WO2019066493A1 - Polycarbonate resin composition and optical molded product comprising same - Google Patents

Abstract

The present invention relates to: a polycarbonate resin composition having excellent transparency and color stability and low UV transmittance; and an optical molded product comprising the same.

Description

 Title of the Invention

 Polycarbonate resin composition and optical molded article comprising the same [Technical Field]

 Cross-reference with related application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0128259 filed on September 29, 2017, and Korean Patent Application No. 10-2018-01144 filed on September 21, 2018, The entire contents of which are incorporated herein by reference.

 The present invention relates to a polycarbonate resin composition excellent in transparency and color stability and having a low ultraviolet transmittance, and an optical molded article comprising the same.

TECHNICAL BACKGROUND OF THE INVENTION

 The polycarbonate resin is produced by the condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene and has excellent stiffness strength, numerical stability, heat resistance, transparency and the like, and is used for exterior materials, automobile parts, And so on.

 On the other hand, in the case of an optical lens used for glasses or sunglasses, a transmittance is required to such an extent that glare on an external light source does not occur without affecting the visual field. In addition, it is necessary to protect the eyes from harmful rays of a specific wavelength such as ultraviolet rays. In addition to the mechanical properties, polycarbonate resins having excellent optical properties are being used to develop various technologies for use as optical lenses for outdoor activities such as glasses or sunglasses.

 However, in the case of the polycarbonate resin, a low transmittance is exhibited in a range of about 380 nm or less in the ultraviolet ray region, but there is a problem that the transmittance is increased in a region above 380 nm. To improve this, various additives are used together to improve the physical properties of the polycarbonate However, there is a problem in that, when the physical properties of any one of them are improved, other physical properties are deteriorated.

Korean Patent Laid-Open Publication No. 10-2017-0036252 discloses a technique in which a polycarbonate resin is combined with a dye and a pigment to improve the visible light shielding property. However, It can not simultaneously realize properties such as proper shielding property and transparency in the region.

[Prior Art Document]

 [Patent Literature]

 (Patent Document 0001) Korean Patent Publication No. 10-2017-0036252

DISCLOSURE OF THE INVENTION

 [Problem to be solved]

 The present invention provides a polycarbonate resin composition excellent in transparency and color stability and having a low ultraviolet transmittance.

 The present invention also provides an optical molded article comprising the polycarbonate resin composition. MEANS FOR SOLVING THE PROBLEMS

 In order to solve the above problems, the present invention relates to a benzotriazole-based compound comprising a polycarbonate resin, a coloring agent, a yellow coloring agent and at least one hydroxy group; Benzophenone compounds; And an ultraviolet absorber selected from the group consisting of triazine compounds; and an average transmittance of 1.0% to 6.5% in a wavelength region of 380 nm to 420 nm according to ASTM D1003. The polycarbonate resin is a resin which is produced by the condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene and has excellent mechanical properties and optical characteristics per se. However, it is necessary to satisfy various physical properties simultaneously have. When a polycarbonate resin is used in an outdoor lens or the like, it is necessary to reduce the transmittance of the ultraviolet region. Various techniques have been developed to improve the transmittance of the ultraviolet region. However, There was a problem.

Accordingly, the present inventors have found that while realizing a low ultraviolet transmittance, In order to realize transparency and hue stability, a polycarbonate resin composition using a combination of an additive having a high light absorptivity in a specific wavelength region and a specific colorant has been developed.

Hereinafter, the present invention will be described in detail. The polycarbonate resin composition according to the present invention is characterized by containing a specific ultraviolet absorber and a specific combination of colorants to provide a wavelength range from 380 nm to 420 nm according to ASTM D1003 _. The average transmittance in the range of 1.0% to 6.5% is satisfied. In the case of the resin composition satisfying the above range, excellent transparency and color stability can be realized while realizing a low ultraviolet transmittance. The average transmittance of the region may preferably be between 3.0% and 6.2%. When the above-mentioned range is satisfied, the above-mentioned physical properties are more excellent, and thus it is easy to apply to an optical molded article, particularly a spectacle lens or a sunglass lens.

