CN101747602A - Glass fiber-reinforced polyester resin composition and molded product using the same - Google Patents
Glass fiber-reinforced polyester resin composition and molded product using the same Download PDFInfo
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- CN101747602A CN101747602A CN200910260659A CN200910260659A CN101747602A CN 101747602 A CN101747602 A CN 101747602A CN 200910260659 A CN200910260659 A CN 200910260659A CN 200910260659 A CN200910260659 A CN 200910260659A CN 101747602 A CN101747602 A CN 101747602A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/04—Homopolymers or copolymers of nitriles
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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Abstract
The present invention relates generally to a glass fiber-reinforced polyester resin composition including: (A) about 30 to about 80 wt % of a polyester resin; (B) about 5 to about 30 wt % of a vinyl-based copolymer; and (C) about 10 to about 50 wt % of a glass fiber with a cross-sectional aspect ratio of about 1.5 or more; and a molded product using the same.
Description
The application requires korean patent application 10-2008-0129331 number submitted in Korea S State Intellectual Property Office on December 18th, 2008 and the right of priority and the rights and interests of the korean patent application submitted in Korea S State Intellectual Property Office on December 16th, 2009 10-2009-0125503 number, and it all incorporates this paper in full by reference into.
Technical field
The present invention relates to glass fibre enhanced polyester and resin composition and with the moulded product of its preparation.
Background technology
Vibrin has excellent physical strength, chemical-resistant, electrology characteristic, molded character and outward appearance, therefore extensively is used in the various application.In addition, can vibrin is molded to improve its physical strength with various inorganic materials, this can enlarge the range of application of this resinoid.
Therefore yet vibrin is generally crystalline, and compare it to demonstrate dimensional stability not good with noncrystalline resin.Therefore, when temperature variation, the moulded product ratio that is formed by crystallized polyurethane resin is bigger by the contraction meeting of the moulded product of noncrystalline resin formation.Therefore, existing a large amount of research relates to vibrin and noncrystalline resin, mixes with the improvement dimensional stability as polycarbonate, ABS, ASA etc., and keeps the advantage of vibrin simultaneously.For example, when the needs weathering resistance, the ASA resin can be mixed with vibrin.
Usually, when strengthening thermoplastic resin with glass fibre, the gained resin can keep its molded character that comes from thermoplastic resin, and also can demonstrate improved tensile strength and flexural strength, particularly You Yi modulus in flexure and thermotolerance.Therefore, glass fibre enhanced thermoplastic resin can be used to the product for preparing load-bearing and be heated.Because these characteristics, glass fibre enhanced thermoplastic resin extensively are used in as in the application such as automobile, electron device.
Yet owing in injection moulding process the glass fibre orientation can take place, so glass fibre enhanced vibrin can demonstrate different shrinking percentages on injection direction and vertical direction.Therefore, if the crooked or distortion of moulded product after the injection moulding, glass fibre enhanced thermoplastic resin can not have desired size or shape.For head it off, mould may need repeatedly to revise or injection moulding process may need more complicated working conditions, and this can reduce workability.
In addition, in vibrin, add glass fibre and can reduce resin flow.Therefore, fibre-reinforced vibrin also needs higher injection temperature to carry out injection moulding.
Therefore, glass fibre enhanced thermoplastic resin should have improved flowability and dimensional stability, and keeps owing to adding tensile strength, flexural strength, modulus in flexure and the thermotolerance that glass fibre produces.
Summary of the invention
One aspect of the present invention provides glass fibre enhanced polyester and resin composition, has excellent balance between its dimensional stability, thermotolerance and the flexural strength.
Another aspect of the present invention provides the moulded product with the preparation of glass fibre enhanced polyester and resin composition.
According to an aspect of the present invention, provide glass fibre enhanced polyester and resin composition, it comprises: (A) about vibrin of 30 to about 80wt%; (B) about vinyl-based copolymer of 5 to about 30wt%; (C) about cross-sectional aspect ratio of 10 to about 50wt% is about 1.5 or bigger glass fibre.
