KR102318049B1 - Thermoplastic composite material having excellent flame retardancy and low temperature impact strength and molded article comprising the same - Google Patents

Abstract

The present invention relates to a composite material using a thermoplastic resin composition having excellent flame retardancy and low-temperature impact strength. It relates to a composite material that exhibits excellent flame retardancy and low-temperature impact strength by impregnating fibers.

Description

Thermoplastic resin composite material having excellent flame retardancy and low-temperature impact strength and molded article thereof

The present invention relates to a thermoplastic resin composite material having excellent flame retardancy and low-temperature impact strength, and more particularly, a thermoplastic resin comprising a polycarbonate resin, a polysiloxane-polycarbonate copolymer and a polyarylate in a specific content is impregnated into a substrate. As such, it relates to a composite material exhibiting excellent flame retardancy and low-temperature impact strength.

Composite material is a material produced by impregnating a matrix material such as glass fiber or carbon fiber, which is a reinforcing agent. It has high strength, high elasticity, excellent dimensional stability and heat resistance. It is a material that does not rust. In the past, thermosetting composite materials were actively developed, but now, composite materials using various thermoplastic resins are being actively developed.

In particular, in the case of a composite material using a polycarbonate resin developed so far, it has high gloss and high mechanical properties, but has a problem of low flame retardancy and low-temperature impact strength. In addition, despite not using a flame retardant in terms of economy, the demand from consumers for a new composite material having excellent flame retardancy continues.

Therefore, there is still a need for a polycarbonate composite material with improved flame retardancy and low-temperature impact strength.

The present invention is to solve the problems of the prior art, and by impregnating the base material with a thermoplastic resin containing a polycarbonate resin, a polysiloxane-polycarbonate copolymer, and a polyarylate in a specific content, excellent flame retardancy and low-temperature impact strength. It is a technical task to provide a composite material showing

In order to achieve the above technical problem, according to a first aspect of the present invention, a substrate; and a thermoplastic resin impregnated in the substrate, wherein the thermoplastic resin is based on 100 wt% of the total, (A) 65 to 85 wt% of a polycarbonate resin; (B) 5 to 30% by weight of a polysiloxane-polycarbonate copolymer; (C) 1 to 12% by weight of polyarylate; There is provided a thermoplastic resin composite material comprising (D) 0.1 to 1% by weight of a lubricant and (E) 0.1 to 1% by weight of a heat stabilizer.

According to another aspect of the present invention, (1) based on 100% by weight of the total composition, (A) 65 to 85% by weight of a polycarbonate resin; (B) 5 to 30% by weight of a polysiloxane-polycarbonate copolymer; (C) 1 to 12% by weight of polyarylate; (D) preparing a film comprising a thermoplastic resin composition comprising 0.1 to 1% by weight of a lubricant and (E) 0.1 to 1% by weight of a heat stabilizer; and (2) disposing the thermoplastic resin film on a substrate, and impregnating the thermoplastic resin film into the substrate by heating and pressing.

The thermoplastic composite material according to the present invention has excellent flame retardancy, heat resistance, and low-temperature impact strength despite not containing a flame retardant compared to a general polycarbonate resin composite material or thermosetting composite material. Such a thermoplastic composite material can be usefully applied to automobile parts or other structures in which various composite materials are used.

Hereinafter, the present invention will be described in more detail.

The present invention is a substrate; and a thermoplastic resin impregnated in the substrate;

The thermoplastic resin is based on 100% by weight of the total, (A) 65 to 85% by weight of a polycarbonate resin; (B) 5 to 30% by weight of a polysiloxane-polycarbonate copolymer; (C) 1 to 12% by weight of polyarylate; It provides a thermoplastic resin composite material comprising (D) 0.1 to 1% by weight of a lubricant and (E) 0.1 to 1% by weight of a heat stabilizer.

Hereinafter, the present invention will be described in detail for each component.

The substrate may be, for example, fiber roving, woven fabric, knitted fabric, non-woven fabric, or a combination thereof.

