Coating composition and its uses

Abstract

To provide a leather coating composition comprising or consisting of a hydrosilylation curable silicone elastomer composition designed to be used as a topcoat for a synthetic leather material, particularly a silicone-based synthetic leather composite material.SOLUTION: A leather coating composition comprising a hydrosilylation curable silicone elastomer composition contains: Component (i) one or more organopolysiloxane polymers having a viscosity of from 1000 to 500,000 mPa. s at 25°C; Component (ii) a reinforcing silica filler which may optionally be hydrophobically treated; Component (iii) a silicone resin cross-linker having terminal (M) groups comprising silicone bonded hydrogen; Component (iv) a hydrosilylation catalyst; and Component (v) silicon-free organic microparticles having a number average particle size of from 0.5 to 500 μm determined using a field emission scanning electron microscope.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a silicone-based synthetic leather composite as a topcoat for synthetic leather materials, particularly silicone-based synthetic leather composites. Hydrosilylation-curable silicone elastomer composition for use in coatings or topcoats, Silicone coating as a top coat for synthetic leather materials, which is a cured product of the composition, A method for producing the topcoat and synthetic leather material using the same, and the synthetic leather material The topcoat is designed to minimize or reduce the change in gloss after abrasion. In order to prevent or at least reduce the amount of silicon-containing inorganic particles, highly crosslinked silicones containing silicon-free inorganic particles are used. The method is designed to provide a linear matrix.

[0002] Polyurethane (PU) or polyvinyl chloride (PVC)-based materials are mainly used as alternatives to natural leather. A wide variety of synthetic alternatives have been developed that are used in furniture, decoration, handbags, etc. A wide variety of applications including clothing, luggage, clothing, footwear, car interiors, car seats, etc. However, its use as synthetic leather is subject to increasingly strict safety regulations. In order to meet these regulations, for example, strict physical property requirements regarding flame retardancy and smoke density must be met, and Adequate adhesive strength is required to prevent the coating layer from peeling off, and heat resistance is required. It is necessary to maintain the resistance to dirt, solvents, hydrolysis, etc. However, PVC-based materials often fail to meet the above physical property requirements.

[0003] Other alternatives to natural leather include silicone-based synthetic leather composites. Such silicone-based synthetic leather composites are superior to PU and / or PVC-based alternatives. These may have several advantages. For example, they generally do not use plasticizers or toxic heavy metals. In addition, the production of organic synthetic leather is at least partially residual in synthetic leather products after production. Depends on the use of environmentally problematic solvents such as dimethylformamide (DMF), which is high in In view of this, more environmentally friendly manufacturing methods can be used to prepare it.

[0004] Silicone-based synthetic leather composites can be fabricated via several routes, including: Generally, the present invention comprises two components: a textile support layer and a hydrosilylation-curable liquid silicone rubber composition. The above layers and a release liner are used to manufacture the film. For example, the first liquid silicone rubber ( The LSR composition may be coated onto a release liner and then cured to form a first layer or forms a skin layer. A second LSR composition, usually having different physical properties than the first layer, is A second adhesive layer is applied over the cured first layer to form an adhesive layer, and then a textile support layer is applied over the second adhesive layer. A second LSR composition is then cured to form a slab. Form an adhesive layer located between the kin layer and the textile support layer. When the adhesive is applied, the release liner is then removed. If the release liner is deemed ineffective, a hydrosilylation reaction may be performed between the release liner and the textile layer. A layer of the curable silicone elastomer composition may be applied, for example, over a skin layer. A third layer may be provided as a protective topcoat.

[0005] Such silicone-based synthetic leather composites may, for example, exhibit better mechanical properties over a wide temperature range. Its ability to provide superior flexibility, as well as excellent UV and heat resistance, makes it superior to conventional polymers in terms of physical properties. It is possible to achieve better performance than PU and PVC synthetic leather. is of particular importance as it helps provide advantageous properties such as abrasion resistance and stain resistance. They are also believed to be gentle on human skin and provide a superior feel to the user. Unfortunately, however, topcoats made from such silicone-based materials have The same desired gloss appearance cannot be maintained after abrasion. After abrasion, the gloss is reduced or The decrease in gloss can be attributed to the solid unevenness of the abrasive and the silicone-based synthetic leather composite. This is caused by the appearance of wear patterns due to adhesive contact between the material and the surface. This is a typical wear phenomenon of polymer elastomers. Alternatively, an increase in gloss may be observed. In some cases, the root cause is repeated frictional interactions with harder materials. This means that the rough surface with small grains becomes smooth, i.e., the surface roughness is reduced. The increase in gloss caused by this is

[0006] Therefore, upon curing, the change in the level of gloss change after abrasion is visually minimal. To form a topcoat for a silicone-based synthetic leather composite topcoat that can There remains a need for suitable and improved silicone coating compositions.

[0007] A leather coating composition comprising a hydrosilylation-curable silicone elastomer composition. There was, Component (i) One or more olefins having a viscosity of 1000 to 500,000 mPa.s at 25°C. A luganopolysiloxane polymer having at least 5 weight percent of said polymer per molecule. % (wt.%) of the unsaturated alkyl group is selected from an alkenyl group, an alkynyl group, or a mixture thereof. and organopolysiloxane polymer. Component (ii) is optionally treated with one or more filler treating agents (to render the filler hydrophobic). a treated inorganic reinforcing silica filler; Component (iii) a silicone resin crosslinker having terminal (M) groups containing silicone-bonded hydrogen. wherein the molar ratio of Si-H groups in component (iii) to unsaturated groups in the composition is A silicone resin crosslinker having a ratio of 0.5:1 to 20:1; Component (iv) a hydrosilylation catalyst; and Component (v) Number average of 0.5 to 500 μm determined using a field emission scanning electron microscope Silicon-free organic fine particles having a uniform particle size, which are thermally stable up to a temperature of at least 180°C. The hydrosilylation-curable silicone elastomer is present in an amount of 5 to 35% by weight of the composition. non-silicon-containing organic fine particles present in the elastomer composition; A composition comprising:

[0008] The topcoat contains silicon-free particulates to reduce gloss change after abrasion. The silicone is designed to provide a highly crosslinked silicone matrix that

[0009] A topcoat in the form of a cured layer of the leather coating composition described herein, particularly a silicone Also provided is a synthetic leather having a topcoat for a polyester-based synthetic leather composite.

[0010] The silicone formed as a reaction product upon curing of the leather coating composition described herein. Ricon coating and its use in topcoats and silicone-based synthetic leather composite materials Also provided are methods for making and using products made from silicone-based synthetic leather composites. will be done.

[0011] (i) Organopolysiloxane polymer Components of the hydrosilylation-curable silicone elastomer composition of the leather coating composition (i) is one or more organometallic compounds having a viscosity of 1,000 to 500,000 mPa.s at 25°C; Polysiloxane polymers, as determined using quantitative infrared analysis in accordance with ASTM E168. At least 5% by weight of the polymer per molecule is an alkenyl group, an alkyl group, an unsaturated group selected from the group consisting of an organopolysiloxane polysiloxane, an alkyl group, an aryl group, or a mixture thereof; For example, the organopolysiloxane polymer (i) is a polymer having a plurality of groups of the formula (I) : R a SiO (4-a) / 2 (I) wherein each R is independently an aliphatic hydrocarbyl group, an aromatic hydrocarbyl group, or an aryl group. Alkanyl group (i.e., one free valence at a carbon atom, regardless of the type of functional group) and any organic substituent having a number of units selected from the group consisting of saturated Aliphatic hydrocarbyls include methyl, ethyl, propyl, pentyl, octyl, unicyclic, Alkyl groups such as decyl and octadecyl, and cycloalkyl groups such as cyclohexyl. Examples of unsaturated aliphatic hydrocarbyl include, but are not limited to, aryl groups. Alkyl, such as aryl, allyl, butenyl, pentenyl, cyclohexenyl, and hexenyl; Examples of aromatic hydrocarbon groups include, but are not limited to, aryl groups, and alkynyl groups. Examples include phenyl, tolyl, xylyl, benzyl, styryl, and 2-phenylethyl. Examples of the organyl group include, but are not limited to, chloromethyl and 3 -Halogenated alkyl groups such as chloropropyl, amino groups, amide groups, imino groups, imide groups Nitrogen-containing groups such as the aryl group, polyoxyalkylene groups, carbonyl groups, alkoxy groups, and hydroxyl groups. Examples include, but are not limited to, oxygen-containing groups such as aryloxyl groups. The groups may include sulfur-containing groups, phosphorus-containing groups, and / or boron-containing groups. The letter "a" may be 0, 1, 2 or 3, but is typically predominantly 2 or 3.

[0012] Siloxy groups are also known by the abbreviated (short) nomenclature, when R is an organic group, typically a methyl group. i.e. - can be described by "M", "D", "T", and "Q" (Silicone Nomenclature For further guidance on the law, see Walter Noll, Chemistry and Theory. Chnology of Silicones,dated 1962,Chapter I, pages 1-9). The M unit is a siloxy group where a=3. Si group, i.e., R 3 SiO 1 / 2 and the D units correspond to siloxy groups, where a=2, That is, R 2 SiO 2 / 2 The T unit corresponds to a siloxy group where a=1, i.e. Chi, R 1 SiO 3 / 2 and the Q unit is a siloxy group where a=0, i.e., S iO 4 / 2 is equivalent to.

