HYDROCOLLOID ADHESIVE COMPOSITIONS

Abstract: The present invention is directed to pressure sensitive hydrocolloid adhesive compositions having probe tack of about 300-750 grams force, tensile strength of about 500-3500 grams/cm<2> and saline absorbency of about 500-5000 grams/m<2>/24 hours.

Description: HydrocoUoid Adhesive Compositions BACKGROUND OF THE INVENTION The present invention relates to pressure sensitive adhesive compositions and more particularly to pressure sensitive hydrocoUoid adhesive compositions suited for use in ostomy, wound and incontinence care. The compositions of this invention can be used for example to hold ostomy or incontinence devices onto the body of the user or to hold wound dressings in position for treating skin ailments or as the wound dressing itself. Various hydrocoUoid adhesive compositions suitable for medical uses are disclosed in the patent literature, e.g., U.S. Patent Nos. 3,339,549 (Chen); 4,192,785 (Chen, et al.); 4,166,051 (Cilento, et al.); 4,393,080 (Pawelchak, et al.); 3,612,053 (Pratt,et al.); 4,231,369 (Sorensen, et al.); 3,908,658 (Marsan); 4,367,732 (Poulsen, et al.); 4,378,018 (Alexander,et al.); and 4,393,150 (Krones). HydrocoUoid adhesives are composed of powdered hydrocolloids dispersed in an elastomeric polymer matrix. They have been found to make excellent pressure sensitive adhesives for attachment of devices to the skin. Useful hydrocoUoid adhesives depend on their initial tack, cohesive strength, and absorbency to achieve wearing times on skin of up to 10 days or longer. It is also required that components of hydrocoUoid adhesives be cost effective, easy to process, and compatible with other device components. OBJECT OF THE INVENTION It is an object of the present invention to provide a biocompatible hydrocoUoid adhesive composition simultaneously having preferred probe tack, tensile strength and saline absorbency as provided in Table 1. It is also an object of the present invention to provide a biocompatible adhesive that is easy to process, cost efficient, durable and that doesn't swell excessively when hydrated. It is an object to achieve with the present invention probe tack values above about 300 grams, force, as this value has been found to be desirable for attaining a strong initial bond to the skin. Improved bonds are generally obtained with increased tack, though too strong a bond may damage skin upon removal It is also an objective of the present invention to achieve acceptable shear strength and peel properties. It has been determined that tensile strengths of about 500 - 3500 g/square centimeter are desirable. It is also recognized, however, that decreased flexibility or reduced adhesion may result if cohesive strength is excessive. DESCRIPTION OF THE INVENTION The adhesive compositions of the present invention utilize a poly(ethylene-propylene) rubber (EPR) having a broad molecular weight, amorphous structure and an ethylene content of 50% or less. The EPR is also a random copolymer and easy to process. The preferred EPR is Vistalon 404, Exxon Chemical Co. Low molecular weight species in the EPR favor bond formation while higher molecular weight species enhance cohesive and peel strength. A compatible tackifying resin for this elastomer preferred for optimum tackification is a low molecular weight, highly hydrogenated polyvinylcyclohexane. Commercially available examples are Regalrez® 1085 or Regalrez® 1094. (Hercules, Inc.). It is further preferred that the polyvinylcyclohexane have a softening point below body temperature and most preferably below room temperature such that it may further improve the wetting of skin by the elastomeric component. A commercially available example is Regalrez® 1018 (Hercules, Inc.). In particular, the use of low softening point resin allows for increasing the concentration of tackifier by a corresponding reduction in the concentration of plasticizing components. Both factors favorably influence adhesion, while retaining flexibility that may be lost when resins