite resin particles.
  • the seed particles are the above-described polyethylene-based resins, and include a low-density polyethylene-based resin and an ethylene-vinyl acetate copolymer having a specific mass ratio. Seed particles can be obtained, for example, by a method of mixing and melting and kneading these resins, extruding them into strands, and cutting them with a desired particle diameter.
  • the particle diameter of the core resin particles can be appropriately adjusted according to the average particle diameter of the composite resin particles, and the preferable particle diameter is in the range of 0.2 to 1.5 mm, and the average mass is 10 to 100 mg / 100 particles. It is.
  • examples of the shape include a true spherical shape, an elliptical spherical shape (egg shape), a cylindrical shape, and a prismatic shape.
  • aqueous medium examples include water and a mixed medium of water and a water-soluble solvent (for example, a lower alcohol such as methyl alcohol or ethyl alcohol).
  • a water-soluble solvent for example, a lower alcohol such as methyl alcohol or ethyl alcohol.
  • a dispersant In the aqueous medium, a dispersant may be used in order to stabilize the dispersibility of the styrene monomer droplets and seed particles.
  • a dispersant include organic dispersants such as partially saponified polyvinyl alcohol, polyacrylate, polyvinyl pyrrolidone, carboxymethyl cellulose, and methyl cellulose; magnesium pyrophosphate, calcium pyrophosphate, calcium phosphate, calcium carbonate, magnesium phosphate, Examples thereof include inorganic dispersants such as magnesium carbonate and magnesium oxide. Among these, an inorganic dispersant is preferable because a more stable dispersion state may be maintained.
  • a surfactant in combination. Examples of such surfactants include sodium dodecylbenzene sulfonate and sodium ⁇ -olefin sulfonate.
  • Styrene monomers are usually polymerized in the presence of a polymerization initiator.
  • the polymerization initiator is usually impregnated into the seed particles simultaneously with the styrene monomer.
  • the polymerization initiator is not particularly limited as long as it is conventionally used for the polymerization of styrene monomers.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is, for example, in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the styrene monomer.
  • the polymerization initiator is suspended or emulsified and dispersed in advance in the aqueous medium when the polymerization initiator is added to the aqueous medium. It is preferable to add to the dispersion liquid above, or to add the polymerization initiator to the aqueous medium after previously dissolving it in the styrene monomer.
  • a preferable addition amount of the polymerization initiator is 0.1 to 0.9 parts by mass per 100 parts by mass of the styrene monomer.
  • the addition amount of the polymerization initiator is less than 0.1 part by mass, the molecular weight becomes too high and foamability may be lowered.
  • the addition amount of the polymerization initiator exceeds 0.9 parts by mass, the polymerization rate may become too fast, and the dispersion state of the polystyrene resin particles in the polyolefin resin may not be controlled.
  • a preferable addition amount of the polymerization initiator is 0.2 to 0.5 parts by mass.
  • the composite resin particles have a plasticizer, a binding inhibitor, a bubble regulator, a crosslinking agent, a filler, a lubricant, a colorant, a fusion accelerator, an antistatic agent, and a spreading agent as long as the physical properties are not impaired. Additives such as may be added.
  • the composite resin particles may contain a flame retardant other than bromine flame retardant and a flame retardant aid within a range where physical properties are not impaired.
  • the composite resin particles can contain a plasticizer having a boiling point exceeding 200 ° C. under 1 atm in order to maintain good foam moldability even when the pressure of water vapor used at the time of heat foaming is low.
  • the plasticizer include glycerin fatty acid esters such as phthalic acid ester, glycerin diacetomonolaurate, glycerin tristearate and glycerin diacetomonostearate, adipic acid esters such as diisobutyl adipate, and plasticizers such as coconut oil.
  • the content of the plasticizer in the composite resin particles is preferably 0.1 to 3.0% by mass.
  • binding inhibitor examples include calcium carbonate, silica, zinc stearate, aluminum hydroxide, ethylene bis stearamide, tricalcium phosphate, and dimethyl silicon.
  • air conditioner examples include ethylene bis stearamide and polyethylene wax.
  • crosslinking agent examples include 2,2-di-t-butylperoxybutane, 2,2-bis (t-butylperoxy) butane, dicumyl peroxide, 2,5-dimethyl-2,5-di-t. -Organic peroxides such as butylperoxyhexane.