Vibrin can be aromatic polyester resin, such as but not limited to pet resin, polytrimethylene terephthalate, polybutylene terephthalate resin, poly terephthalic acid hexylene glycol ester resin, poly-cyclohexanedimethyleterephthalate terephthalate resin (polycyclohexanedimethylene terephthalate resin), by with these resin modifieds being the vibrin of noncrystalline form preparation, or its combination.
Vinyl-based copolymer can comprise about 65 to about 80wt% first vinyl monomer, and it comprises aromatic vinyl monomer, acrylic monomer or its combination; With about 20 to about 35wt% second vinyl monomer, it comprises unsaturated nitrile monomer, acrylic monomer or its combination.
Glass fibre can have about 1.5 to about 8 cross-sectional aspect ratio, and can comprise cross-sectional aspect ratio be about 1.5 or bigger glass fibre and cross-sectional aspect ratio less than about 1.5 glass fibre.Based on cross-sectional aspect ratio be about 1.5 or bigger glass fibre and cross-sectional aspect ratio less than the gross weight of the mixture of about 1.5 glass fibre, cross-sectional aspect ratio is about 1 to about 80wt% less than about 1.5 content of glass fiber.
Glass fibre enhanced polyester and resin composition may further include impact-reinforcement, and it comprises core-shell type multipolymer, linear alpha-olefin analog copolymer or its combination.Based on the glass fibre enhanced polyester and resin composition of about 100 weight parts, impact-reinforcement content can be for about 1 to about 20 weight parts.
The core-shell type multipolymer can prepare by unsaturated compound is grafted on the rubber polymer, described unsaturated compound comprises by one or more polymkeric substance that prepare in polypropylene acids monomer, aromatic vinyl monomer, unsaturated nitrile monomer or its combination, and described rubber polymer comprises that by polymerization the monomer of dienes monomer, acrylic monomer, silicon-containing monomer or its combination prepares.The linear alpha-olefin analog copolymer can be the multipolymer of olefin monomer and acrylic monomer, described olefin monomer comprises ethene, propylene, butylene, iso-butylene or its combination, and described acrylic monomer comprises (methyl) acrylic acid alkyl ester, (methyl) acrylic acid ester or its combination.
According to another aspect of the present invention, provide by the molded goods that obtain of glass fibre enhanced polyester and resin composition.
Hereinafter will describe others of the present invention in detail.
Description of drawings
Fig. 1 is the synoptic diagram according to the glass fibre cross-sectional aspect ratio of an embodiment.
Embodiment
Now in following detailed description of the present invention the present invention is described more completely, wherein having illustrated partly is not whole embodiment of the present invention.In fact, the present invention can be with many multi-form enforcements, and should not be limited to embodiment as herein described; On the contrary, provide these embodiments so that the disclosure satisfies applicable legal requirements.
As used herein, unless other specific definitions is arranged, term " (methyl) acrylate ((meth) acrylate) " is meant " acrylate " or " methacrylic ester ".Term " (methyl) acrylic acid alkyl ester ((meth) acrylic acid alkyl ester) " is meant " acrylic acid alkyl ester " and " alkyl ester of methacrylic acid ", and term " (methyl) acrylic acid ester ((meth) acrylic acid ester) " is meant " acrylic acid ester " and " ester of methacrylic acid ".
According to an embodiment, glass fibre enhanced polyester and resin composition comprises: (A) about vibrin of 30 to about 80wt%; (B) about vinyl-based copolymer of 5 to about 30wt%; (C) about cross-sectional aspect ratio of 10 to about 50wt% is about 1.5 or bigger glass fibre.
According to embodiment, the exemplary compositions that comprises in the glass fibre enhanced polyester and resin composition will describe in detail hereinafter.Yet these embodiments only are exemplary, the invention is not restricted to this.
(A) vibrin
According to an embodiment, vibrin can be aromatic polyester resin, and it can prepare by the alkyl ester and the polycondensation of C2 to C10 diol component of terephthalic acid or terephthalic acid.Alkyl ester as terephthalic acid in the literary composition is used, and alkyl can be C1 to C10 alkyl.