of higher softening point are employed. Adhesion is easily measured by using a task test to determine the bond forming capability. Because hydrocoUoid adhesives are composed of an elastomeric phase and a hydrocoUoid phase, proper optimization of the adhesive formulation requires simultaneous optimization of the individual phases. While some interaction does occur between phases, the elastomeric phase is primarily responsible for the adhesive and cohesive strength properties, and the hydrocoUoid phase is primarily responsible for the overall moisture handling and moisture interaction characteristics of the formulation. Adhesion and cohesion typically represent a balance of competing behaviors, and strong elastomers may not yield very effective adhesives. Moisture handling is more than just absorption, per se, but must be thought of in terms of absorption rate, absorption capacity, and the properties of the hydrated material. The hydrocoUoid phase is key in determining these characteristics. The ability of the adhesive to form a bond to the skin is directly related to the probe tack of the adhesive. Tack is generated by the action of tackifying resins to enhance wetting of the skin by the elastomeric components of the formulation. Modification of elastomers by tackifiers enables elastomers to form bonds while retaining their cohesiveness and contribute strength to the overall formulation. Compatibility of the tackifier with the elastomer is believed to be a key factor in tackifier effectiveness, as is the presence of low molecular weight species in the elastomer. Typically, the elastomer is blended with a styrenic block copolymer for optimum cohesive strength. In order to attain adhesion to the skin for more than 1 or 2 days, it is necessary that the adhesive absorb fluid at a rate greater than or equal to the rate of transepidermal water loss (TEWL), approximately 7-10 g/square meter per hour on average. The actual absorption rate required to maintain skin adhesion can in practice be somewhat greater than this value as a function of weather, physical activity, etc. To obtain the minimum absorption capacity, this absorption rate should be multiplied over the wearing time. Absorption by the adhesive is necessary to effectively manage perspiration from the skin. Without this capability, the adhesive would fail after short wearing times, and skin condition would be adversely affected. However, absorption also causes degradation of the adhesive component resulting from hydration and chemical attack by stomal discharge. This degradation occurs because the absorbent hydrocolloids act regardless of the source of the fluid absorbed, either perspiration or stoma effluent. Therefore, limiting absorption to the minimum necessary to manage perspiration will limit how stoma fluid will impact dressing integrity. Denture adhesives are an example of water activated adhesives. Typically, sodium carboxy-methyl cellulose (NaCMC) is used as a component of these formulations. A blend of NaCMC grades is used to achieve desired properties. Differences between grades are defined by the degree of substitution (DS) of carboxymethyl groups onto the anhydroglucose repeat units of the cellulose chain. Higher DS grades (>1.0) are used to impart a high rate of absorption, while lower to moderate DS grades (<1.0) are included for their long term cohesiveness. One further requirement of the formulation is that its response to moisture must not compromise the performance of the device for which the adhesive was intended. As hydrocoUoid adhesives absorb moisture they begin to swell. The hydrating hydrocoUoid powders transform the rubbery elastomer phase into a more gelatinous composition that appears to grow. Typically this growth occurs in the direction of a free surface. For wound dressings the growth is into the wound. For ostomy skin barriers the growth is toward the stoma, and is called turtlenecking for its resemblance to the collar on a turtleneck sweater. In some cases turtlenecking is desirable, as