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CN114514284A - Resin composition, resin molded article comprising same, and method for producing resin molded article - Google Patents

Resin composition, resin molded article comprising same, and method for producing resin molded article Download PDF

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Publication number
CN114514284A
CN114514284A CN202080068560.4A CN202080068560A CN114514284A CN 114514284 A CN114514284 A CN 114514284A CN 202080068560 A CN202080068560 A CN 202080068560A CN 114514284 A CN114514284 A CN 114514284A
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CN
China
Prior art keywords
resin
resin composition
aluminum flake
coupling agent
flake particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202080068560.4A
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Chinese (zh)
Other versions
CN114514284B (en
Inventor
冈崎信平
杉生大辅
刘洋
札场哲哉
黑井秀一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honda Motor Co Ltd
Toyo Aluminum KK
Original Assignee
Honda Motor Co Ltd
Toyo Aluminum KK
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Publication of CN114514284A publication Critical patent/CN114514284A/en
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Publication of CN114514284B publication Critical patent/CN114514284B/en
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The invention provides a resin composition which is used for manufacturing an injection molding body and can inhibit mold pollution. A resin composition for use in the production of an injection molded body, comprising a thermoplastic resin and aluminum flake particles, wherein a coupling agent is adhered to at least a part of the surface of the aluminum flake particles.

Description

Resin composition, resin molded article comprising same, and method for producing resin molded article
Technical Field
The present invention relates to a resin composition, a resin molded article containing the resin composition, and a method for producing the resin molded article.
Background
In the injection molded article, a weld line, also called a weld line, is sometimes formed at a position corresponding to a portion where the molten resin in the mold joins. This weld line may cause a defect in appearance and structure in the injection molded article. As a means for preventing the formation of a weld line, a cold-hot method is known, in which injection molding is performed by heating a mold temperature to a temperature equal to or higher than the glass transition temperature of a resin that is a raw material of the injection molded body.
On the other hand, as the resin composition for producing the injection molded body, there are known: for the purpose of imparting a high-grade feeling to the injection molded article, differentiating the injection molded article from another injection molded article, or the like, a resin composition containing an aluminum pigment or the like is used. However, it is known that: when an injection molded article is obtained by injection molding using the resin composition as a raw material and the cold-hot method, the formation of weld lines is prevented, but the aluminum pigment is unevenly distributed on the surface of the molten resin in the mold and adheres to the mold, which causes the mold to be contaminated. In contrast, japanese patent application laid-open nos. 2016-: the aluminum flake particles constituting the aluminum pigment are coated with a resin, thereby suppressing the above-mentioned mold contamination.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-010957
Patent document 2: japanese patent laid-open No. 2014-185328
Disclosure of Invention
However, further improvements for suppressing mold contamination are required for the techniques disclosed in patent documents 1 and 2. This is because: in the techniques disclosed in patent documents 1 and 2, there is a possibility that the resin coating the aluminum flake particles is melted in the mold at a high temperature, and it is estimated that: the resin is mixed with the molten resin that melts around the aluminum flake particles, and therefore, the aluminum flake particles cannot be sufficiently prevented from being unevenly distributed on the surface of the molten resin. Therefore, in injection molding in which the weld line is prevented by the cold-hot method, a technique for suppressing mold contamination when a resin composition containing an aluminum pigment or the like is used as a raw material has not been realized, and development of the technique is strongly desired.
In view of the above circumstances, an object of the present invention is to provide a resin composition capable of suppressing mold contamination, a resin molded article including the resin composition, and a method for producing the resin molded article.
The present inventors have conducted intensive studies to solve the above problems, and have completed the present invention. Specifically, although the detailed mechanism is unclear, it was found that: among the numerous additives incorporated in such a resin composition, the coupling agent effectively acts to suppress mold contamination. Based on this insight, consider: the present invention has been achieved by a resin composition comprising a thermoplastic resin and aluminum flake particles having a coupling agent adhered to at least a part of the surface thereof, wherein the resin composition is capable of suppressing mold contamination when injection molding by a cold-hot method is performed.
That is, the present invention has the following features.
The resin composition according to the present invention is a resin composition for use in the production of an injection molded article, and the resin composition contains a thermoplastic resin and aluminum flake particles, and a coupling agent is adhered to at least a part of the surface of the aluminum flake particles.
The coupling agent is preferably a silane coupling agent.
The coupling agent is more preferably an amino silane coupling agent.
The content of the coupling agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the aluminum flake particles.
