Patent Publication Number: US-2019169478-A1

Title: Debondable compositions

Description:
BACKGROUND 
     Field 
     Dual-cure compositions for use in high temperature adhesive applications, and particularly for temporarily adhesively attaching one substrate to another substrate, are provided. These dual-cure adhesives are silicone-based compositions that can be B-staged by exposure UV radiation to provide initial green strength, followed by a C-stage cure to give adhesives that can survive high temperature processes above 200° C., especially above 300° C., yet easy to debond afterwards to allow separation of the top and bottom substrates. 
     Brief Description of Related Technology 
     Within a number of industries, there is growing interest in the use of flexible and/or very thin substrates in the assembly of goods, particularly consumer goods like personal electronics. For example, stainless steel, silicon wafers, glass, ceramic, polyimide and polyester films are oftentimes used as such substrates. Flexible and very thin substrates are too fragile to be handled freestanding in downstream manufacturing conditions, and must be supported on a suitable carrier to survive. After the fabrication processes are done, the substrate must be removable from the carrier undamaged, preferably at ambient temperature. 
     In the electronics industry, as one example, imaging displays, sensors, photovoltaics and RFIDs, increasingly require thin and/or flexible substrates for display applications for cell phones, personal digital assistants, iPADs, or TVs. An exemplary substrate is a very thin (100 μm) glass packed with functionalities. The glass is processed at 400° C. to deposit thin film transistors (“TFT”) or at 350° C. to deposit indium tin oxide (“ITO”) as a transparent conductor. Due to the fragility of the glass and the harsh process conditions, this glass must be reinforced or protected by a more stable substrate during fabrication. 
     Uses such as this call for a high temperature stable adhesive that is easily and cleanly debondable, that permits temporary bonding at high processing temperatures, and that does not compromise handling or performance of the substrates. The design and development of such adhesives is desirable as it would allow existing fabrication methods, such as for semiconductors, active matrix thin film transistors, touch membranes, or photovoltaics, to use the currently installed base of manufacturing tools and machines. Most currently available temporary adhesives are not thermally stable at the maximum processing of the manufacturing steps, which can be as high as 400° C. 
     Adhesives suitable for high temperature temporary bonding applications, which can later be removed at room temperature without causing damage to the target component, would advance the use of thinner and/or more flexible substrates across various industries. 
     Recently, International Patent Publication No. WO 2015/000150 described a debondable adhesive composition comprising (A) the hydrosilation reaction product of the reaction between the vinyl groups on 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and the terminal Si—H hydrogens on a silane or siloxane having terminal Si—H hydrogens, (B) a crosslinker for the hydrosilation reaction product, and (C) a metal catalyst and/or radical initiator. 
     Despite this recent advance in debondable adhesives to which reference is made in the preceding paragraph, in order to improve the throughput of such processes, it would be highly desirable for an adhesive composition to provide quick fixture after exposure to UV irradiation, followed by exposure to elevated temperature conditions to thermally cure the adhesive composition to reach its ultimate cure state. 
     SUMMARY 
     The adhesive compositions and processes disclosed herein satisfy that desire. 
     The inventive composition can be cured upon exposure to radiation in the electromagnetic spectrum from a liquid to a gel or a solid in a B-stage cure. The state transformation forms a pressure sensitive adhesive, achieving a storage modulus G′&gt;5.0×10 3  Pa, desirably &gt;1.0×10 4  Pa, at 25° C. and 1 Hz. These properties provide sufficient adhesive strength. In order to confer upon the inventive composition pressure sensitive adhesive properties, a storage modulus of have G′ of less than or equal to 3.0×10 5  Pa, at 25° C. and 1 Hz, according to Dahlquist criterion [see Dahlquist, C. A., Creep, in  Handbook of Pressure Sensitive Adhesive Technology , Satas D. ed., Warwick, R.I. (1999)] for tack is desirable. After a C-stage cure by exposure to elevated temperature conditions, the inventive composition desirably achieves a storage modulus of G′&gt;1.0×10 6  Pa, at 25° C. and 1 Hz. These properties provide the composition with a tack-free surface, thus allowing for ready separation/debonding of substrates attached to one another by the composition. 
     Broadly speaking, the inventive composition is directed to a composition comprising
         (a) a polysiloxane resin having one or more vinyl groups;   (b) a (meth)acrylated polysiloxane resin having at least two (meth)acrylate groups; and   (c) an initiator comprising the combination of a photoinitiator and one of a peroxide and a hydridosiloxane or hydridopolysiloxane.       

