Adhesion-enhancing agent composition, adhesive composition containing the same, and process for preparing the same.

Abstract

The present invention relates to an adhesion-enhancing agent composition comprising at least one organic borate additive and at least one organic titanate additive, and to an adhesive composition comprising this composition. The present invention also relates to the use of a combination of at least one organic borate additive and at least one organic titanate additive as an adhesion-enhancing agent in an adhesive composition, preferably a pressure-sensitive adhesive composition. The present invention further relates to a process for preparing an adhesion-enhancing agent composition.

Description

Technical Field

[0001] The present invention relates to an adhesion promoter composition containing at least one organic borate additive and at least one organic titanate additive, and an adhesive composition containing this adhesion promoter composition. The present invention also relates to the use of a combination of at least one organic borate additive and at least one organic titanate additive, and also to a process for preparing such an adhesion promoter composition.

Background Art

[0002] Adhesives, particularly pressure-sensitive adhesives (PSAs), have been widely used in various applications. Among the types of PSAs, silicone PSAs have attracted high interest due to their resistance to extreme high and low temperatures, applicability to high-energy and low-energy surfaces, and excellent insulating performance. Silicone PSAs can be applied to low-energy surfaces such as silicone, fluoropolymer, and polyolefin materials. However, without some surface treatment, silicone PSAs provide low adhesion to those surfaces, generally less than 300 gf / inch when peeled at 180° as required by the FINAT test method No. 1.

[0003] To increase the adhesion of silicone PSAs to such low-energy surfaces, additives such as trialkyl borates (most commonly tri-n-butyl borate) have been incorporated into silicone PSAs. Although the adhesion can be improved by the addition of trialkyl borates, when trialkyl borates are added in the amounts previously used in PSAs, the resulting adhesives remain insufficient. The adhesion can be increased with the amount of trialkyl borates. However, it is not desirable to use a large amount of trialkyl borates because they are incompatible with PSAs at high loading levels.

[0004] Therefore, there remains a need to develop silicone pressure-sensitive adhesive compositions that include alternative additives or additive systems and provide improved adhesion to low-energy surfaces such as silicones, fluoropolymers, and polyolefin materials, particularly at relatively low loading amounts. [Overview of the project]

[0005] In one embodiment, the present invention is: At least one organic borate additive; and The present invention provides an adhesion-enhancing composition comprising at least one organotinate additive.

[0006] In yet another embodiment, the present invention provides an adhesive composition, preferably a pressure-sensitive adhesive composition, which is: a) Adhesion-enhancing composition according to the present invention; and b) Includes a silicone adhesive composition, which in particular: Polyorganosiloxane gum; Formula M=R3SiO 1 / 2 At least one M unit of the formula T=RSiO 3 / 2 The units of T and the formula Q = SiO 4 / 2 At least one unit selected from the group consisting of Q units, and optionally, the formula D = R2SiO 2 / 2 The silicone resin comprises at least one D unit, where each R is independently a monovalent hydrocarbon group of 1 to 6 carbon atoms; and c) It optionally contains a curing catalyst.

[0007] In another embodiment, the present invention provides an adhesive composition, preferably a pressure-sensitive adhesive composition, in which a combination of at least one organic borate additive and at least one organic titanate additive is used as an adhesion-enhancing additive.

[0008] In yet another embodiment, the present invention provides a process for preparing the adhesion-improving composition of the present invention, which comprises optionally mixing at least one organoborate additive and at least one organotinate additive in a solvent, preferably an organic solvent, in particular xylene or heptane.

[0009] According to the present invention, the combination of an organic borate additive and an organic titanate additive in a silicone pressure-sensitive adhesive composition achieves a synergistic effect with respect to adhesion to low-energy surfaces such as silicones, fluoropolymers, and polyolefin materials, compared to the adhesion achieved when the organic borate additive and the organic titanate additive are used individually under the same conditions. [Modes for carrying out the invention]

[0010] definition

[0011] In the specification and claims of this application, the following terms and expressions shall be understood as set forth below.

[0012] The singular forms "aru" (aru), "hitotsu" (hitotsu), and "sono" (sono) include the plural form, and references to specific numbers include at least that specific number unless otherwise specified in the context.

[0013] All examples or use of exemplary terms (e.g., "like") presented herein are intended solely to provide a clearer description of the invention and, unless otherwise noted, do not impose any limitations on the scope of the invention.

[0014] No term used herein should be construed as indicating that any component not described in the claims is essential to carrying out the invention.

[0015] The terms “include,” “contain,” and “contain,” and their grammatically equivalent expressions, are understood to be inclusive or non-restrictive terms that do not exclude additional unspecified components or methodological processes, and also include the more restrictive terms “consist of” and “essentially consist of.”

[0016] Except in the examples, or unless otherwise specified, all numerical values ​​expressing quantities of materials, temperatures, durations of time, quantified properties of substances, and other matters described herein and in the claims shall be understood in all cases as being modified by the term "about," whether or not the term "about" is used in the expression.

[0017] It is understood that any numerical range described herein includes all subranges within that range, and any combination of various endpoints of such ranges or subranges.

