CN108117738B - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- CN108117738B CN108117738B CN201710498101.XA CN201710498101A CN108117738B CN 108117738 B CN108117738 B CN 108117738B CN 201710498101 A CN201710498101 A CN 201710498101A CN 108117738 B CN108117738 B CN 108117738B
- Authority
- CN
- China
- Prior art keywords
- mass
- resin
- parts
- resin composition
- polyphenylene ether
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a resin composition. The purpose of the present invention is to provide a resin composition having excellent impact resistance and vibration fatigue properties while maintaining whiteness. The resin composition of the present invention is characterized by comprising 40 to 99 parts by mass of (a) a polyphenylene ether resin, (b) 1 to 60 parts by mass of an inorganic filler, (c) 0.1 to 5 parts by mass of titanium oxide, and (d) 0.3 to 10 parts by mass of calcium carbonate, based on 100 parts by mass of the total of (a) the polyphenylene ether resin and (b) the inorganic filler.
Description
Technical Field
The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition having excellent impact resistance and vibration fatigue properties, which is used as a component for home appliances, OA equipment, audio/video equipment, automobile, and the like.
Background
Polyphenylene ether resins are used in various fields such as electronic/electric parts, OA equipment parts, audio/video equipment parts, and automobile parts as molding materials having excellent heat resistance, dimensional stability, and flame retardancy.
In recent years, improvement in fluidity and impact resistance at the time of hot-melt processing has been strongly demanded for reduction in size, fineness, and weight of resin parts. However, the polyphenylene ether resin containing an inorganic filler colored in white has a problem that impact resistance and vibration fatigue characteristics are remarkably reduced.
For this reason, many methods for improving the use of an elastomer have been proposed from the material viewpoint. However, the resin composition containing an inorganic filler colored in white is not practical because the impact resistance-imparting effect of the elastomer is small.
Further, white coloring cannot be stopped from the viewpoint of appearance and prevention of assembly errors.
At present, a specific solution to this problem has not been disclosed, and an improved resin composition is desired.
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a resin composition having excellent impact resistance and vibration fatigue properties while maintaining whiteness.
Means for solving the problems
The present inventors have intensively studied to solve the above problems and found that a resin composition containing specific amounts of a polyphenylene ether resin, an inorganic filler, titanium oxide and calcium carbonate can provide good impact resistance and vibration fatigue characteristics while maintaining whiteness, thereby completing the present invention.
Namely, the present invention is as follows.
[1]
A resin composition characterized by containing, as a main component,
the resin composition comprises, based on 100 parts by mass of the total of (a) a polyphenylene ether resin and (b) an inorganic filler:
(a) 40 to 99 parts by mass of a polyphenylene ether resin,
(b) 1 to 60 parts by mass of an inorganic filler,
(c) 0.1 to 5 parts by mass of titanium oxide,
(d) 0.3 to 10 parts by mass of calcium carbonate.
[2]
The resin composition according to [1], wherein the calcium carbonate (d) has an average particle diameter of 0.1 to 10 μm.
[3]
The resin composition according to [1] or [2], wherein,
(a) the polyphenylene ether resin comprises polyphenylene ether and polystyrene resin,
the mass ratio of the polyphenylene ether to the polystyrene resin (polyphenylene ether/polystyrene resin) is 99/1-5/95.
[4]
The resin composition according to [3], wherein the polystyrene-based resin is atactic polystyrene and/or high impact polystyrene.
[5]
The resin composition according to any one of [1] to [4], which comprises (e) 2 to 20 parts by mass of a condensed phosphate ester-based flame retardant per 100 parts by mass of the total of the polyphenylene ether-based resin (a) and the inorganic filler (b).
[6]
The resin composition according to any one of [1] to [5], which comprises (f) 1 to 20 parts by mass of an elastomer per 100 parts by mass of the total of the polyphenylene ether resin (a) and the inorganic filler (b).
[7]
The resin composition according to [6], wherein the elastomer (f) is a block copolymer and/or a hydrogenated block copolymer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resin composition having excellent impact resistance and vibration fatigue properties while maintaining whiteness can be provided.
Detailed Description
The mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
[ resin composition ]
The resin composition of the present embodiment contains (a) a polyphenylene ether resin (sometimes referred to as "component (a)" in the present specification), (b) an inorganic filler (sometimes referred to as "component (b)" in the present specification), (c) titanium oxide (sometimes referred to as "component (c)" in the present specification), and (d) calcium carbonate (sometimes referred to as "component (d)" in the present specification), and the content of component (a) is 40 to 99 parts by mass, the content of component (b) is 1 to 60 parts by mass, the content of component (c) is 0.1 to 5 parts by mass, and the content of component (d) is 0.3 to 10 parts by mass, based on 100 parts by mass of the total of component (a) and component (b).
With such a configuration, the resin composition of the present embodiment can exhibit excellent impact resistance and vibration fatigue characteristics while maintaining whiteness.
Next, the constituent components of the resin composition of the present embodiment will be described.
((a) polyphenylene ether resin)
The resin composition of the present embodiment contains (a) a polyphenylene ether resin (may be abbreviated as "PPE-based resin" in the present specification), and therefore has excellent flame retardancy and heat resistance.
The PPE resin preferably contains a polyphenylene ether (which may be referred to as "PPE" in the present specification) and a polystyrene resin, and may be a mixed resin composed of PPE and polystyrene resin or a resin composed of PPE alone.
Since the PPE resin contains PPE, the resin composition of the present embodiment is more excellent in flame retardancy and heat resistance.
Examples of the PPE include homopolymers having a repeating unit structure represented by the following formula (1) and copolymers having a repeating unit structure represented by the following formula (1).
