JPH07728B2 - Polyacetal resin composition - Google Patents
Polyacetal resin compositionInfo
- Publication number
- JPH07728B2 JPH07728B2 JP62124500A JP12450087A JPH07728B2 JP H07728 B2 JPH07728 B2 JP H07728B2 JP 62124500 A JP62124500 A JP 62124500A JP 12450087 A JP12450087 A JP 12450087A JP H07728 B2 JPH07728 B2 JP H07728B2
- Authority
- JP
- Japan
- Prior art keywords
- polyacetal resin
- resin composition
- weight
- polyacetal
- heat stabilizer
- 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
- 229920006324 polyoxymethylene Polymers 0.000 title claims description 27
- 229930182556 Polyacetal Natural products 0.000 title claims description 26
- 239000011342 resin composition Substances 0.000 title claims description 13
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000012760 heat stabilizer Substances 0.000 description 12
- 229920001519 homopolymer Polymers 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- -1 copolyamide Polymers 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- 229920004943 Delrin® Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003673 urethanes Chemical class 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） 本発明はポリアセタール樹脂組成物に係り、詳しくはポ
リアセタールの熱安定性を向上してなるポリアセタール
樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a polyacetal resin composition, and more particularly to a polyacetal resin composition obtained by improving the thermal stability of polyacetal.
（従来技術） ポリアセタール樹脂は、その優れた機械的強度、耐疲労
性及び耐摩擦摩耗特性等により歯車、軸受、機械部品、
電気部品等に広く使用されているエンジニアリングプラ
スチックである。(Prior Art) Polyacetal resin is used for gears, bearings, mechanical parts, because of its excellent mechanical strength, fatigue resistance and friction and wear resistance.
It is an engineering plastic that is widely used for electrical parts.
しかしながら、ポリアセタール樹脂は射出成形、押出成
形される際にポリマー末端から解重合を起こすため、こ
れを防止するためにホモポリマーの場合は、アセチル
化、エーテル化、ウレタン化して末端基を安定化した
り、また主鎖にオキシメチレン基以外の基を導入したり
オキメチレン共重合体は、これを安定末端まで分解する
ことにより熱安定化されるが、これだけでは充分でない
ので、更に熱安定剤、酸化防止剤を末端安定化されたポ
リアセタールに添加して実用に供されいる。However, polyacetal resin causes depolymerization from the polymer end during injection molding and extrusion molding, so in order to prevent this, in the case of homopolymer, acetylation, etherification, urethane formation stabilizes the end group or In addition, the introduction of groups other than oxymethylene groups into the main chain and oxymethylene copolymers are heat-stabilized by decomposing them to stable terminals, but this alone is not sufficient. The agent is added to the end-stabilized polyacetal for practical use.
ポリアセタールの安定剤としては、フェノール系酸化防
止剤、好ましくはヒンダードフェノール系酸化防止剤と
ポリアミド、コポリアミド、ポリエステルアミド、尿
素、尿素誘導体、ウレタン類等の含窒素化合物系と熱安
定剤とを組合せて用いるのが一般的である。As the polyacetal stabilizer, a phenolic antioxidant, preferably a hindered phenolic antioxidant and a polyamide, copolyamide, polyesteramide, urea, urea derivative, a nitrogen-containing compound such as urethanes and a heat stabilizer. It is generally used in combination.
特にコポリアミドとヒンダードフェノールとの組合せ
は、ポリアセタールの安定化に対して良好な組合せの安
定剤として用いられる。In particular, the combination of copolyamides and hindered phenols is used as a good combination stabilizer for the stabilization of polyacetals.
（発明が解決しようとする問題点） しかしながら、これを配合したポリアセタール樹脂組成
物は成形機のシリンダーの中で酸素の作用を受けて黄褐
色や黒色に変色して成形品の外観品質を著しく損なう場
合が多く、その改善は強く望まれていた。(Problems to be solved by the invention) However, a polyacetal resin composition containing the same is discolored to yellowish brown or black by the action of oxygen in the cylinder of a molding machine, and the appearance quality of the molded product is significantly impaired. In many cases, the improvement was strongly desired.
本発明はその様な欠点を克服し優れた熱安定性を有する
ポリアセタール樹脂組成物を提供することを目的とす
る。An object of the present invention is to provide a polyacetal resin composition that overcomes such drawbacks and has excellent thermal stability.
（問題点を解決するための手段） 本発明は構造式、 で表わされるヒンダードフェノール系化合物を所定量含
有させた樹脂組成物にある。(Means for Solving Problems) The present invention provides a structural formula, A resin composition containing a predetermined amount of a hindered phenolic compound represented by.
即ち、本発明はポリアセタール樹脂100重量部に対し
て、上記構造式で示されるヒンダードフェノール系化合
物であるテトラキス−［メチレン−３−（３′、５′−
ジ−tert−ブチル−４′−ヒドロキシル−フェニル）プ
ロピオネイト］−メタンである熱安定剤を0.01〜10重量
部を均一に混合した熱安定性を著しく改良したポリアセ
タール樹脂組成物にある。That is, the present invention relates to tetrakis- [methylene-3- (3 ', 5'-) which is a hindered phenol compound represented by the above structural formula, based on 100 parts by weight of the polyacetal resin.
