Classifications

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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
  • C08L27/22—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 a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L27/24—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 a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
  • B29C44/34—Auxiliary operations
  • B29C44/3461—Making or treating expandable particles
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  • 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
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/141—Hydrocarbons
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  • 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
  • C08J9/22—After-treatment of expandable particles; Forming foamed products
  • C08J9/228—Forming foamed products
  • C08J9/232—Forming foamed products by sintering 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
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/03—Extrusion of the foamable blend
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/10—Water or water-releasing compounds
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
• • 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
  • C08J2327/00—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
  • C08J2327/22—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 modified by chemical after-treatment
  • C08J2327/24—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 modified by chemical after-treatment halogenated
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  • 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
  • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
  • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2425/02—Homopolymers or copolymers of hydrocarbons
  • C08J2425/04—Homopolymers or copolymers of styrene
  • C08J2425/08—Copolymers of styrene
  • C08J2425/12—Copolymers of styrene with unsaturated nitriles
• • 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
  • C08J2433/04—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 esters
  • C08J2433/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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  • 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
  • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
  • C08J2491/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/01—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • 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
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

• the present invention relates to effervescent chlorinated vinyl chloride resin particles, the effervescent particles thereof, a chlorinated vinyl chloride resin foam molded product using these, and a method for producing effervescent chlorinated vinyl chloride resin particles.
• Resin foam has light weight, heat insulating property, cushioning property, etc., and has been widely used as a heat insulating material for houses and a heat insulating material for piping and the like.
• the styrene resin foam molded body obtained by using the foamable styrene resin particles containing a foaming agent has a high degree of freedom in shape.
• the foamed molded product obtained from the foamable styrene resin particles is a heat insulating material that can be applied to a part where construction is difficult with a styrene resin foam having a simple shape such as a board shape obtained by an extrusion foaming method or the like. Widely used.
• Styrene-based resin is a flammable resin. Therefore, a flame retardant can be added to the styrene-based resin foam molded product. As a result, the flame retardant performance of the styrene resin foam molded product is ensured.
• heat insulating materials for construction are required to have higher flame retardant performance than before.
• Examples of the foam having excellent flame retardancy include a vinyl chloride resin having excellent flame retardancy or a resin foam molded product using a chlorinated vinyl chloride resin as a base resin.
• Patent Document 1 describes a plastic agent, a pyrolytic foaming agent, and a foamable vinyl chloride resin paste containing vinyl chloride resin particles having different degrees of polymerization and particle structure in a specific ratio.
• a vinyl chloride resin foamed sheet obtained by heating above the decomposition temperature of is described.
• Patent Document 2 and Patent Document 3 are obtained by in-mold foam molding of chlorinated vinyl chloride resin pre-foamed particles obtained by using a solvent and a foaming agent compatible with the chlorinated vinyl chloride resin. The foam is listed.
• JP-A-2018-131594 Japanese Patent Application Laid-Open No. 64-132 Japanese Patent Application Laid-Open No. 2-182735
• an object of the embodiment of the present invention is to provide foamable chlorinated vinyl chloride resin particles capable of providing a chlorinated vinyl chloride resin foam molded article having both a high foaming ratio and excellent surface beauty. It is in.
• the inventors of the present application independently discovered that the pore volume (porosity) of the effervescent chlorinated vinyl chloride resin particles contributes to effervescence. Based on this new finding, the present inventors have produced novel foamable chlorinated vinyl chloride resin particles capable of providing a chlorinated vinyl chloride resin foam molded product having excellent lightness (high foaming ratio) and surface beauty. We have succeeded in doing so and have completed the present invention.
• the effervescent chlorinated vinyl chloride resin particles according to the embodiment of the present invention have a porosity of 5.5 (ml / 100 g) or less.
• the method for producing the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention is a die having a plurality of holes of a foaming agent-containing chlorinated vinyl chloride resin melt that has been melt-kneaded by an extruder.
• the resin temperature of the foaming agent-containing chlorinated vinyl chloride resin melt at the tip of the extruder is 130 to 250 ° C. be.
• a die having a plurality of pores of a foaming agent-containing chlorinated vinyl chloride resin melt that has been melt-kneaded with an extruder Immediately after being extruded into pressurized water, the mixture is cut with a rotary cutter to be granulated and solidified by cooling, and the pressure at the tip of the extruder is 4 to 20 MPa.
• the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention can provide a chlorinated vinyl chloride resin foam molded product having a high foaming ratio and excellent surface beauty.
• fluorescence-sensitive vinyl chloride-based resin particles may be simply referred to as “foamable resin particles”
• chlorinated vinyl chloride-based resin foamed particles may be simply referred to as “foamed particles”.
• chlorinated vinyl chloride resin foam molded product is simply referred to as the "foam molded product”.
• the invention described in Patent Document 1 obtains a sheet-like foam having a very low expansion ratio of 1 to 3 times.
• the foam obtained by the technique described in Patent Document 1 has an extremely low foaming ratio and has a simple shape such as a sheet shape. Therefore, the technique described in Patent Document 1 has a problem from the viewpoint of the degree of freedom in shape.
• the inventions described in Patent Documents 2 and 3 are excellent in flame retardancy because the base resin is a chlorinated vinyl chloride resin which is superior in flame retardancy to vinyl chloride resin. Further, according to the techniques described in Patent Documents 2 and 3, it is possible to obtain a foam molded product having a degree of freedom in shape.
• a foaming agent having a high warming coefficient is used and a large amount of organic solvent is used. Therefore, the techniques described in Patent Documents 2 and 3 have problems in terms of environment and cost.
• the present inventors have diligently studied, and as a result, the present inventors have found that the effervescent chlorinated vinyl chloride resin particles have pores and the volume (porosity) of the pores. ) Can contribute to foamability. Then, the present inventors have succeeded in achieving the effect according to one embodiment of the present invention by using the novel foamable chlorinated vinyl chloride resin particles developed based on the new findings.
• the effervescent chlorinated vinyl chloride resin particles according to the embodiment of the present invention are characterized by having a porosity of 5.5 (ml / 100 g) or less.
• the porosity value in the present specification includes a range included by rounding to the first decimal place. According to the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention, it is possible to obtain a chlorinated vinyl chloride resin foam molded product having a high foaming ratio and excellent surface beauty.
• the effervescent chlorinated vinyl chloride resin particles according to one embodiment of the present invention preferably have a porosity of 5.4 (ml / 100 g) or less, and more preferably have a porosity of 5.3 (ml / 100 g). It is less than or equal to, more preferably 5.2 (ml / 100 g) or less, and more preferably 5.1 (ml / 100 g) or less.
