JPH0735459B2 - Thermoplastic high specific gravity resin composition - Google Patents
Thermoplastic high specific gravity resin compositionInfo
- Publication number
- JPH0735459B2 JPH0735459B2 JP2010156A JP1015690A JPH0735459B2 JP H0735459 B2 JPH0735459 B2 JP H0735459B2 JP 2010156 A JP2010156 A JP 2010156A JP 1015690 A JP1015690 A JP 1015690A JP H0735459 B2 JPH0735459 B2 JP H0735459B2
- Authority
- JP
- Japan
- Prior art keywords
- specific gravity
- resin composition
- weight
- high specific
- thermoplastic resin
- 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.)
- Expired - Lifetime
Links
- 230000005484 gravity Effects 0.000 title claims description 21
- 239000011342 resin composition Substances 0.000 title claims description 16
- 229920001169 thermoplastic Polymers 0.000 title claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 6
- 229920005992 thermoplastic resin Polymers 0.000 claims description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 3
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 claims 2
- 239000005973 Carvone Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- -1 polytetramethylene terephthalate Polymers 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、熱可塑性樹脂にタングステン粉末を高充填し
た射出成形用材料に係り、靭性と高比重性とを必要とす
る電気部品や機械部品等に好適な樹脂組成物に関する。Description: TECHNICAL FIELD The present invention relates to an injection molding material in which a thermoplastic resin is highly filled with tungsten powder, and an electric component or a mechanical component that requires toughness and high specific gravity. For example, the present invention relates to a resin composition suitable.
（従来の技術） 従来、熱可塑性樹脂に金属粉末を高充填して高比重性を
付与した熱可塑性樹脂組成物が多くの産業分野で広く使
用されている。例えば、特開昭56−159248号公報では、
ポリテトラメチレンテレフタレートに銅、鉄、ニッケ
ル、アルミニウム、金等の金属粉末を配合した高比重で
且つ、成形性、熱伝導性に優れた熱可塑性樹脂組成物が
示されている。また、特公昭61−11261号公報には、熱
可塑性樹脂に平均粒径８μ〜40μの亜鉛粉末を配合した
高比重熱可塑性樹脂組成物の製造方法が挙げられてい
る。(Prior Art) Conventionally, a thermoplastic resin composition in which a metal powder is highly filled in a thermoplastic resin to impart high specific gravity has been widely used in many industrial fields. For example, in JP-A-56-159248,
There is disclosed a thermoplastic resin composition having a high specific gravity, which is obtained by blending polytetramethylene terephthalate with a metal powder such as copper, iron, nickel, aluminum and gold and which is excellent in moldability and thermal conductivity. Japanese Patent Publication No. 61-11261 discloses a method for producing a high specific gravity thermoplastic resin composition in which a thermoplastic resin is mixed with zinc powder having an average particle size of 8 to 40 µ.
しかしながら、金属粉末が配合された熱可塑性樹脂組成
物は、金属粉末の配合量増加に伴ない、高比重化する
が、一方では流動性が低下し、成形品外観不良等の問題
点を有する。例えば、比重９以上の極めて高比重の熱可
塑性樹脂組成物を得ようとする場合には、金、白金、タ
ングステン粉末等を使用し、且つ、高充填しなければな
らず、混練、及び射出成形が極めて困難となる。更に、
金属粉末を高充填した熱可塑性樹脂組成物を射出成形す
る場合には、金属粉末間の摩擦による局部発熱が大き
く、熱可塑性樹脂の熱分解によるガスの発生、及び成形
品外観不良とい問題点がある。However, the thermoplastic resin composition in which the metal powder is blended has a high specific gravity as the blending amount of the metal powder is increased, but on the other hand, the fluidity is deteriorated, and there are problems such as poor appearance of the molded product. For example, in order to obtain an extremely high specific gravity thermoplastic resin composition having a specific gravity of 9 or more, gold, platinum, tungsten powder, etc. must be used and must be highly filled, and kneading and injection molding are required. Becomes extremely difficult. Furthermore,
When a thermoplastic resin composition highly filled with metal powder is injection-molded, local heat generation due to friction between the metal powders is large, gas is generated due to thermal decomposition of the thermoplastic resin, and there are problems such as poor appearance of the molded product. is there.
また、靭性に関しても、金属粉末を高充填した熱可塑性
樹脂組成物は、硬く、且つ脆くなり十分とはいえない。Also regarding the toughness, the thermoplastic resin composition in which the metal powder is highly filled is hard and brittle, and is not sufficient.