The substrate may be a reinforcement (Reinforcement), and the reinforcement may be made of carbon fiber, glass fiber, or a combination thereof, preferably carbon fiber.

In one embodiment, the substrate used in the thermoplastic composite material of the present invention may have a sheet form woven with carbon fibers.

(A) polycarbonate resin

As a polycarbonate resin that can be included in the resin composition used in the present invention, an aromatic polycarbonate resin is preferable, but as long as it can implement the technical idea of the present invention, the type is not particularly limited thereto, and is commonly used in the art. A thermoplastic aromatic polycarbonate resin may be used.

In one embodiment, the aromatic polycarbonate resin may be prepared from a dihydric phenol compound, a carbonate precursor, and a molecular weight regulator. The dihydric phenol compound is one of the monomers constituting the aromatic polycarbonate resin, and may be represented by the following formula (1).

[Formula 1]

In Formula 1,

X is an alkylene group, a straight, branched or cyclic alkylene group without a functional group, or a straight, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, isobutylphenyl represents the group. Preferably, X may be a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms or a cyclic alkylene group having 3 to 6 carbon atoms.

R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, such as a linear, branched, or cyclic alkyl group having 1-20 carbon atoms or a cyclic alkyl group having 3-20 carbon atoms (preferably, 3-6).

n and m independently represent an integer of 0 to 4. Here, when n and/or m is 0, it means that _{R 1} and/or R _{2 are hydrogen.}

Non-limiting examples of the dihydric phenol compound include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, and bis(4-hydroxylmethane). Roxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1 ,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10- bis(4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), and the like. , preferably bisphenol A.

The carbonate precursor is another monomer constituting the aromatic polycarbonate resin, and non-limiting examples thereof include carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate, dimethyl carbonate, and the like. . Preferably, carbonyl chloride (phosgene) may be used.

As the molecular weight control agent, a material already known in the art, that is, a monofunctional compound similar to a monomer used for preparing a thermoplastic aromatic polycarbonate resin may be used. Non-limiting examples of the molecular weight modifier include phenol-based derivatives (eg, para-isopropylphenol, para-tert-butylphenol (PTBP), para-cumylphenol, para-isooctylphenol, para-isononylphenol, etc.) and aliphatic alcohols. Preferably, para-tert-butylphenol (PTBP) can be used.

Examples of the aromatic polycarbonate resin prepared from such dihydric phenols, carbonate precursors and molecular weight regulators include linear polycarbonate resins, branched polycarbonate resins, copolycarbonate resins, and polyester carbonate resins. , these may be used alone or in combination of two or more.

A preferred viscosity average molecular weight (Mv, measured in a methylene chloride solution at 25° C.) of the aromatic polycarbonate resin may be 25,000 to 30,000, more preferably 28,000 to 30,000. If the viscosity average molecular weight of the aromatic polycarbonate resin is less than 25,000, mechanical properties such as low-temperature impact strength may be greatly reduced, and if it exceeds 30,000, a problem in processing the resin may occur due to an excessive increase in the glass transition temperature.

In one embodiment, the content of the (A) polycarbonate resin included in the thermoplastic resin composition of the present invention is, based on 100% by weight of the composition, 63% by weight or more, 64% by weight or more, 65% by weight or more, 66% by weight or more or more, 67 wt% or more, 70 wt% or more, or 72 wt% or more, 99 wt% or less, 95 wt% or less, 90 wt% or less, 85 wt% or less, 82 wt% or less, 80 wt% or less, 78 Weight % or less, 75 wt% or less, 73 wt% or less, or 72 wt% or less, for example, 65 to 85 wt%, or 67 to 80 wt% or 67 to 75 wt%. If the content of the polycarbonate resin in the composition (A) is less than the above level, impact resistance (low temperature impact strength, etc.) may be lowered, and on the contrary, if it is greater than the above level, the low temperature impact property may be lowered and the glass transition temperature may be lowered.

(B) polysiloxane -Polycarbonate copolymer

The thermoplastic resin composition of the present invention includes a polysiloxane-polycarbonate copolymer. According to a preferred embodiment of the present invention, the polysiloxane-polycarbonate resin included in the resin composition of the present invention includes hydroxy-terminated siloxane and a polycarbonate block as repeating units.

