WO2006132231A1 - Composition de résine thermoplastique et mousse de celle-ci - Google Patents

Composition de résine thermoplastique et mousse de celle-ci Download PDF

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Publication number
WO2006132231A1
WO2006132231A1 PCT/JP2006/311304 JP2006311304W WO2006132231A1 WO 2006132231 A1 WO2006132231 A1 WO 2006132231A1 JP 2006311304 W JP2006311304 W JP 2006311304W WO 2006132231 A1 WO2006132231 A1 WO 2006132231A1
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weight
thermoplastic resin
parts
thermoplastic
resin composition
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PCT/JP2006/311304
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English (en)
Japanese (ja)
Inventor
Koji Noda
Tohru Nakashima
Takeshi Yao
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Kaneka Corporation
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Priority to JP2007520114A priority Critical patent/JPWO2006132231A1/ja
Publication of WO2006132231A1 publication Critical patent/WO2006132231A1/fr

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    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • C08J2427/00—Characterised by the use 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 a halogen; Derivatives of such polymers
    • 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
    • C08J2433/00—Characterised by the use 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; Derivatives of such polymers

Definitions

  • Thermoplastic resin composition and foam thereof are Thermoplastic resin composition and foam thereof.
  • the present invention relates to a thermoplastic resin composition having a specific thermoplastic block copolymer strength and a thermoplastic resin foam obtained by foaming the composition.
  • Foams made of thermoplastic resin are excellent in molding processability, have properties such as flexibility and buffering properties, and are widely used in various applications.
  • Patent Document 1 An example of such a foam is one formed by foaming a hydrogenated product of a styrene / conjugated gen block copolymer (Patent Document 1).
  • Patent Document 1 the foam of the foam obtained by the method of Patent Document 1 is not sufficient, and has a drawback that it is harder and lacks flexibility.
  • Patent Document 2 a foam (Patent Document 2) has been developed that has a mixture power of a thermoplastic acrylic polymer and a hydrogenated styrene / conjugated block copolymer.
  • an acrylic polymer needs to be synthesized separately and mixed with other components.
  • the process is more complicated than that of a single resin system, and the cost is increased, which is not preferable.
  • foams made of soft salty vinyl resin are excellent in processability and durability, and also have excellent flexibility at room temperature, so that they can be used as artificial leather (foamed leather). It is widely used for sheet.
  • a large amount of plasticizer is used, and bleeding (bleed out) and migration of the plasticizer are often problematic.
  • the salt-bulb resin has a relatively high glass transition temperature, so it becomes hard at low temperatures and loses its flexibility.
  • Patent Document 3 a foam (Patent Document 3) comprising an isobutylene block copolymer and a foaming agent has been developed.
  • Patent Document 3 when performing normal molding, the foam shape is not stable due to insufficient surface tension at the time of foaming, surface roughness occurs, and the appearance of the resulting foam is remarkably poor.
  • Patent Document 1 Japanese Patent Laid-Open No. 6-218741
  • Patent Document 2 Japanese Patent Laid-Open No. 9-241414
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2002-20522
  • An object of the present invention is to provide a plasticizer that can be easily adjusted and molded, and has high flexibility at room temperature and low temperature, cushioning properties, vibration damping properties, sound insulation properties, heat retention properties, and gas barrier properties.
  • An object of the present invention is to provide a thermoplastic resin foam that does not ooze out and has excellent weather resistance, thermal stability, and the like after appearance.
  • thermoplastic resin composition comprising a thermoplastic block copolymer having a specific material composition. It has been found out that it can be done, and has led to the present invention.
  • thermoplastic block copolymer (a) 100 parts by weight
  • Foaming agent (c) O. 05-20 parts by weight
  • thermoplastic rosin composition that also has strength
  • thermoplastic block copolymer (a) comprises a polymer block having an aromatic vinyl compound as a constituent monomer and a polymer block having an aliphatic hydrocarbon compound as a constituent monomer. It is related with the thermoplastic resin composition characterized.
  • the present invention also relates to a thermoplastic resin foam obtained by foaming the above composition.
  • thermoplastic block copolymer which is the component (a) of the present invention includes a polymer block having an aromatic bur compound as a constituent monomer and a polymer block having an aliphatic hydrocarbon compound as a constituent monomer.
  • a thermoplastic block copolymer comprising blocks.
  • the aromatic bur compound is not particularly limited, but for example, styrene, o-, m- or p-methyl styrene, ⁇ -methyl styrene, ⁇ -methylol styrene, 2, 6 dimethyl styrene, 2, 4 dimethyl styrene, ⁇ -methyl- ⁇ -methyl styrene, ⁇ -methyl m-methyl styrene, ex-methyl- p-methylstyrene, j8-methyl-o-methylstyrene, 13-methyl-m-methylstyrene, 13-methyl-p-methylstyrene, 2, 4, 6 trimethylstyrene, ⁇ -methyl-2, 6 dimethylstyrene, ⁇ -methyl-2, 4— Dimethylstyrene, 13-Methyl-2,6 Dimethylstyrene, 13-Methyl-2,4 Dimethylenstyrene, o-,
  • styrene, p-methylstyrene, a-methylstyrene, and indene power are selected as at least one kind of force, which is desirable from the viewpoint of easy availability and balance of physical properties.