（発明が解決しようとする課題） 本発明は、このような事情に鑑みなされたものであっ
て、その目的とするところは、高比重で、溶融時の流動
性が良好で混練、成形性に優れ、更に靭性に優れた熱可
塑性高比重樹脂組成物を提供するにある。(Problems to be Solved by the Invention) The present invention has been made in view of such circumstances, and an object thereof is to have high specific gravity, good fluidity at the time of melting, kneading, and moldability. Another object of the present invention is to provide a thermoplastic high specific gravity resin composition which is excellent and has excellent toughness.
（課題を解決するための手段） 上記の目的は、熱可塑性樹脂に、アクリル酸エステル共
重合体、全体重量中90〜98重量％のタングステン粉末、
及び同じく0.01〜0.5重量％の下記一般式（Ｉ）で示さ
れる飽和脂肪族カルボン酸化合物を配合し、且つ比重が
7.5以上であることを特徴とする熱可塑性高比重樹脂組
成物によって達成される。(Means for Solving the Problems) The above-mentioned objects are: a thermoplastic resin, an acrylic acid ester copolymer, 90 to 98% by weight of tungsten powder in the total weight,
And 0.01 to 0.5% by weight of a saturated aliphatic carboxylic acid compound represented by the following general formula (I) is mixed, and the specific gravity is
It is achieved by a thermoplastic high specific gravity resin composition characterized by being 7.5 or more.
〔CH3（CH2）mCOO〕nR ……（Ｉ） （式中、ｍは20〜32の整数、ｎは１または２、Ｒはアル
カリ金属、アルカリ土類金属、あるいは脂肪族炭化水素
を表わす。） すなわち、本発明者らは、金属粉末としてタングステン
粉末を用い、これを熱可塑性樹脂に高充填し、更に、ア
クリル酸エステル共重合体、及び飽和脂肪族カルボン酸
化合物を配合することにより、熱可塑性樹脂に金属粉末
を高充填しても溶融時の流動性が良好で成形性に優れ、
更に靭性に優れた熱可塑性高比重樹脂組成物が得られる
ことを見いだし本発明を完成した。[CH 3 (CH 2) mCOO] nR ...... (I) (wherein, m is an integer of 20 to 32, n represents 1 or 2, R is an alkali metal, alkaline earth metal or aliphatic hydrocarbons, That is, the present inventors have used tungsten powder as the metal powder, highly filling the same with a thermoplastic resin, and further blending the acrylic ester copolymer and the saturated aliphatic carboxylic acid compound, Even if the thermoplastic resin is highly filled with metal powder, the fluidity at the time of melting is good and the moldability is excellent,
The present invention has been completed by finding that a thermoplastic high specific gravity resin composition having excellent toughness can be obtained.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明に使用する熱可塑性樹脂としては、一般に射出成
形加工に供せられているものであれば特に制限はなく、
例えば、ポリアミド、ポリエステル、ポリカーボネー
ト、ポリエーテルサルフオン、ポリオレフィン、ポリフ
ェニレンオキサイド、ポリフェニレンサルファイド、ポ
リエーテルエーテルケトン、AS樹脂、AN樹脂、ABS樹脂
等を挙げることができる。これらの中で特に好ましいも
のとして、ポリアミド、ポリエステル、ポリフェニレン
サルファイドが挙げられる。The thermoplastic resin used in the present invention is not particularly limited as long as it is generally used for injection molding.
For example, polyamide, polyester, polycarbonate, polyether sulfone, polyolefin, polyphenylene oxide, polyphenylene sulfide, polyether ether ketone, AS resin, AN resin, ABS resin and the like can be mentioned. Of these, polyamide, polyester, and polyphenylene sulfide are particularly preferable.
本発明に使用するタングステン粉末としては、その平均
粒径が50μｍ以下であることが望ましい。更に、粒径10
μｍ以下のものが、タングステン粉末全体の割合で50重
量％以上、且つ、粒径20μｍ以上のものが30重量％以上
の粒径分布となっているタングステン粉末が好適であ
る。このような粒径分布の場合に、特に溶融時の流動性
が良好となる。The tungsten powder used in the present invention preferably has an average particle size of 50 μm or less. Furthermore, particle size 10
A tungsten powder having a particle size distribution of 50 μm or less in a proportion of the entire tungsten powder and a particle size distribution of 30 μ% or more in a particle size of 20 μm or more is preferable. In the case of such a particle size distribution, the fluidity at the time of melting is particularly good.
