JP2020023650A - Styrene-based resin composition and molded article - Google Patents

Abstract

To provide a styrene-based resin composition that generates an extremely small amount of a gelled substance and produces a molded article having excellent appearance.SOLUTION: The styrene-based resin composition includes a styrene-based resin and an ether compound. In the styrene-based resin composition, the styrene-based resin is produced by copolymerizing a monomer mixture including a styrene-based monomer and a (meth)acrylic acid-based monomer and the ether compound has a specific structure.SELECTED DRAWING: None

Description

  The present invention relates to a styrene resin composition and a molded product.

  Styrene- (meth) acrylic acid-based copolymer resin has excellent heat resistance as compared with general polystyrene, and is mainly used as a material for food packaging materials for microwave oven heating. Specifically, after being formed into an extruded foam sheet or a biaxially stretched sheet, it is used by being shaped into a food container or a lid. Further, since it has an excellent balance between transparency and heat resistance, it is also suitable for a light-diffusing resin plate containing a light-diffusing agent, such as a lighting cover or a light-diffusing plate for a transmissive display.

  As a drawback of styrene- (meth) acrylic acid-based copolymer resin, carboxyl group in polymer causes condensation reaction between polymer molecules due to heat history when processing into sheet etc. to generate gel-like substance It has been pointed out that a gel-like substance may be produced by a similar reaction in the process of producing a copolymer resin.

  Patent Document 1 discloses a technique of suppressing the formation of a gel-like substance by adding a polyoxyethylene alkyl ether.

WO2007 / 034789

  However, even if the technique of Patent Document 1 is adopted, the generation of a gel-like substance cannot be completely suppressed, and it is desired to further suppress the generation of a gel-like substance.

  The present invention has been made in view of such circumstances, and provides a styrene-based resin composition that can effectively suppress the generation of a gel-like substance.

  According to the present invention, there is provided a styrene resin composition containing a styrene resin and an ether compound, wherein the styrene resin is a monomer mixture containing a styrene monomer and a (meth) acrylic acid monomer. And a styrene-based resin composition represented by the general formula (1) is provided as the ether compound.

  The present inventors have conducted intensive studies and found that the addition of the ether compound represented by the general formula (1) can effectively suppress the formation of a gel-like substance. It has arrived.

1. Styrene resin composition The styrene resin composition of the present invention contains a styrene resin A and an ether compound B. Hereinafter, each component will be described in detail.

<<< Styrene resin A >>>
The styrene resin A is obtained by copolymerizing a monomer mixture containing a styrene monomer and a (meth) acrylic acid monomer.

  The styrene monomer is a monocyclic or polycyclic aromatic vinyl monomer, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5 -Dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, p-tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenylbenzene (α-methylstyrene), isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, etc. of One or a mixture of two or more, preferably styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene , 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, p-tert-butylstyrene, or a mixture of two or more thereof, more preferably styrene.

  The (meth) acrylic acid-based monomer is one or both of acrylic acid monomers such as acrylic acid and methacrylic acid, and is preferably methacrylic acid.

  The monomer mixture may contain only a styrene-based monomer and a (meth) acrylic acid-based monomer, and may contain other monomers copolymerizable therewith as long as the effects of the present invention are not impaired. Is fine. Other monomers include acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, acrylic monomers such as butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, and α such as maleic anhydride and fumaric acid. And imide monomers such as .beta.-ethylenically unsaturated carboxylic acids, phenylmaleimide and cyclohexylmaleimide.

  The monomer mixture preferably contains a styrene monomer and a (meth) acrylic acid monomer as main components, and the styrene monomer and the (meth) acrylic acid monomer in the monomer mixture. The total proportion of the body is preferably 50% by mass or more, for example, 50 to 100% by mass, and specifically, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 %, And may be in the range between any two of the numerical values exemplified herein.

  The content of the structural unit derived from the (meth) acrylic acid-based monomer is preferably 0.1 to 30% by mass based on 100% by mass of the styrene-based resin composition. The structural unit derived from the (meth) acrylic acid-based monomer is, for example, a (meth) acrylic acid-based monomer unit. If the value is too small, the heat resistance may be insufficient. If the value is too large, the fluidity at the time of melting may be reduced and the moldability may be deteriorated. This ratio is specifically, for example, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, and 30% by mass, and may be in the range between any two of the numerical values exemplified here.

