WO2005040276A1 - フェノール樹脂成形材料およびその成形品 - Google Patents
フェノール樹脂成形材料およびその成形品 Download PDFInfo
- Publication number
- WO2005040276A1 WO2005040276A1 PCT/JP2003/013816 JP0313816W WO2005040276A1 WO 2005040276 A1 WO2005040276 A1 WO 2005040276A1 JP 0313816 W JP0313816 W JP 0313816W WO 2005040276 A1 WO2005040276 A1 WO 2005040276A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phenolic resin
- molding material
- mass
- modified
- polyvinyl acetate
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
Definitions
- the present invention relates to a phenolic resin molding material used for producing heat-resistant parts such as a commutator of a motor for an automobile electric motor, and a molded article obtained therefrom.
- phenolic resin molding materials have been used for commutators of motors for automobile electrical components or structural components around them due to their excellent moldability and excellent heat resistance and strength obtained by molding and hardening.
- the mechanical and thermal loads in the commutator failing process performed after the molding from the phenolic resin molding material or the hyging process performed in the commutator mounting process, or the heat generated by the motor itself when the motor is driven.
- the heat generated by the engine of a car causes a dimensional change in the commutator.
- the phenol tree lumber molding material used for manufacturing commutators in the prior art cannot meet the demand for noise reduction because of large dimensional changes with respect to mechanical or thermal loads. .
- An object of the present invention is to provide a phenolic resin molding material having a small dimensional change with respect to a mechanical or thermal load, and a molded article obtained therefrom. .
- a phenolic resin molding material comprising a novolak-type phenolic resin and a filler, wherein at least a part of the nopolak-type phenolic resin is a polyvinyl acetate-modified nopolak-type phenolic resin.
- the polyvinyl acetate-modified novolak phenolic resin in the present invention is a modified nopolak-type phenolic resin produced using polyvinyl acetate in a synthesis step from phenol and formaldehyde, particularly phenol and formaldehyde in the presence of polyvinyl acetate.
- the step between the commutator copper segments and the deterioration of the roundness of the commutator caused in the environment where a mechanical or thermal load is applied are reduced by manufacturing the commutator using the phenolic resin molding material of the present invention. And can be prevented. As a result, it is possible to satisfy the demand for noise reduction in the commutator.
- the phenolic resin molding material of the present invention is characterized by containing a novolac type phenolic resin modified with polyvinyl acetate.
- the polyacetate-modified novolak-type phenol resin can be produced as follows:
- the nopolak type phenolic resin is usually produced by performing an addition reaction of phenol and formanolaldehyde in water in the presence of an acid catalyst, followed by dehydration condensation.
- the polyacetate-vinyl-modified novolak phenolic resin of the present invention is produced by adding polyacetate to a reaction mixture formed from phenol and formaldehyde before the dehydration condensation in the production of the nopolak-type phenolic resin.
- the addition of poly (vinyl acetate) is added before and after the addition reaction between phenol and formaldehyde. Can be done in between.
- Such acid catalysts are p-toluenesulfonic acid, hydrochloric acid, formic acid, phthalic anhydride, boric acid and oxalic acid, preferably oxalic acid. .
- Formaldehyde is usually used in the form of an aqueous formalin solution.
- Formaldehyde concentration in formalin aqueous solution is usually 3 7-5 0% by weight, preferably instrument 4 0-5 0 weight 0/0.
- the addition reaction between phenol and formaldehyde is carried out usually at 80 to 120 ° C, preferably 90 to 110 ° C, for usually 1 to 4 hours, preferably for 2 to 3 hours.
- dehydration and condensation of phenol and formaldehyde (dehydration and condensation of phenol and formaldehyde adducts) are performed in the presence of polyvinyl acetate.
- the dehydration condensation is carried out at a temperature of usually 130-180 ° C., preferably 150-170 ° C., and usually 50-: L 0 0 kPa, preferably 60-7. It is carried out under a pressure of 5 kP'a, usually for 1 to 5 hours, preferably for 2 to 3 hours.