it has been reported to provide an effective seal around the stoma itself and prevents leakage of stomal effluent and undermining of the skin barrier. However, excessive amounts of turtlenecking can have the opposite effect, causing effluent to be diverted from the pouch and against the skin. Excessive turtlenecking in hydrocoUoid adhesives can be avoided by limiting elongation of the elastomeric phase during hydration. Key factors in attaining acceptable turtlenecking are the choice of elastomer, the balance of absorption rate and capacity within the limits described above, the balance of cohesive and adhesive properties in the elastomer phase. In contrast to denture adhesives, it has been discovered that use of higher DS CMC grades in combination with low to moderate DS grades reduces the rate of moisture absoφtion in hydrocoUoid adhesives. In other words, as the average degree of substitution of the CMC in the formulation increases, the absoφtion rate of the hydrocoUoid adhesive decreases. Further, overall absoφtion capacity increases. As a result, longer wearing times are possible because the influence of stomal effluent on adhesive integrity is reduced, though the film forming and water activated bonding capabilities of CMC are retained. Additionally, turtlenecking characteristics are favorably impacted. Although it is possible to lower the absoφtion rate of the formulation by using different hydrocolloids having a weaker affinity for water, the impact on overall adhesive properties is not as favorable as with the use of higher DS CMC. Examples 34 and 35 below show how use of pregelatinized starch, a low absorbing hydrocoUoid, reduces the absoφtion rate of the formulation. However, in contrast with the performance of high DS CMC, the overall absoφtion capacity of the adhesive is not increased. Further, the water activated bonding power of hydrated starch to human skin is not believed to be as effective as either pectin or especially CMC. Therefore, addition of a minor amount of starch, or other low absorbing hydrocolloids, may expand the useful range of this invention to the extent that the effectiveness of the preferred hydrocolloids in extending wear time is not compromised. Addition of a small amount of a powdered cellulose, which is not a hydrocoUoid but a water swellable powder, is also useful for reducing moisture absoφtion while still being of similar composition to NaCMC. A further benefit of adding powdered cellulose is that it improves cohesive strength of the overall formulation. As a result of the fact that the EPR is can be readily blended with the other formulation components, a variety of conventional compounding processes are believed to be suitable for obtaining a homogeneous mixture. Potential mixing processes would include solvent blending, continuous or semi-continuous compounding, calendering or milling, and internal or external mixers. The preferred mixing process utilizes a high intensity batch mixer, which has been heated to between 250 and 330DF. The process proceeds by alternating additions of rubber or block copolymer with any of the powders and one of the low molecular weight components, which are mixed in groups until homogeneous. The entire process proceeds for as long as about 90 minutes or more. The low molecular weight components include any of the tackifiers and the plasticizer. The plasticizer used should be a low molecular weight polymer appropriately chosen to reduce the modulus of the formulation, promote flexibility and conformability of the adhesive, and be suitable for contact with the skin or mucosal tissue. Preferably petrolatum may be used. Formulated adhesive mass may then be formed by any of various means into smooth sheets. The preferred forming methods are extrusion or compression. A useful thickness range for the adhesive is believed to be in the range between 0.005 inch and 0.25 inch. This adhesive sheet may be laminated with a wide variety of films, foams, non-woven or other fabrics, etc. and also to paper, some