Silicone polyether having branched chain-like pendant polyether groups

Abstract

The composition has the following chemical structure: (CH3)3SiO-Y(CH3)SiO-Si(CH3)3, where Y is -(CH2)3O(CH2)CH[CH2O(CH2) m CH2CH3]O(CH2CH2O) n The material contains a silicone polyether, where H is the subscript m has an average value in the range of 10 to 14, and n has an average value in the range of 1 to 500.

Description

[Technical Field]

[0001] (Field of Invention) The present invention relates to a polyether polyol having branched, pendant polyethers extending from a siloxane main chain.

[0002] (Introduction) Release coatings for bakery paper benefit from water resistance and, needless to say, high release properties for baked products. Using silicone emulsions to coat bakery paper to achieve these desirable properties is an attractive alternative to release coatings containing chromium complexes and fluoropolymers, due to the health issues associated with these latter materials. However, a challenge with silicone emulsion coatings is that in bakery release tests, the amount of material used is 12 grams per square meter (g / m²). 2 The goal is to achieve food peeling performance with bakery residue values ​​lower than 20 g / m² in the Cobb water resistance test. 2 Less than 17 g / m², preferably 17 g / m² 2 Less than 15 g / m², more preferably 15 g / m² 2 Achieving sufficient water resistance while simultaneously achieving a water absorption value below a certain level is particularly difficult. [Overview of the Initiative]

[0003] According to the present invention, 12 g / m² in the bakery peel test. 2 Less than 20 g / m² of bakery residue and 20 g / m² in the Cobb water resistance test. 2 Less than 15g / m² 2 A solution is provided to the demand for silicone emulsions that can provide a peelable coating with a water absorption value of less than 100%.

[0004] The present invention is the result of surprisingly discovering a silicone polyether (SPE) that imparts bakery residue performance and water resistance to silicone emulsions, whereas other SPE materials do not impart these performances. The SPE has a specific 3-silicon siloxane backbone that appears to impart emulsion stability, in contrast to longer siloxane backbone SPEs. It also has one branched-chain polyether pendant group. A specific bond between the siloxane backbone and the polyether unit has been found to be important for achieving the targeted fired residue value.

[0005] In a first aspect, the present invention relates to a composition comprising a silicone polyether having the following chemical structure: (CH3)3SiO-Y(CH3)SiO-Si(CH3)3, where Y is -(CH2)3O(CH2)CH[CH2O(CH2) m CH2CH3]O(CH2CH2O) n H, where the subscript m has an average value in the range of 10 to 14, and n has an average value in the range of 1 to 500.

[0006] The composition can consist of or contain only the silicone polyether. Alternatively, the composition can contain additional components. The composition can include components for forming a curable release coating composition emulsion, including aliphatic unsaturated polyorganosiloxane, polyorganohydrogensiloxane, hydrosilylation reaction catalyst, hydrosilylation reaction inhibitor, water, buffer, silicone polyether, optionally polyvinyl alcohol, optionally biocide, optionally co-surfactant, and optionally defoamer. The composition can further include a substrate such as a paper sheet, with the coating composition coated on at least one surface of the substrate.

[0007] The present invention is useful for use in baking paper to provide a substrate that is water-resistant and achieves low bakery residues.

Embodiments for Carrying Out the Invention

[0008] Products identified by trade names refer to compositions available under those trade names as of the priority date of this document.

[0009] "Multiple" means two or more. "And / or" means "and, or as an alternative." All ranges include the endpoint unless otherwise specified.

[0010] "Alkyl" refers to a hydrocarbon group that can be derived from alkanes by removing a hydrogen atom. Alkyl groups can be linear or branched.

[0011] The viscosity of the material is determined using a Brookfield Viscometer DV-I Prime with 2-4 spindles at a speed of 20-100 revolutions per minute and a temperature of 25 degrees Celsius (°C), unless otherwise specified.

[0012] The present invention has the following chemical structure (I), (CH3)3SiO-Y(CH3)SiO-Si(CH3)3(I) In the formula, Y is -(CH2)3O(CH2)CH[CH2O(CH2) m CH2CH3]O(CH2CH2O) n The composition is H, and comprises a silicone polyether, where the subscript m has an average value in the range of 10 to 14, and the subscript n has an average value in the range of 1 to 500. The subscript m can have an average value of 10 or more, 11 or more, 12 or more, and even 13 or more, and at the same time typically has an average value of 14 or less, 13 or less, 12 or less, or even 11 or less. The subscript n can be 1 or more, preferably 10 or more, and can be 20 or more, even 30 or more, 40 or more, 50 or more, 60 or more, and even 65 or more, and at the same time typically 500 or less, 300 or less, 150 or less, 135 or less, 100 or less, 75 or less, 50 or less, and even 40 or less.

[0013] The composition may consist of a silicone polyether. Alternatively, the composition may contain other components in addition to the silicone polyether. For example, the composition may be an aqueous emulsion containing a silicone polyether. One preferred such aqueous emulsion is a coating composition emulsion comprising (a) an aliphatic unsaturated polyorganosiloxane, (b) a polyorganohydrogensiloxane, (c) a hydrosilylation reaction catalyst, (d) a hydrosilylation reaction inhibitor, (e) water, (f) a buffer, (g) a silicone polyether having chemical structure (I), (h) optionally a polyvinyl alcohol, (i) optionally a biocide, and optionally (j) an auxiliary surfactant.