In the present invention, the average transmittance is measured according to ASTM D1003. The transmittance at 380 nm to 420 nm is measured in units of 5 nm, and the average value (T380-420) is calculated. Specifically, the polycarbonate resin composition of the present invention was produced at a rate of 80 kg per hour in a twin-screw extruder (L / D = 36, Φ = 45, barrel temperature 240 ^° C) (Horizontal / vertical / thickness = 60 隱 / 40 薩 / 3 mm) by injection molding at a cylinder temperature of about 270 ^없이 C without retention time and using Ul traScan PRO (HunterLab) according to ASTM D1003 . Ultraviolet absorber

 The polycarbonate resin composition according to the present invention is a composition comprising a benzotriazole-based compound; Benzophenone compounds; And at least one ultraviolet absorber selected from the group consisting of triazine-based compounds. These ultraviolet absorbers include at least one hydroxyl group and are used in combination with a specific combination of colorants described below to provide low transparency while exhibiting excellent transparency And tint stability.

Specifically, the ultraviolet absorber has an ultraviolet ray region of more than about 380 nm, As a compound having a high light absorptivity in the region of about 420 nm, it can be used together with a specific combination of colorants to improve the ultraviolet absorption of the polycarbonate resin composition in the area.

 The benzotriazole-based compound may include at least one hydroxy group in the molecule, specifically, a compound represented by the following formula (1): < EMI ID =

 The benzophenone-based compound contains at least one hydroxyl in the molecule, specifically, a compound represented by the following formula (2): < EMI ID =

 The triazine-based compound may include at least one hydroxy group in the molecule, specifically, a compound represented by the following formula (3)

In the present invention, the ultraviolet absorber may be included in the range of Ι, ΟΟΟρρ, to 15,000ρρικι, and preferably in the range of 3,000 ppmw to ΙΟ, ΟΟΟρρος, or 4,000 ppmw to 9 ᅳ OOOpp , Number have. By incorporating in the above content range, the desired effect of the present invention can be realized by using in combination with a colorant described later. coloring agent

 The polycarbonate resin composition according to the present invention simultaneously contains a black colorant and a yellow colorant and is used together with the specific ultraviolet absorber described above to realize a low ultraviolet transmittance while simultaneously realizing excellent transparency and color stability.

 In particular, by using a combination of a black colorant and a yellow colorant, it is possible to solve the problem that the color stability is deteriorated when only the yellow colorant is used alone. In addition, due to their synergistic effect, low light transmittance in the ultraviolet region, particularly 420 nm, can be realized, and excellent color stability can be realized at the same time.

 The coloring agent may be an anthraquinone compound, azophenyl

(azophenyl) -based compounds, acetamide-based compounds. A compound, and a carbon-based compound, and may be at least one selected from the group consisting of an anthraquinone-based compound and a carbon-based compound.

 Commercially available black colorants include Nigrosine Black G from BASF,

Nigrosin BASE BA, Nubi an Black PC-0870 from Orth chemi cal, Abbey Co lor

ABCOL Nigrosine Z1630 and the like.

 In the present invention, the black colorant may be present in an amount of from 1 to 100 parts by weight, based on the total dry weight of the composition. Oppmw to ΙΟ. And may preferably be comprised between 3.0 ppmw and < RTI ID = 0.0 >

5.0 ppmw, or 5.0 ppmw to 7. Opp. By incorporating in the above content range, the desired effect of the present invention can be achieved by using the ultraviolet absorber in combination with the ultraviolet absorber of the present invention.

 The yellow colorant may be at least one selected from the group consisting of a quinolinone compound, a pyrazole compound, and a naphthalene compound. Preferably, the yellow colorant is a quinolinone compound, Pyrazole-based compound.

Commercially available yellow colorants include Macrolex Yellow G from Bayer, Sandoplast Yel low 2G from Clariant, Transparent Yel low 3 from Yabang, Albion Kenawax YellowBGP, Solvent Yel low 114 (CAS No. 7576-65-0), and the like. In the present invention, the yellow colorant may be contained in an amount of 0.5 ppm to 5.0 ppm of the total dry weight of the composition, preferably 1.0 ppmw to 1.5 ppΩ or 1.5 ppmw to 2.0 ppmw. By incorporating in the above content range, the desired effects of the present invention can be realized by using the ultraviolet absorber in combination with the ultraviolet absorber of the present invention.

 In the present invention, the optical properties of the polycarbonate resin composition can be efficiently improved by controlling the ratio of the yellow colorant to the black colorant. The weight ratio of the yellow colorant to the coloring colorant is 1: 1 to 10: 1 < / RTI > Preferably 2: 1 to 8: 1, more preferably 4: 1 to 6: 1. Polycarbonate resin

 The polycarbonate resin according to the present invention is a resin produced by condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene. Preferably, the polycarbonate resin includes a repeating unit represented by the following formula (4)

 In Formula 4,

R'i to R'4 are each independently hydrogen, CHO alkyl, d- ₁₀ alkoxy, or halogen,

Z 'is C ₃ _ ₁₅ cycloalkylene, O, S, SO, SO ₂ , or CO, unsubstituted or substituted by phenyl ( ₁₀ alkylene, unsubstituted or CHO alkyl).

