WO2023182709A1 - Thermoplastic resin composition and molded product manufactured therefrom - Google Patents

Abstract

A thermoplastic resin composition according to the present invention comprises: approximately 100 parts by weight of a polyester resin; approximately 10-40 parts by weight of glass fiber; approximately 0.5-10 parts by weight of an ethylene-glycidyl methacrylate-methyl acrylate copolymer; and approximately 1-15 parts by weight of a glass transition temperature control agent. The thermoplastic resin composition has excellent glass bonding strength, impact resistance, stiffness, chemical resistance, balance of physical properties thereof, and the like.

Description

Thermoplastic resin composition and molded articles made therefrom

The present invention relates to thermoplastic resin compositions and molded articles made therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent glass adhesion, impact resistance, rigidity, chemical resistance, and balance of physical properties, and molded articles manufactured therefrom.

Polycarbonate resin can be produced in a variety of colors, has excellent impact resistance properties, and when reinforced with glass fiber, etc., can secure high rigidity and impact resistance, so it is widely used as a housing material for IT products such as mobile phones.

However, as the bezels of mobile products have recently become thinner, the adhesive space between plastic parts and display glass is becoming thinner. This causes the display to detach more easily than before when assembling the product, and the plastic parts and display glass Problems such as decreased waterproofing performance are occurring due to decreased adhesion between devices.

Therefore, there is a need to develop a thermoplastic resin composition with excellent glass adhesion, impact resistance, rigidity, chemical resistance, and balance of these properties.

The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2015-0076650, etc.

The purpose of the present invention is to provide a thermoplastic resin composition with excellent glass adhesion, impact resistance, rigidity, chemical resistance, and balance of these properties.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

The above and other objects of the present invention can all be achieved by the present invention described below.

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition includes about 100 parts by weight of polycarbonate resin; About 10 to about 40 parts by weight of glass fiber; About 0.5 to about 10 parts by weight of ethylene-glycidyl methacrylate-methylacrylate copolymer; And about 1 to about 15 parts by weight of a glass transition temperature regulator.

2. In the first embodiment, the ethylene-glycidyl methacrylate-methylacrylate copolymer is about 50 to about 75% by weight of ethylene, about 1 to about 10% by weight of glycidyl methacrylate, and methyl acrylate. It may be about 15 to about 40 weight percent of the terpolymer.

3. In embodiment 1 or 2, the glass transition temperature regulator may be a compound represented by the following formula (1):

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Alkenyl group with 2 to 7 carbon atoms, substituted or unsubstituted cycloalkyl group with 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group with 2 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms , an aryloxy group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group, or It is a hydroxyl group.

4. In embodiments 1 to 3, the weight ratio of the glass fiber and the ethylene-glycidyl methacrylate-methylacrylate copolymer may be about 1:0.01 to about 1:0.8.

5. In embodiments 1 to 4, the weight ratio of the glass fiber and the glass transition temperature regulator may be about 1:0.03 to about 1:0.9.

6. In embodiments 1 to 5 above, the weight ratio of the ethylene-glycidyl methacrylate-methylacrylate copolymer and the glass transition temperature regulator may be about 1:0.1 to about 1:10.

7. In embodiments 1 to 6, the thermoplastic resin composition is prepared by applying 0.018 g of a polyurethane-based adhesive (EH9777BS, HB Fuller) to a thickness of 1 mm at 110°C on a specimen measuring 50 mm × 50 mm × 3 mm. After attaching a glass measuring 12 mm After 72 cycle retention and thermal shock, The weight of the weight when the specimen is detached from the glass, measured by hitting the specimen with a dart from a height of 50 cm using a falling weight evaluation equipment of the Dupont drop test method, may be about 240 to about 400 g. there is.

8. In embodiments 1 to 7, the thermoplastic resin composition may have a notched Izod impact strength of about 10 to about 25 kgf·cm/cm for a 1/8" thick specimen measured according to ASTM D256.

