WO2019098602A1 - Resin blend composition and resin molded article comprising same - Google Patents

Resin blend composition and resin molded article comprising same Download PDF

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Publication number
WO2019098602A1
WO2019098602A1 PCT/KR2018/013549 KR2018013549W WO2019098602A1 WO 2019098602 A1 WO2019098602 A1 WO 2019098602A1 KR 2018013549 W KR2018013549 W KR 2018013549W WO 2019098602 A1 WO2019098602 A1 WO 2019098602A1
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Prior art keywords
resin
weight
polyamide
blend composition
polyester resin
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PCT/KR2018/013549
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French (fr)
Korean (ko)
Inventor
백지원
김도균
김태영
황신영
Original Assignee
에스케이케미칼주식회사
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Publication of WO2019098602A1 publication Critical patent/WO2019098602A1/en

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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a resin blend composition
  • a resin blend composition comprising a polyamide resin and a polyester resin, and a resin molded article containing the same.
  • Polyamide resins exhibit excellent properties in terms of mechanical strength, heat resistance, abrasion resistance, and chemical resistance and are known as materials applicable to various industrial fields.
  • the polyamide resin exhibits a high moisture absorption rate and thus has a problem of poor long-term dimensional stability.
  • the polyamide resin has low compatibility with other polymer resins, may cause defects in the extrusion process, and there is a high possibility that the physical properties of the produced molded article do not reach a predetermined level.
  • the present invention is directed to a resin blend composition comprising a polyamide resin and a polyester resin and having improved compatibility.
  • the present invention also provides a resin molded article comprising the resin blend composition and having excellent mechanical properties and dimensional stability. 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • a resin mixture including a polyamide resin, a polyester resin, and a glass fiber
  • a compatibilizer having an epoxy equivalent equivalent of 100 to 1500 equivalents having an epoxy equivalent equivalent of 100 to 1500 equivalents
  • the compatibilizer is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture.
  • a resin molded article comprising the resin blend composition.
  • the resin blend composition and the resin molded article including the resin blend composition according to embodiments of the present invention will be described in detail.
  • Means one containing 1 as used herein is a specific characteristic, region, integers, steps, operations, elements, and / or and refine the components, other specific characteristics, regions, integers, steps, operations, elements, components and / or the group And the like.
  • a resin mixture including a polyamide resin, a polyester resin, and a glass fiber
  • the compatibilizer is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture.
  • the resin blend composition comprises a polyamide resin, a polyester resin, a glass fiber, and a compatibilizer.
  • polyamide resin a polyamide resin well-known in the art to which the present invention belongs may be applied without particular limitation.
  • the polyamide resin is £ - is the number of days the polymer that can be obtained as a ring-opening polymerization product of lactam, such as caprolactam dodeca-caprolactam and 00.
  • the polyamide resin may be a polymer obtainable from an amino acid such as aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
  • the polyamide resin may be an aliphatic, alicyclic or aromatic diamine; And a polymer obtained by the reaction of an aliphatic, alicyclic or aromatic dicarboxylic acid.
  • the diamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • dicarboxylic acid examples include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, .
  • the polyamide resin may be a copolymer of the polymers exemplified above.
  • the polyamide resin is selected from the group consisting of polyamide-6, polyamide-66, polyamide-610, polyamide-11, polyamide- And polyaramid. ≪ / RTI > Some of the above-exemplified polyamide resins may include the following repeating units.
  • the polyamide resin may be a branched or hyperbranched star (large, 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • a macromolecular chain a linear macromolecular chain.
  • the star or Polymers containing macromolecular chains can be prepared, for example, 5959069, 0682057 and Table 1 # 0832149.
  • the polyamide resin may be a random tree (a rhomboidal polymer, preferably a copolyamide having a random tree structure.
  • the copolyamides of the randon tree structure and the preparation method thereof are described in document JP-A-09903909.
  • the relative viscosity of the polyamide resin (25, 100 1111 , 90% formic acid Based on the polymer solution) may vary from 2.0 to 3.7.
  • the number-average molecular weight of the polyamide resin may vary from 5000 to 70,000 / 1 !.
  • the content of the polyamide resin is selected from the group consisting of a polyamide resin, a polyester resin, Or 30 to 75 wt.%, Alternatively 35 to 70 wt.%, Alternatively 35 to 60 wt.%, Based on the total weight of the composition.
  • the polyester resin comprises ) And a repeating unit derived from the copolymerization of a diol compound including 1,4-cyclohexanedicarboxylic acid dimethanol (1,4 - 0 ) in the range of 01 ⁇ 6 ⁇ £ 111 ⁇ 2 ( 1 ⁇ 3 ⁇ 41101 ) Lt; / RTI >
  • the polyesther resin is prepared by polycondensation of 100 mol% of terephthalic acid as a dicarboxylic acid component and 100 mol% of 1,4-cyclohexanedicarboxylic acid dimethanol as a diol component. Resin.
  • the above-mentioned polyester resin can be produced by reacting 1,4-cyclohexanedimethanol with diol 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • the resulting repeating unit is contained in an amount of 1 mol% or less.
  • the polyester resin may be a copolycycloucleus silylene dimethylene terephthalate resin containing, in addition to terephthalic acid, a repeating unit derived from a dicarboxylic acid in an amount of 20 mol% or less.
  • the polycycloheuclear silylene dimethylene terephthalate resin has a crystallization rate remarkably faster than a polyethylene terephthalate label used in general use in a pulley ester resin, has a high heat resistance while being capable of injection molding, and has a relatively high price competitiveness. It is a very high resin.
  • the polycyclohexanediyldimethylene terephthalate resin is one of the resins having the highest melting point in polyester resins, has a low water absorption rate, and has excellent heat discoloration resistance.
  • the polycyclohexanediyldimethylene terephthalate resin is remarkably low in the amount of volatile components generated by pyrolysis or hydrolysis even when exposed to a high temperature environment for a long time under high stability.
  • the resin blend composition according to the present invention containing the polycyclohexane silylene dimethylene terephthalate resin in a certain amount can have a high heat resistance and can be prevented from deforming under long-term use under high temperature and high humidity conditions.
  • the polyester resin can exhibit improved properties in terms of mechanical properties, heat resistance, crystallization temperature, and shape stability by controlling the kind and content of the dicarboxylic acid compound.
  • the total dicarboxylic acid derived 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • terephthalic acid-derived repeating units May contain 80 mol% or more, or 90 mol% or more, or 95 mol% or more, or 97 mol% or more, or 99 mol% or more of terephthalic acid-derived repeating units based on 100 mol% of the repeating units, and the remainder is terephthalic acid And may contain repeating units derived from other dicarboxylic acids or esters thereof.
  • the dicarboxylic acid other than terephthalic acid is a dicarboxylic acid having a carbon number of 8 -
  • the ester compound of the dicarboxylic acid may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms or an ester of an aliphatic dicarboxylic acid having 4 to 20 carbon atoms,
  • the polyester resin may contain a repeating unit represented by the following formula (1) as a repeating unit derived from a dicarboxylic acid. Ahjung than 80 mol%, or 90 mol% or more, or at least 95 mol%, or 97 mol% or more, or 99 mol% or more has the repeating units derived from terephthalic acid, i.e., to show in Formula 1: 1 1,4 - phenylene group.
  • the repeating unit derived from the dicarboxylic acid may contain 80 to 100 mol% of terephthalic acid-derived repeating units and 0 to 20 mol% of repeating units derived from isophthalic acid or an ester compound. or 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • terephthalic acid-derived repeating units From 90 to 100 mol% of terephthalic acid-derived repeating units and from 0 to 10 mol% of repeating units derived from isophthalic acid or an ester compound thereof. Or terephthalic acid-derived repeating units in an amount of 90 to 99 mol% and 1 to 10 mol% of repeating units derived from isophthalic acid or an ester compound thereof.
  • a repeating unit derived from a terephthalic acid may be used as a main component of a repeating unit derived from a dicarboxylic acid, and a repeating unit derived from a small amount of another dicarboxylic acid or an ester thereof may be included, if necessary, .
  • the polyester resin includes repeating units derived from di-methanol derived from 1,4-cyclohexanedic acid as repeating units derived from diol.
  • the polyester resin may include repeating units derived from trans 1,4-cyclohexane dimethanol, cis 1,4-cyclohexanedimethanol, or a mixture thereof.
  • the content of trans 1,4-cyclohexanedimethanol is 60 mol% or more, preferably 60 to 90 mol%, based on 100 mol% of total 1,4-cyclohexanedimethanol combined with trans and cis , Or 65 to 90 mol%, or 70 to 80 mol%.
  • the heat resistance and the crystallization temperature of the polyester resin containing them as a repeating unit and the resin composition containing the same can be improved at the same time.
  • the moisture absorption rate can be lowered to enhance the morphological stability.
  • the polyester resin containing it can exhibit improved heat resistance, shape stability and high crystallization temperature. 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • the polyester resin By controlling the kind and content of the diol compound, the polyester resin can exhibit improved properties in terms of heat resistance and mechanical properties.
  • polyester resin 90 mol% or more, or 95 mol% or more, or 97 mol% or more of repeating units derived from 1,4-cyclohexanedic acid dimethanol are contained in 100 mol% Or 99 mol% or more, and the remainder may include repeating units derived from diol-based compounds other than 1,4-cyclohexanedimethanol.
  • 1,4-cyclohexanedic acid dimethanol in addition to the 1,4-cyclohexanedic acid dimethanol, other repeating units derived from diol compounds such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, neopentyl glycol, Or more.
  • diol compounds such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, neopentyl glycol, Or more.
  • ethylene glycol-derived repeating units may be included to improve the impact resistance of the polyester resin.
  • polyester resin comprises 5 repeating unit represented by formula (2)
  • Y 1 is a substituted or unsubstituted, linear, branched or cyclic alkylene group having 1 to 6 carbon atoms
  • 5 is a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms
  • 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • the content of the polyester resin is 1 to 40% by weight, or 5 to 40% by weight, or 6 to 40% by weight, based on the total weight of the resin mixture including the polyamide resin, 30% by weight.
  • the ratio 2/1 of the weight (2) of the polyester resin to the weight ( ⁇ ) of the polyamide resin may be 0.01 to 0.8, or 0.05 to 0.75, or 0.1 to 0.7.
  • the polyamide resin The ratio (2 / ⁇ 1) of the weight ( ⁇ 2) of the polyester resin to the polyester resin is preferably 0.01 or more.
  • the ratio ( ⁇ ⁇ 2 / '1 ⁇ ) by weight ( ⁇ ⁇ 2) in the polyester resin relative to the weight ( ⁇ ⁇ 1) of the polyamide resin is preferably not more than 0.08.
  • glass fiber glass fiber well-known in the technical field of the present invention can be applied without particular limitation.
  • the glass fiber enhances the crystallization temperature of the resin blend composition to facilitate injection molding.
  • the glass fibers improve the heat resistance of the resin blend composition and are effective in suppressing the deformation of the shape.
  • the glass fiber may be contained in an amount of 15 to 40% by weight based on the total weight of the resin mixture including the polyamide resin, the polyester resin and the glass fiber.
  • the polyamide resin is low in compatibility with polyester resin, it is difficult to exhibit desired physical properties with a simple blend of the polyamide and polyester resins.
  • the resin blend composition according to embodiments of the invention comprises a compatibilizer having a predetermined epoxy equivalent.
  • the compatibilizing agent may be an oligomer having two or more glycidyl methacrylates.
  • the compatibilizing agent may be one or more compounds selected from the group consisting of styrene-glycidyl methacrylate oligomers and ethylene-glycidyl methacrylate oligomers.
  • a compound having an epoxy equivalent number of from 100 to 1500 equivalents may be preferably used.
  • the compatibilizing agent is commercially available show pyosa>: one set, ⁇ ® Show 0 mu -43685 (epoxy equivalent: 300 / eq.), (Diglycidyl ether of bisphenol-A) type epoxy resin (epoxy equivalent: 1,400
  • the epoxy equivalent weight of the compatibilizing agent can be measured by various known methods. In particular, examples include the standard 115 X 7236-1986, the show 01652-73 and the 3 ⁇ 40 3001- 1978, etc. In the case of the distribution of the epoxy equivalents for the compatibilizing agent, the average value thereof can be considered.
  • the compatibilizer may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture. Specifically, the compatibilizing agent may be included in an amount of 0.1 to 10 parts by weight, or 0.5 to 10 parts by weight, or 1 to 10 parts by weight.
  • the compatibility of the polyamide resin and the polyester resin is insufficient, and as a result, the processability is deteriorated and the properties such as rigidity and strength may be poor.
  • the content of the compatibilizing agent is too large, the viscosity of the resin blend composition is increased to deteriorate the fluidity, and as a result, the processability may deteriorate.
  • the resin blend composition may further comprise one or more additives.
  • the kind of the additive may be selected in consideration of the properties to be imparted to the resin blend composition.
  • the resin blend composition may further comprise one or more compounds selected from the group consisting of anti-dripping agents, flame retardants, antioxidants, pigments, dyes, and nucleating agents.
  • the content of the additive may be adjusted within a range that does not impair the physical properties of the resin blend composition.
  • the additive may be included in an amount of 0.01 to 5 parts by weight, or 0.01 to 2 parts by weight, or 0.01 to 1 part by weight, or 0.01 to 0.5 parts by weight, based on 100 parts by weight of the resin mixture.
