KR101737013B1 - Copolymer Polyester Resin Composition and Molding Comprising the Same - Google Patents

Abstract

More particularly, the present invention relates to a copolymerized polyester resin composition comprising a polyethylene terephthalate resin and a polyethylene naphthalate resin and having excellent thermal properties, mechanical properties and transparency .

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymerized polyester resin composition,

The present invention relates to a copolymer polyester resin composition and a molded article comprising the same.

Recently, electronic parts such as a computer monitor, a TV frame, a cradle, and a cellular phone housing are manufactured in a transparent housing form. Recently, polycarbonate or polymethylmethacrylate is molded into a resin such as an electronic device to meet such a trend. However, a sufficient degree of mechanical properties are not exhibited in an electronic device component molded with such a resin .

On the other hand, in order to be used for electronic parts and the like as described above, heat resistance and flame retardancy to some degree are required due to heat generated by long-term use of electronic devices. In addition, in order to be used as a TV frame, a stand, etc., mechanical properties are required to withstand loads of electronic devices including TVs and the like.

The present invention provides a copolymer polyester resin composition having excellent thermal and mechanical properties and improved transparency and a molded article produced using the same.

The present invention also provides a molded article comprising the above-mentioned copolymer polyester resin composition.

Accordingly, the present invention provides, as a first preferred embodiment, a polyester resin composition comprising 92.3 to 99.05% by weight of a polyester resin; 0.65 to 6.5% by weight of a phosphorus-containing flame retardant improver represented by the general formula (1); And 0.05 to 1.2% by weight of the scratch resistance improver represented by the general formula (2) or (3).

[Chemical Formula 1]

Wherein R ₅ and R ₆ are each a hydrogen atom or a C ₁ -C ₆ hydroxyalkyl group.

(2)

이고, l, 및 n은 각각 6~20의 정수이고, m은 0또는 1이다.
Here, Q is

, L and n are each an integer of 6 to 20, and m is 0 or 1.

(3)

Here, Q is

이고, l 및 n은 각각 6~20의 정수이고, m은 0또는 1이며, p는 1~5의 정수이다.

And l and n are each an integer of 6 to 20, m is 0 or 1, and p is an integer of 1 to 5.

The polyester resin according to the embodiment may be a copolymer of polyethylene terephthalate (PET) resin and polyethylene naphthalate (PEN) resin; Or a polyethylene naphthalate (PEN) resin.

The copolymer of the polyethylene terephthalate (PET) resin and the polyethylene naphthalate (PEN) resin according to the embodiment may contain PET: PEN in a molar ratio of 1: 0.06 to 1:15.

The flame retardant improver according to the embodiment may be selected from arylphosphinyl-carboxylic acid or derivatives thereof selected from 3-hydroxyphenylphosphinylpropanecarboxylic acid and (2'-hydroxymethyl) -3-hydroxyphenylphosphinylpropane ester Lt; / RTI >

The scratch resistance improver according to this embodiment may be a plant-based fatty acid derivative.

The copolymer polyester resin composition according to this embodiment may further comprise a polyester resin.

And may further include a multifunctional branching agent according to the above embodiment.

The copolymer polyester resin composition according to this embodiment has a transmittance of 85% or more as measured by the UV / Vis method, a flame retardancy as measured by the UL-94 vertical flame retardancy evaluation method is not less than V1, and is measured by a pencil hardness method according to JIS K5401 One surface hardness may be at least HB.

The present invention also provides, as a second preferred embodiment, a molded article comprising the copolymerized polyester resin composition.

The copolymer polyester resin composition according to the present invention is excellent in mechanical properties including thermal properties including flame retardancy and heat resistance and surface hardness and is excellent in transparency and is excellent in the field of molding products requiring cosmetic transparency such as external parts of electronic equipment It is expected that it will be usefully applied to.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a copolymer polyester resin composition having excellent thermal properties, mechanical properties and transparency.

Specifically, the present invention relates to a polyester resin composition comprising 92.3 to 99.05% by weight of a polyester resin; 0.65 to 6.5% by weight of a phosphorus-containing flame retardant improver represented by the general formula (1); And 0.05 to 1.2% by weight of the scratch resistance improver represented by the general formula (2) or (3).