[0018] Furthermore, all compounds, materials, or substances explicitly or implicitly disclosed herein and / or described in the claims as belonging to a group of compounds, materials, or substances that are constitutively, compositionally, and / or functionally related are understood to include the individual components of that group and all combinations thereof.

[0019] As used herein, the term "alkyl" has from about 30 carbon atoms, preferably from 1 to about 20 carbon atoms, and more preferably from 1 to about 10 carbon atoms, and is optionally substituted with one or more halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms, and means any monovalent saturated straight-chain or branched-chain hydrocarbon group. Exemplary and non-limiting examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl, isooctyl, and 2-ethylhexyl, nonyl such as n-nonyl, and decyl such as n-decyl. Adhesion improver composition

[0020] In one aspect, the present invention provides: At least one organic borate additive; and An adhesion improver composition comprising at least one organic titanate additive.

[0021] The organic borate additive of the present invention is not particularly limited. Preferably, the organic borate additive comprises a borate of the formula (I) B-(OR 1 )3, wherein each of R 1 is the same or different and is independently selected from the group consisting of H and C1-C 18 , preferably C1-C 16 , more preferably C1-C 12 , even more preferably C1-C8, still more preferably C1-C6, and most preferably C1-C4 straight-chain or branched-chain, substituted or unsubstituted hydrocarbon groups, particularly straight-chain or branched-chain, substituted or unsubstituted alkyl; provided that at least one, preferably at least two of R 1 is not H, and most preferably none of R 1 is H.

[0022] Preferably, the organic borate additive includes one or more compounds selected from the group consisting of trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, triisobutyl borate, tri-tert-butyl borate, tri-sec-butyl borate, and combinations thereof.

[0023] The organic titanate additive of the present invention is not particularly limited. Preferably, the organic titanate additive is of formula (II)Ti-(OR 2 ) Contains titanate of 4, where R 2 Each of them is either identical or different, and independently H and C1-C 18 Preferably C1-C 16 , more preferably C1-C 12 More preferably C1-C8, even more preferably C1-C6, and most preferably C1-C4 linear or branched hydrocarbon groups, selected from the group consisting of substituted or unsubstituted alkyl groups; however, at least one, preferably at least two, more preferably at least three R 2 It is not H, but most preferably R 2 None of them are H.

[0024] Preferably, formula (II)Ti-(OR 2 )4, R 2 Each of these is independently selected from the group consisting of methyl, ethyl, propyl, and butyl groups, preferably all R 2 is an n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group, more preferably all R 2 This is an n-butyl group.

[0025] In addition, organic titanate additives may further include silicon-containing organic titanate additives, preferably formula (III)Ti-(OR 3 -Si(R 4 )3)4 can contain titanates, where R 3 Each of them is either identical or different, and they are also independently covalent and C1-C.18 Preferably C1-C 16 , more preferably C1-C 12 More preferably, selected from the group consisting of substituted or unsubstituted hydrocarbon groups, particularly substituted or unsubstituted alkyl groups, of linear or branched chains, of C1-C8, even more preferably C1-C6, and most preferably C1-C4. 3 Each of them is either identical or different, and is independently selected from the group consisting of covalent bonds, methylene, and ethylene, where R 3 If the bond is covalent, O is directly bonded to Si; and R 4 Each of them is either identical or different, C1-C 18 Preferably C1-C 16 , more preferably C1-C 12 More preferably, C1-C8, even more preferably C1-C6, and most preferably C1-C4 linear or branched hydrocarbon groups, substituted or unsubstituted, are independently selected from the group consisting of substituted or unsubstituted alkyl groups.

[0026] Preferably, all R 3 It is a covalent bond, and also R 4 Each of them may be the same or different, and is independently selected from the group consisting of methyl, ethyl, propyl, and butyl groups, preferably all R 4 It is methyl.

[0027] In one preferred embodiment, formula (II)Ti-(OR 2 The organic titanate additive in )4 contains Ti(On-Bu)4, tetra-n-butyl titanate, which has the following structure.

[0028] [ka]

[0029] In one preferred embodiment, formula (III)Ti-(OR 3 -Si(R 4The silicon-containing organic titanate additive in )3)4 contains Ti(OSiMe3)4 and titanium trimethylsiloxide (tetrakis(trimethylsiloxy)titanium), which have the following structures.

[0030] [ka]

[0031] In one preferred embodiment, the organic borate additive comprises B(On-Bu)3, tri-n-butyl borate having the following structure.

[0032] [ka]

[0033] According to embodiments of the present invention, when used in combination with an organoborate, formula (III)Ti-(OR 3 -Si(R 4 )3)4 The silicon-containing organic titanate additive is formula (II)Ti-(OR 2 It has been found that it can achieve an even higher level of synergistic effect than the organotinate additives in 4.

[0034] When organic borate additives and organic titanate additives are used in combination, for example as an adhesion-enhancing agent composition, or when used in an adhesion-enhancing agent composition, the weight ratio between at least one organic borate additive and at least one organic titanate additive is about (1-10):about (0.1-5), preferably about (1-7):about (0.2-4), more preferably about (1-6):about (0.2-3), even more preferably about (1-5):about (0.2-2), and most preferably about (3-5):about (0.3-2).

