CN113330062B - Expandable polystyrene resin particles, polystyrene pre-expanded particles, and expanded molded article - Google Patents
Expandable polystyrene resin particles, polystyrene pre-expanded particles, and expanded molded article Download PDFInfo
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- CN113330062B CN113330062B CN202080009987.7A CN202080009987A CN113330062B CN 113330062 B CN113330062 B CN 113330062B CN 202080009987 A CN202080009987 A CN 202080009987A CN 113330062 B CN113330062 B CN 113330062B
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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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/224—Surface treatment
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K5/10—Esters; Ether-esters
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- 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
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Abstract
The object is to provide expandable polystyrene resin particles suitable for obtaining an expanded molded article capable of reducing the occurrence of friction noise. A foamable polystyrene resin particle is obtained by coating a surface of a main body of the foamable polystyrene resin particle with a specific oil or fat and a metal salt of a higher fatty acid, and the difference between the static friction coefficient and the dynamic friction coefficient of a foamed molded article obtained by foaming the foamable polystyrene resin particle 40 times is within a specific range.
Description
Technical Field
The present invention relates to expandable polystyrene resin particles, polystyrene pre-expanded particles, and expanded molded articles.
Background
Foamed molded articles obtained by foaming expandable polystyrene resin particles are widely used as packaging materials (trays) for food containers and the like, various packaging materials, building and civil engineering members, automobile members and the like, because of their light weight and excellent cushioning and heat insulation properties.
However, the foam molded article has the following problems: when the foam molded articles are rubbed against each other or against other metal such as a resin member or a steel plate, unpleasant friction noise (stick-slip phenomenon) such as "squeak" is likely to occur. In particular, in the field of automobile members, since vibration is likely to occur when an automobile runs on a poor road or the like, unpleasant frictional noise is likely to occur due to the foam molded body, and this is a cause of deterioration in use feeling.
To solve this problem, attempts have been made to: (a) Coating the surface of the expandable polystyrene resin particles with an aliphatic compound and/or an organosilicon compound; or (b) kneading an aliphatic compound and/or a silicone compound with a foamable polystyrene resin to prepare foamable polystyrene resin particles. However, the method of coating the surface of the expandable polystyrene resin particles with the aliphatic compound and/or the silicone compound may be as follows: when the expandable polystyrene resin particles are molded, the coating material is detached from the surfaces of the expandable polystyrene resin particles. This causes a problem of contamination of devices such as a molding die. In addition, in the method of kneading an aliphatic compound and/or a silicone compound into a foamable polystyrene resin, the proportion of these kneaded materials present on the surface of the foamable polystyrene resin particles is low. Therefore, in order to obtain an undesirable effect of suppressing the generation of friction noise, it is necessary to mix a large amount of an aliphatic compound and/or a silicone compound with a foamable polystyrene resin, and as a result, there is a problem that the strength and the like of the produced foam molded body are impaired.
In order to overcome such a problem, patent document 1 proposes expandable polystyrene resin particles in which polysiloxane is present in the surface portion of the resin particles, and the expandable polystyrene resin particles are copolymers of a polysiloxane-containing monomer and a styrene-based monomer.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-183255
Disclosure of Invention
Problems to be solved by the invention
However, the above-described conventional techniques have room for further improvement for the purpose of providing expandable polystyrene resin particles suitable for obtaining a foamed molded article capable of easily reducing the occurrence of unpleasant friction noise.
An object of one embodiment of the present invention is to provide expandable polystyrene resin particles which are free from the application of a large amount of an external additive, which do not cause contamination of devices such as a pre-foaming machine and a molding die, and which are suitable for obtaining a foam molded article capable of easily reducing the occurrence of an unpleasant frictional noise, and also to provide polystyrene pre-expanded particles and a foam molded article.
Solution for solving the problem
The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a difference between a static friction coefficient of a foam molded article obtained by foaming expandable polystyrene resin particles and a dynamic friction coefficient of the foam molded article can be reduced by coating the surface of the expandable polystyrene resin particles with a grease and a metal salt of a higher fatty acid, wherein the grease contains an ester of a fatty acid having a specific structure. The inventors of the present invention have found that by controlling the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article to an appropriate value, expandable polystyrene resin particles which are free from the application of a large amount of external additives, which are free from the contamination of devices such as a pre-foaming machine and a molding die, and which are suitable for obtaining a foamed molded article capable of easily reducing the generation of unpleasant friction noise, have been achieved.
It is to be noted that, in order to reduce the generation of the unpleasant frictional noise (stick-slip phenomenon), it is a novel finding of the present inventors that the control of the static friction coefficient alone is insufficient and that the difference between the static friction coefficient and the dynamic friction coefficient needs to be controlled to an appropriate value.
Specifically, in the expandable polystyrene resin beads according to one embodiment of the present invention, the surface of the main body of the expandable polystyrene resin beads is coated with a fat or oil containing an ester of a fatty acid containing 50 wt% or more of a carboxylic acid having 8 or more carbon atoms, which has no hydroxyl group and 1 or less double bond, and a metal salt of a higher fatty acid, and the static friction coefficient of the expanded molded article obtained by expanding the expandable polystyrene resin beads 40 times is 0.400 or less, and the difference between the static friction coefficient and the dynamic friction coefficient of the expanded molded article is 0.025 or less.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one aspect of the present invention, the difference between the coefficient of static friction and the coefficient of dynamic friction of the foamed molded article obtained by foaming the expandable polystyrene resin particles and the coefficient of static friction of the foamed molded article can be reduced and controlled to an appropriate value. As a result, according to one aspect of the present invention, it is possible to obtain expandable polystyrene resin particles which are free from the application of a large amount of external additive, which do not cause contamination of devices such as a pre-foaming machine and a molding die, and which are suitable for obtaining a foam molded article obtained by molding polystyrene pre-expanded particles, which can easily reduce the occurrence of unpleasant friction noise (stick-slip phenomenon).