[0014] (a) Aliphatic unsaturated polyorganosiloxane The aliphatic unsaturated polyorganosiloxane of component (a) has the unit formula (AI), (R 1 3SiO 1 / 2 ) i (R 1 2R 2 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g (R 1 R 2 SiO 2 / 2 ) h (SiO 4 / 2 ) j (AI) In the formula, each R 1 However, each R is an independently selected alkyl group. 2 However, the alkenyl group is independently selected, and the subscripts i, f, g, h, and j represent the average number of each siloxane unit per molecule, with i being in the range of 0 to 4, f being in the range of 0 to 4, g being in the range of 0 to 1400, h being in the range of 0 to 200, and j being 0 or 1, provided that if the quantity (i+f) is in the range of 2 to 4, then the quantity (f+h) is at least 2, and the quantity (i+f+g+h) is in the range of 15 to 1400.

[0015] R 1 Suitable alkyl groups can have 1 to 8 carbon atoms and can be selected from the group consisting of 1 to 8 carbon atoms, such as methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including n-butyl, t-butyl, sec-butyl, and isobutyl), pentyl (including linear, branched, and cyclic saturated hydrocarbon groups having 5 carbon atoms), hexyl (including linear, branched, and cyclic saturated hydrocarbon groups having 6 carbon atoms), heptyl (including linear, branched, and cyclic saturated hydrocarbon groups having 7 carbon atoms), and octyl (including linear, branched, and cyclic saturated hydrocarbon groups having 8 carbon atoms). 1 The preferred aryl group contained in can have 6 to 20 carbon atoms and can be selected from the group consisting of phenyl, tolyl, xylyl, naphthyl, and styryl. The aryl group may also be phenyl. Each R 1 R may be methyl or ethyl. 1 R may be methyl or phenyl. 1 It may also be methyl.

[0016] Ideally, R 2 R is selected from the group consisting of vinyl groups, allyl groups, and hexenyl groups. 2 It can be selected from the group consisting of vinyl and allyl. Alternatively, R 2 The components may be selected from the group consisting of vinyl and hexenyl. Alternatively, each R 2 It may be made of vinyl.

[0017] Preferably, when the subscript j=0, the aliphatic unsaturated polyorganosiloxane is linear. Linear aliphatic unsaturated polyorganosiloxane has the unit formula (A-II):(R 1 3SiO 1 / 2 ) i (R 1 2R 2 SiO 1 / 2 ) f (R 1 2SiO2 / 2 ) g (R 1 R 2 SiO 2 / 2 ) h It can include, in the formula, R 1 R is an independently selected alkyl group or aryl group as described above. 2 is an independently selected alkenyl group as described above, where the subscript i is 0, 1, or 2, the subscript f is 0, 1, or 2, the subscript g is 0 to 1200, and the subscript h is 0 to 200, provided that the quantity (i+f)=2, the quantity (f+h)≧2, and the quantity (i+f+g+h) is 15 to 1200.

[0018] Linear aliphatic unsaturated polyorganosiloxanes may include bis-alkenyl-terminated blocked polydialkylsiloxanes (when i=0, f=2, and h=0). Bis-alkenyl-terminated blocked polydialkylsiloxanes have the unit formula (A-III):(R 1 2R 2 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g It may have, in the formula, each R 1 Each R is an alkyl group, 2 It is an alkenyl group, and the subscript g is between 15 and 1200.

[0019] Linear aliphatic unsaturated polyorganosiloxanes may include poly(dialkyl / alkylvinyl)siloxanes (when g>0 and h>0). Poly(dialkyl / alkylvinyl)siloxanes have the unit formula (A-IV):(R 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g (R 1 R 2 SiO 2 / 2 ) h It may have, in the formula, each R 1 Each R is an alkyl group, 2is an alkenyl group, the subscript g is greater than 0 and up to 1200, and the subscript h is between 2 and 200.

[0020] Aliphatic unsaturated polyorganosiloxanes may include one linear aliphatic unsaturated polyorganosiloxane or any combination of one or more linear aliphatic unsaturated polyorganosiloxanes, such as those selected from the group consisting of: (i) α,ω-dimethylvinylsiloxy-terminated polydimethylsiloxane, (ii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), (iii) α,ω-dimethylvinylsiloxy-terminated polymethylvinylsiloxane, (iv) α,ω-trimethylsiloxy-terminated poly(dimethyl (v) α,ω-trimethylsiloxy-terminated polymethylvinylsiloxane, (vi) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methylvinylsiloxane), (vii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), (viii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), and (ix) α,ω-phenyl,methyl,vinyl-siloxy-terminated polydimethylsiloxane.

[0021] In addition to (or instead of) the linear aliphatic unsaturated polyorganosiloxanes described above, the aliphatic unsaturated polyorganosiloxanes may include branched aliphatic unsaturated polyorganosiloxanes. Preferably, the branched aliphatic unsaturated polyorganosiloxane has more than 0 mole percent (mol%) and at the same time 5 mol% or less of tetrafunctional units, based on the total siloxane units in the branched aliphatic unsaturated polyorganosiloxane. For example, the branched aliphatic unsaturated polyorganosiloxane has the unit formula (AV):(R 1 3SiO 1 / 2 ) i (R 1 2R 2 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g(SiO 4 / 2 ) j may be included, wherein R 1 and R 2 are as described above, and the subscripts i, f, g, and j have average values such that 2 ≥ i ≥ 0, 4 ≥ f ≥ 0, 995 ≥ g ≥ 4, j = 1, (i + f) = 4, and (i + f + g + j) > 50. Alternatively, the quantity (i + f + g + j) may have a value sufficient to impart a viscosity exceeding 170 millipascal seconds (mPa * s). Alternatively, the dynamic viscosity may be 170 mPa * s to greater than 1000 mPa * s, or greater than 170 to 500 mPa * s, or greater than 180 mPa * s to 450 mPa * s, or greater than 190 mPa * s to 420 mPa * s. * There is a possibility of being.

