TW200900466A - Polyamide resin composition - Google Patents
Polyamide resin composition Download PDFInfo
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- TW200900466A TW200900466A TW97111339A TW97111339A TW200900466A TW 200900466 A TW200900466 A TW 200900466A TW 97111339 A TW97111339 A TW 97111339A TW 97111339 A TW97111339 A TW 97111339A TW 200900466 A TW200900466 A TW 200900466A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
Description
200900466 九、發明說明: 【發明所屬之技術領域】 形品 本务明係關於一種树知組成物,包含以聚酿胺作為硬鏈段並 以口ΑΒΑ型三嵌段聚醚作為軟鏈段之聚醯胺系彈性體,並關於其成 【先前技術】 ,酿胺樹脂由於财離、而才溶劑性、耐熱性、韌 廣泛用於作騎•軟管、電線賴1構件、汽車構 ^ 樹脂之錄性或耐衝擊性,有人提出配合離子聚合物 树月曰或酸改質聚烯烴樹脂之提案。 4 物 出日本特公昭55—41659號公報(專利文獻1)中,有人提 =二_樹脂中配合乙婦υ—不鮮酸共聚物之離子聚 胺系彈性ί==4射i61,1 公報(專利文獻7),記載含聚醯 ΐ方生樹脂及聚醯胺系彈性體之樹脂組= 脂組成物,適於用在汽車用f ·軟以,賦予之聚醯胺樹 002915 2) t ^t " 5 2〇〇1~ 表面積嶋二上 2004 —352790 ^ί=ΐΐίΐ填劑5〜100 f量份。於日本特開 系彈性體及可9) ’繼__旨、聚《 彈性ί者 於日太ί&Ρθ ^電線被後、电構件、汽車構件等。 於日本特開2〇〇2〜138197 性聚醯胺組成物,由(專利文獻3),揭示-難燃 由(A)⑻、(C)、(D)所構成’其特徵在於:該 200900466 聚驢胺組成物依據UL94規格所測定之難燃 胺組成物成形為丸粒狀時,該丸粒二' ’ 數 料八心qn *早位所構成’該二舰成分單位由對苯二甲 /或脂環族二元成早=:=二元胺成分單位及 測定之觀為仙〜3(%/1Μη ί範圍負^ = 族聚«: 20〜80 f量%.⑻益機,點:起過290 C之方香 ㈣化苯二== 物·〇 1〜10浙曰) 3銻之化合物及/或含鋅之複合氧化 :量%;。貝爾,上細、⑻、(C)、⑼成分之伽 ^mlmtTirX A]5 二質量份,及三獅二 1〇)A 0 i 物。 辱利文獻丨1),記載含難燃劑之聚醯胺組成 可藉:f 一,已知為樹脂磁石。樹脂磁石, 成成形為製品形狀,即使複雜形狀亦能輕 人掘^邮人使用在各種領域。為改良樹脂磁石之柔軟性,有 人揭不配合烯烴系之彈性體之技術。 有 樹脂磁石之磁性特性,必需提高磁性粉末之含量及 配向°,然而’若磁性粉末之含量加多,則會有熔 題了有^H、=性粉末之配向亦變差的問題。為解決此問 通有人育试在树月曰中添加可塑劑,提高对綸樹脂炼融時之流動 200900466 性。 樹月·2—2丽9號公報(糊文獻5),揭示—聚驗胺 胳^,軸磁性粉末與聚酿胺樹脂構成,其特徵在於:該聚· 由=2如目ί於該聚酿胺樹脂磁石全體,纟3〜20 之範圍, Τι:/~ΓΒ Ω以上且吸水率不滿〇. 之芳香族聚醯胺,與熔點265 水率不滿2.⑽之脂肪族聚醯胺之混合物構成。 胺车娜;^細3—041116號公報(專利文獻6)中,揭示—聚醯 及⑹仿材料’特徵在於:將(A)磁性粉末、⑻》胺樹脂, =胺樹脂為3〜30質量%之下式R1—晴1 日本特Μ 9^1又飽和脂肪酸醯胺,予以捏揉得到。 4-號公報(專利文獻12)及日本特開 物、成形物及樹脂"磁石^文獻13)中,記縣聚_樹脂組成 iiriif1】日本特公昭阳―41659號公報 【i矛日本特開聰―隱15號公報 2;f3】曰本特開_ —138197號公報 曰本特開_〇67號公報 【ί= 特開2〇〇3-_16號公報 【專利文獻8】曰ί特開腿一161964號公報 "tff^004-352789^ [容射ί 1本特開2〇04—352790號公報 rii41 ^10】日本特開2004 — 352794號公報 i利特開2_-352795號公報 丄文f12】日本特開2GQ4-352791就公勒 '文獻13】日本特開2004 — 352792錄公報 【發明内容】 200900466 (發明欲解決之問題) 播人ίΙΞΪ熱紐樹脂之柔軟性或对衝擊性,在熱塑性樹脂中 十各合蛐黏度相較於基礎之熱可塑性樹脂,會變高, …本條件,材料劣化且使用受限的問題。 基礎之轨塑性樹的在於提供—種樹脂組成物,不會對於 改善柔軟性或耐優異不使成形性變化,且能 本發明之-ϋ λ量’會有可塑劑滲出等問題。 情形,要求_性L 被覆、輯件、汽車構件等之 於在高溫高濕下之苛酷環境下使用nf件等之情形,由 用之情形,會因水解使樹俨:用古ϋ,長期在此種環境下使 性能的問題。 曰有…、决維持作為彈性體之優異 即使is;?;苛燃性之樹脂組成物, 維持作為彈性體之優異性能。兄’、不因水解導致樹脂劣化,能 又為了使樹脂磁石之磁性牿神挺4 量提高。然而,若磁性粉末u升,必需使磁性粉末之含 足,會有發生破裂等之問題‘夕^樹脂磁石之柔軟性不 作為黏結樹脂之情形,有ϋ兴此相靖,使用聚醯胺樹脂 分,改善樹脂磁石之柔軟性中配t彈性體成 之耐熱性或耐水解性不足,太含、w二 '、、里配合之彈性體成分 本發明之-態樣,在;^=用解=述 200900466 下’尤其高溫高濕下不因水解所致黏結樹脂劣 提高再ί兹兹性特性,需要使磁爾^ 體成;=:Ξ=='ϊ!ΐί:樹脂磁石,彈性 為磁性特性優異之材料,作是,:㈡^變好,因此可成 不僅在成品表面;動於情 要求尺寸安定性之電•電子機器構件。又,尤^ 在 孚屋外及/或喊之_、_發熱所致 二j ;s:反複溫度變化而造成樹脂磁石部;;=;些-=; 本發明之一態樣,目的在於提供—種 將金屬構件予以插人而成之樹脂磁石日中7 於苛酷環境下,尤豆古、、西古、晶下:人阳在於提供一種樹脂磁石, 得性能降^ _⑷訂不㈣水解所致黏結樹脂劣化使 (解決問題之方式) 本發明係關於下述[1]規定之事項。 [1] 一種樹脂組成物,其特徵在於: 以來㈣緖性體作為必要成分,該聚醯胺系彈性體包 200900466 含聚醚醯胺彈性體(χ)5〇質量%以上, (A)、(Β)、(C)之成分予以聚合得到; 该聚醚醯胺彈性體(X)係將 並包含(a)、⑹中至少之—作為就共 ⑷:工元胺化合物⑷,包含下 之 元=物=式二"胺及降觀二胺所構成族群中至少1種二 (Β):聚醯胺形成性單體(Β); (C): 一叛酸化合物(C); (a) 熱塑性樹脂; (b) 難燃劑或磁性粉末; um3 Π 1 - r 9H3 h2n- -chch2o· -CH2CH2CH2CH2-〇i 1 ch2cho- rn X L _ y _ ch3 I CH2CH—Nhl· ⑴ 式中,x表示1〜20之整數、y表示4〜50之整數,及z表示 20之整數。 本發明之代表的態樣如下所示。 [2] 如上述[1]之樹脂組成物,其中,包含前述熱塑性樹脂。200900466 IX. Description of the invention: [Technical field to which the invention pertains] The product of the invention relates to a tree-like composition comprising a poly-branched amine as a hard segment and a tricyclic polyether as a soft segment. Polyamide-based elastomer, and according to the prior art, the amine resin is widely used for riding, hose, wire and wire, and resin for the sake of wealth, solvent, heat resistance and toughness. For the recording or impact resistance, a proposal has been made to cooperate with an ionic polymer tree or a modified polyolefin resin. (4) In the Japanese Patent Publication No. 55-41659 (Patent Document 1), it is proposed that the ionic polyamine-based elastomer is blended with the bis-resin-containing non-acid copolymer ί==4 shot i61,1 (Patent Document 7) A resin group containing a polyanthracene resin and a polyamide-based elastomer = a fat composition, which is suitable for use in automobiles, and is imparted to a polyamine tree 002915 2) t ^t " 5 2〇〇1~ Surface area 嶋二上2004 —352790 ^ί=ΐΐίΐ Filling agent 5~100 f parts. In Japan, the special elastic body and the 9) ’ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ In Japanese Patent Laid-Open No. 2 to 138197, a poly-polyamine composition is disclosed in (Patent Document 3), and it is disclosed that (refractory is composed of (A), (8), (C), and (D), which is characterized in that: When the polyacetamide composition is formed into a pellet shape according to the UL94 specification, the pellet is formed by the two-dimensional number qn *early position. / or alicyclic binary formation early =: = diamine composition unit and the measurement of the view is sen ~ 3 (% / 1 Μ η ί range negative ^ = agglomeration «: 20 ~ 80 f amount%. (8) benefit machine, point : Compound oxidized by a compound of 290 C (tetra) benzene (= 〇 〜 1 ~ 10 曰 曰) 3 锑 compound and / or zinc containing: amount %; Bell, on the fine, (8), (C), (9) component of the gamma ^mlmtTirX A] 5 two parts by mass, and three lions two 1 〇) A 0 i. Insulting literature 丨 1), the composition of the polyamine containing the flame retardant can be described as: f, known as a resin magnet. The resin magnet is shaped into a product shape, and even a complicated shape can be used in various fields. In order to improve the softness of the resin magnet, it has been revealed that the technique of the olefin-based elastomer is not disclosed. In the magnetic properties of the resin magnet, it is necessary to increase the content and orientation of the magnetic powder. However, if the content of the magnetic powder is increased, there is a problem that the alignment of the powder of the H and the powder is also deteriorated. In order to solve this problem, a humanized test was added with a plasticizer in the tree raft to improve the flow of the resin during the refining of the resin. Shuyue·2-2 Li 9 (Paste Document 5), reveals that the polyamine amine, the axial magnetic powder and the polyamine resin are characterized in that the poly is composed of =2 Aramid resin magnets, 纟3~20 range, Τι:/~ΓΒ Ω or more and water absorption is less than 〇. Aromatic polyamine, and a mixture of aliphatic polyamines having a melting point of 265 water rate less than 2. (10) Composition. In the Japanese Patent Publication No. 3-041116 (Patent Document 6), it is disclosed that the poly (A) and (6) imitation materials are characterized by: (A) magnetic powder, (8) "amine resin, = amine resin of 3 to 30 masses. % below R1 - Qing 1 Japanese special 9 ^ 1 and saturated fatty acid guanamine, obtained by kneading. In the No. 4 publication (Patent Document 12) and the Japanese special product, the molded article, and the resin "Magnetite^Document 13), the prefecture poly_resin composition iiriif1] Japanese special public Zhaoyang-41659 bulletin [i spear Japan special open Cong-Hid 15th Bulletin 2; f3] 曰本特开__138197 曰本特开_〇67号公告 [ί= 特开2〇〇3-_16号 [PTL 8] 曰ί特开Leg No. 161964 Gazette "tff^004-352789^ [容容ί 1本特开2〇04-352790号 rii41 ^10] Japanese Patent Laid-Open No. 2004-352794, i Li Tekai 2_-352795 Text f12] Japanese special open 2GQ4-352791 on the Gongle 'Document 13】 Japanese Special Open 2004 - 352792 recorded in the publication [invention] 200900466 (invention to solve the problem) broadcast people ΙΞΪ ΙΞΪ thermal resin resistance or impact, In the thermoplastic resin, the ten-part enthalpy viscosity becomes higher than that of the basic thermoplastic resin, and this condition, the material is deteriorated and the use is limited. The underlying plasticity tree is provided with a resin composition which does not change the moldability for improving flexibility or durability, and can cause problems such as bleeding of the plasticizer in the amount of ϋ λ of the present invention. In the case of the case, it is required to use the nf piece or the like in a harsh environment under high temperature and high humidity, and the case may be caused by hydrolysis. Performance issues in this environment.曰 ... 、 、 决 决 决 决 决 决 作为 作为 作为 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使 即使Brother, the resin is not deteriorated by hydrolysis, and the magnetic properties of the resin magnet can be increased. However, if the magnetic powder is u liter, it is necessary to make the magnetic powder contain enough, and there is a problem that cracking or the like occurs. [The softness of the resin magnet is not used as a bonding resin, and there is a sensation in this case, using polyamine resin. In order to improve the softness of the resin magnet, the heat resistance or hydrolysis resistance of the t-elastomer is insufficient, and the elastomer component which is too complex, w, and the inner body of the present invention is in the form of the invention; According to 200900466, under the high temperature and high humidity, the adhesive resin is not improved due to hydrolysis, and the magnetic properties are required to be formed. =:Ξ=='ϊ!ΐί: Resin magnet, elasticity is magnetic property The excellent material is: (2) ^ is good, so it can be made not only on the surface of the finished product, but also in the electrical and electronic components that require dimensional stability. Moreover, especially in the outside of the house and / or shouting _, _ heat caused by two j; s: repeated temperature changes caused by the resin magnet;; =; some - =; one aspect of the invention, the purpose is to provide - A resin magnet that is inserted into a metal component. 7 In a harsh environment, Yudougu, Xigu, Jingxia: Renyang provides a resin magnet, which has a performance drop ^ _ (4) order not (four) hydrolysis Deterioration of the bonding resin (method of solving the problem) The present invention relates to the matters specified in the following [1]. [1] A resin composition characterized in that the polyamine-based elastomer package 200900466 contains a polyether phthalamide elastomer (χ) in an amount of 5 % by mass or more, (A), The components of (Β) and (C) are obtained by polymerization; the polyether phthalamide elastomer (X) contains at least one of (a) and (6) as a total (4): an amine compound (4), including the following (==================================================================================================== a) thermoplastic resin; (b) flame retardant or magnetic powder; um3 Π 1 - r 9H3 h2n- -chch2o · -CH2CH2CH2CH2-〇i 1 ch2cho- rn XL _ y _ ch3 I CH2CH—Nhl· (1) where x An integer of 1 to 20 is represented, y represents an integer of 4 to 50, and z represents an integer of 20. Representative aspects of the invention are as follows. [2] The resin composition according to the above [1], which comprises the aforementioned thermoplastic resin.
[3] 如上述[2]之樹脂組成物,其中’前述熱塑性樹脂,包 含聚醯胺。 [4] 如上述[2]或者[3]之樹脂組成物,其中,包含前述熱塑 性樹脂95〜50質量%、前述聚醯胺系彈性體5〜5〇質量%。 [5] 如上述[2]〜[4]中任一項之樹脂組成物,其中,相對於 前述聚醯胺系彈性體及前述熱塑性樹脂之合計量丨⑻質量份,更 包含1〜30質量份之可塑劑。 [6] 如上述[1]之樹脂組成物,其中,包含前述難燃劑,且 相對於前述聚醯胺系彈性體1〇〇質量份,包含前述難燃劑5〜4〇 質量份。 12 200900466 乂34 6之樹脂組成物,其中,包含前述熱塑性樹脂 及難燃浏,且相對於前述聚醯胺系彈性體與前述熱塑性樹脂之人 計量100質量份,前述難燃劑之比例為5〜40質量份。 σ [8] 士吐述[7]之樹脂組成物,其中,前述熱塑性樹脂為聚 月女0 [9] 如上述[7]或者[8]之樹脂組成物,其中, 龜胺”性體與前述胁_旨之合計量⑽趣,包含前^ 塑性树知95〜50質量%、前述聚醯胺系彈性體5〜5◦質量%。’、、、 聚醚:二 :性:==:==2 ΓΙΟΙ . ΜΠΊ 4-' 4^Γ之中,含有5〜20質量%之比例。 更包含聚醯。S 11]之樹脂域物,其中,前雜結樹脂, 月係關於含此等組成物之成形物。 本發明中,較佳態樣如下。 又[3] The resin composition according to the above [2], wherein the aforementioned thermoplastic resin contains polyamine. [4] The resin composition according to the above [2] or [3], which comprises 95 to 50% by mass of the thermoplastic resin and 5 to 5% by mass of the polyamine-based elastomer. [5] The resin composition according to any one of the above [2] to [4], which further comprises 1 to 30 masses based on the total mass of the polyamine-based elastomer and the thermoplastic resin (8) parts by mass. A portion of plasticizer. [6] The resin composition according to the above [1], wherein the flame retardant is contained in an amount of 5 to 4 parts by mass based on 1 part by mass of the polyamine-based elastomer. The resin composition of the above-mentioned thermoplastic resin and the flame retardant, and the amount of the flame retardant is 5, based on 100 parts by mass of the person of the polyamine-based elastomer and the thermoplastic resin. ~40 parts by mass. σ [8] The resin composition of the above [7], wherein the thermoplastic resin is a polyether female [9], such as the resin composition of the above [7] or [8], wherein the toramine "physical body" The total amount of the above-mentioned threats is 10 to 50% by mass, and the polyamine-based elastomer is 5 to 5% by mass. ',,, Polyether: Two: Sex: ==: ==2 ΓΙΟΙ . ΜΠΊ 4-' 4^Γ, containing a ratio of 5 to 20% by mass. Further comprising a resin domain of polysulfonium. S 11], wherein the pre-hybrid resin, the monthly system contains such The molded article of the composition. In the present invention, the preferred embodiment is as follows.
二缓酸化合物⑹,町述式⑵表示。The di-lowering acid compound (6) is represented by the formula (2).
HOOC—fR1-)—C〇〇H (2) (惟R:表示包含_之連 聚醯胺形成性單體(β),土:录不0或1。) 酿胺化合物、二元胺與_ ^自擇自於:從胺基幾酸化合物、内 至少1種脂肪族、脂環酸、所合成者及此等之鹽所構成族群中 聚醯胺形成性單體(Β),g敎。 物(B1)與下述式(4)# ,匕3下述式(3)表示之胺基羧酸化合 ,、内胺化合物(B2)中至少之一。 13 (3) 200900466HOOC—fR1-)—C〇〇H (2) (R: R represents a condensed amide-forming monomer (β) containing _, soil: not recorded as 0 or 1.) Amine amine compound, diamine and _ ^Self-selected from: a polyamine-forming monomer (Β) from a group consisting of an amino acid compound, at least one aliphatic, an alicyclic acid, a synthon, and the like; . The substance (B1) is at least one of the following formula (4) #, 匕3, an amino group carboxylic acid represented by the following formula (3), and a lactam compound (B2). 13 (3) 200900466
H2N——R2 COOH (惟R2表示含烴鏈之連結基。)H2N - R2 COOH (only R2 represents the linking group of the hydrocarbon chain.)
(惟R3表示含烴鏈之連結基。)(R3 only represents a linking group containing a hydrocarbon chain.)
