CN117897447A - Resin composition, molded article, and method for producing resin composition - Google Patents
Resin composition, molded article, and method for producing resin composition Download PDFInfo
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- CN117897447A CN117897447A CN202280058012.2A CN202280058012A CN117897447A CN 117897447 A CN117897447 A CN 117897447A CN 202280058012 A CN202280058012 A CN 202280058012A CN 117897447 A CN117897447 A CN 117897447A
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- resin composition
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- olefin polymer
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- 239000011342 resin composition Substances 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229920000098 polyolefin Polymers 0.000 claims abstract description 69
- 229920002545 silicone oil Polymers 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 229930182556 Polyacetal Natural products 0.000 claims abstract description 52
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 52
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 30
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 30
- -1 polyethylene Polymers 0.000 claims description 36
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000008188 pellet Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 abstract description 14
- 239000001993 wax Substances 0.000 description 46
- 239000002253 acid Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000001125 extrusion Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000004898 kneading Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 125000005702 oxyalkylene group Chemical group 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000009759 San-Chi Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- CZLMRJZAHXYRIX-UHFFFAOYSA-N 1,3-dioxepane Chemical compound C1CCOCOC1 CZLMRJZAHXYRIX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OCXPJMSKLNNYLE-UHFFFAOYSA-N 2-prop-2-enylbutanedioic acid Chemical compound OC(=O)CC(C(O)=O)CC=C OCXPJMSKLNNYLE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PQPVPZTVJLXQAS-UHFFFAOYSA-N hydroxy-methyl-phenylsilicon Chemical group C[Si](O)C1=CC=CC=C1 PQPVPZTVJLXQAS-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- 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
- C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a resin composition, a molded article and a method for producing the resin composition, wherein the obtained molded article has excellent sliding property and excellent molding property. The resin composition contains (B) 0.1 to 30.0 parts by mass of an olefin polymer, (C) 0.1 to 30.0 parts by mass of a silicone oil having a kinematic viscosity of 1000 to 55000cSt at 25 ℃ and (D) 0.1 to 15.0 parts by mass of a hydrocarbon wax, based on 100 parts by mass of the polyacetal resin (A), and the mass ratio of the olefin polymer (B) to the silicone oil (C), that is, the ratio of (B)/(C) is 2.00 or less.
Description
Technical Field
The present invention relates to a resin composition, a molded article, and a method for producing a resin composition.
Background
Polyacetal resins have balanced mechanical properties and are excellent in friction and wear resistance, chemical resistance, heat resistance, electric characteristics, etc., and therefore have been widely used in the fields of automobiles, electric/electronic products, etc.
Among them, as one of the utilization forms of polyacetal resins, a sliding member is known. As examples of using polyacetal resin as a sliding member, patent document 1 and patent document 2 are cited.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2008-214490
Patent document 2: international publication No. 2018/230389
Disclosure of Invention
Problems to be solved by the invention
The resin compositions described in patent document 1 and patent document 2 are excellent in sliding properties, but in patent document 1 and patent document 2, it is necessary to prepare the resin compositions after preparing a masterbatch from an organosilicon compound. For this reason, the present inventors have studied on the use of silicone oil as an organosilicon compound that does not require masterbatch gelation. However, even if silicone oil is blended into polyacetal resin, the slidability is not necessarily sufficient, and the moldability is poor. That is, in the case of molding a resin composition by, for example, injection molding, the molten resin composition is measured and then injected into a mold to mold, and the measurement is very time-consuming.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a resin composition which gives a molded article excellent in sliding properties and moldability, a molded article, and a method for producing the resin composition.
Means for solving the problems
The present inventors have studied to solve the above problems, and as a result, have found that the above problems can be solved by blending a silicone oil, an olefin polymer, and a hydrocarbon wax having a predetermined kinematic viscosity in a polyacetal resin at a predetermined ratio.
Specifically, the above-described problems can be solved by the following means.
1 > a resin composition comprising, per 100 parts by mass of (A) a polyacetal resin, 0.1 to 30.0 parts by mass of (B) an olefin polymer, (C) 0.1 to 30.0 parts by mass of a silicone oil having a kinematic viscosity at 25 ℃ of 1000 to 55000cSt, and (D) 0.1 to 15.0 parts by mass of a hydrocarbon wax, wherein the mass ratio of (B) the olefin polymer to (C) the silicone oil, i.e., (B)/(C), is 2.00 or less.
< 2 > the resin composition according to < 1 >, wherein,
the mass ratio of the olefin polymer (B) to the silicone oil (C), i.e., (B)/(C), is 0.10 or more.
< 3 > the resin composition according to < 1 > or < 2 >, wherein,
the olefin polymer (B) is selected from polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-butene copolymer.
< 4 > the resin composition according to < 1 > or < 2 >, wherein,
the above-mentioned (B) olefin polymer comprises an ethylene-butene copolymer.
A resin composition according to any one of < 1 > < 4 >,
the olefin polymer (B) has a Vicat softening temperature of 30 ℃ or higher in accordance with JIS K7206.
A resin composition according to any one of < 1 > < 5 >,
the content of the olefin polymer (B) is 0.1 to 3.0 parts by mass based on 100 parts by mass of the polyacetal resin (A).
A resin composition according to any one of < 1 > < 6 >,
the silicone oil (C) is contained in an amount of 0.5 to 5.0 parts by mass per 100 parts by mass of the polyacetal resin (A).