  • the filler examples include synthetic or naturally produced silicon dioxide.
  • the lubricant examples include paraffin wax and zinc stearate.
  • Colorants include furnace black, ketjen black, channel black, thermal black, acetylene black, carbon black such as graphite and carbon fiber, chromate such as yellow lead, zinc yellow and barium yellow, and ferrocyanides such as bitumen Sulfides such as cadmium yellow and cadmium red, oxides such as iron black and red husk, silicates such as ultramarine blue, inorganic pigments such as titanium oxide, monoazo pigments, disazo pigments, azo lakes, condensed azo pigments, chelate azos Organic pigments such as azo pigments such as pigments, polycyclic pigments such as phthalocyanine, anthraquinone, perylene, perinone, thioindigo, quinacridone, dioxazine, isoindolinone, quinophthalone, and the like can be mentioned.
  • Examples of the fusion accelerator include stearic acid, stearic acid triglyceride, hydroxystearic acid triglyceride, sorbitan stearate, and polyethylene wax.
  • Examples of the antistatic agent include polyoxyethylene alkylphenol ether, stearic acid monoglyceride, polyethylene glycol and the like.
  • Examples of the spreading agent include polybutene, polyethylene glycol, and silicone oil.
  • Expandable particles include composite resin particles and a volatile foaming agent, and can be produced by impregnating composite resin particles with a volatile foaming agent by a known method.
  • the temperature at which the composite resin particles are impregnated with the volatile foaming agent is low, it takes time for the impregnation, and the production efficiency of the expandable particles may be reduced. Since it may occur in a large amount, it is preferably 50 to 130 ° C, more preferably 60 to 100 ° C.
  • the volatile foaming agent is not particularly limited as long as it is conventionally used for foaming polystyrene-based resins.
  • isobutane, n-butane, isopentane, n-pentane, neopentane and the like having 5 or less carbon atoms are used.
  • volatile foaming agents such as aliphatic hydrocarbons, and butane-based foaming agents and pentane-based foaming agents are particularly preferable.
  • Pentane can also be expected to act as a plasticizer.
  • the content of the volatile blowing agent in the expandable particles is usually in the range of 5 to 13% by mass, preferably in the range of 8 to 12% by mass, and particularly preferably in the range of 9 to 11% by mass.
  • the content of the volatile foaming agent is small, for example, less than 5% by mass, it may not be possible to obtain a low-density foam molded article from the foamable particles, and the effect of increasing the secondary foaming power during in-mold foam molding Cannot be obtained, the appearance of the foamed molded product may deteriorate.
  • the content of the volatile foaming agent is large and exceeds 13% by mass, for example, the time required for the cooling step in the production process of the foamed molded article using the foamable particles becomes long and the productivity may be lowered.
  • the foamable particles can contain a foaming aid together with the foaming agent.
  • the foaming aid is not particularly limited as long as it is conventionally used for foaming polystyrene resins.
  • aromatic organic compounds such as styrene, toluene, ethylbenzene, xylene, cyclohexane, methylcyclohexane, etc.
  • solvents having a boiling point of 200 ° C. or less under 1 atm such as cycloaliphatic hydrocarbons, ethyl acetate, and butyl acetate.
  • the content of the foaming aid in the foamable particles is usually in the range of 0.3 to 2.5% by mass, and preferably in the range of 0.5 to 2% by mass.
  • the content of the foaming aid is small, for example, less than 0.3% by mass, the plasticizing effect of the polystyrene resin may not be exhibited.
  • the content of the foaming aid is large and exceeds 2.5% by mass, the foamed molded product obtained by foaming the foamable particles may be shrunk or melted to deteriorate the appearance, or foamable.
  • the time required for the cooling step in the production process of the foamed molded article using the particles may be long.
  • Expanded particles also referred to as “pre-expanded particles”
  • the foamed particles are obtained by pre-foaming the foamable particles to a predetermined bulk density by a known method, and examples thereof include batch-type foaming in which steam is introduced, continuous foaming, and release foaming under pressure.
  • the expandable particles of the present invention preferably have a bulk density in the range of 20 to 200 kg / m 3 .
  • the bulk density of the expandable particles is less than 20 kg / m 3 , the foamed molded product tends to shrink and the appearance may be impaired.
