CA1182942A - Phenolic resin compositions containing bisphenol type epoxy resin and novolac type epoxy resin - Google Patents
Phenolic resin compositions containing bisphenol type epoxy resin and novolac type epoxy resinInfo
- Publication number
- CA1182942A CA1182942A CA000399657A CA399657A CA1182942A CA 1182942 A CA1182942 A CA 1182942A CA 000399657 A CA000399657 A CA 000399657A CA 399657 A CA399657 A CA 399657A CA 1182942 A CA1182942 A CA 1182942A
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- CA
- Canada
- Prior art keywords
- phenolic resin
- type epoxy
- epoxy resin
- parts
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
PHENOLIC RESIN COMPOSITIONS CONTAINING EPOXY RESINS
Abstract of the Disclosure The properties of phenolic resins are improved by incorporating epoxy resins therein. Suitable epoxy resins are the bisphenol type epoxy resins and the novolac type epoxy resins. The products of the invention are useful in applications such as molding materials, grinding wheels, abrasives, foundry applications, friction materials and other organic or inorganic binders.
Abstract of the Disclosure The properties of phenolic resins are improved by incorporating epoxy resins therein. Suitable epoxy resins are the bisphenol type epoxy resins and the novolac type epoxy resins. The products of the invention are useful in applications such as molding materials, grinding wheels, abrasives, foundry applications, friction materials and other organic or inorganic binders.
Description
Case Background of the Invention This invention relates to a phenolic resin composition having an epoxy resin incorporated therein.
~ It is well known to incorporate epoxy resins into a novolac type phenolic resin so as to make such phenolic resins flexible. It is also well known to employ a novolac type phenolic resin as a hardener for epoxy resins. In the former instance of the prior art, a phenollc resin composition ls prepared by mixing a bisphenol type epoxy resin with a novolac type phenolic resin, or prepared by adding an epoxy resin into said phenolic resin during its reaction. However, when such a resin composition ls cured by heat when used as a binder, effective crosslinking is uncertain because epoxy groups present in said composition are poor in reactivity. Thus in the past, molded articles excellent in heat resistance could not be obtained because of low crosslinking density of the composition.
After much investigation to overcome such drawbacks, the inventor has found that a particular ratio of incorporation of a bisphenol type epoxy resin into a solid phenolic resin improves the brittleness of the pheno~ic resin itself, improves flexibility (improving impact resistance) thereof, as well as retaining heat resis-tance thereof.
Summary of the Invention The phenolic resin composition according to the present invention is prepared by incorporating 3 to 20 parts by weight of a solid bisphenol type epoxy resin and 0.5 to 10 parts by weight of a novolac type epoxy 5 resin into 100 parts by weight of a novolac or resole type solid phenolic resin.
Description of Embodiments The novolac type phenolic resin according to the present invention is obtained by reacting phenols and aldehydes in the presence of catalysts such as hydrochloric acid, sulfuric acid, oxalic acid and phosphoric acid, employed either jointly or alone. A resole type phenolic resin according to the present invention is obtained by reacting phenols and aldehydes in the presence of catalysts such as hydroxides of alkali metals (sodium hydroxide, potassium hydroxide, etc.), or of alkali earth metals (calcium hydroxide, magnesium hydroxide, barium hydroxide, etc.), ammmonia and amines, employed either jointly or alone.
Phenols employed in the present invention are such as phenol, cresol, xylenol, resorcinol, para-ter-t-butylphenol, para-octylphenol, para-nonylphenol, and para-phenylphenol, employed either jointly or alone. Aldehydes employed in the present invention are such as formaldehyde, para-formaldehyde, acetaldehyde, benzaldehyde and fulFural, employed either jointly or alone.
The bisphenol type epoxy resin used in the present invention has an epoxide equivalent of 170 to 4000, preferably 400 to 1500, and may or may not contain a halogen atom. The novolac type epoxy resin used in the present invention is selected from phenol novolac type, cresol novolac type and halogenated epoxies.
Following are four embodiments of the method for preparing the phenolic resin compositions oF the present invention:
(1) Method for preparing said composition first by adding a bisphenol type and novolak type epoxy resin to a solid }~heno1ic resin, successive]y adding or not adding hexamethylene tetramine (hereinafter called as hexamine) thereto, followed by grinding the resulting product-mix.
~2) Method for preparing said composition by adding a bisphenol type epoxy resin to a solid phenolic resin during its preparation process, successively adding a novolac type epoxy resin, if necessary hexamine too, and by grinding the resulting product-mix.