- Polyvinyl acetate Biel-modified novolac-type Fueno one Honoré resin of the present invention based on the weight of polyvinyl acetate Bulle modified Noporakku type phenolic resin, of 6 0-7 5 wt% Fueno le, 1 5 to 2 0 mass 0/0 formaldehyde, 0.2 0 to 0.2 5 weight 0/0 using a polyvinyl acetate Bulle of oxalic acid and 5-2 0 weight 0/0, preferably to produce.
- the ratio of poly (vinyl acetate) in the poly (vinyl acetate) -modified novolak type phenol resin is 5% by mass or more. This is because the dimensional change of the phenolic resin molding material with respect to mechanical and thermal loads can be more effectively reduced by setting the polyacetic acid butyl compounding ratio to 5% by mass or more.
- the blending ratio of polyacetate in the polyacetate-modified nopolak-type phenolic resin increases, the curing rate of the phenolic resin molding material containing the polyacetate-modified nopolak-type phenolic resin decreases. Therefore, in order to secure the desired curing rate, the polyacetic acid in the polyacetic acid-modified novolak type phenol resin
- the vinyl compounding ratio is preferably 20% by mass or less.
- polyacetate-modified vinyl acetate novolak phenol resin having good water resistance and chemical resistance
- a polyacetate biale having a weight average molecular weight of 1000 or more.
- the polyvinyl acetate-modified nopolak phenol resin in order to ensure good dispersibility of the polyvinyl acetate in the reaction mixture, the polyvinyl acetate modified with a molecular weight of 100 Q It is preferred to use.
- the polyacetic acid-modified nopolak type phenol resin produced as described above preferably has a weight average molecular weight of 2000 to 600.
- the polyvinyl sulphate-modified nopolak type phenolic resin having a weight average molecular weight in this range has a melt viscosity suitable for kneading and the like in the subsequent production of a phenolic resin molding material.
- the nopolak phenol resin preferably has a weight-average molecular weight of 2000 to 400.
- the polyphenol-modified nopolak-type phenol resin is usually taken out in a vat at a high temperature after its production, cooled and solidified, and then used for the production of a phenol resin molding material. In order to improve the subsequent handleability, it is preferable to pulverize the cooled and solidified polyvinyl acetate novolak type phenol resin.
- Phenolic resin molding material of the present invention preferably, based on the weight of the phenolic resin molding material, 1 0-3 0% by weight of polyvinyl acetate Bulle modified Noporakku type phenolic resins, novolac type 5-2 0 weight 0/0 phenol ⁇ , 4 0 - including 6 0 mass 0/0 glass fibers and 5-2 0% by weight of an inorganic filler.
- the phenolic resin molding material of the present invention can be produced.
- the compounding ratio of the polyacetic acid-modified nopolak type phenol resin in the phenol resin molding material is preferably 10% by mass or more. This is because the dimensional change of the phenolic resin molding material can be reduced more effectively by setting the compounding ratio of the polyacetic acid butyl modified nopolak phenolic resin to 10% by mass or more. Because it can.
- the blending ratio of the modified nopolak type phenol resin is preferably 30% by mass / 0 or less.
- a commutator having good strength can be obtained from a phenol resin molding material containing 40% by mass or more of glass fibers.
- the glass weight is preferably 60% by mass or less.
- inorganic fillers included in the phenolic resin molding material include, but are not limited to, wollastonite, calcium carbonate, talc, mushylin and my mushy. These inorganic fillers can be used alone or in combination. .
- the present invention also provides a commutator obtained by molding the phenolic resin molding material of the present invention.
- Examples of the method for molding the phenolic resin molding material of the present invention include, but are not limited to, injection molding, transfer molding, and compression molding.
- a curing agent is used to harden the phenolic resin molding material of the present invention containing a nopolak-type phenolic resin as a component.
- Hexamethylenetetramine is preferred as the curing agent.
- Hexamethylenetetramine is more preferably a granular hexamethylenetetramine, particularly a fine-particle hexamethylenetetramine containing at least 99% by mass of particles passing through an 80-mesh sieve, particularly a 150-mesh sieve.
- Hexamethylenetetramine in the form of fine particles containing 98% by mass or more of particles passing through is used.