  • the bulk density of the expandable particles exceeds 200 kg / m 3 , the advantage of weight reduction as a foamed molded product may be impaired.
  • the density (kg / m 3 ) of the expanded particles is, for example, 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, 40, 42.5, 45, 48, 50, 75, 100, 125, 150, 175, 200.
  • a preferred bulk density of the expandable particles is in the range of 20 to 48 kg / m 3 .
  • air may be introduced simultaneously with steam when foaming as necessary.
  • the foam molded body is a known method, for example, the foam particles are filled in a mold of a foam molding machine and heated again to foam the foam particles, and the foam particles are thermally fused. Can be obtained.
  • the foamed molded article of the present invention preferably has a density in the range of 20 to 200 kg / m 3 . When the density of the foamed molded product is less than 20 kg / m 3 , the retarded flame resistance and impact resistance may not be sufficient. On the other hand, if the density of the foamed molded product exceeds 200 kg / m 3 , the weight mass of the foamed molded product increases and the transportation cost increases, which may not be preferable.
  • the density (kg / m 3 ) of the foamed molded product is, for example, 20, 22.5, 25, 27.5, 30, 32.5, 35, 37.5, 40, 42.5, 45, 48, 50. 75, 100, 125, 150, 175, 200.
  • the density of the preferred foamed molded product is in the range of 20 to 48 kg / m 3 .
  • ⁇ Vinyl acetate content of polyethylene resin particles (seed particles)> A 0.1-0.5 mg sample is precisely weighed and wrapped so as to be crimped to a ferromagnetic metal body (Pyrofoil: manufactured by Nippon Analytical Industrial Co., Ltd.) having a Curie point of 445 ° C., and Curie Point Pyrolyzer JPS-700 type (Japan) Acetic acid produced by decomposition in an analytical industry apparatus was measured using a gas chromatograph GC7820 (manufactured by Agilent Technologies) (detector: FID), and an absolute calibration curve prepared in advance using the peak area. calculate.
  • a gas chromatograph GC7820 manufactured by Agilent Technologies
  • the average particle diameter is a value expressed by D50.
  • sieve openings are 4.00 mm, 3.35 mm, 2.80 mm, 2.36 mm, 2.00 mm, 1.70 mm, 1.40 mm. 1.18mm, 1.00mm, 0.85mm, 0.71mm, 0.60mm, 0.50mm, 0.425mm, 0.355mm, 0.300mm, 0.250mm, 0.212mm and 0.180mm JIS About 25 g of the sample is classified for 10 minutes with a standard sieve (JIS Z8801-1: 2006), and the sample mass on the sieve mesh is measured. A cumulative mass distribution curve is created from the obtained results, and the particle diameter (median diameter) at which the cumulative mass is 50% is defined as the average particle diameter.
  • the Z-average molecular weight (Mz) and the weight-average molecular weight (Mw) of the polystyrene-based resin mean the average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the various average molecular weights of the composite resin particles, the expandable particles and the pre-expanded particles are the same as those of the foamed molded product.
  • the foamed molded product is sliced into 0.3 mm in thickness, 100 mm in length, and 80 mm in width with a slicer (FK-4N manufactured by Fujishima Koki Co., Ltd.), and this is handled as a sample for molecular weight measurement.
  • the standard polystyrene samples for the calibration curve have a weight average molecular weight of 5,480,000, 3,840,000, 355,000, 102,000, 37,900, 9 manufactured by Tosoh Corporation and trade name “TSK standard POLYSTYRENE”. , 100, 2,630, 500, and those having a weight average molecular weight of 1,030,000, manufactured by Showa Denko KK and trade name “Shodex STANDARD” are used.
  • the standard polystyrene samples for the calibration curve were group A (1,030,000), group B (3,840,000, 102,000, 9,100, 500) and group C (5,480,000, 355,000).
  • Group A was weighed 5 mg and then dissolved in 20 mL of THF
  • Group B was also weighed 5 to 10 mg and then dissolved in 50 mL of THF
  • Group C was also weighed 1 mg to 5 mg and then THF 40 mL. Dissolved in.
