Silicone composition for release paper or release film, and release paper and release film

Abstract

A compound that is devoid of epoxy groups and has a quantity of alkenyl groups corresponding to 5-1000 times the alkenyl content of a base polymer, and/or an organopolysiloxane that is devoid of alkenyl groups, has an average degree of polymerization of 2-50, and contains, per molecule, 30 mol % or more of siloxane units having epoxycyclohexyl groups bonded to silicon atoms via carbon atoms, are/is blended with a silicone composition for a release film as adhesion-enhancing components.

Claims

1. A release paper or film-forming silicone composition comprising (A) 100 parts by weight of an organopolysiloxane containing at least two alkenyl groups per molecule and having an alkenyl content of 0.001 to 0.15 mol/100 g and a 30 wt % toluene dilution viscosity at 25° C. of 0.01 to 70 Pa.Math.s, and is represented by the following general formula (5): ##STR00029## wherein each R.sup.5, which may be identical or different, is independently selected from the group consisting of a substituted or unsubstituted C.sub.1-C.sub.20 monovalent hydrocarbon group free of aliphatic unsaturation and a C.sub.2-C.sub.12 alkenyl group, the monovalent hydrocarbon group being selected from the group consisting of C.sub.1-C.sub.6 alkyl groups, C.sub.6-C.sub.10 aryl groups, C.sub.7-C.sub.10 aralkyl groups, and 3,3,3-trifluoropropyl, the alkenyl group may contain an ether bond, wherein at least two of R.sup.5 are alkenyl, wherein h, i, j and k are independently selected from a positive number to meet a viscosity in the above range, wherein h is an integer of at least 2, i is an integer of at least 100, j is an integer of at least 0, and k is an integer of at least 0, and further wherein 150≤h+i+j+k≤20,000; (B) an adhesion improving component comprising: compound (B1) and compound (B2): (B1) 0.1 to 30 parts by weight of a compound containing at least two alkenyl groups per molecule, having an alkenyl content corresponding to 5 to 1,000 times the alkenyl content of component (A), being free of epoxy groups, and having a viscosity at 25° C. of less than 1 Pa.Math.s or a 30 wt % toluene dilution viscosity of less than 0.1 Pa.Math.s, and component (B1) being a hydrocarbon compound which has at least two alkenyl groups per molecule, may contain a hydroxyl group, and may contain an aryl group, an ether bond, or an ester bond, or an organopolysiloxane having the general formula (6) ##STR00030## wherein R.sup.6, which may be identical or different, is a substituted or unsubstituted C.sub.1-C.sub.20 monovalent hydrocarbon group free of aliphatic unsaturation or a C.sub.2-C.sub.12 alkenyl group, the monovalent hydrocarbon group being selected from the group consisting of C.sub.1-C.sub.6 alkyl groups, C.sub.6-C.sub.10 aryl groups, C.sub.7-C.sub.10 aralkyl groups and 3,3,3-trifluoropropyl, the alkenyl group may contain an ether bond, at least two of R.sup.6 being alkenyl, m, n, o and p are independently selected from a positive number to meet a viscosity in the above range, wherein m is an integer of at least 2, n is an integer of at least 0, o is an integer of at least 0, and p is an integer of at least 0, and further wherein 2≤m+n+o+p≤502; (B2) 0.5 to 15 parts by weight of an organopolysiloxane containing at least 30 mol % per molecule of siloxane units having an epoxycyclohexyl group bonded to a silicon atom via a carbon atom, and further wherein the compound (B2) is free of alkenyl groups, has an average degree of polymerization of 2 to 50, and is a cyclic siloxane structure having the general formula (2): ##STR00031## wherein Ep is a monovalent organic group having epoxycyclohexyl, R.sup.1 which may be identical or different is a substituted or unsubstituted C.sub.1-C.sub.20 monovalent hydrocarbon group free of aliphatic unsaturation, the monovalent hydrocarbon group being selected from the group consisting of alkyl groups, aryl groups and aralkyl groups, d is an integer of 0 to 3, e is an integer of 1 to 6, d+e is 3 to 6, and are selected so as to satisfy that the organopolysiloxane contains at least 30 mol % of epoxycyclohexyl-containing siloxane units, (C) an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms per molecule, and represented by the average compositional formula (7),
R.sup.7.sub.sH.sub.tSiO.sub.(4-s-t)/2  (7) wherein R.sup.7, which may be identical or different, is a substituted or unsubstituted monovalent hydrocarbon group free of aliphatic unsaturation, the monovalent hydrocarbon group being selected from the group consisting of C.sub.1-C.sub.6 alkyl groups, C.sub.6-C.sub.10 aryl groups, C.sub.7-C.sub.10 aralkyl groups and 3,3,3-trifluoropropyl, s is 0.1 to 2, t is 0.1 to 3, and s+t is up to 3.1, (C) is present in such an amount that the moles of silicon-bonded hydrogen atoms corresponds to 0.5 to 10 times the moles of alkenyl groups in components (A) and (B1), (D) a catalytic amount of a platinum group metal base catalyst, (E) 0 to 20,000 parts by weight of an organic solvent or water, and (F) 0.1 to 20 parts by weight of a release force controlling component comprising an acrylic-silicone graft copolymer obtained from radical polymerization of (a) an organopolysiloxane compound having an acrylic and/or methacrylic group, represented by the general formula (3), and (b) a radically polymerizable monomer having one radically polymerizable group per molecule, the graft copolymer having a weight average molecular weight of 1,000 to 100,000, ##STR00032## wherein R.sup.2 is hydrogen or methyl, X is a group selected from oxygen, NH and sulfur, Y is a C.sub.1-C.sub.12 divalent hydrocarbon group which may contain an ether bond, R.sup.3 which may be identical or different is a substituted or unsubstituted C.sub.1-C.sub.20 monovalent hydrocarbon group, hydrogen, hydroxyl, C.sub.1-C.sub.10 alkoxy group or substituent group having the general formula (4): ##STR00033## wherein R.sup.4 which may be identical or different is a substituted or unsubstituted C.sub.1-C.sub.20 monovalent hydrocarbon group, hydrogen, hydroxyl or C.sub.1-C.sub.10 alkoxy group, and g is an integer of 0 to 300, wherein the silicone composition is addition curable, and wherein the weight ratio of (a) the organopolysiloxane compound having an acrylic and/or methacrylic group to (b) the radically polymerizable monomer having one radically polymerizable group per molecule ranges from 60/40 to 99/1.

