ARYLCYCLOBUTENES

Abstract

Arylcyclobutene polymers having improved physical properties, such as elongation, 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 allyl moieties; wherein the one or more second monomers are free of arylcyclobutene moieties; and wherein the one or more second monomers are not allyl-substituted bismaleimide derivatives.

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.

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

4. The polymer of claim 1 wherein the allyl moieties are chosen from allyl ether moieties, allyl ester moieties, allyl amine moieties, allyl amide moieties, allyl ketone moieties, and allylaryl moieties.

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: ##STR00009## wherein B.sup.1 is an n-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; wherein 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 wherein 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 are chosen from compounds of formula (5): ##STR00010## wherein each R.sup.17 is independently chosen from H and C.sub.1-30 monovalent hydrocarbyl residue; E is chosen from O, S, SS, N(R.sup.18), C(O), OC(O)O, N(R.sup.18)C(O), N(R.sup.18)C(O)N(R.sup.18), S(O).sub.2, C.sub.6-20 aryl, substituted C.sub.6-20 aryl, and O-G.sup.1-O; each R.sup.18 is independently chosen from H, C.sub.1-12 alkyl, C.sub.2-12 alkenyl, C.sub.6-10 aryl, and substituted C.sub.6-10 aryl; G.sup.1 is an n+1 valent organic residue; and n is an integer from 1 to 5.

8. The polymer of claim 7 wherein n=1 to 2.

9. The polymer of claim 7 wherein each R.sup.17H.

10. The polymer of claim 7 wherein G.sup.1 is an n+1 valent organic residue having from 1 to 100 carbon atoms.

11. The polymer of claim 7 wherein G.sup.1 is chosen from C(O)R.sup.19C(O), C.sub.1-20 alkyl, substituted C.sub.1-20 alkyl, C.sub.2-20 alkenyl, substituted C.sub.2-20 alkenyl, C.sub.2-20 alkynyl, substituted C.sub.2-20 alkynyl, (C.sub.2-8 alkyleneoxy).sub.y1, C.sub.6-30 aryl, substituted C.sub.6-30 aryl, and Ar.sup.1-G.sup.2-Ar.sup.2; wherein R.sup.19 is chosen from a chemical bond, C.sub.1-20 alkyl, substituted C.sub.1-20 alkyl, C.sub.2-20 alkenyl, substituted C.sub.2-20 alkenyl, C.sub.2-20 alkynyl, substituted C.sub.2-20 alkynyl, C.sub.6-20 aryl, and substituted C.sub.6-20 aryl; y1 is an integer from 1 to 100; Ar.sup.1 and Ar.sup.2 are independently C.sub.6-20 aryl or substituted C.sub.6-20 aryl; G.sup.2 is chosen from a chemical bond, C(O), S(O).sub.2, C.sub.1-20 alkyl, substituted C.sub.1-20 alkyl, and (CR.sup.20R.sup.21Ar.sup.3).sub.y2CR.sup.20R.sup.21; each of R.sup.20 and R.sup.21 are independently chosen from H, OH, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, and C.sub.6-20 aryl; each Ar.sup.3 is independently chosen from C.sub.6-20 aryl and substituted C.sub.6-20 aryl; and y2 is an integer from 1 to 50.

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

13. The composition of claim 12 further comprising one or more photoactive compounds.

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

Description

EXAMPLE 1

[0039] In a nitrogen purged reaction vessel, a mixture of benzocyclobutene acrylic acid (BCB-AA, 14.63 g, 84.00 mmol), DVS-bisBCB (12.66 g, 32.40 mmol) as first monomers and diallylphthalate (0.887 g, 3.60 mmol) as the second monomer in 3-methoxybutylacetate (41 g) was heated to 175 C. for 24 hours. The temperature was then lowered to 165 C. and continued to react with 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 using polystyrene standards. When the observed M.sub.w was 4800-6500 AMUs, the reactor was cooled to 80 C. and the mixture was filtered hot though a 1 am polypropylene filter to provide Polymer 1.

EXAMPLE 2

[0040] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (14.63 g, 84.00 mmol), DVS-bisBCB (11.25 g, 28.80 mmol) as first monomers and diallylphthalate (1.773 g, 7.20 mmol) as the second monomer in 3-methoxybutylacetate (41 g) were B-staged as before to provide Polymer 2.

