Autocatalytic silicone composition, adhesive formed therefrom, and method for producing the same

Abstract

This application describes a process for forming a silicone material. This process involves reacting (i) MQ silicone resin, (ii) polyorganosiloxane, and (iii) hydrophilic functional siloxane, where the reaction is carried out in the absence of an external catalyst. The mixture of (i), (ii), and (iii) is autocatalytic and does not require an external condensation catalyst. This process is suitable for forming a cured silicone material, such as a pressure-sensitive adhesive.

Description

[Technical Field]

[0001] The present invention relates to a silicone composition suitable for forming a silicone pressure-sensitive adhesive, and a method for producing the same. In particular, the present invention relates to a composition that does not contain an external catalyst and may be considered self-catalyzed, and a method for producing a pressure-sensitive adhesive substance from such a composition. [Background technology]

[0002] Silicone pressure-sensitive adhesives are an important type of adhesive used in a wide variety of applications. They are used in high-temperature applications, industrial applications, electronics, medical / healthcare, and pharmaceutical delivery applications.

[0003] Many silicone pressure-sensitive adhesives are produced by solution condensation of branched-chain silicone resins (MQ resins) and polydiorganosiloxanes in the presence of a condensation catalyst. This reaction has traditionally been carried out in a solvent, which is mostly an aromatic solvent, such as benzene, toluene, and / or xylene (BTX solvent), and then cured via peroxide radicals. Another route for forming silicone pressure-sensitive adhesives is addition curing of vinyl-containing siloxane polymers and hydride-containing siloxane oligomers using a platinum catalyst.

[0004] Solution condensation is generally the industrially preferred route for the preparation of silicone pressure-sensitive adhesives. Solution condensation generally yields pressure-sensitive adhesives with better adhesion and thermal properties compared to pressure-sensitive adhesives prepared via two-component addition curing methods. In addition, most MQ resins are dispersed in BTX (benzene, toluene, and xylene) type solvents, thus facilitating the use of the process. The condensation process has several drawbacks, such as discoloration or clouding of the adhesive, and the formation of salts / inclusion of residual ions due to the neutralization of the catalyst after condensation.

[0005] The residual catalyst remaining in the system after the synthesis of pressure-sensitive adhesives (PSAs) can cause other problems compared to conventional methods. One problem is the increase in viscosity over time, which can occur due to ongoing condensation hardening caused by the catalyst remaining in the system after synthesis. This increase in viscosity reduces processability and alters the physical properties of the PSA. The residual catalyst in the PSA after synthesis can also cause molecular chain cleavage, which increases the cyclic content of the PSA and, in some applications, contributes to its purity.

[0006] Neutralizing the catalyst is one method for removing it from the adhesive matrix. As a result of neutralization, salts may precipitate, potentially discoloring the adhesive or degrading its optical clarity. Precipitation can also lead to a loss of the adhesive properties of the PSA. Filtration of the precipitate often results in material loss and increased process cycle time.

[0007] Catalysts can also be deactivated using thermal deactivation. Achieving this requires a high energy input, which also increases the process cycle time. [Overview of the Initiative]

[0008] The following is an overview of the disclosure, providing a basic understanding of several embodiments. This overview is not intended to identify any important or essential elements, nor to impose any limitations on the embodiments or claims. Furthermore, this overview may present a simplified outline of several embodiments, which may be described in detail in other parts of the disclosure.

[0009] There is provided a process for forming a pressure-sensitive adhesive. This process is a self-catalytic reaction and is carried out without the assistance of an external condensation catalyst, such as a conventional metal-based or non-metal-based catalyst. This reaction involves reacting a silicone resin with a polyorganosiloxane and a siloxane containing a hydrophilic group selected from an ionic group, an ionizable group, and / or an amphoteric ionic group. A mixture of these substances results in a composition that can be self-catalytic and promoted by heating, and it has been found to provide a cured substance.

[0010] The absence of an external condensation catalyst provides a substance that has a low cyclic siloxane content, exhibits a good adhesion profile, and can have other desirable properties such as, for example, optical transparency (i.e., clear and colorless) and odorlessness.

[0011] In one aspect, there is provided a process for producing a pressure-sensitive adhesive, which includes reacting (i) an MQ silicone resin, (ii) a polyorganosiloxane, and (iii) a siloxane containing a hydrophilic group, where the reaction is carried out in the absence of an external catalyst.

[0012] In one embodiment, the hydrophilic functional group is selected from an ionic group, an ionizable group, an amphoteric ionic group, or a combination of two or more of these.

[0013] In one embodiment according to any of the previous embodiments, the siloxane (iii) containing a hydrophilic group is selected from compounds of the following formula: M 1 a M 2 b M 3 c D 1 d D 2 e D 3 f T 1 g T 2 h T 3 iQ 1 j Q 2 k Q 3 l Q 4 o Q 5 p wherein M 1 =R 5 R 6 R 7 SiO 1 / 2 M 2 =R 8 R 9 R 10 SiO 1 / 2 M 3 =R 11 R 12 R 13 SiO 1 / 2 D 1 =R 14 R 15 SiO 2 / 2 D 2 =R 16 R 17 SiO 2 / 2 D 3 =R 18 R 19 SiO 2 / 2 T 1 =R 20 SiO 3 / 2 T 2 =R 21 SiO 3 / 2 T 3 =R 22 SiO 3 / 2 Q 1 =Si(OR 23 )1O 3 / 2 Q 2 =Si(OR 24 )2O 2 / 2 Q 3 =Si(OR 25 )3O 1 / 2 Q4 =Si(OR 26 )4 Q 5 =SiO 4 / 2 Here: a, b, c, d, e, f, g, h, i, j, k, l, o, and p are zero or any integers, subject to the following constraints: 1 ≦ [a + b + c + d + e + f + g + h + i + j + k + l + o + p] ≦ 6000; [b + e + h + k] ≧ 1; R 5 、R 6 、R 7 、R 9 、R 10 、R 12 、R 13 、R 14 、R 15 、R 17 、R 19 、and R 20 are each independently selected from hydrogen, C1 - C60 alkyl, C6 - C60 aromatic - containing group, C1 - C10 alkoxy, and hydroxyl; R 8 、R 16 、R 21 、and R 24 are each independently selected from monovalent hydrophilic groups of the following formula, where G ≧ 0:

Chemical formula

Chemical formula

[0014] In one embodiment according to any of the previous embodiments, the siloxane containing a hydrophilic group has the formula M 1 a M 2b M 3 c Q 5 p The equation has such that b is ≥ 1.

[0015] In one embodiment according to any of the above embodiments, I is carboxylate-COO - , dicarboxylate (-R(COO-)2), sulfone-SO2-, sulfonate-SO3 - Sulfate-OSO3 - phosphonate-PO3 2- phosphate-OPO3 2- group, -NR 30 R 31 H, -NH2R 32 Selected from , -NH3, or ammonium salts, each containing a cation independently selected from hydrogen or alkali metals, alkaline earth metals, transition metals, quaternary ammonium groups, and phosphonium groups, where R 30 , R 31 , and R 32 These are independently selected from C1-C30 hydrocarbons.

[0016] In one embodiment according to any of the above embodiments, I is formula -R 33 -N + (R 34 )2-R 35 -I z A group is selected from those having R 33 R is a divalent hydrocarbon group having 1 to 20 carbon atoms. 34 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms. 35 is a divalent hydrocarbon group having 2 to 20 carbon atoms; and I z is carboxylate-COO - , sulfone-SO2-, sulfonate-SO3 - Sulfate-OSO3 - phosphonate-PO3 2- , and phosphate-OPO3 2- It is an ionic group selected from the available groups.

[0017] In one embodiment according to any of the preceding embodiments, I is a polar group selected from polyetheramines, polyethers, polyamides, polyesters, polyurethanes, polysulfones, and / or polycarbonates.

[0018] In one embodiment according to any of the above embodiments, the hydrophilic group is a polyetheramine group selected from the following compounds: R 36 -(OR 37 -) q -NH2 R in the formula 36 R is selected from C1-C60 hydrocarbons, 37 q is selected from C1 to C60 hydrocarbons, and q is ≥ 1.

[0019] In one embodiment according to any of the preceding embodiments, the polyetheramine is selected from the following compounds: R 36 -(O-CH2CH2) x -(O-CCH2CH2CH2) y -(OCH2CH2CH(CH3)) z -NH2 Then x, y, and z are independent of each other, ranging from 0 to approximately 300, where x+y+z is ≥ 2.

[0020] In one embodiment according to any of the preceding embodiments, the polyetheramine group is selected by the following general formula: [ka] [ka] [ka] [ka] [ka]

[0021] In one embodiment according to any of the preceding embodiments, the hydrophilic siloxane (iii) is present in an amount of about 0.1% to about 20% by weight based on the total weight of the composition.

[0022] In one embodiment according to any of the preceding embodiments, the hydrophilic siloxane (iii) is present in an amount of about 1.5% to about 8% by weight based on the total weight of the composition.

[0023] In one embodiment according to any of the preceding embodiments, reacting (i), (ii), and (iii) involves first forming a mixture of (i) and (ii), and then adding (iii) to the mixture of (i) and (ii).