  • the dye may be a compound such as anthraquinone (anthraquinone), perinone (perinone), messin (me ⁇ l ine) used.
  • the antioxidant suppresses the yellowing of the polymer resin, 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • compositions and the molded article are improved, and oxidation or pyrolysis can be suppressed.
  • antioxidants examples include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based light stabilizers.
  • phenol-based antioxidants examples include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based light stabilizers.
  • a complex antioxidant comprising a monomer having both a phenol-based antioxidant and a phosphorus-based antioxidant in one molecule may be used.
  • the antioxidant a phenol-based antioxidant and a phosphorus-based antioxidant may be mixed and used to prevent coloring of the molded article due to heat or oxidation and deterioration of physical properties without deteriorating the heat resistance.
  • the antioxidant may include a phenol-based antioxidant and a phosphorus-based antioxidant in a weight ratio of 2: 1 to 1: 2.
  • phosphorus antioxidant examples include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethylphosphonoacetate, bis (2, 6-dihydroxybutyl-4-methylphenyl) pentaerythritol- (2,6 - demon -
  • phosphorus antioxidants include 11 < nd > ® 168 from Basri.
  • the antioxidant may be included in an amount of 0.01 to 5 parts by weight, or 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight based on 100 parts by weight of the resin mixture.
  • the nucleating agent acts as a nucleus of crystallization during the molding of the resin blend composition to improve the crystallization speed and to improve the heat resistance and injection moldability of the resin blending composition.
  • the nucleating agent examples include a talc / organometallic salt mixture, a sorbitan type metal salt, a phosphate type metal salt, a quinacridone, a calcium carboxylate, a montanic metal salt, an amide type organic compound, boron nitride, .
  • boron nitride which is an inorganic nucleating agent, can be preferably used in consideration of the improvement effect of the use of a nucleating agent.
  • Commercially available inorganic nucleating agents may be used, such as IND-11 from Spear Advanced Materials.
  • the flame retardant may be a phosphorus flame retardant.
  • the phosphorus flame retardant is eco-friendly and has an advantage of substituting for a halogen-based flame retardant and excellent in compatibility with a polyamide resin and a polyester resin, and fluidity.
  • the phosphorus flame retardant may be, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), trisilyl phosphate bixylenyl phosphate, TXP, resorcinolbis (diphenyl phosphate), RDP, phenyl diresorcinolphosphate, bisphenol diphenyl phosphate (BDP) Cresyl diphenyl phosphate, xylenyl phosphate, diphenyl phosphate, phenyl di (isopropylphenyl) phosphate, triisophenyl phosphate, diphenyl phosphate, resorcinol diphosphate, and aromatic And aromatic polyphosphate may be used.
  • TPP triphenyl phosphate
  • TCP tricresyl phosphate
  • TXP trisilyl phosphate bixylenyl phosphate
  • phosphorus flame retardants include OP-1230 and OP-1240 from Clariant. OP-1230 or OP-1240 may be used alone, or a mixture thereof may be used for compatibility of the polyamide resin and the polyester resin.
  • the drip inhibitor include silica, asbestos, and fibrillating-type fluoropolymers.
  • fluoropolymer examples include poly (tetrafluoroethylene), tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, poly (vinylidene fluoride), poly (chlorotrifluoro Ethylene), and the like.
  • the resin blend composition may be prepared by a simple mixing of the above-mentioned components.
  • the resin blend composition may be in a melt-mixed state under pressure at a predetermined temperature of the mixture of the above-described components.
  • the resin blend composition can have a heat distortion temperature (heat deflection temperature, HDT) of 250 to 280 ° C, or 250 to 270 ° C, or 255 to 270 ° C measured at 1.8 MPa.
  • the resin blend composition may also have a melting point of 230 to 270 ° C, 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • the resin blend composition preferably has a melt flow rate of 0.6 011 / ⁇ or more calculated from the viscosity measured at 35 after dissolving in the solvent 0 -chlorophenol (00) It is preferred that the polymer has an intrinsic viscosity of less than 0.9 31 / ⁇ .
  • Resin molded article comprising the resin blend composition.
  • the resin molded article can be obtained by molding the resin blend composition in various ways according to the form and use thereof.
  • the resin blend composition can be made into the resin molded article through a molding process such as injection, extrusion, extrusion blow, injection blow, and profile extrusion.
  • the shape and size of the resin molded article are not particularly limited.
  • the resin molded article may be a film, a sheet, a container, a pellet, or the like.
  • the resin molded product is capable of acting on automobile parts, particularly parts for automobile engine peripheral parts, which are required to have excellent dimensional stability when used for a long time under high temperature and high humidity conditions.
  • the resin molded article may be used in various applications such as precision machine parts, automotive exterior parts, electrical and electronic parts including connectors, construction materials, fibers, and sports equipment.
  • the resin blend composition according to the present invention has improved compatibility and is excellent It is possible to provide a resin molded article having mechanical properties and dimensional stability.
  • polyester resin examples include terephthalic acid, isophthalic acid, 1,4-cyclohexanecarboxylic acid dimethanol (1,4-CHDM, trans content of 70-80 mol%), and polyester condensed with ethylene glycol (SKYPURA TM 0302HQ SK Chemicals).
  • the polyester resin was used after drying at 100 ° C for 6 hours.
  • (JONCRYL® ADR-4368S epoxy equivalent weight: 300 g / eq., BASF
  • BASF high molecular weight chain extender
  • DGEBA diglycidyl ether of bisphenol A
  • compatibilizer (C) an epoxy resin (epoxy equivalence: 2,000 g / equivalent, Kykdo Chemical) of DGEBA (diglycidyl ether of bisphenol A) was prepared.
  • Antioxidants include phenolic antioxidants (AO-60 TM, ADEKA) and phosphorous 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • Biaxial extruder (min 40 100 parts by weight of a resin mixture consisting of 39% by weight of a polyamide resin, 26% by weight of a polyester resin and 35% by weight of a glass fiber was mixed with a compatibilizing agent (1 part by weight, 0.2 part by weight of the oxidizing stabilizer and 0.2 part by weight of the phosphorus-containing oxidizing stabilizer were mixed to prepare a resin blend composition, and then 295 , The pellets were prepared by uniformly performing the kneading extrusion. The prepared pellets were dried at 100 for 6 hours.
  • a compatibilizing agent (1 part by weight, 0.2 part by weight of the oxidizing stabilizer and 0.2 part by weight of the phosphorus-containing oxidizing stabilizer were mixed to prepare a resin blend composition, and then 295 .
  • the pellets were prepared by uniformly performing the kneading extrusion. The prepared pellets were dried at 100 for 6 hours.
  • a resin blend composition and a pellet containing the resin blend composition were prepared in the same manner as in Example 1, except that 1 part by weight of a compatibilizing agent (1 part by weight) was used per 100 parts by weight of the resin mixture.
  • Example 6
  • a resin blend composition and pellets containing the same were prepared in the same manner as in Example 1 except that 100 parts by weight of a resin mixture consisting of 65% by weight of a polyamide resin and 35% by weight of a glass fiber was used instead of the resin mixture. Comparative Example 2
  • Example 2 Was prepared in the same manner as in Example 1, except that 13 parts by weight of a compatibilizing agent ((b)) was used with respect to 100 parts by weight of a resin mixture consisting of 52% by weight of a polyamide resin, 13% by weight of a polyester resin and 35% A resin blend composition and pellets containing the same were prepared.
  • the components, content, and intrinsic viscosity of the resin blend compositions according to the above Examples and Comparative Examples are shown in Table 1 below.
  • the intrinsic viscosity is a value calculated from the viscosity of the resin blend composition measured in 35 directions after dissolving the resin blend composition in the solvent 0 -chlorophenol (00).
  • the pellets prepared in the above Examples and Comparative Examples were injected at the injection temperature of 295 using an injection machine to prepare test pieces.
  • the properties of the prepared test pieces were measured in the following manner under the conditions of 23 ⁇ 2 C and 50 ⁇ 5% relative humidity, and the results are shown in Table 2 below.
  • a specimen was prepared in accordance with ASTM D 638 and tensile strength was measured using a universal testing machine (Zwick Roell Z010).
  • a specimen was prepared in accordance with ASTM D 648 and heat distortion temperature under 1.8 MPa was measured using a heat deflection temperature (HDT) tester (Toyoseiki).
  • HDT heat deflection temperature
  • the thermal history of the resin blend composition was removed by heating at 320 ° C at 20 ° C / min from room temperature using a differential scanning calorimeter (DSC). After cooling, at room temperature to 320 ° C at 10 C / min 2019/098602 1 (: 1 ⁇ ⁇ 2018/013549
  • the size of the flat plate specimens was measured before and after storage at high temperature and high humidity. Specifically, the injection direction ( ⁇ 11) of a flat specimen of 100 _ X 100 111111 standard and the injection flow
  • Example 1 the dimensional change rate was measured to be not more than 0.5% MD and not more than 10 0.9% under high temperature and high humidity conditions, and thus showed excellent dimensional stability.
  • Comparative Example 1 containing only polyamide resin, the dimensional change rate was measured to be 1.1% and 10 1.6%, indicating poor dimensional stability. It is considered that this is due to the high moisture absorption rate of the polyamide resin.
  • Comparative Example 2 in which the polyamide resin and the polyester resin were applied in the same amount (32.5 wt% each), considerable swelling occurred at the exit of the extruder, so that no pellets could be obtained, and thus the physical properties and the rate of dimensional change could not be measured.
  • Comparative Example 3 which did not use a compatibilizing agent,

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Abstract

The present invention relates to a resin blend composition comprising a polyamide resin and a polyester resin. The resin blend composition according to the present invention has improved compatibility and thus makes it possible to provide a resin molded article having excellent mechanical properties and dimensional stability.

Description

2019/098602 1»（：1^1{2018/013549  2019/098602 1 (: 1 ^ {2018/013549
【발명의 설명】 DESCRIPTION OF THE INVENTION
【발명의 명칭】  Title of the Invention
수지블렌드조성물및 이를포함하는수지 성형품 【기술분야】  Resin blend composition and resin molded article containing the same
본 발명은 폴리아미드 수지 및 폴리에스터 수지를 포함한 수지 블렌드조성물및 이를포함하는수지 성형품에 관한것이다.  The present invention relates to a resin blend composition comprising a polyamide resin and a polyester resin, and a resin molded article containing the same.
【발명의 배경이 되는기술】 TECHNICAL BACKGROUND OF THE INVENTION
폴리아미드 수지는 기계적 강도, 내열성,내마모성, 내약품성 등에서 우수한 특성을 나타내어, 다양한 산업 분야에 적용 가능한 소재로 알려져 있다.  Polyamide resins exhibit excellent properties in terms of mechanical strength, heat resistance, abrasion resistance, and chemical resistance and are known as materials applicable to various industrial fields.
다만, 폴리아미드 수지는 높은 흡습율을 나타내어 장기적인 치수 안정성이 불량한문제가있다.  However, the polyamide resin exhibits a high moisture absorption rate and thus has a problem of poor long-term dimensional stability.
상기 문제점을 해결하기 위한 연구가 꾸준히 진행되어 왔다. 일 예로, 고습도 하에서 물성 변화가 거의 없는 특성을 갖는 고분자 수지와 폴리아미드수지를블렌딩하는여러 시도가있었다.  Studies for solving the above problems have been steadily progressed. For example, there have been various attempts to blend a polyamide resin with a polymer resin having properties that hardly change physical properties under high humidity.
그러나, 폴리아미드 수지는 다른 고분자 수지와의 상용성이 낮아, 압출공정의 불량을야기할수있고,생산된성형품의 물성이 소정의 수준에 미치지 못할가능성이 높다.  However, the polyamide resin has low compatibility with other polymer resins, may cause defects in the extrusion process, and there is a high possibility that the physical properties of the produced molded article do not reach a predetermined level.
그에 따라, 치수 안정성이 우수한 성형품을 제조할 수 있는 폴리아미드수지의 물성 개선이 여전히 요구되는실정아다.  Accordingly, it is still required to improve the physical properties of a polyamide resin capable of producing a molded article having excellent dimensional stability.
【발명의 내용】 DISCLOSURE OF THE INVENTION
【해결하고자하는과제】  [Problem to be solved]
본 발명은 폴리아미드 수지 및 폴리에스터 수지를 포함하고 향상된 상용성을갖는수지 블렌드조성물을제공하기 위한것이다.  The present invention is directed to a resin blend composition comprising a polyamide resin and a polyester resin and having improved compatibility.
그리고, 본 발명은 상기 수지 블렌드 조성물을 포함하고 우수한 기계적 물성과치수안정성을갖는수지 성형품을제공하기 위한것이다. 2019/098602 1»（：1^1{2018/013549 The present invention also provides a resin molded article comprising the resin blend composition and having excellent mechanical properties and dimensional stability. 2019/098602 1 (: 1 ^ {2018/013549
【과제의 해결수단】 MEANS FOR SOLVING THE PROBLEMS
본발명에 따르면,  According to the present invention,
폴리아미드 수지, 폴리에스터 수지 및 유리 섬유를 포함한 수지 혼합물;및  A resin mixture including a polyamide resin, a polyester resin, and a glass fiber; and
100 당량 내지 1500 당량의 에폭시 당량여표\\0을 가지는 상용화제;  A compatibilizer having an epoxy equivalent equivalent of 100 to 1500 equivalents;
를포함하고,  Lt; / RTI >
상기 상용화제는상기 수지 혼합물 100중량부에 대하여 0.1내지 10 중량부로포함되는,수지 블렌드조성물이 제공된다. 또한, 본 발명에 따르면, 상기 수지 블렌드조성물을 포함하는수지 성형품이 제공된다. 이하, 발명의 구현 예들에 따른 수지 블렌드 조성물 및 이를 포함하는수지 성형품에 대해상세히 설명하기로한다.  Wherein the compatibilizer is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture. Further, according to the present invention, there is provided a resin molded article comprising the resin blend composition. Hereinafter, the resin blend composition and the resin molded article including the resin blend composition according to embodiments of the present invention will be described in detail.