 Preferably, each of R'i to R'4 is independently hydrogen, methyl, chloro, or bromo.

Also preferably, Z 'is a straight or branched chain ( ₁₀ alkylene), unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, Propane-2, 2-diyl, butane-2,2-diyl, 1-phenylethane-1, 1-diyl, or diphenylmethylene. Also preferably, Z is cyclic nucleic acid-1, 1-diyl, O, S, SO, SO ₂ , or CO.

 The repeating unit represented by the formula (4) is formed by reaction between an aromatic diol compound and a carbonate precursor.

 Preferably, the repeating unit represented by the formula (4) is at least one selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis Bis (4-hydroxyphenyl) sulfide bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane bisphenol A, Roxy phenyl) butane,

1. 1-bis (4-hydroxyphenyl) cyclo-

2, 2-bis (4-hardox-3, 5-dibromophenyl) propane,

2.2-bis (4-hydroxv-3, 5-dichlorophenyl ⁾ propane,

2, 2-bis (4-hydroxyl ^s, 3-bromophenyl) propane,

2, 2-bis (4-hydroxy-3-chlorophenyl) propane,

2, 2-bis (4-hydroxo-3-methylphenyl) propane,

2, 2-bis (4-hydroxo-3, 5-dimethylphenyl) propane,

Bis (3-hydroxyphenyl) propyl] polydimethylsiloxane is used as a starting material in the presence of a catalyst such as 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis Or from one or more aromatic diol compounds selected from the group consisting of:

 Derived from the aromatic diol compound means that the hydroxy group and the carbonate precursor of the aromatic diol compound are countered with each other to form the repeating unit represented by the above formula (1).

 For example, when the aromatic diol compound bisphenol A and the carbonate precursor triphosgene are polymerized, the first repeating unit is represented by the following formula 4-1.

[Formula _4-1 ]

상기 카보네이트 전구체로는， 디쩨틸 카보네이트， 디에틸 카보네이트, 디부틸 카보네이트， 디시클로핵실 카보네이트， 디페닐 카보네이트 디토릴 카보네이트， 비스 (클로로페닐) 카보네이트， 디 -m-크레실 카보네이트， 디나프틸 카보네이트， 비스 (디페닐) 카보네이트， 포스겐， 트리포스겐， 디포스겐， 브로모포스겐 및 비스할로포르메이트로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 바람직하게는， 트리포스겐 또는 포스겐을 사용할 수 있다.

Examples of the carbonate precursor include dibutyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexylcarbonate, diphenyl carbonate ditolyl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, At least one selected from the group consisting of bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate can be used. Preferably, triphosgene or phosgene can be used.

 The polycarbonate resin according to the present invention may have a weight average molecular weight of 1,000 to 100,000 g / mol, and preferably 15,000 to 70,000 g / nrol.

 More preferably, the weight average molecular weight is 20,000 g / mol or more,

At least 22,000 g / mol, at least 23,000 g / mol, at least 24,000 g / mol, at least 25,000 g / mol, at least 26,000 g / mol, at least 27,000 g / mol, or at least 28,000 g / mol. Also, the weight average molecular weight is 65,000 g / mol or less, 60,000 g / mol or 55,000 g / nl. Polycarbonate resin composition

 The polycarbonate resin composition according to the present invention includes polycarbonate resin, a coloring agent, a yellow colorant and an ultraviolet absorber as described above, and achieves excellent transparency and color stability and low ultraviolet transmittance due to the synergistic effect of the combination of the above components . In particular, it is preferable that the above-mentioned average transmittance value in the specific wavelength range is satisfied and excellent physical properties can be realized when applied to a desired product (particularly, an optical molded article).

The resin composition according to the present invention may contain, if necessary, at least one member selected from the group consisting of antioxidants, heat stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, And may further include additives to be selected. The resin composition according to the present invention can be used in combination with a polycarbonate, a cyclic phosphite ester compound, a linear phosphite ester compound, a vinyl polymer containing a (meth) acrylate repeating unit containing an epoxy functional group, and a photo- , ≪ / RTI > As will be described below, in order to produce an optical molded article,

It is preferable to make pellets. The melting may be performed by a method commonly used in the art, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum-tumble short axis extruder, a twin screw extruder, a cone, a multiaxial screw extruder . Temperature of the molten heunryeon can be appropriately adjusted as necessary, for example, be adjusted to a temperature of 200 ^° C to 300 ^° C.

