JP2017226739A - Carbon fiber-reinforced molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon fiber-reinforced molded article having a clear marking portion.SOLUTION: A carbon fiber-reinforced molded article is formed of a composition which contains (A) a thermoplastic resin (excluding polyamide 6, polyamide 66, and polycarbonate) and (B) a carbon fiber, and does not contain an ethylene-α olefin copolymer having a reactive functional group reactive with a terminal group of the polyamide resin and/or an amide group of a main chain thereof, a metal plating organic fiber, a mixture of a hydrogenated product of a block copolymer of a vinyl aromatic polymer and a conjugated diene polymer and a substance obtained by subjecting the hydrogenated product to acid modification at 0.1 to 5 mass% of a modification ratio, and a flame retardant formed of a bromine compound having no C-O-C bond in the molecule. In the composition, a content ratio of the (A) component is 30 to 80 mass% and a content ratio of the (B) component is 70 to 20 mass% in the total amount of the (A) component and the (B) component, the molded product has a stamp formed by laser irradiation thereon, and ΔE of a marking portion and a non-marking portion is 2 or more.SELECTED DRAWING: None

Description

  The present invention relates to a carbon fiber reinforced molded article having markings on the surface by irradiation with energy rays.

  Laser marking is widely used as an alternative to printing and painting with ink for electrical / electronic parts, automotive parts, building material parts, machine parts, and the like.

Claim 1 of Patent Document 1 includes (A) 50-90% by mass of a polyamide resin, (B) (B-1) hydrogenation of a block copolymer comprising a vinyl aromatic polymer and a conjugated diene polymer. (B-2) 50 to 10% by mass of a mixture of the above-mentioned hydrogenated product of (B-1) modified with an acid modification rate of 0.1 to 5% by mass, (C) C—O in the molecule 30 to 55 parts by mass with respect to 100 parts by mass of the total amount of the flame retardant (A) component and the (B) component made of a bromine compound having no -C bond, and (D) the flame retardant auxiliary (A) component and (B) 1 to 15 parts by mass with respect to 100 parts by mass of the total amount of components, (E) 1 to 400 parts by mass with respect to 100 parts by mass of the total amount of the fibrous reinforcing filler (A) component and (B) component Inventions of polyamide resin compositions for laser marking containing
The invention of Patent Document 1 has an effect that the laser marking is prevented from fading and disappearing even in a high-temperature and high-humidity environment. Table 1 shows components (A) to (E) (however, It is shown that the “laser marking water resistance test 1” of the resin composition comprising (E) glass fiber) is good.

Claim 1 of Patent Document 2 includes (A) 70 to 50 parts by mass of a polyamide resin, (B) 10 to 20 parts by mass of an antistatic agent, (C) an end group of the polyamide resin and / or an amide group of the main chain. 15-30 parts by mass of an ethylene-α-olefin copolymer having a reactive functional group capable of reacting, (D) 0.5-3 parts by mass of a black pigment, (E) 0.5-3 parts by mass of metal-plated organic fibers, and (F) Carbon fiber 0.5-3 mass part is included, and the sum total of (A)-(F) is 100 mass parts, and the sum total of (E) component and (F) component is 3.5 mass parts or less. When a voltage of 5 kV is applied to the other arbitrary end in a state where the ground is connected to an arbitrary end of a molded product obtained by injection molding of the resin composition. Residual voltage value of 1 kV or less is a polyamide-based conductive resin composition Invention have been described.
Table 1 shows that the laser marking property of the resin composition comprising the components (A) to (F) is good.

Claim 1 of Patent Document 3 is a composite material containing a black pigment, carbon fiber, and a resin, in which 1) the area ratio of the carbon fiber in the extreme surface layer is 10 to 90%, and 2) the composite material A composite in which the ratio of the black pigment contained is 0.2 to 20% by mass, and 3) the composite is marked with a laser beam having a wavelength of 100 to 2,000 nm on a composite material having an average fiber length of 1 mm or more. The invention is described.
The resin contained in the composite material may be either a thermosetting resin or a thermoplastic resin. As for the thermoplastic resin, 18 types including polyamide are exemplified in paragraph No. 0042, and further 24 types of polyamide are exemplified, but those used in the examples and confirmed to be effective are polyamide 6 and polycarbonate. Only.
In paragraph No. 0045, when the ratio of the black pigment is less than 0.2% by mass, there is a problem that the structural color is difficult to appear on the surface of the composite material after marking. It is described that the contrast with the marking portion becomes worse and the weather resistance tends to be lowered.

