Functional polysiloxanes

Abstract

This invention relates to functional polyorganosiloxanes and in particular to their use as adhesion promoters in curable silicone compositions. [Selection diagram] None

Description

[Technical Field]

[0001] The present invention relates to a novel functional polysiloxane comprising at least one organic group bonded to a silicon atom via a carbon atom containing at least one SiH group, at least one diorganosiloxy group, and at least one acid anhydride group. The functional polysiloxane exhibits improved adhesive properties, particularly as an additive in LSR (liquid silicone rubber) formulations or as an additive in silicone coatings of paper and various polymer substrates. [Background technology]

[0002] Unless reactive additives are part of the coating composition, the fixation (permanent adhesion) of silicone coatings to substrates such as paper and various polymer substrates, particularly polyester films, is generally insufficient.

[0003] One common approach to improving adhesion is to add an excess of siloxane crosslinking agent with SiH moieties to cause fixation by forming silyl esters or ethers at the substrate interface, in addition to covalent bonding with the siloxane network. A limitation of this approach is that the effect is more pronounced when using poly(methylhydrogensiloxane) homopolymer crosslinking agents than when using the faster-reacting poly(dimethylsiloxane-co-methylhydrogensiloxane) copolymer crosslinking agents. As a result, when using such compositions, it may be necessary to reduce the line speed of the coating machine to achieve complete curing and fixation. A further limitation of this approach is that the formation of silyl ethers at the substrate interface is significantly reduced in compositions with low catalyst packing and low curing temperatures.

[0004] Another approach involves the addition of an epoxide moiety to a siloxane polymer, which provides improved fixation through ether formation at the substrate interface. This technique has been taught for both hydride-functionalized siloxanes such as US7842394 or US7906605B2 and vinyl-functionalized siloxanes such as US9562149B2. However, the epoxide moiety has limited effect on paper substrates. Furthermore, the solubility of polyfunctional epoxysiloxanes in silicone-release coating polymers is low.

[0005] US7199205 relates to organopolysiloxane-modified polysaccharides prepared by esterifying (A) organopolysiloxanes having residual carboxylic acid anhydride groups and (B) polysaccharides having hydroxyl groups. An example of the starting material (A), an organopolysiloxane having residual carboxylic acid anhydride groups, is prepared by reacting a SiH-functionalized polysiloxane with an unsaturated carboxylic acid anhydride to a polysiloxane that does not have SiH functionality.

[0006] US7090923, US8343632, and US7842394, among others, disclose an additive for fixing release coatings prepared by reacting anhydrous carbonic acid with polymethylhydrosiloxane. This additive still exhibits insufficient fixing performance in paper release coatings.

[0007] US3899515 discloses anhydrous functionalized silanes useful for promoting adhesion in silicone rubber compositions.

[0008] US4381396 discloses silyl norbornane anhydride as an adhesion promoter for RTV silicone rubber. An example of a SiH-functionalized disiloxane is shown that does not have a diorganosiloxy group but has only two terminal trimethylsiloxy groups.

[0009] US5015700 and US6743884 disclose dimethylsiloxane polymers having carboxylic acid anhydride functional groups. The siloxane polymers lack residual SiH functional groups. [Overview of the Initiative]

[0010] In one non-limiting embodiment provided herein, a functional polyorganosiloxane is provided comprising at least one SiH group, at least one diorganosiloxy group not comprising an acid anhydride group, and at least one siloxy group having at least one organic group bonded to a silicon atom via a carbon atom, wherein the organic group comprises at least one acid anhydride group.

[0011] Functionalized polysiloxanes exhibit improved adhesive properties, particularly as additives in LSR (liquid silicone rubber) formulations or as additives in silicone coatings for paper and various polymer substrates. [Modes for carrying out the invention]

[0012] When evaluating the ability of anhydride-containing siloxane crosslinking agents to improve fixation, the inventors have surprisingly found that significant advantages are provided by polymers having anhydride functional groups selectively positioned at the ends of the crosslinked polymer, and preferably having a specific ratio of methylhydridosiloxane to dimethylsiloxane in the polymer backbone. A group of such structures provides improved fixation properties compared to mixtures with a random distribution of functional groups.

[0013] The fundamental objective of the present invention is to provide a novel fixing additive that exhibits improved adhesive properties, particularly as an additive in LSR (liquid silicone rubber) formulations, or in silicone coatings for paper and various polymer substrates.

[0014] The present invention provides a functional polyorganosiloxane comprising at least one SiH group, at least one diorganosiloxy group (i.e., a D=R2SiO2 / 2 group as defined below) that does not contain an acid anhydride group, and at least one organic group bonded to a silicon atom via a carbon atom, wherein the organic group comprising at least one acid anhydride group comprises at least one siloxy group. That is, the organic portion of the at least one diorganosiloxy group does not contain an acid anhydride group. In particular, the diorganosiloxy group is a dialkyl-, diaryl-, or alkyl / aryl-siloxy group, most preferably a dimethylsiloxy group.

[0015] In preferred embodiments of the present invention, the functional polyorganosiloxane is a linear polyorganosiloxane. Preferably, the linear polyorganosiloxane has at least one terminal organic group containing an acid anhydride group and / or at least one pendant terminal organic group containing an acid anhydride group. A terminal organic group means that the organic group is bonded to a terminal silicon atom (i.e., an M group in silicone nomenclature), while a pendant organic group is a group bonded to a non-terminal silicon atom (i.e., a D group in silicone nomenclature).

[0016] Preferably, the functional polyorganosiloxane of the present invention has a number average molecular weight M in the range of about 500 to about 1000, preferably about 800 to about 8200, as determined by GPC using a polystyrene standard. n It holds.

[0017] A preferred functional polyorganosiloxane according to the present invention comprises at least three siloxy units of formula (I): R a R 1 b H c SiO (4-a-b-c) / 2 (I) Here a is 0, 1, 2, or 3. b is either 0 or 1. c is either 0 or 1. R represents an organic group that does not contain an acid anhydride group, and R 1 represents an organic group that contains at least one, preferably one, acid anhydride group, provided that there are at least one siloxy unit where b = 1 and c = 0, at least one siloxy unit where c = 1 and b = 0, and at least one siloxy unit where a = 2 and b = c = 0.

[0018] The condition that there is at least one siloxy unit where b = 1 and c = 0 means that there is at least one residue R 1 representing an organic group that contains at least one, preferably one, acid anhydride group, and such a siloxy group has no hydrogen substituents. The condition that there is at least one siloxy unit where c = 1 and b = 0 means that there is at least one SiH-functional siloxy group without R 1 substituents. The condition that there is at least one siloxy unit where a = 2 and b = c = 0 means that there is at least one diorganosiloxy group, and the organic group has no acid anhydride group.

[0019] R is bonded to the silicon atom via a carbon atom and represents an organic group that has no acid anhydride group. Preferably, R is selected from optionally substituted hydrocarbyl groups having up to 30 carbon atoms and poly(C2 - C4)-alkylene ether groups having up to 1000 alkyleneoxy units.

[0020] Preferably, the organic group R does not contain aliphatic unsaturation.

[0021] The organic group R is preferably further substituted by one or more O-, N-, S- or F-atoms, and is n-, iso, or tertiary alkyl, alkoxyalkyl, C5 - C 30 -cyclic alkyl, or C6 - C 30- Selected from aryl, alkylaryl, or poly(C2-C4)-alkylene ethers having up to 500 alkylene oxy units.

[0022] Suitable examples of monovalent hydrocarbon radicals include alkyl radicals, preferably CH3-, CH3CH2-, (CH3)2CH-, and C8H 17 - and C 10 H 21 - and also include alicyclic radicals such as cyclohexylethyl, aryl radicals such as phenyl, tolyl, and xylyl, and aralkyl radicals such as benzyl and 2-phenylethyl. Preferred monovalent halohydrocarbon radicals are those of formula C n F 2n+1 It has CH2CH2-, where n has a value from 1 to 10, for example CF3CH2CH2-, C4F9CH2CH2-, C6F 13 CH2CH2-, C2F5-O(CF2-CF2-O) 1-10 CF2-, F[CF(CF3)-CF2-O] 1-5 -(CF2) 0-2 The groups are -, C3F7-OCF(CF3)-, and C3F7-OCF(CF3)-CF2-OCF(CF3)-. Preferred groups for R are methyl, phenyl, and 3,3,3-trifluoropropyl, with methyl being particularly preferred.

[0023] R 1 This represents an organic group that contains at least one, preferably one, acid anhydride group, bonded to a silicon atom via a carbon atom. Therefore, basically, the group R 1 It is derived from an acid anhydride group, for example, an organic group R having a hydrocarbyl group with up to 30 carbon atoms that has an acid anhydride group.

[0024] The acid anhydride group of the present invention is a functional group of the following formula: [ka] Here, the dotted line represents the residual valence attached to the organic part bonded to the silicon atom.

[0025] Preferably, the functional polyorganosiloxane according to the present invention comprises siloxy units of formula (I). Preferably, the functional polyorganosiloxane according to the present invention contains at least 3, preferably at least 5, and more preferably at least 10 siloxy units of formula (I). More preferably, the functional polyorganosiloxane according to the present invention comprises 3 to 200, preferably 10 to 100 siloxy units of formula (I).

[0026] In a preferred embodiment of the present invention, the functional polyorganosiloxane comprises a siloxy unit selected from the group consisting of the following: M: R3SiO 1 / 2 D: R2SiO 2 / 2 D H : R(H)SiO 2 / 2 M H : R2(H)SiO 1 / 2 M * : R2R 1 SiO 1 / 2 D * : RR 1 SiO 2 / 2 T: RSiO 3 / 2 T * : R 1 SiO 3 / 2 T H : HSiO 3 / 2 Q: SiO 4 / 2 Here As described above, R represents an organic group that does not contain an acid anhydride group. R 1 As described above, represents an organic group containing at least one, preferably one, acid anhydride group. However, polysiloxane is M * , D * , and T * at least one siloxy group selected from the group, at least one group D HThe conditions are that it contains at least one group D.

[0027] In a preferred embodiment of the present invention, the functional polysiloxane is defined above as T, T based on the total amount of siloxy units. H , T * The total molar content of the Q units is less than 5 mol%, preferably less than 2 mol%. More preferably, the functional polysiloxane is T, T H , T * And units that do not include Q units, but preferably the following units: M: R3SiO 1 / 2 D: R2SiO 2 / 2 D H : R(H)SiO 2 / 2 M H : R2(H)SiO 1 / 2 M * : R2R 1 SiO 1 / 2 , and D * : RR 1 SiO 2 / 2 It consists of.

[0028] A particularly preferred functional polyorganosiloxane of the present invention is a linear polysiloxane having formula (II). M t D x D H y D * z M t (II) and a mixture thereof is selected, Here M t M, M H , and M * A group consisting of M and M is selected, where M is selected. H and M * , D, M * , D H , and D * These are defined as described above, x is an average value of 1 or more, preferably 2 or more, more preferably 5 or more, y is an average value of 1 or more, preferably 2 or more, more preferably 5 or more, z is an average value of 0 or more, and groups D, D H , and D * can be arranged in any order, provided that * and D * there is at least one group selected from the condition that it exists.

[0029] Preferably, x + y + z = 2 to 200, more preferably, x + y + z = 3 to 100.

[0030] In a more preferred embodiment of the functional polyorganosiloxane according to the present invention, D / D H The molar ratio of is from about 1:99 to about 99:1, preferably from about 5:95 to about 95:5, more preferably from about 10:90 to about 90:10, more preferably from about 20:80 to about 80:20, more preferably from about 30:70 to about 70:30, more preferably from about 40:60 to about 60:40, where D and D H are as defined above.

[0031] In a more preferred embodiment of the present invention, the functional polyorganosiloxane is M H (R2(H)SiO 1 / 2 ) contains at least one group selected from.

[0032] In a more preferred embodiment of the present invention, the functional polyorganosiloxane is M * (R2R 1 SiO 1 / 2 ) contains at least one group selected from.

[0033] In a more preferred embodiment of the present invention, the functional polyorganosiloxane is M H (R2(H)SiO 1 / 2 ) and M * (R2R1 SiO 1 / 2 It includes at least two groups selected from ).

[0034] The present invention also encompasses the possibility of functional polyorganosiloxanes containing at least two M groups, particularly linear functional polyorganosiloxanes having two terminal M groups, although this embodiment is less preferred.

[0035] The functional polyorganosiloxane according to the present invention preferably contains at least 3, preferably at least 5, more preferably at least 8, and even more preferably at least 10 siloxy units. Preferably, the upper limit of the number of siloxy units in the functional polyorganosiloxane according to the present invention is 200, preferably 100.

[0036] In the functional polyorganosiloxane according to the present invention, the at least one acid anhydride group in the organic group bonded to the silicon atom via a carbon atom containing at least one acid anhydride group is selected from the following structures: - The succinic anhydride portion of the following formula: [ka] - The maleic anhydride portion of the following formula: [ka] - The glutaric acid portion of the following formula: [ka] - The phthalic anhydride portion of the following formula: [ka] - The acyclic anhydride part of the following equation, [ka] Here, the dotted lines in the above formula each represent a single bond to the rest of the organic group bonded to the silicon atom via a carbon atom, and in some cases may also represent a direct bond to the silicon atom, and R is the organic group defined above, preferably the alkyl group defined above.

[0037] The functional polyorganosiloxanes according to the present invention are preferably prepared by a hydrosilylation reaction between an unsaturated anhydride and a SiH-functional siloxy group of a polysiloxane. It is well known to those skilled in the art that the hydrosilylation reaction is catalyzed with a transition metal catalyst, particularly a platinum-based catalyst, preferably Pt supported on silica as described in US 9,993,812 B2.