[0013] Typical groups for the organopolysiloxane polymer (i) are mainly alkenyl, The groups may be at the pendant positions (D or T siloxy groups), alkyl and / or aryl groups. It can be either at the end (on the M siloxy group) or at the terminal (on the M siloxy group). Suitable alkenyl groups in the polysiloxane polymer (i) are typically 2 to 10 carbon atoms, such as vinyl, isopropenyl, allyl, and 5-hexenyl, typically The aryl group is preferably at least 5% by weight of the polymer per molecule, as previously indicated. is 5-15% by weight of the polymer per molecule, or 6-15% by weight of the polymer per molecule. % by weight, or 7-15% by weight of the polymer per molecule, can be determined using quantitative infrared analysis according to ASTM E168.

[0014] Typically, the unsaturated groups are selected from the group consisting of alkenyl and / or alkynyl groups. The silicon-bonded organic groups attached to the polysiloxane polymer (i) are typically 1 to 5000 carbon atoms. A monovalent saturated hydrocarbon group containing 10 carbon atoms and unsubstituted or Typically 6 to 12 carbon atoms substituted with groups that do not interfere with the cure of the composition, such as Preferred species of silicon-bonded organic groups are selected from those containing monovalent aromatic hydrocarbon groups, e.g. For example, alkyl groups such as methyl, ethyl, and propyl, and aryl groups such as phenyl. It is.

[0015] The molecular structure of the organopolysiloxane polymer (i) is typically linear, but may be branched. Some branching may be present due to the presence of T groups (as described above) in the molecule.

[0016] As described above, by curing the hydrosilylation-curable silicone elastomer composition, To achieve useful levels of physical properties in elastomers prepared by The viscosity of the polysiloxane polymer (i) is at least 1000 mPa.s at 25°C. The upper limit of the viscosity of the organopolysiloxane polymer (i) is 5°C at 25°C. It is limited to a viscosity of 00,000 mPa.s.

[0017] Generally, each organopolysiloxane contains at least 5% by weight of the polymer per molecule. It contains an unsaturated group selected from an alkenyl group, an alkynyl group, or a mixture thereof. The amount of unsaturated groups present (wt%) was determined using quantitative infrared analysis according to ASTM E168. Component (i) is measured using a spindle appropriate for the viscosity range, unless otherwise indicated. and relying on the cup / spindle method of ASTM D1084-16 Method B Measured at 25℃, the viscosity is 1000mPa.s to 500,000mPa.s at 25℃. or 1000mPa.s to 150,000mPa.s at 25°C, or 200 0mPa.s to 125,000mPa.s, or 2000mPa.s to 10 at 25°C Viscosity of 0,000mPa.s or 5000mPa.s to 80,000mPa.s Yes.

[0018] The organopolysiloxane polymer (i) may, for example, contain alkenyl and / or alkynyl groups. Polydimethylsiloxane, alkylmethylpolysiloxane, alkylaryl or copolymers thereof, and any other suitable end groups. For example, they may be trialkyl-terminated, alkenyl-dialkyl-terminated. Alternatively, each organopolysiloxane polymer (i) may contain, as described above, Any other suitable combination of end groups, provided that it contains at least 5% by weight of the polymer. The joining may be at the end.

[0019] Thus, the organopolysiloxane polymer (i) can be, for example, dimethylvinyl Polydimethylsiloxane terminated with dimethylvinyl, dimethylmethylphenylsiloxane terminated with dimethylvinyl, Trialkyl-terminated dimethylmethylvinyl polysiloxane or dialkylvinyl-terminated dimethyl The copolymer may be a methyl vinyl polysiloxane copolymer, but may contain high levels of alkenyl and In view of the presence of an alkynyl group, or in view of the presence of a trialkyl-terminated dimethylmethyl group, Dialkylvinyl polysiloxane or dialkylvinyl-terminated dimethylmethylvinyl polysiloxane It may also be a copolymer.

[0020] For example, the aryl group may have unsaturated groups selected from alkenyl groups and / or alkynyl groups at two ends. The organopolysiloxane polymer (i) contained therein can be represented by the general formula (II): can. R'R”R”'SiO-(R”R”'SiO) m -SiOR'''R”R' (II) In formula (II), each R' is typically an alkenyl group containing 2 to 10 carbon atoms or may be an alkynyl group. Examples of the alkenyl group include vinyl, propenyl, butenyl, Pentenyl, hexenyl, alkenyl cyclohexyl, heptenyl, octenyl, aryl, decenyl, or similar straight-chain and branched alkenyl groups, as well as alkenylated aromatic Alkynyl groups include, but are not limited to, ethynyl, propynyl, phenyl ... aryl, butynyl, pentynyl, hexynyl, alkynylated cyclohexyl groups, heptynyl, Octynyl, nonynyl, decynyl, or similar linear and branched alkenyl groups, as well as alkynyl, nonynyl, decynyl, or similar linear and branched alkenyl groups. The aromatic ring structure may be selected from, but is not limited to, aryl aromatic ring structures.

[0021] R'' does not contain ethylenic unsaturation, and each R'' may be the same or different. may be, typically a monovalent saturated hydrocarbon group containing 1 to 10 carbon atoms, and typically R'' is independently selected from monovalent aromatic hydrocarbon radicals containing 6 to 12 carbon atoms. may be unsubstituted or may be substituted with a hydrosilylation curing agent as described herein, such as a halogen atom. The hydroxyl group is substituted with one or more groups that do not interfere with the cure of the curable silicone elastomer composition. R''' may be R' or R''.

[0022] The organopolysiloxane polymer (i) typically comprises 3% or 1% by weight of the composition. 0% to 50% or 45% by weight of the composition, e.g., The polysiloxane polymer (i) is present in an amount of 10 to 50% by weight, or 10 to 45% by weight, of the composition. The amount of the component may be in the range of %.

[0023] (ii) Reinforcing Silica Filler A leather coating composition comprising a hydrosilylation-curable silicone elastomer composition Component (ii) is a reinforcing silica filler. Preferably, it is a hydrosilylation-curable silica filler. Component (ii) of the leather coating composition comprising the elastomeric composition is preferably A reinforcing silica filler provided in powdered form. A phenomenon called "creping" or "crepe hardening" during processing of polypropylene elastomer compositions. To prevent this, the reinforcing silica filler (ii) is often one or more of the known fillers. Treated with a treatment agent.

[0024] Precipitated silica and / or fumed silica, or fumed silica is typically less At least 50m 2 / g (BET method according to ISO9277:2010) Particularly preferred due to its large surface area. 50~450m 2 / g (according to ISO9277:2010 BET method) or 50~300m 2 / g (in accordance with ISO9277:2010 Fillers having a surface area of ​​0.01 to 0.01 mm (measured by the BET method) are typically used. Any type of silica are also commercially available. Preferably, they are provided in micronized form.

[0025] The reinforcing silicone in the hydrosilylation-curable silicone elastomer composition of the present invention The amount of the filler (ii), e.g., finely divided silica, is 5 to 40% by weight, alternatively 5 to 30% by weight. %. In some cases, the amount of reinforcing silica filler is 7.5% based on the weight of the composition. % by weight, alternatively 10-30% by weight, alternatively 15-30% by weight based on the weight of the composition It may be in weight percent.

[0026] When the reinforcing silica filler (ii) is inherently hydrophilic (e.g., untreated silica filler), The filler is typically treated with a treatment agent to make it hydrophobic. These surface-modified organopolysiloxane polymers (i) are easily wettable. The reinforcing silica filler (ii) does not aggregate and is uniformly distributed in the organopolysiloxane polymer (i). As a result, the hydrosilylation-curable silicone elastomer composition and and curing the resulting cured material to provide improved room temperature mechanical properties.

[0027] The surface treatment may be carried out prior to introduction into the composition, or may be carried out in situ (i.e. The ingredients are blended together at or above room temperature until the filler is fully processed. and may be carried out in the presence of at least some of the other components of the compositions herein. Typically, the untreated reinforcing silica filler (ii) is an organopolysiloxane polysiloxane. After being treated and mixed with a treating agent in situ in the presence of mer (i), the silicone rubber A base material is obtained to which other ingredients may be added.

[0028] Typically, the reinforcing silica filler (ii) is a hydrosilylation curable silicone during processing. In order to prevent creping of the elastomeric composition, the applicable art disclosed The filler may be surface treated with any of the low molecular weight organosilicon compounds known in the art. For example, to render the filler hydrophobic, to make it easier to handle and to obtain a homogeneous mixture with the other ingredients. Organosilanes, organopolysiloxanes, or hexaalkyldisilazanes for Organosilazanes such as siloxane diols, short chain siloxane diols, fatty acids, or stearic acid esters. Specific examples include silanol-terminated trifluoropropanes and fatty acid esters. Propylmethylsiloxane, silanol-terminated ViMe siloxane, tetramethyldi(trifluoromethyl)siloxane (fluoropropyl)disilazane, tetramethyldivinyldisilazane, silanol-terminated MeP h Siloxane, containing an average of 2-20 diorganosiloxane repeating groups per molecule Liquid Hydroxyl-Terminated Polydiorganosiloxane, Hexaorganodisiloxane, Hexa Silica Processing Aids include, but are not limited to, organodisilazanes. A small amount of water may be added together with the agent.

