CN113330062A - 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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- CN113330062A CN113330062A CN202080009987.7A CN202080009987A CN113330062A CN 113330062 A CN113330062 A CN 113330062A CN 202080009987 A CN202080009987 A CN 202080009987A CN 113330062 A CN113330062 A CN 113330062A
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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 problem is to provide expandable polystyrene resin particles suitable for obtaining a foamed molded article capable of reducing the generation of frictional noise. An expandable polystyrene resin particle, which is obtained by coating a specific fat or oil and a metal salt of a higher fatty acid on the surface of the main body of the expandable polystyrene resin particle, wherein the difference between the static friction coefficient and the dynamic friction coefficient of an expanded molded article obtained by expanding the expandable 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 lightweight and excellent in cushioning properties and heat insulating properties, and therefore 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.
However, the above foamed molded article has the following problems: when the foamed molded articles rub against each other or against other resin members or metal such as steel plates, unpleasant frictional noise (stick-slip phenomenon) such as "squeak" is easily generated. 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 be generated by the foamed molded article, which causes a loss of the feeling of use.
In order to solve this problem, attempts have been made to: (a) coating the surface of expandable polystyrene resin particles with an aliphatic compound and/or a silicone compound; or (b) mixing an aliphatic compound and/or a silicone compound with an expandable polystyrene resin to prepare expandable 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, these coatings are released from the surfaces of the expandable polystyrene resin particles. This causes a problem of contamination of the molding die and other devices. In the method of kneading the aliphatic compound and/or the silicone compound into the expandable polystyrene resin, the ratio of the kneaded product present on the surface of the expandable polystyrene resin particles is low. Therefore, in order to obtain an undesirable effect of suppressing the generation of frictional noise, it is necessary to knead a large amount of an aliphatic compound and/or a silicone compound into a foamable polystyrene-based resin, and as a result, there is a problem that the strength and the like of the foamed molded article to be produced are impaired.
In order to overcome such a problem, patent document 1 proposes expandable polystyrene resin particles in which polysiloxane is present on the surface portion of the resin particles, and the expandable polystyrene resin particles are a copolymer of a polysiloxane-containing monomer and a styrene monomer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-183255
Disclosure of Invention
Problems to be solved by the invention
However, the above-mentioned prior art has room for further improvement in order to provide expandable polystyrene resin particles suitable for obtaining a foamed molded article which can easily reduce the generation of undesirable frictional noise.
An object of one embodiment of the present invention is to provide expandable polystyrene resin particles suitable for obtaining a foamed molded article in which generation of unpleasant frictional noise can be easily reduced without applying a large amount of external additives, without causing contamination of devices such as a pre-expander and/or a molding die, and polystyrene pre-expanded particles, and a foamed molded article.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that expandable polystyrene resin particles in which a surface of a main body of the expandable polystyrene resin particles is coated with an oil or fat and a metal salt of a higher fatty acid, and the oil or fat contains an ester of a fatty acid having a specific structure can reduce the static friction coefficient of an expanded molded article obtained by expanding the expandable polystyrene resin particles, and the difference between the static friction coefficient and the dynamic friction coefficient of the expanded molded article. The present inventors have also confirmed that the above-mentioned static friction coefficient and the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article are controlled to appropriate values, whereby expandable polystyrene resin beads suitable for obtaining a foamed molded article capable of easily reducing the generation of unpleasant frictional noise without applying a large amount of an external additive and without causing contamination of devices such as a pre-expander and/or a molding die can be obtained, and have completed the present invention.
It is a new finding discovered by the present inventors that it is not sufficient to control only the static friction coefficient and it is necessary to control the difference between the static friction coefficient and the dynamic friction coefficient to an appropriate value in order to reduce the generation of unpleasant frictional noise (stick-slip phenomenon).
Specifically, the expandable polystyrene resin particles according to one embodiment of the present invention are obtained by applying a fat or oil containing 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 no more than 1 double bond to the surface of the main body of the expandable polystyrene resin particles, and a metal salt of a higher fatty acid, wherein the foamed molded article obtained by foaming the expandable polystyrene resin particles 40 times has a static friction coefficient of 0.400 or less, and the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article is 0.025 or less.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one embodiment of the present invention, the static friction coefficient of the foamed molded article obtained by foaming the expandable polystyrene resin particles and the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article can be reduced and controlled to appropriate values. As a result, according to one aspect of the present invention, there can be obtained expandable polystyrene resin particles and an expanded molded article obtained by molding polystyrene pre-expanded particles, which are suitable for obtaining expandable polystyrene resin particles and an expanded molded article obtained by molding polystyrene pre-expanded particles, without applying a large amount of external additives, without causing contamination of devices such as a pre-expander and/or a molding die, and without easily reducing generation of unpleasant frictional noise (stick-slip phenomenon).
