KR101914822B1 - Fiberglass reinforced polycarbonated resin composition and article using the same - Google Patents
Fiberglass reinforced polycarbonated resin composition and article using the same Download PDFInfo
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- KR101914822B1 KR101914822B1 KR1020150138244A KR20150138244A KR101914822B1 KR 101914822 B1 KR101914822 B1 KR 101914822B1 KR 1020150138244 A KR1020150138244 A KR 1020150138244A KR 20150138244 A KR20150138244 A KR 20150138244A KR 101914822 B1 KR101914822 B1 KR 101914822B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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Abstract
The present invention relates to a resin composition comprising 100 parts by weight of a base resin comprising polycarbonate, amorphous polyester resin, and glass fiber; And 0.1 to 1.5 parts by weight of a reactive silane compound, and a molded article using the glass fiber reinforced polycarbonate resin.
Description
The present invention relates to a glass fiber reinforced polycarbonate resin composition excellent in bending strength and impact resistance and a molded article using the same. More particularly, the present invention relates to a glass fiber reinforced polycarbonate resin composition which is obtained by simultaneously applying an amorphous polyester resin and a reactive silane compound to improve impact resistance without lowering bending strength, and a molded article using the same.
BACKGROUND ART Polycarbonate resins have excellent mechanical properties such as moldability, impact resistance and tensile strength, and are excellent in electrical characteristics and transparency, and are widely used in automobiles and electronic products. In addition, the glass fiber reinforced polycarbonate resin can be used for parts which are required to be continuously subjected to load or heat because the rigidity and flexural strength can be improved while maintaining excellent moldability of the polycarbonate resin.
However, when the glass fiber is added to the polycarbonate resin, the rigidity and the bending strength are improved but the impact resistance is greatly reduced, which is problematic because it is vulnerable to damage by external impact. Therefore, a method of adding an impact modifier such as a core-shell graft copolymer to reinforce the impact resistance of the glass fiber reinforced polycarbonate resin has been proposed. However, when the core-shell graft copolymer is added, the flowability of the polycarbonate resin is decreased and the molding injection operation temperature must be increased. As a result, the glass fiber is broken and the bending strength is lowered.
A related prior art is Korean Patent Laid-Open No. 10-2009-0018569.
Disclosure of Invention Technical Problem [8] The present invention provides a glass fiber reinforced polycarbonate resin composition having excellent bending strength and impact resistance.
In one aspect, the present invention provides a glass fiber-reinforced polycarbonate resin comprising 100 parts by weight of a base resin comprising polycarbonate, amorphous polyester resin, and glass fiber, and 0.1 to 1.5 parts by weight of a reactive silane compound.
The base resin may include 35 to 75% by weight of polycarbonate, 5 to 20% by weight of amorphous polyester resin and 20 to 50% by weight of glass fibers.
The amorphous polyester resin may include a dicarboxylic acid component and a diol component, and the content of cyclohexane dimethanol (CHDM) in the entire diol component may be 10 to 50 mol%.
In addition, the amorphous polyester resin may include a dicarboxylic acid component and a diol component, and the content of ethylene glycol in the entire diol component may be 50 to 90 mol%.
The glass fibers may have a length of 2 to 5 mm.
The reactive silane compound may contain at least one reactive functional group selected from an epoxy group, an amino group, an acryl group, an isocyanate group and a mercapto group.
The polycarbonate resin composition may further include an additive selected from the group consisting of an ultraviolet absorber, an inorganic additive, a flame retardant, a lubricant, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, a dye and a mixture thereof.
The polycarbonate resin composition may have a flexural modulus of 55000 kgf / cm 2 or more as measured according to ASTM D790 standard after specimen molding.
The polycarbonate resin composition may have an impact resistance of 70 cm or more as measured using a Dupont drop test in which a specimen of 5 cm × 5 cm × 1 mm is molded and aged at room temperature for 6 hours and impacted on a specimen with a weight of 500 g.