A resin composition according to any one of < 1 > < 7 >,
(B) The mass ratio of the olefin polymer to the silicone oil (C), i.e., (B)/(C), is 0.80 or less.
A resin composition according to any one of < 1 > - < 8 >, wherein,
the mass ratio of the olefin polymer (B) to the silicone oil (C), i.e., (B)/(C), is 0.50 or less.
A resin composition according to any one of < 1 > < 9 >,
the mass ratio of the hydrocarbon wax (D) to the silicone oil (C), i.e., (D)/(C), is 1.0 or less.
A resin composition according to any one of < 1 > < 9 > which is a resin composition for forming a sliding member.
< 12 > a pellet which is a pellet of the resin composition described in any one of < 1 > - < 11 >.
A molded article of < 13 > which is formed from the resin composition of any one of < 1 > - < 11 >.
< 14 > a molded article formed from the pellets < 12 >.
A shaped article according to < 15 > to < 13 > or < 14 > is a sliding member.
A method for producing a resin composition according to any one of < 1 > - < 11 >, the method comprising:
after the polyacetal resin (A), the olefin polymer (B) and the hydrocarbon wax (D) are fed from the feed port of the extruder and kneaded, silicone oil having a kinematic viscosity of 1000 to 55000cSt at 25℃is fed from a liquid feed pump and kneaded.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resin composition, a molded article, and a method for producing a resin composition, each of which has excellent sliding properties and excellent moldability, can be provided.
Drawings
Fig. 1 is a schematic explanatory view of an example of an extruder used in the method for producing a resin composition according to the present embodiment.
Symbol description
1. Extrusion machine
2. Raw material supply port
3. Resin melting part
4. Mixing and dispersing unit
5. Liquid supply pump
6. Extrusion part
7. Extraction part
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "present embodiment") will be described in detail. The present embodiment described below is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
In the present specification, "to" is used in the sense of including numerical values described before and after the "to" as a lower limit value and an upper limit value.
In the present specification, unless otherwise specified, various physical property values and characteristic values are values at 23 ℃.
The standard shown in the present specification is based on 2021, 1 and 1 day time points unless otherwise specified, when the measurement method and the like differ depending on the year.
The resin composition of the present embodiment contains (B) 0.1 to 30.0 parts by mass of an olefin polymer, (C) 0.1 to 30.0 parts by mass of a silicone oil having a kinematic viscosity at 25 ℃ of 1000 to 55000cSt, and (D) 0.1 to 15.0 parts by mass of a hydrocarbon wax, based on 100 parts by mass of the polyacetal resin (A), and the mass ratio of the olefin polymer (B) to the silicone oil (C), that is, (B)/(C), is 2.00 or less. With such a constitution, a resin composition excellent in the sliding property and moldability of the obtained molded article can be obtained.
Polyacetal resin (A)
The resin composition of the present embodiment contains a polyacetal resin. By including the polyacetal resin, a molded article excellent in slidability and mechanical strength can be obtained.
The polyacetal resin used in the present embodiment is a polyacetal resin having an acetal structure- (-O-CRH-) in a repeating structure n Polymers containing (wherein R represents a hydrogen atom or an organic group), and an oxymethylene group (-CH) having R as a hydrogen atom 2 O-) as a main structural unit. The polyacetal resin used in the present embodiment includes, in addition to an acetal homopolymer composed only of the repeating structure, a copolymer (including a block copolymer) and a terpolymer each containing 1 or more structural units other than the oxymethylene group, and may have not only a linear structure but also a branched or crosslinked structure.
Examples of the structural unit other than the oxymethylene group include: ethylene oxide (-CH) 2 CH 2 O-), oxypropylene group (-CH) 2 CH 2 CH 2 O-), oxybutylene (-CH) 2 CH 2 CH 2 CH 2 O-) and the like, wherein the optionally branched oxyalkylene group has 2 to 10 carbon atoms, among them, the optionally branched oxyalkylene group having 2 to 4 carbon atoms is preferable, and the oxyethylene group is particularly preferable. The content of the oxyalkylene structural unit other than the oxymethylene group in the polyacetal resin is preferably 0.1mol% or more and 20mol% or less, more preferably 0.1mol% or more and 15mol% or less.
The polyacetal resin used in the present embodiment may be produced by any conventionally known method. For example, a polyacetal resin having an oxymethylene group and an oxyalkylene group having 2 or more and 4 or less carbon atoms as structural units can be produced by copolymerizing a cyclic oligomer of an oxymethylene group such as a trimer (trioxymethylene) or a tetramer (tetrapolyoxymethylene) of formaldehyde with a cyclic oligomer of an oxyalkylene group having 2 or more and 4 or less carbon atoms such as ethylene oxide, 1, 3-dioxolane, 1,3, 6-trioxane, 1, 3-dioxepane or the like.
Among them, the polyacetal resin used in the present invention is preferably a cyclic oligomer such as trioxymethylene or tetralylmethylene, or a copolymer with ethylene oxide and/or 1, 3-dioxolane, and particularly preferably a copolymer of trioxymethylene and 1, 3-dioxolane. In this case, the total amount of ethylene oxide and/or 1, 3-dioxolane is preferably from 1 to 20% by mass relative to 80 to 99% by mass of the cyclic oligomer.