of which may have been coated with release agents to promote removal. The adhesive sheet may be cut into useful sizes, shapes and dimensions including discs, profiles, contours or other constructions of adhesive articles. Laminates may be added readily to the adhesive when it is maintained at elevated temperature. Preferred methods of lamination include a roll based lamination station or a compression type process. Cutting may be accomplished using several methods, the preferred ones being a rotary cutting die or a platen type cutting die. EXAMPLES Table 2 provides a listing of 25 hydrocoUoid adhesives pursuant to the present invention. Each of these compositions are blended to produce compositions with the characteristics listed in Table 2 A within the usefulness ranges of Table 1. Additional examples showing the utility of the invention are shown in Table 6. Examples of the trade names for components of the compositions are the following: ethylene propylene rubber - Vistalon 404, Exxon Chemical Co.; styrenic block copolymer - Kraton Dl 107, Shell Chemical Co.; tackifier (solid) - Piccotac 95, Hercules, Inc.; tackifier (liquid) - Regalrez 1018, Hercules, Inc.; NaCMC - Sodium Carboxymethyle cellulose FCC grade with DS7 = degree of substitution = 0.7 DS12 = degree of substitution = 1.2 pectin - Pectin, USP 100; powdered cellulose, FCC - Solka Floe 200 FCC, Fiber Sales & Development Coφ. Antioxidant - Irganox 1010, Ciba Geigy Coφ.; Plasticizer - white petrolatum, USP; Cyclo-aliphatic tackifying resin - Relarez 1094, Hercules, Inc.; Hydrogenated rosin ester - Pentalyn H., Hercules, Inc.; Pregelatinized starch - Prejel PA5, Avebe, Inc. Examples 1-4 and 17-20 of Tables 2 and 2 A demonstrate acceptable performance within the usefulness ranges of Table 1. These examples represent a base adhesive which has no liquid tackifier, high DS DMC, or powdered cellulose but still achieves useful properties. Improvements to probe tack resulting from the use of low softening point tackifier are shown in Table 3. The effectiveness of high degree of substitution sodium carboxymethyl cellulose to reduce absoφtion is shown in Table 5. The ability of powdered cellulose to reduce absoφtion and increase strength is demonstrated in Table 4. Measurements of probe tack were based on the method described in ASTM D2979 using an inverted probe machine. In this test, conducted at room temperature, the dwell time was 1 second, and the approach speed was 1 cm/second. Tensile measurements were based on ASTM test method D412 with the crosshead speed set to 200 mm/minute using a dumb bell shaped test specimen. The peak tensile strength is reported. Absorbency measurements were conducted based on the British Pharmacopoeia method wherein a flat adhesive specimen of known weight and area is exposed to 0.9% saline solution. The exposed adhesive is incubated at body temperature for 24 hours and re-weighed. The weight difference per area is reported. Table 2 Example Ethylene- Styrenic Tackifying Anti- NaCMC : Pechn Low Plasticizer NaCMC Powdei Propylene Block Resin oxidanl DS7 Softening DS12 Cellule Rubber Copolymer Point Tackifier 1 6 0% 13 0% 28 0% 0 5% 33 0% 10 0% 9 5% 2 2 0% 10 0% 33 0% 0 5% 27 0% 20 0% 7 5% 3 10 0% 16 0% 24 0% 0 5% 32 5% 5 0% 12 0% 4 7 0% 10 5% 28 0% 0 5% 26 0% 20 0% 8 0% 5 6 0% 13 0% 30 0% 0 5% 35 0% 7 0% 8 5% 6 6 0% 13 0% 28 0% 0 5% 35 0% 7 0% 2 0% 8 5% oo c= 7 6 0% 13 0% 25 0% 0 5% 35 0% 7 0% 5 0% 8 5% 00 00 8 6 0% 13 0% 28 0% 0 5% 35 0% 7 0% 5 0% 5 5% 9 β.0% 13 0% 28 0% 0 5% 30 0% 7 0% 5 0% 5 5% 5 0% 10 6 0% 13 0% 28 0% 0 5% 20 0% 7 0% 5 5% 5 5% 15 0% 00 11 6 0% 13 0% 28 0% 0 5% 10 0% 7 0% 5 5% 5 5% 25 0% 3- m 12 6 0% 13 0% 25 0% 0 5% 15 0% 15 0% 5 5% 5 0% 15 0% 13 5 0% 12 5% 25 0% 0 5% 28 0% 15 0% 2 0% 7 0% 5 0% 14 5 0% 12.5% 25 0% 0 5% 25 0% 15 0% 2 0% 7 0% 5 0% 3 0% 15 5 0% 12.5% 25 0% 0 5% 22 0% 15 0% 2 0% 7 0% 5 0% 6 0% 16 5 0% 12 5% 28 0% 0 5% 20 0% 15 0% 2 0% 7 0% 8 0% 2 0% 17 5 0% 12 5% 28 0% 0 5% 30 0% 15 0% 9 0% IS 2 0% 15 5% 28 0% 0 5% 30 0% 15 0% 9 0% 19 8 0% 9 5% 28 0% 0 5% 