[0038] Other hydrosilylation catalysts can be selected from the group of organometallic compounds, salts or metals having the ability to catalyze hydrosilylation, where the metals are US 3,159,601; US 3,159,662; US 3,419,593; US 3,715,334; US 3,775,452, US 3,814,730, US 20130158281 A1, WO 2013090548 A1, WO 2011006049 A1, US 20110009573 A1, WO 2011006044 A2, US 20110009565 A1, US 9,387,468, US20180015449, US 20180201634, US 9,890,182, and US 9,371,339, which are incorporated herein by reference, and are selected from the group of Mn, Fe, Co, Ni, Ir, Rh, Ru, Os, Pd and Pt compounds. Most preferred are platinum compounds. The hydrosilylation catalyst is a catalyst compound that promotes the reaction of the silicon-bonded hydrogen atoms of the starting SiH-functional polysiloxane with the unsaturated anhydride. The metal or organometallic compound is generally based on platinum group metals. The catalyst includes, for example, complexes with sigma and pi bond carbon ligands, as well as ligands having S, N, or P atoms, metal colloids or salts of the aforementioned metals. The catalyst is present on a support such as silicon dioxide or silica gel or powdered carbon and can have a metal, or a compound or complex of that metal. Preferably, the catalyst is any platinum complex compound. Typical platinum-containing catalysts are platinum(0), (II) or (IV) compounds in any form that can form complexes. Preferred complexes are Pt- (0) -alkenyl complexes because they are easily dispersed in the polyorganosiloxane composition. A particularly useful form of the platinum complex is 1,3-divinyltetramethyldisiloxane (vinyl-M2 or Karstedt catalyst, as described in, for example, US 3,419,593, which is incorporated herein by reference: [Chemical formula] ) and Pt with aliphatic unsaturated organosilicon compounds such as (0) Complexes, such as cyclohexene-Pt, cyclooctadiene-Pt, and tetravinyltetramethyl-tetracyclosiloxane (vinyl-D4)-Pt, for example, the Ashby catalyst, with the empirical formula Pt[(C3H6SiO)4] x The Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane having is particularly preferred. Also preferred is the so-called Lamoreaux catalyst which is a platinum(II) complex compound obtained from chloroplatinic acid hexahydrate and octyl alcohol (for example, described in US 3,197,432 or US 3,220,972, each incorporated by reference in its entirety). Preferably, it is a Pt(0) or Pt(II) catalyst, with the Ashby and Lamoreaux platinum catalysts being preferred. As described in US 9,993,812 B2, Pt supported on silica is particularly preferred. The amount of the platinum-containing catalyst component used to catalyze the reaction between the unsaturated anhydride and the SiH-functional siloxy groups of the starting polysiloxane is not narrowly limited as long as there is an amount sufficient to promote hydrosilylation at the desired temperature. The exactly required amount of the catalyst component will depend on the particular catalyst. Generally, the amount of the applied platinum-containing catalyst component preferably provides a weight ratio of platinum of about 1 to about 200 ppm, preferably about 2 to about 100 ppm, particularly preferably about 4 to about 60 weight ppm, per weight of the SiH-functional starting polysiloxane.

[0039] Examples of unsaturated anhydride compounds include the following (the names in parentheses are IUPAC names): - Allyl succinic anhydride (3-allyltetrahydrofuran-2,5-dione):

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

[0040] In a preferred embodiment of the present invention, the functional polyorganosiloxane has at least one succinic anhydride moiety of the following formula: [ka] The portion may be monovalent or divalent and may be bonded to the silicon atom by a single bond or a divalent or trivalent organic group, preferably the succinic anhydride portion is monovalent and bonded to the silicon atom of the functional polysiloxane via a divalent organic group.

[0041] The functional polyorganosiloxane according to the present invention is typically used in curable compositions, where it forms a fixation additive that improves the adhesion of the curable composition to the substrate to which it is applied.

[0042] Preferred curable compositions according to the present invention include: (A) At least one polyorganosiloxane having at least two unsaturated hydrocarbyl residues, (B) at least one polyorganic hydrogen siloxane, (C) At least one hydrosilylation catalyst containing a transition metal, (D) at least one functional polysiloxane as defined above, (E) One or more fillers of any choice, (F) One or more optional auxiliary additives.

[0043] It should be noted that components (A), (B), and (D) are distinct polyorganosiloxanes.

[0044] Component (A) Component (A) may include one or more polyorganosiloxanes having, on average, at least two alkenyl groups. Suitable components (A) can be represented by the general formula (1), [M 2 a D 2 b T 2 c Q 2 d Z e m (1) where the subscripts in formula (1) represent the ratios of the siloxy units M 2 , D 2 , T 2 and Q 2 , and these can be distributed in block or random form in the polysiloxane. Within such a polysiloxane, each siloxane unit may be the same or different, and preferably, a = 0 - 10 b = 0 - 2000 c = 0 - 50 d = 0 - 10 e = 0 - 300 m = 1 - 1000 a + b + c + d + e ≧ 2, and M 2 = R3SiO 1 / 2 , or M 2* D 2 = R2SiO 2 / 2 , or D 2* T 2 = RSiO 3 / 2 , or T 2* Q 2 = SiO 4 / 2 , Z is a divalent optionally substituted hydrocarbyl bridging group having up to 14 carbon atoms between two siloxy groups as defined above, ​Here, R is the organic group defined above, preferably selected from optionally substituted hydrocarbyl groups having up to 30 carbon atoms and poly(C2-C4)-alkylene ether groups having up to 1000 alkylene oxy units, and group R does not contain aliphatic unsaturated groups, where M 2* =R 2 p R 3-p SiO 1 / 2 , D 2* =R 2 q R 2-q SiO 2 / 2 , T 2* =R 2 SiO 3 / 2 , Here p=1-3, q = 1 - 2, and R 2 This is selected from unsaturated, optionally substituted hydrocarbyl groups having up to 30 carbon atoms, and the unsaturated, optionally substituted hydrocarbyl is preferably an alkenyl group. However, M 2* , D 2* , and T 2* The condition is that there are at least two groups that can be selected from the set.

[0045] Preferably, a, b, c, d, and m are such that the viscosity of component (A) at 25°C is less than 100,000 mPa·s (D = 10s at 25°C). -1 (Measured at the shear rate).

[0046] The viscosity of component (A) refers to the viscosity of a single component (A) or a mixture of components (A). The latter mixture includes the presence of individual components (A), e.g., resin components (A) containing units Q and / or T, which may have a viscosity greater than 100,000 mPa·s at 25°C.

[0047] In equation (1), the subscript represents the number-average molecular weight M. n Average degree of polymerization P based on nIt should be represented appropriately.

[0048] In equation (1): M 2 =R3SiO 1 / 2 , or M 2* D 2 =R2SiO 2 / 2 , or D 2* T 2 =RSiO 3 / 2 , or T 2* Q=SiO 4 / 2 , The divalent Z is a crosslinking group between the siloxy groups mentioned above. Here, each R is an organic group as defined above, which may be the same or different, and is preferably selected from optionally substituted alkyl groups having up to 30 carbon atoms, optionally substituted aryl groups having up to 30 carbon atoms, and poly(C2-C4)-alkylene ethers having up to 1000 alkylene oxy units, wherein the group R is not aliphatic unsaturated, and Here M 2* =R 2 p R 3-p SiO 1 / 2 , D 2* =R 2 q R 2-q SiO 2 / 2 , T 2* =R 2 SiO 3 / 2 , Here p = 0-3, preferably 1-3, q=1-2, and Z is defined as follows:

[0049] R is an organic group as defined above, and R may preferably be further substituted with one or more O-, N-, S- or F- atoms, such as n-, iso, or tertiary alkyl, alkoxyalkyl, or C5-C 30 -Cyclic alkyl, or C6-C 30- Selected from aryl, alkylaryl, or poly(C2-C4)-alkylene ethers having up to 500 alkylene oxy units, where group R is non-aliphatic unsaturated.

[0050] Suitable examples of monovalent hydrocarbon radicals include, preferably, alkyl radicals such as CH3-, CH3CH2-, (CH3)2CH-, and C8H. 17 - and C 10 H 21 - and alicyclic radicals, e.g., cyclohexylethyl, aryl radicals, e.g., phenyl, tolyl, xylyl, aralkyl radicals, e.g., benzyl and 2-phenylethyl. Preferred monovalent halohydrocarbon radicals are of formula C n F 2n+1 It has CH2CH2-, where n has a value from 1 to 10, for example CF3CH2CH2-, C4F9CH2CH2-, C6F 13 CH2CH2-, C2F5-O(CF2-CF2-O) 1-10 CF2-, F[CF(CF3)-CF2-O] 1-5 -(CF2) 0-2 -, C3F7-OCF(CF3)- and C3F7-OCF(CF3)-CF2-OCF(CF3)-.

[0051] The preferred groups for R are methyl, phenyl, and 3,3,3-trifluoropropyl, with methyl being particularly preferred.

[0052] R 2 This refers to C=C group-containing groups (alkenyl groups), such as n-, iso-, tertiary or cyclic alkenyls, C6-C 30 -Cycloalkenyl, C8-C 30- Selected from aliphatic unsaturated groups including alkenylaryl, cycloalkenylalkyl, vinyl, allyl, methallyl, 3-butenyl, 5-hexenyl, 7-octenyl, ethylidene-norbornyl, styryl, vinylphenylethyl, norborneylethyl, limonenyl, which are optionally substituted with one or more O- or F- atoms, or C≡C group-containing groups (alkynyl groups) which are optionally substituted with one or more O- or F- atoms.

[0053] The alkenyl radical is preferably bonded to a terminal silicon atom, and the olefin functional group is located at the terminal of the alkenyl group of the higher alkenyl radical for the easier availability of alpha-,omega-dienes used to prepare alkenylsiloxanes.

[0054] R 2 The preferred groups are vinyl, 5-hexenyl, cyclohexenyl, limonyl, styryl, and vinylphenylethyl. The most preferred group is R 2 It is vinyl.

[0055] Z includes, for example, divalent aliphatic or aromatic n-, iso-, tertiary or cyclic alkylenes having up to 14 carbon atoms, arylenes, or alkylene aryl groups. Z forms a crosslinking element between two siloxy units. The content of the Z group does not exceed 30 mol% of all siloxy units, preferably not exceeding 20 mol%. Preferably, Z is absent. Preferred examples of suitable divalent hydrocarbon group Z include any alkylene residue, preferably for example, -CH2-, -CH2CH2-, -CH2(CH3)CH-, -(CH2)4-, -CH2CH(CH3)CH2-, -(CH2)6-, -(CH2)8-, and -(CH2) 18-; cycloalkylene radicals, e.g., cyclohexylene; arylene radicals, e.g., phenylene, xylene; and combinations of hydrocarbon radicals, e.g., benzylene, i.e., -CH2CH2-C6H4-CH2CH2-, -C6H4CH2-. Preferred groups are alpha, omega-ethylene, alpha, omega-hexylene, or 1,4-phenylene.

[0056] Further examples include divalent halohydrocarbon radicals Z, such as any divalent hydrocarbon group Z in which one or more hydrogen atoms are replaced by halogens such as fluorine, chlorine, or bromine. A preferred divalent halohydrocarbon residue is of the formula -CH2CH2(CF2). 1-10 Other suitable examples of divalent hydrocarbon ether radicals and halohydrocarbon ether radicals include those having CH2CH2-, for example, -CH2CH2CF2CF2CH2CH2-, and -CH2CH2OCH2CH2-, -C6H4-O-C6H4-, -CH2CH2CF2OCF2CH2CH2-, and -CH2CH2OCH2CH2CH2-.

[0057] R, R 2 The polymers, such as component (A) which optionally contains a Z radical, are preferably, for example, alkenyl-dimethylsiloxy or trimethylsiloxy-terminated polydimethylsiloxanes, which may contain other siloxane units in the chain, such as alkenylmethylsiloxy groups or diphenylsiloxy groups, forming poly(dimethyl-co-diphenyl)siloxane chains terminated, for example, with dimethylsiloxy or trimethylsiloxy groups.

[0058] The broad component (A) of the curable composition of the present invention may be any polyorganosiloxane compound containing two or more silicon atoms linked by oxygen and / or divalent groups Z, wherein each silicon atom is bonded to 0 to 3 monovalent groups, provided that the polyorganosiloxane compound contains at least two silicon-bonded unsaturated hydrocarbon residues.

[0059] Radical R and / or R 2 The siloxane units having may be equal or different for each silicon atom. In a preferred embodiment, the structure of component (A) of the curable composition of the present invention is R 2 p R 3-p SiO[R2SiO] m1 [R 2 RSiO] n SiR 2 p R 3-p Here R and R 2 This is as defined above, p = 0 - 3, preferably 1 m1 = 10 - 2000, preferably 100 - 1000. n = 0-500, preferably 0-200, provided that at least two groups R 2 The condition is that it exists.

[0060] One preferred polyorganosiloxane component (A) for the compositions of the present invention is a substantially linear polyorganosiloxane (A1). The expression "substantially linear" includes a polyorganosiloxane (A1) containing 0.2 mol% (trace amount) or less of type T or Q siloxy units. This means that the polymer (A) is preferably linear, preferably a fluid (A1), R 2 p R 3-p SiO(R2SiO) m1 SiR 3-p R p 2 (1a) Here R 2 R, p, and m1 are as defined above, provided that at least two alkenyl groups are present per molecule. More preferred structures of component (A) include: Vi p Me 3-p SiO(Me2SiO) 10-2000 SiMe 3-p Vi p (1b) PhMeViSiO(Me2SiO) 10-2000 SiPhMeVi (1c) (Vi = vinyl, Ph = phenyl, Me = methyl).