In the state where the coupling agent is adhered to the surface, the content of the aluminum flake particles is preferably 0.5 to 230 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
The thermoplastic resin is preferably at least 1 resin selected from the group consisting of acrylonitrile-butadiene-styrene resin, styrene-acrylonitrile copolymer, polystyrene, and polyethylene.
The resin molded article according to the present invention contains the above resin composition.
The method for producing a resin molded article according to the present invention includes: a step of preparing the resin composition; injecting the resin composition into a mold having an inner wall surface maintained at a temperature higher by at least 70 ℃ than the glass transition temperature of the thermoplastic resin; and a step of cooling the resin composition in the mold to obtain a resin molded body.
Effects of the invention
According to the present invention, a resin composition capable of suppressing mold contamination, a resin molded article including the resin composition, and a method for producing the resin molded article can be provided.
Detailed Description
Hereinafter, embodiments according to the present invention (hereinafter also referred to as "the present embodiment") will be described in further detail. In the present specification, the expression "a to B" means the upper limit and the lower limit of the range (i.e., a to B), and when no unit is described in a and only a unit is described in B, the unit of a is the same as the unit of B.
[ resin composition ]
The resin composition according to the present embodiment is a resin composition for producing an injection molded body. The resin composition contains a thermoplastic resin and aluminum flake particles. A coupling agent is attached to at least a part of the surface of the aluminum flake particle. In the case where injection molding by a cold-hot method is performed on the resin composition having the above-described characteristics, mold contamination can be suppressed. Hereinafter, each feature of the resin composition according to the present embodiment will be described.
The resin composition is used for producing an injection molded article as described above. "injection molded body" means: a molded article obtained by applying a conventionally known injection molding method to a resin composition containing a thermoplastic resin. In particular to: the resin composition is heated and fluidized in a cylinder provided in a conventionally known injection molding machine, and then injected into a mold, and cooled in the mold to obtain a molded article. In the present specification, the term "resin molded article" means: an injection molded article obtained by applying an injection molding method to the resin composition according to the present embodiment.
< thermoplastic resin >
The resin composition according to the present embodiment includes the thermoplastic resin and the aluminum flake particles as described above. The "thermoplastic resin" in the present specification means: a resin that can be used in the above-described injection molding method by softening it by heating. Therefore, even a resin generally included in the concept of "thermosetting resin" may be treated as a "thermoplastic resin" in the present specification as long as it is a resin that is softened by heating and can be used in the above-described injection molding method.
Examples of the thermoplastic resin contained in the resin composition include: rubber-reinforced resins such as acrylonitrile-butadiene-styrene resins (ABS resins), acrylonitrile-styrene-acrylate resins (ASA resins), and acrylonitrile-ethylene-propylene-diene-styrene resins (AES resins); styrene-based (copolymer) polymers such AS polystyrene (PS resin), styrene-acrylonitrile copolymer (AS resin), styrene-maleic anhydride copolymer, and (meth) acrylate-styrene copolymer; olefin resins such as polyethylene (PE resin) and polypropylene; a cyclic polyolefin resin; a polyester resin; a polyamide resin; a polycarbonate resin; a polyarylate resin; a polyacetal resin; vinyl chloride resins such as polyvinyl chloride, ethylene-vinyl chloride polymers, and polyvinylidene chloride; a (meth) acrylic resin such as a (copolymer) polymer of 1 or more kinds of (meth) acrylic acid esters such as polymethyl methacrylate (PMMA); polyphenylene ether; polyphenylene sulfide; fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride; a liquid crystalline polymer; imide resins such as polyimide, polyamideimide, and polyetherimide; ketone resins such as polyether ketone and polyether ether ketone; sulfone resins such as polysulfone and polyethersulfone; a polyurethane resin; polyvinyl acetate; polyethylene oxide; polyvinyl alcohol; a polyvinyl ether; polyvinyl butyral; phenoxy resin; a photosensitive resin; biodegradable plastics, and the like.
The various thermoplastic resins may be contained in the resin composition alone, or may be contained in the resin composition in a mixture of 2 or more. The term "(meth) acrylic acid" as used herein refers to at least one of acrylic acid and methacrylic acid. The term "(meth) acryloyl" also means at least either acryloyl or methacryloyl.
The thermoplastic resin is preferably 1 or more resins selected from the group consisting of ABS resins, AS resins, PS resins, and PE resins. Accordingly, a resin molded article having a desired shape can be obtained from the resin composition with a high yield, and the resin molded article can be applied to various applications.
