TWI535764B - Thin-wall molded article, manufacturing method of same and use of electronic device housing - Google Patents

Description

Thin meat molded body, manufacturing method and use of electronic machine cover

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 of manufacturing the same, and the use of the electronic device cover.

The electronic device cover or the internal chassis of a mobile phone or the like is composed of a thin meat molded body, and is required to have a high flexural modulus, excellent impact resistance, and a small dimensional change rate due to water absorption.

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 No.) Item 1) The use of the frame as a mobile phone is described in Item 28 of the patent application.

The glass fiber system is described in paragraph numbers 0048 and 0049, and it is described that long glass fibers are excluded.

In the comparative examples (CE) 1 and 2 of Table 1, the 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 10 μm is circular) is described. The beam impact strength (or the inspection impact strength) (having a notched) becomes a low value of 22 kJ/m ² and 17 kJ/m ² . It is considered that in the method for adjusting the polyamide molding material described in paragraph No. 0,058, the glass fiber is broken and becomes small, and is substantially the same as in the case of using short fibers.

Japanese Laid-Open Patent Publication No. 2010-511778 discloses a portable electronic device cover jig composed of a thermoplastic polyamide and a fibrous reinforcing agent having a non-circular cross section.

Although most thermoplastic polyamines are listed in the second paragraph of the patent application, only PA10, 10, PA6, 6, PA6, I/6, T are used in the examples.

In paragraph number 0021, it is described 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 that the single beam impact strength (or the inspection impact strength) (with notched) shown in Table 2 is small, which is obviously short fiber. .

In the Japanese Patent Publication No. 2010-510375, JP-A-2009-79212, JP-A-2010-510375, and JP-A-2008-106265, a composition comprising a polyamide and a glass fiber is described. However, PA11, PA12, and PA612 were not used as polyamines, and a combination of specific glass long fibers was used.

The present invention has an object of providing a thin meat molded body of an electronic device outer cover or an inner chassis which is excellent in impact resistance and small in dimensional change due to water absorption, and is suitable as a mobile phone.

The invention provides

A thin meat molded body which is bundled in a state in which a long glass fiber is uniformly oriented in a longitudinal direction, and an aliphatic polyamine is impregnated into the glass long fiber bundle in a molten state and integrated, and then a thin meat molded body having a thickness of 0.8 to 2.0 mm obtained by cutting a resin composition of a resin impregnated fiber bundle having a length of 5 to 15 mm, and a glass fiber having a weight average fiber length of 0.5 to 1.5 mm; the resin impregnated fiber The bundle contains a material selected from the group consisting of PA11, PA12, PA610, and PA612, and the content of the glass fiber is 40 to 70% by mass; the molded body obtained from the foregoing resin composition satisfies the requirements of the following (a) and (b); Means of solution.

(a) When using an ISO multipurpose test piece (A shape, thickness: 2 mm) and performing a tension test at 500 mm/min, the nominal tensile strain is 2.0% or more, and is in an absolute dry state. The bending elastic modulus is 10 GPa or more;

(b) single beam impact strength (or skin impact strength) (according to ISO 179/1eA (edgewise) (test piece thickness 2 mm, with notch) is 30 kJ or more;

As a solution to the problem.

The invention provides

A method for producing a thin meat molded body, which is a method for producing a thin meat molded body according to any one of claims 1 to 5, wherein after the melting of the resin composition, injection molding is carried out to form a needle. The pin gate is used as a solution to other problems as a mold for injection molding.

The present invention is further related to the use of the electronic machine cover of the above-mentioned thin meat molded body.

The thin meat molding system of the present invention is composed of a resin composition comprising an aliphatic polyamine selected from the group consisting of PA11, PA12, PA610, PA612 and a resin impregnated fiber bundle containing glass long fibers, although the thickness is as thin as 0.8 to 2 mm, It has high impact strength and a small dimensional change rate due to water absorption. Therefore, it is suitable for use as an electronic machine cover or an internal chassis such as a mobile phone cover or an internal chassis.

<Resin composition>

The resin impregnated with the fiber bundle contained in the resin composition of the present invention is bundled in a state in which the long glass fibers are uniformly oriented in the longitudinal direction, and impregnated into the glass long fiber bundle in the state of molten polyamine. After being integrated, it is cut into a length of 5 to 15 mm (preferably 6 to 12 mm). The length of the glass fibers 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 PA11 (condensed polymer of undecane decylamine), PA12 (condensed polymer of dodecane decylamine), PA610 (hexamethylenediamine and a condensation polymer of sebacic acid), PA612 (a condensation polymer of caprolactam and dodecane decylamine).