[0022] Methods for preparing linear aliphatic unsaturated polyorganosiloxanes include, for example, methods such as hydrolysis and condensation of corresponding organohalosilanes and oligomers, or equilibration of cyclic polydiorganosiloxanes, which are known in the art. See, for example, U.S. Patent Nos. 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087. Branched-chain aliphatic unsaturated polyorganosiloxanes suitable for use in aliphatic unsaturated polyorganosiloxanes can be prepared by known methods, for example, methods disclosed in U.S. Patent No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0023] (b) Polyorganohydrogensiloxane The polyorganohydrogensiloxane has a unit formula (B-I): (R 1 3SiO 1 / 2 ) w (R 1 2HSiO 1 / 2 ) x (R 1 2SiO2 / 2 ) y (R 1 HSiO 2 / 2 ) z It may have, in the formula, R 1 As described above, the subscripts w, x, y, and z represent the average number of each siloxane per molecule, with w having a value of 0, 1, or 2, the subscript x being 0, 1, or 2, the subscript y being 0 to 250, and the subscript z being 1 to 250, provided that the quantity (w+x)=2, the quantity (x+z)≧2, and the quantity (w+x+y+z) being 10 to 300. Alternatively, the subscript w may be 2, and the subscript x may be 0. Alternatively, the subscript y may be greater than 0 and up to 250. Alternatively, when the aliphatic unsaturated polyorganosiloxane (a) has two silicon-bonded alkenyl groups per molecule, for example, when (a) is i) α,ω-dimethylvinylsiloxy-terminated polydimethylsiloxane, the quantity (x+z) is preferably 3 or more. Alternatively, when x=y=0 and w=2, polyorganohydrogensiloxane has the unit formula (B-II):(R 1 3SiO 1 / 2 )2(R 1 HSiO 2 / 2 ) z It can have, in the formula, R 1 As stated above, z is between 3 and 250.

[0024] Suitable polyorganohydrogensiloxanes include any one or more combinations selected from the group consisting of (i) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (ii) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, (v) α-dimethylhydrogensiloxy-ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (vi) α-dimethylhydrogensiloxy-ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, and (vii) α,ω-dimethylhydrogensiloxy-terminated polydimethylsiloxane.

[0025] Suitable polyorganohydrogensiloxanes are commercially available, for example, those from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as HMS-H271, HMS-071, HMS-993, HMS-301, HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, and HMS-HM271. Methods for preparing linear and branched polyorganohydrogensiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known in the art and are exemplified in U.S. Patents No. 2,823,218, No. 3,957,713, and No. 4,329,273.

[0026] The polyorganohydrogensiloxane (b) is preferably present in the coating composition emulsion at a concentration sufficient to give the molar ratio (i.e., SiH:Vi ratio) of silicon-bonded hydrogen atoms in the polyorganohydrogensiloxane (b) to alkenyl groups in the aliphatic unsaturated polyorganosiloxane (a) to a range of 1.2:1 to 3.0:1 or 1.4:1 to 2.5:1.

[0027] (c) Hydrosilylation reaction catalyst Hydrosilylation catalysts are useful for promoting the hydrosilylation reaction between the alkenyl group of an aliphatic unsaturated polyorganosiloxane (a) and the silyl hydride (SiH) group in a polyorganohydrogensiloxane (b). Hydrosilylation catalysts may include metals selected from the group consisting of iron (Fe), nickel (Ni), cobalt (Co), zirconium (Zr), titanium (Ti), and platinum group metals. Preferably, the catalyst is a platinum group metal catalyst selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Preferably, the hydrosilylation catalyst is a platinum-based catalyst.

[0028] Hydrosilylation catalysts may be induceable, meaning they can catalyze a hydrosilylation reaction upon exposure to an inducer. For example, catalysts can be induced by exposure to visible light or ultraviolet light (radiation-activated catalysts) or by heating (thermal-activated catalysts). Radiation-activated catalysts include any one or any combination of two or more selected from the group consisting of cyclopentadienyl platinum complexes, such as cyclopentadienyl platinum complexes like η5-cyclopentadienyl)tri(α-alkyl)platinum(IV), cyclopentadienyltrimethylplatinum and trimethyl(methylcyclopentadienyl)platinum(IV), cyclooctadienediarylplatinum complexes like η4-1,5-cyclooctadienediarylplatinum complexes, and Pt(II)-β-diketonate complexes such as bis(acetylacetonate)platinum(II). Examples of cyclopentadienyl platinum complexes are known in the art and are disclosed, for example, in U.S. Patent No. 4,510,094. Cyclooctadienylplatinum complexes are disclosed, for example, in U.S. Patent No. 6,046,250.