• the porosity of the foamable resin particles is within the above range, the foaming agent is less likely to disperse from the foamable resin particles when the foamable resin particles are foamed. As a result, it becomes possible to obtain a foam molded product having a high foaming ratio.
• the conventional method for producing effervescent vinyl chloride resin particles is a method in which a large amount of solvent is used and a foaming agent is impregnated. Therefore, in the conventional method for producing foamable vinyl chloride resin particles, additives and the like are eluted into the foaming agent when the foaming agent is impregnated, so that pores are generated in the obtained foamable vinyl chloride resin particles. It is estimated that it will be easier.
• the lower limit of the porosity of the effervescent chlorinated vinyl chloride resin particles according to the embodiment of the present invention is not particularly limited, but is, for example, 0.5 (ml / 100 g) or more.
• porosity is a pore volume measured by a mercury intrusion method, and can be specifically determined by a measuring method described later.
• the effervescent chlorinated vinyl chloride resin particles according to the embodiment of the present invention preferably have a maximum expansion ratio (times) / volatile content at the time of expansion (% by weight) of 2.2 or more, more preferably 2. 3 or more, more preferably 2.4 or more, more preferably 2.5 or more, more preferably 2.6 or more, still more preferably 2.7 or more, still more preferably 2. It is 8 or more, more preferably 2.9 or more.
• the maximum foaming ratio (times) / volatile matter at the time of foaming (% by weight) is in the above range, high foaming is possible with a small amount of foaming agent, and the foaming efficiency is excellent.
• the maximum foaming ratio is the highest ratio when foaming is evaluated in a heated air atmosphere.
• the method for evaluating foaming in a heated air atmosphere will be described later.
• the volatile matter at the time of foaming is the weight change rate when the foamable chlorinated vinyl chloride resin particles used for the evaluation of foaming in a heated air atmosphere are heated at 150 ° C. for 30 minutes. Can be obtained by the measurement method described later. Since the volatile matter in the effervescent chlorinated vinyl chloride resin particles changes with time, it is preferable that the volatile matter at the time of effervescence and the effervescence evaluation are measured without opening a period.
• chlorinated vinyl chloride resin In one embodiment of the present invention, by using a chlorinated vinyl chloride resin, it is possible to obtain foamable chlorinated vinyl chloride resin particles capable of giving a foamed molded product having both excellent flame retardancy and high foaming ratio. can.
• the chlorinated vinyl chloride resin used in one embodiment of the present invention is usually produced by the following methods (a) and (b) using a vinyl chloride resin as a raw material: (a) the chlorination. With the vinyl-based resin dispersed in an aqueous medium, chlorine is supplied into the aqueous medium, and (i) the obtained mixture is irradiated with a mercury lamp to photochlorine, or (ii) the obtained mixture is used.
• a method of chlorinating in an aqueous medium such as heating chlorination; and (b) a method of chlorinating the vinyl chloride resin in the air layer, such as chlorinating the vinyl chloride resin in the air layer under irradiation with a mercury lamp.
• chlorinated vinyl chloride resin chlorinated various vinyl chloride resins are used.
• the vinyl chloride-based resin to be chlorinated include (a) a homopolymer of vinyl chloride, (b) (i) vinyl chloride, and (ii) another monomer copolymerizable with vinyl chloride. Examples thereof include copolymers. Examples of other monomers copolymerizable with vinyl chloride include ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid ester, vinyl ether and the like.
• the average degree of polymerization of the vinyl chloride resin before chlorination which is the raw material, is not particularly limited.
• the lower limit of the average degree of polymerization is preferably 300 or more, more preferably 400 or more.
• the upper limit of the average degree of polymerization is preferably 3000 or less, more preferably 1500 or less.
• foamed particles having a high foaming ratio tend to be obtained.
• the average degree of polymerization of the chlorinated vinyl chloride resin is considered to be substantially the same as the average degree of polymerization of the vinyl chloride resin before chlorination.
• the average degree of polymerization of the vinyl chloride resin before chlorination is measured according to JIS K67220-2.
• the weight average molecular weight of the chlorinated vinyl chloride resin is not particularly limited, but is preferably in the range of 30,000 or more and 400,000 or less. When the weight average molecular weight is in the above range, foamed particles having a high foaming ratio tend to be obtained.
• the weight average molecular weight is evaluated by gel permeation chromatography in terms of polystyrene-equivalent molecular weight.
• the chlorine content of the chlorinated vinyl chloride resin is preferably in the range of 60% by weight or more and 75% by weight or less from the viewpoint of ensuring foamability.
• the chlorine content is more preferably 64% by weight or more and 70% by weight or less.
• the higher the chlorine content the more foamed particles having a higher foaming ratio tend to be obtained.
• the chlorine content is too high, the melt viscosity tends to increase, and the processability at the time of extrusion tends to be significantly impaired.
• the chlorine content of the chlorinated vinyl chloride resin and the vinyl chloride resin is measured according to the JIS K7385 B method.
• chlorinated vinyl chloride resin only one type of chlorinated vinyl chloride resin may be used, or two or more types may be used in combination.
• foaming agent As the foaming agent contained in the foamable chlorinated vinyl chloride resin particles of one embodiment of the present invention, a known foaming agent can be used, and the foaming agent is not particularly limited, and examples thereof include the following foaming agents.
• the foaming agent include (a) and (i) hydrocarbons such as normal butane, isobutane, normal pentane, isopentan, neopentane, cyclopentane, normal hexane, and cyclohexane, and (ii) dimethyl ether, diethyl ether, and methyl ethyl ether.
• the foamable chlorinated vinyl chloride resin particles according to one embodiment of the present invention preferably contain a physical foaming agent as a foaming agent, and among the physical foaming agents, the carbon number 4 to 6 (carbon number 4, 5 and) It is more preferable to contain at least one saturated hydrocarbon of 6).
• saturated hydrocarbons having 4 to 6 carbon atoms include normal butane, isobutane, normal pentane, isopentane, neopentane, cyclopentane, normal hexane, and cyclohexane.
• the effervescent chlorinated vinyl chloride resin particles according to the embodiment of the present invention can be used as saturated hydrocarbons having 4 to 6 carbon atoms in the foamable chlorinated vinyl chloride resin particles and in the foamable resin particles. From the viewpoint of retention in chlorinated vinyl chloride resin foamed particles, it is preferable to contain at least pentane.
• the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention preferably contain a ketone as a foaming agent from the viewpoint of improving the solubility of the foaming agent in the resin.
• a ketone as a foaming agent from the viewpoint of improving the solubility of the foaming agent in the resin.
• the solubility of saturated hydrocarbons having 4 to 6 carbon atoms in a resin can be further improved.
• the content of the foaming agent is preferably 1 to 40% by weight with respect to 100% by weight of the foamable chlorinated vinyl chloride resin particles.
