KR20100071716A - Polycarbonate thermoplastic resin composition - Google Patents

Abstract

PURPOSE: A polycarbonate thermoplastic resin composition is provided to secure the excellent property balance, and to apply the composition for manufacturing a liquid crystalline display back-light, a television, a monitor, or a notebook. CONSTITUTION: A polycarbonate thermoplastic resin composition contains a polycarbonate resin, titanium dioxide, organic siloxane, a phosphate compound, and a sulfur compound. The polycarbonate resin is produced by reacting diphenol with a compound selected from the group consisting of phosgene, halogen formate, carbonate, or their compound. 5~50 parts of titanium dioxide by weight is contained in 100 parts of polycarbonate resin by weight.

Description

Polycarbonate-based thermoplastic resin composition {POLYCARBONATE THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a polycarbonate-based thermoplastic resin composition, and more particularly to a polycarbonate-based thermoplastic resin composition having a physical property balance excellent in thermal stability, impact strength and flame retardancy.

Polycarbonate resin is an engineering plastic having excellent mechanical strength, heat resistance, and transparency, and is used in various fields such as office automation devices, electrical / electronic parts, and building materials. In particular, resins used as LCD (Liquid Crystalline Display) back light components in the field of electric / electronic components require high light reflectance, light resistance, color fastness, etc., and high fluidity due to slimming and thinning of products such as TVs, monitors, and notebooks. Is required.

When the polycarbonate resin is used as a back light component of the LCD, the resin is colored in a high white color in order to minimize the back light loss and is often used as a back-light frame. As such, titanium dioxide (TiO ₂ ) having a highest refractive index in air is mainly used as a white pigment for coloring the resin in a high white color.

However, when titanium dioxide is used in polycarbonate, the thermal stability of polycarbonate is lowered due to titanium dioxide. In order to compensate for this, titanium dioxide is used as inorganic materials such as silicon dioxide, zircon dioxide, sodium silicate, sodium aluminate, sodium aluminum silicate, and mica. Although it is modified with a surface treating agent and organic surface treating agents such as polydimethylsiloxane, trimethyl propane, pentaerythritol, the effect of improving thermal stability is insignificant.

One embodiment of the present invention is to provide a polycarbonate-based thermoplastic resin composition having a balance of physical properties excellent in thermal stability, impact strength and flame retardancy.

Another embodiment of the present invention is to provide a molded article prepared from the polycarbonate-based thermoplastic resin composition.

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, and other technical problems will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention () polycarbonate resin; (B) titanium dioxide; (C) organosiloxanes; (D) phosphorus compounds; And (E) provides a polycarbonate-based thermoplastic resin composition comprising a sulfur compound.

Another embodiment of the present invention provides a molded article prepared from the polycarbonate-based thermoplastic resin composition.

Other specific details of embodiments of the present invention are included in the following detailed description.

Since the polycarbonate-based thermoplastic resin composition of the present invention has excellent physical property balance of thermal stability, impact strength, and flame retardancy, it can be usefully applied to materials of parts such as liquid crystal display (LCD) backlights or TVs, monitors, and laptops. Can be.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified in the present invention, "substituted" means an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 36 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and having 6 to 30 carbon atoms. Aryloxy group, NRR '(wherein R and R' are each independently a substituent selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms), a carboxyl group, and hydroxy Mean substituted by a substituent selected from the group consisting of groups.

Also, unless otherwise specified in the present invention, "alkyl group", "aryl group", "alkenyl group", "aryloxy group", and "alkoxy group" are each an alkyl group having 1 to 30 carbon atoms, an aryl having 6 to 30 carbon atoms, respectively. A group, a C2-C30 alkenyl group, a C6-C30 aryloxy group, and a C1-C30 alkoxy group are meant.

The polycarbonate-based thermoplastic resin composition according to one embodiment of the present invention includes (A) polycarbonate resin, (B) titanium dioxide, (C) organosiloxane, (D) phosphorus compound, and (E) sulfur compound .

Hereinafter, each component of the polycarbonate-based thermoplastic resin composition according to an embodiment of the present invention will be described in detail.

(A) polycarbonate resin

The polycarbonate resin may be prepared by reacting a compound selected from the group consisting of diphenols represented by the following Chemical Formula 1 with phosgene, halogen formate, carbonate, and combinations thereof.

[Formula 1]

(In the formula 1,

A is a single bond, substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, substituted or unsubstituted alkylidene group having 2 to 5 carbon atoms, substituted or unsubstituted cycloalkylene group having 5 to 6 carbon atoms, substituted or unsubstituted A cycloalkylidene group having 5 to 10 carbon atoms, CO, S, and SO ₂ ;

Each of R ₄₀ and R ₄₁ is independently a substituent selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

n ₄₀ and n ₄₁ are each independently an integer of 0 to 4).