酸化ίΪ酸化合物⑹,為脂肪族二_化合物及/或脂環族二叛 相對於二元胺化合物(Α)、聚_形成性單體 合物(c)之總量,聚醯胺形成性單體(Β)之比例為1〇〜95質量〇/〇。 相對於一元胺化5物(Α)、聚醯胺形成性單體(β)及二羧酸化 合物(c)之總量,聚醯胺形成性單體(Β)之比例為15〜8〇質量0/〇、 一元化合物(Α)及二羧酸化合物(〇合計之比例為2〇〜85質量%。 式(3)之R2包含碳原子數2〜20之伸烷基。 式(4)之R3包含碳原子數3〜20之伸烷基。 式(1)之X表示2〜6之整數、y表示6〜12之整數,及z表示 1〜5之整數。 式(1)之X表示2〜10之整數、y表示13〜28之整數’及z 表示1〜9之整數。 相對於二元胺化合物(A)、聚醯胺形成性單體(B)及二羧酸化 合物(C)之總量,二元胺化合物(A2)之比例為0. 5〜10質量°/〇。 碳數6〜22之分支型飽和二元胺,係擇自於2, 2, 4—三甲基一 1,6——胺基己烧、2, 4, 4 —三甲基一1,6—二胺基己燒、1,2 —二 胺基丙烷、1,3 —二胺基戊烷、2—甲基一 1,5 —二胺基戊烷、2 — 曱基一1,8 —二胺基辛烷或此等混合物之二元胺。 碳數6〜16之分支脂環式二元胺為擇自於5 —胺基一2, 2, 4一 三甲基一1 一環戊烷甲胺、5—胺基一1,3, 3 —三曱基環己烷甲胺或 14 200900466 此等之混合物之二元胺。 降伯烷二胺為擇自於2, 5~降宿烷二曱胺、2, 6—降萡烷二曱 胺或此等之混合物之二元胺。 ’ 式(2)之m為1,R1表示碳原子數1〜2〇之伸烷基。 【實施方式】 (實施發明之最佳形態) 本發明之樹脂組成物之代表態樣說明如下。 [第1態樣] 本發明第1態樣之樹脂組成物, 以聚醯胺系彈性體作為必要成分,該聚醯胺系彈性體包含聚 醚醯胺彈性體(X)50質量%以上,該聚醚醯胺彈性體(X)係將(a)、 (B)、(C)之成分予以聚合得到; ” 並包含(a)作為共存成分; (A) .一元胺化合物(A),包含式(1)表示之三嵌段聚醚二胺化 合物(A1),及擇自於碳數6〜22之分支型飽和二元胺、碳數6〜16 之分支脂環式二元胺及降掐烷二胺所構成族群中至少丨種二元 化合物(A2); (B) :聚醯胺形成性單體(B); (C) :二羧酸化合物(C); (a)熱塑性樹脂。 队阳矛_L股休,肐恁取對於|礎之熱塑性樹脂之熔融黏产 影響、成形性不變化,能改善柔軟性或鴨擊性,而且耐水$ 優異之樹脂組成物。 第1態樣之樹脂組成物,以含熱塑性樹脂95>50質 «系彈性體之5〜5G質!:%較佳,更佳為含熱塑性樹脂9 $ 質量%與聚醯胺系彈性體之10〜40 !量%,尤佳為含熱塑性 〜7〇質量%及聚醯胺系彈性體之15〜30質量%。惟,埶塑性 ^ 聚醯胺系彈性體合計為100質量%。 曰/、 15 200900466 關於聚醯胺系彈性體及熱塑性樹脂 材料之説明]項目説明。 %之、、、田即’於後述[各成分及 此態樣之樹脂組成物,熔融成形性優 強韋刃性優異、耐衝擊性優異、耐水解性等優、絲加工性優異、 得到樹脂,成物之方法不特別限制,可 法。例如’可應用將》胺等熱塑性 l 方 或視需要各種之添加劑既定量,以v型擒、作性體, J低速旋轉混合機或亨舍耳齡轉高賴觀、肖(gH 單轴擠製機、雙軸擠製機#進魏融捏ϊ後iitSr :速劑既定量:以 射出成形機或擠製成形機,直接=== 此態樣之樹脂組成物,可用於運重鞋 機械·電精密機器之齒輪·連接器運二、丨u之表面材、 材、各種管•軟管、片材、薄膜 材4車,邊、密封 速接頭防塵套。 、、義、、’糸&車用鏡防塵套、等 =脂組成物’水解後之斷裂伸長保持率以 製^^旨組成物,可使用擠製成形、射出成形等公知之 衣n到管、纖絲、片材、薄膜等成形物。a知之成形法, !第2態樣] 士此ί發明第2態樣之樹脂組成物,係於前诚笛〗 成物中,相對於聚醯胺系彈性^^兑叶、、 悲樣之樹脂組 量份’更包含卜3〇質量述熱塑性樹腊合計量⑽質Acidified phthalic acid compound (6), which is an aliphatic bis-compound and/or an alicyclic bismuth relative to a diamine compound (Α), a poly-formative monomer compound (c), a polyamine forming property The ratio of monomer (Β) is 1〇~95 mass〇/〇. The ratio of the polyamine forming monomer (Β) is 15 to 8 相对 with respect to the total amount of the monoamined product (Α), the polyamine forming monomer (β), and the dicarboxylic acid compound (c). A mass of 0/〇, a monobasic compound (Α), and a dicarboxylic acid compound (the total amount of the compound is 2 〇 to 85% by mass. R 2 of the formula (3) contains an alkylene group having 2 to 20 carbon atoms. R3 includes an alkylene group having 3 to 20 carbon atoms. X of the formula (1) represents an integer of 2 to 6, y represents an integer of 6 to 12, and z represents an integer of 1 to 5. Formula X (1) An integer of 2 to 10, y represents an integer of 13 to 28', and z represents an integer of 1 to 9. Relative to the diamine compound (A), the polyamine forming monomer (B), and the dicarboxylic acid compound ( The ratio of the diamine compound (A2) is 0.5 to 10 mass ° / 〇. The branched type saturated diamine having a carbon number of 6 to 22 is selected from 2, 2, 4 - 3 Methyl-1,6-amino-hexane, 2,4,4-trimethyl- 1,6-diaminohexanone, 1,2-diaminopropane, 1,3-diaminopentane Alkane, 2-methyl-1,5-diaminopentane, 2-mercapto-1,8-diaminooctane or mixtures thereof a branched amine alicyclic amine having a carbon number of 6 to 16 is selected from the group consisting of 5-amino-2,2,4-trimethyl- 1 1-cyclopentanylamine, 5-amino-1,3 , 3 - trimethylcyclohexanemethylamine or 14 200900466 a mixture of such diamines. The norbornane diamine is selected from 2,5~noranediamine, 2,6-norbornane Diamine or a diamine of such a mixture. 'M of the formula (2) is 1, and R1 represents an alkylene group having 1 to 2 carbon atoms. [Embodiment] (Best Mode for Carrying Out the Invention) A representative aspect of the resin composition of the invention is as follows. [First aspect] The resin composition according to the first aspect of the present invention contains a polyamine-based elastomer as an essential component, and the polyamine-based elastomer contains a polyether. 50% by mass or more of the phthalamide elastomer (X) obtained by polymerizing the components (a), (B), and (C); and including (a) as a coexisting component (A). The monoamine compound (A), which comprises the triblock polyether diamine compound (A1) represented by the formula (1), and a branched saturated diamine having a carbon number of 6 to 22, carbon number; 6 to 16 branched alicyclic diamine At least a quinone binary compound (A2) in a group consisting of norbornane diamine; (B): polyamine forming monomer (B); (C): dicarboxylic acid compound (C); (a) thermoplastic Resin. The team is a resin composition that is excellent in softness or ducking, and which is excellent in water resistance and excellent water resistance. The resin composition of the aspect is composed of a thermoplastic resin 95 > 50 quality «system of elastomer 5~5G quality! : % is preferable, more preferably 10% by mass of the thermoplastic resin and 10 to 40% by weight of the polyamine-based elastomer, and particularly preferably 15% by mass of the thermoplastic and 75% by mass of the polyamine-based elastomer. 30% by mass. However, the total of the 埶 plastic ^ polyamine-based elastomer was 100% by mass.曰/, 15 200900466 Explanation of Polyamide Amine Elastomer and Thermoplastic Resin Material] Item Description. (The composition of each component and the resin composition of this aspect is excellent in melt formability, excellent in impact resistance, excellent in impact resistance, hydrolysis resistance, and excellent in wire workability, and resin is obtained. The method of forming a product is not particularly limited and can be used. For example, 'applicable to' thermoplastics such as amines or various additives as needed, both quantitative, v-type 作, sex, J low-speed rotary mixer or Henschel ear turn high Lai Guan, Xiao (gH uniaxial extrusion Machine, double-axis extrusion machine #进魏融ϊϊiitSr: speed agent is both quantitative: injection molding machine or extrusion molding machine, direct === this kind of resin composition, can be used for heavy machinery ·Electric precision machine gears·Connectors 2, 丨u's surface materials, materials, various tubes, hoses, sheets, film materials, 4 cars, side, sealed joints, dust jackets, yiyi, '糸& Vehicle mirror dust jacket, etc. = fat composition 'the elongation at break after hydrolysis is a composition of the composition, and can be used for extrusion, injection molding, etc., to a tube, a filament, a sheet, A molded product such as a film. A known molding method, !Second aspect] The resin composition of the second aspect of the invention is in the form of the former scent, relative to the polyamine-based elastic ^^ ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
日g當q Α 土月J 而且耐水解性彳可達射纏轉巾,錄性優異, 優異之含可塑劑的樹脂組成物。 此人’於後述[各成分及材料之説明]項目説明。 16 200900466 優異、耐水解性優異。 此含有可塑劑之樹脂組成物, 吹塑成形等成形方法,得到管、 精由射出成形、擠製成形、 得到第2態樣之組成物之方片材、薄膜等成形物。 樣同樣之公知之各種方法。/不特別限制,可使用與第1態 此含可塑劑之樹脂組成物, 材、機械•電精密機器之齒輪·」運動鞋材、滑雪板之表面 密封材、各種管•軟管、片材、薄 t ·密封材、汽車用鑲邊、 等速接頭防塵套、被覆材料等。Λ、、早纖絲、汽車用鏡防塵套、 此含可塑劑之樹脂組成物 以上,較佳為100%以上。 呷岍衣伸長率之保持率為90% [第3態樣] 本發明第3態樣之樹脂組成物, 以聚醯胺系彈性體作為必要 醚醯胺彈性體(x)5()質量% 取刀’遠來酿胺系彈性體含有聚 ⑻、、(〇之成分予以聚合得到者^嶋胺彈性體⑴係將(A)、 並包含(b)作為共存成分; (A) :一元胺化合物(A),包含4门、主― 合物⑽,及擇自於碳數6〜22 ja)f =之三嵌段聚醚二胺化 之分支脂環式二元胺飽和二元胺、碳數6〜16 化合物(A2); 伯’凡一月女所構成族群中至少1種二元胺 (B) :聚醯胺形成性單體 (〇:二鲮酸化合物(〇; ’ (b)難燃劑。 昨女依a第3態樣’能達成即使於高溫高渴下之^印+& + 月曰亦不因水解劣化,能維持作為下中樹 組成物。 作胁【生體之優異性能的難燃性樹脂 關於聚胺系彈性體及難揪劑 之説明]項目説明。 亂、、此㈣卩’於纽[各成分及材料 17 200900466 弟3態樣中,難辦劍之4旦 量份,佳為5〜40質量份,更"V相胺系彈性體_質 〜30質量份。 為0〜35 A量份,又更佳為15 得到第3態樣之組成物之方 樣同樣之公知之各種方法。料特舰制,可㈣與第]態 此樹脂組成物,在不妨礙其特性 外線吸收劑、光安定劑、抗氧化^ ^圍’可4、加耐熱劑、紫 結晶核劑、黏著性賦予劑、密封性改劑^滑劑、 料、染料、香料、補強材等。 務蜊、脫模劑、顏 此樹脂組成物,熔融成形性優显、 =質異、伸長回復性優異、消音特以 ^樹脂組成物,可藉由射出成形、擠製成形 幵ν方法,得到成形物。 人^成Φ4成 此樹脂組成物之射出成形品,強韌性、 彈性、低比重之材料,例如較佳為野球、足球出二|性、、反跳 底材,其他射出成形品,例如機械•電精密機=領域之鞋 密封材、汽車用鑲邊、密封材等。山機⑤之齒輪•連接器· 此樹脂組成物,可用於運動鞋材、骨雪柘 ;2密,之齒輪.連接器.密封材、面s封r各The day g is q Α 月 J J and the hydrolysis resistance 彳 can reach the entangled whirl, excellent recording, excellent resin composition containing plasticizer. This person's description of the [Description of each component and material] will be described later. 16 200900466 Excellent in excellent hydrolysis resistance. The resin composition containing a plasticizer, a molding method such as blow molding, and the like, and a molded article such as a tube or a film obtained by injection molding, extrusion molding, and a composition of the second aspect, and a film are obtained. The same various methods are known. /Unspecially, it is possible to use the resin composition containing the plasticizer in the first state, the gear of the material, the mechanical and electrical precision machine, the "sports shoe material, the surface seal material for the skis, various tubes, hoses, sheets, Thin t · Sealing material, automotive trim, constant velocity joint boot, covering material, etc. The enamel, the early fibril, the mirror dust cover for automobiles, and the resin composition containing the plasticizer are preferably 100% or more. The retention ratio of the elongation of the coating is 90%. [Third aspect] The resin composition of the third aspect of the present invention, the polyamine-based elastomer is used as the essential ether amide amine elastomer (x) 5 (% by mass) Taking a knife, the far-stranded amine-based elastomer contains poly(8), (the component of the oxime is polymerized, the phthalamide elastomer (1) is (A), and (b) is a coexisting component; (A): monoamine Compound (A) comprising 4 gates, a main compound (10), and a branched alicyclic diamine saturated diamine which is selected from a triblock polyether diamined carbon number 6 to 22 ja)f = Carbon number 6 to 16 compound (A2); at least one type of diamine in the group of females in January (B): polyamine forming monomer (〇: dicarboxylic acid compound (〇; ' (b ) The flame retardant. Yesterday, according to the third aspect of the woman's ability to achieve even the high temperature and high thirst, the seal + & + the moon is not due to hydrolysis degradation, can maintain as a composition of the lower tree. Description of the flame retardant resin with excellent performance of the body. Description of the polyamine elastomer and refractory agent] Item description. Chaos, this (4) 卩 'Yu New [components and materials 17 200900466 brother 3, the difficult sword 4 denier parts, 5 to 40 parts by mass, more "V-phase amine elastomer _ mass ~ 30 parts by mass. 0 to 35 A parts, and more preferably 15 to obtain the composition of the third aspect is also known. Various methods. The special ship system can be used to make the resin composition (4) and the state of the resin, without impeding its characteristics, such as an external absorbent, a light stabilizer, an antioxidant, and a heat-resistant agent, a purple crystal nucleating agent. Adhesive imparting agent, sealing agent, slip agent, material, dye, perfume, reinforcing material, etc. 蜊, release agent, and this resin composition, excellent melt formability, = quality, elongation recovery The resin composition can be obtained by injection molding and extrusion into a shape 幵ν method to obtain a molded product. The product is formed into a molded article of the resin composition, and a material having high toughness, elasticity, and low specific gravity. For example, it is preferably a wild ball, a soccer ball, a rebounding substrate, and other injection molded articles, such as a mechanical and electric precision machine = a shoe sealing material in the field, a car edging, a sealing material, etc. Gear • Connector · This resin composition can be used for sports shoes and bone sleigh; 2 , The gear connector sealing member, each of r sealing surfaces s
Si套ί管、片材、薄膜、單纖絲、汽車用鏡防塵套、等Li [第4態樣] 成物ΐ發ί 成物,係於前述第3態樣之樹脂組 机奶甲,更包含熱塑性樹脂。 亦即’本發明第4態樣之樹脂組成物, ,以聚醯胺系彈性體作為必要成分,該聚醯胺系彈性濟句合命 峻醯胺彈性體(X)5Q質量%以上,該聚__彈性體⑴係&將(心 18 200900466 (B)、(C)之成分予以聚合得到者; 並包含(a)及(b)作為共存成分; (A) :-兀胺化合物(A),包含式⑴表示之三♦段聚醚二胺化 合物(A1),及擇自於碳數6〜22之分支型飽和二元胺、碳數6〜16 之分支脂環式二元胺及降蓓烷二胺所構成族群中至少丨 化合物(A2); 性一匕妝 (B) :聚醯胺形成性單體(β); (C) :二羧酸化合物(〇; (a) 熱塑性樹脂; (b) 難燃劑。 依照第4祕,能達齡使於高溫高釘之苛_ 鳩使劣化,能轉作為彈性體之優異性能的難燃性樹 「夂:胺系彈性體、熱塑性樹脂及難燃劑之細節,於後述 [各成分及材料之説明]項目説明。 傻疋 100 ί旦械於聚釀胺系彈性體與熱塑性樹脂之合計量 〇〇吳里伤,難燃劑之比例,較佳為5〜40質量份 ^ 30質量份,又更佳為2〇〜30質量份。 土為0 脂’含有聚醯胺較佳,尤佳為 。 此含有難燃劑之樹脂組成物中钟八 95^50 f 5^5〇 性樹脂90〜60量%與聚胺系彈性體( 更^二j 塑性獅〜70質量_胺系彈性體15〜匕 脂與聚醯胺系彈性體之合計為100質量%)。 、里°(”,、』性樹 外線吸收劑、光安定:不性,::‘可添加耐熱劑、紫 潤滑劑、增滑劑ί性ft電劑、導電性填充劑、 此含有難月料、難燃劑、補強材等。 ^丨之娜組成物,_成雜倾、成形加 200900466 優異、強轫性優異、耐衝擊性優異、财水解性等彳尾里。 此含有難燃劑之樹脂組成物中,得到樹月旨組i1 別限制,能使用與第!態樣同樣之公知的各種^物之方法不特 此樹脂組成物,可藉由射出成形、擠形 形方法,得到成形物。 人塑成形專成 此樹脂組成物之成形品,可應用於管、 構件、汽車構件等要求難燃性之構件。 被设、電 ^者,此樹脂組成物之成形品,即使 境了中=因水解而劣化,能應用在於此種苛酷^=== 之官、軟管、電線被覆、電構件、、汽車構件等。下中了使用 此含有難燃劑之樹脂組成物,水解後 以上較佳,更佳為95%以上。 衣1甲食保持羊以90% [第5態樣] 本發明第5態樣之樹驗成物,侧於樹脂磁石, ,以^胺㈣性體作為必要成分,該聚_衫彈性 性讀以上,該聚醚_彈性體⑴係將⑷: 、(C)之成分予以聚合得到者; 並包含(b)作為共存成分; r元胺化合物(A) ’包含下赋⑴表示之三紐聚醚二 月=合物U1),及擇自於碳數6〜22之分支型飽和二元胺、碳數β 了16之分支脂環式二元胺及降舰二胺所構成 少丨種二 凡胺化合物(A2); (B):聚醯胺形成性單體(B); (〇:二羧酸化合物(〇; (b)磁性粉末。 在此,聚_醯胺彈性體⑴中,存在作為用以使磁性粉末凝聚 之黏結樹脂之至少一部分。 依照第5態樣,能達成於苛酷環境下,尤其高溫高满下不因 水解使黏結樹脂劣化導致性能降低之樹脂磁石。 20 200900466 物,樹脂合収為⑽f量%而言,此樹脂誕成 性於太質量%與黏結樹脂20〜5 f量%,較佳為磁 〜與黏結樹脂15〜5質量%,更佳為磁性粉9〇 、,:/’、丄、°树月旨1〇〜5質量%之比例。 其餘ίίΐϊϊί聚酿胺系彈性體G〜1GG質量%(不含G質量%), 旦性樹脂,尤佳為聚醯胺0〜100質量%(不含100質 里%)(1醯胺糸彈性體與聚醯胺之合計為100質量%)。 ο黏,樹脂為聚酿齡雜體與聚醯胺之組成物之情形,以雙 ΐ巧體i〜30質量%與_胺95〜70質量%之組成物較佳Λ, 物tr,胺系彈性體ig〜25 f量%與輯胺⑽〜75 f量%之組成 承系,性體及構絲結劑之熱塑性樹脂,尤 細即,,1述[各成分及材料之説明]項目説明。 妝( 成物,可將黏結樹脂與磁⑽末予以簡或進行熔 此ϋ組成物’可由㈣成形、擠製成料成形方法予以 成形。成形物可作為樹脂磁石使用。 j脂組成物’可與金屬構件组合形成樹脂磁石構件。例如, 插人而製造樹脂磁石構件。得到之樹脂磁石構件, 之熱ίΓ浸泡2000小時後,亦不因水解而使黏結 祕月曰劣化,樹脂磁石構件不生龜裂,為能耐受長期使用者。 來而成物,係將圖1所示圓盤狀金屬構件Η以插入成 而成報第石構件等,與金屬構件加^後iii用成 L弟b態樣] 發態樣之樹脂組成物,係關於樹脂磁石,前述第5 =樣^黏結樹月旨包含可塑劑,且尤其前述黏 j = 中,含有可塑劑為5〜20質量%之比例。 貝里 依照第6態樣,於將金屬構件插入而成之樹脂磁石構件中, 21 200900466 二、::即使在因為冬季屋外之低溫環境及夏季屋外及/或組裝成 ^機^内之發熱所致高溫環境之實際使用環境下之反複温度變 典奏’、Ttt龜裂二且即使於高溫環境,尺寸變化亦少之樹脂磁石。 致斑成於苛@°環^下’尤其於高溫高濕下亦不會因水解導 夂站…树月曰劣化而致性能降低之樹脂磁石。 诚笛tii之樹脂組成物中,磁性粉末與黏結樹脂之比例,盘前 1質=二脂,較佳為包含樹脂成分、80 質旦0/=f可塑齊1 20〜5胃量%,更佳為包含樹脂成分80〜10 量|)°。。㈣2〇〜1〇質量%(樹脂成分與可塑劑之合計為⑽質 脂中之樹脂成分,包含聚㈣系彈性體卜⑽質旦 ^含”量%),及熱塑性樹脂,尤其包含〜⑽貝二 )(輯胺系彈性體與聚_之合計為⑽質量 树月曰成分包含聚醯胺系彈性體& $ 、) 聚醯胺系 广綠性體10〜25質量%與_胺9G〜7 再, Μ(聚_緖性體與㈣_之合計為⑽f7^。