The glass fiber system included in the resin impregnated fiber bundle may have a fiber diameter (single wire diameter) of 6 to 30 μm, and the number of glass fibers of one fiber bundle is 100 to 30,000, preferably 500 to 20,000, more Good for about 1,000 to 10,000.

The resin impregnated fiber bundle system can be produced by a well-known manufacturing method using a dies, for example, in addition to paragraph number 7 of JP-A-H06-313050, and paragraph number 23 of JP-A-2007-176227. Japanese Patent Publication No. 6-2344 (Manufacturing Method and Forming Method of Resin-Coated Long Fiber Bundle), JP-A-6-114832 (Fiber-reinforced Thermoplastic Resin Structure and Method of Producing the Same), and Japanese Patent Laid-Open Japanese Laid-Open Patent Publication No. Hei 7-205317 (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei 7-205317) (Method for Extracting Fiber Bundles and Method for Producing Long Fiber Reinforced Resin Structure), Japanese Patent Laid-Open No. Hei 7-216104 Japanese Laid-Open Patent Publication No. Hei 7-251437 (Manufacturing Method and Manufacturing Apparatus of Long Fiber Reinforced Thermoplastic Composite Material), Japanese Laid-Open Patent Publication No. Hei 8-118490 (right angle die ( A manufacturing method described in the cross-head die and the method for producing a long fiber reinforced resin structure.

The ratio of the glass fiber to the aliphatic polyamine in the resin impregnated fiber bundle used in the present invention is 40 to 70% by mass, preferably 50 to 60% by mass, and the total amount of the aliphatic polyamine is The ratio of the remaining portion of 100% by 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 impregnated 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 in the injection molding machine can be shortened, and the measurement error can be reduced.

The lubricant includes a conventional lubricant, a liplip, a wax, a silicone resin, and the like.

Examples of the lipids include higher fatty acids (for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid). Saturated C8-35 fatty acids (preferably saturated C12-30 fatty acids, such as stearic acid, arachidic acid, behenic acid, montanic acid, 12-hydroxystearic acid, etc. More preferably, it is a saturated C16-22 fatty acid), a palmitoleic acid, an oleic acid, an unsaturated C10-35 fatty acid such as erucic acid, or the like, or a derivative thereof [for example, Higher fatty acid salts (for example, lauric acid laurate, zinc laurate, calcium stearate, magnesium stearate, zinc stearate, etc., C8-35 fatty acid metal salts, etc.); higher fatty acid esters [for example, the aforementioned higher fatty acids and Esters of monohydric alcohols such as cetyl alcohol, stearyl alcohol, oleyl alcohol, etc.; sucrose fatty acid esters (for example, sucrose and the like of sucrose mono-hexa-stearate) An ester of the above higher fatty acid) or a glycerin fatty acid ester (for example, glycerol mono to stannic acid ester or the like) An ester of glycerin and the above-mentioned higher fatty acid), an ester of neopentyltetraol with the above-mentioned higher fatty acid, an ester of diglycerin and the above-mentioned higher fatty acid, an ester of a higher fatty acid and a polyhydric alcohol such as an ester of a polyglycerin and a higher fatty acid. Higher fatty acid guanamine (for example, C8-35 fatty acid decylamine such as stearic acid decylamine, decyl methylene bis-stearate, decyl bis-stearate, bis-hydroxy stearate An alkylamine bis-stearate such as decylamine or the like). These lipids may be used alone or in combination of two or more.

Examples of the wax include aliphatic hydrocarbon-based waxes (polyethylene C2-4 olefin waxes such as polyethylene wax, ethylene copolymer wax, and polypropylene wax; paraffin wax and microcrystalline wax). Etc.), botanical or animal wax (carnauba wax, beeswax, shellac wax, montan wax, etc.). These waxes may 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; and diphenyl polyfluorene oxide; An aryl polyoxyalkylene such as an alkane; an alkylaryl polyoxyalkylene such as a methylphenyl polysiloxane or the like. The polyoxyxylene resin may be a linear polyoxane or a cyclic polyoxane. These polyoxygenated resins 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 these lubricants, at room temperature (about 5 to 35 ° C), a solid lubricant is preferred.

