KR101201832B1 - Glass fiber-reinforced polyester resin composition - Google Patents

Abstract

(A) A polymer comprising a base resin comprising a mixture of (A-1) polyester resin and (A-2) acrylic graft copolymer and vinyl copolymer, (B) glass fiber, and (C) epoxy group Provided is a glass fiber reinforced polyester resin composition comprising a.

Polyester, acrylic graft copolymer, vinyl copolymer, glass fiber, epoxy group

Description

Glass fiber reinforced polyester-based resin composition {GLASS FIBER-REINFORCED POLYESTER RESIN COMPOSITION}

The present substrate relates to a glass fiber reinforced polyester resin composition.

Polyester resins are excellent in mechanical strength, chemical resistance, electrical properties, precision moldability, and the like, and are particularly excellent in appearance and are used in various applications. In addition, when the polyester resin is molded together with various types of inorganic materials, it is easy to increase mechanical strength, and its application range is greatly expanded.

However, since polyester resins generally have crystallinity, shrinkage of molded articles is larger than amorphous resins, and in many cases, improvement in dimensional stability is required. Accordingly, by partially mixing the amorphous resin such as polycarbonate, ABS (acrylonitrile-butadiene-styrene), ASA (acrylonitrile-styrene-acrylate) with polyester, the advantages of polyester while improving dimensional stability A lot of materials are being developed, and especially in the case of materials requiring weather resistance, ASA resin is used to develop a mixture with polyester.

In addition, although the mechanical strength of the polyester resin is proportional to the content of the fillers used, the specific gravity increases as the content of the filler increases, and when the content of the filler exceeds a certain level, the mechanical strength no longer increases. This point is pointed out as a barrier to expanding the application range of the polyester resin, various studies have been attempted to overcome this.

Meanwhile, automobiles use a variety of plastics for exterior and interior materials, and engine rooms. Glass fiber reinforced polyester resins are widely used as exterior materials and interior materials. The case of the headlamp exterior material is also one of the representative examples. The housing part of the headlamp is exposed to the underhood, which may expose it to high heat from the engine or to extreme environments in contact with various oils and detergents used in automobiles. Polyester resins are excellent in chemical resistance and have a high heat resistance when reinforced with glass fibers, etc., and thus are recognized as materials suitable for extreme environments exposed to high heat and various chemical substances.

However, these materials do not constitute a product alone but are assembled with other materials. Polyester, which is a crystalline resin, has a higher shrinkage rate than an amorphous resin, so that the dimensional stability of the molded article is different depending on the injection conditions. Problems can arise during the process. Accordingly, an ASA resin which is excellent in weather resistance and can offset the disadvantage of the polyester resin with an amorphous resin is used as a mixed resin with the polyester.

However, when the amorphous resin is used in combination with the polyester resin, the stiffness is greatly lowered, which does not satisfy the target physical property level. In order to solve this problem, when the content of glass fiber is increased, the specific gravity is greatly increased, which does not meet the trend of light weight of automobiles, and the appearance quality is greatly deteriorated due to a large amount of glass fiber. Accordingly, there is a need for a method that can have the required mechanical properties without increasing the amount of existing glass fibers.

One embodiment of the present invention is to provide a glass fiber reinforced polyester resin composition having a balance of physical properties excellent in mechanical strength, impact strength and fluidity.

Another embodiment of the present invention is to provide a molded article prepared from the glass fiber reinforced polyester-based resin composition.

One embodiment of the present invention is based on (A) (A-1) polyester (50) 50 to 90% by weight resin; and (A-2) 10 to 50% by weight of the mixture of acrylic graft copolymer and vinyl copolymer 100 parts by weight of resin; (B) 10 to 150 parts by weight of glass fibers; And (C) provides a glass fiber reinforced polyester resin composition comprising 0.1 to 5 parts by weight of a polymer containing an epoxy group.

The mixture of the acrylic graft copolymer and the vinyl copolymer (A-2) may include 2 to 60 wt% of the acrylic graft copolymer and 40 to 98 wt% of the vinyl copolymer.

In the glass fiber reinforced polyester resin composition, Y may have a value of 0.3 to 2 g / eq in Equation 1 below.

[Equation 1]

Y = [Epoxy Group Equivalent in Polymer Containing Epoxy Group] × [Content of Polymer Containing Epoxy Group] ÷ [Content of Polyester Resin]

The polyester resin (A-1) is polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin and these resins are amorphous It may be an aromatic polyester resin selected from the group consisting of a polyester resin modified with.