  The weight average molecular weight (Mw) of the styrene resin A is preferably 150,000 to 700,000, and more preferably 150,000 to 400,000. Specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 700,000, and a range between any two of the numerical values exemplified here. May be inside. If Mw is too small, the strength of the molded product will be insufficient, and if Mw is too large, the moldability will decrease. The weight average molecular weight of the styrenic resin A is controlled by the reaction temperature, residence time, type and amount of polymerization initiator, type and amount of chain transfer agent, type and amount of solvent used during polymerization, and the like in the polymerization step. be able to.

The weight average molecular weight (Mw) can be measured using gel permeation chromatography (GPC) under the following conditions.
GPC model: Shodex GPC-101 manufactured by Showa Denko KK
Column: PLgel 10 μm MIXED-B manufactured by Polymer Laboratories
Mobile phase: tetrahydrofuran Sample concentration: 0.2% by mass
Temperature: oven 40 ° C, inlet 35 ° C, detector 35 ° C
Detector: Differential refractometer The molecular weight is calculated as the molecular weight in terms of polystyrene by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene.

<<< ether compound B >>>
The ether compound B is represented by the general formula (1).

  Z1 to Z5 in the general formula (1) are the same or different and are a hydrogen atom or a hydrocarbon group which may have a hetero atom. It is preferable that three or four of Z1 to Z5 are hydrogen atoms and the rest are hydrocarbon groups which may have a hetero atom.

  Examples of the hetero atom include oxygen, nitrogen, sulfur, and fluorine. The hydrocarbon group preferably has 1 to 30 carbon atoms, and more preferably 2 to 20 carbon atoms. This carbon number is specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 , 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 and may be in the range between any two of the numerical values exemplified here.

  The hydrocarbon group is preferably an aliphatic hydrocarbon group which may have a substituent. Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an allyl group, and a vinyl group. Specifically, the carbon number of the aliphatic hydrocarbon group is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and may be in the range between any two of the numerical values exemplified here. Examples of the substituent of the aliphatic hydrocarbon group include an aromatic hydrocarbon group such as a phenyl group. The aromatic hydrocarbon group may be substituted with a substituent such as a hydroxyl group. It is preferred that a substituent is bonded to the 1-position carbon of the aliphatic hydrocarbon group.

  The hydrocarbon group may be an aromatic hydrocarbon group which may have a substituent. Examples of the aromatic hydrocarbon group include a phenyl group and a tolyl group. Examples of the substituent include an aliphatic hydrocarbon group such as alkyl and a hydroxyl group.

  At least two of Z1 to Z5 may be crosslinked to form an alicyclic or aromatic ring.

  At least one of Z1 to Z5 is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent. This substituent is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, more preferably an aromatic ring, and more preferably phenyl bonded to the alkyl group. And more preferably a 1-phenylethyl group.

  N in the general formula (1) represents the number of carbon atoms in the alkylene oxide structure, and is an integer of 1 to 10 (preferably 2 to 4). n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, for example, and may be in a range between any two of the numerical values exemplified here. .

  X in the general formula (1) represents the average number of addition of alkylene oxide units, and is an integer of 1 to 100 (preferably 5 to 50). X is specifically, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 And may be in the range between any two of the numerical values exemplified here.

  Examples of the ether compound B include polyoxyethylene distyrenated phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, and polyoxyethylene phenyl Ether, polyoxyethylene β-naphthyl ether, polyoxyethylene bisphenol A ether, polyoxyethylene bisphenol F ether and the like.

  The content of the ether compound B is preferably 0.001 to 10% by mass based on 100% by mass of the styrene resin composition. If this value is too small, the formation of a gel-like substance may not be sufficiently suppressed, and if this value is too large, the heat resistance may decrease. The content is specifically, for example, 0.001, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7. , 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by mass, within the range between any two of the numerical values exemplified herein. Is also good.

<< Other additives >>
Various additives can be added to the styrene-based resin composition as needed as long as the properties of the present invention are not impaired. The type of additive is not particularly limited as long as it is generally used for plastics, but an antioxidant, a flame retardant, a lubricant, a processing aid, an antiblocking agent, an antistatic agent, an antifogging agent, and an improvement in light resistance. Agents, softeners, plasticizers, inorganic reinforcing agents, crosslinking agents, pigments, dyes, and the like, or mixtures thereof. Further, the styrene-based resin composition may contain only the ether compound B as the ether compound, or may contain an ether compound other than the ether compound B (eg, polyoxyethylene alkyl ether).

