TW201221557A - Thin-wall molded article, manufacturing method of same and use of electronic device housing - Google Patents

Abstract

The present invention provides a thin-wall molded article which contains glass fibers having a weight average fiber length of 0.5-1.5mm and has thickness of 0.8-2.0mm. The thin-wall molded article is obtained from resin composition that contains resin impregnated fiber bundle cut to length of 5-15mm after impregnated and united in state of fusing aliphatic PA in long glass fiber bundle. The resin impregnated fiber bundle contains member selected from PA11, PA12, PA610, PA612, and has glass fiber content of 40-70wt%. The resin composition is a thin-wall molded article and molded article obtained from such a resin composition satisfies requirements of (a) and (b). (a)Nominal tensile strain is more than 2.0% when a tensile test is carried out at 500mm/min by using ISO multi-purpose test sheet (A type, thickness is 2mm) and bend elastic constant is more than 10GPa in absolute dry state. (b) Charpy impact intensity (according to ISO179/1eA (edgewise) (thickness of test sheet is 2mm, there is notch on it)) is more than 30kJ.

Description

[Technical Field] The present invention relates to a thin meat molded body suitable for use as an electronic device cover or an internal chassis for a mobile phone or the like, a method for manufacturing the same, and the use of the electronic device cover. [Prior Art] An electronic device cover or an internal chassis such as a mobile phone is composed of a thin meat molded body. The bending elastic modulus is required to be high, the impact resistance is excellent, and the dimensional change rate due to water absorption is small. JP-A-2008-163340 discloses an invention relating to two kinds of polyamines containing crystalline polyamine and non-crystalline or microcrystalline, and glass fibers having a non-circular cross section (Application Patent Range) Item 1) 'The use of the frame as a mobile phone is described in item 28 of the patent application scope. The glass fiber system is described in paragraph number 〇〇48, 0049, and it is described that the long glass fiber is excluded. In the comparative examples (CE) 1 and 2 of Table 1, an example in which the combination pa is A type (PA12) and the glass fiber is B type (a length of 4.5 mm and a diameter of 1 〇 is circular) is described. However, the single beam impact strength (or the skin impact strength) (with notched) becomes a low value of 22 kJ/m 2 , 17 kJ/m 2 , which is considered to be the adjustment method of the polyamide molding material described in paragraph No. 0,058. In the case where the glass fiber is broken and becomes small, it is substantially the same as when short fibers are used. In Japanese Patent Application Publication No. 2010-511778, a portable electronic device cover template (jig) composed of a thermoplastic polyamine and a fibrous reinforcing agent having a non-circular cross section is described. The majority of thermoplastic polyamines listed in the second paragraph of the patent range are only PA1〇1〇, pA6 6 and pA6 I/6 T used in the examples. In paragraph 021 1 it is stated that long glass fibers can be used as the fibrous reinforcing agent. Although the type of the glass fiber used in the examples is not clearly described, it is considered to be a short fiber from the small value of the single beam impact strength (or the inspection impact strength) (with notched) shown in Table 2. . In the Japanese Patent Publication No. 2010-510375, the Japanese Patent Publication No. 2009-79212, the Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. A composition of an amine and a glass fiber, but without the use of PA丨i, pA j 2, pA6 1 2 as a poly-tank' and a combination of specific glass long fibers. SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a thin meat molded body of an electronic device cover or an internal chassis which is excellent in impact resistance and which has a small dimensional change due to water absorption, and which is suitable as a mobile phone. The present invention provides a carcass shaped body which is bundled in a state in which the long glass fibers are in a uniform orientation direction, and the aliphatic polyamine is impregnated into the glass long fiber bundle in a molten state. After the integration, the thickness of the resin composition containing the resin impregnated fiber bundle having a length of 5 to 15 mm is 0.8 to 2.0 mm, and the weight average fiber length of the glass fiber is 0.5 to 1.5 mm. The resin-impregnated fiber bundle contains a material selected from the group consisting of pa11, pa12, Pa61q, and PA6i2, and the content of the glass fiber is 4 to 7 mass%; 201221557 The molded body obtained from the foregoing resin composition satisfies the following (4) And the requirements of (8) are used as a solution to the problem. (a) When using an IS〇 multi-purpose test piece (A shape, thickness 2 is called and the tension is applied at 500 mm/min (the nominal tensile strain at the time of tensi〇nm is 20 〇/〇) With μ „ . 