     The inventive composition is curable by two different modalities. The first, exposure to radiation in the electromagnetic spectrum (e.g., UV), and the second, exposure to elevated temperature conditions. These modalities may be used in tandem too. 
     The inventive composition is useful in various methods. For instance, methods of bonding and debonding with the inventive composition are provided herein. 
     As regards methods of bonding, a method for bonding a substrate to a carrier is provided. The method includes the steps of:
         (a) providing a substrate and a carrier;   (b) disposing the inventive composition on the substrate and/or the carrier;   (c) contacting the substrate and carrier so that the inventive composition is disposed between the carrier and the substrate, forming an assembly;   (d) curing the inventive composition by
           (i) exposing the assembly to elevated temperature conditions, or   (ii) exposing the assembly to radiation in the electromagnetic spectrum, or   (iii) exposing the assembly to radiation in the electromagnetic spectrum followed by to elevated temperature conditions.   
               

     As regards methods of debonding, a method for debonding a substrate from a carrier is provided. The method includes the steps of:
         (a) providing a substrate adhesively bound to a carrier with the inventive composition; and   (b) separating the substrate from the carrier.       

    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
         FIG. 1 : Storage modulus development of photoinitiated vinylsiloxane (VDT-731)-radical photoinitiator (Irgacure 2100) compositions with and without acrylate-functional silicone (UMS-182). 
         FIG. 2 : Storage modulus development of photoinitiated vinylsiloxane (VDT-731)-radical photoinitiator (Irgacure 2100) compositions with different levels of acrylate-functional silicone (UMS-182). 
         FIG. 3 : Storage modulus development of photoinitiated vinylsiloxane (VDT-731)-radical photoinitiator (Irgacure 2100) compositions using acrylate-functional silicone (UMS-182) versus methacrylate-functional silicone (RMS-083). 
         FIG. 4 : Storage modulus development of photoinitiated vinylsiloxane (VDT-731)-acrylate-functional silicone (UMS-182) compositions using different radical photoinitiators. 
         FIG. 5 : Storage modulus development of thermally-initiated vinylsiloxane (VDT-731)-radical photoinitiator (Irgacure 2100)/peroxide initiator (Luperox 531M80) compositions. 
         FIG. 6 : Storage modulus development of dual cure UV/thermally-initiated vinylsiloxane (VDT-731) acrylate-functional silicone (UMS-182)/-peroxide initiator (Luperox 531M80) compositions. 
         FIG. 7 : Depicts a schematic of the peel strength test specimen. 
         FIG. 8 : Depicts a schematic of the peel strength test specimen showing the force F recorded as peel force on a 180 degree peel tester. 
     
    
    
     DETAILED DESCRIPTION 
     As used within this specification and the claims, “substrate” refers to the target component for the fabrication processes, and “carrier” refers to the support structure for the “substrate”. A “B-stage” process generally involves partial curing, solvent evaporation, or both, of the adhesives system, oftentimes using UV or heat. This typically allows easy handling of the adhesives, or provides initial adhesives strength as in the case of debondable adhesives described above. When the adhesive system is then heated at elevated temperatures, more complete cross-linking of the adhesive system can occur and a “C-Stage” cure is reached. 
     The vinyl silicone resins are linear or branched polysiloxane compounds having Si—CH═CH 2  groups. 
     A representative structure for the vinyl silicone resins is shown below: 
     
       
         
         
             
             
         
       
     
     where R 1 , R 2 , R 3 , and R 4  are independently selected from hydrogen, C 1-10  aliphatic or C 6-10  aromatic hydrocarbons with or without heteroatoms or unsaturation, and w, x, y, and z are molar fractions of the repeating units (w+x+y+z=1, w&gt;0). Generally, the chain-ends of these resins are terminated by trimethylsilyl group or vinyldimethylsilyl groups. Exemplary vinyl silicones are available from Gelest under VDT product designation. 
     The (meth)acrylate silicone resins are linear or branched polysiloxane compounds having (meth)acrylate groups either at the backbone or chain-ends. 
     A representative structure for the (meth)acrylate silicone resins is shown below: 
     
       
         
         
             
             
         
       
     