The PPE may be used singly or in combination of two or more kinds.
[ CHEM 1]
In the above formula (1), R1、R2、R3And R4Each independently is a hydrogen atom, a halogen atomA monovalent group selected from the group consisting of a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, and a halohydrocarbonoxy group having at least 2 carbon atoms separating a halogen atom from an oxygen atom.
The PPE preferably has a reduced viscosity of 0.15 to 2.0dL/g, more preferably 0.20 to 1.0dL/g, and still more preferably 0.30 to 0.70dL/g, as measured with an Ubbelohde viscometer at 30 ℃ using a 0.5g/dL chloroform solution, from the viewpoints of fluidity during processing, toughness, and chemical resistance.
Examples of the PPE include, but are not limited to, homopolymers such as poly (2, 6-dimethyl-1, 4-phenylene ether), poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1, 4-phenylene ether), poly (2, 6-dichloro-1, 4-phenylene ether), etc.; copolymers such as copolymers of 2, 6-dimethylphenol with other phenols (e.g., 2,3, 6-trimethylphenol or 2-methyl-6-butylphenol); and so on. Among them, from the viewpoint of balance between toughness and rigidity in preparing a resin composition and easiness of obtaining raw materials, poly (2, 6-dimethyl-1, 4-phenylene ether) and a copolymer of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol are preferable, and poly (2, 6-dimethyl-1, 4-phenylene ether) is more preferable.
The PPE mentioned above can be produced by a known method. Examples of the method for producing PPE include, but are not limited to: a method proposed by Hay for oxidative polymerization of 2, 6-xylenol using a complex of cuprous salt and amine as a catalyst, described in U.S. patent No. 3306874; the methods described in, for example, U.S. Pat. No. 3306875, U.S. Pat. No. 3257357, U.S. Pat. No. 3257358, Japanese patent publication No. 52-17880, Japanese patent application laid-open No. 50-51197, and Japanese patent application laid-open No. 63-152628.
The PPE may be a modified PPE obtained by reacting the homopolymer and/or the copolymer with a styrene monomer or a derivative thereof and/or an α -unsaturated carboxylic acid or a derivative thereof, and the amount of the styrene monomer or a derivative thereof and/or α -unsaturated carboxylic acid or a derivative thereof grafted or added is preferably 0.01 to 10% by mass based on 100% by mass of the component (a).
Examples of the method for producing the modified PPE include the following methods: the reaction is carried out in the presence or absence of a radical generator in a molten state, a solution state or a slurry state at a temperature of 80 to 350 ℃.
As the PPE, a mixture of the above homopolymer and/or the above copolymer with the above modified PPE in an arbitrary ratio can be used.
Examples of the polystyrene resin contained in the component (a) include polymers obtained by polymerizing monomer components including a styrene compound. The monomer component may contain a compound copolymerizable with the styrene-based compound.
The polystyrene resin may be used alone or in combination of two or more.
The polystyrene-based resin preferably contains more than 60 mass%, more preferably 70 mass% or more of structural units derived from a styrene-based compound per 100 mass% of the styrene-based resin.
The styrene-based compound includes, but is not limited to, styrene, α -methylstyrene, 2, 4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, etc. particularly, styrene is preferably used from the viewpoint of the practicability of the raw material.
Examples of the polystyrene resin include atactic polystyrene, rubber-reinforced polystyrene (high impact polystyrene, HIPS), styrene-acrylonitrile copolymer (AS) having a styrene content of 50 wt% or more, and AS resin obtained by rubber-reinforcing the styrene-acrylonitrile copolymer, and the like, and atactic polystyrene and/or high impact polystyrene are preferable.
As the component (a), a polyphenylene ether resin which is composed of PPE and a polystyrene resin and in which the mass ratio of PPE to polystyrene resin (PPE/polystyrene resin) is 99/1-5/95 can be used. The mass ratio of PPE to polystyrene resin (PPE/polystyrene resin) is preferably 90/10-10/90 in terms of heat resistance and molding flowability.
The content of the component (a) in the resin composition of the present embodiment is 40 to 99 parts by mass, preferably 40 to 98 parts by mass, and more preferably 50 to 95 parts by mass, based on 100 parts by mass of the total amount of the components (a) and (b), from the viewpoints of processability, heat resistance, impact resistance, and vibration fatigue characteristics. When the content of the component (a) is in the range of 40 to 99 parts by mass, the balance among workability, heat resistance, impact resistance and vibration fatigue characteristics can be sufficiently improved.
The content of the component (a) in the resin composition of the present embodiment is preferably 2 to 98% by mass based on the total amount (100% by mass) of the resin composition from the viewpoint of flame retardancy. The content of PPE in the resin composition of the present embodiment is preferably 0.25 to 92.2 mass% based on the total amount (100 mass%) of the resin composition from the viewpoint of flame retardancy.
(b) inorganic Filler)
Examples of the inorganic filler (b) used in the present embodiment include fibrous inorganic fillers and sheet-like inorganic fillers. The inorganic filler may contain 0.1% by mass or more of a white inorganic filler (for example, an inorganic filler having a whiteness of 70% or more as measured in accordance with JIS Z8715). The inorganic filler may be used alone or in combination of two or more.
The component (b) does not include titanium oxide (c), calcium carbonate (d), a condensed phosphate ester flame retardant (e), and an elastomer (f), which will be described later.
Examples of the fibrous inorganic filler include glass fibers, carbon fibers, silicone fibers, silica-alumina fibers, silicon nitride fibers, silicon carbide fibers, whiskers such as potassium titanate and silicon nitride, wollastonite, and metal fibers such as aluminum, titanium and copper.