30 0% 15 0% 9 0% 20 5 0% 12 5% 28 0% 0 5% 30 0% 15 0% 9 0% 21 5 0% 12 5% 28 0% 0 5% 30 0% 15 0% 3 0% 6 0% 22 2 0% 15 5% 28 0% 0 5% 30 0% 15 0% 6 0% 3 0% 23 8 0% 9 5% 25 0% 0 5% 30 0% 15 0% 3 0% 9 0% 24 8 0% 9 5% 25 0% 0 5% 30 0% 15 0% 6 0% 6 0% 25 8 0% 9 5% 28 0% 0 5% 20 0% 15 0% 3 0% 6 0% 10 0% Table 2Λ <amρlie Probe Tack Tensile 24 Hr Saline Strength Absorption g tack force g/cm A 2 g/sq.m/24 hr (non-extruded) (non-extruded) 1 432 852 1937 2 411 2966 3459 3 470 860 1439 4 418 1465 2936 5 559 1690 2111 6 481 1451 2479 7 517 1637 2947 8 615 1690 3507 9 586 1587 2859 10 418 1574 2113 11 438 2065 1538 12 477 1757 2257 13 572 1032 3590 14 449 1919 3237 15 425 1830 2446 16 599 1312 1869 17 508 662 2200 18 426 1538 2705 19 529 824 3249 20 491 1205 2209 21 531 998 2843 22 420 2183 2861 23 394 587 2326 24 450 632 3107 25 597 873 2426 Table 3 Examples Showing Improvement in Tack Using Low Softening Point Tackifier Low Example Ethylene- Styrenic Tackifying Anti- NaCMC Pectin Softening NaCMC Powdered Probe Tack Propylene Block Resin oxidant Lo DS Point Plasticizer High DS Cellulose Rubber Copolymer Tackifier % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w g tack force 1 6.0% 13.0% 28.0% 0.5% 33.0% 10.0% 9.5% 432 2 2.0% 10.0% 33.0% 0.5% 27.0% 20.0% 7.5% 411 3 10.0% 16.0% 24.0% 0.5% 32.5% 5.0% 12.0% 470 4 7.0% 10.5% 28.0% 0.5% 26.0% 20.0% 8.0% 418 c 6 6.0% 13.0% 28.0% 0.5% 35.0% 7.0% 2.0% 8.5% 481 00 7 6.0% 13.0% 25.0% 0.5% 35.0% 7.0% 5.0% 8.5% 517 8 6.0% 13.0% 28.0% 0.5% 35.0% 7.0% 5.0% 5.5% 615 rπ 21 5.0% 12.5% 28.0% 0.5% 30.0% 15.0% 3.0% 6.0% 531 oo X 25 8.0% 9.5% 28.0% 0.5% 20.0% 15.0% 3.0% 6.0% 10.0% 597 m 2 c Table 4 r- m Examples Showing Improvement in Tensile Strength Using Powdered Cellulose Low Tensile Example Ethylene- Styrenic Tackifying Anti- NaCMC Pectin Softening Plasticizer NaCMC Powdered Strength Propylene Block Resin oxidant Low DS Point High DS Cellulose Rubber Copolymer Tackifier % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w g/cm Λ 2 13 5.0% 12.5% 25.0% 0.5% 28.0% 15.0% 2.0% 7.0% 5.0% 1032 14 5.0% 12.5% 25.0% 0.5% 25.0% 15.0% 2.0% 7.0% 5.0% 3.0% 1919 15 5.0% 12.5% 25.0% 0.5% 22.0% 15.0% 2.0% 7.0% 5.0% 6.0% 1830 16 5.0% 12.5% 28.0% 0.5% 20.0% 15.0% 2.0% 7.0% 8.0% 2.0% 1312 Table 5 Examples Showing Reduced Absoφtion Using High Degree of Substitution CMC Low 24 Hr Example Ethylene- Styrenic Tackifying Anti- NaCMC Softening NaCMC Powdered Saline Propylene Block Resin oxidant Low DS Pectin Point Plasticizer High DS Cellulose Absoφtion Rubber Copolymer Tackifier % w/w % w/w % w/w % w/w % w/w % w/w % w/w g/sq.m/24 hr 8 6.0% 13.0% 28.0% 0.5% 35.0% 7.0% 5.0% 5.5% 3507 CO <= 9 6.0% 13.0% 28.0% 0.5% 30.0% DO 7.0% 5.0% 5.5% 5.0% 2859 00 10 6.0% 13.0% 28.0% 0.5% 20.0% 7.0% 5.5% 5.5% 15.0% 2113 c= 11 6.0% 13.0% 28.0% 0.5% 10.0% 7.0% 5.5% 5.5% 25.0% 1538 H m 12 6.0% 13.0% 25.0% 0.5% 15.0% 15.0% 5.5% 5.0% 15.0% 2257 oo 3. 25 8.0% 9.5% 28.0% 0.5% 20.0% 15.0% 3.0% 6.0% 10.0% 2426 m m • Ό 5 <S

Claims: What is claimed is: 1. A pressure sensitive hydrocoUoid adhesive comprising the following composition by percentage weight: a) from about 2% to about 10% ethylene propylene rubber b) from about 9.5% to about 16% styrenic block copolymer c) from about 24% to about33% tackifying resin d) from about up to .5% anti-oxidant e) from about 15% to about35% NaCMC (Low DS) f) from about 5% to about20% pectin g) from 0% to about 6% tackifier with low softening point h) from about 3% to aboutl2% plasticizer i) from 0% to about 25% NaCMC (high DS) j) from 0% to about 6% powdered cellulose wherein the probe tack force in grams is in the range of 400-750. 2. The hydrocoUoid adhesive of claim 1 wherein the ethylene propylene rubber has a broad molecular weight distribution. 3. The hydrocoUoid adhesive of claim 1 wherein the ethylene propylene rubber is amorphous and random. 4. The hydrocoUoid adhesive of claim 1 wherein the ethylene propylene rubber has an ethylene content of 50% or less. 5. The hydrocoUoid adhesive of claim 1 wherein the probe tack force in grams is in the range of 500-650 grams. 