In terms of their lubricants, lipids, particularly preferably lauric acid, palmitic acid, stearic acid, behenic acid, montanic acid a saturated C12-30 fatty acid; a saturated C12-30 fatty acid metal salt such as calcium stearate or magnesium stearate; a glycerol mono to succinic stearate-like glycerol mono-saturated C12-30 fatty acid ester; Ethylene alkyl di-saturated C12-30 fatty acid decylamine such as bis-stearate, particularly suitable for use with saturated C16-22 fatty acids such as palmitic acid, stearic acid, etc.; calcium stearate or magnesium stearate Saturated C16-22 fatty acid alkaline earth metal salt and the like.

The content of the lubricant is preferably from 50 to 2,000 ppm, more preferably from 100 to 1,000 ppm, based on the mass of the resin impregnated fiber bundle. When it is 50 ppm or more, the effect of shortening the measurement time and the effect of improving the error are sufficient, and when it is 2000 ppm or less, stable measurement can be performed.

The resin composition used in the present invention may contain various known resin additives insofar as it can solve the problems of the present invention.

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, stabilizer (hindered phenol-based antioxidant, phosphorus-based antioxidant, anti-oxidant such as sulfur-based antioxidant, ultraviolet absorber, thermal stabilizer, etc.), antiblocking agent, crystal A nuclear growth agent, a filler (a granular filler such as silica or talc), or the like.

The molded body obtained from the raw material of the thin meat molded body of the present invention and the resin composition to be formed 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. In the range of 0.8 to 2.0 mm in thickness, the following requirements (a) and (b) may also be thin meat molded bodies of different thicknesses, which can provide high quality, that is, have a high nominal tensile strain (nominal tensile strain). Strain) and single beam impact strength (or skin impact strength) as a product.

Essentials (a)

When using an ISO multipurpose test piece (A shape, thickness 2 mm) and performing a tension test at 500 mm/min, the nominal tensile strain is 2.0% or more, and the bending elasticity in an absolute dry state The rate is 10,000 MPa or more;

Essentials (b)

Single beam impact strength (or skin impact strength) (according to ISO 179/1eA (edgewise) (test piece thickness 2 mm, with notch) is 30 kJ or more.

<thin meat molding body>

In the thin meat molding system of the present invention, the resin composition (resin impregnated fiber bundle or resin impregnated fiber bundle and other components contained in the case) may be used, and it may be molded by a molding machine such as an injection molding machine.

In the present invention, a needle having a pin gate is used as an injection molding die at the time of injection molding.

The size (diameter) of the needle gate is preferably from 0.5 to 2.0 mm, more preferably from 0.7 to 1.5 mm. When the size of the needle gate is 0.5 mm or more, the breakage of the glass fiber is suppressed, and the weight average fiber length in the thin meat molded body can be 0.5 mm or more. When the needle shape is 2.0 mm or less, the gate material is cut well. The moldability is improved.

The thin meat molded body of the present invention has a thickness of 0.8 to 2.0 mm and can be adjusted depending on the specific use.

The glass fiber contained in the thin meat molded body of the present invention has a weight average fiber length of 0.5 to 1.5 mm, preferably 0.5 to 1.0 mm.

Further, the resin impregnated fiber bundle length (i.e., the length of the glass fiber) contained in the resin composition is 5 to 15 mm, preferably 6 to 12 mm. In the production of the thin meat molded body, the glass fiber breakage rate is reduced during the injection molding using the resin impregnated fiber bundle in the above range, and is in the range of 0.5 to 1.5 mm. The injection molding conditions at this time are as follows.

Injection molding machine type (30T to 220T)

Cylinder temperature and mold temperature: suitable adjustment by base resin (cylinder temperature is 200 to 300 ° C, mold temperature is 50 to 120 ° C)

The high-speed injection and injection pressures are 40 to 200 MPa, the back pressure is 0 to 10 MPa, and the rotation speed is 20 to 200 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.

The thin meat molding system of the present invention is produced by using a specific resin impregnated fiber bundle (i.e., a specific resin composition), and is formed into a thin meat having a thickness of 0.8 to 2.0 mm by uniformly dispersing the long glass fibers in the molded body. In the case of body, 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, hits a table or the like, it is not easy 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 producing the thin meat molded body of the present invention is preferably a dimensional change rate (by a thickness of 1 mm) of the molded body obtained from the resin composition due to water absorption. The 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 0.8 to 2.0 mm in thickness can provide a high quality (dimension change due to water absorption). The rate is small) 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 player, a CD 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, it is particularly suitable for use as a mobile phone, a mobile personal digital assistant (PDA), a smart phone cover (a combination of an upper case and a lower case) or an internal chassis disposed inside the cover.