また、タングステン粉末の配合量は90〜98重量％である
ことが肝要であり、特に93〜98重量％が好ましい。配合
量が90重量％未満の場合には、十分は高比重性を得られ
ず、また、98重量％を超える場合には、加熱溶融時の流
動性が悪く、射出成形が困難となる。Further, it is important that the content of the tungsten powder is 90 to 98% by weight, particularly preferably 93 to 98% by weight. When the content is less than 90% by weight, a sufficiently high specific gravity cannot be obtained, and when it exceeds 98% by weight, the fluidity during heating and melting is poor and injection molding becomes difficult.
本発明に使用するアクリル酸エステル共重合体は、炭素
数１−５の飽和もしくは不飽和の直鎖もしくは分岐鎖脂
肪族炭化水素基を有するアクリル酸エステルと、炭素数
１−５の飽和もしくは不飽和の直鎖もしくは分岐鎖脂肪
族炭化水素基を有するメタクリル酸エステルとの共重合
体が好ましい。ここに、炭素数１−５の飽和もしくは不
飽和の直鎖もしくは分岐鎖脂肪族炭化水素基を有するア
クリル酸エステルとしては、好ましくはアクリル酸メチ
ル、アクリル酸エチル、アクリル酸イソブチル、ジアク
リル酸−1,4−ブタンジオール、ジアクリル酸−1,3−ブ
チレン等が挙げられる。また炭素数１−５の飽和もしく
は不飽和の直鎖もしくは分岐鎖脂肪族炭化水素基を有す
るメタクリル酸エステルとしては、メタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸イソブチル、ジ
メタクリル酸−1,3−ブチレン、メタクリル酸−ｎ−ブ
チル等が挙げられる。かゝるアクリル酸エステル共重合
体としては、ローム＆ハース社から商品名「パラロイド
KM−330」として市販されているものが好ましい。The acrylic acid ester copolymer used in the present invention comprises an acrylic acid ester having a saturated or unsaturated linear or branched chain aliphatic hydrocarbon group having 1 to 5 carbon atoms and a saturated or unsaturated carbon atom having 1 to 5 carbon atoms. A copolymer with a methacrylic acid ester having a saturated linear or branched aliphatic hydrocarbon group is preferable. Here, as the acrylate ester having a saturated or unsaturated linear or branched chain aliphatic hydrocarbon group having 1 to 5 carbon atoms, methyl acrylate, ethyl acrylate, isobutyl acrylate, diacrylic acid-1 are preferable. 1,4-butanediol, diacrylic acid-1,3-butylene and the like can be mentioned. Examples of the methacrylic acid ester having a saturated or unsaturated linear or branched chain aliphatic hydrocarbon group having 1 to 5 carbon atoms include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, dimethacrylic acid-1,3- Butylene, methacrylic acid-n-butyl and the like can be mentioned. As such an acrylic acid ester copolymer, a trade name "Paraloid" is available from Rohm & Haas Company.
What is marketed as "KM-330" is preferable.
アクリル酸エステル共重合体の配合量は、好ましくは0.
1〜５重量％、特に好ましくは0.3〜３重量％である。ア
クリル酸エステル共重合体の配合量が0.1重量％未満の
場合には、靭性、すなわち耐衝撃性の改善が不十分とな
り易い。一方、５重量％を超える場合には、衝撃強度以
外の機械物性が低下してしまう傾向がある。The amount of the acrylic ester copolymer is preferably 0.
It is 1 to 5% by weight, particularly preferably 0.3 to 3% by weight. When the amount of the acrylic acid ester copolymer is less than 0.1% by weight, the toughness, that is, the impact resistance is apt to be insufficiently improved. On the other hand, if it exceeds 5% by weight, mechanical properties other than impact strength tend to deteriorate.
本発明では、上記一般式（Ｉ）で示される飽和脂肪族カ
ルボン酸化合物を配合することが肝要である。飽和脂肪
族カルボン酸化合物は、式中のｍが20〜32の飽和脂肪族
カルボン酸の金属塩またはエステルである。金属塩とし
ては、リチウム、ナトリウム、カリウム等のアルカリ金
属、マグネシウム、カルシウム等のアルカリ土類金属か
ら成るものが挙げられる。エステルとしては、エチレン
グリコール、1,2−又は1,3−プロパンジオール、1,3−
又は1,4−ブタンジオール等のアルコールでエステル化
したもの等が挙げられる。また、飽和脂肪族カルボン酸
化合物は１種でも、２種以上組み合わされた混合物でも
よく、混合物としてモンタンワックスが挙げられる。In the present invention, it is important to blend the saturated aliphatic carboxylic acid compound represented by the above general formula (I). The saturated aliphatic carboxylic acid compound is a metal salt or ester of a saturated aliphatic carboxylic acid having m in the formula of 20 to 32. Examples of the metal salt include those composed of alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium and calcium. Examples of the ester include ethylene glycol, 1,2- or 1,3-propanediol, 1,3-
Alternatively, those esterified with an alcohol such as 1,4-butanediol may be used. The saturated aliphatic carboxylic acid compound may be one kind or a mixture of two or more kinds, and examples thereof include montan wax.