〇 'U/〇 above, and the bending elastic modulus in absolute dry state is l〇GPa or more; () single beam impact strength (or inspection impact strength) (according to IS〇179/leA (edgewise )) (the thickness of the test piece has a notch on both sides) of 30 kJ or more; as a solution to the problem. The present invention provides a method for preparing a thin meat molded body, which is a patent application. The method for producing a thin meat molded body according to any one of the items 5 to 5, wherein, after the melting of the resin composition, injection molding is performed to form a mold using a pin (four) port as an injection molding die. Means for Solving Other Problems The present invention relates to the use of an electronic machine cover for the above-mentioned thin meat molded body. The thin meat forming system of the present invention comprises an aliphatic polyamine selected from the group consisting of η, p2, ΡΑ610, ΡΑ612, and Glass long fiber The composition of the resin composition of the resin-impregnated fiber bundle is composed of ^^r-^, although the thickness is as thin as 〇.8 to 2 mm', it still has high impact strength, and the dimensional change rate due to water absorption is also small. [Embodiment] <Resin Composition> The resin impregnated fiber bundle included in the resin composition of the present invention is used as an electronic machine cover or an internal chassis. The glass long fibers are bundled in a state of being uniformly oriented in the longitudinal direction, and impregnated into the glass long fiber bundle in the state of molten polyamine, and integrated, and then cut into 5 to 15 mm (preferably 6). The length of the glass fiber contained in the resin impregnated fiber bundle is the same as the length of the resin impregnated fiber bundle. The aliphatic polyamine contained in the resin impregnated fiber bundle is selected from the group consisting of ρΑ11 (undecane). Condensation polymer of indoleamine), pA12 (condensed polymer of dodecane decylamine), PA610 (condensed polymer of hexamethylenediamine and sebacic acid), PA612 (caprolactam and dodecane yttrium) Amine condensation polymer) _. The glass fiber contained in the resin impregnated fiber bundle can be a fiberglass with a fiber shuttle (single wire diameter) of 6 to 30 // m, 1 key 雉缶 雉缶 * * j M tea 1 fiber bundle The number of roots is from 100 to 30,000, and the movement: s is preferably from 500 to 20,000, more preferably from about 1 to about 10,000. '" The fiber bundle can be made by using dies. For example, in addition to 曰本特开平六·3_号号, 洛编唬7, Japan special opening 2〇〇7 23, can also be applied to 曰本特公平6 23 4: Report paragraph number long fiber bundle Manufacturing # > _ 344 (Resin coated 6-U4832 ^ wide method and molding method), ... Kaiping method), Japan special Kaiping 6-293 () 23 section VIII 4 ^ structure and its fat composition (Manufacturing method; (The method of long-fiber reinforced thermoplastic tree-shaped beam of Atyama, 曰本特开平 7-2〇5317, 隹束之^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Japanese Patent Laid-Open No. 7 _ 2 1 6 1 0 4 (The production method of the _ _ her & u AI 贲 fiber reinforced resin structure), Japan Special Kaiping 7_2514 1 HJ / 公报 ( ( 制造 ( ( ( ( 长 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 -11 The manufacturing method described in the above. The ratio of the glass fiber to the aliphatic polyamine in the resin impregnated fiber bundle used in the present invention is from 4 to 7 % by mass, preferably from 50 to 60% by mass, based on the aliphatic polyamine. Total:: The ratio of the remaining part of the mass%. Further, in order to adjust the content ratio of the glass fiber to the aliphatic polyamine in the resin-impregnated fiber bundle, the above-mentioned aliphatic polyamine may be additionally blended in addition to the resin-containing secondary fiber bundle in the resin composition. The resin composition used in the present invention may further contain a lubricant in addition to the resin impregnated fiber bundle. The lubricant is not added to the inside of the resin impregnated fiber bundle, but is mixed with the resin impregnated fiber bundle (i.e., externally added). Since the lubricant is contained, the measurement time of the composition when the hopper is injected during the injection molding machine can be shortened, and the difference in the measurement can be reduced. The lubricant includes a conventional lubricant, a lipid (丨ipin), a wax, a silicone resin, and the like. The lipids can be exemplified by higher fatty acids (for example, caprylic acid, capric acid, iauric acid, myristic acid, palmitic acid, hard). Saturated acid, arachidic acid, behenic acid, montanic acid, 12-hydroxystearic acid, etc. • 8 - 201221557 C8-35 fatty acids (preferably saturated) C12-30 fatty acid, more