The weight average molecular weight (Mw) of the thermoplastic resin is preferably 2000 to 7000000, and more preferably 2000 to 1000000. The thermoplastic resin preferably has a glass transition temperature of 280 ℃ or lower, and more preferably has a glass transition temperature of 150 ℃ or lower. Even when the thermoplastic resin has at least one of the weight average molecular weight and the glass transition temperature, a resin molded article having a desired shape can be obtained from the resin composition with a high yield, and the resin molded article can be applied to various applications.
< aluminum flake particle >
The resin composition according to the present embodiment contains the thermoplastic resin and the aluminum flake particles as described above. A coupling agent is attached to at least a part of the surface of the aluminum flake particle. In the present specification, "aluminum flake particles" mean: particles containing aluminum and having a flat flake shape. That is, the aluminum flake particles may be flake particles composed of aluminum, flake particles composed of an aluminum alloy, or flake particles obtained by vapor deposition of aluminum on a base material of a metal (copper, nickel, iron, tin, or an alloy thereof) or a base material of a non-metal (ceramic particles such as aluminum oxide and titanium dioxide, glass, mica, or the like). These aluminum flake particles can be obtained by a conventionally known method. The surface of the aluminum flake particles is preferably smooth from the viewpoint of exhibiting desired surface gloss, whiteness, and brilliance in the resin composition.
In the resin composition, the content of the aluminum flake particles is preferably 0.5 to 230 parts by mass with respect to 100 parts by mass of the thermoplastic resin in a state where a coupling agent, which will be described later, is adhered to the surfaces of the aluminum flake particles. In the case where the content of the aluminum flake particles in the resin composition is within the above range with respect to 100 parts by mass of the thermoplastic resin, the mold contamination can be more sufficiently suppressed. Here, in the case where the resin composition is not prepared in a master batch form as described later, the content of the aluminum flake particles in the resin composition is preferably 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin in a state where a coupling agent described later is adhered to the surface of the aluminum flake particles.
When the resin composition is not prepared in the form of a master batch as described later, if the content of the aluminum flake particles is less than 0.5 parts by mass, the resin composition tends to fail to have desired surface glossiness. When the content of the aluminum flake particles exceeds 50 parts by mass, the dispersibility of the aluminum flake particles in the thermoplastic resin is deteriorated, and sufficient strength tends not to be obtained in the resin molded product obtained from the resin composition. In the case where the resin composition is not prepared in the form of a master batch as described later, the content of the aluminum flake particles is more preferably 0.5 to 25 parts by mass with respect to 100 parts by mass of the thermoplastic resin in a state where the coupling agent is adhered to the surfaces of the aluminum flake particles, from the viewpoint of more sufficiently exhibiting the effects of the present invention.
On the other hand, the resin composition may be prepared in the form of a masterbatch as described below. In this case, the content of the aluminum flake particles is preferably 5 parts by mass or more and 230 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin in a state where a coupling agent described later is adhered to the surface of the aluminum flake particles.
The average particle diameter (D50) of the aluminum flake particles is preferably 2 to 150 μm, more preferably 5 to 50 μm. The average thickness (t) of the aluminum flake particles is preferably 0.01 to 10 μm, more preferably 0.08 to 1.6. mu.m. The average aspect ratio of the aluminum flake particles is preferably 5 to 2500, and more preferably 10 to 150.
Here, the "average aspect ratio" refers to a ratio of an average particle diameter (D50) to an average thickness (t) of the aluminum flake particles, and specifically can be determined from a formula of an average particle diameter (D50) (in μm)/an average thickness (t) of the aluminum flake particles (in μm).
The average particle diameter (D50) and the average thickness (t) of the aluminum flake particles can be determined by the following measurement methods in the case where the resin composition is used as a measurement object and in the case where a resin molded product obtained by applying an injection molding method to the resin composition is used as a measurement object.
When the average particle diameter (D50) and the average thickness (t) of the aluminum flake particles are measured using the resin composition as a measurement object, the average particle diameter and the average thickness (t) can be determined by the following methods. That is, the particles of the resin composition were observed by a Scanning Electron Microscope (SEM), the particle diameters of 50 or more aluminum flake particles were measured, and the average particle diameter of the aluminum flake particles was calculated based on the particle diameters of 50 or more. When it is difficult to observe the particle size of the aluminum flake particles due to the particles, the average particle size of the aluminum flake particles can be calculated by SEM with respect to the particles after the treatment by polishing the surface of the particles to form a flat surface or by forming the particles into a film shape by using a hot press. As for the average thickness of the aluminum flake particles, 50 or more aluminum flake particles may be measured by SEM to calculate the average thickness, similarly to the measurement of the average particle diameter. When it is difficult to observe the thickness of the aluminum flake particles due to the particles, the surface of the particles may be polished or formed into a thin film, and the average thickness of the aluminum flake particles may be calculated by SEM with respect to the treated particles, as in the measurement of the average particle diameter.