[0029] Other suitable platinum catalysts include any one or more combinations selected from the group consisting of chlorotris(triphenylphosphine)rhodium(I) (Wilkinson catalyst), rhodium diphosphine chelates such as [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride, and complexes of compounds with alkenyl-functional organopolysiloxane oligomers such as alkenyl-functional polydialkylsiloxanes, or platinum group metal compounds microencapsulated in a matrix or core-shell structure. Examples of complexes between platinum and alkenyl-functional organopolysiloxane oligomers include a complex of 1,3-diethyl-1,1,3,3-tetramethyldisiloxane and platinum (Karstedt catalyst), and a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby complex). The hydrosilylation catalyst may be one of the above compounds or complexes microencapsulated in a resin matrix. Suitable hydrosilylation catalysts are commercially available, for example, as SYL-OFF® 4000 Catalyst and SYL-OFF® 2700 from The Dow Chemical Company (Midland, Michigan, USA) (SYL-OFF is a trademark of Dow Silicones Corporation).

[0030] The hydrosilylation catalyst (c) may be any single hydrosilylation catalyst, any combination of hydrosilylation catalysts, or two or more hydrosilylation catalysts. The amount of hydrosilylation catalyst in the coating composition emulsion should be sufficient to catalyze the hydrosilylation reaction between SiH and the alkenyl group. Preferably, the concentration of hydrosilylation catalyst (c) is 10 parts per million by weight (ppm) or more, 15 ppm or more, 20 ppm or more, 50 ppm or more, and more than 100 ppm or more, and at the same time, typically 1,000 ppm or less, 800 ppm or less, 500 ppm or less, or more than 100 ppm or less, where the ppm of the hydrosilylation catalyst is the mass of the metal component in the catalyst relative to the total mass of the aliphatic unsaturated polyorganosiloxane (a) and polyorganohydrogensiloxane (b).

[0031] (d) Hydrosilylation reaction inhibitors Hydrosilylation inhibitors are useful for altering the hydrosilylation reaction rate of coating composition emulsions. Examples of suitable hydrosilylation inhibitors include any one or any combination of two or more components selected from the group consisting of acetylene alcohol, silylated acetylene alcohol, en-yine compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, ethers, carbon monoxide, and alkenyl-functionalized siloxane oligomers.

[0032] Suitable examples of acetylene alcohols include 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyne-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol, and combinations thereof.

[0033] Suitable examples of silylated acetylene compounds include (3-methyl-1-butyne-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyne-3-oxy)dimethylsilane, bis(3-methyl-1-butyne-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyne-3-oxy))silane, (3-methyl-1-butyne-3-oxy)dimethylphenylsilane, (3-methyl-1-butyne-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyne-3-oxy)triethylsilane, bis(3-methyl- This includes (1-butyl-1-butyne-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyne-3-oxy)trimethylsilane, (3-phenyl-1-butyne-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyne-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyne-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyne-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyne-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyne-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyne-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyne-1-oxy)trimethylsilane, and combinations thereof.

[0034] Suitable en-yne compounds include 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and combinations thereof. Suitable triazoles include benzotriazole. Suitable amines include tetramethylethylenediamine, 3-dimethylamino-1-propyne, n-methylpropargylamine, propargylamine, 1-ethynylcyclohexylamine, or combinations thereof. Suitable fumarates include dialkyl fumarates such as diethyl fumarate, dialkenyl fumarates such as diallyl fumarate, and dialkoxyalkyl fumarates such as bis-(methoxymethyl)ethyl fumarate. Suitable maleates include dialkyl maleates such as diethyl maleate, dialkenyl maleates such as diallyl maleate, and dialkoxyalkyl maleates such as bis-(methoxymethyl)ethyl maleate. Suitable siloxane oligomers include cyclic and linear siloxane oligomers such as methylvinylcyclosiloxanes, exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane. They may also be cyclic or linear, such as methylvinylcyclosiloxanes, exemplified by 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and combinations thereof.

[0035] The concentration of the hydrosilylation reaction inhibitor (d) is typically greater than zero parts by mass, can be 0.02 parts by mass or more, and even 0.8 parts by mass or more, based on 100 parts by mass of aliphatic unsaturated polyorganosiloxane (a), and at the same time, is typically 1.0 part by mass or less.

[0036] (e) water The water component can be treated or untreated. Treated water includes water purified by one or more of the following: distillation, filtration, or deionization. Untreated water includes tap water and well water that have not undergone further purification. Water is typically the main component of the continuous phase or support phase of the coating composition emulsion. The amount of water in the coating composition emulsion is typically 30% by weight (wt%) or more, 50% by weight or more, and even 60% by weight or more, based on the weight of the coating composition emulsion, and at the same time typically 99% by weight or less, 95% by weight or less, or even 90% by weight or less.

[0037] (f) buffer The buffering agent may contain a monobasic acid or a polybasic acid and its conjugate base, and is useful for maintaining a desired pH in the coating composition emulsion. Examples of suitable buffering agents include HCO3. - / CO3 2- and H2PO4 - / HPO4 2- The buffer may include NaCO3 and NaHCO3, and / or citric acid and citrate, such as potassium citrate or sodium citrate. The buffer may alternatively include sodium hydroxide and citric acid. The concentration of the buffer may be, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a), preferably more than 0 parts by weight, preferably 0.2 parts by weight or more, 0.4 parts by weight or more, and at the same time, typically 1.6 parts by weight or less, 1.5 parts by weight or less, or even 1.25 parts by weight or less.