Detailed Description
The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the above description, and various modifications can be made within the scope described, and embodiments obtained by appropriately combining technical means disclosed in different embodiments and examples are also included in the technical scope of the present invention. In the present specification, "a to B" indicating a numerical range means "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, expandable polystyrene resin particles themselves (themselves) are referred to as "expandable polystyrene resin particle bodies", expandable polystyrene resin particles having a surface coated with a metal salt of an oil or fat or a higher fatty acid are referred to as "expandable polystyrene resin particles", and particles obtained by pre-expanding the expandable polystyrene resin particles are referred to as "polystyrene pre-expanded particles".
The present inventors have found out a new approach and there is room for further improvement in the technique described in patent document 1. The details are as follows. In the technique described in patent document 1, a large amount of the polysiloxane-containing monomer is required to obtain the effect, and there is room for improvement from the viewpoint of preventing contamination of the apparatus such as the prefoamer and/or the molding die. Further, it is preferable that: improve the fusion of expandable polystyrene resin particles having polysiloxane on the surface, and further improve the strength of the foamed molded article. Therefore, the technique described in patent document 1 has 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 generation of undesirable frictional noise.
[ 1. Expandable polystyrene resin particles ]
An expandable polystyrene resin particle according to an embodiment of the present invention is a foamed molded article obtained by foaming 40 times an expandable polystyrene resin particle, the foamed molded article having a static friction coefficient of 0.400 or less and a difference between the static friction coefficient and a dynamic friction coefficient of 0.025 or less, the expandable polystyrene resin particle being obtained by coating a surface of a main body of the expandable polystyrene resin particle with a fat or oil containing an ester of a fatty acid, the fatty acid containing 50% by weight or more of a carboxylic acid having 8 or more carbon atoms and having no hydroxyl group and no 1 or less double bond, and a metal salt of a higher fatty acid.
The expandable polystyrene resin particles according to one embodiment of the present invention, having the above-described configuration, can reduce the static friction coefficient of the foamed molded article obtained by foaming the expandable polystyrene resin particles and reduce the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article, and can be 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 in which generation of unpleasant frictional noise (stick-slip phenomenon) can be easily reduced without applying a large amount of an external additive thereto and without causing contamination of devices such as a prefoamer and/or a molding die.
[ foamable polystyrene resin particle body ]
The styrene resin constituting the main body of the expandable polystyrene resin particles according to one embodiment of the present invention is preferably a polymer containing 60 wt% or more of styrene as a monomer component. Specific examples of the styrene resin include a styrene homopolymer, a styrene-ethylene copolymer, a styrene-butadiene copolymer, a styrene-acrylonitrile copolymer, and a styrene-acrylate copolymer. In one embodiment of the present invention, a styrene-acrylate copolymer obtained by copolymerizing a styrene monomer and an acrylate monomer is more preferably used as the main component of the expandable polystyrene resin particles of the base resin.
Examples of the styrene-based monomer include: (a) styrene; and (b) styrene derivatives such as α -methylstyrene, p-methylstyrene, t-butylstyrene, chlorostyrene, and the like. One or more of these styrene monomers may be used in combination.
Examples of the acrylate monomer include alkyl acrylates such as methyl acrylate and butyl acrylate. These acrylate monomers may be used alone or in combination of two or more.
The method for producing the main body of expandable polystyrene resin particles (polymerization method) is not particularly limited, and any known production method can be used. When the seed suspension polymerization method is employed as the polymerization method, the monomer component further includes a monomer in the resin particles to be the seed.
[ grease ]
The fat or oil according to an 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 comprises an ester of a fatty acid comprising 50% by weight or more of a carboxylic acid having 1 or less double bonds and having 8 or more carbon atoms and no hydroxyl group, and glycerol, preferably triglyceride. The carbon number of the carboxylic acid is more preferably 12 or more, 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 bonds" means having no double bonds or 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: (a) saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid; (b) and mono-unsaturated fatty acids such as palmitoleic acid, oleic acid, elaidic acid, arachidic acid, and erucic acid. 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 thereof.
Specific examples of the fat or oil include: olive oil (oleic acid: about 78 wt%), rapeseed 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 them, the fat and oil is more preferably 1 or more selected from the group consisting of olive oil and coconut oil. These oils and fats may be used alone or in a mixture of two or more kinds. The fat or oil may be a natural product (vegetable oil) or a synthetic product, and a natural product (vegetable oil) is more preferable in terms of easiness of obtaining and the like.