Detailed Description
Embodiments of the present invention are described in detail below. However, the present invention is not limited to these descriptions, and various modifications can be made within the scope described, and embodiments in which the technical means disclosed in the different embodiments and examples are appropriately combined are also included in the technical scope of the present invention. In the present specification, "a to B" representing a numerical range indicates "a or more (including a and more than a) and B or less (including B and more than B)", unless otherwise specified.
In the present specification, the expandable polystyrene resin particles themselves (themselves) are referred to as "expandable polystyrene resin particles main bodies", the expandable polystyrene resin particles having the surface coated with the metal salt of the fat or oil or the higher fatty acid are referred to as "expandable polystyrene resin particles", and the particles obtained when the expandable polystyrene resin particles are pre-expanded are referred to as "polystyrene pre-expanded particles".
The present inventors have found that the technique described in patent document 1 has room for further improvement. The details are as follows. In the technique described in patent document 1, a large amount of a polysiloxane-containing monomer is required to be used to obtain the effect, and there is room for improvement from the viewpoint of preventing contamination of devices such as a pre-foaming machine and/or a molding die. Further, it is preferable that: improving the welding of the expandable polystyrene resin particles having polysiloxane on the surface portion, and further improving the strength of the produced foam molded body. Accordingly, there is room for further improvement in the technique described in patent document 1 described above for the purpose of providing expandable polystyrene resin particles suitable for obtaining a foamed molded article capable of easily reducing the occurrence of unpleasant friction noise.
[ 1. Expandable polystyrene resin particles ]
In the expandable polystyrene resin particles according to one embodiment of the present invention, the surface of the main body of the expandable polystyrene resin particles is coated with a fat or oil containing an ester of a fatty acid containing 50 wt% or more of a carboxylic acid having 8 or more carbon atoms, which has no hydroxyl group and 1 or less double bond, and a metal salt of a higher fatty acid, and the difference between the static friction coefficient and the dynamic friction coefficient is 0.025 or less, and the static friction coefficient of the foamed molded article obtained by foaming the expandable polystyrene resin particles 40 times is 0.400 or less.
The expandable polystyrene resin beads according to one embodiment of the present invention have the above-described configuration, and thus the static friction coefficient of the foamed molded article obtained by foaming the expandable polystyrene resin beads and the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article can be reduced and controlled to an appropriate value. As a result, the expandable polystyrene resin beads according to one embodiment of the present invention can provide a foamed molded article that can easily reduce the occurrence of unpleasant friction noise (stick-slip phenomenon) without applying a large amount of external additives and without causing contamination of devices such as a pre-foaming machine and a molding die.
[ Main body of Expandable polystyrene resin particles ]
The styrene resin constituting the main body of the expandable polystyrene resin beads according to one embodiment of the present invention is preferably a polymer containing 60% by weight or more of styrene as a monomer component. Specific examples of the styrene resin include styrene homopolymers, styrene-ethylene copolymers, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, and styrene-acrylate copolymers. In one embodiment of the present invention, it is more preferable that the main body of the expandable polystyrene resin particles of the base resin is a styrene-acrylate copolymer obtained by copolymerizing a styrene monomer and an acrylate monomer.
Examples of the styrene monomer include: (a) styrene; and (b) styrene derivatives such as α -methylstyrene, p-methylstyrene, t-butylstyrene, and chlorostyrene. One kind of these styrene monomers may be used, or two or more kinds may be used in combination.
Examples of the acrylic acid ester monomer include alkyl acrylates such as methyl acrylate and butyl acrylate. One kind of these acrylic acid ester monomers may be used, or two or more kinds may be used in combination.
The method for producing the main body of the expandable polystyrene resin particles (polymerization method) is not particularly limited, and a known production method may be applied. When the seed suspension polymerization method is used as the polymerization method, the monomer component is also contained in the resin particles serving as the seeds.
[ fat and oil ]
The grease according to one embodiment of the present invention is applied to the surface of the main body of the expandable polystyrene resin particles and used as an external additive. The fat or oil contains an ester of a fatty acid containing 50% by weight or more of a carboxylic acid having 8 or more carbon atoms and having 1 or less double bond and no hydroxyl group, and glycerin, preferably a triglyceride. The carbon number of the carboxylic acid is more preferably 12 or more, still more preferably 14 or more, and still more preferably 16 or more. The carbon number of the carboxylic acid is more preferably 20 or less, and still more preferably 18 or less.
"having 1 or less double bond" means having no double bond or having 1 double bond. That is, the carboxylic acid is either a saturated carboxylic acid or a monounsaturated carboxylic acid.
Specific examples of the carboxylic acid include, for example: (a) Saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, and lignoceric acid; (b) And (3) monobasic unsaturated fatty acids such as palmitoleic acid, oleic acid, elaidic acid, arachic acid, erucic acid and the like. Among them, the carboxylic acid is more preferably 1 or more selected from the group consisting of oleic acid, lauric acid, myristic acid and palmitic acid. These carboxylic acids may be used alone or as a mixture of two or more.
Specific examples of the fat include, for example: vegetable oils such as olive oil (oleic acid: about 78 wt%), canola oil (oleic acid: about 64 wt%), high oleic sunflower oil (oleic acid: about 84 wt%), safflower oil (oleic acid: about 78 wt%), coconut oil (coconut oil) (total amount of lauric acid, myristic acid and palmitic acid: about 69.6 wt%), and the like. Among these, the fat and oil is more preferably 1 or more selected from the group consisting of olive oil and coconut oil. These oils may be used alone or as a mixture of two or more. The fat or oil may be a natural product (vegetable oil) or a synthetic product, and is more preferably a natural product (vegetable oil) in view of ease of obtaining.