In one embodiment, the weight average molecular weight (Mw) of the hydroxy-terminated siloxane included in the polysiloxane-polycarbonate copolymer may be 2,500 to 15,000, more specifically 3,500 to 13,000, and more specifically 4,000 to 9,000. can be If the weight average molecular weight of the hydroxy-terminated siloxane is less than 2,500, the effect of improving the low-temperature impact resistance may be insignificant, and if it exceeds 15,000, the reactivity is lowered and there may be a problem in synthesizing the polysiloxane-polycarbonate copolymer to a desired molecular weight.

In the present invention, the content of the hydroxy-terminated siloxane in the polysiloxane-polycarbonate copolymer is 6% to 12% by weight, or 7% to 10% based on 100% by weight of the copolymer. If the content of the hydroxy-terminated siloxane in the copolymer is less than 6% by weight, the low-temperature impact property is poor.

In one embodiment, the hydroxy-terminated siloxane in the polysiloxane-polycarbonate copolymer may be of Formula 2 or Formula 2-1:

[Formula 2]

In Formula 2,

R ₃ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group. For example, the halogen atom may be Cl or Br, the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, It may be ethoxy or propoxy, and the aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl.

R ₄ independently represents a hydrocarbon group or hydroxyl group having 1 to 13 carbon atoms. For example, R ₄ is an alkyl group or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, It may be an aralkyl group or aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or alkaryloxy group having 7 to 13 carbon atoms.

R ₅ independently represents an alkylene group having 2 to 8 carbon atoms.

m is independently an integer from 0 to 4, n independently represents an integer from 15 to 100, preferably an integer from 20 to 80, more preferably an integer from 25 to 60,

A represents the structure of Formula 2-2 or 2-3 below.

[Formula 2-2]

In Formula 2-2, X is Y or NH-Y-NH, wherein Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (eg, a cycloalkylene group having 3 to 6 carbon atoms); or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms that is unsubstituted or substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. For example, Y is an aliphatic group substituted or unsubstituted with a halogen atom, an aliphatic group containing an oxygen, nitrogen or sulfur atom in the backbone, or an aryl which may be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol. It may be a ren group, for example, it may be represented by the following Chemical Formulas 2a to 2h.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Formula 2g]

[Formula 2h]

[Formula 2-3]

In Formula 2-3, R ₆ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, an aromatic/aliphatic mixed hydrocarbon group, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Here, R ₄ may have a structure including halogen, oxygen, nitrogen, or sulfur in addition to a carbon atom. For example, R ₄ may be phenyl, chlorophenyl or tolyl (preferably phenyl).

[Formula 2-1]

In Formula 2-1, R ₃ , R ₄ , R ₅ and m are as defined in Formula 2 above, and n is an integer of 30 to 200, preferably an integer of 40 to 170, more preferably 50 to 120 is the integer of

In one embodiment, the hydroxy-terminated siloxane of Formula 2 may be a reaction product of the aforementioned hydroxy-terminated siloxane of Formula 2-1 (provided that n is an integer of 15 to 100) and an acyl compound. Here, the acyl compound may have, for example, an aromatic, aliphatic, or mixed structure including both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and when aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 2 may be a reaction product of a hydroxy-terminated siloxane of Formula 2-1 (provided that n is an integer of 15 to 100) and a diisocyanate compound. Here, the diisocyanate compound may be, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, or 4,4'-methylenediphenyl diisocyanate.

In another embodiment, the hydroxy-terminated siloxane of Formula 2 is a reaction of a hydroxy-terminated siloxane of Formula 2-1 (provided that n is an integer of 15 to 100) and a phosphorus-containing compound (aromatic or aliphatic phosphate compound) can be a product. Here, the phosphorus-containing compound may be represented by the following Chemical Formula 2-4.