The acrylic graft copolymer may be a copolymer in which a polymer of an aromatic vinyl monomer and an unsaturated nitrile monomer is grafted to an acrylic rubber.

The vinyl copolymer may be a copolymer consisting of aromatic vinyl monomers of 65 to 80% by weight and unsaturated nitrile monomers of 20 to 35% by weight.

The glass fiber (B) may have a diameter of 8 to 20 ㎛ and a length of 1.5 to 8 mm.

The glass fiber (B) may be used by mixing with a fiber selected from the group consisting of carbon fibers, basalt fibers, fibers made from biomass, and combinations thereof.

Another embodiment of the present invention provides a molded article prepared from the glass fiber reinforced polyester-based resin composition.

Other specific details of embodiments of the present invention are included in the following detailed description.

Glass fiber reinforced polyester-based resin composition according to an embodiment of the present invention has a balance of mechanical strength, impact strength, and fluidity of the flexural strength, flexural modulus and tensile strength, the automotive, in particular of the headlamp It can be usefully used as a material for exterior materials, interior materials, engine rooms and the like.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Glass fiber reinforced polyester-based resin composition according to an embodiment of the present invention is (A) (A-1) of the polyester-resin 50 to 90% by weight and (A-2) acrylic graft copolymer and vinyl copolymer 100 parts by weight of the base resin including 10 to 50% by weight of the mixture, (B) 10 to 150 parts by weight of the glass fiber, and (C) 0.1 to 5 parts by weight of the polymer including the epoxy group.

Hereinafter, it looks at in detail with respect to each component constituting the glass fiber reinforced polyester resin composition according to an embodiment of the present invention.

(A) basic resin

The base resin according to an embodiment of the present invention includes a mixture of a polyester resin, an acrylic graft copolymer and a vinyl copolymer.

(A-1) polyester resin

Polyester resin according to an embodiment of the present invention can be used as an aromatic polyester resin, a resin polycondensed by melt polymerization from a terephthalic acid or a terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms. In this case, the alkyl means alkyl having 1 to 10 carbon atoms.

Specific examples of such aromatic polyester resins include polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, or some of these resins. A polyester resin modified to be amorphous by mixing other monomers may be used, and more specifically, among them, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, amorphous polyethylene terephthalate resin, and the like. Can be used.

The polyester resin according to one embodiment of the present invention may have an intrinsic viscosity [η] of 0.85 kPa to 1.52 kPa / g, and specifically, may have a range of 1.03 kPa to 1.22 kPa / gk.

In addition, the polyester resin according to an embodiment of the present invention may have a specific gravity of 1.15 kPa to 1.40 g / cm 3 and a melting point of 210 kPa to 280 ° C. When the polyester resin has the specific gravity and melting point range, excellent mechanical properties and moldability can be secured.

The polyester resin may be included in 50 to 90% by weight relative to the total amount of the base resin, specifically, may be included in 60 to 85% by weight. When the polyester resin is included in the above range it can ensure excellent mechanical strength and impact strength.

(A-2) Mixture of Acrylic Graft Copolymer and Vinyl Copolymer

The acrylic graft copolymer may be prepared by graft reacting an acrylic rubber with a polymer of an aromatic vinyl monomer and an unsaturated nitrile monomer.

As the acrylic rubber, a (meth) acrylic acid alkyl ester monomer or a (meth) acrylic acid ester monomer is used. In this case, the alkyl means alkyl having 1 to 10 carbon atoms, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like.

The aromatic vinyl monomer may be selected from the group consisting of styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, alphamethyl styrene, and combinations thereof.

The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.

The vinyl copolymer may be a copolymer comprising an aromatic vinyl monomer of 65 to 80% by weight and an unsaturated nitrile monomer of 20 to 35% by weight. When the aromatic vinyl monomer and the unsaturated nitrile monomer are composed of the above content, the thermochromic resistance and the chemical resistance are excellent.

The aromatic vinyl monomer may be selected from the group consisting of styrene, alkyl having 1 to 10 carbon atoms or halogen substituted styrene, and combinations thereof. Specific examples of the alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, alphamethyl styrene, and the like.

The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.