The L/D of the fibrous inorganic filler, which is represented by the ratio of the average diameter (D) to the average length (L) of the fibers, is preferably 5 or more, more preferably 20 or more, further preferably 100 or more, and preferably 500 or less, from the viewpoint of the reinforcing effect.
Examples of the flaky inorganic filler include scaly glass, mica, talc, and metal foils such as aluminum flakes.
The R/H of the sheet-like inorganic filler represented by the ratio of the average thickness (H) to the average plate diameter (R) is preferably 5 or more, more preferably 10 or more, further preferably 20 or more, and preferably 3000 or less, from the viewpoint of the reinforcing effect.
The inorganic filler is preferably glass fiber, carbon fiber, glass flake, mica, talc or flake graphite, in order to obtain more excellent processability, heat resistance, impact resistance and vibration fatigue characteristics.
The inorganic filler may be surface-treated.
Examples of the surface treatment to be performed on the inorganic filler include surface treatment with various coupling agents such as a silane-based coupling agent and a titanate-based coupling agent. Among them, surface treatment with aminosilane or epoxysilane is preferable in view of adhesion to the resin. The resin is closely adhered to the inorganic filler, whereby the vibration fatigue characteristics and the impact strength are further improved.
As a method for surface-treating the inorganic filler, for example, in the case where the inorganic filler is a glass fiber, a method of immersing the fiber in a silane coupling agent solution and drying the fiber when the fiber is pulled; when the inorganic filler is a short fiber or a powder, a method of impregnating a silane coupling agent solution and drying the impregnated silane coupling agent solution may be used.
The content of the component (b) in the resin composition of the present embodiment is 1 to 60 parts by mass, preferably 2 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the total of the components (a) and (b), from the viewpoints of processability, heat resistance, impact resistance, and vibration fatigue characteristics. When the content of the component (b) is in the range of 1 to 60 parts by mass, the balance among workability, heat resistance, impact resistance and vibration fatigue characteristics can be sufficiently improved.
The total amount of the component (a) and the component (b) in the resin composition of the present embodiment is preferably 64.5 to 99.6% by mass, more preferably 80.0 to 96.7% by mass, from the viewpoints of whiteness, processability, impact resistance and vibration fatigue characteristics.
((c) titanium oxide)
The titanium oxide (c) used in the present embodiment is not particularly limited, and a known titanium oxide can be used.
The 1 st order particle diameter of the titanium oxide (c) is preferably 0.01 to 0.5. mu.m, more preferably 0.05 to 0.4. mu.m, and still more preferably 0.15 to 0.3. mu.m, from the viewpoint of the balance between dispersibility, white coloration, and handling properties during production.
The 1 st particle size may be measured according to JIS Z8825.
(c) The titanium oxide may be surface-treated with a surface-treating agent such as a hydrous oxide and/or oxide of aluminum, magnesium, zirconium titanium oxide, tin or the like, a higher fatty acid salt of stearic acid or the like, an organosilicon compound or the like.
(c) Titanium oxide can be produced by a dry method or a wet method. The crystal structure of the titanium oxide (c) may be either rutile or anatase, and rutile is preferred from the viewpoint of white colorability and thermal stability of the resin composition.
The amount of the titanium oxide (c) to be mixed is 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total of the polyphenylene ether resin (a) and the inorganic filler (b). When the component (c) is 0.1 part by mass or more, the whiteness of the resin composition is remarkably improved, and when the component (c) is less than 5 parts by mass, the reduction of impact resistance can be suppressed.
((d) calcium carbonate)
The calcium carbonate (d) used in the present embodiment preferably has an average particle diameter in the range of 0.1 to 10 μm, more preferably 0.5 to 5 μm. When the average particle diameter is in the above range, the dispersibility and the white coloring property are preferably balanced with handling property, impact resistance and vibration fatigue property at the time of production.
The average particle diameter can be measured, for example, by an electron microscope (JIS Z8827) or a laser diffraction particle size distribution measuring apparatus in accordance with JIS Z8825.
(d) The calcium carbonate may be surface treated.
The surface treatment of calcium carbonate (d) is not particularly limited, and examples thereof include surface treatment with fatty acid, resin acid, silicic acid, phosphoric acid, silane coupling agent, alkyl aryl sulfonic acid or a salt thereof, and the like. Examples of the fatty acid include saturated or unsaturated fatty acids having 6 to 31 carbon atoms, preferably 12 to 28 carbon atoms. Among them, from the viewpoint of dispersibility and handling property at the time of production, it is preferable to perform surface treatment with a fatty acid. When calcium carbonate surface-treated with a fatty acid is used as the component (d), the inorganic filler is more uniformly dispersed in the resin, and the resin composition is more excellent in vibration fatigue characteristics and impact strength.
The amount of the calcium carbonate (d) to be mixed is 0.3 to 10 parts by mass, preferably 0.3 to 8 parts by mass, and more preferably 0.5 to 7 parts by mass, based on 100 parts by mass of the total of the polyphenylene ether resin (a) and the inorganic filler (b). When the component (d) is 0.3 parts by mass or more, the whiteness of the resin composition is remarkably improved, and when the component (d) is 10 parts by mass or less, the reduction of impact resistance can be suppressed.
In the resin composition of the present embodiment, the mass ratio of the content of the component (b) to the total of the content of the component (c) and the content of the component (d) (the total of the inorganic filler/titanium oxide and calcium carbonate) is preferably 1/15 to 60/0.4, and more preferably 1/10 to 60/0.8, from the viewpoints of whiteness, impact resistance, and vibration fatigue characteristics.