In the case of (a) an ester containing a fatty acid and containing 50% by weight or more of a carboxylic acid having 2 or more double bonds in the molecule, (b) an ester containing a fatty acid and containing 50% by weight or more of a carboxylic acid having a hydroxyl group in the fatty acid, (c) an ester containing a fatty acid and containing 50% by weight or more of a carboxylic acid having a carbon number of less than 8 in the fatty acid, and (d) an ester containing a fatty acid and containing only less than 50% by weight of a carboxylic acid having 8 or more carbon numbers and having no hydroxyl group and 1 or less double bonds in the fatty acid, the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article obtained by foaming the foamable polystyrene resin particles cannot be controlled (reduced) to an appropriate value.
In one embodiment of the present invention, the amount of the fat or oil to be applied is preferably 0.01 to 0.10 parts by weight, more preferably 0.02 to 0.10 parts by weight, and still more preferably 0.03 to 0.10 parts by weight, based on 100 parts by weight of the main body of the expandable polystyrene resin particles. When the amount of the oil or fat applied is 0.01 parts by weight or more, the effect of the applied oil or fat can be sufficiently exhibited. As a result, the static friction coefficient, the dynamic friction coefficient, and the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article obtained by foaming the expandable polystyrene resin particles are reduced, and the effect of reducing the generation of friction noise is improved. When the coating amount of the oil or fat is 0.10 parts by weight or less, blocking during pre-foaming (primary foaming) is suppressed.
As a method of applying the oil or fat to the surface of the main body of the expandable polystyrene resin particles, specifically, a method of adding the oil or fat to the main body of the expandable polystyrene resin particles, mixing the mixture, and applying the mixture to the surface thereof, there are various methods. For example, a method of sufficiently mixing the main body of the expandable polystyrene resin particles with the fat or oil using a mixing device such as a mixer is mentioned.
The grease applied to the main body of the expandable polystyrene resin particles is substantially all of the grease attached to the main body of the expandable polystyrene resin particles, and functions as an external additive.
[ Metal salts of higher fatty acids ]
The metal salt of a higher fatty acid according to one embodiment of the present invention is applied to the surface of the main body of the expandable polystyrene resin particles and used as an external additive. The carbon number of the alkyl moiety of the metal salt of the higher fatty acid is preferably 12 to 20, more preferably 16 to 18.
Specific examples of the metal salt of a higher fatty acid include, for example: (a) Metal stearate such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, etc.; (b) oleic acid metal salts such as zinc oleate and magnesium oleate; and (c) a metal laurate such as zinc laurate or calcium laurate. Among them, from the viewpoint of having a higher affinity with the styrene resin and exhibiting a melting point suitable for coating, a metal stearate which is a metal salt of a higher fatty acid is more preferable, and zinc stearate and/or magnesium stearate are more preferable. The metal salts of these higher fatty acids may be used singly or in combination.
In one embodiment of the present invention, the amount of the metal salt of the higher fatty acid applied is preferably 0.03 to 0.20 parts by weight, more preferably 0.05 to 0.20 parts by weight, still more preferably 0.05 to 0.15 parts by weight, and still more preferably 0.08 to 0.15 parts by weight, based on 100 parts by weight of the main body of the expandable polystyrene resin particles. When the coating amount of the metal salt of the higher fatty acid is 0.03 parts by weight or more, blocking at the time of pre-foaming (primary foaming) is suppressed. When the coating amount of the metal salt of the higher fatty acid is 0.20 parts by weight or less, the heat sealing property at the time of molding the expandable polystyrene resin beads becomes good.
As a method of applying a metal salt of a higher fatty acid to the surface of the main body of the expandable polystyrene resin beads, specifically, a method of adding a metal salt of a higher fatty acid to the main body of the expandable polystyrene resin beads and mixing them to apply the mixture to the surface thereof, there are various methods. For example, a method of sufficiently mixing the main body of the expandable polystyrene resin beads and the metal salt of the higher fatty acid using a mixing apparatus such as a mixer is exemplified.
The metal salt of the higher fatty acid applied to the main body of the expandable polystyrene resin beads substantially adheres to the main body of the expandable polystyrene resin beads, and functions as an external additive.
[ additives, etc. ]
The expandable polystyrene resin particles according to one embodiment of the present invention may contain additives such as a monomer component or a solvent, a plasticizer, a foaming agent, a bubble regulator, a nucleating agent, a flame retardant aid, and the like, which remain in the resin particles, within a range that does not inhibit the effects of one embodiment of the present invention. For example, the additives may be (a) added to the polystyrene resin particles during the production of the main body of the expandable polystyrene resin particles, and the polystyrene resin particles and the additives may be kneaded, or (b) added to the main body of the expandable polystyrene resin particles before or after the application of the oil or fat and/or the metal salt of the higher fatty acid. The time point and/or the addition method of these additives are not particularly limited.
The monomer component remaining in the expandable polystyrene resin beads according to one embodiment of the present invention is preferably less than 0.3 parts by weight relative to 100 parts by weight of the expandable polystyrene resin beads main body. The residual monomer component tends to volatilize from the foamed molded article obtained by foaming and molding the expandable polystyrene resin particles. Therefore, the expandable polystyrene resin particles having a residual monomer component of less than 0.3 parts by weight can be suitably used in the medical field, the packaging material field such as food containers which are in direct contact with food, or the automobile field or the building field.