preferably saturated C16-22 fatty acid), palmitic acid (palmitoleic acid), oleic acid (oleic ugly (^(1), sinapic acid (61:11(^〇&<^(1 Or unsaturated (: 10-35 fatty acids, etc.) or derivatives thereof [eg, higher fatty acid salts (eg, barium laurate, lauric acid, calcium stearate, magnesium stearate, zinc stearate) a C 8 - 3 5 fatty acid metal salt or the like; a higher fatty acid ester [for example, a monovalent element of the above higher fatty acid and cetyl alcohol, stearyl alcohol, oleyl alcohol, etc. Esters of alcohols; sucrose fatty acid esters (for example, sucrose with sucrose mono-hexa-stearate) An ester of a higher fatty acid, a glycerin fatty acid ester (for example, an ester of glycerin such as glycerol mono-stearate and an ester of the above-mentioned higher fatty acid), an ester of neopentyltetraol with the above-mentioned higher fatty acid, and diglycerin An ester of a higher fatty acid, a higher fatty acid such as a polyglycerol and an ester of the above higher fatty acid, and a vinegar of a polyhydric alcohol, etc.; a higher fatty acid guanamine (for example, a c 8 3 5 fatty acid guanamine such as stearic acid or the like) , amidoxime bis-stearate octadecylamine, bis-bis-stearic acid sulphate, succinyl bis-hydroxystearate decylamine, etc., etc. Two or more types may be used alone or in combination. Examples of the terpenoids include aliphatic hydrocarbon-based waxes (polybutylene copolymer waxes such as polyethylene wax, ethylene copolymer wax, and polypropylene wax; paraffin).躐, microcrystalline wax, etc., vegetal or animal wax (carnauba wax, beeswax, shellac wax, montan wax, etc.). These waxes can be used alone or in combination of two or more. Examples of the polyoxyxylene resin include alkyl polyoxyalkylenes such as dimethyl polyoxane, diethyl polyoxyalkylene, and trifluoropropyl polyoxyalkylene; -9- 201221557, benzene Polycondensation: aryl polyoxetane such as oxane; methyl strepto-polycene oxide, aryl ioxane, and the like. The polyoxynene resin is a linear polyoxane or a ring-shaped polygas, and a sulfonium can be used. The poly-resin resin of the exclusive use may be used alone or in combination of two or more. These lubricants may be used alone or in combination of two or more. Among the lubricants, it is preferably a solid lubricant in the case of , b ^ i 3 5 ° Γ 士 · , ^ ^ / / (5 main: U or so). In terms of their lubricants, lipids, particularly preferably lauric acid, palmitic acid 'stearic acid (f), acid), behenic acid, montanic acid a saturated C12-30 fatty acid; a saturated C 1 2-30 fatty acid metal salt such as calcium stearate or magnesium stearate; glycerol mono to ginsyl stearate, etc. Ester; a dialkyl-saturated C12-30 fatty acid decylamine such as bis-stearate; particularly suitable for the use of saturated C1 6-22 fatty acids such as palmitic acid, stearic acid, etc.; calcium stearate or stearic acid A saturated C16-22 fatty acid alkaline earth metal salt such as acid town or the like. The content of the lubricant is preferably from 50 to 2000 ppm', more preferably from 1 to 1000 ppm, based on the mass of the resin impregnated fiber bundle. When the temperature is 5 〇 ppm or more, the effect of shortening the measurement time and the effect of improving the error are sufficient, and if it is 200 ppm or less, stable measurement can be performed. The resin composition used in the present invention may contain various well-known various resin additives in the range in which the problems of the present invention can be solved. The well-known additive may include a thermoplastic resin other than the above (except for the aliphatic polyamine other than the above), a release agent, an antistatic agent, a flame retardant, a colorant, a plasticizer, a softener, Dispersant, -10- 201221557 Antagonizer (hindered phenol antioxidant, phosphorus antioxidant, antioxidant, UV absorber, thermal ampoules, etc.), antiblocking agent a granular filler such as a crystal growth agent, a filler (silica) or talc (talc), etc., which are obtained from the raw material of the thin meat molded body of the present invention and the resin composition. The molded body satisfies the requirements of the following (a) and (b). The following requirements (a) and (b) are properties of the thin meat molded body of the present invention having the same thickness. The thickness is 〇·8 to 2 〇mm. The scope of the requirements, the following requirements (a) and (b) can also provide high quality for thin skin molded bodies of different thickness, that is, have high nominal tensile strain and single beam impact strength ( Or check the impact strength) As a product. (a) When using iso multi-purpose test piece (A shape, thickness 2mm) and tensile stress (tensi〇n) test with SOOmm/min, the nominal tensile strain (n〇minaltensilestrain) is 2· 0% or more, and the flexural modulus in absolute dry state is l〇, 〇〇〇MPa or more; Requirement (b) Single-standard impact strength (or inspection impact