2. The release paper or film-forming silicone composition of claim 1, wherein component (B2) is present in an amount of 0.5 to 5.0 parts by weight per 100 parts by weight of the organopolysiloxane as component (A).

3. The release paper or film-forming silicone composition of claim 1, wherein component (B1) is present in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the organopolysiloxane as component (A).

4. The release paper or film-forming silicone composition of claim 1, wherein component (B1) is present in an amount of 0.35 to 7.6 parts by weight per 100 parts by weight of the organopolysiloxane as component (A).

5. The release paper or film-forming silicone composition of claim 1, wherein component (A) has a 30 wt % toluene dilution viscosity at 25° C. of 0.01 to 50 Pa.Math.s.

6. The release paper or film-forming silicone composition of claim 1, wherein the component (A) contains an alkenyl content of 0.001 to 0.04 mol/100 g.

7. The release paper or film-forming silicone composition of claim 1, wherein the alkenyl content of component (B1) corresponds to 5 to 500 times the alkenyl content of component (A).

8. The release paper or film-forming silicone composition of claim 1, wherein the alkenyl content of component (B1) corresponds to 5 to 400 times the alkenyl content of component (A).

9. The release paper or film-forming silicone composition of claim 1, wherein the alkenyl content of component (B1) corresponds to 5 to 130 times the alkenyl content of component (A).

10. The release paper or film-forming silicone composition of claim 1, wherein the component (B1) is the hydrocarbon compound.

11. The release paper or film-forming silicone composition of claim 1, wherein the amount of (C) is such that the moles of silicon-bonded hydrogen atoms corresponds to 0.5 to 5 times the moles of alkenyl groups in components (A) and (B1).

12. The release paper or film-forming silicone composition of claim 1, wherein the weight ratio of (a) the organopolysiloxane compound having an acrylic and/or methacrylic group to (b) the radically polymerizable monomer having one radically polymerizable group per molecule ranges from 85/15 to 99/1.