The average particle diameter (D50) and the average thickness (t) of the aluminum flake particles can be calculated in the same manner as the method for calculating the average particle diameter and the average thickness of the aluminum flake particles using the resin composition as the object to be measured when the resin molded article is used as the object to be measured. When the state of the resin molded body is difficult to measure, the surface of the resin molded body may be cut to form a flat cross section, and the cross section may be observed with an SEM to determine the average particle diameter and the average thickness.
(coupling agent)
A coupling agent is attached to at least a part of the surface of the aluminum flake particle. The coupling agent is: a compound having a reactive group which chemically bonds to an inorganic compound and a reactive group which chemically bonds to an organic compound in one molecule, and having an action of bonding the inorganic compound and the organic compound by itself. Accordingly, the adhesion between the aluminum flake particles and the thermoplastic resin can be improved, and therefore, when the resin composition is used for injection molding, the aluminum flake particles can be prevented from being unevenly distributed on the surface of the molten thermoplastic resin in the mold.
Here, "attaching" a coupling agent to the surface of the aluminum flake particle means: the coupling agent is chemically bonded to the surface of the aluminum flake particle by a reactive group of the coupling agent that is chemically bonded to the inorganic compound.
The coupling agent is preferably a silane coupling agent. For example, as the silane coupling agent, R is preferably usedA-Si(ORB)3Or RA-SiRB(ORB)2(RA: an alkyl, aryl or alkenyl group having 2 to 18 carbon atoms, RB: alkyl group having 1 to 3 carbon atoms) of a silane coupling represented by the formulaAnd (4) a coupling agent. Furthermore, RAPreferably with functional groups. As RAExamples of the functional group include: amino groups, ureido groups, epoxy groups, thioether groups, vinyl groups, (meth) acryloxy groups, mercapto groups, ketimino groups, glycidyl groups, phenyl groups, imidazolyl groups, isocyanate groups, and the like. The coupling agent is more preferably an amino silane coupling agent.
Specific examples of the silane coupling agent include: gamma-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris (beta-methoxyethoxy) silane, vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, N '-bis [3- (trimethoxysilyl) propyl ] ethylenediamine, N-methacryloxypropyltrimethoxysilane, N-propyltrimethoxysilane, N-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, N' -bis [3- (trimethoxysilyl) propyl ] ethylenediamine, N-dimethylbutylidene, N-butylidene, N-or a mixture of a compound, a mixture of a compound of formula (I, a compound of formula (I) or a compound of formula (I, a compound of formula (I) or a compound of formula (I or a compound of formula, Tetraisocyanatosilane, monomethyltriisocyanatosilane, and the like.
As the coupling agent, a titanium (titanate) -based coupling agent, a zirconia-based coupling agent, an aluminum-based coupling agent, or the like can be used. Specific examples of the titanate-based coupling agent include: isopropyl isostearyl diacrylic acid ester titanate, isopropyl triisostearoyl titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate, tetrakis (2, 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, and the like. Specific examples of the zirconia-based coupling agent include: zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium tributoxystearate, zirconium acetate, etc. Specific examples of the aluminum-based coupling agent include: alkylalkoxyaluminum diisopropyl ester, zirconium aluminate, alkylaluminum acetoacetate, and alkylaluminum alkoxy diisopropyl ester.
The content of the coupling agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the aluminum flake particles. The content of the coupling agent is more preferably 0.15 to 3 parts by mass, and still more preferably 0.2 to 2 parts by mass, per 100 parts by mass of the aluminum flake particles. When the content of the coupling agent is in the above range, the adhesion between the aluminum flake particles and the thermoplastic resin can be further improved.
When the content of the coupling agent is less than 0.1 parts by mass with respect to 100 parts by mass of the aluminum flake particles, the adhesion between the aluminum flake particles and the thermoplastic resin tends to be insufficient. When the content of the coupling agent exceeds 10 parts by mass with respect to 100 parts by mass of the aluminum flake particles, the aluminum flake particles tend to aggregate easily.
The method for adhering the coupling agent to the surface of the aluminum flake particle is not particularly limited as long as the effect of the present invention is not adversely affected, and conventionally known methods can be employed. For example, the coupling agent can be attached to the surface of the aluminum flake particles by kneading the coupling agent and the aluminum flake particles with a conventionally known kneader, mixer, or stirrer. In this case, an organic solvent may be appropriately added. As the organic solvent, for example, 1 selected from the group consisting of ethanol, isopropanol, toluene, xylene, MEK, methanol, hexane, butanol, acetone, ethylene glycol, methyl cellosolve, and butyl cellosolve can be used alone. A mixed solvent obtained by mixing 2 or more selected from the group consisting of the above organic solvents may also be used.
