KR102282504B1 - Thermoplastic composite having excellent low temperature impact properties and flame retardancy and method for preparing the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composite material and a method for producing the same, and more particularly, a thermoplastic copolymer resin obtained by copolymerizing an ester oligomer and a siloxane monomer of a specific structure with a polycarbonate oligomer is impregnated into a substrate, and low-temperature impact properties and It relates to a thermoplastic resin composite material having excellent flame retardancy and a method for manufacturing the same.

Description

Thermoplastic composite having excellent low temperature impact properties and flame retardancy and method for preparing the same

The present invention relates to a thermoplastic resin composite material and a method for producing the same, and more particularly, a thermoplastic copolymer resin obtained by copolymerizing an ester oligomer and a siloxane monomer of a specific structure with a polycarbonate oligomer is impregnated into a substrate, and low-temperature impact properties and It relates to a thermoplastic resin composite material having excellent flame retardancy and a method for manufacturing the same.

Polycarbonate resins are generally used extensively as mechanical parts, electrical parts, and industrial resins because of their excellent mechanical properties (especially impact strength) and transparency. In particular, in the case of using a polycarbonate resin as a material for a computer monitor housing, copier, TV housing, copier, printer, secondary battery case, etc. that emits a lot of heat in the field of electrical and electronic devices, excellent heat resistance as well as mechanical properties are required. And in the case of automobiles, impact resistance properties at low temperatures are also required for operation in extreme areas.

In general, there are cases where only polysiloxane is introduced into a polycarbonate resin to supplement impact resistance, but in this case, there is a disadvantage in that heat resistance is reduced. And in order to increase the heat resistance of the polycarbonate resin, bisphenol A is modified to introduce a three-dimensional substituent at the ortho position to increase hydrolysis properties and heat-resistant polycarbonate resins that increase the heat deformation temperature have been developed, but general polycarbonate resins have been developed. There is a problem that the impact resistance is significantly lower than that of the carbonate resin (Related prior art documents: US Patent No. 6,630,525, US Patent No. 5,070,177, US Patent No. 4,918,149).

In the case of composite materials, the development of thermosetting resin-based composites in which additives such as flame retardants are added to thermosetting resins are being actively developed, but flame retardant composites capable of exhibiting flame retardancy without using flame retardants are not known.

An object of the present invention is to provide a thermoplastic resin composite material that can exhibit excellent low-temperature impact resistance and can exhibit excellent flame retardancy without using a flame retardant.

The present invention in order to solve the above technical problem, the description; and a polyester-polysiloxane-polycarbonate copolymer impregnated in the substrate, wherein the polyester-polysiloxane-polycarbonate copolymer (A) a polyester block comprising a structure represented by the following formula (1) as a repeating unit ; (B) a polysiloxane block comprising a structure represented by the following formula (2) as a repeating unit; and (C) a polycarbonate block; provides a thermoplastic resin composite material comprising:

[Formula 1]

[Formula 2]

In Formula 2,

R ₁ independently represents a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group;

R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms;

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms;

m independently represents an integer from 0 to 4;

n independently represents an integer of 2 to 1,000.

According to another aspect of the present invention, (1) (A) a polyester block comprising the structure represented by Formula 1 as a repeating unit; (B) a polysiloxane block comprising the structure represented by Formula 2 as a repeating unit; And (C) a polycarbonate block; polyester comprising a-polysiloxane-preparing a film comprising a polycarbonate copolymer; and (2) disposing the polyester-polysiloxane-polycarbonate copolymer film on a substrate, heating and pressing to impregnate the polyester-polysiloxane-polycarbonate copolymer into the substrate; comprising, a thermoplastic resin composite material A method of manufacturing is provided.

The thermoplastic resin composite material according to the present invention has excellent low-temperature impact properties, and at the same time has excellent flame retardancy and heat resistance, so it can be usefully used in products such as automobile interior and exterior parts, office equipment, and housings of electrical and electronic products.

