KR20170100081A

KR20170100081A - Flame retardant Carbon fiber/polycabonate prepreg

Info

Publication number: KR20170100081A
Application number: KR1020160021734A
Authority: KR
Inventors: 한문희; 정재호; 방윤혁
Original assignee: 주식회사 효성
Priority date: 2016-02-24
Filing date: 2016-02-24
Publication date: 2017-09-04

Abstract

The present invention relates to a carbon fiber polycarbonate prepreg consisting of 40-65 wt% of carbon fibers and 35-60 wt% of a polycarbonate resin composition. The polycarbonate resin composition further contains: 65-75 wt% of a polycarbonate resin selected among a pure polycarbonate resin or a siloxane copolymeric polycarbonate resin; 20-30 wt% of a phosphorus-based flame retardant; and 1-10 wt% of other additives.

Description

Flame retardant carbon fiber / polycarbonate prepreg < RTI ID = 0.0 >

The present invention relates to a carbon fiber / polycarbonate prepreg having excellent flame retardancy, and has excellent flame retardancy of V-0 even when the thickness is 1.0 mm or less.

The polycarbonate composition having the carbon fiber as a reinforcing material has drawbacks in that flame retardancy can not be imparted due to the heat shrinkage ratio different from the high thermal conductivity of the carbon fiber, unlike the resin composition or the resin containing other reinforcing fibers except for the carbon fiber . A carbon fiber / polycarbonate prepreg made using a polycarbonate resin composition having a flame retardancy of 1.6 mm or 0.8 mm at normal V-0 exhibits a flame retardancy of V1 to V2 or less.

Open Patent Publication No. 10-2008-0079278 (published on Aug. 29, 2008) discloses a polycarbonate composition comprising 5-70% by weight of a polycarbonate composition; 5-60 wt% of a fiber reinforced composition comprising glass fiber or a combination of glass fiber and carbon fiber; 1-10 weight percent flame retardant composition comprising phosphorus-based flame retardant; (Such as a polysiloxane) composition having a tensile strength of about 1.6 mm at UL-94 test measurements at a thermodynamic temperature condition of at least about 76 [deg.] C when a stress of about 1.8 megapascals is applied, A flame retardancy of V-1 or higher, and a method of producing the polycarbonate composition, and a molded article thereof. The phosphorus-based flame retardant includes aromatic bis (phenyl) bis Bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) phospholyl] - phosphonium salts, which are multifunctional phosphate compound materials, It is known that many phosphorus compounds such as piperazine can be used singly or in combination. A polycarbonate resin composition having excellent light resistance and flame retardancy has been disclosed in Japanese Patent Application Laid-Open No. 10-2014-0075517 (published on June 19, 2019), and a polyorganosiloxane-containing graft copolymer 0.1-5 parts by weight; 0.1-5 parts by weight of an organosiloxane polymer; 1-5 parts by weight phosphorus flame retardant; And 5 to 50 parts by weight of titanium dioxide, and further 1 to 100 parts by weight of a filler (carbon fiber, etc.). The phosphorus flame retardant may be phosphate, phosphonate, phosphinate, phosphine Oxides, phosphazenes, and metal salts thereof, and mixtures thereof, having an impact strength of 14-16 kgf cm / cm measured according to ASTM D 256 and a flexural modulus measured according to ASTM D 790 of 37000 Lt; -3 > kgf / cm < 2 >. A flame retardant thermoplastic resin composition and a molded article containing the flame retardant thermoplastic resin composition are disclosed in Japanese Patent Application Laid-Open No. 10-2014-0085246 (published on July 21, 2014), and a thermoplastic resin (10 to 99% by weight of a polycarbonate resin and an aromatic vinyl resin To 90% by weight) 100 parts by weight; 5-25 parts by weight of a flame retardant (phosphoric acid, etc.); 1 to 50 parts by weight of a filler (carbon fiber, glass fiber or the like), wherein the flame retardant includes phosphoric acid, a phosphoric acid ester compound, a polyphosphate compound, a phosphoric acid compound and a halogen flame retardant, Phenol A diphosphate) and the filler has an oil absorption of 0.1-10 ml / 100 g as measured according to ASTM D 281. A thermoplastic polycarbonate resin composition excellent in thermal stability has been disclosed in Japanese Patent Application Laid-Open No. 10-1999-0047019 (published on May 5, 1999) A flame-retardant polycarbonate resin composition is disclosed in Japanese Patent Application Laid-Open No. 10-2014-0146772 (published Dec. 29, 2014) Japanese Patent Application Laid-Open No. 10-2015-0023341 (published on May 05, 2015) discloses a flame-retardant polycarbonate composition, a method for producing the same, Japanese Unexamined Patent Application Publication No. 2000-34398 (published on Mar. 2, 2000, 2000) discloses a carbon material comprising 100 parts by weight of an aromatic polycarbonate resin, 5-100 parts by weight of carbon fibers, 5-100 parts by weight of graphite and 0.001-1 parts by weight of an organic metal salt compound Reinforced aromatic polycarbonate resin composition and an electronic apparatus box containing the same, Japanese Unexamined Patent Application Publication No. 2014-80564 (published on May 20, 2014) discloses a carbon fiber-reinforced flame-retardant polycarbonate resin composition and a molded article thereof, A thermally conductive polycarbonate resin composition is disclosed in Japanese Laid-Open Patent Application No. 2014-177547 (published on Sep. 25, 2014) Japanese Unexamined Patent Publication No. 2000-309699 (published on Nov. 11, 2000) discloses a flame retardant resin composition, A flame retardant resin composition is disclosed in Japanese Laid-Open Patent Publication No. 2012-57022 (published on Mar. 22, 2012) Japanese Unexamined Patent Application Publication No. 2013-177545 (published on Sep. 19, 2013) discloses a composite fiber reinforced polycarbonate resin composition.

