KR102194551B1 - Polyarylate resin composition having enhanced flowability - Google Patents

Abstract

Disclosed is a high heat-resistant polyarylate resin composition having improved fluidity and excellent fluidity while preventing a decrease in heat resistance and mechanical properties of the polyarylate resin. The present invention is a polyarylate resin comprising 0.01 to 5 parts by weight of a styrene-acrylate copolymer based on a total of 100 parts by weight of the resin containing 50 to 99% by weight of the polyarylate and 1 to 50% by weight of the polycarbonate-siloxane copolymer The composition is provided.

Description

Polyarylate resin composition having enhanced flowability

The present invention relates to a polyarylate resin composition, and more particularly, to a high heat-resistant polyarylate resin composition with improved fluidity.

Polyarylate resin is a wholly aromatic polyester resin composed of a polycondensate of dihydric phenol and aromatic polycarboxylic acid and is classified as an engineering plastic. It has excellent heat resistance, cold resistance, transparency, weather resistance, and chemical resistance. It is used in the medical field.

However, the polyarylate resin has a problem of poor processability due to insufficient fluidity during molding due to its high melt viscosity. In order to improve the processability, there is known a method of improving fluidity by preparing other polyester resins and alloys.

Japanese Laid-Open Patent No. 2011-074095 discloses a resin composition with improved fluidity, including polyarylate, polycarbonate, and cycloolefin-based resin, but has not secured sufficient fluidity required for the recent trend of miniaturization of products. There is no suggestion for a solution to the decrease in heat resistance.

Japanese Patent Laid-Open No. 2011-074163 discloses a resin composition with improved fluidity, including polyarylate, polycarbonate, and polyamide, but also has not secured sufficient fluidity required for the recent trend of miniaturization of products, and heat resistance. It does not present a solution to the decline.

An object of the present invention is to provide a high heat-resistant polyarylate resin composition having improved fluidity and excellent fluidity while preventing a decrease in heat resistance and mechanical properties of the polyarylate resin.

In order to solve the above problems, the present invention is based on a total of 100 parts by weight of a resin containing 50 to 99% by weight of polyarylate and 1 to 50% by weight of a polycarbonate-siloxane copolymer, 0.01 to 5 weight of a styrene-acrylate copolymer It provides a polyarylate resin composition comprising a part.

In addition, the polycarbonate-siloxane copolymer is a block copolymer, a polyarylate resin composition comprising 40 to 80% by weight of the carbonate repeating unit and 20 to 60% by weight of the siloxane repeating unit. to provide.

In addition, the styrene-acrylate copolymer provides a polyarylate resin composition, characterized in that the styrene-(meth)acrylate copolymer.

In addition, the polyarylate resin composition has a flow index (ASTM D1238, 330°C, 2.16 kgf) of 15 g/10min or more, a heat deflection temperature (ASTM D648, 18.6 kgf) of 135°C or more, and room temperature IZOD impact strength ( ASTM D256, 23°C) is 25 kgf·cm/cm or more, and low-temperature IZOD impact strength (ASTM D256, -30°C) is 20 kgf·cm/cm or more.

According to the present invention, a styrene-acrylate copolymer is added to improve the fluidity of the polyarylate resin, and a polycarbonate-siloxane copolymer is added to minimize the deterioration of impact resistance and heat resistance to improve the heat resistance and mechanical properties of the polyarylate resin. It is possible to provide a high heat-resistant polyarylate resin composition having improved fluidity and excellent fluidity while preventing a decrease in the.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components, unless otherwise stated.

In the case of the method of improving the flowability by manufacturing alloys with other polyester-based resins in improving the flowability problem due to the high melt viscosity of the polyarylate resin, the present inventors have not secured sufficient flowability required by the recent trend of miniaturization of products In addition, as a result of facing the situation where there is no solution to the problem of lowering heat resistance and continuing research to solve it, surprisingly, styrene-acrylate copolymer and polycarbonate-siloxane copolymer in polyarylate resin It was discovered that even by blending the polyarylate resin, excellent fluidity can be imparted while preventing deterioration of the heat resistance and mechanical properties of the polyarylate resin, and the present invention was reached.

Accordingly, the present invention is a polyarylate comprising 0.01 to 5 parts by weight of a styrene-acrylate copolymer based on a total of 100 parts by weight of a resin comprising 50 to 99% by weight of polyarylate and 1 to 50% by weight of a polycarbonate-siloxane copolymer A resin composition is disclosed.

Hereinafter, each component of the polyarylate resin composition according to the present invention will be described in more detail.