EXAMPLE 3

[0041] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (14.63 g, 84.00 mmol), DVS-bisBCB (9.845 g, 25.20 mmol) as first monomers and diallylphthalate (2.660 g, 10.80 mmol) as the second monomer in 3-methoxybutylacetate (41 g) were B-staged as before to provide Polymer 3.

EXAMPLE 4

[0042] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (17.68 g, 101.5 mmol), DVS-bisBCB (15.29 g, 39.15 mmol) as first monomers and diallylisophthalate (1.07 g, 4.35 mmol) as the second monomer in 3-methoxybutylacetate (50 g) were B-staged as before to provide Polymer 4.

EXAMPLE 5

[0043] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (18.29 g, 105 mmol), DVS-bisBCB (14.06 g, 36 mmol) as first monomers and diallylisophthalate (2.22 g, 9.00 mmol) as the second monomer in 3-methoxybutylacetate (51 g) were B-staged as before to provide Polymer 5.

EXAMPLE 6

[0044] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (18.29 g, 105 mmol), DVS-bisBCB (12.31 g, 31.5 mmol) as first monomers and diallylisophthalate (3.32 g, 13.5 mmol) as the second monomer in 3-methoxybutylacetate (50 g) were B-staged as before to provide Polymer 6.

EXAMPLE 7

[0045] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (18.29 g, 105 mmol), DVS-bisBCB (15.82 g, 40.5 mmol) as first monomers and 4,4-bis-A-diphenol-diallylether (1.388 g, 4.50 mmol) as the second monomer in 3-methoxybutylacetate (51 g) were B-staged as before to provide Polymer 7.

EXAMPLE 8

[0046] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (18.29 g, 105 mmol), DVS-bisBCB (14.06 g, 36.0 mmol) as first monomers and 4,4-bis-A-diphenol-diallylether (2.776 g, 9.00 mmol) as the second monomer in 3-methoxybutylacetate (50 g) were B-staged as before to provide Polymer 8.

EXAMPLE 9

[0047] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (18.9 g, 108.5 mmol), DVS-bisBCB (12.72 g, 32.55 mmol) as first monomers and 4,4-bis-A-diphenol-diallylether (4.302 g, 13.95 mmol) as the second monomer in 3-methoxybutylacetate (52 g) were B-staged as before to provide Polymer 9.

EXAMPLE 10

[0048] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (12.72 g, 73.0 mmol), DVS-bisBCB (10.19 g, 26.1 mmol) as first monomers and trimethylolpropane diallyl ether (1.08 g, 5.04 mmol) as the second monomer in Proglyde DMM (36.6 g) were B-staged as before to provide Polymer 10.

EXAMPLE 11

[0049] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (13.2 g, 75.8 mmol), DVS-bisBCB (8.54 g, 21.8 mmol) as first monomers and trimethylolpropane diallyl ether (2.37 g, 11.0 mmol) as the second monomer in Proglyde DMM (36.0 g) were B-staged as before to provide Polymer 11.

EXAMPLE 12

[0050] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (13.8 g, 79 mmol), DVS-bisBCB (6.76 g, 17.3 mmol) as first monomers and trimethylolpropane diallyl ether (3.76 g, 17.5 mmol) as the second monomer in Proglyde DMM (40 g) were B-staged as before to provide Polymer 12.

EXAMPLE 13

[0051] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (14.4 g, 82.7 mmol), DVS-bisBCB (4.63 g, 11.6 mmol) as first monomers and trimethylolpropane diallyl ether (5.2 g, 24.4 mmol) as the second monomer in Proglyde DMM (37 g) were B-staged as before to provide Polymer 13.

EXAMPLE 14

[0052] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (12.6 g, 72.6 mmol), DVS-bisBCB (10.2 g, 26.1 mmol) as first monomers and pentaerythritol triallyl ether (1.36 g, 5.3 mmol) as the second monomer in Proglyde DMM (36 g) were B-staged as before to provide Polymer 14.

EXAMPLE 15

[0053] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (13.0 g, 74.9 mmol), DVS-bisBCB (8.35 g, 21.4 mmol) as first monomers and pentaerythritol triallyl ether (2.80 g, 10.9 mmol) as the second monomer in Proglyde DMM (37 g) were B-staged as before to provide Polymer 15.

EXAMPLE 16

[0054] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (13.5 g, 77.5 mmol), DVS-bisBCB (6.47 g, 16.6 mmol) as first monomers and pentaerythritol triallyl ether (4.33 g, 16.9 mmol) as the second monomer in Proglyde DMM (32 g) were B-staged as before to provide Polymer 16.