In another aspect, the present invention provides a molded article molded using the glass fiber-reinforced polycarbonate resin composition described above.
The glass fiber reinforced polycarbonate resin composition according to the present invention is excellent in both bending strength and impact resistance after molding and can be usefully used as a material for various electronic products such as mobile phone exterior materials.
Hereinafter, the present invention will be described more specifically.
The glass fiber reinforced polycarbonate resin composition according to one embodiment of the present invention comprises (A) a base resin comprising (a1) a polycarbonate resin, (a2) an amorphous polyester resin, and (a3) Reactive silane compounds. Each component of the resin composition of the present invention will be described in detail below.
(A) Base resin
(a1) Polycarbonate resin
As the polycarbonate resin used in the present invention, polycarbonate resins generally known in the art can be used without limitation.
For example, the polycarbonate resin may be prepared by reacting a diphenol represented by the following formula (1) with phosgene, a halogen acid ester, a carbonic ester, or a combination thereof.
[Chemical Formula 1]
In Formula 1, A represents a single bond, a substituted or unsubstituted C1 to C30 linear or branched alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylidene group , A substituted or unsubstituted C1 to C30 linear or branched haloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkenylene group, a substituted or unsubstituted C5 A substituted or unsubstituted C1 to C20 linear or branched alkoxysilyl group, a halogen acid ester group, a carbonate ester group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 straight or branched alkoxysilyl group, 2, and, R1 and R2 are the same or different, is a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, n 1 and n 2 is an integer from 0 to 4, respectively.
The diphenols represented by the above formula (1) may be composed of two or more of them to form a repeating unit of a polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether, and the like. Preferred examples thereof include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1- Hexane can be used. More preferably, 2,2-bis (4-hydroxyphenyl) propane can be used.
The polycarbonate resin may have a weight average molecular weight of 10,000 to 200,000 g / mol measured by gel permeation chromatography (GPC) using polystyrene as a standard, preferably 15,000 to 80,000 g / mol. However, the present invention is not limited thereto.
The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin.
Examples of the linear polycarbonate resin include a bisphenol-A type polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid and the like with a diphenol and a carbonate. The polyfunctional aromatic compound may be contained in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. As the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate and the like can be used.
The polycarbonate resin may be contained in an amount of 35 to 75% by weight, preferably 45 to 75% by weight, based on the total content of the base resin. When the content of the polycarbonate resin satisfies the above range, a composition excellent in physical properties such as rigidity, flexural strength and impact resistance can be obtained.
(a2) Amorphous polyester resin
The polycarbonate resin composition of the present invention comprises an amorphous polyester resin in the base resin. When the amorphous polyester resin and the reactive silane compound are applied to the polycarbonate resin together, the impact resistance can be greatly improved without lowering the flexural strength of the polycarbonate resin.
The amorphous polyester resin is a polymer of a dicarboxylic acid component and a diol component, and is a polyester resin in which a crystal structure is not formed in the molecular structure. Specifically, the amorphous polyester resin may be a resin in which a part of the dicarboxylic acid component and / or the diol component is modified.
For example, the amorphous polyester resin may be a polyester resin in which a part of the entire diol component is 1,4-cyclohexane dimethanol (CHDM). The 1,4-cyclohexane dimethanol may be contained in an amount of 10 to 50 mol%, preferably 25 to 35 mol%, of the total diol component.
Examples of the diol component other than 1,4-cyclohexane dimethanol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,3 -Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like, but not limited thereto. The remaining diol components may be used alone or in combination of two or more. Preferably, the amorphous polyester resin may comprise 50 to 90 mol%, preferably 65 to 75 mol% of ethylene glycol in the total diol component.
The dicarboxylic acid component is not particularly limited and includes, for example, terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid Naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, Aromatic dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid and the like, dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl- Naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,8-naphthalate, dimethyl-2,3-naphthalate, Phthalate, dimethyl-2,6-naphthalate, dimethyl-2,7-naphthalate, and the like, but not limited thereto. On the other hand, the carboxylic acid components may be used alone or in combination of two or more.