6. The hydrocoUoid adhesive of claim 1 wherein the saline absorbency in grams per square meter for a 24 hour period is in the range of 1250 - 5000. 7. The hydrocoUoid adhesive of claim 1 wherein the saline absorbency in grams per square meter for a 24 hour period is in the range of 2000 - 3500 when extruded. 8. The hydrocoUoid adhesive of claim 1 wherein the saline absorbency in grams per square meter for a 24 hour period is in the range of 1500 - 2500 when non-extruded. 9. The hydrocoUoid adhesive of claim 1 wherein the non-extruded tensile strength in grams per square centimeter is in the range of 800 - 1500. 10. The hydrocoUoid adhesive of claim 1 wherein the tensile strength in grams per square centimeter is in the range of 500 - 3500. 11. The hydrocoUoid adhesive composition of claim 1 wherein the extruded tensile strength is in the range of 1500 - 2500 grams per square centimeter. 12. The hydrocoUoid adhesive of claim 1 wherein the probe tack is between about 300 to about 750 grams, force. 13. The hydrocoUoid adhesive of claim 1 wherein the absoφtion of saline at 37°C is between about 500 and about 5,000 grams per square meter per day. 14. The hydrocoUoid adhesive of claim 1 wherein the tensile strength is between about 500 and 3,500 grams per square centimeter. 15. The hydrocoUoid adhesive of claim 1 wherein the tackifier softening point is below about 37°C. 16. A pressure sensitive hydrocoUoid adhesive comprising the following composition by percentage weight: a) from about 2% to about 20% ethylene propylene rubber. b) zfrom about 2% to about 16% styrenic block copolymer. c) from about 14% - about 33% tackifying resin selected from the group of aliphatic, cyclo-aliphatic, mixed aliphatic-aromatic, hydrocarbon, pure monomer, rosins, gums and their esters and derivatives, or terpene or polyterpene resins. d) from 0% to about 0.5% anti-oxidant. e) from about 10% to about 35% NaCMC with degree of substitution below 1.0. f) from 0% to about 30.5% pectin. g) from about 3% to about 12% plasticizer. h) from 0% to about 6% tackifier with softening point below about 37°C. i) from 0% to about 25% NaCMC with degree of substitution above 1.0. j) from 0% to about 6% powdered cellulose. 17. The hydrocoUoid adhesive of claims 16 wherein the probe tack is between about 300 to about 750 grams, force. 18. The hydrocoUoid adhesive of claims 16 wherein the absoφtion of saline at 37°C is between about 500 and about 5,000 grams per square meter per day. 19. The hydrocoUoid adhesive of claims 16 wherein the tensile strength is between about 500 and 3,500 grams per square centimeter. 20. A pressure sensitive hydrocoUoid adhesive comprising the following composition by percentage weight: a) from about 11.5% to about 36% of a hydrocoUoid blend of ethylene propylene rubber and styrenic block copolymer. b) from about 24% to about 39% tackifying resin c) from 0% to about 0.5% anti-oxidant. d) from about 20% to about 52% absorbent powder selected from the group NaCMC, Pectin, powdered cellulose, and pregelatinized starch, optionally including minor amounts of powdered fillers, fibers, absorbents, or super absorbents. e) from about 3% to about 12% plasticizer. f) from 0% to about 6% tackifier with softening point below about 37°C. g) from 0% to about 25% NaCMC with degree of substitution above 1.0. h) from 0% to about 6% powdered cellulose. 21. The hydrocoUoid adhesive of claim 20 wherein the probe tack is between about 300 to about 750 grams, force. 22. The hydrocoUoid adhesive of claim 20 wherein the absoφtion of saline at 37°C is between about 500 and about 5,000 grams per square meter per day. 23. The hydrocoUoid adhesive of claim 20 wherein the tensile strength is between about 500 and 3,500 grams per square centimeter.

Inventors: FATTMAN GEORGE, FATTMAN, GEORGE
Applicants: SQUIBB BRISTOL MYERS CO, BRISTOL-MYERS SQUIBB COMPANY
Application year: 1999
Main classification: C08L15
IPC codes: A61L15, A61L28, C08L1, C08L23, C08L53, C08L55, C09J101, C09J105, C09J123, C09J153