Arylcyclobutenes

Abstract

Arylcyclobutene polymers having improved physical properties, such as tensile strength, are provided. Compositions and methods for coating such arylcyclobutene polymers are also provided.

Claims

1. A polymer comprising as polymerized units one or more arylcyclobutene first monomers and one or more second monomers having two or more dienophilic moieties and one or more acid moieties chosen from carboxylic acid, protected carboxylic acid, and sulfonic acid; wherein the protected carboxylic acid is an ester having a quaternary carbon bonded directly to the alkoxy oxygen of the ester group; and wherein the one or more second monomers are free of benzocyclobutene moieties.

2. The polymer of claim 1 wherein the one or more arylcyclobutene first monomers further comprises one or more moieties chosen from carboxylic acid, protected carboxylic acid and sulfonic acid; wherein the protected carboxylic acid is an ester having a quaternary carbon bonded directly to the alkoxy oxygen of the ester group.

3. The polymer of claim 1 further comprising two distinct arylcyclobutene first monomers.

4. The polymer of claim 1 wherein the dienophilic moieties are chosen from ethylenically unsaturated and acetylenically unsaturated carbon-carbon bonds.

5. The polymer of claim 1 further comprising as polymerized units one or more third monomers comprising one or more diene or dienophilic moieties.

6. The polymer of claim 1 wherein the one or more arylcyclobutene first monomers have the formula: ##STR00012## wherein B.sup.1 is an m-valent linking group; Ar is a polyvalent aryl group and the carbon atoms of the cyclobutene ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar; m is an integer of 1 or more; n is an integer of 1 or more; each of R.sup.1 and R.sup.2 is independently a monovalent group; the two R.sup.1 moieties may be taken together along with the carbon to which they are attached to form a carbonyl or thiocarbonyl; and the two R.sup.2 moieties may be taken together along with the carbon to which they are attached to form a carbonyl or thiocarbonyl.

7. The polymer of claim 1 wherein the one or more second monomers have the formula
(A).sub.p-Z(E).sub.q wherein each A is independently an organic residue having from 1 to 20 carbon atoms and a one or more moieties chosen from carboxylic acid, protected carboxylic acid and sulfonic acid; each E is independently an organic residue having from 2 to 20 carbon atoms and one or more dienophilic moieties; Z is a chemical bond or an organic residue having from 1 to 30 carbon atoms; p is an integer from 1 to 6; and q is an integer from 2 to 6; wherein the protected carboxylic acid is an ester having a quaternary carbon bonded directly to the alkoxy oxygen of the ester group.

8. The polymer of claim 7 wherein p is an integer from 1 to 4.

9. The polymer of claim 7 wherein q is an integer from 2 to 4.

10. A composition comprising the polymer of claim 1 and one or more organic solvents.

11. The composition of claim 10 further comprising one or more photoactive compounds.

12. A method of forming a film on a substrate comprising: providing a substrate; coating a layer of a composition of claim 10 on a surface of the substrate; and curing the coating.

13. The polymer of claim 1 wherein at least one second monomer is chosen from formulae (6) to (9): ##STR00013## wherein each R.sup.17 is independently chosen from C.sub.3-10 alkenyl; R.sup.18 is chosen from C.sub.1-10 alkyl, C.sub.3-10 alkenyl, and OR.sup.15; and R.sup.19 is chosen from C.sub.2-10 alkyl and C.sub.2-10 alkenyl; ##STR00014## wherein each R.sup.20 is independently chosen from C.sub.3-10 alkenyl and C.sub.1-10 alkyl-(OC.sub.3-10 alkenyl).sub.z; x and y are independently 1 or 2; and z is an integer of 1-3; provided that y=2 when R.sup.20 is C.sub.3-10 alkenyl; and ##STR00015## wherein each R.sup.21 is independently chosen from H and C.sub.1-10 alkyl; each R.sup.22 is independently C.sub.2-20 alkenyl, each R.sup.23 is chosen from C.sub.2-10 alkyl and C.sub.2-10 alkenyl.