9. In embodiments 1 to 8, the thermoplastic resin composition may have a flexural modulus of about 30,000 to about 90,000 MPa, as measured at a speed of 2.8 mm/min using a 1/4" thick specimen, according to ASTM D790. there is.

10. In embodiments 1 to 9, the thermoplastic resin composition was prepared by immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying it at 80°C for 20 minutes, leaving it at room temperature for 24 hours, and then weighing 2 kg. The height at which the specimen is destroyed may be about 27 to about 70 cm, as measured by impact using a Dupont drop test type falling weight evaluation equipment.

11. Another aspect of the present invention relates to molded articles. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of items 1 to 10 above.

12. Another aspect of the present invention relates to composite materials. The composite material includes a plastic member formed from the thermoplastic resin composition according to any one of 1 to 10 above; and a glass member in contact with the plastic member.

13. In the above 12 embodiments, the plastic member and the glass member may be adhered with an adhesive.

14. In embodiment 13 or 14 above, the plastic member is Apply 0.018 g of polyurethane-based adhesive (HB Fuller, EH9777BS) to a thickness of 1 mm at 110°C on a specimen measuring 50 mm × 50 mm × 3 mm, and apply a specimen measuring 12 mm × 12 mm × 2.8 mm on top of the applied adhesive. After attaching the glass, it was cured for 72 hours at a temperature of 25℃ and 50% humidity, and then subjected to thermal shock by staying for 72 cycles of 30 minutes each at -40℃ and 85℃. The weight of the weight when the specimen is detached from the glass, measured by hitting the specimen with a dart from a height of 50 cm using a falling weight evaluation equipment of the Dupont drop test method, may be about 240 to about 400 g. there is.

The present invention has the effect of providing a thermoplastic resin composition with excellent glass adhesion, impact resistance, rigidity, chemical resistance, and balance of physical properties, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail as follows.

The thermoplastic resin composition according to the present invention includes (A) polycarbonate resin; (B) glass fiber; (C) ethylene-glycidyl methacrylate-methylacrylate copolymer; and (D) a glass transition temperature regulator.

In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

(A) Polycarbonate resin

The polycarbonate resin according to one embodiment of the present invention can improve the impact resistance and appearance characteristics of a thermoplastic resin composition, and polycarbonate resins used in conventional thermoplastic resin compositions can be used. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with precursors such as phosgene, halogen formate, and carbonic acid diester can be used.

In a specific example, the diphenols include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Examples include propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, but are not limited thereto. . For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4- Hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl)cyclohexane can be used, specifically, bisphenol- 2,2-bis(4-hydroxyphenyl)propane, called A, can be used.

In a specific example, the polycarbonate resin may be one having a branched chain, and for example, 0.05 to 2 mol% of a trivalent or higher polyfunctional compound based on the total of diphenols used in polymerization, specifically, 3 Branched polycarbonate resin prepared by adding a compound having one or more phenol groups can also be used.

In a specific example, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin can be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, for example, a difunctional carboxylic acid.

In an embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 50,000 g/mol, for example, about 15,000 to about 40,000 g/mol. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity (processability), etc.

(B) Glass fiber

Glass fiber according to one embodiment of the present invention is applied together with an ethylene-glycidyl methacrylate-methylacrylate copolymer and a glass transition temperature regulator to improve the glass adhesion and impact resistance of a thermoplastic resin composition containing polycarbonate resin. , rigidity, chemical resistance, balance of these properties, etc. can be improved, and glass fibers used in conventional thermoplastic resin compositions can be used.

In specific examples, the glass fiber may be in the form of a fiber and may have a cross-section of various shapes such as circular, oval, or rectangular. For example, it may be desirable in terms of mechanical properties to use fibrous glass fibers of circular and/or rectangular cross-section.