[0061] In the group of alkenyls containing siloxane (A), the addition of a second or third siloxane as component (A2) and / or (A3) is preferred. The purpose of the so-called vinyl-rich polymers of components (A2) and (A3) is to modify the mechanical properties and crosslinking density of the cured composition.

[0062] Polymer (A2) is selected from the group consisting of polymers of formulas (1d) to (1i), i.e., linear polyorganosiloxanes having additional alkenyl side groups in which the concentration of T groups and Q groups is less than 0.2 mol%, and polyorganosiloxanes having higher concentrations of T groups and Q groups than the previous polymer types (A1) or (A2).

[0063] The polymer (A2) is preferably represented by formula (1d to 1f): R 2 p R 3-p (R2SiO) b1 (R 2 RSiO) b1x SiR 3-p R p 2 (1d) Me3SiO(Me2SiO) b1 (MeR 2 SiO) b1x SiMe3(1e), R 2 Me2SiO(Me2SiO) b1 (MeR 2 SiO) b1x SiMe2R 2 (1f) Here b1=>0-2000 b1x => 0 - 500 b1 + b1x = > 10 - 100 R 2 R and p are as defined above, R 2 = Preferably vinyl, hexenyl, cyclohexenyl, limonyl, styryl, vinylphenylethyl. Most preferred R 2 It is vinyl.

[0064] The preferred groups for R are methyl, phenyl, and 3,3,3-trifluoropropyl, with methyl being the most preferred.

[0065] A preferred value for b1x is less than 0.5*b1, preferably between 0.0001*b1 and 0.25*b1, and more preferably between 0.0015*b1 and 0.2*b1.

[0066] A more preferred structure of (A2) is: Vi p Me 3-p SiO(Me2SiO) 10-2000 (MeViSiO) 1-1000 SiMe 3-p Vi p (1g) Me3SiO(Me2SiO) 10-2000 (MeViSiO) 1-1000 SiMe3 (1h), PhMeViSiO(Me2SiO) 10-2000 (MePhSiO) 1-1000 SiPhMeVi (1i), and Here, Me = methyl, Vi = vinyl, Ph = phenyl, and p = 0 to 3, preferably p = 1.

[0067] In a preferred embodiment, component (A) is a mixture of components (A1) and (A2), more preferably R 2 p R 3-p SiO(R2SiO) m1 SiR 3-p R p 2 (1a) and R 2 p R 3-p (R2SiO) b1 (R2 RSiO) b1x SiR 3-p R p 2 (1d) It is a mixture of, Here R, R 2 p, q, m1, b1 and b1x are as defined above, and R is preferably methyl, R 2 It is preferably vinyl.

[0068] A third, preferably optional, component polymer (A) comprises a branched polymer (A3) selected from those of formula (4a), where the polyorganosiloxane (A3) containing an alkenyl group is present in a concentration greater than 0.2 mol%. 2 =RSiO 3 / 2 or Q 2 =SiO 4 / 2 It has units. [M 2 0.4-4 D 2 0-1000 T 2 0-50 Q 2 0-10 ] 1-1000 (4a) Here M 2 =R3SiO 1 / 2 , or M 2* D 2 =R2SiO 2 / 2 , or D 2* T 2 =RSiO 3 / 2 , or T 2* Q 2 =SiO 4 / 2 , Here, R is as defined above, Here M 2* , D 2* , and T 2* As defined above, the unsaturated group R 2 It has such an M 2* , D 2* and T 2*The amount of units is preferably 0.001 to 20 mol%, more preferably 0.01 to 15 mol%, and most preferably 0.1 to 10 mol%, based on all siloxy units.

[0069] A preferred branched polymer (A3) has at least one branched unit (T 2 =RSiO 3 / 2 , or T 2* Q 2 =SiO 4 / 2 The silicone resin contains ), which is advantageous in providing strength to the composition, such as tensile strength, while simultaneously increasing its hardness. More specifically, the silicone resin contains M 2 =R3SiO 1 / 2 , or M 2* , and T 2 =RSiO 3 / 2 , T 2* and Q 2 =SiO 4 / 2 It includes at least one unit selected from and optionally D 2 =R2SiO 2 / 2 , or D 2* Selected from D 2 Includes units.

[0070] M when preferably incorporated 2 The unit T 2 and Q 2 The molar ratio to the unit is as follows: M 2 / (Q 2 +T 2 ) = 0.6 to 1.2, preferably 0.7 to 1.1

[0071] Silicone resins can be synthesized, for example, by hydrolyzing a suitable alkoxysilane or chlorosilane in a ratio that satisfies the above composition.

[0072] A preferred embodiment of the addition-curable silicone rubber composition comprises at least one polyorganosiloxane selected from (A1) and (A2), and at least one polyorganosiloxane selected from (A3).

[0073] The range of the subscript is the number-average molecular weight M. n Possible average degree of polymerization P n This defines the scope.

[0074] The subscript corresponds to the appropriate viscosity as defined below and indicates a polymer that does not contain a viscosity-adjusting solvent.

[0075] Preferred branched polyorganosiloxanes (A2) and (A3) typically have a higher concentration of unsaturated groups R 2 It has. The branched polymer (A3) is described, for example, in US 5,109,095, which is incorporated in whole by reference. Preferably, the branched vinyl-rich polymer (A3) is D 2 :T 2 >10:1, preferably >33:1, and / or each (M 2 :Q 2 ) = 0.6 - 4:1, for example [M 2 0.7 M 2* 0.05 Q 2 ] 10-500 It has ranges such as (1j).

[0076] All of these polymers can be prepared by any of the conventional methods for preparing triorganosiloxane-terminated polydiorganosiloxanes. For example, suitable hydrolyzable silanes, such as vinyldimethylchlorosilane, trimethylchlorosilane, tetrachlorosilane, methyltrichlorosilane, and dimethyldichlorosilane, or suitable ratios of their corresponding alkoxysilanes, can be co-hydrolyzed and condensed. Another reaction pathway involves alternately performing equilibrium reactions with 1,3-divinyltetraorganodisiloxanes, such as symmetric divinyldimethyldiphenylsiloxane or divinyltetramethylsiloxane, which provide the terminal groups of the polydiorganosiloxane and can be equilibrated with suitable polydiorganosiloxanes, such as octamethylcyclotetrasiloxane, in the presence of an acidic or basic catalyst.

[0077] In a preferred embodiment, polymer component (A) is a mixture of polymers of formula (1a) and / or formula (1d) and / or (1j), wherein the mixture preferably has an alkenyl content of less than 2 mol% of all siloxy units of mixture (A) on average, where polymer (A1) is present in greater amounts than (A2) or (A3).

[0078] For the purposes of the present invention, the viscosity of the polydiorganosiloxane (A) as defined above preferably refers to a polyorganosiloxane that is essentially free of cyclic polydiorganosiloxanes (less than 1% by weight, preferably less than 0.5% by weight, measured at 1 hour at 150°C and 20 millibars).

[0079] The siloxane units (M) of polymer (A) measured by GPC measurement 2 , D 2 , T 2 Q 2 ) Average degree of polymerization P n Average molar weight M based on polystyrene standards n Preferably, P nThe viscosity is in the range of >10 to 2000, with a more preferred range of 40 to 1000. The viscosity of such polymers is preferably D=10s at 25°C. -1 The shear rate is in the range of approximately 10 to approximately 100,000 mPa·s, and more preferably in the range of approximately 40 to approximately 70,000 mPa·s.

[0080] Preferably, the alkenyl content of component (A) is in the range of about 0.001 to about 20 mol%, particularly 0.01 to 10 mol%, based on the total number of organic groups bonded to the silicon atom.

[0081] The alkenyl content of component (A) is as follows: 1 It can be determined by 1H NMR - see AL Smith (ed.): The Analytical Chemistry of Silicones, J. Wiley & Sons 1991 Vol. 112pp. 356 et seq. in Chemical Analysis ed. by JD Winefordner.

[0082] Component (B) - Crosslinking agent A suitable polyorganic hydrogen siloxane (B) containing SiH units can be described by general formula (2), [M 1 a2 D 1 b2 T 1 c2 Q d2 Z e2 ] m2 (2) Here, siloxy units M 1 =M 2 , as defined above, or M ** , D 1 =D 2 , as defined above, or D ** , T 1 =T 2 , as defined above, or T ** , Q=Q2 As defined above, Z, as defined above, M ** =HR2SiO 1 / 2 , D ** =HRSiO 2 / 2 , T ** =HSiO 3 / 2 , a2 = 0.01 - 10, preferably = 2 - 5, most preferably = 2. b2 = 0 - 1000, preferably = 10 - 500 c2 = 0 - 50, preferably = 0 d2 = 0 - 5, preferably = 0 e² = 0 - 3, preferably = 0 m2 = 1 - 1000, preferably = 1 - 500, most preferably = 1. However, M ** , T ** , and Q ** The condition is that there are at least two groups selected from the set.

[0083] Preferably, component (B) is selected from polysiloxanes having only methyl groups or phenyl groups, and more preferably only methyl groups as organic residues.

[0084] Preferably, the polyorganic hydrogen siloxane (B) has at least 10, preferably at least 15, more preferably at least 20, even more preferably at least 25, and most preferably at least 30 silicon atoms.

[0085] Siloxy units can be distributed in a blocky or random manner within the polymer chain.

[0086] The subscripts mentioned above represent the number-average molecular weight M. n Average degree of polymerization P based on n It should represent this.

[0087] M present within the molecule 1 -, D 1 -, T 1 -, and Q 1- The range of units can cover almost all values ​​representing fluids, fluid polymers, liquids, and solid resins. Liquid linear, cyclic, or branched siloxanes are preferred. Optionally, these siloxanes may further contain trace amounts of C1-C6-alkoxy or Si-hydroxy groups remaining from the synthesis.

[0088] The preferred structure of component (B) in the composition of the present invention is a siloxane of formula (2a) to (2e). H a1 (R) 3-a1 Nut [RHSiO] x [R2SiO] y [RR 2 SiO] z Si(R) 3-a1 H a1 (2a) More specifically, HR2SiO(R2SiO) y (RR 2 SiO) z (RHSiO) x SiR2H (2b) HMe2SiO(Me2SiO) y (RR 2 SiO) z (MeHSiO) x SiMe2H (2c) Me3SiO(MeHSiO) x SiMe3(2d) Me3SiO(Me2SiO) y (RR 2 SiO) z (MeHSiO) x SiMe3(2e) Here R and R 2 R is as defined above, and R is preferably methyl and / or phenyl, 2 is preferably vinyl, and the subscript 'a1' is 0-1, preferably 0, and preferably x = 2 - 1000, preferably = 2 - 500, y = 0 - 650, preferably = 0 - 100. z = 0 - 65, preferably = 0 2 ≤ x + y + z < 1000, preferably 10 ≤ x + y + z < 650.

[0089] Most preferably, Me3SiO(Me2SiO) y (RR 2 SiO) z (MeHSiO) x SiMe3(2e) Here R and R 2 This is as defined above, Here, x, y, and z are as defined above, i.e., z is preferably 0.

[0090] Furthermore, the following resinous polyorganic hydrogen siloxane can be used: {[T 1 ][R 29 O 1 / 2 ] n2} m2 (2f) {[SiO 4 / 2} ][R 29 O 1 / 2 ] n2 [M 1 ] 0,01-10 [T 1 ] 0-50 [D 1 ] 0-1000} m2 (2g) Here T 1 M 1 , D 1 This is as defined above, n2 = 0 to 3 m2 is as defined above, R 29 is hydrogen, C1-C 25 -Alkyl, e.g., methyl, ethyl, n-propyl, isopropyl, n-, iso- and tert.-butyl; alkanoyl, e.g., acyl, aryl; -N=CHR, e.g., butanonoxime; alkenyl, e.g., propenyl; Here, in each of the formulas (2e)-(2f), the molar ratio of the SiH group to all Si atoms is preferably greater than 0.01 and preferably up to 0.7, and the total number of Si atoms is preferably at least 7, more preferably at least 15, and even more preferably at least 20.

[0091] One preferred embodiment of compound (2f) is, for example, derived from a monomer of the formula [(Me2HSiO 0.5 ) k SiO 4 / 2 ] 1,5-1000 These are provided by polymer compounds that can be represented as such, where the subscript k is from 0.3 to 4. Such liquid or resin molecules may contain a considerable concentration of SiOH- and / or (C1-C6)-alkoxy-Si groups, up to 10 mol% with respect to silicon atoms.

[0092] Specific examples of suitable compounds preferred for component (B) in the composition of the present invention include: Me3SiO-(MeHSiO) 2-50 -SiMe3, Me3SiO-(MeHSiO) 2-50 (Me2SiO) 1-100 SiMe3 (MeHSiO)7, HMe2SiO-(MeHSiO) 0-60 (Me2SiO) 1-250 SiMe2H HMe2SiO(Me2SiO) 0-30 (MePhSiO) 0-30 (MeHSiO) 2-50 SiMe2H, Me3SiO(Me2SiO) 0-30 (MePhSiO) 0-30 (MeHSiO) 2-50 SiMe3 Me3SiO(Me2SiO) 0-30 (Ph2SiO) 0-30 (MeHSiO) 2-50 SiMe3 In each of these formulas, the molar ratio of the SiH group to all Si atoms is preferably greater than 0.01, and the total number of Si atoms is preferably at least 7, more preferably at least 10, more preferably at least 15, and most preferably at least 20 atoms.

[0093] Most preferably, the formula Me3SiO-(MeHSiO) 2-50 (Me2SiO) 0-100 The compound is SiMe3, where the SiH content is at least 0.2 mmol / g, preferably at least 1.5 mmol / g, and more preferably 2 mmol / g.