The present invention provides a polyacetal resin composition in which 0.01 to 10 parts by weight of a heat stabilizer, which is di-tert-butyl-4'-hydroxyl-phenyl) propionate] -methane, is uniformly mixed to significantly improve the heat stability.
本発明の組成物に用いるポリアセタール樹脂は、ホルム
アルデヒド若しくはその環状オリゴマーであるトリオキ
サンやテトラオキサンの単独重合、又はこれらと共重合
可能なコモノマーとの共重合によって得られた重合体で
あって、その末端からの解重合防止のためにホモポリマ
ーの場合はアセチル化、エステル化やウレタン化等によ
って、またコポリマーの場合は不安定な末端を熱分解さ
せることなどによってその末端を安定化させたものであ
る。The polyacetal resin used in the composition of the present invention is homopolymerization of formaldehyde or its cyclic oligomer trioxane or tetraoxane, or a polymer obtained by copolymerization with a comonomer copolymerizable therewith, from its end. In order to prevent depolymerization, the terminal of the homopolymer is stabilized by acetylation, esterification or urethanization, and the terminal of the copolymer is stabilized by thermally decomposing the unstable terminal.
また、本発明において用いる熱安定剤の含有量はポリア
セタール樹脂100重量部に対して0.01〜10重量部、好ま
しくは0.1〜1.0重量部である。0.01重量部以下の場合は
充分な熱安定性が得られず、また10重量以上では機械的
強度の低下が大きく実用上好ましくない。The content of the heat stabilizer used in the present invention is 0.01 to 10 parts by weight, preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the polyacetal resin. If the amount is less than 0.01 parts by weight, sufficient thermal stability cannot be obtained, and if the amount is more than 10 parts by weight, the mechanical strength is greatly reduced, which is not preferable in practice.
本発明の組成物においては該熱安定剤以外の熱安定剤、
例えばポリアミド樹脂、アミド化合物、尿素誘導体や酸
化防止剤、例えばヒンダードフェノール系化合物あるい
は光安定剤、滑剤、補強剤、充填剤、顔料、ポリマー類
も添加することができる。In the composition of the present invention, a heat stabilizer other than the heat stabilizer,
For example, polyamide resins, amide compounds, urea derivatives and antioxidants such as hindered phenol compounds or light stabilizers, lubricants, reinforcing agents, fillers, pigments and polymers can also be added.
本発明の組成物においてポリアセタール樹脂と熱安定剤
との混合は、通常用いられている溶融混合法によって行
なうことができ、また他の配合剤と併用する場合は同時
に溶融混合してもよい。In the composition of the present invention, the polyacetal resin and the heat stabilizer can be mixed by a commonly used melt mixing method, and when they are used in combination with other compounding agents, they may be simultaneously melt mixed.
本発明の熱安定剤を添加したポリアセタール樹脂組成物
は、従来工業的に用いられている熱安定剤、例えばポリ
アミド樹脂等を含有させたポリアセタール樹脂組成物に
比べて耐変色性、耐熱分解性において著しく優れてい
る。The polyacetal resin composition to which the heat stabilizer of the present invention is added is a heat stabilizer that has been conventionally used industrially, for example, in terms of resistance to discoloration and thermal decomposition compared to a polyacetal resin composition containing a polyamide resin or the like. Remarkably excellent.
尚、樹脂組成物の熱安定性は次に示すような方法に従っ
て重量保存率（％）及び変色を調べて評価した。The thermal stability of the resin composition was evaluated by examining the weight storage rate (%) and discoloration according to the following method.
（評価方法） アルミフオイルでカバーした時計皿にサンプルのペレッ
ト1.0gを精秤し、190℃のオーブン中で加熱し重量保持
率（％）及び変色の度合を調べて評価した。(Evaluation method) 1.0 g of sample pellets were precisely weighed on a watch glass covered with aluminum oil and heated in an oven at 190 ° C to examine the weight retention rate (%) and the degree of discoloration for evaluation.
（変色の評価） ◎・・・白色 ○ △・・・淡黄褐色 × ××・・・黄褐色 以下に本発明を一層明確にするために実施例を挙げて説
明するが、本発明の実施例によりその範囲は限定される
ものではない。(Evaluation of discoloration) ◎ ・ ・ ・ white ○ △ ・ ・ ・ light yellowish brown XX ・ ・ ・ yellowish brown In the following, examples will be described to further clarify the present invention. The range is not limited by the example.