     where R 1 , R 2 , and R 3  are independently selected from hydrogen, C 1-10  aliphatic or C 6-10  aromatic hydrocarbons with or without heteroatoms or unsaturation, X is a linking group selected from C 1-10  aliphatic or C 6-10  aromatic hydrocarbons with or without heteroatoms or unsaturation, x 1 , x 2 , y 2 , and z are molar fractions of the repeating units (where x 1 +x 2 +y 1 +y 2  +z=1), and A is either a hydrogen, or (meth)acrylate group. Exemplary (meth)acrylate silicones include products available commercially from Gelest Inc. under the trade designations DMS-R, RMS, and UMS, and TEGO RC silicone resins for release coating available commercially Evonik. More details on each of these is provided in the Examples section. In addition, acrylate silicones are also available from Siltech Corporation under the Silmer ACR product line, such as Silmer ACR D208, Silmer ACR D2, Silmer ACR Di-10, Silmer ACR Di-50, Silmer ACR Di-1508, Silmer ACR Di-2510, Silmer ACR Di-4515-O, and Fluorosil ACR C7-F. 
     The radical thermal initiators are substances that can produce radical species under heat to initiate radical reactions. Typical thermal initiators are azo compounds, and organic/inorganic peroxides that have weak bonds and small bond dissociation energies. 
     Suitable radical thermal initiators are well known and may be chosen from dicumene peroxide, cumene hydroperoxide, and perbenzoates, such as t-butyl perbenzoate. Organic peroxides available commercially from Arkema under the Luperox trade name, such as Luperox 531M80 [1,1-di-(t-amylperoxy)-cyclohexane], are particularly useful herein. 
     The hydridosilane and hydridosiloxane resins are compounds having Si—H group capable of hydrosilation reaction with the double bond on the vinyl silicone resin structure. Exemplary compounds include, but not limited to the following structures: 
     
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
     
     where R 1 , R 2 , R 3 , and R 4  are independently selected from hydrogen, C 1-10  aliphatic or C 6-10  aromatic hydrocarbons with or without heteroatoms or unsaturation, and w, x, y, z are molar fractions of the repeating units (w+x+y+z=1, w&gt;0). 
     The hydridosilane and hydridosiloxane resins may also exist in a cyclic siloxane structure, examples of which are cyclotrisiloxane (D3), cyclopentasiloxane (D5), or even higher. 
     Hydrosilation catalysts (also called hydrosilylation catalysts) promote the addition of Si—H bonds across unsaturated double bonds. These are typically metal catalysts such as platinum and rhodium compounds. 
     In another embodiment, this invention is an assembly of a substrate and carrier, in which the adhesive composition is disposed between the substrates. 
     In a further embodiment, a method of debonding a substrate from a carrier is provided. The method comprises the steps of: (a) providing a substrate and a carrier, (b) disposing a debondable adhesive on the substrate and/or the carrier, (c) contacting the substrate and carrier so that the debondable adhesive is disposed between, forming an assembly, (d) exposing the assembly to conditions favorable to adhere the substrate to the carrier, such conditions being heating at an elevated temperature, exposure to radiation in the electromagnetic spectrum, or exposure to radiation in the electromagnetic spectrum followed by heating, and (e) separating the substrate from the carrier. 
     When step (d) involves heating, the temperature should be in the range of 100° C. to 175° C. for a period of time of 1 to 30 minutes. When step (d) involves radiation exposure, radiation may be generated and applied using a 400 Watt lamp for about 1 to 4 minutes. When a combination of radiation and heat is used to obtain the desired cure, suitable conditions can be determined by one skilled in the art without undue experimentation. 
     EXAMPLES 
     Gel Permeation Chromatography was used to determine the molecular weight of the silicone materials. A Waters model 717GPC, equipped with an autosampler and a refractive index detector, was used with polystyrene of various molecular weights as standards (1.1 M -162 Da) and tetrahydrofuran as solvent. 
     In the tables below, averaged molecular weights (Mn and Mw in Daltons) and (relative to polystyrene standards) and polydispersivity (Mn/Mw) calculations are shown for the various silicone materials. 
     
       
         
           
               
               
               
               
               
             
               
                   
                   
               
               
                   
                   
                 Mn 
                 Mw 
                 Polydispersity 
               
               
                   
                 Sample 
                 (Da) 
                 (Da) 
                 (Mw/Mn) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 VDT-131 
                 17646 
                 33365 
                 1.9 
               
               
                   
                 VDT-431 
                 15543 
                 35534 
                 2.3 
               
               
                   
                 VDT-731 
                 18540 
                 40153 
                 2.2 
               
               
                   
                   
                 599 
                 635 
                 1.1 
               
               
                   
                 VDT-954 
                 42613 
                 242352 
                 5.7 
               
               
                   
                   
                 587 
                 608 
                 1.0 
               
               
                   
                   
               
            
           
         
       
     
     The data above is illustrative for the VDT series, vinylmethylsiloxane-dimethylsiloxane copolymers, trimethylsiloxy terminated, which is represented by the 
     
       
         
         
             
             
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                   
               
               
                   
                   
                 Mn 
                 Mw 
                 Polydispersity 
               
               
                   
                 Sample 
                 (Da) 
                 (Da) 
                 (Mw/Mn) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 DMS-V05 
                 1486 
                 2323 
                 1.6 
               
               
                   
                 DMS-V21 
                 6047 
                 10963 
                 1.8 
               
               
                   
                 DMS-V25 
                 12097 
                 26432 
                 2.2 
               
               
                   