When the coupling agent and the aluminum flake particles are kneaded by a conventionally known kneader or the like, deionized water is preferably added as needed. This makes it possible to facilitate the adhesion of the coupling agent to the surface of the aluminum flake particle. The amount of deionized water added may be 0.03 to 3 parts by mass per 100 parts by mass of the aluminum flake particles. For the purpose of promoting the adhesion reaction of the coupling agent to the surface of the aluminum flakes, the temperature in the cylinder of the kneader containing the coupling agent and the aluminum flake particles may be heated to 20 to 80 ℃, or the temperature of a kneaded product containing the coupling agent and the aluminum flake particles obtained by using the kneader may be heated to 20 to 80 ℃.
(organic Compounds such as fatty acids)
The aluminum flake particles may have 1 or more organic compounds selected from the group consisting of fatty acids such as oleic acid and stearic acid, aliphatic amines, aliphatic amides, aliphatic alcohols, and ester compounds adhered to the surfaces thereof. These organic compounds inhibit unnecessary oxidation of the surface of the aluminum flake particles, thereby enabling improvement of surface glossiness. When aluminum flake particles are obtained by grinding aluminum powder, the organic compound may be added thereto as a grinding aid. The content of the organic compound is preferably less than 2 parts by mass with respect to 100 parts by mass of the aluminum flake particles.
When the organic compound such as the fatty acid adheres to the surface of the aluminum flake particle, it is estimated that: the coupling agent and the organic compound are present on the surface of the aluminum flake particle in the form of a layer in which the organic compound and the coupling agent are mixed or coexist by chemical equilibrium.
(other additives)
The resin composition according to the present embodiment may further contain the following additives according to the purpose as long as the effects of the present invention are not adversely affected. Examples of the additives include: mica, a coloring pigment, a light-storing pigment, a coloring dye such as a coloring dye and a fluorescent dye, a filler, an antioxidant, an antiaging agent, a heat stabilizer, a weather resistance stabilizer, an ultraviolet absorber, an infrared absorber, a photochromic agent, an antifouling agent, an antistatic agent, a plasticizer, a lubricant, a flame retardant, a fluorescent whitening agent, a light diffusing agent, a crystal nucleating agent, a flow modifier, an impact modifier, a pigment dispersing agent and the like.
[ method for producing resin composition ]
The resin composition according to the present embodiment can be produced by a conventionally known method. The resin composition can be obtained, for example, by the following production method. That is, first, as described above, the coupling agent and the aluminum flake particles are kneaded by a kneader or the like, thereby preparing the aluminum flake particles to which the coupling agent adheres to the surface (hereinafter, also referred to as "coupling agent-adhered aluminum flake particles"). Next, the resin composition can be obtained by melt-kneading the aluminum flake particles to which the coupling agent has adhered and the thermoplastic resin using any one melt-kneading machine selected from the group consisting of a banbury mixer, a uniaxial extruder with an exhaust port, a biaxial extruder with an exhaust port, a kneader, a roll, and a feeding device (Feeder Ruder). The temperature at the time of melt kneading may be appropriately selected based on the glass transition temperature of the resin used as the thermoplastic resin, and may be, for example, 100 to 300 ℃.
The resin composition obtained by the above-described production method may be prepared in the form of a master batch in which a predetermined amount of aluminum flake particles are filled in a thermoplastic resin, for the purpose of obtaining better dispersibility of the aluminum flake particles in a resin molded article described later. In this case, the content of the aluminum flake particles in the resin composition is preferably 5 parts by mass or more and 230 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin in a state where the coupling agent is adhered to the surface of the aluminum flake particles.
[ resin molded article ]
The resin molded article according to the present embodiment includes the resin composition. Thus, resin molded bodies having various shapes and having a bright property can be provided without contaminating the mold. The resin molded body also suppresses the formation of weld lines. The resin molded article is suitable for use as a resin molded article having a bright property, for example, in housings of electronic devices such as notebook personal computers and cellular phones, housings of household appliances such as vacuum cleaners, electric fans, telephones and printers, housings of office equipment, interior and exterior parts of automobiles, sundries, residential equipment, and the like. The resin molded body is not limited to a final product, and may be used as a component in a product. Therefore, the present invention is not limited to the above applications, and can be used for a wide range of applications.