  • the standard polystyrene calibration curve was prepared by injecting 50 ⁇ L each of the prepared A, B, and C solutions, and using the retention time obtained after measurement, a calibration curve (cubic equation) was obtained from the GPC workstation (EcoSEC-WS), a data analysis program dedicated to HLC-8320GPC. The average molecular weight is calculated using the calibration curve.
  • the number of test pieces is 3, and the symbol “23/50” (temperature 23 ° C., relative humidity 50%) of JIS K7100: 1999 “Plastics-Standard atmosphere for conditioning and testing”, under a standard atmosphere of grade 2 After adjusting the state for 16 hours, the measurement is performed under the same standard atmosphere.
  • ⁇ Bending strength and bending breaking point displacement of foam molded article The bending strength and the amount of displacement at the bending break point are measured by the method described in JIS K7221-1: 2006 “Hard foam plastic—Bending test—Part 1: Determination of flexural properties”. That is, using Tensilon universal testing machine UCT-10T (Orientec) and universal testing machine data processing software UTPS-237 (Softbrain), the test piece size is 25 x 130 x 20 mm in thickness. The test surface is 10 mm / min, the pressure wedge is 5R, and the support base is 5R, the distance between the fulcrums is 100 mm, and the surface of the test piece without skin is stretched and measured.
  • the number of specimens shall be five, and the symbol “23/50” (temperature 23 ° C., relative humidity 50%) of JIS K7100: 1999 “Plastic – Standard atmosphere for conditioning and testing”, under a second grade standard atmosphere After adjusting the state for 16 hours, the measurement is performed under the same standard atmosphere.
  • the bending strength (MPa) is calculated by the following formula.
  • R (1.5F R ⁇ L / bd 2 ) ⁇ 10 3
  • F Bending strength (MPa)
  • F R Maximum load (kN)
  • L Distance between supporting points (mm)
  • b Width of test piece (mm)
  • d Test piece thickness (mm)
  • the fracture detection sensitivity was set to 0.5%, and when the decrease exceeded the set value of 0.5% (deflection: 30 mm) compared to the previous load sampling point, the previous sampling point was Measured as the displacement at the bending break point (mm), and the average of 5 tests is obtained.
  • the obtained bending fracture point displacement is evaluated according to the following criteria. It shows that the flexibility of a foaming molding is so large that a bending fracture point displacement amount is large.
  • ⁇ good: Bending rupture point displacement is 15 mm or more
  • ⁇ possible: Bending rupture point displacement is in the range of 12 mm or more and less than 15 mm
  • ⁇ not possible: Bending rupture point displacement is less than 12 mm
  • the falling ball impact strength is measured in accordance with the method described in JIS K7211: 1976 “General Rules for Hard Plastic Drop Weight Impact Test Method”.
  • the obtained foamed molded article is dried at a temperature of 50 ° C. for 1 day, and then a 40 mm ⁇ 215 mm ⁇ 20 mm (thickness) test piece (six surfaces are not covered) is cut out from the foamed molded article.
  • both ends of the test piece are fixed with clamps so that the distance between the fulcrums is 150 mm, and a hard ball having a weight of 321 g is dropped from a predetermined height onto the center of the test piece to check whether the test piece is broken or not. Observe.
  • test height the falling height of the hard sphere at 5 cm intervals from the lowest height at which all five specimens were destroyed to the highest height at which all were not destroyed
  • falling ball impact value cm
  • H50 Hi + d [ ⁇ (i ⁇ ni) /N ⁇ 0.5]
  • H50 50% fracture height (cm)
  • Hi Test height (cm) when the height level (i) is 0, and the height at which the test piece is expected to break
  • d Height interval (cm) when the test height is raised or lowered
  • ni Number of test pieces destroyed (or not destroyed) at each level, whichever data is used (in the case of the same number, either may be used)
  • ⁇ 0.5 Use a negative number when using destroyed data, and a positive number when using data that was not destroyed
  • the obtained falling ball impact value is evaluated according to the following criteria. The larger the falling ball impact value, the greater the impact resistance of the foamed molded product. ⁇ (Good): Falling ball impact value is 30 cm or more. ⁇ (possible): Falling ball impact value is a range of 20 cm or more and less than 30 cm. X (Not possible): Falling ball impact value is less than 20 cm.