strength) (according to IS0179/leA (edgeWise)) The test piece has a thickness of 2 mm and has a notch of 30 kJ or more. <Thin meat molded body> The thin meat molding system of the present invention uses the above resin composition (resin impregnated fiber bundle, or resin impregnated fiber bundle and if necessary) In the present invention, it is possible to use a molding machine such as an injection molding machine. In the present invention, a needle-shaped mouth is used as a mold for injection molding in a fine mold or a gentleman (four). =: The weight average fiber in the molded body is good, and the moldability is improved to 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ^月薄肉& Some glass fibers have a length of .5 to 丨.5, preferably .5 to 1 () 匪. 千千均W ί ^ resin impregnated fiber bundle length, resin fiber length ) is 5 to 15 _, preferably "to the heart of the thin meat molding body compensation, _ 纟 use the range of resin impregnated fiber bundle into the lamp injection molding process #, glass fiber breakage rate becomes smaller, becomes 〇.5 The range of 1.5 to 1. The injection molding conditions at this time are as follows. Injection molding machine type (30Τ to 220Τ) Cylinder temperature and mold temperature: Adjusted by the basic coffee called resin (the cylinder temperature is 200 to 3〇〇t', the mold temperature is 5 〇 〇 2〇.) High-speed injection, The injection pressure is 4 〇 to 2 〇〇 Mpa, the back pressure is 〇 to 10 MPa, and the rotation speed is 2 〇 to 2 rpm. Further, even when other molding machines and other molding conditions are applied, by using a resin impregnated fiber bundle having a length of 5 to 15 mm, the weight average fiber length data in the molded body at the time of changing molding conditions can be obtained, and the molding can be easily adjusted. The weight average fiber length in the body is within a predetermined range. 0 -12 - 201221557 The thin meat molding system of the present invention is manufactured using a specific resin impregnated fiber bundle (i.e., a specific resin composition), since the glass long fibers are uniformly Dispersed in the molded body 'when it becomes a thin meat molded body having a thickness of 8 to 2 mm, it also has a high nominal tensile strain and high impact resistance. Therefore, when the thin meat molded body of the present invention is used as, for example, a cover or an internal chassis of a mobile phone, even when the mobile phone falls to the floor and hits a table or the like, it is less likely to damage the outer cover or the inner chassis. In addition, the molded body obtained from the resin composition which is a raw material for the production of the thin meat molded body of the present invention is preferably a dimensional change rate (by thickness) of the molded body obtained from the resin composition due to water absorption. The mm measurement was 0.05% or less (saturated water absorption state in an environment of 23 ° C / 50% RH). The dimensional change rate is a property of a thin meat molded body having the same thickness as the measurement test, and even a thin meat molded body having a thickness of 〇8 to 2 〇mm can provide a high quality product (due to water absorption). The product with a small dimensional change rate is used as a product. The thin meat forming system of the present invention is suitable for being selected from the group consisting of a mobile phone, a mobile personal digital assistant (PDA), a smart phone, a car navigation, a game machine, a cassette tape, a (10) player, a DVD player, an electronic diary, an electronic dictionary, Computer, hard disk recorder, personal computer, camera, digital camera, electronic machine cover or internal chassis. Among them, 'especially suitable as a mobile phone, a mobile personal digital assistant (PDA), an external mobile phone for smart phones, a cover (a combination of upper and lower) or an internal chassis disposed inside the cover. . -13- 201221557 [Examples] (Polyuramine) PA12-1 : DAIAMID1600 (Daice Bu Evonik Co., Ltd.) PA12-1 : DAIAMID1700 (Daicel-Evonik Co., Ltd.) PA612 : DAIAMIDBS1090 (Daicel-Evonik) )) PA610 : VESTAMID ierra HS 1 6 (Daicel-Evonik) (Comparative Polyamide) MXD6 : Reny6002 (Mitsubishi Plastics Co., Ltd.) PA6T-1 : VESTAMID HTplusM 1000 (Daicel-Evonik) (share) system) PA6: UBE resistance 1013B (Ube Industries Co., Ltd.) PA66: UBE nylon 2020B (Ube Industries Co., Ltd.) (glass fiber) GF_1 : RS240QR-483 (made by Nitto Spinning Co., Ltd.) Glass fiber roving, 4000 fiber bundles, average fiber diameter 17" ''The cross-sectional shape is circular' GF_2 · CSX_3J-451S (made by Nitto Spinning Co., Ltd.) [Chopped strand] (Other ingredients) External lubricant. St-Ca (calcium stearate, sc_1〇〇 (manufactured by Sigma Chemical Industry Co., Ltd.) (Method for producing test piece for physical property measurement) Device: (share) manufactured by Nippon Steel Co., Ltd., J-150E Π Screw: special screw for long fiber-14- 