(a) In the case of a fat or oil containing a fatty acid ester and containing 50% by weight or more of a carboxylic acid having 2 or more double bonds in the molecule, (b) a fat or oil containing a fatty acid ester and containing 50% by weight or more of a carboxylic acid having a hydroxyl group, (c) a fat or oil containing a fatty acid ester and containing 50% by weight or more of a carboxylic acid having a carbon number of less than 8, and (d) a fat or oil containing a fatty acid ester and containing only less than 50% by weight of a carboxylic acid having 1 or less double bonds and having no hydroxyl group, the static friction coefficient of a foamed molded article obtained by foaming expandable polystyrene resin particles and the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article cannot be controlled (reduced) to appropriate values.
In one embodiment of the present invention, the amount of the oil or fat 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 expandable polystyrene resin particle main body. When the amount of the fat or oil to be applied is 0.01 parts by weight or more, the effects of the fat or oil to be applied can be sufficiently exhibited. As a result, the effect of reducing 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 is improved. When the amount of the fat or oil applied is 0.10 parts by weight or less, blocking during pre-foaming (primary foaming) is suppressed.
Various methods are available for applying the oil or fat to the surface of the main body of the expandable polystyrene resin particles, specifically, for applying the oil or fat to the surface of the main body of the expandable polystyrene resin particles by mixing the oil or fat with the main body of the expandable polystyrene resin particles. For example, a method of sufficiently mixing the main body of expandable polystyrene resin particles and the fat or oil using a mixing device such as a mixer can be mentioned.
The oil or fat applied to the main body of the expandable polystyrene resin particles substantially entirely adheres 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 expandable polystyrene resin particles and used as an external additive. The number of carbon atoms in the alkyl moiety of the metal salt of a higher fatty acid is preferably 12 to 20, more preferably 16 to 18.
Specific examples of the metal salt of the higher fatty acid include: (a) metal stearates such as zinc stearate, calcium stearate, magnesium stearate, and aluminum stearate; (b) metal oleate such as zinc oleate and magnesium oleate; and (c) metal laurate salts such as zinc laurate and calcium laurate. Among them, a metal stearate which is a metal salt of a higher fatty acid is more preferable, and zinc stearate and/or magnesium stearate are further preferable, from the viewpoint of having more excellent affinity with a styrene-based resin and showing a melting point suitable for coating. These metal salts of higher fatty acids may be used alone or in combination of two or more.
In one embodiment of the present invention, the amount of the metal salt of a higher fatty acid to be applied is preferably 0.03 to 0.20 part by weight, more preferably 0.05 to 0.20 part by weight, even more preferably 0.05 to 0.15 part by weight, and even more preferably 0.08 to 0.15 part by weight, based on 100 parts by weight of the expandable polystyrene resin particle main body. When the amount of the metal salt of a higher fatty acid to be applied is 0.03 parts by weight or more, blocking at the time of prefoaming (primary foaming) is suppressed. When the amount of the metal salt of a higher fatty acid to be applied is 0.20 parts by weight or less, the expandable polystyrene resin particles can be favorably shaped for weldability.
Various methods are available as a method of applying a metal salt of a higher fatty acid to the surface of expandable polystyrene resin particles, specifically, a method of adding a metal salt of a higher fatty acid to expandable polystyrene resin particles, mixing them, and applying them to the surface. For example, a method of sufficiently mixing the main body of expandable polystyrene resin particles and the metal salt of a higher fatty acid using a mixing device such as a mixer is exemplified.
The metal salt of the higher fatty acid applied to the main body of the expandable polystyrene resin particles is substantially entirely adhered to the main body of the expandable polystyrene resin particles and functions as an external additive.
[ additives, etc. ]
The expandable polystyrene resin particles according to an embodiment of the present invention may contain additives such as monomer components, solvents, plasticizers, foaming agents, bubble control agents, nucleating agents, flame retardants, and flame retardant aids, which remain in the resin particles, in a range that does not inhibit the effects of an embodiment of the present invention. These additives may be added to the polystyrene resin particles during production of the expandable polystyrene resin particle main body, and the polystyrene resin particles and the additives may be kneaded together, or (b) may be added to the expandable polystyrene resin particle main body before or after application of the fat or oil and/or the metal salt of a higher fatty acid. The time point and/or the method of addition of these additives are not particularly limited.
The amount of the monomer component remaining in the expandable polystyrene resin particles according to one embodiment of the present invention is preferably less than 0.3 part by weight based on 100 parts by weight of the expandable polystyrene resin particle 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, expandable polystyrene resin particles having a residual monomer content of less than 0.3 parts by weight can be suitably used in the medical field, the field of packaging materials such as food containers which come into direct contact with foods, the automobile field or the construction field.
