200904898 九、發明說明： 【發明所屬之技術領域】 本發明係剛性高、焊接強度優異之聚醯胺樹脂組成物， .且係關於將成形薄壁成形品時之成形品的翹曲降低的玻 .璃纖維強化聚醯胺樹脂組成物。 【先前技術】 隨著近年來之商用機器•電子機器之小型化，外殼、底 板正向著薄壁化方向發展。自先前，為了提高樹脂^成物 之物性，係調配入具有圓形剖面之玻璃纖維，而對其進行 強化。然而，玻璃纖維具有向樹脂之流動方向進行配向的 性質’其會產生強度之異向性，而導致翹曲。為了改善此 情況，有調配入滑石粉或雲母等板狀填充料，來降低異向 性之方法。但是，此方法亦存在雖可 機械物性之問題。 。㈣但會降低 專利文獻！中，作為機械物性之降低較少且可 ==曲的方法，揭示有將扁平形狀之玻璃纖維盘且 有通书之圓形剖面的玻璃纖維進行混合，酿胺 纖維，其谭接強度亦較低，作為成形薄壁成形品== 成物’並無兼具充分之機械物性與仙曲性 2 聚醯胺樹脂組成物。 坪接強度之 專利文獻1 :曰本專利特λ 寻利特開平^-219026號公報 【發明内容】 & (發明所欲解決之問題） 97111824 200904898 本發明之目的在於提供一種聚醯胺樹脂組成物，該聚酿 胺樹脂組成物作為成形如電子機ϋ之外殼、底板之薄壁成 形品的樹脂組成物，兼具充分之機械物性與低翹曲性、 接強度。 ％ » (解決問題之手段） 本發明者等為解決此種課題而進行潛心研究，結果發 現：特定之樹脂組成物可解決上述課題，而完成了本發明。 即’本發明之要旨如下所述。 γλ 〇)一種玻璃纖維強化聚醯胺樹脂組成物，其係相對於 聚醯胺樹脂組成物100質量份，調配入1分子中具有2個 以上之官能基之有機化合物〇. 〇5〜4. 0質量份而成者，該 聚酿胺樹脂組成物係將使用烏別洛德型黏度計，以96質 量％之硫酸作為溶媒，於溫度25。(：、濃度1 g/dl之條件 下進行測定時之相對黏度為1. 5〜4. 0的聚醯胺樹脂30〜 80質量％、及具有長徑/短徑之比值為1. 5〜1 〇之扁平剖 面之扁平玻璃纖維20〜70質量％混合而成者，該有機化合 I 物係選自三羥甲基丙烷聚環氧丙基醚、聚甘油聚環氧丙基 醚、三環氧丙基異氰尿酸酯、苯乙烯/馬來酸酐共聚物中 之1種以上之有機化合物。 (2) —種玻璃纖維強化聚醯胺樹脂組成物，其中，（〇 之聚醯胺樹脂係選自尼龍6、尼龍66、尼龍11中之1種 之聚醯胺。 (3) —種玻璃纖維強化聚醯胺樹脂組成物，其中，（1) 之扁平玻璃纖維係具有葫蘆形、繭形、長圓形、橢圓形、 97111824 7 200904898 矩形中之任一個異形剖面形狀的玻璃纖維，且係利用選自 石夕燒偶合劑、鈦系偶合劑、氧化結系偶合劑中之1種以上 之偶合劑進行表面處理而成。 (4) 一種樹脂成形品，其係對如（1)〜（3)之玻璃纖維強 化聚醯胺樹脂組成物進行成形而成。 (發明效果）。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Glass fiber reinforced polyamide resin composition. [Prior Art] With the miniaturization of commercial machines and electronic machines in recent years, the outer casing and the bottom plate are moving toward a thin wall. Since the prior art, in order to improve the physical properties of the resin, it has been blended into a glass fiber having a circular cross section and strengthened. However, the glass fiber has a property of aligning the flow direction of the resin, which causes anisotropy of strength and causes warpage. In order to improve this situation, it is possible to reduce the anisotropy by blending a plate-like filler such as talc or mica. However, this method also has problems with mechanical properties. . (4) But it will reduce the patent literature! In the method of reducing the mechanical properties and reducing the amount of mechanical properties, it is disclosed that a glass fiber disc having a flat shape and a circular cross section of the book is mixed, and the amine fiber has a tantalum strength. It is low, and it is a composition of a thin-walled molded product == a product which does not have sufficient mechanical properties and a succulent 2-polyamide resin. Patent Document 1: Patent Application No. PCT Patent Application Laid-Open Patent Publication No. Hei No. H-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- The composition of the polyamine resin is a resin composition for forming a thin-wall molded article such as an outer casing of an electronic casing or a bottom plate, and has sufficient mechanical properties, low warpage, and joint strength. %»» The present inventors have conducted intensive studies to solve such a problem, and as a result, have found that a specific resin composition can solve the above problems, and completed the present invention. That is, the gist of the present invention is as follows. Γλ 〇) A glass fiber reinforced polyamide resin composition which is formulated with an organic compound having two or more functional groups in one molecule with respect to 100 parts by mass of the polyamide resin composition. 〇5~4. In the case of 0 parts by mass, the polyamine resin composition is a Ubbelode type viscometer, and 96% by mass of sulfuric acid is used as a solvent at a temperature of 25. 5〜 The ratio of the long diameter / short diameter is 1. 5~4. The ratio of the long diameter / short diameter is 1. 5~4. 1 : The flat glass fiber of the flat profile of 〇 is mixed with 20 to 70% by mass, and the organic compound I is selected from the group consisting of trimethylolpropane polyepoxypropyl ether, polyglycerol polyepoxypropyl ether, and tricyclic ring. One or more organic compounds of oxypropyl isocyanurate and styrene/maleic anhydride copolymer. (2) A glass fiber reinforced polyamide resin composition, wherein (polyamide resin) A polyamine which is one selected from the group consisting of nylon 6, nylon 66, and nylon 11. (3) A glass fiber reinforced polyamide resin composition, wherein the flat glass fiber of (1) has a gourd shape and a enamel shape. Shape, oblong, elliptical, 97111824 7 200904898 A glass fiber having a profiled cross-sectional shape of any one of a rectangular shape, and one or more selected from the group consisting of a ceramsite coupling agent, a titanium coupling agent, and an oxidative coupling agent The coupling agent is surface-treated. (4) A resin molded article, such as (1) to (3) The glass fiber is reinforced with a polyamide resin composition for forming. (Invention effect)