201221557 Direct screw control: 5 1 mm Forming condition (back pressure): 〇.3MPa ( Gauge (gUage) (1) Molded product 1: ISO multi-purpose test piece A-shaped product (thickness: 2 mm) Side-washed (20) wide side gate (2) Molded product 2 : 1 OOmmx 1 00 mm square flat molded product (thickness: 1 mm) Washing type is 1 宽mm wide side gate (measurement method) (1) Single beam impact test (or inspection of impact test; Charpy impact test According to IS0179/leA (edgewise). Test piece shape: length 80mmx width i〇mmx thickness 2mm with notch (depth 2mm) From [ISO multipurpose test piece type A shape (thickness 2mm) ] Notching machine (automatic notch machine) Using N〇.189-PNCA_2 (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) for processing. (2) Tension test (tension strength and nominal pull) Nominal tensile strain) Use molded product 1 with the clamp spacing! The measurement was carried out at i5 mm and a test speed of 500 mm/min. (3) Bending test (bending elastic modulus) The molded product was measured using a pulverization pitch of 32 mm and a test speed of 1 mm/min. 201221557 (4) Moisture rate (water absorption rate) and dimensional change rate (rate change rate) The water-induced ruler is individually immersed in 6 (rc water after individual measurement molding) and molded product 2 molded product quality. Let the % hour ° state then 'take the paper towel to fully wipe the quality of the molded product. 〆 俊 俊 ' Then 'placed in 23 ° C / 50% RH environment, record the quality of the record _ between the changes, can not The state of the mass change is confirmed as the saturated water absorption state in the environment of 23, that is, the water absorption (hygroscopic state). 水分 The water rate and the dimensional change rate are determined by the following formula (the length L change rate between the arrows of the third arrow) ^ Absolute moisture rate (%) = (water absorption (hygroscopic) state of the molded product quality dry molded product quality V absolute dry molded product mass xl 〇〇 size change rate (%) = water absorption state length L eight absolute The degree of drying LxlOO * The bending elastic modulus (the water absorption state and the absolute dry state shown in Tables 1 and 2) was measured by "(3) bending test (bending elastic modulus)" (weight average fiber length) from molded article 1, 2 cut about 3g of sample to 65〇〇c The fiber was austenated by heat and the fiber was taken out. The weight average fiber length was determined from a part of the fiber taken out (V 艮 。). The formula is used in [0044] and [0045] of JP-A-20 06-274061. (Measuring time measurement method) Injection molding machine: S-200〇i 100B (screw diameter: 32), -16- 201221557 The sample granules were placed in the feed hopper of the injection molding machine to determine the measurement time under the following conditions. It is confirmed by 1 shot injection. The measurement time (seconds) is confirmed by the injection molding machine operation panel screen. • Measurement value: 40mm • Number of revolutions: 80rpm • Back pressure: 3MPa • Tube temperature: 2 5 0. (: [ Example 1] A glass fiber yarn bundle (GF i ) was pulled out by a cross head die which had processed a continuous fiber passage into a wave shape, while being melted from an extruder connected to a right angle die. (26 (rc) is supplied as pAi2i as a thermoplastic resin and impregnated into glass fiber. ',,; then passed through a forming die and pulled as a strand, and then cut after cooling to obtain a glass fiber content of 6 〇. %, 9mm length particles (resin Dip fiber bundle). 200 ppm of calcium stearate (St_Ca) was added to the obtained particle U. The p-filled alpha agent was injection-molded (barrel temperature was 2 $ 〇, mold temperature was 9 CTC (measured)) 'Preparation of test pieces for each measurement. [Example 2] By processing a continuous fiber passage into a wavy right angle die = glass fiber yarn bundle (GF)), while being connected from a right angle die = In the molten state (260t), the plastic resin is supplied and impregnated into the glass fiber. Then, 'through the forming die and pulled as the strands' cooling and then: 'the glass fiber content is 6〇 mass%, the length is 9匪 granules (1⁄4 grease impregnated fiber bundles). -17- 201221557 The obtained pellets were directly injection-molded (the cylinder temperature was 25 〇c, and the mold temperature was 90. (: (measured))'. The test piece for each measurement was prepared. [Example 3] The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, while being melted from the extruder connected to the right angle die (260. 