The Melt Flow Rate (MFR) of the polyacetal resin is arbitrary, and the value measured at 190℃under a load of 2.16kg according to ASTM-D1238 is usually 1g/10 min or more, preferably 10g/10 min or more, more preferably 13g/10 min or more, still more preferably 20g/10 min or more, still more preferably 32g/10 min or more, still more preferably 35g/10 min or more, still more preferably 40g/10 min or more. The MFR is usually 150g/10 min or less, preferably 100g/10 min or less, more preferably 70g/10 min or less, still more preferably 60g/10 min or less, still more preferably 50g/10 min or less.
When the resin composition of the present embodiment contains 2 or more polyacetal resins, it is preferable that the MFR of the mixture satisfies the above range.
The resin composition of the present embodiment preferably contains the polyacetal resin in an amount of 80 mass% or more of the resin composition, more preferably 85 mass% or more, and still more preferably 90 mass% or more. The upper limit is that the total amount excluding the (B) olefin polymer, (C) silicone oil and (D) hydrocarbon wax is the amount of polyacetal resin.
The resin composition of the present embodiment may contain only 1 polyacetal resin, or may contain 2 or more polyacetal resins. When the content is 2 or more, the total amount is preferably within the above range.
Olefin Polymer (B)
The resin composition of the present embodiment contains (B) an olefin polymer in a proportion of 0.1 to 30.0 parts by mass relative to 100 parts by mass of (a) a polyacetal resin. By including the olefin polymer, a molded article excellent in sliding properties can be obtained. Further, a resin composition excellent in moldability can be obtained. Further, there is a tendency to obtain a molded article excellent in mechanical strength.
The olefin polymer used in the present embodiment may be any known olefin polymer. The olefin polymer is preferably selected from polyethylene, polypropylene, ethylene-propylene copolymers, and ethylene-butene copolymers, and more preferably comprises an ethylene-butene copolymer. These olefin polymers are olefin polymers comprising an acid-modified polyolefin polymer having the above-mentioned polyolefin backbone. That is, for example, polyethylene refers to a polymer comprising both polyethylene that is not acid-modified and acid-modified polyethylene.
The number average molecular weight of the olefin polymer in the present embodiment is preferably 1×10 4 The above is more preferably 2×10 4 The above is preferably 50×10 4 The following is given. When the olefin polymer having a number average molecular weight of the lower limit or more is used, a harder molded article can be formed, and the slidability of the obtained molded article can be further improved. In addition, by using the olefin polymer having a number average molecular weight of the above upper limit or less, the polymer can be uniformly dispersed under shearing during kneading, and the decrease in mechanical properties tends to be suppressed.
Further, the Melt Flow Rate (MFR) measured at 190℃under a load of 2.16kg according to ASTM-D1238 is preferably 70g/10 min or less, more preferably 50g/10 min or less, still more preferably 25g/10 min or less, still more preferably 15g/10 min or less. By setting the upper limit value or less, a harder molded article can be formed, and the sliding properties of the obtained molded article tend to be further improved. The lower limit of the Melt Flow Rate (MFR) may be, for example, 0.1g/10 min or more. By setting the lower limit value or more, the dispersion can be uniformly dispersed under shearing during kneading, and the decrease in mechanical properties can be effectively suppressed.
When the resin composition of the present embodiment contains 2 or more polyolefin polymers, the MFR of the mixture is set.
The vicat softening temperature of the olefin polymer in accordance with JIS K7206 in the present embodiment is preferably 30 ℃ or higher. The vicat softening temperature, which is a rough benchmark for the temperature at which thermoplastics begin to soften rapidly, is an indicator of short term heat resistance. In the present embodiment, the use of such an olefin polymer makes the heat resistance during sliding excellent. In the present embodiment, the vicat softening temperature is set to the vicat softening temperature at a load of 50N and a temperature rise rate of 50 ℃/hour. The upper limit of the vicat softening temperature is not particularly limited, but is usually lower than the melting point of the polyacetal resin, preferably 150 ℃ or lower.
The olefin polymer in the present embodiment may be an acid-modified polyolefin polymer, an olefin polymer modified with at least 1 of an unsaturated carboxylic acid and an acid anhydride thereof, or an olefin polymer modified with at least 1 of an acid anhydride of an unsaturated carboxylic acid (preferably, maleic anhydride) as described above. Examples of the unsaturated carboxylic acid include maleic acid, acrylic acid, methacrylic acid, maleic acid, citraconic acid, itaconic acid, tetrahydrophthalic acid, nadic acid, methylnadic acid, and allylsuccinic acid, and maleic acid is preferable.
Details of the modified olefin polymer modified with at least 1 of the unsaturated carboxylic acid and its anhydride can be found in Japanese patent application laid-open No. 10-130458, paragraph 0005, which is incorporated herein by reference.
The acid value of the acid-modified olefin polymer may be 0mgKOH/g, or may be 2.0mgKOH/g or more, or may be 5.0mgKOH/g or more. The acid value of the acid-modified olefin polymer may be, for example, 70.0mgKOH/g or less, 30.0mgKOH/g or less, or 20.0mgKOH/g or less. When the tensile failure is equal to or less than the upper limit, the tensile failure nominal strain tends to be further increased.
When the olefin polymers are contained in an amount of 2 or more, the acid value here is obtained by multiplying the acid value of each olefin polymer by the blending amount (mass) fraction of each olefin polymer.