In order to solve the above problems, it is an object of the present invention to provide a flame-retardant carbon fiber / polycarbonate system exhibiting excellent flame retardancy even at a thickness of 1.0 mm or less.

In order to accomplish the above object, the present invention provides a resin composition comprising 40-65 wt% of carbon fibers and 35-60 wt% of a polycarbonate resin composition, wherein the polycarbonate resin composition is selected from pure polycarbonate resin or siloxane copolymerized polycarbonate resin A flame retardant carbon fiber / polycarbonate prepreg containing 65 to 75 wt% of a polycarbonate resin, 20 to 30 wt% of a phosphorus flame retardant, and 1 to 10 wt% of other additives.

The flame retardant carbon fiber / polycarbonate prepreg of the present invention has an advantage that it has excellent flame retardancy of V-0 even at a thickness of 1.0 mm or less.

The present invention will now be described in detail with reference to the following examples, which should not be construed as limiting the invention.

The flame retardant carbon fiber / polycarbonate prepreg according to the present invention is composed of 40-65 wt% of carbon fibers and 35-60 wt% of a polycarbonate resin composition, wherein the polycarbonate resin composition is a pure polycarbonate resin or a siloxane copolymerized poly From 65 to 75 wt% of a polycarbonate resin selected from a carbonate resin, from 20 to 30 wt% of a phosphorus-based flame retardant and from 1 to 10 wt% of other additives.

As the flame retardant of the present invention, it is preferable to apply a phosphorus flame retardant so as to have synergy with the self-flame retarding mechanism of the polycarbonate. The flame retardancy is improved as the content of the flame retardant increases. However, the flame retardancy of the flame retardant carbon fiber / polycarbonate prepreg In order to show stable flame retardant performance (UL-94 V0) at 1.0 mm thickness, it should be added more than 20 wt%. If flame retardant content is more than 30 wt%, stable compounding can not be achieved.

As other additives, ordinary impact modifiers, flame retardant auxiliaries, antioxidants, lubricants and the like may be used.

Although there is no limitation on the kind of polycarbonate, it is preferable to have a viscosity of 1,000 to 200,000 cps at the process temperature for smooth impregnation between filaments in the carbon fiber. If the polycarbonate viscosity is less than 1,000 cps, the physical properties of the resin are low and the properties of the flame retardant carbon fiber / polycarbonate prepreg deteriorate. If the viscosity exceeds 200,000 cps, the resin can not penetrate into the filaments sufficiently, .

The flame retardancy of ordinary carbon fiber / polycarbonate composites is lower than that of the resin alone, which allows the heat of the outer / surface layer to be readily transferred to the interior due to the very high thermal conductivity of the carbon fibers during the combustion process, The interface of the carbon fiber / resin is peeled off due to a low thermal expansion rate to form a passage channel of oxygen and a low molecular material. Therefore, it is effective to use a flame retardant that can solve the above-mentioned problem in order to impose flame retardancy on a UD-prepreg composite material having a high carbon fiber content.

In the flame retardant, the phosphorus flame retardant forms a bridge with the polymer during the combustion process to form a char, and the formed char surrounds the microchannel between the surface of the burning sample and the CF resin, thereby blocking the permeation of oxygen and low molecular substances.

In the present invention, a phosphate based flame retardant is applied to the phosphorus flame retardant. However, the present invention is not limited to the phosphorus based phosphorus system, and the same phosphorous flame retardant such as phosphonate system or phosphinate system can be applied.

Examples of the ginseng base flame retardant include bisphenol A bis (diphenylphosphate), triphenylphosphate (TPP), resorcinol bis (diphenyl phosphate) (BDP) phosphine (RDP), and ammonium polyphosphate (APP). It is more preferable to use bisphenol A bis (diphenylphosphate) (BDP) Do.

The phosphonate-based flame retardant is preferably dimethyl methylphosphonate (DMMP), triazine phosphonate, or the like.

The phosphinate-based flame retardant is preferably aluminum diethyl phosphinate, aluminum methylethylphosphinate, or the like.