[Examples] (polyamine)

PA12-1: DAIAMID1600 (Daicel-Evonik (share) system)

PA12-1: DAIAMID1700 (Daicel-Evonik (share) system)

PA612: DAIAMIDBS1090 (Daicel-Evonik (share) system)

PA610: VESTAMID terra HS16 (Daicel-Evonik)

(Compared with polyamine)

MXD6: Reny6002 (Mitsubishi Engineering Plastics Co., Ltd.)

PA6T-1: VESTAMID HTplusM1000 (Daicel-Evonik)

PA6: UBE nylon 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 of 17.4 μm; cross-sectional shape is circular]

GF-2: CSX-3J-451S (made by Nitto Spin Co., Ltd.) [Chopped strand]

(other ingredients)

External lubricant: St-Ca (calcium stearate, SC-100 (manufactured by Dai Chemical Industry Co., Ltd.)

(Method for producing test piece for physical property measurement)

Device: (share) made by Nippon Steel Co., Ltd., J-150E II

Screw: special screw for long fiber

Screw diameter: 51mm

Molding conditions (back pressure): 0.3MPa (guage)

(1) Molded product 1: ISO multi-purpose test piece A-shaped product (thickness: 2 mm)

The gate is 20mm wide with a side gate

(2) Molded product 2: 100 mm × 100 mm square flat molded product (thickness: 1 mm)

The gate shape is a 10mm wide side gate

(test methods)

(1) Single beam impact test (or Charpy impact test; Charpy impact test)

According to ISO179/1eA (edgewise).

Test piece shape: length 80 mm × width 10 mm × thickness 2 mm with notch (depth 2 mm)

From the [ISO multi-purpose test piece type A shape (thickness: 2mm)] notching machine (automatic notch machine)

No. 189-PNCA-2 (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used for processing.

(2) Tension test (tension strength ‧ nominal tensile strain)

The molded article 1 was used, and the measurement was performed at a jig pitch of 115 mm and a test speed of 500 mm/min.

(3) Bending test (bending elastic modulus)

Using the molded article 1, the measurement was carried out at a fulcrum pitch of 32 mm and a test speed of 1 mm/min.

(4) Moisture rate (water absorption rate) and dimensional change rate (dimension change rate due to water absorption)

After individually measuring the molded product quality of the molded article 1 and the molded article 2 in an absolutely dry state, they were individually immersed in water at 60 ° C for 96 hours.

Then, the molded articles 1 and 2 were taken out, and the water was sufficiently wiped with a paper towel, and then the molded product quality was measured.

Then, placed in a 23 ° C / 50% RH environment, the quality of the recording changes with time, the state of the mass change can not be confirmed as a saturated water absorption state in the environment of 23 ° C / 50% RH, that is, water absorption (hygroscopic) state .

The water content and the dimensional change rate (the change rate of the length L between the arrows shown in Fig. 1) were obtained by the following formula.

Moisture rate (%) = (mass of molded product in water absorption (hygroscopic) state - absolute dry molded product quality) / absolute dry molded product quality × 100

Dimensional change rate (%) = length of water absorption state L / absolute dry length L × 100

The flexural modulus (the water absorption state and the absolute dry state shown in Tables 1 and 2) were measured by "(3) bending test (bending elastic modulus)".

(weight average fiber length)

Approximately 3 g of the sample was cut out from the molded articles 1 and 2, and ash was heated at 650 ° C to take out the fibers. The weight average fiber length was determined from a part (500 pieces) of the taken fibers. The equations are [0044] and [0045] of JP-A-2006-274061.

(measurement time measurement method)

Injection molding machine: S-2000i 100B (screw diameter is 32),

The sample pellets were placed in a feed hopper of an injection molding machine, and the measurement time under the following conditions was determined. The error is confirmed with 10 injections. 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: 250 ° C

[Example 1]

The glass fiber yarn bundle (GF-1) is pulled out by a cross-head die that has processed the continuous fiber passage into a wave shape while being in a molten state from the extruder connected to the right angle die (260) °C) PA12-1 was supplied 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 after cooling to obtain pellets (resin impregnated fiber bundle) having a glass fiber content of 60% by mass and a length of 9 mm.

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 250 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Embodiment 2]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA12-1 is supplied in a molten state (260 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated into glass fibers.