Japanese Patent Laying-Open No. 2015-143312 JP 2011-32320 A WO2015 / 137093 A1

  An object of the present invention is to provide a carbon fiber reinforced molded product in which the difference in color developability between the marking portion and the non-marking portion is clear.

The present invention contains (A) a thermoplastic resin (excluding polyamide 6, polyamide 66 and polycarbonate) and (B) carbon fiber,
Consists of an ethylene-α olefin copolymer having a reactive functional group capable of reacting with a terminal group of a polyamide resin and / or an amide group of the main chain, a metal plating organic fiber, a vinyl aromatic polymer, and a conjugated diene polymer. It consists of a mixture of a hydrogenated block copolymer and an acid-modified mixture of the hydrogenated product with a modification rate of 0.1 to 5% by mass and a bromine compound having no C—O—C bond in the molecule. A carbon fiber reinforced molded article comprising a composition not containing a flame retardant,
In the total amount of the component (A) and the component (B), the content of the component (A) is 30 to 80% by mass, and the content of the component (B) is 70 to 20% by mass. ,
Provided is a carbon fiber reinforced molded article, wherein the molded article has a marking by laser irradiation on the surface, and ΔE of a marking portion and a non-marking portion is 2 or more.

  In the carbon fiber reinforced molded product of the present invention, the difference in color developability between the marking portion and the non-marking portion is clear.

<Composition>
The thermoplastic resin (except for polyamide 6, polyamide 66 and polycarbonate) as the component (A) is not particularly limited, and can be selected according to the application.
The component (A) can be selected from polyolefins such as polyamide, polyethylene, and polyprene, polyesters such as thermoplastic polyurethane (TPU) and polybutylene terephthalate, styrenic resins such as PPS and ABS resin, and various polymer alloys. . Among these, polyamide, polyethylene, and polypropylene are preferable.
The polyamide is preferably selected from polyamide 12, polyamide MXD, and polyamide 9T, and polyamide 6 (nylon 6) and polyamide 66 (nylon 66) are excluded.
The polypropylene preferably has a weight average molecular weight of 100,000 to 400,000, particularly preferably 120,000 to 250,000.

The (B) component carbon fiber may be either PAN-based or pitch-based, and may also be rayon-based, cellulose-based, lignin-based, phenol-based, or the like.
Moreover, the carbon fiber of (B) component can also be used with the form of a well-known resin impregnation fiber bundle.
A resin-impregnated fiber bundle is obtained by impregnating a continuous fiber bundle in which continuous fibers are aligned in the length direction by impregnating a molten thermoplastic resin in a heated die and then integrating them. It is obtained by cutting to a length (for example, 3 to 50 mm).
The number of fibers in the continuous fiber bundle is preferably 100 to 60000, more preferably 500 to 48000, and still more preferably 1000 to 24000.
As the thermoplastic resin used in the resin-impregnated fiber bundle, the above-described thermoplastic resin of the component (A) can be used.
The composition used in the present invention may be composed of only a resin-impregnated fiber bundle containing the component (A) and the component (B), or may be composed of the component (A) and the resin-impregnated fiber bundle.

  A method for producing a resin-impregnated fiber bundle using a thermoplastic resin is known per se. For example, JP 2013-109779 A (Manufacturing of a resin-impregnated glass long fiber bundle of Production Example 1), JP 2013-121988 A (Production of resin-impregnated glass long fiber bundle of Production Example 1), JP 2012-52093 A (Examples 1 to 9), JP 2012-131104 A (Production of resin impregnated glass long fiber bundle of Production Example 1) Production of resin-impregnated carbon fiber long fiber bundle of Production Example 2), JP 2012-131918 A (Production of resin-impregnated carbon fiber bundle of Production Example 1, production of resin-impregnated glass fiber bundle of Production Example 2), It can be produced according to the methods described in Japanese Unexamined Patent Publication No. 2011-162905 (Example 1) and Japanese Patent Application Laid-Open No. 2004-14990 (Examples 1 to 7).

The ratio of the component (A) and the component (B) in the composition used in the present invention is the total amount of the component (A) and the component (B).
(A) The content rate of a component is 30-90 mass%, Preferably it is 40-80 mass%, More preferably, it is 50-70 mass%,
(B) The content rate of a component is 70-10 mass%, Preferably it is 60-20 mass%, More preferably, it is 50-30 mass%.
In addition, when using an above-mentioned resin impregnation fiber bundle, the (A) component contained in the said resin impregnation fiber bundle is also contained in content of (A) component.

The composition used in the present invention may further contain a black pigment as the component (C) in addition to the components (A) and (B) described above.
Carbon black can be used as the black pigment. Examples of the carbon black include known furnace black, channel black, acetylene black, and ketjen black. The particle size of carbon black is preferably 10 to 200 nm, more preferably 10 to 70 nm, from the viewpoint of printing efficiency.