[0035] In a preferred embodiment, at least one organoborate additive is tri-n-butyl borate, and at least one organotinate additive is Ti(On-Bu)4, where n-Bu=n-butyl group, and the weight ratio between the at least one organoborate additive and the at least one organotinate additive is approximately (3-5):approximately (0.5-2).

[0036] In another embodiment, at least one organoborate additive is tri-n-butyl borate, and at least one organotinate additive is Ti(OSiMe3)4, where Me = methyl group, and the weight ratio between the at least one organoborate additive and the at least one organotinate additive is approximately (3-5):approximately (0.3-1).

[0037] In one embodiment, the adhesion-enhancing composition further comprises a solvent, preferably an organic solvent such as xylene or heptane. The use of a solvent can facilitate the handling of the additive.

[0038] In another embodiment, the present invention provides a process for preparing the adhesion-enhancing composition described above, comprising optionally mixing at least one organoborate additive and at least one organotinate additive in a solvent, preferably an organic solvent, such as xylene or heptane. Adhesive composition

[0039] The present invention also provides an adhesive composition, preferably a pressure-sensitive adhesive composition comprising the adhesion-enhancing agent composition of the present invention. The adhesive composition is: a) The adhesion-enhancing compositions specified above; and b) Includes a silicone adhesive composition, which in particular: Polyorganosiloxane gum; Formula M=R3SiO 1 / 2 At least one M unit of the formula T=RSiO 3 / 2 The units of T and the formula Q = SiO 4 / 2At least one unit selected from the group consisting of Q units, and optionally, the formula D = R2SiO 2 / 2 The silicone resin comprises at least one D unit, where each R is independently a monovalent hydrocarbon group of 1 to 6 carbon atoms; and c) It optionally contains a curing catalyst.

[0040] In fact, the adhesive composition may be a pressure-sensitive adhesive (PSA), and it may contain an adhesion-enhancing agent composition and a silicone pressure-sensitive adhesive (silicone PSA).

[0041] Next, the silicone adhesive composition b) may preferably be a silicone pressure-sensitive adhesive composition. The component b) shown above is merely descriptive and illustrative, and is not limiting in any sense.

[0042] The silicone PSA (component b) may be any one of the technically known ones. The silicone PSA generally comprises a polyorganosiloxane gum and a silicone resin; and optionally further comprises a curing catalyst, a solvent, a filler, and other optional components as needed or desired. The pressure-sensitive adhesive composition may be cured by a radical reaction or a hydrosilylation reaction.

[0043] In one embodiment, in the adhesive composition of the present invention, the adhesion improving agent composition a) is present in an amount of about 1.1 to about 15 parts by weight, preferably about 1.2 to about 11 parts by weight, more preferably about 1.2 to about 9 parts by weight, even more preferably about 1.2 to about 7 parts by weight, and most preferably about 5.5 to about 7 parts by weight, per 100 parts by weight of the silicone adhesive composition b), and / or the curing catalyst is present in an amount of about 0.1 to about 6 parts by weight, preferably about 0.3 to about 5 parts by weight, more preferably about 1 to about 3 parts by weight, and most preferably about 1.5 to about 2 parts by weight, per 100 parts by weight of the silicone adhesive composition b).

[0044] As used in this application, the term "polyorganosiloxane gum" refers to a polyorganosiloxane having a viscosity of at least about 300,000 cps, preferably about 500,000 cps to about 150,000,000 cps, more preferably about 1,000,000 cps to about 100,000,000 cps, and even more preferably about 2,000,000 cps to about 80,000,000 cps, measured at a temperature of 25°C using a Brookfield viscometer according to its manual. The polyorganosiloxane gum may have a number average molecular weight of at least 100,000, preferably about 120,000 to about 1,000,000, and preferably about 150,000 to about 800,000. Polyorganosiloxane gum may contain one or more functional groups selected from the group consisting of hydroxyl, vinyl, alkenyl, alkoxy, alkoxyalkenyl, and hydride.

[0045] A suitable polyorganosiloxane gum may have the following general formula: R2R F SiO(R2SiO) x (RR F SiO) y SiR F R2(IV) In the formula, each of R is independently a monovalent hydrocarbon group having up to about 12 carbon atoms, for example an alkyl group having 1 to about 6 carbon atoms, such as methyl, ethyl, and propyl; or an aryl group having about 6 to about 12 carbon atoms, such as phenyl; R F Each of these is independently a hydroxyl, hydride, vinyl, alkenyl, alkoxy, or alkoxyalkenyl group having 1 to about 10 carbon atoms; x and y are each independently positive numbers (or integers) from 0 to 10000, preferably from 1 to about 8000, and more preferably from 10 to about 5000, where x + y is at least 1000.

[0046] Exemplary examples of polyorganosiloxane gums include, but are not limited to, polydimethylsiloxane and hydroxyl-terminated polydimethylsiloxane-polydiphenylsiloxane copolymers, and vinyl-functionalized polyorganosiloxanes.

[0047] The term "silicone resin" as used in this application refers to at least one (RSiO 3 / 2 ) Siloxy unit or (SiO 4 / 2 ) represents any organopolysiloxane containing siloxy units. In the embodiment, the silicone resin is given by formula M=R3SiO 1 / 2 At least one M unit of and the formula T=RSiO 3 / 2 The units of T and the formula Q = SiO 4 / 2 At least one unit selected from the group consisting of Q units, and optionally, the formula D = R2SiO 2 / 2 It contains at least one D unit, where each R is independently a monovalent hydrocarbon group of 1 to about 6 carbon atoms, an alkyl group of 1 to about 4 carbon atoms such as methyl, or a phenyl group.

[0048] The molecular weight of the silicone resin is not limited and may vary over a wide range. For example, the silicone resin may have a number average molecular weight of about 300 or more, preferably about 500 to about 50,000, and more preferably about 1,000 to about 30,000.

[0049] In one embodiment, the silicone resin is an MQ resin, comprising at least one Q unit and at least one M unit. The (mol) ratio of M units to Q units may be, for example, about 0.5:1 to about 1.5:1, preferably about 0.6:1 to about 1.2:1, more preferably about 0.7:1 to about 1.1:1, and even more preferably about 0.85:1 to about 1.0:1. The MQ resin may further contain, for example, D units, T units, or both in an amount of about 20 mol% or less, preferably about 10 mol% or less, and more preferably about 5 mol% or less, of the total number of units of the silicone resin.

[0050] Generally, MQ resins may be functionalized with hydroxyl groups. The total hydroxyl content of MQ resins is typically about 1–10% by weight, preferably about 2–8% by weight, and more preferably about 2–5% by weight. MQ resins may also be optionally functionalized with one or more functional groups selected from the group consisting of alkenyls such as vinyl, alkoxys, alkoxyalkenyls, and hydrides.

[0051] In another embodiment, the silicone resin is an MT resin containing at least one T unit and at least one M unit, preferably an MDT resin further containing at least one D unit in addition to the T and M units. The MT resin and MDT resin may further contain at least one Q unit. The amounts of the T and D units (if present) may be, for example, about 60 mol% or more, preferably about 70 mol% or more, and more preferably about 80 mol% or more, of the total number of units in the silicone resin.

[0052] In MT resins or MDT resins, the molar ratio of hydrocarbon group "R" to Si atoms (R / Si) is typically about 1.0:1 to about 1.8:1, preferably about 1.1:1 to about 1.7:1, and more preferably about 1.2:1 to about 1.6:1. In exemplary examples, the hydrocarbon group "R" includes methyl and phenyl (Ph), and the ratio of phenyl to hydrocarbon group (Ph / R) is, for example, about 0.1:1 to about 0.8:1, preferably about 0.2:1 to about 0.7:1, and more preferably about 0.2:1 to about 0.6:1.

[0053] MT resin or MDT resin may optionally be functionalized with one or more functional groups selected from the group consisting of hydroxyl, vinyl, alkenyl, alkoxy, alkoxyalkenyl, and hydride.

[0054] The silicone resin may be present in the silicone pressure-sensitive adhesive composition in an amount of about 50 to about 150 parts by weight, preferably about 70 to about 130 parts by weight, and more preferably about 80 to about 120 parts by weight, based on 100 parts by weight of polyorganosiloxane gum.

[0055] A great number of suitable silicone pressure-sensitive adhesives, including both polyorganosiloxane gum and silicone resin, are commercially available. Exemplary examples of such silicone pressure-sensitive adhesives include, but are not limited to, SilGrip from Momentive Performance Materials. TM Series, for example, SilGrip TM This includes PSA 5080, PSA510, PSA518, PSA529, PSA590LD, PSA595, PSA610, PSA6573A, PSA6574, PSA810, PSA820, and PSA915.

[0056] In one embodiment, the silicone pressure-sensitive adhesive composition of the present application preferably includes a curing catalyst to improve properties such as cohesive force, although the catalyst may be omitted in some embodiments. The curing catalyst used in the present application is not particularly limited and is generally selected according to the curing mechanism of the silicone pressure-sensitive adhesive. For example, when the silicone pressure-sensitive adhesive is cured by a radical reaction, the curing catalyst may include peroxides such as inorganic peroxides and organic peroxides. Exemplary examples of peroxides include, but are not limited to, aryl peroxides, such as dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and combinations thereof. When the silicone pressure-sensitive adhesive is cured by a hydrosilylation reaction, the curing catalyst may include, for example, noble metal catalysts using ruthenium, rhodium, palladium, osmium, iridium, and platinum, and complexes of these metals. Exemplary examples of hydrosilylation catalysts include, but are not limited to, Ashby catalysts; Lamoreax catalysts; Karstedt catalysts; Modic catalysts; and Jeram catalysts, and combinations thereof.

[0057] The curing catalyst may be present in an amount of up to about 10 parts by weight, preferably about 0.1 to about 8 parts by weight, and more preferably about 0.5 to about 5 parts by weight, based on 100 parts by weight of polyorganosiloxane gum.