[0094] Component (B) can be used as a single component of a polyorganic hydrogen siloxane polymer or as a mixture thereof.

[0095] If you need to increase the curing speed, use HMe2SiO 0,5 -It is preferable to adjust the curing speed to a shorter time by using some organopolysiloxane (B) having units or homo-MeHSiO-polymers.

[0096] If it is necessary to further increase the curing rate, this can be achieved, for example, by increasing the molar ratio of SiH to Si-alkenyl, or by increasing the amount of catalyst (C).

[0097] Component (B) preferably has a pressure of about 2 to about 2000 mPa·s at 25°C, preferably about 2 to about 1000 mPa·s, and more preferably about 5 to about 100 mPa·s (preferably D=10s). -1 It has a viscosity (measured at a shear rate of ).

[0098] Preferably, the crosslinking agent (B) should have at least 2, more preferably 3, and in some examples also 15 and 20 SiH groups per molecule.

[0099] The total number of SiH groups in component (B) is equal to the unsaturated hydrocarbyl residues R in component (A) and, if present, in component (B). 1 The molar ratio of the compound to the total is 0.8 to 5, preferably 0.9 to 4, more preferably 1 to 2.5, and more preferably 1.1 to 2.2, in order to provide good adhesion to the hydroxyl group-containing substrate.

[0100] Component (B) is a different compound from component (D). In particular, component (B) contains an acid anhydride group.

[0101] Component (C) - Catalyst The compositions of the present invention comprise at least one hydrosilylation catalyst as component (C) selected from the group of organometallic compounds, salts, or metals having the ability to catalyze hydrosilylation, where the metal is incorporated into the present invention by reference in all of the following: US 3,159,601; US ​​3,159,662; US 3,419,593; US 3,715,334; US 3,775,452; US 3,814,730; US 20130158281 A1;WO 2013090548 A1;WO 2011006049 A1; US ​​20110009573 A1;WO 2011006044 A2; US 20110009565 A1; US ​​9,387,468; US 20180015449; US A selection is made from the group of Mn, Fe, Co, Ni, Ir, Rh, Ru, Os, Pd, and Pt compounds, as taught in 20180201634;US 9,890,182 and US 9,371,339. Platinum compounds are the most preferred.

[0102] Component (C) for the hydrosilylation reaction of the composition of the present invention is a catalytic compound that facilitates the reaction between the silicon-bonded hydrogen atom of component (B) and the silicon-bonded olefin hydrocarbon substituent of component (A). The metal or organometallic compound is generally based on platinum group metals. While not wishing to be bound by theory, catalyst (C) is thought to include complexes, metal colloids, or salts of the aforementioned metals with sigma-bonded and pi-bonded carbon ligands, as well as with ligands having S, N, or P atoms. The catalyst can be present on a support such as silica gel or powdered charcoal having the metal, or a compound or complex of that metal. Preferably, the metal of component (C) is any platinum complex compound.

[0103] A typical platinum-containing catalyst component in the polyorganosiloxane composition of the present invention is a platinum(0), (II), or (IV) compound of any form capable of forming a complex. Preferred complexes are alkenyls such as alkenyls, cycloalkenyls, vinylsiloxanes, and other alkenylsiloxanes, due to their easy dispersibility in the polyorganosiloxane composition. (0) -It is an alkenyl complex.

[0104] Particularly useful forms of platinum complexes include, for example, 1,3-divinyl-tetramethyl-disiloxane (vinyl-M2 or Karstedt catalyst), as described in US 3,419,593, which is incorporated herein by reference: [ka] Pt with aliphatic unsaturated organosilicone compounds such as ) (0) The complex is particularly preferably cyclohexene-Pt, cyclooctadiene-Pt, and tetravinyltetramethyl-tetracyclosiloxane(vinyl-D4)-Pt, for example, Ashby catalyst, empirically formulated Pt[(C3H6SiO)4] x This is a Pt(0) complex of tetramethyltetravinylcyclotetrasiloxane having [a specific characteristic].

[0105] Preferably, the catalyst is a so-called Lamoreaux catalyst, which is a platinum(II) complex compound obtained from chloroplatinic acid hexahydrate and octyl alcohol (for example, described in US 3,197,432 or US 3,220,972, which are each incorporated herein by reference in their entirety). Preferably, it is a Pt(0) or Pt(II) catalyst, with Ashby and Lamoreaux platinum catalysts preferred.

[0106] The amount of platinum-containing catalyst component used in the composition of the present invention is not narrowly limited, as long as there is enough to promote hydrosilylation between (A) and (B) at the desired temperature at the required time (B) in the presence of all other components of the composition of the present invention. The exact amount of catalyst component required will depend on the specific catalyst, the amount of other inhibitory compounds, and the SiH-to-olefin ratio, and is not easily predictable. However, in the case of platinum catalysts, for cost reasons, the amount can be as small as possible. Preferably, more than 1 part by weight of platinum should be added for every 100 parts by weight of organosilicon components (A) and (B) to ensure curing in the presence of other indeterminate inhibitory traces. For the composition of the present invention, the amount of platinum-containing catalyst component applied is preferably sufficient to provide about 1 to about 200 ppm, preferably about 2 to about 100 ppm, and particularly preferably about 4 to about 60 ppm by weight of platinum per weight of polyorganosiloxane components (A) and (B). Preferably, the amount is platinum by weight of at least about 4 ppm per total of (A) and (B).

[0107] The curable composition of the present invention can be cured with the help of heat or light. Photocuring is initiated by irradiation with light, particularly UV light with a maximum wavelength of 300 to 550 nm. Irradiation curing is preferably carried out at room temperature (25°C).

[0108] Therefore, the hydrosilylation catalyst can also be selected from a group of photoactivatable catalysts. These photoactivatable catalysts preferably contain at least one metal selected from the group consisting of Pt, Pd, Rh, Co, Ni, Ir, or Ru. The photoactivatable catalyst preferably contains a platinum compound. The photoactivatable catalyst is preferably selected from organometallic compounds, i.e., contains a carbon-containing ligand or a salt thereof. In a preferred embodiment, the photoactivatable catalyst (C) has a metal-carbon bond including a sigma bond and a pi bond.

[0109] Furthermore, the photoactivatable platinum compounds that can be used are selected from the group having ligands selected from diketones, such as benzoylacetone or acetylenedicarboxylic acid esters, and platinum catalysts embedded in photodegradable organic resins.

[0110] Component (E) - Filler The addition-curable polyorganosiloxane composition optionally comprises one or more fillers, preferably reinforcing fillers, and, where appropriate, a surface-modified reinforcing filler (E). The reinforcing filler (E) is particularly 50 m 2 It is characterized by a BET surface area of ​​1 / g or more.

[0111] The fillers include, for example, all particulate fillers, i.e., those having particles smaller than about 100 μm, i.e., preferably composed of such particles. These may be mineral fillers such as silicates, carbonates, nitrides, oxides, or silica. The fillers are preferably those known as reinforcing silica, which also enables the production of elastomers with sufficient transparency for irradiation. Reinforcing silica, especially those that enhance strength, is preferred. For example, with a BET surface area of ​​about 50 to about 400 m². 2 / g, preferably about 80 to about 350m 2Silica in a weight of / g, particularly fumed or precipitated silica. Preferably, these fillers are surface hydrophobic. When component (E) is used, its amount is preferably about 1 to about 100 parts by weight, more preferably 0 to about 70 parts by weight, even more preferably 0 to about 50 parts by weight, and even more preferably about 5 to about 45 parts by weight, based on about 100 parts by weight of components (A) and (B).

[0112] BET surface area: 50m 2 Fillers exceeding / g enable the production of silicone elastomers with improved properties. From the viewpoint of strength and transparency, fumed silica is preferred, and more preferred silicas are, for example, Aerosil® 200, 300, HDK® N20 or T30, Cab-O-Sil® MS7 or HS5, at 200m 2 These materials have a BET surface area greater than / g. As the BET surface area increases, the transparency of the silicone mixture in which these materials are present also increases. Examples of trade names for materials known as precipitated silica or wet silica include Vulkasil® VN3, or FK160 from Evonik (formerly Degussa), or Nipsil® LP from Nippon Silica K.K., and others.

[0113] 50m 2 Having a BET surface area of ​​150m² or more, preferably at least 150m² 2 It is preferable to use a silica filler having a BET surface area of ​​1 / g. Such compositions can also be photoactivated as needed for sufficient transparency.

[0114] The filler (E) may be subject to any suitable conventional surface treatment with a suitable surface treatment agent, which includes hydrophobic treatment with a suitable hydrophobic agent, dispersion treatment with a suitable dispersant, etc., affecting the interaction between the filler and the silicone polymer, for example, affecting the thickening effect. Surface treatment of the filler is preferably hydrophobic with a silane or siloxane. For example, this can be done in situ by adding a silazane such as hexamethyldisilazane and / or 1,3-divinyltetramethyldisilazane with water, and “in situ” hydrophobicity is preferred. It can also be done with other well-known filler treatment agents having polyorganosiloxane diols with chain lengths of 2 to 50 and having unsaturated organic radicals, for the purpose of providing reactive sites for crosslinking reactions.

[0115] Examples of commercially available silica pre-hydrophobized with various silanes include Aerosil® R972, R974, R976, or R812, or, for example, HDK2000 or H30. Examples of trade names for materials known as hydrophobized precipitated silica or wet silica include, for example, Sipernat D10 or D15 from Evonik (formerly Degussa).

[0116] The rheological properties, or technical processing properties, of an uncured silicone rubber mixture can be influenced by the type and amount of filler, as well as the choice of its hydrophobic properties.

[0117] The filler (E) may also be any type of filler different from the reinforcing filler, such as functional fillers for increasing thermal or electrical conductivity, low-surface or inert fillers, fillers for so-called expanding volume, solvents, and optionally natural or synthetic fibers for reinforcement (e.g., polyester fibers, cellulose fibers (cotton fibers), polyamide fibers such as nylon fibers, polyurethane fibers such as spandex fibers, glass fibers, etc.).

[0118] Filler or bulking agent (BET surface area < 50 m²) 2Examples of materials that function as non-reinforcement fillers ( / g) are known as non-reinforcement fillers. These include, for example, powdered quartz, diatomaceous earth, powdered cristobalite, mica, aluminum oxide, and aluminum hydroxide. BET surface area is 0.2 to 50 m². 2 Titanium dioxide or iron oxide, zinc oxide, chalk, or carbon black in amounts less than 1g / g can also be used as heat stabilizers. These fillers are available under various trade names such as Sicron®, Min-U-Sil®, Dicalite®, and Crystallite®. BET surface area 50m² 2 Materials known as inert fillers or fillers with less than 100 μm (<0.005 wt%) are advantageous when used in silicone rubber because they do not contain particles larger than 100 μm, so that further processing does not generate problems during downstream processing, such as passage through sieves or nozzles, or adverse effects on the mechanical properties of articles produced therefrom.

[0119] Opaque fillers include those that are particularly opaque, particularly inorganic, pigments, or carbon black.

[0120] The use of these opacifying fillers is preferable only when coloring is required or when physical functions such as thermal or electrical conductivity are needed.

[0121] The use of opaque, non-transparent fillers requires a change in the usual sequence of process activation and molding steps. Typically, when no filler is used, or when transparent fillers are used, photoactivation by irradiation is performed after the final molding process. If an opaque, non-transparent filler is used, which would inhibit the photoactivation of the photoactivatable catalyst, the photoactivation step is performed before the opaque, non-transparent filler is incorporated and the mixture is molded.

[0122] Ingredient (F) - Auxiliary Additive Addition-curable polyorganosiloxane compositions may also contain one or more auxiliary additives. Such auxiliary additives are suitable conventional additives used in curable polyorganosiloxane compositions.

[0123] Such auxiliary additives include, for example: - Controlled release additives as described in US7846550(B2), US3527659, US5308887; - Anti-fogging additives as described in US20080281055(A1); - Low friction coefficient additives such as those described in US5942557(A) using Tospearl® microspheres; - Antistatic additives as described in US20090197100A1 and US9,487,639; - Polyether compounds as antistatic agents; - Metal salts such as lithium salts; - Ionic liquid; - Ionic conductive compounds as described in JP-A2005-344102; and - Ionic substances as described in WO-A12009 / 084730 and WO-A1 2009 / 084733.

[0124] Such auxiliary additives include, for example, further adhesion promoters such as those described in WO2011 / 107592: (Compound (D1)-(D3), for example, (D1): At least one organosiloxane containing at least one alkoxysilyl group, (D2): At least one organosilane containing at least one alkoxysilyl group, (D3): At least one aromatic organic compound having at least two aromatic moieties and at least one group that is reactive in hydrosilylation, These compounds must be different from any of components A) through F) of the composition of the present invention. Preferred ones are included herein by reference to WO2011 / 107592 (hereinafter, the definitions of substituents refer to the definitions given in WO2011 / 107592). Component (D1) is preferably, RHSiO 2 / 2 , and R 5 (R)SiO 2 / 2 A polyorganosiloxane comprising at least one unit selected from the group consisting of, Here, R is as defined above and may be the same or different, 5 This is selected from the group consisting of unsaturated aliphatic groups having up to 14 carbon atoms, epoxy group-containing aliphatic groups having up to 14 carbon atoms, cyanurate-containing groups, and isocyanurate-containing groups, and Further comprising at least one unit of equation (3), O 2 / 2 (R)Si-R 4 -SiR d (OR 3 ) 3-d (3) Here R is selected from optionally substituted alkyls having up to 30 carbon atoms, or optionally substituted aryls having up to 30 carbon atoms, and may be the same or different. R 3 These are selected from H (hydrogen) and alkyl radicals having 1 to 6 carbon atoms, and may be the same or different. R 4 It is a bifunctional, optionally substituted hydrocarbyl radical having up to 15 carbon atoms, which may contain one or more heteroatoms selected from O, N, and S atoms, and is bonded to a silicon atom via a Si-C bond, and d ranges from 0 to 2.