In an embodiment, the glass fiber of the circular cross-section may have a cross-sectional diameter of about 5 to about 20 ㎛ measured using a scanning electron microscope (SEM), a length before processing of about 2 to about 20 mm, and a rectangular cross-section of the glass fiber. The glass fiber may have an aspect ratio of the cross-section (major axis of the cross-section/minor axis of the cross-section) measured using a SEM (Scanning Electron Microscope) of about 1.5 to about 10, a minor diameter of about 2 to about 10 ㎛, and a length before processing. It may be about 2 to about 20 mm. Within the above range, the rigidity, processability, etc. of the thermoplastic resin composition may be improved.

In a specific example, the glass fiber may be treated with a common surface treatment agent. The surface treatment agent may include, but is not limited to, silane-based compounds, urethane-based compounds, and epoxy-based compounds.

In an embodiment, the glass fiber may be included in an amount of about 10 to about 40 parts by weight, for example, about 15 to about 35 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the glass fiber is less than about 10 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a risk that the rigidity, etc. of the thermoplastic resin composition (molded product) may decrease, and if it exceeds about 40 parts by weight, the thermoplastic resin There is a risk that the glass adhesion, impact resistance, chemical resistance, and appearance characteristics of the composition (molded product) may be reduced.

(C) Ethylene-glycidyl methacrylate-methyl acrylate copolymer

The ethylene-glycidyl methacrylate-methylacrylate copolymer according to one embodiment of the present invention is applied together with glass fiber and a glass transition temperature regulator to improve the glass adhesion and impact resistance of a thermoplastic resin composition containing polycarbonate resin. , rigidity, chemical resistance, and the balance of these properties can be improved.

In an embodiment, the ethylene-glycidyl methacrylate-methylacrylate copolymer contains about 50 to about 75% by weight of ethylene, for example, about 60 to about 70% by weight, and about 1 to about 1% by weight of glycidyl methacrylate. It may be a terpolymer of 10% by weight, for example about 4 to about 8% by weight, and about 15 to about 40% by weight, for example, about 20 to about 30% by weight of methyl acrylate. Within the above range, the thermoplastic resin composition (molded product) may have excellent impact resistance, glass adhesion, chemical resistance, etc.

In an embodiment, the ethylene-glycidyl methacrylate-methylacrylate copolymer has an MFI (Melt Flow Index, 290° C., 2.16 kg condition) value of about 1 to about 15 g/10 min, for example, about 4. It may be from about 9 g/10 min. Within the above range, the thermoplastic resin composition (molded product) may have excellent impact resistance, glass adhesion, chemical resistance, etc.

In an embodiment, the ethylene-glycidyl methacrylate-methylacrylate copolymer may be included in an amount of about 0.5 to about 10 parts by weight, for example, about 1 to about 7 parts by weight, based on about 100 parts by weight of the polycarbonate resin. You can. If the content of the ethylene-glycidyl methacrylate-methyl acrylate copolymer is less than about 0.5 parts by weight based on about 100 parts by weight of the polycarbonate resin, there is a risk that the chemical resistance, etc. of the thermoplastic resin composition (molded article) may decrease. If it exceeds about 10 parts by weight, there is a risk that the glass adhesion and chemical resistance of the thermoplastic resin composition (molded product) may decrease.

In an embodiment, the weight ratio (B:C) of the glass fiber and the ethylene-glycidylmethacrylate-methylacrylate copolymer is from about 1:0.01 to about 1:0.8, for example from about 1:0.03 to about It can be 1:0.5. Within the above range, the thermoplastic resin composition (molded product) may have better rigidity, glass adhesion, chemical resistance, impact resistance, etc.

(D) Glass transition temperature regulator

The glass transition temperature regulator according to one embodiment of the present invention is applied together with glass fiber and ethylene-glycidyl methacrylate-methyl acrylate copolymer to improve glass adhesion and impact resistance of a thermoplastic resin composition containing polycarbonate resin. , cyclic phosphazene can be used to improve rigidity, chemical resistance, and the balance of these properties.

