Polyalkylene oxides as dispersants for graphene materials

Abstract

The subject of the present invention is the use of a polyalkylene oxide having at least one aromatic group as a dispersing agent for graphene material; a method for dispersing graphene material, which uses said polyalkylene oxide as a dispersing agent; and a composition comprising said dispersing agent and a graphene material.

Description

[Technical Field]

[0001] This invention relates to polyalkylene oxides as dispersants for graphene materials.

[0002] Graphene materials are used in many technological fields. Graphene, its manufacturing process, properties, and applications are discussed in detail in technical literature (Roempp online, https: / / roempp.thieme.de / lexicon / RD-07-02758 (See Angew. Chem. Int. Ed. 2014, 53, 7714-7718; Mater. Today 2012, 15(3) 86-97).

[0003] Graphene material is commercially available as a powder with a very low bulk density, often in the range of 2-400 g / l. Not only is the bulk density low, but graphene material is also poorly fluid or generates a high amount of dust when transported by gravity. As a result, handling becomes difficult, leading to problems during weighing and feeding, which must be considered critical from an environmental protection and labor safety perspective. Similarly, closed systems for introducing solids have limited effectiveness because, while they certainly address labor safety issues, they do not solve the so-called bridging problem during continuous or semi-continuous feeding of graphene material in dispersion containers, kneaders, or extrusion lines. Bridging is understood as the uneven feeding of solids, which can lead to feeder blockage, potentially requiring mechanical release, which is undesirable. Consequently, volumetric feeding often becomes impossible, and gravimetric feeding is compromised.

[0004] Poor handling is evident, for example, when incorporating powdered graphene materials into solvents or monomer resins of so-called thermal interface materials, sealants, and adhesives. Incorporating graphene materials into liquid systems is generally difficult. For instance, in the manufacture of well-filled sealants and adhesives, it is usually crucial to incorporate the powdered filler at the appropriate time and for the appropriate duration. The shear forces acting during the mixing process break up filler aggregates and contribute to dispersion. Therefore, the maximum achievable filling level is substantially determined by the shear forces acting on it. Solvents and resins themselves have insufficient adhesion and stabilization to newly formed surfaces and functional groups, resulting in separation and sedimentation. Consequently, a stable dispersion that can be used for further processing in the formulation may not be obtained. Furthermore, in sealants and adhesives where viscosity can be easily controlled, accurate and reliable metering and dispensing are important to achieve good interfacial contact, and thus strong adhesion, or even thermal and electrical conductivity, during use. The quality of adhesives and sealants, and the strength of the desired effects, such as improved thermal or electrical conductivity, strongly depend on the dispersibility of the filler and its influence on the overall properties of the compound (e.g., viscosity). The above considerations also apply to other liquid systems.

[0005] However, there are problems in producing stable dispersions of graphene material. Graphene material has a tendency to aggregate. These aggregates lead to undesirable sedimentation.

[0006] Prior art has proposed the use of dispersants to improve the dispersibility of graphene materials in solid and liquid systems.

[0007] International Publication No. 2012 / 059489 discloses polymer compositions, particularly for thermoplastic or thermosetting resins, comprising, for example, an electrically conductive carbon substrate, such as carbon black, carbon fiber, graphite, graphene, and / or CNTs (carbon nanotubes), and salts having nonmetallic cations, or synergistic mixtures of such salts with metal salts, in which combination with a specific dispersant is essential. These specific dispersants are ester or amide-based dispersants. Herein, it is preferable that the dispersant is selected from the following: c1) A polyacrylate alkyl ester obtained by polymerization (the alkyl group having 1 to 3 carbon atoms), and the following: a) Saturated aliphatic alcohols having 4 to 50 carbon atoms and / or b) Unsaturated aliphatic alcohols having 4 to 50 carbon atoms A polyacrylic acid ester that can be produced by transesterification with, where a) and b) are used in amounts such that 30-100% of the ester groups are transesterified, and / or c2) Below: A) One or more amino-functional polymers having at least four amino groups, B) General formula (I) / (Ia) TC(O)-[OAC(O)] x -OH (I) TO-[C(O)-AO-] y -Z (Ia) One or more types of polyester, C) General formula (II) / (IIa) TC(O)-BZ (II) TOBZ (IIa) One or more polyethers and A polyester-polyamine condensation product obtained by a partial or complete reaction, wherein T is a hydrogen group and / or an optionally substituted linear or branched aryl, arylalkyl, alkyl or alkenyl group having 1 to 24 carbon atoms, A is at least one divalent group selected from the group consisting of linear, branched, cyclic and aromatic hydrocarbons, Z is at least one group selected from the group consisting of sulfonic acid, sulfuric acid, phosphonic acid, phosphoric acid, carboxylic acid, isocyanate, epoxide, especially phosphoric acid and (meth)acrylic acid, B is represented by general formula (III) -(C l H 2l O) a -(C m H 2m O) b -(C n H 2n O) c -(SO) d (III) which is a group, SO is -CH2-CH(Ph)-O-, wherein Ph is a phenyl group, a, b and c are each independently a value of 0 to 100, provided that the sum of a+b+c≧0, advantageously 5 to 35, especially 10 to 20, the sum of a+b+c+d>0, d≧0, advantageously 1 to 5, l, m and n are each independently ≧2, advantageously 2 to 4, x and y are each independently ≧2, which is a polyester-polyamine condensation product.

[0008] Examples of dispersants c1) include the commercially available TEGOMER® DA 100 N (Evonik), TEGOMER® DA 102 (Evonik), and TEGOMER® P121 (Evonik). An example of dispersant c2) is the commercially available TEGOMER® DA 626 (Evonik). Thus, a large number of different dispersants are disclosed, and these are also suitable for dispersing a large number of different carbon substrates. Combinations of graphene materials with polyalkylene oxides having at least one aromatic group are not disclosed.

[0009] Other commercially available polyester-polyamine condensation products are known from the prior art, such as Solsperse® 39000 (Lubrizol). Solsperse® 39000 does not contain aromatic groups.