[0125] Examples of component (D1) include compounds of formula (3a-3d): [ka] R 11 is R or R 5 And here R, R 3 , R 4 , and R 5 These are as defined above and may be the same or different. s1 = 0 - 6, preferably 1 t1 = 0 - 6, preferably 1 or 2 s1 + t1 = 2 - 6, preferably 2 or 3 However, the compound contains -(OSi(R)H)- or -(OSi(R)(R 11 The condition is that there is at least one group of )-, preferably a compound of the following formula. [ka] Here, R, R 3 , R 4 and R 11 As defined above, and its ring positional isomers, Compounds of the following formula [ka] and its ring positional isomers, compounds of the following formula. Further compounds [ka] Here R, R 3 , R 4 , R 5 This is as defined above, s = 0 - 10, preferably = 0 - 5 t = 0-50, preferably = 2-30 u = 1 - 10, preferably = 1 s + t + u ≤ 70 However, if the compound contains -(OSi(R)H)- or -(OSi(R)(R 5The condition is that there is at least one group of )-. These compounds may contain Q or T branched groups instead of D units up to a certain content. R 5 For example, the following can be selected. [ka]

[0126] Component (D2) is preferably selected from the compounds of formula (4): X-(CR 6 2) e -Y-(CH2) e SiR d (OR 3 ) 3-d Here X is selected from the group consisting of halogens, pseudohalogens, unsaturated aliphatic groups having up to 14 carbon atoms, epoxy group-containing aliphatic groups having up to 14 carbon atoms, cyanurate-containing groups, and isocyanurate-containing groups. Y is selected from the group consisting of a single bond and a heteroatom group selected from -COO-, -O-, -S-, -CONH-, and -HN-CO-NH-. R 6 is selected from hydrogen and R as defined above, e is 0, 1, 2, 3, 4, 5, 6, 7, or 8, and may be the same or different. R is as defined above, and may be the same or different. R 3 These are as defined above, and may be the same or different. d is 0, 1, or 2.

[0127] Preferred examples of component (D2) include: [ka] Here, R is defined as described above.

[0128] In addition to functioning as an adhesion promoter, component (D2) can also function as an in-situ surface treatment agent for the filler (E). It is preferable to use a silane mixture of component (D2) to obtain acceptable adhesive properties at low cost.

[0129] Component (D3) is preferably selected from the compounds of formula (3i): [ka] Here r is either 0 or 1, R 7 These may be the same or different groups, including hydrogen atoms, hydroxyl groups, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, alkenylcarbonyloxy groups and aryl groups, formula-E f -Si(OR) 3-d R d Based on this, where R is identical or different, and d is as defined above, Formula -O-Si(R)2R 1 Based on this, here R and R 1 This is as defined above, formula-E f -Si(R)2H base, where R is as defined above. Here, E is a divalent organic group having up to 8 carbon atoms and 0 to 3 heteroatom groups selected from -O-, -NH-, C=O, and -C(=O)O-, and f is either 0 or 1. Z is then selected from the group consisting of the following elements: [ka] Here R 8 This is selected from hydrogen atoms, halogen atoms, or substituted or unsubstituted alkyl groups, aryl groups, alkenyl groups, and alkynyl groups. and g is a positive number of at least 2, Here R7 and R 8 At least one of the groups selected is reactive in hydrosilylation. It is selected from the group consisting of the following.

[0130] Preferred components (D3) include: [ka] Here, Zr, R 7 , R 3 (R and d are defined above, respectively.)

[0131] Further auxiliary additives include reactive surfactants such as Tego Glide 450, TegoRad 2100, TegoRad 2200N, BYK-UV 3530, BYK-UV 3570, BYK-UV 3505, and BYK-UV3500.

[0132] Auxiliary or conventional additives (F) may further include stabilizers against hot air, oil and solvents, processing aids, mold release agents, wetting agents, pigments, foaming agents for initiating foaming, antimicrobial agents, bactericidal agents, or additives for enhancing mold resistance.

[0133] Auxiliary or conventional additives may further include plasticizers or softeners, preferably silicone oils, preferably containing [R2SiO] units, selected from diorganopolysiloxanes where R is a C-Si bonded organic group. Silicone oils are typically clear, colorless, non-toxic, inert, odorless, chemically inert, thermally stable, and hydrophobic liquids, preferably with a number-average molecular weight of about 162 to about 150,000 g / mol and a molecular weight of about 0.76 to about 1.07 g / cm³. 3 It has a density and a viscosity of about 0.6 to about 1,000,000 mPa·s (20°C). Preferred silicone oils include polydimethylsiloxane oil. The use of silicone oil is preferred to achieve a Shore A hardness ≤ 20.

[0134] Auxiliary or conventional additives may further include, for example, plasticizers or release oils, or hydrophobic oils such as polydimethylsiloxane oil having a viscosity of preferably about 0.001 to about 10 Pa·s at 25°C. Further mold-release agents or flow improvers may also be used, for example, fatty acid derivatives or fatty alcohol derivatives, or fluoroalkyl surfactants. Compounds advantageously used here are those that rapidly separate and migrate to the surface. Stability after exposure to hot air can be enhanced using known hot air stabilizers such as, for example, Fe-, Mn-, Ti-, Ce-, or La- compounds, and their organic salts, preferably their organic complexes.

[0135] Auxiliary additives may also include so-called inhibitors for controlling the crosslinking reaction. This is intended to extend the pot life of the molded silicone composition. The use of such inhibitors may be suitable for reducing the curing rate. Examples of advantageous inhibitors include vinylsiloxanes such as 1,3-divinyltetramethyldisiloxane, or tetravinyl-tetramethyl-tetracyclosiloxane. Other known inhibitors, such as ethynylcyclohexanol, 3-methylbutynol, or dimethyl maleate, may also be used. In a preferred embodiment of the present invention, the addition-curable silicone rubber composition includes at least one inhibitor for controlling the crosslinking reaction to reduce the curing rate and extend the pot life of the addition-curable silicone rubber composition.

[0136] In preferred embodiments, the curable silicone composition comprises an inhibitor; a plasticizer or softener, preferably selected from silicone oils, more preferably from polydimethylsiloxane oil; a non-reinforcing filler, preferably selected from finely ground silica or quartz; and auxiliary additives selected from the group of fibrous materials such as polyester fibers, cellulose fibers, polyamide fibers such as nylon fibers, polyurethane fibers such as spandex fibers, and glass fibers. In further specific embodiments, the addition-curable silicone rubber composition of the present invention comprises at least one inhibitor.

[0137] In a preferred embodiment of the present invention, (B) at least one polyorganic hydrogen siloxane, (D) At least one functional polysiloxane as defined in any of the embodiments described above, (E) Optionally, one or more fillers, and (F) optionally includes one or more auxiliary additives. Component (I), and (A) At least one polyorganosiloxane having at least two unsaturated hydrocarbyl residues, (C) At least one hydrosilylation catalyst containing a transition metal, (E) Optionally, one or more fillers, and (F) optionally includes one or more auxiliary additives. Component (II) Regarding a curable two-component composition comprising the following: Here, these components are defined as described above.

[0138] In preferred embodiments of the present invention, the curable composition according to the present invention comprises less than about 5% by weight, preferably less than about 2% by weight, of the functional polysiloxane of the present invention. Preferably, the curable composition according to the present invention comprises about 0.05 to about 3% by weight, more preferably about 0.1 to about 2% by weight, of the functional polysiloxane of the present invention, based on the total amount of the curable composition.

[0139] The compositions of the present invention can be prepared by uniformly mixing components (A)-(F) using suitable mixing means such as a spatula, drum roller, mechanical stirrer, 3-roll mill, sigma blade mixer, dough mixer, planetary mixer, horizontal mixer, screw, dissolver, butterfly mixer, press mixer, or vacuum mixer.

[0140] The mixing order of components (A)-(F) is not important; however, it is preferable to mix specific components to form two or more packages, which can be stored as needed and mixed in the final step immediately before their intended use.

[0141] The addition-curable silicone rubber composition according to the present invention is preferably, Approximately 100 parts by weight of component (A), Approximately 0.01 to approximately 100 parts by weight of component (B), preferably approximately 0.5 to approximately 50 parts by weight. Based on the weight of the transition metal and the total weight of components (A) and (B), the amount of component (C) is about 0.5 to about 1000 ppm, preferably about 1 to about 00 ppm. Approximately 0.01 to approximately 10 parts by weight of component (D), preferably approximately 0.02 to approximately 5 parts by weight of component (D), 0 to about 100 parts by weight of component (E), preferably about 1 to about 50 parts by weight of component (G). and 0 to about 100 parts by weight of component (F), preferably about 0.001 to about 15 parts by weight of component (H), preferably about 0.002 to about 6 parts by weight Includes.

[0142] Preferably, the curable composition according to the present invention cures at room temperature (RTV -25°C) or at a high temperature of about 40 to about 200°C, preferably about 80 to about 160°C, or under exposure such as UV light.

[0143] The present invention further relates to a cured composition obtained by curing the above-mentioned curable composition.

[0144] The present invention further relates to a composite article comprising the above-mentioned cured composition in contact with at least one substrate selected from a metal substrate, a glass substrate, a ceramic substrate, a paper substrate, a polymer substrate, preferably polyethylene, polypropylene, polycarbonate, polyethylene terephthalate (PET), polyimide, polyamide, etc. The composite article according to the present invention means that the cured composition of the present invention is in contact with at least a portion of the surface of the substrate.

[0145] The surface of the substrate may be subjected to surface treatment such as a wet chemical treatment method using ozone, plasma, caroic acid (persulfuric acid), piranha solution, etc., and other treatment methods before applying the curable composition of the present invention.

[0146] The present invention further relates to the use of the above-mentioned curable compositions for the manufacture or use of release coatings, elastomers, particularly self-adhesive elastomers, (optical) bonding materials, and silicone encapsulants for electronic devices such as electronic circuits, solar cells, and integrated circuits.

[0147] Therefore, the curing composition according to the present invention is preferably selected from release coatings, elastomers, particularly self-adhesive elastomers, (optical) bonding materials, and silicone encapsulants for electronic devices such as electronic circuits, solar cells, and integrated circuits.

[0148] The present invention further, (B) at least one polyorganic hydrogen siloxane as defined above, and (D) at least one functional polysiloxane as defined above This relates to the components of a two-component curable composition, in particular.

[0149] The present invention further relates to a method for producing a functional polysiloxane according to the present invention, comprising the reaction of a polysiloxane having at least one SiH group and at least one diorganosiloxy group with an organic compound having at least one acid anhydride group and at least one unsaturated hydrocarbyl group in the presence of a hydrosilylation catalyst. The process and hydrosilylation catalyst are as described above. With respect to the polysiloxane having at least one SiH group and at least one diorganosiloxy group, it can be basically referred to as the corresponding polyorganohydrogensiloxane used as component B). Preferably, the production of a functional polysiloxane according to the present invention is carried out in the presence of a hydrosilylation catalyst immobilized on a support such as platinum on nanoSiO2. Thus, the present invention also relates to a functional polysiloxane such as one obtained by this process.

[0150] The present invention further relates to the use of the functionalized polysiloxane of the present invention as an adhesion promoter, preferably in a curable silicone composition.

[0151] The present invention further relates to the use of functionalized polysiloxanes for the manufacture of release coatings, elastomer articles, particularly self-adhesive elastomer articles, silicone encapsulants for electronic devices, and binding materials.

[0152] The present invention further, a) Applying a curable coating composition, preferably a curable poroganosiloxane composition, comprising at least one functional polysiloxane as defined above to at least one substrate, and b) Curing the curable coating composition on the substrate. The present invention relates to a method for coating a substrate, including the following steps.

[0153] The present invention further relates to a substrate having a release coating prepared from a curable composition comprising at least one functional polysiloxane as defined above, wherein the substrate is preferably selected from polyethylene (PE), polypropylene (PP), and PET (polyethylene terephthalate) and poly-coated PET. In preferred embodiments of the present invention, the substrate is selected from paper substrates such as polycoated paper, polycoated kraft paper (PE and / or PP), glassine paper, CCK (clay-coated kraft paper), SCK (supercalendered kraft paper), HCK (hybrid clay-coated paper), MG (machine-glazed paper) parchment, and bakery paper.

[0154] In a preferred embodiment, the present invention relates to a substrate in contact with a silicone rubber composition prepared from the curable composition defined above.

[0155] Preferred Embodiments of the Invention The following summarizes preferred embodiments of the present invention.

[0156] 1. A functional polyorganosiloxane comprising at least one SiH group, at least one diorganosiloxy group not containing an acid anhydride group, and at least one organic group bonded to a silicon atom via a carbon atom, wherein the organic group comprising at least one acid anhydride group comprises at least one siloxy group.

[0157] 2. The functional polyorganosiloxane according to the above embodiment, wherein the polyorganosiloxane is a linear polyorganosiloxane.

[0158] 3. A functional polyorganosiloxane according to any of the above embodiments, wherein the polyorganosiloxane is a linear polyorganosiloxane having at least one terminal organic group containing an acid anhydride group and / or at least one pendant organic group containing an acid anhydride group.

[0159] 4. A functional polyorganosiloxane according to any of the above embodiments, wherein the polyorganosiloxane has a molecular weight Mn in the range of about 500 to about 1000, preferably about 800 to about 8200, as determined by GPC using a polystyrene standard.