• the content of the foaming agent is preferably 1 to 40% by weight with respect to 100% by weight of the foamable chlorinated vinyl chloride resin particles.
• the effervescent chlorinated vinyl chloride resin particles may contain a processing aid.
• the processing aid is not particularly limited as it is a processing aid generally used for chlorinated vinyl chloride resins.
• the processing aid include (a) a copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer, such as a styrene-acrylonitrile copolymer (a).
• an impact resistance improver such as a methyl methacrylate-butadiene-styrene polymer.
• Chlorinated polyethylene Chlorinated polyethylene, and the like. From the viewpoint that it is easy to obtain foamed particles having a high foaming ratio and a foamed molded product, the foamable chlorinated vinyl chloride resin particles are a structural unit derived from an aromatic vinyl monomer and an unsaturated nitrile monomer as a processing aid.
• the foamable chlorinated vinyl chloride resin particles are used as processing aids for structural units derived from aromatic vinyl monomers and structural units. It is more preferable to contain a copolymer having a structural unit derived from an unsaturated nitrile monomer and / or an acrylic resin, and chlorinated polyethylene.
• the following Excellent effect In pre-foaming and foam molding under steam heating conditions, it is easy to obtain foamed particles having a high foaming ratio and a foamed polymer.
• Examples of the aromatic vinyl monomer in the copolymer having a structural unit derived from the aromatic vinyl monomer and a structural unit derived from the unsaturated nitrile monomer include styrene, ⁇ -methylstyrene, ethylstyrene, and halogenated. Examples include styrene derivatives such as styrene. Examples of the unsaturated nitrile monomer include acnironitrile and methacrylonitrile.
• the copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer is the above-mentioned aromatic vinyl single amount.
• Structural units derived from other monomers other than the body and unsaturated nitrile monomers ie, structures derived from other monomers copolymerizable with aromatic vinyl monomers and / or unsaturated nitrile monomers It may be said that it is a unit).
• Other monomers copolymerizable with aromatic vinyl monomers and / or unsaturated nitrile monomers include methyl (meth) acrylate, ethyl (meth) acrylate, and N-butyl (meth) acrylate.
• (Meta) acrylic acid ester such as isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid, maleic anhydride, N-substituted maleimide and the like.
• a preferable range of the structural unit derived from the unsaturated nitrile monomer in the copolymer having the structural unit derived from the aromatic vinyl monomer and the structural unit derived from the unsaturated nitrile monomer is as follows.
• the total weight of the copolymer having the structural unit derived from the monomer and the structural unit derived from the unsaturated nitrile monomer is 100% by weight, preferably 5 to 45% by weight, and more preferably 8 to 35% by weight. %, More preferably 10 to 30% by weight.
• the structural unit derived from the unsaturated nitrile monomer is within the above range, it is easy to obtain foamed particles having a high foaming ratio and a foamed molded product.
• a preferred embodiment of the copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer is a styrene-acrylonitrile copolymer.
• the copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer only one type may be used, or two or more types may be used in combination. good.
• a styrene-acrylonitrile copolymer is used as at least one of the copolymers having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer.
• a copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer can easily secure a high expansion ratio of the obtained foamed particles. It is preferable that the weight average molecular weight is higher than the weight average molecular weight of the chlorinated vinyl chloride resin used.
• the weight average molecular weight of the copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer is evaluated by gel permeation chromatography in terms of polystyrene-equivalent molecular weight. ..
• Blendex 869 manufactured by Galata can be used as a copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer.
• the content of a copolymer having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer in the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention is not particularly limited as long as the effect of one embodiment of the present invention is not impaired, but is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the chlorinated vinyl chloride resin, and is preferably 3 to 40 parts by weight. Parts are more preferable, 5 to 35 parts by weight are further preferable, and 8 to 30 parts by weight are particularly preferable.
• the content is (a) 1 part by weight or more with respect to 100 parts by weight of the chlorinated vinyl chloride resin, it becomes easy to obtain foamed particles and / or foamed molded product having a high foaming ratio, and (b) 50.
• foamed particles and / or foamed molded product having excellent flame retardant performance can be obtained.
• the acrylic resin include (a) methyl polymethacrylate obtained by polymerizing methyl methacrylate, methyl polyacrylate obtained by polymerizing methyl acrylate, and (b) (i) methacrylic acid.
• Examples thereof include a copolymer of methyl methacrylate such as ester, butylene, substituted styrene, and acrylonitrile, or at least one monomer copolymerizable with methyl acrylate.
• the acrylic resin it is possible to use an acrylic resin in which the weight average molecular weight of the acrylic resin is higher than the weight average molecular weight of the chlorinated vinyl chloride resin used. It is preferable from the point of view. The weight average molecular weight of the acrylic resin is evaluated by gel permeation chromatography in terms of polystyrene-equivalent molecular weight.
• the acrylic resin for example, Kaneka PA-40 manufactured by Kaneka can be used.
• the content of the acrylic resin in the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention is not particularly limited as long as the effect of the embodiment of the present invention is not impaired, but is chlorinated. It is preferably 1 to 50 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 8 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
• the content is (a) 1 part by weight or more with respect to 100 parts by weight of the chlorinated vinyl chloride resin, it becomes easy to obtain foamed particles and / or foamed molded product having a high foaming ratio, and (b).
• foamed particles and / or foamed molded product having excellent flame retardant performance can be obtained.
• the content of chlorinated polyethylene in the effervescent chlorinated vinyl chloride resin particles according to the embodiment of the present invention is not particularly limited as long as the effect of the embodiment of the present invention is not impaired, but chlorine. It is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and even more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
• the chlorine content of chlorinated polyethylene is measured according to the JIS K7385 B method.
• the effervescent chlorinated vinyl chloride resin particles according to one embodiment of the present invention are, if necessary, flame retardants, stabilizers, lubricants, nucleating agents, as long as the effects of one embodiment of the present invention are not impaired. It may contain a foaming aid, an antistatic agent, a radiant heat transfer inhibitor, a plasticizer, a solvent and a colorant such as a pigment / dye.
• the flame retardant a known flame retardant can be used.
• the flame retardant include (a) brominated flame retardant, (b) phosphorus flame retardant, (c) boron flame retardant, (d) intomesent flame retardant such as melamine polyphosphate and ammonium polyphosphate.
• Examples include (e) melamine-based flame retardants such as melamine cyanurate, (f) hydroxide compounds such as aluminum hydroxide and magnesium hydroxide, and (g) flame retardants such as antimony oxide, zinc oxide and zinc borate. Be done.
• the stabilizer those conventionally used for chlorinated vinyl chloride resin can be used.