14. A polymer comprising as polymerized units one or more arylcyclobutene first monomers of the formula: ##STR00016## wherein B.sup.1 is an m-valent linking group; Ar is a polyvalent aryl group and the carbon atoms of the cyclobutene ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar; m is an integer of 1 or more; n is an integer of 1 or more; each of R.sup.1 and R.sup.2 is independently a monovalent group; the two R.sup.1 moieties may be taken together along with the carbon to which they are attached to form a carbonyl or thiocarbonyl; and the two R.sup.2 moieties may be taken together along with the carbon to which they are attached to form a carbonyl or thiocarbonyl, and one or more second monomers of the formula
(A).sub.p-Z(E).sub.q wherein each A is independently an organic residue having from 1 to 20 carbon atoms and a moiety chosen from carboxylic acid, protected carboxylic acid and sulfonic acid; each E is independently an organic residue having from 2 to 20 carbon atoms and one or more dienophilic moieties; Z is a chemical bond or an organic residue having from 1 to 30 carbon atoms; p is an integer from 1 to 6; and q is an integer from 2 to 6; wherein wherein the protected carboxylic acid is an ester having a quaternary carbon bonded directly to the alkoxy oxygen of the ester group; and wherein the one or more second monomers are free of benzocyclobutene moieties.

15. The polymer of claim 14 wherein the dienophilic moieties comprise one or more of ethylenic unsaturation (double bond) and acetylenic unsaturation (triple bond).

16. The polymer of claim 14 wherein at least one second monomer is chosen from formulae (6) to (9): ##STR00017## wherein each R.sup.17 is independently chosen from C.sub.3-10 alkenyl; R.sup.18 is chosen from C.sub.1-10 alkyl, C.sub.3-10 alkenyl, and OR.sup.15; and R.sup.19 is chosen from C.sub.2-10 alkyl and C.sub.2-10 alkenyl; ##STR00018## wherein each R.sup.20 is independently chosen from C.sub.3-10 alkenyl and C.sub.1-10 alkyl-(OC.sub.3-10 alkenyl).sub.z; x and y are independently 1 or 2; and z is an integer of 1-3; provided that y=2 when R.sup.20 is C.sub.3-10 alkenyl; and ##STR00019## wherein each R.sup.21 is independently chosen from H and C.sub.1-10 alkyl; each R.sup.22 is independently C.sub.2-20 alkenyl, each R.sup.23 is chosen from C.sub.2-10 alkyl and C.sub.2-10 alkenyl.

Description

EXAMPLE 1: SYNTHESIS OF 4-(2,2-BIS((ALLYLOXY)METHYL)BUTOXY)-4-OXOBUTANOIC ACID (COMPOUND 6A)

(1) A 500-mL 3-neck round bottom flask equipped with a condenser, nitrogen inlet, septa and a stir bar, was charged with trimethylolpropane diallyl ether (NEOALLYL T-20, 10.0 g, 46.9 mmol), succinic anhydride (11.7 g, 117 mmol) and toluene (120 mL). The mixture was stirred for five minutes before p-toluenesulfonic acid (0.085 g, 0.45 mmol) and hydroquinone (0.057 g, 0.49 mmol) were added to the stirred mixture. The reaction was heated to 70 C. for 18 hours and then cooled to room temperature. The mixture was filtered and the organic layer was then transferred to a separatory funnel. The organic layer was then washed five times with equal parts of water. The organic phase was dried over Na.sub.2SO.sub.4 and the solvent was removed under reduced pressure. The procedure above was repeated and the combined crude products were purified by chromatography over silica gel, eluting with ethyl acetate/hexanes, giving 20.3 g (49%) of the desired product, Compound 6a. .sup.1H NMR (400 MHz, CDCl.sub.3) 5.86 (ddt, J=17.2, 10.7, 5.4 Hz, 2H), 5.29-5.06 (m, 4H), 4.07 (s, 2H), 3.92 (d, J=5.5 Hz, 4), 3.31 (s, 4H), 2.78-2.52 (m, 4H), 1.43 (q, J=7.6 Hz, 2H), 0.84 (t, J=7.6 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) 178.08, 171.80, 134.95, 116.36, 77.30, 76.99, 76.67, 72.22, 70.22, 65.39, 42.28, 28.92, 28.89, 22.89, 7.49.