((e) condensed phosphate-based flame retardant)
The resin composition of the present embodiment may contain (e) a condensed phosphate-based flame retardant. The polyphenylene ether resin composition of the present embodiment has a great effect of imparting flame retardancy to the resin composition by the synergistic flame retardant effect of the polyphenylene ether resin containing the component (e) and the component (a) and the flame retardancy-imparting effect of the component (e).
As the condensed phosphate-based flame retardant (e), for example, a phosphate represented by the following formula (2) and/or a condensate thereof can be used without being limited thereto.
[ CHEM 2]
In the formula (2), R5、R6、R7And R8Each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl-substituted alkyl group, an aryl group, a halogen-substituted aryl group and an alkyl-substituted aryl group. X represents an arylene group. n is an integer of 0 to 5.
In the case where the phosphate esters and/or condensates thereof have different n, n represents the average value of these. When n is 0, the compound of formula (2) represents a phosphate ester monomer.
Representative examples of the phosphate ester monomer include, but are not limited to, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and the like.
The condensate of the phosphate ester is usually 1 to 5 on average, preferably 1 to 3 on average.
In addition, the above R is a group represented by R in terms of flame retardancy and heat resistance exhibited when kneaded with another resin5、R6、R7And R8Preferably at least 1 is aryl, more preferably all are aryl. In addition, from the same viewpoint, preferable aryl groups include phenyl, xylyl, tolyl, and halogenated derivatives thereof.
Examples of the arylene group of X include residues obtained by removing 2 hydroxyl groups from resorcinol, hydroquinone, bisphenol a, bisphenol, or a halogenated derivative thereof.
Examples of the condensed phosphate ester compound include, but are not limited to, resorcinol-bis-phenyl phosphate ester compounds, bisphenol a-polyphenyl phosphate ester compounds, bisphenol a-poly-toluene phosphate ester compounds, and the like.
The content of the condensed phosphate-based flame retardant (e) in the resin composition of the present embodiment is preferably 2 to 20 parts by mass, more preferably 3 to 20 parts by mass, and still more preferably 5 to 18 parts by mass, from the viewpoints of flowability, heat resistance, and flame retardancy, when the total amount of the component (a) and the component (b) is 100 parts by mass. When the content of the component (e) is in the range of 2 to 20 parts by mass, the balance among fluidity, heat resistance and flame retardancy can be further sufficiently improved.
((f) Elastomers)
The resin composition of the present embodiment may contain an elastomer as the component (f) as necessary.
The component (f) may be a block copolymer composed of at least 2 polymer blocks mainly composed of an aromatic vinyl compound and at least 1 polymer block mainly composed of a conjugated diene compound (hereinafter, may be abbreviated as "block copolymer") and/or a hydrogenated product of the block copolymer. By containing these block copolymers, the resin composition of the present embodiment has more excellent impact resistance.
When the component (f) contains a polymer containing a structural unit derived from a styrene-based compound, the polymer may contain 60% by mass or less of the structural unit derived from the styrene-based compound with respect to 100% by mass of the polymer.
The term "mainly" in the polymer block mainly composed of an aromatic vinyl compound as used herein means that at least 50 mass% or more of the polymer block is a block having a structural unit derived from an aromatic vinyl compound. More preferably 70% by mass or more, still more preferably 80% by mass or more, and most preferably 90% by mass or more.
In addition, the term "mainly" in the polymer block mainly composed of the conjugated diene compound also means a block in which at least 50 mass% or more of the constituent units derived from the conjugated diene compound are contained. More preferably 70% by mass or more, still more preferably 80% by mass or more, and most preferably 90% by mass or more.
For example, even in the case of a polymer block in which a small amount of a structural unit derived from another compound such as a conjugated diene compound is randomly bonded to a polymer block mainly composed of an aromatic vinyl compound, a block copolymer mainly composed of an aromatic vinyl compound is considered as long as 50% by mass or more of the polymer block is formed of a structural unit derived from an aromatic vinyl compound. The same applies to a polymer block mainly composed of a conjugated diene compound.
The aromatic vinyl compound may include styrene, α -methylstyrene, vinyltoluene, and the like, and 1 or more compounds selected from these are used, with styrene being preferred.
Examples of the conjugated diene compound include butadiene, isoprene, piperylene, and 1, 3-pentadiene, and 1 or more compounds selected from these are used, and among these, butadiene, isoprene, and a combination thereof are preferable.
The block copolymer is preferably a block copolymer in which the polymer block (I) mainly composed of an aromatic vinyl compound and the polymer block (II) mainly composed of a conjugated diene compound have a linkage form selected from the group consisting of I-II-I type and I-II-I-II type. Among them, the form I-II-I is more preferable.
(f) The component (B) may be a mixture of the above block copolymers.
The above block copolymer is preferably a hydrogenated block copolymer. The hydrogenated block copolymer is a block copolymer obtained by hydrogenating the aromatic vinyl compound and the conjugated diene compound, and thereby the amount of aliphatic double bonds (i.e., the hydrogenation ratio) of the polymer block mainly composed of the conjugated diene compound is controlled to be in a range of more than 0% and 100%. The hydrogenated block copolymer preferably has a hydrogenation ratio of 50% or more, more preferably 80% or more, and most preferably 98% or more.
The hydrogenated block copolymer in the present embodiment is a conventionally known and commercially available hydrogenated block copolymer, and any hydrogenated block copolymer can be used as long as it falls within this category.
As the component (f), a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer may also be used without problems.
Further, as the component (f), a block copolymer obtained by modifying all or part of the components described in International publication No. 02/094936 or a block copolymer obtained by mixing an oil in advance may be suitably used.