The boiling point of the solvent is preferably 50 ℃ or higher, and specific examples thereof include: (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 during (at the time of) production of the main body of the expandable polystyrene resin particles. The plasticizer is preferably a compound having a boiling point of 200 ℃ or higher, which is generally used as a plasticizer, and 1 kind of the plasticizer may be used, or two or more kinds of the plasticizer may be used in combination.
Specific examples of the blowing agent include: (a) aliphatic hydrocarbons having 3 to 5 carbon atoms such as propane, n-butane, isobutane, n-pentane, isopentane, and neopentane; and (b) volatile blowing agents such as fluorocarbons having an ozone destruction coefficient of zero, e.g., difluoroethane and tetrafluoroethane. One of these blowing agents may be used, or two or more of these blowing agents may be used in combination. The amount of the blowing agent 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 expandable polystyrene resin particle main body. When the amount of the blowing agent is 2 parts by weight or more, a desired expansion ratio can be easily obtained. When the amount of the blowing 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 blowing agent.
Specific examples of the bubble control agent include: (a) aliphatic bisamides such as methylene bisstearamide and ethylene bisstearamide; and (b) polyethylene wax, etc. One of these bubble control agents may be used, or two or more of them may be used in combination.
Specific examples of the nucleating agent include methyl methacrylate copolymers, polyethylene wax, talc, fatty acid bisamides, ethylene-vinyl acetate copolymers, and the like. Specific examples of the fatty acid bisamide include methylene bisstearyl amide, ethylene bisstearyl amide, hexamethylene bispalmitic amide, and ethylene bisoleic amide. One of these nucleating agents may be used, or two or more of these nucleating agents 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, 2,4, 6-tribromophenol and the like; (c) bromophenol derivatives such as tetrabromobisphenol A-bis (2, 3-dibromopropyl ether), tetrabromobisphenol A-bis (2, 3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-diglycidyl ether, and 2, 2-bis [4 ' - (2 ", 3" -dibromoalkoxy) -3 ', 5 ' -dibromophenyl ] -propane; and (d) a brominated butadiene-vinyl aromatic hydrocarbon copolymer such as a brominated styrene-butadiene block copolymer, a brominated random styrene-butadiene copolymer, or a brominated styrene-butadiene graft copolymer (for example, a copolymer described in EMERALD3000 manufactured by Chemtura corporation or Japanese patent application laid-open No. 2009-516019), and a known flame retardant can be used. One of these flame retardants may be used, or two or more of them may be used in combination.
Specific examples of the flame retardant aid include cumene hydroperoxide, dicumyl peroxide, tert-butyl hydroperoxide, and 2, 3-dimethyl-2, 3-diphenylbutane, 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 an embodiment of the present invention may further contain known external additives such as an antiblocking agent, an antistatic agent, and a water repellent agent, in a range that does not inhibit the effects of the embodiment of the present invention. These external additives may be added to the expandable polystyrene resin particle main body after completion of application of the fat or oil, for example, and the time of addition is not particularly limited.
[ mixing apparatus ]
In one embodiment of the present invention, when the expandable polystyrene resin particles are coated with a mixture of fats and oils and metal salts of higher fatty acids added to the main body of the expandable polystyrene resin particles, it is preferable to use a mixing device capable of uniformly mixing the components. Examples of the mixing device include: (a) mixers such as super mixers, nauta mixers, universal mixers, process mixers, APEX mixers, henschel mixers, Loedige mixers and the like; and (b) a stirrer such as a ribbon stirrer or a drum stirrer. The mixing equipment can adjust conditions such as mixing time in consideration of (a) mixing ability and (b) coating amount of the fat or oil and the metal salt of the higher fatty acid.
[ method for producing Expandable polystyrene resin particles ]
The method for producing expandable polystyrene resin particles according to an embodiment of the present invention includes, for example, the following methods: (i) charging a main body of expandable polystyrene resin particles and an oil or fat (and an additive and an external additive as needed) into a mixing device, mixing them, and applying the oil or fat on the surface of the resin particles, and (ii) charging a metal salt of a higher fatty acid (and an additive and an external additive as needed) into the mixing device, mixing them, and further applying a metal salt of a higher fatty acid on the surface. However, the method for producing expandable polystyrene resin particles according to an embodiment of the present invention is not particularly limited as long as the oil or fat and the metal salt of a higher fatty acid can be applied to the surface of the main body of the expandable polystyrene resin particles in the above amounts.