• the stabilizer include (a) tin-based stabilizers, (b) antioxidants such as phenol-based compounds, phosphorus-based compounds and amine-based compounds, (c) epoxy-based stabilizers, and (d) zeolites. Be done.
• the amount of each stabilizer used in the effervescent chlorinated vinyl chloride resin particles according to the embodiment of the present invention is not particularly limited as long as the effect of the embodiment of the present invention is not impaired. , 10 parts by weight or less is preferable with respect to 100 parts by weight of the chlorinated vinyl chloride resin.
• lubricant examples include (a) waxes such as ester wax and polyethylene wax, and (b) fatty acid metal salts such as calcium stearate and zinc stearate.
• nucleating agent examples include inorganic compounds such as silica, calcium silicate, wallastonite, kaolin, clay, mica, zinc oxide, calcium carbonate, sodium hydrogen carbonate, zeolite or talc.
• Examples of the radiant heat transfer inhibitor include substances having the property of reflecting, scattering or absorbing light in the near infrared or infrared region, and examples thereof include graphite, graphene, carbon black, expanded graphite, titanium oxide and aluminum. be.
• thermoplastic resin and thermosetting resin may be used in combination with the chlorinated vinyl chloride resin as long as the effect of one embodiment of the present invention is not impaired.
• a vinyl chloride resin is preferable from the viewpoint of flame retardancy.
• the vinyl chloride resin the co-weight of (a) a homopolymer of vinyl chloride, and (b) (i) a vinyl chloride monomer and (ii) another monomer copolymerizable with vinyl chloride. Coalescence and the like can be mentioned.
• examples of other monomers copolymerizable with vinyl chloride include ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid ester, vinyl ether and the like.
• the average degree of polymerization of the vinyl chloride resin is not particularly limited, but is preferably 300 or more and 7,000 or less.
• the blending amount of the other resin is not particularly limited as long as the effect of one embodiment of the present invention is not impaired, but the chlorinated vinyl chloride resin 100 0 to 99 parts by weight is preferable with respect to parts by weight.
• the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention may have any shape as long as they can be pre-foamed and foam-molded as described later.
• the foamable chlorinated vinyl chloride resin particles of one embodiment of the present invention include only general particles (for example, small rounded particles such as spherical, substantially spherical, convex lens-shaped, concave lens-shaped, and spindle-shaped). However, it is assumed that particles with dents are also included.
• the grain weight of the foamable chlorinated vinyl chloride resin particles according to the embodiment of the present invention is from the viewpoint of ensuring the moldability such as the filling property of the foamed particles into the molding die and the surface beauty of the foamed molded product. , 0.5 to 10 mg / grain, more preferably 1 to 8 mg / grain, and even more preferably 3 to 7 mg / grain.
• the foamable chlorinated vinyl chloride resin particles of one embodiment of the present invention reduce the diffusion rate of the foaming agent from the foamable chlorinated vinyl chloride resin particles, or further improve the foaming ratio of the obtained foamed particles.
• true density is preferably 1100 kg / m 3 or more, more preferably 1150 kg / m 3 or more, more preferably 1200 kg / m 3 or more, 1250 kg / m 3 or more is particularly preferable.
• the true density referred to here can be obtained by a measuring method described later.
• Manufacturing method of effervescent chlorinated vinyl chloride resin particles As one embodiment of the method for producing effervescent chlorinated vinyl chloride resin particles (hereinafter, may be referred to as "manufacturing method") of one embodiment of the present invention, the following (1) to (4) are performed.
• a chlorinated vinyl chloride resin and various additives are supplied to the extruder as needed, and the supplied raw materials are melt-kneaded; (2) The foaming agent is dissolved and dispersed in the melt-kneaded product by the extruder or the dispersion equipment after the extruder; (3) A melt-kneaded product (resin melt) of a foaming agent-containing chlorinated vinyl chloride resin composition in a cutter chamber filled with pressurized circulating water through a die having many small holes attached after the extruder.
• foamable chlorinated vinyl chloride resin particles having a predetermined porosity according to the embodiment of the present invention can be easily obtained.
• a chlorinated vinyl chloride resin foam molded product having a high expansion ratio and excellent surface beauty can be obtained by using the foamable chlorinated vinyl chloride resin particles.
• the viscosity of the molten resin can be lowered by melt-kneading the foaming agent and the chlorinated vinyl chloride resin, and the molding processing temperature of the chlorinated vinyl chloride resin can be lowered. Is possible. As a result, thermal decomposition of the chlorinated vinyl chloride resin and, if necessary, the vinyl chloride resin and the additive used in combination is less likely to occur.
• a general extruder can be used as the extruder, and specific examples thereof include a single-screw extruder, a twin-screw extruder, and a tandem extruder.
• the tandem extruder include one in which two single-screw extruders are connected, and one in which a single-screw extruder is connected to a twin-screw extruder.
• the extruder may be used in combination with a dispersion facility such as a static mixer and / or a stirrer without a screw.
• the chlorinated vinyl chloride resin and the vinyl chloride resin used in combination as needed are sufficiently gelled. If the chlorinated vinyl chloride resin or the like is not sufficiently gelled, the rate of dissipation of the foaming agent from the foamable resin particles increases when the chlorinated vinyl chloride resin is used as the foamable resin particles. Therefore, it tends to be difficult for the foaming agent to contribute to foaming. As a result, it may be difficult to obtain foamed particles and a foamed molded product having a high foaming ratio or a high closed cell ratio.
• the resin temperature during resin melt-kneading may affect the thermal decomposition of the chlorinated vinyl chloride-based resin and, if necessary, the vinyl chloride-based resin and additives used in combination. Therefore, the resin temperature of the resin melt at the tip of the extruder is preferably 130 to 250 ° C, more preferably 140 to 240 ° C, and even more preferably 150 to 220 ° C.
• the resin temperature of the resin melt at the tip of the extruder is a value measured by a temperature sensor attached to the tip of the extruder. When two or more extruders are mounted on the upstream side of the die, the tip temperature of the extruder on the most downstream side is defined as the resin temperature of the resin melt at the tip of the extruder in the present specification.
• the "extruder tip” is intended to be the tip on the downstream side of the extruder along the extrusion direction. Therefore, when two or more extruders are mounted on the upstream side of the die, the tip temperature of the extruder mounted on the most downstream side on the downstream side along the extrusion direction is determined in the present specification.
• the resin temperature of the resin melt at the tip of the extruder is 130 ° C. or higher, the resin viscosity of the resin melt decreases and sufficient melt-kneading in the extruder becomes possible.