13. A release paper or film which is obtained by coating the release paper or film-forming silicone composition of claim 1 onto a paper or film substrate, and curing the composition.

Description

EXAMPLE

(1) Synthesis Examples, Examples and Comparative Examples are given below although the invention is not limited thereto. In Examples, all parts are parts by weight (pbw).

(2) Preparation of Silicone Composition and Release Film

(3) <Starting Materials>

(4) Component (A)

(5) (A-1) organopolysiloxane consisting of 0.04 mol % of trivinylsiloxane units: (CH.sub.2═CH).sub.3SiO.sub.1/2, 0.4 mol % of methylvinylsiloxane units: (CH.sub.3)(CH.sub.2═CH)SiO.sub.2/2, and 99.56 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2. 30 wt % toluene dilution viscosity at 25° C.=15 Pa.Math.s alkenyl content=0.01 mol/100 g (A-2) organopolysiloxane consisting of 0.02 mol % of dimethylvinylsiloxane units: (CH.sub.3).sub.2(CH.sub.2═CH)SiO.sub.1/2, 3.4 mol % of methylvinylsiloxane units: (CH.sub.3)(CH.sub.2═CH)SiO.sub.2/2, and 96.58 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2. 30 wt % toluene dilution viscosity at 25° C.=10 Pa.Math.s alkenyl content=0.04 mol/100 g
Component (B) (B1-1) organopolysiloxane consisting of 50 mol % of (CH.sub.3).sub.2(CH.sub.2═CH)SiO.sub.1/2 units and 50 mol % of (CH.sub.3)SiO.sub.3/2 units. viscosity at 25° C.=0.1 Pa.Math.s alkenyl content=0.55 mol/100 g (B1-2) organopolysiloxane consisting of 10 mol % of dimethylvinylsiloxane units: (CH.sub.3).sub.2(CH.sub.2═CH)SiO.sub.1/2 and 90 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2. viscosity at 25° C.=0.01 Pa.Math.s alkenyl content=0.25 mol/100 g (B1-3) organopolysiloxane consisting of 4 mol % of dimethylvinylsiloxane units: (CH.sub.3).sub.2(CH.sub.2═CH)SiO.sub.1/2 and 96 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2. viscosity at 25° C.=0.1 Pa.Math.s alkenyl content=0.06 mol/100 g (B1-4) organopolysiloxane consisting of 1.5 mol % of dimethylvinylsiloxane units: (CH.sub.3).sub.2(CH.sub.2═CH)SiO.sub.1/2, 12.8 mol % of methylvinylsiloxane units: (CH.sub.3)(CH.sub.2═CH)SiO.sub.2/2, and 85.7 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2. viscosity at 25° C.=0.3 Pa.Math.s alkenyl content=0.2 mol/100 g (B1-5)

(6) ##STR00018## (B1-6)

(7) ##STR00019## (B1-7) organopolysiloxane consisting of 1.4 mol % of dimethylvinylsiloxane units: (CH.sub.3).sub.2(CH.sub.2═CH)SiO.sub.1/2 and 98.6 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2. viscosity at 25° C.=0.4 Pa.Math.s alkenyl content=0.02 mol/100 g (B2-1) organopolysiloxane of the formula below.

(8) ##STR00020##
(w=4, Ep.sup.1=2-(3,4-epoxycyclohexyl)ethyl, Me=methyl) (B2-2) organopolysiloxane of the formula below.

(9) ##STR00021## (B2-3) organopolysiloxane of the formula below.

(10) ##STR00022## (B2-4) organopolysiloxane of the formula below.

(11) ##STR00023## (B2-5) organopolysiloxane of the formula below.

(12) ##STR00024## (B2-6) organopolysiloxane of the formula below.

(13) ##STR00025## (B2-7) organopolysiloxane of the formula below.