  • the polymer block containing an aromatic vinyl compound as a constituent monomer may or may not contain a monomer other than the aromatic bur compound.
  • a monomer other than an aromatic vinyl compound it is preferable that the monomer of the aromatic vinyl compound occupies 60% by weight or more in the entire polymer block. I prefer to occupy it. If the aromatic bur compound is less than 60% by weight in the entire polymer block, the cohesive strength of the polymer block is lowered, which is not preferable.
  • the monomer other than the aromatic vinyl compound is not particularly limited as long as it is a monomer that can be polymerized with the aromatic vinyl compound, and examples thereof include aliphatic olefins, alicyclic alkenes, and And butyl ethers, and monomers such as / 3 pinene. These can be used alone or in combination of two or more.
  • Examples of the aliphatic hydrocarbon compounds include the above aliphatic olefins and gens.
  • the “aliphatic hydrocarbon compound” includes alicyclic compounds such as alicyclic alkenes.
  • examples of the aliphatic olefins include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, 4-methyl-1 pentene, otaten and the like.
  • Examples of the alicyclic alkenes include cyclohexene, burcyclohexane, norbornene, and the like.
  • Examples of the genes include butadiene, isoprene, hexagen, cyclopentagen, cyclohexagen, dicyclopentagen, dibutenebenzene, ethylidene norbornene, and the like. These may be used alone or in combination of two or more.
  • the polymer block having an aliphatic hydrocarbon compound as a constituent monomer may or may not contain a monomer other than the aliphatic hydrocarbon compound.
  • a monomer other than an aliphatic hydrocarbon compound it is preferred that the aliphatic hydrocarbon compound occupies 60% by weight or more in the entire polymer block. This power is also preferable from the viewpoint of ease of synthesis and balance of physical properties.
  • the monomer other than the aliphatic hydrocarbon compound in the polymer block is not particularly limited, and examples thereof include monomers such as vinyl ethers.
  • butyl ethers include methyl butyl ether, ethyl butyl ether, ( n— , iso-) propyl butyl ether, (n—, sec—, tert—, iso-) butyl benzene, methyl propylene.
  • -Ruether, ethylproper ether and the like can be used alone or in combination of two or more.
  • thermoplastic block copolymer as component (a), a polymer block having an aliphatic hydrocarbon compound as a constituent monomer and a polymer block having an aromatic bur compound as a constituent monomer.
  • the number average molecular weight of the thermoplastic block copolymer as the component (a) is not particularly limited, but is preferably 10,000 to 300,000.
  • the moldability of the thermoplastic resin composition at a high temperature and foamability of the composition, and the shape retention at room temperature and the appreciability of brittleness are preferred from 50,000 to 150,000! /.
  • the number average molecular weight of each polymer is a value obtained by gel permeation chromatography (GPC) in terms of polystyrene, for example, a GPC system (column: Showa, Showa). It can be measured by using Sho dex K-804 (polystyrene gel) manufactured by Denko Co., Ltd. (mobile phase: black mouth form).
  • thermoplastic block copolymer as component (a) is not particularly limited.
  • a block copolymer or diblock having a linear, branched, or star structure is used. Any of a copolymer, a triblock copolymer, and a multiblock copolymer may be used, or a mixture thereof.
  • a polymer block containing an aromatic vinyl compound as a constituent monomer and a polymer block containing an aliphatic hydrocarbon compound as a constituent monomer from the viewpoint of moldability and physical property balance.
  • Triblock copolymer consisting of polymer block with constituent monomer, polymer block with aromatic bur compound as constituent monomer Polymer block force with aliphatic hydrocarbon compound as constituent monomer Mixtures of diblock copolymers are preferred. Further, the higher the mechanical strength isotropic blocking ratio, the more preferred is 70% or more, and the more preferred is 80% or more.
  • the blocking ratio was determined as follows.
  • the obtained block copolymer was immersed in methyl ethyl ketone and allowed to stand for 1 day.
  • the solid and the solution were separated by decantation, and the obtained solid was dried at 100 ° C. for 2 hours.
  • the solid and the solution were separated by decantation, and the obtained solid was dried at 100 ° C for 2 hours.
  • the ratio of the weight of the finally obtained solid matter to the weight of the initial block copolymer was shown as a percentage of blocking.
  • thermoplastic block copolymer as component (a) includes availability and high temperature.
  • a block copolymer consisting of a styrenic block and a block of butadiene and Z or isoprene and its hydrogenated product are preferably mentioned.