[0024] In one embodiment according to any of the preceding embodiments, first forming a mixture of (i) and (ii) involves dispersing MQ silicone (i) in polyorganosiloxane (ii) and heating this first mixture at a temperature of about 80 to about 150°C.

[0025] In one embodiment according to any of the preceding embodiments, the reaction of (i), (ii), and (iii) is carried out at a temperature of about 80 to about 150°C.

[0026] In one embodiment according to any of the preceding embodiments, the process includes removing water from the product obtained from the process to yield a solid substance.

[0027] In one embodiment according to any of the preceding embodiments, the process includes dissolving a solid material in a solvent to obtain a final pressure-sensitive adhesive composition.

[0028] Another embodiment provides a pressure-sensitive adhesive composition obtained from one of the processes of the preceding embodiments.

[0029] In one embodiment, the adhesive contains less than 2500 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

[0030] In one embodiment, the adhesive contains less than 1000 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

[0031] In one embodiment, the adhesive contains less than 500 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

[0032] In one embodiment, the adhesive contains less than 100 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

[0033] In one embodiment, the pressure-sensitive adhesive does not show precipitation after being stored at room temperature for one year.

[0034] The following description discloses various exemplary aspects. Some improvements and novel aspects may be explicitly identified, while others may be evident from the description. [Modes for carrying out the invention]

[0035] Referencing the following exemplary embodiments, examples are illustrated in the accompanying drawings. As will be understood, other embodiments may also be used, and structural and functional modifications may be made. Furthermore, features of various embodiments may be combined or modified. Thus, the following description is presented merely as an example and does not in any way limit the various alternatives or modifications that may be made to the exemplary embodiments. In this disclosure, several specific details will lead to a complete understanding of the disclosed subject matter. It should be understood that embodiments of this disclosure may be carried out in other embodiments, which do not necessarily include all aspects described in this application or elsewhere.

[0036] As used in this application, the terms “example” and “illustration” mean examples or illustrations. The terms “example” or “illustration” do not indicate essential or preferred embodiments or forms. The term “or” is intended to be inclusive, not exclusive, unless the context suggests otherwise. For example, the statement “A uses B or C” includes any inclusive substitution (e.g., A uses B; A uses C; or A uses both B and C). Separately, the articles “one” and “a” are generally intended to mean “one or more,” unless the context suggests otherwise.

[0037] It is understood that the ranges for specific components can be combined to form new, unspecified ranges.

[0038] As used in this application, the term "hydrocarbon radical" generally refers to acyclic, cyclic (or alicyclic), and aromatic hydrocarbons, which may be saturated or unsaturated and may be optionally substituted or interrupted by one or more atoms or functional groups, such as carboxyl, cyano, hydroxyl, halo, and oxy. As understood, this term may include monovalent, divalent, and trivalent radicals, and in the context of combining such radicals within a given formula or structure, the appropriate type of radical is intended.

[0039] As used in this application, the term “acyclic hydrocarbon radical” means a linear or branched hydrocarbon radical, preferably comprising 1 to 60 carbon atoms per radical, which may be saturated or unsaturated, and which may optionally be substituted or interrupted by one or more atoms or functional groups, such as carboxyl, cyano, hydroxy, halo, and oxy. Suitable monovalent acyclic hydrocarbon radicals include, for example, alkyl, alkenyl, alkynyl, hydroxyalkyl, cyanoalkyl, carboxyalkyl, alkyloxy, oxaalkyl, alkylcarbonyloxaalkylene, carboxyamide, and haloalkyl, such as methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl, butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl, and 3,3,3-fluoropropyl.

[0040] As used in this application, the term "alicyclic hydrocarbon radical" means a radical comprising one or more saturated hydrocarbon rings, preferably comprising 4 to 12 carbon atoms per ring and per radical, and optionally, one or more of the rings may be substituted with one or more alkyl radicals, halo radicals or other functional groups, each preferably comprising 2 to 6 carbon atoms per alkyl radical, and in the case of monovalent alicyclic hydrocarbon radicals comprising two or more rings, they may be fused rings. Suitable monovalent alicyclic hydrocarbon radicals include, for example, cyclohexyl and cyclooctyl.

[0041] As used in this application, the term “aromatic hydrocarbon radical” means a hydrocarbon radical containing one or more aromatic rings per radical, where the aromatic rings may optionally be substituted with one or more alkyl radicals, halo radicals, or other functional groups, each preferably containing 2 to 6 carbon atoms per alkyl radical, and in the case of a monocyclic aromatic hydrocarbon radical containing two or more rings, the rings may be fused. Suitable monovalent aromatic hydrocarbon radicals include, for example, phenyl, tolyl, 2,4,6-trimethylphenyl, 1,2-isopropylmethylphenyl, 1-pentalenyl, naphthyl, and anthryl. As used in this application, the term “aralkyl” means an aromatic derivative of an alkyl group, preferably a (C2-C6) alkyl group, where a portion of the alkyl partial aromatic derivative may optionally be interrupted by an oxygen atom, such as phenylethyl, phenylpropyl, 2-(1-naphthyl)ethyl, preferably phenylpropyl, phenoxypropyl, biphenyloxypropyl, etc.

[0042] In the context of this application, viscosity may be evaluated using any suitable method. Unless otherwise specified, viscosity is measured using a Brookfield (DV1) viscometer at 25°C.

[0043] Provided are compositions and processes for producing silicone-based materials. The compositions comprise a mixture of components for producing silicone-based materials, including ionic or amphoteric functional siloxane components. The use of ionic / amphoteric functional siloxanes has been found to result in autocatalytic activity, eliminating the need for external catalysts to produce silicone-based materials. These processes and compositions can be used to produce silicone-based materials, such as silicone pressure-sensitive adhesives. Materials produced from these compositions and processes may exhibit excellent properties, avoiding problems associated with the use of external catalysts, including solution clarity, reduced viscosity increase, low cyclic content, and others.

[0044] The process of the present invention involves reacting a polyorganosiloxane with a silicone resin in the presence of a siloxane containing hydrophilic groups selected from ionic groups, ionizable groups, and / or amphoteric groups. In one embodiment, a solid silicone resin (in the form of an MQ-type resin) is dispersed in a polyorganosiloxane polymer and heated at a temperature of about 40 to about 80°C, about 80 to about 150°C, about 90 to about 125°C, or about 100 to about 110°C. A siloxane containing hydrophilic groups is added to the mixture of polyorganosiloxane and silicone resin and heated for a time sufficient to allow condensation to occur to a selected degree. In this process, no additional catalyst (e.g., metal catalysts such as those conventionally used for addition curing, condensation curing, or other processes) is required to promote condensation and form a cured material.

[0045] To be understood, the condensation between polyorganosiloxane and silicone resin may also be called “bodimentation.” As used in this application, the terms “bodimentation” and “bodimentation” refer to a condensation reaction between the hydroxyl functional groups of the silicone polymer and the hydroxyl functional groups of the silicone resin for increasing molecular weight, crosslinking, or both.

[0046] The composition for forming the silicone material comprises (i) a silicone resin; (ii) a polyorganosiloxane; and (iii) a siloxane containing a hydrophilic group. This composition is substantially free of or completely free of external catalysts. As used in this application, the composition is considered substantially free of external catalysts if it contains 0.1% by weight or less, less than 0.01% by weight, or less than 0.001% by weight of the composition.

[0047] The composition contains a silicone resin (i). This silicone resin is typically called MQ silicone resin or MQ resin, and its formula is R3SiO 1 / 2 The M unit represented by, and the formula SiO 4 / 2 The Q unit is represented by , where R is generally selected from hydrocarbons from C1 to C60. This hydrocarbon can be selected from acyclic radicals, alicyclic radicals, and aromatic radicals. In one embodiment, R is selected from C1-C60 alkyl radicals, C2-C60 unsaturated radicals, C5-C60 alicyclic radicals, and C6-C60 aromatic radicals. In one embodiment, R is selected from C1-C10 alkyl radicals. In one embodiment, R is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, or octyl.

[0048] In one embodiment, each R group is independently selected from monovalent C1-C6 hydrocarbons, C5-C20 alicyclic radicals, C2-C6 olefinic radicals, and C6-C20 aromatic radicals. Suitable examples of monovalent C1-C6 hydrocarbon radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, and hexyl. Suitable examples of alicyclic radicals include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and others. Suitable examples of C2-C6 olefinic radicals include, but are not limited to, vinyl, allyl, and others. Suitable examples of aromatic radicals include, but are not limited to, phenyl. In one embodiment, about 95 to 100% of the R groups are methyl. In one embodiment, substantially all of the R groups are non-unsaturated. In one embodiment, 0 to 0.5 mol% of the R groups in the MQ resin are non-unsaturated.

[0049] MQ resin is mainly formed from such M and Q units, but also contains some residual D units (R2SiO2). 2 / 2 ) and T units (RSiO 3 / 2 ) may contain. Within a given M, D, or T unit, the R groups may be the same or different. Generally, MQ resin contains less than 20 mol% of D and T units, less than 15 mol% of D and T units, less than 10 mol% of D and T units, less than 5 mol% of D and T units, and even less than 1 mol% of D and T units.

[0050] The ratio of M units to Q units in the silicone resin may be approximately 0.2:1 to approximately 1.7:1, approximately 0.4:1 to approximately 1.5:1, approximately 0.6:1 to approximately 1.2:1, or approximately 0.8:1 to approximately 1:1.

