KR101286149B1

KR101286149B1 - Glass Fiber Reinforced Polyester Resin Composition With Color Stability at High Temperature

Info

Publication number: KR101286149B1
Application number: KR1020100102549A
Authority: KR
Inventors: 김혜영; 하두한; 허진영
Original assignee: 제일모직주식회사
Priority date: 2010-10-20
Filing date: 2010-10-20
Publication date: 2013-07-15
Also published as: CN102453312A; KR20120041003A; CN102453312B

Abstract

The glass fiber reinforced polyester resin composition according to the present invention comprises (A) polybutylene terephthalate (PBT), (B) polyethylene terephthalate (PET), (C) glass fiber, and (D) hindered phenolic compound, It includes a heat stabilizer composed of phosphite and phosphonite, and is excellent in color stability, glossiness, and heat resistance at high temperature for a long time.

Description

Glass Fiber Reinforced Polyester Resin Composition With Color Stability at High Temperature}

The present invention relates to a glass fiber reinforced polyester resin composition. More specifically, the present invention relates to a glass fiber reinforced polyester resin composition capable of preventing discoloration at high temperatures over a long period of time.

In general, polyester resins have good chemical resistance and are widely applied to a wide range of fields including oven handles and automotive exterior materials, and glass fibers are used together to supplement mechanical or thermal properties.

On the other hand, glass fiber reinforced polyester resins have excellent effects on properties such as surface hardness, solvent resistance, impact strength, stiffness, heat resistance, appearance, colorability, etc. The problem that gloss is degraded occurs.

In particular, the above problem occurs more seriously in the case of a polyester resin using a white or light color dye, and the polyester resin is applied to an apparatus exposed to heat such as an oven handle, a toaster, a dryer, a hair styling tool, an iron, and the like. It is a limiting factor.

On the other hand, additives such as UV stabilizers, pigments, dyes, minerals, lubricants, plasticizers, antioxidants, etc. may help to maintain the mechanical properties of the polyester, but is insufficient to solve the above problems.

In order to solve the problem of discoloration at high temperature, US Patent No. 6,187,848 proposes a reinforced polyester molding composition in which a stabilizer composed of phosphate, thioester and phosphonite is added to glass fiber reinforced polyester. However, the molding composition disclosed in this document still suffers from the problem of discoloration at high temperatures, which leads to the problem that the molding composition cannot be applied to electronic products and home appliances in which a bright appearance is important for a long time. The molding composition does not solve the problem of deterioration of glossiness at a high temperature of the polyester resin.

Accordingly, the present inventors have come to invent a glass fiber-reinforced polyester resin composition excellent in color stability and gloss at high temperature over a long period of time as well as chemical and mechanical properties.

An object of the present invention is to provide a glass fiber reinforced polyester resin composition excellent in color stability at high temperature over a long period of time as well as chemical resistance and mechanical properties.

Another object of the present invention is to provide a glass fiber-reinforced polyester resin composition which is excellent in color stability at high temperature as well as glossiness at high temperature over a long period of time.

Still another object of the present invention is to provide a glass fiber reinforced polyester resin composition having excellent heat resistance as well as color stability and gloss at high temperature.

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

The glass fiber reinforced polyester resin composition according to the present invention comprises (A) polybutylene terephthalate (PBT), (B) polyethylene terephthalate (PET), (C) glass fiber, and (D) hindered phenolic compound, Thermal stabilizers consisting of phosphites and phosphonites.

In one embodiment of the present invention, the glass fiber reinforced polyester resin composition (A) 40 to 60 parts by weight of polybutylene terephthalate (PBT), (B) 25 to 45 parts by weight of polyethylene terephthalate (PET), ( C) 10 to 30 parts by weight of glass fiber, and (D) 0.1 to 5 parts by weight of a heat stabilizer consisting of a hindered phenolic compound, phosphite and phosphonite.

Hereinafter, the present invention will be described in detail.

The glass fiber-reinforced polyester resin composition according to the present invention is excellent not only in chemical resistance and mechanical properties, but also in color stability at high temperatures for a long time, glossiness and heat resistance at high temperatures for a long time.

(A) Polybutylene Terephthalate (PBT)

In one embodiment of the present invention, as the polybutylene terephthalate, polybutylene terephthalate condensation polymerization of 1,4-butanediol and terephthalic acid or dimethyl terephthalate by direct esterification or transesterification Can be used.