                 DMS-V31 
                 15087 
                 36028 
                 2.4 
               
               
                   
                 DMS-V41 
                 42938 
                 80479 
                 1.9 
               
               
                   
                 DMS-V51 
                 76987  
                 162933 
                 2.2 
               
               
                   
                   
               
            
           
         
       
     
     The data above is illustrative for the DMS series, vinyl terminated polydimethylsiloxanes, which is represented by the 
     
       
         
         
             
             
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                   
               
               
                   
                   
                 Mn 
                 Mw 
                 Polydispersity 
               
               
                   
                 Sample 
                 (Da) 
                 (Da) 
                 (Mw/Mn) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 PDV-0346 
                 63671  
                 145752 
                 2.3 
               
               
                   
                   
                 2066 
                 2444 
                 1.2 
               
               
                   
                   
                 498 
                 515 
                 1.0 
               
               
                   
                 PDV-0541 
                 25703 
                 74421 
                 2.9 
               
               
                   
                   
                 552 
                 573 
                 1.0 
               
               
                   
                 PDV-1625 
                 7363 
                 13386 
                 1.8 
               
               
                   
                   
                 497 
                 512 
                 1.0 
               
               
                   
                 PDV-1641 
                 21127  
                 102786 
                 4.9 
               
               
                   
                   
                 496 
                 511 
                 1.0 
               
               
                   
                 TEGO RC-90 
                 7524 
                 17532 
                 2.3 
               
               
                   
                 UMS-182 
                 7591 
                 12286 
                 1.6 
               
               
                   
                   
                 676 
                 713 
                 1.1 
               
               
                   
                 UMS-992 
                 1924 
                 2183 
                 1.1 
               
               
                   
                   
                 775 
                 796 
                 1.0 
               
               
                   
                   
               
            
           
         
       
     
     The data above is illustrative for the PDV series, diphenylsiloxane-dimethylsiloxane copolymers, which are represented by 
     
       
         
         
             
             
         
       
         
         TEGO RC-902, which is an acrylated silicone having the following CAS No.: 155419-56-and is described by the manufacturer as siloxanes and silicones, di-Me, hydrogen-terminated, reaction product with acrylic acid and 2-ethyl-2[(2-propenyloxy)methyl]-1,3-propanediol; and 
         For the UMS series, (acryloxypropyl)methylsiloxane-dimethylsiloxane copolymers, 
       
    
     
       
         
         
             
             
         
       
         
         UMS-182: 15-20% (acryloxypropyl)methylsiloxane repeating unit 
         UMS-992: 99-100% (acryloxypropyl)methylsiloxane repeating unit. 
       
    
     Example 1 
     Impact of Acrylated Polysiloxane on UV Cure of Vinyl Silicone Resin 
     A 100:0.9 (by weight) blend of vinyl silicone resin VDT-731 (Gelest) having 7-8% vinyl groups and Irgacure 2100 was cured under 230 mW/cm 2  UVA. Curing was monitored with an Anton Paar Physica MCR501 photorheometer using 8 mm plate, 1 mm gap at 1 Hz. UV curing started at 60 seconds. This sample was compared with a 90:10:0.9 blend (by weight) of VDT-731:UMS-182:Irgacure 2100, in which UMS-182 (Gelest) is a silicone resin having 15-20% acrylate groups along the silicone polymer chain. As shown in  FIG. 1 , the use of small amounts of acrylated silicone resulted in dramatically improved cure speed and roughly two orders of magnitude increase in storage modulus. Considering that the level of acrylate functional group is very low (˜2%) among all siloxane repeating units in the composition, the improvement in curing is extremely efficient. Most importantly, the storage modulus exceeded 10 4  Pa. It was also noted that the formulation containing UMS-182 gelled at only 1.5 seconds according to Tan Delta, the ratio of loss modulus to storage modulus. Without the acrylated silicone, the gelation process took over 2 minutes. 
     Irgacure 2100 has the following structure 
     
       
         
         
             
             
         
       
     
     This was repeated with a 94.6:5.4:0.9 blend (by weight) of VDT-731:UMS-182:Irgacure 2100. Again, a very efficient modulus buildup was observed even at extremely low levels of acrylate functionality. (See  FIG. 2 .) 
     Example 2 
     Model Studies of Vinyl Siloxane and Acrylate Monomers 
     A 90:0 (by weight) blend of SIV9082:butyl acrylate was photopolymerized using 2 weight percent Darocur 1173. The mixture was sealed in a quartz NMR tube and irradiated under ˜50 mW/cm 2  UVA for 5 minutes. SIV9082 (Gelest) is a vinyl siloxane monomer having the following structure: 
     
       
         
         
             
             
         
       
     
     Darocur 1173 has the following structure 
     
       
         
         
             
             
         