In one embodiment of the present invention, an appropriate amount of the oil or fat is applied to the surface of the main body of the expandable polystyrene resin particles, whereby an appropriate amount of the metal salt of the higher fatty acid can be efficiently applied to the surface. Thus, expandable polystyrene resin beads can be obtained which are suitable for obtaining a foamed molded article which is free from application of a large amount of an external additive, which does not cause contamination of a device such as a prefoamer and/or a molding die, and which is capable of easily reducing generation of unpleasant frictional noise.
[ 2. polystyrene series prefoaming particles ]
The polystyrene pre-expanded particles according to an embodiment of the present invention can be obtained by pre-expanding (primary expansion) the expandable polystyrene resin particles. The polystyrene pre-expanded beads according to one embodiment of the present invention have such a structure, and therefore, it is possible to provide a foamed molded article which does not require a large amount of external additives to be applied, does not cause contamination of the apparatus, and can easily reduce generation of unpleasant frictional noise.
As a method for pre-foaming expandable polystyrene resin particles, a general method can be employed, for example, a method in which expandable polystyrene resin particles are heated and expanded by a heating medium such as steam using a cylindrical pre-foaming device. The apparatus used for the prefoaming and the conditions for the prefoaming may be appropriately set depending on the composition of the expandable polystyrene resin particle body, the desired prefoaming ratio, and the like, and are not particularly limited.
[ 3. foamed molded article ]
The foamed molded article according to an embodiment of the present invention can be obtained by thermally foaming (secondary foaming) the polystyrene-based pre-expanded particles. The foamed molded article according to an embodiment of the present invention can be said to be formed by molding the polystyrene pre-expanded beads.
The foamed molded article according to an embodiment of the present invention may have the following configuration. Specifically, a foamed molded article according to another embodiment of the present invention is obtained by foaming expandable polystyrene resin particles, wherein the expandable polystyrene resin particles are obtained by coating a surface of a main body of the expandable polystyrene resin particles with a fat and a metal salt of a higher fatty acid, the fat and the fat comprise an ester of a fatty acid, the fatty acid comprises 50 wt% or more of a carboxylic acid having 8 or more carbon atoms, the carboxylic acid has no hydroxyl group and 1 or less double bond, and the foamed molded article has a static friction coefficient of 0.400 or less and a difference between the static friction coefficient and a dynamic friction coefficient of 0.025 or less.
The foamed molded article according to an embodiment of the present invention may have the following configuration. That is, a foamed molded article according to another embodiment of the present invention includes an oil and fat including an ester of a fatty acid including 50% by weight or more of a carboxylic acid having 8 or more carbon atoms, the carboxylic acid having no hydroxyl group and having 1 or less double bonds, and a metal salt of a higher fatty acid, and the foamed molded article has a static friction coefficient of 0.400 or less and a difference between the static friction coefficient and a dynamic friction coefficient of 0.025 or less.
The foamed molded article according to an embodiment of the present invention has an advantage that generation of unpleasant frictional noise can be easily reduced by the above-described configuration.
As a method for heat-foaming polystyrene-based pre-expanded particles, a general method such as 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 can be used. The apparatus used for the thermal foaming and the conditions for the thermal foaming may be appropriately set depending on the composition of the expandable polystyrene resin particle main body, the desired expansion ratio, and the like, and are not particularly limited. The foamed molded article, particularly the in-mold foamed molded article, has advantages such as easy production of a molded article of a desired shape, and is lightweight and excellent in cushioning properties and heat insulating properties, and therefore is suitable as a packaging material (tray) for food containers and the like, various packaging materials, building and civil engineering members, automobile members, and the like.
The type and content of the fat or oil in the foamed molded article according to an embodiment of the present invention may be the same as those of the fat or oil in the item [ 1. expandable polystyrene resin beads ], including the preferred embodiments. The type and content of the metal salt of a higher fatty acid in the expanded molded article 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 ], including preferred embodiments.
[ coefficient of static friction and coefficient of dynamic friction ]
In one embodiment of the present invention, the foamed molded article obtained by foaming the expandable polystyrene resin particles to an expansion ratio (volume ratio) of 40 times 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 is, for example, 0.350 or less. The smaller the difference between the static friction coefficient and the dynamic friction coefficient, the more preferable it is, for example, 0.020 or less, more preferably 0.015 or less, still more preferably 0.012 or less, and particularly preferably 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, scratching is increased when the foamed molded bodies rub against each other, and the effect of reducing the generation of unpleasant frictional noise is reduced.