In one embodiment of the present invention, in order to increase the impact strength of the glass fiber reinforced polyester resin composition, the polybutylene terephthalate is polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG) , Copolymers copolymerized with impact improving compounds such as aliphatic polyesters and aliphatic polyamides, or modified polybutylene terephthalates obtained by mixing the polybutylene terephthalate with the impact improving compound may be used.

In one embodiment of the present invention, the intrinsic viscosity [η] of the polybutylene terephthalate measured according to ASTM D2857 is preferably 0.36 to 1.60 dl / g, more preferably 0.52 to 1.25 dl / g. When the intrinsic viscosity of the polybutylene terephthalate has the above range, a glass fiber-reinforced polyester resin composition having excellent balance of mechanical properties and moldability can be obtained.

In one embodiment of the present invention, the polybutylene terephthalate may be included in 40 to 60 parts by weight of 100 parts by weight of the total glass fiber reinforced polyester resin composition. When the polybutylene terephthalate is included in the above range, it is possible to secure a glass fiber reinforced polyester resin composition having excellent balance of chemical resistance and mechanical properties.

(B) polyethylene terephthalate (PET)

In one embodiment of the present invention, as the polyethylene terephthalate, a linear polyethylene feterephthalate prepared by condensation polymerization of terephthalic acid and ethylene glycol may be used.

In one embodiment of the present invention, as the polyethylene terephthalate, a polyethylene terephthalate glycol resin obtained by substituting 1,4-cyclohexane dimethanol for a part of the ethylene glycol component of the polyethylene terephthalate may be used. . In this case, the 1,4-cyclohexane dimethanol may be included in 3 to 48 mol%, preferably 5 to 20 mol% with respect to the ethylene glycol component. When the 1,4-cyclohexane dimethanol is included in the above range, it is possible to ensure a glass fiber reinforced polyester resin composition excellent in the balance of surface smoothness and heat resistance.

In one embodiment of the present invention, the intrinsic viscosity [η] of the polyethylene terephthalate measured according to ASTM D2857 is preferably 0.5 to 1 dl / g. When the intrinsic viscosity of the polyethylene terephthalate has the above range, a glass fiber-reinforced polyester resin composition having excellent balance of mechanical properties and moldability can be secured.

In one embodiment of the present invention, the polyethylene terephthalate is included in 20 to 45 parts by weight of 100 parts by weight of the total glass fiber reinforced polyester resin composition. When the polyethylene terephthalate is included in 25 parts by weight or less, the color stability and gloss at high temperature of the glass fiber-reinforced polyester resin composition is lowered, and when included in excess of 45 parts by weight may be lowered in heat resistance. .

(C) Glass Fiber

In one embodiment of the present invention, the diameter of the glass fiber is 8 to 20 ㎛, the length is 2.5 to 6 mm. In addition, the cross section of the glass fiber may have a shape such as circular, rectangular, elliptical, dumbbell, rhombus.

In one embodiment of the present invention, the glass fiber may be used together with other inorganic fibers, the inorganic fiber is at least one selected from the group consisting of carbon fibers, basalt fibers, and natural fibers such as hemp and hemp.

In one embodiment of the present invention, the glass fiber may be treated by a glass fiber treatment agent (sizing compositions) during the fabrication or post-treatment process, the glass fiber treatment agent is a lubricant, coupling agent, surfactant, etc. .

The lubricant is mainly used to form a good strand in the production of glass fibers, the coupling agent to enable good adhesion between the glass fiber and the polyester resin, considering the type of the polyester resin and glass fiber as appropriate When selected and used, it can impart excellent physical properties to the glass fiber reinforced polyester resin composition.

As the method of using the coupling agent, there is a method of treating the glass fiber directly, adding it to an organic matrix, and the like, and in order to sufficiently exhibit the performance of the coupling agent, its content should be appropriately selected.

Examples of the coupling agent include amines; Acrylic; And γ-aminopropyltriethoxy silane, γ-amino propyltrimethoxy silane, N- (beta-aminoethyl) γ-amino propyltriethoxy silane (N -(β-amino ethyl) γ-amino propyltriethoxy silane, γ-methacryloxy propyltriethoxy silane, γ-methacryloxy propyltrimethoxy silane, γ-glycidoxy propyltriethoxy silane, β (3,4-epoxyethyl) γ-amino propyltrimethoxy silane (β (3,4-epoxyethyl) γ-amino propyltrimethoxy silane) There exist silane systems, and it is preferable to use the said silane coupling agent.