^之、、且成物 1¾&胺系彈性體及構成黏結劑之执' :節’如後述[各成分及材料之説,,聚酿胺之 劑,亦可為後述[各成分及材料之説明]須1月。又,關於可塑 衍生自對或_基苯甲酸與具 四:之材料’尤其’ 以例如含雜合物等之可_触,亦可2^=之=之化合物, 可塑劑’含有衍生自對或_基苯甲可塑劑。 _以上,更佳為 r r-- 用。 』]組合2種以上使 具碳數12〜22之侧鏈之醇,可使用i辛基辛醇、2〜辛基― 22 200900466 2 —癸基十二醇、2 — 3-辛醇、2-乙基十二醇、2—辛基十二醇 癸基癸醇、2-己基癸醇、2—乙基癸醇等。 可塑劑’就仿生自對或鄰羥基苯 醇之酉旨化合物而言,例如對__酸;〜^侧鏈 羥基苯曱酸2—辛基—3〜辛、 肀基辛§曰、對或鄰 |旨、對或鄰經基苯甲酸對甲酸2—乙基十二 基十二酿、對或鄰經S甲^十;或=基苯甲酸2-癸 —己細旨、對f鄰經基笨曱酸㈣苯甲酸2 可塑劑,可單,使用,亦可組合2種以上使用。 體及時=====、聚醯胺系彈性 胺系綱進行細職聚醜 成形此樹脂組成物,可藉由射出成形、擠製成形等成形方法進行 脂磁組成物,可經過成形而得成形物。此成形物可作為樹 構件此:樹=在成=金屬構件插入而成的樹脂磁石 冬料卩賴反複經過 度變騎石部分林生_,能環境之溫 成物’係將如圖1所示圓盤狀金屬構件1進行插入 成_之^^石構件’或如圖2所示棒狀金屬構件3進行插入 7後之I狀树脂磁石構件等,以與金屬構件組合後之狀能使用。 23 200900466 此樹脂組成物及此等之成形品中,質量減少率較 下,更佳為0. 4%以下,尤佳為〇. 25%以下。 .b/o以 此耐綸樹脂組成物及此等之成形品中,尺寸變 0. 25%以下,更佳為〇· 2%以下,尤佳為Q. 15%以下。β較佳為 [各成分及材料之説明] 以下說明各成分及材料。 «聚醯胺系彈性體》 ' ♦醯胺系彈性體,可包含公知之聚醯胺彈性體。 彈性體。可使用聚醯胺紐與聚峨 =專,該細嫌段擇自於耐綸6、耐綸66、对論u、以平 氧4 ΐΐΓίΓ,棘醚嵌段擇自於聚氧乙烯、聚氧丙两歸、 彈性系彈性體’以由聚_嵌段與聚_段構成之執塑性 ’較佳為15〜7q之範11,更佳為18 圍X更j土為20〜70之範圍,尤佳為25〜7〇 广胺系彈性體之彈性率,較佳為2〇〜權化 ^圍 侧Pa,又更佳為20〜35〇MPa,尤佳為2〇〜3〇〇MPa。為 ^胺系彈性體’以斷裂伸長率為嶋以上較佳。 性體脂,物中,爾系彈性體’含有聚醚醯胺彈 更佳為80貝置%以上,尤佳為90質量%以上(1〇〇0/朮可、。 性體⑴之含量多之聚_系彈性體,耐水性優显、熔 優異、伸性、低溫柔卿異、低溫耐衝擊性 異。、”设性^、消音特性優異、橡膠性質及透明性等優 單體體00,係將二元胺化合物⑷、聚驢胺形成性 化否下逑式(1)表示之三换段聚_二胺化合物⑽,及擇 24 200900466 自於2數6:22之分支型飽和二元胺、碳數6〜16之分支脂環式 二兀胺及降蓓烷二胺所構成族群中至少1種二元胺化合物(A2)。 um3 Μ 1 - ch3 h2n- -chch2o- — -CH2CH2CH2CH2-〇- 1 ch2cho- - y - J2 CH, 式中’ X表示1〜20之整數、y表示4〜50之整數,Z表示1〜20 之整數。 ⑴ —„本發明之聚醚醯胺彈性體(x)之尤佳態樣之一為一種聚醚醯 胺彈性體(X) ’係將二元胺化合物(A)與聚醯胺形成性單體(B)及式 (2)表示^—羧酸化合物(C)聚合得到: 二元胺巧合物(A),包含式(1)表示之XYX型三嵌段聚醚二胺 (jl)(Y為聚氧丁烯),及擇自於碳數6〜22之分支型飽和二元胺、 碳數6〜16之分支脂環式二元胺、降萡烷二胺中至少丨種二元胺 化合物(A2); 聚酿胺形成性單體(B),擇自於式表示之胺基羧酸化合物 (B1)及式(4)表示之内醯胺化合物(B2)。Si sleeves, sheets, films, monofilaments, mirror sleeves for automobiles, etc. Li [4th aspect] The formation of a material, which is based on the third aspect of the resin group machine armor, It also contains a thermoplastic resin. In other words, the resin composition of the fourth aspect of the present invention contains a polyamine-based elastomer as an essential component, and the polyamine-based elastomeric conjugated amine elastomer (X) is 5 mass% or more. Poly-_elastomer (1) is a compound obtained by polymerizing the components of (heart 18 200900466 (B), (C); and (a) and (b) as coexisting components; (A) :-guanamine compound ( A) comprising a polystyrene diamine compound (A1) represented by the formula (1), and a branched aliphatic diamine having a carbon number of 6 to 22, and a branched alicyclic diamine having a carbon number of 6 to 16. And at least a ruthenium compound (A2) in a group consisting of norbornanediamine; a bismuth-forming composition (B): a polyamine-forming monomer (β); (C): a dicarboxylic acid compound (〇; (a) (b) a flame retardant. According to the fourth secret, it is a flame retardant tree that can be used as an elastomer for the deterioration of the high temperature and high nail strength. The details of the thermoplastic resin and the flame retardant are described in the [Explanation of each component and material] item. The silly 100 ί 旦 于 于 聚 聚 里 里 里 里 里The ratio of the wound and the flame retardant is preferably from 5 to 40 parts by mass to 30 parts by mass, more preferably from 2 to 30 parts by mass. The soil is 0%, and the polyamine is preferably used, particularly preferably. Resin composition of resin composition Zhong Ba 95 ^ 50 f 5 ^ 5 树脂 resin 90 ~ 60% by volume with polyamine elastomer (more ^ two j plastic lion ~ 70 mass _ amine elastomer 15 ~ rouge The total amount of the polyamine-based elastomer is 100% by mass.), 里°(", 』, Sex tree external absorbent, light stability: not,:: 'Addition of heat-resistant agent, violet lubricant, slip agent性 ft electric agent, conductive filler, this contains difficult materials, flame retardant, reinforcing materials, etc. ^ 丨 娜 娜 娜 娜 娜 娜 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 In the resin composition containing the flame retardant, the resin composition containing the flame retardant is not limited by the tree-shaped group i1, and the same method as the first aspect can be used. The object can be obtained by a method of injection molding and extrusion molding. The plastic molding is a molded article of the resin composition, and can be applied to a tube. A component that requires flame retardancy, such as a component or an automobile component. The molded article of the resin composition, if it is in the middle of the body = deteriorates due to hydrolysis, can be applied to such a harsh ^=== official, Hose, wire covering, electrical component, automobile component, etc. The resin composition containing the flame retardant is used in the lower part, and more preferably 95% or more after hydrolysis. The clothing 1 is kept at 90%. [Fifth Aspect] The invention of the fifth aspect of the present invention is directed to the resin magnet, and the amine (tetra) is used as an essential component, and the polyether is read above, and the polyether_elastomer (1) A component obtained by polymerizing the components of (4): and (C); and (b) as a coexisting component; the r-amine compound (A) 'containing the three-bond polyether of the lower group (1) = compound U1), And a branched-type saturated diamine having a carbon number of 6 to 22, a branched alicyclic diamine having a carbon number of β of 16, and a lower diamine compound (A2); ): Polyamine forming monomer (B); (〇: dicarboxylic acid compound (〇; (b) magnetic powder. Here, in the poly-amine elastomer (1), at least a part of the binder resin for agglomerating the magnetic powder is present. According to the fifth aspect, it is possible to achieve a resin magnet which does not deteriorate in performance due to deterioration of the binder resin by hydrolysis in a severe environment, in particular, at a high temperature and a high temperature. 20 200900466, the resin is collected in a quantity of (10)f, the resin is about 50% by mass of the resin and 20% to 5f of the binder resin, preferably 15 to 5% by mass of the magnetic resin and the binder resin, more preferably Magnetic powder 9 〇, , : / ', 丄, ° tree month to 1 〇 ~ 5 mass% ratio. The remaining ίίΐϊϊί polyamine-based elastomer G~1GG mass% (excluding G mass%), denier resin, especially poly-polyamine 0~100% by mass (excluding 100% by mass) (1 amidoxime elasticity) The total of the body and the polyamine is 100% by mass). ο sticky, the resin is a composition of the poly-branched compound and the polyamine, and the composition of the bismuth body i~30% by mass and the _amine 95-70% by mass is preferably Λ, the substance tr, the amine system The amount of the elastomer ig~25 f% and the amount of the amine (10) to 75 f% of the constituents, the thermoplastic resin of the physical body and the structuring agent, especially fine, 1 [Description of each component and material] item description . Makeup (formation, the bonding resin and magnetic (10) can be simply or melted. The composition can be formed by (4) forming and extrusion forming method. The molded product can be used as a resin magnet. The resin magnet member is formed by combining with a metal member. For example, a resin magnet member is inserted and inserted into the resin magnet member, and after being immersed for 2,000 hours in the heat, the resin is not deteriorated by hydrolysis, and the resin magnet member is not produced. In order to be able to withstand long-term users, the disc-shaped metal member shown in Fig. 1 is inserted into a stone member, and the metal member is added to the metal member. b state] The resin composition of the hair-like state is related to the resin magnet, and the above-mentioned 5th sample contains a plasticizer, and particularly, in the above-mentioned viscosity j = , the proportion of the plasticizer is 5 to 20% by mass. Berry is in accordance with the sixth aspect, in the resin magnet member in which the metal member is inserted, 21 200900466 2.:: Even in the low temperature environment outside the winter house and in the summer, and/or the heat generated in the machine High temperature environment The repeated temperature change in the actual use environment, 'Ttt cracking two and even in the high temperature environment, the resin magnet with less dimensional change. The spot is formed under the harsh @°环^', especially under high temperature and high humidity. Resin magnet which is degraded by the hydrolysis of the sputum station... The composition of the magnetic powder and the binder resin in the resin composition of the tifu tii, the first product = the second fat, preferably contains the resin component, 80 quality denier 0 / = f can be plasticized 1 20 ~ 5 stomach amount%, more preferably contains resin components 80 ~ 10 amount |) °. . (4) 2〇~1〇% by mass (the total of the resin component and the plasticizer is (10) the resin component in the resin, including the poly(tetra) elastomer (10), the thermoplastic resin, especially the ~(10) shell b) (The total amount of amine-based elastomer and poly-_ is (10) The quality of the tree is composed of polyamine-based elastomers & $,) Polyamine-based broad green body 10~25% by mass and _amine 9G~ 7 Further, Μ (the combination of poly _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is said that the agent of polyamine can also be described in the following [Description of each component and material] in January. In addition, the plastic-derived or benzoic acid and the material of the four: 'especially' The compound may be a touch, or a compound of 2^==, the plasticizer 'containing a derivative derived from p- or benzoyl styrene. _above, more preferably r r--. 』] combination of 2 kinds The above alcohol having a side chain of 12 to 22 carbon atoms can be used, ioctyl octanol, 2 octyl ― 22 200900466 2 — decyldodecanol, 2- 3 - octanol, 2-ethyl 12 Alcohol, 2— Base dodecanol decyl sterol, 2-hexyl decyl alcohol, 2-ethyl decyl alcohol, etc. The plasticizer 'is biomimulated from the compound of p- or hydroxy phenyl sterol, for example, _ _ acid; Side chain hydroxybenzoic acid 2-octyl-3~xin, fluorenyl cis oxime, para or ortho-, or p- ortho-benzoic acid to formic acid 2-ethyldodecyl 12, or adjacent It can be used alone or in combination with two or more kinds of plastics, which can be used alone or in combination with 2-methyl benzoic acid (2-benzoic acid). ====, Polyamide-based Elastamine-based Elastomers The resin composition can be formed by a molding method such as injection molding or extrusion molding, and a molded product can be obtained by molding. This shaped product can be used as a tree member. This is a tree magnetized in the form of a metal magnet inserted into a metal member. The tree is partially reinforced by repeated cycles. The environment can be as shown in Figure 1. The disc-shaped metal member 1 is inserted into a metal member or the rod-shaped metal member 3 as shown in FIG. 2 is inserted into the I-shaped resin magnet member, etc. 23 200900466 The resin composition and the molded article of the present invention have a mass reduction rate of less than 0.4%, more preferably 0.4% or less. 2b or less. In the nylon resin composition and the molded article, the size is changed to 0.25% or less, more preferably 〇·2% or less, and particularly preferably Q. 15% or less. β is preferably [components and materials. Explanation] Each component and material will be described below. «Polyurethane-based elastomer" ♦ Amidoxime-based elastomer may contain a known polyamine elastomer. Elastomer. Polyamide can be used. The subtle segment is selected from Nylon 6, Nylon 66, Parallel u, with flat oxygen 4 ΐΐΓίΓ, and the spine ether block is selected from polyoxyethylene, polyoxypropylene, and elastic elastomers. The plasticity of the poly-block and the poly-segment is preferably 15 to 7q, more preferably 18, and more j is 20 to 70, and particularly preferably 25 to 7 Å. The elastic modulus of the body is preferably 2 〇 to the right side of the Pa, and more preferably 20 to 35 MPa, and particularly preferably 2 〇 to 3 MPa. It is preferred that the amine-based elastomer ' has an elongation at break of 嶋 or more. In the body fat, the elastomeric body containing the polyetheramide bomb is more preferably 80% or more, more preferably 90% by mass or more (1〇〇0/ surgery, and the content of the body (1) is large. Poly-based elastomer, excellent water resistance, excellent melting, extensibility, low temperature and softness, low temperature impact resistance, "Excellent properties, excellent sound-absorbing properties, rubber properties and transparency" Is the formation of the diamine compound (4) and the polyamine, whether it is a three-stage poly-diamine compound (10) represented by the formula (1), and a branching type of saturated salt of 2:6:22 from 2:6:22 At least one diamine compound (A2) in the group consisting of a monoamine, a branched alicyclic diamine and a norbornane diamine having a carbon number of 6 to 16. um3 Μ 1 - ch3 h2n- -chch2o- — -CH2CH2CH2CH2 - 〇 - 1 ch2cho- - y - J2 CH, wherein 'X represents an integer from 1 to 20, y represents an integer from 4 to 50, and Z represents an integer from 1 to 20. (1) - „The flexibility of the polyether amide of the present invention One of the particularly preferable aspects of the body (x) is a polyether phthalamide elastomer (X) 'based on the diamine compound (A) and the polyamine forming monomer (B) and the formula (2) - Carboxylation The compound (C) is polymerized to obtain: a diamine complex (A) comprising an XYX-type triblock polyether diamine (jl) represented by the formula (1) (Y is a polyoxybutylene), and is selected from carbon. a branching type saturated diamine of 6 to 22, a branched alicyclic diamine having a carbon number of 6 to 16, and at least a diamine compound (A2) of a decane diamine; a polyamine-forming monomer (B) is selected from the group consisting of the aminocarboxylic acid compound (B1) represented by the formula and the indoleamine compound (B2) represented by the formula (4).