飽和脂肪族カルボン酸化合物の配合量は、0.01〜0.5重
量％であり、好ましくは0.03〜0.3重量％である。配合
量が0.01重量％未満の場合には、流動性が不十分とな
り、射出成形時に、タングステン粉末間の摩擦による局
部発熱でガスが発生し、成形品外観が不良となるばかり
でなく、物性低下も著しい。また、0.5重量％を超える
場合には物性、特に衝撃強度の低下が著しい。The content of the saturated aliphatic carboxylic acid compound is 0.01 to 0.5% by weight, preferably 0.03 to 0.3% by weight. If the blending amount is less than 0.01% by weight, the fluidity will be insufficient, and the gas will be generated due to local heat generation due to friction between the tungsten powders during injection molding, which not only deteriorates the appearance of the molded product but also deteriorates the physical properties. Is also remarkable. On the other hand, when it exceeds 0.5% by weight, the physical properties, particularly the impact strength, are significantly lowered.
熱可塑性樹脂へのタングステン粉末、アクリル酸エステ
ル共重合体、及び飽和脂肪族カルボン酸化合物の配合方
法は、いくつか挙げられるが、例えば、熱可塑性樹脂粉
末、タングステン粉末、アクリル酸エステル共重合体、
及び飽和脂肪族カルボン酸化合物粉末をヘンシェルミキ
サー等の高速回転翼を有する混練機で撹拌による摩擦溶
融で造粒する方法や、単軸、或いは２軸混練機で溶融混
練する方法、また、この両者を組み合わせる方法等が挙
げられる。Tungsten powder to the thermoplastic resin, an acrylic acid ester copolymer, and a method of compounding the saturated aliphatic carboxylic acid compound, there are several, for example, thermoplastic resin powder, tungsten powder, acrylic acid ester copolymer,
And a method of granulating the saturated aliphatic carboxylic acid compound powder by friction melting by stirring with a kneader having a high-speed rotating blade such as a Henschel mixer, a method of melt-kneading with a single-screw or twin-screw kneader, or both. And the like.
（発明の効果） 以上のように、本発明にかゝる熱可塑性高比重樹脂組成
物は、熱可塑性樹脂にタングステン粉末更にアクリル酸
共重合体、及び上記一般式（Ｉ）で示される飽和脂肪族
カルボン酸化合物を配合させることにより、極めて高比
重で、且つ優れた成形性、及び靭性を有する。したがっ
て高比重で靭性と寸法精度を必要とする電気部品や機械
部品用の成形材料として好適である。(Effects of the Invention) As described above, the thermoplastic high specific gravity resin composition according to the present invention comprises the thermoplastic resin, the tungsten powder, the acrylic acid copolymer, and the saturated fat represented by the general formula (I). By incorporating a group carboxylic acid compound, it has extremely high specific gravity and excellent moldability and toughness. Therefore, it is suitable as a molding material for electric parts and mechanical parts which have high specific gravity and require toughness and dimensional accuracy.
以下、実施例を挙げて、本発明を具体的に説明する。Hereinafter, the present invention will be specifically described with reference to examples.
尚、実施例に示す物性の測定は以下の方法で行なった。The physical properties shown in the examples were measured by the following methods.