In one embodiment of the present invention, the glass fiber may be included in 10 to 30 parts by weight of 100 parts by weight of the total glass fiber reinforced polyester resin composition, excellent mechanical properties can be achieved when the glass fiber is included in the above range have.

(D) heat stabilizer

The heat stabilizer according to the present invention consists of a hindered phenolic compound, phosphite and phosphonite, and provides the glass fiber-reinforced polyester resin composition with a color stability effect at high temperature for a long time.

In one embodiment of the present invention, the heat stabilizer may be included in 0.1 to 5 parts by weight of 100 parts by weight of the total glass fiber reinforced polyester resin composition, it is preferably included in 0.6 to 2 parts by weight. When the heat stabilizer is included in the glass fiber reinforced polyester resin composition in an amount of 5 parts by weight or more, glossiness at a high temperature may be lowered.

(D-1) Hindered Phenolic Compound

In one embodiment of the present invention, a general commercial product may be used as the hindered phenolic compound. Examples of the hindered phenolic compound include octadiyl-3- (4-hydroxy-3,5-dibutylbutylphenyl) propionate (Octadeeyl-3- (4-hydroxy-3,5-ditert-butylphenyl) propionate), tetrabis [methylene-3- (3,5-dibutylbutyl-4-hydroxyphenyl) propionate] methane (Tetrabis [methylene-3- (3,5-di-tert-butyl-4-) hydroxyphenyl) propionate] methane), 1,3,5-tri-methyl-2,4,6, -tri (3,5-dibutylbutyl-4-hydroxybenzyl) benzene (1,3,5-Tri- methyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene), pentaerythritol tetrakis (3- (3,5-dibutylbutyl-4-hydroxyphenyl) prop Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), and pentaerythritol tetrakis (3- (3,5-dibutylbutyl-4-hydroxyphenyl) Preference is given to using propionate.

(D-2) phosphite

In one embodiment of the present invention, as the phosphite, triphenyl phosphite (Triphenyl phosphite), tris (nonyl phenyl) phosphite (Tris (nonyl phenyl) phosphite), triisodecyl phosphite (Triisodecyl phosphite), diphenyl -Iso-octyl-phosphite, bis (2,6-dibutylbutyl-4-methylphenyl) pentaerythritol diphosphite (Bis (2,6-di-tert-butyl-4- methylphenyl) pentaerythritol diphosphite), tris (2,4-di-tert-butylphenyl) phosphite and the like, tris (2,4-dibutylbutyl) phosphite It is preferred that the pit be used.

(D-3) phosphonite

In one embodiment of the present invention, a compound represented by the following formula (1) may be used as the phosphonite.

[Formula 1]

In Formula 1, R ₁ or R ₂ are each independently alkyl, aryl, alkylaryl, C ₁ -C ₃₀ alkyl or C ₆ -C ₃₀ aryl, Ar is a phenyl, naphthyl, bipetyl, terphenyl, etc. It is an aryl group.

In one embodiment of the present invention, as the phosphonite, a compound represented by the following Formula 2 in which two phosphonites are bonded to one aryl group may be used.

[Formula 2]

In Formula 2, R ₁ , R ₂ , R ₃ or R ₄ are each independently alkyl, aryl, alkylaryl, C ₁ -C ₃₀ alkyl or C ₆ -C ₃₀ aryl, Ar is phenyl, naphthyl, bi Aryl groups such as petyl and terphenyl.

In one embodiment of the present invention, in Formula 2 R ₁ , R ₂ , R ₃ and R ₄ are alkyl-substituted phenol, Ar may be derived from biphenyl, as the phosphonite, tetrakis ( Preference is given to using 2,4-di-tertiary-butylphenyl) 4,4'-biphenylene diphosphonite.

The glass fiber reinforced polyester resin composition according to the present invention may be prepared by a method known in the art. For example, the glass fiber reinforced polyester resin composition may be prepared in the form of pellets by melt extruding a mixture of each component and other additives in an extruder, and the pellets may be used in injection and extrusion molded articles. Can be.

In one embodiment of the present invention, the pellet is injected at a temperature of 250 to 280 ℃, the mold temperature is preferably in the range of 80 ℃ to 100 ℃ ℃. When the mold temperature is 80 ° C. or less, the glossiness may be lowered, and when the mold temperature is 100 ° C. or more, the pellet may stick to the mold and the mold release property may be reduced.

The invention will be further illustrated by the following examples, which are used only for the purpose of illustrating the invention and are not intended to limit the scope of the invention.