[Formula 2-4]

In Formula 2-4, R ₆ is as defined in Formula 2-3 above, and Z independently represents phosphorus, a halogen atom, a hydroxy group, a carboxyl group, an (C 1 to C 20) alkyl group, an alkoxy group, or an aryl group. .

In one embodiment, the polycarbonate block in the polysiloxane-polycarbonate copolymer has the following formula 3:

[Formula 3]

In Chemical Formula 3, R ₇ is a (C1 to C20) divalent alkyl group (eg, a C1 to C13 divalent alkyl group), a cycloalkyl group (eg, a C3 to C6 divalent cycloalkyl group) , an alkenyl group (eg, a divalent alkenyl group having 2 to 13 carbon atoms), an alkoxy group (eg, a divalent alkoxy group having 1 to 13 carbon atoms), or a halogen atom or nitro-substituted or unsubstituted C6-C30 A divalent aromatic hydrocarbon group is represented.

Here, the aromatic hydrocarbon group may be derived from a compound having a structure of the following Chemical Formula 3a.

[Formula 3a]

In Formula 3a, X is an alkylene group, a straight, branched or cyclic alkylene group having no functional group, or a straight, branched straight line containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, or isobutylphenyl. represents a topographical or cyclic alkylene group, preferably, X may be a straight, branched or cyclic alkylene group having 1 to 10 carbon atoms or a cyclic alkylene group having 3 to 6 carbon atoms; R ₈ independently represents a hydrogen atom, a halogen atom, or an alkyl group, such as a straight, branched, or cyclic alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms); n and m are independently integers from 0 to 4.

The compound of Formula 3a is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl) )-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1 -bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis( 4-Hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy Phenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)nonane, 2,2- Bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl-2,2-bis(4-hydroxyphenyl)pentane , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, resorcinol (Resorcinol), hydroquinone (Hydroquine), 4,4'-dihydroxyphenyl ether [bis(4-hydroxyphenyl)ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether , bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1, 4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4- Hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis (4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl)butane , 1,4-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl- 4-Hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis( 3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2 -Methyl-butane, 4,4'-thiodiphenol [bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydro Roxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4- Hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4 ,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, but is not limited thereto. . A representative of these is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to US Pat. Nos. 2,999,835, US 3,028,365, US 3,153,008, and US 3,334,154, and the like, and the dihydric phenols are singly or in combination of two or more. can be used

In the case of the carbonate precursor, as another monomer of the polycarbonate resin, for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate, or dimethyl carbonate may be used.

The polysiloxane-polycarbonate copolymer used in the present invention preferably has a viscosity average molecular weight (Mv) of 15,000 to 30,000, more preferably 17,000 to 22,000. If the viscosity average molecular weight of the polysiloxane-polycarbonate copolymer is less than 15,000, mechanical properties may be significantly reduced, and if it exceeds 30,000, problems in processing the resin may occur due to an increase in melt viscosity.

The content of the polysiloxane-polycarbonate copolymer included in the thermoplastic resin composition of the present invention may be 5 wt% or more, 10 wt% or more, 15 wt% or more, or 20 wt% or more, based on 100 wt% of the composition, 50 Weight % or less, 45 wt% or less, 40 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, 23 wt% or less, for example 5-30 wt%, 10-30 wt% or 15 to 25% by weight. If the content of the polysiloxane-polycarbonate copolymer in the composition is less than the above range, flame retardancy and low-temperature impact strength may be reduced, and if it exceeds the above range, the effect of increasing the glass transition temperature may be insignificant.

The composition of the present invention may have a Si content of 1 to 8% by weight, 1 to 6% by weight, 1 to 4% by weight, or 1 to 3% by weight based on 100% by weight of the total composition. When the Si content is less than 1% by weight or exceeds 8% by weight based on 100% by weight of the total composition, low-temperature impact properties may be deteriorated.

(C) polyarylate

In the present invention, at least one selected from the group consisting of arylate, phenophthalein, and phthalimidine may be used as the polyarylate. Preferably, it may be a polyarylate having an arylate chemical structure, and may be, for example, U100.