[Chemical Formula 1]

Wherein R ₅ and R ₆ are each a hydrogen atom or a C ₁ -C ₆ hydroxyalkyl group.

(2)

이고, l, 및 n은 각각 6~20의 정수이고, m은 0또는 1이다.
Here, Q is

, L and n are each an integer of 6 to 20, and m is 0 or 1.

(3)

Here, Q is

이고, l 및 n은 각각 6~20의 정수이고, m은 0또는 1이며, p는 1~5의 정수이다.

And l and n are each an integer of 6 to 20, m is 0 or 1, and p is an integer of 1 to 5.

Unless explicitly stated otherwise, the acid component and the diol component in the present specification are defined as a compound containing a carboxyl group-containing compound and a diol as reactants for the polymerization reaction of the copolymer polyester resin composition .

In the present invention, the copolymerized polyester resin composition comprises a polyester resin, and the polyethylene naphthalate (PEN) resin is used alone as the polyester resin, or the polyethylene terephthalate (PET) resin and polyethylene naphthalate ) ≪ / RTI > resin may be used.

On the other hand, in order to optimize the transparency, mechanical properties, and thermal characteristics of the copolymer polyester resin composition, the polyester resin may be contained in an amount of 92.3 to 99.05% by weight based on the entire copolymer polyester resin composition.

 The polyethylene terephthalate (PET) resin is produced by condensation polymerization of ethylene glycol as a diol component with at least one acid component selected from the group consisting of terephthalic acid, dimethyl terephthalate, isoterephthalic acid, and dimethyl isoterephthalic acid. Polyethylene naphthalate (PEN) resin may be prepared by condensation polymerization of naphthalene dicarboxylate or naphthalene dicarboxylic acid as an acid component and ethylene glycol as a diol component.

The copolyester resin composition comprising the polyethylene terephthalate resin and the polyethylene naphthalate resin as described above has excellent transparency and excellent mechanical properties including thermal properties including flame retardancy and surface hardness.

In order to ensure mechanical properties and thermal properties while exhibiting transparency to a degree suitable for use as parts of electronic devices such as TV stands, terephthalic acid, dimethyl terephthalate, isoterephthalic acid, and dimethyl isoterephthalic acid And polyethylene terephthalate resin in which ethylene glycol is condensed as a diol component and at least one member selected from the group consisting of naphthalene dicarboxylate or naphthalene dicarboxylic acid and diol component ) Is preferably at least 8 mol% or more based on the total copolymerized polyester resin.

The molar ratio of the polyethylene terephthalate (PET) resin to the polyethylene naphthalate (PEN) resin of the copolymer polyester resin composition is not limited, but the mechanical properties such as thermal deformation temperature, heat resistance and flame retardancy are excellent. Preferably in a molar ratio of 1: 0.06 to 1: 15, more preferably in a molar ratio of 1: 0.08 to 1: 8, most preferably in a molar ratio of 1: 0.09 to 1: 1.5 Lt; / RTI > The inventors of the present invention have confirmed that the copolyester resin as described above exhibits transparency, mechanical properties, and heat resistance properties to an extent suitable for molding into electronic parts and the like.

The flame retardant improver represented by the general formula (1) includes phosphorus, increases the flame retardant property, and can control the flame retardancy to various values between V2 and V0. The flame retardancy improver may be contained in an amount of 0.65 to 6.5% by weight based on the total polyester resin composition. If the flame retardancy is less than 0.65% by weight, the flame retardancy is deteriorated. If the content is more than 6.5% by weight, the thermoplastic and mechanical properties of the copolymer polyester resin composition deteriorate have.

The flame retardant improver may be an arylphosphinyl-carboxylic acid or a derivative thereof such as 3-hydroxyphenylphosphinylpropanecarboxylic acid or (2'-hydroxymethyl) -3-hydroxyphenylphosphinylpropane ester .

[Chemical Formula 1]

Wherein R ₅ and R ₆ are each a hydrogen atom or a C ₁ -C ₆ hydroxyalkyl group.