[0051] The silicone resin may contain some residual free silanol groups (Si-OH). In one embodiment, the silicone resin may have a silanol content of about 0.5% to about 12.0% by weight, about 0.75% to about 10% by weight, about 1% to about 7.5% by weight, or about 2.5% to about 5% by weight, based on the weight of the silicone resin.

[0052] Silicone resins can also be provided in any suitable form. In embodiments, silicone resins can be provided as a solid, liquid, dispersion, or solution in a solvent.

[0053] In an embodiment, the silicone resin may have a viscosity of about 1 cps to about 10,000 cps, about 10 cps to about 7,500 cps, about 25 cps to about 5,000 cps, about 50 cps to about 2,500 cps, or about 75 cps to about 1,000 cps. In an embodiment, the silicone resin may have a viscosity of about 1 cps to about 100 cps, about 100 to about 1,000 cps, or about 1,000 to about 10,000 cps. The viscosity of the silicone resin may be based on the silicone resin as a liquid; or on the silicone resin in a dispersion or solution, where the solids content of the silicone resin in the dispersion or solution is about 10% to about 98% solids. In one embodiment, the viscosity is based on a solution with about 60% solids.

[0054] Silicone resins can be a single type of silicone resin or a mixture of two or more different types of resins. Different resins can differ in terms of structure, viscosity, molecular weight, ratio of M units to Q units, and other properties.

[0055] MQ resin materials are generally provided or obtained in aromatic, volatile solvents such as BTX-type solvents. The solvent can be removed in any suitable manner. In one embodiment, a solvent-free MQ resin can be provided by removing the solvent via an extrusion process. Such a process is described in U.S. Patent No. 8,017,712, the contents of which are incorporated in whole by reference. In another embodiment, a solvent-free MQ resin can be provided by removing the solvent via a spray-drying process, as described in U.S. Patent No. 5,324,806.

[0056] Polyorganosiloxane (ii) is selected from silanol-terminated polyorganosiloxanes. In one embodiment, polyorganosiloxane (ii) is a silanol-terminated compound having the following formula: [ka] R in the formula 1 is hydroxy(-OH), and R 2 , R 3 , and R 4 The elements are independently selected from C1-C60 hydrocarbons, which may be optionally substituted with one or more halogen atoms, and n+m≧50 at 25°C.

[0057] In one embodiment, R 2 , R 3 , and R 4 The group is independently selected from C1-C60 alkyl, C1-C60 fluoroalkyl, C2-C60 alkenyl, C6-C60 aromatic-containing group, phenyl, aryl, arylalkyl, fluoroalkyl, or two or more combinations thereof. The aromatic-containing compound may include alkylaryl groups, arylalkyl groups, and groups containing two or more aromatic rings that may be separated or fused by bonding, linking groups. In one embodiment, R 2 , R 3 , and R 4These are independently selected from C1-C10 alkyl and C6-30 aromatic, or include two or more combinations thereof. In one embodiment, R 2 R is selected from C1-C10 alkyl groups, 3 is selected from C1-C10 alkyl groups, and R 4 is selected from C6-C30 aromatic groups. In one embodiment, R 2 , R 3 , and R 4 Each of these is methyl. In one embodiment, R 2 and R 3 is methyl, and R 4 It is phenyl.

[0058] Polyorganosiloxane (ii) is available in the following ranges: 300 to 200,000,000, approximately 500 to approximately 150,000,000, approximately 1,000 to approximately 100,000,000, approximately 2,500 to approximately 75,000,000, approximately 5,000 to approximately 50,000,000, approximately 10,000 to approximately 25,000,000, and approximately 20,000. The viscosity may range from approximately 10,000,000, 30,000 to approximately 5,000,000, 50,000 to approximately 1,000,000, 75,000 to approximately 750,000, 100,000 to approximately 500,000, or approximately 250,000 to approximately 400,000 centipoise (cps) at 25°C. The viscosity of polyorganosiloxane(II) can be easily measured using known conventional viscometers and techniques.

[0059] In one embodiment, the polyorganosiloxane(ii) has a viscosity of about 50,000 to about 750,000, about 75,000 to about 500,000, about 100,000 to about 400,000, or about 200,000 to about 300,000 cps.

[0060] As can be understood, polyorganosiloxane(ii) can be provided as a mixture of two or more different polyorganosiloxane compounds. Different polyorganosiloxanes can differ from one another in terms of structure, viscosity, size, and other respects. In one embodiment, polyorganosiloxane(ii) can include a mixture of a first polyorganosiloxane having an alkyl group and a second polyorganosiloxane having an alkyl group and an aromatic group. In one embodiment, polyorganosiloxane(ii) comprises a first polyorganosiloxane having a first viscosity and a second polyorganosiloxane having a second viscosity. In one embodiment, the first polyorganosiloxane has a viscosity greater than 15,000 cps, and the second polyorganosiloxane has a viscosity less than 12,000 cps. In one embodiment, the first polyorganosiloxane has a viscosity of about 15,000 cps to about 1,000,000 cps, about 25,000 cps to about 750,000 cps, about 50,000 cps to about 500,000 cps, or about 75,000 cps to about 250,000 cps; and the second polyorganosiloxane has a viscosity of about 500 cps to about 12,000 cps, about 1,000 cps to about 10,000 cps, about 2,500 cps to about 7,500 cps, or about 3,000 cps to about 5,000 cps.

[0061] The silicone resin (i) may be present in amounts of approximately 40% to approximately 70% by weight, approximately 45% to approximately 65% ​​by weight, or approximately 50% to approximately 55% by weight, based on the total weight of the silicone resin (i) and the polyorganosiloxane (ii). The polyorganosiloxane (ii) may be present in amounts of approximately 30% to approximately 60% by weight, approximately 35% to approximately 55% by weight, or approximately 45% to approximately 50% by weight, based on the total weight of the silicone resin (i) and the polyorganosiloxane (ii).

[0062] The composition comprises a siloxane containing a hydrophilic group. The siloxane containing a hydrophilic group can be selected from hydrophilic functionalized silicone resins (e.g., MQ-type resins) and / or hydrophilic functionalized polyorganosiloxanes. The hydrophilic functional group can be selected from ionic groups, ionizable groups, or amphoteric functional groups.

[0063] In the context of this application, the term "ionizable group" refers to a group that can form an ionic group.

[0064] In one embodiment, the functionalized siloxane is a compound of the following formula: M 1 a M 2 b M 3 c D 1 d D 2 e D 3 f T 1 g T 2 h T 3 i Q 1 j Q 2 k Q 3 l Q 4 o Q 5 p During the ceremony M 1 =R 5 R 6 R 7 SiO 1 / 2 M 2 =R 8 R 9 R 10 SiO 1 / 2 M 3 =R 11 R 12 R 13 SiO 1 / 2 D 1 =R 14 R15 SiO 2 / 2 D 2 =R 16 R 17 SiO 2 / 2 D 3 =R 18 R 19 SiO 2 / 2 T 1 =R 20 SiO 3 / 2 T 2 =R 21 SiO 3 / 2 T 3 =R 22 SiO 3 / 2 Q 1 =Si(OR 23 )1O 3 / 2 Q 2 =Si(OR 24 )2O 2 / 2 Q 3 =Si(OR 25 )3O 1 / 2 Q 4 =Si(OR 26 )4 Q 5 =SiO 4 / 2 Here:

[0065] a, b, c, d, e, f, g, h, i, j, k, l, o, and p are each independently chosen from zero or any positive integer, subject to the following constraints:

[0066] 1≦[a+b+c+d+e+f+g+h+i+j+k+l+o+p]≦6000;

[0067] [b+e+h+k]≧1;

[0068] R 5 , R 6 , R 7 , R 9 , R 10 , R 12, R 13 , R 14 , R 15 , R 17 , R 19 , and R 20 Each of these is independently selected from hydrogen, C1-C60 alkyl, C6-C60 aromatic-containing group, C1-C10 alkoxy, and hydroxyl;

[0069] R 8 , R 16 , R 21 , and R 24 Each is independently selected from the monovalent hydrophilic groups of the following equation, where G≧0:

[0070] [ka]

[0071] Here, A is a crosslinking unit between the siloxane moiety and the hydrophilic group I, having at least one spacer atom selected from C1-C60 acyclic hydrocarbon radicals, C4-C60 alicyclic radicals, C6-C60 aromatic hydrocarbon radicals, polyetheramines, polyethers, polyamides, polyesters, polyurethanes, polysulfones, polycarbonates, or two or more combinations thereof, where the crosslinking unit may contain one or more parts selected from alkoxys, carboxyls, urethanes, ureas, ketones, or two or more combinations thereof;

[0072] I is an ionic group, an ionizable group, an amphoteric group, or a polar hydrophilic group or moiety;

[0073] G is a polymerizable group having the following general formula:

[0074] [ka]

[0075] Formula --FK nonpolymerizable group, where F is a linking group selected from C1-C60 acyclic hydrocarbon radicals, C4-C60 alicyclic radicals, C6-C60 aromatic hydrocarbon radicals, polyetheramines, polyethers, polyamides, polyesters, polyurethanes, polysulfones, polycarbonates, or two or more combinations thereof, where the crosslinking group may include one or more parts selected from alkoxys, carboxyls, urethanes, ureas, ketones, or two or more combinations thereof;

[0076] R 27 , R 28 , and R 29 These are independently selected from hydrogen or a monovalent hydrocarbon radical with 1 to 5 carbon atoms, and

[0077] K is independently selected from hydrogen, C1-C60 acyclic hydrocarbon radicals, C4-C60 alicyclic radicals, C6-C60 aromatic hydrocarbon radicals, epoxy groups, or ether groups;

[0078] R 11 , R 18 , and R 22 Each is independently selected from the base-AG, where A and G are as described above; and

[0079] R 23 , R 25 , and R 26 is R 5 From R 22 Alternatively, these combinations can be selected independently.

[0080] In one embodiment, A is a C1-C10 alkyl, C1-C10 cycloalkyl, or C6-C12 aromatic group. In one embodiment, A is a C1-C4 alkyl. As can be understood, depending on whether G is 0 or 1, the radical A is divalent or trivalent.

[0081] If I is an ionic group or an ionizable group, then I is a carboxylate-COO- , dicarboxylate (-R(COO-)2), sulfone-SO2-, sulfonate-SO3 - Sulfate-OSO3 - phosphonate-PO3 2- phosphate-OPO3 2- group, -NR 30 R 31 H, -NH2R 32 An acid or base selected from , -NH3, or ammonium salts, each containing a cation independently selected from hydrogen or alkali metals, alkaline earth metals, transition metals, quaternary ammonium groups, and phosphonium groups, where R 30 , R 31 , and R 32 These are independently selected from C1-C30 hydrocarbons.

[0082] If I is an amphoteric moiety, the amphoteric group moiety is selected from groups that include anionic and cationic groups in the covalently bonded compound and whose total charge is neutralized. In one embodiment, the amphoteric group is of formula -R 33 -N + (R 34 )2-R 35 -I z A group having R is selected, where R 33 R is a divalent hydrocarbon group having 1 to 20 carbon atoms. 34 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms. 35 is a divalent hydrocarbon group having 2 to 20 carbon atoms; and I z is carboxylate-COO - , sulfone-SO2-, sulfonate-SO3 - Sulfate-OSO3 - phosphonate-PO3 2- , and phosphate-OPO3 2- It is an ionic group selected from the available groups.

[0083] In one embodiment, I is a polar group or polar moiety. A polar group or polar moiety refers to a group that is not inherently ionizable or ionic but contains a heteroatom that makes the group polar. Although not bound by any particular theory, a polar group may act as a hydrogen bond acceptor, and a group having a hydrogen atom directly bonded to a heteroatom may further act as a hydrogen bond donor. Suitable examples of polar groups or polar moieties include, but are not limited to, polyetheramines, polyethers, polyamides, polyesters, polyurethanes, polysulfones, and / or polycarbonates.

[0084] In one embodiment, the hydrophilic group is selected from polyetheramines. The polyetheramine can be selected from compounds comprising an amine group and at least one polyalkylene oxide group. In one embodiment, the polyetheramine is selected from compounds of the following formula:

[0085] R 36 -(OR 37 -) q -NH2

[0086] R in the formula 36 R is selected from C1-C60 hydrocarbons, 37 is selected from C1 to C60 hydrocarbons, and q is ≥ 1. In one embodiment, R 36 and R 37 R is independently selected from C1-C60 alkyl, C4-C30 cycloalkyl, and C6-C30 aromatic groups, where R 36 and R 37 It can optionally contain amine functional groups. In one embodiment, R 36 and R 37 R is independently selected from C1-C10 alkyl, C4-C10 cycloalkyl, and C6-C20 aromatic groups, where R 36 and R 37The amine functional group may optionally be included. In one embodiment, q is 1 to about 200, about 4 to about 100, about 10 to about 50, or about 20 to about 40. In one embodiment, q is 2 to about 40, about 4 to about 30, about 6 to about 25, about 8 to about 20, or about 10 to about 15.

[0087] In one embodiment, the polyetheramine is selected from the following compounds:

[0088] R 36 -(O-CH2CH2) x -(O-CCH2CH2CH2) y -(OCH2CH2CH(CH3)) z -NH2

[0089] R in the formula 36 As stated above, x, y, and z are independent of each other, ranging from 0 to approximately 300, where x+y+z is ≥ 2.

[0090] Some suitable polyetheramines include, but are not limited to, the following: [ka] [ka] [ka] [ka] [ka]

[0091] In one embodiment, the hydrophilic siloxane (iii) is selected from MD-type polyorganosiloxanes. In one embodiment, the functionalized siloxane (iii) is selected from MQ-type silicone resins, and one or more M having the hydrophilic functional groups described above. 2 It contains a group. In embodiments where the functionalized siloxane(iii) is an MQ-type resin, the hydrophilic siloxane is of formula M 1 a M 2 b M 3 c Q 5 p It can be such that b ≥ 1.

[0092] Siloxane(iii) containing hydrophilic groups can be a solid, a liquid, a dispersion, or a solution in a solvent.

[0093] Siloxane(iii) containing hydrophilic groups can, in embodiments, have viscosities of 1 cps to about 10,000 cps, about 10 cps to about 7,500 cps, about 25 cps to about 5,000 cps, about 50 cps to about 2,500 cps, or about 75 cps to about 1,000 cps. Siloxane(iii) containing hydrophilic groups can, in embodiments, have viscosities of about 1 cps to about 100 cps, about 100 cps to about 1,000 cps, or about 1,000 cps to about 10,000 cps. The viscosity of siloxane containing hydrophilic groups can be based on siloxane as a liquid; or siloxane in a dispersion or solution, where the solids content of siloxane containing hydrophilic groups in a dispersion or solution is about 10% to about 98% solids. In one embodiment, the viscosity is based on siloxane as a liquid.

[0094] Siloxane(iii) containing a hydrophilic group may be present in amounts of about 0.1% to about 20% by weight, about 0.5% to about 15% by weight, about 1% to about 10% by weight, about 2% to about 8% by weight, or about 3% to about 5% by weight, based on the total weight of the composition.

[0095] Siloxanes containing hydrophilic groups are prepared by the reaction of an olefin supporting at least one polar group with a silyl hydride in the presence of a hydrosilylation catalyst.

[0096] Silyl hydrides are selected from silicon-containing compounds that include at least one -SiH group. This -SiH group can be part of the M, D, or T unit of a siloxane. In one embodiment, silyl hydrides are selected when the -SiH is part of an M unit bonded to a Q unit. As used in this application, M is of the formula R3SiO 1 / 2 D represents the monofunctional group of the formula R2SiO 2 / 2 It represents a difunctional group, and T is in the formula RSiO 3 / 2 Q represents the trifunctional group of the formula SiO 4 / 2 This represents the tetrafunctional group.

[0097] Some non-limiting examples of silyl hydrides include pentamethyldisiloxane, e.g., P1535; tetramethyldisiloxane, e.g., T1437; heptamethyltrisiloxane, e.g., H1267; and tris(trimethylsiloxy)silane, e.g., T3520, all available from TCI; polymethylhydrosiloxanes include HMS-082, HMS-501, HPM-502, 65HMS-992, and HMS-064, all available from Gelest; polyhydrosilsesquioxanes, octakis(dimethylsiloxy)-T8-silsesquioxane, e.g., SiO6696.5 from Gelest; and other hydride-containing copolymers or homopolymers of dimethylsiloxane or phenyl-containing siloxanes, e.g., HDP-111-hydride-terminated poly-15phenyl(dimethylhydrosiloxy)siloxane, all available from Gelest.

[0098] Other examples of silyl hydride agents include, but are not limited to, Q resins, which may be referred to as MQ hydride or hydride-modified silica Q resin. These silyl hydrides have an activity of 1 to 25 equivalents / kg. Examples of these compounds, but are not limited to, those commercially available under the following trade names: MQH-9 (Milliken), which is a hydride-modified silica Q resin characterized by a molecular weight of 900 g / mol and an activity of 9.5 equivalents / kg; HQM-105 (Gelest), which is a hydride-modified silica Q resin characterized by a molecular weight of 500 g / mol and an activity of 8 to 9 equivalents / kg; and HQM-107 (Gelest), which is a hydride-modified silica Q resin characterized by a molecular weight of 900 g / mol and an activity of 8 to 9 equivalents / kg.

[0099] The solids content of the resulting pressure-sensitive adhesive can be adjusted as desired using a suitable solvent. The solids content of the pressure-sensitive adhesive can be selected as desired depending on the specific purpose or intended use. In one embodiment, the solids content of the pressure-sensitive adhesive can be adjusted from about 30% to about 80%, from about 40% to about 70%, or from about 50% to about 60%. The solvent is preferably a non-aromatic solvent, and more preferably a solvent other than a BTX (benzene, toluene, xylene) type solvent. Examples of suitable solvents that may be used to dissolve the pressure-sensitive adhesive include, but are not limited to, hydrocarbon solvents, silicone solvents, amides, esters, ketones, alcohols, or ethers. The solvent can be a natural or synthetic substance.

[0100] Suitable examples of aliphatic hydrocarbons include linear, branched, or cyclic aliphatic hydrocarbons having 6 to 16 carbon atoms, such as saturated acyclic aliphatic hydrocarbons (paraffins) like heptane, hexane, octane, isooctane, decane, and dodecane, and their isomers such as isodecane, isohexadecane, dodecene, or isododecane, as well as cyclic aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, or decahydronaphthalene, but not limited to these. The aliphatic hydrocarbon solvent can be an alkene, such as hebutene, cyclohexadiene, cyclohexene, or 2,5-dimethyl-2,4-hexadiene. Mixtures of aliphatic hydrocarbons are also suitable, such as the trademark ISOPAR. 登録商標 There are mixtures of branched-chain paraffins sold under the heading. Other suitable materials include natural terpenes, such as, but are not limited to, pinene isomers, myrcene, bisabolene, cadinene, and others.

[0101] Examples of suitable volatile silicone solvents include, but are not limited to, linear, branched, and cyclic polydiorganosiloxanes, such as linear trimethylsilyl-terminated polydimethylsiloxanes having viscosities of 0.65 to 5 cP at 25°C, and cyclic polydimethylsiloxanes such as decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane. Volatile silicone solvents may contain organic groups other than methyl, such as higher alkyl or phenyl groups. One example is 3-octylheptamethyltrisiloxane. In one embodiment, viscosity is determined by dissolving the resulting PSA molten material in a suitable solvent with a solid content of 60% and measuring the viscosity at 25°C using a Brookfield (DV1) viscometer.

[0102] Suitable ester solvents include, but are not limited to, carboxylate esters, such as alkyl carboxylate esters, and carbonate esters, such as alkyl carbonate esters. For example, volatile solvents may include at least one C1-C8 alkyl ester of a C2-C4 carboxylic acid, such as ethyl acetate or butyl acetate. Suitable carbonate ester solvents include, but are not limited to, diethyl carbonate and dicaprylyl carbonate.

[0103] Suitable ketone solvents include, but are not limited to, methyl isobutyl ketone (4-methyl-2-pentanone), 2-pentanone, 3-hexanone, methyl isoamyl ketone (5-methyl-2-hexanone), camphor, menthone, carvone, pulegone, and others.

[0104] Suitable ether solvents include, but are not limited to, dibutyl ether, volatile polyethers such as 1-(propoxymethoxy)propane, and cyclic ethers such as cyclopentamethyl ether.

[0105] Suitable alcohol solvents include, but are not limited to, methanol, ethanol, propanol, butanol, cis-3-hexanol, trans-2,cis-6-nonadienol, cis-6-noneol, linalool, geraniol, nerol, citronellol, nerolidol, farnesol, benzyl alcohol, phenylethyl alcohol, cinnamyl alcohol, citronellol, hydroxycitronellol, linalool, dihydrolinalool, tetrahydrolinalool, ethyllinalool, geraniol, nerol, tetrahydrogeraniol, myrcenol, dihydromyrcenol, tetrahydromyrcenol, osimenol, terpineol, menthol, borneol, phenethyl alcohol, farnesol, nerolidol, cedrol, terpineol, and others.

[0106] The silicone pressure-sensitive adhesives prepared by the method of this invention readily adhere to and support solid supports or substrates, whether flexible or rigid. These pressure-sensitive adhesive compositions may be applied to the bonding surface by any suitable means, such as rolling, spreading, or spraying. The surface of the support and the substrate to which the support is bonded may be any known solid material, such as metal, paper, wood, leather, textiles, organic polymer materials, painted surfaces, siliceous materials such as concrete, brick, concrete blocks, and glass cloth. After application to the surface, the adhesive may be cured by air drying or by heating at a temperature of, for example, up to 300°C.

[0107] In addition, the pressure-sensitive adhesive produced by this technology may exhibit a low concentration of cyclic siloxanes. In embodiments, the pressure-sensitive adhesive contains one or more of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), or dodecamethylcyclohexasiloxane (D6) in amounts of less than 2500 ppm, less than 2000 ppm, less than 1800 ppm, less than 1500 ppm, less than 1250 ppm, less than 1000 ppm, less than 750 ppm, less than 500 ppm, less than 250 ppm, and even less than 100 ppm. In one embodiment, the pressure-sensitive adhesive contains each of the cyclic siloxanes D4, D5, or D6 in amounts less than 2500 ppm, less than 2000 ppm, less than 1800 ppm, less than 1500 ppm, less than 1250 ppm, less than 1000 ppm, less than 750 ppm, less than 500 ppm, less than 250 ppm, and even less than 100 ppm.

[0108] In one embodiment, the pressure-sensitive adhesive composition does not show precipitation after being stored at room temperature for one year. In pressure-sensitive adhesives prepared using an external catalyst, precipitation may occur due to insufficient neutralization of the catalyst after condensation and subsequent filtration. In this embodiment of the art, the pressure-sensitive adhesive does not show precipitation even after being stored at room temperature for one year. That is, the pressure-sensitive adhesive composition may remain homogeneous even after being stored at room temperature for one year.

[0109] This technology has been described in the above detailed description with reference to various aspects and embodiments. This technology may be further understood by referring to the following examples. The examples are intended to further illustrate aspects and embodiments of this technology and are not necessarily limited to such aspects or embodiments.

[0110] Examples

[0111] MQ silicone resin

[0112] Solid MQ silicone resins used in the preparation of PSA. The solid MQ silicone resins used for the preparation of the pressure-sensitive adhesive had silanol content ranging from 95,473 ppm to 47,746 ppm. The MQ resins used are referred to as MQ1 resin (silanol content 95,473 ppm), MQ2 resin (silanol content 47,746 ppm), MQ3 resin (silanol content 56,642 ppm), and MQ4 resin (silanol content 80,722 ppm).

[0113] Polyorganosiloxane rubber

[0114] Ingredients 1-3

[0115] Components 1, 2, and 3 describe polyorganosiloxane rubber according to the aspects and embodiments of the present invention, and also describe properties such as molecular weight (MW) and cyclic siloxane content.

[0116] The mass quantities (MWs) of the components, examples, and comparative examples were determined by gel filtration chromatography (GPC) using chloroform solvent and calibrated using polystyrene standards. The viscosity of the components, examples, and comparative examples was determined at 25°C using a Brookfield (DV1) viscometer with spindles #2 to #6. The cyclic siloxane content of the components, examples, and comparative examples was quantified using gas chromatography.

[0117] The polyorganosiloxane rubbers of components 1 to 3 are listed in Table 1 below:

[0118] [Table 1]

[0119] 4 siloxane components containing hydrophilic groups

[0120] Dicarboxylate polydimethylsiloxane was prepared as described in Synthesis Example 1 of EP3280496A1.

[0121] Ingredient 5

[0122] Potassium salt of dicarboxylate polydimethylsiloxane

[0123] Ingredient 6

[0124] 4-((2-(methacryloyloxy)-4-ethylcyclohexyl)oxy)-4-oxobutyrate-functionalized polydimethylsiloxane was prepared as described in Synthesis Example 5 of WO2018 / 152392A1.

[0125] Ingredient 7

[0126] Silsoft TM BAPD fluid, aminopolydimethylsiloxane, was used as component 7.

[0127] Ingredient 8

[0128] MQH-9, or MQ hydride (100 grams), was introduced into a 500 mL three-necked round-bottom flask equipped with a water condenser, a thermo-pocket, and a dropping funnel, while sparging nitrogen into the flask. The dropping funnel was filled with allyl succinic anhydride (CAS No. 7539-12-0) (72.2 g). The contents of the round-bottom flask were heated to 85°C, and 7.22 g of allyl succinic anhydride was added to the flask. To this mixture, 10 ppm of Karstedt catalyst (CAS No. 68478-92-2) was added, followed by the addition of the remaining allyl succinic anhydride from the dropping funnel dropwise. The reaction was allowed to proceed for 4 to 5 hours. Next, triisopropoxy(vinyl)silane (CAS No. 18023-33-1) (119.8 g) was poured into a dropping funnel and added dropwise to a round-bottom flask, and the reaction was allowed to proceed again for 4 to 5 hours. After the reaction, the round-bottom flask was cooled to 50°C and held under vacuum for 2 hours to obtain ionic MQ resin. The ionic MQ resin was analyzed using GPC and showed a single-peaked resin peak.

[0129] Ingredient 9

[0130] MQH-9, or MQ hydride (100 grams), was introduced into a 500 mL three-necked round-bottom flask equipped with a water condenser, a thermo-pocket, and a dropping funnel, while sparging nitrogen into the flask. The dropping funnel was filled with vinylcyclohexene oxide (CAS No. 106-86-5) (64.0 g). The contents of the round-bottom flask were heated to 85°C, and 6.4 g of vinylcyclohexene oxide was added to the flask. To this mixture, 10 ppm of Karstedt catalyst (CAS No. 68478-92-2) was added, followed by the addition of the remaining vinylcyclohexene oxide in the dropping funnel dropwise. The reaction was allowed to proceed for 4 to 5 hours. Next, triisopropoxy(vinyl)silane (CAS No. 18023-33-1) (119.8 g) was poured into a dropping funnel and added dropwise to a round-bottom flask, and the reaction was allowed to proceed again for 4 to 5 hours. After the reaction, the round-bottom flask was cooled to 50°C, Jeffamine M-600 (CAS No. 83713-01-3) (300.93 g) was added, and the reaction was allowed to proceed for 24 hours. After 24 hours, the contents of the round-bottom flask were held under vacuum for 2 hours to obtain a polyether-functionalized MQ resin. The polyether-functionalized MQ resin was analyzed using GPC and showed a single-peaked resin peak.

[0131] Ingredient 10

[0132] Ethylene glycol monoallyl ether (CAS No. 111-45-5) (100 g), N,N-dimethylcarbamilcloride (CAS No. 79-44-7) (115.83 g), and 4-(dimethylamino)pyridine (CAS No. 1122-58-3) (5.98 g) were placed in a two-necked round-bottom flask equipped with a condenser and a thermo-pocket. The contents of the round-bottom flask were heated to 80°C, and the reaction was allowed to proceed for 24 hours to synthesize 2-allyloxyethyl N,N-dimethylcarbamate. This product was dissolved in hexane and washed with a 1N HCl solution, followed by 1N sodium bicarbonate and saturated brine. The organic phase was dried over anhydrous sodium sulfate, and then hexane was removed by vacuum distillation. 200 g of 2-allyloxyethyl N,N-dimethylcarbamate was obtained.

[0133] MQH-9, or MQ hydride (100 grams), was introduced into a 1000 mL three-necked round-bottom flask equipped with a water condenser, a thermo-pocket, and a dropping funnel, while sparging nitrogen. The dropping funnel was filled with 2-allyloxyethyl N,N-dimethylcarbamate (89.3 g). The contents of the round-bottom flask were heated to 85°C, and 8.9 g of 2-allyloxyethyl N,N-dimethylcarbamate was added to the round-bottom flask. To this mixture, 10 ppm of Karstedt catalyst (CAS No. 68478-92-2) was added, followed by the addition of the remaining 2-allyloxyethyl N,N-dimethylcarbamate from the dropping funnel dropwise. The reaction was allowed to proceed for 4 to 5 hours. Next, triisopropoxy(vinyl)silane (CAS No. 18023-33-1) (119.8 g) was poured into a dropping funnel and added dropwise to a round-bottom flask, and the reaction was allowed to proceed again for 4 to 5 hours. After the reaction, the round-bottom flask was cooled to 50°C. Tetrahydrofuran (CAS No. 109-99-9) (300 mL) and chloroacetic acid (CAS No. 79-11-8) (48.7 g) were added to the round-bottom flask, and the reaction was allowed to proceed for 24 hours. Tetrahydrofuran was removed under reduced pressure distillation to obtain an amphoteric MQ resin. The amphoteric MQ resin was analyzed using GPC and showed a monomodal resin peak.

[0134] Preparation of silicone PSA

[0135] Example 1

[0136] Polyorganosiloxane Component 1 (52.07 g) and polyorganosiloxane Component 2 (52.07 g) were placed in a 3-liter planetary mixer equipped with helical blades and a heating device, thermocouple, and sparge tube (for nitrogen sparging), followed by the addition of MQ3 (171.84 g), or the order was reversed. The reactor temperature was initially set to 125-130°C under a positive nitrogen flow. The above mixture was stirred at a final temperature of 135-145°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1-4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 12 g (4%) RD x Component 4 of the -R type (where R=11-carboxy-1-undecyl, D=Me2SiO, and x=90) was added, and the reaction was continued for a further 7 hours. The reactor temperature was maintained at 145°C under vacuum for 1 to 2 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 grams) at 50°C to adjust the solid content to 60%. The viscosity of the PSA was 1904 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0137] Example 2

[0138] Component 2, polyorganosiloxane (104 g), was placed in a 3-liter planetary mixer equipped with helical blades and a heating device, thermocouple, and sparge tube (for nitrogen sparging), followed by the addition of MQ3 (171.0 g), or the order was reversed. The reactor temperature was initially set to 125–130°C under a positive nitrogen flow. The mixture was stirred at 135–145°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1–4 hours until the MQ resin was completely dissolved or dispersed in the rubber mixture. 24 g (8%) of component 4 was added, and the reaction was continued for a further 7 hours. The reactor temperature was maintained at 145°C under vacuum for 1–2 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 g) at 50°C to adjust the solids content to 60%. The viscosity of PSA was 460 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0139] Example 3

[0140] 52.07 grams of the polyorganosiloxane of Component 1 and 52.07 grams of the polyorganosiloxane of Component 2 were placed into a 3-liter planetary mixer equipped with a helical blade, a heating device, a thermocouple, and a sparge tube (for nitrogen sparging), and then MQ3 (171.84 grams) was added, or the order was reversed. The temperature of the reactor was initially set to 125 - 130 °C under a positive nitrogen flow. The above mixture was stirred at 135 - 145 °C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1 - 4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 24 grams (8%) of Component 4 was added and then the reaction was continued for an additional 7 hours. The temperature of the reactor was maintained at 145 °C under vacuum for 1 to 2 hours. After this reaction step, the reactor was cooled. Then the resulting highly viscous mass was dissolved in 40 parts of ethyl acetate (~200 grams) at 50 °C to adjust the solid content to 60%. The viscosity of the PSA was 1200 cP at 25 °C and had peaks of a multi-modal resin and polymer by GPC.

[0141] Example 4

[0142] Component 2 polyorganosiloxane (52.07 g) and Component 3 polyorganosiloxane (52.07 g) were placed in a 3-liter planetary mixer equipped with helical blades and a heating device, thermocouples, and sparge tubes (for nitrogen sparging), followed by the addition of MQ3 (171.84 g), or the order was reversed. The reactor temperature was initially set to 125–130°C under a positive nitrogen flow. The above mixture was stirred at 135–145°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1–4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 24 g (8%) of Component 4 was added, and the reaction was continued for a further 7 hours. The reactor temperature was maintained at 145°C under vacuum for 2 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 grams) at 50°C to adjust the solid content to 60%. The viscosity of the PSA was 1200 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0143] Example 5

[0144] Component 2, polyorganosiloxane (115.2 g), was placed in a 3-liter planetary mixer equipped with helical blades and a heating device, thermocouple, and sparge tube (for nitrogen sparging), followed by the addition of MQ3 (172.8 g), or the order was reversed. The reactor temperature was initially set to 125–130°C under a positive nitrogen flow. The mixture was stirred at 135–145°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1–4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 12 g (4%) of component 5 was added, and the reaction was continued for a further 7 hours. The reactor temperature was maintained at 145°C under vacuum for 2 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 g) at 50°C to adjust the solids content to 60%. The viscosity of PSA was 408 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0145] Example 6

[0146] 115.2 grams of the polyorganosiloxane of Component 2 was placed into a 3-liter planetary mixer equipped with a helical blade, heating device, thermocouple, and a sparge tube (for nitrogen sparging), and subsequently MQ3 (172.8 grams) was added, or the order was reversed. The temperature of the reactor was initially set to 125 - 130 °C under a positive nitrogen flow. Finally, the above mixture was stirred at 135 - 145 °C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1 - 4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 12 grams (4%) of Component 6 was added, and then the reaction was continued for an additional 7 hours. The temperature of the reactor was maintained at 145 °C under vacuum for 2 hours. After this reaction step, the reactor was cooled. Subsequently, the resulting highly viscous mass was dissolved in 40 parts of ethyl acetate (~200 grams) at 50 °C to adjust the solid content to 60%. The viscosity of the PSA was 330 cP at 25 °C and had peaks of a multi-modal resin and polymer by GPC. Reference is made to a radical catalyst for acrylate polymerization.

[0147] Example 7

[0148] Component 2, polyorganosiloxane (36 g), was placed in a 3-liter planetary mixer equipped with helical blades and a heating device, thermocouple, and sparge tube (for nitrogen sparging), followed by the addition of MQ4 (54 g), or the order was reversed. The reactor temperature was initially set to 125–130°C under a positive nitrogen flow. The mixture was stirred at 135–145°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1–4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 3.6 g (4%) of component 7 was added, and the reaction was continued for a further 12 hours. The reactor temperature was maintained at 145°C under vacuum for 2 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 g) at 50°C to adjust the solids content to 60%. The viscosity of PSA was 256 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0149] Example 8

[0150] Components 2 (18 g) and 3 (18 g), followed by MQ4 (54 g) in heptane (36 g), were added to a glass reactor equipped with a helical blade, heating device, thermocouple, sparge tube (for nitrogen sparging), and a Dean-Stark water trap filled with heptane. The mixture was homogeneously mixed under a positive nitrogen stream at 90°C for 3 hours. 3.6 g (4%) of component 4 was added, and the reaction was continued for 12 hours. The reaction temperature was increased to 110°C, and the mixture was refluxed until the last drop of water was observed. The resulting PSA was obtained in heptane solution. The viscosity of the PSA was 162 cP at 25°C, and GPC showed multimodal resin and polymer peaks.