• the resin temperature of the resin melt exceeds 250 ° C., there is a risk of thermal decomposition of the chlorinated vinyl chloride resin, and if necessary, the vinyl chloride resin and the additive used in combination. As a result, deterioration of the effervescent chlorinated vinyl chloride resin particles may be induced, leading to deterioration of the effervescent performance.
• the die is not particularly limited, but for example, it is preferably as small as 0.3 mm to 2.0 mm in diameter, and more preferably 0.4 mm to 1.5 mm in diameter. Those having holes can be mentioned.
• the tip pressure of the extruder mounted on the upstream side of the die is preferably 4 to 20 MPa, more preferably 6 to 18 MPa, and 7 to 15 MPa. Is more preferable.
• the pressure at the tip of the extruder is a value measured by a pressure sensor attached to the tip of the extruder.
• the tip pressure of the extruder mounted on the most downstream side on the downstream side along the extrusion direction is described herein.
• the tip pressure of the extruder is 4 MPa or more, the foaming agent can be easily dissolved and dispersed in the resin during melt-kneading, and foamable chlorinated vinyl chloride resin particles can be stably obtained.
• tip pressure of the extruder is 20 MPa or less, shear heat generation during melt-kneading can be suppressed, and thermal decomposition of the chlorinated vinyl chloride-based resin and, if necessary, the vinyl chloride-based resin and additives used in combination. Is less likely to occur.
• the temperature of the molten resin (resin melt) immediately before being extruded from the die is assumed to be Tg, which is the glass transition temperature of the resin in a state where no foaming agent is contained. , Tg + 20 ° C. or higher, Tg + 20 ° C. to Tg + 130 ° C., more preferably Tg + 30 ° C. to Tg + 110 ° C., and particularly preferably Tg + 40 ° C. to Tg + 90 ° C.
• the glass transition temperature rises as the chlorine content increases.
• the temperature of the molten resin (resin melt) immediately before being extruded from the die is Tg + 20 ° C. or higher, the viscosity of the extruded molten resin (resin melt) becomes low, and small pore clogging of the die is unlikely to occur.
• the small hole opening rate of the actual die does not decrease. Therefore, it is possible to avoid a situation in which the shapes of the obtained foamable chlorinated vinyl chloride resin particles are distorted or irregular.
• the temperature of the molten resin (resin melt) immediately before being extruded from the die is Tg + 130 ° C. or less, the extruded molten resin (resin melt) is likely to solidify, and the molten resin (resin) is applied to the rotary cutter.
• the molten resin (melt) is less likely to wrap around, and the molten resin (resin melt) can be cut stably.
• the above-mentioned "resin without foaming agent” is intended to be a chlorinated vinyl chloride resin, and a resin containing a vinyl chloride resin, a processing aid and an additive (other than a foaming agent), which are used in combination as necessary. do.
• the "resin without a foaming agent” can be said to be a base resin described later.
• the cutting device for cutting the molten resin (resin melt) extruded into the circulating pressurized cooling water is not particularly limited.
• the cutting device for example, the molten resin (resin melt) is cut into globules with a rotary cutter in contact with a die, and the obtained foamable resin particles are not foamed in pressurized circulating cooling water.
• Examples thereof include an apparatus for transferring foamable resin particles to a centrifugal dehydrator for dehydration and aggregation.
• the conditions of the pressurized circulating cooling water should be adjusted according to the type of resin, additive, foaming agent, etc. used, and / or the content of each component.
• the condition of the pressurized circulating cooling water it is preferable that the foaming of the molten resin (resin melt) extruded from the die is suppressed and the molten resin (resin melt) is stably cut by the cutter.
• the temperature condition of the pressurized circulating cooling water is preferably 40 ° C. to 99 ° C., more preferably 60 to 90 ° C.
• the foaming ratio of the foamable chlorinated vinyl chloride resin particles is obtained by dividing the true density (kg / m 3 ) of the base resin by the true density (kg / m 3 ) of the foamable chlorinated vinyl chloride resin particles. Refers to the value that was set.
• the true density of the base resin and the effervescent chlorinated vinyl chloride resin particles referred to here is the weight W (kg) of the chlorinated vinyl chloride resin pellets or the effervescent chlorinated vinyl chloride resin particles containing ethanol. It is calculated by submerging it in a graduated cylinder and calculating the volume V (m 3 ) from the amount of liquid level rise in the graduated cylinder (submersion method). Specifically, it can be obtained from the measurement method described later.
• the pressure condition of the pressurized circulating cooling water is preferably 0.6 to 2.0 MPa, more preferably 0.7 to 1.8 MPa, still more preferably 0.8 to 0.8. It is 1.6 MPa.
• the foamable chlorinated vinyl chloride resin particles of one embodiment of the present invention are pre-foamed 2 to 110 times by a heating medium such as heated air and / or steam to become chlorinated vinyl chloride resin foam particles. After that, the chlorinated vinyl chloride resin foamed particles can be used for the foamed molded product.
• the steam that can be used may be saturated steam or superheated steam.
• the heating temperature at the time of foaming should be appropriately adjusted depending on the glass transition temperature or melting point of the resin, the content of the foaming agent, and the like, but 90 ° C. or higher is preferable, and 100 ° C. or higher is more preferable.
• the heating temperature at the time of foaming is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, from the viewpoint of suppressing variation in the foaming magnification between the foamed particles or preventing shrinkage of the foamed particles.
• chlorinated vinyl chloride resin foam molded article and its manufacturing method The obtained chlorinated vinyl chloride resin foamed particles are molded by, for example, steam (for example, in-mold molding) using a conventionally known molding machine to produce a chlorinated vinyl chloride resin foam molded product. Depending on the shape of the mold used, it is possible to obtain a molded product having a complicated shape or a block-shaped molded product.
• the chlorinated vinyl chloride resin foam particles and the chlorinated vinyl chloride resin foam molded product according to the embodiment of the present invention have an average cell diameter of preferably 70 to 1000 ⁇ m, more preferably 90 to 800 ⁇ m, and further preferably 100. It is ⁇ 600 ⁇ m.
• the chlorinated vinyl chloride resin foamed molded product has higher heat insulating properties.
• the average cell diameter is 70 ⁇ m or more, it tends to be easy to increase the foaming ratio.
• the average cell diameter is 1000 ⁇ m or less, it is possible to avoid deterioration of the heat insulating performance.
• the average cell diameter of the foamed particles and the foamed molded product in the present specification is determined by the measuring method described later.
• the chlorinated vinyl chloride resin foamed particles and the chlorinated vinyl chloride resin foamed molded product according to the embodiment of the present invention have a closed cell ratio of preferably 70% or more, more preferably 80% or more, still more preferably 90. % Or more.