The example of aromatic polyester resin includes but not limited to pet resin, polytrimethylene terephthalate, polybutylene terephthalate resin, poly terephthalic acid hexylene glycol ester resin, poly-cyclohexanedimethyleterephthalate terephthalate resin, by these resins are mixed the vibrin that is modified as noncrystalline form etc. and its combination with different monomers.In the exemplary embodiment, aromatic polyester resin can comprise pet resin, polytrimethylene terephthalate, polybutylene terephthalate resin, noncrystalline pet resin, or its combination.
The degree of crystallinity scope of vibrin can be about 10～about 60%.
Vibrin can have about 1.15 to about 1.4g/cm
3Proportion and about 210 to about 280 ℃ fusing point.When vibrin had suitable limiting viscosity and proportion in above-mentioned scope and fusing point, it can provide excellent mechanical property and molded character.
Based on the gross weight of glass fibre enhanced polyester and resin composition, glass fibre enhanced polyester and resin composition can comprise about vibrin of 30 to about 80wt%, and for example about 40 to about 60wt%.The vibrin content that comprises when glass fibre enhanced polyester and resin composition is in these scopes the time, and composition exhibiting goes out excellent intensity and shock resistance.
(B) vinyl-based copolymer
Vinyl-based copolymer can comprise and contains following monomeric multipolymer: about 65 to about 80wt% first vinyl monomer, and it comprises aromatic vinyl monomer, acrylic monomer or its combination; With about 20 to about 35wt% second vinyl monomer, it comprises unsaturated nitrile monomer, acrylic monomer or its combination.As used herein, first vinyl monomer and second vinyl monomer differ from one another.When vinyl-based copolymer comprises that these comprise first vinyl monomer and second vinyl monomer with the amount in the above-mentioned scope, can help the improvement of thermochromism and chemical-resistant.
Exemplary aromatic vinyl monomer can non-limitingly comprise vinylbenzene that vinylbenzene, C1 to C10 alkyl replaces, halogenated styrenes etc. and its combination.The vinylbenzene that exemplary alkyl replaces can non-limitingly comprise adjacent ethyl styrene, an ethyl styrene, to ethyl styrene, alpha-methyl styrene etc. and its combination.
Exemplary acrylic monomer can non-limitingly comprise (methyl) acrylic acid alkyl ester, (methyl) acrylic acid ester etc. and its combination.Used as (methyl) acrylic acid alkyl ester in the literary composition, alkyl is meant C1 to C10 alkyl.Exemplary (methyl) acrylic acid alkyl ester can non-limitingly comprise (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate etc. and its combination.Exemplary (methyl) acrylate can non-limitingly comprise (methyl) acrylate etc.
Exemplary unsaturated nitrile monomer can non-limitingly comprise vinyl cyanide, methacrylonitrile, ethyl acrylonitrile etc. and its combination.
When preparing the vinyl-based graft copolymer of modified rubber, the core-shell type impact-reinforcement can prepare vinyl-based copolymer as by product as detailed in this article.For example, when excessive vinyl-based copolymer is grafted to a small amount of rubber polymer, maybe when using excessive chain-transfer agent as molecular weight regulator, can prepare vinyl-based copolymer.
Exemplary vinyl-based copolymer can non-limitingly comprise: comprise the multipolymer of vinylbenzene and vinyl cyanide, or comprise the multipolymer of vinylbenzene, vinyl cyanide and methyl methacrylate; Comprise the multipolymer of alpha-methyl styrene and vinyl cyanide, or comprise the multipolymer of alpha-methyl styrene, vinyl cyanide and methyl methacrylate; Comprise the multipolymer of vinylbenzene, alpha-methyl styrene and vinyl cyanide, or comprise multipolymer of vinylbenzene, alpha-methyl styrene, vinyl cyanide and methyl methacrylate etc.; With its combination.
Vinyl-based copolymer can prepare by letex polymerization, suspension polymerization, solution polymerization or mass polymerization, and can have about 15,000 to about 300, the weight-average molecular weight of 000g/mol.
Based on the gross weight of glass fibre enhanced polyester and resin composition, glass fibre enhanced polyester and resin composition can comprise about vinyl-based copolymer of 5 to about 30wt%, and for example about 10 to about 20wt%.When glass fibre enhanced polyester and resin composition with above-mentioned scope in amount when comprising vinyl-based copolymer, composition can have excellent consistency and less character departs from, this can provide excellent thermotolerance.