As the scratch resistance improver represented by the general formula (2) or (3), a slip property improving agent such as a plant-based fatty acid derivative may be used. The content of the scratch resistance improver is 0.05 to 1.2% by weight . When the content of the scratch resistance improver is less than 0.05 wt%, the scratch resistance is not improved. When the scratch resistance improver is more than 1.2 wt%, the transparency of the product is deteriorated.

(2)

이고, l, 및 n은 각각 6~20의 정수이고, m은 0또는 1이다.
Here, Q is

, L and n are each an integer of 6 to 20, and m is 0 or 1.

(3)

Here, Q is

이고, l 및 n은 각각 6~20의 정수이고, m은 0또는 1이며, p는 1~5의 정수이다.

And l and n are each an integer of 6 to 20, m is 0 or 1, and p is an integer of 1 to 5.

The plant-based fatty acid derivative may be C ₆ -C ₃₀ .

On the other hand, the copolymer polyester resin composition according to the present invention may further comprise a polyester resin.

The polyester resin may contain at least one acid component selected from the group consisting of terephthalic acid, dimethyl terephthalate, isoterephthalic acid, and dimethyl isoterephthalic acid and at least one selected from the group consisting of 1,4-cyclohexanedimethanol or 2,2,4,4- Tetramethyl-1,3-cyclobutanediol may be polycondensed polyester resin.

Further, the polyester resin may contain naphthalene dicarboxylate or naphthalene dicarboxylic acid as an acid component and 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl-1,3-cyclobutanediol May be a polycondensation polyester resin.

Preferably, the polyester resin contains at least one acid component selected from the group consisting of terephthalic acid, dimethyl terephthalate, isoterephthalic acid, and dimethyl isoterephthalic acid and at least one selected from the group consisting of 1,4-cyclohexanedimethanol or 2,2, 4,4-tetramethyl-1,3-cyclobutanediol polycondensed polyester resin, and naphthalene dicarboxylate or naphthalene dicarboxylic acid as an acid component and 1,4-cyclohexanedimethanol as a diol component or 2, 2,4,4-tetramethyl-1,3-cyclobutanediol may be in a form containing a polycondensed polyester resin.

 As described above, in addition to ethylene glycol, a copolymer resin further comprising a polyester resin containing a diol component such as 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl-1,3-cyclobutanediol It was confirmed that the polyester resin was further improved in mechanical properties and heat resistance while maintaining improved transparency.

Thus, a polyester resin comprising a diol component such as 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl-1,3-cyclobutanediol can be used to optimize transparency, mechanical properties, , Preferably 0 to 40 mol%, more preferably 5 to 30 mol%, based on the entire copolymerized polyester resin.

Further, the copolymer polyester resin composition according to the present invention may further comprise a multifunctional branching agent

The multifunctional branching agent is selected from the group consisting of glycerol, trimethylol propane, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis hydroxymethylcyclohexane, tris (2- Ethyl) isocyanurate, dipentaerythritol or alkylene oxide addition reaction product with a polyhydric alcohol such as hemimellic liquid, hemimellic liquid, anhydrous trimellitic, trimellitic liquid, But are not limited to, melitic liquid seeds, pyromellitic liquid seed anhydrides, 1,1,2,2-ethanetetracarboxylic liquidsides, 1,1,2-ethanetricarboxylic acid liquids, 1,3,5-pentanetricarboxylic acid liquids , And 1,2,3,4-cyclopentane tetracarboxylic acid liquid, and the like.

The content of the multifunctional franching agent may be 0.01 to 4 mol%, preferably 0.05 to 0.5 mol%. When the content of the multifunctional branching agent is less than 0.01 mol%, it is difficult to realize high viscosity. If the mol% is exceeded, a large amount of unmelted material may be generated.

In addition, the copolymer polyester resin composition may further contain additives such as a fluorescent whitening agent, a heat stabilizer, an antioxidant, a dye, an antistatic agent, and an antimicrobial agent within the scope of the present invention. In particular, a fluorescent whitening agent, a complementary colorant or an organic dye can be used during polymerization or extrusion for color stability in a post-process.