(14) ##STR00026## (B2-8) epoxy-containing organopolysiloxane obtained by reacting 43 wt % of an organopolysiloxane consisting of 20 mol % of silanol-terminated siloxane units: (CH.sub.3).sub.2(OH)SiO.sub.1/2, 40 mol % of methylvinylsiloxane units: (CH.sub.3)(CH.sub.2═CH)SiO.sub.2/2, and 40 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2 and having a viscosity at 25° C. of 20 mm.sup.2/s with 57 wt % of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in the presence of potassium siliconate at 100° C. for 1 hour. viscosity at 25° C.=0.6 Pa.Math.s alkenyl content=0.20 mol/100 g average DOP=20 siloxane units having epoxycyclohexyl bonded to silicon via carbon=40 mol % (B2-9) organopolysiloxane of the formula below.

(15) ##STR00027## (B2-10) epoxy-containing siloxane oligomer obtained from partial hydrolytic condensation of 99.98 wt % of 3-glycidoxypropyltriethoxysilane with 0.02 wt % of water in the presence of hydrochloric acid at 100° C. for 5 hours. viscosity at 25° C.=0.01 Pa.Math.s average DOP=3 siloxane units having epoxy bonded to silicon via carbon=100 mol %
Component (C) (C-1) organohydrogenpolysiloxane consisting of 2 mol % of trimethylsiloxane units: (CH.sub.3).sub.3SiO.sub.1/2, 68 mol % of methylhydrogensiloxane units: (CH.sub.3)HSiO.sub.2/2, and 30 mol % of dimethylsiloxane units: (CH.sub.3).sub.2SiO.sub.2/2. viscosity at 25° C.=0.1 Pa.Math.s SiH content=1.1 mol/100 g (C-2) organohydrogenpolysiloxane consisting of 5 mol % of trimethylsiloxane units: (CH.sub.3).sub.3SiO.sub.1/2 and 95 mol % of methylhydrogensiloxane units: (CH.sub.3)HSiO.sub.2/2. viscosity at 25° C.=0.02 Pa.Math.s SiH content=1.5 mol/100 g
Component (D)

(16) platinum-vinyl siloxane complex as catalyst

(17) Component (E)

(18) solvent mixture of toluene and hexane in a weight ratio of 1:1

(19) Component (F)

(20) (F-1) release force-controlling component: acrylic-silicone graft copolymer obtained in Synthesis Example 1

Synthesis Example 1

(21) A glass reactor equipped with a stirrer, thermometer, reflux condenser and dropping funnel was charged with 30.0 parts of toluene and heated at 90-100° C. Under nitrogen stream, a mixture of 55.7 parts (0.067 mol) of a radically polymerizable silicone macromonomer having the formula (8), 9.8 parts (0.098 mol) of methyl methacrylate, 2.5 parts (0.012 mol) of tert-butyl 2-ethylperoxyhexanoate, and 51.8 parts of toluene was added dropwise to the reactor over 4 hours. After polymerization at 90-100° C. for 2 hours, 0.4 part (0.002 mol) of tert-butyl 2-ethylperoxyhexanoate was added, and polymerization continued for 2 hours. The reaction solution was then dried in a vacuum dryer under conditions of 150° C./10 mmHg, yielding an acrylic-silicone graft copolymer. It had a Mw of 12,000 as measured by GPC versus polystyrene standards.

(22) ##STR00028##
Component (G)

(23) pot-life prolonging agent: 3-methyl-1-butyn-3-ol

Examples 1 to 15 and Comparative Examples 1 to 8

(24) A coating composition was prepared by the following procedure using the foregoing components (A) to (E) and (G) as starting materials.

(25) Components (A) to (C) were fed into a flask in accordance with the formulation in Table 1, 3,200 parts of component (E) and 3 parts of component (G) were added thereto, and the contents were stirred and dissolved. Component (D) was added to the solution in an amount to give 100 ppm of platinum based on the weight of component (A). The solution was stirred and mixed, yielding the coating composition. Using the coating composition, a coated article was prepared and evaluated by the procedures described below.

(26) <Evaluation>

(27) [Curability (Adhesion Immediately after Curing)]

(28) The composition was coated to a PET film of 38 μm thick by means of a bar coater in a coating weight of 0.1 g/m.sup.2 as solids and heated in a hot air dryer at 100° C. for a predetermined time (second) to form a release agent layer. The release agent layer was rubbed with the finger 10 strokes, after which it was visually observed for smear and rub-off and evaluated according to the following criterion.