Then, it was taken as a strand by a forming die and pulled, and then cut after cooling to obtain pellets (resin impregnated fiber bundle) having a glass fiber content of 60% by mass and a length of 9 mm.

The obtained pellets were directly injection-molded (the cylinder temperature was 250 ° C, and the mold temperature was 90 ° C (measured)), and test pieces for each measurement were 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, and the PA12-1 is supplied in a molten state (260 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated into glass fibers.

Then, it was taken as a strand by a forming die and pulled, and then cut after cooling to obtain pellets (resin impregnated fiber bundle) having a glass fiber content of 60% by mass and a length of 9 mm.

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 250 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece. At this time, the back pressure of the test piece production molding conditions was 1.98 MPa (gauge pressure display)).

Comparing Example 3 of Table 1 with the other examples, the length of the fiber bundle was compared, and the weight average fiber length was shorter, because the back pressure at the time of injection molding was higher than that of the other examples (0.3 MPa) (1.98). MPa). Therefore, by adjusting the injection molding conditions, the weight average fiber length of the glass fibers in the molded body can be adjusted.

[Example 4]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA12-1 is supplied in a molten state (260 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated into glass fibers.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 50% by mass and a length of 6 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 250 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Example 5]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA12-1 is supplied in a molten state (260 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated into glass fibers.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 50% by mass and a length of 12 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 250 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Embodiment 6]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA12-2 is supplied in a molten state (270 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated into glass fibers.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 50% by mass and a length of 9 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 250 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Embodiment 7]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA612 is supplied as a thermoplastic in a molten state (280 ° C) from an extruder connected to a right angle die. Resin and impregnated into fiberglass.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 50% by mass and a length of 9 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 280 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Embodiment 8]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA612 is supplied as a thermoplastic in a molten state (280 ° C) from an extruder connected to a right angle die. Resin and impregnated into fiberglass.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 40% by mass and a length of 9 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 280 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Embodiment 9]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA610 is supplied as a thermoplastic in a molten state (290 ° C) from an extruder connected to a right angle die. Resin and impregnated into fiberglass.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 50% by mass and a length of 9 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 280 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Comparative Example 1]

After mixing 50% by mass of PA12-1 as a thermoplastic resin and 50% by mass of glass fiber chopped strand (GF-2) by a tumbler blender, it was melted by an extruder (220 ° C). The mixture was kneaded to obtain a pelletized resin composition.

The obtained pellets were injection-molded (the cylinder temperature was 250 ° C, and the mold temperature was 90 ° C (measured)), and test pieces for each measurement were prepared.

[Comparative Example 2]

After mixing 50% by mass of PA612 as a thermoplastic resin and 50% by mass of glass fiber strands (GF-2) by a roller mixer, the mixture was melt-kneaded by an extruder (240 ° C) to obtain a pelletized resin composition. .

The obtained pellets were injection-molded (the cylinder temperature was 280 ° C, and the mold temperature was 90 ° C (measured)), and test pieces for each measurement were prepared.

[Comparative Example 3]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the MXD6 is supplied as a thermoplastic in a molten state (290 ° C) from an extruder connected to a right angle die. Resin and impregnated into fiberglass.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 50% by mass and a length of 6 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 280 ° C, mold temperature: 130 ° C (measured)), and was prepared for each measurement. Test piece.

[Comparative Example 4]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA6T-1 is supplied in a molten state (340 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated into glass fibers.

Then, the strands were drawn and drawn as strands, and after cooling, they were cut to obtain pellets having a glass fiber content of 50% by mass and a length of 9 mm (resin impregnated fiber bundles).

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (barrel temperature: 330 ° C, mold temperature: 140 ° C (measured)), and was prepared for each measurement. Test piece.

[Comparative Example 5]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA66 is supplied as a thermoplastic in a molten state (320 ° C) from an extruder connected to a right angle die. Resin and impregnated into fiberglass.

Then, it was taken as a strand by a forming die and pulled, and then cut after cooling to obtain pellets (resin impregnated fiber bundle) having a glass fiber content of 60% by mass and a length of 9 mm.

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 300 ° C, mold temperature: 100 ° C (measured)), and was prepared for each measurement. Test piece.

[Comparative Example 6]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA6 is supplied as a thermoplastic in a molten state (290 ° C) from an extruder connected to a right angle die. Resin and impregnated into fiberglass.

Then, it was taken as a strand by a forming die and pulled, and then cut after cooling to obtain pellets (resin impregnated fiber bundle) having a glass fiber content of 60% by mass and a length of 9 mm.