The content of the component (f) in the resin composition of the present embodiment is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 2 to 15 parts by mass, from the viewpoint of heat resistance, impact resistance, and vibration fatigue characteristics, when the total amount of the components (a) and (b) is 100 parts by mass. When the content of the component (f) is in the range of 1 to 20 parts by mass, the balance among heat resistance, impact resistance and vibration fatigue characteristics can be sufficiently improved.
(other Components)
In addition to the above components, the resin composition of the present embodiment may contain other components as necessary within a range that does not impair whiteness maintenance, impact resistance, and vibration fatigue characteristics of the resin composition.
Examples of the other components include, but are not limited to, thermoplastic elastomers (polyolefin elastomers), heat stabilizers, antioxidants, metal inactivators, crystal nucleating agents, flame retardants (organophosphate compounds, ammonium polyphosphate compounds, silicone flame retardants, etc., which do not conform to component (e)), plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather (light) -resistant modifiers, slip agents, organic fillers and reinforcements (polyacrylonitrile fibers, aramid fibers, etc.), various colorants, antiblocking agents, and the like.
[ method for producing resin composition ]
The resin composition of the present embodiment can be produced by melt-kneading the above-mentioned components (a) to (d), and further, if necessary, component (e), component (f), and other components.
The melt-kneading machine for melt-kneading is not limited to the following equipment, and examples thereof include a heating melt-kneading machine such as a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a brabender plastograph, and a banbury mixer, and particularly, a twin-screw extruder is preferable from the viewpoint of kneading property. Specific examples thereof include ZSK series manufactured by COPERION, TEM series manufactured by Toshiba mechanical Co., Ltd, and TEX series manufactured by Nippon Steel works, Ltd.
A preferred production method using an extruder is described below. The L/D (effective cylinder length/inner cylinder diameter) of the extruder is preferably in the range of 20 to 60, more preferably 30 to 50.
The structure of the extruder is not particularly limited, and for example, it is preferable to provide a1 st raw material supply port on the upstream side in the flow direction of the raw materials, a1 st vacuum exhaust port downstream of the 1 st raw material supply port, a2 nd raw material supply port downstream of the 1 st vacuum exhaust port (the 3 rd and 4 th raw material supply ports may be further provided as necessary), and a2 nd vacuum exhaust port downstream of these raw material supply ports. In particular, it is more preferable to provide a kneading section upstream of the 1 st vacuum exhaust port, a kneading section between the 1 st vacuum exhaust port and the 2 nd raw material supply port, and a kneading section between the 2 nd to 4 th raw material supply ports and the 2 nd vacuum exhaust port.
The method of supplying the raw material to the 2 nd to 4 th raw material supply ports is not particularly limited, and the method of supplying the raw material from the extruder side open port by the forced side feeder tends to enable more stable supply than the simple addition supply from the open ports of the 2 nd to 4 th raw material supply ports of the extruder, and is therefore preferable.
In particular, when the raw material contains powder and it is desired to reduce the generation of crosslinked products or carbides due to the thermal history of the resin, a method using a forced side feeder supplied from the side surface of the extruder is more preferable, and a method in which a forced side feeder is provided at the 2 nd to 4 th raw material supply ports and the raw material powder is separately supplied is more preferable.
In addition, in the case of adding a liquid raw material, a method of adding to an extruder using a plunger pump, a gear pump, or the like is preferable.
Further, the upper opening of the 2 nd to 4 th raw material supply ports of the extruder may be used as an opening for discharging air sent together.
The melt-kneading temperature and the screw rotation speed in the melt-kneading step of the resin composition are not particularly limited, and in the case of a crystalline resin, a temperature at which the crystalline resin is melted by heating at a temperature equal to or higher than the melting point of the crystalline resin and can be processed smoothly may be generally selected, and in the case of an amorphous resin, a temperature at which the amorphous resin is melted by heating at a temperature equal to or higher than the glass transition temperature of the amorphous resin and can be processed smoothly may be generally selected from 200 to 370 ℃, and the screw rotation speed is set to 100 to 1200 rpm.
As a preferred embodiment of the method for producing the resin composition of the present invention by using a twin-screw extruder, there can be mentioned, for example, the following methods: the polyphenylene ether resin (a), the titanium oxide (c), the calcium carbonate (d) and the elastomer (f) are supplied to a first supply port of a twin-screw extruder, a melting temperature of the polyphenylene ether resin is set in a heating melting zone, and melt-kneading is performed at a screw rotation speed of 100 to 1200rpm, preferably 200 to 500rpm, and in a state where the polyphenylene ether resin (a), the titanium oxide (c), the calcium carbonate (d) and the elastomer (f) are melt-kneaded, the condensed phosphate ester flame retardant (e) is supplied from a second supply port of the twin-screw extruder, the inorganic filler (b) is supplied from a third supply port, and further melt-kneading is performed. The positions at which the component (a), the component (c), the component (d) and the component (f) are supplied to the twin-screw extruder may be supplied collectively from the first supply port of the extruder as described above, or the components may be supplied separately by providing a second supply port, a third supply port and a fourth supply port.
In addition, in the case where the generation of crosslinked products or carbides due to the thermal history of the resin in the presence of oxygen is to be reduced, it is preferable to keep the oxygen concentration of each process line in the path of adding each raw material to the extruder to be less than 1.0 vol%. The addition route is not particularly limited, and specific examples thereof include a configuration comprising a pipe, a gravimetric feeder having a solution replenishment tank, a pipe, a hopper, and a twin-screw extruder in this order from a storage tank. The method for maintaining the low oxygen concentration as described above is not particularly limited, and a method of introducing an inert gas into each process line having improved airtightness is effective. Generally, it is preferable to introduce nitrogen gas to maintain the oxygen concentration at less than 1.0 vol%.