〇 supply PA12-1) It is a thermoplastic resin and is impregnated into glass fiber. Then, it is drawn into a strand by a forming die, and is cut after cooling to obtain particles having a glass fiber content of 60% by mass and a length of 9 mm (resin impregnated fiber bundle) 200 ppm of calcium stearate (St_Ca) was added to the obtained granules. The p-lubricator was injection-molded (the cylinder temperature was 2 5 〇, and the mold octave was 9 0 c (measured) ()) A test piece for each measurement was prepared. The back pressure of the test piece preparation molding conditions at this time was 198 MPa (gauge pressure display). Comparing Example 3 of Table 1 with other examples, the length of the fiber bundle was compared. The weight average fiber length is shorter, The odd pressure when the above is emitted as 1 is also higher than that of the other examples (〇3Mpa) (1.98 MPa). Therefore, by adjusting the injection molding conditions, the weight average fiber of the glass fiber in the body can be adjusted. [Example 4] The glass fiber yarn bundle (GF-1)' was pulled out and passed through a right angle die which processed the continuous fiber passage into a wavy shape, and was squeezed from the right angle die. Cancer (26〇c), PA121 as thermoplastic resin, 3 immersed in glass fiber. -18- 201221557 Then, through the forming die and pulling as a strand, after cooling, cutting to obtain the glass fiber content 50% by mass of particles having a length of 6 ( (resin impregnated fiber bundle). 200 ppm of calcium stearate (St_Ca) was added to the obtained granules as an external lubricant for injection molding (the cylinder temperature was 25 〇). It, the mold temperature was 9 (TC (measured))', and the test piece for each measurement was made. [Example 5; | The glass fiber yarn bundle was pulled out by processing the continuous fiber passage into a wavy right angle die ( GF]), simultaneously from the extruder connected to the right angle die In the molten state (26 (). 〇 supply, as a thermoplastic resin, sub-impregnated into glass fiber. Then, through the shaping die and pull as a strand, after cooling and cutting, to obtain a glass fiber content of 5 〇% by mass, length is the accompanying granules (resin impregnated fiber bundles). 200 ppm of stearic acid strontium stearate (St_Ca) is added to the obtained granules as an external lubricant for injection molding (cylinder temperature is 2) A test piece for each measurement was prepared with a mold temperature of 9 (TC (measured)). [Example 6] A glass fiber yarn bundle (GF) was produced by processing a continuous fiber passage into a wavy right angle die. ]), at the same time, from the extruder connected to the right-angle die, in a molten state (2 scratch), PA12_2 is used as a thermoplastic resin, and impregnated into the glass fiber. Then, it was taken as a strand by a forming die and pulled, and then cut after cooling to obtain a glass fiber content of 5. 9% by mass (resin impregnated fiber bundle). -19- 201221557 Add 200 ppm of calcium stearate (St-Ca) to the obtained pellets as an external lubricant for injection molding (cylinder temperature is 25 (TC, mold temperature is 90 ° C (measured)) A test piece for each measurement was prepared. [Example 7] A glass fiber yarn bundle (GF-1) was pulled out by processing a continuous fiber passage into a wavy right angle die while being connected from a right angle die. The extruder supplies PA612 as a thermoplastic resin in a dazzling state (28 (TC), and is impregnated into the glass fiber. Then, it is taken as a strand by a forming die and drawn as a strand, and then cut and cooled to obtain a glass fiber. Particles having a content of 50% by mass and a length of 9 mm (resin impregnated fiber bundles). 200 ppm of calcium stearate (st-Ca) was added to the obtained pellets as an external lubricant for injection molding (the cylinder temperature was A test piece for each measurement was prepared at a mold temperature of 9 (TC (measured)). [Example 8] A broken fiber yarn was pulled out by processing a continuous fiber passage into a wavy right angle die. Bunch (GF-i) while simultaneously squeezing from a right angle die The machine is in a molten state (280. 〇 supply! > 612 as a thermoplastic resin, and impregnated into the glass fiber. Then, it is taken as a strand by a forming die and pulled, and then cut to obtain a glass fiber. Particles having a content of 40% by mass and a length of 9 mm (resin impregnated fiber bundles). 200 ppm of calcium stearate (St_Ca) was added to the obtained pellets as an external lubricant for injection molding (the cylinder temperature was 28 〇). 〇, the mold temperature was 90t (measured)), and the test piece for each measurement was produced., -20-201221557 [Example 9] The glass fiber yarn was pulled out by processing the continuous fiber passage into a wavy right angle die. Bunch (purchase), while dragging from a right angle die