EXAMPLE 2: SYNTHESIS OF 4-(2,2-BIS((ALLYLOXY)METHYL)BUTOXY)-4-OXOBUTENOIC ACID (COMPOUND 6B)

(2) A 500-mL 3-neck round bottom flask equipped with a condenser, nitrogen inlet, septa and a stir bar, was charged with trimethylolpropane diallyl ether (Neoallyl T-20, 50.0 g, 233 mmol), maleic anhydride (57.2 g, 583 mmol) and toluene (250 mL). The mixture was stirred for five minutes before p-toluenesulfonic acid (0.480 g, 2.52 mmol) and hydroquinone (0.240 g, 0.2.17 mmol) were added to the stirred mixture. The reaction was heated to 70 C. for 18 hours and then cooled to room temperature. The mixture was then filtered and the organic layer was then transferred to a separatory funnel. The organic layer was then washed five times with equal parts of water. The organic phase was dried over Na.sub.2SO.sub.4 and the solvent was removed under reduced pressure to give 58.3 g (80%) of Compound 6b as a clear viscous oil. .sup.1H NMR (400 MHz, CDCl.sub.3) 6.36 (q, J=12.7 Hz, 2H), 5.82 (ddt, J=17.1, 10.6, 5.4 Hz, 2H), 5.31-5.09 (m, 4H), 4.24 (s, 2H), 3.90 (dd, J=5.5, 1.5 Hz, 4H), 3.31 (s, 4H), 1.45 (q, J=7.6 Hz, 2H), 0.84 (t, J=7.5 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) 167.31, 165.15, 135.26, 134.69, 129.50, 116.63, 72.24, 70.04, 67.62, 42.31, 22.91, 7.47.

EXAMPLE 3: PREPARATION OF (Z)-4-(3-(ALLYLOXY)-2,2-BIS((ALLYLOXY)METHYL)-PROPOXY)-4-OXOBUT-2-ENOIC ACID (COMPOUND 6C)

(3) A 1000 mL 3-neck round bottom flask equipped with a condenser, nitrogen inlet, septa and a stir bar, was charged with pentaerythritol triallyl ether (Neoallyl P-30, 20.01 g, 78.06 mmol), maleic anhydride (19.46 g, 198.4 mmol) and toluene (240 mL). The mixture was stirred for five minutes before p-toluenesulfonic acid (0.146 g, 0.768 mmol) and hydroquinone (0.103 g, 0.772 mmol) were added to the stirred mixture. The reaction was heated to 70 C. for 18 hours and then cooled to room temperature. The mixture was then filtered and the organic layer was then transferred to a separatory funnel. The organic layer was then washed five times with equal parts of water. The organic phase was dried over Na.sub.2SO.sub.4 and the solvent was removed under reduced pressure, giving 20.3 g (49%) of Compound 6c. .sup.1H NMR (400 MHz, CDCl.sub.3) 6.53-6.29 (m, 2H), 5.85 (ddt, J=17.3, 10.5, 5.4 Hz, 3H), 5.36-5.05 (m, 6H), 4.40 (s, 2H), 3.94 (dt, J=5.4, 1.5 Hz, 6H), 3.46 (s, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) 167.87, 163.80, 137.41, 134.58, 128.85, 116.68, 72.31, 68.94, 66.84, 44.46.

EXAMPLE 4: PREPARATION OF 4-(3-(ALLYLOXY)-2,2-BIS((ALLYLOXY)METHYL)PROPOXY)-4-OXOBUTANOIC ACID (COMPOUND 6D)

(4) A 500 mL 3-neck round bottom flask with a bottom drain, equipped with a condenser, nitrogen inlet, septa and an overhead mechanical stirrer was charged with pentaerythritol triallyl ether (Neoallyl P-30, 50.0 g, 195 mmol), succinic anhydride (48.8 g, 487 mmol) and toluene (500 mL). The mixture was stirred for five minutes before p-toluenesulfonic acid (0.371 g, 1.95 mmol) and hydroquinone (0.214 g, 1.95 mmol) were added to the stirred mixture. The reaction was heated to 70 C. and stirred overnight. The following day the reaction mixture was allowed to cool to room temperature and water (250 mL) was added to the reaction with stirring. After stirring for 20 minutes, stirring was stopped and the layers were allowed to separate. The water layer was then remover via the bottom drain. This water wash was repeated five times. The reactor was equipped with a Dean-Stark tray heated to reflux to remove residual water. After drying, the mixture was cooled to room temperature and the solvent removed under reduced pressure to give 66.5 g (96%) of Compound 6d as viscous oil. .sup.1H NMR (400 MHz, CDCl.sub.3) 5.85 (m, 3H), 5.23 (dq, J=17.3, 1.8 Hz, 6H), 4.18 (s, 2H), 3.92 (dt, J=5.4, 1.6 Hz, 6H), 3.43 (s, 6H), 2.69-2.58 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) 178.05, 171.71, 134.89, 116.36, 72.26, 68.97, 64.31, 44.45, 28.92.