In a specific example, the glass transition temperature regulator may be a compound (phosphazene) represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Alkenyl group with 2 to 7 carbon atoms, substituted or unsubstituted cycloalkyl group with 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group with 2 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms , an aryloxy group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group, or It is a hydroxyl group.

Here, the "substitution" means that the hydrogen atom is an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a carbon number 3 to 10 group. It means being substituted with a substituent such as a heterocycloalkyl group, a heteroaryl group having 4 to 10 carbon atoms, or a combination thereof.

In addition, the substituents including “alkyl,” “alkoxy,” and other “alkyl” moieties include both straight-chain or branched forms, and “alkenyl” has 2 to 8 carbon atoms and contains one or more double bonds. It includes both straight-chain or branched forms, and the term “cycloalkyl” includes all saturated monocyclic or saturated bicyclic ring structural forms having 3 to 20 carbon atoms. The "aryl" is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen atom, and has a single or fused ring system containing 4 to 7 ring atoms, preferably 5 or 6 ring atoms in each ring. Includes. Specifically, phenyl, naphthyl, biphenyl, tolyl, etc. may be exemplified, but are not limited thereto.

The "heterocycloalkyl" refers to a cycloalkyl group containing 1 to 3 heteroatoms selected from N, O, and S as a saturated cyclic hydrocarbon skeleton atom, and the remaining saturated monocyclic or bicyclic ring skeleton atom is carbon. Meaning, pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valerolactamyl, Oxyranyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyri Examples include dinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanil, and azepanil.

The "heteroaryl" refers to an aryl group containing 1 to 3 heteroatoms selected from N, O, and S as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atom is carbon. The heteroaryl group is a heteroaryl group in the ring. and divalent aryl groups whose atoms may be oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specifically, furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazinyl. Examples include zolyl, tetrazolyl, furazinyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl, but are not limited thereto.

In an embodiment, the glass transition temperature regulator may be included in an amount of about 1 to about 15 parts by weight, for example, about 2 to about 10 parts by weight, based on about 100 parts by weight of the polycarbonate resin. If the content of the glass transition temperature regulator is less than about 1 part by weight based on about 100 parts by weight of the polycarbonate resin, there is a risk that the glass adhesion and appearance characteristics of the thermoplastic resin composition (molded product) may be reduced, and about 15 parts by weight If it is exceeded, there is a risk that the impact resistance and chemical resistance of the thermoplastic resin composition (molded product) may decrease.

In an embodiment, the weight ratio (B:D) of the glass fiber and the glass transition temperature regulator may be about 1:0.03 to about 1:0.9, for example, about 1:0.05 to about 1:0.6. Within the above range, the appearance characteristics, glass adhesion, chemical resistance, impact resistance, rigidity, etc. of the thermoplastic resin composition (molded article) may be superior.

In an embodiment, the weight ratio (C:D) of the ethylene-glycidyl methacrylate-methylacrylate copolymer and the glass transition temperature regulator is about 1:0.1 to about 1:10, for example, about 1:0.3. It may be from about 1:7. Within the above range, the appearance characteristics, glass adhesion, chemical resistance, impact resistance, rigidity, etc. of the thermoplastic resin composition (molded article) may be superior.

The thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additives include, but are not limited to, flame retardants, antioxidants, anti-dripping agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. When using the additive, its content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the polycarbonate resin.

The thermoplastic resin composition according to one embodiment of the present invention is in the form of a pellet obtained by mixing the above components and melt-extruding the components at about 240 to about 300°C, for example, about 260 to about 290°C using a conventional twin-screw extruder. You can.

In a specific example, the thermoplastic resin composition is prepared by applying 0.018 g of a polyurethane-based adhesive (HB Fuller, EH9777BS) to a thickness of 1 mm at 110°C on a 50 mm × 50 mm × 3 mm specimen. After attaching glass with a size of 12 mm After adding, The weight of the weight when the specimen is detached from the glass, measured by hitting the specimen with a dart from a height of 50 cm using a falling weight evaluation equipment of the Dupont drop test method, is about 240 to about 400 g, e.g. For example, it may be about 250 to about 300 g.