       
     
     The SIV9082:butyl acrylate blend has a molar ratio of 4.6:1. This blend helps to promote the co-polymerization reaction between two monomers instead of homopolymerization of the fast acrylate monomer. 
       1 H NMR analyses before and after UV irradiation were conducted. Further, residual monomers were removed from the UV polymerized sample under 400 micron vacuum at 95° C., and  1 H NMR confirms the formation of polymers incorporating both vinyl siloxane SIV9082 and butyl acrylate monomers. 
     Example 3 
     Comparison of Acrylate and Methacrylate Silicones 
     In this example, methacrylated silicone RMS-083 (Gelest) having 7-9% methacrylate groups in the silicone repeating units was tested. VDT-731:RMS-083:Irgacure 2100 blends at a 90:10:0.9 ratio as well as a 80:20:0.9 ratio were compared with the acrylated silicone formulation made and evaluated above in Example 1. Although slower curing was observed, both samples were eventually cured to 5×10 3  Pa region. (See  FIG. 3 .) 
     Example 4 
     Use of High Functional Acrylate Silicone 
     In this example, UMS-992 (Gelest), an acrylate silicone with 99-100% acrylate groups on all siloxane repeating units was tested. A blend of VDT-731:UMS-182:UMS-992:Irgacure 2100 in a 90:10:5:0.9 ratio was cured by photorheometry, and was found to have a storage modulus was ˜10 4  Pa. 
     Example 5 
     Comparison of Different Photoinitiators 
     In this example, a resin blend of VDT-731:UMS-182:photoinitiator was prepared at a 90:10:0.9 ratio. Three different types of photoinitiators were evaluated: Irgacure 2100, Darocur 1173, and Irgacure MBF. Irgacure 2100 is an acylphosphine oxide type initiator, Darocur 1173 is alpha-hydroxyl ketone type initiator, and Irgacure MBF is phenylglyoxylate initiator. Irgacure MBF has the structure shown below: 
     
       
         
         
             
             
         
       
     
     When cured using photorheometry, all three yielded a cured product having a storage modulus exceeding 5×10 3  Pa after cure. However, Irgacure 2100 was found to be the fastest photoinitiator. (See  FIG. 4 .) On the other hand, Darocur 1173 resulted in higher storage modulus after cure. 
     Further, TEGO Al 8 (Evonik) was tested as a less volatile replacement for Darocur 1173 and similar performance was observed. Structures of this initiator is shown below where R is an alkyl group having C10-13 alkyl chains: 
     
       
         
         
             
             
         
       
     
     Example 6 
     Thermal Cure of VDT 731 
     An important attribute of a debondable adhesive is the ability to easily peel off after processing. Generally speaking, adhesives having storage modulus above 10 6  Pa are beyond the pressure sensitive adhesive region and are tack-free. VDT-731 was blended with 2 and 4 weight percent Luperox 531M80 and cured on a rheometer. The samples were cured by exposure to elevated temperature conditions, which ramped from room temperature to a temperature of 150° C. at 10° C./minute intervals and then held at a temperature of 150° C. for a period of time of 1 hour. As shown in  FIG. 5 , the cured samples resulted in storage modulus exceeding 10 6  Pa. This example demonstrates that samples based on this chemistry are suitable for thermally induced C stage cure. 
     Example 7 
     Dual-Cure Formulation 
     VDT-731 (9.0 g), UMS-182 (1.0 g), Irgacure 2100 (0.1 g), and Luperox 531M80 (0.2 g) were mixed together, and dispensed onto a glass die (4 mm 2 ) over which a microscope glass slide was positioned. Radiation in the electromagnetic spectrum (50 mw/cm 2  UVA) was directed toward the glass die/glass slide assembly for a period of time of 30 seconds. The assembly was then exposed to elevated temperature conditions of 150° C. for a period of time of 60 minutes. Next, the assembly was subjected to 30 minutes of baking either at 350° C. or 400° C. to mimic a TFT/ITO processes. At these two baking conditions, the die adhered to the glass slide. The die however was observed to be easily debonded, using the peel strength evaluation technique described herein. 
     With reference to  FIG. 6 , the photorheometry measurements indicate the development of modulus initially after exposure to electromagnetic radiation and then to exposure to elevated temperature conditions. 
     Example 8 
     Preparation of Three Master Batches 
     Master batch A contains 20.0 g VDT-731, 0.20 g Irgacure 2100, and 0.40 g Luperox 231. Master batch B contains 10.0 g UMS-182, 0.10 g Irgacure 2100, and 0.20 g Luperox 231. Master batch C contains 10.0 g Tego RC-902 acrylate silicone resin (Evonik), 0.10 g Irgacure 2100, and 0.20 g Luperox 231. Various blended samples were prepared from these master batches, and are set forth below in Table 1. The blended samples were cured in the photorheometer using the conditions of Example 1 for a period of time of 5 minutes. The G′ values for each of the blended samples are also recorded in Table 1. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                   
                   
                   
                 Classification 
               
            
           
           
               
               
               
            
               
                 A:B Mixtures 
                 A:C Mixtures 
                 according to 
               
            
           
           
               
               
               
               
               
            
               
                 A:B (wt) 
                 G′ (Pa) 
                 A:C (wt) 
                 G′ (Pa) 
                 Dahlquist criterion 
               
               
                   
               
               
                 100:0  
                 1.95 × 10 3   
                 — 
                 — 
                 Non-PSA Region 
               
               
                 97:3  
                 1.32 × 10 4   
                 97:3  
                 1.19 × 10 4   
                 PSA Region 
               
               
                 95:5  
                 2.10 × 10 4   
                 — 
                 — 
                 PSA Region 
               
               
                 90:10 
                 4.04 × 10 4   
                 90:10 
                 5.47 × 10 4   
                 PSA Region 
               
               
                 85:15 
                 5.23 × 10 4   
                 — 
                 — 
                 PSA Region 
               
               
                 80:20 
                 5.37 × 10 4   
                 80:20 
                 8.03 × 10 4   
                 PSA Region 
               
               
                 70:30 
                 9.61 × 10 4   
                 — 
                 — 
                 PSA Region 
               
               
                 60:40 
                   
                 60:40 
                 2.87 × 10 5   
                 PSA Region 
               
               
                 50:50 
                 1.18 × 10 5   
                 50:50 
                 4.00 × 10 5   
                 PSA Region 
               
               
                 40:60 
                 4.04 × 10 5   
                 40:60 
                 5.49 × 10 5   
                 PSA Region 
               
               
                   
                   
                   
                   
                 (borderline) 
               
               
                 30:70 
                 7.63 × 10 6   
                 — 
                 — 
                 Non-PSA Region 
               
               
                 10:90 
                 1.12 × 10 7   
                 — 
                 — 
                 Non-PSA Region 
               
               
                  0:100 
                 1.25 × 10 7   
                 — 
                 — 
                 Non-PSA Region 
               
               
                   
               
            
           
         
       
     
     From these data, it seems that in order to achieve pressure sensitive adhesive properties for the inventive compositions, a vinyl silicone to acrylate silicone ratio desirably is within the range of 97:3 to 40:60 so that the vinyl functionality to acrylate functionality falls roughly within the range of 21:1 to 0.29:1. 
     Example 9 
     Preparation of Three Master Batches 
     UMS-992, an acrylate silicone resin having 99-100 mole % (acryloxypropyl)methylsiloxane units, was evaluated as a blended with VDT-731 and the initiator package. One drop of each sample was placed between two microscope slides, and exposed to radiation in the electromagnetic spectrum (50 mW/cm 2  UVA) for a period of time of 60 seconds. Then the so-formed assembly was exposed to elevated temperature conditions of 150° C. for a period of time of 1 hour. The results are summarized in Table 2. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 2 
               
             
            
               
                   
                   
               
               
                   
                 Constituents 
                 After UV Cure 
                 G′ (Pa) 
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Sample 
                 VDT-731 
                 UMS-992 
                 Initiator 
                 (50 mw/cm 2   
                 After 5 minutes 
                 After Thermal Cure 
               
               
                 Nos. 
                 (part) 
                 (part) 
                 Package 
                 UVA), 60 s 
                 in Photorheometer 
                 (150° C./1 h) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 99 
                 1 
                 IP 
                 Tacky PSA 
                 1.0 × 10 4   
                 Easy debond CF 
               
               
                 2 
                 97 
                 3 
                 IP 
                 Tacky PSA 
                 7.0 × 10 3   
                 Easy debond CF 
               
               
                 3 
                 95 
                 5 
                 IP 
                 Tacky PSA 
                 6.0 × 10 3   
                 Easy debond CF 
               
               
                 4 
                 90 
                 10 
                 IP 
                 Tacky PSA 
                 4.4 × 10 3   
                 Easy debond CF 
               
               
                 5 
                 80 
                 20 
                 IP 
                 Not tested, 
                 2.8 × 10 3   
                 Not tested 
               
               
                   
                   
                   
                   
                 formulation 
               
               
                   
                   
                   
                   
                 phase separated 
               
               
                   
               
               
                 IP (Initiator Package): 1 part Irgacure 2100 plus 2 parts Luperox 231 
               
               
                 CF: cohesive failure during debonding 
               
            
           
         
       