• the closed cell ratios of the foamed particles and the foamed molded product are in the above range, the foamed particles are likely to be secondarily foamed during molding of the foamed particles, the moldability of the foamed particles is improved, and the surface property of the obtained foamed molded product is improved. Etc. have the effect of improving.
• the closed cell ratio is in the above range, the strength such as the compressive strength of the foamed molded product tends to be increased.
• the foam molded product formed by using the foamable chlorinated vinyl chloride resin particles of one embodiment of the present invention has a high foaming ratio and a high closed cell ratio, and is excellent in flame retardancy. Therefore, it is suitable for various applications such as building heat insulating materials, ceiling materials, metal sandwich panel core materials, food container boxes, cold storage boxes, cushioning materials, agricultural and fishery boxes, bathroom heat insulating materials, and hot water storage tank heat insulating materials. Is.
• One embodiment of the present invention may have the following configuration.
• Effervescent chlorinated vinyl chloride resin particles having a porosity of 5.5 (ml / 100 g) or less.
• foamable chlorinated vinyl chloride resin particles according to any one of [1] to [6], which comprises a chlorinated vinyl chloride resin having an average degree of polymerization of 300 or more and 3000 or less.
• the foamable chlorinated vinyl chloride according to any one of [1] to [9], which contains a copolymer having an aromatic vinyl monomer and an unsaturated nitrile as a structural unit and / or an acrylic resin. Based resin particles.
• a method for producing foamable chlorinated vinyl chloride resin particles which comprises a step and has a resin temperature of a foaming agent-containing chlorinated vinyl chloride resin melt at the tip of the extruder of 130 to 250 ° C.
• a method for producing foamable chlorinated vinyl chloride resin particles which comprises a step and the pressure at the tip of the extruder is 4 to 20 MPa.
• a method for producing a chlorinated vinyl chloride resin foam molded article which comprises the step of molding the chlorinated vinyl chloride resin foamed particles according to any one of [18] [14] or [15].
• effervescent chlorinated vinyl chloride resin particles were weighed and added to the cells described below.
• the cell used was a cell for powder, with a sample chamber volume of 5 cc, a maximum measurement volume of 0.366 cc, a total stem volume of 0.392 cc, a maximum mercury head pressure of 4.45 psia, a cell constant of 11.117 ⁇ L / pF, and external dimensions.
• Cells having I (measurement stem length) 215 mm, H (total stem length) 230 mm, and D (stem diameter) 1.473 mm were used. In addition, None was selected as the Direction measurement, and the measurement was performed without correction.
• the cell to which the sample was added was depressurized to 50 ⁇ mHg and further depressurized for 5 minutes (after holding the state of 50 ⁇ mHg for 5 minutes, mercury was introduced and evaluated). After the cell after depressurization was filled with mercury at a pressure of 1.52 psia, a pressure of 2 to 33000 psia was applied to the mercury to evaluate porosity.
• porosity the amount of mercury that has penetrated into the sample in the pressure range of 20 to 33000 psia is referred to as porosity.
• the amount of mercury that has penetrated into the pores of the effervescent chlorinated vinyl chloride resin particles that are the sample can be determined from the displacement of the mercury column in the sample container.
• the displacement is calculated from the change in capacitance between mercury and the electrodes on the tube wall of the sample container.
• the Autopore IV9500 uses a capacitance type detector to calculate the displacement of the mercury column from the measured capacitance, and calculates the amount of mercury (porosity) that has penetrated into the sample.
• the pressure profile at the time of measurement is as follows, and the pressure was increased to each of the listed pressures (press-fitting pressure), and the equilibrium time at each pressure was measured in 10 seconds.
• r Pore radius
• ⁇ Mercury surface tension
• ⁇ Mercury contact angle
• P Press-fitting pressure.
• the pores existing in the sample are defined as the mercury contact angle of 130 ° and the surface tension of 485 days / cm. Calculated. Both the press-fit contact angle and the exit contact angle were set to 130 °, and the mercury density was set to 13.535 g / ml.
• Volatile content (% by weight) (W 1- W 2 ) / W 1 x 100
• the value (volatile content) measured under the above conditions and calculated based on the above formula is defined as the foaming volatile content (% by weight).
• Grain weight (mg) [Weight of 100 effervescent chlorinated vinyl chloride resin particles (mg)] / 100.
• Effervescent chlorinated vinyl chloride resin particles having a weight of W (kg) are submerged in a measuring cylinder containing ethanol, and the volume V (m 3 ) is obtained from the liquid level rise (submersion method) of the measuring cylinder. Calculated by the formula.
• a uniform formulation was obtained by blending a chlorinated vinyl chloride resin with auxiliary materials such as processing aids, stabilizers, and lubricants. Then, the compound was melt-kneaded using an extruder to obtain chlorinated vinyl chloride resin pellets.
• a chlorinated vinyl chloride resin pellet having a weight of W (kg) is submerged in a measuring cylinder containing ethanol, and the volume V (m 3 ) is obtained from the liquid level rise (submersion method) of the measuring cylinder, and the volume V (m 3) is calculated by the following formula. Calculated.
• ⁇ Measurement of foaming magnification of chlorinated vinyl chloride resin foamed particles The chlorinated vinyl chloride resin foam particles having a weight of W (kg) are submerged in a measuring cylinder containing ethanol, and the volume V (m 3 ) is obtained from the liquid level rise (submersion method) of the measuring cylinder. Calculated in. From the above-mentioned ⁇ Measurement of true density of chlorinated vinyl chloride resin pellets (base resin)>, a base resin density of 1430 kg / m 3 was used.
• Foaming magnification (times) 1430 / (W / V) of chlorinated vinyl chloride resin foamed particles.
• the effervescent chlorinated vinyl chloride resin particles were put into an oven (manufactured by AS ONE Corporation, forced convection constant temperature dryer SOFW-600) heated to 130 ° C. Effervescent resin particles were foamed by changing the heating time in a heated air atmosphere at a temperature of 130 ° C. to obtain foamed particles for each heating time. The heating time is changed at 30-second intervals such as 30 seconds, 60 seconds, 90 seconds, etc. after the effervescent resin particles are put into the oven, and shrinkage of the effervescent particles (decrease in the effervescent particle magnification) due to excessive heating is confirmed. Heated up to.
• the foaming ratio of the obtained foamed particles for each heating time was measured based on the above-mentioned ⁇ Measurement of foaming ratio of chlorinated vinyl chloride resin foamed particles>.
• the highest foaming ratio among the obtained foaming ratios was taken as the maximum foaming ratio of the chlorinated vinyl chloride resin foamed particles.
• the volatile matter is determined on the same day as the foaming evaluation date in the heated air atmosphere. It was calculated and used as the volatile content at the time of foaming (% by weight).