In an embodiment, the amorphous polyester resin comprises a dicarboxylic acid component comprising terephthalic acid and a diol comprising 10 to 50 mol%, for example 25 to 35 mol% 1,4-cyclohexanedimethanol (CHDM) And the components can be polycondensed.
The amorphous polyester resin may be contained in an amount of 5 to 20% by weight based on the entire content of the base resin. When the content of the amorphous polyester resin satisfies the above range, a composition excellent in physical properties such as rigidity, flexural strength and impact resistance can be obtained.
(a3) Glass fiber
The glass fiber used in the present invention is well known to those skilled in the art and is commercially available and can be prepared by a conventional method.
The shape of the glass fiber is not particularly limited, and the cross-section can be changed according to a specific use purpose besides the circular shape. In the present invention, any shape of the glass fiber may be used, and any kind of glass fiber may be used.
For example, the glass fibers may be glass fibers of circular and / or rectangular cross-section. The glass fiber having a circular section may have a length of 2 to 5 mm and a section diameter of 5 to 20 탆. The glass fiber having a rectangular section may have a length of 2 to 5 mm, a width of 20 to 40 탆 and a thickness of 5 to 15 탆.
On the other hand, the glass fiber may be coated with a surface treatment agent on the surface thereof in order to increase the bonding force with the amorphous polyester resin. The surface treating agent may be, for example, a silane compound, a urethane compound or an epoxy compound, but is not limited thereto. The glass fiber may be contained in an amount of 20 to 50% by weight based on the entire content of the base resin. When the content of the glass fiber satisfies the above range, a composition excellent in physical properties such as rigidity, flexural strength and impact resistance can be obtained.
(B) a reactive silane compound
The polycarbonate resin composition of the present invention comprises a reactive silane compound together with the base resin. According to the studies of the present inventors, when the reactive silane compound is added to the glass fiber reinforced polycarbonate resin together with the amorphous polyester resin, the flexural strength and the impact resistance are both improved.
The reactive silane compound is a silane compound containing a reactive functional group, and the reactive functional group may be, for example, an epoxy group, an amino group, an acryl group, an isocyanate group or a mercapto group. In consideration of the reactivity with the amorphous polyester resin, an epoxy group-containing silane compound is particularly preferable.
Specific examples of the reactive silane compound include glycidoxypropyltrimethoxysilane, methacryloxypropyltri-methoxysilane, vinyltriethoxysilane, aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltriethoxysilane, Aminopropyltriethoxysilane, aminopropyltrimethoxysilane, ethylaminopropyltrimethoxysilane, aminopropyltripropoxysilane, aminoisobutyltrimethoxysilane, aminobutyltriethoxysilane, and the like can be used. More specifically, examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropylmethyldiethoxysilane, N-3-aminoethyl-3-aminopropylmethyldiethoxysilane, N- 3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, , 3-isocyanatepropyltriethoxysilane, and the like, but the present invention is not limited thereto.
The reactive silane compound is preferably contained in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the base resin. When the content of the reactive silane compound is less than 0.1 part by weight, the effect of improving impact resistance is insignificant. When the content of the reactive silane compound is more than 1.5 parts by weight, the flexural strength may be lowered.
On the other hand, the polycarbonate resin composition of the present invention may further contain additives other than the above-mentioned components, if necessary. The additive may include an inorganic filler, a flame retardant, a flame retardant, a releasing agent, a lubricant, a plasticizer, a heat stabilizer, a dripping inhibitor, an antioxidant, a light stabilizer, a pigment, a dye and a mixture thereof.
Examples of the inorganic filler include, but are not limited to, carbon fiber, wollastonite, whisker, basalt fiber, talc, mica, and alumina. When an inorganic filler is added, physical properties such as mechanical strength and heat distortion temperature can be further improved.