The diphenols represented by the formula (1) may combine two or more kinds to constitute a repeating unit of the polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane (also called 'bisphenol-A'), 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydrate Hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, etc. are mentioned. 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, or 1,1-bis- in the said diphenols (4-hydroxyphenyl) -cyclohexane can be preferably used. In addition, 2,2-bis- (4-hydroxyphenyl) -propane can be used more preferably.

The polycarbonate resin may preferably use a weight average molecular weight of 10,000 to 200,000 g / mol, and more preferably 15,000 to 80,000 g / mol, but is not limited thereto.

The polycarbonate resin may be a mixture of copolymers prepared from two or more kinds of diphenols. In addition, the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.

Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as said linear polycarbonate resin. Examples of the branched polycarbonate resins include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. The polyfunctional aromatic compound is preferably contained in 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. As said polyester carbonate copolymer resin, what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, diaryl carbonates such as diphenyl carbonate, ethylene carbonate, etc. may be used .

(B) titanium dioxide

As the titanium dioxide, general titanium dioxide may be used, and a manufacturing method and a particle diameter thereof are not limited.

Titanium dioxide according to an embodiment of the present invention is preferably used to modify the surface by an inorganic surface treatment agent or an organic surface treatment agent. The surface modification is also carried out by a method of coating the titanium dioxide surface.

The inorganic surface treatment agent may be aluminum oxide (alumina, Al ₂ O ₃ ), silicon dioxide (silica, SiO ₂ ), zirconia (zircon dioxide, ZrO ₂ ), sodium silicate, sodium aluminate, sodium aluminum silicate, zinc oxide, mica Etc., These can also be used in mixture of 2 or more types. The inorganic surface treating agent is used in an amount of 2 parts by weight or less based on 100 parts by weight of titanium dioxide.

Examples of the organic surface treatment agent include polydimethylsiloxane, trimethyl propane (TMP), pentaerythritol, and two or more kinds thereof. The organic surface treating agent is used in an amount of 0.3 parts by weight or less based on 100 parts by weight of titanium dioxide.

In a preferred embodiment of the present invention, titanium dioxide coated with 2 parts by weight or less of alumina (Al ₂ O ₃ ) is used for 100 parts by weight of titanium dioxide.

In addition, the titanium dioxide coated with alumina is an inorganic surface treatment agent such as silicon dioxide, zirconium dioxide, sodium silicate, sodium aluminate, sodium aluminum silicate, mica, organic surface such as polydimethylsiloxane, trimethylpropane (TMP), pentaerythritol, etc. It can be further modified with a treatment agent.

The titanium dioxide is included in 5 to 50 parts by weight, preferably 10 to 35 parts by weight based on 100 parts by weight of polycarbonate resin. When titanium dioxide is included in the above range, the resin composition has excellent characteristics of light reflection and impact resistance.

(C) organosiloxane

The organosiloxane may be represented by the following formula (2).

[Formula 2]

(In Formula 2,

R ₁ to R ₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms And substituted or unsubstituted NRR ', wherein R and R' are each independently a hydrogen atom and a substituent selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms. Is a substituent,

0≤n <10,000.)

Preferred examples of the organic siloxane according to one embodiment of the present invention include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer, and the like. .

The organosiloxane is included in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polycarbonate resin. When organosiloxane is contained in the said range, it is excellent in the flame retardance and extrudability of a resin composition.

(D) phosphorus compounds

The phosphorus compound may be represented by the following Chemical Formula 3.

(3)

(In Chemical Formula 3,

R ₁₁ to R ₁₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms And it is a substituent selected from the group consisting of a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms,

R ₉ and R ₁₀ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms , A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted NRR ', wherein R and R' are each independently a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms A substituent selected from the group consisting of: a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted hydroxy group.

The phosphorus compound is included in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polycarbonate resin. When the phosphorus compound is included in the above range, there is a characteristic that the resin composition has excellent thermal stability and impact resistance.

(E) Sulfur compounds

The sulfur compound may be represented by the following formula (4).

[Formula 4]

(In Formula 4,

R ₁₉ to R ₂₆ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms And it is a substituent selected from the group consisting of a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms,

R ₂₇ to R ₃₀ are each independently a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxylene group having 1 to 30 carbon atoms, substituted Or an unsubstituted aryloxylene group having 6 to 30 carbon atoms, a substituted or unsubstituted NRR ', wherein R and R' are each independently a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. A substituent selected from the group), a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted hydroxy group.

R ₃₁ to R ₃₄ are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms , A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted NRR ', wherein R and R' are each independently a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms A substituent selected from the group consisting of: a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted hydroxy group.