Example

In one embodiment of the present invention, each component used in the preparation of the glass fiber reinforced polyester resin composition is as follows.

(A) Polybutylene Terephthalate (PBT)

Shinite K006 from SHINKONG with a viscosity of 1.10 ± 0.02 (dl / g) was used.

(B) polyethylene terephthalate (PET)

SK Chemical's SKYPET 1100 having a viscosity of 0.77 ± 0.02 (dl / g) was used.

(C) glass fiber

A chop strand glass fiber having a diameter of 13 μm, a length of 3 mm and coated with an epoxy-based material was used.

(D-1) Hindered Phenolic Compound

Pentaerythritol tetrakis (3- (3,5-dibutylbutyl-4-hydroxyphenyl) propionate), IRGANOX 1010 from CIBA GEIGY, was used.

(D-2) phosphite

Tris (2,4-dibutylbutylphenyl) phosphite, IRGAFOS 168 from CIBA GEIGY, was used.

(D-3) phosphonite

Tetrakis (2,4-dibutylbutylphenyl) [1,1-biphenyl] -4,4'diylbisphosphonite, IRGAFOS P-EPQ from CIBA GEIGY, was used.

(D-4) phosphate

Young Soda Phosphate (NaH ₂ PO ₄ ) from Youngjin Chemical was used.

(D-5) Thioester

Tetrakis (methylene-3-dodecylthiopropionate) methane, which is ADK STAB AO-412S from ASAHI DENKA, was used.

Etc

Sachtolith GRADE HD-L was used as a ZnS-based pigment to measure color change, and HI-WAX 400P of MITSUI Petrochemical Co., Ltd. was used as a lubricant.

Examples 1-8

After mixing each of the components according to the contents shown in Table 1, the mixture was fed at a rate of 60 kg / hr, the screw was 250 rpm, the diameter was 45 mm, and the twin screw extruder with L / D = 36. Extruded in the form of pellets. The prepared pellets were dried at 100 ° C. for at least 4 hours, and then injected at a temperature of 80 ° C. to prepare 2.5 mm × 50 mm × 90 mm specimens. The physical properties of the prepared specimens were measured by the following method.

(1) Color stability: The color chips were placed in a hot air drying oven at 150 ° C., taken out after 4 days and 12 days, and cooled to room temperature. Then, color change was measured with a CM-3600 colorimeter manufactured by MINOLTA.

(2) Glossiness: Color chip specimens were placed in a hot air drying oven at 150 ° C., after 4 days and after 12 days, and cooled to room temperature. .

(3) Heat resistance (HDT): Measured according to ASTM D648 under a load of 18.56 kgf / cm ² .

　
Example One 2 3 4 5 6 7 8 (A) PBT 43 51 54 57 57 57 50 48 (B) PET 42 34 31 28 28 28 33 32 (C) GF 15 15 15 15 15 15 17 20 (D-1) Hindered phenolic antioxidant 0.1 0.1 0.1 0.1 0.1 0.15 0.1 0.1 (D-2) phosphite 0.2 0.2 0.2 0.2 0.2 0.15 0.2 0.2 (D-3) phosphonite 0.3 0.3 0.3 0.3 0.5 0.3 0.3 0.3 ZnS 2 2 2 2 2 2 2 2 △ E (150 ℃, 4days) 0.35 0.46 0.50 0.58 0.68 0.63 0.56 0.59 △ E (150 ℃, 12days) 0.45 0.52 0.66 0.67 0.76 0.69 0.65 0.68 △ Gloss (150 ℃, 4days) -2 -2 -4 -11 -8 -10 -9 -11 △ Gloss (150 ℃, 12days) -7 -8 -8 -19 -12 -15 -15 -17 Heat resistance 193.2 197.9 198.2 198.7 198.7 198.7 201.2 205.8

In Examples 1 to 8 prepared according to Table 1, ΔE values after 4 days are all 0.68 or less, and ΔGloss values are all −11 or more, ΔE values after 12 days are all 0.76 or less and ΔGloss value is They are all above -19 and the heat distortion temperature is above 193.2 ℃, which shows excellent color stability, glossiness and heat resistance at high temperatures. .

Comparative Example 1-6

Specimens were prepared in the same manner as in the preparation method of Example, except that the components were mixed in the amounts shown in Table 2 below, and physical properties of the prepared specimens were measured in the same manner as in Example.