The mechanical properties of the carbon fiber prepreg to which the flame retardant polycarbonate resin is applied are most affected by the content of the carbon fibers, and the flexural modulus of the flame retardant carbon fiber / polycarbonate prepreg is at least 40 wt% , And when it exceeds 65 wt%, impregnation is unstable, resulting in poor appearance and poor physical properties of the prepreg.

Further, the sheet obtained by press-molding the laminate of the flame-retardant carbon fiber / polycarbonate-based prepreg exhibits flame retardancy of V-0 grade based on UL-94 with a thickness of 1.0 mm.

Hereinafter, the flame retardant carbon fiber / polycarbonate prepreg of the present invention will be described by way of examples.

[ Example ]

Example 1 to 7

Flame retardant polycarbonate resin compositions were prepared according to the contents of flame retardant (BDP), impact modifier (rubber) and other additives (Metal Hydrate and FR synergist, etc.)

Thereafter, carbon fiber unidirectional prepregs were prepared by melt impregnation using an extruder and an impregnation die according to the carbon content shown in Table 1 using the resin composition. In detail, a plurality of carbon fibers loosened from the krill band were uniformly aligned in the width direction by using a guide comb and a roller, and then the width of the tow was widened by using the fixed roll and the right and left vibration rolls in the carding machine. Thereafter, the flame-retardant polycarbonate resin composition passes through an impregnation die and flows into an impregnation die through an extruder to be impregnated between the filaments in the fiber after contact with the carbon fibers. The prepreg that has passed through the impregnation die is then wound after being passed through a press roll and a drawing roller. The prepared prepreg had an average thickness of 0.13 to 0.17 mm.

The prepared prepreg was laminated and press-molded to prepare a flame retardancy evaluation sample having a thickness of 1.0 to 1.2 mm.

[ Comparative Example ]

Comparative Example 1-3

&Lt; tb > < TABLE >

Hereinafter, the flame retardancy and the like of the composition prepared according to the examples are tested to demonstrate the superiority of the present invention.

[ Experimental Example ]

Flame-retardant evaluation (UL-94, vertical burning test of five samples, V0 requirement standard: individual sample burning time within 10 seconds) of samples prepared by the methods described in Examples and Comparative Examples was carried out. Reference)

division Flame Retardant Polycarbonate Resin Composition Prepreg Flame retardant performance (UL-94) In resin
Flame retardant
content
(wt%) In resin
Shock
Reinforcing agent
content
(wt%) In resin
Other
additive
content
(wt%) Carbon fiber
content
(wt%) Suzy
content
(wt%) thickness
(mm) Rating 5
Sample
Burning time
synthesis
(second) Example 1 25 - 2 60 40 1.0 V0 18.8 Example 2 23 - 2 60 40 1.0 V0 25.4 Example 3 20 - 2.5 60 40 1.0 V0 26.8 Example 4 25 5 2 60 40 0.9 V1 57.9 Example 5 25 5 2 60 40 1.0 V0 32.0 Example 6 25 5 2 60 40 1.1 V0 25.1 Example 7 25 5 2 60 40 1.2 V0 26.1 Comparative Example 1 16 5 One 60 40 1.0 F 236.9 Comparative Example 2 16 5 2 60 40 1.0 V1 114.8 Comparative Example 3 - - - 60 40 1.2 V1 121.2

Claims

Wherein the polycarbonate resin composition comprises 65 to 75 wt% of a polycarbonate resin selected from pure polycarbonate resin or siloxane copolymerized polycarbonate resin, Flame retardant carbon fiber / polycarbonate prepreg containing 20 to 30 wt% of a flame retardant and 1 to 10 wt% of other additives.

The flame-retardant carbon fiber / polycarbonate prepreg according to claim 1, wherein the polycarbonate resin composition has a viscosity of 1,000 to 200,000 cps.

The flame retardant carbon fiber / polycarbonate prepreg according to claim 1, wherein the phosphorus flame retardant is selected from the group consisting of a phosphate flame retardant, a phosphonate series and a phoshinate series.

The flame retardant according to claim 3, wherein the phosphate flame retardant is bisphenol A bis (diphenylphospate), triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) Wherein the resin is selected from Resorcinol bis (diphenyl phosphate), RDP, and Ammonium polyphosphate (APP).

The flame retardant carbon fiber / polycarbonate prepreg according to claim 3, wherein the phosphonate flame retardant is selected from the group consisting of dimethyl methylphosphonate (DMMP) and triazine phosphonate. Legs.

The flame-retardant carbon fiber-reinforced thermoplastic resin composition according to claim 3, wherein the phosphinate-based flame retardant is selected from the group consisting of aluminum diethyl phosphinate and aluminum methylethylphosphinate. Legs.

The flame-retardant carbon fiber / polycarbonate prepreg according to claim 1, wherein the prepreg has an average thickness of 0.15 mm and a flexural modulus of 50 Gpa to 110 Gpa.

The flame retardant carbon fiber / polycarbonate prepreg according to claim 1, wherein the prepreg has flame retardancy of V-0 even at an average thickness of 1.0 mm or less.