The content of the olefin polymer in the resin composition of the present embodiment is 0.1 part by mass or more, preferably 0.4 part by mass or more, and more preferably 0.8 part by mass or more, based on 100 parts by mass of the polyacetal resin. When the lower limit value is not less than the above, the obtained molded article tends to be more excellent in slidability and moldability. The content of the olefin polymer in the resin composition of the present embodiment is 30.0 parts by mass or less, preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, still more preferably 5.0 parts by mass or less, still more preferably 3.0 parts by mass or less, still more preferably 2.5 parts by mass or less, and still more preferably 1.5 parts by mass or less, based on 100 parts by mass of the polyacetal resin. When the tensile failure nominal strain of the obtained molded article is set to the above upper limit or less, the tensile failure nominal strain tends to be further improved.
The resin composition of the present embodiment may contain only 1 kind of olefin polymer, or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
Silicone oil (C)
The resin composition of the present embodiment contains (C) a silicone oil having a kinematic viscosity at 25℃of 1000 to 55000cSt in an amount of 0.1 to 30.0 parts by mass per 100 parts by mass of (A) a polyacetal resin. By including silicone oil, a molded article excellent in sliding properties can be obtained. Unlike conventional slip modifiers, the resin composition can be compounded with polyacetal resin or the like without the need for masterbatch, and can be easily produced.
The silicone oil used in the present embodiment has a kinematic viscosity at 25 ℃ of 1000cSt or more, preferably 2000cSt or more, more preferably 4000cSt or more, still more preferably 6000cSt or more, still more preferably 8000cSt or more. When the lower limit value is not less than the above, moldability (metering property) tends to be further improved. The silicone oil has a kinematic viscosity at 25 ℃ of 55000cSt or less, preferably 45000cSt or less, more preferably 35000cSt or less, still more preferably 25000cSt or less, still more preferably 15000cSt or less, still more preferably 12000cSt or less. When the upper limit value is equal to or less than the above, the limit PV tends to be increased.
In the case where the resin composition of the present embodiment contains 2 or more silicone oils, the mixing ratio is determined as described below in such a manner that the desired kinematic viscosity is achieved. In the graph in which the vertical axis represents the kinematic viscosity on a logarithmic scale and the horizontal axis represents the% used, the kinematic viscosity on the left axis and the kinematic viscosity on the right axis are each connected by a straight line. The amount of the additive is determined by reading the amount of the viscosity from the upper and lower sides of the horizontal line passing through the scale of the desired kinematic viscosity and the straight line, and drawing the vertical line downward from the intersection point of the horizontal line and the straight line.
As the silicone oil used in the present embodiment, any conventionally known silicone oil can be used. Specifically, examples of the silicone oil include a silicone oil composed of polydimethylsiloxane, and substituted silicone oils in which part or all of methyl groups in the polydimethylsiloxane are substituted with hydrogen, an alkyl group having 2 or more carbon atoms, a phenyl group, a halophenyl group, an ester group, a halogenated ester group such as fluorine, a polyether group, or the like; modified silicone oils further having an epoxy group, an amino group, an alcoholic hydroxyl group, a polyether group, or the like in the polydimethylsiloxane; alkyl aralkyl silicone oils comprising dimethylsiloxane units and phenylmethylsiloxane units; and alkyl aralkyl polyether-modified silicone oils containing a siloxane unit having a structure in which a part of methyl groups of the dimethylsiloxane unit is substituted with polyether, and a phenyl methyl siloxane unit. Among them, preferred are a polymer of dimethylsiloxane and a copolymer of dimethylsiloxane and methylphenylsiloxane.
The content of the silicone oil (C) in the resin composition of the present embodiment is 0.1 part by mass or more, preferably 0.5 part by mass or more, more preferably 1.0 part by mass or more, still more preferably 1.5 parts by mass or more, and still more preferably 2.1 parts by mass or more, based on 100 parts by mass of the polyacetal resin (a). When the sliding property is set to the lower limit value or more, the sliding property tends to be further improved. The content of the silicone oil (C) in the resin composition of the present embodiment is 30.0 parts by mass or less, preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, still more preferably 5.0 parts by mass or less, and still more preferably 3.0 parts by mass or less, based on 100 parts by mass of the polyacetal resin (a). When the upper limit value is less than or equal to the above, moldability tends to be further improved.
The resin composition of the present embodiment may contain only 1 (C) silicone oil, or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
Preferably, the resin composition of the present embodiment contains substantially no silicone oil other than the silicone oil having a kinematic viscosity at 25 ℃ of 1000 to 55000 cSt. Substantially not including means that the content of the silicone oil other than the silicone oil having a kinematic viscosity at 25 ℃ of 1000 to 55000cSt is 5 mass% or less, preferably 1 mass% or less of the content of the silicone oil having a kinematic viscosity at 25 ℃ of 1000 to 55000 cSt.
In the resin composition of the present embodiment, the mass ratio of (B) the olefin polymer to (C) the silicone oil, that is, (B)/(C), is 2.00 or less. With such a configuration, slidability can be improved. The ratio (B)/(C) is preferably 1.50 or less, more preferably 1.00 or less, still more preferably 0.80 or less, still more preferably 0.60 or less, still more preferably 0.50 or less, and may be 0.45 or less. The lower limit of (B)/(C) is preferably 0.10 or more, more preferably 0.15 or more.
Hydrocarbon wax (D)
The resin composition of the present embodiment contains (D) a hydrocarbon wax in an amount of 0.1 to 15.0 parts by mass relative to 100 parts by mass of (a) a polyacetal resin. By including the hydrocarbon wax, the slidability of the obtained molded article tends to be further improved. In the case of the hydrocarbon wax, the hydrocarbon wax may be a material having a vicat softening temperature of 30 ℃ or higher, which is considered to be a material belonging to the olefin polymer, or a material having a vicat softening temperature of less than 30 ℃ or a vicat softening temperature of which cannot be measured. Examples of the material for which the vicat softening temperature cannot be measured include a case where a test piece for measuring the vicat softening temperature cannot be molded. In general, hydrocarbon waxes cannot be used to produce test pieces for measuring vicat softening temperatures.