(29) A: no smear or rub-off at time of 30 seconds

(30) B: smear and rub-off at time of 30 seconds, but not at 40 seconds

(31) C: smear and rub-off at time of 40 seconds, but not at 50 seconds

(32) D: smear and rub-off at time of 50 seconds

(33) [Release Force]

(34) The composition was coated to a PET film of 38 μm thick by means of a bar coater in a coating weight of 0.1 g/m.sup.2 as solids and heated in a hot air dryer at 120° C. for 40 seconds to form a release agent layer. Evaluation was made by the following procedure according to the FINAT test method.

(35) A PSA tape of 25 mm wide (Tesa 7475 tape by Tesa Tape Inc.) was rested on the surface of the release agent layer. With a load of 20 g/cm.sup.2 rested on the PSA tape, the assembly was heat treated in a dryer at 70° C. for 20 hours. The assembly was cooled in air for 30 minutes. Using a tensile tester (DSC-500 model tester by Shimadzu Corp.), a release force (N/25 mm) was measured by peeling the Tesa 7475 tape from the release agent layer at an angle of 180° and a peel rate of 0.3 m/min.

(36) [Residual Adhesion]

(37) A release agent layer was formed as in the above release force test. A polyester PSA tape of 25 mm wide (Nitto 31B by Nitto Denko Corp.) was rested on the surface of the release agent layer. With a load of 20 g/cm.sup.2 rested on the PSA tape, the assembly was heat treated in a dryer at 70° C. for 20 hours. Thereafter, the polyester PSA tape was peeled from the release agent layer and in turn, attached to a stainless steel plate. Next, using a tensile tester, a release force F required to peel the polyester PSA tape from the steel plate was measured.

(38) Also, a polyester PSA tape was bonded to a tetrafluoroethylene plate instead of the release agent layer and similarly treated, after which a release force F.sub.0 was measured.

(39) A percent residual adhesion was computed from the formula:
(release force F/release force F.sub.0)×100(%).
[Adhesion]

(40) A release agent layer was formed as in the above release force test. The sample was stored at 25° C. and 50% RH for one week or at 60° C. and 90% RH for one week. The release agent layer was rubbed with the finger 10 strokes, after which it was visually observed for smear and rub-off and evaluated according to the following criterion.