  • SBS styrene butadiene styrene Block copolymer
  • SIS styrene-isoprene styrene block copolymer
  • SEBS styrene (ethylene Z-butylene) mono-styrene block copolymer
  • SEPS styrene mono- (ethylene / propylene) mono-styrene block copolymer) Polymer
  • thermoplastic block copolymer which is the component (a) of the present invention
  • the polymer block containing the aliphatic hydrocarbon compound of the component (a) as a constituent monomer is composed mainly of isobutylene.
  • An isobutylene block copolymer which is a polymer block to be used is also exemplified. Isobutylene block copolymer is flexible at room temperature and low temperature, buffering, damping, soundproofing, heat retention, gas nore, and sardine, weather resistance when exposed outdoors, and thermal stability. Because of its excellent properties and the like, it can be suitably used for foam applications.
  • isobutylene block copolymer There are no particular restrictions on the structure of the isobutylene block copolymer.For example, block copolymers, diblock copolymers, triblock copolymers, multiblock copolymers having a linear, branched, or star structure. Any combination or the like can be selected.
  • a polymer block containing an aromatic vinyl compound as a constituent monomer (a polymer block containing isobutylene as a main component) (an aromatic bur system) Triblock copolymer, (polymer block containing aromatic vinyl compound as constituent monomer) (Polymer block containing isobutylene as the main component)
  • the diblock copolymer is preferably a mixture thereof.
  • the monomer component containing isobutylene as a main component may or may not contain a monomer other than isobutylene. There are no particular restrictions on monomers other than isoprene, as long as they are cationically polymerizable monomers!
  • the method for producing the isobutylene block copolymer is not particularly limited.
  • isobutylene is used as a main component. It is obtained by sequentially polymerizing the monomer and the monomer mainly composed of an aromatic vinyl compound.
  • R 3 (CR ' ⁇ X) R 3 (1)
  • X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, a substituent selected
  • R ⁇ R 2 represents a hydrogen atom or 1 to In the monovalent hydrocarbon group of 6, RR 2 may be the same or different.
  • R 3 is a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1 to 6.
  • the compound represented by the general formula (1) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization.
  • Examples of the compound of the general formula (1) used in the present invention include the following compounds.
  • Isopropyl) benzene, bis (2-chloro-2-propynole) benzene! / ⁇ is also called dicuminochloride, and tris (1-chloro-1- 1-methylethyl) benzene is tris (cyclochloroisopropyl) benzene, tris ( 2—Black mouth 2—Propyl) Benzene! / ⁇ ⁇ is called “Tricuminole mouth ride”. ]
  • a Lewis acid catalyst may be allowed to coexist.
  • Such Lewis acids can be used for cationic polymerization.
  • Metal halides such as FeCl, ZnBr, A1C1, and AlBr; Organics such as Et A1C1 and EtAlCl
  • Metal halides can be preferably used. Of these, TiCl, BF 2 -OEt, and SnCl are preferred in view of the ability as a catalyst and industrial availability. Use of Lewis acid
  • the dose is not particularly limited, but can be set in consideration of the polymerization characteristics or polymerization concentration of the monomer used. Usually, 0.1 to 100 molar equivalents can be used with respect to the compound represented by the general formula (1), and the range is preferably 1 to 50 molar equivalents.
  • an electron donor component may be allowed to coexist if necessary.
  • This electron donor component is considered to have an effect of stabilizing the growth carbon cation during cationic polymerization, and a polymer having a controlled molecular weight distribution is formed by the addition of the electron donor.
  • the electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom. it can.
  • the polymerization of the isobutylene-based block copolymer can be carried out in an organic solvent as necessary, and the organic solvent can be used without particular limitation as long as it does not essentially inhibit cationic polymerization.
  • organic solvent can be used without particular limitation as long as it does not essentially inhibit cationic polymerization.
  • halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, chloro chloride, dichloroethane, n -propyl chloride, n-butyl chloride, and black benzene; benzene, toluene, xylene, ethylbenzene, propyl Alkylbenzenes such as benzene and butylbenzene; linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane; 2-methylpropane, 2-
  • solvents can be used alone or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer.
  • the amount of the solvent used is determined in consideration of the viscosity of the polymer solution obtained and ease of heat removal.
  • the concentration of the polymer is determined to be 1 to 50 wt%, preferably 5 to 35 wt% of the total amount of the polymer solution.
  • each component is mixed under cooling, for example, at a temperature of 100 ° C or higher and lower than 0 ° C.
  • the temperature range is particularly preferably from 30 ° C to 80 ° C.
  • Examples of the foaming agent (c) used in the present invention include chemical foaming agents (thermal decomposition type foaming agents) and physical foaming agents (foaming agents composed of inert gas or inert gas). Both can be used. Among them, a chemical foaming agent is preferably used. As the chemical foaming agent, both inorganic chemical foaming agents and organic chemical foaming agents can be used. Examples of such chemical foaming agents include carbonates such as sodium bicarbonate and ammonium carbonate.
