KR101676900B1 - Acrylate based copolymer for polycarbonate resin, and polycarbonate resin composition - Google Patents

Abstract

The present invention relates to an acrylate-based copolymer for polycarbonate resin, and a hard and transparent polycarbonate resin composition obtained using the same. According to the present invention, compatibility with a polycarbonate resin is improved, In addition to being suitable for large-sized molding that is difficult to mold in existing resin in accordance with the enlargement of the product, it also has high surface hardness and transparent and clear feeling like glass, while improving the scratch resistance while maintaining the transmittance of polycarbonate resin. A resin composition suitable for use as a transparent housing of a product can be provided.

Description

[0001] The present invention relates to an acrylate-based copolymer for polycarbonate resin, a polycarbonate resin-based acrylate-based copolymer, and a polycarbonate resin composition,

The present invention relates to an acrylate-based copolymer for polycarbonate resin, and a polycarbonate resin composition. Specifically, the present invention relates to a polycarbonate resin composition which is excellent in compatibility with a polycarbonate resin and improved in flow characteristics, Which is suitable for forming a large-sized surface, and has an excellent scratch resistance while maintaining the transparency of the polycarbonate resin, and has a high surface hardness and a transparent and clear feeling like glass, Rate copolymer and a polycarbonate resin composition using the same.

Polycarbonate resin (PC) is a resin widely used for excellent physical properties, high heat resistance, transparency and flame retardancy. However, in spite of these excellent physical properties, the extremely low scratch resistance makes it difficult to apply directly to the appearance of electronic products or sheets.

Numerous attempts have been made to overcome these limitations, for example by introducing inorganic additives or using copolymers based on polymethylmethacrylate (PMMA), which are compatible.

However, these methods have shown limitations in the application as information electronic materials because of decreasing the transparency of PC.

Therefore, it is attempted to commercialize the PC by modifying the PC by copolymerization of other compounds. However, it is expensive to introduce additional facilities and expensive monomers in the conventional PC manufacturing process. Uneasy.

Therefore, it is necessary to develop a technique for improving the scratch resistance while maintaining the transmittance of the PC.

Accordingly, the present invention provides an acrylate-based copolymer for polycarbonate resin suitable for use as a transparent housing for electrical and electronic products, having a high surface hardness and a transparent and clear feel as glass, and a poly It is an object of the present invention to provide a carbonate resin composition.

In order to achieve the above object, the acrylate copolymer for polycarbonate resin of the present invention is composed of an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a vinyl silane monomer, The monomer is 89 to 99 wt% of the copolymer and the weight average molecular weight (Mw) of the copolymer is 0.9 to 3.9 million g / mol.

Further, the polycarbonate resin composition of the present invention is characterized by comprising 20 to 40 wt% of the acrylate-based copolymer and 60 to 80 wt% of the polycarbonate resin.

Hereinafter, the acrylate-based copolymer for polycarbonate resin according to the present invention will be described, and then the resin composition obtained therefrom will be specifically described.

In the present invention, the (meth) acrylate monomer is composed of an alkyl (meth) acrylate monomer, an aryl (meth) acrylate monomer and a vinyl silane monomer in an amount of 89 to 99 wt% And has a technical characteristic of providing an acrylate-based copolymer for a polycarbonate resin having a molecular weight (Mw) of 0.9 to 3.9 million g / mol.

Specifically, the alkyl (meth) acrylate monomer has a high surface hardness. For example, the alkyl (meth) acrylate monomer may be a monomer having an alkyl group having 1 to 30 carbon atoms, or methyl methacrylate.

The aryl (meth) acrylate monomer may be used to improve the surface hardness and to improve the compatibility between the alkyl (meth) acrylate monomer and the polycarbonate resin. For example, the aryl (meth) (Meth) acrylate monomer having an aryl group having 6 to 30 carbon atoms and a (meth) acrylate monomer having an arylalkyl group having 6 to 30 carbon atoms, and specific examples thereof may be phenyl methacrylate.

Also, the vinyl silane monomer may be used to form the outer hard coat layer when compounding with the polycarbonate resin through proper content control.

[Chemical Formula 1]

Wherein R ₁ and R ₃ are independently alkyl or aryl of 1 to 10 carbon atoms,

R ₂ is independently alkyl or aryl having 1 to 10 carbon atoms or a hydrolysable group, n is 0 or an integer of 1 to 10, m and o are each 0 or 1, and m, n and o are both 0 It is not.)