[0029] The filler may be a masterbatch or a mixture of the filler and an organopolysiloxane polymer. It can be introduced into the hydrosilylation-curable silicone elastomer composition in the form of a base. The organopolysiloxane polymer used in the star batch or base is similar to component (i). or may be of similar structure to component (i), but having a viscosity in the same range as component (i), provided that Alkenyl and / or alkynyl content of <5% by weight of the polymer (ASTM E168) If necessary, the organopolysiloxane polymer may be a masterbatch. The fumed silica can be prepared in situ by introducing a suitable hydrophobizing agent into the mixture during the preparation of the The hydrophobicity may be improved by treating the surface with a hydrophobic agent.

[0030] The hydrosilylation-curable silicone elastomer composition described herein contains, per molecule, Organohydrogenpolysiloxane having 3 or more silicon-bonded hydrogen atoms (component iii) and a hydrosilylation catalyst (component iv). The resin is then cured using a curing agent.

[0031] (iii) Organohydrogenpolysiloxane Leather coating composition comprising a hydrosilylation-curable silicone elastomer composition The component (iii) is a silicon bond of the component (iii) under the catalytic activity of the component (iv) described below. by addition reaction of combined hydrogen atoms with alkenyl and / or alkynyl groups of component (i), having end groups containing silicone-bonded hydrogen that act as crosslinkers for polymer (i); Component (iii) is a silicone resin crosslinking agent in which the silicon-bonded hydrogen atoms of this component are: The alkenyl and / or alkynyl groups of component (i), typically alkenyl groups, especially vinyl groups, The aryl groups react sufficiently with these to form a network therewith, thereby hardening the composition. At least 5,000 parts per million (ppm) of silicon-bonded hydrogen (S iH), or at least 7000 ppm, or 7000 to 12,000 ppm silicon-bonded hydrogen, or 8000 ppm to 11,000 ppm silicon-bonded hydrogen The amount of silicon-bonded hydrogen present was also determined by quantitative infrared analysis in accordance with ASTM E168. It can be found using

[0032] The molecular structure of component (iii) is resinous and contains a mixture of Q, T, D, and M groups; To obtain good compatibility with component (i), Brookfield DV 3T rheometer was used. 10 to 5000 mPa.s at 25°C or 10 to 1000 mPa.s at 25°C using a Pa.s, or has a viscosity of 10 to 500 mPa.s at 25°C.

[0033] Leather coating composition comprising a hydrosilylation-curable silicone elastomer composition Examples of component (iii) include: (CH 3 ) 2 HSiO 1 / 2 M groups containing Si-H, such as the (CH 3 ) 3 SiO 1 / 2 Trialkyl M groups such as the SiO 4 / 2 Silicone containing or consisting of groups Resin, (CH 3 ) 2 HSiO 1 / 2 Group and SiO 4 / 2 M groups containing Si-H such as the or silicone resins made of them; (CH 3 ) 2 HSiO 1 / 2 M groups containing Si-H, such as the (CH 3 )2 SiO 2 / 2 Group, and SiO 4 / 2 a silicone resin comprising or consisting of a group; (CH 3 ) 2 HSiO 1 / 2 M groups containing Si-H such as SiO 4 / 2 Groups, and (C 6 H 5 ) 3 SiO 1 / 2 Silicone resins containing or consisting of groups, as well as methyl Examples of alternatives include those in which the alkyl group is replaced by a phenyl group or other alkyl group or mixtures thereof. The silicone resin may also include, but is not limited to, T and / or D groups, or T groups.

[0034] Optionally, other cross-linking agents may also be utilized. These may include: . 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, Tris(hydrogendimethylsiloxy)methylsilane, Tris(hydrogendimethylsiloxy)phenylsilane, methylhydrogencyclopolysiloxane, trimethylsiloxy endblocked methylhydrogen polysiloxane, Trimethylsiloxy endblocked dimethylsiloxane / methylhydrogensiloxane copolymers. -- dimethylhydrogensiloxy endblocked dimethylpolysiloxane, Dimethylhydrogensiloxy endblocked dimethylsiloxane / methylhydrogensiloxane copoly Ma, Trimethylsiloxy endblocked methylhydrogensiloxane / diphenylsiloxane copoly Ma, Trimethylsiloxy endblocked methylhydrogen siloxane / diphenylsiloxane / -di methylsiloxane copolymer, Trimethylsiloxy endblocked methylhydrogen siloxane / methylphenyl siloxane / -dimethylsiloxane copolymers, Dimethylhydrogensiloxy endblocked / Dimethylsiloxane / -Diphenylsiloxane Polymers, and / or Dimethylhydrogensiloxy endblocked methylhydrogensiloxane / dimethylsiloxane / -methyl However, component (iii) may be any one or more of the above. It is preferable that the silicone resin is a silicone resin of the above formula.

[0035] Component (iii) typically comprises from 5 to 30% by weight of the composition, from 5 to 20% by weight, or It is present in the total composition in an amount of 10-20% by weight, but the amount present is typically determined by the amount of component (i ii) all unsaturated groups of silicon-bonded hydrogen atoms, such as alkenyl and alkynyl groups; In most cases, it is determined by the molar ratio to the total number of vinyl groups. The molar ratio of silicon-bonded hydrogen atoms in iii) to the total number of all unsaturated groups is 0.5: 1~20:1, or 0.5:1~10:1, or 0.5:1~5:1, or The ratio is 1:1 to 5:1, and preferably Si-H is in excess.

[0036] iv) Hydrosilylation catalyst As previously mentioned, the leather coating composition contains platinum group metals, i.e. platinum, ruthenium, osmium, a metal selected from the group consisting of tungsten, rhodium, iridium, and palladium, or a metal such as Hydrosilylation (addition cure) catalysts (iv) of the genus They are cured via a silylation (addition) reaction. The high activity of these catalysts in hydrosilylation reactions Due to their activity levels, platinum and rhodium compounds are preferred.

[0037] Catalyst (iv) The catalyst (iv) may be a platinum group metal, activated carbon, aluminum oxide, silicon dioxide, or the like. a platinum group metal supported on a support such as a metal oxide, silica gel or powdered charcoal; or It may be a compound or complex of a platinum group metal.

[0038] Preferred examples of the hydrosilylation catalyst (iv) include platinum-based catalysts, such as platinum black and platinum oxide. (Adams catalyst), platinum on various solid supports, chloroplatinic acid, and alcoholic solutions of chloroplatinic acid and chloroplatinic acid, and ethylenically unsaturated compounds such as olefins and ethylenically unsaturated ketones. It is a complex with organosiloxane containing an isovalent hydrocarbon group. The gold compound is, for example, a compound represented by the formula (PtCl 2 (Olefin) 2 and H(PtCl 3 .Me In view of this situation, the platinum-olefin complexes of ethylene, propylene, alkenes having 2 to 8 carbon atoms, such as the isomers of cyclohexene, butene and octene, or cyclohexene; Cyclohexene, cyclopentene, cyclohexene, and cycloheptene, Preference is given to the use of chloroalkanes. Other soluble platinum catalysts are, for example, of the formula (PtCl 2 C 3 H 6 ) 2 It is a platinum-cyclopropane complex that reacts with alcohols, ethers, and aldehydes or or mixtures thereof, or the reaction products of hexachloroplatinic acid with heavy metals in ethanol solution. Hexachloroplatinum with methylvinylcyclotetrasiloxane in the presence of sodium carbonate The reaction product of an acid. Platinum catalysts with phosphorus, sulfur, and amine ligands, e.g., (P h 3 P) 2 PtCl 2 , and sym-divinyltetramethyldisiloxane, Complexes of platinum with platinum siloxanes can also be used.

[0039] Therefore, specific examples of suitable platinum-based catalysts include: (i) The ethylenically immobilized chloroplatinic acid described in U.S. Pat. No. 3,419,593. Complexes with organosiloxanes containing saturated hydrocarbon groups; (ii) Chloroplatinic acid in either the hexahydrate or anhydrous form; (iii) Platinum chloride is mixed with an aliphatic unsaturated organic ketone such as divinyltetramethyldisiloxane. a platinum-containing catalyst obtained by a process comprising reacting a platinum compound with an isopropyl compound; (iv) (COD)Pt(SiMeCl 2 ) 2 (In the formula, "COD" is 1,5-cyclooxygen Alkenes described in U.S. Pat. No. 6,605,734, such as alkane- Platinum-silyl complexes; and / or (v) A solution containing about 1% by weight of platinum, typically in a solvent, for example toluene, may be used. The Karstedt catalyst, a complex of platinum and divinyltetramethyldisiloxane, is These are U.S. Patent No. 3,715,334 and U.S. Patent No. 3,814,73 It is listed in issue 0.