EXAMPLE 17

[0055] The procedure of Example 1 was repeated except that the amounts of monomers were as follows: BCB-AA (13.3 g, 76.3 mmol), DVS-bisBCB (4.54 g, 11.6 mmol) as first monomers and pentaerythritol triallyl ether (5.71 g, 22.3 mmol) as the second monomer in Proglyde DMM (36 g) were B-staged as before to provide Polymer 17.

EXAMPLE 18

[0056] The procedure of Example 1 is repeated except that the amounts of the monomers are varied and the second monomer is varied as shown in Table 1 and is expected to provide the polymers indicated in Table 1.

TABLE-US-00001 TABLE 1 BCB-AA/DVS-bisBCB/ Second Monomer Mole Second Monomer Ratio Sample Trimethylolpropane triallyl ether 2/4/1 Polymer 18 Pentrerythritol tetraallyl ether 1/2/1 Polymer 19 Triallylamine 2/4/1 Polymer 20 Diallyl ketone 2/4/1 Polymer 21 Bisphenol AF diallyl ether 2/3.5/1.5 Polymer 22 Bisphenol S Diallyl ether 2/3.5/1.5 Polymer 23 1,3-Diallyloxybenzene 1/1.5/1 Polymer 24 Diallyl maleate 1/3/1.5 Polymer 25 Diallyl succinate 1/2/1 Polymer 26 Bisphenol F diallyl ether 1/3/1.5 Polymer 27 Diallyl furan-2,5-dicarboxylate 2/4/1.5 Polymer 28

EXAMPLE 19

[0057] A coating composition was prepared by dissolving 3.216 g of diazonaphthoquinone (DNQ) photoactive compound (PAC) in 2.930 g propylene glycol methyl ether acetate (PGMEA), 1.604 g of 3-methoxybutylacetate, 1.755 g of anisole, and 0.62 g of DCT L-7604 surfactant in PGMEA solvent in a bottle. The PAC is a 2,1,5-DNQ sulfonic ester of 4,4-((2-hydroxyphenyl)methylene)bis(2,3,6-trimethylphenol) with an average of 65 mole % of esterified phenols. Next, 4.679 g of a 50 wt % solution N-540 epoxy cross-linker solution in PGMEA was added along with 12.504 g of Polymer 1 from Example 1 (41 wt % in 3-methoxybutylacetate) and 0.288 g of triethoxysilylpropylmaleamic acid (50 wt % in PGMEA) as an adhesion promoter. The bottle was rolled for 12 hours to form a homogeneous solution. After de-foaming, the solution was filtered through a 0.45 am nylon filter before use to provide Coating Composition 1.

EXAMPLE 20

[0058] The procedure of Example 19 was repeated using Polymers 2 and 3 from Examples 2 and 3, respectively, to provide Coating Compositions 2 and 3, respectively.

COMPARATIVE EXAMPLE 1

[0059] The procedure of Example 19 was repeated except that Polymer 1 was replaced with Comparative Polymer 1 to provide Comparative Coating Composition 1. Comparative Polymer 1 is a commercially available arylcyclobutene polymer composed of as polymerized units only BCB-AA and DVS-bis-BCB in a mole ratio of 70:30.

EXAMPLE 21

[0060] Each of the Coating Compositions 1 to 3, and Comparative Coating Composition 1 were sputtered on a 200 mm prime grade Copper coated silicon wafer 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-6680F-4) under nitrogen at 250 C. for 60 minutes. The final film thickness of each coating was approximately 5 am, and wafers were cleaved into 10 mm by 90 mm samples. The wafer samples were subjected to a 10% solution of ammonium persulfate in order to lift the polymer films off wafer samples. The films were carefully rinsed with water and allowed to fully dry. Once dried, the samples were mounted using transparent tape on an elongation template 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 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 along with the difference in tensile strength and % elongation between the samples of the invention and the comparative sample. As can be seen from these results, the films formed from the arylcyclobutene polymers of the invention have improved elongation and tensile strength as compared to films formed from conventional arylcyclobutene polymers.

TABLE-US-00002 TABLE 2 Average Tensile Coating Tensile Strength % % Composition Strength MPa Elongation Elongation Comparative 110.25 13.49 1 114.14 3.89 18.07 4.58 2 121.6 11.35 23.12 9.63 3 120.36 10.11 20.75 7.26