（１） 曲げ強度:ASTM Ｄ−790 （２） 曲げ弾性率:ASTM Ｄ−790 （３） 衝撃強度:ASTM Ｄ−256 （アイゾット、ノッチ付,1/4インチ） （４） 比 重:ASTM Ｄ−792 （実施例１〜３、比較例１〜４） 粉末状ナイロン６樹脂（鐘紡（株）製,MC−102）アクリ
ル酸エステル共重合体（ローム＆ハース社製、パラロイ
ドKM−330）、飽和脂肪族カルボン酸部分けん化エステ
ル（ヘキスト社製、ヘキストワックスOP）、及び、平均
粒径12μｍで、粒径分布が粒径10μｍ以下が55重量％、
10〜20μｍが10重量％、そして20μｍ以上が35重量％で
あるタングステン粉末を表−１に示す割合で配合した。
次いでこれを、ヘンシェルミキサーを用いて高速撹拌下
で摩擦溶融した後、冷却固化して再粉管し、更に30mmφ
で軸混練機を用いて、シリンダー温度250℃〜260℃で溶
融混練、成形用ペレットを得た。(1) Bending strength: ASTM D-790 (2) Bending elastic modulus: ASTM D-790 (3) Impact strength: ASTM D-256 (Izod, notched, 1/4 inch) (4) Specific gravity: ASTM D -792 (Examples 1 to 3, Comparative Examples 1 to 4) Powdery nylon 6 resin (manufactured by Kanebo Ltd., MC-102) acrylic acid ester copolymer (manufactured by Rohm & Haas, Paraloid KM-330), Saturated aliphatic carboxylic acid partially saponified ester (Hoechst Wax OP, manufactured by Hoechst Co., Ltd.), and having an average particle size of 12 μm and a particle size distribution of 10 μm or less is 55% by weight,
Tungsten powder having 10 to 20 μm of 10% by weight and 20 μm or more of 35% by weight was blended in the proportions shown in Table 1.
Next, this was friction-melted using a Henschel mixer under high-speed stirring, then cooled and solidified and re-powdered, and further 30 mmφ
Then, using a shaft kneader, melt kneading was performed at a cylinder temperature of 250 ° C. to 260 ° C. to obtain pellets for molding.
尚、比較例２の試料は、溶融流動性が悪く、ペレット化
することが出来なかった。The sample of Comparative Example 2 had poor melt fluidity and could not be pelletized.
次いで、得られたペレットを用いて、通常実施されてい
るナイロン６樹脂の成形条件で射出成形して試験片を得
た。Then, the obtained pellets were injection-molded under the commonly used molding conditions of nylon 6 resin to obtain test pieces.
得られた試験片の物性評価結果を表−２に示す。Table 2 shows the physical property evaluation results of the obtained test pieces.
以上の結果より、実施例のナイロン樹脂組成物は、極め
て高比重で、物性、特に耐衝撃性に優れ、かつ成形品外
観も良好であった。 From the above results, the nylon resin compositions of Examples had extremely high specific gravity, excellent physical properties, particularly impact resistance, and good appearance of molded products.
一方、比較例のナイロン樹脂組成物は、流動性が悪かっ
たり、比重が低すぎたり、物性に問題があったりした。On the other hand, the nylon resin compositions of Comparative Examples had poor fluidity, too low specific gravity, and problems with physical properties.
Claims (1)
合体、全体重量中90〜98重量％のタングステン粉末、及
び同じく0.01〜0.5重量％の下記一般式（Ｉ）で示され
る飽和脂肪族カルボン酸化合物を配合し、且つ比重が7.
5以上であることを特徴とする熱可塑性高比重樹脂組成
物。 〔CH3（CH2）mCOO〕nR ……（Ｉ） （式中、ｍは20〜32の整数、ｎは１または２、Ｒはアル
カリ金属、アルカリ土類金属、あるいは脂肪族炭化水素
基を表わす。）1. A thermoplastic resin comprising an acrylic ester copolymer, 90 to 98% by weight of the total weight of a tungsten powder, and 0.01 to 0.5% by weight of a saturated aliphatic carvone represented by the following general formula (I). Contains an acid compound and has a specific gravity of 7.
A thermoplastic high-specific-gravity resin composition, which is 5 or more. [CH 3 (CH 2 ) mCOO] nR (I) (In the formula, m is an integer of 20 to 32, n is 1 or 2, R is an alkali metal, alkaline earth metal, or an aliphatic hydrocarbon group. Represent)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010156A JPH0735459B2 (en) | 1990-01-18 | 1990-01-18 | Thermoplastic high specific gravity resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010156A JPH0735459B2 (en) | 1990-01-18 | 1990-01-18 | Thermoplastic high specific gravity resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03215566A JPH03215566A (en) | 1991-09-20 |
| JPH0735459B2 true JPH0735459B2 (en) | 1995-04-19 |
Family
ID=11742416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010156A Expired - Lifetime JPH0735459B2 (en) | 1990-01-18 | 1990-01-18 | Thermoplastic high specific gravity resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0735459B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003004892A (en) * | 2001-04-16 | 2003-01-08 | Kanebo Ltd | Radiation shielding container |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191254A (en) * | 1984-10-12 | 1986-05-09 | Seiko Epson Corp | Wrist watch case |
| JPS61254661A (en) * | 1985-05-07 | 1986-11-12 | Seiko Epson Corp | Surface part composition for clock |
-
1990
- 1990-01-18 JP JP2010156A patent/JPH0735459B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03215566A (en) | 1991-09-20 |
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