The hydrocarbon wax is a wax containing a hydrocarbon as a main component, and may have a functional group such as an acid group.
The molecular weight of the hydrocarbon wax used in the present embodiment by the viscosity method is preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more, and may be 2500 or more. By setting the lower limit value or more, the occurrence of bleeding on the surface of the molded article can be more effectively prevented. The upper limit of the molecular weight by the viscosity method is preferably 7000 or less, more preferably 6000 or less, and may be 5500 or less. By setting the upper limit value or less, frictional wear characteristics, molding processability, and the like can be further improved.
As the hydrocarbon wax, those called paraffin wax, polyolefin wax, fischer-tropsch wax hydrocarbon wax are included. In this embodiment, polyolefin wax is preferable, and polyethylene wax is more preferable.
Examples of the hydrocarbon wax include FT-100 and FT-0070 sold by Japan refined wax, paraflin manufactured by SASOL Co.
In particular, examples of the polyolefin WAX include Hi-WAX (manufactured by Sanjing Chemical Co., ltd.), sun WAX (manufactured by Sanyo Chemical industry Co., ltd.), EPOLENE (manufactured by Eastman Chemical Co., ltd.), allied WAX (manufactured by Allied Singnals), and the like.
The polyethylene wax used in the present embodiment is preferably a modified polyethylene wax obtained by acid-modifying a low molecular weight polyethylene or a low molecular weight polyethylene copolymer. In the acid modification treatment, the wax may be treated with an inorganic acid, an organic acid, an unsaturated carboxylic acid, or the like in the presence of a peroxide or oxygen, if necessary, to introduce a polar group such as a carboxyl group or a sulfonic acid group.
These polyethylene waxes are commercially available under the names of medium acid value type polyethylene waxes, high acid value type polyethylene waxes, acid modified type polyethylene waxes, and the like, and are readily available on the market.
The acid value of the polyethylene wax used in the present embodiment is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, and may be 26mgKOH/g or more. The upper limit of the acid value of the polyethylene wax is preferably 60mgKOH/g or less, more preferably 50mgKOH/g or less, still more preferably 40mgKOH/g or less, still more preferably 37mgKOH/g or less, or may be 35mgKOH/g or less, or may be 30mgKOH/g or less. By setting the range as described above, high friction characteristics and wear resistance can be achieved.
The acid value can be measured as described in examples described below.
The content of the hydrocarbon wax (D) in the resin composition of the present embodiment is 0.1 part by mass or more, preferably 0.5 part by mass or more, more preferably 0.8 part by mass or more, still more preferably 1.0 part by mass or more, still more preferably 1.2 parts by mass or more, still more preferably 1.3 parts by mass or more, based on 100 parts by mass of the polyacetal resin (a). When the sliding property is set to the lower limit value or more, the sliding property tends to be further improved. The content of the hydrocarbon wax (D) is 15.0 parts by mass or less, preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, further preferably 3.5 parts by mass or less, further preferably 2.5 parts by mass or less, further preferably 2.0 parts by mass or less, based on 100 parts by mass of the polyacetal resin (a). When the upper limit value is less than or equal to the above, moldability tends to be further improved.
The resin composition of the present embodiment may contain only 1 kind (D) of hydrocarbon wax, or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
The mass ratio of the hydrocarbon wax (D) to the silicone oil (C), i.e., (D)/(C), in the resin composition of the present embodiment is preferably 1.0 or less, more preferably 0.9 or less, still more preferably 0.8 or less, still more preferably 0.7 or less, still more preferably 0.65 or less. It is more practical that the lower limit value of (D)/(C) is 0.1 or more.
< other Components >)
The resin composition of the present embodiment may contain known additives and fillers within a range that does not impair the object of the present invention. Specific examples of the additive and filler that can be used in the present embodiment include: known thermoplastic polymers, antistatic agents, ultraviolet absorbers, light stabilizers, carbon fibers, glass flakes, talc, mica, calcium carbonate, potassium titanate whiskers, and the like.
The content of these components is preferably 10% by mass or less of the total resin composition.
In the resin composition of the present embodiment, the total of (a) the polyacetal resin, (B) the olefin polymer, (C) the silicone oil having a kinematic viscosity of 1000 to 55000cSt at 25 ℃ and (D) the hydrocarbon wax is preferably 90 mass% or more, more preferably 95 mass% or more, and may be 99 mass% or more of the resin composition.
Physical Property values of the resin composition
The limiting PV value of the resin composition of the present embodiment is preferably 10.0 or more, more preferably 11.0 or more. It is more practical that the upper limit of the limit PV value is, for example, 25.0 or less. The limiting PV value is a value obtained by molding a cylindrical thrust test piece, performing a test by pressurizing the surface pressure to 0.15, 0.25, 0.49, 0.74, 0.98, 1.23, 1.47MPa every 3 minutes in an atmosphere at a temperature of 23 ℃ and a humidity of 50%, and multiplying the linear velocity by the surface pressure immediately before the surface pressure at which the test piece melts or wears abnormally.