The content of the polyarylate may be 1 wt% or more, 3 wt% or more, or 5 wt% or more, or 7 wt% or more, based on 100 wt% of the total composition, 14 wt% or less, 12 wt% or less, 10 wt% or less or 7 wt% or less, for example 1 to 14 wt%, 1 to 13 wt%, 1 to 12 wt%, 3 to 12 wt% or 5 to 10 wt%. When the polyarylate exceeds the above range, the low-temperature impact strength may be reduced, and if it is less than the above range, the low-temperature impact strength may decrease and the synergistic effect of the glass transition temperature may be insignificant.

(D) lubricant and (E) heat stabilizer

The lubricant may be used without limitation as long as it is a commonly used lubricant, for example, a polyethylene lubricant, ethylene-ester lubricant, ethylene glycol-glycerin ester lubricant, montan lubricant, ethylene glycol-glycerin montanic acid-ester One selected from the group consisting of a lubricant or a combination thereof may be used. In one embodiment, it is appropriate to use at least one lubricant selected from the group consisting of LICOWAX-E, LICOWAX-OP, and EP861.

The thermal stabilizer may be used without limitation as long as it is a conventionally used thermal stabilizer, and in one embodiment, LA300K, S9228, and the like may be used.

The lubricant and the heat stabilizer may each be included in an amount of 0.1 to 1% by weight, preferably 0.1 to 0.5% by weight, respectively.

(F) any other optional additional ingredients

In the resin composition of the present invention, other additives may be added as necessary within the range capable of achieving the object of the present invention in addition to the above-described components.

The type and content of the other additives can be easily selected by those skilled in the art according to various purposes. In one embodiment, inorganic fillers, antioxidants, light stabilizers, hydrolysis stabilizers, mold release agents, colorants, UV stabilizers, antistatic agents, conductivity imparting agents, magnetism imparting agents, crosslinking agents, antibacterial agents, processing aids, friction-resistant agents, abrasion-resistant agents and couples The ring agent may be added to the composition alone or in combination of two or more.

As the antioxidant, a phenol-type, phosphite-type, thioether-type or amine-type antioxidant may be used, and the release agent includes a fluorine-containing polymer, silicone oil, a metal salt of stearic acid, and montanic acid. of metal salt, montanic acid ester wax or polyethylene wax can be used. In addition, as the ultraviolet stabilizer, benzophenone or benzotriazole and an amine-type ultraviolet stabilizer may be used, and as the colorant, a dye or a pigment may be used.

The content of other additives is not particularly limited, and is included in an amount of 1 to 5% by weight, preferably 2 to 5% by weight, based on the total weight of the composition of the present invention, depending on the purpose and purpose of use. have.

In the thermoplastic composite material of the present invention, the content of the impregnated thermoplastic resin may be 30% by volume or more, 35% by volume or more, 40% by volume or more, 45% by volume or more, or 50% by volume or more, based on 100% by volume of the total composite material, 60% by volume or less, 55% by volume or less, 50% by volume or less, 45% by volume or less, or 40% by volume or less, for example, 30 to 60% by volume, 35 to 55% by volume, or 40 to 50% by volume . If the content of the thermoplastic resin is out of the above range, the thermoplastic resin may not properly perform the role of the base material of the fiber, so it may be difficult to manufacture a composite material, and physical properties (eg, low-temperature impact strength, etc.) may be reduced.

The composite material may be manufactured by various methods, for example, melt impregnation, film impregnation, compression film impregnation, or mixed fiber impregnation (Co-Mingled Fiber Impregnation). may be, but is not limited thereto.

According to an example of the present invention, based on 100% by weight of the total thermoplastic composite material, (A) 65 to 85% by weight of a polycarbonate resin; (B) 5 to 30% by weight of a polysiloxane-polycarbonate copolymer; (C) 1 to 12% by weight of polyarylate; (D) preparing a thermoplastic resin composition comprising 0.1 to 1% by weight of a lubricant and (E) 0.1 to 1% by weight of a heat stabilizer; preparing a melt or film of the thermoplastic resin composition; and disposing a melt or film of the thermoplastic resin composition on a substrate and heating and pressing to impregnate the thermoplastic resin into the substrate.