本發明之聚醯胺樹脂組成物，於成形如電子機器之外 设、底板之薄壁成形品時，兼具充分之機械物性與低魅曲 性、焊接強度，因此，可獲得尺寸穩定性優異且堅固之樹 脂成形品’於產業上之利用價值極高。 【實施方式】 以下，對本發明進行詳細說明。 本發明所使用之聚醯胺樹脂可為主鏈中具有醯胺鍵之 聚合物：聚ε-癸醯胺（尼龍6)、聚丁二醯己二胺（尼龍 46)、聚己二醯己二胺（尼龍66)、聚己二醯癸二胺（尼龍 610)、聚己二醯十二烷二胺（尼龍612)、聚十一烷醯己二 胺（尼龍116)、聚十-烧醯胺（尼龍⑴、聚十二烧醢胺（尼 龍12)、聚己二酿間#二胺（尼龍61)、聚己二酿對苯二胺 (尼龍—6Τ)、聚壬二輯苯二胺（尼龍9T)、聚間苯二甲醯 己一fe (尼龍MXD6)及含有該蓉由+ s η ν 负忑寺中之至少2種不同的聚醯 胺成分的聚醯胺共聚物，或者兮 ^ ^ 飞耆該等之混合物等。較佳的聚 醢胺樹脂可列舉：尼龍6、尼蒱 .^ ^ + ^ 庀龍66、尼龍11、尼龍12、 尼龍6T，最佳為尼龍6、尼龍66、尼龍u。 本發明所使狀輯胺樹㈣分子量（相對減），較佳 97111824 200904898 為使用烏別洛德型黏度計，以96質量％之硫酸 黏度為i.5〜4.0,更佳I u〜35。若 對 1〜3.5,可確保適度之樹脂流動，又，可 .之轉印優異’且外觀經改良之成形品。又，可獲；告具 焊接強度。相對黏度未達丨.5者，存在 ^、备之 差的傾向。相對黏度變得越大，流動性變得越差，== 二之時間變長且模具轉印性降低等問題，進 形品之優異外觀。於相對黏度超過U之情 况下，存在成形性、焊接強度顯著降低 變得越大，流動前端之樹脂溫度降得越低 』= 之樹脂之接合變差而使焊接強度降低的傾向。存料接^ 之=現Γ胃焊接’尤其指對樹脂進行射出成形時所引起 M U ’且係於模具㈣融樹㈣流，而於融著部分 良現象。若為了於成形品中形成中空部等， ;會再或芯等，則於熔融樹脂迴繞後，此部分 上之門生谭接線。又，於需要設置2個以 [之情況下，無法避免焊接線之產生。 蓉接ΐ因融著不良而損害外觀’或顯著降低機械特性 樹月匕及模善該等不良現象’必需實施⑴提高炼融 之位曰署2 ⑵提高射出壓力及射出速度’將閉極 -悝 里大小等改變’等處理。所謂焊接強度，表 不焊接邛之機械特性（例如彎曲彈性率）。 本發月之破璃纖維可藉由公知之玻璃纖維之製造方法 97111824 200904898 而製造，其可使用如下之形態：將為了提高與基質樹脂之 密著性、均勻分散性而調配入矽烷偶合劑、鈦系偶合劑、 氧化錯系偶合劑等偶合劑中之至少1種，及皮膜形成劑等 而成的樹脂，藉由適合其之公知的上漿劑進行上漿，再聚 集經上漿之玻璃纖維股繩，將其切斷為一定長度之切股的 形態。 於本發明中，此玻璃纖維之剖面形狀為扁平的扁平破璃 纖維。所謂扁平剖面，表示與玻璃纖維之長度方向垂直之 方向的切面形狀並非圓形，而為異形之形狀的情況。係指 具有定義為通過中心點之最大長度的長徑、定義為通過中 心點之最小長度的短徑的形狀。作為此種形狀，扁平剖面 可例示萌蘆形、繭形、長圓形、橢圓形、矩形或該等之類 ，形狀’例如於賴形中，根據上述定義，長徑係相當於 1產之兩個頭於凸部方向上的距離，短徑係相當於萌廬之 中間細的部分於凹部方向上的距離。When the polyamine resin composition of the present invention is formed into a thin-walled molded article other than an electronic device and a bottom plate, it has sufficient mechanical properties, low temperament and weld strength, and therefore excellent dimensional stability is obtained. And the solid resin molded product is extremely valuable in industrial use. [Embodiment] Hereinafter, the present invention will be described in detail. The polyamidamide resin used in the present invention may be a polymer having a guanamine bond in the main chain: poly-ε-decylamine (nylon 6), polybutylene diamine (nylon 46), polyhexamethylene Diamine (nylon 66), polyhexamethylenediamine (nylon 610), polyhexamethylenediamine diamine (nylon 612), polyundecylene hexamethylenediamine (nylon 116), poly-sinter Indoleamine (nylon (1), polydodecanamide (nylon 12), polyhexanol #diamine (nylon 61), polyhexamethylene p-phenylenediamine (nylon-6Τ), polyfluorene II Amine (nylon 9T), poly(m-xylylene hexanyl)-fee (nylon MXD6), and a polyamidamide copolymer containing at least two different polyamines in the 由 忑 忑 忑 temple, or 兮^ ^ Fly the mixture of these, etc. Preferred polyamine resins are: nylon 6, nicotine, ^ ^ + ^ 庀 66 66, nylon 11, nylon 12, nylon 6T, preferably nylon 6, nylon 66, nylon u. The molecular weight (relatively reduced) of the amine tree (4) of the present invention is preferably 97111824 200904898 using a Ubbelode type viscometer, and having a sulfuric acid viscosity of 96% by mass of i.5 to 4.0, more preferably I u~35. If it is 1 to 3.5, it can ensure the proper flow of the resin, and it can transfer the molded article with excellent appearance and improved appearance. Also, it can be obtained; the welding strength of the notification device. The relative viscosity is less than 丨5. ^, the tendency to prepare for the difference. The greater the relative viscosity becomes, the worse the fluidity becomes, the longer the time becomes, the lower the mold transferability is, the better the appearance of the preform. The relative viscosity exceeds U. In the case of the moldability, the weld strength is remarkably lowered, and the resin temperature at the end of the flow is lowered. The bonding of the resin is deteriorated, and the weld strength tends to be lowered. The stomach welding 'in particular refers to the MU ' caused by the injection molding of the resin and is tied to the mold (4) to melt the tree (four), and to melt the partial good phenomenon. If a hollow portion or the like is formed in the molded product, the core or the like may be re-formed. Then, after the molten resin is rewound, the door on this part is wired. Also, if two pieces need to be set [in case, the welding line cannot be avoided. The joint is damaged by the poor fusion or the appearance is significantly reduced. Mechanical characteristics, such as the moon and the good "Inappropriate phenomenon" must be implemented (1) Improve the position of refining 2 (2) Increase the injection pressure and the