The boiling point of the solvent is preferably 50 ℃ or higher, and specific examples thereof include, for example: (a) Aliphatic hydrocarbons having 6 or more carbon atoms such as toluene, hexane, and heptane; and (b) alicyclic hydrocarbons having 6 or more carbon atoms such as cyclohexane and cyclooctane. One kind of these solvents may be used, or two or more kinds may be used in combination.
The plasticizer may be added at the time of producing the main body of the expandable polystyrene resin particles (at the time of polymerization). The plasticizer is preferably a compound having a boiling point of 200℃or more, which is generally used as a plasticizer, and 1 or two or more kinds may be used in combination.
Specific examples of the foaming agent include, for example: (a) Aliphatic hydrocarbons having 3 to 5 carbon atoms such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane, etc.; and (b) a volatile blowing agent such as fluorocarbon having zero ozone depletion factor such as difluoroethane or tetrafluoroethane. One kind of these foaming agents may be used, or two or more kinds may be used in combination. The amount of the foaming agent to be used is preferably 2 to 10 parts by weight, more preferably 3 to 10 parts by weight, still more preferably 4 to 10 parts by weight, and still more preferably 5 to 9 parts by weight based on 100 parts by weight of the main body of the expandable polystyrene resin particles. When the amount of the foaming agent is 2 parts by weight or more, a desired foaming ratio can be easily obtained. When the amount of the foaming agent is 10 parts by weight or less, aggregation of the main body of the expandable polystyrene resin particles is less likely to occur in the step of impregnating the foaming agent.
Specific examples of the bubble regulator include, for example: (a) Aliphatic bisamides such as methylene bisstearamide and ethylene bisstearamide; and (b) polyethylene wax, etc. One kind of these bubble regulator may be used, or two or more kinds may be used in combination.
Specific examples of the nucleating agent include methyl methacrylate copolymer, polyethylene wax, talc, fatty acid bisamide, ethylene-vinyl acetate copolymer, and the like. Specific examples of the fatty acid bisamide include methylene bis-stearylamide, ethylene bis-stearylamide, hexamethylenedipalmitoylamide, and ethylene bis-oleanamide. One kind of these nucleating agents may be used, or two or more kinds may be used in combination.
Specific examples of the flame retardant include: (a) Halogenated aliphatic hydrocarbon compounds such as hexabromocyclododecane, tetrabromobutane, and hexabromocyclohexane; (b) Brominated phenols such as tetrabromobisphenol A, tetrabromobisphenol F, and 2,4, 6-tribromophenol; (c) Brominated phenol derivatives such as tetrabromobisphenol a-bis (2, 3-dibromopropyl ether), tetrabromobisphenol a-bis (2, 3-dibromo-2-methylpropyl ether), tetrabromobisphenol a-diglycidyl ether, 2-bis [4' - (2 ",3" -dibromoalkoxy) -3',5' -dibromophenyl ] -propane; and (d) bromobutadiene-vinyl aromatic hydrocarbon copolymers such as bromostyrene-butadiene block copolymers, bromorandom styrene-butadiene copolymers and bromostyrene-butadiene graft copolymers (for example, copolymers described in EMERALD3000 or Japanese patent application laid-open No. 2009-516019, manufactured by Chemtura Co., ltd.) and the like, and known flame retardants can be used. One kind of these flame retardants may be used, or two or more kinds may be used in combination.
Specific examples of the flame retardant aid include cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, 2, 3-dimethyl-2, 3-diphenylbutane, and the like, and known flame retardant aids can be used. One kind of these flame retardant aids may be used, or two or more kinds may be used in combination.
[ other external additives ]
The expandable polystyrene resin particles according to one embodiment of the present invention may further contain known external additives such as an antiblocking agent, an antistatic agent, and a water repellent, within a range that does not inhibit the effect of one embodiment of the present invention. These external additives may be added to the main body of the expandable polystyrene resin particles after the completion of the application of the grease, for example, and the time point of the addition is not particularly limited.
[ mixing device ]
In one embodiment of the present invention, when the expandable polystyrene resin particles are coated on their surfaces by adding and mixing oils and fats, metal salts of higher fatty acids, and the like to the main bodies of the expandable polystyrene resin particles, it is preferable to use a mixing device capable of uniformly mixing. As the mixing apparatus, for example, there may be mentioned: (a) Super mixer, norta mixer, general mixer, processing mixer, APEX mixer, henschel mixer, loedige mixer, etc.; and (b) a ribbon blender, a drum blender, etc. The mixing time and other conditions can be adjusted by taking into consideration (a) the mixing ability and (b) the coating amount of the metal salt of the fat or oil and the higher fatty acid.
[ method for producing Expandable polystyrene resin particles ]
As a method for producing expandable polystyrene resin particles according to one embodiment of the present invention, for example, the following methods are mentioned: (i) Adding a main body of expandable polystyrene resin particles and grease (and additives and external additives as needed) to a mixing device, mixing the materials, and coating the grease on the surface of the resin particles, (ii) adding a metal salt of higher fatty acid (and additives and external additives as needed) to the mixing device, mixing the materials, and further coating the metal salt of higher fatty acid on the surface. However, the method for producing expandable polystyrene resin beads according to one embodiment of the present invention is not particularly limited as long as the method is a method in which the metal salts of oils and fats and higher fatty acids can be applied to the surfaces of the main bodies of expandable polystyrene resin beads in the amounts described above, respectively.
In one embodiment of the present invention, by applying an appropriate amount of oil or fat to the surfaces of the main body of the expandable polystyrene resin particles, an appropriate amount of a metal salt of a higher fatty acid can be efficiently applied to the surfaces. Thus, expandable polystyrene resin particles which are suitable for obtaining a foamed molded article capable of easily reducing the occurrence of unpleasant friction noise without applying a large amount of an external additive and without causing contamination of devices such as a pre-foaming machine and a molding die.