Optical molded article The present invention also provides an optical molded article comprising the resin composition. Preferably, the optical molded article is an optical lens requiring ultraviolet ray shielding, such as a spectacle lens, a sunglass lens, or the like. The resin composition according to the present invention is excellent in transparency and color stability, and has low ultraviolet transmittance, so that it can be usefully used as an optical molded article. The production method of the molded article can be produced by a method conventionally used in the art. For example, the resin composition according to the present invention may be produced by melt casting or pellets as a raw material, such as injection molding, injection compression molding, extrusion molding, vacuum molding, blow molding, press molding, A molding method such as a calendar molding method and a rotary molding method can be applied. The size, thickness, and the like of the molded article can be appropriately adjusted according to the purpose of use, and may have a flat plate or a curved shape depending on the purpose of use.

【Effects of the Invention】

As described above, the polycarbonate resin composition according to the present invention is excellent in transparency and color stability and has a low ultraviolet transmittance by using a specific colorant in combination with an additive having a high light absorptivity in a specific wavelength range Can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

 1 is an image showing appearance evaluation standards of Examples and Comparative Examples.

DETAILED DESCRIPTION OF THE INVENTION

 Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto. Materials Used

 The following materials were used in Examples and Comparative Examples.

 1) (A) Polycarbonate resin [Polycarbonate, PC]

A bisphenol A type linear polycarbonate resin (A-1) having a weight average molecular weight of 31,000 g / iiKl and MFR (300 ^° C, 1.2 kg) of 9.5 g / min was used.

2) (B) Colorant

 B-1: Coloring agent Oriental chemical Nubian Black PC-0870

 B-2: Yellow colorant Yabang Transparent Yellow 3G

 B-3: Red colorant Lanxess Macrolex Reed E2G

2) (C) Ultraviolet absorber

 C-1: a compound of the formula (1) (Tinuvin 326),

 C-2: Compound of formula (2) (Uvinul 3049)

(2)

 C-4: Compound (5) (Tinuvin 360)

 C-5: Compound of formula 6 (Tinuvin 329)

실시예 및 비교예

Examples and Comparative Examples

Pellets were produced at a rate of 80 kg per hour in a twin-screw extruder (L / D = 36, Φ = 45, barrel temperature 240 ^° C) after the contents of each component as shown in Table 1 below. In Table 1, the content of the polycarbonate resin (A) refers to the content excluding the content of the remaining colorant (B) and the ultraviolet screening agent (C) based on 100 wt% of the total composition.

[Table 1]

실험 방법

Experimental Method

(1) Experimental Example 1: transmittance (T), 420nm transmittance (T _420), 380-420nra average transmittance (T ₃₈₀一₄₂₀₎

Each of the resin pellets prepared in the above Examples and Comparative Examples was injection-molded at a cylinder temperature of 270 ^° C using a JSW N-20C injection molding machine without a retention time to prepare a test piece (width / length / thickness = 60 mm / And the transmittance (T) value was measured using Ul traScan PRO (HunterLab) (apparatus setting: 360 to 750 nm) according to ASTM D1003. The results are shown in Table 2 below.

Further, the transmittance at 420 nm (T ₄₂₀ ) was measured, and the transmittance The transmittance at 420 nm is measured in units of 5 nm, and the average value (T _{38 and 420} ) is shown in Table 2 below.

(2) Experimental Example 2: Evaluation of color stability

 The color stability was evaluated by integrating the following yellow color and appearance test results. The higher the value of ΥΙ, the lower the stability of chromaticity stability. However, even if the value of ΥΙ is less than 20, if the yellow color is observed with the naked eye, the color stability may be degraded.

(2-1) Evaluation of yellowness index (YI, Yel low Index)

Each of the resin pellets prepared in the above Examples and Comparative Examples was injection-molded at a cylinder temperature of 270 ^° C without a retention time using a JSW N-20C injection molding machine to prepare a test piece (width / length / thickness = 60 mm / And the YI value was measured using Ul traScan PROOnterLab according to ASTM D1925. The results are shown in Table 2 below.

 (2-2) Appearance evaluation

Each of the resin pellets prepared in the above Examples and Comparative Examples was injection-molded at a cylinder temperature of 270 ^° C using a JSW N-20C injection molding machine without a retention time to prepare a test piece (width / length / thickness = 60 匪 /瞧 / 3 麵) were manufactured, and the yellowness of the sample specimen was visually confirmed. The evaluation of O, Δ, and X was relative to the target sample.