injection speed 'change the size of the closed pole - the size of the crucible, etc." The so-called welding strength, the mechanical properties of the welded joint (such as bending elasticity) The glass fiber of the present month can be produced by the well-known method for producing glass fiber 97111824 200904898, and the following form can be used: the decane is blended in order to improve the adhesion to the matrix resin and the uniform dispersibility. A resin obtained by using at least one of a coupling agent such as a coupling agent, a titanium coupling agent, and an oxidative coupling agent, and a film forming agent, is sizing by a known sizing agent, and is then condensed. The glass fiber strand of the pulp is cut into a shape of a strand of a certain length. In the present invention, the cross-sectional shape of the glass fiber is a flat flat glass fiber. The flat cross section shows a case where the shape of the cross section perpendicular to the longitudinal direction of the glass fiber is not a circular shape but a shape of a deformed shape. A shape having a major axis defined by the maximum length of the center point, defined as a short diameter passing through the minimum length of the center point. As such a shape, the flat cross section may be exemplified by a creeping shape, a scorpion shape, an oblong shape, an elliptical shape, a rectangular shape, or the like, and the shape 'is, for example, in a sag, according to the above definition, the long diameter system is equivalent to 1 production. The distance between the two heads in the direction of the convex portion is a distance corresponding to the distance between the thin portion of the middle portion of the sprout in the direction of the concave portion.
;本發月中係使用扁平形狀之長徑/短徑的比值為1. 5 :10、較佳為2. G〜6. G之扁平玻璃纖維。長徑/短徑之比 ^糸根據上述定義，由自扁平玻璃纖維之切割剖面的垂 方向進行顯微鏡觀察且以微刻度作為基準所測得之長 :於ΓΓ算出，並使用1G個之平均值。若長徑/短徑比 破螭纖维太貝i將剖面製成扁平狀的效果小；若超過10，則 敬哨纖維本身難以製造。 於本發明甲，係使用平均長度為 為2〜in ^ 丁 J焚度曷1〜15则1、較佳 则1之扁平玻璃纖維。此處，所謂平均長度，係 971Π824 200904898 私對扁平玻璃纖維進行顯微鏡觀察且以微刻度作為基準 而測仔之20個的平均值。若纖維之平均長度大於15顏， 則於樹脂成形時樹脂之流動會變差，且作業性會變差； 又，若小於1 mm，則無法確保充分之機械強度。 聚醯胺樹脂（A)與扁平狀玻璃纖維（B)之調配量為 ⑴/⑻= 25/75〜80/20(質量％)、較佳為（A)/⑻=3〇/7〇 〜75/25(質量 ％)、更佳為（Α)/(Β) = 3〇/7〇〜7〇/3〇(質量 «。於扁平狀玻璃纖維（B)之調配量為2〇質量％以下之情 T下，曲會變大，故而不佳。另一方面，若爲平狀玻璃 纖維⑻之調配量超過75質量％，則流動特性會變差，於 熔融混練時無法將樹脂拉出為股繩狀，而難以製造玻璃纖 維強化聚醯胺樹脂組成物。The flat glass fiber of the flat shape of the flat shape is 1. 5:10, preferably 2. G~6. The ratio of the long diameter to the short diameter is determined by microscopic observation from the vertical direction of the cut section of the flat glass fiber and measured by the micro scale as a reference according to the above definition: calculated by ΓΓ, and using an average of 1G . If the long diameter/short diameter ratio is less than 10, the effect of the flat fiber is too small. If it exceeds 10, the whistle fiber itself is difficult to manufacture. In the present invention A, a flat glass fiber having an average length of 2 to in ^ □ J incineration 曷 1 to 15 and preferably 1 is used. Here, the average length is 971 Π 824 200904898. The flat glass fiber is observed microscopically and the average value of 20 pieces measured on the micro scale is used. When the average length of the fibers is more than 15 Å, the flow of the resin is deteriorated during the molding of the resin, and the workability is deteriorated. Further, if it is less than 1 mm, sufficient mechanical strength cannot be ensured. The blending amount of the polyamide resin (A) and the flat glass fiber (B) is (1) / (8) = 25 / 75 to 80 / 20 (% by mass), preferably (A) / (8) = 3 〇 / 7 〇 ~ 75/25 (% by mass), more preferably (Α)/(Β) = 3〇/7〇~7〇/3〇 (mass«. The amount of the flat glass fiber (B) is 2〇% by mass. On the other hand, if the blending amount of the flat glass fiber (8) exceeds 75% by mass, the flow characteristics may be deteriorated, and the resin may not be pulled out during melt-kneading. It is a strand shape, and it is difficult to manufacture a glass fiber reinforced polyamide resin composition.