The sulfur-based compound is included in 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight based on 100 parts by weight of polycarbonate resin. When the sulfur-based compound is included in the above range there is a feature excellent in the thermal stability and impact resistance of the resin composition.

(F) other additives

Polycarbonate-based thermoplastic resin composition according to an embodiment of the present invention may further include an additive.

The additives include antidropping agents, antibacterial agents, antioxidants, mold release agents, thermal stabilizers, light stabilizers, compatibilizers, dyes, inorganic additives, surfactants, coupling agents, fillers, admixtures, colorants, stabilizers, and electrostatic agents. It can be used as an inhibitor, a pigment, a flame retardant, a weathering agent, an ultraviolet ray shielding agent, a nucleation agent, an adhesive agent, an adhesive agent, or a combination thereof.

As said antioxidant, a phenol type, a phosphide type, a thioether type, or an amine type antioxidant can be used preferably.

As the mold release agent, a fluorine-containing polymer, silicone oil, a metal salt of stearyl acid, a metal salt of montanic acid, a montanic acid ester wax, or a polyethylene wax can be preferably used.

As the filler, glass fiber, carbon fiber, silica, mica, alumina, clay, calcium carbonate, calcium sulfate, or glass beads may be preferably used, and when the filler is added, mechanical properties such as mechanical strength and heat resistance may be improved. You can.

As said coloring agent, dye or a pigment can be used preferably.

As said weathering agent, a benzophenone type or an amine type weathering agent can be used preferably.

Titanium oxide or carbon black may be preferably used as the sunscreen.

As the nucleating agent, talc or clay can be preferably used.

The additive is preferably included in 0.1 to 30 parts by weight based on 100 parts by weight of polycarbonate resin. When the additive is included in the above range it is possible to obtain the effect of the additive according to each application and to obtain excellent mechanical properties and improved appearance of the surface.

Polycarbonate-based thermoplastic resin composition according to an embodiment of the present invention can be prepared by a known method. For example, after mixing the components and additives of the present invention described above, it can be melt-extruded in an extruder and produced in pellet form.

According to another embodiment of the present invention, there is provided a molded article manufactured by molding the polycarbonate-based thermoplastic resin composition of an embodiment of the present invention. The molded article may have, for example, a form in which titanium dioxide, an organic siloxane, a phosphorus compound, and a sulfur compound are uniformly dispersed in the polycarbonate resin. Accordingly, improved thermal stability, impact strength, and flame retardancy can be ensured by the interaction of the components. Thereby, it can be usefully applied to the material of an LCD backlight or a component of a television, a monitor, and a notebook.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

EXAMPLE

Each component used in the preparation of the polycarbonate-based thermoplastic resin composition according to the embodiment of the present invention is as follows.

(A) polycarbonate resin

As a bisphenol-A type polycarbonate having a weight average molecular weight (Mw) of 25,000 g / mol, PANLITE L-1250WP manufactured by Teijin, Japan was used.

(B) titanium dioxide

As titanium dioxide, US-made TI-PURE R-106 from Dupont was used.

(C) organosiloxane

As the organosiloxane, TSF-433 polymethylphenylsiloxane oil manufactured by GE-Toshiba Silicone Co., Ltd. was used.

(D) phosphorus compounds

As the phosphorus compound, PEP 36 from ADK STAB was used.

(E) Sulfur compounds

As a sulfur compound, AO # 412S of ADK STAB was used.

(F) Phenolic Compounds

As the phenolic compound used in Comparative Example (F-1), IRGANOX 1010 manufactured by Ciba-Gaiji Co. was used.

(F-2) As a phenolic compound used in Comparative Example, IRGANOX 1076 manufactured by Ciba-Gaiji Co. was used.

Examples 1 to 3 and Comparative Examples 1 to 4

To prepare a polycarbonate-based thermoplastic resin composition by mixing each component shown in Table 1 in each content range, and each resin composition was melt kneaded in a twin screw melt extruder heated to 280 ℃ to 300 ℃ to prepare a chip state It was. Subsequently, after the obtained chip was dried at 130 ° C. for at least 5 hours, a flat plate specimen (10 cm × 10 cm × 0.3 cm thickness) was prepared for evaluation of various physical properties using a screw-type injection machine heated to 280 to 300 ° C. In addition, the plate specimen (width 10cm × length 10cm × thickness 0.3cm) was prepared after 10 minutes at 300 ℃ for thermal stability evaluation.

TABLE 1

Various physical properties of the specimens prepared according to Examples 1 to 3 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 2 below.

(1) Notched Izod impact strength: 1/8 "test piece was measured according to ASTM D256 standard.

(2) Flame retardant: evaluated by using 2.0mm thick specimens in accordance with UL-94.

(3) Thermal Stability: The delta E was measured by using a color meter on the plate specimens before and after 10 minutes at 300 ° C.