[0160] 5.R a R 1 b H c SiO (4-a-b-c) / 2 (I) Here a is 0, 1, 2, or 3. b is either 0 or 1. c is either 0 or 1. R represents an organic group, and R 1 This represents an organic group containing at least one, preferably one, acid anhydride group. However, this is subject to the condition that there is at least one siloxy unit where b=1 and c=0, at least one siloxy unit where c=1 and b=0, and the sum of a is 2, and at least one siloxy unit where b=c=0. A functional polyorganosiloxane according to any of the above embodiments, preferably comprising a siloxy unit of formula (I).

[0161] 6.M: R3SiO 1 / 2 D: R2SiO 2 / 2 D H : R(H)SiO 2 / 2 M H : R2(H)SiO 1 / 2 M * : R2R 1 SiO 1 / 2 D * : RR 1 SiO 2 / 2 T: RSiO 3 / 2 T * : R 1 SiO 3 / 2 T H : HSiO 3 / 2 Q: SiO 4 / 2 Here R represents an organic group, R 1 This represents an organic group containing at least one, preferably one, acid anhydride group. However, polysiloxane is M * , D * , and T * at least one siloxy group selected from the group, at least one group D H , and the condition that it contains at least one base D, A functional polyorganosiloxane according to any of the above embodiments, comprising a siloxy unit selected from the group consisting of the above.

[0162] 7. T, TH, T as defined above *A functional polyorganosiloxane according to any of the above embodiments, wherein the total molar content of the Q units is less than 5 mol%, preferably less than 2 mol%, based on the total amount of siloxy units.

[0163] 8.M t D x D H y D * z M t (II) Here M t M, M H , and M * A group consisting of M and M is selected, where M is selected. H and M * , D, M * , D H , and D * These are defined as described above, x is an average number greater than or equal to 1. y is an average number greater than or equal to 1. z is a mean number greater than or equal to 0, and Base D, D H , D * They can be arranged in any order. However, M * and D * The condition is that there exists at least one base selected from, A functional polyorganosiloxane according to any of the above embodiments, selected from linear polyorganosiloxanes having formula (II) and mixtures thereof.

[0164] 9. D / D H The functional polyorganosiloxane according to the above embodiment, wherein the molar ratio is 1:99 to 99:1, preferably 5:95 to 95:5, more preferably 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and more preferably 40:60 to 60:40.

[0165] 10. A functional polyorganosiloxane according to any of the above embodiments, comprising at least 3, preferably at least 5, more preferably at least 8, and even more preferably at least 10 siloxy units.

[0166] 11.M H (R2(H)SiO 1 / 2 A functional polyorganosiloxane according to any of the above embodiments, comprising at least one group selected from ).

[0167] 12.M * (R2R 1 SiO 1 / 2 A functional polyorganosiloxane according to any of the above embodiments, comprising at least one group selected from ).

[0168] 13. At least one acid anhydride group in an organic group bonded to a silicon atom via a carbon atom containing at least one acid anhydride group has the following structure: - The succinic anhydride portion of the following formula: [ka] - The maleic anhydride portion of the following formula: [ka] - The glutaric acid portion of the following formula: [ka] - The phthalic anhydride portion of the following formula: [ka] - [ka] Here, the dotted line in the above equation represents a single bond to the rest of the organic group that is bonded to the silicon atom via a carbon atom, and in some cases may also represent a direct bond to the silicon atom, and R is the organic group defined above, preferably an alkyl group. A functional polyorganosiloxane according to any of the above embodiments, selected from the above.

[0169] 14. A functional polyorganosiloxane according to any of the above embodiments, wherein at least one acid anhydride group is derived from a hydrosilylation reaction between an unsaturated anhydride and a SiH-functionalized siloxy group.

[0170] 15. Unsaturated anhydrous compounds are as follows (IUPAC names in parentheses): - Allyl succinic anhydride (3-allyltetrahydrofuran-2,5-dione): [ka] - 2-Butene-1-ylsuccinate anhydride (3-[(Z) or (E)-buto-2-enyl]tetrahydrofuran-2,5-dione): [ka] - 3-(2-methylallyl)succinic anhydride (3-(2-methylallyl)tetrahydrofuran-2,5-dione): [ka] - (1-propenyl)succinic anhydride (3-[(E) or (Z)-prop-1-enyl]tetrahydrofuran-2,5-dione): [ka] - 3-(1,9-decadien-1-yl)dihydro-2,5-frangione (3-[(1E) or (1Z)-deca-1,9-dienyl]tetrahydrofuran-2,5-dione): [ka] - 3-(hexadeca-1-enyl)oxolane-2,5-dione (3-[(E) or (Z)-hexadeca-1-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - Dihydro-3-(3-octen-1-yl)-2,5-frangione(3-[(E)-octa-3-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - 2-Octadecenylsuccinate anhydride (3-[(E)-Octadec-2-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - 3-methyl-4-pento-3-enyloxolane-2,5-dione (3-methyl-4-[(E)-pento-3-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - Dihydro-3-(2-methylenebutyl)-2,5-frangione (3-(2-methylenebutyl)tetrahydrofuran-2,5-dione): [ka] - Dihydro-3-(1,1,2-trimethyl-2-propen-1-yl)-2,5-franzione(3-(1,1,2-trimethylallyl)tetrahydrofuran-2,5-dione): [ka] - 3-(1,2-dimethyl-2-propen-1-yl)dihydro-2,5-franzione (3-(1,2-dimethylallyl)tetrahydrofuran-2,5-dione): [ka] - 3-Hexa-4-en-2-yloxolane-2,5-dione (3-[(E)-1-methylpento-3-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - 2-Hexen-1-yl succinic anhydride (3-[(E)-Hexa-2-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - 3-pento-2-enyloxolane-2,5-dione (3-[(E)-pento-2-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - 1-Octenyl succinic anhydride (3-[(E)-octa-1-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - 2-Octenyl succinic anhydride (3-[(E)-octa-2-enyl]tetrahydrofuran-2,5-dione): [ka] or its (Z) isomer; - 3-(2-neopentylallyl)tetrahydrofuran-2,5-dione: [ka] - Maleic anhydride: [ka] - 4-Cyclohexene-1,2-dicarboxylic acid anhydride: [ka] - 2-norbornene-5,6-dicarboxylic acid anhydride: [ka] - Methyl-5-norbornene-2,3-dicarboxylic acid anhydride: [ka] - 3-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride: [ka] - 3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride: [ka] - 1-Methyltetrahydrophthalic anhydride: [ka] - 4-ethenyl-3a,4,7,7a-tetrahydro-1,3-isobenzofranion: [ka] - Bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic dianhydride: [ka] - 4-methyl-3a,4,7,7a-tetrahydro-4,7-epoxy-2-benzofuran-1,3-dione: [ka] - 5-methyl-4-(3-methylbut-2-enyl)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione: [ka] - 1,4,5,6,7-Hexachloro-5-norbornene-2,3-dicarboxylic acid anhydride: [ka] and - Carboxylobuto-3-enoate of the following formula: [ka] For example, acetylbuto-3-enoate: [ka] A functional polyorganosiloxane according to the above embodiment, selected from the group consisting of the above.

[0171] 16. At least one acid anhydride group is the succinic anhydride portion of the following formula: [ka] The portion may be monovalent or divalent and can be bonded to the silicon atom by single bonds or divalent or trivalent organic groups, preferably the succinic anhydride portion is monovalent and bonded to the silicon atom via divalent organic groups. A functional polyorganosiloxane according to any of the above embodiments.

[0172] 17. A curable composition comprising at least one functional polyorganosiloxane as described in any of the above embodiments.

[0173] 18. (A) At least one polyorganosiloxane having at least two unsaturated hydrocarbyl residues, (B) at least one polyorganic hydrogen siloxane, (C) At least one hydrosilylation catalyst containing a transition metal, (D) At least one functional polysiloxane as defined in any of the embodiments described above, (E) One or more fillers of any choice, (F) One or more auxiliary additives of any choice, A curable composition according to the above embodiment, comprising:

[0174] 19. (B) At least one polyorganic hydrogen siloxane, (D) At least one functional polysiloxane as defined in any of the embodiments described above, (E) One or more fillers of any choice, and (F) optionally includes one or more auxiliary additives. Component (I), and (A) At least one polyorganosiloxane having at least two unsaturated hydrocarbyl residues, (C) At least one hydrosilylation catalyst containing a transition metal, (E) One or more fillers of any choice, (F) optionally includes one or more auxiliary additives. Component (II) A curable two-component composition according to any of the above embodiments, comprising:

[0175] 20. A curable composition according to any of the above embodiments, comprising less than about 5% by weight, preferably less than about 2% by weight, of a functional polysiloxane as defined in any of the above embodiments.

[0176] 21. A curable composition according to any of the above embodiments, which cures at room temperature (RTV) or at a high temperature of about 40 to 200°C, or under exposure.

[0177] 22. A cured composition obtained by curing the curable composition described in any of the embodiments described above.

[0178] 23. A composite article comprising a cured composition according to the above embodiment in contact with at least one substrate selected from a metal substrate, glass substrate, ceramic substrate, paper substrate, polymer substrate, preferably polyethylene, polypropylene, polycarbonate, polyester, for example polyethylene terephthalate (PET).

[0179] 24. Use of the curable composition according to any of the above embodiments for the manufacture or use of release coatings, elastomers, particularly self-adhesive elastomers, (optical) bonding materials, and silicone encapsulants for electronic devices.

[0180] 25. A cured composition according to Embodiment 22, selected from release coatings, elastomers, particularly self-adhesive elastomers, (optical) bonding materials, and silicone encapsulants for electronic devices.

[0181] 26. (B) At least one polyorganic hydrogen siloxane, (D) Component (I) of a curable two-component composition comprising at least one functional polysiloxane as defined in any of the embodiments described above.

[0182] 27. A method for producing a functional polysiloxane as defined in any of the above embodiments, comprising the reaction of a polysiloxane having at least one SiH group and at least one diorganosiloxy group with an organic compound having at least one acid anhydride group and at least one unsaturated hydrocarbyl group, in the presence of a hydrosilylation catalyst.

[0183] 28. A method for producing a functional polysiloxane according to any of the above embodiments, wherein a hydrosilylation catalyst is immobilized on a support.

[0184] 29. A functional polysiloxane obtained by the method of any embodiment of the above method.

[0185] 30. Use as an adhesion promoter for functional polysiloxanes as defined in any of the above embodiments.

[0186] 31. Use of functional polysiloxanes as defined in any of the above embodiments for the manufacture of release coatings, elastomer articles, particularly self-adhesive elastomer articles, silicone encapsulants for electronic devices, and binding materials.

[0187] 32.a) Applying a curable coating composition comprising at least one functional polysiloxane as defined in any of the embodiments described above to at least one substrate, and b) Curing the curable coating composition, A method for coating a substrate, including the step of [step name].

[0188] 33. A substrate having a release coating prepared from a curable composition defined in any of the embodiments described above, the substrate being selected from polyethylene, polypropylene, and PET.

[0189] 34. Substrates having a release coating prepared from a curable composition as defined in any of the above embodiments, selected from film, sheet, and paper substrates, such as polycoated paper, polycoated kraft paper (PE and / or PP), glassine paper, CCK (clay-coated kraft paper), SCK (supercalendered kraft paper), HCK (hybrid clay-coated paper), MG (machine-glazed paper) parchment, and bakery paper.

[0190] 35. A substrate in contact with a silicone rubber composition prepared from a curable composition defined in any of the above embodiments.

[0191] It should be understood that any numerical range described herein includes all subranges within that range as described in the examples or elsewhere in the specification, and any combination of various endpoints of such ranges or subranges.

[0192] Unless otherwise shown in the examples or elsewhere, all numerical values ​​relating to quantities of materials, reaction conditions, durations, quantified properties of materials, etc., described in the specification and claims should be understood to be modified in all cases by the term “approximately,” regardless of whether the term “approximately” is used in the expression. Any component of the present invention described by any particular genus or species detailed in the Examples section of this specification may be used in one embodiment to define the respective definitions of any endpoint of any range described elsewhere herein with respect to that component, and thus it will also be understood herein that in one non-limiting embodiment it may be used to replace the endpoint of such range described elsewhere.

[0193] Any compound, material, or substance explicitly or implicitly disclosed in the specification and / or described in the claims as belonging to a group of compounds, materials, or substances that are structurally, compositionally, and / or functionally related will also be understood to include individual representatives and all combinations of those groups.

[0194] While the above description contains many details, these details should not be construed as limitations on the scope of the invention, but merely as examples of preferred embodiments. Those skilled in the art will be able to envision many other possible variations that fall within the scope and spirit of the invention as defined by the claims appended herein. [Examples]

[0195] The immobilized additive is manufactured in a two-step process. In the first step, the SiH-functionalized polysiloxane is manufactured by acid-catalyzed equilibration. In the second step, the allyl succinic anhydride is bonded to the polymer chain by using a solid-supported hydrosilylation catalyst, as described in US 9,993,812 B2. Correlation spectroscopy ( 29 Si / 1 The obtained structure was established using H(HMQC). Unless otherwise specified, polysiloxanes have a methyl group as an organic group (i.e., D is a dimethylsiloxy group).

[0196] Example 1; H MD 15 D H 30 M H In a four-necked round-bottom flask equipped with a reflux condenser connected to a mechanical stirrer, thermowell, and nitrogen bubbler, octamethylcyclotetrasiloxane (D4, 556.14 g, 1.875 mol), tetramethyldisiloxane (TMDSO, 67.17 g, 0.5 mol), and tetramethylcyclotetrasiloxane (D4) were added. H 901.91 g, 3.7 mol) was added. The flask was inactivated (N2). Triflulinic acid (TfOH, 0.44 mL, 0.005 mol) was added via a Teflon syringe, and the reaction mixture was heated to 70°C and stirred for 4.5 hours.

[0197] The reaction mixture was cooled to 45°C. A paste of NaHCO3 (25.6 g, 0.305 mol) and water (3.05 mL, 0.169 mol) was gradually added while stirring, and the mixture was stirred at 70°C for 1.5 hours. Aliquots were brought into contact with a small amount of water and the pH was confirmed to be between 6.5 and 7.5.

[0198] The reaction mixture was cooled to room temperature, the salt was removed by filtration, and the product was defoliated at 150°C and 0.1 Torr to obtain the title product as a clear, colorless oil. Yield: 1361.9 g (87.3%).

[0199] Example 2: H MD 25 D H 27 M H In a four-necked round-bottom flask equipped with a reflux condenser connected to a mechanical stirrer, thermowell, and nitrogen bubbler, octamethylcyclotetrasiloxane (D4, 741.53 g, 2.5 mol), tetramethyldisiloxane (TMDSO, 53.73 g, 0.4 mol), and tetramethylcyclotetrasiloxane (D H 4 (649.38 g, 2.7 mol) was added. The flask was inactivated (N2). Triflic acid (TfOH, 0.35 mL, 0.004 mol) was added via a Teflon syringe, and the reaction mixture was heated to 70°C and stirred for 4.5 hours.

[0200] The reaction mixture was cooled to 45°C. A paste of NaHCO3 (20.5 g, 0.244 mol) and water (2.44 mL, 0.135 mol) was gradually added while stirring, and the mixture was stirred at 70°C for 1.5 hours. Aliquots were brought into contact with a small amount of water and the pH was confirmed to be between 6.5 and 7.5.

[0201] The reaction mixture was cooled to room temperature, the salt was removed by filtration, and the product was defoliated at 150°C and 0.1 Torr to obtain the title product as a clear, colorless oil. Yield: 1298.5 g (89.8%).

[0202] Example 3: Functional polysiloxane A1 A four-necked round-bottom flask equipped with a reflux condenser attached to a mechanical stirrer, thermowell, and nitrogen bubbler, from Example 1 H MD 15 D H 30 M H Fluid (137.27 g, 45.0 mmol), toluene (111.95 g), and a catalytic amount of silica-supported Pt (5.0 mg Pt, 0.025 mmol) as described in US 9,993,812 B2 were added. The mixture was heated to 100°C, and allyl succinic anhydride (12.61 g, 90.0 mmol) was added dropwise through a dropping funnel over 15 minutes. After 10 hours, the reaction mixture was cooled to room temperature, the catalyst was removed by filtration, and the product was defoliated at 90°C and 2 Torr to obtain the title product as a cloudy yellow oil. Yield: 145.0 g (96.7%). The resulting functional polysiloxane contained SiH, D groups and succinic anhydride-containing siloxy groups.

[0203] Example 4: Functional polysiloxane A2 A four-necked round-bottom flask equipped with a mechanical stirrer, a thermowell, and a reflux condenser attached to a nitrogen bubbler, from Example 2 H MD 25 D H 27 M H Fluid (306.99 g, 85.0 mmol), toluene (211.46 g), and a catalytic amount of silica-supported Pt (9.4 mg Pt, 0.048 mmol) as described in US 9,993,812 B2 were added. The mixture was heated to 100°C, and allyl succinic anhydride (23.82 g, 170.0 mmol) was added dropwise through an addition funnel over 15 minutes. After 7 hours, the reaction mixture was cooled to room temperature, the catalyst was removed by filtration, and the product was defoliated at 90°C and 2 Torr to obtain the title product as a cloudy yellow oil. Yield: 316.8 g (95.8%). The resulting functional polysiloxane contained SiH, D groups and succinic anhydride-containing siloxy groups.

[0204] test: When evaluating the performance of the above-mentioned examples of immobilization additives, the pilot coater test was designed to apply a heat-solvent-free release coating containing the immobilization additive to a given substrate.

[0205] Formulas 1 to 3 were designed using a vinyl-end-stopped PDMS / inhibitor package, 50 ppm Karstedt-like catalyst, and polymethylhydrogen siloxane sufficient to achieve a hydride-to-vinyl ratio of 2.0.

[0206] An example of a fixative additive was added at 1.0% by weight of the total weight of formulations 2 and 3. The fixative additive was not included in the calculation of the hydride-to-vinyl ratio.

[0207] Comparative formulation 1 did not contain any fixation additives. Next, samples of cured silicone-coated substrates were prepared for testing. Fixation tests were performed by rubbing the silicone-coated substrates with fingers, and their ability to fix to a given substrate was evaluated.

[0208] Immediately after the completion of the designed pilot coater experiment, a fixation test was performed on the samples. Next, the samples were placed in a 60°C, 100% relative humidity (RH) environment and repeated multiple times over a two-week period.

[0209] The following results were generated. [Table 1]

[0210] Example 5: M H D 15 D H 30 M H synthesis Octamethylcyclotetrasiloxane (36.46 g, 0.1229 mol), 1,3,5,7-tetramethylcyclotetrasiloxane (59.13 g, 0.2459 mol), tetramethyldisiloxane (4.40 g, 0.03276 mol), and perfluorobutanesulfonic acid (1000 ppm, 0.1 g) were heated at 70°C for 4.5 hours. After the reaction mixture was cooled to room temperature, water (0.2 g) and potassium bicarbonate (2 g) were added, and the mixture was heated at 70°C for a further 1.5 hours. The pH of the mixture was then confirmed to be neutral. Filtration was performed using a pressure-operated Nash filter (Nutsch). Volatile substances were removed under vacuum (0.4 mbar) at 150°C for 1 hour. The pure product was obtained as a colorless oil (yield 77.6 g). The structure is 1 H- and 29 Confirmed by Si-NMR.

[0211] Example 6: Functional polysiloxane A3 0.2 wt% Pt; 17.86 g) on ​​nanoSiO2 in toluene (1100 g) (as prepared in Example 5, M H D 15 D H 30 M H The catalyst was added at 80°C to a solution of 628.2 g (10.0454 mmol SiH / g), followed by the slow addition of allyl succinic anhydride (57.7 g, 0.41185 mol). The reaction mixture was then heated at 110°C for 20 hours, cooled to room temperature, and the catalyst was removed by filtration. The solvent was removed under vacuum (<1 mbar) at 40°C. The untreated product was obtained as a clear, slightly yellowish oil (yield 642.6 g). The resulting functional polysiloxane contained SiH, D groups, and succinic anhydride-containing siloxy groups.

[0212] Example 7: Functional polysiloxane A4 formula M 0.72 D 17.32 D H 19.51 M H 1.28The silicone hydrogenated fluid was prepared from octamethylcyclotetrasiloxane, tetramethyldisiloxane, polymethylhydrosiloxane (SiH = 0.04 wt%), and perfluoro-n-butanoic acid as a catalyst by an equilibrium reaction at 70°C for 2.5 hours. Acid neutralization was carried out with sodium bicarbonate.

[0213] In the next step, formula M is dissolved in 721.0 g of toluene. 0.72 D 17.32 D H 19.51 M H 1.28 400.0 g of the silicone hydride fluid was reacted with 27.6 g of allyl succinic anhydride under reflux conditions in the presence of 11.5 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After 5 hours, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). The product was obtained as a colorless, transparent liquid. The anhydride content bound to the polymer chain was: 1 H- and 29 The Si-NMR spectrum was determined to be 0.37 mmol / g, while the residual SiH content was determined to be 6.95 mmol / g. The resulting functional polysiloxane contained SiH, D groups, and succinic anhydride-containing siloxy groups.

[0214] Example 8: Functional polysiloxane A5 (comparison) Formula MD dissolved in 36.9 g of toluene H 39.10 19.7 g of polymethylhydrosiloxane M (SiH = 1.6 wt%) was reacted with 1.4 g of allyl succinic anhydride (ASA) under reflux conditions in the presence of 1.2 g of Pt (0.2 wt%) immobilized on SiO2 (from patent publication WO2013 / 158272A1). After 9 hours of reaction, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). Formula MD H 37.73 D ASA 0.66 M( 1 H and 29The product (determined by Si-NMR) was obtained as a clear, colorless liquid. The resulting functional polysiloxane did not contain a dimethylsiloxy group (D).

[0215] Example 9: Functional polysiloxane A6 (comparison) Formula MD dissolved in 36.9 g of toluene H 39.10 19.7 g of polymethylhydrosiloxane (M, SiH = 1.6 wt%) was reacted with 1.4 g of allyl succinic anhydride under reflux conditions in the presence of 5 ppm cis-dichlorobis(diethyl sulfide)platinum(II) (0.5 wt% solution in toluene) as a homogeneous catalyst. After 5 hours of reaction, the solvent was removed under vacuum (1 mbar, 40°C). Formula MD H 37.02 D ASA 1.11 M product ( 1 H- and 29 The obtained product (determined by Si-NMR) was a clear, colorless liquid. The resulting functional polysiloxane did not contain a dimethylsiloxy group (D).

[0216] Example 10: Functional polysiloxane A7 (comparison) Formula D dissolved in 33.5g of toluene H 12.0 g of polymethylhydrosiloxane 4 (cyclic structure, SiH = 1.4 wt%) was reacted with 7.0 g of allyl succinic anhydride under reflux conditions in the presence of 0.03 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After 5 hours, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). Formula D H 3D ASA Product of 1 ( 1 H- and 29 The result (determined by Si-NMR) was obtained as a pale yellow liquid. The obtained functional polysiloxane did not contain a dimethylsiloxy group (D).

[0217] Example 11: Functional polysiloxane A8 (comparison) Formula D dissolved in 33.5g of tolueneH 12.0 g of polymethylhydrosiloxane (cyclic structure, SiH = 1.4 wt%) was reacted with 7.0 g of allyl succinic anhydride under reflux conditions in the presence of 0.03 g of 5 ppm cis-dichlorobis(diethyl sulfide)platinum(II) (0.5 wt% solution in toluene) as a homogeneous catalyst. After 5 hours, the solvent was removed under vacuum (1 mbar, 40°C). Formula D H 3D ASA Product of 1 ( 1 H- and 29 The result (determined by Si-NMR) was obtained as a slightly cloudy, yellowish liquid. The resulting functional polysiloxane did not contain a dimethylsiloxy group (D).

[0218] Example 12: Functional polysiloxane A9 (comparison) The silicone hydrogenated logistics body contains hexamethyldisiloxane and polymethylhydrosiloxane (linear structure, SiH = 0.9 wt%, M2D H 3.07 It was prepared by an equilibrium reaction at 70°C for 2.5 hours using perfluoro-n-butanoic acid as a catalyst. Acid neutralization was carried out with sodium bicarbonate.

[0219] In the next step, 10.4 g of the prepared silicone hydrogenated fluid, dissolved in 38.8 g of toluene, was reacted with 12.9 g of allyl succinic anhydride (ASA) under reflux conditions in the presence of 0.8 g of immobilized Pt (0.2 wt%) catalyst on SiO2 (Patent Publication WO2013 / 158272A1). After 19 hours of reaction, the solid was separated, and the solvent was subsequently removed under vacuum (1 mbar, 40°C). Formula MD H 0.14 D ASA 3.23 M product ( 1 H- and 29 The result (determined by Si-NMR) was obtained as a dark yellow liquid. The obtained functional polysiloxane did not contain a dimethylsiloxy group (D).

[0220] Example 13: Functional polysiloxane A10 (comparison) The formula is a silicone hydrogenated logistics body containing tetramethyldisiloxane and polymethylhydrosiloxane (linear structure, SiH = 0.6 wt%, M2D H 3.27 It was prepared by an equilibrium reaction at 70°C for 2.5 hours using perfluoro-n-butanoic acid as a catalyst. Acid neutralization was carried out with sodium bicarbonate.

[0221] In the next step, 45.0 g of the prepared silicone hydrogenated fluid, dissolved in 38.8 g of toluene, was reacted with 33.7 g of allyl succinic anhydride (ASA) under reflux conditions in the presence of 0.8 g of SiO2-immobilized Pt (0.2 wt%) catalyst (Patent Publication WO2013 / 158272A1). After 7 hours of conversion (with respect to ASA), the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). Formula M ASA 2D 4.40 Products of ( 1 H- and 29 The obtained functional polysiloxane (determined by Si-NMR) was a clear liquid. The resulting functional polysiloxane did not contain SiH groups.

[0222] Example 14: Functional polysiloxane A11 (comparison) A mixture of 13.4 g of tetramethyldisiloxane, 14.8 g of vinyltrimethoxysilane, and 10 ppm of Lamoreaux catalyst was heated at 130°C for 4 hours. Subsequently, the intermediate product was reacted with 18.2 g of allyl succinic anhydride (ASA), and the reaction was further carried out by adding 10 ppm of Lamoreaux catalyst. The reaction mixture was heated at 110°C for 9 hours. Finally, the general formula was obtained. ASA MM (CH2CH2Si(OCH3)3) Products of ( 1 H- and 29 The obtained product (measured by Si-NMR) was a brownish transparent liquid. The resulting functional polysiloxane did not contain either SiH or D groups.

[0223] Example 15: Functional polysiloxane A12 (comparison) H MD 3.35 M (CH2CH2Si(OCH3)3)It was prepared according to the synthesis procedure described in WO2017012714A.

[0224] Next, 10.0g of intermediate M (H) D 3.35 M (CH2CH2Si(OCH3)3) The mixture was reacted at 100°C for 4 hours using 3.3 g of allyl succinic anhydride (ASA) in the presence of 10 ppm chloroplatinic acid as a hydrosilylation catalyst. ASA MD 3.35 M (CH2CH2Si(OCH3)3) ( 1 H and 29 The product (determined by Si-NMR) was obtained as a slightly brownish liquid. The resulting functional polysiloxane did not contain any SiH groups.

[0225] Example 16: Functional polysiloxane A13 (invention) formula md 24.76 D (H) 55.72 10.0 g of SiH hydrogenation flux M was dissolved in 17.0 g of toluene and reacted with 0.5 g of allyl succinic anhydride under reflux conditions in the presence of 0.3 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After 5 hours of reaction, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). The product was obtained as a clear liquid. The resulting functional polysiloxane contained SiH, D groups and succinic anhydride-containing siloxy groups. The polymer chain-bound anhydride content was: 1 H and 29 It was determined to be 0.25 mmol / g by Si-NMR.

[0226] Example 17: Functional polysiloxane A14 (invention) formula H M2D 18.94 D H 36.30The silicone hydrogenated fluid was prepared from octamethylcyclotetrasiloxane, tetramethyldisiloxane, polymethylhydrosiloxane (SiH = 1.7 wt%), and perfluoro-n-butanoic acid as a catalyst by an equilibrium reaction at 70°C for 2.5 hours. Acid neutralization was carried out with sodium bicarbonate.

[0227] In the next step, 33.0 g of the prepared silicone hydrogenated fluid, dissolved in 57.8 g of toluene, was reacted with 3.03 g of allyl succinic anhydride (ASA) under reflux conditions in the presence of 1.1 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After a conversion time of 6 hours, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). The product was obtained as a clear liquid. The anhydride content bound to the polymer chain was: 1 H and 29 The SiH content was determined to be 0.49 mmol / g by Si-NMR, while the residual SiH content was determined to be 8.78 mmol / g. The resulting functional polysiloxane contained SiH, D groups, and succinic anhydride-containing siloxy groups.

[0228] Example 18: Functional polysiloxane A15 (invention) formula H M2D 9.08 D H 8.36 The silicone hydrogenated fluid was prepared from octamethylcyclotetrasiloxane, tetramethyldisiloxane, polymethylhydrosiloxane (SiH = 1.7 wt%), and perfluoro-n-butanoic acid as a catalyst by an equilibrium reaction at 70°C for 2.5 hours. Acid neutralization was carried out with sodium bicarbonate.

[0229] In the next step, 20.0 g of the above silicone hydrogenated material was dissolved in 40.0 g of toluene and reacted with 3.0 g of allyl succinic anhydride under reflux conditions in the presence of 0.6 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After 5 hours of reaction, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). The product was obtained as a colorless, transparent liquid. The anhydride content bound to the polymer chain was: 1 H and 29 Si-NMR determined the SiH content to be 0.94 mmol / g, while the remaining SiH content was determined to be 6.05 mmol / g. The resulting functional polysiloxane contained SiH, D groups, and succinic anhydride-containing siloxy groups. The product is a short-chain polymer with a D / DH ratio of approximately 1 / 1 and a high ASA concentration.

[0230] Example 19: Functional polysiloxane A16 (invention) formula H M2D 32.95 D H 10.18 The silicone hydrogenated fluid was prepared from octamethylcyclotetrasiloxane, tetramethyldisiloxane, polymethylhydrosiloxane (SiH = 1.7 wt%), and perfluoro-n-butanoic acid as a catalyst by an equilibrium reaction at 70°C for 2.5 hours. Acid neutralization was carried out with sodium bicarbonate.

[0231] In the next step, 20.0 g of the above silicone hydrogenated material was dissolved in 40.2 g of toluene and reacted with 1.23 g of allyl succinic anhydride under reflux conditions in the presence of 0.6 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After 5 hours of reaction, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). The product was obtained as a colorless, transparent liquid. The anhydride content bound to the polymer chain was: 1 H and 29The SiH content was determined to be 0.34 mmol / g by Si-NMR, while the residual SiH content was determined to be 3.24 mmol / g. The resulting functional polysiloxane contained SiH, D groups, and succinic anhydride-containing siloxy groups.

[0232] Example 20: Functional polysiloxane A17 (invention) formula M H 2D 9.08 D H 8.36 The silicone hydrogenated fluid was prepared from octamethylcyclotetrasiloxane, tetramethyldisiloxane, polymethylhydrosiloxane (SiH = 1.7 wt%), and perfluoro-n-butanoic acid as a catalyst by an equilibrium reaction at 70°C for 2.5 hours. Acid neutralization was carried out with sodium bicarbonate.

[0233] In the next step, 20.0 g of silicone hydride solution was dissolved in 40.0 g of toluene and reacted with 1.3 g of allyl succinic anhydride under reflux conditions in the presence of 0.6 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After 5 hours of reaction, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). The product was obtained as a colorless, transparent liquid. The anhydride content bound to the polymer chain was: 1 H- and 29 The Si-NMR spectrum was determined to be 0.38 mmol / g, while the residual SiH content was determined to be 8.00 mmol / g. The resulting functional polysiloxane contained SiH, D groups, and succinic anhydride-containing siloxy groups.

[0234] Example 21: Functional polysiloxane A18 (invention) formula M H 2D 106.77 D H 105.43The silicone hydrogenated fluid was prepared from octamethylcyclotetrasiloxane, tetramethyldisiloxane, polymethylhydrosiloxane (SiH = 1.7 wt%), and perfluoro-n-butanoic acid as a catalyst by an equilibrium reaction at 70°C for 2.5 hours. Acid neutralization was carried out with sodium bicarbonate.

[0235] In the next step, 20.0 g of the silicone liquid hydrogenation fluid was dissolved in 35.5 g of toluene and reacted with 1.53 g of allyl succinic anhydride under reflux conditions in the presence of 0.6 g of SiO2-immobilized Pt (0.2 wt%) catalyst (from patent publication WO2013 / 158272A1). After 5 hours of reaction, the solid was separated and the solvent was removed under vacuum (1 mbar, 40°C). The product was obtained as a colorless, transparent liquid. The anhydride content bound to the polymer chain was: 1 H- and 29 The Si-NMR spectrum was determined to be 0.46 mmol / g, while the residual SiH content was determined to be 6.35 mmol / g. The resulting functional polysiloxane contained SiH, D groups, and succinic anhydride-containing siloxy groups.

[0236] The performance of functionalized polysiloxanes A4-A18 was tested using a typical paper-release coating formulation consisting of the following: [Table 2]

[0237] After thoroughly mixing the ingredients, the mixture was deposited onto UPM Golden Biocoat Glassine paper (reel width = 800mm, core = 76mm, order number CH-5878964-02) using a Mathis Lab Coater coating knife, with a weight of 1.2g / m². 2 The samples were coated with [the specified material]. All samples were subjected to the same curing conditions, using an oven temperature of 130°C and a curing time of 30 seconds.

[0238] The fixation performance of the various prepared samples was evaluated by a finger rub test after all samples had been aged at room temperature for 24 hours. Furthermore, the fixation strength to the paper substrate was assessed by a fixation test that provides a measure of the weight loss of the removed silicone coating as an effect of mechanical abrasion. 1 Quantified using (see table below).

[0239] 1 Fixed test: Paper test piece (round; 10.0 cm) 2 The coated surface of the paper is pressed against the textile felt strip with a weight of 4.4 kg. Subsequently, the paper test piece is pressed onto the felt strip (at room temperature) at a constant speed of 9.2 cm / second until it completes a total distance of 70.0 cm. The felt strip is replaced with each test sample to ensure the same abrasion conditions. The weight loss of the paper sample (weight before and after the abrasion test) is used as a measure of the adhesion strength of the coating layer to the substrate; that is, a 75 wt% material loss due to abrasion indicates a 25 wt% retention of the Ducal test material. [Table 3]

[0240] The performance of functional polysiloxane A4 was also tested by using a typical release coating formulation on a film liner consisting of the following: [Table 4]

[0241] After thoroughly mixing the ingredients, use a Mathis Lab Coater coating knife to coat the mixture onto Rexor 23 micron thick PET (untreated with corona) at a rate of 1.2 g / m². 2 The samples were coated with the specified deposition weight. All samples were subjected to the same curing conditions, using an oven temperature of 130°C and a curing time of 30 seconds.

[0242] The fixation performance of the various prepared samples was evaluated by a finger rub test after all samples had been aged at room temperature for 24 hours. In addition, the fixation strength to the PET substrate was evaluated by a fixation test that provides a measure of the weight loss of the removed silicone coating as an effect of mechanical abrasion. 2 Quantified using (see table below).

[0243] 2 Fixation test: PET test specimen (round; 10.0 cm) 2 The coated surface of the PET sample is pressed against a textile felt strip with a weight of 4.4 kg. Subsequently, the PET sample is pressed onto the felt strip (at room temperature) at a constant speed of 9.2 cm / second until it completes a total distance of 70.0 cm. The felt strip is replaced with each test sample to ensure the same abrasion conditions. The weight loss of the PET test piece (weight before and after the abrasion test) is adopted as a measure of the adhesion strength of the coating layer to the substrate, i.e., a 75 wt% material loss due to abrasion means a 25 wt% Durlac test material retention. [Table 5]

Claims

1. A functional polysiloxane comprising at least one SiH group, at least one diorganosiloxy group not containing an acid anhydride group, and at least one organic group bonded to a silicon atom via a carbon atom, wherein the organic group comprises at least one acid anhydride group and at least one siloxy group, The functionalized polysiloxane is M: R 3 SiO 1 / 2 D: R2SiO2 / 2 DH: R(H)SiO2 / 2 M H : R 2 (H)SiO 1 / 2 M*: R 2 R 1 SiO 1 / 2 D*: RR 1 SiO 2 / 2 T: RSiO 3 / 2 T*: R 1 SiO 3 / 2 TH: HSiO 3 / 2 Q: SiO 4 / 2 It includes a siloxy unit selected from the group consisting of, Here, R represents an organic group, R1 represents an organic group containing at least one acid anhydride group, However, the polysiloxane is subject to the condition that it contains at least one siloxy M* unit, at least one siloxy DH unit, and at least one siloxy D unit. Functional polysiloxane.

2. The functional polysiloxane according to claim 1, wherein the polyorganosiloxane is a linear polysiloxane and has at least one terminal organic group containing an acid anhydride group.

3. A functional polysiloxane according to claim 1 or 2, comprising at least three siloxy units.

4. In an organic group bonded to a silicon atom via a carbon atom, at least one acid anhydride group has the following structure: - The succinic anhydride portion of the following formula: 【Chemistry 1】 - The maleic anhydride portion of the following formula: 【Chemistry 2】 - The glutaric acid portion of the following formula: 【Transformation 3】 - The phthalic anhydride portion of the following formula: 【Chemistry 4】 or - The acyclic anhydrous portion of the following equation: 【Transformation 5】 Here, the dotted line in the above formula represents a single bond to the rest of the organic group bonded to the silicon atom via a carbon atom, or possibly a direct bond to the silicon atom, and R is the organic group defined above, preferably an alkyl group. A functional polysiloxane according to any one of claims 1 to 3, comprising at least one acid anhydride group selected from the above.

5. The functional polysiloxane according to any one of claims 1 to 4, wherein at least one acid anhydride group is derived from a hydrosilylation reaction between an unsaturated anhydride and an SiH-functionalized siloxy group.

6. At least one acid anhydride group is the succinic anhydride portion of the following formula, 【Transformation 6】 The functional polysiloxane according to any one of claims 1 to 5, wherein the portion can be monovalent or divalent and can be bonded to the silicon atom by a single bond or a divalent or trivalent organic group, preferably the succinic anhydride portion is monovalent and bonded to the silicon atom via a divalent organic group.

7. A curable composition comprising at least one functional polysiloxane according to any one of claims 1 to 6, preferably, (A) At least one polysiloxane having at least two unsaturated hydrocarbyl residues, (B) at least one polyorganic hydrogen siloxane, (C) At least one hydrosilylation catalyst containing a transition metal, (D) at least one functional polysiloxane as defined in any of the claims above, (E) One or more fillers of any choice, (F) One or more auxiliary additives of any choice, A curable composition containing the following:

8. A cured composition obtained by curing the curable composition described in claim 7.

9. A composite article comprising the cured composition according to claim 7 or 8, which is in contact with at least one substrate selected from the group consisting of a metal substrate, a glass substrate, a ceramic substrate, a paper substrate, a polymer substrate, preferably polyethylene, polypropylene, polycarbonate, and polyester, preferably polyethylene terephthalate (PET).

10. Use of the curable composition according to claim 7 or 8 for the manufacture or use of release coatings, elastomers, self-adhesive elastomers, (optical) bonding materials, and / or silicone encapsulants for electronic devices.

11. Use of functional polysiloxanes as defined in any one of claims 1 to 6 for the manufacture of adhesion promoters and / or release coatings, elastomer articles, self-adhesive elastomer articles, silicone encapsulants for electronic devices, and binding materials.

12. a) Applying a curable coating composition comprising at least one functional polysiloxane as defined in any one of claims 1 to 6 to at least one substrate, and b) including curing a curable coating composition, A method for coating a substrate.

13. A substrate having a release coating prepared from a curable composition as defined in claim 7 or 8, wherein the substrate is selected from polyethylene, polypropylene, or PET, and preferably the substrate is a film, sheet, or paper substrate having a release coating selected from polycoat paper, polycoat kraft paper (PE and / or PP), glassine paper, CCK (clay-coated kraft paper), SCK (supercalendered kraft paper), HCK (hybrid clay-coated paper), MG (machine-glazed paper) parchment, or bakery paper.

14. A substrate in contact with a silicone rubber composition prepared from a curable composition as defined in claim 7 or 8.

Images