[0151] Example 9

[0152] In a glass reactor equipped with helical blades, a heating device, thermocouples, sparge tubes (for nitrogen sparging), and a Dean-Stark water trap filled with heptane, 16.98 grams of polyorganosiloxane component 1 and 16.98 grams of polyorganosiloxane component 2 were added, followed by the addition of MQ4 (53.79 grams), or the order was reversed. The reactor temperature was initially set to 125-130°C under a positive nitrogen flow. This mixing process was continued overnight until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 2.25 grams of component 8 were added, and the reaction was continued for a further 12 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 grams) at 50°C to adjust the solids content to 60%. The viscosity of PSA was 461 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0153] Example 10

[0154] In a glass reactor equipped with helical blades, a heating device, thermocouples, sparge tubes (for nitrogen sparging), and a Dean-Stark water trap filled with heptane, 38.30 grams of polyorganosiloxane (component 2) were added, followed by 49.45 grams of MQ4 (component 49.45 grams), or the order was reversed. The reactor temperature was set to 125–130°C under a positive nitrogen flow. This mixing process was continued overnight until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 2.25 grams (2.5%) of component 9 were added, and the reaction was continued for a further 7 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 grams) at 50°C to adjust the solids content to 60%. The viscosity of the PSA was 365 cP at 25°C and showed multi-modal resin and polymer peaks by GPC.

[0155] Example 11

[0156] In a glass reactor equipped with helical blades, a heating device, thermocouples, sparge tubes (for nitrogen sparging), and a Dean-Stark water trap filled with heptane, 16.98 grams of polyorganosiloxane component 1 and 16.98 grams of polyorganosiloxane component 2 were added, followed by the addition of MQ4 (53.79 grams), or the order was reversed. The reactor temperature was set to 125-130°C under a positive nitrogen flow. This mixing process was continued overnight until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 2.25 grams (2.5%) of component 10 were added, and the reaction was continued for a further 7 hours. The reactor temperature was maintained at 145°C under vacuum. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 grams) at 50°C to adjust the solids content to 60%. The viscosity of PSA was 556 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0157] Comparative Example 1

[0158] In a 3-liter planetary mixer equipped with helical blades and a heating device, thermocouples, and sparge tubes (for nitrogen sparging), Component 2 polyorganosiloxane (127.34 g) was added, followed by MQ3 (172.65 g), or the order was reversed. The reactor temperature was set to 125-130°C under a positive nitrogen flow. The mixture was stirred at 125-130°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1-4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 2.0 g of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane (CAS-No: 5505-72-6) was added, and the reaction was continued for a further 3 hours. Finally, the reactor temperature was raised to 150°C and maintained under nitrogen for 2-3 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~200 grams) at 50°C to adjust the solid content to 60%. The viscosity of the PSA was 1664 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0159] Comparative Example 2

[0160] In a 3-liter planetary mixer equipped with helical blades, a heating device, a thermocouple, and sparge tubes (for nitrogen sparging), 287.23 grams of polyorganosiloxane component 1 and 95.74 grams of polyorganosiloxane component 3 were added, followed by the addition of MQ3 (517.02 grams), or the order was reversed. The reactor temperature was set to 125–130°C under a positive nitrogen flow. The mixture was stirred at 125–130°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1–4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 7.5 grams of tetramethylammonium siloxanolate (CAS-No. 68440-88-0) was added, and the reaction was continued for a further 3 hours. Finally, the reactor temperature was raised to 150°C and maintained under nitrogen for 2–3 hours. After this reaction step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~600 grams) at 50°C to adjust the solid content to 60%. The viscosity of the PSA was 15900 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0161] Comparative Example 3:

[0162] In a 3-liter planetary mixer equipped with helical blades and a heating device, thermocouples, and sparge tubes (for nitrogen sparging), 18 grams of polyorganosiloxane component 2 and 18 grams of polyorganosiloxane component 3 were added, followed by 54 grams of MQ4, or the order was reversed. The reactor temperature was set to 125-130°C under a positive nitrogen flow. The mixture was stirred at 125-130°C until a completely homogeneous solution / dispersion was obtained. This mixing process was continued for 1-4 hours until the MQ resin was completely dissolved or dispersed in the polyorganosiloxane. 0.45 grams (0.5%) of acetic acid (CAS-No. 64-19-7) was added, and the reaction was continued for a further 7 hours. A neutralization step was carried out at 70°C using 1% lithium hydroxide in ethanol. After this step, the reactor was cooled. The resulting highly viscous mass was then dissolved in 40 parts ethyl acetate (~600 grams) at 50°C to adjust the solid content to 60%. The viscosity of the PSA was 406 cP at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0163] Comparative Example 4

[0164] In a 1-liter planetary mixer equipped with a helical blade, heating device, thermocouple, sparge tube (for nitrogen sparging), and a Dean-Stark water trap filled with heptane, solutions of component 1 (76.59 g) and component 3 (25.53 g) were added along with 60% MQ3 (229.78 g) in heptane, and 68.1 g of heptane was added. This mixture was homogenously mixed under a positive nitrogen stream at 90°C for 3 hours. 1.5 g of 1% lithium hydroxide solution was added, and the reaction was continued for a further 3 hours. The reaction temperature was raised to 110°C, and the mixture was refluxed until the last drop of water was observed. A neutralization step was carried out at 70°C using 1% phosphoric acid in IPA. Finally, the heptane solvent was removed using a rotary evaporator, and the mixture was redissolved in ethyl acetate. The viscosity of the PSA was 9700 cP in ethyl acetate at 25°C, and GPC showed multi-modal resin and polymer peaks.

[0165] Estimation of Silanol Content

[0166] The silanol content was 29 determined using Si nuclear magnetic resonance technology.

[0167] Experimental Method:

[0168] Samples were prepared by adding ~2 g of the sample to 3 mL of CDCl3. 30 mg of Cr(acac)3 was added as a relaxant. 2.5 mL of the sample solution was transferred to a 10 mm Teflon tube, 29 and Si spectra were obtained. The mole % was obtained by integrating all the peaks of the NMR spectrum and converted to weight % by multiplying by the repeating unit weight of the corresponding species. The samples were quantified 29 by Si NMR spectroscopy.

[0169] Experimental Parameters:

[0170] System: Bruker 400 MHz

[0171] Probe: 10 mm 29 Si Probe

[0172] Pulse Program: ZGIG45

[0173] Recycling Delay: 5 seconds

[0174] Decoupling Method: Inverse Gate Attached

[0175] Decoupling Sequence: WALTZ16

[0176] Scan Number: 9472

[0177] Viscosity Measurement of PSA Samples

[0178] A PSA sample was prepared with 60% solids content by swelling it with ethyl acetate. The solution viscosity of this substance was determined at 25°C using a Brookfield (DV1) viscometer with spindle #4. [Table 2]

[0179] Testing of PSA samples

[0180] PSA samples were coated to a thickness of 70-80 micrometers, and probe tack adhesion and peel strength adhesion were measured. The adhesive used was 3M's Scotchpak. TM Applied onto a 9733 polyester film laminate support, and 3M's Scotchpak TM 1022 release liner was used. The adhesive was dried in an oven at 90°C for 10 minutes. Tack tests were performed according to FINAT Test Method 9, and tack was measured in grams. Peel adhesion tests were performed according to ASTM D3330 / D3330M, and the adhesion to a mirror-finish stainless steel plate was measured at a peel angle of 180°. Peel adhesion results were recorded per inch strip as peel force in N / inch at a peel rate of 12 inches per minute from the stainless steel panel. [Table 3]

[0181] Estimation of cyclic siloxane content

[0182] The cyclic siloxane content in PSA was quantified using gas chromatography. Samples were extracted over 24 hours as described below.

[0183] Experimental method:

[0184] Approximately 0.5 g of the sample was weighed into a vial. The exact weight was recorded. Using acetone as the solvent, the sample was extracted for 24 hours in 10 mL of working solution prepared with toluene and dodecane as internal standards (0.05 mg / mL). Calibration plots for cyclic siloxanes D4, D5, and D6 were generated by preparing various concentration standards ranging from 0.005 to 0.1 mg / mL in acetone. The peak areas were normalized by dividing by the peak area for dodecane and plotted against concentration. The cyclic siloxanes present in the sample were calculated using the normalized peak areas and calibration curves in the sample's GC chromatogram.

[0185] GC conditions Equipment: Agilent 7890A GC Detector: FID 350℃; H2: 30 mL / min, Air: 300 mL / min, Makeup flow: 25.4 mL / min Sample introduction: Split injection / 225°C / Split ratio 50:1 Injection volume: 2 μL (Agilent 7693 autosampler) Carrier gas: Nitrogen (1.4 mL / min, constant flow mode) Capillary column: Agilent HP-5 (30m x 0.32mm x 0.25μm) Temperature program: From 50°C (5 minutes) to 200°C at a rate of 15°C / minute, then up to 315°C (20 minutes). [Table 4]

[0186] Viscoelastic properties

[0187] The viscoelastic properties of silicone PSAs prepared by the process described herein were fully characterized by dynamic rheological analysis. G' at low angular frequencies (w=0.01 rad / s) represents the adhesive strength during application, while G' at high angular frequencies (w=100 rad / s) relates to the peeling force during desorption. Complex viscosity values, on the other hand, compare the cold flow properties of these adhesives. The data shown in Table 5 suggest that for all given compositions [Examples 1 to 11], the PSA properties are comparable to those using known state-of-the-art condensation catalysts. The experimental method involved molding the PSA onto a suitable release liner, drying at 150°C for 1 hour, and then transferring it from the release liner to a DHR3 rheometer (TA Instruments). A 25 mm parallel plate configuration was used in vibration mode, and flow curves were generated with an angular strain of 0.01%. [Table 5]

[0188] Storage life

[0189] Samples from the examples and comparative examples were stored at room temperature for one year without filtration after synthesis, and the precipitate in the samples was monitored.