As used herein, the term “reaction product” refers to a substance formed by the reaction of two or more reactants.

In addition, the English letter "R" used to represent hydrogen, a halogen atom, and/or a hydrocarbon group, etc. in the chemical formulas described herein has a subscript represented by a number, but the "R" is in this subscript is not limited by The "R" represents, independently of each other, hydrogen, a halogen atom and/or a hydrocarbon group. For example, two or more "R"s may represent the same hydrocarbon group or different hydrocarbon groups, regardless of whether two or more "R"s have the same or different number of subscripts.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composite material of the present invention includes a substrate; and a polyester-polysiloxane-polycarbonate copolymer impregnated in the substrate.

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

The polyester-polysiloxane-polycarbonate copolymer may include (A) a polyester block including a structure represented by the following Chemical Formula 1 as a repeating unit; (B) a polysiloxane block comprising a structure represented by the following formula (2) as a repeating unit; and (C) a polycarbonate block; as a repeating unit.

(A) polyester block

The polyester block included in the polyester-polysiloxane-polycarbonate copolymer includes a structure represented by the following Chemical Formula 1 as a repeating unit:

[Formula 1]

In one embodiment, the polyester block has a structure represented by the following Chemical Formula 1-1:

[Formula 1-1]

In Formula 1-1, n may be an integer of 2 to 100, and more specifically, an integer of 2 to 90, 2 to 80, 2 to 70, 2 to 60, or 2 to 50.

In one embodiment, the polyester block may be obtained by polycondensing phenolphthalein and isophthalic acid.

(B) polysiloxane block

The polysiloxane block included in the polyester-polysiloxane-polycarbonate copolymer includes a structure represented by the following Chemical Formula 2 as a repeating unit:

[Formula 2]

In Formula 2,

R ₁ independently represents 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, and the alkyl group is an alkyl group having 1 to 13 carbon atoms, For example, it may be methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, 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 ₂ independently represents a hydrocarbon group or hydroxyl group _{having 1 to 13 carbon atoms, for example, R 2} 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, or an alkenyloxy group having 3 to 13 carbon atoms. It may be a cycloalkyl group or cycloalkoxy group of 6, an aryloxy group having 6 to 10 carbon atoms, 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 ₃ independently represents an alkylene group having 2 to 8 carbon atoms,

m independently represents an integer of 0 to 4, preferably an integer of 0 to 2,

n independently represents an integer from 2 to 500, preferably an integer from 10 to 400, more preferably an integer from 20 to 300, even more preferably an integer from 30 to 200.

In a preferred embodiment, the structure of formula (2) in the polysiloxane block is derived from a compound of formula (2-1):

[Formula 2-1]

In Formula 2-1, n independently represents an integer of 2 to 500, preferably an integer of 10 to 400, more preferably an integer of 20 to 300, even more preferably an integer of 30 to 200.

(C) polycarbonate block

The polyester-polysiloxane-polycarbonate block included in the polycarbonate copolymer may include a structure represented by the following Chemical Formula 3 as a repeating unit:

[Formula 3]

In Formula 3,

R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is unsubstituted or substituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom or a nitro group. Specifically, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, the cycloalkyl group may be a cycloalkyl group having 3 to 6 carbon atoms, the alkenyl group may be an alkenyl group having 2 to 13 carbon atoms, and the alkoxy group may be an alkenyl group having 2 to 13 carbon atoms. to 13 may be an alkoxy group.

Here, the aromatic hydrocarbon group may be derived from a compound having the structure of Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

X is a straight, branched or cyclic alkylene group having no functional group; or a straight, branched or cyclic alkylene group comprising at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl, preferably, X is from 1 to C1 It may be a linear alkylene group of 10, a branched alkylene group of 3 to 10 carbon atoms, or a cyclic alkylene group of 3 to 6 carbon atoms,

R ₆ each independently represents a halogen atom, or an alkyl group (such as a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6)) ,

n and m independently represent an integer of 0 to 4.