[0040] The hydrosilylation catalyst (iv) for the hydrosilylation-curable silicone elastomer composition is , a catalytic amount in the total composition, i.e., to catalyze the addition / hydrosilylation reaction and under desired conditions The hydrosilane is present in an amount or content sufficient to cure the composition into an elastomeric material. Varying the level of polymerization catalyst (iv) can be used to adjust the reaction rate and cure rate. The catalytic amount of the hydrosilylation catalyst (iv) is generally about one million parts by weight of the composition. Parts by weight of platinum group metals per part (ppm) from 0.01 ppm to 10,000 ppm, or 0.01 to 5000 ppm, or 0.01 to 3,000 ppm, or 0. In certain embodiments, the catalytic amount of the catalyst is in the range of 0.1 to 1,000 ppm by weight of the composition. Based on the amount, 0.01 to 1,000 ppm, or 0.01 to 750 ppm, or may be metals in the range of 0.01 to 500 ppm, or alternatively 0.01 to 100 ppm. The ranges may refer to just the metal content in the catalyst, or to the entire catalyst (including its ligands), as specified. Typically, these ranges relate only to the metal content in the catalyst. The catalyst may be added as a single species or as a mixture of two or more different species. Generally, the amount of catalyst present will depend on the form / concentration in which the catalyst package is provided. 0.001 to 3.0% by weight of the composition, or 0.01 to 3.0% by weight of the composition, or 0.1 to 3.0% by weight of the composition, or 0.1 to 2.0% by weight of the composition, or The range is 0.1 to 1.5% by weight.

[0041] (v) Silicon-free organic fine particles Component (v) of the hydrosilylation-curable silicone elastomer composition herein is , 0.5 to 500 μm, or 0.5 to 250 μm, or 0.5 to 100 μm, or or silicon-free with a number average particle size of 0.5 to 75 μm or 1.0 to 50 μm The number average particle size is measured by Thermo Fisher Scientific. Field emission scanning electron microscopes such as the FEI Nova NanoSEM™ 630 scanning electron microscope For example, the particle size can be measured using a field emission scanning electron microscope. A mirror photograph was taken, and then 10 particles were randomly selected from the photograph, and the directivity of each particle in the image was measured. This can be accomplished by measuring the diameter of the selected particles. The average diameter is calculated.

[0042] The silicon-free inorganic fine particles of component (v) are thermally stable up to a temperature of at least 180°C. and in an amount of 5 to 35% by weight of the composition, alternatively in an amount of 5 to 30% by weight, alternatively in an amount of 5 to 25% by weight. %. They are typically maintained at temperatures between 80°C and 180°C. It is necessary that the material is thermally stable throughout the entire curing process. " means that the silicon-free inorganic particles are not thermally decomposed at temperatures below 180°C. This is done by placing a sample of the non-silicon-containing inorganic particulate in a suitable container, then removing the container from the container for 18 It is determined by placing it in a preheated oven at 0°C and atmospheric pressure for 30 minutes. After 30 minutes in the oven, the samples were visually evaluated to determine whether the particles were in their original form. In this case, it is considered to be thermally stable up to a temperature of 180°C ( or whether it has changed in some way that is visually evident, e.g., agglomerated, liquefied, or charcoaled. Determine whether the text is visually decomposed by shaping and / or decomposing.

[0043] Component (v) non-silicon-containing inorganic fine particles are generally or preferably spherical and / or semi-spherical. The non-silicon-containing organic fine particles of component (v) may be a thermosetting material. For the avoidance of doubt, component (v) silicon-free inorganic fine particles is silicon-free and contains trace amounts of In other words, silicon-free organic fine particles do not contain silicon atoms or silicon-containing compounds. The term "substantially" as used above typically refers to the form of impurities. "Si" is intended to mean that only trace amounts of silicon are present.

[0044] Component (v) non-silicon-containing organic fine particles may be any suitable organic material as long as it meets the specified requirements. The microparticles may be made of polyurethane microparticles, acrylic microparticles, methacrylic microparticles, etc. Particles, polytetrafluoroethylene microparticles, polyester microparticles, polyamide microparticles, and and / or polyolefin microparticles, and derivatives and / or mixtures thereof. For example, the fine particles may be polyethylene, polystyrene, polyvinyl acetate, poly Polyvinyl chloride, Polyvinylidene chloride, Polyacrylonitrile, Polymethyl methacrylate , polybutadiene, polychloroprene, and other vinyl polymers, and their copolymers. mer; polyamides such as nylon 6 and nylon 66; and polyethylene terephthalate , polyacetal, and blends thereof. The silicon-free inorganic particulates of component (v) minimize the visual change in gloss after rubbing. It has been found to be effective as a means of suppressing the graininess of leather, because the small grains on the surface of the leather During rubbing, the surface is worn down, but fine particles appear on the topcoat surface and help compensate for the loss of surface roughness. In this case, the increase in gloss is avoided. The presence of robust silicon-free inorganic particles helps to avoid further wear of the matrix. Helpful.

[0045] Optional Additives The leather coating composition may contain one or more additives. These optional additives Examples of curing inhibitors, cured silicone elastomer powders, Inorganic non-reinforcing fillers, conductive additives, pot life extenders, lubricants, flame retardants, pigments, colorants , chain extenders, heat stabilizers, diluents (designed to evaporate during cure), compression set improvement Additives, anti-squeak agents, antioxidants, antistatic agents, antifouling agents and light stabilizers, antifreeze agents and and / or biocides, as well as mixtures thereof.

[0046] Inhibitors Optionally, a hydrosilylation cure system is utilized, so that the leather coating composition Hydrosilylation-curable silicones used in leather coating compositions In order to obtain a longer working or pot life of the corn elastomer composition, a suitable inhibitor may be incorporated into the composition to retard or inhibit the activity of the catalyst.

[0047] Inhibitors for platinum metal based catalysts, and platinum group metal based catalysts in general, are well known in the art. Hydrosilylation or addition reaction inhibitors include hydrazines, triazoles, phosphines, Mercaptans, organic nitrogen compounds, acetylene alcohols, methyl (tris(1,1-dimethyl) Silylated acetylenic alcohols such as silane, maleic acid, ethylenically or aromatic unsaturated amides, ethylenically unsaturated isocyanates , olefin siloxanes, unsaturated hydrocarbon monoesters and diesters, conjugated ene-ynes , hydroperoxides, nitriles, and diaziridines. Alkenyl-substituted siloxanes such as those described in US Pat. No. 989,667 may also be used. Of these, cyclic methylvinylsiloxane is preferred.

[0048] Another class of known platinum catalyst inhibitors is disclosed in U.S. Pat. No. 3,445,422. 0. 2-Methyl-3-butyne-2-ol Acetylenic alcohols such as ethanol are preferred molecules that inhibit the activity of platinum-containing catalysts at 25°C. The inhibitors are of the class of hydrosilylation-curable silicone elastomers containing these inhibitors. The curing composition typically requires heating to a temperature of 70° C. or higher to cure at a practical rate. It is necessary to do so.

[0049] Examples of acetylene alcohols and their derivatives include 1-ethynyl-1-cyclohexa 2-methyl-3-butyn-2-ol, 3-butyn-1-ol, 3-Butyn-2-ol, Propargyl Alcohol, 3,5-Dimethyl-1-hexyne 3-ol, 1-ethynylcyclopentanol, 1-phenyl-2-propynol, 3- methyl-1-penten-4-yn-3-ol, and mixtures thereof.

[0050] Optionally, when present, there is about one mole of inhibitor per mole of metal in catalyst (iv). Low inhibitor concentrations result in satisfactory storage stability and cure speed. v) Inhibitor concentrations of up to 500 moles of inhibitor per mole of metal are required. The optimum concentration for a given inhibitor in a composition can be readily determined by routine experimentation. When present in the composition, the selected inhibitor is present in the concentration and form in which it is provided / commercially available. Accordingly, the inhibitor is typically present in an amount of from 0.0125 to 10% by weight of the composition. Mixtures of the above may also be used.

[0051] Cured Silicone Elastomer Powder Another optional additive that may be included in the hydrosilylation-curable silicone elastomer composition is The additive is a suitable cured silicone elastomer powder. The results are available publicly upon request from Dow Silicone Corporation. Measured using Corporate Test Method CTM 1138 When the particles are mixed, any suitable average particle size may be selected, for example, 0.01 to 100 μm, or 0.01 to 50 μm, or alternatively 0.01 to 25 μm. They may have chemical functional groups, e.g. It may contain epoxy groups (meth)acryloxy groups or may be, for example, silica-treated. It may be coated with a coating.

[0052] The cured silicone elastomer powder is made from a suitable curable silicone composition. The curable silicone composition may be, for example, a silicone that cures through addition (hydrosilylation) reaction. silicone composition, condensation reaction curing silicone composition, organic peroxide curing silicone composition Examples of the composition include silicone compositions that cure with addition reaction and silicone compositions that cure with ultraviolet light. Condensation reaction curing silicone compositions are preferred due to their ease of handling.