本發明中使用之聚醚醯胺彈性體(χ)中,二元胺化合物(A)、 水酉藍&c形成性單體(B),及二羧酸化合物(c)中,所含末端之羧酸 或羧基與末端之胺基,較佳為成為大致等莫耳之比例。 山尤其,於聚醯胺形成性單體(β)其中之一之末端為胺基,另一 末端為羧酸或羧基之情形,二元胺化合物(Α)之胺基與二羧酸化合 物(C)之羧基,較佳為成為大致等莫耳之比例。 二元胺化合物(Α)中,以式(1)表示之χγχ型三嵌段聚醚二胺 ^匕合物(Α1) ’可使用藉由於聚(氧四亞曱基)二醇等之兩末端加成 氧化丙烯使成為聚丙二醇後,於此聚丙二醇之末端使氨等反應所 製造之聚醚二胺等。 、χγχ型三嵌段聚醚二胺化合物(A1)中,X及z為1〜20,較佳 為1〜18 ’更佳為1〜16,又更佳為丨〜14,尤佳為丨〜12,y為4 25 200900466 〜50,較佳為5〜45,更佳為6〜40,又更佳為7〜35,尤佳 〜30 〇 ΧΥΧ型二嵌段聚醚二胺化合物(Α1)中,\及2各小於上述範圍 之情形,得到之彈性體之特性中,尤其透明性降低,y小於上 圍之情形:橡膠彈性變低。又,x及z大於上述範圍之情形,或y 大於上述範圍之情形,與聚醯胺成分之相容性變低,有時 到強韌的彈性體。 XYX型二嵌段聚醚二胺化合物(A1)之具體例,可使用 HUNTSMBN公司製XTJ —533(式(1)中,x為約12、y為約u、z為 約 11)、XTJ - 536(式(1)中,x 為約 8. 5、y 為約 i7、z 為約 7. 5/、 XTJ —542(式(1)中’X為約3、y為約9、z為約2),及χτ】一559(式 (1)中’ X為約3、y為約14、z為約2)等。 又,XYX型二肷段聚鱗二胺化合物(Μ),亦可使用χγχ—1(式 ⑴中’X為約3、y為約14、Z為約2)、χγχ—2(式⑴中,χ為約 ic; 為約2),及χγχ—3(式⑴中,χ為約3、y為約 19、z為約2)等。 心ΛίΥΧ型三紐?侧二胺化合物(A1k_,相對於二元胺化合 單體⑻及二舰化合物⑹之總量,較佳為 11貝^ 〜78質量%°χγχ型三嵌段聚鱗二胺化合物 t列〉於上述範圍之情形,屈曲疲勞性等作為彈性體之特 性不能充分表現,有時作為聚_系彈性體不佳。χγχ型 _二,化合物(Α1)之比例大於上述範圍之情形,由於聚酿胺成分 Ϊ彈展現聚醯胺特徵之優異力學強度,有時作為聚醯胺 偷ΐ,9=元胺化合物(Α2)中,碳數6〜22之分支型餘和二元胺, _口 .2, 2, 4 —二甲基—I 6—己院二胺、2, 4, 4-三甲基—1 6—己 釔:,、1,2 —二胺基丙燒、ι,3 —二胺基戊烧、2—甲基—j 5__ j基戊奴2-曱基-1,8 —二祕辛鮮。鱗可使 或者將2種以上以適當比例混合使用。 26 200900466 二元胺化合物(A2)中,碳數R〜1C \丄 如:5 —胺基-⑴—三甲基—卜枣二士脂:署二式二元胺’例 兀胺可為順式體及反式體任一者, 妝」)等又,此4一 再者,此等二祕可單獨使用,或構物之混合物。 使用。 X考將2種以上以適當比例混合 二元胺化合物(A2)中,降宿燒 ’ :2二==之_等。此二In the polyether amide elastomer (χ) used in the present invention, the diamine compound (A), the indigo blue & c-forming monomer (B), and the dicarboxylic acid compound (c) are contained. The terminal carboxylic acid or carboxyl group and the terminal amine group are preferably in a ratio of approximately equimolar. In particular, in the case where one of the polyamine-forming monomers (β) is an amine group at the end and the other end is a carboxylic acid or a carboxyl group, the amine group of the diamine compound (Α) and the dicarboxylic acid compound ( The carboxyl group of C) is preferably in a ratio of approximately equimolar. In the diamine compound (Α), the χγχ type triblock polyether diamine compound (Α1) represented by the formula (1) can be used by two of poly(oxytetradecyl) diols and the like. A polyether diamine produced by reacting propylene oxide at the end to form polypropylene glycol and reacting ammonia or the like at the end of the polypropylene glycol. In the χγχ type triblock polyether diamine compound (A1), X and z are from 1 to 20, preferably from 1 to 18', more preferably from 1 to 16, more preferably from 丨 to 14, especially preferably 丨. 〜12, y is 4 25 200900466 ~ 50, preferably 5 to 45, more preferably 6 to 40, and even more preferably 7 to 35, especially preferably ~ 30 〇ΧΥΧ type diblock polyether diamine compound (Α1 In the case where \ and 2 are each smaller than the above range, among the characteristics of the obtained elastomer, especially the transparency is lowered, and y is smaller than the upper circumference: the rubber elasticity becomes low. Further, when x and z are larger than the above range, or when y is larger than the above range, the compatibility with the polyamide component becomes low, and sometimes the tough elastomer is obtained. Specific examples of the XYX-type diblock polyether diamine compound (A1) can be XTJ-533 manufactured by HUNTSMBN Co., Ltd. (in the formula (1), x is about 12, y is about u, z is about 11), and XTJ - 536 (in the formula (1), x is about 8.5, y is about i7, z is about 7. 5/, XTJ - 542 (in the formula (1), 'X is about 3, y is about 9, z is About 2), and χτ]-559 (in the formula (1), 'X is about 3, y is about 14, z is about 2), etc. Further, the XYX-type diterpenoid polyfluorinated diamine compound (Μ), Χγχ-1 can be used (in the formula (1), 'X is about 3, y is about 14, Z is about 2), χγχ-2 (in the formula (1), χ is about ic; about 2), and χγχ-3 (formula) In (1), χ is about 3, y is about 19, z is about 2), etc. Heart Λ ΥΧ 三 纽 ? 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 侧 总量Preferably, it is 11 Å to 78% by mass. In the case of the above range, the buckling fatigue property and the like are not sufficiently expressed as the properties of the elastomer, and sometimes it is used as a poly _ system. The elastomer is not good. χγχ type _2, the ratio of the compound (Α1) is larger than the above range, due to the polyamine content The scorpion bomb exhibits the excellent mechanical strength of polyamine, sometimes as a polyamine, and in the 9=monoamine compound (Α2), the branching type of carbon 6~22 and the diamine, _ mouth. 2, 2,4-Dimethyl-I 6-hexamethylenediamine, 2,4,4-trimethyl-11-6-hexane: 1,2,diaminopropanone, iota,3-diamine Kefen, 2-methyl-j 5__ j kekenol 2-mercapto-1,8-Second-small fresh. Scales can be used in combination with two or more kinds in appropriate proportions. 26 200900466 Diamine compounds ( In A2), the carbon number R~1C \丄如:5—Amino-(1)-trimethyl-Bujubs: The diamine of the formula II can be cis and trans. One, makeup"), etc. Again, these two secrets can be used alone, or a mixture of structures. Use X. Mix 2 or more kinds of diamine compounds (A2) in appropriate proportions,宿烧' : 2 2 == _ etc. These two
Mv ’透雅不犯充么表現,有時不佳。二元胺化合物之比 列大^上述範圍之情形,來自於聚_形成性單體之結晶性降 低,無法展現足夠力學強度,有時不佳。 又’二兀胺化合物⑷’可含三嵌段㈣$ 元胺化合物⑽以外之其他二元胺化合物⑽。口物⑼及一 其他二元胺化合物⑽,例如:乙二胺、三亞甲基二胺、四亞 Ιί:ΐ、:亞甲基專七亞甲基二胺、八亞甲基二胺、九亞 土「女一、十亞曱基二胺、十-亞甲基二胺、十二亞甲基二胺、 2, 2 4「三甲基六亞曱基二胺、2, 4, 4—三甲基六亞曱基二胺、3 — 甲土戊文元亞曱基二胺等脂肪族二元胺;雙(4_胺基環己基)甲烧、 雙(4-胺基環己基)丙烧、13〜二胺基曱基環己烧、υ—二胺基 曱基環己;ka專脂環式一元胺;間二曱苯二胺、對二甲苯二胺等芳香 族二凡胺等,鱗二元胺可單獨仙,或者可將2種社適當組 合使用。 其次,對於聚醯胺形成性單體(B)中,胺基羧酸化合物(β1)及 内醢胺化合物(B2)加以說明。 胺基羧酸化合物(B1)中,R2為碳數2〜20之烴之分子鏈,尤 27 200900466 其具碳原子2〜20之伸烷基較佳,更佳為碳數3〜 鏈,尤其具碳原子3〜18之伸烷基,更佳為喂數δ之分子 子鏈’尤其具碳原子4〜15之伸烧基,尤佳為石炭 ,之分 分子鏈’尤其具碳原子10〜15之伸燒基。 〜丨5之烴之 内醯胺化合物(Β2)中,R3為碳數3〜2〇之_ 具碳原子3〜20之伸烧基較佳,更佳為破數^刀、·’ ’尤其 尤其具碳原子3〜18之舰基,更佳為魏^ 子鏈’ 尤其具碳軒4〜15之狀基,尤佳為碳數1Q : f子鏈, 鏈,尤佳為具碳原子10〜15之伸烷基。 之烴之分子 胺基羧酸化合物(B1),例如:6—胺基己酸、 7胺基辛酸、10—胺基癸酸、u —胺基十一酸、 專石厌數5〜20之脂肪族ω —胺基綾酸等。 7〜胺基庚酸、8 胺基十二酸 ω —厌内醯胺 内胺、2 — π比略 η職妝化合物幻,例如:ε—己内醯胺 (enantholactam)、ω —十—内醯胺、ω 一十二 酮等碳數5〜20之脂肪族内醯胺等。 η相對於聚醚醯胺彈性體⑴之全部成分,聚酿胺形成 之比例,較佳為10〜95質量%,更佳為15〜95皙1 早體() 15〜趴晳吾〇/ 士、灶去^更住為 b,又更佳為 85貝夏/«,尤佳為15〜8〇質量%。相對於聚醚醯 ί 分’聚驢胺形成性單體⑻之比例少於上述範圍之, 胺成*之結晶性變低,強度、彈性率等機械物性月低, 圭。相對於聚魏胺彈性體(χ)之全部成分,親胺形成性 軟,ii 大之情形,由於難以展現橡膠彈性或柔 性4作為弹性體之機能、性能,故有時不佳。 二羧酸化合物(〇中,^表示碳數丨〜罚之分 且 J子1〜20之钟貌基較佳,更佳為碳數 Ln 其具碳原子1〜15之伸烷美,f枰為石山叙0 工之刀子鏈,尤 尤佳為且禮盾石9 10 土更仏為厌數2〜12之烴之分子鏈, 鏈U其呈Si二之伸烧,’尤佳為石炭數4〜1〇之烴之分子 射n之伸L基。m表示G或1,較佳為表示卜 -魏化合物⑹,可使冊自於脂肪族、脂環式及芳香族二 28 200900466 羧酸之中至少1種二羧酸或此等之衍生物。 一二羧酸化合物(C)之具體例,例如:草酸、琥賴、戊、 己^、庚二酸、辛二酸、壬二酸、癸二酸、十二烧二酸等石 7,直鏈脂肪族二魏,或藉由將三酸甘油g旨之分顧得^ 予以二聚化之碳數14〜48之二聚化脂肪族 4酉〇及此等之氫化物(氫化二聚酸)等脂肪族二羧酸、i 4二(^ 烧二叛酸等脂環式二舰,及對苯二甲酸、間苯二曱酸= 二魏。二聚酸及氫化二聚酸,可使用「,方= 1006」、「Plyp〇1 1009」、「Plypol 1〇13」等。 P1_ 對本發明使用之聚醚醯胺彈性體⑴之製造方法 明,可使用將聚醯胺形成性單體⑻、χγχ型三紐聚鱗 = 物⑻、二元胺化合物(Α2),及二醜化合物⑹,共4成^化二 崎合’視需要,再於減壓下進行溶融聚 Α步驟所構成之方法,亦可使用將雜胺形紐單體 型二巍段W二胺化合物(A1)、二元胺化合物(A2),及二細 合物(C)之4成分同時於加壓及/或常壓下精縣聚合 要於減壓下進行縣聚合之步騎構狀方法。又 聚醢胺形成性單體⑻與二羧酸化合物⑹之2成分先聚合^使 使XYX型之二後段聚_二胺(A1)與二元胺化合物⑽聚合 聚醚醢胺,性體⑴之製造時,捕之添加方法紐別限I, 聚I&胺形成性單體(B)、χγχ型三嵌段聚_二胺化合物(A1)、 化合物(A2),及二羧酸化合物(c)之添加比例,相對於全部 分,聚醯胺形成性單體⑻較佳為丨〇〜95質量%,尤佳5〜 質量%之範圍,XYX型三後段聚驗二胺化合物(A1),,較佳為2 質,尤佳為7〜78質量%,二元胺化合物(A2),較佳為◦. 5〜1〇 質量% ’尤佳為1〜5質量%。χγχ型三紐聚醚二胺化合物(A1)與 二兀胺化合物(A2)及二羧酸化合物(c),較佳為投予使得χγχ型^ 嵌段聚_二胺化合物(Α1)與二元胺化合物⑽之胺基及二缓酸;^ 合物(C)之羧基成為大致等莫耳。 29 200900466 佳為造’聚合溫度較佳為150〜·。c,更 度之情幵,靡 14 m〜25(rc進行。聚合溫度低於上述溫 有時得不到良好物性之聚合物。 奋易么生熱刀角中, D°辦胺彈性體⑴,於使用ω—胺基細&作胺㈣、性 :體⑻之情形,可以進行 二 進行減壓熔融聚合之步驟所構成方法製造^^合,並接續 使^内_作為聚雜形成性單體⑻之情形,可 仃吊左熔嘁聚合及/或減壓熔融聚合之方法製造。 、.貫進 胺彈性體(x),能以聚合時間通f Q 5〜 ♦ &時間若短於上述範圍,則 每 圍,則會發生由祕分解之’右長於上述範 望物性之輯,竭可騎不到具所 聚,胺彈性體⑴之製造,可為批式亦可以連 岸=早,用或適當組合批式反、單槽式或多ί式連心 應扁置、官狀連續反應裝置等。 '連、,、貝反Mv ‘Too’s not doing anything, sometimes it’s not good. When the ratio of the diamine compound is larger than the above range, the crystallinity of the poly-forming monomer is lowered, and sufficient mechanical strength cannot be exhibited, and sometimes it is not preferable. Further, the 'diamine compound (4)' may contain other diamine compound (10) other than the triblock (tetra)$-amine compound (10). Oral material (9) and a further diamine compound (10), for example: ethylenediamine, trimethylenediamine, tetraammine: oxime, methylene-7-methylenediamine, octamethylenediamine, IX Sub-soil "female, ten-decyldiamine, deca-methylenediamine, dodecamethylenediamine, 2,24" trimethylhexamethylenediamine, 2, 4, 4- Aliphatic diamines such as trimethylhexylimidyldiamine, 3-carbazone, fluorenyldiamine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl) Propylene, 13-diaminomercaptocyclohexene, hydrazine-diamine fluorenylcyclohexane; ka-aliphatic cyclic monoamine; m-diphenylene diamine, p-xylene diamine and other aromatic diamine Etc., the squamous diamine may be used alone, or two kinds of compounds may be used in combination. Next, in the polyamine-forming monomer (B), the aminocarboxylic acid compound (β1) and the indoleamine compound (B2) In the aminocarboxylic acid compound (B1), R2 is a molecular chain of a hydrocarbon having 2 to 20 carbon atoms, particularly 27, 200900466, preferably having an alkyl group having 2 to 20 carbon atoms, more preferably a carbon number of 3 ~ chain, especially with a carbon atom of 3 to 18 alkyl, more preferably The molecular sub-chain of the number δ is especially composed of a carbon atom of 4 to 15 and is preferably a charcoal. The molecular chain of the molecule has a carbon atom of 10 to 15 in particular. In the amine compound (Β2), R3 is a carbon number of 3 to 2 Å. A stretching group having a carbon atom of 3 to 20 is preferred, and more preferably a number of knives, especially a carbon atom of 3 to 18 The ship base, more preferably the Wei ^ sub-chain, especially has a carbon-based 4~15 base, especially a carbon number 1Q: f sub-chain, chain, especially preferably a carbon atom 10~15 alkyl group. Hydrocarbon molecular amine carboxylic acid compound (B1), for example: 6-aminohexanoic acid, 7 aminooctanoic acid, 10-amino decanoic acid, u-aminoundecanoic acid, fat of 5 to 20 Family ω - amino decanoic acid, etc. 7 ~ amino heptanoic acid, 8 amino octanoic acid ω - anaerosamine amine, 2 - π ratio slightly η makeup compound magic, for example: ε - caprolactam (enantholactam), omega-deca-indoleamine, ω-dodecanone, etc., aliphatic decylamine having a carbon number of 5 to 20, etc. η is formed by the polyamine relative to all components of the polyether amide amine elastomer (1) The ratio is preferably 10 to 95% by mass, more For 15~95皙1 Early body () 15~趴明吾〇/士,灶去^更住为b, and more preferably 85 贝夏/«, especially good for 15~8〇% by mass. Relative to poly The proportion of the ether 醯 分 'polyamine-forming monomer (8) is less than the above range, the crystallinity of the amine formation* is low, and the mechanical properties such as strength and modulus are low, which is relative to the poly-weidiamide elastomer (全部) All components, kinophilic formability is soft, and ii is large, because it is difficult to exhibit rubber elasticity or flexibility 4 as an elastomer's function and performance, it is sometimes poor. Dicarboxylic acid compounds (〇, ^ represents carbon The number of 丨 罚 罚 且 且 且 且 且 且 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J Jiawei and Lidangshi 9 10 soil is the molecular chain of the hydrocarbons with the number 2~12, the chain U is the extension of Si, and the molecule of the hydrocarbon is 4~1〇. Extend the L base. m represents G or 1, preferably represents a compound (6), which may be derived from at least one dicarboxylic acid or a derivative thereof from an aliphatic, alicyclic or aromatic carboxylic acid. Specific examples of the monocarboxylic acid compound (C) include, for example, oxalic acid, arsine, pentane, hexamethylene, pimelic acid, suberic acid, azelaic acid, sebacic acid, and decanoic acid. a chain aliphatic diwei, or a dimerized aliphatic 4酉〇 having a carbon number of 14 to 48 and a hydride (hydrogenated dimer acid) by dimerizing the triglyceride g ) such as aliphatic dicarboxylic acid, i 4 bis (^ sulphuric acid and other alicyclic second ships, and terephthalic acid, isophthalic acid = diwei. dimer acid and hydrogenated dimer acid, can be used ", square = 1006", "Plyp〇1 1009", "Plypol 1〇13", etc. P1_ For the production method of the polyether amide elastomer (1) used in the present invention, a polyamine-forming monomer (8) can be used. , χγχ type three-new scales = material (8), diamine compound (Α2), and two ugly compounds (6), a total of 40% ^ two-sand combination 'as needed, and then under the reduced pressure to carry out the melt-polymerization step Alternatively, it is also possible to use the four components of the hetero-amine-shaped haplo-type di-diamine compound (A1), the diamine compound (A2), and the di-compound (C) simultaneously under pressure and/or Jingxian County under normal pressure It is necessary to carry out the step-by-step configuration method of the county polymerization under reduced pressure. The polyamine-forming monomer (8) and the second component of the dicarboxylic acid compound (6) are first polymerized to make the XYX-type second-stage poly-diamine (A1). Polymerization of polyether amide with diamine compound (10), addition method for the production of physique (1), addition of I, amine I forming monomer (B), χγχ type triblock poly-diamine The addition ratio of the compound (A1), the compound (A2), and the dicarboxylic acid compound (c) is preferably 丨〇95 to 95% by mass, particularly preferably 5 to 重量%, based on the entire portion of the polyamine-forming monomer (8). The range of %, the XYX type three-stage polydiamine compound (A1), preferably 2, more preferably 7 to 78% by mass, the diamine compound (A2), preferably ◦. 5~1〇 The mass % ' is particularly preferably 1 to 5 mass%. The χγχ type tri-nuclear polyamine diamine compound (A1) and the diamine compound (A2) and the dicarboxylic acid compound (c) are preferably administered so that χγχ type ^ The block poly-diamine compound (Α1) and the amine group of the diamine compound (10) and the bis-acid acid; the carboxyl group of the compound (C) becomes substantially equimolar. 29 200900466 Preferably, the polymerization temperature is preferably 150. ~ · c, more inferior, 靡 14 m ~ 25 (rc. Polymerization temperature is lower than the above temperature sometimes can not get good physical properties of the polymer. In the heat of the knife corner, D ° amine flexibility The body (1) can be produced by a method in which the ω-amino group is used as the amine (4) or the substance (8), and the method of performing the step of performing the vacuum polymerization is carried out, and then the _ is used as the poly In the case of the forming monomer (8), it can be produced by a method of entangled left melt polymerization and/or vacuum melt polymerization. The feed amine elastomer (x) can pass the polymerization time f Q 5 ♦ ♦ & time If it is shorter than the above range, then each of the circumferences will be produced by the secret decomposition of 'the right is longer than the above-mentioned fan-like physical properties, so that it can not be worn, the amine elastomer (1) can be manufactured, and the batch can also be connected. Shore = early, with or with a combination of batch reverse, single-tank or multi-thickness should be flat, official continuous reaction device. 'Lian,,, Beibei