(A) polyarylate

The polyarylate used in the present invention is an aromatic polyester resin composed of an aromatic dicarboxylic acid residue unit and a bisphenol residue unit.

The preparation of the polyarylate is not particularly limited, and known methods such as interfacial polymerization and melt polymerization may be used.

A precursor for introducing the aromatic dicarboxylic acid residue may include terephthalic acid and isophthalic acid. In the present invention, a polyarylate resin composition obtained by mixing both is preferable from the viewpoint of melt processability and mechanical properties. The mixing ratio of terephthalic acid and isophthalic acid can be arbitrarily selected, but the molar fraction is preferably in the range of 90:10 to 10:90, more preferably 70:30 to 30:70. When the mole fraction of terephthalic acid is out of the above range, it may be difficult to obtain a sufficient degree of polymerization during polymerization by an interfacial polymerization method.

Precursors for introducing the bisphenol moiety are, for example, 2,2-bis(4-hydroxyphenyl)propane, 2.2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4 -Hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenylsulfone, 4,4 '-Dihydroxydiphenylether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylmethane, 1,1- Bis(4-hydroxyphenyl)cyclohexane, and the like, and the above compounds may be used alone or in combination of two or more.

In the present invention, the content of the polyarylate may be 50 to 99% by weight, preferably 70 to 90% by weight. When the polyarylate content is less than 50% by weight, heat resistance is rapidly deteriorated, and when it exceeds 99% by weight, the effect of improving fluidity is insignificant.

Meanwhile, in the present invention, the polyarylate has a number average molecular weight (Mn) of 1,000 to 100,000 g/mol, preferably 5,000 to 30,000 g/mol, and a weight average molecular weight (Mw) of 10,000 to 100,000 g/mol, preferably May be used in the form of a powder of 20,000 ~ 50,000 g / ㏖.

(B) Polycarbonate-siloxane copolymer

The polycarbonate-siloxane copolymer used in the present invention is used to minimize deterioration in impact resistance and heat resistance of the polyarylate, and includes a carbonate block and a siloxane block as a block copolymer.

The carbonate block may be prepared by reacting a diphenol compound represented by Formula 1 below with phosgene, a halogen acid ester, a carbonate ester, or a combination thereof.

[Formula 1]

In Formula 1, A is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 30 carbon atoms, or a heteroarylene group having 2 to 30 carbon atoms , Nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements may be included in the structure, and R ₁ and R ₂ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms Is an aryl group, and n ₁ and n ₂ are each an integer of 0 to 4.

Here, as the diphenol compound represented by Formula 1, two or more types may be combined to form a repeating unit of the carbonate block.

Specific examples of the diphenol compound include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also referred to as'bisphenol-A'), 2 ,4-bis(4-hydroxyphenyl)-2-methylbutane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3- Chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl) ) Ether and the like, preferably 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or 1,1-bis (4-hydroxyphenyl)cyclohexane can be used.

In addition, the siloxane block may include a structural unit represented by Formula 2 below.

[Formula 2]

In Formula 2, R ³ and R ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and 2≦m<10,000.

In the present invention, the composition of the polycarbonate-siloxane copolymer may include 1 to 99% by weight of the carbonate repeating unit and 1 to 99% by weight of the siloxane repeating unit, but preferably, the carbonate repeating unit is 40 In the case of including ~80% by weight and 20-60% by weight of the siloxane repeating unit, excellent impact resistance and heat resistance of the final polyarylate resin composition may be implemented. That is, the polycarbonate-siloxane copolymer reinforces the impact resistance and heat resistance of the polyarylate resin composition, which is degraded by the use of a styrene-acrylate copolymer described below.

In the present invention, the content of the polycarbonate-siloxane copolymer may be 1 to 50% by weight, and preferably 10 to 30% by weight. In the case of the polyarylate resin composition in which the polycarbonate-siloxane copolymer is included within the above content range, the impact resistance and heat resistance are minimized and the fluidity is improved.

Meanwhile, in the present invention, the polycarbonate-siloxane copolymer may have a melt index (300°C, 1.2kg load) of 5 to 30 g/10 min, preferably 10 to 20 g/10 min.

(C) Styrene-acrylate copolymer

The styrene-acrylate copolymer used in the present invention is used to improve the fluidity of the polyarylate, and one or more comonomers and vinylidene aromatic monomers having a functional group such as carboxylic acid and/or carboxylic acid derivative It may be a polymer of vinylidene aromatic monomers such as a copolymer of.