In an embodiment, the thermoplastic resin composition has a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of about 10 to about 25 kgf·cm/cm, for example, about 11 to about 20 kgf·cm. It may be /cm.

In an embodiment, the thermoplastic resin composition has a flexural modulus of about 30,000 to about 90,000 MPa, for example, about 40,000 to about 40,000 MPa, as measured at a rate of 2.8 mm/min using a 1/4" thick specimen according to ASTM D790. It may be 75,000 MPa.

In a specific example, the thermoplastic resin composition is prepared by immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying it at 80°C for 20 minutes, leaving it at room temperature for 24 hours, and then applying a Dupont drop using a 2 kg weight. The height at which the specimen is destroyed, as measured by impact using a Dupont drop test type drop evaluation equipment, may be about 27 to about 70 cm, for example, about 28 to about 60 cm.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition can be manufactured in the form of pellets, and the manufactured pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. This forming method is well known to those skilled in the art. The molded product has excellent glass adhesion, impact resistance, rigidity, chemical resistance, and balance of physical properties, and is therefore useful as a housing material for mobile products.

The composite material according to the present invention includes a plastic member as the molded article; and a glass member in contact with the plastic member.

In a specific example, the plastic member and the glass member may be bonded with an adhesive.

In an embodiment, the plastic member is Apply 0.018 g of polyurethane-based adhesive (HB Fuller, EH9777BS) to a thickness of 1 mm at 110°C on a specimen measuring 50 mm × 50 mm × 3 mm, and apply a specimen measuring 12 mm × 12 mm × 2.8 mm on top of the applied adhesive. After attaching the glass, it was cured for 72 hours at a temperature of 25℃ and 50% humidity, and then subjected to thermal shock by staying for 72 cycles of 30 minutes each at -40℃ and 85℃. The weight of the weight when the specimen is detached from the glass, measured by hitting the specimen with a dart from a height of 50 cm using a falling weight evaluation equipment of the Dupont drop test method, is about 240 to about 400 g, e.g. For example, it may be 250 to 300 g.

Hereinafter, the present invention will be described in more detail through examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, the specifications of each component used in the examples and comparative examples are as follows.

(A) Polycarbonate resin

Bisphenol-A polycarbonate resin (PC, manufacturer: Lotte Chemical, weight average molecular weight: 25,000 g/mol) was used.

(B) Glass fiber

Circular cross-section glass fiber (manufacturer: Owenscorning, product name: 183F, average diameter: 13 ㎛) was used.

(C1) Ethylene-glycidyl methacrylate-methyl acrylate copolymer

Ethylene-glycidyl methacrylate-methyl acrylate copolymer (manufacturer: SUMITOMO Chemical, product name: IGETABOND BF-7M) was used.

(C2) (meth)acrylate modified polyolefin

Ethylene-methylacrylate copolymer (manufacturer: ARKEMA, product name: LOTRYL®29MA03T) was used.

(D) Glass transition temperature regulator

A phosphazene compound (manufacturer: Pharmicell, product name: Phoretar201) was used.

Examples 1 to 7 and Comparative Examples 1 to 7

Each of the above components was added in the amounts shown in Tables 1 and 2 below, and then extruded at 270°C to prepare pellets. For extrusion, a twin-screw extruder with L/D = 44 and a diameter of 45 mm was used, and the produced pellets were dried at 100℃ for more than 4 hours and then injection molded in a 10 oz injection machine (molding temperature: 320℃, mold temperature: 80℃). A specimen was prepared. The physical properties of the manufactured specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

How to measure physical properties

(1) Evaluation of glass adhesion force: Apply 0.018 g of polyurethane-based adhesive (HB Fuller, EH9777BS) to a thickness of 1 mm at 110°C on a 50 mm After attaching the glass with a size of mm next, Using the Dupont drop test type falling weight evaluation equipment, the specimen is struck with a dart weighing 10 to 500 g from a height of 50 cm, and the weight of the dart when the specimen is detached from the glass (unit: g) was measured.