The additive excluding the inorganic filler may be a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a phosphazene compound, Flame retardants such as metal salts thereof; Release agents such as polyethylene wax, fluorine-containing polymer, silicone oil, metal salts of stearic acid, metal salts of montanic acid, and montanic ester wax; Nucleating agents such as clay; Antioxidants such as hindered phenol-based compounds; Mixtures thereof, and the like may be used, but the present invention is not limited thereto.
Meanwhile, the polycarbonate resin composition according to the present invention can be prepared by a known method well known in the art. For example, the above-mentioned components of the present invention and other additives may be mixed and then melt-extruded in an extruder to produce pellets.
Preferably, the glass fiber-reinforced polycarbonate resin composition according to the present invention can be produced in the form of a pellet by extruding a polycarbonate resin and an amorphous polyester resin into a main feeder and glass fibers into a side feeder. At this time, the temperature of the extruder may be about 200 ° C to 350 ° C.
On the other hand, the polycarbonate resin composition according to the present invention produced as described above is excellent in flexural strength and impact resistance after molding.
Specifically, the polycarbonate resin composition preferably has a bending modulus of elasticity of 55000 kgf / cm 2 or more, preferably 56000 kgf / cm 2 to 150,000 kgf / cm 2 , more preferably 58000 kgf / cm 2 To 120000 kgf / cm < 2 >.
The polycarbonate resin composition was prepared by molding a 5 cm x 5 cm x 1 mm specimen, aging it at room temperature for 6 hours, measuring impact resistance of 70 cm or more, preferably 72 cm or more, as measured using a Dupont drop test, To 120 cm, and more preferably from 75 cm to 120 cm.
Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
Example
Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.
(A) Base resin
(a1) Polycarbonate resin: PANLITE L1225WX manufactured by TEIJIN CHEMICALS, which is a bisphenol A type linear polycarbonate, was used.
(a2) Amorphous polyester resin: TX-1000 manufactured by Eastman Chemical Co., Ltd. was used.
(a3) Glass fiber: An epoxy coated glass fiber having a length of 3 mm and a rectangular cross section (28 탆 x 7 탆) was used.
(B) Reactive silane compound: KBM-303 from ShinEtsu was used.
Example 1 to 2 and Comparative Example 1-5
The components were blended in the amounts shown in Table 1 below, blended and dry blended, and then processed using a twin screw extruder having a diameter of 45 mm at a nozzle temperature of 280 캜 to produce pellets. At this time, the components other than the glass fiber were fed into the main feeder and the glass fibers were fed into the side feeder. The prepared pellets were dried at 100 ° C. for 3 hours or more, and then molded in a 10 oz injection machine at a molding temperature of 320 ° C. and a mold temperature of 80 ° C. to prepare test pieces.
The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.
How to measure property
(1) Impact resistance (cm): A flat specimen having a thickness of 1 mm, a width of 5 cm and a length of 5 cm was injected and aged at room temperature for 6 hours or more, and then 20 or more specimens were impacted using a descent- The height at which 50% of the specimen was destroyed was measured in terms of cm.
(2) Flexural modulus (kgf / cm 2 ): A specimen of 1/4 "thickness was prepared according to ASTM D790 using a 10 oz injection machine. The elongation was measured with a modulus of elasticity of 1% Respectively.
(weight%)
(Parts by weight *)
(kgf / cm 2 )
* Parts by weight: (A) parts by weight based on 100 parts by weight of the base resin
As shown in Table 1, in the case of Examples 1 and 2 according to the present invention, Comparative Examples 1 and 2 which contained the same amount of glass fibers and did not use amorphous polyester resin, and the reactive silane It is understood that both the impact resistance and the flexural modulus are superior to those of Comparative Examples 3 and 4 which are not used. Also, in Comparative Example 5 using only the amorphous polyester resin and the reactive silane, the impact resistance and the flexural modulus were lower than those of Example 2 including the same amount of glass fiber.