Particularly, the copolymer polyester resin of the above-mentioned embodiments has a heat deflection temperature (HDT) of 75 占 폚 or higher, preferably 85 占 폚 or higher, measured on the basis of ASTM D648. As such, it has excellent heat resistance and is suitable for use as an external component such as an electronic appliance. In addition, it was confirmed that the flame retardancy test grade of UL-94 standard is V-2 or more, which indicates sufficient flame retardancy.

In addition, the copolymer polyester resin of the above-mentioned embodiments exhibited a transparency of 85% or more, preferably 90% or more, measured on the basis of ASTM D570, and it was found that the aesthetic requirements of the transparent plastic were also satisfied. Finally, the copolyester resin according to the above-described embodiments exhibits a sufficient mechanical property. Although the pencil hardness test according to JIS K5401 shows a surface hardness of more than HB, the scratch resistance is excellent. However, in order to improve the surface hardness Appropriate addition of plant-based fatty acid carboxylic acid amides can improve scratch resistance.

The copolymerized polyester resin composition according to the present invention is excellent in heat resistance, flame retardance and surface hardness while exhibiting sufficient transparency, and can be used not only as a container for a film, sheet, . Particularly, when used as an electronic device component, a specific product group can be used as a TV holder, a TV frame, a housing for a mobile phone, and the like, but is not limited to the above example.

The copolymerized polyester resin composition according to the present invention can be produced by the following method.

At least one acid component selected from the group consisting of terephthalic acid, dimethyl terephthalate, isoterephthalic acid, dimethyl isoterephthalic acid, naphthalene dicarboxylate, and naphthalene dicarboxylic acid and at least one member selected from the group consisting of ethylene glycol ≪ / RTI > And condensation polymerization of the esterification reaction product.

At this time, 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl-1,3-cyclobutanediol may be added to the esterification reaction step as a diol component other than ethylene glycol. The specific acid component, the kind of the diol component, and the content ratio thereof can also be adjusted in consideration of the ratio of the polyethylene terephthalate resin contained in the copolymer polyester resin to be finally polymerized and the molar ratio of the polyethylene naphthalate resin.

On the other hand, the ratio of the polyethylene terephthalate resin and the polyethylene naphthalate resin contained in the copolymer polyester resin composition thus produced, the ratio and the content of the specific condensation polymer contained in the resin composition, the heat distortion temperature of the resin, Flame retardance, transparency, surface hardness and the like are the same as those described in the embodiment of the copolymer polyester resin composition.

On the other hand, after the esterification reaction, a condensation polymerization catalyst, a stabilizer, a coloring agent, a fluorescent whitening agent, and the like may be added to the product of the esterification reaction before the start of the condensation polymerization reaction. At this time, as the condensation polymerization catalyst, at least one selected from the group consisting of general titanium, germanium, antimony, aluminum, and tin compounds can be used. Further, a slip property improving agent such as a plant-based fatty acid derivative may be included for improving the scratch resistance.

The present invention can provide a molded article comprising the copolymer polyester resin composition thus produced, specifically, a molded article obtained by thermosetting the copolymer polyester resin composition. At this time, the molded article may be a film, a sheet, a beverage bottle, a bottle, a fiber, an optical product, and an electronic device external component.

Particularly, the copolymer polyester resin composition according to the present invention has excellent mechanical properties and thermal properties as well as transparency, and is expected to be widely used in industrial fields related to the manufacture of exterior parts for electronic devices.

In this case, examples of the external components of the electronic device include a frame of a display device such as a TV, a monitor, and an electronic dictionary, a supporting part of the above-mentioned display devices, an operation plate of the above-mentioned display devices, a housing such as a mobile phone, It is not limited to one example.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example  1 to 6 and Comparative Example  1-4

According to the composition shown in the following Table 1, a resin composition comprising polyethylene terephthalate, polyethylene naphthalate and 3-hydroxyphenylphosphinyl propanecarboxylic acid as a flame retardant improver was mixed with plant-based carboxyimide of Croda as a scratch resistance improver Incromax 100, an additive, was mixed by melt kneading to prepare a copolymer polyester resin composition.