[ 2. Polystyrene Pre-expanded particles ]
The polystyrene-based pre-expanded particles according to an embodiment of the present invention can be obtained by pre-expanding (once expanding) the expandable polystyrene-based resin particles. The polystyrene-based pre-expanded particles according to an embodiment of the present invention have such a constitution that they do not apply a large amount of external additives, do not cause contamination of devices, and can provide a foam molded body that can easily reduce the generation of unpleasant frictional noise.
As a method for pre-foaming the expandable polystyrene resin beads, a general method may be employed, for example, a method in which the expandable polystyrene resin beads are heated by a heating medium such as steam using a cylindrical pre-foaming device to foam them. The apparatus used in the pre-foaming and the conditions of the pre-foaming are appropriately set according to the composition of the main body of the expandable polystyrene resin particles and/or the desired pre-expansion ratio, and are not particularly limited.
[ 3. Foam molded article ]
The foam molded article according to an embodiment of the present invention can be obtained by heating and foaming (secondary foaming) the polystyrene-based pre-expanded particles. The foam molded article according to an embodiment of the present invention can be said to be obtained by molding the above-mentioned polystyrene-based pre-expanded particles.
The foam molded body according to an embodiment of the present invention may have the following structure. That is, in another embodiment of the present invention, the foamed molded article is obtained by foaming expandable polystyrene resin particles, wherein the expandable polystyrene resin particles are coated with a grease and a metal salt of a higher fatty acid on the surface of the main body of the expandable polystyrene resin particles, wherein the grease contains an ester of a fatty acid containing 50% by weight or more of a carboxylic acid having 8 or more carbon atoms, which has no hydroxyl group and 1 or less double bond, and wherein the static friction coefficient of the foamed molded article is 0.400 or less and the difference between the static friction coefficient and the dynamic friction coefficient is 0.025 or less.
The foam molded body according to an embodiment of the present invention may have the following structure. That is, another embodiment of the present invention provides a foam molded article comprising a fat and a metal salt of a higher fatty acid, wherein the fat comprises an ester of a fatty acid, and the fatty acid comprises 50% by weight or more of a carboxylic acid having 8 or more carbon atoms, which has no hydroxyl group and 1 or less double bond, and the foam molded article has a coefficient of static friction of 0.400 or less and a difference between the coefficient of static friction and the coefficient of dynamic friction of 0.025 or less.
The foam molded body according to an embodiment of the present invention has an advantage that the generation of unpleasant frictional noise can be easily reduced due to the above-described configuration.
As a method for heating and foaming the polystyrene-based pre-expanded particles, a usual method, for example, an in-mold foaming method in which the pre-expanded particles are filled into a mold and heated by blowing a heating medium such as steam, or the like, may be used. The apparatus used for the heat foaming and the conditions for the heat foaming are not particularly limited, and may be appropriately set according to the composition of the main body of the expandable polystyrene resin particles and/or the desired expansion ratio. The foam molded article, in particular, the in-mold foam molded article has advantages such as easy production of a molded article of a desired shape, light weight, excellent cushioning property and heat insulation property, and is therefore suitable as a packaging material (tray) for food containers, various packaging materials, building and civil engineering members, automobile members, and the like, for example.
The type and content of the fat in the foam molded body according to an embodiment of the present invention, including preferred embodiments, may be the same as those of the fat in item [ 1. Expandable polystyrene resin particles ]. The type and content of the metal salt of a higher fatty acid in the foam molded body according to an embodiment of the present invention may be the same as those of the metal salt of a higher fatty acid described in the item [ 1] expandable polystyrene resin beads, inclusive of preferred embodiments.
[ static coefficient of friction and dynamic coefficient of friction ]
In one embodiment of the present invention, the foam molded article obtained by foaming the expandable polystyrene resin beads to 40 times the expansion ratio (volume ratio) has a static friction coefficient of 0.400 or less and a difference between the static friction coefficient and the dynamic friction coefficient of 0.025 or less. The smaller the static friction coefficient is, the more preferable, for example, 0.350 or less. The smaller the difference between the static friction coefficient and the dynamic friction coefficient, the more preferable is, for example, 0.020 or less, the more preferable is 0.015 or less, the more preferable is 0.012 or less, and the particularly preferable is 0.010 or less. When the static friction coefficient exceeds 0.400 or the difference between the static friction coefficient and the dynamic friction coefficient exceeds 0.025, for example, scraping is increased when the foam molded bodies rub against each other, and the effect of reducing the generation of unpleasant friction noise is reduced.
The smaller the dynamic friction coefficient, the more preferable is, for example, 0.350 or less, preferably 0.330 or less, preferably 0.320 or less, and further preferably 0.315 or less.
The static friction coefficient and the difference between the static friction coefficient and the dynamic friction coefficient can be easily controlled by changing the amount of the oil or fat applied to the surface of the expandable polystyrene resin particle body and the amount of the metal salt of the higher fatty acid to the above-mentioned ranges depending on the composition of the expandable polystyrene resin particle body, etc.
In one embodiment of the present invention, the expansion ratio of the expanded molded article obtained by expanding the expandable polystyrene resin particles may be 0.400 or less, and the difference between the static friction coefficient and the dynamic friction coefficient may be 0.025 or less, if not 40 times. Therefore, it can be said that the foamed molded article having a static friction coefficient of 0.400 or less and a difference between the static friction coefficient and the dynamic friction coefficient of 0.025 or less is produced with a high probability by using the expandable polystyrene resin particles according to one embodiment of the present invention, in other words [ 1] the expandable polystyrene resin particles.
An embodiment of the present invention may have the following configuration.