In the above-mentioned method for producing a resin composition, when the polyphenylene ether resin (a) or the elastomer (f) contains a powdery (volume average particle diameter of less than 10 μm) component, the resin composition of the present embodiment is produced using a twin-screw extruder, and the resin composition obtained by the above-mentioned production method has an effect of further reducing the residue on the screws of the twin-screw extruder, and furthermore, the resin composition obtained by the above-mentioned production method has an effect of reducing the generation of foreign matter such as black spots or carbides.
As a specific method for producing the resin composition of the present embodiment, it is preferable to use an extruder in which the oxygen concentration at each raw material supply port is controlled to be less than 1.0 volume, and to carry out any of the following methods 1 to 3.
1. The manufacturing method comprises the following steps: the whole amount or a part of the components (a), (c), (d) and (f) and, if necessary, a part of the component (b) contained in the resin composition of the present embodiment are melt-kneaded (first kneading step), the remaining amounts of the components (a), (c), (d) and (f) and the whole amount of the component (e) are supplied to the molten kneaded product obtained in the first kneading step, and melt-kneading is performed (second kneading step), and the whole amount or a part of the component (b) is supplied to the molten kneaded product obtained in the second kneading step, and melt-kneading is performed (third kneading step).
2. The manufacturing method comprises the following steps: the whole amounts of the component (a), the component (e), and the component (f) contained in the resin composition of the present embodiment are melt-kneaded (first kneading step), cooled once and granulated, and then the whole amounts of the other components (b), the component (c), and the component (d) are supplied and melt-kneaded (second kneading step).
3. A method of melt-kneading the entire amounts of the components (a) to (f) contained in the resin composition of the present embodiment.
In particular, since the polyphenylene ether as a raw material of the component (a) and the hydrogenated block copolymer of the component (f) having a certain molecular structure are in the form of powder, and the component (e) may be in the form of liquid, the compound is inferior in the biting property into an extruder, and it is difficult to increase the amount of production per unit time. Further, since the residence time of the resin in the extruder is long, thermal deterioration is likely to occur. As described above, the resin composition obtained by the production method of 1 or 2 is more preferable than the resin composition obtained by the production method of 3 because the miscibility of the respective components is excellent, the generation of crosslinked products or carbides due to thermal deterioration can be reduced, the production amount per unit time of the resin can be increased, and a resin composition having excellent productivity and quality can be obtained.
Here, in the first to second kneading steps, the kneaded mixture may be brought into a molten state, and melting of the component (a) once melted and granulated and then melting again may be avoided.
[ molded article ]
The molded article of the resin composition of the present embodiment can be widely used as molded articles such as optical device mechanism parts, light source lamp peripheral parts, sheets or films for metal film laminated substrates, hard disk interior parts, optical fiber ferrule ferrules, automobile engine compartment interior parts such as printer parts, copier parts, automobile radiator tank parts, and automobile lamp parts.
Examples
The present invention will be described below by referring to specific examples and comparative examples, but the present embodiment is not limited thereto.
The methods for measuring physical properties used in examples and comparative examples are as follows.
(1) Charpy impact test)
According to the method described in ISO 179, the Sabbitta impact strength (kJ/m) was measured2). The higher the value, the more excellent the impact resistance is evaluated.
(2) vibration fatigue test
The number of times of vibration at break was determined according to JIS K7118 and K7119 using a hydraulic servo fatigue tester (EHF-50-10-3, manufactured by Lugong, Ltd.) under an atmosphere of 23 ℃ and a sine wave load tensile load (50MPa) having a frequency of 30 Hz. The more the number of vibrations until fracture, the more excellent the vibration fatigue resistance was evaluated.
((3) whiteness degree)
The L value was determined by using a colorimeter (ZE-2000, manufactured by Nippon Denshoku industries Co., Ltd.) according to JIS Z8715. The higher the L value, the higher the evaluation whiteness.
((4) flame retardancy)
The test was carried out according to the vertical burning test method of UL94 (standard specified by the underwriters laboratories, USA).
The raw materials used in examples and comparative examples are as follows.
[ polyphenylene ether resin (a) ]
(a1) The method comprises the following steps PPE (polyphenylene ether)
Polyphenylene ether (reduced viscosity measured at 30 ℃ in a chloroform solution having a concentration of 0.5 g/dL: 0.51dL/g) obtained by oxidative polymerization of 2, 6-xylenol.
(a2) The method comprises the following steps High impact POLYSTYRENE (trade name "POLYSTYRENE H9405", manufactured by PS Japan).
< inorganic Filler >
(b1) The average diameter was 13 μm and the average length was 3,000. mu.m. A glass fiber surface-treated with an aminosilicone-based coupling agent.
(b2) The average diameter was 6 μm and the average length was 3,000. mu.m. A carbon fiber surface-treated with an epoxy silane coupling agent.
(b3) The average diameter of the plate was 130 μm and the average thickness was 5 μm. And glass flakes surface-treated with an aminosilicone-based coupling agent.
(b4) Talc having an average particle diameter of 3 μm (trade name "High toron A", manufactured by Diatom chemical industries, Ltd.).
(b5) Carbon black (trade name "# 980", manufactured by Mitsubishi chemical corporation).
[ titanium oxide (c) ]
(c1) Titanium oxide (having a primary particle size of 0.3 μm, trade name "RTC-30", manufactured by HUNTSMAN (British corporation)).