(C) glass fibre
According to an embodiment, glass fibre can have flattened cross-section and predetermined aspect ratio.
Fig. 1 is the synoptic diagram according to the glass fibre aspect ratio of an embodiment.With reference to Fig. 1, aspect ratio is defined as the diameter (a) the longest in the glass fibre cross section and the ratio of the shortest diameter (b).
Glass fibre can have about 1.5 or bigger aspect ratio, for example about 1.5 to about 8, for example is again about 2 to 6.During cross-sectional aspect ratio in glass fibre has these scopes, the flowability of glass fibre enhanced polyester and resin composition reduces degree and can significantly diminish.Therefore, do not have and depend on vibrin mobile orienting effect, and can at utmost reduce or eliminate the distortion of the moulded goods for preparing by glass fibre enhanced polyester and resin composition.
Glass fibre can have about length of 2 to about 13mm, and for example about 3 to about 6mm.
In addition, glass fibre can have about 10 cross-sectional diameters to about 20 μ m.
According to an embodiment, can be with aspect ratio about 1.5 or bigger glass fibre and aspect ratio be mixed together less than about 1.5 glass fibre.As described herein, in this mixture, aspect ratio be about 1.5 or the consumption of bigger glass fibre can be for about 20 to about 99wt%, aspect ratio can be for about 1 to about 80wt% less than the consumption of about 1.5 glass fibre.When mix aspect ratio in the aforementioned proportion scope is about 1.5 or bigger glass fibre and aspect ratio during less than about 1.5 glass fibre, and glass fibre enhanced polyester and resin composition can keep excellent workability and shock resistance.
According to an embodiment, predetermined material can be coated on the surface of glass fibre to prevent and vibrin reaction and improve degree of steeping.
Coating material can change overall flow, shock strength of glass fibre enhanced polyester and resin composition etc.Those of ordinary skills know the material of character such as the flowability that is suitable for coated glass fiber and influences glass fibre enhanced polyester and resin composition, shock strength, and can select need not too much experiment according to the required character of resulting composition.
Based on the gross weight of glass fibre enhanced polyester and resin composition, glass fibre enhanced polyester and resin composition can comprise about glass fibre of 10 to about 50wt%, and for example about 10 to about 40wt%.When glass fibre enhanced polyester and resin composition comprises the glass fibre of measuring in these scopes, glass fibre can improve the flexural strength and the thermotolerance of glass fibre enhanced polyester and resin composition, therefore improve it and flow, so that excellent moulding form to be provided thus.
(D) impact-reinforcement
According to an embodiment, glass fibre enhanced polyester and resin composition may further include impact-reinforcement.
Impact-reinforcement can be core-shell type multipolymer, linear alpha-olefin analog copolymer or its combination.
The core-shell type multipolymer can comprise by unsaturated monomer being grafted to the shell that forms on the rubbery kernel.For example, nuclear-shell can form by unsaturated compound is grafted on the rubber polymer, described unsaturated compound comprises by polymerization and comprises the polymkeric substance that one or more monomers in acrylic monomer, aromatic vinyl monomer, unsaturated nitrile monomer or its combination form that described rubber polymer comprises that by polymerization the monomer of dienes monomer, acrylic monomer, silicon-containing monomer or its combination prepares.
Exemplary dienes monomer can non-limitingly comprise C4 to C6 divinyl, isoprene etc. and its combination.Exemplary rubber polymer by the preparation of polymerization dienes monomer can non-limitingly comprise divinyl rubber, acrylic rubber, styrene/butadiene rubbers, acrylonitrile/butadiene rubber, synthetic polyisoprene, ethylene-propylene-diene terpolymer (EPDM) etc. and its combination.
Exemplary acrylic monomer can non-limitingly comprise (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) ethyl acrylate, (methyl) Ethyl acrylate etc. and its combination.Can use stiffening agent or solidifying agent, as ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, (methyl) allyl acrylate, triallyl cyanurate etc., or its combination.