 <Appearance Evaluation Standard>

 O: Yellow almost does not appear in the sample, which is similar to the sample specimen image of Fig. 1 (A).

 ?: The sample shows a light yellow color, which is similar to the sample specimen image of FIG. 1 (B).

X: The sample is yellow in color and / or similar to the sample specimen of FIG. 1 (C). [Table 2]

As can be seen from the above Table 2, it was confirmed that the embodiments of the present invention have excellent transparency and low ultraviolet transmittance in the 420 nm region by using a specific colorant in combination with an additive having a high light absorptivity in a specific wavelength region. In addition, when the sample was visually observed, no yellow color appeared, and it was confirmed that the YI value was 20 or less, and thus the color stability was excellent.

 In the case of the comparative examples not using the ultraviolet screening agent and the coloring agent of the present invention,

The average transmittance of 380 nm-420 nm was very high and the sample often showed a deep yellow color. Particularly, in the comparative example using other materials conventionally used as an ultraviolet absorber

In the case of 1 to 5, the overall average transmittance was excellent, but it was confirmed that the transmittance in the 420 ran region was significantly higher than that in the Example.

 In the case of Comparative Example 11, the average transmittance of 380 nm-420 nm was equal to that of the Example, but it was confirmed that the application of the product was not easy due to a dark yellow color.

Claims

Claims:  [Claim 1]  Polycarbonate resin, a coloring agent, a yellow coloring agent, and  Benzotriazole-based compounds; Benzophenone compounds; And a triazine compound; and at least one ultraviolet absorber selected from the group consisting of  And an average transmittance of 1.0% to 6.5% in a wavelength region of 380 nm to 420 nm according to ASTM D1003. [Claim 2]  The method according to claim 1,  Wherein the benzotriazole-based compound is a compound represented by the following formula (1): &lt; EMI ID =

[3]  The method according to claim 1,  Wherein the benzophenone compound is represented by the following formula (2): &lt; EMI ID =

Claim 4  In the above, Wherein the triazine-based compound is a compound represented by the following formula (3)

[Claim 5]  In the first aspect, Wherein the black colorant is at least one selected from the group consisting of anthraquinone (3 1 1 ⁽ 111 1 1 1) based compound, azophenyl based compound, acetamide based compound and carbon based compound) Resin composition. [Claim 6]  In Item 1,  Wherein the yellow colorant is at least one selected from the group consisting of a quinoline compound, a pyrazole compound, and a naphthalene compound. 7.  In Item 1,  The ultraviolet absorber may be present in an amount of from 1,000 ppmw to &lt; RTI ID = 0.0 &gt; 15,000 &lt; / RTI &gt; ppk of the polycarbonate resin composition. [8] The method of claim 1, wherein Wherein the coloring agent is included in an amount of from about 1.0 ppmw to about 1.00 ppm based on the total dry weight of the composition. [Claim 9]  In Item 1,  Wherein the yellow colorant is contained in an amount of 0.5 ppmw to 5.0 ppmw based on the total dry weight of the composition. [Claim 10]  The method according to claim 1,  Wherein the polycarbonate resin comprises a repeating unit represented by the following formula (4):

 In Formula 4,  i to R ' 4 are each independently hydrogen, Cwo alkyl, diu) alkoxy, or halogen, Z 'is unsubstituted or substituted by phenyl-κ d) alkylene, an unsubstituted or substituted alkyl or C ₃ - ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO. Claim 11  11. The method of claim 10,  The repeating unit represented by the general formula (4) is preferably a repeating unit derived from bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 1,1- 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) 2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2, 2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2, 2-bis (4-hydroxy-3-bromophenyl) propane, 2, 2-bis (4-hydroxy-3-chlorophenyl) propane, 2, 2-bis (4-hydroxy-3-methylphenyl) propane  2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane,  Bis (3-hydroxyphenyl) propyl] polydimethyl, bis (4-hydroxyphenyl) Siloxane, and mixtures thereof. The polycarbonate resin composition according to claim 1, Claim 12  In the first aspect,  Wherein the polycarbonate resin has a weight average molecular weight of 1, 000 to 100, 000 g / nK) l. [13]  In Item 1,  Wherein the polycarbonate resin composition further comprises at least one additive selected from the group consisting of an antioxidant, a heat stabilizer, a plasticizer, an antistatic agent, a nucleating agent, a flame retardant, a lubricant, an impact modifier, and a fluorescent brightener. 14.  An optical molded article comprising a polycarbonate resin composition according to any one of claims 1 to 13.