(2) Impact resistance evaluation: Based on ASTM D256, the notched Izod impact strength (unit: kgf·cm/cm) of a 1/8" thick specimen was measured.

(3) Stiffness evaluation: According to ASTM D790, the flexural modulus (unit: MPa) of a 1/4" thick specimen was measured at a speed of 2.8 mm/min.

(4) Evaluation of chemical resistance (impact resistance after painting): A 1 mm thick specimen was immersed in a thinner solution for 2 minutes and 30 seconds, dried at 80°C for 20 minutes, left at room temperature for 24 hours, and then placed under a 2 kg weight. The height (unit: cm) at which the specimen was destroyed upon impact was measured using a falling weight evaluation equipment using the Dupont drop test method.

	Example
	One	2	3	4	5	6	7
(A) (parts by weight)	100	100	100	100	100	100	100
(B) (part by weight)	15	23	35	23	23	23	23
(C1) (parts by weight)	3.7	3.7	3.7	One	7	3.7	3.7
(C2) (parts by weight)	-	-	-	-	-	-	-
(D) (parts by weight)	5	5	5	5	5	2	10
Glass bonding force (g)	275	270	260	280	265	260	280
Notched Izod impact strength (kgf·cm/cm)	19	18	15	12	19	19	19
Flexural modulus (MPa)	44,000	46,000	70,000	48,000	42,000	46,000	45,000
Chemical resistance (cm)	55	50	35	30	50	53	45

	Comparative example
	One	2	3	4	5	6	7
(A) (parts by weight)	100	100	100	100	100	100	100
(B) (part by weight)	5	45	23	23	23	23	23
(C1) (parts by weight)	3.7	3.7	0.1	15	-	3.7	3.7
(C2) (parts by weight)	-	-	-	-	3.7	-	-
(D) (parts by weight)	5	5	5	5	5	0.5	20
Glass bonding force (g)	290	230	290	200	230	230	270
Notched Izod impact strength (kgf·cm/cm)	21	9	11	13	19	19	8
Flexural modulus (MPa)	26,000	90,000	49,000	38,000	45,000	46,000	42,000
Chemical resistance (cm)	70	10↓	10↓	20	25	55	20

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in glass adhesion, impact resistance (notched Izod impact strength), rigidity (flexural modulus), chemical resistance, and balance of these properties.

On the other hand, in the case of Comparative Example 1 in which a small amount of glass fiber was applied, the stiffness, etc. were found to be reduced, and in the case of Comparative Example 2 in which an excessive amount of glass fiber was applied, the glass bonding strength, impact resistance, chemical resistance, etc. were found to be reduced. In the case of Comparative Example 3 in which a small amount of ethylene-glycidyl methacrylate-methyl acrylate copolymer was applied, it can be seen that chemical resistance, etc. was reduced, and in the case of comparative example 3 in which a small amount of ethylene-glycidyl methacrylate-methyl acrylate copolymer was applied, In the case of Comparative Example 4, it can be seen that glass bonding strength, chemical resistance, etc. were reduced, and instead of the ethylene-glycidyl methacrylate-methyl acrylate copolymer of the present invention, (meth)acrylate modified polyolefin (C2) was used. In the case of Comparative Example 5, it can be seen that the glass bonding strength and chemical resistance were reduced. In addition, in the case of Comparative Example 6, where a small amount of the glass transition temperature regulator was applied, the glass bonding strength, etc., was found to be reduced, and in the case of Comparative Example 7, where an excessive amount of the glass transition temperature regulator was applied, the impact resistance, chemical resistance, etc. were found to be reduced. .

So far, the present invention has been examined focusing on the embodiments. A person skilled in the art to which the present invention pertains will understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the equivalent scope should be construed as being included in the present invention.