Preferably the styrene-acrylate copolymer may be a copolymer of a vinyl aromatic monomer and a (meth)acrylate, more preferably the vinyl aromatic monomer is unsubstituted styrene, or methyl, ethyl and propyl, More preferably, it may be styrene substituted with one or more groups selected from the group consisting of methyl or ethyl; The alcohol moiety in the (meth)acrylate is one derived from a C1-C10 alkyl alcohol, preferably a C1-C4 alkyl alcohol, more preferably methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol or 2-ethyl hexyl alcohol. I can.

In a preferred embodiment of the present invention, the styrene-acrylate copolymer may be a styrene-(meth)acrylate copolymer.

In the present invention, when the styrene-acrylate copolymer is a copolymer of a vinyl aromatic monomer and (meth)acrylate, the molar ratio of the vinyl aromatic monomer and (meth)acrylate may be 1:100-100:1, It may be preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and most preferably 1:1.5 to 1.5:1.

In the present invention, the content of the styrene-acrylate copolymer is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably, based on 100 parts by weight of the polyarylate and polycarbonate-siloxane copolymer. It may be 0.5 to 3 parts by weight. In the case of the polyarylate resin composition in which the styrene-acrylate copolymer is contained within the above content range, the degree of improvement in fluidity is maximized.

Meanwhile, in the present invention, the styrene-acrylate copolymer has a weight average molecular weight (Mw) of 1,000 to 50,000 g/mol, preferably 2,000 to 10,000 g/mol, and a glass transition temperature (Tg) of 40 to 70°C, Preferably, those of 50 to 60 ℃ can be used.

In addition to the above-described main components, the polyarylate resin composition according to the present invention may further include inorganic fillers and functional additives suitable for the intended use or effect. For example, carbon fibers, talc, flame retardants, light stabilizers, lubricants, toning agents, lubricants, ultraviolet stabilizers, antioxidants, coupling reinforcing agents, heat stabilizers, plasticizers, impact modifiers, etc. can be added and applied for various purposes.

The polyarylate resin composition according to the present invention maintains excellent fluidity while reducing heat resistance and mechanical properties. Specifically, the polyarylate resin composition according to the present invention has a flow index (ASTM D1238, 330°C, 2.16 kgf) of 15 g/10min or more, a heat deflection temperature (ASTM D648, 18.6 kgf) of 135°C or more, and room temperature The IZOD impact strength (ASTM D256, 23℃) may be 25 kgf·cm/cm or more, and the low-temperature IZOD impact strength (ASTM D256, -30℃) may be 20 kgf·cm/cm or more, preferably the flow index (ASTM D1238, 330℃, 2.16 kgf) is 20 g/10min or more, heat deflection temperature (ASTM D648, 18.6 kgf) is 140℃ or more, and room temperature IZOD impact strength (ASTM D256, 23℃) is 30 kgf·cm/cm Or more, and the low-temperature IZOD impact strength (ASTM D256, -30°C) may be 23 kgf·cm/cm or more.

Hereinafter, a specific example according to the present invention will be described.

First, specifications of the components including the polyarylate resin used in Examples and Comparative Examples of the present invention are as follows.

(A) polyarylate

A polyarylate (PAR-RK, UNITIKA) in the form of a low molecular weight powder having a number average molecular weight (Mn) of 13,700 g/mol and a weight average molecular weight (Mw) of 31,000 g/mol was used.

(B) Polycarbonate-siloxane copolymer

A polycarbonate-siloxane copolymer (EXL-1132, SABIC-carbonate block content 60-70% by weight and siloxane block content 30-40% by weight) having a melt index of 17 g/10min (300°C, 1.2 kg load) was used. .

(B') polycarbonate

A bisphenol-A type polycarbonate (PC-1150, Lotte Chemical) having a melt index of 15 g/10min (300°C, 1.2 kg load) was used.

(C) Styrene-acrylate copolymer

Styrene-(meth)acrylate copolymer with a weight average molecular weight of 4,000 g/mol and a glass transition temperature (Tg) of 54°C (John Cryl (registered trademark) ADF-1350, BASF-styrene:meth)acrylate molar ratio = 1:1) was used.

Example 1

(A) 90 parts by weight of polyarylate and 1 part by weight of (C) styrene-acrylate copolymer were mixed with respect to 100 parts by weight of the resin including 10 parts by weight of (B) polycarbonate-siloxane copolymer, and heated to 320°C The thermoplastic resin composition was made into a chip using a twin-screw extruder, dried at 140° C. for 6 hours using a hot air dryer, and then the specimens of Examples and Comparative Examples were injection-molded using a specimen preparation mold.