Comparative Example One 2 3 4 5 6 (A) PBT 73 65 51 51 73 51 (B) PET 12 20 34 34 12 34 (C) GF 15 15 15 15 15 15 (D-1) Hindered phenolic antioxidant 0.1 0.1 0.3 0.3 - - (D-2) phosphite 0.2 0.2 - - - - (D-3) phosphonite 0.3 0.3 0.3 - 0.15 - (D-4) phosphate - - - 0.3 0.6 - (D-5) thioester - - - - 0.3 - ZnS 2 2 2 2 2 2 △ E (150 ℃, 4days) 0.40 0.21 0.76 0.62 0.69 0.65 △ E (150 ℃, 12days) 1.94 1.06 1.41 1.11 2.85 1.22 △ Gloss (150 ℃, 4days) -44 -41 -3 -7 -44 -One △ Gloss (150 ℃, 12days) -49 -47 -7 -10 -49 -5 Heat resistance 203.2 202.0 198.7 198.7 203.2 197.9

Among Comparative Examples 1 to 6 prepared according to Table 2, Comparative Examples 1 and 2 show that both the color stability and gloss at high temperatures were reduced by using 25 parts by weight of (B) polyethylene terephthalate. . Comparative Example 3 shows that the color stability at high temperature was lowered using only the hindered phenol compound and phosphonite as the heat stabilizer.

Comparative Example 4 shows that the color stability at high temperature was lowered using only the hindered phenol compound and phosphate as the heat stabilizer. Comparative Example 5 shows that both color stability and gloss at high temperatures were deteriorated by using 25 parts by weight or less of (B) polyethylene terephthalate and using phosphonite, phosphate, and thioester as heat stabilizers. Comparative Example 6 shows that the color stability at high temperature was lowered because no heat stabilizer was used.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

(A) 40 to 60 parts by weight of polybutylene terephthalate (PBT);
(B) 25 to 45 parts by weight of polyethylene terephthalate (PET);
(C) 10 to 30 parts by weight of glass fibers; And
(D) 0.1 to 5 parts by weight of a heat stabilizer consisting of a hindered phenolic compound, phosphite and phosphonite;
Glass fiber reinforced polyester resin composition comprising a.

delete

According to claim 1, wherein the (A) polybutylene terephthalate (PBT) is (A) polybutylene terephthalate (PBT) and polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol ( PPG), a copolymer of an impact improvement compound composed of an aliphatic polyester, an aliphatic polyamide, or a mixture thereof, or a modified polybutyl (A) polybutylene terephthalate (PBT) mixed with the impact improvement compound It is a terephthalate lene glass fiber reinforced polyester resin composition.

The glass fiber-reinforced polyester resin composition according to claim 1, wherein the intrinsic viscosity [?] Of the (A) polybutylene terephthalate (PBT) measured according to ASTM D2857 is 0.36 to 1.60 dl / g.

The glass fiber-reinforced polyester resin composition according to claim 1, wherein the polyethylene terephthalate (PET) is a polyethylene terephthalate glycol resin.

The glass fiber-reinforced polyester resin composition according to claim 1, wherein the intrinsic viscosity [?] Of the polyethylene terephthalate (PET) (B) measured according to ASTM D2857 is 0.5 to 1 dl / g.

The compound according to claim 1, wherein the hindered phenolic compound is octadil-3- (4-hydroxy-3,5-dibutylbutylphenyl) propionate, tetrabis [methylene-3- (3,5-diter). Sherylbutyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tri-methyl-2,4,6, -tri (3,5-dibutylbutyl-4-hydroxybenzyl) benzene, And pentaerythritol tetrakis (3- (3,5-dibutylbutyl-4-hydroxyphenyl) propionate; and a glass fiber reinforced polyester resin composition.

The method of claim 1, wherein the phosphite is triphenyl phosphite, tris (nonyl phenyl) phosphite, triisodecyl phosphite, diphenyl-iso-octyl-phosphite, bis (2,6-dibutylbutyl-4) -Methylphenyl) pentaerythritol diphosphite, and tris (2,4-dibutylbutylphenyl) phosphite. The glass fiber reinforced polyester resin composition characterized by the above-mentioned.

The glass fiber reinforced polyester resin composition according to claim 1, wherein the phosphonite is a compound represented by the following Chemical Formula 2:

(2)

In Formula 2, R ₁ , R ₂ , R ₃ or R ₄ are each independently alkyl, aryl, or alkylaryl, Ar is an aryl group selected from the group consisting of phenyl, naphthyl, bifetyl, and terphenyl.