As specific examples, the vinylsilane monomer having the formula (1) may be at least one selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri- (2-methoxyethoxysilane), vinyltriacetoxysilane, Methacryloxypropyltrimethoxysilane, 2-methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, allyltrimethoxysilane, allyltriethoxysilane, 3-acryl Methyltrimethoxysilane, oxypropyltrimethoxysilane, 3- (N-styrylmethyl-2-amino-ethylamino) propyltrimethoxysilane hydrochloride, and vinyltrichlorosilane.

In the present invention, the weight average molecular weight (Mw) of the copolymer may be from 0.9 to 40,000 g / mol, or from 15,000 to 30,000 g / mol.

Within the above range, compatibility with the polycarbonate resin can be enhanced, and high flow characteristics can be imparted to meet large-sized household electrical appliances, which is suitable for large-scale molding that is difficult to mold in conventional resin.

In the present invention, the (meth) acrylate monomer may be 89 to 99 wt%, 90 to 99 wt%, or 95 to 99 wt% of the copolymer. The remaining balance may be the vinylsilane monomer, and may be, for example, 1 to 11 wt%, 1 to 10 wt%, or 1 to 5 wt% of the copolymer.

A copolymer having a vinyl silane outer hard coating can be formed in order from the top when compounding with a polycarbonate resin within the above range, thereby maximizing the use effect of each monomer. Thus, a resin composition having a high hardness and a completely transparent property can be provided can do.

For reference, unless otherwise specified, the term "(meth) acrylate monomer" used in the present invention refers to an alkyl (meth) acrylate monomer and an aryl (meth) acrylate monomer.

The (meth) acrylate-based monomer may be 89 to 99 wt%, 90 to 99 wt%, or 95 to 99 wt% of the copolymer. The remaining balance may be the vinylsilane monomer, and may be, for example, 1 to 11 wt%, 1 to 10 wt%, or 1 to 5 wt% of the copolymer.

Although the surface hardness was increased by incorporating the alkyl (meth) acrylate monomer within the above range, in order to complement the reduced compatibility with the polycarbonate resin by using the aryl (meth) acrylate monomer, The maximized effect can be obtained while minimizing the usage amount.

The copolymer according to the present invention is applied as an additive for a polycarbonate resin or as an additive for crosslinking a polycarbonate resin, and has technical characteristics.

For example, 20 to 40 wt% of the acrylate-based copolymer and 60 to 80 wt% of the polycarbonate resin. As a specific example, the copolymer and the polycarbonate resin, in which the vinyl silane compound in the copolymer forms a hard coating in order from the top when compounding with the acrylate-based copolymer and the polycarbonate resin, Can be provided.

In this case, the polycarbonate resin is not limited to the polycarbonate resin. However, the polycarbonate resin can be expected to have a fluidity improvement of at least two times higher than that of a generally applicable polycarbonate resin. For example, the polycarbonate resin has a fluidity of 10 to 30 g / min Can be used.

As the antioxidant, a hindered phenol antioxidant may be used alone or in combination with a phosphite antioxidant in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total composition By weight. ≪ / RTI > If the amount is less than 0.01 part by weight, the effect of suppressing yellowing due to thermal history in a high volatilizing tank is small. If the amount is more than 1 part by weight, there is a problem that the refractive index increases due to decrease in polymerization conversion.

In this case, the mixing ratio of the antioxidant is not limited thereto, but it is preferably 9: 1 to 1: 5, 5: 1 to 1: 3, or 2: 1 to 1: 2 by weight of the phenol antioxidant: phosphite antioxidant .

At this time, when the amount of the phosphite antioxidant is more than 1: 5 in the composition ratio of the phenol antioxidant and the phosphite antioxidant, there is a problem in that it is vulnerable to thermal history during polymerization. If the amount of the antioxidant used is small, it is not preferable because it is vulnerable to volatilization and thermal history during processing.

The phenolic antioxidants include, but are not limited to, tetrakis methylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate methane, 1,3,5- butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) - (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione.

The phosphite-based antioxidant is not limited thereto, but is preferably one selected from tris (2,4-t-butylphenyl) phosphite and tris- (nonylphenyl) phosphite.