At this time, the temperature of the extruder was set to 150 ° C, 200 ° C, 220 ° C, 230 ° C and 250 ° C in order from the first inlet to the die, and the screw was rotated at 230 RPM.

The mixed resin was solidified in a cooling bath at a temperature of 35 DEG C while being discharged onto a strand, and then obtained as a pelletized product through a pelletizer.

division
PET
content PEN
content Flame retardant improver Scratch resistance improver 3-hydroxyphenyl
Phosphinylpropanecarboxylic acid Icromax
100 Example One 91.05 8 0.65 0.3 2 77.7 20 2 0.3 3 56.2 40 3.5 0.3 4 47.5 46 6 0.5 5 10.3 85 4 0.7 6 0 92.8 6.5 0.7 Comparative Example One 83.7 8 8 0.3 2 0 91.7 8 0.3 3 14.2 85 0.5 0.3 4 95.5 0 4 0.5

The resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were dried at 100 ° C for 5 hours using a dehumidifying type hot air drier to remove water and molded into specimens for measurement of physical properties using an injection molding machine, Evaluation was carried out according to the method, and the results are shown in Table 2 below.

 The specific physical properties are measured as follows.

(1) Transparency

The transparency was measured using a UV / VIS spectrophotometer.

(2) Flammability

Plastic Flame Retardancy Measurement Standard A specimen of 1.6 mm in thickness was prepared in accordance with UL94 and measured according to the UL94 vertical burning method.

(3) scratch resistance

And measured by a pencil hardness method according to JIS K5401.

division Transparency Flammability Scratch resistance Example One 89% V1 HB 2 88% V1 F 3 88% V1 1H 4 86% V1 2H 5 85% V0 2H 6 85% V0 3H Comparative Example One 80% V1 F 2 78% V0 2H 3 85% V2 1H 4 83% V2 B

As a result of measurement of physical properties, it is understood that the copolyester resin compositions according to Examples 1 to 6 have transparency of 85% or more, flame retardancy of V1 or more, and scratch resistance of HB or more, as shown in Table 2.

On the other hand, the copolyester resin compositions according to Comparative Examples 1 to 4 showed lowered transparency, flame retardancy, and scratch resistance as compared with Examples in which each component was contained in an optimized amount.

Therefore, it can be understood that the copolymer polyester resin composition of the examples can be applied to exterior parts of electronic devices which require both transparency, flame retardance and scratch resistance as in the evaluation of physical properties.

Claims (9)

92.3 to 99.05% by weight of a polyester resin;
0.65 to 6.5% by weight of a phosphorus-containing flame retardant improver represented by the general formula (1); And
And 0.05 to 1.2% by weight of the scratch resistance improver represented by the general formula (2) or (3)
It further includes a multifunctional branching agent,
The polyester resin may be a copolymer of a polyethylene terephthalate (PET) resin and a polyethylene naphthalate (PEN) resin; Or a polyethylene naphthalate (PEN) resin,
The copolymer of the polyethylene terephthalate (PET) resin and the polyethylene naphthalate (PEN) resin contains PET: PEN in a molar ratio of 1: 0.06 to 1:15,
The scratch resistance improver is a plant-based fatty acid derivative,
A transparency as measured by a UV / Vis method of 85% or more, a flame retardancy measured by UL-94 vertical flame retardancy evaluation method of not less than V1, and a surface hardness measured by a pencil hardness method according to JIS K5401 of not less than HB Polyester resin composition.
[Chemical Formula 1]

Wherein R ₅ and R ₆ are each a hydrogen atom or a C ₁ -C ₆ hydroxyalkyl group.

(2)

Here, Q is

, L and n are each an integer of 6 to 20, and m is 0 or 1.

(3)

Here, Q is

And l and n are each an integer of 6 to 20, m is 0 or 1, and p is an integer of 1 to 5.
delete delete delete delete delete delete delete A molded article comprising the copolymer polyester resin composition of claim 1.