  • azo compounds eg, azodicarbonamide, azobisisobutyloditolyl, azodiaminobenzene, azohexahydrobenzo-tolyl, barium azodicarboxylate, etc.
  • nitroso compounds For example, N, N, -dinitrosopentamethylenetetramine, N, N, -dinitroso-N, N, -dimethylterephthalamide, t-butylamino-tolyl, etc.
  • hydrazide compounds eg p-toluenesulfol hydrazide, p , p, oxybis
  • Benzenesulfurhydrazide and the like
  • organic foaming agents such as hydrazone compounds (for example, p-toluenesulfurone acetone hydrazone and the like).
  • a foam can be produced using one or more of the above-mentioned foaming agents, and among them, carbonates, azo compounds and hydrazide compounds are preferably used. More preferably, sodium bicarbonate, azodicarbonamide, or hydrazide compound is preferably used. These are preferably used in combination of two or more.
  • Examples of the physical blowing agent include aliphatic hydrocarbons such as butane, pentane, hexane, propane, and heptane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclobutane, and dichlorodiflurane.
  • Halogenated hydrocarbons such as fluoromethane, dichlorofluoromethane, trichlorofluoromethane, chloromethane, dichloromethane, black ethane, dichlorotetrafluoroethylene, trichlorofluoromethane, perfluorocyclobutane, etc. 1 type or 2 types or more.
  • the amount of foaming agent used can be adjusted according to the foaming ratio (specific gravity) of the foam intended for production, the use of the foam, the amount of gas generated by the foaming agent, etc.
  • Thermoplastic block copolymer Body (a) 0.05 to 20 parts by weight per 100 parts by weight. Preferably, the content is 0.1 to 5 parts by weight.
  • the foaming agent is used at a ratio of 0.05 to 20 parts by weight, a foam having a specific gravity in the range of 0.9 to 0.1 can be generally obtained. If the amount of the foaming agent used is too small, the foaming ratio will be too low, and it will be difficult to obtain a foam with excellent flexibility. As a result, coarse bubbles are generated, making it difficult to obtain a foam having uniform and fine bubbles.
  • the acrylic polymer (b-1) and the polytetrafluoric mouth are used to smoothly foam and obtain a foam having more uniform and fine bubbles.
  • Acrylic polymer (b-1) is methyl methacrylate 30 ⁇ : L00 wt%, (meth) acrylic acid ester monomer excluding methyl methacrylate 0 ⁇ 70 wt%, and copolymerizable with these It is obtained by copolymerizing 0 to 20% by weight of a vinyl monomer (however, the total of the above methyl methacrylate, (meth) acrylic acid ester monomer and vinyl monomer is 100% by weight).
  • a vinyl monomer (however, the total of the above methyl methacrylate, (meth) acrylic acid ester monomer and vinyl monomer is 100% by weight).
  • a copolymer obtained by dissolving 0.4 g of the copolymer in 100 ml of toluene is preferably a copolymer having a specific viscosity of 0.5 to 7 measured at 30 ° C.
  • (meth) acrylic acid ester means acrylic acid ester and methacrylic acid ester.
  • methacrylic acid ester monomer excluding methyl methacrylate contained in the acrylic polymer (b-1) include, for example, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid 2 —Methacrylic acid alkyl esters such as ethylhexyl.
  • acrylate ester include alkyl acrylates of alkyl groups such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethyl hexyl acrylate. These may be used alone or in combination of two or more.
  • the number of carbon atoms in the alcohol residue of the (meth) acrylic acid ester of the acrylic polymer (b-1) is preferably 1 to 12 from the viewpoint of processability.
  • Specific examples of the butyl monomer copolymerizable with these include aromatic bur such as styrene and a-methyl styrene, and unsaturated-tolyl such as acrylonitrile. These may be used alone or in combination of two or more.
  • the acrylic polymer (b-1) is composed of 30 to 100% by weight of methyl methacrylate and 0 to 70% by weight of (meth) acrylic acid ester monomer excluding methacrylic acid methyl. It is preferable that the polymerizable bulle monomer is 0 to 20% by weight in terms of processability and uniformity of the obtained resin composition. More preferably, methyl methacrylate is 60 to 90% by weight, (meth) acrylic acid ester monomer excluding methyl methacrylate is 0 to 40% by weight, and vinyl monomer is 0 to 10% by weight.
  • methyl methacrylate is 70 to 85% by weight
  • (meth) acrylic acid ester-based monomer strength excluding methyl methacrylate is 30 to 30% by weight
  • vinyl monomer is 0 to 5% by weight.
  • the total of methyl methacrylate, (meth) acrylic acid ester monomer and bulle monomer is 100% by weight.
  • V V — ⁇ ) / ⁇
  • the power is known to be 0.522!
  • the specific viscosity is, for example, a sample of a toluene solution of the acrylic polymer (b-1) and kept at a constant temperature in a 30 ° C water bath at a Ubbelohde type viscometer. Can be measured.