Exemplary silicon-containing monomer can non-limitingly comprise the cyclosiloxane compound, as hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, trimethyl triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, octaphenyl cyclotetrasiloxane etc. and its combination.Can use stiffening agent or solidifying agent, such as but not limited to trimethoxymethylsila,e, triethoxyphenylsilan, tetramethoxy-silicane, tetraethoxysilane etc., or its combination.
Have about 0.4 favourable to the balance of shock resistance and color to the rubber polymer of about 1 μ m average rubber particle size.
Based on the gross weight of core-shell type multipolymer, rubber polymer content is about 20 to about 80wt%.During the rubber polymer measured in the core-shell type multipolymer comprises this scope, the core-shell type multipolymer can at utmost increase the anti-impact reinforced effects and thermotolerance is improved, and significantly improves mobile.
In unsaturated compound, exemplary acrylic monomer can non-limitingly comprise (methyl) acrylic acid alkyl ester, (methyl) acrylic acid ester etc. and its combination.Used as (methyl) acrylic acid alkyl ester in the literary composition, alkyl is meant C1 to C10 alkyl.Exemplary (methyl) acrylic acid alkyl ester can non-limitingly comprise (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate etc. and its combination.Exemplary (methyl) acrylic acid ester can non-limitingly comprise (methyl) acrylate etc.
In unsaturated compound, exemplary aromatic vinyl monomer can non-limitingly comprise vinylbenzene that vinylbenzene, C1 to C10 alkyl replaces, halogenated styrenes etc. and its combination.The vinylbenzene that exemplary alkyl replaces can non-limitingly comprise adjacent ethyl styrene, an ethyl styrene, to ethyl styrene, alpha-methyl styrene etc. and its combination.
In unsaturated compound, exemplary unsaturated nitrile monomer can non-limitingly comprise vinyl cyanide, methacrylonitrile, ethyl acrylonitrile etc. and its combination.
The exemplary unsaturated compound that comprises the polymkeric substance that is prepared by more than one monomers can comprise polymethylmethacrylate.
The core-shell type multipolymer can have about 0.1 median size to about 10 μ m.During median size in the core-shell type multipolymer has this scope, it can disperse in the polyester matrix well.Therefore, when composition was subjected to external impact, it can absorb impact at an easy rate to increase the anti-impact reinforced effects.
The linear alpha-olefin analog copolymer can comprise the multipolymer of olefin monomer and acrylic monomer.
Exemplary olefins class monomer can non-limitingly comprise ethene, propylene, butylene, iso-butylene etc. and its combination.
Exemplary acrylic monomer can non-limitingly comprise (methyl) acrylic acid alkyl ester, (methyl) acrylic acid ester etc. and its combination.Used as (methyl) acrylic acid alkyl ester in the literary composition, alkyl is meant C1 to C10 alkyl.Exemplary (methyl) acrylic acid alkyl ester can non-limitingly comprise (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate etc. and its combination.Exemplary (methyl) acrylic acid ester can non-limitingly comprise (methyl) acrylate etc.
The linear alpha-olefin analog copolymer can prepare with conventional olefin polymerization catalysis Ziegler-Natta catalyst.In order to have the stronger structure of selectivity, the linear alpha-olefin analog copolymer also can prepare with metallocene class catalyzer.
According to an embodiment, impact-reinforcement can not contain functional group, with the injection outward appearance that prevents to inject the standstill period colour-change and realize excellence.
Based on the glass fibre enhanced polyester and resin composition of about 100 weight parts, glass fibre enhanced polyester and resin composition can comprise about 1 impact-reinforcement to about 20 weight parts, and for example about 5 to about 15 weight parts.When impact-reinforcement content is in this scope, can at utmost increase the anti-impact reinforced effects, increase stable on heating lifting and improve flowability, this can improve injection moulding character.
(E) other additive
According to an embodiment, glass fibre enhanced polyester and resin composition may further include one or more additives.
The example of additive can non-limitingly comprise antiseptic-germicide, thermo-stabilizer, antioxidant, releasing agent, photostabilizer, expanding material, inorganic materials additive, tensio-active agent, coupling agent, softening agent, admixture, stablizer, lubricant, static inhibitor, flame-proofing agent, weather resisting agent, tinting material, ultraviolet ray (UV) blocking agent, filler, nucleator, bonding agent, tackiness agent etc. and its combination.