[0010] European Patent Application Publication No. 1078946 describes a styrene oxide-containing polyalkylene oxide block copolymer obtained by alkoxylation, and its use as an aqueous, optionally auxiliary solvent-containing pigment paste, and as a low-foaming pigment wetting agent in aqueous and low-solvent lacquers and printing inks. Numerous inorganic and organic pigments are listed as pigments. Particularly preferred are dispersion additives for producing aqueous (gas) carbon black pastes. Specifically, a black paste containing carbon black (Raven® 1170) in addition to the aforementioned polyalkylene oxide is described. However, graphene materials are not disclosed.

[0011] Therefore, there was still a need for dispersants for graphene materials that had at least one advantage over the prior art. In particular, such dispersants were desirable to enable stable dispersion at low viscosity while allowing for high packing levels of graphene materials. Furthermore, the dispersants were desirable to enable dispersion of graphene materials in polar and nonpolar continuous phases, preferably in a liquid phase, where the continuous phase, preferably in a liquid phase, was particularly desirable to be a solvent composition, monomer composition, oligomer composition, or polymer composition.

[0012] Surprisingly, it has now been discovered that this problem can be solved by using a polyalkylene oxide having at least one aromatic group as a dispersant for graphene materials.

[0013] Therefore, the first subject of the present invention is the use of polyalkylene oxides having at least one aromatic group as dispersants for graphene materials.

[0014] A further subject of the present invention is a method for dispersing graphene material, characterized by using the polyalkylene oxide used in the present invention as a dispersant.

[0015] Another subject of this invention is as follows: (a) Continuous phase and (b) A dispersant corresponding to the use according to the present invention, (c) Graphene material and It is a composition containing or consisting of these.

[0016] Another subject of this invention is as follows: (i) A dispersant corresponding to the use according to the present invention, (j) Graphene material and It is a composition containing or consisting of these.

[0017] The advantageous configurations of the subject matter of the present invention can be derived from the claims, examples, and detailed description of the invention. Furthermore, it is explicitly noted that the disclosure relating to the subject matter of the present invention includes all combinations of the individual features of the detailed description of the invention and the claims. In particular, one embodiment of the subject matter according to the present invention is also applicable mutatis mutandis to another embodiment of the subject matter according to the present invention.

[0018] The inventors have confirmed that using a polyalkylene oxide having at least one aromatic group as a dispersant for graphene materials offers many advantages.

[0019] One advantage of the present invention is that it improves the dispersibility of graphene materials in polar and nonpolar continuous phases, particularly in the liquid phase, selected from the group consisting of solvent compositions, monomer compositions, oligomer compositions, and polymer compositions. In contrast, dispersants for graphene materials known from the prior art are suitable for only a very small number of continuous phases and tend to result in segregation or inefficient dispersion, even at very high dispersant concentrations.

[0020] Another advantage of the present invention is that a dispersion containing graphene material with a high packing level can be obtained. A high packing level makes it possible to achieve or improve electrical and thermal conductivity in the dispersion.

[0021] A further advantage of the present invention is that, compared to graphene powder in particular, the handling and metering / dispensing properties in the formulation are improved.

[0022] Another advantage of the present invention is the improved safety during handling, particularly compared to powdered graphene materials.

[0023] Another advantage of the present invention is that the viscosity of the composition containing graphene material can be precisely controlled. This is because, normally, the viscosity increases significantly when dispersing graphene material, potentially leading to solidification of the composition and rendering it unusable. On the other hand, at very low viscosities, the desired shear effect cannot be generated during dispersion. This makes the dispersion process inefficient, resulting in insufficient dispersion of the graphene material. In contrast, the polyalkylene oxide used in the present invention acts as a viscosity modifier, allowing the viscosity to be precisely controlled, thus enabling effective dispersion at both low and high viscosities and obtaining a stable, high-load dispersion of graphene material.

[0024] A further advantage of the present invention is that the polyalkylene oxides used in this invention do not adversely affect the intrinsic properties of the graphene material. The incorporation of dispersions into thermoplastic, thermosetting, or elastomer polymer systems of adhesives and sealants becomes significantly easier, or even possible.

[0025] The subject matter of the present invention and its preferred embodiments are described below illustratively, but the invention is not intended to be limited to these exemplary embodiments. Where ranges, general formulas, or compound classes are specified below, these are intended to include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subcompound groups that can be obtained by selecting individual values ​​(ranges) or compounds. Any embodiment that can be obtained by combinations of ranges / subranges and / or groups / subgroups is considered to be entirely within the disclosure of the invention and is deemed to be disclosed explicitly, directly and uniquely.

[0026] Where average values ​​are listed below, they are numerical averages unless otherwise specified. Where measured values ​​or material properties are listed below, they are measured at 25°C and, favorably, at a pressure of 101325 Pa (atmospheric pressure) unless otherwise specified. Room temperature (RT) means a temperature of 25°C.

[0027] Where a numerical range is described below in the form of "X to Y" or "X~Y", X and Y represent the limits of the range, and unless otherwise specified, this is equivalent to "at least from X to Y (including Y)". Therefore, unless otherwise specified, the range data includes the range limits X and Y.

[0028] If a molecule or molecular fragment has one or more stereocenters, or can be distinguished into isomers due to symmetry, or can be distinguished into isomers due to other effects, such as restricted rotation, any possible isomer is included in the present invention.

[0029] The term "poly" includes compounds composed of at least two monomer units.

[0030] "C" relating to a compound or group x ~C y The phrase "C1~C" represents a compound or group having x to y carbon atoms. 20 The term "organyl group" refers to an organyl group having 1 to 20 carbon atoms, i.e., an organic group. Similarly, the term "C1-C8 acyl group" refers to an acyl group having 1 to 8 carbon atoms. Similarly, the term "C1-C8 alkyl group" refers to an alkyl group having 1 to 8 carbon atoms. Similarly, "C6-C 13 The term "hydrocarbon group" refers to a hydrocarbon group that has 6 to 13 carbon atoms.