  • the acrylic polymer (b-1) can be obtained, for example, by carrying out emulsion polymerization in the presence of a suitable medium, an emulsifier and a polymerization initiator.
  • the monomer component constituting the acrylic polymer (b-1) is emulsion-polymerized to obtain a polymer latex of the acrylic polymer (b-1), and the monomer component is further added.
  • Polymerization can also be performed.
  • a medium used in this emulsion polymerization water is usually used.
  • emulsifier known key-on surface activity And nonionic surfactants are used.
  • As the polymerization initiator a usual water-soluble or oil-soluble single type or redox type is used.
  • the polytetrafluoroethylene component (b-2) is added for the purpose of improving the processability of the isobutylene block copolymer.
  • Polytetrafluoroethylene having a molecular weight of 500,000 or more and 20 million or less is preferably used.
  • the molecular weight of polytetrafluoroethylene is less than 500,000, it is difficult to improve the processability because it is impossible to eliminate sizing die contamination, that is, plate-out. If the molecular weight exceeds 20 million, molding becomes difficult.
  • the polytetrafluoroethylene (b-2) used in the present invention is preferably one that is made into a fiber by applying a shearing force, and has a high molecular weight obtained by, for example, an emulsion polymerization method.
  • examples thereof include powders produced by agglomerating an emulsified dispersion of polytetrafluoroethylene, and powders produced by high molecular weight polytetrafluoroethylene obtained by suspension polymerization.
  • Typical examples of polytetrafluoroethylene that is fiberized by shear force include, for example, Polyflon TFE—F103, Polyflon TFE—F104 (manufactured by Daikin Industries, Ltd.), Teflon (registered trademark) TFE-6J, And Teflon (registered trademark) 6C-J (Mitsui's DuPont Fluorochemical Co., Ltd.).
  • the fiber diameter of the polytetrafluoroethylene fiberized in this way is too large, the processability improving effect tends not to be sufficiently exhibited. It is particularly preferable that it is 5 ⁇ m or less, more preferably 2 ⁇ m or less. In addition, the fiber diameter of polytetrafluoroethylene that has become a strong fiber tends to exhibit a sufficient effect of improving workability even when it is too small. Therefore, the thickness is preferably about 0.001 ⁇ m or more, more preferably about 0.01 ⁇ m or more.
  • the fiber length of polytetrafluoroethylene is not particularly limited.
  • the acrylic polymer (b-1) and the polytetrafluoroethylene (b-2) are useful for improving the processability of the thermoplastic block copolymer (a), and are used alone. However, both may be used together. The mixing ratio when both are used in combination is not particularly limited.
  • Metaprene A3000 manufactured by Mitsubishi Rayon
  • the thermoplastic resin composition according to the present invention comprises an acrylic polymer (b-1) and a polytetrafluoroethylene (a) based on 100 parts by weight of the thermoplastic block copolymer (a).
  • b-2) is contained in a total of 0.01 to 30 parts by weight, more preferably 0.3 to 10 parts by weight. If the added amount is less than 0.01 parts by weight, sufficient effect of improving the workability cannot be obtained, and if it exceeds 30 parts by weight, the viscosity of the resin during processing becomes high and the processing becomes difficult. Furthermore, foaming aids can be used together depending on the molding conditions.
  • foaming aids in this case include metal salts of aliphatic monocarboxylic acids and metal salts of alkylaryl sulfonic acids. More specifically, strength prillic acid, strength purine acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, hydroxystearic acid, L-force acid, behenic acid, montanic acid, other carbon number Periodic Table Group I or Group X metals (Li, Na) of 8-30 aliphatic monocarboxylic acids (which may have side chains, hydroxyl groups, ketone groups, aldehyde groups, epoxy groups, etc.
  • alkylbenzene sulfonic acids substituted with alkyl groups of 3 to 16 carbon atoms such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid.
  • Periodic table of alkyl naphthalene sulfonic acids such as Group II metal salts, isopropylenonaphthalene sulphonic acid, dibutino sulphthalene sulphonic acid, and amino sulphona sulphonic acid Mention may be made of Group I or Group II metal salts.
  • the composition that is effective in the present invention can be mixed with a polyolefin-based resin as the component (d).
  • Polyolefin resins include a-olefin homopolymers, random copolymers, block copolymers, and mixtures thereof. Or a random copolymer of ⁇ -olefin and other unsaturated monomer, a block copolymer, a graft copolymer, and an oxidized, halogenated or sulfonylated polymer of these polymers alone or in combination The above can be used in combination.
  • polyethylene ethylene-propylene copolymer, ethylene-propylene non-conjugated diene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene otaten copolymer, ethylene acetate butyl copolymer, ethylene Polypropylene resins such as vinyl alcohol copolymer, ethylene ethyl acrylate copolymer, polyethylene resin such as chlorinated polyethylene, polypropylene, propylene ethylene random copolymer, propylene ethylene block copolymer, chlorinated polypropylene, etc.