[ method for producing resin molded article ]
The method for producing a resin molded body according to the present embodiment includes: the method for producing a thermoplastic resin molding comprises a step (first step) of preparing the resin composition, a step (second step) of injecting the resin composition into a mold having an inner wall surface maintained at a temperature higher by at least 70 ℃ than the glass transition temperature of the thermoplastic resin, and a step (third step) of cooling the resin composition in the mold to obtain a resin molded product. By the method for producing a resin molded article having the above features, resin molded articles having various shapes which have bright properties and in which the formation of weld lines is suppressed can be obtained without contaminating a mold. Hereinafter, each of the first to third steps will be described.
< first step >
The first step is a step of preparing a resin composition. In this step, specifically, the resin composition can be prepared by performing the above-described method for producing a resin composition.
< second step >
The second step is a step of injecting the resin composition into a mold having an inner wall surface maintained at a temperature higher by at least 70 ℃ than the glass transition temperature of the thermoplastic resin. In this step, specifically, according to the conventionally known cooling and heating method, first, a mold for injection molding is prepared, and the temperature of the inner wall surface of the mold is heated to a temperature higher by at least 70 ℃ than the glass transition temperature of the thermoplastic resin by the conventionally known mold temperature adjusting means. Next, the thermoplastic resin contained in the resin composition is heated and melted in a cylinder of a conventionally known injection molding machine or the like. Finally, a resin composition containing a molten thermoplastic resin is injected into the mold with the inner wall surface maintained at the above temperature.
Accordingly, the formation of weld lines can be prevented in the resin molded article obtained by the present production method. Further, since the adhesion between the aluminum flake particles and the thermoplastic resin is improved by the coupling agent, the aluminum flake particles are prevented from being unevenly distributed on the surface of the molten thermoplastic resin in the mold.
Here, the temperature of the inner wall surface of the mold is preferably a temperature higher by 70 ℃ or more than the glass transition temperature of the thermoplastic resin as described above, more preferably a temperature higher by more than 80 ℃ or, for example, a temperature higher by 90 ℃ or more than the glass transition temperature of the thermoplastic resin. The upper limit of the temperature of the inner wall surface of the mold may be equal to the molding temperature of the thermoplastic resin. The glass transition temperature of the thermoplastic resin can be determined by Differential Thermal Analysis (DTA).
< third Process step >
The third step is a step of cooling the resin composition in the mold to obtain a resin molded body. In this step, specifically, the resin composition injected into the mold is cooled according to a conventionally known cooling and heating method. After that, the mold is separated, whereby a resin molded body can be obtained. Since the resin molded body is produced by a cold-hot method, the formation of weld lines can be prevented. Further, since the adhesion between the aluminum flake particles and the thermoplastic resin is improved by the coupling agent, the aluminum flake particles are prevented from being unevenly distributed on the surface of the molten thermoplastic resin in the mold, and the mold after division can be prevented from being contaminated with the aluminum flake particles. In the resin molded article, since the presence of the aluminum flake particles on the surface of the molten resin is suppressed, the surface of the resin molded article can be highly smooth.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[ production of resin composition (masterbatch) ]
Resin compositions of examples 1 to 3 and comparative examples 1 to 2 were produced by the following method.
< example 1 >
An aluminum paste (trade name (model number): 5422NS, manufactured by Toyo aluminum Co., Ltd., solid content 500g) prepared in the form of a paste and containing aluminum flake particles having an average particle diameter (d50) of 21 μm and an average thickness (t) of 0.5 μm was dispersed in 2L of mineral spirits to obtain a dispersion. This dispersion was subjected to filtration and washing, thereby obtaining aluminum flake particles. Next, the above aluminum flake particles, 3g of deionized water and 3g of gamma-aminopropyltriethoxysilane (trade name (model number) "KBE-903", manufactured by shin-Etsu chemical Co., Ltd.) were dissolved in 60g of isopropanol to obtain a treated solution, and the treated solution was placed in a commercially available kneader mixer. These materials were further kneaded in the kneader mixer for 1 hour, whereby an aluminum flake particle dispersion having a solid content of 55 mass% and a coupling agent adhered thereto was obtained.
730g (solid content: 400g) of the aluminum flake particle dispersion having the coupling agent adhered thereto and 1600g of an acrylonitrile-butadiene-styrene resin (ABS resin, trade name (type): GA-501 ", manufactured by NIPPON A & L Co., Ltd., glass transition temperature: 90 ℃) were mixed by a mixer to obtain a mixture. The mixture was kneaded and granulated by using an extruder (trade name: ZSK type twin-screw extruder, manufactured by Coperion Co., Ltd.) at a temperature of 190 to 220 ℃ in a cylinder to prepare a resin composition (master batch) molded into a pellet form. In the resin composition, the content of the aluminum flake particles is 25 parts by mass per 100 parts by mass of the thermoplastic resin in a state where the coupling agent is adhered to the surface of the aluminum flake particles.