[0031] The following formulas represent compounds or structural units that may consist of repeating units, e.g., repeating fragments, repeating blocks, or repeating monomer units, and which may have a molar mass distribution. The frequency of these repeating units is indicated by subscripts. The corresponding subscripts are the numerical mean of all repeating units unless otherwise specified. Therefore, the subscripts of these units used in the formulas should be considered as statistical mean values ​​unless otherwise specified. Accordingly, the values ​​of the subscripts used and the range of values ​​of the subscripts described are understood to be the mean values ​​of the possible statistical distributions of the structures and / or mixtures thereof that actually exist, unless otherwise specified. The repeating units in the following formulas may have any distribution. Structures composed of repeating units may be blocky with any number of blocks and any sequence, may follow a randomized distribution, may be arranged alternately, may form a gradient along a chain if chains exist, and in particular may form any mixed form in which groups having arbitrarily different distributions may follow each other. In certain embodiments, the statistical distribution may be limited by the embodiment. For all ranges unaffected by the restrictions, the statistical distribution remains unchanged.

[0032] The first subject of the present invention is the use of polyalkylene oxides having at least one aromatic group as dispersants for graphene materials.

[0033] Here, the plural form "polyalkylene oxide" refers to one or more types, preferably more than one type of polyalkylene oxide.

[0034] The singular "graphene material" refers to one or more types of graphene materials, preferably one type.

[0035] Therefore, "the use of polyalkylene oxides having at least one aromatic group as a dispersant for graphene materials" is synonymous with "the use of one or more polyalkylene oxides having at least one aromatic group as a dispersant for one or more graphene materials."

[0036] Therefore, "the use of a polyalkylene oxide having at least one aromatic group as a dispersant for graphene materials" is synonymous with "the use of at least one polyalkylene oxide having at least one aromatic group as a dispersant for at least one type of graphene material."

[0037] Therefore, in the following, polyalkylene oxide will also be referred to as a dispersant. Accordingly, the dispersant consists of polyalkylene oxide that can be used according to the present invention.

[0038] To solve the problems of the present invention, the polyalkylene oxide usable by the present invention must have at least one aromatic group. Although not bound by any particular theory, it is assumed that the aromatic group improves the interaction between the polyalkylene oxide and the graphene material.

[0039] Preferably, at least one aromatic group is a phenyl group.

[0040] To achieve optimal results, the weight ratio of the total aromatic groups to the total weight of the dispersant is preferably 2% to 40%, more preferably 5% to 25%, and especially preferably 7% to 15%.

[0041] Polyalkylene oxides are given by formula (A) [ka] Includes the unit of, where the base R A , R B , R C and R D Each of these is independently an organic group or hydrogen (H). Here, each of the organic groups may independently be linear, branched, or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted, or a combination thereof where possible (e.g., alicyclic). However, here the group R A , R B , RC and R D The polyalkylene oxide contains at least one unit in which at least one of the groups is an aromatic group. The organic group is preferably a hydrocarbon group that does not contain a heteroatom, in particular a C1-C8 hydrocarbon group that does not contain a heteroatom. A , R B , R C and R D It is preferable that the unit contains exactly one phenyl group and the other three groups are hydrogen (H). Therefore, it is preferable that the polyalkylene oxide has at least one unit of the formula -O-CH2-CHPh- or -CH2-CHPh-O-, where Ph represents a phenyl group.

[0042] Polyalkylene oxides have the general formula (B) R 1 [O(SO) a (PO) b (BO) c (EO) d R 2 ] n (B) It is even more preferable to select from the compounds, where, R 1 These are, independently of each other, n-valence C1~C 20 Selected from the group of organyl groups, R 2 Each of these is independently selected from the group consisting of C1-C8 acyl groups, C1-C8 alkyl groups, and hydrogen atoms. SO = styrene oxide, PO = propylene oxide, BO = butylene oxide, EO = ethylene oxide, n=1 to 6, with 1 to 4 being advantageous, and especially 1 to 3. a = 1 to 10, advantageously 1 to 5, especially 1 to 3. b = 0 to 50, preferably 0 to 20, and especially 0 to 15. c = 0 to 10, preferably 0 to 5, and especially 0 to 3. d = 0 to 50, advantageously 0 to 20, and especially 0 to 15.

[0043] In equation (B), it is preferable that a+b+c+d≧3.

[0044] For example, polyalkylene oxides have the general formula (C) R 1 O(SO) a (PO) b (BO) c (EO) d R 2 (C) It is preferable to select from the compounds, where, R 1 These are, independently of each other, monovalent C6~C 13 Selected from the group of hydrocarbon groups, R 2 Each of these is independently selected from the group consisting of C1-C8 acyl groups, C1-C8 alkyl groups, and hydrogen atoms. SO = styrene oxide, PO = propylene oxide, BO = butylene oxide, EO = ethylene oxide, a = 1 to 1.9, b = 0 to 3, c = 0 to 3, d = 3 to 50, However, d ≥ a + b + c.

[0045] In equation (C), it is preferable that a+b+c+d≧3.

[0046] Polyalkylene oxides have the general formula (D) R 1 [O(SO) a (PO) b (BO) c (EO) d R 2 ] n (D) It is even more preferable to select from the compounds, where, R1 These are, independently of each other, n-valence C1~C 20 Selected from the group of organyl groups, R 2 Each of these is independently selected from the group consisting of C1-C8 acyl groups, C1-C8 alkyl groups, and hydrogen atoms. SO = styrene oxide, PO = propylene oxide, BO = butylene oxide, EO = ethylene oxide, n=1 to 6, with 1 to 4 being advantageous, and especially 1 to 3. a = 1 to 10, advantageously 1 to 5, especially 1 to 3. b = 0 to 50, favorably between 3 and 20, and especially between 3 and 15. c=0, d = 0.

[0047] In equation (B), (C), or (D), it is preferable that a+b+c+d≧3, more favorably ≧4, and especially ≧5.

[0048] In formula (B), (C), or (D), SO (styrene oxide) has four R groups. A , R B , R C and R D This represents the unit of formula (A), in which exactly one of the groups is a phenyl group and the other three are hydrogen (H) atoms.

[0049] In formula (B), (C), or (D), EO (ethylene oxide) has four R groups. A , R B , R C and R D This shows the units of equation (A), where all are hydrogen (H).

[0050] In formula (B), (C), or (D), PO (propylene oxide) has four R groups. A , R B , R C and R DThis represents the unit of formula (A), in which exactly one of the groups is a methyl group and the other three are hydrogen atoms (H).

[0051] In formula (B), (C), or (D), BO (butylene oxide) has four groups R A , R B , R C and R D Either exactly one of them is an ethyl group and the other three are hydrogen (H), or all four are R groups. A , R B , R C and R D This represents the unit of formula (A), in which exactly two of the groups are methyl groups and the other two are hydrogen (H) groups.