The expandable polystyrene resin particles are obtained by coating the surfaces of the main bodies of expandable polystyrene resin particles with a fat or oil containing an ester of a fatty acid containing 50 wt.% or more of a carboxylic acid having 8 or more carbon atoms and having one or more double bonds and a metal salt of a higher fatty acid, wherein the difference between the static friction coefficient and the dynamic friction coefficient of a foamed molded article obtained by foaming 40 times the expandable polystyrene resin particles is 0.400 or less.
The expandable polystyrene resin particles according to [ 1], wherein 0.01 to 0.10 parts by weight of the oil or fat is coated on 100 parts by weight of the surface of the main body of the expandable polystyrene resin particles.
The expandable polystyrene resin particles according to [ 1] or [ 2], wherein the carboxylic acid is 1 or more selected from the group consisting of oleic acid, lauric acid, myristic acid and palmitic acid.
The expandable polystyrene resin particles according to any one of [ 1] to [ 3 ], wherein the fat or oil is 1 or more selected from the group consisting of olive oil and coconut oil.
The expandable polystyrene resin beads according to any one of 1 to 4, wherein 0.03 to 0.20 parts by weight of the metal salt of a higher fatty acid is coated on 100 parts by weight of the surface of the main body of the expandable polystyrene resin beads.
The expandable polystyrene resin beads according to any one of [ 1] to [ 5 ], wherein the metal salt of a higher fatty acid is zinc stearate and/or magnesium stearate.
The expandable polystyrene resin particles according to any one of [ 1] to [ 6 ], wherein the static friction coefficient is 0.35 or less.
The expandable polystyrene resin particles according to any one of [ 1] to [ 7 ], wherein the difference between the static friction coefficient and the dynamic friction coefficient is 0.015 or less.
The polystyrene-based pre-expanded particles of any one of [ 1] to [ 8 ], wherein the polystyrene-based resin particles are pre-expanded.
[ 10 ] A foam molded article obtained by molding the polystyrene-based pre-expanded particles of [ 9 ].
Examples
The present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
The method for producing polystyrene-based pre-expanded beads and expanded molded articles, and various measurement methods and evaluation methods in examples and comparative examples are as follows. In addition, "parts" and "%" are weight basis unless otherwise specified.
< manufacturing of polystyrene-based Pre-expanded particles >
The expandable polystyrene resin particles classified into a predetermined particle size by the sieve were charged into a pressurized pre-foaming machine (BHP, manufactured by large-scale industries, ltd.). Then, the expandable polystyrene resin particles are pre-expanded (primary expansion) by heating the expandable polystyrene resin particles using steam as a heating medium and setting the vapor pressure of the blowing gas to 0.08 to 0.12 MPa. Then, the obtained polystyrene-based pre-expanded particles were left at room temperature for 24 hours to obtain polystyrene-based pre-expanded particles.
< determination of blocking >
Polystyrene-based pre-expanded particles having an expansion ratio (volume ratio) of 40 times were produced by the above method. In the process of producing the polystyrene-based pre-expanded beads (pre-expansion ratio: 40 times), when the polystyrene-based pre-expanded beads were taken out from the pre-expander, the pre-expanded beads were passed through a net having a mesh size of 1 cm. The pre-expanded particles that failed the mesh were then recovered and their weight was determined as blocking. The blocking ratio was then calculated based on the following calculation formula.
Blocking ratio [ wt% ] = blocking amount [ g ]/total amount of polystyrene-based pre-expanded particles [ g ] ×100
The blocking was evaluated on the following 4 grades. If the blocking ratio is small, the blocking property is good, and the "good" or more is judged as being acceptable.
Excellent: the blocking rate is below 0.10 wt%
O (good): the blocking ratio exceeds 0.10 wt% and is not more than 0.15 wt%
Delta (bad): the blocking ratio exceeds 0.15 wt% and is not more than 0.20 wt%
X (very bad): the blocking ratio exceeded 0.20% by weight.
< production of foam molded article >
Polystyrene-based pre-expanded particles produced in the above-described manner were filled into a mold having a size of 450mm in the longitudinal direction, 300mm in the transverse direction, and 25mm in the depth. Then, using a molding machine (KR-57, DAISEN, inc.), in-mold foam molding was performed under molding conditions in which the vapor pressure of the blowing gas was set to 0.06MPa using steam as a heating medium, and the polystyrene-based pre-expanded particles were heat-expanded (secondary expanded) to 40 times the expansion ratio (volume ratio) to obtain foam molded articles. The obtained foam molded article was dried at room temperature for 24 hours, and then, the weld ratio and the frictional noise were evaluated. The static friction coefficient and the dynamic friction coefficient were measured using the obtained foam molded article.
(1) Evaluation of weldability
The obtained foam molded body was broken, and the broken surface was observed. The ratio of the fracture surface to the fracture of the expanded beads was determined, and the ratio was evaluated on the following 4 grades. When the ratio of the broken expanded beads is large, the weldability is good, and the "good" or more is judged as being acceptable.
Excellent: the ratio of broken expanded particles is more than 90 percent
O (good): the ratio of breakage of the expanded particles is 80% or more and less than 90%
Delta (bad): the ratio of breakage of the expanded particles is 70% or more and less than 80%
X (very bad): the proportion of broken expanded particles is less than 70%.
(2) Method for measuring static friction coefficient and dynamic friction coefficient
The obtained foam molded body was cut into a plurality of test pieces each having a skin layer on one side thereof by a vertical slicer (manufactured by Sakura engineering service). The test piece was allowed to stand in a constant temperature and humidity chamber at a temperature of 23℃and a humidity of 50% for 12 hours. Thereafter, the skin layers of the two test pieces were rubbed with each other under the same conditions by a surface property tester (HEIDON: 14FW, manufactured by Xindong scientific Co., ltd.) under a load of 10N, a round trip distance of 50mm and a sliding speed of 1.0mm/s 5 times. Then, the coefficient of static friction and the coefficient of dynamic friction are measured at the time of friction, the average value of the coefficient of static friction and the average value of the coefficient of dynamic friction are obtained for 5 times (5 times of round trip), and the difference between the average value of the coefficient of static friction and the average value of the coefficient of dynamic friction is obtained.