EXAMPLE 5: PREPARATION OF ARYLCYCLOBUTENE POLYMER 1 (AP1)

(5) In a nitrogen purged reaction vessel, a mixture of benzocyclobutene acrylic acid (BCB-AA) (12.02 g, 69.00 mmol), DVS-bisBCB (13.48 g, 34.50 mmol) and Compound 6a from Example 1 (3.615 g, 11.50 mmol) in 3-methoxybutylacetate (42 g) was heated to 175 C. for 24 hours. The temperature was then lowered to 165 C. and continued to react while monitoring for molecular weight build by periodically removing a small sample and measuring the M.sub.w of the resulting polymer by gel permeation chromatography (GPC) using polystyrene standards. When the observed M.sub.w was 5000-6500 atomic mass units (AMUs), the reactor was cooled 80 C. and the mixture was filtered hot though a 1 m polypropylene filter over layered with a bed of celite. The resulting polymer of the invention (AP1) contained 10 mole % of Compound 6a.

EXAMPLE 6

(6) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (10.02 g, 57.50 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6a from Example 1 (7.23 g, 23.0 mmol) as the second monomer in 3-methoxybutylacetate (44 g) were B-staged as before to provide Polymer AP2 of the invention containing 20 mol % of Compound 6a.

EXAMPLE 7

(7) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (8.013 g, 46.00 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6a from Example 1 (10.85 g, 34.5 mmol) as the second monomer in 3-methoxybutylacetate (47 g) were B-staged as before to provide Polymer AP3 of the invention containing 30 mol % of Compound 6a.

EXAMPLE 8

(8) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (12.02 g, 69.00 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6b from Example 2 (3.592 g, 11.5 mmol) as the second monomer in 3-methoxybutylacetate (42 g) were B-staged as before to provide Polymer AP4 of the invention containing 10 mol % of Compound 6b.

EXAMPLE 8

(9) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (10.02 g, 57.5 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6b from Example 2 (7.18 g, 23.0 mmol) as the second monomer in 3-methoxybutylacetate (44 g) were B-staged as before to provide Polymer AP5 of the invention containing 20 mol % of Compound 6b.

EXAMPLE 9

(10) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (8.01 g, 46.0 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6b from Example 2 (10.78 g, 34.5 mmol) as the second monomer in 3-methoxybutylacetate (44 g) were B-staged as before to provide Polymer AP6 of the invention containing 30 mol % of Compound 6b.

EXAMPLE 8

(11) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (12.02 g, 69.00 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6c from Example 3 (3.592 g, 11.5 mmol) as the second monomer in 3-methoxybutylacetate (42 g) were B-staged as before to provide Polymer AP7 of the invention containing 10 mol % of Compound 6c.

EXAMPLE 9

(12) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (10.02 g, 57.5 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6c from Example 3 (7.18 g, 23.0 mmol) as the second monomer in 3-methoxybutylacetate (44 g) were B-staged as before to provide Polymer AP8 of the invention containing 20 mol % of Compound 6c.

EXAMPLE 10

(13) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (8.01 g, 46.00 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6c from Example 3 (10.78 g, 34.5 mmol) as the second monomer in 3-methoxybutylacetate (46 g) were B-staged as before to provide Polymer AP9 of the invention containing 30 mol % of Compound 6c.

EXAMPLE 11

(14) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (12.02 g, 69.00 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6d from Example 4 (4.099 g, 11.5 mmol) as the second monomer in 3-methoxybutylacetate (43 g) were B-staged as before to provide Polymer AP10 of the invention containing 10 mol % of Compound 6d.

EXAMPLE 12

(15) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (10.02 g, 57.5 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6d from Example 4 (8.197 g, 23.0 mmol) as the second monomer in 3-methoxybutylacetate (46 g) were B-staged as before to provide Polymer AP11 of the invention containing 20 mol % of Compound 6d.

EXAMPLE 13

(16) The procedure of Example 5 was repeated except that the amounts of monomers were as follows: BCB-AA (8.013 g, 46.0 mmol), DVS-bisBCB (13.48 g, 34.5 mmol) as first monomers and Compound 6d from Example 4 (12.30 g, 34.5 mmol) as the second monomer in 3-methoxybutylacetate (49 g) were B-staged as before to provide Polymer AP12 of the invention containing 30 mol % of Compound 6d.