Wn本之聚醚醯胺彈性體⑴,以相對黏度2〜 ..貝里/各量%間曱酚溶液、25°C)之範圍較俨。 . ,醚彈性體⑴之製造中、視需要,為了^分 成形加工時之熔融黏度安定, 里或使 二胺、間二甲苯二胺等一細-元胺二硬,月女、六亞甲基 P -舱八-灿 寻妝忒一月,乙酸、苯曱酸、硬脂酴、 ——夂、六一@夂、十二烷二酸等單羧酸或二 較佳為適當添加,使得最線得到之雜以^ j錢用量, ^3.5(0.5 1.2 聚醚醯胺彈性體⑴之製造中’上述—元胺及二 及一幾·酸專之添加量,較佳為設定在不姑虛彡B 單瘦酉文 體(X)之特性的範圍。 妨礙件到之聚_胺彈性 聚義胺彈性體⑴之製造中,視需要,可添加磷酸、_酸、 30 200900466 聚構酸等,為觸媒,且為了得到觸 亞·、次亞罐酸,及此等之驗金屬鹽、屬 ^ 5〇ί3〇^^" 加耐熱劑、紫外線吸收劑、' 靶圍可添 滑劑、增滑劑、結晶^、抗靜電劑、獨 <<熱塑性樹脂〉科捕、香料、難燃劑、補強材等。 糊_ '芳香族 等改質物等聚_、二取二=、,丙缚等献等之馬來酸 尤佳為下成形溫度較佳為靴以下,更佳為靴以下, 又,IS:;广聚醯胺作為纖佳。聚醯胺可單獨使用, 聚胺聚氯乙稀、 等熱塑性樹月旨。 文改貝來乙席、酸改質聚丙埽等聚烯烴 自於Ϊ=Γ係主鍵中具有酸_鍵(—_-)者,可使用含握 族r.芳香族中至少1種者2 成分得到之聚人^Ι ϋ為’擇自於脂肪族及脂環族中至少1種 或脂環族至少2種成分所得到之聚合物等脂肪族 中=,_胺。尤其,脂肪族聚酿胺較佳。 合得到Γ月女’係由内義、胺基叛酸、或者二元胺與二羧酸之組 胺、2料之内酸胺’例如:ε —己内酿胺、ω—庚内醯 如:卜胺美己2 f、α —°比侧、α —派°定酉同等,胺基叛酸例 12-胺基ί二^等。—胺基庚酸、9 —胺基壬酸、η〜胺基十一酸、 成為衍生自於二元胺及二叛酸之聚醯胺原料的二元胺,例如: 31 200900466 乙二胺、四亞曱基二胺、五亞甲基二胺、六亞曱基 基二胺、八f甲基二胺、九亞甲基二胺、十亞甲基二胺、十一亞 甲ί二胺、十三烷二胺、十四烷二胺、十五炫 一妝、十,、烷—胺、十七烷二胺、十八烷二胺、十九烷二二 十烧二胺、2-甲基—;[,8—辛烧二胺、2, 2, 甲基二胺等脂肪族二元胺;—環己基二胺、4雙 if甲)Γ完(、3雙(二胺己基)丙烷、雙(3—甲基-4-胺基環己 Γ二ί——胺基環己基㈣完”我卜二胺基甲 基衣己从、卜胺基-2, 2,4 —三甲基—卜環戊垸甲胺、5 —胺基 -1,3, 3-二甲基環己烷甲胺、雙(胺基丙基) ::等降芳S等脂環㈣ 二烷:ΐ酸、十四烷二酸、十五烷二酸、十六烷二酸、 酸:一·^;^十=酸等脂肪族二叛酸;U/U-環己炫二羧 上—二羧酸、降掐烷二羧酸等脂環式二羧酸; 間酸、對本二曱酸、h 4/1,8/2,6/2,7—萘二舰等芳香族 一^緩酸等。 此等聚醯胺,可個別單獨使用,也可將2種以上丨 者^可使用2種以上組合成之共聚合聚醯胺。 論親胺’例如,聚己_(雜—6)、聚胺基十-酸(耐 二胺義 士4甲基一月女基癸一酸(而于綸―610)、聚六亞甲基 胺妓=私厂烷二酸(耐綸~612)之聚合物、己内醯胺/月桂基内^ 6/1^勿(耐綸—6/12)、己内》/絲十-烧酸共聚物(耐論— 己内醯ί舰胺/六亞甲基二胺基己二酸共聚物(耐輪〜6/邮)、 6/66/〗?t六亞甲基二胺基己二酸/胺基十二烷二酸(耐綸一 J、己内醯胺/六亞曱基二胺基己二酸/月桂基内醯胺(耐綸 32 200900466 —6/66/12)、己内醯胺/六亞曱基二胺基己二 删)、讓 基::烷二酸(价_2)等(共)聚 醯胺樹脂,可個別單獨使用,亦可將2種以 11' ^km 1 6' 66 ^ 610 ^ 12及耐綸612中至少1種脂肪族聚醯胺。 两 «可塑劑》 太蘇為擇自於酯類及烷基醯胺類中1種以上之化合物。 甲酸··丁π 本一甲馱一曱酉曰、鄰本二曱酸二乙酯、鄰苯二 酉旨、鄰苯二甲酉ίΛ^Γ:酸二異癸酉1、鄰苯二甲酸二-十三 異壬醋、鄰笨廿鄰笨二甲酸丁基节酯、鄰苯二甲酸二 S旨、鄰苯二甲酸-\基甘_乙§旨、鄰苯二甲基丁基甘醇酸丁 脂肪酸四氫鄰苯m乙基己醋等。 己二酸二異丁隨/己^ ’例如:己二酸二"、己二酸二丁酉旨、 r曰、己二酸二正4-,:基二-二醇醋、己二酸二2-乙基已. 酸二正—混呼日己—^二異癸S旨、己二酸二異壬醋、己二 -乙基己醋、‘:酸一甲醋、癸二酸二丁醋、癸二酸二2 十二烧二酸雙2—乙^ ^基己醋、二2—乙基己基混合酸輯、 馬酸雙卩一fAet f專二元飽和羧酸酯;富馬酸二丁酯、富 來酸:乙醋 紐醋;油酸丁r、;;=日、馬來酸雙2—乙基己醋等二元不飽和 萨- 丁咕A 7曰油^異丁醋、蓖麻酸乙酿基丁醋、乙烯基檸檬 酉义二JS日及乙酸2—乙基己黯等。 單異ίί:Γ旨?ίί體例甲” ’ 4 4一二甲基一1,3 —戊烷二醇二異丁酸酯、二乙 33 200900466 二醇二苯曱酸,、三乙二醇二2一乙基丁酸酯、季戊四醇單油酸 醋、季戊四醇單硬脂酸g旨、季戊四醇三;):完醋、辣木子油酸單甘油 酸酯、2—乙基己基三甘油酸酯、甘油三乙酸酯及甘油三丁酸酯等。 石粦酸S旨類之具體例,例如:碟酸三曱g旨、磷酸三乙酯、鱗酸三 丁酯、磷酸三2〜乙基己酯、磷酸三丁氧基乙酯、磷酸三苯酯、磷 酸正辛基二苯酯、磷酸曱酚基二苯酯、磷酸三曱酚基、磷酸三_二 甲苯酯及磷酸2—乙基己基二苯酯等。 偏苯三甲酸酯類之具體例,例如:偏苯三甲酸三丁酯、偏苯三 曱酸三2—乙基己酯、偏苯三曱酸三正辛酯、偏苯三曱酸三異壬 酯、偏苯三甲酸三異癸酯及偏苯三甲酸三混合醇酯等。 /、 羥基苯曱酸酯類之具體例,例如:鄰或對羥基苯甲酸乙基己 醋、、鄰或雌基苯曱酸己基癸_、鄰或_基苯甲酸乙基癸^、 郇或對羥基笨曱酸辛基辛酯、鄰或對羥基苯曱酸癸基十二酯、鄰 或對羥基苯甲酸甲酯、鄰或對羥基苯曱酸丁酯、鄰或對羥基苯甲 酉1其基苯Ψ酸正辛_、鄰或_基笨甲酸ϋ及鄰 或對經基本曱酸十二酯等。 類。’為甲苯雜烧基醯胺類或笨石驗烧基》 頡甲本碩駄烷基&胺類之具體例,例如:Ν—乙基—鄰 丁基醯胺、Ν—乙基一對曱苯磺酸丁基醯胺、 酸2-乙基己基_、N—乙基—對甲苯績酸2—乙基 =酸ϊίΓ2類ΐί體例,例如:苯磺酸丙―胺、苯續酸丁基 在匕等可塑劑之中,較佳為使用:鄰苯二甲酸二丁酿 甲其?ΐ二甲酸二2—乙基己酯等鄰苯二曱酸酯類,·對羥 石黃酸丁細胺、苯魏2—乙基己基醯胺等絲曰類,本 《難燃劑》 糧鎖 難燃劑’可使用 >臭系難燃劑與三哄系難燃劑等。漠化難燃劑, 34 200900466 Z!·/臭自化苯氧基樹月旨、填化聚碳酸酿、淳化雙笼,膝 本乙烯、溴化聚苯醚等。 磔化聚本乙烯、聚溴化 二啡系難燃劑,可使用二 三聚氰酸三聚氰胺等。一胃4、"二聚氰酸、三聚氰胺、 〜40=^;相對於細安系彈性體⑽質量广么 仙賀里份,較佳為1〇〜3〇 股川υ貝里份,為5 難燃助劑,可使用含銻之化:: 化録、五氧化録、四氧化銻、錄i鱗。5物’例如:三氧 份),為。.W2質量份樹脂,〇。質量 溴系難燃劑併用,使難燃性提高。 、知。可藉由將此等與 «磁性粉末》 本發明使用之磁性粉末,可使用公知之 鋇鐵酸鹽、賴酸鹽等鐵酸鹽系磁性材料例如 硼系等稀土類磁性材料等粉末。 鉛糸、斂-鐵— 本發明使狀雜粉末,為了改良與翻旨 =利】矽烷偶合劑、鈦酸鹽偶合劑、錯鋁酸 :丄: 等經表面處理後使用。 '"剎鋁偶合劑 (實施例) 實施^,舉實施例及比較舰明本㈣’本發明不限於此等 特性値以如下方式測定。 1) 相對黏度(7/0(0.5質量/容量%間甲酚溶液、25t:)· 以試藥特級品之間甲酚作為溶劑,於5g/dm3之濃度,使用 Ostwald黏度計,於25°C進行測定。 又 2) 彎曲試驗(彎曲彈性率): 使用試驗片尺寸6. 35mmxl2. 7mmxl27mm之試驗片,依照astm D790,進行測定。 … 35 200900466 3) 衝擊強度(附Iz〇d缺口): 尺寸3·18mmXl2· 7_Xl27mm之試驗片,依據腿 D256,於23°C進行測定。 4) 溶融流動速率(meit flow rate): 使用丸粒,於溫度235t:、負載2160g之條件進行測定。 5) 耐水解性(1): 將從以射出成形成形而成之1〇〇臟3〇〇)<厚度2醜 JIS3號啞鈴切出之試樣,以不使重疊之方式,放入 不銹鋼容器,加人約2公升之蒸馏水,加蓋使 後,使用拉伸試驗機,以夾頭間距離5〇_夾持,以刀.牙、 速度進行拉伸試驗,败拉伸_伸铸 試驗片【=’以下述數式⑴,_伸斷裂 100(1) 拉伸斷裂保持举(%)=水解處理試樣之袓伸断繫伸長率 来處理試樣之拉伸斷裂伸長牟 6) 拉伸物性: 使用ASTM1號片,依據ASTM D638 7) 燃燒性之評價: 進订測疋。 使用0. 8mmxl2. 7mmxl27mm之試驗片,依據 又’關於含磁性粉末之樹脂組成物 '樹^^ ^丁測定。 第6態樣之實施例•比較例),物性値以如下第5及 8) 樹脂磁石組成物之質量變化率之測定 、疋 將樹脂磁石丸粒以壓縮成形機,製作成厚度 此片材切出25麵xl5Q_之尺寸,作為試驗片。將^片材,從 ◦C之熱風循環式怪溫槽Μ日,之後,使試存在120 量減少。 至》皿,蜊定質 9) 樹脂磁石組成物之尺寸變化率之測定 36 200900466 將樹脂磁石丸粒以壓縮成形機,製作 此片材切出25_150_之尺寸,作為試二,::二:材,從 t之熱風彳《式恆溫槽14日,之後使顺120 方向之尺寸變化。 n w剞至/皿,測疋長度 10)樹脂磁石組成物之表面之黏糊(stick 此片以壓縮成形機,製作成厚度洫之片材,從 此片材切出25mnixl50mm之尺寸,作為試驗片 1 = t熱風循環式怪溫槽14日’以手指接觸試驗^面,”並子^^ Π )樹脂磁石成形品因為溫度變化產生龜穸之呷俨 將如圖1所示,直徑30_、厚度30咖之圓柱形狀貝金 為全體直徑為4Qmni之樹脂磁石,並製作樹脂磁石i金 驗片,於—2〇〜赋之範圍,進行1000個週期3 週期處理後,確認職磁;δ部妓;^發生㈣。 熱 12)樹脂磁石成形品之耐水解性評價 , 將如圖1所示,直徑30臟、厚度30職之圓柱形狀金屬構 j形為全體餘為40_之樹脂磁石,製作樹脂磁石與金 、、且δ之試驗片,泡在80°C之溫水中,進行2〇〇〇小時處理後, 試驗片,確認發生龜裂。 印 〔製造例1:PAE1之製造〕 於附有攪拌機、溫度計、扭矩計、壓力計、氮氣導入口、 ,整裝置及聚合物取出口之7G公升之壓力容器中,添加宇部; 產(山股)製12—胺基十二酸10. 354kg、己二酸1· 581kg、XY)(型^ 三嵌段聚醚二胺(HUNTSMAN公司製XTJ —542(式(1)中,x為約3、 y為約9、z為約2)、胺價:1.94meq/g)7.452kg、異佛爾酮二胺 (DegUssa公司製商品名:VESTAMIN Ιρ〇)〇· 612kg、次亞磷酸鈉 1水合物6g及耐熱劑(吉富製藥製TOMINOX917)60g。將容器内充 分進行氮氣取代後,一面將氮氣以186公升/小時供給,一面將容 器内之壓力調整為0. 05MPa,花費3. 5小時從室溫升溫到23(rc^ 200900466 再者,-面將容器内之壓力調整為〇5MPa,一面於2 小時聚合’得到聚合物。聚合結束後,停止擾摔,從聚合物取出 口將熔融狀態之無色透明聚合物以繩狀抽出,水冷後造 約15kg之丸粒。得到之丸粒為無色半透明強動且富橡膠彈性: 合物,7? r = l. 96。 人 〔製造例2:PAE2之製造] 於附紐拌機、溫度計、扭輯、壓力計、I氣導入口、壓 力調整裝置及聚合物取出CT之70公升之壓力容器巾,添加宇部興 產(股)製12-胺基十二酸7. 557kg、己二酸1· 691kg、XYX型之三 嵌段聚醚二胺(HUNTSMAN公司製XTJ —542(式(1)中,x為約3 為約9、z為、約2)、胺價·丄94meq/g)10,517kg、異佛爾酉同二胺 (Degussa公司製商品名:VESTAMIN IpD)〇 234kg、次亞磷酸納 1水合,ρ及耐熱劑(吉富製藥製TOMINOX917)6〇g。將容器内充 分進行氮氣取代後,一面將氮氣以186公升/小時供給,一面將容 器内之壓力調整為G, 〇5MPa,花費3. 5小時從室溫升溫到230X:, 再一,將容器内之壓力調整為〇 〇5MPa,於23(rc進行4小時聚 合,=到聚合物。聚合結束後,停止攪拌,從聚合物取出口將熔 融狀態之無色透明聚合物以繩狀抽出,水冷後造粒,得到約15kg 之丸粒。得到之丸粒為無色半透明強韌且富橡膠彈性之聚合物, β r= 1. 96。 〔製造例3:PAE3之製造〕 於附有撥拌機、溫度計、扭矩計、壓力計、氮氣導入口、壓 力调整裝置及聚合物取出口之7〇公升之壓力容器中,添加宇部興 產(股)製12 —胺基十二酸ι〇· 37〇kg、己二酸丨· 585kg、χγχ型之 三嵌段聚醚二胺(HUNTSMAN公司製XTJ —542(式(1)中,X為約3、 7為約9、2為約2)、胺價:1.9411^9/&)7.4761^、2,2,4 —三甲基 一 1,6 —二胺基己烷與2, 4, 4 —三曱基一丨,6一二胺基己烷之混合 物(Degussa公司製、商品名:vestamin TMD)0. 569kg、次亞磷 酸納1水合物6g及耐熱劑(吉富製藥製T〇MIN〇X917)6〇g。將容器 38 200900466 仃,代後,一膽氮氣以186公升/小時供給,-面 之壓力調整為G. G5MPa,花費3. 5小時從室溫升溫到23〇 取入再-面將容器内之壓力調整為G· G5MPa,於23{rc進行4小時 ♦ S,侍到聚合物。聚合結束後,停止攪拌,從聚合物取出口將 嫁融狀紅無色透卿合物以驗抽出,水冷後造粒,得 之丸粒。得到之丸粒為無色半透明強韌且富橡膠彈性之、八 ??r=1.98。 米 〔製造例4:PAE4之製造〕 =附有擾拌機、温度計、扭矩計、壓力計、氮氣導入口、壓 =调正,置及聚合物取出π之7G公升之壓力容財,添加宇部興 產(股)4 12—胺基十二酸1〇. 426kg、己二酸1. 582kg、χγχ型之 三嵌段聚醚二胺(HUNTSMAN公司製XTJ —542(式(1)中,χ為約3、 y為約9、Ζ為約2)、胺價:1. 94meq/g)7. 436kg、降梅烷1胺(二 井化學製商品名:_A)0. 556kg、次亞磷酸鈉丄水合物^及^ 熱劑(吉富製藥製TOMINOX917)60g。將容器内充分進行氮氣取代 後,一面將氮氣以186公升/小時供給,一面將容器内之^力調整 為0· 05MPa,花費3. 5小時從室溫升溫至230〇C,再一面將容器内 之壓力調整為0· 05MPa,於23(TC進行4. 5小時聚合,得到聚合物。 聚合結束後,停止攪拌,從聚合物取出口將熔融狀態之無色透明 聚合物以繩狀抽出,水冷後造粒,得到約15kg之丸粒。彳^到之丸 粒為無色半透明強韌且富橡膠彈丨生之聚合物, 〔製造例5:PAE5之製造〕 於附有擾拌機、溫度計、扭矩計、壓力計、氮氣導入口、壓 力調整裝置及聚合物取出口之70公升之壓力容器中,添加宇部興 產(股)製12-胺基十二酸7. 985kg、己二酸1. U5kg、χγχ型之三 嵌段聚醚二胺(HUNTSMAN公司製XTJ —559(式(1)中,x為約3 為約14、z為約2)、胺價:1. 40meq/g)l〇· 900kg、次亞磷酸鈉} 水合物6g及耐熱劑(吉富製藥製TOMINOX917)60g。將容器内充分 進行乳氣取代後,一面將氣氣以186公升/小時供給,一面將容哭 39 200900466 内之壓力凋整為〇. 〇5MPa,花費3. 5小時從室溫升'溫至23〇。〇,再 -面將容器内之壓力調整為M5MPa,於2默進行4小時聚合, 得到聚合物。聚合結束後,停止獅、從聚合物取出口將炼^狀 態之^色透明聚合物以繩狀抽出、水冷後造粒,得到約15吆之丸 fVe得到之丸粒為無色半透明強韌且富橡膠彈性之聚合物,77r= [製造例6:PAE6之製造]The polyether amide elastomer (1) of Wn is relatively inferior in the range of relative viscosity 2 to .. Berry/various amount of decyl phenol solution, 25 ° C). . In the manufacture of the ether elastomer (1), if necessary, in order to stabilize the melt viscosity during the forming process, or to make a fine-densamine such as diamine or m-xylene diamine, the moon, the girl Base P-cabin eight-can find makeup in January, acetic acid, benzoic acid, stearic acid, 夂, 六, @夂, dodecanedioic acid and other monocarboxylic acids or two are preferably added, so that The most common line is the amount of ^ j money, ^ 3.5 (0.5 1.2 polyether amide elastomer (1) in the manufacture of the above-mentioned - amine and two and a few acid special addition amount, preferably set in the aunt The range of the characteristics of the imaginary B-small scorpion (X). In the manufacture of the poly-amine elastomeric polyamine elastomer (1), if necessary, phosphoric acid, _acid, 30 200900466 poly-acid, etc. may be added. For the catalyst, and in order to get the touch, the sub-tank acid, and the metal salt of the test, the genus ^ 5 〇 〇 〇 ^ 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加 加Slip agent, crystallize, antistatic agent, sole <<thermoplastic resin> Branch, fragrance, flame retardant, reinforcing material, etc. Paste _ 'Aromatic and other modified substances, etc. _ The second forming temperature is preferably lower than the boot, preferably less than the boot, and IS:; broad polyamine as the fiber. Polyamide can be used. Used alone, polyamine polyvinyl chloride, and other thermoplastic trees. The modified polyolefins such as beryllium acetonitrile and acid-modified polyacrylonitrile have the acid _ bond (-_-) in the primary bond of lanthanum. It is possible to use a polymer obtained from at least one of the two components of the r-aromatic group, which is obtained by polymerization of at least one of the aliphatic and alicyclic groups or at least two components of the alicyclic group. Among the aliphatics, etc., the amines are preferred. In particular, the aliphatic polyamines are preferably obtained from the internal sense, the amino acid, or the histamine of the diamine and the dicarboxylic acid. The acid amine 'for example: ε - caprolactam, ω - heptane ruthenium such as: oxime mei 2 f, α - ° ratio side, α - 派 ° 酉 酉 equivalent, amine oxo acid 12-amine — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 31 200900466 Ethylenediamine, Siam Diamine, pentamethylenediamine, hexamethylenediamine, octamethyldiamine, nonamethylenediamine, decamethylenediamine, eleven methylenediamine, tridecane Diamine, tetradecanediamine, fifteen, one makeup, ten, alkane-amine, heptadecanediamine, octadecanediamine, nonadecane dioctadecene diamine, 2-methyl-; [8-octylamine diamine, 2, 2, methyl diamine and other aliphatic diamines; - cyclohexyl diamine, 4 double if A) Γ (, 3 double (diamine hexyl) propane, double ( 3-Methyl-4-aminocyclohexane Γ —— - Aminocyclohexyl (4) End" I diaminomethyl hexamethylene, oxime-2, 2,4-trimethyl-b ring Ethyl pentaamine, 5-amino-1,3,3-dimethylcyclohexanemethylamine, bis(aminopropyl):-equal aryl alicyclic (tetra) dioxane: citric acid, fourteen Alkanedioic acid, pentadecanedioic acid, hexadecandioic acid, acid: one ^ ^; ^ ten = acid and other aliphatic ditolic acid; U / U - cyclohexyl dicarboxylic acid - dicarboxylic acid, hail An alicyclic dicarboxylic acid such as an alkanedicarboxylic acid; an acid such as an aromatic acid or an acid such as a diterpene acid or a h 4/1, 8/2, 6/2, 7-naphthalene or the like. These polyamines may be used singly or in combination of two or more kinds thereof to form a copolymerized polyamine. On nucleophilic 'for example, polyhexyl-(hetero-6), polyamino-deca-acid (diamine-resistant 4-methyl-January-based succinic acid (and Yulun-610), polyhexamethyleneamine妓 = polymer of alkane diacid (Nylon ~ 612), caprolactam / lauryl ^ 6 / 1 ^ Do not (Nylon - 6 / 12), hexene / silk ten - burnt acid copolymerization (Resistance - 己 醯 舰 舰 舰 舰 舰 / hexamethylene diamine adipic acid copolymer (resistant round ~ 6 / post), 6 / 66 / 〗 〖 hexamethylene diamine adipic acid /Aminododecanediic acid (Nylon-J, caprolactam / hexamethylenediaminediamine adipic acid / lauryl decylamine (Nylon 32 200900466 - 6/66/12), within Indoleamine/hexamethylenediaminediamine has been removed, and the base: alkanoic acid (valence 2) and other (co)polyamine resins can be used individually or in combination with 2's. Km 1 6' 66 ^ 610 ^ 12 and at least one aliphatic polyamine in nylon 612. Two «plasticizers" Taisu is a compound selected from esters and alkylamines. ··丁 