[0038] (g) Silicone polyether The silicone polyether is as described above and has chemical structure (I). The concentration of the silicone polyether in the coating composition emulsion is preferably 0.05 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, 2 parts by weight or more, and more preferably 2.5 parts by weight or more, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a), and at the same time, typically 3 parts by weight or less, or 2.5 parts by weight or less, 2 parts by weight or less, 1.5 parts by weight or less, or more preferably 1 part by weight or less.

[0039] (h) Polyvinyl alcohol Polyvinyl alcohol is known in the art and is disclosed, for example, in paragraphs

[0172] and

[0173] of U.S. Patent Application Publication 2007 / 0099007. Polyvinyl alcohol may be prepared by saponification of polyvinyl acetate, and up to 65 mol% of polyvinyl acetate may remain in the polyvinyl alcohol used herein. Alternatively, the polyvinyl alcohol may be 35 mol% to 99 mol% polyvinyl alcohol (the remainder being 65 mol% to 1 mol% polyvinyl acetate). Alternatively, the polyvinyl alcohol can be hydrolyzed by 80% to 98%. The minimum viscosity of polyvinyl alcohol is 5 mPa in a 4% aqueous solution at 20°C. * s, or up to 200 mPa * It could be s. Alternatively, polyvinyl alcohol has a viscosity of 15 mPa. * s~55mPa * It could be s.

[0040] The concentration of polyvinyl alcohol in the coating composition emulsion is preferably 0 parts by weight or more, and can be 1.5 parts by weight or more, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a), and at the same time, it is typically 10 parts by weight or less, 5 parts by weight or less, or even 3 parts by weight or less. The total concentration of silicone polyether (g) and polyvinyl alcohol (h) is preferably 3.0 parts by weight or more, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a).

[0041] (i) Biocides The coating composition emulsion may optionally contain a biocide. Suitable biocides include one or a combination of fungicides, herbicides, insecticides, and antimicrobial agents. Examples of suitable biocides include those described in U.S. Patent No. 9,221,041. The concentration of the biocide is 0 parts by weight or more, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a), and at the same time, typically 1.0 part by weight or less.

[0042] (j) auxiliary surfactant This composition may optionally contain auxiliary surfactants. The auxiliary surfactants may be nonionic, ionic, or a combination of nonionic and ionic surfactants. Suitable nonionic auxiliary surfactants include alkylphenols, fatty alcohols, or fatty acids having alkylene oxide groups, such as ethylene oxide or propylene oxide groups. Suitable ionic auxiliary surfactants include anionic surfactants such as sulfates, sulfons, phosphates, and sulfosuccinates. Suitable surfactants for use herein as auxiliary surfactants are exemplified by those described as surfactant (G) in paragraphs

[0167] to

[0176] of U.S. Patent Application Publication No. 2007 / 0099007. One preferred auxiliary surfactant is poly(oxy-1,2-ethanediyl), which is marketed by BASF under the name LUTENSOL® XP100 (LUTENSOL is a trademark of BASF SE), and another is ethoxylated isotridecanol, which is marketed by the PCC Group under the name ROKANol® IT12 (ROKAnol is a trademark of PCC Exol SA). The concentration of the auxiliary surfactant is 0 parts by weight or more, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a), and at the same time typically 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, or even 0.5 parts by weight or less, or 0.3 parts by weight or less.

[0043] The coating composition may optionally contain one or more combinations of further components selected from, for example, defoamers, non-functional polyorganosiloxanes, fungicides (e.g., sorbic acid), colorants (e.g., dyes or pigments), fillers (e.g., silica), and wetting agents (e.g., glycols such as propylene glycol or ethylene glycol).

[0044] Examples of suitable defoamers include emulsions containing silica and polydimethylsiloxane. Suitable commercially available defoamers include those available under trade names DOWSIL® AFE-1520, DOWSIL® 7989, SYL-OFF® EM 7989 ANTIFOAM, XIAMETER® AFE-0100, XIAMETER® AFE-1510, XIAMETER® AFE-1520, and XIAMETER® AFE-1530. DOWSIL is a trademark of The Dow Chemical Company. XIAMETER and SYL-OFF are trademarks of Dow Silicones Corporation. The concentration of the defoamer is 0 parts by weight or more, and simultaneously 0.3 parts by weight or less, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a).

[0045] "Non-functional polyorganosiloxanes" refer to polymers having a main chain in which silicon and oxygen atoms alternate, with organic groups bonded to other valencies of silicon atoms, such organic groups do not undergo hydrosilylation reactions with aliphatic unsaturated polyorganosiloxanes (a) or polyorganohydrogensiloxanes (b). Non-functional polyorganosiloxanes generally have the chemical formula (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c It has, in the formula, R 1 As stated above, the subscript c indicates a viscosity of 5 mPa. * s~60,000 mPa *The value is sufficient to provide a non-functional organopolysiloxane of which s is present. An example of a non-functional organopolysiloxane is an α,ω-trialkylsiloxy-terminated polydialkylsiloxane, such as an α,ω-trimethylsiloxy-terminated polydimethylsiloxane. The concentration of the non-functional organopolysiloxane in the coating composition emulsion is 0 parts by weight or more and 15 parts by weight or less, based on 100 parts by weight of aliphatic unsaturated polyorganosiloxane (a).

[0046] The silicone polyether emulsion of the present invention can be prepared by combining the components together, preferably under shear, or by applying shear after combining them. To avoid premature hydrosilylation reactions in the coating composition emulsion, it is possible to withhold the reactants and / or catalyst from the emulsion until the desired time for the hydrosilylation reaction to occur, and then mix in the withheld components. Shearing can be applied, for example, using a rotor and stator mixer, homogenizer, microfluidizer, colloid mill, or sonorator (ultrasonic mixer). The emulsion can also be diluted by blending with additional water if desired.