그에 앞서,본명세서에서 명시적인언급이 없는한,전문용어는단지 특정 실시예를 언급하기 위한 것이며, 본 발명을 한정하는 것을 의도하지 않는다.  Prior to that, unless explicitly stated to the contrary, the terminology is used merely to refer to a specific embodiment and is not intended to limit the invention.
본명세서에서 사용되는단수형태들은문구들이 이와명백히 반대의 의미를나타내지 않는한복수형태들도포함한다.  The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it.
본명세서에서사용되는 1포함1의 의미는특정 특성,영역,정수,단계, 동작, 요소 및/또는 성분을 구체화하며, 다른 특정 특성, 영역, 정수, 단계, 동작,요소,성분및/또는군의 존재나부가를제외시키는것은아니다. 본발명자들의 계속적인 연구 .결과,흡습조건 하에서 물성 및 치수 변화가 거의 없는 열가소성 폴리에스터 수지를 폴리아미드 수지와 블렌딩함으로써, 우수한 기계적 물성과 치수 안정성을 갖는 수지 성형품을 제공할수있음이 확인되었다. Means one containing 1 as used herein is a specific characteristic, region, integers, steps, operations, elements, and / or and refine the components, other specific characteristics, regions, integers, steps, operations, elements, components and / or the group And the like. As a result, it has been confirmed that a thermoplastic polyester resin having little change in physical properties and dimensional changes under moisture absorption conditions can be blended with a polyamide resin to provide a molded resin article having excellent mechanical properties and dimensional stability.
특히, 소정의 에폭시 당량을 가지는 상용화제를 사용함으로써 상기 폴리아미드 수지와 상기 폴리에스터 수지의 안정적인 화학적 블렌딩이 2019/098602 1»（：1^1{2018/013549 In particular, by using a compatibilizer having a predetermined epoxy equivalent, stable chemical blending of the polyamide resin and the polyester resin 2019/098602 1 (: 1 ^ {2018/013549
가능함이 확인되었다. It is confirmed that it is possible.
이를 통해 물성 저하가 거의 없으면서도 고온 고습한 환경에서 우수한치수안정성（형태 안정성）을갖는수지 성형품이 제공될수있다. 1.수지 블렌드조성물 발명의 일구현 예에 따르면,  As a result, a resin molded article having excellent dimensional stability (shape stability) can be provided in a high-temperature and high-humidity environment with little physical property deterioration. 1. Resin Blend Composition According to one embodiment of the invention,
폴리아미드 수지 , 폴리에스터 수지 및 유리 섬유를 포함한 수지 혼합물;및  A resin mixture including a polyamide resin, a polyester resin, and a glass fiber; and
100 당량 내지 1500 당량의 에폭시
Figure imgf000004_0001
가지는 상용화제; 100 to 1500 equivalents of epoxy
Figure imgf000004_0001
A propellant;
를포함하고, Lt; / RTI >
상기 상용화제는상기 수지 혼합물 100중량부에 대하여 0.1내지 10 중량부로포함되는,수지 블렌드조성물이 제공된다. 상기 수지 블렌드조성물은폴리아미드수지,폴리에스터 수지,유리 섬유,및상용화제를포함한다.  Wherein the compatibilizer is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture. The resin blend composition comprises a polyamide resin, a polyester resin, a glass fiber, and a compatibilizer.
（ 폴리아미드수지 (Polyamide resin
상기 폴리아미드수지로는본발명이 속하는기술분야에서 잘알려진 폴리아미드수지가특별한제한없이 적용될수있다.  As the polyamide resin, a polyamide resin well-known in the art to which the present invention belongs may be applied without particular limitation.
예를들어,상기 폴리아미드수지는 £-카프로락탐 및 00 -도데카락탐과 같은락탐의 개환중합생성물로서 수득될수있는중합체일수있다. For example, the polyamide resin is £ - is the number of days the polymer that can be obtained as a ring-opening polymerization product of lactam, such as caprolactam dodeca-caprolactam and 00.
또한,상기 폴리아미드수지는아미노카프로산, 11 -아미노운데칸산및 12 -아미노도데칸산과 같은 아미노산으로부터 수득될 수 있는 중합체일 수 있다.  In addition, the polyamide resin may be a polymer obtainable from an amino acid such as aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
또한, 상기 폴리아미드 수지는 지방족, 지환족 또는 방향족 디아민; 및 지방족, 지환족 또는 방향족 디카르복실산의 반응에 의해 수득되는 중합체일 수 있다. 여기서, 상기 디아민으로는 에틸렌디아민, 테트라메틸렌디아민, 핵사메틸렌디아민, 운데카메틸렌디아민, 2019/098602 1»（：1^1{2018/013549 The polyamide resin may be an aliphatic, alicyclic or aromatic diamine; And a polymer obtained by the reaction of an aliphatic, alicyclic or aromatic dicarboxylic acid. Examples of the diamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, 2019/098602 1 (: 1 ^ {2018/013549
도데카메틸렌디아민, 2, 2, 4 -트리메틸핵사메틸렌디아민, 2,4,4- 트리메틸핵사메틸렌디아민, 5 -메틸노나핵사메틸렌디아민, ! 자일렌디아민, p 자일렌디아민, 1,3 -비스아미노메틸시클로핵산, 1,4 -비스아미노메틸시클로핵산, 1 -아미노- 3 -아미노메틸- 3, 5, 5 -트리메틸시클로핵산, 비스（4- 아미노시클로핵산）메탄, 비스（4 -메틸- 4 -아미노시클로핵실）메탄, 2,2 -비스（4- 아미노시클로핵실）프로판, 비스（아미노프로필）피페라진, 및 아미노에틸피페리딘 등을 예로 들 수 있다. 그리고, 상기 디카르복실산으로는 아디프산, 세바크산, 아젤라산, 도데칸디오산, 테레프탈산, 이소프탈산, 2 -클로로테레프탈산, 2 -메틸테레프탈산, 및 5- 메틸이소프탈산등을예로들수있다. Dodecamethylenediamine, 2, 2, 4-trimethylnucleosamethylenediamine, 2,4,4-trimethylnucleosamethylenediamine, 5-methylnonucleosamethamine diamine,! 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclo-nucleic acid, bis (4-methylimidazolylaminopyrimidine), p-xylylenediamine, 1,3-bisaminomethylcyclo nucleic acid, 4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, and aminoethylpiperidine And the like. Examples of the dicarboxylic acid include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, .
또한, 상기 폴리아미드 수지는 위에 예시된 중합체들의 공중합체일 수있다.  In addition, the polyamide resin may be a copolymer of the polymers exemplified above.
구체적으로, 상기 폴리아미드 수지는 폴리아미드- 6, 폴리아미드- 66, 폴리아미드- 610, 폴리아미드- 11, 폴리아미드- 12, 폴리테레프탈아미드
Figure imgf000005_0001
및 폴리아라미드로 이루어진군에서 선택된 1종이상의수지일수있다. 상기 예시된 폴리아미드 수지 중 일부는 아래와 같은 반복 단위를 포함할수있다. Specifically, the polyamide resin is selected from the group consisting of polyamide-6, polyamide-66, polyamide-610, polyamide-11, polyamide-
Figure imgf000005_0001
And polyaramid. ≪ / RTI > Some of the above-exemplified polyamide resins may include the following repeating units.
Figure imgf000005_0003
Figure imgf000005_0003
66의 반복단위에 테레프탈산으로부터 유래한아로마틱 링이 도입된 구조를 갖는개질된폴리아미드수지이다. And an aromatic ring derived from terephthalic acid is introduced into the repeating unit of formula (I).
Figure imgf000005_0002
상기 폴리아미드수지는분지형 또는과분지형 스타（ 크 ,또는 형 2019/098602 1»（：1^1{2018/013549
Figure imgf000005_0002
The polyamide resin may be a branched or hyperbranched star (large, 2019/098602 1 (: 1 ^ {2018/013549
거대분자 사슬, 선형 거대분자 사슬을 포함하는 중합체일 수 있다. 상기 스타 또는
Figure imgf000006_0002
거대분자 사슬을 포함하는 중합체는, 예를 들어 문헌
Figure imgf000006_0001
5959069,
Figure imgf000006_0003
0682057및표1ᅳ 0832149등에 기재되어 있다. A macromolecular chain, a linear macromolecular chain. The star or
Figure imgf000006_0002
Polymers containing macromolecular chains can be prepared, for example,
Figure imgf000006_0001
5959069,
Figure imgf000006_0003
0682057 and Table 1 # 0832149.
상기 폴리아미드 수지는 랜덤 트리（ 근句형의 중합체, 바람직하게는 랜덤 트리 구조를 갖는 코폴리아미드일 수 있다. 상기 랜던 트리 구조의 코폴리아미드및그제조방법은문헌 \ 099/ 03909에 기재되어 있다. 상기 폴리아미드 수지의 상대 점도（25 껀, 100 1111 의 90 % 포름산
Figure imgf000006_0004
중합체용액기준）는 2.0내지 3.7로가변적일수있다. The polyamide resin may be a random tree (a rhomboidal polymer, preferably a copolyamide having a random tree structure. The copolyamides of the randon tree structure and the preparation method thereof are described in document JP-A-09903909. The relative viscosity of the polyamide resin (25, 100 1111 , 90% formic acid
Figure imgf000006_0004
Based on the polymer solution) may vary from 2.0 to 3.7.
상기 폴리아미드수지의 수-평균분자량은 5000내지 70,000 / 1!\이로 가변적일수있다， 일 실시예에 따르면, 상기 폴리아미드 수지의 함량은, 폴리아미드 수지, 폴리에스터 수지 및 유리 섬유를 포함한 수지 혼합물의 총 중량을 기준으로 30 내지 80 중량%, 혹은 30 내지 75 중량%, 혹은 35 내지 70 중량%,혹은 35내지 60중량%일수있다.  The number-average molecular weight of the polyamide resin may vary from 5000 to 70,000 / 1 !. According to one embodiment, the content of the polyamide resin is selected from the group consisting of a polyamide resin, a polyester resin, Or 30 to 75 wt.%, Alternatively 35 to 70 wt.%, Alternatively 35 to 60 wt.%, Based on the total weight of the composition.
상기 폴리아미드 수지의 함량이 너무 적으면 수지 블렌드 조성물의 기계적 물성 또는성형성이 저하될수 있다. 다만,상기 폴리아미드수지의 함량이 너무많으면형태 변형 억제효과가미미할수있다. 比）폴리에스터 수지  If the content of the polyamide resin is too small, the mechanical properties or moldability of the resin blend composition may be deteriorated. However, if the content of the polyamide resin is too large, the shape deformation inhibiting effect may be insignificant. Ratio) Polyester resin
발명의 구현 예에 따르면, 상기 폴리에스터 수지는
Figure imgf000006_0005
）을 포함한 디카르복실산계 화합물 및 1,4- 사이클로핵산디메탄올（1,4 - 0｝년01^6\£11½（ 1^ ¾1101）을포함한디올계 화합물의 공중합으로부터 유래한반복단위를갖는중합체일수있다. According to an embodiment of the invention, the polyester resin comprises
Figure imgf000006_0005
) And a repeating unit derived from the copolymerization of a diol compound including 1,4-cyclohexanedicarboxylic acid dimethanol (1,4 - 0 ) in the range of 01 ^ 6 \ £ 11½ ( 1 ^ ¾1101 ) Lt; / RTI >
구체적으로, 상기 폴리에스타 수지는 디카르복실산 성분으로 테레프탈산 100몰%와,디올성분으로 1,4 -사이클로핵산디메탄올 100몰%의 중축합에 의해 제조관폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지일 수있다.  Specifically, the polyesther resin is prepared by polycondensation of 100 mol% of terephthalic acid as a dicarboxylic acid component and 100 mol% of 1,4-cyclohexanedicarboxylic acid dimethanol as a diol component. Resin.
상기 폴리에스터 수지는, 1,4 -사이클로핵산디메탄올 외에 다른 디올 2019/098602 1»（：1^1{2018/013549 The above-mentioned polyester resin can be produced by reacting 1,4-cyclohexanedimethanol with diol 2019/098602 1 (: 1 ^ {2018/013549
유래 반복단위가 1 몰% 이하의 함량으로 포함된, 코폴리사이클로핵실렌디메틸렌테레프탈레이트수지일수있다. And the resulting repeating unit is contained in an amount of 1 mol% or less.
상기 폴리에스터 수지는, 테레프탈산 외에 다른 디카르복실산 유래 반복단위가 20몰% 이하의 함량으로포함된,코폴리사이클로핵실렌디메틸렌 테레프탈레이트수지일수있다.  The polyester resin may be a copolycycloucleus silylene dimethylene terephthalate resin containing, in addition to terephthalic acid, a repeating unit derived from a dicarboxylic acid in an amount of 20 mol% or less.