The press supplies PA61G as a thermoplastic tree in a molten state (war): impregnated into glass fiber. I Then, by forming a die and pulling it as a strand, after cooling, it is cut to obtain a glass fiber content of 5 〇 mass% and a length of 9 _: a pellet (resin impregnated fiber bundle). 200 ppm of calcium stearate (St_Ca) was added to the obtained pellets as an external lubricant for injection molding (barrel temperature of 28 〇 1, mold temperature of 90 t (measured)), and the test was performed for each measurement. sheet. [Comparative Example 1] After mixing 50% by mass of PA12-1 as a thermoplastic resin and 〇5% by mass of glass fiber (Ch〇Ppedstrand) (GF_2) by a tumbler blender, The extruder (22 (rc) was melt-kneaded to obtain a pelletized resin composition. The obtained pellets were injection-molded (barrel temperature was 25 〇〇c, and mold temperature was 90 °C (measured)) A test piece for each measurement was prepared. [Comparative Example 2] After mixing 50% by mass of PA6 12 as a thermoplastic resin and 50% by mass of glass fiber strands (GF_2) by a roller mixer, 'extruding machine (240) C) The resin composition was obtained by melt-kneading to obtain a pellet. The obtained pellets were injection-molded (the cylinder temperature was 280. (:, the mold temperature was 90 ° C (actual measurement)), and the pellets were prepared for each measurement. Test piece. 201221557 [Comparative Example 3] The glass fiber yarn bundle (GF-丨) was pulled out by processing the continuous fiber passage into a wavy right angle die, while being melted from the extruder connected to the right angle die. (29(rc) supplies MXD6 as a thermoplastic resin and impregnates The glass fiber is then passed through a shaping die and pulled as a strand, and after cooling, it is cut to obtain particles having a glass fiber content of 50% by mass and a length of 6 mm (resin impregnated fiber bundle). 20 〇 ppm will be added. The calcium stearate (St_Ca) was injection-molded as the external lubricant (the barrel temperature was 28 〇. (:, the mold temperature was 13 CTC (measured)), and test pieces for each measurement were prepared. [Comparative Example 4] The glass fiber yarn bundle (GF-D was pulled out by processing the continuous fiber passage into a wavy right angle die, and at the same time, from the extruder connected to the right angle die to the molten state (340. The PA6T is supplied as a thermoplastic resin and impregnated into the glass fiber. Then, it is drawn into a strand by a forming die, and is cut after cooling to obtain a glass fiber content of 50 mass%/. and a length of 9 mm. Granules (resin impregnated fiber bundles). 200 ppm of calcium stearate (St_Ca) was added to the obtained pellets as an external lubricant for injection molding (cylinder temperature of 33 〇 c > c, mold temperature of 14 (TC) (measured)), A test piece for each measurement was prepared. [Comparative Example 5], the straight angle of the die angle die of the extrusion head was connected to the wave connection wave from the working time plus the same path, and the F 隹G fiber bundle of the pass-1) continued. Yarn Lianwei will pass through the glass through the glass--22- 201221557 The press supplies the PA66 as a thermoplastic resin in a molten state (320〇C) and impregnates it into the glass fiber. Then, by shaping the die and pulling it as The strands were cut after cooling to obtain pellets (resin impregnated fiber bundles) having a glass fiber content of 6 〇 mass% and a length of 9 mm. 20 〇ppm of calcium stearate (St_Ca) was added to the obtained granules. The lubricant was subjected to injection molding (the cylinder temperature was 3 〇 、, and the mold temperature was loot (measured)), and test pieces for each measurement were prepared. [Comparative Example 6] The glass fiber yarn bundle ((4)) was pulled out by processing the continuous fiber passage into a wavy right angle die, and was supplied from the extruder connected to the right angle die in a molten state (2 赃). PA6 is used as a thermoplastic resin and impregnated into glass fibers. Then, it was taken as a strand by a forming die and pulled, and then cut by cooling to obtain particles having a glass fiber content of 6 〇 mass% and a length of 9 Å (resin impregnated fiber bundle). 200 ppm of stearin was added, and the obtained pellet was used as an external lubricant for injection molding (the cylinder temperature was 28 generations, and the mold temperature was HHTC (measured)), and test pieces for each measurement were prepared. A horn-shaped right-angle die is processed, and the extruded PA12-1 attached to the right-angle die is used as a thermoplastic resin, and the press is melted by pulling the continuous fiber passage out of the glass fiber bundle (GF-1). (27CTC) supplied and impregnated into the glass fiber. -23- 201221557 Then 'through the forming die and pulling it as a strand, and then cutting it after cooling to obtain particles with a glass fiber content of 30% by mass and a length of 9 mm. (Resin impregnated fiber bundle). Add 2 〇〇ppm of calcium stearate (St_Ca) to the obtained granules as an external lubricant for injection molding (cylinder temperature of 25 (TC, mold)