• the effervescent chlorinated vinyl chloride resin particles were put into a prefoaming machine (manufactured by Daikai Kogyo Co., Ltd.). 0.16 MPa of water vapor was introduced into the pre-foaming machine, and the foamable resin particles were foamed under the condition of the temperature inside the pre-foaming machine at 90 to 110 ° C. to obtain foamed particles (chlorinated vinyl chloride resin foamed particles).
• the foamable chlorinated vinyl chloride resin particles were foamed under the condition that the amount of the foamable chlorinated vinyl chloride resin particles charged into the pre-foaming machine was 1000 g to obtain foamed particles.
• the foaming ratio of the obtained foamed particles was measured based on the above-mentioned ⁇ Measurement of foaming ratio of chlorinated vinyl chloride resin foamed particles>.
• ⁇ Measurement of average cell diameter of chlorinated vinyl chloride resin foamed particles The chlorinated vinyl chloride resin foam particles were cut with a razor so as to pass through the center of the chlorinated vinyl chloride resin foam particles, and the cut surface was observed with an optical microscope. The number of cells existing in the area of 2000 ⁇ m ⁇ 2000 ⁇ m square of the cut surface was measured, and the value calculated by the following formula (area average diameter) was taken as the average cell diameter. The average cell diameter of the chlorinated vinyl chloride resin foam particles of each of the five samples was measured, and the average of them was taken as the average cell diameter of the level.
• Average cell diameter ( ⁇ m) 2 ⁇ [2000 ⁇ m ⁇ 2000 ⁇ m / (number of cells ⁇ ⁇ )] 1/2 .
• Closed cell ratio (%) (Vc / Va) x 100 ⁇ Molding evaluation of chlorinated vinyl chloride resin foam particles>
• the foamed particles obtained by the method described in ⁇ Effervescence evaluation in a steam atmosphere> were filled in an in-mold molding die having a length of 400 mm, a width of 400 mm, and a thickness of 25 mm attached to a styrofoam molding machine.
• 0.12 MPa of water vapor was introduced into the mold for 30 seconds to foam the foamed particles in the mold, and then water was sprayed onto the mold for 20 seconds to cool the mold.
• the chlorinated vinyl chloride resin foam molded body was held in the mold until the pressure at which the chlorinated vinyl chloride resin foam molded body pressed the mold became 0.05 MPa (gauge pressure). Then, the chlorinated vinyl chloride resin foam molded product was taken out from the mold to obtain a rectangular parallelepiped chlorinated vinyl chloride resin foam molded product.
• ⁇ Magnification measurement of chlorinated vinyl chloride resin foam molded product The vertical dimension X (mm), the horizontal dimension Y (mm), and the thickness dimension Z (mm) of the foamed molded product were measured with a caliper, and the weight W (g) of the foamed molded product was measured with an electronic balance. The magnification of the foam molded product was calculated from the following formula. From the above-mentioned ⁇ Measurement of true density of chlorinated vinyl chloride resin pellets (base resin)>, a base resin density of 1430 kg / m 3 was used.
• (Vinyl chloride resin) (A-1) Chlorinated vinyl chloride resin [manufactured by Kaneka Corporation, H716S, average degree of polymerization 600, chlorine content 67.6% by weight] (Processing aid) (B-1) Acrylic resin [Kaneka Corporation, Kaneka PA-40] (B-2) Styrene-acrylonitrile copolymer (manufactured by Galata, Blendex 869, weight average molecular weight 2.86 million, component ratio derived from acnillonitrile in the copolymer; 20% by weight) (Foaming agent) (C-1) Normal Pentane [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] (C-2) Acetone [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] (Example 1) [Preparation of effervescent chlorinated vinyl chloride resin particles] 10 parts by weight of acrylic resin (B-1), 5 parts by weight of butyl tin
• a compound was obtained by adding 5 parts by weight of chlorinated polyethylene having a chlorine content of 35% by weight. This formulation was blended to obtain a uniform formulation. Then, the compound was melt-kneaded with a meshing type isodirectional twin-screw extruder to obtain pellets having the above compounding ratio.
• the obtained pellets are pellets of a chlorinated vinyl chloride resin, and are sometimes referred to as a base resin.
• the obtained pellets were subjected to a twin-screw extruder at a feed amount of 40 kg / hr, and the pellets were melt-kneaded.
• the twin-screw extruder used was a meshing type same-directional twin-screw extruder with a shaft diameter of ⁇ 40 mm.
• the discharge rate was 45 kg / hr
• the temperature was 85 ° C. and 1.3 MPa.
• the resin melt was extruded into the pressurized circulating water of. At this time, the pressure at the tip of the extruder was 10 MPa, and the resin temperature of the melt (that is, the resin temperature of the resin melt at the tip of the extruder) was 167 ° C.
• the extruder tip refers to the uniaxial extruder tip.
• the extruded resin melt was cut and granulated using a rotary cutter in contact with the die, and transferred to a centrifugal dehydrator to obtain foamable chlorinated vinyl chloride resin particles having a grain weight of 5.5 mg. ..
• Example 2 In Example 1, the grain weight was 5.5 mg in the same manner as in Example 1 except that 10 parts by weight of the acrylic resin (B-1) was changed to 13 parts by weight of the styrene-acrylonitrile copolymer (B-2). Effervescent chlorinated vinyl chloride resin particles were obtained. At this time, the pressure at the tip of the extruder was 9 MPa, and the resin temperature of the melt was 167 ° C.
• the obtained effervescent chlorinated vinyl chloride resin particles were subjected to porosity evaluation in the same manner as in Example 1.
• the obtained foamable chlorinated vinyl chloride resin particles were evaluated for foaming in a heated air atmosphere in the same manner as in Example 1.
• the obtained foamed particles are subjected to the cell diameter by the methods described in ⁇ Measurement of average cell diameter of chlorinated vinyl chloride resin foamed particles> and ⁇ Measurement of closed cell ratio of chlorinated vinyl chloride resin foamed particles>. And the closed cell ratio was measured. As a result, the average cell diameter was 580 ⁇ m and the closed cell ratio was 96%.
• Example 3 In Example 1, 10 parts by weight of the acrylic resin (B-1) was changed to 13 parts by weight of the styrene-acrylonitrile copolymer (B-2), and 3.8 parts by weight of acetone (C-2) was changed to 2.2.
• a resin melt cooled to a resin temperature of 165 ° C. was prepared in the same manner as in Example 1 except that the temperature was changed to parts by weight and the die temperature of 250 ° C. was changed to 245 ° C. The resin melt was extruded into pressurized circulating water at a temperature of 85 ° C.
• the obtained foamable chlorinated vinyl chloride resin particles were evaluated for porosity and foaming in a heated air atmosphere in the same manner as in Example 1.