상기 폴리에스터 수지는, 1,4 -사이클로핵산디메탄올 외에 다른 디올 유래 반복단위가 1 몰% 이하의 함량으로 포함되고, 테레프탈산 외에 다른 디카르복실산 유래 반복단위가 20 몰% 이하의 함량으로 포함된, 코폴리사이클로핵실렌디메틸렌테레프탈레이트수지일수있다. 상기 폴리사이클로핵실렌디메틸렌 테레프탈궤이트 수지는 풀리에스터계 수지 중에서 범용으로 사용되는 폴리에틸렌테레프탈레이트 표지보다 결정화 속도가 현저히 빠르고, 사출 성형이 가능하면서도높은내열성을가지며 상대적으로가격 경쟁력이 높아 활용가능성이 매우높은수지이다.  The above-mentioned polyester resin contains diol-derived repeating units other than 1,4-cyclohexanedic acid dimethanol in an amount of 1 mol% or less, and other than terephthalic acid, repeating units derived from dicarboxylic acid are contained in an amount of 20 mol% Lt; RTI ID = 0.0 > copoly-cyclohexanediyl < / RTI > dimethylene terephthalate resin. The polycycloheuclear silylene dimethylene terephthalate resin has a crystallization rate remarkably faster than a polyethylene terephthalate label used in general use in a pulley ester resin, has a high heat resistance while being capable of injection molding, and has a relatively high price competitiveness. It is a very high resin.
또한, 상기 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지는, 폴리에스터계수지 중에서 가장높은용융점을갖는수지 중하나이며,수분 흡수율이 낮고,열에 의한내변색성이 매우우수한특성을갖고있다.  The polycyclohexanediyldimethylene terephthalate resin is one of the resins having the highest melting point in polyester resins, has a low water absorption rate, and has excellent heat discoloration resistance.
또한, 상기 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지는, 높은 안정성으로 고온 환경에 장시간 노출되어도 열분해 또는 가수분해에 의해 생성되는휘발성 성분의 발생량이 현저히 낮다.  In addition, the polycyclohexanediyldimethylene terephthalate resin is remarkably low in the amount of volatile components generated by pyrolysis or hydrolysis even when exposed to a high temperature environment for a long time under high stability.
따라서, 상기 폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지를 일정 함량으로 포함하는 본 발명에 따른 수지 블렌드 조성물은 높은 내열성을가지면서,고온고습조건에서 장시간사용시 형태 변형이 억제될 수있다. 한편, 상기 폴리에스터 수지는 디카르복실산계 화합물의 종류 및 함량을 제어함으로써, 기계적 물성, 내열성, 결정화 온도, 및 형태 안정성 면에서 보다개선된특성을나타낼수있다.  Accordingly, the resin blend composition according to the present invention containing the polycyclohexane silylene dimethylene terephthalate resin in a certain amount can have a high heat resistance and can be prevented from deforming under long-term use under high temperature and high humidity conditions. On the other hand, the polyester resin can exhibit improved properties in terms of mechanical properties, heat resistance, crystallization temperature, and shape stability by controlling the kind and content of the dicarboxylic acid compound.
예를들어,상기 폴리에스터 수지에 있어서,전체 디카르복실산유래 2019/098602 1»（：1^1{2018/013549 For example, in the polyester resin, the total dicarboxylic acid derived 2019/098602 1 (: 1 ^ {2018/013549
반복단위 100 몰%에 대하여 테레프탈산 유래 반복단위를 80 몰% 이상, 또는 90몰% 이상,또는 95몰% 이상,또는 97몰% 이상,또는 99몰% 이상 포함할 수 있으며, 나머지는 테레프탈산이 아닌 다른 디카르복실산 또는 이의 에스테르로부터 유래된반복단위를포함할수있다. May contain 80 mol% or more, or 90 mol% or more, or 95 mol% or more, or 97 mol% or more, or 99 mol% or more of terephthalic acid-derived repeating units based on 100 mol% of the repeating units, and the remainder is terephthalic acid And may contain repeating units derived from other dicarboxylic acids or esters thereof.
구체적으로, 테레프탈산이 아닌 다른디카르복실산은, 탄소수 8내지 Specifically, the dicarboxylic acid other than terephthalic acid is a dicarboxylic acid having a carbon number of 8 -
20의 방향족디카르복실산,또는탄소수 4내지 20의 지방족디카르복실산일 Aromatic dicarboxylic acid having 20 to 20 carbon atoms or aliphatic dicarboxylic acid having 4 to 20 carbon atoms
301(1; lPA)r나프탈렌 2,6-
Figure imgf000008_0001
DA)등일수있다. 301 (1; lPA) r naphthalene 2,6-
Figure imgf000008_0001
DA).
상기 디카르복실산의 에스테르화합물은탄소수 8내지 20의 방향족 디카르복실산,또는탄소수 4내지 20의 지방족 디카르복실산의 에스테르일 수 있으며;보다구체적으로 디  The ester compound of the dicarboxylic acid may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms or an ester of an aliphatic dicarboxylic acid having 4 to 20 carbon atoms,
디메틸 이소프탈레이트
Figure imgf000008_0002
Dimethyl isophthalate
Figure imgf000008_0002
나프탈렌디카복실레이트 ( 111 1171 2,6-113{?111:1121161½<1止31¾0 }4 6; 2 6-NDC) 등일수있다. 상기 폴리에스터 수지는 디카르복실산 유래 반복단위로서 하기 화학식 1로표시되는반복단위를포함할수있다. 아중 80몰% 이상,또는 90몰% 이상,또는 95몰% 이상,또는 97몰% 이상,또는 99몰% 이상은 테레프탈산에서 유래한 반복단위, 즉 하기 화학식 1에서의 쇼：1이 1,4- 페닐렌기인반복단위일수있다. Naphthalene dicarboxylate (111 1171 2,6- 113 {? 111: 1121161? 1? 314}} 4 6; 2 6 -NDC). The polyester resin may contain a repeating unit represented by the following formula (1) as a repeating unit derived from a dicarboxylic acid. Ahjung than 80 mol%, or 90 mol% or more, or at least 95 mol%, or 97 mol% or more, or 99 mol% or more has the repeating units derived from terephthalic acid, i.e., to show in Formula 1: 1 1,4 - phenylene group.
[화학식 1]
Figure imgf000008_0003
[Chemical Formula 1]
Figure imgf000008_0003
상기 화학식 1에서,쇼 은 치환또는 비치환된 탄소수 6 내지 18의 아릴렌기이다. 일 실시예에 따르면,상기 디카르복실산유래 반복단위는 테레프탈산 유래 반복단위를 80 내지 100 몰%로, 이소프탈산 또는 그 에스테르계 화합물 유래 반복단위를 0 내지 20 몰%로 포함할 수 있다. 또는 2019/098602 1»（：1^1{2018/013549 In the above formula (1), Show is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms. According to one embodiment, the repeating unit derived from the dicarboxylic acid may contain 80 to 100 mol% of terephthalic acid-derived repeating units and 0 to 20 mol% of repeating units derived from isophthalic acid or an ester compound. or 2019/098602 1 (: 1 ^ {2018/013549
테레프탈산 유래 반복단위를 90 내지 100 몰%로, 이소프탈산 또는 그 에스테르계 화합물 유래 반복단위를 0 내지 10 몰%로 포함할 수 있다. 또는 테레프탈산 유래 반복단위를 90 내지 99몰%로, 이소프탈산또는 그 에스테르계화합물유래 반복단위를 1내지 10몰%로포함할수있다. From 90 to 100 mol% of terephthalic acid-derived repeating units and from 0 to 10 mol% of repeating units derived from isophthalic acid or an ester compound thereof. Or terephthalic acid-derived repeating units in an amount of 90 to 99 mol% and 1 to 10 mol% of repeating units derived from isophthalic acid or an ester compound thereof.
상기와같이 디카르복실산유래 반복단위의 주성분으로 테레프탈산 유래 반복단위를포함하되,수지의 물성 조절을위하여 필요에 따라소량의 다른디카르복실산또는이의 에스테르로부터 유래된 반복단위를포함할수 있다. 한편, 상기 폴리에스터 수지는 디올 유래 반복단위로 1,4- 사이클로핵산디메탄올유래 반복단위를포함한다.  As described above, a repeating unit derived from a terephthalic acid may be used as a main component of a repeating unit derived from a dicarboxylic acid, and a repeating unit derived from a small amount of another dicarboxylic acid or an ester thereof may be included, if necessary, . On the other hand, the polyester resin includes repeating units derived from di-methanol derived from 1,4-cyclohexanedic acid as repeating units derived from diol.
1.4 -사이클로핵산디메탄올은 트랜스（仕크매）와 시스（ ）의 두 가지 이성질체의 형태로 존재한다. 상기 폴리에스터 수지는 트랜스 1,4- 사이클로핵산디메탄올, 시스 1,4 -사이클로핵산디메탄올, 또는 이들의 혼합물로부터유래된반복단위를포함할수있다.  1.4-Cyclo-Nucleic Acid Dimethanol is present in the form of two isomers, trans (cis) and cis (). The polyester resin may include repeating units derived from trans 1,4-cyclohexane dimethanol, cis 1,4-cyclohexanedimethanol, or a mixture thereof.
상기 1,4 -사이클로핵산디메탄올의 트랜스/시스 비율은 이들을 반복단위로 포함하는 폴리에스터 수지의 결정 융점（1¾1） 및 결정화
Figure imgf000009_0001
영향을미칠수있다. The 1,4-trans / cis ratio of the nucleic acid dimethanol bicyclo poly crystal melting point of the polyester resin containing them as a repeating unit (1¾ 1) and crystallization
Figure imgf000009_0001
It can have an impact.
일 실시예에 따르면, 트랜스와 시스를 합한 전체 1,4- 사이클로핵산디메탄올 100 몰%에 대하여, 트랜스 1,4- 사이클로핵산디메탄올의 함량이 60몰% 이상이며,바람직하게는 60내지 90 몰%,또는 65내지 90몰%,또는 70내지 80몰%으로포함될수있다.  According to one embodiment, the content of trans 1,4-cyclohexanedimethanol is 60 mol% or more, preferably 60 to 90 mol%, based on 100 mol% of total 1,4-cyclohexanedimethanol combined with trans and cis , Or 65 to 90 mol%, or 70 to 80 mol%.
1.4 -사이클로핵산디메탄올의 트랜스/시스가 상기 범위로 포함될 때, 이들을 반복단위로 포함하는 폴리에스터 수지 및 이를 포함하는 수지 조성물의 내열성과 결정화온도를 동시에 향상시킬 수 있다. 동시에 수분 흡습율을 낮추어 형태 안정성을 높일 수 있다. 특히, 트랜스 1,4- 사이클로핵산디메탄올의 함량이 70 내지 80 몰%일 때, 이를 포함하는 폴리에스터 수지가보다향상된내열성,형태 안정성 및 높은결정화온도를 나타낼수있다. 2019/098602 1»(：1^1{2018/013549 When the trans / cis of 1.4-cyclohexanedimethanol is included in the above range, the heat resistance and the crystallization temperature of the polyester resin containing them as a repeating unit and the resin composition containing the same can be improved at the same time. At the same time, the moisture absorption rate can be lowered to enhance the morphological stability. Particularly, when the content of trans 1,4-cyclohexanedimethanol is 70 to 80 mol%, the polyester resin containing it can exhibit improved heat resistance, shape stability and high crystallization temperature. 2019/098602 1 (: 1 ^ {2018/013549
상기 폴리에스터 수지는 디올계 화합물의 종류 및 함량을 제어함으로써,내열성,기계적 물성 특성 면에서 보다개선된특성을나타낼 수있다. By controlling the kind and content of the diol compound, the polyester resin can exhibit improved properties in terms of heat resistance and mechanical properties.
예를들어,상기 폴리에스터 수지에 있어서,디올유래 반복단위 100 5 몰%에 대하여 1,4 -사이클로핵산디메탄올 유래 반복단위를 90 몰% 이상, 또는 95 몰% 이상, 또는 97몰% 이상, 또는 99 몰% 이상으로 포함할수 있으며, 나머지는 1,4 -사이클로핵산디메탄올이 아닌 다른 디올계 화합물로부터 유래된반복단위를포함할수있다.  For example, in the above polyester resin, 90 mol% or more, or 95 mol% or more, or 97 mol% or more of repeating units derived from 1,4-cyclohexanedic acid dimethanol are contained in 100 mol% Or 99 mol% or more, and the remainder may include repeating units derived from diol-based compounds other than 1,4-cyclohexanedimethanol.
구체적으로, 1,4 -사이클로핵산디메탄올외에 에틸렌 글리콜, 디에틸렌0 글리콜, 1,4 -부탄디올, 1,3 -프로판디올,또는네오펜틸글리콜등과같은기타의 디올계화합물유래 반복단위를 1종이상더 포함할수있다.  Specifically, in addition to the 1,4-cyclohexanedic acid dimethanol, other repeating units derived from diol compounds such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, neopentyl glycol, Or more.
바람직하게는, 폴리에스터 수지의 내충격성의 개선을 위해 에틸렌 글리콜유래 반복단위를포함할수있다.  Preferably, ethylene glycol-derived repeating units may be included to improve the impact resistance of the polyester resin.