[0053] Commercial examples of components (v) that can be used include, for example, Dow Si Dowsil(TM) 23N Addit from Licones Corporation ive, Dowsil(TM) 603T additive, and Dowsil(TM) Examples include 9701 Cosmetic Powder.

[0054] When present, the cured silicone rubber powder is a hydrosilylation curable silicone elastomer. In the mer composition, 2.5 to 20% by weight of the composition, or 2.5 to 15% by weight of the composition % by weight, or from 2.5 to 10% by weight of the composition.

[0055] Inorganic non-reinforcing fillers The inorganic non-reinforcing silica filler in the hydrosilylation-curable silicone elastomer composition is , if present, crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide and carbon Black, wollastonite, as well as graphite, graphene, talc, mica, clay, Platelet-type fillers such as layered silicates, kaolin, and montmorillonite, as well as Other fillers that can be used alone or in addition to the fillers listed above may include mixtures thereof. Inorganic non-reinforcing fillers include aluminite, calcium sulfate (anhydrous gypsum), gypsum, and sulfur. Calcium carbonate, magnesium carbonate, aluminum trihydroxide, magnesium hydroxide (hydrotalcite ), graphite, copper carbonates, e.g. malachite, nickel carbonates, e.g. zarachite, carbonates Barium, e.g. witherite, and / or strontium carbonate, e.g. strontianite Some examples include:

[0056] The inorganic non-reinforcing fillers, if present, may alternatively or additionally be aluminium oxide, Silicates from the group consisting of: Olivine family, Garnet family; Aluminosilicates from the group consisting of: cyclosilicates; chain silicates; and layer silicates. The olivine group may be selected from silicates such as forsterite. and Mg 2 SiO 4 The garnet family includes, but is not limited to, red garnet; Mg 3 Al 2 S 3 O 12 ; green garnet; and Ca 2 Al 2 S 3 O 12 Crushed silica etc. Aluminosilicates include, but are not limited to, sillimanite; Al 2 S O 5 ;Mullite;3Al 2 O 3 2SiO 2 ; Kyanite, and Al 2 SiO 5 etc. The cyclic silicate family includes, but is not limited to, cordierite and Al. 3 (Mg, Fe) 2 [Si 4 AlO 18

[0036] and silicate minerals such as, but not limited to, The chain silicate family includes ground silicate minerals such as wollastonite and Ca[SiO 3 ]of Including, but not limited to:

[0057] Suitable layered silicates, for example silicate minerals that can be utilized include: mica, K 2 Al 14 [Si 6 Al 2 O 20 ](OH) 4 ;phyllite;Al 4 [Si 8 O 20 ](O H) 4 ;Talc;Mg 6 [Si8 O 20 ](OH) 4 ;Snake stones, e.g. asbestos; Rynite;Al 4 [Si 4 O 10 ](OH) 8 and vermiculite, Non-reinforcing fillers, when present, may be present in an amount of from 1 to 50% by weight of the composition. % exists.

[0058] Wherever deemed necessary, non-reinforcing and reinforcing silica fillers may be used. As described above for filler (ii), it is treated to make it hydrophobic, thereby making it easier to handle. It is easy to obtain a homogeneous mixture with the other components. In the case of the non-reinforcing silica filler, the surface treatment can be used to improve the organopolysiloxane composition. The silicon-containing polymer (i) and, if present, the silicon-free inorganic fine particles (v) are easily wetted, The result is better processability (e.g., lower viscosity, better demolding ability, and / or (has lower adhesion to processing equipment such as two-roll mills), heat resistance, and mechanical properties. The improved properties of the hydrosilylation-curable silicone elastomer composition can be obtained. Cut.

[0059] Any suitable antioxidant, antistatic agent, antifouling agent, and / or light stabilizer may be utilized in the composition. may be used.

[0060] Preferably, the conductive additives that can be used herein are inorganic. Examples of conductive fillers that may be present in the composition include metal particles, metal oxide particles, metal coatings, and the like. Metallic particles with a metallic coating (e.g. silver-plated nickel), non-metallic core particles with a metallic coating Examples include silver-coated talc or mica or quartz, and combinations thereof. The metal particles may be in the form of powders, flakes or filaments, as well as mixtures or derivatives thereof. It may be in the form of a body.

[0061] Pot life extenders such as triazoles may be used but are not essential within the scope of the present invention. Therefore, the hydrosilylation-curable silicone elastomer composition is not considered to be , it may not contain a pot life extender.

[0062] In the case of lubricants, the lubricant may be reactive or non-reactive with other components of the composition. These have a similar basic structure to component (i), but contain one unsaturated group per molecule. For example, organopolysiloxanes having only one alkenyl group. Alternatively, the lubricant may be an organic wax, etc. If reactive, the wax may be For example, one molecule of 1-(2-methylphenyl)-1-propanediol with at least one alkenyl group, e.g., a vinyl group, per molecule. or 15-30 carbons per molecule It may also be an alkenylated wax.

[0063] If desired, non-reactive lubricants may be present in the composition. These include nitrides, Boron, graphite, molybdenum sulfide, etc., or mixtures thereof may be mentioned. But not limited to these.

[0064] Examples of flame retardants include aluminum trihydrate, magnesium hydroxide, calcium carbonate, Zinc borate, wollastonite, mica and chlorinated paraffin, hexabromocyclododeca phosphate, triphenyl phosphate, dimethyl methylphosphonate, tris(2,3-dibromo)phosphate propyl) (brominated tris), as well as mixtures or derivatives thereof.

[0065] Examples of pigments include carbon black, iron oxide, titanium dioxide, chromium oxide, and bismuth oxide. vanadium, and mixtures or derivatives thereof.

[0066] Examples of colorants include vat dyes, reactive dyes, acid dyes, mordant dyes, disperse dyes, and cationic dyes. and mixtures thereof.

[0067] The optional additives, e.g., non-reinforcing silica filler and flame retardant, are included for two or more reasons. If they are OK to use, when present they can function in both roles. When present, the aforementioned additional ingredients are present in an amount of from 0.1 to 30% by weight of the composition, Alternatively, it is present in an amount of 0.1 to 20% by weight.

[0068] To prevent premature hardening during storage, the composition must be divided into two parts, Part A and Part B, before use. Typically, Part A is made up of organopolysiloxane polymer (i) and (ii) a portion of the reinforcing silica filler, and (iv) a hydrosilylation catalyst. The remaining part of the resin, together with the organohydrogenpolysiloxane (iii), is an organopolysiloxane polymer (i) and a reinforcing silica filler (ii), and typically Contains an inhibitor, if present, which may vary depending on the choice of inhibitor used. The two-part composition comprises the organopolysiloxane polymer (i) of Part B and the reinforcing siloxane polymer (i) of Part B. The mixture may be designed to be mixed together in any suitable ratio depending on the amount of filler (ii). Therefore, the weight ratio of part A to part B may be from 15:1 to 1:2, but is preferred. or 2:1 to 1:2, or 1.5:1 to 1:1.5, or 1:1 Part A: Part B are mixed in the weight ratio.

[0069] The optional additives may be added to any of the other ingredients of each part, as appropriate. Either Part A or Part B silicone elastomers may be used unless they cause adverse effects. - can be introduced into the composition.

[0070] Hydrosilylation-curable silicone elastomers for use in leather coating compositions The individual parts of the composition can be prepared in any suitable manner. Any of the mixing techniques and devices described in the prior art can be used. The specific device will be determined by the ingredients and the viscosity of the final curable coating composition. Suitable mixers include paddle-type mixers, such as planetary mixers, or knee mixers. These include, but are not limited to, a bell-type mixer. In some cases, it may be desirable to avoid premature curing of the composition.

[0071] As previously discussed, component (ii) the reinforcing silica filler is part A or part B of the composition. Fumed silica masterbatch used to introduce fumed silica into both B and C. It may be introduced into the composition in the form of 25 to 45% by weight of fumed silica. 55 to 75% by weight of at least two alkenyl and / or alkynyl groups per molecule and an organopolysiloxane containing the above-mentioned compound. component (i), and / or a copolymer having the same viscosity range as component (i), but with <5% by weight of the polymer. It may be an organopolysiloxane having alkenyl and / or alkynyl content. In one embodiment, at least 2 per molecule in the fumed silica masterbatch. The organopolysiloxane containing two alkenyl and / or alkynyl groups has a viscosity of 1:1 at 25°C. Viscosity from 30,000 to 80,000 mPa.s, and quantitative according to ASTM E168 The vinyl content of the polymer is between 0.05 and 0.2% by weight, as determined using infrared analysis. or dimethylvinyl terminated with a vinyl content of 0.05 to 0.15% by weight of the polymer. Such masterbatches are made of fumed silica and polydimethylsiloxane. The polymer may contain only 10 to 100 mPa.s of viscosity and (A The 5-fold increase in the molecular weight of the polymer was determined using quantitative infrared analysis according to STM E168. Hexamethyldisilazane having a vinyl content of 20% by weight or 7.5 to 15% by weight. (HMDZ), divinyltetramethyldisiloxane, dimethylhydroxy-terminated methylvinyl The composition may contain small amounts of other ingredients, such as diphenyl siloxane polymers, and / or water.