• Comparative Example 1 [Preparation of chlorinated vinyl chloride resin particles] 10 parts by weight of acrylic resin (B-1), 5 parts by weight of butyl tin mercapto stabilizer, and 3 parts by weight of lubricant (ester wax, polyethylene wax) with respect to 100 parts by weight of chlorinated vinyl chloride resin (A-1).
• a compound was obtained by adding 5 parts by weight of chlorinated polyethylene having a chlorine content of 35% by weight. This formulation was blended to obtain a uniform formulation. Then, the compound was melt-kneaded with a meshing type isodirectional twin-screw extruder to obtain pellets having the above compounding ratio.
• the obtained pellets were melt-kneaded with a twin-screw extruder. Then, the melt-kneaded product was extruded into a strand shape under the condition of a discharge rate of 8 kg / hr through a die provided with 13 small holes having a diameter of 1.7 mm attached to the tip of the extruder. The extruded melt-kneaded product was cooled and solidified in a water tank, and then the solidified product was cut with a strand cutter to obtain chlorinated vinyl chloride resin particles having a grain weight of 6 mg.
• effervescent chlorinated vinyl chloride resin particles 100 parts by weight of the obtained chlorinated vinyl chloride resin particles and 170 parts by weight of normal pentane (C-1) were placed in a pressure-resistant container having a volume of 100 cc and sealed. Subsequently, the pressure-resistant container was heated in an oil bath under the condition of 120 ° C. for 24 hours, and then the pressure-resistant container was cooled. By such an operation, effervescent chlorinated vinyl chloride resin particles were obtained.
• the porosity evaluation was carried out in the same manner as in Comparative Example 1 except that the obtained effervescent chlorinated vinyl chloride resin particles were allowed to stand in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• the foaming evaluation was carried out in a heated air atmosphere in the same manner as in Comparative Example 1 except that the obtained foamable chlorinated vinyl chloride resin particles were stored in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• Comparative Example 3 In Comparative Example 1, the grain weight was 5.5 mg in the same manner as in Comparative Example 1 except that 10 parts by weight of the acrylic resin (B-1) was changed to 13 parts by weight of the styrene-acrylonitrile copolymer (B-2). Effervescent chlorinated vinyl chloride resin particles were obtained.
• the obtained foamable chlorinated vinyl chloride resin particles were evaluated for porosity and foaming in a heated air atmosphere in the same manner as in Comparative Example 1.
• the porosity evaluation was carried out in the same manner as in Comparative Example 1 except that the obtained effervescent chlorinated vinyl chloride resin particles were allowed to stand in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• the foaming evaluation was carried out in a heated air atmosphere in the same manner as in Comparative Example 1 except that the obtained foamable chlorinated vinyl chloride resin particles were stored in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• effervescent chlorinated vinyl chloride resin particles 100 parts by weight of the obtained chlorinated vinyl chloride resin particles, 153 parts by weight of normal pentane (C-1) and 17 parts by weight of acetone (C-2) were placed in a pressure-resistant container having a volume of 100 cc and sealed. Subsequently, the pressure-resistant container was heated in an oil bath under the condition of 100 ° C. for 12 hours, and then the pressure-resistant container was cooled. By such an operation, effervescent chlorinated vinyl chloride resin particles were obtained.
• Foaming evaluation was carried out in a heated air atmosphere in the same manner as in Comparative Example 1 except that the obtained foamable chlorinated vinyl chloride resin particles were stored at 10 ° C. for 14 days.
• the porosity evaluation was carried out in the same manner as in Comparative Example 1 except that the obtained effervescent chlorinated vinyl chloride resin particles were allowed to stand in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• the foaming evaluation was carried out in a heated air atmosphere in the same manner as in Comparative Example 1 except that the obtained foamable chlorinated vinyl chloride resin particles were stored in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• Comparative Example 7 In Comparative Example 5, the grain weight was 5.5 mg in the same manner as in Comparative Example 5 except that 10 parts by weight of the acrylic resin (B-1) was changed to 13 parts by weight of the styrene-acrylonitrile copolymer (B-2). Effervescent chlorinated vinyl chloride resin particles were obtained.
• Foaming evaluation was carried out in a heated air atmosphere in the same manner as in Comparative Example 1 except that the obtained foamable chlorinated vinyl chloride resin particles were stored at 10 ° C. for 14 days.
• foamable chlorinated vinyl chloride resin particles were obtained in the same manner as above, except that an autoclave with a stirring device having a volume of 6 L was used for preliminary foaming and molding evaluation.
• the obtained foamed particles are subjected to the average cell by the methods described in ⁇ Measurement of average cell diameter of chlorinated vinyl chloride resin foamed particles> and ⁇ Measurement of closed cell ratio of chlorinated vinyl chloride resin foamed particles>.
• the diameter and closed cell ratio were measured.
• the average cell diameter was 540 ⁇ m and the closed cell ratio was 99%.
• the porosity evaluation was carried out in the same manner as in Comparative Example 1 except that the obtained effervescent chlorinated vinyl chloride resin particles were allowed to stand in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• the foaming evaluation was carried out in a heated air atmosphere in the same manner as in Comparative Example 1 except that the obtained foamable chlorinated vinyl chloride resin particles were stored in an environment of a temperature of 23 ° C. and a humidity of 50% for 14 days.
• Example 2 has a volatile content (foaming agent amount) of 9.7%, foam particles 19.3 times, and a molded product 31 times, and Comparative Example 7 has a volatile content (foaming agent amount) of 12.7. In%, the foamed particles were 20.4 times and the molded product was 32 times. Comparative Example 7 has a higher volatile content (amount of foaming agent) during foaming than that of Example 2. With the same volatile content of about 9.7% as in Example 2 (Comparative Example 8), the number of foamed particles is 12 times, and it is not possible to obtain a molded product having 30 times as much as in Example 2. That is, when the porosity is 5.5 (ml / 100 g) or less, the foaming agent is less likely to come off, and it can be seen that the examples have a high foaming ratio and excellent surface beauty as compared with the comparative examples.
• foamable chlorinated vinyl chloride resin particles capable of providing a chlorinated vinyl chloride resin foam molded product having both a high foaming ratio and excellent surface beauty. Further, the foamable resin particles, the foamed particles and the foamed molded product according to the embodiment of the present invention are excellent in flame retardant performance. Therefore, one embodiment of the present invention is for building heat insulating materials, ceiling materials, metal sandwich panel core materials, food container boxes, cold storage boxes, cushioning materials, agricultural and marine products boxes, bathroom heat insulating materials, and hot water storage tank heat insulating materials. It is suitable for various applications such as.

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• 2020
  • 2020-09-29 CN CN202080098752.XA patent/CN115298252B/zh active Active
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