구체적으로, 상기 폴리에스터 수지는 하기 화학식 2로 표시되는5 반복단위를 포함하되, 이 중 하기 화학식 2에서 묘1이 사이클로핵실렌디메틸렌이고, 11가 0인 반복단위를 디올 유래 반복단위 100 몰%에 대하여 90몰% 이상,또는 95몰% 이상,또는 97몰% 이상,또는 99 몰% 이상으로 포함하고, 이외 디올계 화합물 유래 반복단위를 잔부로 포함할수있다.Specifically, wherein said polyester resin comprises 5 repeating unit represented by formula (2), this is to seedlings 1 is cycloalkyl nuclear xylene di-methylene in formula (2) wherein 11 is 0. repeated 100 the diol-derived repeating unit unit mole %, Or at least 95 mol%, or at least 97 mol%, or at least 99 mol% of the repeating unit derived from the diol compound.
0 [화학식 2]
Figure imgf000010_0001
0 &lt; / RTI &gt;
Figure imgf000010_0001
상기 화학식 2에서,  In Formula 2,
요1은 치환 또는 비치환된 탄소수 1 내지 의 직쇄, 분지쇄 또는 고리형 알킬렌기이고,Y 1 is a substituted or unsubstituted, linear, branched or cyclic alkylene group having 1 to 6 carbon atoms,
5 於는 치환 또는 비치환된 탄소수 1 내지 10의 직쇄 또는 분지쇄 알킬렌기이며, 5 is a substituted or unsubstituted, linear or branched alkylene group having 1 to 10 carbon atoms,
는 -0 -, - NH-또는名-이고,  Is -O-, -NH- or N &lt;
11는 0또는 1의 정수이다. 2019/098602 1»（：1^1{2018/013549 11 is an integer of 0 or 1. 2019/098602 1 (: 1 ^ {2018/013549
일 실시예에 따르면, 상기 폴리에스터 수지의 함량은, 폴리아미드 수지, 폴리에스터 수지 및 유리 섬유를 포함한 수지 혼합물의 총 중량을 기준으로 1 내지 40 중량%, 혹은 5 내지 40 중량%, 혹은 6 내지 30 중량%일수있다. According to one embodiment, the content of the polyester resin is 1 to 40% by weight, or 5 to 40% by weight, or 6 to 40% by weight, based on the total weight of the resin mixture including the polyamide resin, 30% by weight.
상기 폴리에스터 수지의 함량이 너무 적으면 내열성 향상 및 형태 변형 억제 효과가미미할 수 있다. 다만, 상기 폴리에스터 수지의 함량이 너무많으면 이를포함하는수지 블렌드조성물의 기계적 물성이 저하될수 있다. 바람직하게는, 상기 폴리아미드 수지의 중량（\\ ）에 대한 상기 폴리에스터 수지의 중량（ 2）의 비 2/ 1）는 0.01내지 0.8,혹은 0.05내지 0.75,혹은 0.1내지 0.7일수있다.  If the content of the polyester resin is too small, the effect of improving the heat resistance and suppressing the shape deformation may be insignificant. However, if the content of the polyester resin is too large, the mechanical properties of the resin blend composition containing the polyester resin may deteriorate. Preferably, the ratio 2/1 of the weight (2) of the polyester resin to the weight (\\) of the polyamide resin may be 0.01 to 0.8, or 0.05 to 0.75, or 0.1 to 0.7.
본 발명에 따른 치수 안정성 향상 효과의 발현을 위하여, 상기 폴리아미드 수지의
Figure imgf000011_0001
대한 상기 폴리에스터 수지의 중량（^2）의 비（ 2/\ 1）는 0.01 이상인 것이 바람직하다. 다만,상기 폴리에스터 수지가 과량으로포함될 경우,수지 블렌드조성물와기계적 물성이 저하되고,압출 등의 가공 과정에서 팽윤이 일어나는 등 가공성이 저하될 수 있다. 그러므로,상기 폴리아미드수지의 중량（\^1）에 대한상기 폴리에스터 수지의 중량（\^2）의 비（\¥2/’1\ ）는 0.08이하인것이 바람직하다. In order to exhibit the dimensional stability improving effect according to the present invention, the polyamide resin
Figure imgf000011_0001
The ratio (2 / \ 1) of the weight (^ 2) of the polyester resin to the polyester resin is preferably 0.01 or more. However, when the above-mentioned polyester resin is contained in an excess amount, the mechanical properties of the resin blend composition deteriorate, and the processability such as swelling during processing such as extrusion may be deteriorated. Therefore, the ratio (\ ¥ 2 / '1 \ ) by weight (\ ^ 2) in the polyester resin relative to the weight (\ ^ 1) of the polyamide resin is preferably not more than 0.08.
（ 유리 섬유 (Glass fiber
상기 유리 섬유로는본발명이 속하는기술분야에서 잘 알려진 유리 섬유가특별한제한없이 적용될수있다.  As the glass fiber, glass fiber well-known in the technical field of the present invention can be applied without particular limitation.
상기 유리 섬유는 수지 블렌드 조성물의 결정화 온도를 높여주어 사출성형을유리하게 한다. 또한,상기 유리 섬유는수지 블렌드조성물의 내열성을향상시키고형태 변형 현상의 억제에도효과적이다.  The glass fiber enhances the crystallization temperature of the resin blend composition to facilitate injection molding. In addition, the glass fibers improve the heat resistance of the resin blend composition and are effective in suppressing the deformation of the shape.
이러한 효과의 달성을 위해, 상기 유리 섬유는 폴리아미드 수지, 폴리에스터 수지 및 유리 섬유를 포함한 수지 혼합물의 전체 중량을 기준으로 15내지 40중량%의 함량으로포함될수있다. 2019/098602 1»（：1^1{2018/013549 In order to achieve this effect, the glass fiber may be contained in an amount of 15 to 40% by weight based on the total weight of the resin mixture including the polyamide resin, the polyester resin and the glass fiber. 2019/098602 1 (: 1 ^ {2018/013549
（山상용화제 (Trade name
일반적으로, 폴리아미드 수지는 폴리에스터 수지에 대한 상용성이 낮기 때문에, 상기 폴리아미드와 폴리에스터 수지들의 단순 블렌드로는 목표로하는물성을발현시키기 어렵다.  In general, since the polyamide resin is low in compatibility with polyester resin, it is difficult to exhibit desired physical properties with a simple blend of the polyamide and polyester resins.
발명의 구현예에 따른수지 블렌드조성물은,소정의 에폭시 당량을 가지는상용화제를포함한다.  The resin blend composition according to embodiments of the invention comprises a compatibilizer having a predetermined epoxy equivalent.
상기 상용화제를 첨가함으로써,상술한폴리아미드수지,폴리에스타 수지,또는폴리아미드수지 및폴리에스터 수지 사이의 화학적 결합에 의해 개선된상용성을갖는수지블렌드조성물이 얻어질수있다. 바람직하게는,상기 상용화제는 2이상의 글리시딜 메타크릴레이트를 가지는올리고머일 수 있다. 구체적으로,상기 상용화제는스티텐-글리시딜 메타크릴레이트계 올리고머 및 에틸렌-글리시딜 메타크릴레이트계 올리고머로이루어진군에서 선택된 1종이상의 화합물일수있다. 특히, 상기 상용화제로는 100 당량 내지 1500 당량의 에폭시 당량 표\\0을갖는화합물이 바람직하게사용될수있다.  By adding the compatibilizer, a resin blend composition having improved compatibility with the polyamide resin, the polyesther resin, or the chemical bond between the polyamide resin and the polyester resin can be obtained. Preferably, the compatibilizing agent may be an oligomer having two or more glycidyl methacrylates. Specifically, the compatibilizing agent may be one or more compounds selected from the group consisting of styrene-glycidyl methacrylate oligomers and ethylene-glycidyl methacrylate oligomers. Particularly, as the compatibilizing agent, a compound having an epoxy equivalent number of from 100 to 1500 equivalents may be preferably used.
구체적으로,상기 상용화
Figure imgf000012_0001
1500 /당량,혹은 150내지Specifically,
Figure imgf000012_0001
1500 / equivalent, or 150 -
1500 폰/당량, 혹은 200 내지 1400 /당량, 혹은 300 내지 1400 은/당량의 에폭시 당량여표 을갖는화합물일수있다. 1500 phon / equivalent, or 200 to 1400 / equivalent, or 300 to 1400 / equivalent of epoxy equivalent weight.
상기 상용화제로 에폭시 당량이 너무 높은 화합물을 사용할 경우, 수지 블렌드조성물의 점도가증가하고,그결과로가공성이 악화될수있다. 상업적으로 입수가능한 상기 상용화제로는 쇼표사의 ＞ ：1조、此® 쇼0묘-43685（에폭시 당량: 300 /당량）,
Figure imgf000012_0002
（비스페놀 쇼의 디글리시딜 에테르）유형의 에폭시 수지（에폭시 당량: 1,400
Figure imgf000012_0003
When a compound having too high an epoxy equivalent as the compatibilizer is used, the viscosity of the resin blend composition increases, and as a result, the processability may deteriorate. The compatibilizing agent is commercially available show pyosa>: one set,此® Show 0 mu -43685 (epoxy equivalent: 300 / eq.),
Figure imgf000012_0002
(Diglycidyl ether of bisphenol-A) type epoxy resin (epoxy equivalent: 1,400
Figure imgf000012_0003
들수있다. Can be heard.
상기 상용화제의 에폭시 당량여표 은 공지된 다양한 방법에 의해 측정할수있다. 특히,표준 115 X 7236-1986,쇼 01652-73및 ¾0 3001- 1978등을 예로들수 있다.. 상기 상용화제에 대한에폭시 당량의 분포의 경우에 있어서는,그평균값이 고려될수있다. 발명의 구현 예에 따르면, 상기 상용화제는 상기 수지 혼합물 100 중량부에 대하여 0.1 내지 10중량부로 포함될 수 있다. 구체적으로,상기 상용화제는 0.1 내지 10중량부,혹은 0.5내지 10중량부,혹은 1 내지 10 중량부로포함될수있다. The epoxy equivalent weight of the compatibilizing agent can be measured by various known methods. In particular, examples include the standard 115 X 7236-1986, the show 01652-73 and the ¾0 3001- 1978, etc. In the case of the distribution of the epoxy equivalents for the compatibilizing agent, the average value thereof can be considered. According to an embodiment of the present invention, the compatibilizer may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture. Specifically, the compatibilizing agent may be included in an amount of 0.1 to 10 parts by weight, or 0.5 to 10 parts by weight, or 1 to 10 parts by weight.
상기 상용화제의 함량이 너무 적을 경우, 폴리아미드 수지 및 폴리에스터 수지의 상용성이 불충분하고, 그 결과로서 가공성이 악화되어 강직성 및 강도 등과 같은 특성이 열악해질 수 있다. 다만, 상기 상용화제의 함량이 너무 많을 경우,수지 블렌드조성물의 점도가증가하여 유동성이 악화되고,그결과로서 가공성이 악화될수있다.  When the content of the compatibilizing agent is too low, the compatibility of the polyamide resin and the polyester resin is insufficient, and as a result, the processability is deteriorated and the properties such as rigidity and strength may be poor. However, when the content of the compatibilizing agent is too large, the viscosity of the resin blend composition is increased to deteriorate the fluidity, and as a result, the processability may deteriorate.
(e)기타첨가제 (e) Other additives
발명의 구현 예에 따르면,상기 수지 블렌드조성물에는 1종 이상의 첨가제가더 포함될수있다.  According to an embodiment of the invention, the resin blend composition may further comprise one or more additives.
상기 첨가제의 종류는 상기 수지 블렌드 조성물에 부여하고자 하는 특성을고려하여 선택될수있다.  The kind of the additive may be selected in consideration of the properties to be imparted to the resin blend composition.
예를 들어, 상기 수지 블렌드 조성물은 적하 방지제 (anti-dripping agent),난연제,산화방지제,안료,염료,및 핵제로이루어진군에서 선택된 1종이상의 화합물을더 포함할수있다. 상기 첨가제의 함량은상기 수지 블렌드조성물의 물성을 저해하지 않는범위 내에서 조절될수있다.  For example, the resin blend composition may further comprise one or more compounds selected from the group consisting of anti-dripping agents, flame retardants, antioxidants, pigments, dyes, and nucleating agents. The content of the additive may be adjusted within a range that does not impair the physical properties of the resin blend composition.
예를 들어,상기 첨가제는상기 수지 혼합물 100중량부를 기준으로 각각 0.01내지 5중량부,또는 0.01내지 2중량부,또는 0.01내지 1중량부, 또는 0.01내지 0.5중량부로포함될수있다. 비제한적인 예로, 상기 염료로는 안트라퀴논 (anthraquinone), 페리논 (perinone),메씬 (me比 line)등의 화합물이사용될수있다. 상기 산화 방지제는 고분자 수지의 황변을 억제하여 수지 블렌드 2019/098602 1»（：1^1{2018/013549 For example, the additive may be included in an amount of 0.01 to 5 parts by weight, or 0.01 to 2 parts by weight, or 0.01 to 1 part by weight, or 0.01 to 0.5 parts by weight, based on 100 parts by weight of the resin mixture. A non-limiting example, the dye may be a compound such as anthraquinone (anthraquinone), perinone (perinone), messin (me比l ine) used. The antioxidant suppresses the yellowing of the polymer resin, 2019/098602 1 (: 1 ^ {2018/013549
조성물 및 성형품의 외관을 양호하게 하며, 산화 또는 열분해되는 것을 억제할수있다. The appearance of the composition and the molded article is improved, and oxidation or pyrolysis can be suppressed.