[0052] It is known to those skilled in the art that compounds of formula (B), (C), or (D) usually exist as mixtures. The hydrophobic / hydrophilic balance can be controlled by the various alkylene oxide monomers and their proportions relative to the whole polymer, and in particular, the dispersant can be precisely adapted to the graphene material and continuous phase. Here, EO units exhibit hydrophilicity, while PO, BO, and SO units exhibit hydrophobicity.

[0053] The arrangement of alkylene oxide units can be, for example, statistical or block-like. Particularly preferably, the alkylene oxide units are arranged in a block-like manner. Therefore, the polyalkylene oxide is advantageously a block copolymer. Therefore, the polyalkylene oxide is advantageously a polyalkylene oxide block copolymer. Therefore, it is preferable that the polyalkylene oxide is a styrene oxide-based polyalkylene oxide block copolymer. Here, it is preferable that hydrophobic units such as SO, PO, or BO and hydrophilic EO units form separate blocks. 2 It is preferable to form a block that is bonded to R. 2 The most advantageous is hydrogen (H). The hydrophobic units SO, PO and BO are advantageously EO blocks and R1 exists between. Therefore, the group R 1 , SO, PO and BO units, and R 1 the oxygen atom bonding R to the alkylene oxide unit forms a continuous segment in the polyalkylene oxide, to which R 2 terminated EO units are preferably bonded. Therefore, in one case, it is preferable that d≧a+b+c in formula (B), (C) or (D), and in other cases, it may be preferable that d<a+b+c in formula (B), (C) or (D). In the first case, the polyalkylene oxides are more hydrophobic, and in the second case, they are more hydrophilic.

[0054] R 1 may further contain, in addition to carbon atoms and hydrogen atoms, heteroatoms selected, for example, from N and O, particularly N. However, R 1 preferably does not contain SO units, PO units, BO units and EO units. Preferably, R 1 does not contain heteroatoms. Advantageously, each R 1 , independently of one another, is a monovalent C6 to C 13 selected from the group of hydrocarbon groups. Advantageously, each R 1 , independently of one another, is linear (i.e., unbranched), or branched or cyclic, saturated or unsaturated, aliphatic or aromatic, or a combination thereof where possible. More preferably, each R 1 , independently of one another, is a linear or branched saturated aliphatic group. Even more preferably, each R 1 is a linear or branched or alicyclic group having 6 to 13 carbon atoms. Even more preferably, each R 1 is a linear aliphatic group particularly selected from the group consisting of n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. Suitable compounds of formula (B), (C) or (D) and their synthesis are described in European Patent Application Publication No. 1078946, and are commercially available, for example, under the name TEGOMER® DA 646.

[0055] Group R 1 is derived from the corresponding hydroxy-functional compound R 1 (OH) n n, where n is as defined in formula (B) or (D). Preferred examples of the hydroxy-functional compound R 1 (OH) n are shown in the working examples (see Table 1). More preferred hydroxy-functional compounds R 1 (OH) n can be selected from the group of sugars and sugar alcohols, for example glucose, gulose and sorbitol. It is also possible to use polyglycerin as the hydroxy-functional compound R 1 (OH) n .

[0056] R 2 preferably does not contain SO units, PO units, BO units and EO units. R 2 is advantageously hydrogen (H).

[0057] The number average molecular weight (M n ) of the polyalkylene oxide is preferably from 400 g / mol to 4000 g / mol, advantageously from 500 g / mol to 2500 g / mol, particularly from 600 g / mol to 1500 g / mol. Here, the number average molecular weight (M n ) is advantageously determined by gel permeation chromatography (GPC).

[0058] Polyalkylene oxides may contain other heteroatoms besides oxygen atoms, such as nitrogen atoms. However, it is preferable that the polyalkylene oxide does not contain phosphorus atoms. It is even more preferable that the polyalkylene oxide does not contain sulfur atoms. Therefore, it is also preferable that the polyalkylene oxide does not contain any heteroatoms other than oxygen atoms and optionally nitrogen atoms. Therefore, preferably, the polyalkylene oxide is composed only of carbon atoms, hydrogen atoms, oxygen atoms and optionally nitrogen atoms. Therefore, preferably, the polyalkylene oxide consists of carbon atoms, hydrogen atoms, oxygen atoms and optionally nitrogen atoms. It is particularly preferable that the polyalkylene oxide does not contain any heteroatoms other than oxygen atoms. Therefore, particularly preferably, the polyalkylene oxide is composed only of carbon atoms, hydrogen atoms and oxygen atoms. Therefore, particularly preferably, the polyalkylene oxide consists of carbon atoms, hydrogen atoms and oxygen atoms.

[0059] It is even more preferable that the graphene material conforms to ISO-TS 80004-13, and that the graphene material is advantageously selected from the group consisting of single-layer graphene, two-layer graphene, three-layer graphene, several-layer graphene, multilayer graphene, 1 to 10-layer graphene, epitaxial graphene, exfoliated graphene, graphene nanoribbons, graphene nanoplates, graphene nanoplatelets, graphene nanosheets, graphene microsheets, graphene nanoflakes, graphene quantum dots, graphene oxide, graphene oxide nanosheets, multilayer graphene oxide, and reduced graphene oxide, as well as mixtures thereof, with graphene materials having 1 to 10 graphene layers being particularly preferred.

[0060] It is preferable that the graphene material has a carbon content (weight ratio of carbon to the total weight of the graphene material) of at least 80%, preferably at least 90%, and particularly at least 95%.

[0061] Graphene materials are preferably single-layer or multi-layer graphene materials, that is, graphene materials containing one or more graphene layers. For multi-layer graphene materials, graphene materials having 2 to 10 graphene layers are preferably used.

[0062] The graphene material preferably has a thickness of less than 10 nm, preferably less than 5 nm, and particularly less than 3 nm.

[0063] The graphene material is 0.01 g / cm³ 3 ~0.10 g / cm³ 3 , advantageously 0.01 g / cm³ 3 ~0.08 g / cm³ 3 , especially 0.01 g / cm³ 3 ~0.05 g / cm³ 3 It is preferable that it has a bulk density of [value missing].