(3) Method for preparing said composition by mixing a solid phenolic resin, a bisphenol type epoxy resin and novolac type epoxy resin, if necessary hexamine too, and by grinding the resulting product-mix.
(4) Method for preparing said composition by adding a bisphellol type and a novolac type epoxy resin, if necessary hexamine too, to a solid phenolic resin in a mixing apparatus such as kneader, roll mill or some other available mixers provided with heating, and by grinding the resulting product-mix.
Hexamine employed in the above-mentioned methods is preferably 3 to 20 parts by weight to 100 parts by weight of novolac resin content in the solid phenolic resin.
The ratio of incorporation of a bisphenol type epoxy resin is preferably 3 to 20 parts by weiyht to 100 parts by weight of the solid phenolic resi~. When the ratio of a bisphenol type epoxy resin is less than 3 parts by weight, it is ineffective in enhancing flexibility. When it is more than 20 parts by weight, it reduces heat resistance due to decrease in crosslinking density. The ratio of incorporation of the 3~
novolac type epoxy resin ls preferably 0.5 to 10 parts by welght, more preferably 0.5 - 5 par-ts by weight, to 100 par-ts of the solid phenollc resin. When said ratio of the novolac type epoxy resin is less that 0.5 par-ts by weight, it is ineffective in crosslinking as well as in heat resistance. When it is more than 10 parts by weight, it reduces its flexibility.
As for the pehnolic resin composition of the pre-sent invention, adhesion of the phenolic resin is en-hanced along with improved flexibility and impact strength without reducing heat resistance, due -to good flexibility of the bisphenol type ipoxy resin and the good crosslinking effect of the novolac type epoxy resin.
The phenolic resin compositions of the present inven-tion show excellent characteristics in applications such as molding materials, grinding wheels, abrasives, foundry resins, friction materials, and other organic or inorganic binders.
The present invention is further explained by the following nonlimitative examples, in which "parts"
indicates "par-ts by weight".
Example 1 To 100 parts of a novolac type phenolin resin, 10 parts of a bisphenol type epoxy resin (available under trademark "EPIKOTE" 1004 by Shell Chemical Co.) was added during preparation of the phenolic resin. To the -thus obtained resin, 2 parts of a novolac -type epoxy resin (available under serial number "ECN-1280" by Ciba AG) and 10 parts by hexamine were added. The product-mix was ground to powder composition. A specimen for abrasive testing was prepared with the composi-tion of the inven-tion exemplified in the following formula-tion by hot pressing. Both bending and impact tests were run:
Formulation Abrasive particle Altl2 100 parts Said powder composition 15.0 Pyrite 10.0 Cryolite 10.0 Quick lime 1.5 Furfural 1.0 The formulated material was charged into a mold having the dimensions: 15 (thickness) x 25 (width) x 100 (length) in mm., and pressed at 160C under a pressure of 500Kg/cm2 for 15 minutes. The molded article was baked (10 hours from ambient temperature to 170C1 and successfully 5 hours at 170C; 15 hours as total) and a specimen for abrasive testing was prepared having a bulk density of 3.10. Tests were run for bending strength at both ambient and elevated temperature (250 C) and impact strength at ambient temperature.
The results were indicated in Table 1, in which excellent bending and impact strength, respectively at ambient temperataure were shown.
Comparative Example 1 A powdered novolac type phenolic resin (10 parts of hexamine was incorporated to 100 parts of said phenolic resin) was prepared, and tests were run in the same manner as Example 1.
Comparative Exam~le 2 To 100 parts of a novolac type phenolic resin, 10 parts of a bisphenol type epoxy resin (available under tradename "EPIKOTE" 1004 by Shell Chemical Co.) was added during preparing said phenolic resin. To the product 10 parts of hexamine was added and ground to a powdered phenolic resin composition. Tests were run in the same manner as Example 1 with the same formulation.
Table 1 ComparativeComparatlve Example 1 Example 1Example 2 ____ ~ _ __ _ Bending at ambient temp. 523 462 496 strength _ _ _ _ _ _ . _ ~. _ (Kg/c~) at elevated temp. 274 260 182 _ . ._ Impact stength (Kg/cm2) 1.7 1.2 1.5 Example 2 To 80 parts of a novolac type and 20 parts of a solid resole type phenolic resin, 15 parts of a bisphenol type epoxy resin (available under tradefl~m~ "EPIKOTE" 1001, by Shell Chemical Co.), 3 parts of a novolac type epoxy resin (available under serial number "ECN-127~" by Ciba AG) and 8 parts of hexamine were added. The produc-t-mix was ground to form a powdered composition. Tests for brake lining were run on specimens with the composition of the invention exemplified in the following formulation:
Formulation:
Asbestos 6D 60 Parts Said powder composition 20 Barium sulfate 10 Dusty cashew powder 10 The formulated material was charged into a mold having the dimensions: 15 (thickness) x 25 (width) x 100 (length) in mm., and pressed at 180C with 200Kg/cm2 for 15 minutes. The molded specimens were baked (3 hours at 180C). Tests were run for bending strength and friction characteristics (according to JIS Dk-4411) at both ambient and elevated temperature.