[0072] Therefore, when parts A and B are mixed together, the hydrosilylation curable silicone The cone elastomer composition may include the following:

[0073] Component (i) one or more organopolysiloxane polymers, comprising 3% by weight of the composition; Alternatively, in an amount of from 10% by weight to 50% by weight, or 45% by weight of the composition, per molecule at least 5% by weight of the polymer or 5-15% by weight of the polymer per molecule; or 6 to 15 weight percent of the polymer per molecule, or 7 to 10 weight percent of the polymer per molecule. 15% by weight of unsaturated groups selected from alkenyl groups, alkynyl groups, or mixtures thereof 1000 to 500,000 mPa.s at 25°C, or 1000 mPa.s at 25°C as~150,000mPa.s, or 2000mPa.s~125,0 at 25℃ 00mPa.s, or 2000mPa.s to 100,000mPa.s at 25°C, or or has a viscosity of 5000 mPa.s to 80,000 mPa.s measured at 25°C. , organopolysiloxane polymer. For example, organopolysiloxane polymer (i) is , may be present in the range of 10-50% by weight, alternatively 10-45% by weight of the composition.

[0074] Component (ii) a reinforcing silica filler, preferably hydrophobically treated, which is added to the composition It may be introduced directly or in the form of a masterbatch, and has a BET surface area of ​​about At least 50m 2 / g (BET method according to ISO 9277:2010), reinforced The filler is a soluble silica filler, i.e., fumed silica. The filler is 50-450m 2 / g(IS O 9277:2010 (BET method) or 50-300m 2 / g surface area The reinforcing silicone in the hydrosilylation-curable silicone elastomer composition of the present invention is The amount of silica filler (ii), e.g., finely divided silica, is 5 to 40% by weight, or 5 to 30% by weight. %. In some cases, the amount of reinforcing silica filler is 7.5-30% by weight of the composition. Alternatively, it may be from 10 to 30% by weight of the composition, or from 15 to 30% by weight of the composition. When in the form of a masterbatch, the masterbatch is 25 to 45% by weight of fumed Silica, 55 to 75% by weight of component (i), and / or 50,000 to 80,000 at 25°C 00 mPa viscosity and 0.05 to 0.2% vinyl content by weight of the polymer, or Dimethylvinyl-terminated polydimethylsiloxane having a vinyl content of 0.05 to 0.15% by weight of the monomer. or 55 to 75% by weight of the above-mentioned dimethylvinyl-terminated polydimethylsiloxane. The masterbatch composition may also include a siloxane to initially render the filler hydrophobic. To treat the filler in situ, thereby making it easier to mix with the polymer. The coating material may contain a treatment agent for this purpose.

[0075] Component (iii) a silicone resin crosslinker, comprising 10 to 30% by weight of the Part B composition; Alternatively, in an amount of 10 to 20% by weight of the Part B composition, or 12 to 20% by weight of the Part B composition. However, the amount present is typically determined by the ratio of the silicon-bonded hydrogen atoms of component (iii) to the 0.5:1 to 20:1, determined by the molar ratio to the total number of all unsaturated groups; or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 1:1 to 5:1, Preferably, there is an excess of Si-H, with at least 5,000 parts per million (ppm) of silicon. Silicon-Hydrogen (Si-H) or at least 7000 ppm, or 7000 to 12,000 ppm 00 ppm silicon-bonded hydrogen, or 8000 ppm to 11,000 ppm silicon-bonded hydrogen A silicone resin crosslinker having end groups containing silicone-bonded hydrogen that contain a hydrogen bond. The viscosity of component (iii) is 15 to 50 mPa.s at 25°C, or 15 to 40 mPa.s at 25°C. mPa.s, or 20-35 mPa.s at 25°C.

[0076] The amount of catalyst present provided by component (iv) the hydrosilylation catalyst composition depends on the composition. 0.01 to 3.0% by weight of the composition, or 0.1 to 3.0% by weight of the composition, or 0.1 to 2.0%, or 0.1 to 1.5% of the composition, (ii) and (v), if present, of platinum group metals per million parts by weight. Parts by weight (ppm): 0.01 ppm to 10,000 ppm, or 0.01 to 7.50 Contains 0 ppm, 0.01 to 3,000 ppm, or 100 to 6,000 ppm .Also, Component (v) is a silicon-free organic fine particle having a particle size of 0.5 to 500 μm, or 0.5 to 250μm, or 0.5~100μm, or 0.5~75μm, or 1.0 A number average particle size of up to 50 μm (determined by the method described above, if necessary) Thermally stable up to temperatures of at least 180°C (as determined using the method described above). (v) is present in an amount of 5 to 35% by weight of the composition, alternatively in an amount of 5 to 30% by weight of the composition, or is present in the composition in an amount of 5 to 25% by weight of the composition.

[0077] The total weight percent of the composition including components (i)-(v) and any optional additives is 100 weight percent. or any suitable combination of the above.

[0078] Components in the hydrosilylation-curable silicone elastomer composition of the leather coating composition The order in which the components are mixed is not important. Prepare the appropriate Part A and Part B and then use Immediately before use, Part A and Part B are mixed in a predetermined ratio of 15:1 to 1:2, for example, in a ratio of 1:1. Mix Part A and Part B together.

[0079] Curing of hydrosilylation-curable silicone elastomer compositions for leather coating compositions The process can be carried out at a temperature suitable for hydrosilylation curing. For example, about 80° C. to 18° C. The curing temperature is 0°C, or 80°C to 150°C, or 80°C to 130°C.

[0080] The above leather coating compositions, once cured, provide excellent abrasion and mar resistance protection. Therefore, it is useful as a topcoat for synthetic leather materials, especially silicone-based synthetic leather composite materials. The leather coating composition may also be used on a variety of other types of leather, e.g., conventional leather. It can also be applied to leather, nubuck, or suede. As mentioned above, leather coatings The composition may be applied to finished leather or during the final wetting stage in the finishing of leather, Preferably used as a topcoat for synthetic leather, especially silicone-based synthetic leather composites. A topcoat in the form of a reaction product from the curing of the above leather coating composition is Leather having this coating has significantly improved abrasion resistance. This improvement in abrasion resistance is due to the final coating. This is achieved without compromising the fit and flexibility of the ring and is used to improve wear resistance. Other additives that are often used can make the coated leather rough to the touch and can also cause the coating to become rough. This improves resistance to bending, which can cause cracks in the structure. [Brief description of the drawings]

[0081] The application and use of the aforementioned leather coating composition may be accomplished by the use of silicone-based compounds during or after manufacture. The following is a cross-sectional view of the layers in the structure of a synthetic leather composite material, taken together with the accompanying drawings, Figures 1 to 4. This will become more apparent from further explanation.

[0082] Using the hydrosilylation-curable silicone elastomer composition described above in conjunction with the above figures A detailed description of the method for preparing a silicone-based synthetic leather composite material by

[0083] The coating is a reaction product from the curing of the aforementioned leather coating composition (5). The silicone-based synthetic leather composite material is made up of hardened liquid silicone rubbers, each of which has different functions. The present invention may include several layers (3, 4) of the above-mentioned material, as well as a textile support layer (2). The silicone-based synthetic leather coating composition is not limited to the topcoat, which is made from the above-mentioned leather coating composition. The leather composite material comprises at least a textile support layer (2), a first liquid silicone rubber material, and a second adhesive layer (3) made from a second liquid silicone rubber material. The adhesive layer (3) acts as an effective adhesive to the textile support layer (4). In use, the adhesive layer or the first layer ( 3) is adhered to the textile support layer (2) and adhered or laminated to the skin layer (4). The aforementioned leather coating composition acts as a protective topcoat (5), which is The third layer is on and attached to the first layer (4), i.e., the second layer (4) is , located between the adhesive layer (3) and the topcoat layer (5).

[0084] Typically, the release liner (1) is left on the outside of the silicone-based synthetic leather composite until it is needed. The silicone-based synthetic leather composite material is based on the silicone-based synthetic leather. The release liner (1) is then coated with a skin layer (4) depending on the process being used. ) or a combination of earlier layers adhered to a topcoat (5). Alternatively, the release liner (1) may be removed before applying the topcoat. The topcoat is applied onto the skin prior to applying a release liner onto the topcoat, or The topcoat is first applied over the release liner before applying any additional layers.

[0085] The textile support layer (2) may be made of any suitable textile material, for example synthetic resin fibers. , natural fibers, and / or microfibers. These may be made from polyester fibers, viscose rayon, or non-woven fabrics. Cellulose fibers such as cellulose, polyamide fibers, nylon, acrylic fibers, polyolefin fibers, and cotton Examples of such materials include elastic textile materials such as cellulose fibers and spandex. The present invention is not limited to these, and any mixture of two or more of the above may be used. The style support layer is designed to improve the mechanical strength of the silicone leather.