  • Examples include cocoa resin, polybutene, polyisobutylene, polymethylpentene, (co) polymer of cyclic olefin.
  • polyethylene resin, polypropylene resin, or a mixture thereof can be preferably used in view of the balance of physical properties of thermoplastic resin.
  • the amount of the polyolefin-based resin (d) is preferably 2 to 400 parts by weight, more preferably 5 to 100 parts by weight per 100 parts by weight of the thermoplastic block copolymer (a): L00 Parts by weight. If it exceeds 400 parts by weight, the rubber elasticity of the obtained thermoplastic resin composition is lowered.
  • the plasticizer (e) can be used as long as leaching does not become a problem.
  • plasticizer Usually, a liquid or liquid material is used suitably at room temperature. Both hydrophilic and hydrophobic plasticizers can be used. Examples of such plasticizers include plasticizers for various types of rubbers such as mineral oils, vegetable oils, synthetics, and the like. As mineral oils, naphthenic, paraffinic, etc. process oils, etc. As vegetable oils, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wax, pine oil Examples of synthetic oils include polybutene and low molecular weight polybutadiene.
  • thermoplastic resin composition that is compatible with the thermoplastic block copolymer (a)
  • norafine process oil or polybutene is preferably used.
  • plasticizers can be used in an appropriate combination of two or more in order to obtain the desired viscosity and physical properties.
  • the blending amount of the plasticizer (e) is preferably 0 to 200 parts by weight, more preferably 5 to L00 by weight, with respect to 100 parts by weight of the thermoplastic block copolymer (a). Part. Over 200 parts by weight This is not preferable because bleeding out of the plasticizer occurs.
  • the present invention may further contain a hygroscopic compound (f)!
  • a hygroscopic compound examples include zeolite, silica gel, and alumina, and any of these can be used. Two or more of these may be used in combination.
  • a hygroscopic compound is capable of adsorbing moisture and odors such as atmospheric air in contact with the environment where the thermoplastic resin foam according to the present invention is exposed. It can be suitably used as a sealing material that dries the interior or as a spacer material or as a building interior material that absorbs unpleasant odors in the room.
  • the amount of the hygroscopic compound (f) is preferably 1 to 300 parts by weight with respect to 100 parts by weight of the thermoplastic block copolymer (a). Good.
  • a filler can be blended in the thermoplastic rosin composition of the present invention for improving physical properties or economic merit.
  • Suitable fillers include clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxides, my strength, graphite, flaky inorganic fillers such as hydrated aluminum hydroxide, etc. Examples thereof include metal powder, wood chips, glass powder, ceramic powder, carbon black, granular or powdered solid filler such as granular or powdered polymer, and other various natural or artificial short fibers and long fibers.
  • a hollow filler for example, an inorganic hollow filler such as a glass balloon or a silica balloon, an organic hollow filler that also has a polyvinylidene fluoride / polyvinylidene fluoride copolymer power, light weight can be achieved. .
  • the blending amount of the filler is preferably 0 to 300 parts by weight, more preferably 0 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic block copolymer (a).
  • the amount exceeds 300 parts by weight, the resulting foamed thermoplastic resin foam body is unfavorably deteriorated and the flexibility is impaired.
  • thermoplastic rosin composition of the present invention can be blended with an antioxidant and Z or an ultraviolet absorber as necessary.
  • the amount of the thermoplastic block copolymer (a) is preferably 0 to 10 parts by weight, more preferably 0 to 10 parts by weight in total with respect to 100 parts by weight of the antioxidant and the ultraviolet absorber. 5 parts by weight.
  • Still other additives are flame retardants and antibacterial agents , Light stabilizers, colorants, fluidity improvers, lubricants, antiblocking agents, antistatic agents, crosslinking agents, crosslinking aids, etc., can be added alone or in combination of two or more. Is possible.
  • other various thermoplastic resins, thermosetting resins, thermoplastic elastomers, and the like may be blended so long as the performance of the thermoplastic resin composition of the present invention is not impaired.
  • thermoplastic resin composition of the present invention can be formed into various foams using a known method.
  • thermoplastic resin foam obtained by foaming the thermoplastic resin composition of the present invention is also one aspect of the present invention.
  • thermoplastic block copolymer of the present invention is melted by heating to a temperature of about 120 to 300 ° C. because of its thermoplasticity, it can be melt-molded or heated.
  • various molding methods such as extrusion molding, injection molding, calender molding, casting molding, press molding, casting, etc., various shapes and structures of foam molded products or foamable molded products ( Molded product before foaming).
  • the molding is carried out by heating to a temperature equal to or higher than the decomposition temperature of the foaming agent at least at the stage of molding and processing. You can do it.
  • the foaming temperature may vary depending on the type of foaming agent and the type of foaming aid used in combination, the above heat decomposable foaming agents (chemical foaming agents) generally decompose in the range of 150 to 250 ° C.