（実施例１） ポリアセタールホモポリマー（商品名：デルリン 100
NC−100のフラッフ デュポン社製）100重量部に対し
て、熱安定剤テトラキス−［メチレン−３−（３′、
５′−ジ−tert−ブチル−４′−ヒドロキシル−フェニ
ル）プロピオネイト］−メタンを0.5重量部添加しポリ
エチレン製袋内で充分混合し、２軸押出機（PCM−45
池貝鉄工所社製）で溶融混練してペレットを得た。この
ペレットを用いて190℃のオーブンで加熱溶融し重量保
持率（％）と着色の程度を評価した。その結果を表１と
表２に示す。Example 1 Polyacetal homopolymer (trade name: Delrin 100
NC-100 fluff DuPont) 100 parts by weight, the heat stabilizer tetrakis- [methylene-3- (3 ',
5'-di-tert-butyl-4'-hydroxyl-phenyl) propionate] -methane was added in an amount of 0.5 part by weight and mixed well in a polyethylene bag, and then twin-screw extruder (PCM-45
The pellets were obtained by melt-kneading with Ikegai Iron Works Co., Ltd.). The pellets were heated and melted in an oven at 190 ° C., and the weight retention rate (%) and the degree of coloring were evaluated. The results are shown in Tables 1 and 2.
（実施例２） 実施例１においてポリアセタールホモポリマー（商品
名：デルリン100 NC−10 フラッフ）の代わりに上記
のフラッフから熱安定剤であるポリアミド共重合体を除
いたフラッフを使用した以外は、実施例１と全く同様に
してペレットを得、熱安定性試験を実施した。その結果
を表１と表２に示す。(Example 2) Except that a fluff obtained by removing the polyamide copolymer as the heat stabilizer from the above fluff was used instead of the polyacetal homopolymer (trade name: Delrin 100 NC-10 fluff) in Example 1. Pellets were obtained in exactly the same way as in Example 1 and subjected to a thermal stability test. The results are shown in Tables 1 and 2.
（実施例３） 実施例１においてポリアセタールホモポリマー（商品
名：デルリン100 NC−10のフラッフ）の代わりに上記
のフラッフから熱安定剤である共重合ナイロンと酸化防
止剤であるヒンダードフェールを除いたフラッフを使用
した以外は実施例１と全く同様にしてペレットを得、熱
安定性試験を実施した。その結果を表１と表２に示す。(Example 3) Instead of the polyacetal homopolymer (trade name: fluff of Delrin 100 NC-10) in Example 1, the copolymerized nylon that is a heat stabilizer and the hindered fail that is an antioxidant are removed from the above fluff. Pellets were obtained in the same manner as in Example 1 except that the fluff was used, and a thermal stability test was performed. The results are shown in Tables 1 and 2.
（比較例１） 市販品ポリアセタールホモポリマー（商品名：デルリン
100 NC−10）ペレットを用い実施例１と全く同様に熱
安定性試験を実施した。その結果を表１と表２に示す。Comparative Example 1 Commercially available polyacetal homopolymer (trade name: Delrin
A thermal stability test was carried out in exactly the same manner as in Example 1 using 100 NC-10) pellets. The results are shown in Tables 1 and 2.
（比較例２） ポリアセタールホモポリマー（商品名：デルリン100 D
E9171 NC−10）ペレットを用い実施例１と全く同様に
熱安定性試験を実施した。その結果を表１と表２に示
す。(Comparative Example 2) Polyacetal homopolymer (trade name: Delrin 100 D
E9171 NC-10) pellets were used to carry out a thermal stability test in exactly the same manner as in Example 1. The results are shown in Tables 1 and 2.
（効果） 以上のように本発明のポリアセタール樹脂組成物は、特
定な熱安定剤が含有されているため、重量保持率が大き
く、また変色の度合も小さく優れた熱安定性を有してい
る。 (Effect) As described above, since the polyacetal resin composition of the present invention contains a specific heat stabilizer, the polyacetal resin composition has a large weight retention and a small degree of discoloration and excellent heat stability. .
Claims (1)
とするポリアセタール樹脂組成物。1. A structural formula based on 100 parts by weight of a polyacetal resin. A polyacetal resin composition, characterized in that 0.01 to 10 parts by weight of the compound shown in is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62124500A JPH07728B2 (en) | 1987-05-20 | 1987-05-20 | Polyacetal resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62124500A JPH07728B2 (en) | 1987-05-20 | 1987-05-20 | Polyacetal resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63289054A JPS63289054A (en) | 1988-11-25 |
| JPH07728B2 true JPH07728B2 (en) | 1995-01-11 |
Family
ID=14887028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62124500A Expired - Lifetime JPH07728B2 (en) | 1987-05-20 | 1987-05-20 | Polyacetal resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07728B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA745383B (en) * | 1973-09-25 | 1975-09-24 | Ciba Geigy Ag | Esters of trisubstituted hydroxyphenylalkonoic acids |
| JPS5164559A (en) * | 1974-12-02 | 1976-06-04 | Asahi Chemical Ind | NETSUANTEIKAHORIOKISHIME CHIRENSOSEIBUTSU |
-
1987
- 1987-05-20 JP JP62124500A patent/JPH07728B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63289054A (en) | 1988-11-25 |
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