Specific examples of the vinyl copolymer according to one embodiment of the present invention include a mixture of styrene monomer and acrylonitrile monomer; mixtures of α-methylstyrene monomers and acrylonitrile monomers; Or those prepared from a mixture of styrene monomers, α-methylstyrene monomers and acrylonitrile monomers.

The vinyl copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and it is preferable to use a weight average molecular weight of 15,000 kPa to 300,000 g / mol.

The mixture of the acrylic graft copolymer and the vinyl copolymer is composed of an acrylic graft copolymer 2 to 60% by weight and a vinyl copolymer 40 to 98% by weight. Is reduced, and excellent heat resistance and dimensional stability can be secured.

The mixture of the acrylic graft copolymer and the vinyl copolymer according to the embodiment of the present invention may be included in an amount of 10 to 50 wt%, and specifically 15 to 40 wt%, based on the total amount of the base resin. When the mixture of the acrylic graft copolymer and the vinyl copolymer is included in the above range, the compatibility of the acrylic graft copolymer and the vinyl copolymer may be reduced, thereby securing excellent heat resistance and weather resistance. 　

(B) glass fiber

Glass fiber according to an embodiment of the present invention is a commercially used conventional one, a glass fiber of 8 to 20 ㎛ in diameter, 1.5 to 8 mm in length can be used. When the diameter of the glass fiber has the above range it can be obtained an effect of excellent impact reinforcement. In addition, when the length of the glass fiber has the above range it is easy to put in the extruder and the impact reinforcing effect can be greatly improved.

The glass fibers may be used in combination with fibers selected from the group consisting of carbon fibers, basalt fibers, fibers made from biomass, and combinations thereof.

The glass fiber may be selected from the group consisting of a circular cross-section, elliptical, rectangular and two circular connected dumbbell shape.

The glass fiber may be treated with a predetermined glass fiber treatment agent in order to prevent the reaction of the polyester-based resin and to improve the degree of impregnation. Treatment of the glass fiber may be processed at the time of fiber manufacture or in a later step.

Lubricating agents, coupling agents, surfactants and the like are used as the glass fiber treatment agent. The lubricant is used to form a good strand having a constant diameter in the manufacture of glass fibers, the coupling agent serves to give a good adhesion between the glass fiber and the resin. When such various glass fiber treatment agents are appropriately selected and used according to the type of resin and glass fiber used, the glass fiber reinforcement material has good physical properties.

The glass fiber is included in an amount of 10 to 150 parts by weight, preferably 20 to 110 parts by weight, based on 100 parts by weight of the base resin. When the glass fiber is included in the above range, the bending strength and heat resistance of the glass fiber reinforced polyester resin composition are improved, and excellent flowability can be ensured to have excellent moldability. 　

(C) a polymer containing an epoxy group

The polymer according to the embodiment of the present invention includes an epoxy group, and the epoxy group reacts with the carboxylic acid and the alcohol located at the terminal of the polyester resin so that the polyester resin is present at the side of the polymer. At this time, the length range of the side branch of the polymer containing the epoxy group is not limited, and may be a very short length. Polyester present on the side of the polymer containing such an epoxy group is increased bond with the glass fiber to improve the mechanical strength, such as bending strength, tensile strength.

The polymer may include an ethylene resin, a styrene resin, and the like, but is not limited thereto. Polyethylene etc. are mentioned as said ethylene resin, A styrene-acryl copolymer, a styrene-acrylonitrile copolymer, ethylene- styrene copolymer etc. are mentioned as said styrene resin.

According to one embodiment of the present invention, in consideration of the relationship between the epoxy group equivalent contained in the polymer and the content of the polymer and the polyester containing the epoxy group to provide a Y value of the following formula (1).

[Equation 1]

Y = [Epoxy Group Equivalent in Polymer] × [Content of Polymer Containing Epoxy Group] ÷ [Content of Polyester Resin]

In Equation 1, the content units of the polymer and the polyester including the epoxy group are based on the total amount of the base resin 100.

In one embodiment of the present invention, Y value according to Equation 1 is preferably 0.3 to 2 g / eq. When the Y value is within the above range, by using a polymer containing an epoxy group in an appropriate content, it is possible to improve mechanical properties without a great decrease in flowability, and improve flowability to obtain excellent moldability.

The polymer containing the epoxy group is included in 0.1 to 5 parts by weight based on 100 parts by weight of the base resin, when the polymer containing the epoxy group is included in the above range can ensure excellent mechanical strength and moldability.