     
     Here, the desired vinyl silicone to acrylate silicone ratio is within the range of 99:1 to 90:10, and the vinyl functionality to acrylate functionality is approximately within the range of 19:1 to 1.4:1. 
     Example 10 
     Various Vinyl Silicone Resins 
     A variety of vinyl silicones having different levels of vinyl group along the polymer chains were formulated. One drop of each sample was placed between two microscope slides, and exposed to radiation in the electromagnetic spectrum (50 mW/cm 2  UVA) for a period of time of 60 seconds. Then the so-formed assembly was exposed to elevated temperature conditions of 150° C. for a period of time of 1 hour. The results are summarized in Table 3. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 3 
               
             
            
               
                   
                   
               
               
                   
                 Constituents 
                 After UV Cure 
                 G′ (Pa) 
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Sample 
                   
                 Acrylate Silicone 
                 Initiator 
                 (50 mw/cm 2   
                 After 5 minutes 
                 After Thermal Cure 
               
               
                 Nos. 
                 Vinyl Silicone 
                 UMS-182 
                 Package 
                 UVA, 60 s) 
                 in Photorheometer 
                 (150° C./1 h) 
               
               
                   
               
               
                 1 
                 90 parts 
                 10 parts 
                 IP 
                 Tacky PSA 
                 2.1 × 10 5   
                 Easy debond AF 
               
               
                   
                 VDT-954 
               
               
                   
                 (11-13% VMS) 
               
               
                 2 
                 90 parts 
                 10 parts 
                 IP 
                 Tacky PSA 
                 4.0 × 10 4   
                 Easy debond AF 
               
               
                   
                 VDT-731 
               
               
                   
                 (7.0-8.0% VMS) 
               
               
                 3 
                 90 parts 
                 10 parts 
                 IP 
                 Tacky PSA 
                 5.0 × 10 3   
                 Easy debond CF 
               
               
                   
                 VDT-431 
               
               
                   
                 (4.0-5.0% VMS) 
               
               
                 4 
                 90 parts 
                 10 parts 
                 IP 
                 Not cured 
                 17 
                 Not tested 
               
               
                   
                 VDT-131 
               
               
                   
                 (0.8-1.2% VMS) 
               
               
                   
               
               
                 VMS: vinylmethylsiloxane repeating unit 
               
               
                 IP: 1 part Irgacure 2100 plus 2 parts Luperox 231 
               
               
                 AF: adhesive failure during debonding 
               
               
                 CF: cohesive failure during debonding 
               
            
           
         
       
     
     Example 11 
     Dual-Cure Formulation Using Hydridosiloxane Thermal Cure 
     VDT-731 (9.0 g), UMS-182 (1.0 g), Darocur 1173 (0.1 g), HMS-993 (0.6 g), 3,5-dimethyl-hexyn-3-ol (0.05 g), and SIP6830.3 (0.0062 g) were mixed together. HMS-993 (Gelest) is a hydridosiloxane resin having Si—H group in all repeating units (according to the manufacturer, Gelest, it is a polymethyl hydrosiloxane, trimethylsiloxyterminated having a molecular weight of 2100-2400), 3,5-dimethyl-hexyn-3-ol is a hydrosilation inhibitor for potlife stability, SIP6830.3 (Gelest) is a platinum catalyst for catalyzing hydrosilaton cure of the vinyl siloxane resin and hydridosiloxane resin. More specifically, the platinum catalyst may be described as platinum-divinyltetramethyldisiloxane complex or Karstedt catalyst, where a 3-3.5% platinum concentration in vinyl terminated polydimethylsiloxane is present, and the complex is described as Pt[O(SiMe 2 CH═CH 2 ) 2 ] 1.5 . The samples were cured between a glass die (4 mm 2 ) and a microscope glass slide under exposure to radiation of 50 mW/cm 2  UVA for 60 seconds, followed by heating at a temperature of 150° C. for a period of time of 60 minutes. The cured assemblies were then subjected to 30 minutes of baking either at 350° C. or 400° C. At these two baking conditions, the die adhered to the glass slide. The die however was observed to be easily debonded. 
     The peel test evaluation was conducted on a Cheminstrument 180 degree peel adhesion tester. Peel test samples were prepared by adhering in an off set manner 50 mm×75 mm glass substrate (0.12 mm thickness) on 50×75 mm glass substrate (1 mm thickness) as shown in  FIG. 7 . The overlap is 50 mm. The glass substrates were adhered by a composition having a thickness control to be 0.125 mm.  FIG. 8  shows the force being applied to separate the bonded assembly. An average peel force of over 2N/25 mm is considered not debondable, as substrate failure will ordinarily be observed under such conditions. An average peel force between 1.5-2N/25 mm is considered semi-debondable, and an average peel force of less than 1.5N/25 mm is considered debondable. 
     Comparative Example 1 
     Vinyl-Terminated Polydimethylsiloxane 
     A series of alpha, omega-vinyl terminated linear polydimethylsiloxanes were cured in the presence of 1 weight percent Darocur 1173 under exposure to radiation of 50 mw/cm 2  UVA for a period of time of 60 seconds. The results are summarized in Table 4. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                 Base 
                 Viscosity 
                 Molecular 
                 Vinyl-  
                 State After  
               