< example 2 >
A resin composition (master batch) was produced by performing the same method for producing a resin composition as in example 1, except that 1g of deionized water and 1g of γ -aminopropyltriethoxysilane were added to the treatment solution.
< example 3 >
A resin composition (master batch) was produced by performing the same method for producing a resin composition as in example 1, except that 25g of deionized water and 25g of γ -aminopropyltriethoxysilane were added to the treatment solution.
< comparative example 1 >
An aluminum flake particle dispersion having a solid content of 55 mass% was prepared from the dispersion without kneading the treatment solution containing the coupling agent with respect to the aluminum flake particles contained in the dispersion obtained by dispersing the aluminum paste (trade name (model number): 5422NS, manufactured by toyoyo aluminum co., ltd., 500g as a solid content) in mineral spirits. Next, the aluminum flake particle dispersion (solid content 400g) and the same ABS resin as in example 1 were mixed to obtain a mixture, and the mixture was kneaded and granulated by the same extruder as in example 1 under the same conditions as in example 1 to produce a resin composition (master batch) molded into pellets.
< comparative example 2 >
A resin-coated aluminum paste (trade name (model number): FZ5422, manufactured by Toyo aluminum Co., Ltd.) containing aluminum flake particles having an average particle diameter (d50) of 21 μm and an average thickness (t) of 0.5 μm and having surfaces of the aluminum flake particles coated with an acrylic resin was prepared. Next, this resin-coated aluminum paste (solid content 400g) and the same ABS resin as in example 1 were mixed to obtain a mixture, and the mixture was kneaded and granulated under the same conditions as in example 1 using the same extruder as in example 1 to produce a resin composition (master batch) molded into a pellet shape.
[ production of resin molded article ]
Next, by performing the following steps, resin molded articles of examples 1 to 3 and comparative examples 1 to 2 corresponding to the resin compositions of examples 1 to 3 and comparative examples 1 to 2 were produced from the resin compositions of examples 1 to 3 and comparative examples 2, respectively.
First, 42g of the resin composition (master batch) and 800g of the ABS resin were fed into a 20 mm-diameter biaxial extruder (trade name: "ZSK-type biaxial extruder", manufactured by Coperion corporation) having an exhaust port, and melt-mixed and extruded at a temperature of 220 ℃ in a cylinder to prepare a molding resin composition having a content of aluminum flake particles of 1 mass% (first step). Next, the resin composition for molding was injected into a plate-molding die having a rectangular shape with a width of 120mm, a length of 150mm and a thickness of 5mm and a plurality of through holes, by using an injection molding machine (trade name: "FNX 220 III", manufactured by Hitachi resin industries Co., Ltd.) (second step).
In the second step, the temperature in the cylinder of the injection molding machine is set to 240 ℃. On the other hand, a mold for molding a plate in which the temperature of the inner wall surface was heated to 80 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and 200 ℃ was prepared, and the above-mentioned resin composition for molding was injected from an injection molding machine into each mold for molding a plate.
Further, the molding resin composition in the mold was cooled by setting the temperature of the inner wall surface of each plate molding mold to 30 ℃ using a commercially available low-temperature oil temperature controller and a water-cooling temperature controller, and then each plate molding mold was separated to produce a resin molded article (third step). That is, by performing the third step, each resin molded body (10 in total) molded by using a mold for plate molding in which the temperature of the inner wall surface is heated to 80 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and 200 ℃ is produced.
Here, since the plate molding die has a plurality of through holes, a portion where the molten resins join in the die is generated. Therefore, in the case where injection molding is performed without using a cold-hot method or heating the inner wall temperature of the mold to at least 70 ℃ higher than the glass transition temperature of the ABS resin, a weld line may be formed at a portion of the resin molded article corresponding to a portion where the molten resin is converged in the mold.
[ evaluation of resin molded article ]
< confirmation of the formation of a weld line by visual observation >
Whether or not a weld line was formed on the surface of each of the resin molded articles of examples 1 to 3 and comparative examples 1 to 2 was visually observed. As a result, no weld line was observed on the surface of each of the resin molded articles of examples 1 to 3 and comparative examples 1 to 2 obtained using the mold for plate molding in which the temperature of the inner wall surface was heated to 160 ℃ or higher, which was at least 70 ℃ or higher than the glass transition temperature of the ABS resin. On the other hand, weld lines were observed on the surfaces of the resin molded articles of examples 1 to 3 and comparative examples 1 to 2, which were obtained by using a mold for molding a sheet in which the inner wall surface was heated to 150 ℃ or lower.