Specifically, the impregnation may be performed under heating, pressurization or hot rolling conditions. The temperature conditions during impregnation may be 250° C. to 350° C., and the pressure conditions may be 50 bar to 300 bar. Specifically, it may be 280 ° C. to 320 ° C., 290 ° C. to 310 ° C., and the pressure conditions may be 50 bar to 250 bar, 50 bar to 200 bar, 70 bar to 150 bar, 70 bar to 120 bar, 80 bar to 120 bar, or 80 bar to 100 bar.

According to one embodiment, the thermoplastic resin composite material may be a unidirectional tape (Unidirectional Tape) or an organosheet (Organosheet) which is a continuous fiber composite intermediate material (Prepreg) containing the thermoplastic resin composition of the present invention.

According to one embodiment, the thermoplastic resin composite in the form of a unidirectional tape of the present invention may be manufactured by impregnating the resin using the Melt Impregnation method after going through a spreading step of broadly spreading the carbon fibers. The unidirectional tape has a form in which carbon fibers are arranged in a line.

According to another embodiment, the thermoplastic resin composite in the form of an organo sheet of the present invention is a carbon fiber fabric by hot rolling a film made of a thermoplastic resin between the woven sheets (sheets) of the carbon fiber to the thermoplastic resin. It can be prepared by the impregnation film impregnation method. The carbon fiber woven sheet may be 3 to 10 layers, and the thermoplastic resin film is arranged between the woven sheets.

According to one embodiment of the present invention, (1) based on 100% by weight of the total composition, (A) 65 to 85% by weight of a polycarbonate resin; (B) 5 to 30% by weight of a polysiloxane-polycarbonate copolymer; (C) 1 to 12% by weight of polyarylate; (D) preparing a film comprising a thermoplastic resin composition comprising 0.1 to 1% by weight of a lubricant and (E) 0.1 to 1% by weight of a heat stabilizer; and (2) disposing the thermoplastic resin film on a substrate, and impregnating the thermoplastic resin film in the substrate.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the following examples are provided only for the purpose of illustration to help the understanding of the present invention, and the scope of the present invention is not limited thereto.

[ Example ]

[Compound used]

- Si-PC: polysiloxane-polycarbonate copolymer

(Hydroxy-terminated siloxane content in the copolymer 9% by weight, Mv: 30,000 (Samyang Corporation))

- PC3030: linear polycarbonate derived from bisphenol-A Mv 30,000

- Polyarylate: U100

- Heat stabilizer S9228

- Lubricant: EP861

1. Preparation of thermoplastic resin composition

Resin (1) to resin (6) compositions were prepared having the composition and content shown in Table 1 below.

[Table 1]

2. Manufacture of thermoplastic composites

Example 1

After preparing the resin (2) composition prepared above into a film with a thickness of about 0.15T under the conditions of 300°C and 5 bar using a press equipment, the film is placed on a carbon fiber sheet (Toray T300 3K Satin woven) between them. and impregnated by the film impregnation method. As shown in Table 2, based on 100 v/v% of the total composite material, the film prepared from the resin composition contained 46.43 v/v% and the carbon fiber sheet 53.57 v/v%, and the temperature and pressure during impregnation were It was carried out under the conditions of 280 ~ 320 ℃ and 100 bar. The physical properties of the prepared composite material were measured, and the results are shown in Table 3 below.

Example 2

As shown in Table 2, based on 100 v/v% of the total composite material, the film prepared from the resin (1) composition was 46.43 v/v%, and the carbon fiber sheet was 53.57 v/v%, so that Example 1 and A composite material was prepared in the same manner. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 1 -Composite material prepared from a general polycarbonate resin composition

Based on 100 v/v% of the total composite material, a composite material containing 40 v/v% of a film made of general PC (PC3030) and 60 v/v% of a carbon fiber sheet was prepared. A composite material was prepared in the same manner as in Example 1 except for the components and content. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 2 - Composite material prepared from thermosetting resin composition