Calcium carbonate (d)
(d1) Calcium carbonate having an average particle diameter of 12 μm.
(d2) Calcium carbonate having an average particle diameter of 6 μm (trade name "SUN LIGHT SL-100", manufactured by Zhuyun chemical industries, Ltd.).
(d3) Calcium carbonate having an average particle diameter of 1.3 μm (trade name "SUN LIGHT SL-2200", manufactured by Shigaku Kogyo Co., Ltd.).
(d4) Calcium carbonate having an average particle diameter of 0.08 μm (trade name "NEOLIGHT SP", manufactured by Diatom chemical industries, Ltd.).
(e) condensed phosphate ester-based flame retardant
(e1) An aromatic condensed phosphoric ester (trade name: CR-741, manufactured by Dai chemical industries, Ltd.).
< elastomer (f) >
(f1) A hydrogenated block copolymer having a polystyrene-hydrogenated polybutadiene-polystyrene structure, a bound styrene content of 33%, a number average molecular weight of 246,000, a molecular weight distribution of 1.07, and a hydrogenation rate of a polybutadiene portion of 99.8% was synthesized.
(f2) A block copolymer having a polystyrene-polybutadiene-polystyrene structure, a bound styrene content of 40%, a number average molecular weight of 90,000, and a molecular weight distribution of 1.17 was synthesized.
Examples 1 to 13 and comparative examples 1 to 6
The resin composition was produced using a twin-screw extruder ZSK-40 (manufactured by WERNER & PFLEIDERER Co., Ltd.). In the twin-screw extruder, a1 st raw material supply port is provided on the upstream side in the flow direction of the raw materials, a1 st vacuum exhaust port, a2 nd raw material supply port, and a 3 rd raw material supply port are provided on the downstream side of the 1 st raw material supply port, and a second vacuum exhaust port is provided on the downstream side thereof. The 2 nd raw material supply port was added from an upper opening of the extruder by using a gear pump.
Using the extruder set as described above, the component (a), the component (c), the component (d), and the component (f) were added from the first material supply port with the above-mentioned composition, the condensed phosphate ester-based flame retardant (e) was added from the second material supply port, the inorganic filler (b) was added from the 3 rd material supply port, and the mixture was melt-kneaded under conditions of an extrusion temperature of 240 to 310 ℃, a screw rotation speed of 300rpm, and an ejection volume of 100 kg/hr, to produce pellets. Of the component (b), the component (b4) and the component (b5) were added from the first raw material supply port.
Pellets of the resin composition were fed to a coaxial screw type injection molding machine set to 250 to 310 ℃ and a molded article for vibration fatigue measurement of ASTM type 1 was obtained under injection molding conditions of a mold temperature of 60 to 120 ℃. The molded article obtained here was left to stand at 23 ℃ and a relative humidity of 50% for 24 hours or more, and was subjected to (2) a vibration fatigue test and (3) a measurement of whiteness.
Further, test piece type A was molded under the same injection molding conditions as described above in accordance with ISO 10724-1. The charpy impact strength (ISO 179) of (1) was measured using this sample.
Further, a test piece having a length of 127mm, a width of 12.7mm and a thickness of 1.6mm was molded under the same injection molding conditions as described above. Using the test piece, a vertical burning test according to UL94 was carried out, and (4) the flame retardancy was evaluated.
These results are also shown in tables 1 to 2.
As shown in tables 1 to 2, it can be seen that: the resin compositions of examples 1 to 13 were excellent in impact resistance, vibration fatigue properties and whiteness.
In comparative examples 1 to 6, the results of 1 or more of any of impact resistance, vibration fatigue characteristics and whiteness were inferior to those of examples.
Industrial applicability
The molded article molded from the resin composition of the present embodiment has excellent white coloring property, and is excellent in impact resistance and vibration fatigue property, and thus the degree of freedom in designing the resin molded article can be improved. Therefore, the resin composition is industrially useful as various parts in electric/electronic equipment, automotive equipment, chemical equipment, and optical equipment, for example, chassis and housing of multifunctional digital optical disk, optical equipment mechanism parts such as optical pickup slider, light source lamp peripheral parts, sheet or film for metal film laminated substrate, hard disk interior parts, optical fiber connector ferrules, laser beam printer interior parts (toner cartridge, etc.), inkjet printer interior parts, copier interior parts, automobile engine compartment interior parts such as automobile radiator tank parts, and automobile lamp parts.
Claims (6)
1. A resin composition characterized by containing, as a main component,
the resin composition comprises, based on 100 parts by mass of the total of (a) a polyphenylene ether resin and (b) an inorganic filler:
(a) 40 to 99 parts by mass of a polyphenylene ether resin,
(b) 1 to 60 parts by mass of an inorganic filler,
(c) 0.1 to 5 parts by mass of titanium oxide,
(d) 0.3 to 10 parts by mass of calcium carbonate,
(a) the polyphenylene ether resin is a mixed resin composed of polyphenylene ether and polystyrene resin or a resin composed of only polyphenylene ether,
(b) the inorganic filler does not include (c) titanium oxide, (d) calcium carbonate, a condensed phosphate-based flame retardant and an elastomer,
(d) the calcium carbonate has an average particle diameter of 0.1 to 10 μm.
2. The resin composition according to claim 1, wherein,
(a) the polyphenylene ether resin comprises polyphenylene ether and polystyrene resin,
the mass ratio of the polyphenylene ether to the polystyrene resin, namely the polyphenylene ether/polystyrene resin, is 99/1-5/95.
3. The resin composition according to claim 2, wherein the polystyrene-based resin is atactic polystyrene and/or high impact polystyrene.