EXAMPLE 14. PREPARATION OF COATING COMPOSITION 1

(17) In a bottle were combined 3.22 g of 2,1,5 diazonaphthoquinone sulfonic ester of 4,4-((2-hydroxyphenyl)methylene)-bis(2,3,6-trimethylphenol) with an average 65 mole % of esterified phenols (as photoactive compound or PAC), 2.93 g propylene glycol methyl ether acetate (PGMEA), 1.60 g of 3-methoxybutylacetate, 1.76 g of Anisole, and 0.62 g of DCT L-7604 surfactant in PGMEA solvent. Next, 4.68 g of a 50 wt % solution N-540 epoxy cross-linker solution in PGMEA was added along with 12.5 g of a composition of 41 wt % AP1 from Example 5 in 3-methoxybutylacetate and 0.288 g of an adhesion promoter (50 wt % solution of triethoxysilylpropylmaleamic acid in PGMEA). The bottle was rolled for 12 hours to form a homogeneous solution. After de-foaming, the resulting Coating Composition 1 was filtered through a 0.45 m nylon filter before use.

COMPARATIVE EXAMPLE 1

(18) A conventional arylcyclobutene polymer (comparative polymer CP1) was prepared using BCB-AA and DVS-bisBCB in a mole ratio of 70:30 according to the general procedure of Example 3. A comparative coating composition was prepared according to the general procedure of Example 4 except that comparative polymer CP1 was used in place of arylcyclobutene polymer of the invention AP1.

EXAMPLE 15

(19) The procedure of Example 5 was repeated using 10 mole % of Compound 6a to provide arylcyclobutene polymer AP2, and was repeated a second time using 30 mole % of Compound 6a to provide arylcyclobutene polymer AP3.

(20) The procedure of Example 6 was repeated except that arylcyclobutene polymer AP2 was used to prepare Coating composition 2. The procedure of Example 6 was again repeated except that arylcyclobutene polymer AP3 was used instead of polymer AP1 to prepare Coating composition 3.

EXAMPLE 16

(21) The general procedure of Example 5 is repeated except that the amounts of the BCB-monomers and the second monomer of the invention are varied. The amounts of the monomers are reported in Table 1 and are expected to provide polymers AP13 to AP18. The structures of compounds 7a to 7d are shown below. Structure 7d is a mixture of regioisomers.

(22) TABLE-US-00001 TABLE 1 BCB-AA DVS-bisBCB Second Monomer Polymer (mmol) (mmol) (mmol) AP13 70 35 Compound 7a (31) AP14 54 19 Compound 7b (35) AP15 48 30 Compound 7c (21) AP16 55 35 Compound 7c (17) AP17 35 45 Compound 7d (12) AP18 61 34 Compound 7b (15) + Compound 7c (12) 0

EXAMPLE 17

(23) Each of Coating Compositions 1-3 and comparative coating composition of Comparative Example 1 were sputtered on 200 mm prime grade copper coated silicon wafers using a Site Trac TT5-XP coater at 1735 rpm for 30 seconds followed by a soft bake of 90 C. for 90 seconds to further remove solvent. The film thickness of each coating was approximately 5.5 m. The coated wafers were then hard cured in a Blue M Ultra-Temp oven (Model IGF-6680E-4) under nitrogen at 250 C. for 60 minutes. The final film thickness was approximately 5 m, and wafers were cleaved into 10 mm by 90 mm samples.

(24) Each wafer was subjected to a 10% solution of ammonium persulfate in order to lift the polymer films off the wafer. The films were carefully rinsed with water and allowed to fully dry. Once dried, each sample was mounted on an elongation template with transparent tape with a 25.4 mm gauge length. Elongation measurements were taken on an Instron 33R4464 Model instrument using a crosshead speed of 5 mm/sec and Instron Bluehill2 software. Tensile strength values (MPa) were calculated by dividing the load at break by the original minimum cross-sectional area. The average tensile strength and % elongation of each sample is reported in Table 2. As can be seen from these results, the films formed from the arylcyclobutene polymers of the invention have improved elongation as compared to films formed from conventional arylcyclobutene polymers.

(25) TABLE-US-00002 TABLE 2 Average Tensile Polymer Strength Elongation % CP1 104.8 10.7 AP1 103.8 13.9 AP2 99.8 17.3 AP3 96.9 16.3 AP5 98.58 19.83 AP6 109.56 20 AP7 112.07 18.89 AP8 106.73 17.47 AP9 102.95 16.03