Using an autoclave molding method that injects a flowable thermosetting resin (epoxy resin, YD128) composition into a carbon fiber bundle and applies high temperature and high pressure, based on 100 v/v% of the total composite material, the thermosetting resin (epoxy resin) , YD128) 50 v/v%, a composite material containing 50 v/v% of carbon fiber sheet was prepared. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 3 - Composite material prepared from thermosetting resin composition

After laminating the carbon fiber fabric on the press mold and closing the upper mold, a flowable thermosetting resin (epoxy resin, YD128) composition is put in and the RTM (Resin Transfer Molding) molding method is used to apply pressure to the total composite material 100 v/v% Based on the thermosetting resin (epoxy resin, YD128) 46.43 v / v%, a composite material containing 53.57 v / v% of carbon fiber was prepared. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 4 - Resin Composition Low Content Composite Material

As shown in Table 2, based on 100 v/v% of the total composite material, the film prepared from the resin (1) composition was 20 v/v%, and the carbon fiber sheet was 80 v/v%. A composite material was prepared in the same manner. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 5 - Resin Composition High Content Composite Material

As shown in Table 2, based on 100 v / v% of the total composite material, the film prepared from the resin (1) composition was 70 v / v%, and the carbon fiber sheet was 30 v / v%, so that in Example 1 A composite material was prepared in the same manner as described above. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 6 - Composite material prepared with U100 high content resin composition

As shown in Table 2, based on 100 v/v% of the total composite material, the film prepared with the resin (3) composition contained 46.43 v/v% and the carbon fiber sheet contained 53.57 v/v%, Example 1 A composite material was prepared in the same manner as described above. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 7 - Composite material prepared with SI-PC low content resin composition

As shown in Table 2, based on 100 v/v% of the total composite material, the film prepared with the resin (5) composition contained 46.43 v/v% and the carbon fiber sheet was contained 53.57 v/v%, Example 1 A composite material was prepared in the same manner as described above. The physical properties of the prepared composite material were measured and shown in Table 3 below.

Comparative Example 8 - Composite material prepared with SI-PC high content resin composition

As shown in Table 2, the film prepared from the resin (6) composition based on 100 v/v% of the total composite material contained 46.43 v/v% and the carbon fiber sheet was included 53.57 v/v%, Example 1 A composite material was prepared in the same manner as described above. The physical properties of the prepared composite material were measured and listed in Table 3 below.

How to measure physical properties

- Flame retardancy: The physical properties were measured according to the UL-94 test method.

The UL-94 flame retardant test method, which is a method prescribed by Underwriter's Laboratories (UL) of the United States, is the burning time or drip performance after attaching the flame of a burner to a specimen of a certain size fixed vertically for 10 seconds. It is a method to evaluate the flame retardancy from Combustion time is the length of time that the specimen continues flame burning after the flame is removed, and the ignition of cotton by drip means that the cotton for marking, which is about 300mm below the lower end of the specimen, is ignited by the dripping material from the specimen. It is determined by, and the grade of flame retardancy is divided according to the table below.

- Low temperature impact strength (-30℃): Physical properties were measured according to ASTM D 256.

- Specific gravity: Physical properties were measured according to ASTM D 792.

[Table 2]

[Table 3]

It was confirmed that the thermoplastic resin composite materials of Examples 1 and 2 of the present invention had V0 flame retardancy and had significantly superior low-temperature impact strength than Comparative Examples 1 to 9.

As in Comparative Examples 1 to 3, the generally used polycarbonate composite material and thermosetting resin composite material exhibited a flame retardancy of about V1, and low-temperature impact strength was also lower than Examples 1 and 2 of the present invention.

As in Comparative Examples 4 and 5, when the resin of the present invention is included in a low or high content in the composite material, it was found that the target low-temperature impact strength could not be reached.

As in Comparative Example 6, when the low content of polyarylate (U100) was included in the composite, it was found that the target low-temperature impact strength could not be reached.