  • S (L0-L1) / L0 ⁇ 100
  • S represents a heating dimensional change rate (%)
  • L1 represents an average dimension (mm) after heating
  • L0 represents an initial average dimension (mm).
  • the obtained heating dimensional change rate S is evaluated according to the following criteria. ⁇ : 0 ⁇ S ⁇ 1.5 (Dimensional change rate is low and dimensional stability is good) ⁇ : 1.5 ⁇ S ⁇ 3 (although a change in dimensions is observed, it can be used practically) ⁇ : S ⁇ 3 (dimensional change is noticeable and cannot be used practically)
  • ⁇ Burning rate of foamed molded article Evaluation of slow flammability>
  • the combustion rate is measured by a method in accordance with US automobile safety standard FMVSS302.
  • a 350 mm ⁇ 100 mm ⁇ 12 mm (thickness) test piece is cut out from a molded product of 300 ⁇ 400 ⁇ 30 mm (thickness), and skins are present on at least two sides of 350 mm ⁇ 100 mm.
  • the burning rate obtained is evaluated according to the following criteria. ⁇ : 80 mm / min or less ⁇ : 100 mm / min or less ⁇ : exceeding 100 mm / min
  • Example 1 (Production of composite resin particles) (Preparation of seed particles)
  • Low-density polyethylene resin (LDPE (1): density 923 kg / m 3 , melting point 112 ° C., MFR 0.3 g / 10 min, manufactured by Nippon Polyethylene Co., Ltd., product name: Novatec LD LF122) 100 parts by mass and ethylene-vinyl acetate copolymer 67 parts by mass (EVA (1): vinyl acetate content 15%, melting point 89 ° C., MFR 1.0 g / 10 min, manufactured by Nippon Polyethylene Co., Ltd., product name: Novatec EVA LV430) was put into a tumbler mixer for 10 minutes. Mixed.
  • LDPE (1) density 923 kg / m 3 , melting point 112 ° C., MFR 0.3 g / 10 min, manufactured by Nippon Polyethylene Co., Ltd., product name: Novatec LD LF122
  • EVA (1) vinyl acetate content 15%, melting
  • the obtained resin mixture was supplied to a single screw extruder (made by Hoshi Plastic Co., Ltd., model: CER40Y, 3.7 MB-SX, diameter 40 mm ⁇ , die plate: diameter 1.5 mm) at a temperature of 230 to 250 ° C. Melt-kneaded and cut into a cylindrical shape 0.40 to 0.60 mg / piece (average 0.5 mg / piece) with a fan cutter (made by Hoshi Plastic Co., Ltd., model: FCW-110B / SE1-N) by strand cutting Thus, 4000 g of seed particles made of a polyethylene resin were obtained. The vinyl acetate content of the seed particles was measured and shown in Table 1.
  • the seed particles were impregnated with styrene monomer by holding for 30 minutes. After impregnation, the temperature was raised to 130 ° C., and polymerization was carried out at this temperature for 1 hour and 40 minutes (first polymerization).
  • styrene monomer was added dropwise over 2 hours.
  • the total amount of styrene monomer was 233 parts by mass with respect to 100 parts by mass of seed particles.
  • 8.0 g of ethylene / bisstearic acid amide was added as a bubble adjusting agent, and the seed particles were impregnated with styrene monomer by maintaining at a temperature of 90 ° C. for 1 hour and 30 minutes. After impregnation, the temperature was raised to 143 ° C., and the temperature was maintained at this temperature for 2 hours for polymerization (second polymerization). As a result of this polymerization, 2000 g of composite resin particles could be obtained.
  • Example 2 In the same manner as in Example 1, seed particles, composite resin particles, expandable particles, and expanded particles were obtained, and their physical properties were measured and evaluated. In the production of the foam molded article, 0.07 MPa water vapor was introduced for 35 seconds and heated, and then cooled until the surface pressure of the foam molded article decreased to 0.01 MPa, as in Example 1. A foam molded article having a density of 20.0 kg / m 3 (50 times the expansion ratio) was obtained, and its physical properties were measured and evaluated. The obtained results are shown in Table 1.
  • Example 1 In preparation of seed particles, seed particles, composite resin particles, expandable particles, expanded particles, and expanded molded articles were obtained in the same manner as in Example 1 except that EVA (1) was not used, and their physical properties were measured. ⁇ evaluated. The obtained results are shown in Table 1.