Test pieces for each measurement were prepared at a temperature of 9 (TC (measured))'. [Comparative Example 8 J The glass fiber yarn bundle (GF-i) was pulled out by processing a continuous fiber passage into a wavy right angle die while being in a molten state from an extruder connected to a right angle die (270. 〇Purq is supplied as a thermoplastic resin and impregnated into glass fiber. The strands are cooled and then subjected to a length of 18 mm and then 'cut through a forming die as a cut' to obtain a glass fiber content of 5 〇 mass%. (Resin impregnated fiber bundle). Although it is desired to add 200 Ppm of calcium stearate (St_Ca) to the obtained lubricant as an external lubricant, the injection molding is carried out (cylinder temperature ^ 25 〇 f, mold temperature is 9 ( TC (measured)), since the particles are stuck on the screw and cannot be inserted, the injection molding cannot be performed. [Comparative Example 9] The fiber bundle (GF) is processed by processing the continuous fiber passage into a wavy right angle die. At the same time, from the squeezed state connected to the right angle die, PA12] is used as the thermoplastic resin, and 3 times on the glass fiber. Then the cut, although the particles, are formed by the forming die and pulling For the strands, after cooling, they want to make glass fiber. The content of the dimension is 5〇 mass%, the length is 4mm, but the particles are broken, and the particles cannot be obtained. -24- 201221557 εε 061 ιτ

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Ds (0/0) 跻 妥 ( (%) (跻-剑5 The friend 乂Ν-^) 跻qj, 铋^ν zDs 201221557 Comparison of Example 5 with Comparative Example 1, Example 7 and Comparative Example 2 It can be seen that 'single beam impact strength (or suede impact strength), tension strength and nominal tensile strain are significantly deteriorated when using glass staple fibers (Comparative Examples 1, 2 cannot Have the requirements (a), (b)). From the comparison of Examples 4 to 7 with Comparative Examples 3 and 4, it was confirmed that when the polyamine which is different from the present invention was used, the single beam impact strength, the tensile strength and the nominal tensile strain were significantly deteriorated (Comparative Example) 3, 4 can not have the requirements (a), (b)). Further, in Comparative Example 1 and Table 2 of the Japanese Patent Laid-Open Publication No. Hei. No. Hei.

The results are close, and other results are considered to be 4.5 mm and the diameter is 1 〇 " [Simple Description] The resin impregnated fiber bundle is the same as Comparative Examples 1 and 2 of Table 2.

-27-

Claims (1)

201221557 VII. Patent application scope: 1. A thin meat molded body which is bundled in a state in which the long glass fibers are uniformly oriented in the longitudinal direction, and the aliphatic polyamine is impregnated into the glass long fiber in a molten state. After being bundled and integrated, it is obtained from a resin composition comprising a resin impregnated fiber bundle cut to a length of 5 to 15 with a thickness of 0.8 to 2.0 mm, and the weight average fiber length of the glass fiber contained is 0.5. a thin meat molded body of i.5 mm; wherein the resin impregnated fiber bundle contains an aliphatic polyamine selected from the group consisting of pA11, pA12, PA6 10 , and PA6 1 2 , and the glass fiber content is 40 to 70% by mass; The molded body obtained from the resin composition satisfies the requirements of the following (3) and (b); (a) When an ISO multipurpose test piece (A shape, thickness: 2 mm) is used and the tension is performed at 50 mm/min ( Tensi〇n) The nominal tensile strain at the time of the test is 2.0% or more, and the bending elastic modulus in the absolute dry state is 丨〇Gpa or more; (b) Single beam impact strength (or skin impact strength) ) (according to IS〇179/leA (edge (e Dgewise)) (the test piece has a thickness of 2 mm and has a notch) of 30 kJ or more. 2. The thin meat molded body of the invention of claim 2, wherein the molded body obtained from the resin composition is absorbent The dimensional change rate is 0.05% or less (saturated water absorption state in a 23 t /5 % RH environment). 3. The thin meat molded body according to claim 1 or 2, further containing a lubricant. -28- 201221557 4. The thin meat molded body of claim 1 or 2, wherein the thin meat molded body is a housing or an internal chassis of an electronic machine, and the outer cover or internal chassis of the electronic machine is used for a mobile phone and a mobile personal digital device. PDA (personal digital assistant), a cover for an intelligent mobile phone or an internal chassis. 5. A method for manufacturing a thin meat molded body, which is manufactured as a thin meat molded body according to any one of claims i to 4 In the method, in which the resin composition is melted and then subjected to injection molding to form a mold, a pin gate is used as an injection molding die. Any of the scopes 1 to 4 of the patent scope ~/ The use of the electronic machine cover for the meat-forming body. -29-