In addition, a molecular weight regulator and an organic peroxide initiator are added. Dodecyl mercaptan and the like can be used as the molecular weight regulator, and potassium n-dodecyl mercaptan can be used as the organic peroxide initiator.

The compounding may include melt extrusion, blending, melt-kneading, extrusion, sheet extrusion, and the like.

The resin composition can provide an organic or inorganic hybrid resin which satisfies both of a pencil hardness of 2H or more, a haze of 2.0 or less and a heat resistance of 120 占 폚 or more as measured with a specimen having a thickness of 3 mm. If the pencil hardness H is below H, there is a problem that life scratch on the surface of the product may be caused. If the haze exceeds 2.0, the appearance of the molded product may be problematic. have.

The resin composition may have a flowability measured within a range of 20 to 40 g / min under a load of 1.2 kg under a temperature of 300 캜 to form a large-area structure. When the fluidity is less than 20 g / min, It is possible to induce non-molding, and when it exceeds 40 g / min, it is difficult to satisfy desired heat resistance.

According to the present invention, the refractive index of the polycarbonate resin is 1.59, and the refractive index of the copolymer composed of methyl methacrylate, phenyl methacrylate and vinyltrimethoxysilane is about 1.53 to 1.57, (Measured haze: not more than 2.0) that the high transparency was given without satisfying the refractive index range.

The resin composition of the present invention comprising the above components may be prepared by adding additives selected from a lubricant, an antioxidant, an antistatic agent, a release agent, and a UV stabilizer depending on the application.

The double lubricant may be selected from ethylene bisstearamide, oxidized polyethylene wax, and magnesium stearate, and the amount thereof is in the range of 0.1 to 5 parts by weight, or 0.5 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.

The antioxidant may be a phenolic antioxidant such as IR1076. The amount of the antioxidant is 0.5 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

The ultraviolet light stabilizer may be an ultraviolet absorber such as TINUVIN 326. The amount of the ultraviolet light stabilizer is 0.05 to 3 parts by weight or 0.2 to 1 part by weight based on 100 parts by weight of the thermoplastic resin composition.

The resin composition of the present invention as described above has a surface hardness and a transparent and clear feeling like glass, and is suitable for use as a transparent housing of electrical and electronic products.

According to the present invention, compatibility with a polycarbonate resin is improved and flow characteristics are improved, so that it is suitable for large-scale molding that is difficult to mold in existing resin in accordance with the enlargement of household electric appliances. In addition, while maintaining the transparency of polycarbonate resin, It is possible to provide a resin composition suitable for use as a transparent housing for electrical and electronic products because it has a high surface hardness and a transparent and clear feeling like glass.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example  One

60 parts by weight of methyl methacrylate, 35 parts by weight of phenylmethyl methacrylate and 5 parts by weight of trimethoxyvinylsilane were polymerized to prepare a copolymer (weight average molecular weight (Mw): 1.5000 g / mol, Refractive index: 1.53-1.57).

20 parts by weight of the resin was compounded with 80 parts by weight of a polycarbonate resin having flowability of 1.2 g / min at 300 캜 and compounding to prepare a final resin. A specimen having a thickness of 3 mm was prepared by injection molding.

The glass transition temperature, pencil hardness, fluidity and haze value of the specimens were measured, and the results are summarized in Table 1 below.

Example  2 - 5

The same procedure as in Example 1 was repeated except that the composition and the molecular weight were changed to the contents shown in the following Table 1 in Example 1.

Comparative Example  1 - 5

The same procedure as in Example 1 was repeated except that the composition and molecular weight were changed to the contents shown in the following Table 2 in Example 1.

Comparative Example  6

Polycarbonate resin (product name: LG-DOW 300-10) was used without purification. For reference, the refractive index was 1.59.

Comparative Example  7

In Example 1, methyl methacrylate and trimethoxyvinylsilane were copolymerized in an amount of 95 parts by weight and 5 parts by weight, respectively, and the same processes as in Example 1 were carried out except that phenylmethyl methacrylate was not added separately . The refractive index was 1.08.

< Performance test >

Pencil hardness, fluidity and haze were measured by the following methods for the samples prepared in the examples and comparative examples, and the results are shown in Tables 1 and 2.

* Pencil hardness (Pencil Hardness ) : A pencil was fixed with a load of 0.5 kg and an angle of 45 °, and then the surface of the test piece was scratched by pencil hardness to judge whether or not the surface was scratched visually.