Exemplary antioxidant can non-limitingly comprise phenol antioxidant, phosphorous acid esters antioxidant, thioether class antioxidant, amine antioxidants etc. and its combination.Exemplary releasing agent can non-limitingly comprise metal-salt, montanic acid ester type waxes, polyethylene wax of fluoropolymer, silicone oil, stearic metal-salt, montanic acid etc. and its combination.Exemplary weather resisting agent can non-limitingly comprise benzophenone weather resisting agent, amine weather resisting agent etc. and its combination.Exemplary colorants can non-limitingly comprise dyestuff, pigment etc. and its combination.Exemplary ultraviolet ray (UV) blocking agent can non-limitingly comprise titanium dioxide (TiO
2), carbon black etc. and its combination.Exemplary filler can non-limitingly comprise glass fibre, carbon fiber, silicon oxide, mica, aluminum oxide, clay, lime carbonate, calcium sulfate, granulated glass sphere etc. and its combination.When adding filler, it can improve as character such as physical strength, thermotolerances.Exemplary nucleator can non-limitingly comprise talcum, clay etc. and its combination.
According to an embodiment, based on the glass fibre enhanced polyester and resin composition of about 100 weight parts, glass fibre enhanced polyester and resin composition can comprise about 50 weight parts or lower additive.When additive level is in this scope, can realize therefore can providing excellent mechanical properties and improved appearance by the desired result that uses various additive decisions.
According to an embodiment, available known method prepares glass fibre enhanced polyester and resin composition.For example, said components, or said components and additive can be in forcing machine blend and melt extruding with the preparation particle.
Another embodiment of the invention provides the moulded product that uses the preparation of glass fibre enhanced polyester and resin composition.Moulded product can comprise vibrin, is dispersed with aspect ratio in the described vibrin and is about 1.5 or bigger glass fibre.
This moulded goods demonstrates various useful character, as improved tensile strength and flexural strength, and particularly You Yi thermotolerance, so the parts that can be used for load-bearing and be heated.
In addition, be about 1.5 or during bigger glass fibre, than conventional glass fibre enhanced polyester and resin composition, the flowability of glass fibre enhanced polyester and resin composition of the present invention can sharply reduce when adding cross-sectional aspect ratio.Therefore, during preparation technology, can prevent the crooked or distortion of moulded goods.
Therefore, these plastics can be used for the various products that need accurate dimension stability, for example precision electronic element, accurate element automatically etc.
Following examples are described more specifically the present invention.Yet they are illustrative embodiments and unrestricted.
Embodiment
According to an embodiment, glass fibre enhanced polyester and resin composition comprises following each component.
(A) vibrin
As vibrin, it has proportion, 0.83 limiting viscosity and 228 ℃ the fusing point of 1.31g/cm3 with polybutylene terephthalate, and from SHINKONG company, commodity are called Shinite K001.
(B) vinyl-based copolymer
By adding 0.17 weight part Diisopropyl azodicarboxylate, 0.4 weight part uncle lauryl mercaptan chain-transfer agent and 0.5 weight part tricalcium phosphate in the mixture of 71.5 parts by weight of styrene, 28.5 parts by weight of acrylonitrile and 120 parts by weight of deionized water, and subsequently the gained mixture was prepared the san copolymer resin in 5 hours 75 ℃ of suspension polymerizations.The gained multipolymer is cleaned, dewaters and drying, to prepare Powdered san copolymer resin.
(C) glass fibre
The CSG 3PA-820 that uses the preparation of Nitto Boseki company limited is as the 3mm long glass fibres, and its (C-1) cross-sectional aspect ratio is 4 (longest diameter 28 μ m, the shortest diameter 7 μ m).
Use the CS321-EC10-3 of KCC company preparation, its length be 3mm, diameter be 13 μ m and (C-2) cross-sectional aspect ratio be 1.
(D) impact-reinforcement
The core-shell type multipolymer of use by vinyl cyanide and cinnamic copolymer grafted are prepared on acrylate.Multipolymer has the median size of 3 μ m.