2. Method for Producing Styrenic Resin Composition The styrenic resin composition of the present invention can be produced by adding an ether compound B to a styrenic resin A. Examples of the polymerization method for the styrene resin include known styrene polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. In terms of quality and productivity, bulk polymerization and solution polymerization are preferred, and continuous polymerization is preferred. As the solvent, for example, alkylbenzenes such as benzene, toluene, ethylbenzene and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane can be used.

  At the time of polymerization of the styrene- (meth) acrylic acid copolymer resin, if necessary, a polymerization initiator such as a polymerization initiator, a chain transfer agent, a cross-linking agent, and other polymerization aids can be used. As the polymerization initiator, a radical polymerization initiator is preferable. For example, known and commonly used 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, 2,2- Peroxyketals such as di (4,4-di-t-butylperoxycyclohexyl) propane and 1,1-di (t-amylperoxy) cyclohexane; cumene hydroperoxide; t-butyl hydroperoxide; Alkyl peroxides such as hydroperoxides, t-butyl peroxyacetate, t-amyl peroxy isononanoate, t-butyl cumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t -Dialkyl peroxides such as hexyl peroxide, t-butylperoxyacetate; , Peroxyesters such as t-butylperoxybenzoate and t-butylperoxyisopropyl monocarbonate, and peroxycarbonates such as t-butylperoxyisopropyl carbonate and polyethertetrakis (t-butylperoxycarbonate) , N, N'-azobis (cyclohexane-1-carbonitrile), N, N'-azobis (2-methylbutyronitrile), N, N'-azobis (2,4-dimethylvaleronitrile), N, N '-Azobis [2- (hydroxymethyl) propionitrile] and the like, and one or more of these can be used in combination. Examples of the chain transfer agent include aliphatic mercaptan, aromatic mercaptan, pentaphenylethane, α-methylstyrene dimer, terpinolene, and the like.

  In the case of continuous polymerization, the styrene-based resin composition can be produced by a method including a polymerization step, a devolatilization step, and a granulation step.

  First, in a polymerization step, a polymerization reaction is controlled by adjusting a polymerization temperature or the like so as to obtain a target molecular weight, a molecular weight distribution, and a reaction conversion using a well-known complete mixing tank type stirring tank, a tower type reactor or the like.

  The polymerization solution containing the polymer that has left the polymerization step is transferred to a devolatilization step to remove unreacted monomers and a polymerization solvent. The devolatilization process includes a vacuum devolatilization tank with a heater, a devolatilization extruder with a vent, and the like. The polymer in the molten state that has exited the devolatilization step is transferred to the granulation step. In the granulation step, the molten resin is extruded into a strand shape from a porous die, and processed into a pellet shape by a cold cut method, an air hot cut method, or an underwater hot cut method.

It is preferable to add the ether compound B before or during the devolatilization step. Specifically, the ether compound B is preferably added by any of the following methods (1) to (4).
(1) It is added to the raw material monomer mixture.
(2) Add during the polymerization step.
(3) Add to the polymerization solution after the polymerization step.
(4) When the devolatilization step is composed of two stages, and the resin temperature of the first stage is lower than 200 ° C., it is added between the first stage and the second stage.

3. Uses of styrene resin composition The styrene resin composition of the present invention can be formed into a molded product by a molding method according to the purpose, such as injection molding, extrusion molding, compression molding, blow molding, and the shape thereof is limited. Not something. For example, if it is a plate-like molded product, it can be processed into a light guide plate or the like.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

1. Measurement method (1) Measurement of methacrylic acid unit content 0.5 g of a styrene resin composition was weighed and dissolved in a mixed solution of toluene / ethanol = 8/2 (volume ratio), and then 0.1 mol / L of potassium hydroxide. Neutralization titration was performed with an ethanol solution, the end point was detected, and the content of methacrylic acid unit on a mass basis was calculated from the amount of the potassium hydroxide ethanol solution used.

(2) Measurement of the content of the ether compound 5 g of the styrene resin composition is weighed and dissolved in THF. After dissolution, the polymer component was reprecipitated with methanol and a small amount of hydrochloric acid, and the reprecipitate was removed by filtration. The filtrate was concentrated, and finally a 10 ml methanol solution was concentrated, and the ether compound was quantified by high performance liquid chromatography (HPLC). The quantification was performed by preparing three methanol solutions with known ether compound concentrations and preparing a calibration curve.
HPLC model: Alliance system 2695 separation module manufactured by Nippon Waters Detector: Differential refractometer (RI)
Column: Tosoh TSKgel ODS-120T 4.6 mm (ID) x 15 cm (L)
Mobile phase: methanol / water = 80/20 (volume ratio) phosphoric acid 0.2% by mass added Flow rate: 1.0 ml / min Column oven temperature: 40 ° C.
Detector temperature: 30 ° C

(3) Measurement of Vicat Softening Temperature The Vicat softening temperature was determined according to JIS K-7206 at a heating rate of 50 ° C./hr and a test load of 50 N.