4. The resin composition according to any one of claims 1 to 3, which comprises (e) 2 to 20 parts by mass of a condensed phosphate ester-based flame retardant per 100 parts by mass of the total of the polyphenylene ether-based resin (a) and the inorganic filler (b).
5. The resin composition according to any one of claims 1 to 3, wherein the elastomer (f) is contained in an amount of 1 to 20 parts by mass per 100 parts by mass of the total of the polyphenylene ether resin (a) and the inorganic filler (b).
6. The resin composition according to claim 5, wherein (f) the elastomer is a block copolymer and/or a hydrogenated block copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016232497A JP6827783B2 (en) | 2016-11-30 | 2016-11-30 | Resin composition |
| JP2016-232497 | 2016-11-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108117738A CN108117738A (en) | 2018-06-05 |
| CN108117738B true CN108117738B (en) | 2020-04-21 |
Family
ID=62228018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710498101.XA Active CN108117738B (en) | 2016-11-30 | 2017-06-27 | Resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6827783B2 (en) |
| CN (1) | CN108117738B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4121475A1 (en) * | 2020-03-20 | 2023-01-25 | SHPP Global Technologies B.V. | Poly(phenylene ether) composition, method for the manufacture thereof, and articles made therefrom |
| JPWO2022210593A1 (en) * | 2021-03-29 | 2022-10-06 | ||
| JP2023010586A (en) * | 2021-07-08 | 2023-01-20 | 旭化成株式会社 | Polyphenylene ether-based resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561371A (en) * | 2001-09-14 | 2005-01-05 | 旭化成化学株式会社 | Polyphenylene ether composition |
| WO2012035976A1 (en) * | 2010-09-16 | 2012-03-22 | 三菱エンジニアリングプラスチックス株式会社 | Polyphenylene ether resin composition and molded article of same |
| CN103937206A (en) * | 2014-04-18 | 2014-07-23 | 芜湖凯奥尔环保科技有限公司 | Polypropylene modified polyphenyl ether material for automobile plastic parts |
| CN105694424A (en) * | 2014-11-28 | 2016-06-22 | 上海杰事杰新材料(集团)股份有限公司 | A modified polyphenylene oxide material with low dielectric loss and a preparing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5303854B2 (en) * | 2006-10-24 | 2013-10-02 | 日立化成株式会社 | Novel semi-IPN composite thermosetting resin composition and varnish, prepreg and metal-clad laminate using the same |
-
2016
- 2016-11-30 JP JP2016232497A patent/JP6827783B2/en active Active
-
2017
- 2017-06-27 CN CN201710498101.XA patent/CN108117738B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561371A (en) * | 2001-09-14 | 2005-01-05 | 旭化成化学株式会社 | Polyphenylene ether composition |
| WO2012035976A1 (en) * | 2010-09-16 | 2012-03-22 | 三菱エンジニアリングプラスチックス株式会社 | Polyphenylene ether resin composition and molded article of same |
| CN103937206A (en) * | 2014-04-18 | 2014-07-23 | 芜湖凯奥尔环保科技有限公司 | Polypropylene modified polyphenyl ether material for automobile plastic parts |
| CN105694424A (en) * | 2014-11-28 | 2016-06-22 | 上海杰事杰新材料(集团)股份有限公司 | A modified polyphenylene oxide material with low dielectric loss and a preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 关于二氧化钛颜料;若林茂一郎;《日本橡胶工业杂志》;19631231;第38卷(第3期);第310-317页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6827783B2 (en) | 2021-02-10 |
| CN108117738A (en) | 2018-06-05 |
| JP2018090656A (en) | 2018-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101947547B1 (en) | Reinforced poly(phenylene ether)-polysiloxane block copolymer composition, and article comprising same | |
| EP3053955B1 (en) | Resin composition and molded article thereof | |
| JP5550393B2 (en) | Resin composition | |
| EP2218753A1 (en) | Thermoplastic resin composition, and molded body and sheet made of the composition | |
| CN108117738B (en) | Resin composition | |
| WO2017208945A1 (en) | Resin composition, process for producing resin composition, and molded object | |
| US20070259993A1 (en) | Process for producing polyphenylene ether composition | |
| JP6561122B2 (en) | Resin composition and molded body | |
| JP5787449B2 (en) | Resin composition and molded product | |
| JP2008195801A (en) | Resin composition and method for producing the same | |
| JP6192623B2 (en) | Resin composition and molded body thereof | |
| CN108084691B (en) | Resin composition | |
| JP6100069B2 (en) | Flame retardant resin composition | |
| JP6243795B2 (en) | Molded body containing flame retardant resin composition | |
| JP7296006B2 (en) | THERMOPLASTIC RESIN COMPOSITION, MANUFACTURING METHOD THEREOF, AND MOLDED PRODUCTS MADE THEREOF | |
| JP2008101200A (en) | Thermoplastic resin composition | |
| CN110746762B (en) | Polyphenylene ether resin composition, molded article, and method for improving fluctuation in burning time | |
| CN109912957B (en) | Resin composition, method for producing resin composition, and molded article | |
| JP7032163B2 (en) | Resin composition, manufacturing method of resin composition and molded product | |
| JP6175339B2 (en) | Resin composition and molded body thereof | |
| JP2020037663A (en) | Flame-retardant resin composition | |
| JP6586327B2 (en) | Resin composition and molded body | |
| JP2003277555A (en) | Resin composition and method for producing the same | |
| JP6059053B2 (en) | Method for producing resin composition | |
| JP7344013B2 (en) | Protective housing material for mobile battery units |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |