US6124393A
Expired / Lapsed
US
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Composite of thermosetting resin with metallic oxide and process for the preparation thereof
Assignee: DIC Corp
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Filing: 1998-03-31
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Granted: 2000-09-26
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Expires: 2018-03-31
Abstract
Abstract A composite of a thermosetting resin with a metallic oxide, prepared by a process which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin while effecting the removal of the solvents and/or curling reaction of the resins to incorporate a particulate metallic oxide having an average particle diameter of from 0.01 to 5 μm homogeneously in the thermosetting resin with a good interfacial wettability without causing macroscopic phase separation, as well as a process for the preparation of such a composite of a thermosetting resin with a metallic oxide and a process for the preparation of a crack-free molded composite product. A tribological material such as bearing, brake and clutch material includes such a composite as an essential constituent. The composite provides a thermosetting resin with an enhancement in surface properties such as hardness, sliding properties such as friction coefficient, critical PV value and wearability and mechanical properties such as impact resistance, particularly strength, elastic modulus and elongation. Thus, a cured or uncured composite of a thermosetting resin with a metallic oxide can be used as a molding material, sliding material, friction material, coating material, film-forming material, and the like.
Inventors
- 👤 Kazutoshi Haraguchi
- 👤 Yusho Usami
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 19:25
CPC Classifications
C; C08; C08K; C08K9/00; C08K9/10; C08K3/00; C08K3/34; C08K3/36; C08K2201/00; C08K2201/002; C08K2201/003
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
77 words
A process for the preparation of a composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin while effecting the removal of the solvent and/or curing reaction of the resins to incorporate a particulate metallic oxide homogeneously in said composite without causing macroscopic phase separation.
Claim 2
Dependent Claim
77 words
A process for the preparation of a composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin while effecting the removal of the solvent and/or curing reaction of the resins to incorporate a particulate metallic oxide homogeneously in said composite without causing macroscopic phase separation.
Claim 3
Dependent Claim
149 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to claim 1, which comprises the steps of: (1) preparing a resin solution comprising a phenolic resin and/or thermosetting resin containing a phenolic resin dissolved in a solvent miscible with both said metal alkoxide and water; (2) adding a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof, a solvent miscible with both said metal alkoxide and water, and optionally water and/or catalyst to said resin solution to form a homogeneous solution without causing phase separation of the mixed solution; and (3) simultaneously effecting the hydrolysis and polycondensation of said metal alkoxide and the removal of the solvent and curing reaction of the resins prior to the gelation of the mixed solution to obtain a homogeneous composite of a thermosetting resin with a metallic oxide without causing macroscopic phase separation.
Claim 4
Dependent Claim
115 words
A process for the preparation of a composite of a thermosetting resin with a metallic oxide, which comprises preparing a solution comprising a metal alkoxide and water and/or catalyst, allowing said solution to undergo reaction for a period of time of not more than 90% of the gelation time thereof, preparing a homogeneous solution of the reaction product and a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin, and then subjecting said metal alkoxide-to further hydrolysis and polycondensation in said homogeneous solution while effecting the removal of the solvents and/or curing reaction of the resins to incorporate a particulate metallic oxide homogeneously in said thermosetting resin without causing macroscopic phase separation.
Claim 5
Dependent Claim
115 words
A process for the preparation of a composite of a thermosetting resin with a metallic oxide, which comprises preparing a solution comprising a metal alkoxide and water and/or catalyst, allowing said solution to undergo reaction for a period of time of not more than 90% of the gelation time thereof, preparing a homogeneous solution of the reaction product and a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin, and then subjecting said metal alkoxide-to further hydrolysis and polycondensation in said homogeneous solution while effecting the removal of the solvents and/or curing reaction of the resins to incorporate a particulate metallic oxide homogeneously in said thermosetting resin without causing macroscopic phase separation.
Claim 6
Dependent Claim
197 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to claim 3, which comprises the steps of: (1) preparing a resin solution comprising a phenolic resin and/or thermosetting resin containing a phenolic resin dissolved in a solvent miscible with both said metal alkoxide and water; (2) preparing a solution comprising a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof, a solvent miscible with both said metal alkoxide and water, and water, and optionally a catalyst, and allowing said solution to undergo reaction for a period of time of not more than 90% of the gelation time thereof to prepare a metal alkoxide solution; (3) mixing said resin solution, said metal alkoxide solution, optionally a solvent miscible with both said two solutions, and optionally water and/or catalyst to form a homogeneous solution without causing phase separation thereof; and (4) simultaneously effecting the hydrolysis and polycondensation of said metal alkoxide and the removal of the solvent and curing reaction of the resins prior to the gelation of the mixed solution to obtain a homogeneous composite of a thermosetting resin with a metallic oxide without causing macroscopic phase separation.
Claim 7
Dependent Claim
59 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein the size of the particulate metallic oxide incorporated in said composite of a thermosetting resin with a metallic oxide is from 0.01 to 5 μm as calculated in terms of average particle diameter.