(41) A: no smear or rub-off

(42) B: some smear or rub-off

(43) C: smear or rub-off

(44) TABLE-US-00001 TABLE 1 H/Vi Release Residual Adhesion Alkenyl moles B force adhesion 25° C./ 60° C./ content (C + B2)/ A B1 B2 C Curability (N/25 mm) (%) 50% RH 90% RH B/A (A + B) Example 1 A-1 B1-1 B2-1 C-1 A 0.25 95 A A 55.0 1.7 100 pbw 0.83 pbw 3.3 pbw 2.2 pbw 2 A-1 B1-2 B2-1 C-1 A 0.26 95 A A 25.0 1.7 100 pbw  1.8 pbw 3.3 pbw 2.2 pbw 3 A-1 B1-3 B2-1 C-1 A 0.25 98 A A  6.0 1.7 100 pbw  7.6 pbw 3.3 pbw 2.2 pbw 4 A-1 B1-4 B2-1 C-1 A 0.25 97 A A 20.0 1.7 100 pbw  2.3 pbw 3.3 pbw 2.2 pbw 5 A-1 B1-5 B2-1 C-1 A 0.26 96 A A 130.0  1.7 100 pbw 0.35 pbw 3.3 pbw 2.2 pbw 6 A-1 B1-6 B2-1 C-1 A 0.25 94 A A 70.0 1.7 100 pbw 0.63 pbw 3.3 pbw 2.2 pbw 7 A-1 B1-1 B2-2 C-1 A 0.28 98 A A 55.0 2.0 100 pbw 0.83 pbw 3.3 pbw 2.2 pbw 8 A-1 B1-1 B2-3 C-1 A 0.25 98 A A 55.0 1.7 100 pbw 0.83 pbw 3.3 pbw 2.2 pbw 9 A-1 B1-1 B2-5 C-1 A 0.26 98 A A 55.0 1.7 100 pbw 0.83 pbw 3.3 pbw 2.2 pbw 10 A-1 B1-1 — C-1 A 0.24 96 A B 55.0 1.7 100 pbw 0.83 pbw 2.2 pbw 11 A-1 B1-6 — C-1 A 0.24 95 A B 70.0 1.7 100 pbw 0.63 pbw 2.2 pbw 12 A-1 — B2-1 C-1 A 0.31 97 A A — 2.4 100 pbw 3.3 pbw 2.2 pbw 13 A-1 — B2-4 C-1 A 0.30 98 A A — 2.4 100 pbw 3.3 pbw 2.2 pbw 14 A-1 — B2-5 C-1 A 0.29 98 B A — 2.4 100 pbw 3.3 pbw 2.2 pbw Comparative 1 A-1 — — C-1 A 0.27 100 B C — 2.4 Example 100 pbw 2.2 pbw 2 A-1 B1-7 — C-1 A 0.23 98 B C  2.0 1.7 100 pbw 20.0 pbw 2.2 pbw 3 A-1 — B2-6 C-1 A 0.28 97 B C — 2.4 100 pbw 3.3 pbw 2.2 pbw 4 A-1 — B2-7 C-1 A 0.27 97 B C — 2.4 100 pbw 3.3 pbw 2.2 pbw 5 A-1 — B2-8 C-1 C 0.24 99 A A 20.0 1.5 100 pbw 3.3 pbw 2.2 pbw 6 A-1 — B2-9 C-1 A 0.28 98 B C — 2.4 100 pbw 3.3 pbw 2.2 pbw 7 A-1 — B2-10 C-1 A 0.27 96 B C — 2.4 100 pbw 3.3 pbw 2.2 pbw Example 15 A-2 B1-1 B2-1 C-2 A 0.73 94 B A 13.8 1.2 100 pbw  4.8 pbw 3.3 pbw 5.3 pbw Comparative 8 A-2 — — C-2 A 0.88 99 B C — 2.0 Example 100 pbw 5.3 pbw

Examples 16 to 19 and Comparative Examples 9 to 11

(45) A coating composition was prepared by the following procedure using the foregoing components (A) to (G) as starting materials.

(46) Components (A) to (C) and (F) were fed into a flask in accordance with the formulation in Table 2, 3,200 parts of component (E) and 3 parts of component (G) were added thereto, and the contents were stirred and dissolved. Component (D) was added to the solution in an amount to give 100 ppm of platinum based on the weight of component (A). The solution was stirred and mixed, yielding the coating composition. Using the to coating composition, a coated article was prepared and evaluated by the above-described procedures.

(47) TABLE-US-00002 TABLE 2 Release force Residual Adhesion Alkenyl H/Vi B (N/25 adhesion 25° C./ 60° C./ content moles C/ A B1 B2 C F Curability mm) (%) 50% RH 90% RH B/A (A + B) Example 16 A-1 B1-1 B2-1 C-1 F-1 A 0.18 90 A A 55.0 1.2 100 pbw 1.89 pbw 5.0 pbw 2.2 pbw 5.0 pbw 17 A-1 B1-6 B2-1 C-1 F-1 A 0.17 90 A A 70.0 1.2 100 pbw 1.50 pbw 5.0 pbw 2.2 pbw 5.0 pbw 18 A-1 — B2-1 C-1 F-1 A 0.21 90 B A — 2.4 100 pbw 5.0 pbw 2.2 pbw 5.0 pbw 19 A-1 B1-1 — C-1 F-1 A 0.13 89 B C 55.0 1.2 100 pbw 1.89 pbw 2.2 pbw 5.0 pbw Comparative 9 A-1 — — C-1 F-1 D 0.17 92 C C — 2.4 Example 100 pbw 2.2 pbw 5.0 pbw 10 A-1 — B2-8 C-1 F-1 C 0.15 89 B A 20.0 1.2 100 pbw 5.0 pbw 2.2 pbw 5.0 pbw 11 A-1 — B2-10 C-1 F-1 D 0.18 91 C C — 2.4 100 pbw 5.0 pbw 2.2 pbw 5.0 pbw