The "skin layer" refers to the surface of the foam molded body that directly contacts the inner surface of the mold.
(3) Evaluation of Friction noise
In measuring the static friction coefficient and the dynamic friction coefficient, the degree of discomfort due to friction noise generated when the skin layers of the two test pieces were rubbed against each other was evaluated in the following 4 steps. Then, the "good" or higher was judged as being acceptable.
Excellent: no friction noise is generated at all
O (good): hardly generate friction noise
Delta (bad): generates large friction noise during friction
X (very bad): only the skin layers contact each other to generate a large frictional noise.
[ example 1]
Expandable polystyrene resin particles (product name: kaneoarl TG, manufactured by Kanepool Co., ltd., foaming agent amount: 3.5 to 6.5 parts by weight per 100 parts by weight of resin particles) are used as the main body (base resin) of the expandable polystyrene resin particles according to one embodiment of the present invention. The expandable polystyrene resin particles are prepared by mixing styrene and butyl acrylate in a weight ratio of 95:5 a styrene-butyl acrylate copolymer obtained by copolymerization. The main body of the expandable polystyrene resin particles is classified by a sieve to obtain the main body of the expandable polystyrene resin particles with the particle size of 0.6mm to 1.12 mm.
Vegetable oil (product name: olive oil, manufactured by five industries, co.) was used as the fat and oil according to an embodiment of the present invention. Magnesium stearate (manufactured by daily oil company) is used as the metal salt of the higher fatty acid according to an embodiment of the present invention.
100 parts by weight of the main body of the expandable polystyrene resin particles were put into a Notah mixer (manufactured by HOSOKAWA MICRON Co., ltd.) and then 0.01 part by weight of the vegetable oil was put into the mixer for 120 seconds, followed by stirring for 30 minutes. Thereafter, 0.03 parts by weight of the magnesium stearate was added thereto and stirred for 15 minutes, whereby expandable polystyrene resin particles according to one embodiment of the present invention were obtained.
The obtained expandable polystyrene resin beads were charged into a pressurized pre-foaming machine (BHP, manufactured by large-scale industries, ltd.). Then, the polystyrene-based pre-expanded particles are obtained by pre-expanding (primary expanding) the particles by heating the particles using steam as a heating medium and setting the vapor pressure of the blown air to 0.08 to 0.12 MPa. The pre-expanded particles were then allowed to stand at room temperature for 24 hours and then cured and dried.
The cured and dried polystyrene-based pre-expanded particles were filled into a mold having a size of 450mm in the longitudinal direction, 300mm in the transverse direction, and 25mm in the depth. Then, using a molding machine (KR-57, DAISEN, inc.), in-mold foam molding was performed under molding conditions in which steam was used as a heating medium and the vapor pressure of the blowing gas was set to 0.06MPa, and the polystyrene-based pre-expanded beads were heat-expanded (secondary-expanded) at 40 times the expansion ratio (volume ratio), to obtain foam molded articles. The obtained foam molded article was evaluated for weldability and frictional noise. The static friction coefficient and the dynamic friction coefficient were measured, and the difference between the average value of the static friction coefficient and the average value of the dynamic friction coefficient was obtained. The results are shown in Table 1 together with the composition of the expandable polystyrene resin particles and other evaluations.
[ examples 2 to 9, comparative examples 1 to 8 ]
Expandable polystyrene resin beads, polystyrene pre-expanded beads, and expanded molded articles were obtained in the same manner as in example 1, except that the type and the coating amount of the fat and oil, and the type and the coating amount of the metal salt of the higher fatty acid were changed to the types and the coating amounts shown in table 1 or table 2. The results are shown in Table 1 or Table 2 together with the composition of the expandable polystyrene resin particles and other evaluations.
The fats and oils used in examples 8 and 9 were vegetable oils (product name: coconut oil, manufactured by solar fat and oil Co., ltd.). The metal salt of the higher fatty acid used in examples 2, 5 and 7 to 9 was zinc stearate (manufactured by daily oil Co., ltd.).
In comparative example 1, the foam molded article was not good in weldability, and therefore, the static friction coefficient and the dynamic friction coefficient were not measured and the friction noise was not evaluated. In comparative examples 2 and 5, the polystyrene-based pre-expanded particles were poor in adhesion, and therefore, the static friction coefficient and the dynamic friction coefficient were not measured, and the weldability and the friction noise were not evaluated.
Comparative example 9
As the main body (base resin) of the expandable polystyrene resin particles, expandable polystyrene resin particles having polysiloxane at the surface of the resin particles are used as a copolymer of a polysiloxane-containing monomer and a styrene-based monomer.
The same procedure as in example 1 was repeated except that the type and the coating amount of the fat and oil were changed to those described in table 2, and that the metal salt of the higher fatty acid was not used, to obtain expandable polystyrene resin beads, polystyrene pre-expanded beads and expanded molded articles. The results are shown in Table 2 together with the composition of the expandable polystyrene resin particles and other evaluations.
TABLE 1
TABLE 2
As is clear from the results shown in tables 1 and 2, by applying the metal salts of oils and fats and higher fatty acids to the surfaces of the main bodies of the expandable polystyrene resin particles, expandable polystyrene resin particles can be obtained which are free from the application of a large amount of external additives, which are free from the contamination of devices such as a pre-foaming machine and a molding die, and which are suitable for obtaining expanded molded articles that can easily reduce the generation of unpleasant friction noise.