  • a thermoplastic resin foam obtained by injection foam molding or extrusion foam molding is particularly preferable.
  • thermoplastic resin composition of the present invention is obtained after once producing an unfoamed sheet, film, plate, tube, laminate, or other molded article using the foamable thermoplastic polymer composition. It can also be heated to foam.
  • the foamable thermoplastic polymer composition is molded at a temperature at which the composition can be molded and the foaming agent is not decomposed to produce an unfoamed molded article,
  • the foamed molded product can be obtained by heating and foaming the unfoamed molded product or the like above the decomposition temperature of the foaming agent.
  • a foam molding method by injection foam molding a block copolymer containing a foam material is injected into a mold cavity to fill the mold cavity, and then the volume of the cavity is reduced.
  • a foam-molded article is obtained by enlarging and foaming and molding.
  • the foamed molded product obtained by the above molding method can be obtained in a single layer or multiple layers.
  • the molded article by the multilayer can be obtained by any combination of a foam layer and a foam layer, or a combination of a foam layer and a non-foam layer.
  • a thermoplastic resin foam having a multilayer structure obtained by such injection foam molding is one of the preferred embodiments of the present invention.
  • the foam obtained as described above may be used as it is, and may be combined with another material as a base material, or laminated with the base material or a method other than the base material and laminated. It may be used as a material.
  • the base material used for forming the composite material is not particularly limited, and can be appropriately selected according to the purpose of use and usage of the foam.
  • the base material that can be used in combination with the foam includes, for example, fabrics such as woven fabric, knitted fabric, and non-woven fabric made of natural fiber, synthetic fiber, semi-synthetic fiber, inorganic fiber, etc .; paper Examples include films, sheets, plates, and other shapes having plastic and rubber strength; foils, sheets, plates, and other shapes having metal strength; wood; ceramics and the like.
  • the foam may be combined with the base material after the foam has been produced, or when the foamable thermoplastic polymer composition is foamed. At the same time, it can be integrated with the base material, or it can be integrated with the base material before foaming and then foamed.
  • the foam or foamed thermoplastic polymer composition is combined with the substrate, depending on the affinity and adhesiveness between them, for example, heat pressing, adhesive bonding, extrusion lamination, etc. Any method such as a method of laminating at the same time as molding can be used.
  • the composite material described above is a laminated structure composed of a foam and a base material, for example, even if it is a two-layer structure of one foam layer and one base material, Whether it is a three-layer structure (sandwich structure) with substrates on both sides of the foam, a multilayer structure of four or more layers in which the foam and other materials are laminated alternately, or other laminated structures
  • each layer may have the same material strength. Can be made of different materials.
  • composition according to the present invention specific amounts of specific (b-1) and Z or (b-2) are added to the specific thermoplastic block copolymer (a) and the foaming agent (c). Therefore, it is possible to improve the moldability of the foam and the appearance after the molding, and by using such a thread and composition, a thermoplastic resin particularly excellent in weather resistance, thermal stability, etc. It is possible to produce the foam stably.
  • p-Dicmilk mouthride 0.097 g (0.42 mmol) and N, N-dimethylacetamide 0.073 g (0.84 mmol) were calories.
  • 1.66 mL (15. 12 mmol) of tetrasalt-titanium was added to initiate polymerization. After stirring for 75 minutes from the start of polymerization, remove the sample from the polymerization solution. About 1 mL of the polymerization solution was withdrawn for the ring. Subsequently, 13.71 g (l 31. 67 mmol) of styrene monomer was added into the polymerization vessel. 75 minutes after adding the mixed solution, the reaction was terminated by adding a large amount of water.
  • the reaction solution was washed twice with water, the solvent was evaporated, and the resulting polymer was vacuum-dried at 60 ° C. for 24 hours to obtain the desired block copolymer.
  • the obtained isobutylene block copolymer was subjected to GPC analysis. As a result, the number average molecular weight was 103,000, and the content of polystyrene determined by NMR was 30% by weight.
  • each component except the foaming agent was melt-kneaded for 10 minutes using a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at 200 ° C. in the proportions shown in Table 1. After pelletizing the obtained composition, the foaming agent in the ratio shown in Table 1 was dry blended, and the temperature of the extruder was adjusted as shown in Table 1 (Conicalni screw extruder (Corporation)).
  • Toyo Seiki Seisakusho: TEM-50) is used to supply a thermoplastic resin composition in the form of pellets, with a screw speed of 100 rpm and a T-die force attached to the tip of the slit sheet with a width of 15 mm (foam) )
  • the appearance of this sheet was visually evaluated in the following three stages.
  • Irganox 1010 manufactured by Chinoku's Specialty Chemicals with 0.5 parts added.