The compound of Formula 3-1 is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxy 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, 2,2-bis(4- Hydroxyphenyl)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 (Hydroquinone), 4,4'-dihydroxy Phenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodi phenyl 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'-dihydroxy Phenyl, 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-hydroxyphenyl) )sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxy Phenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4,4 '-dihydroxybenzophenone, 4,4'-dihydroxy diphenyl, 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 a preferred embodiment, the compound of formula 3-1 is a compound of the formula:

The polycarbonate block included in the polyester-polysiloxane-polycarbonate copolymer according to the present invention is a polycarbonate oligomer prepared from a dihydric phenol compound, a compound including a structure represented by Formula 1, and Formula 2 It can be introduced into the copolymer of the present invention by reacting it with a compound containing the structure.

There is no particular limitation on a method for preparing the polycarbonate oligomer. For example, it may be prepared by a phosgene method of mixing a dihydric phenol compound and phosgene together, but is not limited thereto.

The polycarbonate block includes both linear polycarbonate blocks, branched polycarbonate blocks, and combinations thereof.

According to an embodiment of the present invention, a linear polycarbonate block is mainly used, but a branched polycarbonate block is also possible, and a combination of both may be used.

The amount of (A) polyester block contained in the polyester-polysiloxane-polycarbonate copolymer is 0.5 to 50 mol% based on 100 mol (mol)% of the total number of moles of the monomer compounds constituting the copolymer. it is preferable If the relative content of the polyester block having the structure represented by Formula 1 in the copolymer is too small, heat resistance may decrease, and if it is too large, physical properties such as transparency, fluidity, impact strength, etc. may decrease and manufacturing cost may increase. .

The amount of (B) polysiloxane block contained in the polyester-polysiloxane-polycarbonate copolymer is 0.5 to 50 mol% based on 100 mol (mol) % of the total number of moles of the monomer compounds constituting the copolymer. desirable. If the relative content of the polysiloxane block having the structure represented by Formula 2 in the copolymer is too small, the impact strength characteristics may be deteriorated. Conversely, if the relative content of the polysiloxane block having the structure represented by Formula 2 is too large, transparency and heat resistance may decrease and manufacturing cost may increase.

The polyester-polysiloxane-polycarbonate copolymer has a viscosity average molecular weight (Mv) of preferably 10,000 to 200,000, more preferably 10,000 to 150,000, even more preferably 15,000 to 70,000, when measured in a methylene chloride solution. have If the viscosity average molecular weight of the copolymer is less than 10,000, mechanical properties may be significantly reduced, and if it exceeds 200,000, problems may occur in processing the resin due to an increase in melt viscosity.

As described above, the polyester-polysiloxane-polycarbonate copolymer may be prepared by copolymerizing a polycarbonate oligomer with a compound including a structure represented by Formula 1 and a compound including a structure represented by Formula 2 described above. there is.

According to one embodiment, the polyester-polysiloxane-polycarbonate copolymer is (1) mixed with an oligomeric polycarbonate of a compound including a structure represented by Formula 1 and a compound including a structure represented by Formula 2 and then reacting under interfacial reaction conditions to form a polyester-polysiloxane-polycarbonate intermediate; and (2) polymerizing the intermediate.

As the polymerization catalyst, for example, a basic catalyst such as an alkali metal hydroxide, an alkylammonium salt, or an alkylamine may be used.

According to one embodiment, the compound including the structure represented by Formula 1 and the compound including the structure represented by Formula 2 are added to the organic phase-aqueous mixture containing the pre-prepared polycarbonate oligomer, and a molecular weight regulator and The copolymer can be prepared by adding a catalyst.