Glass fiber reinforced polyester-based resin composition according to an embodiment of the present invention may further include an additive.

The additives include antibacterial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, compatibilizers, dyes, inorganic additives, surfactants, coupling agents, plasticizers, impact modifiers, admixtures, colorants, stabilizers, lubricants, antistatic agents, pigments, flame retardants. , Weathering agents, colorants, sunscreens, fillers, nucleating agents, adhesion aids, pressure-sensitive adhesives and mixtures thereof may be used, but is not necessarily limited thereto.

The additive may be appropriately included within the range of not impairing the physical properties of the glass fiber reinforced polyester resin composition.

Glass fiber reinforced polyester-based resin composition according to an embodiment of the present invention can be prepared by a known method. For example, after mixing the components and additives of the present invention described above, it can be melt-extruded in an extruder and produced in pellet form.

According to another embodiment of the present invention, there is provided a molded article manufactured by molding the glass fiber reinforced polyester resin composition of one embodiment of the present invention. The glass fiber reinforced polyester-based resin composition is a molded product in the field requiring excellent mechanical strength, impact strength and fluidity, such as automobiles, machinery parts, electrical and electronic parts, office equipment such as computers, and manufacturing various molded products such as miscellaneous goods. It can be usefully applied to, and in particular can be usefully used as a material for the exterior material, interior material, engine room of the automobile headlamp.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

[Example]

Each component used in the preparation of the glass fiber reinforced polyester-based resin composition according to an embodiment of the present invention is as follows.

(A) Base resin

(A-1) polyester resin

As polybutylene terephthalate, ShinHong DHK002 manufactured by Shinkong Co., Ltd. having an intrinsic viscosity of 0.87 dl / g was used.

(A-2) Mixture of Acrylic Graft Copolymer and Vinyl Copolymer

As the acryl-based graft copolymer, g-ASA, a copolymer in which a polymer of styrene and acrylonitrile was grafted to methyl methacrylate rubber, was used.

As a vinyl copolymer, 0.17 weight part of azobisisobutyronitrile, 0.4 weight part of t-dodecyl mercaptan chain transfer agents, and tricalcium in a mixture of 71.5 weight part of styrene, 28.5 weight part of acrylonitrile, and 120 weight part of deionized water SAN copolymer resin was prepared by suspension polymerization at 75 ° C. for 5 hours by adding 0.5 parts by weight of four states. The copolymer was washed with water, dehydrated and dried to use a powdery SAN copolymer resin.

(B) glass fiber

Owens Corning's CS03-183F product having a length of 3 mm and a diameter of 13 µm was used.

(C) a polymer containing an epoxy group

Daicel Chemical's Celloxide 2021P product having a weight average molecular weight of 6,000 g / mol and an epoxy group equivalent of 280 g / eq was used.

(D) N- (substituted) maleimide copolymer having maleic anhydride

As the N- (substituted) maleimide copolymer having maleic anhydride used as a comparative example, DENKA-IP manufactured by DENKA Corporation was used.

(E) a polymer having carbodiimide

As a polymer having carbodiimide used as a comparative example, a 1: 1 mixture of Stabilizer 9000 and Stabilizer 7000 manufactured by RASCHIG was used.

Examples 1 to 3 and Comparative Examples 1 to 5

The above-mentioned ingredients were mixed to a content as shown in Table 1 below, and prepared into pellets using a L / D = 29, 45 mm diameter twin screw extruder.

[Test Example]

The pellets prepared according to Examples 1 to 3 and Comparative Examples 1 to 5 were dried at 110 ° C. for at least 3 hours, and then injected into a 10 oz injection machine at a molding temperature of 230 ° C. to 300 ° C. and a mold temperature of 60 ° C. to 100 ° C. to prepare a physical specimen. It was. The prepared physical specimens were measured by the following method and the results are shown in Table 1 below.

(1) Flexural strength: measured according to ASTM D790.

(2) Flexural modulus: Measured according to ASTM D790.

(3) Tensile strength: measured according to ASTM D638.

(4) IZOD impact strength: measured according to ASTM D256 (sample thickness 1/4 ").

(5) Fluidity: The fluidity (250 ° C., 10 kg) was measured according to ISO 1133 and expressed as a melt index (MI).