상기 산화 방지제로는 페놀계 산화 방지제, 인계 산화 방지제, 황계 산화방지제,장애 아민계 광안정제 등이사용될수 있다. 또한,상기 산화 방지제로는, 1분자중에 페놀계의 산화방지기와인계의 산화방지기를함께 갖는단량체를포함하는복합형 산화방지제가사용될수도있다.  Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based light stabilizers. As the antioxidant, a complex antioxidant comprising a monomer having both a phenol-based antioxidant and a phosphorus-based antioxidant in one molecule may be used.
상기 산화 방지제로는 페놀계 산화 방지제와 인계 산화 방지제를 혼합하여사용하는것이,내열성의 저하없이 열또는산화에 의한성형체의 착색이나 물성 저하의 방지에 유리할 수 있다. 바람직하게는, 상기 산화 방지제는 페놀계 산화 방지제 및 인계 산화 방지제를 2:1 내지 1:2의 중량 비로포함할수있다.  As the antioxidant, a phenol-based antioxidant and a phosphorus-based antioxidant may be mixed and used to prevent coloring of the molded article due to heat or oxidation and deterioration of physical properties without deteriorating the heat resistance. Preferably, the antioxidant may include a phenol-based antioxidant and a phosphorus-based antioxidant in a weight ratio of 2: 1 to 1: 2.
Figure imgf000014_0001
Figure imgf000014_0001
히드록시페닐）프로피온아미도］프로판（1,6 - ［3-（3,5 -出나안내11 -4- 1년10 7|?1161171）｛）101 011311난（10］ 10 31½）, 테트라키스［메틸렌（3, 5 -디 -七안七-부틸- 4- 히드록시히드로시나메이트）］메탄 크노비!! 仕 15，1 6（3,5 - ｝，］-4- 느7 0 0〔11111311\ 6）］11½1：］13116） 등을 들 수 있다. 상업적으로 입수가능한페놀계산화방지제로는쇼애 사의쇼0-60등을들수있다. 상기 인계 산화 방지제로는 인산， 트리메틸포스페이트， 트리에틸포스페이트， 트리페닐포스페이트， 트리에틸포스포노아세테이트, 비스（2, 6 -디 代-부틸- 4 -메틸페닐）펜타에리트리톨-디 -포스파이트（1由（2,6 -出 마-
Figure imgf000014_0002
Hydroxyphenyl) propionamide amido] propane (1,6 - [3- (3,5 -出or guide 11 4-one years 10 7 |? 1 1611 71) {) 1 10 011 311 I (1 0; 10 31½), tetrakis [methylene (3,5-di-七not七-butyl-4-hydroxy-dihydro-Sinai mate)] methane is greater Novi! There may be mentioned; 13 116) including:仕1 5,1 6 (3, 5 - Ne 70 0 [1 1111311 \ 6},] - - 4)] 11½1. Examples of commercially available phenol calculation inhibitors include Showa's Show 0-60 and the like. Examples of the phosphorus antioxidant include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethylphosphonoacetate, bis (2, 6-dihydroxybutyl-4-methylphenyl) pentaerythritol- (2,6 - demon -
Figure imgf000014_0002
부틸페닐）펜타에리트리톨-디-포스파이트（ 5（2,4-（1나¾木Butylphenyl) pentaerythritol-di-phosphite (5 (2,4 (1 or ¾木
Figure imgf000014_0003
등을 들 수 있다. 상업적으로 입수가능한 인계 산화 방지제로는 Basί 사의 11¾ 05® 168 등을 들 수 있다.
Figure imgf000014_0003
And the like. Commercially available phosphorus antioxidants include 11 &lt; nd &gt; ® 168 from Basri.
수지 블렌드 조성물 내 산화 방지제의 함량이 지나치게 높을 경우, 상기 수지 블렌드조성물의 기계적 물성,특히,내열도등이 저하될수있다. 그러므로, 상기 산화 방지제는 상기 수지 혼합물 100 중량부를 기준으로 0.01 내지 5 중량부, 또는 0.1 내지 1 중량부, 또는 0.1 내지 0.5 중량부로 포함될수있다. 상기 안료로는카본블랙,산화티타늄,산화아연,황화아연,황산아연, 황산바륨,리토폰 (lithopone, BaS04 ZnS), 연백 (white lead, 2PbC03 Pb(OH)2) 탄산칼슘,알루미나등을들수있다. 상기 핵제는 수지 블렌드 조성물의 성형 시 결정화의 핵으로 작용하여 결정화속도를향상시키며,수지 블렌딩 조성물의 내열성 및 사출 성형성을향상시키는역할을한다. When the content of the antioxidant in the resin blend composition is too high, The mechanical properties, particularly the heat resistance, of the resin blend composition may be lowered. Therefore, the antioxidant may be included in an amount of 0.01 to 5 parts by weight, or 0.1 to 1 part by weight, or 0.1 to 0.5 parts by weight based on 100 parts by weight of the resin mixture. The pigment roneun carbon black, titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, lithopone (lithopone, BaS0 4 ZnS), white lead (white lead, 2PbC0 3 Pb ( OH) 2) , calcium carbonate, alumina, etc. Can be heard. The nucleating agent acts as a nucleus of crystallization during the molding of the resin blend composition to improve the crystallization speed and to improve the heat resistance and injection moldability of the resin blending composition.
상기 핵제로는 탈크 /유기금속염 혼합물, 소르비틀계 금속염, 포스페이트계 금속염, 퀴나크리돈, 칼슘 카르복실레이트, 몬탄계 금속염, 아마이드계 유기 화합물, 질화 붕소 (보론나이트라이드, boron nitride), 탈크 등을 들 수 있다. 이 중에서도 핵제 사용에 따른 개선 효과를 고려하여 무기 핵제인 질화 붕소가 바람직하게 사용될 수 있다. 상업적으로 입수 가능한무기 핵제로는스피어 신소재사의 IND-11가사용될수있다. 상기 난연제는 인계 난연제일 수 있다. 상기 인계 난연제는 친환경적이며, 할로겐계 난연제를 대체하고폴리아미드수지 및 폴리에스터 계수지와의상용성 및유동성이 우수한이점이 있다.  Examples of the nucleating agent include a talc / organometallic salt mixture, a sorbitan type metal salt, a phosphate type metal salt, a quinacridone, a calcium carboxylate, a montanic metal salt, an amide type organic compound, boron nitride, . Of these, boron nitride, which is an inorganic nucleating agent, can be preferably used in consideration of the improvement effect of the use of a nucleating agent. Commercially available inorganic nucleating agents may be used, such as IND-11 from Spear Advanced Materials. The flame retardant may be a phosphorus flame retardant. The phosphorus flame retardant is eco-friendly and has an advantage of substituting for a halogen-based flame retardant and excellent in compatibility with a polyamide resin and a polyester resin, and fluidity.
상기 인계 난연제는 예를 들어 트리메틸 포스페이트 (仕 imethyl phosphate), 트리에틸 포스페이트 (triethyl phosphate), 트리페닐 포스페이트 (triphenyl phosphate, TPP), 트리크레실 포스페이트 (tricresyl phosphate, TCP), 트리크실레닐 포스페이트 (bixylenyl phosphate, TXP), 레조시놀비스 (디페닐포스페이 트) [resorcinolbis (diphenyl phosphate), RDP], 페닐디레조시놀포스페이트 (phenyl diresorcinolphosphate),비스페놀디페닐 포스페이트 (bisphenol diphenyl phosphate, BDP), 크레실 디페닐 포스페이트 (cresyl diphenyl phosphate),자일레닐 디페닐포스페이트 (xylenyl diphenyl phosphate), 페닐 디 (이소프로필페닐)포스페이트 [hhenyl di(isopropylphenyl) phosphate], 트리이소페닐 포스페이트 (triisophenyl phosphate), 디페닐포스페이트 (diphenyl phosphate), 레조시놀 디포스페이트 (resorcinol diphosphate), 및 방향족 폴리포스페이트 (aromatic polyphosphate)로이루어진군에서 선택된 1종이상일수있다. The phosphorus flame retardant may be, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), trisilyl phosphate bixylenyl phosphate, TXP, resorcinolbis (diphenyl phosphate), RDP, phenyl diresorcinolphosphate, bisphenol diphenyl phosphate (BDP) Cresyl diphenyl phosphate, xylenyl phosphate, diphenyl phosphate, phenyl di (isopropylphenyl) phosphate, triisophenyl phosphate, diphenyl phosphate, resorcinol diphosphate, and aromatic And aromatic polyphosphate may be used.
상업적으로 입수가능한 인계 난연제로는 Clariant사의 OP-1230 및 OP-1240 등을 들 수 있다. 폴리아미드 수지와 폴리에스터계 수지의 상용성을 위해서 OP-1230 또는 OP-1240가 단독으로 사용되거나, 또는 이들의 혼합물이사용될수있다. 상기 적하방지제로는실리카,석면,및 소섬유타입 (fibrillating-type) 불화폴리머 등이사용될수있다.  Commercially available phosphorus flame retardants include OP-1230 and OP-1240 from Clariant. OP-1230 or OP-1240 may be used alone, or a mixture thereof may be used for compatibility of the polyamide resin and the polyester resin. Examples of the drip inhibitor include silica, asbestos, and fibrillating-type fluoropolymers.
상기 불화 폴리머로는 폴리 (테트라플루오로에틸렌), 테트라 플루오로에틸렌/핵사플루오로프로필렌 코폴리머, 테트라플루오로에틸렌/에틸렌 코폴리머, 폴리 (비닐리.덴 플루오 라이드), 폴리 (클로로트리플루오로에틸렌)등을예로들수있다.  Examples of the fluoropolymer include poly (tetrafluoroethylene), tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, poly (vinylidene fluoride), poly (chlorotrifluoro Ethylene), and the like.
이외에도, 상업적으로 이용 가능한 한나노텍사의 FS-200가 적하 방지제로서 고려될수있다. (f)수지 블렌드조성물의 제법 및물성  In addition, as far as commercially available, FS-200 of Nanotek can be considered as a drip inhibitor. (f) Preparation and properties of resin blend composition
상기 수지 블렌드조성물은상술한성분들을단순혼합하는방법으로 제조될수있다.  The resin blend composition may be prepared by a simple mixing of the above-mentioned components.
또는,상기 수지 블렌드 조성물은상술한성분들의 혼합물을 소정의 온도하에서 압력을가하여 용융혼합된상태의 것일수있다. 상기 수지 블렌드조성물은 1.8 MPa하에서 측정된 250내지 280 °C, 혹은 250내지 270 °C,혹은 255내지 270 °C의 열변형 온도 (heat deflection temperature, HDT)를가질수있다. 또한, 상기 수지 블렌드 조성물은 230 내지 270 °C, 혹은 240 내지 2019/098602 1»（：1^1{2018/013549 Alternatively, the resin blend composition may be in a melt-mixed state under pressure at a predetermined temperature of the mixture of the above-described components. The resin blend composition can have a heat distortion temperature (heat deflection temperature, HDT) of 250 to 280 ° C, or 250 to 270 ° C, or 255 to 270 ° C measured at 1.8 MPa. The resin blend composition may also have a melting point of 230 to 270 ° C, 2019/098602 1 (: 1 ^ {2018/013549
260 의 결정화온도 (!¾!：)를가질수있다. 특히, 발명의 구현 예에 따른효과가충분히 발현될 수 있도록하기 위하여,상기 수지 블렌드조성물은,용매 0 -클로로페놀 (00^)에 용해시킨후 35 에서 측정한 점도로부터 환산된 0.6 011/ § 이상 0.9 31/ §미만의 고유 점도를갖는것이 바람직하다. It can have a crystallization temperature of 260 (! ¾! :). In particular, in order to sufficiently exhibit the effect according to the embodiment of the present invention, the resin blend composition preferably has a melt flow rate of 0.6 011 / § or more calculated from the viscosity measured at 35 after dissolving in the solvent 0 -chlorophenol (00) It is preferred that the polymer has an intrinsic viscosity of less than 0.9 31 / §.
구체적으로,상기 수지블렌드조성물은 0.6出/용이상 0.9 (1\/§미만, 혹은 0.6내지 0.85 (11/은,혹은 0.65내지 0.85 (11/^혹은 0.70내지 0.85 (11/^ 혹은 0.75내지 0.83 (11 의 고유점도를가질수있다. Specifically, the resin blend compositions 0.6出/ more than 0.9 (1 \ / § less, or 0.6 to 0.85 (11 / is, or from 0.65 to 0.85 (11 / ^, or 0.70 to 0.85 (11 / ^, or 0.75 to 0.83 for Lt; RTI ID = 0.0 &gt; 11 &lt; / RTI &gt;
11.수지 성형품 발명의 다른 일 구현예에 따르면, 상기 수지 블렌드 조성물을 포함하는수지 성형품이 제공된다. 11. Resin molded article According to another embodiment of the invention, there is provided a resin molded article comprising the resin blend composition.
상기 수지 성형품은 그 형태 및 용도에 따라 상기 수지 블렌드 조성물을다양한방법으로성형하여 얻어질수있다.  The resin molded article can be obtained by molding the resin blend composition in various ways according to the form and use thereof.