U :為1刀子中具有2個以上之官能基的有機化合物，可 例示：具有多個環氧基、酸縣、辦琳基、缓酸基、胺 =異氰酸酉旨基之官能基者。較佳為具有環氧基、酸肝的 二機:=。其中，三經甲基丙院(單、二、三)環氧丙基 二父：為三經甲基丙炫聚環氧丙基醚，例如可較佳地利 一羥甲基丙烷（一或二）環氧丙基醚、更佳為三羥 三)環氧丙錢、或者聚甘油聚環氧丙基_ 等環氧丙基鍵化合物，三環氧丙基異氛尿 基氰尿㈣之具有環氧基的化合物；苯乙烯 二來=聚物(具有如數量平均分子量4 _〜 5_?夂值為100〜議之酸軒基作為側基的化合物）。 /刀子中具有2個以上之官能基之有機化合物的調配 97111824 11 200904898 量，相對於聚醯胺樹脂組成物1〇〇質量份，為〇. 〇5〜4 c 質量份、較佳為0.1〜3.5質量份。於該調配量為0·05質 置份以下之情況下，熱塑性樹脂組成物之焊接強度的提高 不充分，故而不佳。另一方面，若該調配量超過4.0質量 份，則有熱塑性樹脂組成物之流動性降低，成形加工性變 差’而使機械物性降低的傾向，故而不佳。 又本务明之玻璃纖維強化聚酿胺樹脂組成物，可視需 要，藉由調配入其他無機填充劑，而獲得更加適用於其用 途之成型品。作為此等無機填充劑，可列舉：二氧化矽、 玻璃之微粉末、高嶺土、滑石粉、氧化鈦、碳酸鈣、氧化 鋁等各種粉末。進而，可添加公知之抗靜電劑、著色劑、 潤滑劑、脫模劑、成核劑、阻燃劑、耐衝擊性改良劑等。 作為本發明之玻璃纖維強化聚醯胺樹脂組成物之製造 方法，例如有：使用雙軸擠出機，自位於最上游侧之進料 孔（頂部進料），供給規定量之聚醯胺樹脂，於該聚醯胺樹 脂達到熔融狀態時，使用注液計，自注液孔供給規定量之 有機化合物。進而，自侧進料器供給規定量之扁平狀玻璃 纖”隹/以安裝於擠出機下游側前端的紡孔，將其成形為股 ^狀後’進行冷名ρ ’再冑其切斷為顆粒狀而獲得聚酿胺樹 月曰、且成物。關於所獲得之聚醯胺樹脂組成物的相對黏度， 其以96質量％之硫酸作為溶媒，且於溫度25。(：、濃度1 g/dl之條件下所測定的相對黏度較佳為1.8〜4.5之範 圍、更佳為2.0〜4. 5之範圍。於相對黏度小於18之情 況下會使焊接強度變差，故而不佳。又，於超過4. 5之 97111824 12 200904898 情況下’有玻璃纖維強化聚醯胺樹脂組成物於溶融時之流 動性會極度降低，而給成形性帶來障礙的傾向，故而^ 佳再者本發明所使用之具有扁平剖面的玻璃纖維，可 使用如E玻璃之-般玻璃纖維組成的纖維，只*可製成玻 璃纖維，則可使用任何組成，並無特別限定。 本發明之樹脂組成物成形方法，可於將聚醯胺樹脂組成 物加熱炼融並進行賦型之過程中，使用射出成形、擠出成 =等各種成形法，為了使用本發日狀聚醯胺樹脂組成物而 纹传薄壁成形品，可較佳地使用射出成形法。 於猎由射出成形法進行成形之情況τ，為了將聚酿胺樹 脂組成物進行塑化，射出成形機之料缸溫度較佳為設定在 〜融點徵之範圍内；為了使樹脂之流動盎 樹脂之劣化達到平衡，此溫度更佳為設定在融點+ 3〇〇c〜 融點+ 60°C之範圍内。 模具溫度較佳為設定為稍高於聚醯胺樹脂 ^轉移溫度’其可產生如下作^將於料缸中進行加 二、、塑化之樹脂射出’填充於模具内，再使其冷卻時，可 P制樹脂之急遽冷卻、結晶化之進行，使模具之轉印變得 良好（外表美觀），並提高所獲得之 制結晶化所引起之成形品的_ ”的尺寸精度（抑 胺：：：：：溫度之控制(將模具溫度設定為稍高於聚酿 ==成物之玻璃轉移溫度）’可有效地抑制成形品中 4 模具之轉印方面亦相同，藉由減緩樹脂之 冷p ’可充分確保義之流動，抑_就㈣前端之樹 97111824 13 200904898 脂溫度的降低，且使焊接部之樹脂之接合更加充分地進 行。 [實施例] 以下，藉由實施例進而對本發明進行具體說明，只要不 超出本發明之要旨，則並不限定於以下實施例。再者，實 施例及比較例所使用之原料及物性測定方法如下所述。 原料 (A) 聚醯胺樹脂 •聚酿胺A :尼龍6(UNITIKA公司製造之Ai〇30BRL ,相 對黏度為2. 6) •聚醯胺B :尼龍6(UNITIKA公司製造之Ai 〇30BRT，相 對黏度為3. 4) •聚酿胺C ·尼龍66(UNITIKA公司製造之A125，相對 黏度為2. 8) •聚酿胺D :尼龍11 (ARKEMA公司製造之ΒΜΝ0 TLD，相 對黏度1. 8) (B) 玻璃纖維 •玻璃纖維A :長短徑之比值為2之具有長圓形型剖面 的扁平玻璃纖維 (平均長度3 mm) (日東纺公司製造之CSH3PA870 ’經過石夕烧系表面處理） •玻璃纖維B :長短徑之比值為4之具有長圓形型剖面 的扁平玻璃纖維 (平均長度3 mm) 97111824 14 200904898 (日東紡公司製造之CSG3PA820，經過矽烷系表面處理） •玻璃纖維C:具有直徑為1〇 平均長度為3 mm 之圓形剖面的玻璃纖維 (曰東紡公司製造之CS3J-451，經過矽烷系表面處理） (C)有機化合物 •有機化合物A:三羥曱基丙烷聚環氧丙基醚（阪本藥 品公司製造之SR-TMP) r •有機化合物β :苯乙烯/馬來酸酐共聚物（Herucules 公司製造） t甘/由聚壤氧丙基驗（阪本藥品公司 二環氧丙基異氰尿酸酯（日產化學公 •有機化合物C 製造之SR-4GL) •有機化合物D 司製造之TEPIC) 測定方法 (1 ) t醯胺树及聚醢胺樹脂組成物之相對黏度 以濃度達到1 g/dl之方式’將聚醯胺樹脂之乾燥顆粒 物溶解於96質量％之石奋g# φ，4丨丨r。1 貝里/〇<石瓜0夂〒，利用G_3玻璃過濾器，將聚 酿胺以外之成分濾去後，供於測定。 測定係使用烏別洛德型黏度計，於25X：下進行。對於 聚賴樹脂組成物，於修正玻璃纖維成分後之 方式進行測定。 < (2)彎曲彈性率 以1點閘極，對長度為15〇咖、寬度為10mm、厚度為 3丽之錢片進行射出成形，依據ASTM D79G，於23t 97111824 15 200904898 下進行測定。 越生率係表示相對於應力之撓曲程度的尺度，此值 就抑制相對於製成薄壁成形品時之外力的變形 ..# ^ °於玻璃纖維之調配量為30質量％之情況下， :曲彈性率達到5 GPa，較佳為8咖以上。 (3)焊接部之彎曲彈性率 厚端之2點閘極’對長度為⑽龍、寬度為10mm、 ，:;:二:之試驗片進行射出成形，以與_曲彈性率 ^门之方式，依據ASTMD79〇，於23。〇下對中央 =部進行測定。再者，於製作試驗片時，係於如下7條件 2m：订 成形機之⑽溫度於聚醯胺丨丨之情況下為 23〇c ’於聚醯胺6之情 n兄下為 況下為280°c · ；r且、®；聚醯胺66之情 於聚醯胺6之= 聚醯胺11之情況下為6〇。。， 。。；冷卻時間CL 於聚醯胺66之情況下請 横切試驗片之方式接線’於試驗片之正中央，以 、驗而排=式形成為線狀’且外觀上有異常者不供於 :接部之彎曲彈性率尤其表示相對 撓曲程度的尺度。若焊接部之.彎曲彈性率不 成成形品而供於實際庳 不充为鬲，則製 苻，户—A 之情況下，藉由反覆施加肩*奋 子自焊接部斷裂的情況。不 ^ 、 亦期望焊接部之弯曲彈性率充分高。以方面有要求， 取侍（2)彎曲彈性率、及（3) 值，根據下式算出、f曲彈性率之之号曲彈性率的比 97111824 16 200904898 —彎曲彈性率之保持率⑻叫(焊接部之彎曲彈性 率）/(彎曲彈性率）}xl〇〇 彎曲彈性率之保持率於彎曲 lnno/ h 评陧丰兀全未降低之情況 下為，。一般而言，f曲彈性率會有一定程度之降低， -但要求彎曲彈性率之保持率為7 - ⑷魅曲量 巧⑽上’較佳為75%以上。 。射出成形機之料缸溫度於聚醯胺u之情況 c，於聚醯胺6之情況下為25 ^ 下為280C ’极具溫度於聚醮胺η之情況下為阶，於 撕6之情況下為8(rc，於聚醯胺66之情 、 C ;冷卻時間設定為1分鐘，藉 冲 為〇〇 mm、厚度為h6 mm之圓板進行射出成形。工 將自模具中取出之成形品立即放 r9q〇r s . n ^ ^ I風八钇铋器内，冷卻至室 ( C) ’並且維持在絕對乾燥狀態， 24小時狀態調濕。 乾U進订 水tVi時乾燥器中取出成形品’將成形品靜置於 出翹曲量。 广十盤的距離，由此測定值算 用於測定之4點係以如下方式決定（參照圖卫、圖 將®板之㈣極的位置設為a ’於圓周之逆時針方向上， 將：對於a為90。之位置設為b，將相對於&為⑽。之位 置设為c，將相對於a為270。之位置設為d。 -般而言’翹曲係於bd(或ac)相對於對向 而翹起（或者下垂）之狀態^•發生。 一 d) &艰干盤上，以成形品 97111824 17 200904898 2曲為向下凸出之方式進行靜置，計測其 向上位移了多少距離。 、基丰面 根據下式算出翹曲量。 翹曲量（)= (b+d)/2 — (a+c)/2 :者2式係bd相對於對向之ac(基準線)而麵起時之 ，子’於基準線改變時，適當改變上述式中之基準線（例 高口度=bd) ’並求出與此相對應之位移（bd=^之麵起 根，上述方法求得之麵曲量越小越好，於實際應用方 面’為1. 0 mm以下即可。 [實施例1] 聚醯胺樹脂A係使用久保田製造之減量式連續定量供 給裝置CE-W-1計量，並供於螺桿直徑為37_、l/⑽之 同方向雙軸擠出機（東芝機械公司製造之·3卿之主供 、、’《口。並且，擠出機之料筒溫度設定在23〇t〜， 於螺桿旋轉速度為250 rpm、排出量35 kg/h之條件下進 行熔融混練，於聚醯胺充分熔融時，自注液口注入相對於 樹脂組成物100質量份，為h〇f量份之有機化合物A，' 充分混練後，自側面進料機供給玻璃纖維八，以樹脂組成 物達到聚醯胺樹脂A/玻璃纖維a= 70/30(質量％)之方式 進仃混練。最後，將自模具拉出而成為股繩狀之樹脂組成 物通入水槽中，進行冷卻固化，利用造粒機對其進行切 割，而獲得樹脂組成物之顆粒物。U: an organic compound having two or more functional groups in one knives, and examples thereof include those having a plurality of epoxy groups, acid groups, chlorpheniramine groups, acid groups, and amines = isocyanate groups. . Preferably, it is a two-machine having an epoxy group and a sour liver: =. Among them, trimethyl ketone (single, two, three) epoxy propyl di-parent: trimethyl methacrylate polyepoxypropyl ether, for example, preferably hydroxymethylpropane (one or two Epoxypropyl ether, more preferably trishydroxy) epoxy propylene glycol, or polyglycerol polyepoxypropyl _ and other epoxy propyl bond compounds, trisepoxypropyl acetonide cyanide (4) An epoxy group-containing compound; a styrene bis-polymer (having a compound having a number average molecular weight of 4 _ _ 5 _? 