[0064] Advantageously, graphene materials exist as granules, flakes, powders, films, sheets, platelets, nanoribbons, and / or fibers.

[0065] Further details regarding graphene materials, their manufacturing, properties, and applications can also be found in the technical literature (Roempp online). https: / / roempp.thieme.de / lexicon / RD-07-02758; See Angew. Chem. Int. Ed. 2014, 53, 7714-7718; Mater. Today 2012, 15(3), 86-97).

[0066] The above-mentioned polyalkylene oxides allow the graphene material to be dispersed in a liquid continuous phase. It is preferable to disperse the graphene material in a liquid continuous phase mainly containing compounds selected from the group consisting of polyethers, especially polyether polyols, polyesters, especially polyester polyols, polycarbonates, especially polycarbonate polyols, polybutadienes, especially polybutadiene polyols, epoxy resins, polysiloxanes, silicone oils, vegetable oils, mineral oils, organic synthetic oils, silyl-modified polymers, silyl-modified reactive diluents, (meth)acrylic acid, (meth)acrylates, cyanoacrylates, dihydrolevoglucocenone (Cyrene®), dimethylformamide (DMF), organic carbonates, acetone, glycols, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), methyl ethyl ketone (MEK), acetate, N-methyl-2-pyrrolidone (NMP), alcohols, and dibasic acid esters (DBE).

[0067] Advantageously, the vegetable oil is selected from the group consisting of linseed oil, soybean oil, rapeseed oil, castor oil, epoxidized linseed oil, epoxidized soybean oil, epoxidized rapeseed oil, and epoxidized castor oil.

[0068] The silyl-modified polymers preferably have triethoxysilyl groups and / or trimethoxysilyl groups. The polymer skeleton is preferably a polysiloxane skeleton (silicone skeleton), a polybutadiene skeleton, or a polyether skeleton.

[0069] The name "(meth)acrylic acid" refers to methacrylic acid and / or acrylic acid. The name "(meth)acrylate" refers to methacrylic acid ester and / or acrylic acid ester. (Meth)acrylates are advantageously selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, ethyl methacrylate, vinyl methacrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, ethyl acrylate, and vinyl acrylate.

[0070] The organic carbonate is advantageously selected from the group consisting of dimethyl carbonate, propylene carbonate, allyl ethyl carbonate, vinylene carbonate, methyl ethyl carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, dibutyl carbonate, and chloroethylene carbonate.

[0071] The glycol is advantageously selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.

[0072] The acetate is advantageously selected from the group consisting of methyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate.

[0073] The alcohol is preferably selected from the group consisting of ethanol, methanol, propanol, isoamyl alcohol, 1-butanol, isopropanol, phenoxyethanol, and 2-(2-phenoxyethoxy)ethanol.

[0074] The dibasic acid ester (DBE) is advantageously selected from the group consisting of dimethyl succinate (DBE-4), dimethyl glutarate (DBE-5), and dimethyl adipate (DBE-6). Here, mixtures are usually used, for example, DBE-9, which is a mixture of DBE-4 and DBE-5.

[0075] It is even more preferable that the continuous phase mainly contains a plasticizer selected from the group consisting of phthalates, citrates, and adipates.

[0076] It is even more preferable that the continuous phase mainly contains a baking paint, such as a silicone-based baking paint.

[0077] It is even more preferable that the continuous phase mainly consists of an unsaturated polyester resin (UPES) or a vinyl ester resin.

[0078] It is even more preferable that the continuous phase mainly consists of a phenolic resin (UF, MUF) or an amino resin.

[0079] The principal component of the continuous phase is understood to mean the main component of the continuous phase in terms of its weight percentage. Preferably, the weight percentage of the principal component is at least 50%, favorably at least 90%, and especially 100%, of the total weight of the continuous phase, with an upper limit of 100%.

[0080] A further subject of the present invention is a method for dispersing graphene material, characterized by using the polyalkylene oxide used in the present invention as a dispersant.

[0081] This method involves the following indirectly or directly sequential, or more favorably directly sequential, process steps: a) Process step of charging the continuous phase, b) A process step of adding a dispersant corresponding to the use according to the present invention, c) Process step of adding and dispersing graphene material It is preferable that it includes.

[0082] Furthermore, this method involves the following indirectly or directly consecutive, and more advantageously directly consecutive, process steps: i) A process step of charging a dispersant corresponding to the use according to the present invention, j) Process step of adding and dispersing graphene material It is preferable that it includes.

[0083] Here, the term "dispersant" is understood to mean the polyalkylene oxides described above. Therefore, the dispersant consists of one or more polyalkylene oxides that can be used according to the present invention.

[0084] Here, dispersion is advantageously carried out under shear action, which allows for a high energy input. This results in the fragmentation and detachment of aggregates, forming new unsaturated surfaces. These attack points, namely functional groups and conjugated systems such as hydroxyl groups, carboxyl groups, aldehyde groups, keto groups, epoxy groups, and amino groups, are suitable for the binding of various dispersants and stabilizers. Such in-situ addition makes dispersion highly effective, resulting in higher packing levels and more stable dispersion. Higher packing levels allow for wider clearances in formulations for end applications such as adhesives, sealants, and thermal interface materials.

[0085] In the method according to the present invention, in particular in step c) or j), various dispersion techniques and apparatuses can be used, such as bead mills, dissolvers (e.g., DISPERMAT® dissolvers), three-roll mills, Ultra-Turrax, wet jet mills, Conchier apparatuses, high-shear mixers, preferably high-speed mixers, high-speed mixers, and thermomixers. Dispersion can also be carried out by ultrasonic treatment. Particularly preferably, dispersion is carried out using a dissolver (e.g., a DISPERMAT® dissolver) or a bead mill.

[0086] Here, it is preferable that electricity or energy is introduced or applied over a period of 0.1 minutes to 99 hours, preferably 0.1 minutes to 2 hours, and particularly preferably 1 minute to 15 minutes.

[0087] The method according to the present invention has the advantage of being very easy to implement and therefore capable of producing compositions with a high weight proportion of graphene material.

[0088] Another subject of this invention is as follows: (a) Continuous phase and (b) A dispersant corresponding to the use according to the present invention, (c) Graphene material and It is a composition containing or consisting of these.