예를들어,상기 수지블렌드조성물은사출,압출,압출블로우,사출 블로우, 및 프로파일 압출 등의 성형 공정을 통해 상기 수지 성형품으로 제조될수있다.  For example, the resin blend composition can be made into the resin molded article through a molding process such as injection, extrusion, extrusion blow, injection blow, and profile extrusion.
상기 수지 성형품의 형상이나크기는특별히 제한되지 않는다. 예를 들어,상기수지 성형품은필름,시트,용기,펠렛등일수있다.  The shape and size of the resin molded article are not particularly limited. For example, the resin molded article may be a film, a sheet, a container, a pellet, or the like.
바람직하게는, 상기 수지 성형품은 고온 다습한 조건에서 장시간 사용시 우수한 형태 안정성이 요구되는 자동차용 부품, 특히 자동차 엔진 주변부품소재등에 작용가능하다.  Preferably, the resin molded product is capable of acting on automobile parts, particularly parts for automobile engine peripheral parts, which are required to have excellent dimensional stability when used for a long time under high temperature and high humidity conditions.
상기 수지 성형품은,이외에도정밀기계의부품,자동차내외장부품, 커넥터를 포함한 전기전자 부품, 건설용 재료, 섬유, 및 스포츠 장비의 다양한용도로사용될수있다.  The resin molded article may be used in various applications such as precision machine parts, automotive exterior parts, electrical and electronic parts including connectors, construction materials, fibers, and sports equipment.
【발명의 효과】 【Effects of the Invention】
본발명에 따른수지 블렌드조성물은향상된 상용성을가져 우수한 기계적 물성과치수안정성을갖는수지 성형품의 제공을가능케 한다. The resin blend composition according to the present invention has improved compatibility and is excellent It is possible to provide a resin molded article having mechanical properties and dimensional stability.
【발명을실시하기 위한구체적인내용】 DETAILED DESCRIPTION OF THE INVENTION
이하,본발명의 이해를돕기 위하여 바람직한실시예들을제시한다. 그러나 하기의 실시예들은 발명을 예시하기 위한 것일 뿐, 본 발명을 이들만으로한정하는것은아니다. 이하의 실시예 및 비교예에사용된물질은다음과같다. 폴리아미드 수지로는 고유 점도가 0.87 dl/g인 폴리아미드 수지（ARLEN™ Modified Polyamide 6T, PA6T, Mitsui Chemicals, Inc）를 준비하였다. 상기 폴리아미드수지를 125 °C에서 10시간동안건조시킨후 사용하였다. 폴리에스터 수지로는 테레프탈산, 이소프탈산, 1,4- 사아클로핵산디메탄올（1,4-CHDM, 트랜스 함량이 70-80 몰%）, 및 에틸렌글리콜을축합중합한폴리에스터（SKYPURA™ 0302HQ SK케미칼）를 준비하였다. 상기 폴리에스터 수지를 100 °C에서 6시간동안건조시킨후 사용하였다. 상용화제（시로는 고분자형 사슬 연장제인 JONCRYL® ADR- 4368S（에폭시 당량: 300 g/당량, BASF）를준비하였다. 상용화제（피로는 DGEBA（비스페놀 A의 디글리시딜 에테르） 유형의 에폭시 수지（에폭시 당량: 1,400 g/당량, Dow Chemical）를준비하였다. 상용화제（C）로는 DGEBA（비스페놀 A의 디글리시딜 에테르） 유형의 에폭시 수지（에폭시 당량: 2,000 g/당량, Kykdo Chemical）를준비하였다. 산화 방지제로는 페놀계 산화 방지제（AO-60™, ADEKA） 및 인계 2019/098602 1»（：1^1{2018/013549 Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention, but the invention is not limited thereto. The materials used in the following Examples and Comparative Examples are as follows. As the polyamide resin, a polyamide resin (ARLEN (TM) Modified Polyamide 6T, PA6T, Mitsui Chemicals, Inc.) having an intrinsic viscosity of 0.87 dl / g was prepared. The polyamide resin was used after drying at 125 ° C for 10 hours. Examples of the polyester resin include terephthalic acid, isophthalic acid, 1,4-cyclohexanecarboxylic acid dimethanol (1,4-CHDM, trans content of 70-80 mol%), and polyester condensed with ethylene glycol (SKYPURA ™ 0302HQ SK Chemicals). The polyester resin was used after drying at 100 ° C for 6 hours. (JONCRYL® ADR-4368S (epoxy equivalent weight: 300 g / eq., BASF), a high molecular weight chain extender, was prepared. An epoxy resin (epoxy equivalent: 1,400 g / eq., Dow Chemical) of the type of compatibilizer (DGEBA (diglycidyl ether of bisphenol A)) was prepared as a compatibilizer. As the compatibilizer (C), an epoxy resin (epoxy equivalence: 2,000 g / equivalent, Kykdo Chemical) of DGEBA (diglycidyl ether of bisphenol A) was prepared. Antioxidants include phenolic antioxidants (AO-60 ™, ADEKA) and phosphorous 2019/098602 1 (: 1 ^ {2018/013549
산화방지제（1]¾ 05@ 168, 8쇼510룰준비하였다. 실시예 1 Antioxidants (1) ¾ 05 @ 168, 8 show 510 were prepared. Example 1
이축 압출기（分 40
Figure imgf000019_0001
\,/å> = 44）를 사용하여, 폴리아미드 수지 39 중량%, 폴리에스터 수지 26 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100중량부에 대해,상용화제（시 1 중량부, 페놀계 산화 안정제 0.2 중량부, 인계 산화 안정제 0.2 중량부를 혼합하여 수지 블렌드 조성물을 제조한후, 295
Figure imgf000019_0002
에서 균일하게 혼련 압출을 진행하여 펠렛을제조하였다. 제조한펠렛은 100 에서 6시간동안건조시켰다. 실시예 2 Biaxial extruder (min 40
Figure imgf000019_0001
100 parts by weight of a resin mixture consisting of 39% by weight of a polyamide resin, 26% by weight of a polyester resin and 35% by weight of a glass fiber was mixed with a compatibilizing agent (1 part by weight, 0.2 part by weight of the oxidizing stabilizer and 0.2 part by weight of the phosphorus-containing oxidizing stabilizer were mixed to prepare a resin blend composition, and then 295
Figure imgf000019_0002
, The pellets were prepared by uniformly performing the kneading extrusion. The prepared pellets were dried at 100 for 6 hours. Example 2
상기 수지 혼합물 대신 폴리아미드수지 52중량%,폴리에스터 수지 13 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 수지 블렌드 조성물및 이를포함한펠렛을제조하였다. 실시예 3  Except that 100 parts by weight of a resin mixture composed of 52% by weight of a polyamide resin, 13% by weight of a polyester resin and 35% by weight of a glass fiber was used in place of the resin mixture, and the resin blend composition Pellets were prepared. Example 3
상기 수지 혼합물 대신 폴리아미드수지 59중량%,폴리에스터 수지 6 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 수지 블렌드 조성물및 이를포함한펠렛을제조하였다. 실시예 4  Except that 100 parts by weight of a resin mixture consisting of 59% by weight of a polyamide resin, 6% by weight of a polyester resin and 35% by weight of a glass fiber was used in place of the resin mixture, and the resin blend composition Pellets were prepared. Example 4
폴리아미드 수지 52 중량%, 폴리에스터 수지 13 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100 중량부에 대해, 상용화제（쇼） 10 중량부를사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로수지 블렌드조성물및 이를포함한펠렛을제조하였다. 실시예 5  Except that 10 parts by weight of a compatibilizing agent (SHOW) was used with respect to 100 parts by weight of a resin mixture consisting of 52% by weight of a polyamide resin, 13% by weight of a polyester resin and 35% by weight of a glass fiber, To prepare a resin blend composition and pellets containing the same. Example 5
폴리아미드 수지 52 중량%, 폴리에스터 수지 13 중량%, 유리 섬유 2019/098602 1»（：1^1{2018/013549 52% by weight of a polyamide resin, 13% by weight of a polyester resin, 2019/098602 1 (: 1 ^ {2018/013549
35 중량%부 이루어진 수지 혼합물 100 중량부에 대해, 상용화제（미 1 중량부를사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로수지 블렌드조성물및 이를포함한펠렛을제조하였다. 실시예 6 A resin blend composition and a pellet containing the resin blend composition were prepared in the same manner as in Example 1, except that 1 part by weight of a compatibilizing agent (1 part by weight) was used per 100 parts by weight of the resin mixture. Example 6
폴리아미드 수지 52 중량%, 폴리에스터 수지 13 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100 중량부에 대해, 상용화제여） 10 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로수지 블렌드조성물및 이를포함한펠렛을제조하였다. 비교예 1  Except that 10 parts by weight of a resin mixture consisting of 52% by weight of a polyamide resin, 13% by weight of a polyester resin and 35% by weight of a glass fiber was used as a compatibilizer) was used in place of the resin Blend compositions and pellets containing them were prepared. Comparative Example 1
상기 수지 혼합물대신 폴리아미드수지 65중량% 및 유리 섬유 35 중량%로이루어진수지 혼합물 100중량부를사용한것을제외하고는,상기 실시예 1과 동일한 방법으로 수지 블렌드 조성물 및 이를 포함한 펠렛을 제조하였다. 비교예 2  A resin blend composition and pellets containing the same were prepared in the same manner as in Example 1 except that 100 parts by weight of a resin mixture consisting of 65% by weight of a polyamide resin and 35% by weight of a glass fiber was used instead of the resin mixture. Comparative Example 2
폴리아미드 수지 32.5 중량%, 폴리에스터 수지 32.5 중량%, 유리 섬유 35중량%로 이루어진 수지 혼합물 1⑴중량부에 대해,상용화제 ） 1 중량부를사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 수지 블렌드조성물및 이를포함한펠렛을제조하였다. 비교예 3  Except that 1 part by weight of 1 part by weight of a resin mixture consisting of 32.5% by weight of a polyamide resin, 32.5% by weight of a polyester resin and 35% by weight of a glass fiber was used as a compatibilizing agent) Blend compositions and pellets containing them were prepared. Comparative Example 3
폴리아미드 수지 52 중량%, 폴리에스터 수지 13 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100중량부에 대해, 어떠한 상용화제도 사용하지 않은 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 수지 블렌드조성물및 이를포함한펠렛을제조하였다. 비교예 4  100 parts by weight of a resin mixture comprising 52% by weight of a polyamide resin, 13% by weight of a polyester resin and 35% by weight of a glass fiber was subjected to the same procedure as in Example 1, except that no commercialization system was used, The compositions and pellets containing them were prepared. Comparative Example 4
폴리아미드 수지 52 중량%, 폴리에스터 수지 13 중량%, 유리 섬유 2019/098602 1»（：1^1{2018/013549 52% by weight of a polyamide resin, 13% by weight of a polyester resin, 2019/098602 1 (: 1 ^ {2018/013549
35 중량%로 이루어진 수지 혼합물 100 중량부에 대해, 상용화제 ） 13 중량부를사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로수지 블렌드조성물및 이를포함한펠렛을제조하였다. 비교예 5 35 wt.%), 13 parts by weight of a compatibilizing agent) was used in place of 100 parts by weight of the resin composition of Example 1, and pellets containing the resin blend composition were prepared. Comparative Example 5
폴리아미드 수지 52 중량%, 폴리에스터 수지 13 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100 중량부에 대해, 상용화
Figure imgf000021_0001
5 중량부를사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로수지 블렌드조성물및 이를포함한펠렛을제조하였다. 비교예 6 100 parts by weight of a resin mixture consisting of 52% by weight of a polyamide resin, 13% by weight of a polyester resin and 35% by weight of a glass fiber,
Figure imgf000021_0001
5 parts by weight were used in place of 5 parts by weight of the resin blend composition, and pellets containing the resin blend composition were prepared. Comparative Example 6
폴리아미드 수지 52 중량%, 폴리에스터 수지 13 중량%, 유리 섬유 35 중량%로 이루어진 수지 혼합물 100 중량부에 대해, 상용화제（（그） 13 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 수지 블렌드조성물및 이를포함한펠렛을제조하였다. 상기 실시예들및상기 비교예들에 따른수지 블렌드조성물의 성분, 함량및고유점도를하기 표 1에 나타내었다.  Was prepared in the same manner as in Example 1, except that 13 parts by weight of a compatibilizing agent ((b)) was used with respect to 100 parts by weight of a resin mixture consisting of 52% by weight of a polyamide resin, 13% by weight of a polyester resin and 35% A resin blend composition and pellets containing the same were prepared. The components, content, and intrinsic viscosity of the resin blend compositions according to the above Examples and Comparative Examples are shown in Table 1 below.
고유 점도는 상기 수지 블렌드 조성물을용매 0 -클로로페놀（00^）에 용해시킨후 35方에서 측정한점도로부터 환산된값이다. The intrinsic viscosity is a value calculated from the viscosity of the resin blend composition measured in 35 directions after dissolving the resin blend composition in the solvent 0 -chlorophenol (00).
【표 1】 [Table 1]
Figure imgf000021_0002
Figure imgf000021_0002
Figure imgf000022_0001
시험예
Figure imgf000022_0001
Test Example
상기 실시예들 및 상기 비교예들에서 제조한 펠렛을 각각사출기를 이용하여사출온도 295 에서 동일하게사출하여 시험편을제조하였다. 제조된시험편을 23±2 C, 50±5 %상대습도조건하에서 아래와같은 방법으로각각의 물성을측정하였으며,그결과를하기 표 2에 나타내었다.  The pellets prepared in the above Examples and Comparative Examples were injected at the injection temperature of 295 using an injection machine to prepare test pieces. The properties of the prepared test pieces were measured in the following manner under the conditions of 23 ± 2 C and 50 ± 5% relative humidity, and the results are shown in Table 2 below.