夂 value of 100 Å as the side group). The amount of the organic compound having two or more functional groups in the knives is 97111824 11 200904898, and the amount of the ruthenium resin composition is 〇. 5~4 c parts by mass, preferably 0.1~ 3.5 parts by mass. When the amount of the compound is less than or equal to 0.0 part by mass, the improvement in the weld strength of the thermoplastic resin composition is insufficient, which is not preferable. On the other hand, when the amount is more than 4.0 parts by mass, the fluidity of the thermoplastic resin composition is lowered, and the moldability is deteriorated, and the mechanical properties tend to be lowered, which is not preferable. Further, the glass fiber reinforced polyamine resin composition of the present invention can be obtained by blending other inorganic fillers as needed, thereby obtaining a molded article more suitable for its use. Examples of such inorganic fillers include various powders such as cerium oxide, fine glass powder, kaolin, talc, titanium oxide, calcium carbonate, and aluminum oxide. Further, a known antistatic agent, a colorant, a lubricant, a release agent, a nucleating agent, a flame retardant, an impact resistance improver, or the like can be added. As a method for producing the glass fiber-reinforced polyamine resin composition of the present invention, for example, a predetermined amount of polyamidamide resin is supplied from a feed hole (top feed) located at the most upstream side using a twin-screw extruder. When the polyamide resin reaches a molten state, a predetermined amount of the organic compound is supplied from the liquid injection hole using a liquid injection meter. Further, a predetermined amount of flat glass fiber is supplied from the side feeder, and the spun hole is attached to the tip end of the downstream side of the extruder, and is formed into a strand shape, and then the cold name ρ ' is cut and then cut. In the form of granules, a polystyrene tree sap and a product are obtained. With respect to the relative viscosity of the obtained polyamidamide resin composition, 96% by mass of sulfuric acid is used as a solvent, and the temperature is 25. (:, concentration 1 The relative viscosity measured under the condition of g/dl is preferably in the range of 1.8 to 4.5, more preferably in the range of 2.0 to 4.5. When the relative viscosity is less than 18, the weld strength is deteriorated, which is not preferable. Further, in the case of more than 7.5, 97,118,224, 12, 2009, 0,089,8, the flowability of the glass fiber-reinforced polyamine resin composition is extremely lowered during the melting, and the moldability tends to be impeded, so that it is better. The glass fiber having a flat cross section used in the invention may be a fiber composed of a glass fiber such as E glass, and only * can be made into a glass fiber, and any composition can be used without particular limitation. The resin composition of the present invention Polyamide In the process of heating and smelting and refining the resin composition, various molding methods such as injection molding and extrusion formation are used, and it is preferable to use a hair-like polyimide resin composition to smear a thin-walled molded article. The injection molding method is used. In the case where the molding is performed by the injection molding method, in order to plasticize the polyamine resin composition, the temperature of the cylinder of the injection molding machine is preferably set within the range of the melting point; In order to balance the deterioration of the resin flowing resin, the temperature is preferably set within the range of melting point + 3 〇〇 c ~ melting point + 60 ° C. The mold temperature is preferably set to be slightly higher than polyamine The resin transfer temperature 'can be produced as follows: the resin is injected into the material tank, and the plasticized resin is injected into the mold, and when it is cooled, the resin can be rapidly cooled and crystallized. To make the transfer of the mold good (appearance of appearance), and to improve the dimensional accuracy of the molded article caused by the obtained crystallization (the inhibition of amine::::: temperature (set the mold temperature to Slightly higher than the brewing == adult The glass transfer temperature) can effectively suppress the transfer of the 4 molds in the molded article, and the flow of the resin can be sufficiently ensured by slowing down the cold p' of the resin, and _ (4) the front end of the tree 97118824 13 200904898 the temperature of the grease is lowered, Further, the bonding of the resin of the welded portion is carried out more fully. [Examples] Hereinafter, the present invention will be specifically described by way of examples, and the present invention is not limited to the following examples, without departing from the gist of the present invention. The materials and physical properties of the samples used in the examples and the comparative examples are as follows: Raw material (A) Polyamide resin • Polyamide A: Nylon 6 (Ai〇30BRL manufactured by UNITIKA, relative viscosity of 2.6) • Polyamide B: Nylon 6 (Ai 〇 30BRT manufactured by UNITIKA, relative viscosity is 3.4) • Polyamide C · Nylon 66 (A125 manufactured by UNITIKA, relative viscosity is 2.8) • Polyuramine D :Nylon 11 (ΒΜΝ0 TLD manufactured by ARKEMA, relative viscosity 1. 