[0089] Here, the term "dispersant" is understood to mean at least one of the polyalkylene oxides mentioned above. Therefore, the dispersant consists of one or more polyalkylene oxides that can be used according to the present invention.

[0090] The weight ratio of component (c) to the weight of the composition is preferably 0.1% to 90%, preferably 5% to 60%, and particularly preferably 25% to 40%. Therefore, the value obtained by dividing the weight of component (c) by the weight of the composition is 0.1% to 90%, preferably 5% to 60%, and particularly preferably 25% to 40%.

[0091] The weight ratio of component (b) to the weight of component (c) is preferably 0.01% to 200%, more preferably 30% to 150%, and particularly preferably 50% to 100%. Therefore, the value obtained by dividing the weight of component (b) by the weight of component (c) is 0.01% to 200%, more preferably 30% to 150%, and particularly preferably 50% to 100%.

[0092] Another subject of this invention is as follows: (i) A dispersant corresponding to the use according to the present invention, (j) Graphene material and It is a composition containing or consisting of these.

[0093] Here, the term "dispersant" is understood to mean at least one of the polyalkylene oxides mentioned above. Therefore, the dispersant consists of one or more polyalkylene oxides that can be used according to the present invention.

[0094] The weight ratio of component (j) to the weight of the composition is preferably 0.1% to 90%, preferably 5% to 60%, and particularly preferably 25% to 40%. Therefore, the value obtained by dividing the weight of component (j) by the weight of the composition is 0.1% to 90%, preferably 5% to 60%, and particularly preferably 25% to 40%.

[0095] The weight ratio of component (i) to the weight of component (j) is preferably 0.01% to 200%, more preferably 30% to 150%, and particularly preferably 50% to 100%. Therefore, the value obtained by dividing the weight of component (i) by the weight of component (j) is 0.01% to 200%, more preferably 30% to 150%, and particularly preferably 50% to 100%.

[0096] The compositions according to the present invention may further contain additives, for example, fillers to improve electrical conductivity, preferably selected from the group consisting of poly-3,4-ethylenedioxythiophene (PEDOT), polyaniline, carbon nanotubes, carbon black, carbon fibers, metal particles, metal fibers, silver nanowires, graphite (e.g., expanded graphite), and manganese oxide; fillers to improve thermal conductivity, preferably selected from the group consisting of hBN, AlN, Al2O3, SiO2, ZnO, MgO, SiC, and nanodiamonds; flame retardants; impact modifiers; coloring pigments; UV stabilizers; viscosity modifiers; flow aids; defoamers; ionic liquids; wetting agents; and / or scratch inhibitors.

[0097] The combination of components (a), (b), and (c) results in a stable, and advantageously low-viscosity dispersion, even at high levels of (c) filling.

[0098] Similarly, the combination of components (i) and (j), with a high packing level of (j), also results in a stable, and advantageously low-viscosity dispersion.

[0099] In particular, compositions according to the present invention in paste form are versatile and can be used in, for example, the automotive sector, heat exchangers, electronics applications, thermal management, antistatic applications, the semiconductor industry, housings, sealing, 3D printing, injection molded parts, tube systems, membranes, fuel cells, cable systems, electromagnetic shielding (EMV), thermal management of battery systems, adhesives and sealants, and potting compounds.

[0100] In particular, the composition according to the present invention in paste form is further suitable as an additive for the following materials: elastomers, thermosetting resins, thermoplastic resins, and thermoplastic elastomers.

[0101] The compositions of the present invention, particularly in paste form, are especially suitable as additives for the following materials / uses: - Adhesives and sealants (especially electrically and / or thermally conductive) comprising epoxy resins, phenolic resins, polyurethanes, silane-modified polymers (silyl-modified polymers, SMPs), acrylates, and reactive hot melts. - Silicone (RTV, HTV, LSR, HCR), - Acrylate, - Polyurethane, for example, thermoplastic polyurethane, - Rubber, advantageously SBR, BR, natural rubber, polybutadiene, functionalized polybutadiene, - Thermosetting resins, preferably polyurethane, polyester resins, phenolic resins, epoxy resins, acrylate resins, silicone resins, - Thermal interface materials: gap fillers, tapes, greases, phase change materials, potting, packaging, underfill, casting, coatings, protective coatings, - Standard thermoplastic resins, preferably selected from PE, PP, PS, PVC, α-olefins, butadiene derivatives, and Vestenamer® (Evonik). - In industrial thermoplastics, PET, PMMA, PC, POM, PA, PBT, PEBA, TPU, PU, ​​TPE are advantageous; in high-performance thermoplastics, PPS, PEEK, PES, PI, PEI are advantageous; in copolymers, - semi-finished products, - In the automotive sector: electric drive systems, thermal management of battery systems, in-vehicle and external charging infrastructure, electronics and power electronics, fuel cells, sensors, displays, cockpits, interactive surfaces, EMV shielding (electromagnetic shielding), - Electronics and power electronics (connections), - Connection and heat dissipation of microchips, electronic components, displays, and indicators. - LED headlights / spotlights, LED, surface lighting connection and heat dissipation, - Connection and heat dissipation of the communication system, - Hydrogen technologies and gas systems (seals, fuel cells, tanks, connectors, plugs, tubes / cables) requiring antistatic and airtight properties. - Mineral oils, silicone oils, process oils, vegetable oils, modified vegetable oils, motor oils, hydraulic oils, drivetrain oils, greases, gels, and phase change materials for electrical conductivity, thermal conductivity, and friction reduction.

[0102] In the above uses / materials, the composition advantageously provides at least one of the following effects: - Electrical conductivity (improvement), - Thermal conductivity (improvement), - Reduction of friction, - Improvement of mechanics, - Improved scratch resistance, - Coloring / Pigments, - Absorption of radiation (ultraviolet rays), - Antibacterial / antiviral effect, - Improved flame retardancy, - Reduced gas permeability.

[0103] Examples Examples are shown below, but these are merely for the purpose of illustrating embodiments of the present invention to those skilled in the art. They do not limit the subject matter of the claims in any way.