[0086] The leather coating composition (i.e., topcoat layer (5)) typically has a coating composition of about For dry coating thicknesses of 2-50μm, 2-30μm, or 5-25μm Depending on the application, the thickness of the wet film may be 10 to 100 μm or 10 to 60 μm. This can be done at any suitable temperature, for example, from about 80° C. to 180° C., alternatively from 80° C. to 160° C., or or 80°C to 130°C for a suitable period of time, for example, 30 seconds to 20 minutes, or 30 seconds Cured for a period of ~10 minutes, or 30 seconds to 5 minutes, or 30 seconds to 2.5 minutes. obtain.

[0087] Any suitable liquid silicone rubber composition may be utilized as the adhesive layer or first layer (3). This can be attached to the textile support layer (2) and is typically Typically, after curing, it has a low durometer Shore A hardness of, for example, 20 to 40 and a high resistance to touch. It is sometimes soft to the touch. A suitable heat-resistant adhesive layer (3) is used. Commercial examples of dolosilylated curable liquid silicone rubber compositions are available from Dow Silicon Dowsil™ LCF 8400 Binding from Es Corporation Dowsil™ LCF 8400 Binder is a binder that prevents premature hardening. It remains the standard for hydrosilylation curable compositions for the manufacture of pharmaceuticals and is offered to consumers in a two-part form. As a result, two parts of the Dowsil™ LCF 8400 Binder were The components are mixed together immediately prior to use.

[0088] The adhesive layer (3) may be of any desired dry thickness, for example, from 50 μm to 1 mm, or 50~750μm, or 50~500μm, or 100~500μm, or It may be of a thickness of 100 to 300 μm. It may be applied at any suitable temperature, e.g. 25~180℃, 130~170℃, or 135~160℃ for 20 minutes or more. or 1 to 10 minutes, or 1.5 to 5 minutes, or 1.5 to 4 minutes The mixture is allowed to cure for a suitable period of time.

[0089] As previously indicated, the first layer or adhesive layer (3) is a layer that is bonded to the textile support layer (2) and the second It is designed to be sandwiched between and adhere to the coating layer or skin coating layer (4). There are.

[0090] The second composition or skin coating composition (4) is usually bonded to the adhesive layer (3). It is designed as a protective synthetic leather that is combined with the Any suitable liquid silicone rubber may be used with a suitable topcoat (5), such as The rubber composition can be utilized to form the second or skin layer (4), which is typically After curing, the hardness of the first or adhesive layer (3) is higher, for example, (≧) 50 or more. The second or skin layer (4) has a durometer Shore A hardness of 60 or more. Commercially suitable liquid silicone rubber compositions that can be cured to function as silicone rubbers include any of the following: Dowsil(TM) LC manufactured by Dow Silicones Corporation F 8300 Skin and Dowsil™ LCF 8500 Skin, In view of the fact that these are all hydrosilylation-curable liquid silicone rubber compositions, They are also mixed together just prior to use to avoid premature hardening during storage prior to use. Delivered to users in two parts: Dowsil™ LCF 8300 Skin, Has a high Shore A durometer of approximately 65, providing abrasion resistance and Dowsil™ It has a relatively low viscosity compared to LCF 8500 Skin. The latter has high mechanical strength. It is a fumed silica reinforced version of the former, which has a higher viscosity. In this case, to benefit from the advantages of both compositions, Dowsil™ LCF 830 A mixture of 0 Skin and Dowsil® LCF 8500 Skin was applied to the second and third is used as the skin layer (4).

[0091] The skin layer (4) may be of any suitable dry thickness, for example, the adhesive layer may be of any Any desired thickness, for example, 50 μm to 1 mm, 50 to 750 μm, or 50 to The thickness was 500 μm, or 50 to 350 μm, or 50 to 250 μm. If the skin layer is applied directly onto the release paper and the average thickness of the skin layer is determined, This involves measuring the length and width of a sample of release paper and coating the release paper with a skin layer composition in this case. The resulting coated release paper was then cured and weighed to obtain a weight average of 100 g / g of the following formula: The average thickness was calculated based on the

[0092] Average dry thickness of skin layer = weight of skin layer / (density x width x length) If the average dry coat thickness of each of the other layers is shown, calculate the weight of each layer and use the formula above. In both cases, the density was determined using ASTM D792 The skin layer can be heated at any suitable temperature, for example, from about 100° C. to 150° C. or 110℃~135℃ or 110℃~125℃ for 30 seconds to 5 minutes, or It may be cured for a period of 30 seconds to 2.5 minutes.

[0093] If desired, the final silicone leather product can be heated at a temperature of about 75°C to 180°C, generally but not necessarily. Although not necessarily so, if desired, it is possible to move towards the lower end of the range, e.g., between 75 and 120°C. It may be post-cured for 2 to 48 hours, alternatively 6 to 36 hours, alternatively 10 to 24 hours.

[0094] The above-mentioned leather coating composition can be applied by any suitable coating method, such as spraying, rolling, etc. Coating, brushing, spin coating, dip coating, solution casting coating, slot die coating, spray coating, knife coating, or grating By using the labia coating, a preformed silicone-based synthetic leather composite was formed, as shown in Figure 2. The adhesive layer (3) and the adhesive layer (4) may be applied as a topcoat onto the composite material, for example (2, 3, 4). The skin layer (4) may be applied via the same means.

[0095] The fabric layer may be attached to the adhesive layer in any suitable manner, for example, by lamination.

[0096] In such circumstances, the preformed silicone-based synthetic leather composite is typically It was prepared by several alternative processes. (i) applying a liquid silicone rubber skin type composition (4) onto a release liner (1); And, (ii) curing the skin layer composition of (i) on the release liner (1) to form a cured skin layer ( 4) forming a (iii) applying a silicone adhesive composition onto the cured skin layer (4); (iv) An adhesive layer (3) is sandwiched between the skin layer (4) and the textile support layer (2). In this way, the textile support layer (2) is applied onto the adhesive layer (3) before or during the curing of the adhesive layer (3). and (v) curing the adhesive layer (3); and (vi) Removing the release liner (1) if necessary. The above is shown in Figures 1 and 2, which have a release liner (Figure 1) and Figure 2 shows a silicone-based synthetic leather composite material that does not have the silicone-based synthetic leather. The synthetic leather composite has been prepared and can at this point be applied by any suitable application means as described above, e.g. Spraying, rolling, brushing, spin coating, dip coating, solvent coating Casting, slot die coating, spray coating, knife coating , or gravure coating) on ​​the skin layer (4) as described above. is ready to be applied.

[0097] Next, the above-mentioned leather coating is applied onto the surface of the skin layer (4) from which the release liner (1) has been removed. The composition is applied and cured to provide a protective topcoat on the silicone-based synthetic leather composite. Form.

[0098] In an alternative embodiment, the silicone-based synthetic leather composite is prepared by subjecting the aforementioned leather to a continuous process. The coating composition may be used to prepare a continuous process with a topcoat. In this case, the process followed may be: (i) applying the aforementioned leather coating composition onto a release liner (1); (ii) curing the aforementioned leather coating composition on the release liner (1) to form a cured top forming a coating (5); (iii) applying a silicone skin layer over the cured topcoat (5); (iv) a cured topcoat layer (5) between the release liner (1) and the cured skin layer (4). curing the silicone skin layer to form a cured skin layer (4) so ​​as to sandwich the silicone skin layer; , (v) applying a silicone adhesive composition onto the cured skin layer (4); (vi) Placing a textile support layer (2) on top of the uncured or cured adhesive layer (3). or laminating the textile support layer to the adhesive layer, preferably by effectively laminating the textile support layer to the adhesive layer. height, (vii) The adhesive layer (3) after curing is between the skin layer (4) and the textile support layer (2). hardening the adhesive layer (3) so that the adhesive layer (3) is sandwiched between the (viii) removing the release liner (1) if necessary;

[0099] The different layers of such a process are shown in Figures 3 and 4, where Figure 3 shows the existing release liner ( 1) and FIG. 4 shows the final silicone-based synthetic leather composite with the release liner removed.

[0100] Any suitable release liner, such as Asahi's ultra-matte release paper ARX175DM, Ja Pan Dai Nippon Printing release paper DE-7, DE-90, DE-43C, DE-73J, or Semi-matt release paper DE-73M, also manufactured by Dai Nippon Printing, may be used. This may be accomplished by curing and drying in a suitable oven, for example in a hot air oven. The process may be carried out in a conveyor oven for a continuous process.