In addition, according to one embodiment, the organic phase in which the prepared copolymer is dispersed in methylene chloride is washed with alkali and then separated, and then the organic phase is washed using a hydrochloric acid solution and washed 2-3 times with distilled water repeatedly, , when the washing is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to constant, and granulation is performed using a certain amount of pure water in the range of 40 to 80 ℃. If the temperature of the pure water is less than 40 ℃, the granulation speed is slowed, the assembly time may be very long, and if the temperature of the pure water exceeds 80 ℃, it may be difficult to obtain the shape of the copolymer with a constant size. When the assembly is completed, it is preferable to first dry at 100 to 110° C. for 5 to 10 hours, and secondly at 110 to 120° C. for 5 to 10 hours.

According to another aspect of the present invention, (1) preparing a film comprising the polyester-polysiloxane-polycarbonate copolymer described above; and (2) disposing the polyester-polysiloxane-polycarbonate copolymer film on a substrate, heating and pressing to impregnate the polyester-polysiloxane-polycarbonate copolymer into the substrate; comprising, a thermoplastic resin composite material A method of manufacturing is provided.

There is no particular limitation on a method for producing a film comprising the polyester-polysiloxane-polycarbonate copolymer. According to one embodiment, the prepared copolymer may be prepared in a film shape using a press equipment under heating and pressure (eg, 280° C., 5 bar conditions), but is not limited thereto.

The thus-prepared film is placed on a substrate, heated and pressed to impregnate the polyester-polysiloxane-polycarbonate copolymer into the substrate.

In one embodiment, the temperature condition during the impregnation may be, for example, 250 °C to 300 °C, and the pressure condition may be, for example, 50 bar to 300 bar, but is not limited thereto.

The thermoplastic resin composite material of the present invention has excellent low-temperature impact properties and at the same time has excellent flame retardancy and heat resistance, so that it can be usefully used in products such as automobile interior and exterior parts, office equipment, and housings of electrical and electronic products.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example One

In a solution of 857.6 g of polycarbonate oligomer, 4.53 g of a compound having a structure represented by Formula 1-1 (here n = 7 to 8) and 15.87 g of a compound of Formula 2-1 (here n = 25 to 35) After the layer separation occurred, only the organic phase was collected, the same amount of methylene chloride (1176 g) as the organic phase, 393.65 ml of pure water, 62.722 μL of 15 wt% triethylamine, and 21.44 g of sodium hydroxide were mixed and reacted for 40 minutes, In addition, after adding 649.749 μL of 15 wt% triethylamine, the reaction was further performed for 20 minutes. Thereafter, 1150 g of methylene chloride and 1250 g of pure water were added and the layers were separated. 435 g of pure water and 8 ml of hydrochloric acid were administered together, and then washed with acid first, and then 1210 g of pure water was administered again to perform secondary acid washing. After acid washing, the first water washing was performed using 435 g of pure water, and the second washing was performed using 1210 g of pure water. After washing was completed and the concentration of the organic phase was constant, it was assembled using a predetermined amount of secondary distilled water at 80°C. After the assembly was completed, the block copolymer was prepared by drying the first at 100° C. for 8 hours, and secondly at 120° C. for 10 hours.

The prepared copolymer was prepared as a film under the conditions of 280° C. and 5 bar using a press equipment, and then impregnated with TORAY’s T300 3k, plain weave fabric. The temperature and pressure during impregnation were carried out under conditions of 285 °C and 80 bar. The physical properties of the prepared composite material were measured, and the results are shown in Table 1 below.