< confirmation of mold contamination >
A transparent tape (trade name: Cello tape (registered trademark) "), manufactured by Nichiban corporation) having a length of 80mm × a width of 24mm was attached to the surface of each of the resin molded articles of examples 1 to 3 and comparative examples 1 to 2, the tape was rubbed with a fingertip to closely contact the surface of each of the resin molded articles of examples 1 to 3 and comparative examples 1 to 2, and then the transparent tape was peeled off from the surface so as to be peeled off at 180 degrees. Next, the transparent adhesive tape peeled off from the surface of the resin molded body was stuck to a black backing paper, and the number of aluminum foil particles stuck to the transparent adhesive tape was determined at a magnification of 500 times using a digital microscope (trade name: VHX-6000, manufactured by Keyence). Evaluation was performed in 1 visual field (400 μm × 600 μm), and ranking was performed based on the following criteria. The results are shown in Table 1. Here, it is assumed that: the number of aluminum flake particles adhering to the transparent adhesive tape showed a positive correlation with the number of aluminum flake particles that were unevenly distributed on the surface of the molten resin in the mold and caused mold contamination. Therefore, by determining the number of aluminum flake particles adhering to the transparent adhesive tape and ranking the particles based on the following criteria, it was possible to evaluate whether or not the resin compositions of examples 1 to 3 and comparative examples 1 to 2 can suppress mold contamination when injection molding by the cold-hot method was performed.
A: the number of aluminum flake particles was 3 or less, and it was estimated that mold contamination could be more sufficiently suppressed.
B: the number of aluminum flake particles is 4 to 10, and it is estimated that mold contamination can be suppressed.
C: the number of aluminum flake particles was 11 or more, and it was estimated that the suppression of mold contamination was insufficient.
[ Table 1]
Figure BDA0003572228120000141
[ Observation ]
From the above, it can be seen that: in the case where the resin compositions of examples 1 to 3 and the resin molded articles including these resin compositions were injection-molded using a mold heated to a temperature higher by at least 70 ℃ than the glass transition temperature of the thermoplastic resin, the formation of weld lines could be prevented in the same manner as in the case of the resin molded articles of the conventional examples (comparative examples 1 and 2). Further, as can be understood from table 1: in the case where the resin compositions of examples 1 to 3 and the resin molded articles including these resin compositions are injection molded using a mold heated to a temperature higher by at least 70 ℃ than the glass transition temperature of the thermoplastic resin, the aluminum flake particles can be suppressed from being unevenly distributed on the surface of the molten resin and the mold contamination can be suppressed as compared with comparative examples 1 and 2.
Although the embodiments and examples of the present invention have been described above, it is originally intended to appropriately combine the configurations of the above-described embodiments and examples.
The embodiments and examples disclosed herein are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined not by the above description but by the appended claims, and is intended to include all changes which come within the meaning and range of equivalency of the claims.

Claims (8)

1. A resin composition for use in the production of an injection molded body,
the resin composition is characterized in that,
the resin composition contains a thermoplastic resin and aluminum flake particles,
a coupling agent is attached to at least a part of the surface of the aluminum flake particle.
2. The resin composition according to claim 1,
the coupling agent is a silane coupling agent.
3. The resin composition according to claim 1 or 2,
the coupling agent is an amino silane coupling agent.
4. The resin composition according to any one of claims 1 to 3,
the content of the coupling agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the aluminum flake particles.
5. The resin composition according to any one of claims 1 to 4,
the content of the aluminum flake particles is 0.5 to 230 parts by mass with respect to 100 parts by mass of the thermoplastic resin in a state where the coupling agent is adhered to the surface.
6. The resin composition according to any one of claims 1 to 5,
the thermoplastic resin is at least 1 resin selected from the group consisting of acrylonitrile-butadiene-styrene resin, styrene-acrylonitrile copolymer, polystyrene and polyethylene.
7. A resin molded body comprising the resin composition according to any one of claims 1 to 6.
8. A method for producing a resin molded body, comprising the steps of:
a step of preparing the resin composition according to any one of claims 1 to 6;
a step of injecting the resin composition into a mold, the inner wall surface of the mold being maintained at a temperature higher by at least 70 ℃ than the glass transition temperature of the thermoplastic resin; and
and a step of cooling the resin composition in the mold to obtain a resin molded body.
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