Claims (10)
And 0.1 to 1.5 parts by weight of a reactive silane compound.
In the base resin,
35 to 75% by weight of polycarbonate;
5 to 20% by weight of an amorphous polyester resin; And
Wherein the glass fiber reinforced polycarbonate resin composition contains 20 to 50% by weight of glass fibers.
Wherein the amorphous polyester resin comprises a dicarboxylic acid component and a diol component, and the content of cyclohexane dimethanol (CHDM) in the total diol component is 10 to 50 mol%.
Wherein the amorphous polyester resin comprises a dicarboxylic acid component and a diol component, and the content of ethylene glycol in the total diol component is 50 to 90 mol%.
Wherein the glass fiber has a length of 2 to 5 mm.
Wherein the reactive silane compound comprises at least one reactive functional group selected from the group consisting of an epoxy group, an amino group, an acryl group, an isocyanate group and a mercapto group.
Wherein the polycarbonate resin composition further comprises an additive selected from the group consisting of an ultraviolet absorber, an inorganic additive, a flame retardant, a lubricant, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, a dye and a mixture thereof.
Wherein the polycarbonate resin composition has a bending modulus of elasticity of 55000 kgf / cm 2 or more as measured according to ASTM D790 standard after specimen molding.
Wherein the polycarbonate resin composition has an impact resistance of 70 cm or more as measured using a Dupont drop test in which a specimen of 5 cm x 5 cm x 1 mm is molded and aged at room temperature for 6 hours and impacted on a specimen with a weight of 500 g.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150138244A KR101914822B1 (en) | 2015-09-30 | 2015-09-30 | Fiberglass reinforced polycarbonated resin composition and article using the same |
| PCT/KR2016/010871 WO2017057903A1 (en) | 2015-09-30 | 2016-09-29 | Glass fiber-reinforced polycarbonate resin composition and molded article using same |
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| KR1020150138244A KR101914822B1 (en) | 2015-09-30 | 2015-09-30 | Fiberglass reinforced polycarbonated resin composition and article using the same |
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|---|---|---|---|---|
| WO2020111627A1 (en) | 2018-11-30 | 2020-06-04 | 주식회사 포스코 | Forming method for structure for reinforcement and structure for reinforcement |
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| CN112352016B (en) * | 2018-07-11 | 2022-12-16 | 三菱工程塑料株式会社 | Thermoplastic resin composition and method for producing molded article |
| KR102291177B1 (en) * | 2018-10-31 | 2021-08-18 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| KR102393506B1 (en) * | 2019-09-30 | 2022-05-02 | 롯데케미칼 주식회사 | Thermoplastic resin composition and article produced therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4384067A (en) * | 1981-11-19 | 1983-05-17 | Mobay Chemical Corporation | Mineral-filled polycarbonate compositions of improved impact strength |
| JPH0453867A (en) * | 1990-06-21 | 1992-02-21 | Mitsubishi Gas Chem Co Inc | Smooth-surface fiber-reinforced resin composition |
| KR101139137B1 (en) * | 2004-12-14 | 2012-04-30 | 에스케이케미칼주식회사 | Blend of polyester and polycarbonate with good color |
| KR101709375B1 (en) * | 2013-06-25 | 2017-02-22 | 롯데첨단소재(주) | Silane based compound, method for preparing the same and polycarbonate resin composition comprising the same |
| CN104672777A (en) * | 2015-03-24 | 2015-06-03 | 苏州新区华士达工程塑胶有限公司 | High-strength and low-wear polyformaldehyde modified plastic |
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| WO2020111627A1 (en) | 2018-11-30 | 2020-06-04 | 주식회사 포스코 | Forming method for structure for reinforcement and structure for reinforcement |
| KR20200066050A (en) | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Forming method for structure for reinforcement and structure for reinforcement |
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| KR20170038603A (en) | 2017-04-07 |
| WO2017057903A1 (en) | 2017-04-06 |
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