Claims (14)

1. About 100 parts by weight of polycarbonate resin;

   About 10 to about 40 parts by weight of glass fiber;

   About 0.5 to about 10 parts by weight of ethylene-glycidyl methacrylate-methylacrylate copolymer; and

   A thermoplastic resin composition comprising about 1 to about 15 parts by weight of a glass transition temperature regulator.
2. The method of claim 1, wherein the ethylene-glycidyl methacrylate-methylacrylate copolymer contains about 50 to about 75% by weight of ethylene, about 1 to about 10% by weight of glycidyl methacrylate, and about 15% by weight of methyl acrylate. A thermoplastic resin composition characterized in that it is a terpolymer of from about 40% by weight.
3. The thermoplastic resin composition according to claim 1 or 2, wherein the glass transition temperature regulator is a compound represented by the following formula (1):

   [Formula 1]

   

   In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Alkenyl group with 2 to 7 carbon atoms, substituted or unsubstituted cycloalkyl group with 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group with 2 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms , an aryloxy group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group, or It is a hydroxyl group.
4. 4. The method of any one of claims 1 to 3, wherein the weight ratio of the glass fiber and the ethylene-glycidyl methacrylate-methylacrylate copolymer is about 1:0.01 to about 1:0.8. Thermoplastic resin composition.
5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the weight ratio of the glass fiber and the glass transition temperature regulator is about 1:0.03 to about 1:0.9.
6. The method according to any one of claims 1 to 5, wherein the weight ratio of the ethylene-glycidyl methacrylate-methylacrylate copolymer and the glass transition temperature regulator is about 1:0.1 to about 1:10. A thermoplastic resin composition comprising:
7. The method of any one of claims 1 to 6, wherein the thermoplastic resin composition is prepared by applying 0.018 g of a polyurethane-based adhesive (HB Fuller, EH9777BS) on a 50 mm × 50 mm × 3 mm specimen at 110°C. After applying the adhesive to a mm thickness and attaching glass measuring 12 mm After thermal shock was applied by allowing 72 cycles to remain under the conditions for 30 minutes each, The weight of the weight when the specimen is detached from the glass, measured by hitting the specimen with a dart from a height of 50 cm using a falling weight evaluation equipment of the Dupont drop test, is about 240 to about 400 g. A thermoplastic resin composition characterized by:
8. The method of any one of claims 1 to 7, wherein the thermoplastic resin composition has a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of about 10 to about 25 kgf·cm/cm. A thermoplastic resin composition characterized by:
9. The method of any one of claims 1 to 8, wherein the thermoplastic resin composition has a flexural modulus of about 30,000 to about 30,000, as measured at a speed of 2.8 mm/min using a 1/4" thick specimen according to ASTM D790. A thermoplastic resin composition characterized in that it is 90,000 MPa.
10. The method of any one of claims 1 to 9, wherein the thermoplastic resin composition is prepared by immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying it at 80°C for 20 minutes, and leaving it at room temperature for 24 hours. Next, a thermoplastic resin composition characterized in that the height at which the specimen is destroyed is about 27 to about 70 cm, as measured by impact with a falling weight evaluation equipment of the Dupont drop test method using a 2 kg weight.
11. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 10.
12. A plastic member formed from the thermoplastic resin composition according to any one of claims 1 to 10; and

    A composite material comprising a glass member in contact with the plastic member.
13. The composite material of claim 12, wherein the plastic member and the glass member are bonded to each other using an adhesive.
14. The method of claim 12 or 13, wherein the plastic member is formed by applying 0.018 g of polyurethane-based adhesive (HB Fuller, EH9777BS) at 110°C to a thickness of 1 mm on a specimen measuring 50 mm × 50 mm × 3 mm. , After attaching a glass measuring 12 mm After maintaining the cycle and applying thermal shock, The weight of the weight when the specimen is detached from the glass, measured by hitting the specimen with a dart from a height of 50 cm using a falling weight evaluation equipment of the Dupont drop test, is about 240 to about 400 g. Characterized composite material.