Claim 8
Dependent Claim
49 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein the content of metallic oxide in said composite of a thermosetting resin with a metallic oxide is from 1 to 35% by weight.
Claim 9
Dependent Claim
66 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein the amount of water to be used is from 0.5 to 12 mol per mol of the metal alkoxide used and the amount of solvent to be used is high enough to be miscible said metal alkoxide and water therein.
Claim 10
Dependent Claim
68 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein the hydrolysis and polycondensation of said metal alkoxide is effected with water content in the air with which said metal alkoxide is brought into contact during solvent casting without incorporating water in said solution containing a thermosetting resin and a metal alkoxide.
Claim 11
Dependent Claim
51 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein said catalyst is an organic acid or inorganic acid and its amount is from 0 to 0.3 mol per mol of the metal alkoxide used.
Claim 12
Dependent Claim
46 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein said phenolic resin and/or thermosetting resin containing a phenolic resin is soluble in a solvent compatible with said metal alkoxide.
Claim 13
Dependent Claim
44 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to claim 10, wherein said phenolic resin and/or thermosetting resin containing a phenolic resin is soluble in an alcohol obtained by the hydrolysis of said metal alkoxide.
Claim 14
Dependent Claim
34 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein said phenolic resin is a resol phenolic resin.
Claim 15
Dependent Claim
35 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein said phenolic resin is a high ortho phenolic resin.
Claim 16
Dependent Claim
38 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein said metal alkoxide is a silicon alkoxide or a low condensate thereof.
Claim 17
Dependent Claim
57 words
The process for the preparation of a composite of a thermosetting resin with a metallic oxide according to any one of claims 1 to 4, wherein said metal alkoxide comprises a monoalkyltrialkoxysilane or dialkyldialkoxysilane in an amount of from 1 to 40 parts by weight based on 100 parts by weight of tetraalkoxysilane and/or low condensate thereof.
Claim 18
Dependent Claim
98 words
A process for the preparation of an uncured composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin while removing the solvents until the apparent solvent content represented by the following equation (1) reaches 1 to 20% by weight: Apparent solvent content (wt.%)={(weight of composite including solvent)-(weight of composite from which solvent has been completely removed)}/(weight of composite from which solvent has been completely removed)×100 (1).
Claim 19
Dependent Claim
98 words
A process for the preparation of an uncured composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin while removing the solvents until the apparent solvent content represented by the following equation (1) reaches 1 to 20% by weight: Apparent solvent content (wt.%)={(weight of composite including solvent)-(weight of composite from which solvent has been completely removed)}/(weight of composite from which solvent has been completely removed)×100 (1).
Claim 20
Dependent Claim
86 words
A process for the preparation of an uncured composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a novolak phenolic resin capable of melt-molding without any organic solvent and soluble in an organic solvent while drying the polycondensation product at a temperature of not higher than the melt temperature of said novolak phenolic resin so that the organic solvent used is removed therefrom.
Claim 21
Dependent Claim
86 words
A process for the preparation of an uncured composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a novolak phenolic resin capable of melt-molding without any organic solvent and soluble in an organic solvent while drying the polycondensation product at a temperature of not higher than the melt temperature of said novolak phenolic resin so that the organic solvent used is removed therefrom.
Claim 22
Dependent Claim
37 words
The process for the preparation of an uncured composite of a thermosetting resin with a metallic oxide according to claim 17, wherein said novolak phenolic resin or solution thereof has previously comprised a curing agent incorporated therein.
Claim 23
Dependent Claim
139 words
A process for the preparation of an uncured composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin while removing the solvents until the apparent solvent content represented by the following equation (1) reaches 1 to 20% by weight to prepare an uncured composite of a thermosetting resin with a metallic oxide containing a solvent, and then thermoforming said uncured composite at a higher temperature or higher temperature and pressure than those used for the removal of the solvents: Apparent solvent content (wt. %)={(weight of composite including solvent)-(weight of composite from which solvent has been completely removed)}/(weight of composite from which solvent has been completely removed)×100 (1).
Claim 24
Dependent Claim
139 words
A process for the preparation of an uncured composite of a thermosetting resin with a metallic oxide, which comprises subjecting a metal alkoxide containing a silicon alkoxide and/or a low condensate thereof to hydrolysis and polycondensation in a solution of a phenolic resin and/or thermosetting resin containing a phenolic resin while removing the solvents until the apparent solvent content represented by the following equation (1) reaches 1 to 20% by weight to prepare an uncured composite of a thermosetting resin with a metallic oxide containing a solvent, and then thermoforming said uncured composite at a higher temperature or higher temperature and pressure than those used for the removal of the solvents: Apparent solvent content (wt. %)={(weight of composite including solvent)-(weight of composite from which solvent has been completely removed)}/(weight of composite from which solvent has been completely removed)×100 (1).
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2003-09-26 | 2004-03-27 | 2004-09-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2007-09-26 | 2008-03-27 | 2008-09-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2011-09-26 | 2012-03-27 | 2012-09-26 | $7700.00 | Window Closed / Lapsed |