Industrial applicability
An embodiment of the present invention can provide expandable polystyrene resin particles which are suitable for obtaining a foam molded article which can easily reduce the occurrence of unpleasant friction noise (stick-slip phenomenon) without applying a large amount of an external additive and without causing contamination of a device such as a pre-foaming machine and/or a molding die, and a foam molded article obtained by molding the polystyrene pre-expanded particles. Therefore, an embodiment of the present invention can be suitably used in the fields of packaging materials (trays) such as food containers, various packaging materials, building and construction components, automobile components, and the like, and particularly in the field of automobile components.
Claims (9)
1. A foamable polystyrene resin particle, characterized in that it is obtained by coating the surface of the main body of the foamable polystyrene resin particle with a grease and a metal salt of a higher fatty acid,
the fat and oil contains an ester of a fatty acid containing 50% by weight or more of a carboxylic acid having 8 or more carbon atoms and having no hydroxyl group and one or less double bond,
the carboxylic acid is more than 1 selected from the group consisting of oleic acid, lauric acid, myristic acid and palmitic acid,
the foam molded body obtained by foaming 40 times the expandable polystyrene resin particles has a static friction coefficient of 0.400 or less and a difference between the static friction coefficient and the dynamic friction coefficient of the foam molded body of 0.025 or less.
2. The expandable polystyrene resin beads according to claim 1, wherein 0.01 to 0.10 parts by weight of the oil or fat is applied to 100 parts by weight of the surface of the main body of the expandable polystyrene resin beads.
3. The expandable polystyrene resin particles according to claim 1 or 2, wherein the fat or oil is 1 or more selected from the group consisting of olive oil and coconut oil.
4. The expandable polystyrene resin beads according to claim 1 or 2, wherein 0.03 to 0.20 parts by weight of the metal salt of a higher fatty acid is coated on 100 parts by weight of the surface of the main body of the expandable polystyrene resin beads.
5. The expandable polystyrene resin particles according to claim 1 or 2, wherein the metal salt of a higher fatty acid is zinc stearate and/or magnesium stearate.
6. The expandable polystyrene resin particles according to claim 1 or 2, wherein the static friction coefficient is 0.35 or less.
7. The expandable polystyrene resin particles according to claim 1 or 2, wherein the difference between the static friction coefficient and the dynamic friction coefficient is 0.015 or less.
8. A polystyrene-based pre-expanded particle, which is obtained by pre-expanding the expandable polystyrene-based resin particles according to any one of claims 1 to 7.
9. A foam molded article obtained by molding the polystyrene-based pre-expanded beads according to claim 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4278730A (en) * | 1980-10-01 | 1981-07-14 | Arco Polymers, Inc. | Fast-cooling styrene polymer foams |
| JP2003327739A (en) * | 2002-05-14 | 2003-11-19 | Mitsubishi Kagaku Form Plastic Kk | Foamable polystyrene resin particle |
| JP2015113418A (en) * | 2013-12-12 | 2015-06-22 | 積水化成品工業株式会社 | Foamable polystyrene resin particle for preventing abnormal noise and method of producing the same, pre-foamed particle, and foam molded body |
| JP2018178065A (en) * | 2017-04-21 | 2018-11-15 | 株式会社カネカ | Expandable polystyrene resin particle, polystyrene pre-expanded particle, and expanded molded body |
| WO2019026972A1 (en) * | 2017-08-04 | 2019-02-07 | 株式会社カネカ | Expandable polystyrene resin particles, polystyrene pre-expanded particles, and foam molded body |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3309921B2 (en) * | 1992-10-08 | 2002-07-29 | 鐘淵化学工業株式会社 | Expandable styrene polymer particles and method for producing the same |
| JP4532255B2 (en) * | 2004-12-21 | 2010-08-25 | 積水化成品工業株式会社 | Expandable styrene resin particles and method for producing the same |
| JP5128246B2 (en) * | 2007-11-13 | 2013-01-23 | 株式会社ジェイエスピー | Manufacturing method and molded product of recycle foamable polystyrene resin particles |
| JP2012131955A (en) * | 2010-12-24 | 2012-07-12 | Sekisui Plastics Co Ltd | Expandable polystyrene-based colored resin particle for producing food container, method for producing the same, colored resin pre-expanded particle for producing food container and food container |
| JP2014193950A (en) * | 2013-03-28 | 2014-10-09 | Sekisui Plastics Co Ltd | Foam molding |
| WO2019026966A1 (en) * | 2017-08-04 | 2019-02-07 | 株式会社カネカ | Foamable polystyrene resin particles, polystyrene prefoamed particles, foam-molded article, and methods for producing these |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4278730A (en) * | 1980-10-01 | 1981-07-14 | Arco Polymers, Inc. | Fast-cooling styrene polymer foams |
| JP2003327739A (en) * | 2002-05-14 | 2003-11-19 | Mitsubishi Kagaku Form Plastic Kk | Foamable polystyrene resin particle |
| JP2015113418A (en) * | 2013-12-12 | 2015-06-22 | 積水化成品工業株式会社 | Foamable polystyrene resin particle for preventing abnormal noise and method of producing the same, pre-foamed particle, and foam molded body |
| JP2018178065A (en) * | 2017-04-21 | 2018-11-15 | 株式会社カネカ | Expandable polystyrene resin particle, polystyrene pre-expanded particle, and expanded molded body |
| WO2019026972A1 (en) * | 2017-08-04 | 2019-02-07 | 株式会社カネカ | Expandable polystyrene resin particles, polystyrene pre-expanded particles, and foam molded body |
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