[0104] Dispersant (dispersion additive, abbreviated as "additive") The following polyalkylene oxides, corresponding to the stoichiometric ratios shown in Table 1, are prepared as dispersants according to the present invention. Here, the numerical values ​​indicate the molar ratio of alkylene oxides (SO, PO, BO, EO) to the starting alcohol. Therefore, additive 4 is based on 1 mol of SO, 2 mol of BO, 8 mol of PO, and 0 mol of EO, respectively, per 1 mol of hexane-1-ol. The synthesis of the starting alcohol and the corresponding alkylene oxides is carried out as described in European Patent Application Publication No. 1078946. Additive group R in Table 1 1 These are derived from the starting alcohol used (for example, hexane-1-ol, R 1 (=hexyl). The following applies to all additives in Table 1: R 2 =H.

[0105] [Table 1]

[0106] Here, the dispersants usable according to the present invention are additives 1 to 16. These have aromatic groups. The dispersants that cannot be used according to the present invention are additives 17 and 18, as well as Solsperse® 39000 (Lubrizol) and TEGOMER® DA 100 N (Evonik). These do not have aromatic groups.

[0107] filler Graphene: The graphene material used had the following properties: Dv50 = 20 μm (measured by laser diffraction), surface resistance ≤ 10 Ω / sq. (four samples on a 25 μm film from a filter film), tap density 3 = 0.251 gcm -3 (According to ASTM D7481).

[0108] Carbon Black: This invention allows the use of carbon black as an unusable filler, which can be used to improve electrical conductivity. This carbon black has a DBP absorption rate of 119 ml / 100g (DBP = dibutyl phthalate) as determined in accordance with ASTM D2414, and 300 g / dm as determined in accordance with ASTM D1513. 3 The bulk density, sieving residue of less than 250 ppm in a 325-mesh sieve, and 135 m as determined in accordance with the ASTM D3765 method. 2 It is characterized by a CTAB surface area per gram (CTAB = cetyltrimethylammonium bromide).

[0109] Manufacturing of paste using DISPERMAT® dissolver Basically, paste is prepared discontinuously (in batches) using a suitable dispersion unit, such as a dissolver (DISPERMAT® Dissolver CV4-Plus, VMA-GETZMANN). The paste is prepared in a 250 mL stainless steel container using a 40 mm diameter dissolver disc. Here, a batch size of 100 g paste is selected for the 250 mL stainless steel container. A specified amount of continuous phase (e.g., polyether polyol, polyester polyol, methyl methacrylate, polybutadiene diol, etc.) is loaded into the stainless steel container as per the experiment. When using dispersion additives, a specified amount of additive relative to the amount of filler used (additive relative to pigment = AoP [%]) is added to the continuous phase. "Pigment" or "filler" is understood to mean graphene material or carbon black. Weight of continuous phase m konti.Phase , total weight of the composition m gesamt , filler weight m Fuellstoff , weight of additive mAdditiv , maximum filling level Fuellgrad max The following relationship holds between the weight of the additive (AoP) relative to the weight of the filler:

number

[0110] The container holding the continuous phase and dispersion additive is clamped to the DISPERMAT® dissolver device, and the stirring device is lowered so that the dissolver disc is in the continuous phase but not touching the bottom of the cup. To prevent the dispersion additive from settling at the bottom of the stainless steel container, the dispersion additive is introduced into the continuous phase by stirring at 750 rpm (rpm = revolutions per minute) for 1 minute. The filler is then added very slowly in small amounts. At this time, the stirrer is set to 750 rpm to 1000 rpm depending on the amount of dust generated. The addition is carried out in small amounts over approximately 5 minutes. After the addition is complete, the rotation speed of the DISPERMAT® dissolver stirrer is increased to 2000 rpm to 2500 rpm to achieve ideal dispersion. This state is maintained for another 5 minutes until the graphene-based paste is completely dispersed.

[0111] Visual evaluation of the storage stability of pastes. A glass test container with a base diameter of 2.5 cm is filled with 40 g of paste and stored at room temperature for 12 and 72 hours before being tested. Further samples are stored at 50°C for 72 hours before being tested. The test includes visual inspection by two individuals regarding syneresis and the appearance of the paste. The leakage of the paste onto a metal spatula is also examined. The following evaluation criteria, "unstable" or "stable," are used: Unstable (Stability: "None"): The paste forms a clear serous layer at least 2 mm thick on its surface. The paste appears granular. The paste does not flow evenly from the spatula. Stability (Stability: "Yes"): The clear serous fluid formed by the paste is less than 2 mm thick. The paste appears homogeneous and creamy. The paste flows evenly from the spatula.

[0112] Viscosity - Rheological testing of pastes The viscosity of the paste is measured using a rheometer (Physica MCR 301 / Anton Paar). The test uses a transponder-less measuring shaft D-CP / PP7 (Anton Paar) connected to a 25mm disposable measuring plate (D-PP25 / AL / S07 D: 25mm disposable measuring plate / Anton Paar). Before starting the measurement, a zero gap (0.5mm in this case) is set. The subsequent paste is measured at this gap width. The rheometer is now ready for measurement. The specified amount of paste is applied to the rheometer plate, and the preset measuring gap of 0.5mm is adjusted. Then, the excess paste at the edges is removed ("sample trimming"). Only then can the measurement begin. Shear rate: 0.1s -1 ~1000s -1 Then, perform a linear ramp. The following conditions / parameters are used: [ka]

[0113] For graphical evaluation, viscosity is plotted against shear rate. Then, for example, the progression of the curve for paste with additives is compared with the progression of the curve for paste without additives. Shear rate 1s -1 and 10s -1 It is also common to compare only the values ​​at that point.

[0114] Hegman grindmeter test [Table 2]

[0115] The Hegman grindmeter is used to measure the dispersibility of particles or aggregates in a continuous liquid phase. It does not measure the actual particle size or particle size distribution.