8) (B) Glass fiber • Glass fiber A: Flat glass fiber with an oblong profile of length to length ratio of 2 (average length 3 mm) (made by Ridong Textile Co., Ltd. CSH3PA870 'after surface treatment by Shihsingling】 • Glass fiber B: flat glass fiber with an aspect ratio of 4 long and short diameters (average length 3 mm) 97111824 14 200904898 (CSG3PA820 manufactured by Nitto Spinning Co., Ltd., After decane-based surface treatment) • Glass fiber C: Glass fiber having a circular cross section with a diameter of 1 〇 and an average length of 3 mm (CS3J-451 manufactured by Toray Industries, Ltd., surface treated with decane) (C) Organic compounds • Organic Compound A: Trihydroxydecylpropane Polyepoxypropyl Ether (SR-TMP manufactured by Sakamoto Pharmaceutical Co., Ltd.) r • Organic Compound β: Styrene/Maleic Anhydride Copolymer (manufactured by Herucules) t Gan/Yu Soil oxygen oxypropylation (Sakamoto Pharmaceutical Co., Ltd. diepoxypropyl isocyanurate (Nissan Chemical Co., Ltd., SR-4GL manufactured by Organic Compound C) • TEPIC manufactured by Organic Compound D) Determination method (1) t-amine The relative viscosity of the tree and the polyamide resin composition was such that the dry particles of the polyamide resin were dissolved in 96% by mass of Shifen g# φ, 4丨丨r in a concentration of 1 g/dl. 1 Berry / 〇 < 瓜瓜 0 夂〒, using G_3 glass filter, the components other than polyamine are filtered off and used for measurement. The measurement was carried out at 25X using a Ubbelode type viscometer. The polylaid resin composition was measured in such a manner that the glass fiber component was corrected. < (2) Bending Elasticity A sheet of money having a length of 15 〇, a width of 10 mm, and a thickness of 3 Å was injection-molded at a 1-point gate, and was measured in accordance with ASTM D79G at 23t 97111824 15 200904898. The over-production rate is a measure of the degree of deflection with respect to the stress, and this value suppresses the deformation of the external force with respect to the thin-walled molded article. When the compounding amount of the glass fiber is 30% by mass, The modulus of elasticity is 5 GPa, preferably 8 or more. (3) The bending elastic modulus of the welded portion is 2 points of the thick end of the thick end of the pair of (10) dragons, widths of 10 mm, , ::: two: the test piece is injection-molded, in the manner of _ elastic modulus ^ According to ASTM D79〇, at 23. The underarm is measured on the central part. In addition, when the test piece was produced, it was subjected to the following 7 conditions: 2 m: the temperature of the (10) of the molding machine was 23 〇c in the case of polyamidamine, and the case was 280 ° c · ; r and , ®; polyamine 66 in the case of polyamine 6 = polyamine 11 in the case of 6 〇. . , . . ; Cooling time CL In the case of polyamide 66, please cross the test piece to connect 'in the center of the test piece, and check the form to form a line' and the appearance is abnormal. The flexural modulus of the part is especially a measure of the degree of relative deflection. If the bending elastic modulus of the welded portion is not a molded product and the actual 庳 is not filled with 鬲, then the —, 户 - A case, by the repeated application of the shoulder * Fenzi from the welded portion is broken. It is also desirable that the bending elastic modulus of the welded portion is sufficiently high. In terms of requirements, the service (2) bending elastic modulus, and (3) value are calculated according to the following formula: the ratio of the elastic modulus of the elastic modulus of the f-curvature ratio is 97118824 16 200904898—the retention rate of the bending elastic modulus (8) is called ( The bending elastic modulus of the welded portion) / (bending elastic modulus)} xl 〇〇 The retention rate of the bending elastic modulus is determined when the bending lnno/h is evaluated. In general, the flexural modulus of f has a certain degree of