The smaller the dynamic friction coefficient is, the more preferable is, for example, 0.350 or less, preferably 0.330 or less, preferably 0.320 or less, and more 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 fat or oil and the amount of the metal salt of the higher fatty acid applied to the surface of the expandable polystyrene resin particle main body to fall within the above ranges, depending on the composition of the expandable polystyrene resin particle main body, and the like.
In one embodiment of the present invention, the expansion ratio of the foamed molded article obtained by foaming the expandable polystyrene resin particles may be 0.400 or less in static friction coefficient and 0.025 or less in difference between the static friction coefficient and the dynamic friction coefficient, even if the expansion ratio is 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 obtained with a high probability by using, as a raw material, the expandable polystyrene-based resin particles according to one embodiment of the present invention, in other words, the expandable polystyrene-based resin particles described in the item of [ 1. expandable polystyrene-based resin particles ].
An embodiment of the present invention may have the following configuration.
[ 1] Expandable polystyrene resin particles obtained by coating a surface of a main body of expandable polystyrene resin particles with a fat or oil containing 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 bonds, and a metal salt of a higher fatty acid, wherein a foamed molded article 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 a dynamic friction coefficient of 0.025 or less.
[ 2] the expandable polystyrene resin particles according to [ 1], wherein 0.01 to 0.10 parts by weight of the oil or fat is applied to the surface of 100 parts by weight of the main body of the expandable polystyrene resin particles.
[ 3 ] the expandable polystyrene-based resin particles according to [ 1] or [ 2], wherein the carboxylic acid is at least 1 selected from the group consisting of oleic acid, lauric acid, myristic acid and palmitic acid.
[4 ] the expandable polystyrene-based resin particles according to any one of [ 1] to [ 3 ], wherein the oil or fat is at least 1 selected from the group consisting of olive oil and coconut oil.
The expandable polystyrene-based resin particles according to any one of claims 1 to 4, wherein 0.03 to 0.20 parts by weight of the metal salt of the higher fatty acid is applied to 100 parts by weight of the surface of the main body of the expandable polystyrene-based resin particles.
[ 6 ] the expandable polystyrene-based resin particles according to any one of [ 1] to [ 5 ], wherein the metal salt of a higher fatty acid is zinc stearate and/or magnesium stearate.
[ 7 ] the expandable polystyrene-based resin particles according to any one of [ 1] to [ 6 ], wherein the static friction coefficient is 0.35 or less.
[ 8 ] the expandable polystyrene-based 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.
[ 9 ] A polystyrene-based pre-expanded particle which is obtained by pre-expanding the expandable polystyrene-based resin particle according to any one of [ 1] to [ 8 ].
An expanded molded article characterized by being obtained by molding the polystyrene-based pre-expanded particles mentioned in [ 9 ].
Examples
The present invention will be described in further detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
The methods for producing polystyrene pre-expanded beads and expanded molded articles, various measurement methods, and evaluation methods in examples and comparative examples are as follows. In addition, "part(s)" and "%" are based on weight unless otherwise specified.
Production of polystyrene Pre-expanded particles
Expandable polystyrene resin particles classified to a predetermined particle diameter by a sieve are introduced into a pressure prefoamer (BHP, manufactured by kakko corporation). Then, the expandable polystyrene resin particles are pre-expanded (primary expanded) by heating the resin particles using steam as a heating medium with an injection vapor pressure of 0.08 to 0.12 MPa. And then placing the obtained polystyrene pre-expanded particles for 24 hours at room temperature to obtain the polystyrene pre-expanded particles.
< measurement of blocking Property >
Polystyrene-based pre-expanded beads having an expansion ratio (volume ratio) of 40 times were produced by the above-described method. In the production of the polystyrene pre-expanded beads (pre-expansion ratio: 40 times), when the polystyrene pre-expanded beads are taken out from the pre-expander, the pre-expanded beads are passed through a net having a mesh opening of 1 cm. The pre-expanded particles that failed to pass through the web were then recovered and their weight was measured as the amount of blocking. The blocking rate was then calculated based on the following calculation formula.
Blocking ratio [% by weight ] -, blocking amount [ g ]/total amount of polystyrene-based pre-expanded beads [ g ]. times.100
The blocking property was evaluated on the following 4 grades. When the blocking rate was small, the blocking property was good, and it was judged as "good" or more as "good".
Excellent: the blocking rate is 0.10 wt% or less
O (good): the blocking rate is more than 0.10 wt% and 0.15 wt% or less
Δ (poor): the blocking rate is more than 0.15 wt% and 0.20 wt% or less
X (very poor): the blocking rate is more than 0.20 wt%.