Examples 2 to 5 and Comparative Examples 1 to 15

In Example 1, a specimen was molded in the same manner as in Example 1, except that components (A) to (C) were adjusted to the contents of Tables 1 and 2 below.

Test example

The flow index, thermal deformation temperature, and IZOD impact strength were measured according to the following method for the specimens according to the Examples and Comparative Examples, and the results are shown in Tables 3 and 4 below.

(1) Flow Index (MFR)

The flow index was measured by ASTM D1238. The measurement temperature was 330°C, a 2.16 kg weight was used, and the mass of the resin flowing out for 10 minutes was measured.

(2) Heat deflection temperature

Measured according to ASTM D648 at a load of 18.6 kgf.

(3) IZOD impact strength

According to ASTM D256, at 23°C and -30°C temperature conditions, 6J of energy was applied to the notched 3T specimen by impacting the notched surface with a hammer, and the impact strength was calculated by measuring the angle of the hammer after the impact.

Referring to Tables 3 and 4, according to the present invention, (A) polyarylate, (B) polycarbonate-siloxane copolymer, and (C) styrene-acrylate copolymer are included in a specific amount (Examples 1 to 5) The thermal deformation temperature of the polyarylate resin is 137~147℃, the IZOD impact strength at room temperature is 26~35 kgf·cm/cm, and the low-temperature IZOD impact strength is 23~27 kgf·cm/cm. While minimizing the decrease in impact resistance, it can be seen that the flow index is at the level of 16 to 39 g/10min, preferably at the level of 25 to 39 g/10min, and the fluidity is improved.

On the other hand, (A) in the case of using a general polycarbonate resin (B') for the polyarylate resin (Comparative Examples 2 to 7), even if the fluidity is improved through the (C) styrene-acrylate copolymer (Comparative Example 3, 4, 5 and 7) It can be seen that the low-temperature impact resistance is significantly lowered.

In addition, when only (A) polyarylate and (B) polycarbonate-siloxane copolymer is used and (C) styrene-acrylate copolymer is not added (Comparative Examples 8 to 10), it is difficult to implement sufficient fluidity, However, it can be seen that the fluidity improved as the content of the (B) polycarbonate-siloxane copolymer increased, but the heat resistance and low temperature impact resistance rapidly decreased.

In addition, even if the (C) styrene-acrylate copolymer is added to the (A) polyarylate and (B) polycarbonate-siloxane copolymer, if the content does not reach a certain level (Comparative Example 1), heat resistance and impact resistance are It is excellent, but the fluidity is rapidly lowered, and when it is excessively prescribed (Comparative Examples 12 to 15), the fluidity is improved, but the heat resistance and low-temperature impact strength are sharply decreased, and (A) polyarylate and (B) polycarbonate -In case the siloxane copolymer content ratio is 50:50 (Comparative Example 11), the impact strength decreases rapidly, so that the heat resistance and impact resistance of the polyarylate resin composition are minimized while improving the fluidity (A) It can be seen that an ideal content range of polyarylate, (B) polycarbonate-siloxane copolymer and (C) styrene-acrylate copolymer exists.

The preferred embodiments of the present invention have been described in detail above. The description of the present invention is for illustration only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Accordingly, the scope of the present invention is indicated by the claims to be described later rather than the description of the invention, and all changes or modified forms derived from the meaning, scope and equivalent concepts of the claims are interpreted as being included in the scope of the present invention. Should be.

Claims (4)

Including 0.5 to 3 parts by weight of a styrene-acrylate copolymer based on a total of 100 parts by weight of the resin including 70 to 90% by weight of polyarylate and 10 to 30% by weight of polycarbonate-siloxane copolymer ,
The polycarbonate-siloxane copolymer is a block copolymer, comprising 40 to 80% by weight of the carbonate repeating unit and 20 to 60% by weight of the siloxane repeating unit,
The styrene-acrylate copolymer is a styrene-(meth)acrylate copolymer, and the molar ratio of the styrene and (meth)acrylate is 1:1.5 to 1.5:1. delete The method of claim 1,
The styrene-acrylate copolymer is a polyarylate resin composition, characterized in that the styrene-(meth)acrylate copolymer. The method of claim 1,
The polyarylate resin composition has a flow index (ASTM D1238, 330°C, 2.16 kgf) of 15 g/10min or more, a heat deflection temperature (ASTM D648, 18.6 kgf) of 135°C or more, and room temperature IZOD impact strength (ASTM D256 , 23°C) is 25 kgf·cm/cm or more, and low-temperature IZOD impact strength (ASTM D256, -30°C) is 20 kgf·cm/cm or more.