[0058] To adjust the viscosity of the silicone pressure-sensitive adhesive composition, a suitable solvent may be included; however, in this application, solvent-free silicone pressure-sensitive adhesives are also applicable. Exemplary examples of solvents included, but not limited to, include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane, octane, and isoparaffin; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and isobutyl acetate; and ethers such as diisopropyl ether and 1,4-dioxane, or combinations thereof. The amount of solvent generally depends on the viscosity of the gum and the means by which the silicone pressure-sensitive adhesive composition is applied. As an exemplary example, a solvent included in an amount of about 40% to about 70% by weight results in a solution with a viscosity suitable for coating. The solvent may be removed in a drying step at a relatively low temperature before the silicone PSA composition cures.

[0059] Fillers may be optionally included to increase cohesive force and reduce cost. Exemplary examples of fillers, but not limited to, include quartz powder, zinc oxide, aluminum hydroxide, titanium dioxide, light calcium carbonate, or combinations thereof. The amount of filler may vary over a wide range depending on the silicone PSA, the properties of the filler, and the intended application. For example, the filler may be present in an amount of 0 to about 150 parts by weight, and preferably about 1 to about 100 parts by weight, based on 100 parts by weight of polyorganosiloxane gum.

[0060] Other optional components may include, for example, condensation accelerators such as dibutyltin diacetate to accelerate the condensation reaction of silanol groups; unreactive polyorganosiloxanes, such as polydimethylsiloxane and silsesquioxane resin; antioxidants, such as amine, phosphorus, phosphite, sulfur, and thioether type antioxidants; light stabilizers, such as triazole and benzophenone type light stabilizers; flame retardants, such as phosphate ester, halogen, phosphorus, and antimony type flame retardants; and dyes and their content.

[0061] Several optional additives are commercially available. Exemplary examples of commercially available additives include, but are not limited to, fixation promoters for improving the adhesion of silicone PSA to a substrate, such as AnchorSil, particularly for polyester substrates. TM 2000, SilForce TM SL6020 or SilForce TM SS4300C, or SilQuest TM A-186 silane; and silicone resin additives for controlling tacking, such as SilGrip TM This includes SR500 resin and SR545 resin, all of which are available from Momentive Performance Materials.

[0062] The silicone pressure-sensitive adhesive compositions described herein can have improved peel adhesion to low-energy surfaces such as silicones, fluoropolymers, and polyolefin materials. In one embodiment, the low-energy surface in this application may be silicone rubber. The adhesion to silicone rubber peeled at a 180-degree angle may be at least about 800 gf / inch, preferably about 900 gf / inch to about 1500 gf / inch, as tested according to ASTM D3330.

[0063] In one embodiment, the adhesive composition according to the present invention may be prepared by mixing an adhesion-enhancing agent composition with a polyorganosiloxane gum and a silicone resin, and optionally mixing it with any of the optional components described above in this application, such as a curing catalyst, a solvent, a filler, and other additives. The mixing may be carried out at room temperature or at a high temperature not higher than about 50°C, for example, from about 30°C to about 45°C, for a time effective to obtain a homogeneous mixture, for example, from a few seconds to several hours.

[0064] In another embodiment, the adhesive composition according to the present invention may be prepared by a process comprising mixing an organoborate additive, an organotinate additive (optionally in a solvent as described above) with polyorganosiloxane gum and silicone resin, and optionally any of the optional components described above in this application, such as a curing catalyst, solvent, filler, and other additives. The mixing may be carried out at room temperature or a high temperature not higher than about 50°C, for example, from about 30°C to about 45°C, for a time effective in obtaining a homogeneous mixture, for example, from a few seconds to several hours. The organoborate additive and the organotinate additive may be added together or separately. The components to be mixed may be added in any order. For example, in one embodiment, the organic borate additive and the organic titanate additive may be added together with or separately to a dispersion of polyorganosiloxane gum and silicone resin, with or without a solvent, together with the curing catalyst; or they may be mixed with the polyorganosiloxane gum, to which the silicone resin and curing catalyst may be added simultaneously or sequentially, with or without a solvent. Synergistic effect

[0065] The combination of organic borate and organic titanate additives was found to achieve a synergistic effect in terms of adhesion to low-energy surfaces such as silicones, fluoropolymers, and polyolefin materials, compared to the adhesion achieved when the organic borate and organic titanate additives are used individually under the same conditions.

[0066] In one embodiment, the synergistic effect is defined as follows: The synergistic effect is achieved when the actual performance obtained by using a combination of organic borate and organic titanate additives is higher than the baseline performance. The baseline performance is established as the sum of the net improvements in adhesion obtained beyond a blank test (without the use of adhesion-enhancing additives) by using the individual additives (organoborate or organic titanate additives). The actual performance is the sum of the net improvements in adhesion achieved beyond the blank test by using a combination of organic borate and organic titanate additives.

[0067] For example, the standard performance can be determined in the following way: The peel adhesion to silicone rubber (Si rubber) measured for a standard adhesive composition without adhesion-enhancing additives ("blank") is defined as P0. The peel adhesion to Si rubber measured for the same adhesive composition containing organic borate additives is defined as P B The peel adhesion to Si rubber measured for the same adhesive composition containing an organic titanate additive was then determined to be P T Let's assume that.

[0068] At this time, the standard performance is: (P B -P0)+(P T -P0)

[0069] The benchmark performance can be considered as the expected improvement in adhesion, based on the numerical sum of the improvements achieved by using individual additives (borate or titanate).

[0070] Actual performance can be determined as follows: The peel adhesion to Si rubber measured for the same adhesive composition containing both organic borate additives and organic titanate additives is P B+T Let's assume that.

[0071] At this time, the actual performance is: (P B+T -P0)

[0072] (PB+T -P0)>(P B -P0)+(P T When -P0), it means that the organic borate salt additive and the organic titanate salt additive functionally support each other (i.e., there is a favorable interaction between the two additives), and thus the improvement achieved by using both additives is greater than the mere sum of the improvements achieved by using each additive individually.

[0073] As a result, (P B+T -P0)>(P B -P0)+(P T If -P0, then a synergistic effect has been achieved.

[0074] As shown in the following examples, the present invention achieves this synergistic effect by combining at least one organoborate additive and at least one organotinate additive as defined above.

[0075] In one embodiment, the present invention also provides for the use of a combination of at least one organic borate additive and at least one organic titanate additive as defined above in an adhesive composition, preferably as an adhesion-enhancing additive in a pressure-sensitive adhesive composition. Examples

[0076] The present invention will be described more specifically with reference to examples, but these examples should not be construed as limiting the scope of the invention. In the following description, unless otherwise specified, "parts" and "%" refer to "parts by weight" and "% by weight".

[0077] Adhesion-enhancing additives used in the examples ●Organoborate additive: B(On-Bu)3, tri-n-butyl borate having the following structure:

[0078] [ka]

[0079] ●Organo titanate additives: (a) Ti(OSiMe3)4, titanium trimethylsiloxide (tetrakis(trimethylsiloxy)titanium) having the following structure:

[0080] [ka] (b) Ti(On-Bu)4, tetra-n-butyl titanate having the following structure:

[0081] [ka] General procedure for preparing silicone pressure-sensitive adhesive compositions

[0082] In the example, the following amounts of adhesion-enhancing additive and 1.5 parts by weight of dibenzoyl peroxide (abbreviated as BPO, as a curing catalyst) were added to 100 parts by weight (dry weight) of SilGrip, which is a toluene solution of silicone pressure-sensitive adhesive. TM A silicone pressure-sensitive adhesive composition containing an adhesion-enhancing additive (composition) was obtained by uniformly dispersing it within PSA610 (Momentive Performance Materials). General procedure for preparing silicone pressure-sensitive adhesive tape

[0083] Silforce TM A silicone pressure-sensitive adhesive was applied to a 25 μm PET film pre-coated with SS4191A primer (Momentive Performance Materials) under the following conditions: The coating bath uses toluene as a solvent and has a solid content of 40%. Drying is carried out at 85°C for 2 minutes, followed by curing at 170°C for 2 minutes to obtain silicone pressure-sensitive adhesive tape; The average thickness of the adhesive composition on the dried and cured tape is approximately 43 μm. Test method for peel adhesion to silicone rubber

[0084] The peel adhesion strength at 180° was tested for Si rubber LSR2640 (Momentive Performance Materials) according to the ASDM S3330 standard. The test temperature and humidity were 25°C and 50%RH, respectively. The silicone pressure-sensitive adhesive tape was unwound onto the Si rubber LSR2640, then unwound once and unwound again using a 2kg roller at a speed of 0.3m / min. The residence times after lamination were 20 minutes and 3 days. After residence times of 20 minutes and 72 hours, the tape was peeled from the silicone rubber at a 180° angle and at a speed of 300mm / min, and the peel adhesion was measured.

[0085] Examples of synergistic effects between organic borate and organic titanate additives were investigated as follows. Synergistic effect of the combination of IB(On-Bu)3 and Ti(On-Bu)4

[0086] To demonstrate the synergistic effect of the combination of organic borate and organic titanate additives of the present invention, a baseline performance must be established. For this purpose, peel adhesion tests to silicone rubber were performed on the compositions according to Table 1 below, where the test results are also shown. The amounts of the components are expressed in parts by weight.

[0087] [Table 1]

[0088] "Standard performance" ((P B -P0)+(P T From the data in Table 1 that constitute -P0), it is possible to establish the expected improvement in adhesion when both B(On-Bu)3 and Ti(On-Bu)4 are used.

[0089] Specifically, the improvement in adhesion over a blank of C1 (i.e., 5 parts by weight of B(On-Bu)3) is 520-318=202 (gf / inch) for a residence time of 20 minutes, and also for a residence time of 72 hours ((PB For -P0), the improvement in adhesion over the blank is 630-512=118 (gf / inch). Next, the improvement in adhesion over the blank of C2 (i.e., 0.5 parts by weight of Ti(On-Bu)4) is 285-318=-33 (gf / inch) for a residence time of 20 minutes, and also for a residence time of 72 hours ((P T For -P0), the value is 672.5 - 512 = 160.5 (gf / inch).

[0090] As a result, the reference performance for the combination of 5 parts by weight of B(On-Bu)3 and 0.5 parts by weight of Ti(On-Bu)4 is 202 + (-33) = 169 (gf / inch) for a residence time of 20 minutes, and also for a residence time of 72 hours ((P B -P0)+(P T For -P0), the result is 118 + 160.5 = 278.5 (gf / inch). This baseline performance corresponds to the expected level of improvement when using the combination of adhesion-enhancing additives on the "blank sample".

[0091] In this way, the baseline performance can be calculated and compared with the actual performance for a series of combinations of B(On-Bu)3 and Ti(On-Bu)4. The actual performance corresponds to the actual level of improvement obtained on a "blank sample" by using these combinations of adhesion-enhancing additives. If the actual performance is higher than the baseline performance, a synergistic effect has been achieved for that combination.

[0092] To obtain actual performance results, peel adhesion tests were performed on the compositions shown in Table 2 below using silicone rubber, and the test results are also shown there.

[0093] [Table 2]

[0094] From the test results in Table 2, the actual performance, i.e., the level of improvement over the blank sample, can be calculated in the same way as shown above, i.e., by subtracting the blank's "peeling on Si rubber" from the actual gf / inch. For example, the actual performance of Example 1 is 878-318=560 (gf / inch) for a residence time of 20 minutes, and also for a residence time of 72 hours (P B+T For -P0), the answer is 1058 - 512 = 546 (gf / inch).

[0095] Next, a comparison was made between the standard performance and the actual performance, and the results are shown in Table 3 below.

[0096] [Table 3]

[0097] The results in Table 3 clearly demonstrate a significant improvement in actual performance that exceeds the baseline (predicted) performance. These results prove that a synergistic effect on peel adhesion on Si rubber is achieved by the combination of B(On-Bu)3 and Ti(On-Bu)4. In other words, the combination of B(On-Bu)3 and Ti(On-Bu)4 achieves a level of improvement far greater than the sum of the improvement levels achieved by using the additives B(On-Bu)3 and Ti(On-Bu)4 individually. II. Synergistic effect of combining B(On-Bu)3 and Ti(OSiMe3)4

[0098] Similar to Section I above, a peel adhesion test was conducted on the silicone rubber; the standard performance and actual performance were calculated from the test results and compared as shown below.

[0099] To illustrate the synergistic effect of the combination of organic borate and organic titanate additives according to the present invention, a baseline performance must be established. For this purpose, peel adhesion tests to silicone rubber were performed on the compositions according to Table 4 below, where the test results are also shown.

[0100] [Table 4]

[0101] To obtain actual performance results, peel adhesion tests were performed on the compositions shown in Table 5 below using silicone rubber, and the test results are also shown there.

[0102] [Table 5]

[0103] Next, a comparison was made between the benchmark performance and the actual performance, and the results are shown in Table 6 below. The benchmark performance and the actual performance were calculated in the same way as described in Section I above.

[0104] [Table 6]

[0105] The results in Table 6 clearly demonstrate a significant improvement in actual performance that exceeds the baseline (predicted) performance. These results prove that a synergistic effect on peel adhesion on Si rubber is achieved by the combination of B(On-Bu)3 and Ti(OSiMe3)4. In other words, the combination of B(On-Bu)3 and Ti(OSiMe3)4 achieves a level of improvement far greater than the sum of the improvement levels achieved by using the additives from B(On-Bu)3 and Ti(OSiMe3)4 individually.

[0106] Based on the above results, the synergistic effect achieved by the combination of B(On-Bu)3 and Ti(OSiMe3)4 is higher than the synergistic effect achieved by the combination of B(On-Bu)3 and Ti(On-Bu)4 alone.

[0107] While this disclosure has been described with reference to preferred embodiments, various modifications may be made to elements of this disclosure, and substitutions may be made with equivalents, without departing from the scope disclosed, as will be understood by those skilled in the art. In addition, many modifications may be made to the disclosed teachings to suit specific circumstances or materials, without departing from the essential scope of the disclosure. Accordingly, this disclosure is not intended to be limited to any particular embodiment disclosed as the best mode considered for carrying out this disclosure, and the disclosure is intended to include all embodiments that are covered within the scope of the appended claims.

Claims

1. Adhesion-enhancing agent composition: At least one organic borate additive; and An adhesion-enhancing composition comprising at least one organotinate additive.

2. The organic borate additive contains a borate of formula (I) B-(OR ３ ), where each R ３ is the same or different and independently is H and C １ -C １ -C １８ , preferably C １ -C １６ , more preferably C １ -C １２ , even more preferably C １ -C ８ , still more preferably C １ -C ６ , most preferably C １ -C ４ of a linear or branched, substituted or unsubstituted hydrocarbon group, particularly selected from the group consisting of linear or branched, substituted or unsubstituted alkyl; provided that at least one, preferably at least two R １ is not H, and most preferably none of R １ is H, the adhesion improver composition of claim 1.

3. The adhesion-improving composition according to claim 2, wherein the organic borate additive comprises one or more compounds selected from the group consisting of trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, triisobutyl borate, tri-tert-butyl borate, tri-sec-butyl borate, and combinations thereof.

4. At least one organotinate additive, -Formula (II) Ti-(OR ２ ) ４ Contains titanate of, in the formula R ２ Each of them is either identical or different, and independently H and C １ -C １８ Preferably C １ -C １６ , more comfortable C １ -C １２ Furthermore, to make it more comfortable C １ -C ８ A more preferable C １ -C ６ , most preferably C １ -C ４ Selected from the group consisting of linear or branched substituted or unsubstituted hydrocarbon groups, particularly substituted or unsubstituted alkyl groups; provided that at least one, preferably at least two, more preferably at least three R groups are present. ２ It is not H, but most preferably R ２ None of them are H; and / or - Silicon-containing organic titanate additive, preferably formula (III) Ti-(OR ３ -Si(R ４ ) ３ ) ４ Contains titanate of, in the formula R ３ Each of them is either identical or different, and they are independently covalently bonded and C １ -C １８ Preferably C １ -C １６ , more comfortable C １ -C １２ Furthermore, to make it more comfortable C １ -C ８ A more preferable C １ -C ６ , most preferably C １ -C ４ Selected from the group consisting of linear or branched substituted or unsubstituted hydrocarbon groups, particularly substituted or unsubstituted alkyl groups, more specifically, R ３ Each of them is either identical or different, and is independently selected from the group consisting of covalent bonds, methylene, and ethylene, where R ３ If the bond is covalent, O is directly bonded to Si; and R ４ Each of them is either the same or different, C １ -C １８ Preferably C １ -C １６ , more comfortable C １ -C １２ Furthermore, to make it more comfortable C １ -C ８ A more preferable C １ -C ６ , most preferably C １ -C ４ An adhesion-enhancing composition according to any one of claims 1 to 3, independently selected from the group consisting of linear or branched substituted or unsubstituted hydrocarbon groups, particularly substituted or unsubstituted alkyl groups.

5. R ２ Each of these is independently selected from the group consisting of methyl, ethyl, propyl, and butyl groups, preferably all R ２ is an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, and more preferably all R ２ The adhesion-improving agent composition according to claim 4, wherein the group is an n-butyl group.

6. All R ３ It is a covalent bond, and R ４ Each of them may be the same or different, and is independently selected from the group consisting of methyl, ethyl, propyl, and butyl groups, preferably all R ４ The adhesion-improving agent composition according to claim 4, wherein is methyl.

7. An adhesion-enhancing composition according to any one of claims 1 to 6, wherein the weight ratio between at least one organic borate additive and at least one organic titanate additive is about (1-10):about (0.1-5), preferably about (1-7):about (0.2-4), more preferably about (1-6):about (0.2-3), even more preferably about (1-5):about (0.2-2), and most preferably about (3-5):about (0.3-2).

8. At least one organoborate additive is tri-n-butyl borate, and at least one organotinate additive is Ti(O-n-Bu) ４ The adhesion-improving composition of claim 7, wherein therein is an n-Bu=n-butyl group, and the weight ratio between at least one organoborate additive and at least one organotinate additive is about (3-5):about (0.5-2).

9. At least one organic borate additive is tri-n-butyl borate, and at least one organic titanate additive is Ti(OSiMe) ３ ) ４ The adhesion-improving composition of claim 7, wherein Me = methyl group, and the weight ratio between at least one organoborate additive and at least one organotinate additive is about (3-5):about (0.3-1).

10. The adhesion improving agent composition further comprises a solvent, preferably an organic solvent, particularly xylene or heptane, any one of claims 1 to 9.

11. An adhesive composition, preferably a pressure-sensitive adhesive composition: a) Adhesion improving agent composition according to any one of claims 1 to 10; and b) Silicone adhesive compositions, in particular: Polyorganosiloxane gum; Formula M=R ３ SiO １／２ At least one M unit of, equation T = RSiO ３／２ The units of T and the formula Q = SiO ４／２ At least one unit selected from the group consisting of Q units, and optionally, equation D = R ２ SiO ２／２ The silicone resin comprises at least one D unit, where each R is independently a monovalent hydrocarbon group of 1 to 6 carbon atoms; and c) An adhesive composition comprising a curing catalyst optionally.

12. The adhesive composition according to claim 11, wherein the adhesion improving agent composition a) is present in an amount of about 1.1 to about 15 parts by weight, preferably about 1.2 to about 11 parts by weight, more preferably about 1.2 to about 9 parts by weight, even more preferably about 1.2 to about 7 parts by weight, most preferably about 5.5 to about 7 parts by weight, per 100 parts by weight of the silicone adhesive composition b), and / or the curing catalyst is present in an amount of about 0.1 to about 6 parts by weight, preferably about 0.3 to about 5 parts by weight, more preferably about 1 to about 3 parts by weight, most preferably about 1.5 to about 2 parts by weight, per 100 parts by weight of the silicone adhesive composition b).

13. Use of at least one organic borate additive and at least one organic titanate additive as defined in any one of claims 1 to 10 as adhesion-enhancing additives in an adhesive composition, preferably a pressure-sensitive adhesive composition.

14. A process for preparing an adhesion-enhancing composition as defined in any one of claims 1 to 10, comprising optionally mixing at least one organoborate additive and at least one organotinate additive in a solvent, preferably an organic solvent, particularly xylene or heptane.

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