- a granular or fine particle of hexamethylenetetramine uniform dispersion thereof is ensured, and the appearance of a molded article can be improved, and variations in moldability and physical properties can be suppressed.
- the phenol resin composition of the present invention may be used.
- Additives or auxiliaries such as coupling agents, mold release agents, lubricants, dyes and pigments can be used with the form material.
- phenol and formalin (about 50% aqueous solution) are reacted at 100 ° C for 90 minutes in the presence of oxalic acid, and emulsified at 100 ° C for 120 minutes.
- Acid beer (weight-average molecular weight: 1500) was added to the reaction mixture, dehydration-condensed at 160 ° C and 70 kPa for 180 minutes, and a polyvinyl acetate-modified novolak phenolic resin was added.
- To manufacture It is taken out at a high temperature, 7 solidified, and pulverized and used for the production of the following molding materials. :. ————
- the raw materials in the amounts shown in parts by mass in the following table were mixed for 1 minute, and the mixture was heated at a product temperature of 100 using a twin-screw kneader. Knead with C ⁇ 110 for 3 minutes. This kneaded material is pulverized after solidification by rejection, and the granulated molding material is used for forming test pieces for evaluating dimensional changes and the like.
- the raw materials listed in the table are:
- Modified phenol resin Polyvinyl acetate-modified novolak phenol resin produced as described above, with a weight average molecular weight of 300. Ratio described in Table (mass. / 0) were used for the production of polyvinyl acetate Bulle modified novolac-type phenolic resin, shows the ratio of polyvinyl acetate Biel.
- Phenol resin Novolak type phenol resin, BRP590P manufactured by Showa Kogyo Co., Ltd.
- Inorganic filler NY CO 400 wollastonite NYAD 400.
- Hardener Hexamethylenetetramine Pulfine form, passing through an 80-mesh sieve, particle content of 99% by mass or more, passing through a 150-mesh sieve Particle content 98 mass. /. (7 parts by mass), Carnava lubricant (1 part by mass) (Carnava F-1 manufactured by Dainichi Kagaku 'Industries Co., Ltd.) and Dye Solvent Black (1 part by mass) (SAP-L manufactured by Orient Chemical Co., Ltd.) .
- the molding material preferably has an outflow time of 60 to 80 seconds from the viewpoint of practical molding.
- the above molding material is formed by extrusion molding using a test piece mold with a JIS bending test shape at a mold temperature of 170 ° C, a curing time of 90 seconds, and an injection pressure of 128 MPa, and shrinks.
- the test piece is annealed at 180 ° C. for 3 hours and then at 210 ° C. for 7 hours, and the dimensional change of the test piece due to the annealing treatment is measured.
- the specimen preferably has a small absolute dimensional change rate.
- the annealed test piece is further subjected to a high-temperature treatment at 200 ° C. for 500 hours, and the dimensional change of the test piece due to the high-temperature treatment is measured.
- the specimen preferably has a small absolute dimensional change rate.
- the bending strength of the test piece [JIS K 6911] was measured.
- the test piece preferably has a bending strength of 15 OMPa or more.