  • High density polyethylene noisy from Mitsui Engineering Co., Ltd. (MFR: 0.3 g / 10 min, hereinafter abbreviated as HDPE2)
  • Hygroscopic compound ⁇ 3A molecular sieves PURMOL 3 ST (hereinafter abbreviated as 3A—MS) manufactured by ZEOCHEM
  • T1 -T4 Extruder temperature
  • T1 Upstream
  • T2 Middle stream
  • T3 Before die
  • T4 Indicates die temperature
  • thermoplastic resin composition of the Examples has good surface properties (appearance) of the foam obtained, and the present invention
  • thermoplastic resin yarn and composition according to the above it is possible to stably produce various foams.
  • thermoplastic resin composition that is effective in the present invention has remarkably improved processability at the time of molding, and molding is performed using extrusion foam molding, injection foam molding, and the like. It turns out that it can be used conveniently for a molded object.
  • thermoplastic resin foam obtained by the present invention is excellent in flexibility, cushioning properties, vibration damping properties, soundproofing properties, heat retention properties, gas barrier properties, weather resistance, thermal stability, and the like.
  • Applications materials for household appliances, food packaging materials, daily goods, toys, sports equipment, clothing, civil engineering sheets' waterproof sheets, gaskets, molded sealing materials, molded spacers for multi-layer glass, etc. It can be used for civil engineering and architectural purposes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L’invention concerne une mousse de résine thermoplastique qui est facile en termes de contrôle de matières première et de formage tout en présentant une flexibilité importante à température ambiante et à faibles températures, des propriétés de tampon, des propriétés d’amortissement, des propriétés d’isolation phonique, des propriétés de rétention de chaleur et des propriétés de barrière contre les gaz. Ladite résine thermoplastique est exempte de coulure d’un plastifiant et confère une apparence excellente après formage, tout en étant excellente en termes de résistance aux intempéries, de stabilité thermique et similaire. L’invention concerne plus particulièrement une composition de résine thermoplastique composée de 100 parties en poids d’un copolymère bloc thermoplastique (a) composé d’un polymère bloc ayant un composé vinyle aromatique en tant que monomère constituant et d’un autre bloc polymère ayant un composé hydrocarbure aliphatique en tant que monomère constituant, 0,01 à 30 parties en poids d’au moins une substance sélectionnée parmi le groupe consistant en polymères acryliques (b-1) et polytétrafluoroéthylènes (b-2) et 0,05 à 20 partie en poids d’un agent de moussage (c).
PCT/JP2006/311304 2005-06-06 2006-06-06 Composition de résine thermoplastique et mousse de celle-ci WO2006132231A1 (fr)

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Cited By (3)

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US20100113636A1 (en) * 2008-10-30 2010-05-06 Paul Van Rheenen Flexible acrylic foam composition
JP2010180325A (ja) * 2009-02-05 2010-08-19 Aron Kasei Co Ltd 難燃性エラストマー組成物
KR20220122157A (ko) * 2021-02-26 2022-09-02 주식회사 데시칸 복층유리용 흡습성 발포그래뉼 및 이를 구비한 복층유리

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JP2004307585A (ja) * 2003-04-03 2004-11-04 Kuraray Co Ltd 発泡体用組成物および発泡体
JP2004331843A (ja) * 2003-05-08 2004-11-25 Kanegafuchi Chem Ind Co Ltd スチレン系樹脂押出発泡体およびその製造方法
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JPH07330935A (ja) * 1994-06-14 1995-12-19 Kanegafuchi Chem Ind Co Ltd 結晶性ポリオレフィン発泡体
JP2001002818A (ja) * 1999-06-23 2001-01-09 Nagano Nova Form Kk 発泡樹脂及びその製造方法
JP2003113265A (ja) * 2001-10-02 2003-04-18 Mitsubishi Rayon Co Ltd 発泡用ポリオレフィン系樹脂組成物
JP2004307585A (ja) * 2003-04-03 2004-11-04 Kuraray Co Ltd 発泡体用組成物および発泡体
JP2004331843A (ja) * 2003-05-08 2004-11-25 Kanegafuchi Chem Ind Co Ltd スチレン系樹脂押出発泡体およびその製造方法
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Publication number Priority date Publication date Assignee Title
US20100113636A1 (en) * 2008-10-30 2010-05-06 Paul Van Rheenen Flexible acrylic foam composition
EP2182024A3 (fr) * 2008-10-30 2011-04-20 Rohm and Haas Company Composition de mousse acrylique souple
US8124664B2 (en) * 2008-10-30 2012-02-28 Rohm And Haas Company Flexible acrylic foam composition
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JP2010180325A (ja) * 2009-02-05 2010-08-19 Aron Kasei Co Ltd 難燃性エラストマー組成物
KR20220122157A (ko) * 2021-02-26 2022-09-02 주식회사 데시칸 복층유리용 흡습성 발포그래뉼 및 이를 구비한 복층유리
KR102542011B1 (ko) * 2021-02-26 2023-06-12 주식회사 데시칸 복층유리용 흡습성 발포그래뉼 및 이를 구비한 복층유리

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