The resin composition of the present embodiment is molded into a cylindrical thrust test piece, and the dynamic friction coefficient measured at a surface pressure of 0.49MPa and a linear velocity of 0.1 m/sec at a temperature of 23℃and a humidity of 50% is preferably 0.17 or less, more preferably 0.15 or less, still more preferably 0.14 or less, still more preferably 0.13 or less. For example, the lower limit value is preferably 0.01 or more.
The limit PV value and the coefficient of dynamic friction can be measured as described in examples described below.
Method for producing resin composition
The resin composition of the present embodiment can be easily produced by a known method conventionally used as a production method of a thermoplastic resin composition. For example, the following method may be employed: (1) A method in which all the components constituting the composition are mixed, supplied to an extruder, and melt-kneaded to obtain a pellet-shaped composition; (2) A method in which a part of the components constituting the composition is fed from a main feed port of an extruder, and the remaining components are fed from a side feed port, and the mixture is melt-kneaded to obtain a pellet-shaped composition; (3) And a method of temporarily preparing pellets having different compositions by extrusion or the like, mixing the pellets, and adjusting the mixture to a predetermined composition.
The kneading machine may be exemplified by a kneader, a Banbury mixer, an extruder, etc. The conditions and apparatuses for mixing/kneading are not particularly limited, and may be appropriately selected and determined from any conventionally known conditions. The kneading is preferably performed at a temperature not lower than the melting temperature of the polyacetal resin, specifically not lower than the melting temperature of the polyacetal resin (usually not lower than 180 ℃).
In particular, the present embodiment preferably includes: after the polyacetal resin (A), the olefin polymer (B) and the hydrocarbon wax (D) are fed from the feed port of the extruder and kneaded, silicone oil having a kinematic viscosity of 1000 to 55000cSt at 25℃is fed from a liquid feed pump and kneaded.
Fig. 1 is a schematic explanatory view of an example of an extruder used in the method for producing a resin composition according to the present embodiment. The extruder 1 is composed of a raw material supply port 2, a resin melting section 3, a kneading dispersion section 4, a liquid supply pump 5, an extrusion section 6, and a take-out section 7. First, (a) polyacetal resin, (B) olefin polymer, (D) hydrocarbon wax, and other components blended as necessary are supplied from a raw material supply port 2 provided in a resin melting section 3. At this time, (C) silicone oil was not supplied. Then, they are sent to the kneading dispersion section 4 and uniformly mixed. Then, the silicone oil (C) is fed from the liquid supply pump 5, and further kneaded. Next, the resin composition is extruded from the extrusion part 6, cooled, taken out from the take-out part 7, and cut after cooling, thereby obtaining a pellet-shaped resin composition.
< shaped article >
The molded article of the present embodiment is formed from the resin composition of the present embodiment. The pellets obtained by granulating the resin composition of the present embodiment can be molded by various molding methods to obtain molded articles. Alternatively, the resin composition after melt-kneading in an extruder may be directly molded without passing through the pellets to obtain a molded article.
The shape of the molded article is not particularly limited, and may be appropriately selected according to the purpose and purpose of the molded article, and examples thereof include: plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, oval, gear-like, polygonal, shaped article, hollow article, frame-like, box-like, panel-like shaped article. The molded article of the present embodiment may be a finished product or a component.
The method for molding the molded article is not particularly limited, and a conventionally known molding method may be employed, and examples thereof include: injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (In-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, compression molding, and the like.
The resin composition of the present embodiment is preferably used as a resin composition for forming a sliding member. Therefore, a molded article formed from the resin composition of the present embodiment is preferably used as a sliding member (sliding part).
Specific examples of the sliding member include: gears, shafts, bearings, various transmission devices, cams, end face materials for mechanical seals, valve seats for valves and the like, V-rings, seals for piston rods, sealing members for piston rings, guide rings and the like, and sliding members for compressor shafts, bushings, pistons, impellers, rollers and the like, which are aimed at achieving high quality required for electric/electronic equipment, office equipment, vehicles (automobiles), industrial equipment and the like.
The sliding member according to the present embodiment can be used as a sliding member in which the sliding members according to the present embodiment are combined with each other, and can be used as a sliding member in which other resin sliding members, fiber reinforced resin sliding members, and ceramic or metal sliding members are combined.
Examples
The present invention will be described in more detail with reference to examples. The materials, amounts, proportions, treatment contents, treatment steps and the like shown in the following examples may be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.
In the case where the measurement apparatus or the like used in the examples is difficult to obtain due to model discarding or the like, the measurement may be performed using other apparatuses having the same performance.