reduction, but the retention of the flexural modulus is required to be 7 - (4) The amount of temperament (10) is preferably 75% or more. . The temperature of the cylinder of the injection molding machine is in the case of polyamide amine c, and in the case of polyamine 6 is 280C at 25 ^', and the temperature is in the case of polyamide η, which is the case of tearing 6 The following is 8 (rc, in the case of polyamine 66, C; the cooling time is set to 1 minute, and the round plate with a thickness of 〇〇mm and a thickness of h6 mm is injection-molded. The molded article taken out from the mold Immediately put r9q〇rs. n ^ ^ I in the wind gossip, cool to room (C) 'and maintain in absolute dry state, 24-hour state conditioning. Dry U to order water tVi when the mold is taken out of the dryer 'The molded product is placed in the amount of warpage. The distance between the ten and ten discs is determined by the following values. The position of the (four) pole of the sheet is set as follows. a 'In the counterclockwise direction of the circumference, the position of a is 90. The position is set to b, and the position relative to & is (10). The position is c, and the position is 270 with respect to a. - Generally speaking, the warp is tied to the state of bd (or ac) with respect to the opposite direction (or sagging) ^. Occurs. d) & Shape 97111824 17 200904898 2 The curve is placed in a downward convex manner, and the distance is measured upwards. The base surface is calculated according to the following formula. The amount of warpage () = (b + d) / 2 — (a+c)/2 : When the type 2 bd is raised with respect to the opposite ac (reference line), when the child 'changes on the reference line, the reference line in the above formula is appropriately changed (example is high) Orality = bd) 'and find the corresponding displacement (bd = ^ face from the root, the smaller the amount of surface curvature obtained by the above method, the better, in practical applications 'is less than 1.0 mm) [Example 1] Polyamine resin A was metered using a reduced-quantity continuous dosing device CE-W-1 manufactured by Kubota, and supplied to a co-axial twin-screw extruder with a screw diameter of 37_, l/(10) (Toshiba) The main supplier of the 3 company, manufactured by the mechanical company, and the 'mouth. Moreover, the barrel temperature of the extruder is set at 23 〇t~, and the screw rotation speed is 250 rpm and the discharge amount is 35 kg/h. In the melt-kneading, when the polyamide is sufficiently melted, 100 parts by mass of the resin composition is injected from the liquid injection port, and the organic compound A is in the amount of h〇f. After the kneading, the glass fiber is supplied from the side feeder, and the resin composition is mixed with the polyamide resin A/glass fiber a=70/30 (% by mass). Finally, the mold is pulled out and becomes The strand-shaped resin composition was passed through a water tank, cooled and solidified, and cut by a granulator to obtain a pellet of the resin composition.
Ik而，使用射出成形機（東芝機械公司製造之， 97111824 18 200904898 於料缸溫度為250°C、模具溫度為80°C之條件下，對所獲 得之樹脂組成物顆粒物進行射出成形，而製作物性測定試 驗片，並進行各種評價試驗。將其結果示於表1。In the case of Ik, an injection molding machine (manufactured by Toshiba Machine Co., Ltd., 97111824 18 200904898) was used for injection molding of the obtained resin composition pellets under the conditions of a cylinder temperature of 250 ° C and a mold temperature of 80 ° C. The test piece was measured for physical properties, and various evaluation tests were carried out. The results are shown in Table 1.
97111824 19 200904898 i 比較例 oo CD c 1—H 1 § LO CO CO 寸_ CO oo OJ 一 oo LO oi 卜 o 1—H 1 CO CO oo C<I LO CO CO <=> CO o C=5 〇 1—^ 1 1 呀 CO LO oo LO c^- LO od LO CD 〇 1 1 1 1 1 CD od CO oo LO i 1 CD 寸 寸 Ό 〇 1 ο 1 1 t LO 寸· 1 1 <鹚玫蟑Og CO o o r—H 1 1 ! 1 1 1 < <〇 C=> 1 1 1 寸 CO CO oo oa LO CO CO 寸 CZ5 οα o 〇> f < 1 1 1 1 § 1 1 CO 1 1 4辣玫蟑Og r—Η 〇 Ό r—H LO 〇〇 t 1 1 1 LO 1 LO d 1 1 1 00 01 呀· LO CO 寸 CT> t>a CO 實施例 CO CZ> o ^"' < 1 1 1 1 1 1 1 1 (〇 CO od ο ai CO LO i—H oo CO CD LO o o 1 1 1 另 i 1 1 1 CD F-H 1 LO oa <NI ai LO LO i i oo CO <〇 寸 o o 1 1 导 1 1 § 1 1 LTD CO 1 1 CO CD oa 卜’ CO oo 1 < <=i CO o o 1—H 1 1 1 1 1 cz> 1 1 1 LO CO CO oo CO cd oa oo 寸 CD oa CD Q 1 1 1 1 1 d> T—^ 1 1 1 呀 CQ CO oo 卜 cd 1 1 t oo 寸 T—H 〇» CD 1 1 t t 1 CD l t l 寸 CO <〇 od CO oo oo d> 聚醯胺/玻璃纖維（質量份） 聚醯胺A 聚醯胺B 聚醯胺C 聚醯胺D 玻璃纖維A 玻璃纖維B 玻璃纖維C 有機化合物A 有機化合物B 有機化合物c 有機化合物D 相對黏度 彎曲彈性率(GPa) 焊接部之彎曲彈性率(GPa) 彎曲彈性率之保持率〇〇 翹曲量（mm) 聚醯胺 玻璃纖維 有機化合物 (質量份） 試驗結果 骤齧省济(鉍®W%) ε； 200904898 [實施例2〜6及比較例1〜9 ] 除使用表1所示之成分比率以外，以與實施例1相同之 方式製作試驗片’並進行各種評價試驗。