[0047] Coating composition emulsions are useful for coating substrates. When coating a substrate with a coating composition emulsion, the coated substrate can be heated to achieve curing of the coating composition emulsion coating the substrate. Typically, heating is performed to a temperature in the range of 50 to 120°C. Heating also achieves drying of the coating. The cured coating is useful as a peel-off coating on the substrate. If desired, multiple coatings can be applied to a single substrate. Multiple coatings may be useful to increase the coating thickness and / or to coat multiple surfaces of the substrate. After curing and drying, the resulting coating typically has a thickness greater than zero micrometers, preferably 0.05 micrometers or more, 0.1 micrometers or more, 0.15 micrometers or more, and even 0.2 micrometers or more, while simultaneously typically being 10 micrometers or less, 5 micrometers or less, 1 micrometer or less, and potentially 0.9 micrometers or less, 0.8 micrometers or less, 0.7 micrometers or less, 0.6 micrometers or less, 0.5 micrometers or less, and even 0.3 micrometers or less.

[0048] Coating of a substrate with a coating composition emulsion can be carried out by essentially any coating method, such as spin coating, brush coating, drop coating, spray coating, dip coating, roll coating, flow coating, slot coating, gravure coating, size press coating, film press coating, curtain coating, and any combination thereof.

[0049] Suitable substrates include those made from plastics, paper, metals, ceramics, and any combination thereof. The substrate may be in the form of a sheet or any shape. [Examples]

[0050] Table 1 identifies materials useful for preparing the following samples.

[0051] [Table 1] LUTENSOL is a trademark of BASF SE, ROKAnol is a trademark of PCC Exol SAJoint Stock Company, PLURIOL is a trademark of BASF SE Societas Europae, DOWSIL is a trademark of The Dow Chemical Company, SYL-OFF is a trademark of Dow Silicones Corporation, KATHON is a trademark of Nutrition & Biosciences USA2, LLC, BIOBAN is a trademark of The Dow Chemical Company, and SURFYNOL is a trademark of Evonik Operations GMBH.

[0052] NMR procedure Proton nuclear magnetic resonance for the sample ( 1 The 1H NMR spectrum was collected using a BRUKER AVIII (400 MHz) NMR spectrum in a silicon-free 10 mm tube and CDCl3 / Cr(AcAc)3 solvent.

[0053] Silicon-29 nuclear magnetic resonance for the sample ( 29 The Si NMR spectrum was collected using a BRUKER AVIII (600 MHz) NMR spectrum in a silicon-free 10 mm tube and in CDCl3 / Cr(AcAc)3 solvent.

[0054] Preparation of Example 1 and SPE 1 A 500 ml (mL) three-necked flask is equipped with a magnetic stirrer, condenser, and nitrogen inlet. 242.68 g of "pre-dried" branched-chain olefin polyether 1 is added to the 500 mL flask. The branched-chain olefin polyether 1 is pre-dried by placing it overnight in an aluminum tray in a vacuum oven at 60°C and a pressure of 3000 Pascals.

[0055] Inject 30.9 g of MDHM into a 500 mL flask. Begin heating the contents of the flask to 90°C, and when the temperature reaches 75°C, add a catalyst composition at a concentration of 15 parts by weight per million (ppm) based on the total weight of branched olefin polyether 1 and MDHM. The catalyst composition contains 5000 ppm of Pt from Pt catalyst 1 diluted with IPA. When the temperature reaches 90°C, maintain that temperature for 5 hours, and then cool. 1 H and 29 Si NMR analysis shows that the resulting product consists of 82.9 mol% (mol%) trisiloxyethyloxyalkyl polyethoxylate (Target SPE 1a; Example 1) having an average of 30 ethylene oxide units per pendant group and no residual SiH functional groups, and 17.1 mol% byproducts obtained from the condensation reaction of MDHM with polyether-terminated alcohols. Mole percentages are relative to all NMR peaks. Target SPE 1a is diluted with water to obtain a 15 wt% aqueous solution of SPE 1a, which is used as SPE 1 for the formulation in Example 3.

[0056] Preparation of Example 2 and SPE 2 A 100 ml (mL) three-necked flask is equipped with a magnetic stirrer, condenser, and nitrogen inlet. 272.51 g of "pre-dried" branched olefin polyether 2 is added to a 500 mL flask. The branched olefin polyether 2 is pre-dried overnight in an aluminum place in a vacuum oven at 60°C and a pressure of 3000 Pascals.

[0057] Inject 29.01 g of MDHM into a 100 mL flask. Begin warming the flask contents to 85°C. After 3 hours, add 15 ppm of catalyst composition based on the total weight of branched olefin polyether 1 and MDHM. The catalyst composition contains 5000 ppm of Pt from Pt catalyst 1 diluted with IPA. When the temperature reaches 90°C, maintain that temperature for 10 hours while mixing. Then, strip the SiH residue under vacuum at a pressure of 4000 Pascals. 1 H and 29 Si NMR analysis shows that the resulting product consists of 92.3 mol% (mol%) trisiloxyethyloxyalkyl polyethoxylate (Target SPE 2a; Example 2) having an average of 40 ethylene oxide units per pendant group and no residual SiH functional groups, and 7.7 mol% byproducts obtained from the condensation reaction of MDHM with polyether-terminated alcohols. Mole percentages are relative to all NMR peaks. Target SPE 1a is diluted with water to obtain a 15 wt% aqueous solution of SPE 1a, which is used as SPE 2 for the formulation in Example 4.