A-1: polyacetal resin (MFR: 45)
Iupital F40-03, manufactured by Mitsubishi engineering plastics Co., ltd., melt Flow Rate (MFR) (measured at 190 ℃ C., under a load of 2.16kg, the following MFR concerning polyacetal resin are the same): 52g/10 min
A-2: polyacetal resin (MFR: 30)
Iuppital F30-03, manufactured by Mitsubishi engineering plastics Co., ltd., melt Flow Rate (MFR): 27g/10 min
A-3: polyacetal resin (MFR: 12)
Iuppital A25-03, manufactured by Mitsubishi engineering plastics Co., ltd., melt Flow Rate (MFR): 14g/10 min
B-1：TAFMER MA9015
Maleic anhydride-modified ethylene-butene copolymer, acid value 11.6mgKOH/g, MFR (measured at 190 ℃ C., load 2.16kg, the following regarding the MFR of polyolefin): 11.0 g/min, vicat softening temperature of about 30-40 ℃, manufactured by Sanjing chemical Co., ltd
B-2：TAFMER MH5020
Maleic anhydride-modified olefin polymer, acid value of 15.5mgKOH/g, MFR of 0.6 g/min, vicat softening temperature of about 30 to 40℃and Sanchi chemical Co Ltd
B-3：TAFMER MH7510
Maleic anhydride-modified olefin polymer, acid value of 7.3mgKOH/g, MFR of 40.0 g/min, vicat softening temperature of about 30 to 40℃and Sanchi chemical Co Ltd
B-4：Novatec LC522
Olefin polymer not modified with acid, acid value of 0mgKOH/g, MFR of 4.0 g/min, vicat softening temperature of about 90℃and manufactured by Japanese polyethylene Co., ltd
C-1：Silicone oil 1000cSt
The manufacturer: the kinematic viscosity at 25℃of KF-96H-1000cs manufactured by Xinyue chemical industry Co., ltd was 1000cSt
C-2：Silicone oil 6000cSt
The manufacturer: the kinematic viscosity at 25℃of KF-96H-6000cs manufactured by Xinyue chemical industry Co., ltd., is 6000cSt
C-3：Silicone oil 10000cSt
The manufacturer: the kinematic viscosity at 25℃of KF-96H-10000cs manufactured by Xinyue chemical industries Co., ltd., is 10000cSt
C-4：Silicone oil 30000cSt
The manufacturer: KF-96H-30000, manufactured by Xinyue chemical industry Co., ltd., kinematic viscosity at 25℃of 30000cSt
C-5：Silicone oil 60000cSt
The manufacturer: KF-96H-60000, available from Xinyue chemical industry Co Ltd, has a kinematic viscosity of 60000cSt at 25 DEG C
D-1：Paraffin Wax 155F
The manufacturer: vicat softening temperature, manufactured by Nippon refined wax Co., ltd.): cannot be measured and has a molecular weight (viscosity method) of 300 to 550
D-2：Hi-WAX 720P
Low molecular weight polyethylene, vicat softening temperature: unable to be measured, molecular weight (viscosity method) 2700, sanjing chemical Co., ltd
D-3：SANWAX 151P
Low molecular weight polyethylene manufactured by Sanyo chemical Co., ltd., vicat softening temperature: unable to determine number average molecular weight 2000
< determination of acid value >)
The mass of potassium hydroxide required for neutralizing 1g of the sample (acid-modified olefin polymer, polyethylene wax, etc.) was measured as an acid value.
Specifically, the measurement was performed by neutralization titration in accordance with JIS K0070. 1g of the sample was precisely weighed, and dissolved in 100mL of xylene with stirring at about 120 ℃. After complete dissolution, a phenolphthalein solution was added, and neutralization titration was performed using 0.1mol/L potassium hydroxide ethanol solution whose exact concentration was previously determined. The acid value was calculated from the amount (T) to be added, the factor (f) of 0.1mol/L of potassium hydroxide ethanol solution, 1/10 (5.611) of the formula weight of potassium hydroxide of 56.11, and the mass (S) of the sample by the following formula.
Acid number = T x f x 5.611/S
The units are expressed in mgKOH/g.
< determination of kinematic viscosity >)
Measurements were made using an Ubbelohde viscometer based on ASTM D445-46T.
Examples 1 to 11 and comparative examples 1 to 5
< Complex >)
After premixing, the components (each component unit in parts by mass) were mixed as shown in tables 1 and 2 below, and melt-mixed in a main feed port of a 30 mm-diameter twin-screw extruder having one vent (extrusion conditions: L/d=35, extrusion temperature=190 ℃, screw rotation speed=120 rpm, vacuum pressure for venting= -0.08MPa, discharge amount=10 kg/hr) to prepare a pellet-shaped resin composition. Resin pellets were produced by charging from the root of a 26mm diameter twin screw extruder (manufactured by Zhi Pu mechanical Co., ltd.) and supplying silicone oil by using a liquid supply pump after melting. The extrusion temperature was 190℃and the screw rotation speed was 120rpm, and the evacuation vacuum pressure was-0.08 MPa, with a discharge amount of 12 kg/hr.
The following evaluation was performed using the obtained resin composition.
< F20-03 limit PV value >)
A cylindrical thrust test piece was produced by injection molding at a cylinder temperature of 200℃and a mold temperature of 80 ℃. The test was performed by using a thrust frictional wear tester manufactured by orintec, in an atmosphere having a temperature of 23 ℃ and a humidity of 50%, with a surface pressure increased to 0.15, 0.25, 0.49, 0.74, 0.98, 1.23, and 1.47MPa every 3 minutes, and the value obtained by multiplying the linear velocity by the surface pressure immediately before the surface pressure at which the test piece was melted or abnormally worn was set as the limit PV.
< pair F20-03 (10 kg) dynamic coefficient of friction (-) >
A cylindrical thrust test piece was produced by injection molding at a cylinder temperature of 200℃and a mold temperature of 80 ℃. The surface pressure was 0.49MPa and the linear velocity was 0.1 m/s in an atmosphere having a temperature of 23℃and a humidity of 50% by using a thrust frictional wear tester manufactured by Orientec.
< wear on F20-03 (F20-03/self-Material) >
A cylindrical thrust test piece was produced by injection molding at a cylinder temperature of 200℃and a mold temperature of 80 ℃. The abrasion loss was calculated from the weight of the test piece before and after 20 hours of testing at a surface pressure of 0.15MPa and a linear velocity of 0.3 m/s in an atmosphere having a humidity of 50% at a temperature of 23℃using a thrust frictional abrasion tester manufactured by Orientec.