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 280 ° C, mold temperature: 100 ° C (measured)), and was prepared for each measurement. Test piece.

[Comparative Example 7]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA12-1 is supplied in a molten state (270 ° C) from an extruder connected to a right angle die. It is 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 pellets (resin impregnated fiber bundle) having a glass fiber content of 30% by mass and a length of 9 mm.

200 ppm of calcium stearate (St-Ca) was added and the obtained pellet was used as an external lubricant for injection molding (cylinder temperature: 250 ° C, mold temperature: 90 ° C (measured)), and was prepared for each measurement. Test piece.

[Comparative Example 8]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA12-1 is supplied in a molten state (270 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated into glass fibers.

Then, it was taken as a strand by a forming die and pulled, and then cut after cooling to obtain pellets (resin impregnated fiber bundle) having a glass fiber content of 50% by mass and a length of 18 mm.

Although it is desired to add 200 ppm of calcium stearate (St-Ca) to the obtained granules as an external lubricant for injection molding (cylinder temperature is 250 ° C, mold temperature is 90 ° C (measured)), due to particle card It cannot be advanced on the screw, so injection molding cannot be performed.

[Comparative Example 9]

The glass fiber yarn bundle (GF-1) is pulled out by processing the continuous fiber passage into a wavy right angle die, and the PA12-1 is supplied in a molten state (270 ° C) from an extruder connected to a right angle die. It is a thermoplastic resin and impregnated with glass fiber.

Then, it was taken as a strand by a forming die and pulled, and then cut after cooling. Although a pellet having a glass fiber content of 50% by mass and a length of 4 mm was produced, the pellet was broken and the pellet could not be obtained.

From the comparison of Example 5 with Comparative Example 1, Example 7 and Comparative Example 2, it was confirmed that the single beam impact strength (or the inspection impact strength), the tension strength and the nominal when the glass staple fiber was used. The tensile strain was significantly deteriorated (Comparative Examples 1 and 2 did not have the requirements (a) and (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 Examples 1 and 2 of Table 1 of JP-A-2008-163340, PA12 and a glass fiber having a length of 4.5 mm and a diameter of 10 μm (circular cross section) were used, and the resin impregnated fiber bundle was used. As an example, the value of the single beam impact strength shows similar results to the comparative examples 1 and 2 of Table 2, and the other results are considered to be the same.

Fig. 1 is an explanatory diagram of a method for measuring the dimensional change rate due to water absorption.

Claims (6)

A thin meat molded body in which a long glass fiber is bundled in a state of being uniformly oriented in a longitudinal direction, and an aliphatic polyamine is impregnated into the glass long fiber bundle in a molten state and integrated, and then a thin meat molded body obtained by cutting a resin composition of a resin impregnated fiber bundle having a length of 5 to 15 mm, a thickness of 0.8 to 2.0 mm, and a glass fiber having a weight average fiber length of 0.5 to 1.5 mm; wherein the resin The impregnated fiber bundle contains, as the aliphatic polyamine, from the group consisting of PA11, PA12, PA610, and PA612, and the glass fiber content is 40 to 70% by mass; the molded body obtained from the resin composition satisfies the following (a) and (b) Requirements: (a) When using an ISO multi-purpose test piece (A shape, thickness 2 mm) and performing a tension test at 500 mm/min, the nominal tensile strain is 2.0% or more. And the flexural modulus in absolute dry state is 10 GPa or more; (b) single beam impact strength (or skin impact strength) (according to ISO 179/1eA (edgewise) (the test piece thickness is 2 mm, with notches ( Notch)) is 30kJ or more. The thin meat molded body according to the first aspect of the invention, wherein the molded body obtained from the resin composition has a dimensional change rate of 0.05% or less due to water absorption (saturated water absorption state in an environment of 23 ° C / 50% RH) . A thin meat molded body according to claim 1 or 2, which further contains a lubricant. The thin meat molded body of claim 1 or 2, wherein the thin meat molded body is used for a housing or an internal chassis of an electronic machine, and the outer cover or the internal chassis of the electronic machine is a mobile phone, a mobile personal digital assistant ( PDA (personal digital assistant), the cover of the smart phone or the internal chassis. The method for producing a thin meat molded body according to any one of claims 1 to 4, wherein, after the resin composition is melted, injection molding is carried out for molding, and the method has A pin gate is used as a mold for injection molding. An electronic machine cover for use in a thin meat molded body according to any one of claims 1 to 4.