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Modified 3% by mass 1---1 phenol 5% by mass ° /. -11-11 mass% resin--15 10-
- Example 11 Example 12 Comparative Example 1 Comparative Example 2 denatured single - A one Fueno, Les 5 wt% one 18 one first resin 10 mass 0/0 eleven eleven
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2003/013816 WO2005040276A1 (ja) | 2003-10-29 | 2003-10-29 | フェノール樹脂成形材料およびその成形品 |
JP2005509865A JP4874649B2 (ja) | 2003-10-29 | 2003-10-29 | フェノール樹脂成形材料およびその成形品 |
AU2003280584A AU2003280584A1 (en) | 2003-10-29 | 2003-10-29 | Phenolic resin molding material and molded article thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2003/013816 WO2005040276A1 (ja) | 2003-10-29 | 2003-10-29 | フェノール樹脂成形材料およびその成形品 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005040276A1 true WO2005040276A1 (ja) | 2005-05-06 |
Family
ID=34509593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/013816 WO2005040276A1 (ja) | 2003-10-29 | 2003-10-29 | フェノール樹脂成形材料およびその成形品 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP4874649B2 (ja) |
AU (1) | AU2003280584A1 (ja) |
WO (1) | WO2005040276A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008184488A (ja) * | 2007-01-26 | 2008-08-14 | Matsushita Electric Works Ltd | フェノール樹脂成形材料及び成形品 |
JP2008184490A (ja) * | 2007-01-26 | 2008-08-14 | Matsushita Electric Works Ltd | フェノール樹脂成形材料及び成形品 |
WO2010061793A1 (ja) * | 2008-11-25 | 2010-06-03 | パナソニック電工株式会社 | フェノール樹脂成形材料及びフェノール樹脂成形品 |
WO2011052127A1 (ja) * | 2009-10-26 | 2011-05-05 | パナソニック電工株式会社 | フェノール樹脂成形材料、及びフェノール樹脂成形品 |
WO2015093260A1 (ja) * | 2013-12-20 | 2015-06-25 | 住友ベークライト株式会社 | 熱硬化性樹脂組成物および金属樹脂複合体 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5175791A (ja) * | 1974-12-26 | 1976-06-30 | Sumitomo Durez Co | |
JPH0269510A (ja) * | 1988-09-02 | 1990-03-08 | Matsushita Electric Works Ltd | フエノール樹脂成形材料 |
JPH0463858A (ja) * | 1990-07-02 | 1992-02-28 | Toshiba Chem Corp | フェノール樹脂成形材料 |
JP2000044771A (ja) * | 1998-07-30 | 2000-02-15 | Sumitomo Bakelite Co Ltd | 熱時寸法安定性に優れるフェノール樹脂成形材料 |
-
2003
- 2003-10-29 JP JP2005509865A patent/JP4874649B2/ja not_active Expired - Fee Related
- 2003-10-29 AU AU2003280584A patent/AU2003280584A1/en not_active Abandoned
- 2003-10-29 WO PCT/JP2003/013816 patent/WO2005040276A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5175791A (ja) * | 1974-12-26 | 1976-06-30 | Sumitomo Durez Co | |
JPH0269510A (ja) * | 1988-09-02 | 1990-03-08 | Matsushita Electric Works Ltd | フエノール樹脂成形材料 |
JPH0463858A (ja) * | 1990-07-02 | 1992-02-28 | Toshiba Chem Corp | フェノール樹脂成形材料 |
JP2000044771A (ja) * | 1998-07-30 | 2000-02-15 | Sumitomo Bakelite Co Ltd | 熱時寸法安定性に優れるフェノール樹脂成形材料 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008184488A (ja) * | 2007-01-26 | 2008-08-14 | Matsushita Electric Works Ltd | フェノール樹脂成形材料及び成形品 |
JP2008184490A (ja) * | 2007-01-26 | 2008-08-14 | Matsushita Electric Works Ltd | フェノール樹脂成形材料及び成形品 |
WO2010061793A1 (ja) * | 2008-11-25 | 2010-06-03 | パナソニック電工株式会社 | フェノール樹脂成形材料及びフェノール樹脂成形品 |
WO2011052127A1 (ja) * | 2009-10-26 | 2011-05-05 | パナソニック電工株式会社 | フェノール樹脂成形材料、及びフェノール樹脂成形品 |
WO2015093260A1 (ja) * | 2013-12-20 | 2015-06-25 | 住友ベークライト株式会社 | 熱硬化性樹脂組成物および金属樹脂複合体 |
CN105829452A (zh) * | 2013-12-20 | 2016-08-03 | 住友电木株式会社 | 热固化性树脂组合物及金属树脂复合体 |
JPWO2015093260A1 (ja) * | 2013-12-20 | 2017-03-16 | 住友ベークライト株式会社 | 熱硬化性樹脂組成物および金属樹脂複合体 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2005040276A1 (ja) | 2007-03-15 |
AU2003280584A1 (en) | 2005-05-11 |
JP4874649B2 (ja) | 2012-02-15 |
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