[0058] Preparation of peelable coating composition First, a base emulsion composition is prepared, then a catalyst emulsion is combined with the base emulsion composition, and then diluted with an aqueous defoaming emulsion to prepare the peel-off coating composition.

[0059] Preparation of base emulsion composition Table 2 provides the composition of the base emulsion composition in terms of weight percentage (W%) relative to the weight of the base emulsion composition.

[0060] First, an aqueous buffer solution is prepared by blending water, citric acid, and sodium hydroxide components together. The vinyl polymer, SiH polymer, and non-reactive polymer components are weighed separately and mixed separately to form a polymer mixture. The PVA surfactant, auxiliary surfactant 1, and SPE or linear olefin polyether component are mixed separately to form a surfactant mixture. The surfactant mix is ​​slowly added to the polymer mix while emulsifying using a high-pressure sonorator at 100 bar until the particle size reaches Dv0.9, which is 1.0 to 2.5 micrometers, preferably 1.5 to 2.0 micrometers (i.e., 90% of the particles are smaller than this value). The Dv0.9 particle size is determined using laser diffraction spectroscopy with a Malvern Mastersizer 3000 instrument. While emulsifying continues, the buffer solution, inhibitor 1, inhibitor 2, biocide 1, and biocide 2 are added to the emulsion.

[0061] [Table 2]

[0062] The catalyst emulsion is added to the obtained base emulsion composition in a concentration ratio of 95:5. The concentration ratio is based on the relative weight of the base emulsion composition and the catalyst emulsion. The resulting mixture is diluted with an aqueous solution containing an antifoaming agent. The resulting bath composition contains 62.45% by weight of water, 35.63% by weight of the base emulsion, 1.88% by weight of the catalyst emulsion, and 0.05% by weight of the antifoaming agent. The bath contains 15% by weight of siloxane.

[0063] Preparation of catalyst emulsions Table 3 provides the composition of the catalyst emulsion as a weight percentage (W%) of the catalyst emulsion.

[0064] First, an aqueous buffer solution is prepared by blending water, citric acid, and sodium hydroxide components together. The vinyl polymer and Pt catalyst 2 are weighed separately and mixed separately to form a polymer mixture. The components of the PVA surfactant and auxiliary surfactant 2 are mixed separately to form a surfactant mixture. The surfactant mix is ​​slowly added to the polymer mix while emulsifying using a high-pressure sonorator at 100 bar until the particle size reaches Dv0.9, which is 1.0 to 2.5 micrometers, preferably 1.5 to 2.0 micrometers (i.e., 90% of the particles are smaller than this value). The Dv0.9 particle size is determined using laser diffraction spectroscopy with a Malvern Mastersizer 3000 instrument. While continuing to emulsify, the components of the buffer solution, biocide 1, and biocide 2 are added to the emulsion.

[0065] [Table 3]

[0066] Preparation of coated paper substrates Test baking paper samples are prepared by coating baking paper samples with release coating emulsions. Four test baking paper samples are formed by applying each of the four release coating emulsions to separate paper substrates (bare cellulose paper, 40 grams per square meter). The release coating emulsions are applied to the paper substrates using a desktop rotary printing and coating machine (The Rotary Koater, manufactured by RK Print-Coat Instrument Ltd.). A standard roll is used for these samples, and the speed is set to 7 meters per minute to achieve a target silicone coating weight of 0.2 to 0.5 grams per square meter on the paper substrate. After coating, the coated paper substrates are cured and dried in-line in an oven at 110 to 180°C. The resulting coated paper substrates are cut into A4 size sheets and characterized for coating weight, water resistance using the Cobb water resistance test, and peel performance using the Bakery peel test.

[0067] Comparative Example C is a coated paper substrate coated using Comparative Example A.

[0068] Comparative Example D is a coated paper substrate coated using Comparative Example B.

[0069] Example 5 is a coated paper substrate coated using Example 3.

[0070] Example 6 is a coated paper substrate coated using Example 4.

[0071] Characterization of the sample Coating weight After silicon element calibration using sample standards, the coating weight of the release coating emulsion on the paper substrate is determined using X-ray fluorescence with an Oxford lab x3500 CRF Analyzer. The signal intensity is related to the sample thickness of the layer being analyzed. Three measurements are performed for each sample, and the average of these three measurements is used as the weight in grams per square meter (g / m²). 2 This is calculated as the average coating weight.

[0072] Bakery peel test The bakery peel test measures the amount of food remaining on a coated substrate after baking it in an oven. The coated substrate is folded to form a rectangular baking mold (typically 15 cm x 18 cm x 2 cm deep). The rectangular baking mold is weighed.