1)인장강도 1) Tensile strength
: ASTM D 638에 의거하여 시편을만들고,만능재료시험기 (Universal Testing Machine, Zwick Roell Z010)를이용하여 인장강도를측정하였다.  : A specimen was prepared in accordance with ASTM D 638 and tensile strength was measured using a universal testing machine (Zwick Roell Z010).
2)내열성 2) Heat resistance
: ASTM D 648에 의거하여 시편을만들고,열변형 온도 (heat deflection temperature, HDT) 시험기 (Toyoseiki사제)를 이용하여 1.8 MPa 하에서의 열변형 온도를측정하였다.  : A specimen was prepared in accordance with ASTM D 648 and heat distortion temperature under 1.8 MPa was measured using a heat deflection temperature (HDT) tester (Toyoseiki).
3)결정화온도 3) Crystallization temperature
: DSC (differential scanning calorimeter)를 이용하여 상온에서 320 °C까지 20 °C/min으로가열하여 수지 블렌드조성물의 열이력 (thermal history)을 제거하였다. 냉각 후 상온에서 320 °C까지 10 C/min으로 2019/098602 1»（：1^1{2018/013549 : The thermal history of the resin blend composition was removed by heating at 320 ° C at 20 ° C / min from room temperature using a differential scanning calorimeter (DSC). After cooling, at room temperature to 320 ° C at 10 C / min 2019/098602 1 (: 1 ^ {2018/013549
가열한 후, 이어서 3201： 에서 상온까지 20 1：/1 11으로 낮추며 결정화 온도를관찰하였다. After heating, the temperature was then lowered from 3201: to room temperature to 20: 1: 11, and the crystallization temperature was observed.
4)치수변화율 4) Dimensional change rate
: 형태 안정성을 평가하기 위해 평판 시편을 고온 고습 조건에서 보관전과후의 크기 변화를측정하였다. 구체적으로, 100 _ X 100 111111 규격의 평판시편의 사출흐름 방향 (^11)) 및 사출흐름의
Figure imgf000023_0001
: In order to evaluate the morphological stability, the size of the flat plate specimens was measured before and after storage at high temperature and high humidity. Specifically, the injection direction (^ 11) of a flat specimen of 100 _ X 100 111111 standard and the injection flow
Figure imgf000023_0001
각각측정 후 85 I： 및상대습도 85 %조건에서 72시간동안보관한후,위 두방향의 크기 변화를측정하여 치수변화율 (%)을산출하였다.  After each measurement, 85% I and 85% relative humidity were maintained for 72 hours, and the change in size in the above two directions was measured to calculate the percent change in size (%).
【표 2】 [Table 2]
Figure imgf000023_0003
상기 표 1과표 2를참고하면,실시예 1내지 6의 경우 1,650
Figure imgf000023_0002
이상의 인장 강도, 1.8 MPa 에서 255 이상의 열변형 온도, 및 247 2019/098602 1»（：1^1{2018/013549
Figure imgf000023_0003
Referring to Table 1 and Table 2, in the case of Examples 1 to 6, 1,650
Figure imgf000023_0002
Or more, a heat distortion temperature of 255 or more at 1.8 MPa, and a heat distortion temperature of 247 2019/098602 1 (: 1 ^ {2018/013549
이상의 결정화온도를나타내었다. Or more.
또한,상기 실시예 1내지 6은고온및 고습조건에서 치수변화율이 MD 0.5 % 이하 및 10 0.9 % 이하로 측정되어 우수한 형태 안정성을 나타내었다. 그러나, 폴리아미드 수지만을 포함하는 비교예 1에서는 상기 치수 변화율이 。 1.1 %및 10 1.6 %로측정되어 치수안정성이 열악한것으로 나타내었다. 이는폴리아미드수지의 높은흡습율에 의한것으로판단된다. 폴리아미드수지와폴리에스터 수지가같은양（각각 32.5중량%）으로 적용된 비교예 2에서는 압출기 출구에서의 상당한 팽윤이 일어나 어떠한 펠릿도수득할수없었고,그에 따라상기 물성 및치수변화율을측정할수 없었다. 또한상용화제를사용하지 않은 비교예 3은상용성의 결핍으로 인해 In Examples 1 to 6, the dimensional change rate was measured to be not more than 0.5% MD and not more than 10 0.9% under high temperature and high humidity conditions, and thus showed excellent dimensional stability. However, in Comparative Example 1 containing only polyamide resin, the dimensional change rate was measured to be 1.1% and 10 1.6%, indicating poor dimensional stability. It is considered that this is due to the high moisture absorption rate of the polyamide resin. In Comparative Example 2 in which the polyamide resin and the polyester resin were applied in the same amount (32.5 wt% each), considerable swelling occurred at the exit of the extruder, so that no pellets could be obtained, and thus the physical properties and the rate of dimensional change could not be measured. Comparative Example 3, which did not use a compatibilizing agent,
1,250노 /다!!2의 열악한인장강도를나타내었다. 1,250 No / Everything !! 2 showed the poor tensile strength.
반면,과량의 상용화제를 첨가한경우（비교예 4및 6）와높은에폭시 당량（2, 000 당량）을갖는상용화제를사용한비교예 5의 경우는,각각수지 블렌드 조성물의 고유 점도가 0.90 （11/은 이상으로 너무 높아서 가공성이 불량하였으며,특히 인장강도가낮게측정 되었다.  On the other hand, in the case of Comparative Example 5 in which an excessive amount of a compatibilizing agent was added (Comparative Examples 4 and 6) and a compatibilizing agent having a high epoxy equivalent (2,000 equivalents), the inherent viscosity of the resin blend composition was 0.90 Was too high to have poor workability, especially tensile strength was measured to be low.

Claims

2019/098602 1»（：1^1{2018/013549 【청구범위】 2019/098602 1 (: 1 ^ {2018/013549)
【청구항 1]  [Claim 1]
폴리아미드 수지, 폴리에스터 수지 및 유리 섬유를 포함한 수지 혼합물;및  A resin mixture including a polyamide resin, a polyester resin, and a glass fiber; and
100 당량 내지 1500 당량의 에폭시
Figure imgf000025_0001
가지는 상용화제; 100 to 1500 equivalents of epoxy
Figure imgf000025_0001
A propellant;
를포함하고,  Lt; / RTI &gt;
상기 상용화제는상기 수지 혼합물 100중량부에 대하여 0.1내지 10 중량부로포함되는,수지 블렌드조성물.  Wherein the compatibilizer is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture.
【청구항 2】 [Claim 2]
제 1항에 있어서,  The method according to claim 1,
상기 폴리아미드 수지의
Figure imgf000025_0002
대한 상기 폴리에스터 수지의 중량 (\¥2)의 비 ( 2/\¥1)는 0.01내지 0.8인,수지 블렌드조성물. The polyamide resin
Figure imgf000025_0002
Wherein the ratio (2 / \ 1) of the weight of the polyester resin to the weight of the polyester resin is in the range of 0.01 to 0.8.
【청구항 3】 [Claim 3]
제 1항에 있어서,  The method according to claim 1,
상기 유리 섬유는상기 수지 혼합물의 전체중량을기준으로 15내지 40중량%의 함량으로포함되는,수지 블렌드조성물.  Wherein the glass fibers are contained in an amount of 15 to 40% by weight based on the total weight of the resin mixture.
【청구항 4】 Claim 4
제 1항에 있어서,  The method according to claim 1,
상기 폴리아미드수지는폴리아미드- 6,폴리아미드- 66,폴리아미드- 610, 폴리아미드- 11, 폴리아미드- 12, 폴리테레프탈아미드 61' 01 6 {)111：]1크131111( 61; ?쇼6지,폴리이소프탈아미드,및폴리아라미드로이루어진군에서 선택된The polyamide resins include polyamide-6, polyamide-66 and polyamide-610, polyamide-11, polyamide-12, poly terephthalamide 61 01 6 {) 111: - one size 131 111 (61; Show 6, polyisopheramide, and polyaramid. &Lt; RTI ID = 0.0 &gt;
1종이상의 수지인,수지블렌드조성물. 1. A resin blend composition which is a resin on a paper.
【청구항 5] [Claim 5]
제 4항에 있어서,  5. The method of claim 4,
상기 폴리아미드수지는콜리테레프탈아미드 61({)01}^ 6{7111：11크1311^(16 2019/098602 1»（：1^1{2018/013549
Figure imgf000026_0001
The polyamide resin is coli terephthalamide 61 ({) 0, 1} ^ {6 7111: 11, 1311 ^ size (16 2019/098602 1 (: 1 ^ {2018/013549
Figure imgf000026_0001
【청구항 6】 [Claim 6]
제 1항에 있어서,  The method according to claim 1,
5 상기 폴리에스터 수지는 테레프탈산 및 1,4 -사이클로핵산디메탄올의 공중합으로부터 유래한반복단위를가지는,수지 블렌드조성물. 5. The resin blend composition of claim 1, wherein the polyester resin has a repeating unit derived from copolymerization of terephthalic acid and 1,4-cyclohexanedimethanol.
【청구항 7】 7.
제 6항에 있어서,  The method according to claim 6,
10 상기 폴리에스터 수지는폴리사이클로핵실렌디메틸렌 테레프탈레이트 수지인,수지 블렌드조성물.  10 The resin blend composition according to claim 1, wherein the polyester resin is a polycyclohexenylsilylene dimethylene terephthalate resin.
【청구항 8】 8.
제 1항에 있어서,  The method according to claim 1,
15 상기 상용화제는 2 이상의 글리시딜 메타크릴레이트를 가지는 올리고머인,수지 블렌드조성물. 15 The compatibilizer is an oligomer having two or more glycidyl methacrylates.
【청구항 9】 [Claim 9]
제 8항에 있어서,  9. The method of claim 8,
20 상기 상용화제는 스티렌-글리시딜 메타크릴레이트계 올리고머 및 에틸렌-글리시딜 메타크릴레이트계 올리고머로 아루어진 군에서 선택된 1종 이상의 화합물인,수지 블렌드조성물. 20 The compatibilizer is at least one compound selected from the group consisting of styrene-glycidyl methacrylate oligomer and ethylene-glycidyl methacrylate oligomer.
【청구항 10】 Claim 10
25 -제 1항에 있어서, 25. The method of claim 1,
상기 수지 블렌드 조성물은 0.6 61 /§ 이상 0.9 61/^ 미만의 고유 점도를가지는,수지 블렌드조성물. Wherein the resin blend composition has an intrinsic viscosity of 0.6 61 / 이상 to less than 0.9 61 /..
【청구항 11】 Claim 11
30 제 1항에 있어서, 2019/098602 1»（：1^1{2018/013549 According to 30 claim 1, 2019/098602 1 (: 1 ^ {2018/013549
적하 방지제, 난연제, 산화 방지제, 안료, 염료, 및 핵제로 이루어진 군에서 선택되된 1종이상의 화합물을더 포함하는,수지블렌드조성물. Wherein the resin blend composition further comprises at least one compound selected from the group consisting of antistatic agents, flame retardants, antioxidants, pigments, dyes, and nucleating agents.
【청구항 12】 Claim 12
5 제 11항에 있어서,  [5] The method of claim 11,
상가산화방지제는 페놀계 산화방지제 및 인계 산화방지제를 2:1 내지 1:2의 중량비로포함하는,수지 블렌드조성물.  Wherein the commercial antioxidant comprises a phenolic antioxidant and a phosphorus antioxidant in a weight ratio of 2: 1 to 1: 2.
【청구항 13】 Claim 13
10 제 1항에 따른수지블렌드조성물을포함하는수지 성형품.  10. A resin molded article comprising the resin blend composition according to claim 1.
PCT/KR2018/013549 2017-11-15 2018-11-08 Resin blend composition and resin molded article comprising same WO2019098602A1 (en)

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KR20010018352A (en) * 1999-08-19 2001-03-05 성재갑 Composition of thermoplastic polyesteric resin improved mechanical strength
JP2013185138A (en) * 2012-03-09 2013-09-19 Mitsubishi Gas Chemical Co Inc Polyester-based resin composition
KR20140133498A (en) * 2012-02-29 2014-11-19 도레이 카부시키가이샤 Thermoplastic resin composition and molded article of same
WO2015199062A1 (en) * 2014-06-25 2015-12-30 ユニチカ株式会社 Resin composition and molded article thereof
KR20160038412A (en) * 2014-09-30 2016-04-07 삼성에스디아이 주식회사 Polyamide resin composition and molded product using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010018352A (en) * 1999-08-19 2001-03-05 성재갑 Composition of thermoplastic polyesteric resin improved mechanical strength
KR20140133498A (en) * 2012-02-29 2014-11-19 도레이 카부시키가이샤 Thermoplastic resin composition and molded article of same
JP2013185138A (en) * 2012-03-09 2013-09-19 Mitsubishi Gas Chemical Co Inc Polyester-based resin composition
WO2015199062A1 (en) * 2014-06-25 2015-12-30 ユニチカ株式会社 Resin composition and molded article thereof
KR20160038412A (en) * 2014-09-30 2016-04-07 삼성에스디아이 주식회사 Polyamide resin composition and molded product using the same

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