(4) Measurement of MEK insoluble content <Before heating>
1 g of the styrene-based resin composition was weighed, and 35 ml of methyl ethyl ketone was added and dissolved. Was settled, and the supernatant was removed by decantation to obtain an insoluble content, which was pre-dried in a safety oven at 90 ° C. for 2 hours, further dried in a vacuum dryer at 120 ° C. for 1 hour, and dried in a desiccator for 20 minutes. After cooling, the mass G of the dried insoluble matter was measured, and the mass% of the insoluble matter was calculated.

<After heating>
1 g of the styrene resin composition was weighed and heat-treated in an oven at 230 ° C. for 3 hours under vacuum. Thereafter, the insoluble content was measured by the same method as before the heating, and the mass% of the insoluble content was calculated.
The gel-like substance is considered to be formed by the condensation reaction of the carboxyl group in the styrene resin between polymer molecules, and is a component insoluble in methyl ethyl ketone.

(5) Measurement of HAZE Pellets of the styrene resin composition were injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 50 ° C. using an injection molding machine (IS130FII-3A) manufactured by Toshiba Machine Co., Ltd. Using the obtained test piece (thickness: 2 mm, dimensions: 40 mm × 40 mm), HAZE (unit:%) was measured using a haze meter (NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K-7105. .

2. Examples and Comparative Examples Examples and comparative examples were carried out by the following methods.

<Example 1>
The polymerization step was constituted by connecting in series a first reactor which was a complete mixing type stirring tank having an internal volume of 39 liters and a second reactor which was a complete mixing type stirring tank having an internal volume of 39 liters. A raw material solution composed of a mixed solution of 71% by mass of styrene, 12% by mass of methacrylic acid, and 17% by mass of ethylbenzene was prepared.

  This raw material solution was continuously supplied to the first reactor at a rate of 12.6 kg per hour, and each reactor was circulated in a full state. At the inlet of the first reactor, 1,1-bis (t-butylperoxy) cyclohexane (Nippon Oil & Fat Co., Ltd., Perhexa C) was 250 ppm by mass based on the total amount of styrene and methacrylic acid in the raw material solution. Mixed. At the inlet of the first reactor, the ether compound [B-1] was continuously added. The reaction temperature of each reactor was adjusted to 130 ° C. in the first reactor and 140 ° C. in the second reactor.

  Subsequently, the solution containing the copolymer resin continuously taken out from the second reactor was introduced into a vacuum devolatilization tank with a preheater provided in two stages in series, and after separating unreacted monomer and ethylbenzene, a strand was formed. The mixture was extruded and cooled, and then cut into pellets to obtain a styrene resin composition. The temperature of the preheater was set at 175 ° C., the pressure of the vacuum devolatilization tank was set at 500 mmHg, and the jacket temperature of the vacuum devolatilization tank was set at 185 ° C. for the first-stage vacuum devolatilization tank. The temperature of the preheater was set to 240 ° C, the pressure of the vacuum devolatilization tank was set to 8 mmHg, and the jacket temperature of the vacuum devolatilization tank was set to 240 ° C for the second stage vacuum devolatilization tank with a preheater. The resin temperature in the first-stage vacuum devolatilization tank was 168 ° C, and the resin temperature in the second-stage vacuum devolatilization tank was 231 ° C.

  Various physical properties were measured for the obtained styrene-based resin composition. Table 1 shows the results.