[0073] Prepare a cake batter in a universal kitchen mixer containing 4 eggs, 80 grams of sugar, 80 grams of potato, 85 grams of flour, and 5.5 grams of baking powder. Pour the cake batter into a rectangular baking pan. Bake the cake batter in the rectangular baking pan at 200°C for 8 minutes. After the resulting cake has cooled in the rectangular baking pan, remove the cake from the pan. Peel the coated substrate from the cake and weigh it again. Subtract the resulting weight from the original weight of the coated substrate (original weight of the rectangular baking pan) to determine the mass of the baking residue. Divide the mass of the baking residue by the area of ​​the coated substrate to obtain the grams of residue per square meter of coated substrate (g / m² of baking residue). 2 The baking residue is determined in units of ). The target is 12 g / m². 2 The goal is to achieve the following baking residue:

[0074] Cobb water resistance test: water absorption The water resistance of the coating on the coated paper substrate is characterized using the Cobb test described in the TAPPI 441 OM-04 test method. A sample of the coated paper substrate is exposed to water, and the mass of the water is measured after 60 seconds. The water absorption value in g / m² is obtained by dividing the mass by the area of ​​the coated paper substrate exposed to water. 2 It is obtained in units of 20g / m³. The target is 20g / m³. 2 Less than 15 g / m², preferably 15 g / m² 2 The goal is to obtain a water absorption value of less than [amount missing].

[0075] Characteristic evaluation results Table 4 provides the characterization results for Comparative Examples C and D, and Examples 5 and 6.

[0076] [Table 4]

[0077] The characterization results in Table 3 show that Examples 5 and 6 achieve the target values ​​for both water absorption and baking residue. The two comparative examples fail to achieve the target baking residue results.

Claims

1. The following chemical structure (I): (CH ３ ) ３ SiO-Y(CH ３ )SiO-Si(CH ３ ) ３ having, in the formula, Y being -(CH ２ ), ３ O(CH ２ ), CH[CH ２ O(CH ２ ), ｍ CH ２ CH ３ O(CH ２ CH ２ O), ｎ H, the subscript m having an average value in the range of 10 to 14, and n having an average value in the range of 1 to 500, a composition containing a silicone polyether.

2. The composition according to claim 1, wherein the subscript n has a value in the range of 10 to 40.

3. The composition according to claim 1 or 2, wherein the composition is an aqueous emulsion containing the silicone polyether.

4. The composition is (a) an aliphatic unsaturated polyorganosiloxane of unit formula (A-I), (R １ ３ SiO １／２ ) ｉ (R １ ２ R ２ SiO １／２ ) ｆ (R １ ２ SiO ２／２ ) ｇ (R １ R ２ SiO ２／２ ) ｈ (SiO ４／２ ) ｊ (A-1) In the formula, each R １ However, each R is an independently selected alkyl group. ２ However, the alkenyl group is independently selected, and the subscripts i, f, g, h, and j represent the average number of each siloxane unit per molecule, with i being in the range of 0 to 4, f being in the range of 0 to 4, g being in the range of 0 to 1400, h being in the range of 0 to 200, and j being 0 or 1, provided that when the amount (i + f) is in the range of 2 to 4, the amount (f + h) is at least 2, and the amount (i + f + g + h) is in the range of 15 to 1400, and the aliphatic unsaturated polyorganosiloxane, (b) a polyorganohydrogensiloxane, wherein the amount of (b) silicon-bonded hydrogen atoms in the polyorganohydrogensiloxane is sufficient to result in a molar ratio of (a) silicon-bonded alkenyl groups in the aliphatic unsaturated polyorganosiloxane being 1.2:1 to 3.0:1, (c) A hydrosilylation reaction catalyst, wherein the amount of the hydrosilylation reaction catalyst is sufficient to provide 10 ppm to 1000 ppm of platinum group metals based on the total weight of (a) the aliphatic unsaturated polyorganosiloxane and (b) the polyorganohydrogensiloxane, (d) (a) A hydrosilylation reaction inhibitor in a concentration of more than 0 to 1.0 part by weight per 100 parts by weight of the aliphatic unsaturated polyorganosiloxane, (e) Water and, (f) (a) A buffer in a concentration of 0.2 to 1.6 parts by weight per 100 parts by weight of the aliphatic unsaturated polyorganosiloxane, (g) (a) The silicone polyether in a concentration of 0.05 to 3 parts by weight per 100 parts by weight of the aliphatic unsaturated polyorganosiloxane, (h) Optionally, (a) a concentration of polyvinyl alcohol in a concentration of 0 to 10 parts by weight per 100 parts by weight of the aliphatic unsaturated polyorganosiloxane, (i) At the discretion of the user, biocides and (j) Optionally, an auxiliary surfactant and (k) The composition according to claim 3, which is a coating composition emulsion comprising an optional defoaming agent.

5. The subscripts i=j=h=0 and the subscript f=2, and the aliphatic unsaturated polyorganosiloxane has the unit formula (R １ ２ R ３ SiO １／２ ) ２ (R １ ２ SiO ２／２ ) ｇ A bis-alkenyl-terminated polydiorganosiloxane having, in the formula, each R １ is methyl, and each R ３ The composition according to claim 4, wherein is vinyl and the subscript g is 15 to 1200.

6. The aforementioned polyorganohydrogensiloxane has the unit formula (R １ ３ SiO １／２ ) ２ (R １ HSiO ２／２ ) ｚ It has, in the formula, R １ The composition according to claim 4 or 5, wherein is methyl and the subscript z is in the range of 3 to 250.

7. The composition according to any one of claims 4 to 6, wherein the hydrosilylation reaction inhibitor comprises acetylene alcohol.

8. The composition according to any one of claims 4 to 7, wherein the buffering agent comprises citric acid and sodium hydroxide.

9. The composition according to any one of claims 4 to 8, wherein the composition further comprises a substrate, and the coating composition emulsion coats at least one surface of the substrate.

10. The composition according to claim 9, wherein the substrate is a paper sheet.

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