  In order to solve the problems of the present invention, the content ratio of the component (C) is preferably 0.01 to 2 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). -0.5 mass part is more preferable, and 0.05-0.1 mass part is further more preferable.

The composition used by this invention can contain a well-known resin additive within the range which does not impair the effect of this invention.
Known resin additives include mold release agents, antistatic agents, flame retardants, colorants, plasticizers, softeners, dispersants, stabilizers (hindered phenolic antioxidants, phosphorus antioxidants, sulfur Antioxidants such as system antioxidants, UV absorbers, heat stabilizers, etc.), anti-blocking agents, crystal nucleus growth agents, particulate fillers (eg, particulate fillers such as silica and talc), lubricants, etc. Can do.
However, the composition used in the present invention is a component described in claim 1 of Patent Documents 1 and 2,
An ethylene-α-olefin copolymer having a reactive functional group capable of reacting with a terminal group of the polyamide resin and / or an amide group of the main chain;
Metal plating organic fiber,
A mixture of a hydrogenated product of a block copolymer comprising a vinyl aromatic polymer and a conjugated diene polymer and an acid-modified product of the hydrogenated product at a modification rate of 0.1 to 5% by mass; The flame retardant which consists of a bromine compound which does not have a C-O-C bond is not included.

<Carbon fiber reinforced molded product>
The carbon fiber reinforced molded product of the present invention is obtained by molding the above-described composition by applying a known resin molding method such as injection molding.
The magnitude | size and shape of the carbon fiber reinforced molded product of this invention can be selected according to a use.

The carbon fiber reinforced molded product of the present invention has a marking by irradiation with energy rays on the surface, and ΔE of the marking portion and the non-marking portion is 2 or more.
When ΔE between the marking part and the non-marking part is 2 or more, the contrast between the marking part (marking part) and the non-marking part becomes clear, and the sharpness of the marking part becomes high.
Since the carbon fiber reinforced molded product of the present invention has high mechanical strength, it is preferable that the weight average fiber length of the carbon fiber contained in the component (B) is 0.3 mm or more, and 0.5 mm or more. Some are more preferable, and those of 0.8 mm or more are more preferable.

<(A) component>
PA12-1: Daiamide L1600, manufactured by Daicel Evonik
PA12-2: Pellets containing 0.1% by mass of CB1 in PA12-1
MXD6: Reny 6002, manufactured by Mitsubishi Engineering Plastics
PA9T: GENESTER N1000A (L41), manufactured by Kuraray Co., Ltd. <(B) component>
CF-1: Trading card T700SC-12000, manufactured by Toray Industries, Inc.
CF-2: Trading card T700GC-12000, manufactured by Toray Industries, Inc.
CB1: CP Black 880B (CB / EBS = 50/50), manufactured by Polycol Kogyo Co., Ltd. <Others>
Stabilizer: Phenolic antioxidant, Irganox 1010FF, manufactured by BASF Japan

<Manufacture of resin-impregnated fiber bundle>
It manufactured according to the manufacture example 1 of Unexamined-Japanese-Patent No. 2012-131918.
While drawing the carbon fiber roving through the crosshead processed into a corrugated continuous fiber passage, the thermoplastic resins shown in Table 1 and Table 2 are supplied in a molten state from the extruder connected to the crosshead, and the carbon fiber roving is supplied. Was impregnated.
The temperatures at which the thermoplastic resins shown in Tables 1 and 2 were melted by the extruder were 270 ° C. for PA12, 300 ° C. for MXD6, 360 ° C. for PA9T, and 260 ° C. for PP-1 and PP-2.
Then, it is taken out as a strand through a shaping die, cut after cooling, and a pellet (resin-impregnated carbon fiber bundle) having the length shown in Table 1 and Table 2 with the carbon fiber content shown in Table 1 and Table 2 is obtained. It was.

<Remaining fiber length (weight average fiber length)>
About 3 g of a sample was cut from the molded product, the resin was dissolved and removed with sulfuric acid, carbon fibers were taken out, and the weight average fiber length was determined from a part (500 pieces) of the taken out fibers. As the calculation formula, [0044] and [0045] of JP-A-2006-274061 were used.

Examples 1 to 5, Comparative Examples 1 and 2
In Examples 1 and 2 and Comparative Examples 1 and 2, resin impregnated fiber bundles shown in Table 1 and polyamide resin pellets were mixed to obtain compositions.
In Examples 3 to 5, only the resin-impregnated fiber bundle shown in Table 1 was used as the composition.
Using each composition shown in Table 1, an ISO test piece (thickness 4 mm) was molded with an injection molding machine (Sumitomo Heavy Industries, Ltd. SH100).