As in Comparative Example 7, when the composite material was prepared using a resin composition having too low a Si-PC content (relatively too high a PC content), it was confirmed that the flame retardancy and low-temperature impact strength fell, as in Comparative Example 8. , it was found that, in the case of a resin composition having a high Si-PC content, the PC content was relatively low, and thus the target low-temperature impact strength did not appear.

Claims (11)

write; and a thermoplastic resin impregnated in the substrate;
The thermoplastic resin is based on 100% by weight of the total, (A) 65 to 85% by weight of a polycarbonate resin; (B) 5 to 30% by weight of a polysiloxane-polycarbonate copolymer; (C) 1 to 12% by weight of polyarylate; A thermoplastic resin composite material comprising (D) 0.1 to 1% by weight of a lubricant and (E) 0.1 to 1% by weight of a heat stabilizer. The thermoplastic resin composite material of claim 1, wherein (A) the polycarbonate resin is prepared using a dihydric phenol compound having a structure of the following formula (1), a carbonate precursor, and a molecular weight modifier:
[Formula 1]

In Formula 1,
X is an alkylene group, a straight, branched or cyclic alkylene group without a functional group, or a straight line containing at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl; represents a branched or cyclic alkylene group,
R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group,
n and m are independently integers from 0 to 4. The thermoplastic resin composite material of claim 1, wherein (B) the polysiloxane-polycarbonate copolymer comprises a hydroxy-terminated siloxane of Formula 2 or Formula 2-1 and a polycarbonate block of Formula 3 below as repeating units. :
[Formula 2]

In Formula 2,
R ₃ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, an alkoxy group or an aryl group having 6 to 10 carbon atoms,
R ₄ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₅ independently represents an alkylene group having 2 to 8 carbon atoms,
A is X or NH-X-NH, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, or a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. Represents a substituted or unsubstituted mononuclear or polynuclear arylene group having 6 to 30 carbon atoms,
m is independently an integer from 0 to 10,
n is independently an integer from 2 to 1,000,
[Formula 2-1]

In Formula 2-1, R ₃ , R ₄ , R ₅ and m are as defined in Formula 2 above, n is an integer of 30 to 200,
[Formula 3]

In Formula 3,
R ₇ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a halogen atom, or nitro-substituted or unsubstituted C 6 to C 30 represents an aromatic hydrocarbon group of The thermoplastic resin composite material of claim 1, wherein the polyarylate is selected from the group consisting of arylate, phenophthalein, phthalimidine, or a combination thereof. The lubricant according to claim 1, wherein the lubricant is selected from the group consisting of a polyethylene lubricant, an ethylene-ester lubricant, an ethylene glycol-glycerin ester lubricant, a Montan lubricant, an ethylene glycol-glycerin montanic acid-ester lubricant, or a combination thereof. That is, a thermoplastic resin composite material. The thermoplastic resin composite material according to claim 1, wherein the content of the thermoplastic resin is 30 to 60% by volume based on 100% by volume of the total composite material. The thermoplastic resin composite material according to claim 1, wherein the substrate is a woven fabric, a knitted fabric, a nonwoven fabric, or a combination thereof. The thermoplastic resin composite material according to claim 1, wherein the substrate has a sheet form woven with carbon fibers. The thermoplastic resin composite material according to claim 1, wherein the composite material is prepared by melt impregnation, film impregnation, compression film impregnation or mixed fiber impregnation method. Based on 100% by weight of the total thermoplastic composite material, (A) 65 to 85% by weight of a polycarbonate resin; (B) 5 to 30% by weight of a polysiloxane-polycarbonate copolymer; (C) 1 to 12% by weight of polyarylate; (D) preparing a thermoplastic resin composition comprising 0.1 to 1% by weight of a lubricant and (E) 0.1 to 1% by weight of a heat stabilizer;
preparing a melt or film of the thermoplastic resin composition; and
disposing the melt or film of the thermoplastic resin composition on a substrate and heating and pressing to impregnate the thermoplastic resin into the substrate;
A method for manufacturing a thermoplastic resin composite material. The method according to claim 10, wherein the temperature condition during impregnation is 250° C. to 350° C., and the pressure condition is 50 bar to 300 bar.