Flowability ( MI ) : measured according to ASTM D1238 at 300 ° C under a load of 1.2 kg and a speed of g / 10 min.

* Haze (Haze): The haze (Haze) was measured using: (HR-100, Murakami Color Research Laboratory under the trade name) type haze transmittance according to JIS K 7105.

division Example 1 Example 2 Example 3 Example 4 Example 5 Acrylate Copolymer 1) Methyl methacrylate 60 60 55 64 47 Phenyl methacrylate 35 35 40 35 50 Trimethoxyvinylsilane 5 5 5 One 3 Molecular weight (Mw) 1.5 million 1.5 million 1.5 million 1.5 million 3 million Blend
Furtherance Polycarbonate 80 70 60 80 60 Copolymer 1) 20 30 40 20 40 Properties Pencil hardness 2H 2H 3H 2H 3H Flowability (g / min) 24 30 37 22 32 Heat resistance (Tg, ℃) 135 132 130 137 127 Haze (T = 3t) 1.0 1.4 1.8 1.8 2.0

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Acrylate Copolymer 1) Methyl methacrylate 60 60 70 58 65 - 95 Phenyl methacrylate 35 35 25 30 35 - - Trimethoxyvinylsilane 5 5 5 12 - - 5 Molecular weight (Mw) 4 only 0.8 million 2 million 2 million 1.5 million - 2 million Blend
Furtherance Polycarbonate 80 80 70 70 80 100 80 Copolymer 1) 20 20 30 30 20 - 20 Properties Pencil hardness H H 2H 2H H 2B H Flowability (g / min) 17 33 27 29 26 10 43 Heat resistance (Tg, ℃) 132 118 126 123 135 148 146,
117 Haze (T = 3t) 3.8 1.0 2.8 6.0 1.0 2.0 Opaque

As shown in Tables 1 and 2, in Examples 1 to 5 according to the present invention, the polycarbonate contains an organic hybrid resin having a molecular weight of 10,000 to 30,000 as compared with Comparative Example 6 in which a polycarbonate resin alone is measured Pencil hardness, fluidity, heat resistance and haze.

On the other hand, as in Comparative Examples 1 and 2, it was confirmed that pencil hardness, fluidity and haze were poor when an organic hybrid resin having a molecular weight of 10,000 to 3,000 was used.

Further, when the compounding ratio between the binary (meth) acrylate mixture constituting the organic / inorganic hybrid resin is inadequate as in Comparative Example 3, or when the vinylsilane monomer is excessively administered as in Comparative Example 4, On the other hand, when the vinylsilane compound was not added at all as in Comparative Example 5, it was confirmed that the desired pencil hardness could not be obtained.

Further, in the case of Comparative Example 7 in which vinyltrimethoxysilane was mixed with methyl methacrylate alone, the blend was not compatible with polycarbonate and was completely opaque and had no compatibility with respect to fluidity, pencil hardness and heat resistance. The results were inferior to the examples.

Claims (14)

delete delete delete delete delete delete delete delete Acrylate copolymer and 60 to 80 parts by weight of a polycarbonate resin, and has a pencil hardness of 2H or more, a haze of 2.0 or less measured with a specimen of 3 mm thickness, a heat resistance of 120 or more,
The acrylate-based copolymer is composed of 47 to 64 wt% of methyl methacrylate, 35 to 50 wt% of phenyl methacrylate, and 1 to 5 wt% of trimethoxyvinylsilane, and has a weight average molecular weight (Mw) of 0.9 to 3.9 g / mol, and the (meth) acrylate-based monomer is 89 to 99 wt% of the acrylate-based copolymer, and is applied as an additive for crosslinking a polycarbonate resin
Polycarbonate resin composition.
delete 10. The method of claim 9,
Wherein the polycarbonate resin is a resin having a fluidity of 10 to 30 g / min measured at 300 캜 under a load of 1.2 kg
Polycarbonate resin composition.
10. The method of claim 9,
Wherein the composition comprises at least one selected from the group consisting of a lubricant, an antioxidant and a UV stabilizer upon compounding
Polycarbonate resin composition.
delete 10. The method of claim 9,
Characterized in that the composition has a fluidity of 20 to 40 g / min measured at 300 캜 under a load of 1.2 kg and is applied for forming a large-area structure
Polycarbonate resin composition.