               
                 Resin 
                 (cSt) 
                 Weight 
                 Eq/kg 
                 UV Cure 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 DMS-V05 
                 4-8 
                 800 
                 2.4-2.9 
                 Liquid 
               
               
                 DMS-V21 
                 100 
                 6000 
                 0.33-0.37 
                 Liquid 
               
               
                 DMS-V25 
                 500 
                 17,200 
                 0.11-0.13 
                 Liquid 
               
               
                 DMS-V31 
                 1000 
                 28,000 
                 0.07-0.10 
                 Liquid 
               
               
                 DMS-V41 
                 10,000 
                 62,700 
                 0.03-0.04 
                 Liquid + sticky gel 
               
               
                 DMS-V51 
                 100,000 
                 140,000 
                 0.016- 
                 Sticky Gel 
               
               
                   
                   
                   
                 0.018 
                   
               
               
                   
               
            
           
         
       
     
     As shown in the table, only those alpha, omega-vinyl terminated linear polydimethylsiloxanes with molecular weights above 60,000 daltons were found to gel or show the potential to be useful as a pressure sensitive adhesive after cure. DMS-V51 was mixed with 1 weight percent Darocur 1173 and 2 weight percent Luperox 231, and a drop placed between two microscope slides. The slide assembly was exposed to radiation in the electromagnetic spectrum in the UV range (50 mw/cm 2  UVA) for a period of time of 60 seconds. Next, the slide assembly was heated at a temperature of 150° C. for a period of time of 1 hour. The cured sample showed good adhesion to the slides but was observed to be hazy and non-uniform. It was difficult to separate the microscope slides by hand and thus not suitable for a debondable adhesive. 
     Comparative Example 2 
     Vinyl Terminated Diphenylsiloxane-Dimethylsiloxane Copolymers 
     A series of alpha, omega-vinyl terminated linear diphenylsiloxane-dimethylsiloxane copolymers were mixed with 1 weight percent Irgacure 2100 and 2 weight percent Luperox 231. One drop of each sample was placed between two microscope slides, and exposed to electromagnetic radiation (50 mW/cm 2  UVA) for a period of time of 60 seconds, and then heated at a temperature of 150° C. for a period of time of 1 hour. The results are summarized in Table 5. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                 Base 
                 Mole % 
                 Viscosity 
                 Mol. 
                 Vinyl- 
                 State After 
                 State After 
               
               
                 Resin 
                 —SiPh 2 O— 
                 (cSt) 
                 Wt. 
                 Eq/kg 
                 UV Cure 
                 Thermal Cure 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 PDV-0346 
                 3.0-3.5 
                 60,000 
                 78,000 
                 0.017-0.021 
                 Liquid 
                 Cured CF 
               
               
                 PDV-0541 
                 4-6 
                 10,000 
                 60,000 
                 0.027-0.038 
                 Liquid 
                 Cured AF 
               
               
                 PDV-1625 
                 15-17 
                 500 
                 9,500 
                 0.19-0.23 
                 Liquid 
                 Not completely 
               
               
                   
                   
                   
                   
                   
                   
                 cured 
               
               
                 PDV-1641 
                 15-17 
                 10,000 
                 55,000 
                 0.033-0.040 
                 Liquid 
                 Almost cured CF 
               
               
                   
               
               
                 AF: adhesive failure during debonding 
               
               
                 CF: cohesive failure during debonding 
               
            
           
         
       
     
     None of these resins contributed to a composition having pressure sensitive adhesive properties after UV cure. And after thermal cure, all the sample slides were difficult to separate by hand. 
     Rheology studies were conducted on formulations in Table 5 by ramping from room temperature to 150° C. at 10° C/minutes and then held at 150° C. for a period of time of 1 hour. The final storage modulus is tabulated in Table 6. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 6 
               
               
                   
                   
               
               
                   
                   
                 Final Modulus After 
               
               
                   
                 Base Resin 
                 150° C./1 h (Pa) 
               
               
                   
                   
               
             
            
               
                   
                 VDT-731 in Example 6 
                 1.61 × 10 6   
               
               
                   
                 PDV-0346 
                  4.0 × 10 4   
               
               
                   
                 PDV-0541 
                  1.1 × 10 5   
               
               
                   
                 PDV-1625 
                  3.6 × 10 4   
               
               
                   
                 PDV-1641 
                  1.6 × 10 4