π 本一甲驮一曱酉曰, o-benzed diacetate diethyl ester, o-benzoic acid, o-phthalic acid Λ Λ Γ: acid diisoindole 1, phthalate Acid di-trifluoroanthracene vinegar, butyl phthalate, butyl phthalate, phthalic acid, phthalic acid, ketone, phthalate, phthalate Alkyd butyl fatty acid tetrahydroortylene methyl hexanoic acid, etc. Diisobutyl adipate with / / ^ For example: adipic acid di ", adipic acid dibutyl hydrazine, r 曰, adipic acid di-positive 4-,: bis-diol vinegar, di-2-ethyl adipic acid. Acid di-n-halo-dimethoate-^ diisoindole S, adipic acid diisoindole vinegar, hexamethylene-ethyl Hex vinegar, ': acid-methyl ketone, dibutyl succinate, azelaic acid 222 succinic acid bis 2-ethyl hexyl vinegar, di-2-ethylhexyl mixed acid series, tanic acid double卩一 fAet f special binary saturated carboxylic acid ester; dibutyl fumarate, rich acid: ethyl vinegar vinegar; oleic acid butyl r;;; day, maleic acid double 2-ethylhexyl vinegar, etc. Unsaturated Sa-Dingsong A 7 曰 oil ^ isobutyl vinegar, ricinoleic acid butyl vinegar, vinyl lemon 酉 2 JS day and acetic acid 2-ethyl hexanate, etc. Single different ίί: Γ Purpose? Ίί体体甲" ' 4 4 -Dimethyl- 1,3 -pentanediol diisobutyrate, diethyl 33 200900466 diol diphenyl Acid, triethylene glycol di-2-ethylbutyrate, pentaerythritol monooleic acid vinegar, pentaerythritol monostearic acid g, pentaerythritol three;): vinegar, moringa oleic acid monoglyceride, 2-B Pyridyl triglyceride, triacetin, glyceryl tributyrate, etc. Specific examples of the metal sulphate S are, for example, trimethyl sulfonate, triethyl phosphate, tributyl phthalate, Tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, n-octyl diphenyl phosphate, nonylphenol diphenyl phosphate, triterpene phosphate, tris-xyl phosphate And 2-ethylhexyl diphenyl phosphate and the like. Specific examples of trimellitates such as tributyl trimellitate, tri-2-ethylhexyl trimellitic acid, tri-n-octyl trimellitate, and triisophthalic acid triisophoric acid An oxime ester, a triisodecyl trimellitate and a tri-methanol ester of trimellitic acid. Specific examples of hydroxybenzoic acid esters, for example, o- or p-hydroxybenzoic acid ethyl hexanoic acid, or o- or e-benzoyl hexyl hydrazine, o- or phenylbenzoic acid ethyl hydrazine, hydrazine or P-hydroxy acyl octyl octyl octyl acrylate, o- or p-hydroxybenzoic acid decyl dodecyl ester, o- or p-hydroxybenzoic acid methyl ester, o- or p-hydroxybenzoic acid butyl ester, o- or p-hydroxybenzamide 1 Benzoyl phthalate n-octyl, o- or _-p-benzoate hydrazine and o- or p-decyl decanoate. class. 'T-toluene-based decylamine or stupid calcined base> Specific examples of the fluorene-based sulfonyl group and amines, for example, Ν-ethyl-o-butyl decylamine, hydrazine-ethyl pair Butyl decyl sulfonate, 2-ethylhexyl _, N-ethyl-p-toluene acid 2-ethyl = acid ϊ Γ 2 ΐ 体 , , , , , , , , , , , , , , , , , , Among the plasticizers such as hydrazine, it is preferred to use: dibutyl phthalate? Terephthalic acid esters such as di-2-ethylhexyl phthalate, ketones such as hydroxyphosphoric acid butylamine and benzoin-2-ethylhexyl decylamine, the "flammable agent" The lock flame retardant 'can be used> odor-based flame retardant and triterpenoid flame retardant. Desertification and flame retardant, 34 200900466 Z!·/Smell self-chemical phenoxy tree, filling polycarbonate, simmering double cage, knee ethylene, brominated polyphenylene ether and so on. For the deuterated polyethylene and polybrominated dimorphic flame retardant, melamine diocyanide or the like can be used. a stomach 4, " cyanuric acid, melamine, ~ 40 = ^; relative to the fine security of the fine elastomer (10), the mass of the sage, preferably 1 〇 ~ 3 〇 υ υ 里 里 , 5 Flame-retardant additives, can be used to contain bismuth:: chemical recording, pentoxide recording, osmium tetroxide, recording i scale. 5 matter 'e.g., trioxane', is. .W2 parts by mass of resin, 〇. Quality Brominated flame retardants are used together to improve flame retardancy. ,know. In the magnetic powder used in the present invention, a powder such as a ferrite-based magnetic material such as a barium ferrite or a lysate such as a boron-based rare earth magnetic material can be used. Lead bismuth, condensed-iron - The pulverized powder of the present invention is used after being surface-treated for the purpose of improvement and rectification of the decane coupling agent, titanate coupling agent, and stearic acid: 丄: '" Brake Aluminum Coupling Agent (Example) Embodiments, and Examples and Comparative Ships (4) The present invention is not limited to these characteristics and is measured in the following manner. 1) Relative viscosity (7/0 (0.5 mass/capacity% cresol solution, 25t:)) Between the test drug grade cresol as a solvent, at a concentration of 5g/dm3, using an Ostwald viscometer at 25° C. Measurement 2) Bending test (bending elastic modulus): A test piece having a test piece size of 6.35 mm x 12.1 mm x 27 mm was used, and measurement was carried out in accordance with astm D790. 35 200900466 3) Impact strength (with Iz〇d notch): A test piece of size 3·18 mm×12·7_Xl27 mm was measured at 23 ° C according to the leg D256. 4) Melt flow rate: The pellet was measured using a pellet at a temperature of 235 t: and a load of 2160 g. 5) Hydrolysis resistance (1): A sample cut out from a 1 viscera 3 〇〇 厚度 厚度 厚度 JIS 3 dumbbell formed by injection molding, and placed in a stainless steel without overlapping The container is filled with about 2 liters of distilled water, and after being capped, the tensile tester is used, and the distance between the chucks is 5 〇 _ clamping, and the tensile test is performed by the knife, the tooth, and the speed, and the tensile test is performed. Sheet [=' with the following formula (1), _ extension fracture 100 (1) tensile fracture retention (%) = hydrolysis treatment of the sample elongation of the tensile elongation of the specimen to treat the tensile elongation of the specimen 牟 6) Extensibility: Use ASTM No. 1 tablet, according to ASTM D638 7) Evaluation of flammability: Order test. A test piece of 0.8 mmxl2. 7 mmxl27 mm was used, and it was measured according to the 'resin composition containing the magnetic powder'. Example of the sixth aspect: Comparative Example) The physical properties of the resin magnets are as follows: 5 and 8) The measurement of the mass change rate of the resin magnet composition, and the resin magnet pellets are formed into a thickness by a compression molding machine. The size of 25 faces xl5Q_ was used as a test piece. The sheet is cut from the hot air circulation type strange temperature tank of ◦C, and then the amount of the test is reduced by 120. To the dish, the sputum quality 9) Determination of the dimensional change rate of the resin magnet composition 36 200900466 The resin magnet pellet is made into a compression molding machine, and the sheet is cut to a size of 25_150_, as a test 2, :: 2: The material is changed from the hot air of t to the "thermometer" for 14 days, and then the size of the direction of the 120 is changed. Nw 剞 to / dish, measuring length 10) the surface of the resin magnet composition paste (stick This sheet is made into a sheet of thickness 压缩 by a compression molding machine, from which the size of 25mnixl50mm is cut out, as a test piece 1 = t hot air circulation type strange temperature tank 14th 'by finger contact test ^ surface," and ^ ^ Π) resin magnet molding products due to temperature changes, the turtle will be shown in Figure 1, diameter 30_, thickness 30 coffee The cylindrical shape of the shellfish is a resin magnet with a diameter of 4Qmni, and a resin magnet i gold test piece is produced, and after 1000 cycles of 3 cycles, the job magnetic field is confirmed; δ part 妓; Occurrence (4). Heat 12) Evaluation of hydrolysis resistance of resin magnetite molded article. As shown in Fig. 1, a cylindrical shape of a metal having a diameter of 30 and a thickness of 30 is a resin magnet of the total amount of 40_, and a resin magnet is produced. The test piece with gold and δ was soaked in warm water of 80 ° C for 2 hours, and the test piece was confirmed to have cracks. Printing [Production Example 1: Production of PAE1] Agitator was attached , thermometer, torque meter, pressure gauge, nitrogen inlet, , in the 7G liter pressure vessel of the whole device and the polymer outlet, add Ube; production (Mountain) 12-aminododecanoic acid 10. 354kg, adipic acid 1. 581kg, XY) (type ^ three embedded Segment polyether diamine (XTJ-542 manufactured by HUNTSMAN Co., Ltd. (in the formula (1), x is about 3, y is about 9, z is about 2), amine price: 1.94 meq/g) 7.452 kg, isophorone Diamine (trade name: VESTAMIN Ιρ〇) manufactured by DegUssa Co., Ltd. 612 612 kg, sodium hypophosphite 1 hydrate 6 g, and heat-resistant agent (TOMINOX917 manufactured by Jifu Pharmaceutical Co., Ltd.) 60 g. After the inside of the vessel was sufficiently substituted with nitrogen, nitrogen gas was used as 186. The liter/hour supply is adjusted to 0. 05 MPa, and the temperature is raised from room temperature to 23 (rc^ 200900466, and the pressure in the container is adjusted to 〇5 MPa, on the side of 2 After hourly polymerization, the polymer was obtained. After the end of the polymerization, the disruption was stopped, and the colorless transparent polymer in a molten state was taken out from the polymer outlet in the form of a rope, and about 15 kg of the pellet was obtained by water cooling. The obtained pellet was colorless and translucent. Strong and rich in rubber elasticity: compound, 7? r = l. 96. Person [manufacturing example 2: manufacture of PAE2] Thermometer, twisting, pressure gauge, I gas inlet, pressure adjusting device and polymer take out 70 liters of pressure vessel towel of CT, adding 12-aminododecanoic acid system of Ube Hiroshi (share) 7. 557kg, two Acid 1· 691kg, XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN Co., Ltd. (in the formula (1), x is about 3 is about 9, z is, about 2), and the amine price is 丄94meq/ g) 10,517 kg, isophora diamine (trade name: VESTAMIN IpD, manufactured by Degussa Co., Ltd.) 〇234 kg, sodium hypophosphite 1 hydrate, ρ and heat-resistant agent (TOMINOX917 manufactured by Jifu Pharmaceutical Co., Ltd.) 6 〇g. After the inside of the vessel was sufficiently substituted with nitrogen, the pressure in the vessel was adjusted to G, 〇 5 MPa, and the temperature was raised from room temperature to 230 X: while the nitrogen gas was supplied at 186 liters/hour. The pressure inside is adjusted to 〇〇5 MPa, and polymerization is carried out at 23 (rc for 4 hours, = to the polymer. After the end of the polymerization, the stirring is stopped, and the colorless transparent polymer in a molten state is taken out from the polymer outlet in a rope shape, after water cooling Granulation, about 15 kg of pellets were obtained. The pellet obtained was a colorless, translucent, tough, rubber-elastic polymer, β r = 1.96. [Manufacturing Example 3: Production of PAE3] , a thermometer, a torque meter, a pressure gauge, a nitrogen gas inlet, a pressure adjusting device, and a 7-liter liter pressure vessel for the polymer outlet, and added 12-aminodialic acid 〇 〇 37〇 from Ube Industries Co., Ltd. Kg, barium adipate · 585 kg, χγχ type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN Co., Ltd. (in the formula (1), X is about 3, 7 is about 9, 2 is about 2), amine Price: 1.9411^9/&) 7.4761^, 2,2,4—trimethyl-1,6-diaminohexane and 2, 4, 4 - Triterpene hydrazine, a mixture of 6-diamino hexane (manufactured by Degussa Co., Ltd., trade name: vestamin TMD) 0. 569 kg, sodium hypophosphite monohydrate 6 g and heat-resistant agent (T〇MIN manufactured by Jifu Pharmaceutical Co., Ltd.) 〇X917)6〇g. Container 38 200900466 仃, after the substitution, a biliary nitrogen gas is supplied at 186 liters / hour, the pressure of the - surface is adjusted to G. G5MPa, and it takes 3.5 hours to warm up from room temperature to 23 〇 The pressure in the vessel was adjusted to G·G5 MPa on the re-surface, and the polymer was applied to the polymer at 23 {rc for 4 hours. After the completion of the polymerization, the stirring was stopped, and the grafted red color was removed from the polymer outlet. The material is extracted, water-cooled, granulated, and the pellet is obtained. The obtained pellet is colorless, translucent and rubbery, and has a rubbery elasticity of 8.9 r = 1.98. m [manufacturing example 4: manufacture of PAE4] There are scrambler, thermometer, torque meter, pressure gauge, nitrogen inlet, pressure = adjustment, and the polymer is taken out of the pressure of 7G liters of π, adding Yubu Xingchan (share) 4 12 - amine base ten Diacid 1〇. 426kg, adipic acid 1. 582kg, χγχ type triblock polyether diamine (XTJ-542 made by HUNTSMAN) (in formula (1), χ It is about 3, y is about 9, Ζ is about 2), amine valence: 1.94 meq/g) 7. 436 kg, normane 1 amine (trade name: 井A, manufactured by Mitsui Chemicals Co., Ltd.) 0. 556 kg, sodium hypophosphite丄 Hydrate ^ and ^ heat agent (TOMINOX917 made by Jifu Pharmaceutical Co., Ltd.) 60g. After fully replacing the inside of the container with nitrogen, the nitrogen gas is supplied at 186 liters/hour, and the force in the container is adjusted to 0. 05 MPa. The temperature was raised from room temperature to 230 ° C for 5 hours, and the pressure in the vessel was adjusted to 0. 05 MPa, and polymerization was carried out at 23 (TC for 4.5 hours) to obtain a polymer. After the completion of the polymerization, the stirring was stopped, and the colorless transparent polymer in a molten state was taken out from the polymer outlet in a rope form, and granulated by water cooling to obtain pellets of about 15 kg. The pellets of 彳^到 are colorless, translucent, tough, rubber-filled polymer, [Production Example 5: Production of PAE5] with a scrambler, thermometer, torque meter, pressure gauge, nitrogen inlet, The pressure adjusting device and the 70 liter pressure vessel of the polymer outlet are added with a 12-aminododecanoic acid 7. 985 kg, adipic acid 1. U5 kg, χγχ type triblock polyether. Diamine (XTJ-559 manufactured by HUNTSMAN Co., Ltd. (in the formula (1), x is about 3 is about 14, z is about 2), amine price is 1.40 meq/g) l〇·900 kg, sodium hypophosphite} hydration 6 g and a heat-resistant agent (TOMINOX917 manufactured by Jifu Pharmaceutical Co., Ltd.) 60 g. After the inside of the container is fully replaced by the milk, the gas is supplied at 186 liters/hour, and the pressure in the crying 39 200900466 is reduced to 〇. 5 MPa, and the temperature is increased from room temperature to 5,000 rpm. 23〇. Then, the pressure in the vessel was adjusted to M5 MPa on the surface, and polymerization was carried out for 2 hours on 2 to obtain a polymer. After the completion of the polymerization, the lion is stopped, and the color transparent polymer of the smelting state is taken out from the polymer, and the water is cooled and granulated to obtain a pellet of about 15 丸 pfe, which is colorless, translucent and strong. Rubber-rich elastic polymer, 77r = [Manufacturing Example 6: Manufacturing of PAE6]