The results were indicated in Fig. 2, in which an excellent bending strength at ambient temperature and friction characteristics were shown.
Comparative Exanlple 3 1o 80 parts of a novolac type phenolic resin and 20 parts of a solid resole type phenolic resin, 8 parts of hexamine was added. The product-mix was ground to form a powdered composition. TPsts were run on specimens prepared with this resin formulation as in the same manner as Example 2.
Table ?
Comparative Example 2Example 3 at amoient temp. 736 615 Bending strength __ __ (Kg/cm2)at elevated temp.433 411 __ at lOODC 2.2 0.39 2.3 0.35 150~C ~ ~ 2.3 0.39 2.5 0.31 Friction properties200 C _ 2.5 0.38 3.1 0.28 250C 5.4 0.39 8.7_ 0.28 300C _ 9.2 0.38 23.3 0.2a (Note) V: Friction ratio (10 7cm3/K~-m) ~: Friction coefficient
~ It is well known to incorporate epoxy resins into a novolac type phenolic resin so as to make such phenolic resins flexible. It is also well known to employ a novolac type phenolic resin as a hardener for epoxy resins. In the former instance of the prior art, a phenollc resin composition ls prepared by mixing a bisphenol type epoxy resin with a novolac type phenolic resin, or prepared by adding an epoxy resin into said phenolic resin during its reaction. However, when such a resin composition ls cured by heat when used as a binder, effective crosslinking is uncertain because epoxy groups present in said composition are poor in reactivity. Thus in the past, molded articles excellent in heat resistance could not be obtained because of low crosslinking density of the composition.
After much investigation to overcome such drawbacks, the inventor has found that a particular ratio of incorporation of a bisphenol type epoxy resin into a solid phenolic resin improves the brittleness of the pheno~ic resin itself, improves flexibility (improving impact resistance) thereof, as well as retaining heat resis-tance thereof.
Summary of the Invention The phenolic resin composition according to the present invention is prepared by incorporating 3 to 20 parts by weight of a solid bisphenol type epoxy resin and 0.5 to 10 parts by weight of a novolac type epoxy 5 resin into 100 parts by weight of a novolac or resole type solid phenolic resin.
Description of Embodiments The novolac type phenolic resin according to the present invention is obtained by reacting phenols and aldehydes in the presence of catalysts such as hydrochloric acid, sulfuric acid, oxalic acid and phosphoric acid, employed either jointly or alone. A resole type phenolic resin according to the present invention is obtained by reacting phenols and aldehydes in the presence of catalysts such as hydroxides of alkali metals (sodium hydroxide, potassium hydroxide, etc.), or of alkali earth metals (calcium hydroxide, magnesium hydroxide, barium hydroxide, etc.), ammmonia and amines, employed either jointly or alone.
Phenols employed in the present invention are such as phenol, cresol, xylenol, resorcinol, para-ter-t-butylphenol, para-octylphenol, para-nonylphenol, and para-phenylphenol, employed either jointly or alone. Aldehydes employed in the present invention are such as formaldehyde, para-formaldehyde, acetaldehyde, benzaldehyde and fulFural, employed either jointly or alone.
The bisphenol type epoxy resin used in the present invention has an epoxide equivalent of 170 to 4000, preferably 400 to 1500, and may or may not contain a halogen atom. The novolac type epoxy resin used in the present invention is selected from phenol novolac type, cresol novolac type and halogenated epoxies.
Following are four embodiments of the method for preparing the phenolic resin compositions oF the present invention:
(1) Method for preparing said composition first by adding a bisphenol type and novolak type epoxy resin to a solid }~heno1ic resin, successive]y adding or not adding hexamethylene tetramine (hereinafter called as hexamine) thereto, followed by grinding the resulting product-mix.
~2) Method for preparing said composition by adding a bisphenol type epoxy resin to a solid phenolic resin during its preparation process, successively adding a novolac type epoxy resin, if necessary hexamine too, and by grinding the resulting product-mix.