Embodiment 1 to 8 and comparative example 1 to 3
According to the amount mixing said ingredients shown in the following table 1, and by using twin screw extruder (Φ=45mm) mixture is made particle.Vibrin, impact-reinforcement and vinyl-based copolymer are placed main feeder, and glass fibre is placed the side feeder.
Experimental example
Will according to the particle of embodiment 1 to 8 and comparative example 1 to 3 110 ℃ dry 3 hours or longer down, and in 10 ounces of forcing machines, extrude subsequently with the preparation sample, the forming temperature that forcing machine is set is that 200 to 300 ℃ and molding temperature are 60 to 100 ℃.Character according to following method working sample.The result is presented in the following table 1.
Melt flow rate (MFR): measure according to ASTM D1238, at 250 ℃ with the 5kg fixed 1 minute effusive resin quality of resurveying.
(2) flexural strength: measure according to ASTM 790.
(3) thermotolerance: measure according to ASTM D648.
(4) shrinking percentage: with 6 " x6 " and 1/8 " thick film shape valve gated mold remains on 80 ℃ and injection moulding in 10 ounces of injection moulding machines of 95% power, in constant temperature/humidity room's (being made as 23 ℃ of temperature and humidity 50%), left standstill 24 hours subsequently without any external power.Subsequently, measure perpendicular to vertical (MD) and flow direction, i.e. shrinking percentage on horizontal (TD) of back flow of sample direction.
Table 1
* weight part: based on (A) vibrin of 100 weight parts, (B) ethylenic copolymer and (C) glass fibre.
With reference to table 1, with comparative example 1 (composition that does not comprise vinyl-based copolymer), comparative example 2 (composition that comprises the vinyl-based copolymer that exceeds content range of the present invention) and comparative example 3 (do not comprise cross-sectional aspect ratio be about 1.5 or the composition of bigger glass fibre) compare, according to embodiment 1 to 8, comprise vibrin, vinyl-based copolymer and cross-sectional aspect ratio be about 1.5 or the composition of bigger glass fibre show excellent balance as character such as flowability, flexural strength, thermotolerance and dimensional stabilitys.
Especially, comparative example 3 (comprising the composition of cross-sectional aspect ratio less than about 1.5 glass fibre) has high shrinkage, so dimensional stability reduces.
Benefit from the instruction of above stated specification, those skilled in the art in the invention will understand many modifications of the present invention and other embodiment.Therefore, should understand and the invention is not restricted to disclosed embodiment, and revise and other embodiment is also included within the scope of appended claims.Though this paper uses particular term, they only use in general and descriptive mode but not are intended to restriction, and scope of the present invention is defined by the claims.
Claims (11)
1. a glass fibre enhanced polyester and resin composition comprises
(A) 30 to 80wt% vibrin;
(B) 5 to 30wt% vinyl-based copolymer; With
(C) 10 to 50wt% cross-sectional aspect ratio is 1.5 or bigger glass fibre.
2. glass fibre enhanced polyester and resin composition as claimed in claim 1, wherein said vibrin is an aromatic polyester resin, described aromatic polyester resin comprises pet resin, polytrimethylene terephthalate, polybutylene terephthalate resin, poly terephthalic acid hexylene glycol ester resin, poly-cyclohexanedimethyleterephthalate terephthalate resin, by being the vibrin that noncrystalline form prepares with these resin modifieds, or their combination.
3. glass fibre enhanced polyester and resin composition as claimed in claim 1, wherein said vinyl-based copolymer comprises 65 to 80wt% first vinyl monomer and 20 to 35wt% second vinyl monomer, and described first vinyl monomer comprises aromatic vinyl monomer, acrylic monomer or its combination; Described second vinyl monomer comprises unsaturated nitrile monomer, acrylic monomer or its combination.
4. glass fibre enhanced polyester and resin composition as claimed in claim 1, wherein said glass fibre has 1.5 to 8 cross-sectional aspect ratio.
5. glass fibre enhanced polyester and resin composition as claimed in claim 1, wherein said glass fibre comprise cross-sectional aspect ratio be 1.5 or bigger glass fibre and cross-sectional aspect ratio less than the mixture of 1.5 glass fibre.