  • Example 2 In preparation of seed particles, seed particles, composite resin particles, expandable particles, and expanded particles were obtained in the same manner as in Example 1 except that EVA (1) was not used, and their physical properties were measured and evaluated.
  • EVA (1) was not used, and their physical properties were measured and evaluated.
  • 0.09 MPa of water vapor was introduced for 35 seconds and heated, and then cooled until the surface pressure of the foam molded article decreased to 0.01 MPa, as in Example 1.
  • EVA (2) vinyl acetate content 19%, density 939 kg / m 3 , melting point 86 ° C., MFR 2.5 g / 10 minutes, Hanwha Chemical Co., Ltd.
  • seed particles, composite resin particles, expandable particles, expanded particles, and expanded molded articles were obtained, and their physical properties were measured and evaluated. The obtained
  • EVA (2) vinyl acetate content 19%, density 939 kg / m 3 , melting point 86 ° C., MFR 2.5 g / 10 minutes, Hanwa Chemical Co., Ltd., product name: EVA2319
  • polyethylene resin / ethylene-vinyl acetate copolymer 45/55
  • Example 10 In preparation of composite resin particles, seed particles and composite resin particles (gel fraction 14.2 mass) were obtained in the same manner as in Example 4 except that the amount of dicumyl peroxide added was reduced from 5.34 g to 3.76 g. ), Expandable particles, expanded particles, and foamed molded articles were obtained, and their physical properties were measured and evaluated. Table 4 shows the obtained results.
  • Example 11 In preparation of composite resin particles, seed particles and composite resin particles (gel fraction 36.8 mass) were obtained in the same manner as in Example 5 except that the amount of dicumyl peroxide added was increased from 5.34 g to 6.32 g. ), Expandable particles, expanded particles, and foamed molded articles were obtained, and their physical properties were measured and evaluated. Table 4 shows the obtained results.

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Abstract

L'invention concerne des particules de résine composite, les particules comprenant une résine de polyéthylène et une résine de polystyrène dans des plages de 50 à 20 % en masse et de 50 à 80 % en masse, respectivement, par rapport à la quantité totale de celles-ci ; la résine de polyéthylène comprenant une résine de polyéthylène basse densité de 910 à 930 kg/m3 et un copolymère d'éthylène et d'acétate de vinyle dans lequel la teneur en acétate de vinyle est de 10 à 30 % en masse dans des plages de 45 à 85 % en masse et de 15 à 55 % en masse, respectivement, par rapport à la quantité totale de ceux-ci ; et les particules ne comprenant sensiblement pas d'agent ignifuge bromé.
PCT/JP2016/053795 2015-02-27 2016-02-09 Particule de résine composite, particule expansible, particule expansée et moulage de celle-ci WO2016136460A1 (fr)

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KR1020177023504A KR101996231B1 (ko) 2015-02-27 2016-02-09 복합 수지 입자와 그 발포성 입자, 발포 입자 및 발포 성형체
JP2017502046A JP6453995B2 (ja) 2015-02-27 2016-02-09 複合樹脂粒子とその発泡性粒子、発泡粒子及び発泡成形体

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JP2018141087A (ja) * 2017-02-28 2018-09-13 積水化成品工業株式会社 発泡粒子の製造方法及び発泡成形体の製造方法
JP2020105340A (ja) * 2018-12-27 2020-07-09 積水化成品工業株式会社 難燃性発泡複合樹脂粒子、その製造方法及び発泡成形体
WO2023243584A1 (fr) * 2022-06-15 2023-12-21 積水化成品工業株式会社 Particules de résine composite, particules expansibles, particules expansées, mousse moulée et procédé de production de particules de résine composite

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JP2018141087A (ja) * 2017-02-28 2018-09-13 積水化成品工業株式会社 発泡粒子の製造方法及び発泡成形体の製造方法
JP2020105340A (ja) * 2018-12-27 2020-07-09 積水化成品工業株式会社 難燃性発泡複合樹脂粒子、その製造方法及び発泡成形体
WO2023243584A1 (fr) * 2022-06-15 2023-12-21 積水化成品工業株式会社 Particules de résine composite, particules expansibles, particules expansées, mousse moulée et procédé de production de particules de résine composite

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