(3) Method for preparing said composition by mixing a solid phenolic resin, a bisphenol type epoxy resin and novolac type epoxy resin, if necessary hexamine too, and by grinding the resulting product-mix.
(4) Method for preparing said composition by adding a bisphellol type and a novolac type epoxy resin, if necessary hexamine too, to a solid phenolic resin in a mixing apparatus such as kneader, roll mill or some other available mixers provided with heating, and by grinding the resulting product-mix.
Hexamine employed in the above-mentioned methods is preferably 3 to 20 parts by weight to 100 parts by weight of novolac resin content in the solid phenolic resin.
The ratio of incorporation of a bisphenol type epoxy resin is preferably 3 to 20 parts by weiyht to 100 parts by weight of the solid phenolic resi~. When the ratio of a bisphenol type epoxy resin is less than 3 parts by weight, it is ineffective in enhancing flexibility. When it is more than 20 parts by weight, it reduces heat resistance due to decrease in crosslinking density. The ratio of incorporation of the 3~
novolac type epoxy resin ls preferably 0.5 to 10 parts by welght, more preferably 0.5 - 5 par-ts by weight, to 100 par-ts of the solid phenollc resin. When said ratio of the novolac type epoxy resin is less that 0.5 par-ts by weight, it is ineffective in crosslinking as well as in heat resistance. When it is more than 10 parts by weight, it reduces its flexibility.
As for the pehnolic resin composition of the pre-sent invention, adhesion of the phenolic resin is en-hanced along with improved flexibility and impact strength without reducing heat resistance, due -to good flexibility of the bisphenol type ipoxy resin and the good crosslinking effect of the novolac type epoxy resin.
The phenolic resin compositions of the present inven-tion show excellent characteristics in applications such as molding materials, grinding wheels, abrasives, foundry resins, friction materials, and other organic or inorganic binders.
The present invention is further explained by the following nonlimitative examples, in which "parts"
indicates "par-ts by weight".
Example 1 To 100 parts of a novolac type phenolin resin, 10 parts of a bisphenol type epoxy resin (available under trademark "EPIKOTE" 1004 by Shell Chemical Co.) was added during preparation of the phenolic resin. To the -thus obtained resin, 2 parts of a novolac -type epoxy resin (available under serial number "ECN-1280" by Ciba AG) and 10 parts by hexamine were added. The product-mix was ground to powder composition. A specimen for abrasive testing was prepared with the composi-tion of the inven-tion exemplified in the following formula-tion by hot pressing. Both bending and impact tests were run:
Formulation Abrasive particle Altl2 100 parts Said powder composition 15.0 Pyrite 10.0 Cryolite 10.0 Quick lime 1.5 Furfural 1.0 The formulated material was charged into a mold having the dimensions: 15 (thickness) x 25 (width) x 100 (length) in mm., and pressed at 160C under a pressure of 500Kg/cm2 for 15 minutes. The molded article was baked (10 hours from ambient temperature to 170C1 and successfully 5 hours at 170C; 15 hours as total) and a specimen for abrasive testing was prepared having a bulk density of 3.10. Tests were run for bending strength at both ambient and elevated temperature (250 C) and impact strength at ambient temperature.
The results were indicated in Table 1, in which excellent bending and impact strength, respectively at ambient temperataure were shown.
Comparative Example 1 A powdered novolac type phenolic resin (10 parts of hexamine was incorporated to 100 parts of said phenolic resin) was prepared, and tests were run in the same manner as Example 1.
Comparative Exam~le 2 To 100 parts of a novolac type phenolic resin, 10 parts of a bisphenol type epoxy resin (available under tradename "EPIKOTE" 1004 by Shell Chemical Co.) was added during preparing said phenolic resin. To the product 10 parts of hexamine was added and ground to a powdered phenolic resin composition. Tests were run in the same manner as Example 1 with the same formulation.