[Table 1]

Example Comparative example One 2 3 One 2 3 4 5 (A)
Basic resin (A-1) polyester resin (% by weight) 73 73 73 73 73 73 73 73 (A-2) Mixture of Acrylic Graft Copolymer and Vinyl Copolymer
(weight%) Acrylic Graft Copolymer 5 5 5 5 5 5 5 5 Vinyl copolymer 22 22 22 22 22 22 22 22 (B) Glass fiber (parts by weight *) 25 25 25 25 25 25 25 25 (C) a polymer containing an epoxy group (parts by weight *) 0.1 0.2 0.5 - 0.05 - - - (D) N- (substituted) maleimide copolymer having maleic anhydride (parts by weight *) - - - - - - - 0.5 (E) A polymer having carbodiimide (parts by weight *) - - - - - 0.3 0.5 - Y ** (g / eq) 0.38 0.77 1.917 - 0.2 - - - Flexural Strength (kgf / cm ² ) 1,430 1,450 1,480 1,300 1,310 1,350 1,370 1,310 Flexural modulus (kgf / cm ² ) 54,000 55,000 56,000 52,000 53,000 53,000 54,000 52,000 Tensile Strength (kgf / cm ² ) 1,050 1,050 1,070 900 990 980 960 950 Impact Strength (kgf? Cm / cm) 5.1 5.3 5.9 4.5 4.9 5.0 5.0 4.8 Fluidity (g / 10min) *** 28 25 21 31 30 20 16 18

* Weight part: (A) The weight part unit based on the total amount 100 of base resin is shown.

** Y = [Epoxy Group Equivalent in Polymer] × [Content of Polymer Containing Epoxy Group] ÷ [Content of Polyester Resin] (The content unit of Polymer and Polyester Resin containing epoxy group is based on Based on the total amount of resin 100)

*** It is not good if the fluidity is 20 g / 10min or less.

Through Table 1, in Examples 1 to 3 according to the present invention has a Y value in the range of 0.3 to 2 g / eq, Comparative Example 1 without using a polymer containing an epoxy group according to an embodiment of the present invention And Comparative Examples 2 to 5 and polymers containing an epoxy group in an amount out of an appropriate range, as well as excellent mechanical strength of flexural strength, flexural modulus and tensile strength, as well as excellent impact strength and fluidity. You can see that the balance is maintained.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (9)

(A) 100 parts by weight of a basic resin comprising (A-1) 50 to 90% by weight of polyester resin and 10 to 50% by weight of a mixture of (A-2) acrylic graft copolymer and vinyl copolymer; (B) 10 to 150 parts by weight of glass fibers; And (C) 0.1 to 0.5 parts by weight of an ethylene resin containing an epoxy group or a styrene resin containing an epoxy group, The acrylic graft copolymer is a copolymer in which a polymer of an aromatic vinyl monomer and an unsaturated nitrile monomer is grafted to an acrylic rubber, The vinyl copolymer is a copolymer consisting of an aromatic vinyl monomer and an unsaturated nitrile monomer, In the following formula 1 Y is a glass fiber reinforced polyester resin composition having a value of 0.3 to 2 g / eq. [Equation 1] Y = [Epoxy Group Equivalent in Polymer Containing Epoxy Group] × [Content of Polymer Containing Epoxy Group] ÷ [Content of Polyester Resin] The method of claim 1, The mixture of the acrylic graft copolymer and the vinyl copolymer (A-2) is made of 2 to 60 wt% of the acrylic graft copolymer and 40 to 98 wt% of the vinyl copolymer. System resin composition. delete The method of claim 1, The polyester resin (A-1) is polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin and these resins are amorphous The glass fiber reinforced polyester resin composition which is an aromatic polyester resin selected from the group which consists of a polyester resin modified by the. delete The method of claim 1, The vinyl copolymer is a glass fiber reinforced polyester resin composition of the aromatic vinyl monomer is a copolymer consisting of 65 to 80% by weight and 20 to 35% by weight of the unsaturated nitrile monomer. The method of claim 1, The glass fiber reinforced polyester resin composition (B) wherein the glass fiber has a diameter of 8 to 20 μm and a length of 1.5 to 8 mm. The method of claim 1, The glass fiber (B) glass fiber reinforced polyester resin composition is used in combination with a fiber selected from the group consisting of carbon fibers, basalt fibers, fibers made from biomass (biomass) and combinations thereof. The molded article manufactured from the glass fiber reinforced polyester-based resin composition of any one of Claims 1, 2, 4, and 6-8.