K 於附有授拌機、溫度計、扭崎、壓力計、氮氣導入口 力5周整裝置及聚合物取出口之公升之壓力容器中,添加 基十二酸(宇部興產(股)製)12.897kg及己二酸Q.嶋g(特 級)。將容H進行充分氮氣取代後,—面將氮氣以流速_ / 小時供給,一面缓慢地加熱。攪拌以速度2〇rpm進行。花 時,室溫升溫至24Gt:,於23GX:進行4小時聚合,合成耐綸 之寡聚物。 明 於此寡聚物中,加入聚四亞曱基 —,一一醇(BASF公司劁、K Addition of dodecanoic acid (Ube Hiroshi Co., Ltd.) to a pressure vessel equipped with a mixer, a thermometer, a torsion, a pressure gauge, a nitrogen inlet for 5 weeks, and a polymer outlet. 12.897kg and adipic acid Q.嶋g (special grade). After the volume H was sufficiently nitrogen-substituted, the nitrogen gas was supplied at a flow rate of _ / hour while slowly heating. Stirring was carried out at a speed of 2 rpm. At the time of flowering, the temperature was raised to 24 Gt at room temperature: at 23 GX: polymerization was carried out for 4 hours to synthesize a nylon-derived oligomer. In this oligomer, polytetradecyl--monohydric alcohol is added (BASF Corporation,
PolyTHFlGGG)6.197kg、四丁基鍅酸酯〇. 02(¾及抗氧化劑(^含 製藥製、商品名:TOMINOX917)0. 050kg。將容器内充分進行 代後,一面將氮氣以流速300公升/小時供給,一面緩慢加I: 拌以速度20rpm進行。花費3小時從室溫升溫至21(rc,於、^ ^ 加熱3小時,其次緩慢減壓,花費1小時成為5〇Pa,進行2 聚合後,再花30分鐘升溫,實施減壓,於23〇°c、約3〇pa淮一8、 小時聚合’並結束。其二欠,停止擾拌,對於聚合層内供 ^' 3 使壓力回到常壓。其次,從聚合物取出口將溶融狀態之^色^ ’ 聚合物以繩狀抽出,水冷後造粒,得到約13吆之九粒。…、巴恧明 得到之聚合物為聚_旨醯胺,丸粒為白色_且 之柔軟聚合物,7^=1.99。 田诼骖焯性 〔製造例7:PAE7之製造〕 於附有攪拌機、溫度計、扭矩計、壓力計、氮氣 力調整裝置及聚合物取出口之70公升之壓力容器中:^ ^ 丄乙〜胺 40 200900466 基十二酸(宇部興產(股)製)9.456kg及己二酸〇.徽以 級)。將容器充分氮氣取代後,一面將氮氣以流速3〇〇公升/、士 供給,一面緩慢加熱。攪拌以速度20rpm進行。花費3小你= g升溫至240 C,於23(TC進行4小時聚合,合成财綸12之寡^ 於此养聚物中,添加聚四亞甲基二醇(BASF公 752kg、四丁基錯酸_ 〇· G2Qkg及抗氧化= 製樂製、商品名:TGMINGX917)(). _kg。將容器内充分進行^田 將a氣⑽速3(30公升/小時供給’ 一面緩慢加熱:撥 、匕速度20rpm進行。花費3小時從室溫升溫至21〇。〇,於2 =3小時加熱,其次緩慢減壓,花費i小時使成5咖 ^時4合後,再花費30分料溫,實施減壓,於23()t S 合,f結束。其次,停止搜拌,對於聚合層内供給 二a日力回到常麼。其次,從聚合物取出口將炼融狀態之無 π ♦ s物以繩狀抽出,水冷後造粒,得到約之丸’、、、 之壬11,之聚合物為聚咖旨醯胺’丸粒為白色絲且富橡膠彈性 之柔軟聚合物,7^ = 2.04。 田体胗弹性 [第1態樣之實施例] 〔實施例A1〜A7、比較例A1〜A3〕 於1所示比例之混合物,使用叙筒徑40麵之雙軸捏揉機, 約乍太朽進H里揉,擠製為帶狀,於水槽冷卻後,使用造粒機, V 12 3020U 〇 X , 仏丰杈e 〇P,進灯拉引,得到内徑6mm、外徑8咖之管。 200900466 【表1】 组成(貧量X) 組成物: 匕评價結果 耐論 聚醯胺系彈 聚醯胺系彈 彎1曲 Izod 熔融流動速 水解處理後之 12 性體 性體之種類 彈性率 衝擊値 率 斷裂伸長保持率 (MPa) (J/m) (g/10min.) (¾) 實施例A1 80 20 PAE-1 960 280 17 > 100 實施例A2 70 30 「 PAE-1 820 305 17 > 100 實施例A3 80 20 PAE-2 890 350 17 > 100 實施例A4 70 30 PAE-2 765 430 18 > 100 實施例A5 80 20 PAE - 3 970 290 18 > 100 實施例A6 80 20 PAE-4 950 270 16 > 100 — 實施例A7 80 20 PAE - 5 900 250 16 > 100 比較例A1 100 0 ~ 1,450 60 17 > 100 ___-— 比較例A2 80 20 PAE-6 1000 285 18 75 ^ 比較例A3 1 — 80 20 —— PAE-7 ' 920 360 18 40 -----1 [第2態樣之實施例] 〔實施例B1〜B6、比較例B1〜B3〕PolyTHFlGGG) 6.197kg, tetrabutyl phthalate oxime. 02 (3⁄4 and antioxidant (including pharmaceutical manufacturer, trade name: TOMINOX917) 0. 050kg. After fully carrying out the container, nitrogen gas at a flow rate of 300 liters / When the supply is small, I slowly add I: and mix at a speed of 20 rpm. It takes 3 hours to raise the temperature from room temperature to 21 (rc, heating at 3 hours, then slowly depressurizing, taking 1 hour to become 5 〇Pa, and performing 2 polymerization. After that, it takes another 30 minutes to heat up, and the pressure is reduced. At 23 ° C, about 3 〇 pa Huai 8 , the hour polymerizes 'and ends. The second owes, stops the disturbance, and gives pressure to the polymerization layer. Returning to normal pressure. Secondly, the polymer in the molten state is taken out from the polymer outlet, and then granulated by water cooling to obtain about 9 grains of about 13 Å. Poly-p-amine, the pellet is white _ and the soft polymer, 7^=1.99. Field property [manufacturing example 7: manufacture of PAE7] with a mixer, thermometer, torque meter, pressure gauge, nitrogen The pressure adjusting device and the 70 liter pressure vessel of the polymer outlet are: ^ ^ 丄 B ~ amine 40 200900466 Dodecanoic acid (manufactured by Ube Industries Co., Ltd.) 9.456 kg and bismuth adipic acid. The emblem is graded. After the container is sufficiently substituted with nitrogen, the nitrogen gas is slowly heated while being supplied at a flow rate of 3 liters/liter. Stirring is carried out at a speed of 20 rpm. It takes 3 small you = g to heat up to 240 C, and is polymerized at 23 (TC for 4 hours, synthesizing oligosaccharide 12). In this polymer, polytetramethylene glycol (BASF) is added. 752kg, tetrabutyl acid _ 〇 · G2Qkg and antioxidant = kosher, trade name: TGMINGX917) (). _kg. Fully carry out the container in the field, a gas (10) speed 3 (30 liters / hour supply ' Slowly heating on one side: dialing and squeezing at 20 rpm. It takes 3 hours to raise the temperature from room temperature to 21 〇. 〇, heating at 2 = 3 hours, followed by slow decompression, taking i hours to make 5 coffees, 4 times, then It takes 30 minutes of material temperature to carry out the pressure reduction, and ends at 23 () t S, and ends with f. Secondly, the search is stopped, and the supply of the second layer of the polymer in the polymerization layer is returned to normal. Secondly, the outlet is taken from the polymer. There is no π in the fused state. ♦ The s objects are taken out in a rope shape, granulated after water cooling, and the granules of the granules are obtained. The phthalamide's pellet is a white silk and rubber-elastic soft polymer, 7^ = 2.04. Field 胗 elasticity [Example of the first aspect] [Examples A1 to A7, Comparative Examples A1 to A3] The mixture shown in the ratio is a double-axis kneading machine with a 40-gauge diameter. The 乍 乍 乍 H H 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 揉 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤 挤Feng Wei e 〇P, into the lamp pull, get the inner diameter of 6mm, the outer diameter of 8 coffee tube. 200900466 [Table 1] Composition (lean X) Composition: 匕Evaluation results 耐 醯 醯 系 弹 弹 弹 弹 弹 弹 Izod Melt flow rate hydrolysis treatment 12 species body elastic rate Impact rate rupture elongation retention (MPa) (J/m) (g/10min.) (3⁄4) Example A1 80 20 PAE-1 960 280 17 > 100 Example A2 70 30 "PAE-1 820 305 17 > 100 Example A3 80 20 PAE-2 890 350 17 > 100 Example A4 70 30 PAE-2 765 430 18 > 100 Example A5 80 20 PAE - 3 970 290 18 > 100 Example A6 80 20 PAE-4 950 270 16 > 100 - Example A7 80 20 PAE - 5 900 250 16 > 100 Comparative Example A1 100 0 ~ 1,450 60 17 > 100 ___- - Comparative Example A2 80 20 PAE-6 1000 285 18 75 ^ Comparative Example A3 1 - 80 20 - PAE-7 ' 920 360 18 40 -----1 [Example of the second aspect] [Examples B1 to B6, Comparative Examples B1 to B3]
將表2所示比例之混合物,使用缸筒彳£ 40mm之雙轴捏摞椴’ 於240。(:進行熔融捏揉,擠製為帶狀,以水槽冷卻後,使用造籼$幾 製作丸粒。將得到之丸粒,以射出成形製 彎曲試驗及衡擊忒 驗用=驗片。試驗片之評價結果如表1所示。 宇部興產(股)製耐論12 3020U° 棬 著,以控制尺寸,以plabor製管成形機,成形為管狀。 徑8刪之管。 乜準模予以冷卻並進行拉引,製造内徑6_、邓 42 200900466 【表2】 組成(質量幻 聚醯胺彈 性體之種 類 組成物之評價結果 而才論* 12 聚醯胺彈 性體 可塑 劑 可塑劑之種類 彎曲 彈性率 (MPa) Izod 衝擊値 (J/m) 水解處理後之 斷裂伸長保持 率 (%) 實施例B1 72 18 10 PAE-1 — 280 未斷裂 > 100 實施例B2 72 18 10 PAE -1 對羥基苯曱酸乙基 己酯 265 未斷裂 > 100 實施例B3 72 18 10 PAE-2 苯磺酸丁基醯胺 255 未斷裂 > 100 實施例B4 72 18 10 PAE-3 笨磺酸丁基醯胺 275 未斷裂 > 100 實施例B5 72 18 10 ΡΛΕ-4 苯磺酸丁基醯胺 285 未斷裂 > 100 實施例B6 72 '18 10 PAE-5 笨磺酸丁基醯胺 280 未斷裂 > 100 比較例B1 90 0 10 — 苯磺酸丁基醯胺 420 210 > 100 比較例B2 72 18 10 ΡΛΕ - 6 苯磺酸丁基醯胺 300 未斷裂 80 比較例B3 72 18 10 PAE-7 苯磺酸丁基醯胺 260 未斷裂 45 [第3態樣之實施例] 〔實施例C1〜C7、比較例C1〜C3〕 將表1所示比例之混合物’使用缸筒徑40麵之雙軸捏揉機, 於240 C進行溶融捏揉,擠製為帶狀,以水槽冷卻後,使用造粒機 製作丸粒。 【表3】 聚酿胺 彈性體 難燃劑 難燃助劑 寶曲 彈性率 (MPa) Izod 衝擊値 (J/m) 斷裂伸長 率 (%) 燃燒性 水解處理後之 斷裂伸長保持 率 _丨 n J· 1 - - (°/〇) __ 43 200900466 實施例C1 PAE1 100重量份 難燃劑A 20重量份 三氧化銻 8重量份 190 NB > 300 V-0 96 實施例C2 PAE1 100重量份 難燃劑B 20重量份 三氧化在弟 8重量份 205 NB > 300 V-0 95 實施例C3 PAE1 100重量份 難燃劑C 20重量份 無 175 NB > 300 V-2 > 100 實施例C4 PAE2 100重量份 難燃劑A 20重量份 三氧化銻 8重量份 120 NB > 300 V-0 93 實施例C5 PAE3 100重量份 難燃劑A 20重量份 三乳化録 8重量份 185 NB > 300 V-0 95 實施例C6 PAE4 100重量份 難燃劑A 20重量份 三氧化録 8重量份 200 NB > 300 V-0 94 實施例C7 PAE5 100重量份 難燃劑A 20重量份 三氧化錄 8重量份 195 NB > 300 V-0 94 比較例C1 PAE6 100重量份 難燃劑A 20重量份 二氧化録 8重量份 195 NB > 300 V-0 3 比較例C2 PAE6 100重量份 難燃劑C 20重量份 無 170 NB > 300 V-2 5 比較例C3 PAE7 100重量份 難燃劑A 20重量份 三氧化銻 8重量份 115 NB > 300 • V-0 2 難燃劑A :溴化苯氧基樹脂難燃劑(東都化成製YPB —43C) 難燃劑B :溴化聚碳酸酯難燃劑(Great Lakes製BC—58) 難燃劑C :三聚氱胺異三聚氰酸酯難燃劑 [第4態樣之實施例] 1 〔實施例D1〜D7、比較例D1〜D3〕 將表4所示比例之混合物,使用缸筒徑40mm之雙軸捏揉機, 於240°C進行熔融捏揉,擠製為帶狀,以水槽冷卻後,使用造粒機 製作丸粒。 【表4】 聚醯胺 聚醯胺 彈性體 難燃劑 難燃助劑 彎曲 彈性率 (MPa) 燃燒性 水解處理後之 斷裂伸長保持率 (%) 實施例D1 耐綸12 80重量份 PAE1 20重量份 難燃劑A 20重量份 三氧化銻 8重量份 980 V-0 98 44 200900466 實施例D2 财输12 80重量份 PAE1 20重量份 難燃劑B 20重量份 三氧化銻 8重量份 1050 V-0 97 實施例D3 耐綸12 80重量份 PAE1 20重量份 難燃劑C 20重量份 無 950 V-2 > 100 實施例D4 耐論12 80重量份 PAE2 20重量份 難燃劑A 20重量份 三氧化銻 8重量份 940 V-0 95 實施例D5 耐綸12 80重量份 PAE3 20重量份 難燃劑A 20重量份 三氧化銻 8重量份 960 V-0 97 實施例D6 财論12 80重量份 PAE4 20重量份 難燃劑A 20重量份 三氧化銻 8重量份 1000 V-0 96 實施例D7 而才論12 80重量份 PAE5 20重量份 難燃劑A 20重量份 P三氧化銻 8重量份 990 V-0 96 比較例D1 耐綸12 80重量份 PAE6 20重量份 難燃劑A 20重量份 三氧化銻 8重量份 1000 V-0 4 比較例D2 耐綸12 80重量份 一PAE6 20重量份 難燃劑C 20重量份 無 980 V-2 5 比較例D3 耐綸12 80重量份 PAE7 20重量份 難燃劑A 20重量份 三氧化銻 8重量份 940 V-0 3 難燃劑A :溴化苯氧基樹脂難燃劑(東都化成製YPB — 43C) 難燃劑B :漠化聚破酸酯難燃劑(Great Lakes製BC — 58) 難燃劑C :三聚氰胺三聚氰酸難燃劑(日產化學工業製MC610) [第5態樣之實施例] 〔實施例E1〜E8、比較例E1〜E4〕 將表5所示对綸12(宇部興產製3〇14U)及聚醯胺系熱塑性彈 進行熔融捏揉丸f 以混合器予以混合後,使用捏揉機 得到之』果如表5所示。又,將得到之丸粒成形, 【表5】j作為磁石使用。 45 200900466 '一 ''-γ- 黏 組成 结樹脂 (質量%) 組成物之評價结果 耐論 12 聚醯胺系 弹性體 聚酿胺系彈性 體之種類 寶曲 彈性率 (GPa) 8〇°C熱水處理 後之痕裂發生 實施例El 0 100 PAE-1 2.3 未發生 實施例E2 0 100 PAE-2 2.1 未發生 實施例E3 0 100 PAE-3 2.0 未發生 實施例E4 0 100 PAE-4 2.2 未發生 實施例E5 80 20 PAE-1 12.5 未發生 實施例E6 80 20 1 PAE-2 10.9 未發生 實施例E7 0 100 PAE-5 2.1 未發生 實施例E8 80 20 PAE-5 10.8 未發生 比較例E1 100 0 — 18.5 未發生 比較例E2 0 100 PAE-6 2.2 發生 比較例E3 — 0 100 PAE —7 2.0 發生 比較例E4 —1 1 80 20 PAE-6 12.9 發生A mixture of the ratios shown in Table 2 was used, and a biaxial pinch of a cylinder of 40 mm was used at 240. (: Melt kneading, extruding into a belt shape, cooling with a water tank, using pellets to make pellets. The pellets obtained are obtained by injection molding bending test and weighing test = test. The evaluation results of the film are shown in Table 1. Ube Hiroshi (share) system resistance theory 12 3020U ° 棬 ,, to control the size, plabor tube forming machine, formed into a tubular shape. Cooling and pulling, manufacturing inner diameter 6_, Deng 42 200900466 [Table 2] Composition (Quality phantom polyamide elastomer type composition evaluation results only * 12 Polyamide elastomer plasticizer plasticizer type Flexural modulus (MPa) Izod impact enthalpy (J/m) Elongation at break (%) after hydrolysis treatment Example B1 72 18 10 PAE-1 - 280 Unbroken > 100 Example B2 72 18 10 PAE -1 Ethylhexyl p-hydroxybenzoate 265 unbroken > 100 Example B3 72 18 10 PAE-2 Butyl decyl benzene sulfonate 255 Unbroken > 100 Example B4 72 18 10 PAE-3 Base amine 275 unbroken > 100 Example B5 72 18 10 ΡΛΕ-4 Benzene sulfonate butyl hydrazine 285 Unbroken > 100 Example B6 72 '18 10 PAE-5 phenyl sulfonamide 280 uncracked > 100 Comparative Example B1 90 0 10 - butyl decyl benzene sulfonate 420 210 > 100 Comparative Example B2 72 18 10 ΡΛΕ - 6 butyl decyl benzene sulfonate 300 unbroken 80 Comparative Example B3 72 18 10 PAE-7 Butyl decyl benzene sulfonate 260 Not broken 45 [Example of the third aspect] [Examples C1 to C7, Comparative Examples C1 to C3] The mixture of the ratios shown in Table 1 was melted and kneaded at 240 C using a biaxial kneading machine having a cylinder bore of 40 faces, and extruded into a belt shape, and then cooled by a water tank. Pellet is produced using a granulator. [Table 3] Polyurethane elastomer flame retardant, flame retardant, Baoqu elastic modulus (MPa) Izod impact enthalpy (J/m) Elongation at break (%) After flammability hydrolysis treatment Elongation at break elongation_丨n J· 1 - - (°/〇) __ 43 200900466 