將其結果示於表 -1 °再者’擠出機之料筒溫度設定，於聚醯胺丨丨之情況下 •係设為210。(：〜25(TC，於聚醯胺6之情況下係設為230 C〜270°C ’於聚醯胺66之情況下係設為25(TC〜290〇C。 又’射出形成機之料缸溫度，於聚醯胺11之情況下係設 ，為230°C，於聚醯胺6之情況下係設為25〇<t，於聚醯胺 66之情況下係設為28(rc ;模具溫度於聚醯胺丨丨之情況 下係設為60°C，於聚醯胺6之情況下係設為8(rc，於聚 酸胺66之情況下係設為1 〇(rc。 於κ鉍例中，藉由併用具有長圓形型剖面之玻璃纖維及 有機化合物，可獲得除低翹曲及剛性以外，焊接部之剛性 亦優異之玻璃纖維強化聚醯胺樹脂組成物。 比較例1由於扁平玻璃纖維之調配量小，故而翹曲量 (J大。比較例2由於扁平玻璃纖維之調配量高，故而於熔融 •混練時流動性差，無法拉出為股繩狀，從而無法獲得聚酿 -胺樹脂組成物之顆粒物。比較们由於所調配之有機化合 物為規定量以下，故而嬋接部之機械強度差，弯曲彈性率 之保持率低。比較例4由於所調配之有機化合物為規定量 以上，故而流動性差，從而無法獲得聚酿胺樹脂組成物之 顆粒物。比較例5、比較例7由於完全未調配入有機化合 物，故而焊接部之機械強度差，，彎曲彈性率之保持率低。 比較例6、比較例8由於未使用具有長圓形型剖面形狀之 97111824 21 / 200904898 玻璃纖維，故而魅曲量高。 【圖式簡單說明】 圖1係本發明之翹曲量 %、β _^、 <汗價中 中之成形 態調濕前）。 之成形 圖2係體發明之翹曲量 態調濕後）。 1胃 【主要元件符號說明 a、b ' c、d 品的立體圖（狀 品的立體圖（狀 剛定部位 97111824 2297111824 19 200904898 i Comparative example oo CD c 1—H 1 § LO CO CO inch _ CO oo OJ oo LO oi 卜 o 1—H 1 CO CO oo C<I LO CO CO <=> CO o C= 5 〇1—^ 1 1 呀 CO LO oo LO c^- LO od LO CD 〇1 1 1 1 1 CD od CO oo LO i 1 CD inch inch Ό1 ο 1 1 t LO inch · 1 1 <鹚玫蟑Og CO oor—H 1 1 ! 1 1 1 <<〇C=> 1 1 1 inch CO CO oo oa LO CO CO inch CZ5 οα o 〇> f < 1 1 1 1 § 1 1 CO 1 1 4 Spicy Rose Og r—Η 〇Ό r—H LO 〇〇t 1 1 1 LO 1 LO d 1 1 1 00 01 呀· LO CO inch CT>t>a CO Example CO CZ> o ^" ;' < 1 1 1 1 1 1 1 1 (〇CO od ο ai CO LO i—H oo CO CD LO oo 1 1 1 another i 1 1 1 CD FH 1 LO oa <NI ai LO LO ii oo CO <〇寸 oo 1 1 导 1 1 § 1 1 LTD CO 1 1 CO CD oa 卜 ' CO oo 1 <<=i CO oo 1—H 1 1 1 1 1 cz> 1 1 1 LO CO CO oo CO cd oa oo inch CD oa CD Q 1 1 1 1 1 d> T—^ 1 1 1 呀 CQ CO oo 卜 cd 1 1 t oo inch T—H 〇» CD 1 1 tt 1 CD ltl inch CO <〇 Od CO oo oo d> Polyamide/glass fiber (parts by mass) Polyamide A Polyamide B Polyamide C Polyamide D Glass Fiber A Glass Fiber B Glass Fiber C Organic Compound A Organic Compound B Organic Compound c Organic Compound D Relative Viscosity Flexural Elasticity (GPa) Flexural Elasticity (GPa) of Welded Section Retention Rate of Flexural Elasticity 〇〇 Warpage Amount (mm) Polyamide Glass Fiber Organic Compound (Parts by Mass) Test Results铋(铋®W%) ε; 200904898 [Examples 2 to 6 and Comparative Examples 1 to 9] Test pieces were prepared in the same manner as in Example 1 except that the component ratios shown in Table 1 were used, and various evaluations were carried out. test. The results are shown in Table -1 ° again. The barrel temperature setting of the extruder was set to 210 in the case of polyamidoxime. (: ~25 (TC, in the case of polyamide 6 is set to 230 C~270 ° C' in the case of polyamide 66 is set to 25 (TC ~ 290 ° C. Also 'injection forming machine The temperature of the cylinder is set at 230 ° C in the case of polyamide 9 and 25 〇 in the case of polyamide 6 and 28 in the case of polyamide 66. Rc ; the mold temperature is set to 60 ° C in the case of polyamidofluoride, 8 (rc in the case of polyamine 6 and 1 〇 in the case of polyamine 66) In the κ 铋 example, by using a glass fiber having an oblong profile and an organic compound in combination, a glass fiber reinforced polyamide resin composition having excellent rigidity in addition to low warpage and rigidity can be obtained. In Comparative Example 1, since the amount of the flat glass fiber is small, the amount of warpage is large (J is large. In Comparative Example 2, since the blending amount of the flat glass fiber is high, the fluidity during melting and kneading is poor, and the strand shape cannot be pulled out. It is impossible to obtain the particulate matter of the polystyrene-amine resin composition. The comparison is due to the fact that the organic compound to be formulated is less than the specified amount, so the mechanical part of the joint portion In the case of the comparative example 4, since the organic compound to be blended was a predetermined amount or more, the fluidity was poor, and the particulate matter of the polyacrylamide resin composition could not be obtained. Comparative Example 5 and Comparative Example 7 were completely Since the organic compound was not blended, the mechanical strength of the welded portion was poor, and the retention rate of the bending elastic modulus was low. In Comparative Example 6 and Comparative Example 8, since the glass fiber of the 97112824 21 / 200904898 having the long circular cross-sectional shape was not used, the charm was obtained. Fig. 1 shows the warpage amount %, β _^, <the middle of the sweat price in the form of warping before the humidity control.) Fig. 2 The warpage amount of the system invention After the state is adjusted to humidity. 1 stomach [main component symbol description a, b ' c, d product stereoscopic view (shaped view of the product (formed just fixed part 97118824 22