< moldability >
The molded article was molded under injection conditions of a cylinder temperature of 200℃and a mold temperature of 80℃and an injection time of 45 seconds and a cooling time of 20 seconds by using an injection molding machine, whereby a molded article in the shape of a multipurpose test piece according to ISO294-1 was obtained. The moldability was evaluated based on the time taken for the measurement.
A: within 15 seconds
B: within 18 seconds
C: over 18 seconds [ Table 1]
TABLE 2
From the above results, it was revealed that the resin compositions of the present invention were excellent in sliding properties and moldability (examples 1 to 11).
In contrast, when the kinematic viscosity of silicone oil is high (comparative example 1), the sliding property is poor. In addition, in the case of not containing silicone oil (comparative example 2), the sliding property was poor. In addition, in the case where hydrocarbon wax was not contained (comparative example 3), the sliding property was poor. In addition, in the case where the mass ratio of (B)/(C) exceeds 2.0 (comparative example 4), the sliding property is poor. In addition, in the case of not containing an olefin polymer (comparative example 5), moldability was poor.
Claims (16)
1. A resin composition, wherein,
the polyacetal resin composition comprises (A) 100 parts by mass of polyacetal resin:
(B) Olefin polymer 0.1-30.0 parts by mass,
(C) 0.1 to 30.0 parts by mass of silicone oil having a kinematic viscosity at 25 ℃ of 1000 to 55000cSt
(D) 0.1 to 15.0 parts by mass of hydrocarbon wax,
the mass ratio of the olefin polymer (B) to the silicone oil (C), i.e., (B)/(C), is 2.00 or less.
2. The resin composition according to claim 1, wherein,
the mass ratio of the olefin polymer (B) to the silicone oil (C), i.e., (B)/(C), is 0.10 or more.
3. The resin composition according to claim 1 or 2, wherein,
the (B) olefin polymer is selected from polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-butene copolymer.
4. The resin composition according to claim 1 or 2, wherein,
the (B) olefin polymer comprises an ethylene-butene copolymer.
5. The resin composition according to claim 1 or 2, wherein,
the Vicat softening temperature of the olefin polymer (B) according to JIS K7206 is above 30 ℃.
6. The resin composition according to claim 1 or 2, wherein,
the content of the olefin polymer (B) is 0.1 to 3.0 parts by mass per 100 parts by mass of the polyacetal resin (A).
7. The resin composition according to claim 1 or 2, wherein,
the silicone oil (C) is contained in an amount of 0.5 to 5.0 parts by mass per 100 parts by mass of the polyacetal resin (A).
8. The resin composition according to claim 1 or 2, wherein,
the mass ratio of the olefin polymer (B) to the silicone oil (C), i.e., (B)/(C), is 0.80 or less.
9. The resin composition according to claim 1 or 2, wherein,
the mass ratio of the olefin polymer (B) to the silicone oil (C), i.e., (B)/(C), is 0.50 or less.
10. The resin composition according to claim 1 or 2, wherein,
the mass ratio of the hydrocarbon wax (D) to the silicone oil (C), i.e., (D)/(C), is 1.0 or less.
11. The resin composition according to claim 1 or 2, which is a resin composition for forming a sliding member.
12. A pellet which is a pellet of the resin composition according to claim 1 or 2.
13. A molded article formed from the resin composition according to claim 1 or 2.
14. A molded article formed from the pellet of claim 12.
15. The molded article according to claim 13, which is a sliding member.
16. A method for producing the resin composition according to claim 1 or 2, comprising:
after the polyacetal resin (A), the olefin polymer (B) and the hydrocarbon wax (D) are fed from the feed port of the extruder and kneaded, silicone oil having a kinematic viscosity of 1000 to 55000cSt at 25℃is fed from a liquid feed pump and kneaded.
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| JP2021-139873 | 2021-08-30 | ||
| JP2021139873 | 2021-08-30 | ||
| PCT/JP2022/030285 WO2023032606A1 (en) | 2021-08-30 | 2022-08-08 | Resin composition, molded article, and method for producing resin composition |
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| JP (1) | JPWO2023032606A1 (en) |
| KR (1) | KR20240051106A (en) |
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| JP2970691B2 (en) * | 1990-12-26 | 1999-11-02 | 三菱瓦斯化学株式会社 | Polyacetal resin composition |
| US8097670B2 (en) * | 2006-06-15 | 2012-01-17 | Mitsubishi Engineering-Plastics Corporation | Polyacetal resin composition, process for producing the same, and sliding member molded from the resin composition |
| JP2008214490A (en) | 2007-03-05 | 2008-09-18 | Mitsubishi Engineering Plastics Corp | Polyacetal resin composition |
| JP5450167B2 (en) * | 2010-03-01 | 2014-03-26 | テクノポリマー株式会社 | Automotive interior parts with reduced squeaking noise |
| JP5726977B2 (en) * | 2013-10-10 | 2015-06-03 | テクノポリマー株式会社 | Automotive interior parts with reduced squeaking noise |
| JP6445226B1 (en) | 2017-06-15 | 2018-12-26 | 三菱エンジニアリングプラスチックス株式会社 | POLYACETAL RESIN COMPOSITION, MOLDED ARTICLE, AND PROCESS FOR PRODUCING POLYACETAL RESIN COMPOSITION |
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