[0101] The above process illustrates the preparation of a silicone-based synthetic leather composite. The reader can see that it may become necessary to introduce layers of

[0102] Synthetic leather, especially silicone-based synthetic leather composites, are available in a wide variety of materials, taking into account the content of different layers. They can be designed to have a variety of properties, e.g., to suit the end-use requirements of the leather. It may have excellent flame retardancy, smoke density, heat resistance, stain resistance, solvent resistance, hydrolysis resistance, etc. Potential end uses include furniture, decoration, handbags, binders, luggage, clothing, Phone covers, covers for electronic products, book covers, footwear, car interiors, car seats, wearable devices, and / or medical beds / sheets, etc. Not limited. EXAMPLES

[0103] The following examples demonstrate the benefits of the coatings described herein in terms of gloss retention after abrasion. To demonstrate the above, a hydrosilylation-curable silicone elastomer that forms a leather coating composition was prepared. The elastomer compositions and some comparative examples were tested. All viscosities are given in units of 100 g / l unless otherwise specified. A Brookfield® rotational viscometer (1,000 ~2,000,000 mPa.s) or 1000 mPa Brookfield® with spindle LV-1 for viscosities below .s Using a rotational viscometer (designed for viscosities in the range of 15 to 20,000 mPa.s), Cup / spindle of ASTM D1084-16 Method B at a rotation speed of 10 rpm It is measured at 25°C according to the Benzene method.

[0104] Alkyl and / or alkynyl content and Si-H content are determined according to ASTM E168 This was determined using quantitative infrared analysis according to the method described above.

[0105] Leather Coating Compositions Used with the Names Given in the Tables / Examples Below The ingredients used in are defined below: The vinyl terminated siloxane polymer has a viscosity of 65,000 mPa.s at 25°C. A dimethylvinyl-terminated polydimethylsiloxane having a vinyl content of about 0.08% by weight. can be, The high vinyl siloxane polymer has a viscosity of 15,000 mPa.s at 25°C and a pH of about 8.0 Dimethylvinyl-terminated dimethylmethylvinyl polysiloxane having a vinyl content of % by weight is a copolymer, Vinyl-terminated siloxane copolymer 2 has a viscosity of 300 mPa.s at 25° C. and a pH of about 1.1 Dimethylvinyl-terminated dimethylmethylvinyl polysiloxane with a vinyl content of 5% by weight copolymer, Fumed silica is 300m 2 HDK® T3 with a BET surface area of ​​1.0 g 0P pyrogenic silica (Wacker Chimie), HMDZ is hexamethyldisilazane; MVD (methyl vinyl diol) has a viscosity of about 30 mPa.s at 25°C and a viscosity of about 12.0 Dimethylhydroxy-terminated polydimethylmethylvinylsiloxane having a vinyl content of 100% by weight. Sun, The platinum catalyst is a polydimethyl ether having about 5000 ppm of platinum metal relative to the remainder of the composition. A platinum catalyst in a solution of siloxane, The inhibitor is methyl(tris(1,1-dimethyl-2-propynyloxy))silane. the law of nature, Silicone elastomer powder is Dowsil® 23N Additive (Dow Silicones Corporation), The resinous SiH crosslinker has a viscosity of 25 mPa.s at 25°C and approximately 9,000 ppm of silica. is a Si-H dimethyl terminated resinous Si-H polysiloxane having a hydrogen content of 100 to 2000 mol / L, The polyurethane particles are RH polyurethane (manufactured by Dainichi Seika Chemicals Co., Ltd.) with an average particle size of 1 to 10 μm (supplier information). U-5070D polyurethane microparticles Acrylic microparticles 1 are manufactured by Soken Chemical Industries, Ltd. with an average particle size of 1 to 10 μm (supplier information). isnow® MZ-5HN, Acrylic microparticles 2 are made by Soken Chemical Industries, Ltd. with an average particle size of approximately 0.4 μm (supplier information). isnow (registered trademark) MX-40T, The lubricant is C It is a 24-28 olefin.

[0106] Table 1 provides details of the starting materials used in the silica masterbatches of the following compositions: Fumed silica is vinyl terminated in the presence of small molecules that act as hydrophobic treatment agents for the silica. Mix the silica with the siloxane polymer to separate the silica from the polymer while the silica and polymer are mixed. As indicated above, the polymer used was treated in situ with component (i) or, if desired, with component (ii). It may be a mixture of (i) with another polymer, in which case component (i) is a masterbatch. does not exist within.

[0107] [Table 1]

[0108] Several LSR compositions were prepared as two-part compositions in the following examples (Examples 1-4) and comparative examples (Comparative The total composition of each composition after mixing Part A and Part B is as follows: The results are shown in Table 2a (Examples) and Table 3a (Comparative Examples).

[0109] Prior to mixing, the Part A composition incorporated the following: High vinyl siloxane copolymers, Part of the master batch, platinum catalyst, The lubricant (if present) and a portion of the particulate and diluent (if present). The diluent is It is designed to evaporate during the curing process.

[0110] The Part B composition incorporated the following: The remainder of the masterbatch, Resinous SiH crosslinker, The inhibitor, if present, and the remainder of the microparticles and any diluents present.

[0111] Diluents: Diluents are designed to evaporate during the curing process.

[0112] Immediately prior to use, mix the Part A composition and its respective Part B composition in a 1:1 weight ratio. were mixed together to produce the final hydrosilylation-curable silicone elastomer composition under test. Made.

[0113] [Table 2]

[0114] After preparation, the topcoat composition is applied to the silicone-based synthetic leather through the following process: The skin layer (4) used was Dowsil LCF A mixture of Dowsil® LCF 8300 Skin and Dowsil® LCF 8500 Skin. and the adhesive layer (3) is in the form of Dowsil™ LCF 8400 Binder. This is then subjected to a lamination bonding process to a microfiber-based textile layer (2) before curing. The combination was then cured at a temperature of 150° C. for 3 minutes. 1) The topcoat mixture is applied onto a release liner and heated at 120° C. for 1.4 minutes (m The dry film thickness was determined to be approximately 10 μm. 2) The skin layer was then applied over the topcoat and cured under the same conditions. The thickness was 100 to 150 μm. 3) An adhesive layer was applied over the skin layer and the fabric was attached using a lamination bonding process. The combination is then cured at 150°C for 3 minutes, and the thickness of the adhesive layer is 150-250μm. become. 4) The release liner is then removed to reveal the top-coated silicone leather sump. 5) Finally, the silicone leather material is post-cured at a temperature of 80°C for 16 to 20 hours. Ta.

[0115] The resulting silicone leather was then treated with a TABER® Abraser (Abraser®) The Taber abrasion test was performed using a Taber abrasion tester (Taber Ader Model 5131). The abrasion resistance performance of the leather samples is evaluated using a bar abrasion test. Three samples were rubbed with a CS-10 wheel and a 1 kg weight for 500 cycles. After the rubbing step, the rubbing surfaces were washed with deionized water and air-dried prior to evaluation. Each sample was then visually evaluated for any desirable characteristics of gloss, color, or texture. To pass the test, the coating had to be worn down, and the gloss, color, and It is necessary that there be substantially no undesirable changes in grain or grain.

[0116] Results for examples having a topcoat according to the present disclosure are provided in Table 2b.

[0117] [Table 3]

[0118] (SC) indicates slight change.

[0119] Due to the nature of the polymer and crosslinker, high crosslink density limits chain mobility and therefore adhesion. This is believed to minimize contact of the agent with the surface. This avoids wear patterns and reduces abrasion. On the other hand, fine particles in the topcoat appeared on the surface after abrasion. As a result, small grains are worn away, but the fine particles that appear compensate for the loss of surface roughness. This helps to avoid an increase in gloss.

[0120] The comparative composition was then topcoated using the same process and test methods as above. The same test was carried out on silicone leather that had been coated with the top coat. and the results are shown in Table 3b.

[0121] [Table 4]

[0122] [Table 5]

[0123] SDG represents the noticeable decrease in gloss and ΔGrey value represents the change in grey value.

[0124] Examples 1, 2, and 3 passed the Taber test with no obvious change in gloss. Comparative Examples 1, 3, 4, and 5 were rejected due to a significant decrease in gloss, while Comparative Example 2 was unsatisfactory due to a significant decrease in gloss. From Comparative Example 5, the particle size of the fine particles is at least 5 μm. In Comparative Example 1, the high vinyl siloxane used in the Examples was Instead of the copolymer, vinyl-terminated siloxane copolymer 2 is used. The elastomer obtained by the above process has a lower crosslink density and therefore, In view of the results of the above, it can be recognized that high vinyl siloxane copolymers are essential. .

Claims

[Claim 1] 1. A leather coating composition comprising a hydrosilylation-curable silicone elastomer composition, comprising: Component (i) one or more organopolysiloxane polymers having a viscosity of 1000 to 500,000 mPa.s at 25°C, wherein at least 5% by weight of said polymer are unsaturated groups selected from alkenyl groups, alkynyl groups, or mixtures thereof, as determined using quantitative infrared analysis in accordance with ASTM E168; Component (ii) a reinforcing silica filler which may be optionally hydrophobically treated; and component (iii) a silicone resin crosslinker having terminal (M) groups containing silicone-bonded hydrogen, wherein the molar ratio of Si-H groups in component (iii) to unsaturated groups in said composition is from 0.5:1 to 20:1; Component (iv) a hydrosilylation catalyst; and Component (v) a silicon-free inorganic particulate having a number average particle size of 0.5 to 500 μm as determined using a field emission scanning electron microscope, which is thermally stable up to a temperature of at least 180° C. using the test method disclosed herein, and which is present in the leather coating composition in an amount of 5 to 35% by weight; A composition comprising:

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