[0190] [Table 6]

[0191] The above description includes examples provided herein. Of course, for the purposes of this specification, it is impossible to describe all recognizable combinations of components or methodologies, but those skilled in the art will recognize that many further combinations and substitutions of this specification are possible. Thus, this specification is intended to encompass all such changes, modifications and variations that are included within the idea and scope of the appended claims. Furthermore, wherever the term “encompasses” is used in the detailed description or claims, such term is intended to be as comprehensive as “includes,” as is the case when “includes” is used as a substitute in the claims.

[0192] The above description illustrates various non-limiting embodiments of silicone compositions, adhesives formed from the compositions, and articles using the compositions or adhesives. Modifications may be conceived by those skilled in the art and those who create and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or subject matter described in the claims.

Claims

1. A process for producing pressure-sensitive adhesives: A process comprising reacting (i) MQ silicone resin, (ii) polyorganosiloxane, and (iii) siloxane containing hydrophilic groups, wherein the reaction is carried out in the absence of an external catalyst.

2. The process of claim 1, wherein the hydrophilic functional group is selected from an ionic group, an ionizable group, an amphoteric group, or a combination of two or more of these.

3. A siloxane (iii) containing a hydrophilic group is selected from the following compounds: M １ ａ M ２ ｂ M ３ ｃ D １ ｄ D ２ ｅ D ３ ｆ T １ ｇ T ２ ｈ T ３ ｉ Q １ ｊ Q ２ ｋ Q ３ ｌ Q ４ ｏ Q ５ ｐ During the ceremony M １ =R ５ R ６ R ７ SiO １／２ M ２ =R ８ R ９ R １０ SiO １／２ M ３ =R １１ R １２ R １３ SiO １／２ D １ =R １４ R １５ SiO ２／２ D ２ =R １６ R １７ SiO ２／２ D ３ =R １８ R １９ SiO ２／２ T １ =R ２０ SiO ３／２ T ２ =R ２１ SiO ３／２ T ３ =R ２２ SiO ３／２ Q １ =Si(OR ２３ ) １ O ３／２ Q ２ =Si(OR ２４ ) ２ O ２／２ Q ３ =Si(OR ２５ ) ３ O １／２ Q ４ =Si(OR ２６ ) ４ Q ５ =SiO ４／２ Here: a, b, c, d, e, f, g, h, i, j, k, l, o, and p are zero or any integer, subject to the following constraints: 1≦[a+b+c+d+e+f+g+h+i+j+k+l+o+p]≦6000; [b+e+h+k]≧1; R ５ 、R ６ 、R ７ 、R ９ 、R １０ 、R １２ 、R １３ 、R １４ 、R １５ 、R １７ 、R １９ 、and R ２０ are each independently selected from hydrogen, C1-C60 alkyl, C6-C60 aromatic-containing group, C1-C10 alkoxy, and hydroxyl; R ８ , R １６ , R ２１ , and R ２４ are each independently selected from monovalent hydrophilic groups of the following formula, where G ≧ 0: 【Chemistry 16】 Here, A is a crosslinking unit between the siloxane moiety and the hydrophilic group I, having at least one spacer atom selected from C1-C60 acyclic hydrocarbon radicals, C4-C60 alicyclic radicals, C6-C60 aromatic hydrocarbon radicals, polyetheramines, polyethers, polyamides, polyesters, polyurethanes, polysulfones, polycarbonates, or two or more combinations thereof, where the crosslinking unit may contain one or more parts selected from alkoxys, carboxyls, urethanes, ureas, ketones, or two or more combinations thereof; I includes, but is not limited to, ionic groups, ionizable groups, amphoteric groups, or polar hydrophilic groups or parts thereof, polyetheramines, polyethers, polyamides, polyesters, polyurethanes, polysulfones, or polycarbonates; G is a polymerizable group having the following general formula: 【Chemistry 17】 A nonpolymerizable group of formula F-K, where F is a linking group selected from C1-C60 acyclic hydrocarbon radicals, C4-C60 alicyclic radicals, C6-C60 aromatic hydrocarbon radicals, polyetheramines, polyethers, polyamides, polyesters, polyurethanes, polysulfones, polycarbonates, or two or more combinations thereof, where the crosslinking group may include one or more parts selected from alkoxys, carboxyls, urethanes, ureas, ketones, or two or more combinations thereof; R ２７ , R ２８ , and R ２９ These are independently selected from hydrogen or a monovalent hydrocarbon radical with 1 to 5 carbon atoms, and K is independently selected from hydrogen, C1-C60 acyclic hydrocarbon radicals, C4-C60 alicyclic radicals, C6-C60 aromatic hydrocarbon radicals, epoxy groups, or ether groups; R １１ , R １８ , and R ２２ Each is independently selected from bases A-G, where A and G are as described above; and R ２３ , R ２５ , and R ２６ is R ５ From R ２２ Alternatively, you can choose independently from these combinations. The process of claim 1 or 2.

4. Siloxanes containing hydrophilic groups are given by formula M １ ａ M ２ ｂ M ３ ｃ Q ５ ｐ The process of claim 3, wherein b is ≥ 1.

5. I is carboxylate-COO － , dicarboxylate (-R(COO-) ２ ), sulfone-SO ２ -, sulfonate-SO ３ － Sulfate-OSO ３ － , phosphonate-PO ３ ２－ phosphate-OPO ３ ２－ group, -NR ３０ R ３１ H, -NH ２ R ３２ , -NH ３ Selected from , or ammonium salts, each comprising a cation independently selected from hydrogen or alkali metals, alkaline earth metals, transition metals, quaternary ammonium groups, and phosphonium groups, where R ３０ , R ３１ , and R ３２ The process of claim 3 or 4, wherein is independently selected from C1 to C30 hydrocarbons.

6. I is equation -R ３３ -N ＋ (R ３４ ) ２ -R ３５ -I ｚ A group having R is selected, where R ３３ R is a divalent hydrocarbon group having 1 to 20 carbon atoms. ３４ R is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ３５ is a divalent hydrocarbon group having 2 to 20 carbon atoms; and I ｚ is carboxylate-COO － , sulfone-SO ２ -, sulfonate-SO ３ － Sulfate-OSO ３ － , phosphonate-PO ３ ２－ , and phosphate-OPO ３ ２－ The process of claim 3 or 4, wherein the group is an ionic group selected from the group.

7. The process of claim 3 or 4, wherein I is a polar group selected from polyetheramine, polyether, polyamide, polyester, polyurethane, polysulfone, and / or polycarbonate.

8. The hydrophilic group is a polyetheramine group selected from the following compounds: R ３６ -(O-R ３７ -) ｑ -NH ２ In the formula R ３６ R is selected from C1 to C60 hydrocarbons, ３７ The process of claim 3 or 4, wherein is selected from C1 to C60 hydrocarbons and q is ≥ 1.

9. Polyetheramines are selected from the following compounds: R ３６ -(O-CH ２ CH ２ ) ｘ -(O-C CH ２ CH ２ CH ２ ) ｙ -(OCH ２ CH ２ CH(CH ３ )) ｚ -NH ２ The process of claim 8, wherein x, y, and z are independently from 0 to about 300, where x + y + z ≥ 2.

10. The polyetheramine group is selected by the following general formula: [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 The process of claim 3, 4, 8, or 9.

11. The process according to any one of claims 1 to 10, wherein the hydrophilic group-containing siloxane (iii) is present in an amount of about 0.1% to about 20% by weight based on the total weight of the composition.

12. The process according to any one of claims 1 to 10, wherein the hydrophilic group-containing siloxane (iii) is present in an amount of about 1.5% to about 8% by weight based on the total weight of the composition.

13. The process of claim 1, comprising reacting (i), (ii), and (iii) to first form a mixture of (i) and (ii), and then adding (iii) to the mixture of (i) and (ii).

14. The process of claim 2, wherein first forming a mixture of (i) and (ii) comprises dispersing MQ silicone (i) in polyorganosiloxane (ii), and heating the first mixture at a temperature of about 80 to about 150°C.

15. The process of any one of claims 1 to 14, wherein the reaction of (i), (ii), and (iii) is carried out at a temperature of about 80 to about 150°C.

16. A process according to any one of claims 1 to 15, wherein the process comprises removing water from the product obtained from the process to obtain a solid substance.

17. The process of claim 16, wherein the process comprises dissolving a solid substance in a solvent to obtain a final pressure-sensitive adhesive composition.

18. A pressure-sensitive adhesive composition obtained from any process of claims 1 to 17.

19. The pressure-sensitive adhesive composition of claim 18, wherein the adhesive comprises less than 2,500 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

20. The pressure-sensitive adhesive composition of claim 18, wherein the adhesive comprises less than 1000 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

21. The pressure-sensitive adhesive composition of claim 18, wherein the adhesive comprises less than 500 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

22. The pressure-sensitive adhesive composition of claim 18, wherein the adhesive comprises less than 100 ppm of one or more of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and / or dodecamethylcyclohexasiloxane.

23. The pressure-sensitive adhesive composition according to claim 18, wherein the pressure-sensitive adhesive does not exhibit precipitation after being stored at room temperature for one year.

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