Example 2

Except for using the compound having the structure represented by Formula 1-1 (here n = 7 to 8) in an amount of 6.8 g, and using the compound of Formula 2-1 (here n = 25 to 35) in an amount of 14.5 g Then, a block copolymer was prepared in the same manner as in Example 1, and after it was made into a film in the same manner as in Example 1, the same substrate was impregnated in the same manner to prepare a composite material. The physical properties of the prepared composite material were measured and the results are shown in Table 1 below.

comparative example One

After polysiloxane-polycarbonate (TRIREX ST4-3022) was made into a film in the same manner as in Example 1, the same substrate was impregnated in the same manner to prepare a composite material. The physical properties of the prepared composite material were measured and the results are shown in Table 1 below.

comparative example 2

A thermosetting composite material was prepared by curing carbon fiber prepreg, which is an epoxy resin-based thermosetting resin, for 4 hours at 120° C. and 5 bar conditions using an autoclave process. The physical properties of the prepared composite material were measured, and the results are shown in Table 1 below.

comparative example 3

After mixing 1000 g of epoxy resin (YD128) and 800 g of METHPA (Methyltetrahydrophthalic anhydride), the resin is injected into the carbon fiber fabric (TORAY T300, 3k, plain weave) through the RIM (Reaction injection molding) process, and heated in an oven at 120°C, 3 A thermosetting resin composite material was prepared by curing for a period of time. The physical properties of the prepared composite material were measured and the results are shown in Table 1 below.

[Measurement of physical properties]

The physical properties of each manufactured composite material were measured by the following method.

Low temperature impact strength (-30℃)

It was evaluated according to ASTM D256 (1/8 inch thick, Notch Izod).

flame retardant

It was measured by the UL-94 flame retardant test method, which is a method prescribed by Underwriter's Laboratories (UL) of the United States. This method is a method to evaluate the flame retardancy from the burning time or drip property after attaching the flame of a burner to a specimen of a certain size fixed vertically for 10 seconds. 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 bottom of the specimen, is ignited by the drip It is determined by, and the grade of flame retardancy is divided according to the table below.

Glass transition temperature (℃)

The glass transition temperature was measured using Perkin Elmer's Diamond DSC (Differential Scanning Calorimetry).

[Table 1]

As can be seen from Table 1, it can be confirmed that the thermoplastic resin composite materials prepared in Examples 1 and 2 according to the present invention exhibit superior low-temperature impact properties compared to the composite materials of Comparative Examples, while maintaining excellent flame retardancy. there was.

Claims (7)

write; and a polyester-polysiloxane-polycarbonate copolymer impregnated in the substrate;
The polyester-polysiloxane-polycarbonate copolymer is (A) a polyester block comprising a structure represented by the following Chemical Formula 1-1 as a repeating unit; (B) a polysiloxane block comprising a structure represented by the following Chemical Formula 2-1 as a repeating unit; and (C) a polycarbonate block; containing,
Thermoplastic composites:
[Formula 1-1]

In Formula 1-1, n is an integer of 7 to 8;
[Formula 2-1]

In Formula 2-1, n is independently an integer of 25 to 35. The thermoplastic resin composite material of claim 1 , wherein the substrate is a fiber roving, a woven fabric, a knitted fabric, a nonwoven fabric, or a combination thereof. The thermoplastic resin composite material according to claim 1, wherein the polycarbonate block includes a structure represented by the following formula (3) as a repeating unit:
[Formula 3]

In Formula 3, R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is unsubstituted or substituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom or a nitro group. (1) (A) a polyester block comprising a structure represented by the following formula (1-1) as a repeating unit; (B) a polysiloxane block comprising a structure represented by the following Chemical Formula 2-1 as a repeating unit; And (C) a polycarbonate block; polyester comprising a-polysiloxane-preparing a film comprising a polycarbonate copolymer; and
(2) disposing the polyester-polysiloxane-polycarbonate copolymer film on a substrate, heating and pressing to impregnate the polyester-polysiloxane-polycarbonate copolymer into the substrate;
Method for producing a thermoplastic resin composite material:
[Formula 1-1]

In Formula 1-1, n is an integer of 7 to 8;
[Formula 2-1]

In Formula 2-1, n is independently an integer of 25 to 35. The method for producing a thermoplastic resin composite material according to claim 4, wherein the temperature condition during impregnation is 250°C to 300°C, and the pressure condition is 50bar to 300bar. delete delete