6. glass fibre enhanced polyester and resin composition as claimed in claim 5, wherein based on the gross weight of described mixture, described mixture comprises that 1 to 80wt% cross-sectional aspect ratio is less than 1.5 glass fibre.
7. glass fibre enhanced polyester and resin composition as claimed in claim 1, wherein said glass fibre enhanced polyester and resin composition further comprises impact-reinforcement, and described impact-reinforcement comprises core-shell type multipolymer, linear alpha-olefin analog copolymer or their combination.
8. glass fibre enhanced polyester and resin composition as claimed in claim 7 in the described glass fibre enhanced of 100 weight parts polyester and resin composition, comprises the described impact-reinforcement of 1 to 20 weight part.
9. glass fibre enhanced polyester and resin composition as claimed in claim 7, wherein said core-shell type multipolymer prepares by unsaturated compound is grafted on the rubber polymer, the polymkeric substance that described unsaturated compound comprises acrylic monomer, aromatic vinyl monomer, unsaturated nitrile monomer, formed by more than one described monomer, or their combination, described rubber polymer comprises that by polymerization the monomer of dienes monomer, acrylic monomer, silicon-containing monomer or their combination prepares.
10. glass fibre enhanced polyester and resin composition as claimed in claim 7, wherein said linear alpha-olefin analog copolymer comprises olefin monomer and acrylic monomer, described olefin monomer comprises ethene, propylene, butylene, iso-butylene or their combination, and described acrylic monomer comprises (methyl) acrylic acid alkyl ester, (methyl) acrylic acid ester or their combination.
11. goods are by any molded obtaining of described glass fibre enhanced polyester and resin composition in the claim 1～10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20080129331 | 2008-12-18 | ||
| KR10-2008-0129331 | 2008-12-18 | ||
| KR10-2009-0125503 | 2009-12-16 | ||
| KR1020090125503A KR20100071000A (en) | 2008-12-18 | 2009-12-16 | Glass fiber-reinforced polyester resin composition and molded product using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101747602A true CN101747602A (en) | 2010-06-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910260659A Pending CN101747602A (en) | 2008-12-18 | 2009-12-18 | Glass fiber-reinforced polyester resin composition and molded product using the same |
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| Country | Link |
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| KR (1) | KR20100071000A (en) |
| CN (1) | CN101747602A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102532821A (en) * | 2010-12-21 | 2012-07-04 | 上海日之升新技术发展有限公司 | Alloy material for improving heat resistance performance |
| CN102731950A (en) * | 2011-04-15 | 2012-10-17 | 黑龙江鑫达企业集团有限公司 | High-heat resistance and high-weatherability material specially for heat radiation grid |
| CN102838848A (en) * | 2011-06-23 | 2012-12-26 | 第一毛织株式会社 | Thermoplastic resin composition and molded product using the same |
| CN103289337A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Antistatic antibacterial PET master batch and preparation method thereof |
| CN103571218A (en) * | 2013-10-21 | 2014-02-12 | 黄宣斐 | Glass fiber reinforced thermoplastic resin composite |
| CN103709702A (en) * | 2013-12-11 | 2014-04-09 | 深圳市沃特新材料股份有限公司 | PC/PBT alloy material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102532821A (en) * | 2010-12-21 | 2012-07-04 | 上海日之升新技术发展有限公司 | Alloy material for improving heat resistance performance |
| CN102731950A (en) * | 2011-04-15 | 2012-10-17 | 黑龙江鑫达企业集团有限公司 | High-heat resistance and high-weatherability material specially for heat radiation grid |
| CN102838848A (en) * | 2011-06-23 | 2012-12-26 | 第一毛织株式会社 | Thermoplastic resin composition and molded product using the same |
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| CN105849190B (en) * | 2013-12-30 | 2019-02-01 | 乐天尖端材料株式会社 | With excellent impact resistance and sunproof thermoplastic resin composition |
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| US10822490B2 (en) | 2013-12-30 | 2020-11-03 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition having excellent shock resistance and light resistance |
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| US10131785B2 (en) | 2015-06-30 | 2018-11-20 | Lotte Advanced Materials Co., Ltd. | Polyester resin composition with excellent impact resistance and light reliability and molded article using the same |
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| KR20100071000A (en) | 2010-06-28 |
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