TABLE 2

As shown in Table 1 and 2, in the case of Examples 1 to 3 according to the present invention it can be confirmed that not only thermal stability but also excellent impact strength and flame retardancy.

On the other hand, in Comparative Example 1, which does not use an organosiloxane, it can be seen that the flame retardancy is remarkably decreased, and in Comparative Example 2, in which neither the phosphorus compound nor the sulfur compound is used, the thermal stability is very low. In addition, in the case of Comparative Example 3, which does not use the sulfur-based compound and Comparative Example 4, which does not use the phosphorus-based compound, it can be confirmed that thermal stability is lowered.

From this, it can be seen that when a mixture of titanium dioxide, an organosiloxane, a phosphorus compound, and a sulfur compound is mixed with the polycarbonate resin, it is possible to secure a physical property balance having excellent thermal stability, impact strength, and flame retardancy.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It can be understood that this can be implemented. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (13)

(A) polycarbonate resin; (B) titanium dioxide; (C) organosiloxanes; (D) phosphorus compounds; And (E) Sulfur compounds Polycarbonate-based thermoplastic resin composition comprising a. The method of claim 1, The polycarbonate resin (A) is a polycarbonate-based thermoplastic resin composition prepared by reacting diphenols with a compound selected from the group consisting of phosgene, halogen formate, carbonate, and combinations thereof. The method of claim 1, Wherein (B) titanium dioxide is a polycarbonate-based thermoplastic resin composition is contained in 5 to 50 parts by weight based on 100 parts by weight of (A) polycarbonate resin. The method of claim 1, Wherein (B) titanium dioxide is a polycarbonate-based thermoplastic resin composition surface-modified by a surface treatment agent selected from the group consisting of inorganic surface treatment agent, organic surface treatment agent, and combinations thereof. The method of claim 4, wherein The inorganic surface treatment agent is selected from the group consisting of silicon dioxide, zirconium dioxide, sodium silicate, sodium aluminate, sodium aluminum silicate, mica, and combinations thereof. The method of claim 4, wherein The organic surface treatment agent is a polycarbonate-based thermoplastic resin composition selected from the group consisting of polydimethylsiloxane, trimethyl propane (TMP), pentaerythritol, and combinations thereof. The method of claim 1, The polycarbonate-based thermoplastic resin composition of (C) the organic siloxane is contained in 0.1 to 10 parts by weight based on 100 parts by weight of (A) polycarbonate resin. The method of claim 1, The (C) organosiloxane is a polycarbonate-based thermoplastic resin composition is represented by the following formula (2). [Formula 2]

(In Formula 2, R ₁ to R ₈ are each independently a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted NRR ', wherein R and R 'are each independently a substituent selected from the group consisting of a hydrogen atom and a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, 0≤n <10,000.) The method of claim 1, The polycarbonate-based thermoplastic resin composition of (D) the phosphorus-based compound is contained in 0.01 to 5 parts by weight based on 100 parts by weight of (A) polycarbonate resin. The method of claim 1, The (D) phosphorus compound is a polycarbonate-based thermoplastic resin composition represented by the following formula (3). (3)

(In Chemical Formula 3, R ₁₁ to R ₁₈ are each independently hydrogen or selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkenyl group. A substituent, R ₉ and R ₁₀ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted NRR ′ (wherein R and R ′ are each independently a substituent selected from the group consisting of a hydrogen atom and a substituted or unsubstituted alkyl group), a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted hydroxy group It is a substituent selected from the group consisting of.) The method of claim 1, The sulfur compound (E) is a polycarbonate-based thermoplastic resin composition (A) 0.01 to 5 parts by weight based on 100 parts by weight of the polycarbonate resin. The method of claim 1, The sulfur compound (E) is a polycarbonate-based thermoplastic resin composition represented by the following formula (4). [Formula 4]

(In Formula 4, R ₁₉ to R ₂₆ are each independently hydrogen or selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted alkenyl group. A substituent, R ₂₇ to R ₃₀ are each independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkoxylene group, a substituted or unsubstituted aryloxylene group, a substituted or unsubstituted NRR (Wherein R and R 'are each independently a substituent selected from the group consisting of a hydrogen atom and a substituted or unsubstituted alkyl group), a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted hydroxy group Is a connector selected from the group, R ₃₁ to R ₃₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted group NRR ′ (wherein R and R ′ are each independently a substituent selected from the group consisting of a hydrogen atom and a substituted or unsubstituted alkyl group), a substituted or unsubstituted carboxyl group, and a substituted or unsubstituted hydroxy group It is a substituent selected from the group consisting of.) A molded article prepared from the polycarbonate-based thermoplastic resin composition according to any one of claims 1 to 12.