< production of foamed molded article >
Polystyrene pre-expanded beads produced by the above method were filled into a mold having a size of 450mm in the longitudinal direction x 300mm in the transverse direction x 25mm in depth. Then, the resulting foam was molded by in-mold expansion using a molding machine (KR-57, DAISEN, Inc.) under a molding condition in which the blowing vapor pressure was 0.06MPa using steam as a heating medium, and polystyrene pre-expanded particles were thermally expanded (secondary expansion) to an expansion ratio (volume ratio) of 40, to obtain a foamed molded article. The obtained foam-molded article was dried at room temperature for 24 hours, and then the fusion bonding rate and the frictional noise were evaluated. The resulting foamed molded article was used to measure the static friction coefficient and the dynamic friction coefficient.
(1) Evaluation of weldability
The obtained foamed molded article was broken, and the broken surface was observed. The ratio of the rupture at the rupture surface to the rupture at the expanded bead interface was determined and evaluated on the following 4 grades. When the ratio of the foamed particles broken is large, the weldability is good, and it is judged as "good" or more as acceptable.
Excellent: the breaking rate of the foamed particles is more than 90 percent
O (good): the breaking rate of the foaming particles is more than 80 percent and less than 90 percent
Δ (poor): the breaking rate of the foaming particles is more than 70 percent and less than 80 percent
X (very poor): the proportion of the foamed particles that break is less than 70%.
(2) Method for measuring static friction coefficient and dynamic friction coefficient
The obtained foam-molded article was cut into a length of 60mm, a width of 60mm and a thickness of 4mm by a vertical cutter (manufactured by Sakura engineering service), to prepare a plurality of test pieces each having a skin layer on one surface. 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. Then, the skin layers of the two test pieces were rubbed by reciprocating them 5 times under the conditions of a load of 10N, a reciprocating distance of 50mm and a sliding speed of 1.0mm/s using a surface texture tester (HEIDON type: 14FW, manufactured by New Toyobo scientific Co., Ltd.) under the same environment. Then, the static friction coefficient and the dynamic friction coefficient were measured during friction, and the average value of the static friction coefficient and the average value of the dynamic friction coefficient were obtained 5 times (5 times of reciprocation), and the difference between the average value of the static friction coefficient and the average value of the dynamic friction coefficient was obtained.
The "skin layer" refers to the surface of the foam molding directly contacting the inner surface of the mold.
(3) Evaluation of frictional noise
In the measurement of the static friction coefficient and the dynamic friction coefficient, the degree of discomfort due to frictional noise generated when the skin layers of the two test pieces were rubbed against each other was evaluated in the following 4 stages. Then, it was judged as "good" or more as "pass".
Excellent: no frictional noise at all
O (good): hardly generates frictional noise
Δ (poor): generating large friction noise during friction
X (very poor): the skin layers only contact each other to generate a large frictional noise.
[ example 1]
Expandable polystyrene resin particles (product name: Kanepearl TG, manufactured by kayakiki co., ltd., and amount of foaming agent: 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 to obtain the styrene-butyl acrylate copolymer. The main body of the expandable polystyrene resin particles is classified by a sieve to prepare the main body of the expandable polystyrene resin particles having a particle diameter of 0.6mm to 1.12 mm.
As the fat or oil according to an embodiment of the present invention, vegetable oil (product name: olive oil, manufactured by Wuxi industries, Ltd.) was used. Magnesium stearate (manufactured by Nichigan Ltd.) was used as the metal salt of the higher fatty acid according to one embodiment of the present invention.
100 parts by weight of the main body of expandable polystyrene resin particles were put into a nauta mixer (made by HOSOKAWA MICRON corporation), and then 0.01 part by weight of the vegetable oil was put into the nauta mixer for 120 seconds and stirred for 30 minutes. Thereafter, 0.03 parts by weight of magnesium stearate was added thereto, and the mixture was stirred for 15 minutes to obtain expandable polystyrene resin particles according to an embodiment of the present invention.
The expandable polystyrene resin beads thus obtained were charged into a pressure prefoamer (BHP, manufactured by Daiko industries Co., Ltd.). Then, the resulting mixture is pre-expanded (primary expansion) by heating the mixture using steam as a heating medium at an injection vapor pressure of 0.08 to 0.12MPa to obtain polystyrene pre-expanded particles. The pre-expanded beads were then allowed to stand at room temperature for 24 hours, and then aged and dried.
The cured and dried polystyrene pre-expanded beads were filled in a mold having a length of 450mm, a width of 300mm and a depth of 25 mm. Then, using a molding machine (KR-57, manufactured by DAISEN, ltd.) under molding conditions using steam as a heating medium and a blowing vapor pressure of 0.06MPa, in-mold expansion molding was performed, and polystyrene pre-expanded particles were heat-expanded (secondary expansion) at an expansion ratio (volume ratio) of 40 times to obtain an expanded molded article. The resulting foamed molded article was evaluated for weldability and frictional noise. Further, 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 expandable polystyrene resin particles and other evaluations.