Table 1 ComparativeComparatlve Example 1 Example 1Example 2 ____ ~ _ __ _ Bending at ambient temp. 523 462 496 strength _ _ _ _ _ _ . _ ~. _ (Kg/c~) at elevated temp. 274 260 182 _ . ._ Impact stength (Kg/cm2) 1.7 1.2 1.5 Example 2 To 80 parts of a novolac type and 20 parts of a solid resole type phenolic resin, 15 parts of a bisphenol type epoxy resin (available under tradefl~m~ "EPIKOTE" 1001, by Shell Chemical Co.), 3 parts of a novolac type epoxy resin (available under serial number "ECN-127~" by Ciba AG) and 8 parts of hexamine were added. The produc-t-mix was ground to form a powdered composition. Tests for brake lining were run on specimens with the composition of the invention exemplified in the following formulation:
Formulation:
Asbestos 6D 60 Parts Said powder composition 20 Barium sulfate 10 Dusty cashew powder 10 The formulated material was charged into a mold having the dimensions: 15 (thickness) x 25 (width) x 100 (length) in mm., and pressed at 180C with 200Kg/cm2 for 15 minutes. The molded specimens were baked (3 hours at 180C). Tests were run for bending strength and friction characteristics (according to JIS Dk-4411) at both ambient and elevated temperature.
The results were indicated in Fig. 2, in which an excellent bending strength at ambient temperature and friction characteristics were shown.
Comparative Exanlple 3 1o 80 parts of a novolac type phenolic resin and 20 parts of a solid resole type phenolic resin, 8 parts of hexamine was added. The product-mix was ground to form a powdered composition. TPsts were run on specimens prepared with this resin formulation as in the same manner as Example 2.
Table ?
Comparative Example 2Example 3 at amoient temp. 736 615 Bending strength __ __ (Kg/cm2)at elevated temp.433 411 __ at lOODC 2.2 0.39 2.3 0.35 150~C ~ ~ 2.3 0.39 2.5 0.31 Friction properties200 C _ 2.5 0.38 3.1 0.28 250C 5.4 0.39 8.7_ 0.28 300C _ 9.2 0.38 23.3 0.2a (Note) V: Friction ratio (10 7cm3/K~-m) ~: Friction coefficient
Claims
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
A phenolic resin composition comprising 3 to 20 parts by weight of a bisphenol type epoxy resin and 0.5 to 10 parts by weight of a novolac type epoxy resin per 100 parts by weight of a solid phenolic resin.
A phenolic resin composition according to claim 1 wherein said solid phenolic resin is a solid novolac phenolic resin.
A phenolic resin composition according to claim 1 wherein said solid phenolic resin is a solid resole phenolic resin.
A phenolic resin composition according to claim 1 wherein said solid phenolic resin is a mixture of a solid novolac phenolic resin and a solid resole phenolic resin.
A phenolic resin composition according to claim 2 or 3 wherein 3 to 20 parts by weight of hexamethylene tetramine is incorporated into 100 parts by weight of said novolac type phenolic resin.
A phenolic resin composition according to claim 1 wherein said bisphenol type epoxy resin incorporated therein has an epoxide equivalent of 170 to 4000.
A phenolic resin composition according to claim 1 wherein said solid novolac type epoxy resin incorporated therein is selected from a cresol novolac epoxy resin and a halogenated novolac epoxy resin.
A phenolic resin composition comprising 3 to 20 parts by weight of a bisphenol type epoxy resin and 0.5 to 10 parts by weight of a novolac type epoxy resin per 100 parts by weight of a solid phenolic resin.
A phenolic resin composition according to claim 1 wherein said solid phenolic resin is a solid novolac phenolic resin.
A phenolic resin composition according to claim 1 wherein said solid phenolic resin is a solid resole phenolic resin.
A phenolic resin composition according to claim 1 wherein said solid phenolic resin is a mixture of a solid novolac phenolic resin and a solid resole phenolic resin.
A phenolic resin composition according to claim 2 or 3 wherein 3 to 20 parts by weight of hexamethylene tetramine is incorporated into 100 parts by weight of said novolac type phenolic resin.
A phenolic resin composition according to claim 1 wherein said bisphenol type epoxy resin incorporated therein has an epoxide equivalent of 170 to 4000.
A phenolic resin composition according to claim 1 wherein said solid novolac type epoxy resin incorporated therein is selected from a cresol novolac epoxy resin and a halogenated novolac epoxy resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4942381A JPS57164148A (en) | 1981-04-03 | 1981-04-03 | Phenolic resin composition |
| JP49423/1981 | 1981-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1182942A true CA1182942A (en) | 1985-02-19 |
Family
ID=12830666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000399657A Expired CA1182942A (en) | 1981-04-03 | 1982-03-29 | Phenolic resin compositions containing bisphenol type epoxy resin and novolac type epoxy resin |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS57164148A (en) |
| CA (1) | CA1182942A (en) |
-
1981
- 1981-04-03 JP JP4942381A patent/JPS57164148A/en active Pending
-
1982
- 1982-03-29 CA CA000399657A patent/CA1182942A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57164148A (en) | 1982-10-08 |
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| MKEX | Expiry |