Example C1 PAE1 100 parts by weight of flame retardant A 20 parts by weight of antimony trioxide 8 parts by weight 190 NB > 300 V-0 96 Example C2 PAE1 100 parts by weight of flame retardant B 20 parts by weight of trioxide in 8 parts by weight of 205 NB > 300 V-0 95 Example C3 PAE1 100 parts by weight Flame Retardant C 20 parts by weight without 175 NB > 300 V-2 > 100 Example C4 PAE2 100 parts by weight of flame retardant A 20 parts by weight of antimony trioxide 8 parts by weight 120 NB > 300 V-0 93 Example C5 PAE3 100 parts by weight of flame retardant A 20 parts by weight triple emulsified 8 parts by weight 185 NB > 300 V-0 95 Example C6 PAE4 100 parts by weight of flame retardant A 20 parts by weight of oxidized 8 parts by weight 200 NB > 300 V-0 94 Example C7 PAE5 100 parts by weight of flame retardant A 20 parts by weight of trioxide 8 parts by weight 195 NB > 300 V-0 94 Comparative Example C1 PAE6 100 parts by weight of flame retardant A 20 parts by weight Oxidation record 8 parts by weight 195 NB > 300 V-0 3 Comparative Example C2 PAE6 100 parts by weight of flame retardant C 20 parts by weight without 170 NB > 300 V-2 5 Comparative Example C3 PAE7 100 parts by weight of flame retardant A 20 Parts by weight of antimony trioxide 8 parts by weight 115 NB > 300 • V-0 2 Flame retardant A: brominated phenoxy resin flame retardant (YPB - 43C manufactured by Tohto Kasei Co., Ltd.) Flame retardant B: brominated polycarbonate Flame Retardant (BC-58, manufactured by Great Lakes) Flame Retardant C: Trimeric amide isocyanate flame retardant [Example of the fourth aspect] 1 [Examples D1 to D7, Comparative Example D1~ D3 The mixture ratio shown in Table 4, the use of the cylinder diameter 40mm biaxial kneading machine, melt-kneaded at 240 ° C, extruded as a ribbon, cooled in a water tank, pellets were produced by using a pelletizer. [Table 4] Polyamide polyamine elastomer flame retardant flame retardant auxiliary bending elastic modulus (MPa) elongation at break retention after combustion hydrolysis treatment (%) Example D1 nylon 12 80 parts by weight PAE1 20 weight Incombustant A 20 parts by weight of antimony trioxide 8 parts by weight 980 V-0 98 44 200900466 Example D2 Financial 12 80 parts by weight PAE1 20 parts by weight of flame retardant B 20 parts by weight of antimony trioxide 8 parts by weight 1050 V- 0 97 Example D3 Nylon 12 80 parts by weight PAE1 20 parts by weight of flame retardant C 20 parts by weight without 950 V-2 > 100 Example D4 Resistance 12 80 parts by weight PAE2 20 parts by weight of flame retardant A 20 parts by weight Antimony trioxide 8 parts by weight 940 V-0 95 Example D5 Nylon 12 80 parts by weight PAE3 20 parts by weight of flame retardant A 20 parts by weight of antimony trioxide 8 parts by weight 960 V-0 97 Example D6 Financial 12 80 Weight Part of PAE4 20 parts by weight of flame retardant A 20 parts by weight of antimony trioxide 8 parts by weight 1000 V-0 96 Example D7 and only 12 80 parts by weight of PAE5 20 parts by weight of flame retardant A 20 parts by weight of P3 ruthenium 8 weight Parts 990 V-0 96 Comparative Example D1 Nylon 12 80 parts by weight PAE6 20 parts by weight of flame retardant A 20 parts by weight of antimony trioxide 8 Dosage 1000 V-0 4 Comparative Example D2 Nylon 12 80 parts by weight a PAE6 20 parts by weight of flame retardant C 20 parts by weight without 980 V-2 5 Comparative Example D3 Nylon 12 80 parts by weight PAE7 20 parts by weight of flame retardant A 20 parts by weight of antimony trioxide 8 parts by weight 940 V-0 3 flame retardant A: brominated phenoxy resin flame retardant (YPB - 43C manufactured by Tohto Kasei Co., Ltd.) Flame retardant B: desertification polycondensate is difficult to burn Agent (BC-58, manufactured by Great Lakes) Flame retardant C: Melamine cyanuric acid flame retardant (MC610 manufactured by Nissan Chemical Industries Co., Ltd.) [Example of the fifth aspect] [Examples E1 to E8, Comparative Examples E1 to E4 】 The melted kneading pellets f, which are shown in Table 5, are melted and kneaded by a mixer, and then mixed by a mixer, and then obtained by using a kneading machine. . Further, the obtained pellets were molded, and [Table 5] j was used as a magnet. 45 200900466 'One''-γ- Adhesive composition resin (% by mass) Evaluation result of composition No. 12 Polyamide type elastomeric polyamine-based elastomer type Baoqu elastic modulus (GPa) 8〇°C Trace cracking after hot water treatment Example El 0 100 PAE-1 2.3 Example E2 did not occur 0 100 PAE-2 2.1 Example E3 did not occur 0 100 PAE-3 2.0 Example E4 0 100 PAE-4 2.2 did not occur Example E5 did not occur. 80 PAE-1 12.5 Example E6 did not occur 80 20 1 PAE-2 10.9 Example E7 did not occur 0 100 PAE-5 2.1 Example E8 did not occur 80 20 PAE-5 10.8 Comparative Example E1 did not occur 100 0 — 18.5 Comparative Example E2 0 100 PAE-6 2.2 Comparative Example E3 — 0 100 PAE —7 2.0 Comparative Example E4 —1 1 80 20 PAE-6 12.9 Occurred
\ [第6態樣之實施例] 〔實施例F1〜F9、參考例pi、比較例F1〜F3〕 谢6所示組成之耐綸12(宇部興產製3014U)及聚醯胺系熱 1°«!5 传到之丸粒之評價蛀果 凡叹 得到之成形物,可作為;表6所示。又’將得到之丸粒成形, 【表6】 七使用。[Examples of the sixth aspect] [Examples F1 to F9, Reference Example pi, Comparative Examples F1 to F3] Nylon 12 (made by Ube Industries, Ltd. 3014U) and polyamine-based heat 1 °«!5 The evaluation of the pellets passed to the capsule is the result of the sigh, and can be used as shown in Table 6. Further, the obtained pellets were formed, and [Table 6] was used.
46 200900466 質量% 質量 % 質量 % (%) (%> 實施例F1 81 PAE1 9 10 對羥基苯甲酸 2-乙基癸酉旨 0.21 0.12 無 未發生 未發生 實施例F2 81 PAE1 9 10 對羥基苯甲酸 2-己基癸酯 0. 05 0.07 無 未發生 未發生 實施例F3 81 PAE1 9 10 對羥基苯曱酸 2-癸基癸酯 0.08 0.06 無 未發生 未發生 實施例F4 81 PAE1 9 10 對羥基苯甲酸 2-十二烷基十二 §1 0.07 0.07 無 未發生 未發生 實施例F5 81 PAE2 9 10 對羥基苯甲酸 2-乙基癸酯 0. 19 0. 10 無 未發生 未發生 實施例F6 81 PAE3 9 10 對羥基笨甲酸 2-乙基癸酯 0.20 0, 11 無 未發生 未發生 實施例F7 81 PAE4 9 10 對羥基苯甲酸 2-乙基癸酯 0.22 0.12 無 未發生 未發生 實施例F8 81 PAE5 9 10 對羥基笨甲酸 2-乙基癸酯 0.21 0. 12 無 未發生 未發生 實施例F9 81 PAE1 9 10 正丁基苯磺醯胺 1.02 0.33 有 未發生 未發生 參考例F1 90 PAE1 10 — 無 — — 無 發生 未發生 比較例F1 81 PAE6 9 10 對羥基苯甲酸 2-乙基己酯 0.69 0.26 有 未發生 未發生 比較例F2 90 — 0 10 對羥基苯曱酸 2-辛基辛酯 0.06 0.08 無 發生 未發生_ 比較例F3 81 PAE7 9 10 對羥基苯甲酸 2-乙基癸酯 0.20 0.08 無 未發生 發生 (產業利用性) 依照本發明第1態樣,可提供一種樹脂組成物,對於基礎之 熱塑性樹脂之熔融黏度不帶來影響、不使成形性變化,能改良柔 軟性或耐衝擊性,而且财水解性優異。又,此樹脂組成物,強韋刃 性、熔融成形性、低溫柔軟性、耐衝擊性優異,而且耐水解性優 異。 依照本發明第2態樣,可提供一種含可塑劑之樹脂組成物, 強韋刃性、熔融成形性、低溫柔軟性、耐衝擊性優異,而且对水解 性優異" 47 200900466 播二第3態樣’可提供—種難燃性之樹脂組成物,即 你^=μ·ΙΓ、、下之苛除環境下中亦不因水解使樹脂劣化’能維持 作為弹性體之優異性能。 Μ守 發明第4態# ’能提供—種難燃性之樹脂組成物,即 ;,尚/燕下之兮酷環境下中亦不因水解使樹脂劣化,能維 作為樹脂之優異性能。 寸 日本發明第5態樣,可提供一種樹脂磁石構件,即使為了 提升樹脂磁石之磁性特性’將磁性粉末之含量增加,成形品亦不 易產生破裂,為柔軟的,且於苛酷環境下,尤其高溫高濕下不因 水解導致黏結樹脂劣化,即使於高溫高濕下中亦不發生龜裂。 依照本發明第6態樣,可提供一種優異的樹脂磁石構件,藉 由使用本發明之樹脂組成物,即使於高溫環境之尺寸變化亦少, 將金屬構件插入而成之樹脂磁石構件中,即使在冬季屋外之低溫 環土兄及夏季屋外及/或組裝在機器内之發熱所致高溫環境之實際 使用環境下,經過反複溫度變化,不發生尺寸變化或龜裂。又, 可提供一種樹脂磁石構件,即使於高溫高濕下中亦不因水解導致 黏結樹脂劣化’即使於南溫尚濕下中亦不發生龜裂。 【圖式簡單說明】46 200900466 Quality % Mass % Mass % (%) (%) Example F1 81 PAE1 9 10 2-Hydroxybenzoic acid 2-ethyl oxime 0.21 0.12 No occurrence did not occur Example F2 81 PAE1 9 10 Hydroxybenzene 2-hexyl decyl formate 0. 05 0.07 No occurrence did not occur Example F3 81 PAE1 9 10 2-Hydroxybenzhydranoate 0.08 0.06 No occurrence did not occur Example F4 81 PAE1 9 10 Hydroxybenzene Formic acid 2-dodecyl twelve §1 0.07 0.07 No occurrence did not occur Example F5 81 PAE2 9 10 2-ethyl decyl p-hydroxybenzoate 0. 19 0. 10 No occurrence did not occur Example F6 81 PAE3 9 10 2-hydroxydecyl p-hydroxybenzoate 0.20 0, 11 None did not occur Example F7 81 PAE4 9 10 2-ethyldecyl p-hydroxybenzoate 0.22 0.12 No occurrence did not occur Example F8 81 PAE5 9 10 p-Hydroxybenzoic acid 2-ethyldecyl ester 0.21 0. 12 None did not occur Example F9 81 PAE1 9 10 n-Butylbenzenesulfonamide 1.02 0.33 No occurrence of reference Example F1 90 PAE1 10 — None - No occurrence has not occurred Comparative Example F1 81 PAE6 9 10 Pair 2-ethylhexyl benzoate 0.69 0.26 No occurrence occurred Comparative Example F2 90 — 0 10 2-octyloctyl p-hydroxybenzoate 0.06 0.08 No occurrence occurred _ Comparative Example F3 81 PAE7 9 10 2-ethyl decyl benzoate 0.20 0.08 No occurrence (industrial use) According to the first aspect of the present invention, a resin composition can be provided which does not affect the melt viscosity of the base thermoplastic resin and does not form The change in properties can improve the flexibility and impact resistance, and is excellent in chemical hydrolysis. Further, the resin composition is excellent in strong blade edge, melt moldability, low-temperature flexibility, and impact resistance, and is excellent in hydrolysis resistance. According to a second aspect of the present invention, a resin composition containing a plasticizer can be provided, which is excellent in sharp edge property, melt moldability, low temperature flexibility, and impact resistance, and is excellent in hydrolysis property" 47 200900466 The sample can provide a flame retardant resin composition, that is, you can maintain the excellent performance as an elastomer by reducing the resin in the environment under the harsh environment. Μ 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明In the fifth aspect of the Japanese invention, a resin magnet member can be provided, and even if the magnetic property of the resin magnet is increased to increase the magnetic powder content, the molded article is less likely to be broken, which is soft and in a harsh environment, especially high temperature. Under high humidity, the binder resin is not deteriorated by hydrolysis, and cracking does not occur even under high temperature and high humidity. According to the sixth aspect of the present invention, it is possible to provide an excellent resin magnet member by using the resin composition of the present invention, even if the dimensional change in a high-temperature environment is small, and the metal member is inserted into the resin magnet member, even if In the actual use environment of the low temperature ring outside the winter house and the summer house and/or the high temperature environment caused by the heat generated in the machine, the dimensional change or crack does not occur after repeated temperature changes. Further, it is possible to provide a resin magnet member which does not cause deterioration of the binder resin due to hydrolysis even under high temperature and high humidity, and does not cause cracking even in the case of wetness in the south. [Simple description of the map]
圖1顯示將棒狀金屬構件插入成形而成樹脂磁石構件概略圖。 圖2顯示將圓柱狀金屬構件插入成形而成之樹脂磁石構件概 略圖。 【主要元件符號說明】 1:金屬構件 2:樹脂磁石 3:金屬構件 4:樹脂磁石 48Fig. 1 is a schematic view showing a resin magnet member in which a rod-shaped metal member is inserted and molded. Fig. 2 is a schematic view showing a resin magnet member in which a cylindrical metal member is inserted and formed. [Description of main component symbols] 1: Metal member 2: Resin magnet 3: Metal member 4: Resin magnet 48
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JP5979733B2 (en) | 2014-07-24 | 2016-08-31 | 住友金属鉱山株式会社 | Bonded magnet composition, bonded magnet, and integrally molded part |
JP2016204490A (en) * | 2015-04-21 | 2016-12-08 | 宇部興産株式会社 | Composition and molded article consisting of the same |
WO2016181471A1 (en) * | 2015-05-11 | 2016-11-17 | 株式会社カネカ | Polyamide elastomer, medical device, and method for producing polyamide elastomer |
WO2016181472A1 (en) * | 2015-05-11 | 2016-11-17 | 株式会社カネカ | Polyamide elastomer, medical device, and method for producing polyamide elastomer |
TW201817771A (en) * | 2016-09-26 | 2018-05-16 | 日商日立化成股份有限公司 | Method for producing polyamide |
WO2022075180A1 (en) * | 2020-10-05 | 2022-04-14 | 宇部興産株式会社 | Polyamide resin composition |
WO2023181711A1 (en) * | 2022-03-23 | 2023-09-28 | Ube株式会社 | Polyamide resin composition, magnetic material resin composite material and molded article thereof |
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JPS6274643A (en) * | 1985-09-30 | 1987-04-06 | 東レ株式会社 | Polyamide elastomer laminated structure |
JPS6381801A (en) * | 1986-09-25 | 1988-04-12 | Sumitomo Bakelite Co Ltd | Plastic magnet composition |
JPS63173302A (en) * | 1987-01-13 | 1988-07-16 | ダイセル・ヒユルス株式会社 | Polymer temperature sensitive unit |
DE3909215A1 (en) * | 1989-02-11 | 1990-08-23 | Bayer Ag | POLYETHERAMIDE MELT ADHESIVES |
JP4056912B2 (en) * | 2003-03-19 | 2008-03-05 | ダイセル・デグサ株式会社 | Polyamide resin composition and bonded magnet |
JP4161801B2 (en) * | 2003-05-27 | 2008-10-08 | 宇部興産株式会社 | Polyamide resin composition, resin magnet, resin magnet parts |
JP4106655B2 (en) * | 2003-05-27 | 2008-06-25 | 宇部興産株式会社 | Plasticizer-containing resin composition and molded product |
JP4106656B2 (en) * | 2003-05-27 | 2008-06-25 | 宇部興産株式会社 | Flame retardant-containing resin composition and molded article |
JP4144430B2 (en) * | 2003-05-27 | 2008-09-03 | 宇部興産株式会社 | Polyamide resin composition, molded product, resin magnet parts |
JP2004352793A (en) * | 2003-05-27 | 2004-12-16 | Ube Ind Ltd | Polyamide-based elastomer |
JP4161802B2 (en) * | 2003-05-27 | 2008-10-08 | 宇部興産株式会社 | Polyamide composition |
JP4106654B2 (en) * | 2003-05-27 | 2008-06-25 | 宇部興産株式会社 | Resin composition |
WO2007145324A1 (en) * | 2006-06-16 | 2007-12-21 | Ube Industries, Ltd. | Polyether polyamide elastomer |
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