[ examples 2 to 9, comparative examples 1 to 8 ]
Expandable polystyrene resin particles, polystyrene pre-expanded particles, and expanded molded articles were obtained in the same manner as in example 1, except that the type and amount of the fat or oil and the type and amount of the higher fatty acid metal salt were changed to those 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 SUANYOU GYNOLIA Co., Ltd.). The metal salt of the higher fatty acid used in examples 2, 5, 7 to 9 was zinc stearate (manufactured by Nichikoku corporation).
In comparative example 1, the measurement of the static friction coefficient and the dynamic friction coefficient and the evaluation of the frictional noise were not performed because the weldability of the foamed molded article was poor. In comparative examples 2 and 5, the polystyrene-based pre-expanded beads had poor blocking properties, and therefore, the static friction coefficient and the dynamic friction coefficient were not measured, and the weldability and the frictional noise were not evaluated.
[ comparative example 9 ]
Expandable polystyrene-based resin particles, which are copolymers of a polysiloxane monomer and a styrene-based monomer and in which a polysiloxane is present on the surface portion of the resin particles, are used as the main expandable polystyrene-based resin particle body (base resin).
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 amount of the fat or oil were changed to those shown in table 2, and a metal salt of a higher fatty acid was not used. The results are shown in table 2 together with the composition of 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 oil or fat and the metal salt of a higher fatty acid to the surface of the expandable polystyrene resin particle main body, it is possible to obtain expandable polystyrene resin particles suitable for obtaining an expanded molded article which is free from application of a large amount of external additives, does not cause contamination of devices such as a pre-expander and/or a molding die, and can easily reduce generation of unpleasant frictional noise.
Industrial applicability
One embodiment of the present invention can provide expandable polystyrene resin particles suitable for obtaining an expanded molded article in which generation of unpleasant frictional noise (stick-slip phenomenon) can be easily reduced without applying a large amount of an external additive, without causing contamination of a device such as a pre-expander and/or a molding die, and an expanded molded article obtained by molding polystyrene pre-expanded particles. Therefore, one embodiment of the present invention can be suitably used in the fields of packaging materials (trays) such as food containers, various packaging materials, civil engineering and construction members, automobile members, and the like, particularly in the field of automobile members.
Claims (10)
1. An expandable polystyrene resin particle characterized in that it is obtained by coating a surface of a main body of an expandable polystyrene resin particle with an oil or fat and a metal salt of a higher fatty acid,
the fat or oil contains 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 one or less double bonds,
the foamed molded article obtained by foaming the expandable polystyrene resin particles by a factor of 40 has a static friction coefficient of 0.400 or less, and the difference between the static friction coefficient and the dynamic friction coefficient of the foamed molded article is 0.025 or less.
2. The expandable polystyrene resin particles 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 particles.
3. The expandable polystyrene-based resin particles according to claim 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.
4. The expandable polystyrene resin particles according to any one of claims 1 to 3, wherein the fat or oil is 1 or more selected from the group consisting of olive oil and coconut oil.
5. The expandable polystyrene-based resin particles according to any one of claims 1 to 4, wherein 0.03 to 0.20 part by weight of the metal salt of the higher fatty acid is applied to 100 parts by weight of the surface of the main body of the expandable polystyrene-based resin particles.
6. The expandable polystyrene-based resin particles according to any one of claims 1 to 5, wherein the metal salt of a higher fatty acid is zinc stearate and/or magnesium stearate.
7. The expandable polystyrene-based resin particles according to any one of claims 1 to 6, wherein the static friction coefficient is 0.35 or less.
8. The expandable polystyrene-based resin particles according to any one of claims 1 to 7, wherein the difference between the static friction coefficient and the dynamic friction coefficient is 0.015 or less.
9. Polystyrene-based pre-expanded particles obtained by pre-expanding the expandable polystyrene-based resin particles according to any one of claims 1 to 8.
10. A foamed molded article obtained by molding the polystyrene-based pre-expanded beads according to claim 9.
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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 |
| JP7183161B2 (en) * | 2017-08-04 | 2022-12-05 | 株式会社カネカ | EXPANDABLE POLYSTYRENE-BASED RESIN PARTICLES, POLYSTYRENE-BASED PRE-EXPANDED PARTS, EXPANDED MOLDED PRODUCTS, AND METHOD FOR MANUFACTURING THEREOF |
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| 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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