<Marking method>
After irradiating the surface of the ISO test piece (thickness 4 mm) obtained above with a laser beam and drawing a plurality of BOX of 10 mm × 10 mm for each of Examples and Comparative Examples, laser marking color developability (LM color developability) is obtained. Examined.
YAG laser: Marker engine SL475H (manufactured by NEC)
Aperture diameter: 2.5mm
Light source current value (LC) /: 8.6A
Laser power: 2.0W
bite: 120μm
line pitch: 75μm
Printing speed (SP): 400mm / s

<Color measuring method>
Coloring (C light source, measuring diameter φ4 mm, SCI method) using a spectrophotometer [trade name “CM3600d” manufactured by Konica Minolta Sensing Co., Ltd.] The ΔE of the part was calculated.

From Examples 1 to 5 and Comparative Examples 1 and 2, the higher the carbon fiber content in the molded product, the better the color developability and the larger ΔE.
In Table 1 of Patent Document 2, Comparative Examples 8 and 9 (carbon fiber 2.4%) having the highest carbon fiber content are evaluated as having poor printability, and correspond to Comparative Examples 1 and 2 of the present invention. To do.
In Comparative Example 5 of Table 1 of Patent Document 3, the carbon fiber has a volume content of 43% (the specific gravity of the carbon fiber is greater than 1, so the mass content is higher than 43%), and the carbon black is 0%. In this case, the color was not recognized without being colored, and the color developability was clearly inferior to Example 1 having the same composition except that 1.2% by mass of carbon black was contained. From this result, it is apparent that the invention of Patent Document 3 discloses an invention in which color developability is good only when nylon 6 (or PC of Example 4) and carbon black are combined in a predetermined amount.
Therefore, it can confirm that the effect of Examples 1-5 of this invention is a peculiar effect which is not in a prior art.

Examples 6-8, Comparative Example 3
In Example 6 and Comparative Example 3, resin impregnated fiber bundles shown in Table 2 and polypropylene pellets were mixed to obtain compositions.
In Examples 7 and 8, only the resin-impregnated fiber bundle shown in Table 2 was used as the composition.
Using each composition shown in Table 2, an ISO test piece (thickness 4 mm) was molded in the same manner as in Examples 1-5.
Thereafter, the test piece was marked in the same manner as in Examples 1 to 5, and the color was measured in the same manner to calculate ΔE.

  The same difference in effect as the comparison between the example of Table 1 and the comparative example was obtained.

  The carbon fiber reinforced molded product of the present invention is used for OA equipment, office furniture, liquid crystal projectors, mobile devices and casings such as mobile phones, electrical / electronic parts such as power tool housings, and automobile parts. be able to.

Claims (4)

(A) a thermoplastic resin (except for polyamide 6, polyamide 66 and polycarbonate) and (B) carbon fiber,
Consists of an ethylene-α olefin copolymer having a reactive functional group capable of reacting with a terminal group of a polyamide resin and / or an amide group of the main chain, a metal plating organic fiber, a vinyl aromatic polymer, and a conjugated diene polymer. It consists of a mixture of a hydrogenated block copolymer and an acid-modified mixture of the hydrogenated product with a modification rate of 0.1 to 5% by mass and a bromine compound having no C—O—C bond in the molecule. A carbon fiber reinforced molded article comprising a composition not containing a flame retardant,
In the total amount of the component (A) and the component (B), the content of the component (A) is 30 to 80% by mass, and the content of the component (B) is 70 to 20% by mass. ,
A carbon fiber reinforced molded product, wherein the molded product has a laser-irradiated marking on the surface, and the marking part and the non-marking part have ΔE of 2 or more. In addition to the component (A) and the component (B), (C) a carbon fiber reinforced molded article comprising a composition containing a black pigment,
The composition is
In the total amount of the component (A) and the component (B), the content ratio of the component (A) is 30 to 80% by mass, the content ratio of the component (B) is 70 to 20% by mass,
The carbon fiber reinforced molded product according to claim 1, which contains 0.001 to 2 parts by mass of component (C) with respect to 100 parts by mass of the total of component (A) and component (B).   The thermoplastic resin as component (A) is selected from polyamides selected from polyamide 12, polyamide MXD, and polyamide 9T, and polypropylenes having a weight average molecular weight of 100,000 to 400,000. Carbon fiber reinforced molded product.   The carbon fiber reinforced molded product according to any one of claims 1 to 3, wherein a weight average fiber length of the carbon fiber of the component (B) contained in the carbon fiber reinforced molded product is 0.3 mm or more.