[0116] A grindmeter is a flat steel block with two shallow, wedge-shaped grooves etched into its surface. These grooves extend at a constant depth from the maximum depth at one end of the grindmeter to the zero point at the other end of the steel block. The wedge depth can be read from a scale etched on the side. The Hegman scale ranges from 0 to 8, with a higher Hegman number (Hegman value) indicating smaller particles. Herein, the following Hegman number and μm assignments apply: 0 Hegman = 100 μm 4 Hegman = 50 μm 8 Hegman = 0 μm

[0117] Place the cleaned and dried grindometer on a horizontal, non-slip surface. Fill the deepest part of the grindometer's groove with the test paste. Here, the paste should flow slightly beyond the edge of the groove. Place the scraper parallel to the short side of the grindometer at the deepest part of the groove and quickly pull it perpendicularly toward the shallower end of the groove. Immediately after flattening the sample, observe the grindometer at a right angle to the long side and at an angle of 20° to 30° to the surface, holding it up to the light so that the surface structure of the paste in the groove is visible. Identify the location where a relatively large number of particles or particle scratch marks are first visible in the groove and read the scale value (Hegman scale) related to that location.

[0118] Early occurrence of problems within the groove (high Hegman number) means that the paste may contain, for example, residual aggregates, or that the dispersion of the filler (i.e., graphene material or carbon black) into the continuous phase is worse. Therefore, it is also possible to foresee the above-mentioned drawbacks, such as greater instability of the paste and incomplete dispersion of graphene in the final application.

[0119] The grindmeter test is further evaluated as follows: [Table 3]

[0120] Manufacturing of graphene paste The production of graphene paste according to the following example is carried out as follows: 1. Charge the continuous phase into a 250ml metal cup. 2. Add the dispersion additive (100% AoP). Stir briefly with a spatula to prevent the additive from settling at the bottom. 3. Using a DISPERMAT® dissolver, the additive is introduced into the continuous phase by stirring at 750 rpm for approximately 1 minute on a 40 mm dispersion disc. 4. Add the filler slowly in small amounts over approximately 5 minutes at 750-1000 rpm. 5. After the filler has been added, stir for 5 minutes at 2000-2500 rpm until the filler is completely dispersed.

[0121] Example 1: Paste based on polyether polyol For the production of polyether polyol-based pastes, Desmophen® 1110 BD (Covestro) is used as the continuous phase (see Tables 2 and 3): [Table 4]

[0122] [Table 5]

[0123] Example 2: Polyester polyol-based paste For the production of polyester polyol-based pastes, Dynacoll® 7250 (Evonik) is used as the continuous phase (see Tables 4 and 5): [Table 6]

[0124] [Table 7]

[0125] Example 3: Paste based on polybutadienediol For the production of pastes based on polybutadiene diol, Polyvest® HT (Evonik) is used as the continuous phase (see Tables 6 and 7): [Table 8]

[0126] [Table 9]

[0127] Example 4: Epoxide-based paste For the production of epoxide-based pastes, Epikote® Resin 828 (Hexion) is used as the continuous phase (see Tables 8 and 9): [Table 10]

[0128] [Table 11]

[0129] Example 5: Methyl methacrylate-based paste For the production of methyl methacrylate-based pastes, MERACRYL® MMA (Roehm) is used as the continuous phase (see Tables 10 and 11): [Table 12]

[0130] [Table 13]

[0131] Example 6: Paste based on vegetable oil For the production of vegetable oil-based pastes, castor oil is used as the continuous phase (see Tables 12 and 13): [Table 14]

[0132] [Table 15]

[0133] Example 7: Paste based on silyl-modified polymer (SMP) For the production of pastes based on silyl-modified polymers (SMPs), TEGOPAC® RDS 1 is used as the continuous phase (see Tables 14 and 15): [Table 16]

[0134] [Table 17]

[0135] The present invention provides for compositions that exhibit high stability, low viscosity, and good results in Hegman grindometer tests, solely through combinations of polyalkylene oxide and graphene materials (regardless of the continuous phase).

Claims

1. The use of a polyalkylene oxide having at least one aromatic group as a dispersant for graphene materials, The aforementioned polyalkylene oxide is of general formula (B) R 1 [O(SO) a (PO) b (BO) c (EO) d R 2 ] n (B) Selected from the compounds, here, R1 is independently selected from the group of n-valent C1 to C20 organyl groups. R2 is independently selected from the group consisting of C1-C8 acyl groups, C1-C8 alkyl groups, and hydrogen. SO = styrene oxide, PO = propylene oxide, BO = butylene oxide, EO = ethylene oxide, n = 1 to 6, a = 1 to 5, b = 0 to 50, c = 0 to 10, Use d = 0 to 50.

2. The use according to claim 1, wherein the weight ratio of the total aromatic groups to the total weight of the dispersant is 2% to 40%.

3. The use according to claim 1, wherein the polyalkylene oxide does not contain any heteroatoms other than oxygen atoms and optionally nitrogen atoms.

4. The use according to claim 1, wherein the graphene material is a graphene material conforming to ISO-TS 80004-13.

5. The use according to claim 1, wherein the graphene material is dispersed in a liquid continuous phase mainly comprising a compound selected from the group consisting of polyethers, polyesters, polycarbonates, polybutadienes, epoxy resins, polysiloxanes, vegetable oils, mineral oils, organic synthetic oils, silyl-modified polymers, silyl-modified reactive diluents, (meth)acrylates, cyanoacrylates, dihydrolevoglucocenone (Cyrene®), dimethylformamide (DMF), organic carbonates, acetone, glycols, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetates, N-methyl-2-pyrrolidone (NMP), alcohols, and dibasic acid esters (DBE).

6. A method for dispersing a graphene material, characterized in that a polyalkylene oxide is used as a dispersant and the provisions of claim 1 are applied.

7. The following are indirect or direct sequential process steps: a) Process step of charging the continuous phase, b) A process step of adding a dispersant in accordance with the provisions of claim 1, c) Process step of adding and dispersing graphene material The method according to claim 6, including the method described in claim 6.

8. The following are indirect or direct sequential process steps: i) A process step of charging a dispersant according to the provisions of claim 1, j) Process step of adding and dispersing graphene material The method according to claim 6, including the method described in claim 6.

9. A composition, the following: (a) Continuous phase and (b) A dispersant according to the provisions of claim 1, (c) Graphene material and A composition containing or consisting of the following.

10. A composition, the following: (i) A dispersant according to the provisions of claim 1, (j) Graphene material and A composition containing or consisting of the following.

11. The composition according to claim 9 or 10, wherein the weight ratio of component (c) or (j) to the weight of the composition is 0.1% to 90%.

12. The composition according to claim 9 or 10, wherein the weight ratio of component (b) or (i) to the weight of component (c) or (j) is 0.01% to 200%.

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