Details of the components in Table 1 are as follows.
Ether compound B
B-1: polyoxyethylene distyrenated phenyl ether (manufactured by Kao Corporation, Emulgen A-90, average addition number of ethylene oxide units 18)
B-2: polyoxyethylene distyrenated phenyl ether (manufactured by Kao Corporation, Emulgen A-60, average addition number of ethylene oxide units 12)
B-3: polyoxyethylene distyrenated phenyl ether (manufactured by Kao Corporation, Emulgen A-500, average addition number of ethylene oxide units 50)
B-4: Polyoxyethylene styrenated phenyl ether (manufactured by Aoki Yushi Kogyo KK, KTSP-16, average addition number of ethylene oxide units 16)
B-5: polyoxyethylene nonyl phenyl ether (manufactured by Aoki Yushi Kogyo KK, Brownon N-513, average addition number of ethylene oxide units 13)
Polyoxyethylene alkyl ether (polyoxyethylene lauryl ether) (manufactured by Kao Corporation, Emulgen 109P, average addition number of ethylene oxide units 9)

<Examples 2 to 9>
A styrene resin composition was produced in the same manner as in Example 1 except that the type and / or the amount of the ether compound B were changed as shown in Table 1, and various physical properties were measured.

<Example 10>
Except that the raw material solution was changed to a mixed solution of 77.1% by mass of styrene, 5.9% by mass of methacrylic acid, and 17% by mass of ethylbenzene, a styrene resin composition was produced in the same manner as in Example 1, and various physical properties were obtained. Was measured.

<Example 11>
Except that the raw material solution was changed to a mixed solution of 63.5% by mass of styrene, 19.5% by mass of methacrylic acid, and 17% by mass of ethylbenzene, a styrene-based resin composition was produced in the same manner as in Example 3, and various physical properties were obtained. Was measured.

<Comparative Examples 1 to 3>
Except not adding the ether compound, styrene resin compositions were produced in the same manner as in Examples 1, 10, and 11, and various physical properties were measured.

<Comparative Examples 4 to 6>
Styrene resin compositions were produced in the same manner as in Examples 1, 4, and 10 except that polyoxyethylene alkyl ether was added instead of the ether compound B, and various physical properties were measured.

3. Discussion In all of the examples, the increase in MEK-insoluble content due to heating was very small. Since the MEK-insoluble matter is mainly a gel-like substance, it was demonstrated that the formation of the gel-like substance was suppressed.
When Examples 1, 4, and 10 were compared with Comparative Examples 4 to 6, when the polyoxyethylene alkyl ether was added instead of the ether compound B, the Vicat softening temperature was significantly reduced.

  By using the styrenic resin composition of the present invention, a resin composition and a molded product having extremely low gel can be produced, and a molded product having excellent appearance can be obtained. Further, the generation of gel in the manufacturing process can be suppressed more than before, and the production efficiency can be increased.

Claims (11)

A styrene-based resin composition containing a styrene-based resin and an ether compound,
The styrene resin is obtained by copolymerizing a monomer mixture containing a styrene monomer and a (meth) acrylic acid monomer,
The styrene-based resin composition, wherein the ether compound is represented by the general formula (1).


(Wherein Z1 to Z5 in the formula are the same or different and are each a hydrogen atom or a hydrocarbon group which may have a hetero atom. At least two of Z1 to Z5 are crosslinked to form an alicyclic ring. N represents the number of carbon atoms of the alkylene oxide structure, and is an integer of 1 to 10. X represents the average number of additions of the alkylene oxide unit, and is an integer of 1 to 100. .) The styrenic resin composition according to claim 1,
A styrene-based resin composition, wherein the content of the structural unit derived from the (meth) acrylic acid-based monomer is 0.1 to 30% by mass based on 100% by mass of the styrene-based resin composition. A styrenic resin composition according to claim 1 or claim 2,
A styrene-based resin composition, wherein the content of the ether compound is 0.001 to 10% by mass based on 100% by mass of the styrene-based resin composition. A styrenic resin composition according to any one of claims 1 to 3, wherein
A styrene resin composition, wherein at least one of Z1 to Z5 is an alkyl group having 1 to 20 carbon atoms which may have a substituent. The styrenic resin composition according to claim 4,
The styrene resin composition, wherein the substituent is a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom. The styrenic resin composition according to claim 5, wherein
The styrenic resin composition according to claim 5, wherein the substituent includes an aromatic ring. The styrenic resin composition according to claim 6,
The styrene-based resin composition, wherein the aromatic ring of the substituent is a phenyl group bonded to the alkyl group. The styrenic resin composition according to claim 7,
The styrene resin composition, wherein the substituent is a 1-phenylethyl group. A styrenic resin composition according to any one of claims 1 to 8, wherein
A styrene-based resin composition wherein the alkylene oxide structure has 2 to 4 carbon atoms. A styrenic resin composition according to any one of claims 1 to 9, wherein
A styrene resin composition, wherein the average addition number of the alkylene oxide unit is 5 to 50.   A molded article comprising the styrene resin composition according to any one of claims 1 to 10.