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WO2018030162A1 - Composition de résine pour matériaux de friction et matériau de friction de papier humide - Google Patents

Composition de résine pour matériaux de friction et matériau de friction de papier humide Download PDF

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Publication number
WO2018030162A1
WO2018030162A1 PCT/JP2017/027180 JP2017027180W WO2018030162A1 WO 2018030162 A1 WO2018030162 A1 WO 2018030162A1 JP 2017027180 W JP2017027180 W JP 2017027180W WO 2018030162 A1 WO2018030162 A1 WO 2018030162A1
Authority
WO
WIPO (PCT)
Prior art keywords
resol type
friction material
resin composition
resin
type phenol
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.)
Ceased
Application number
PCT/JP2017/027180
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English (en)
Japanese (ja)
Inventor
裕司 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Publication of WO2018030162A1 publication Critical patent/WO2018030162A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
    • F16D69/02—Composition of linings ; Methods of manufacturing

Definitions

  • the present invention relates to a resin composition for a friction material and a wet paper friction material.
  • Friction materials such as brake linings, disc brake pads, and clutch facings for transmission are used in automobiles, railway vehicles, and aircraft (hereinafter referred to as “automobiles”).
  • a wet paper friction material is used in an automatic transmission or continuously variable transmission of an automobile.
  • This wet paper friction material is generally produced by impregnating a paper base material with a resin composition containing a phenol resin and curing.
  • a resin composition containing a phenol resin and curing Conventionally, a phenol resin composition containing a reaction product of a specific bifunctional phenol and other phenols and aldehydes as an essential component has been proposed as the resin composition (see Patent Document 1). ). In the friction material using such a phenol resin composition, the friction characteristics are improved.
  • the resin composition for a friction material of the present invention contains a resol type phenolic resin having a structural unit represented by the following general formula (r1) and a structural unit represented by the following general formula (r2),
  • the ratio of the ether group (—R 3 —O—R 4 —) in the resol type phenol resin is 0.2 to 1.0 mol per mol of the benzene ring.
  • R 1 to R 4 are each independently a divalent hydrocarbon group which may have a substituent. * Indicates a bond. However, the hydrogen atom bonded to the benzene ring in the formula may be substituted with a substituent. ]
  • the resin composition for a friction material of the present invention may further contain a base material containing an aramid fiber.
  • the wet paper friction material of this invention is a resol type phenol resin which has the base material containing an aramid fiber, the structural unit represented by the following general formula (r1), and the structural unit represented by the following general formula (r2).
  • the resol type phenolic resin is cured in a state of impregnating the base material.
  • R 1 to R 4 are each independently a divalent hydrocarbon group which may have a substituent. * Indicates a bond. However, the hydrogen atom bonded to the benzene ring in the formula may be substituted with a substituent. ]
  • the ratio of ether groups (—R 3 —O—R 4 —) in the resol type phenol resin is 0.2 to 1.0 mol per mol of the benzene ring. preferable.
  • the resin composition for friction material of this embodiment contains the resol type phenol resin which has a specific structural unit.
  • Such a resin composition is suitable for a friction material, and includes both those before curing and those after curing.
  • the resol type phenol resin in this embodiment has a specific structural unit, that is, a structural unit represented by the following general formula (r1) and a structural unit represented by the following general formula (r2).
  • R 1 to R 4 are each independently a divalent hydrocarbon group which may have a substituent. * Indicates a bond. However, the hydrogen atom bonded to the benzene ring in the formula may be substituted with a substituent. ]
  • R 1 and R 2 in the formula (r1), and R 3 and R 4 in the formula (r2) are derived from aldehydes used in the production method described later, respectively, and 2 in R 1 to R 4
  • the valent hydrocarbon group include a chain or cyclic aliphatic hydrocarbon group, and an aromatic hydrocarbon group.
  • the divalent hydrocarbon group in R 1 to R 4 is preferably a chain or cyclic aliphatic hydrocarbon group, and more preferably a chain aliphatic hydrocarbon group.
  • the chain aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group.
  • Examples of the divalent saturated aliphatic hydrocarbon group here include —CH 2 —, —CH (CH 3 ) —, —CH (C 2 H 5 ) —, —CH (C 3 H 7 ) — and the like. Can be mentioned. Examples of the divalent unsaturated aliphatic hydrocarbon group here include —CH (CH ⁇ CH 2 ) —.
  • the divalent hydrocarbon group represented by R 1 to R 4 may have a group that substitutes a hydrogen atom constituting the hydrocarbon group, Alternatively, it may be any group that substitutes for a carbon atom constituting such a hydrocarbon group, and examples thereof include a chlorine atom (—Cl), an oxo group ( ⁇ O), and an oxygen atom (—O—).
  • the substituent for substituting the hydrogen atom bonded to the benzene ring in the formula (r1) or the formula (r2) is derived from phenols used in the production method described later, for example, acetyl group, methyl group, tertiary butyl. Groups and the like.
  • the proportion of the ether group (—R 3 —O—R 4 —) in the resol type phenol resin is defined as It is 0.2 to 1.0 mole per mole, preferably 0.4 to 0.9 mole.
  • the ratio of the ether group (—R 3 —O—R 4 —) is equal to or higher than the lower limit of the above range, the mechanical strength becomes higher. If it is below the upper limit value, moderate flexibility as a resin component is easily developed.
  • the proportion of —R 2 —OH in the resol type phenol resin is 0.1 to 3.0 per mole of benzene ring.
  • the molar ratio is preferably 0.1 to 1.0 mol, and more preferably 0.1 to 0.5 mol.
  • the ratio of the ether group (—R 3 —O—R 4 —) and —R 2 —OH in the resol type phenol resin can be measured by nuclear magnetic resonance (NMR) spectroscopy.
  • the weight average molecular weight (Mw) of the resol type phenol resin in the present embodiment is not particularly limited, and is preferably 100 to 2000, for example, and more preferably 150 to 1200.
  • the weight average molecular weight (Mw) of resin means the value of polystyrene conversion measured by gel permeation chromatography (GPC).
  • Examples of the method for producing a resol type phenol resin in the present embodiment include a method having a step of reacting (condensation reaction) phenols and aldehydes in the presence of a base catalyst.
  • phenols examples include phenol, orthocresol, metacresol, paracresol, xylenol, paratertiary butylphenol, paracumylphenol, paraphenylphenol, bisphenol A, bisphenolmethane, bisphenolsulfone, bisphenol ether, resorcin, hydroquinone, and the like. Can be mentioned. Phenols may be used alone or in combination of two or more.
  • aldehydes examples include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, acrolein and the like. Aldehydes may be used alone or in combination of two or more.
  • the base catalyst examples include weak acid salts of divalent metals composed of divalent metals (for example, zinc, calcium, manganese, cobalt, nickel, lead, etc.) and weak acids (for example, acetic acid, naphthenic acid, etc.); alkali metals (for example, Lithium, sodium, potassium, etc.) hydroxides; Alkaline earth metals (eg, magnesium, calcium, barium, etc.) hydroxides; Etc.
  • weak salts of divalent metals are preferable, and manganese acetate, calcium acetate, and zinc acetate are particularly preferable.
  • a base catalyst may be used individually by 1 type, and may use 2 or more types together.
  • the reaction molar ratio of phenols to aldehydes is preferably 0.6 to 1.5 moles, more preferably 0.8 to 1.2 moles with respect to 1 mole of phenols. .
  • the amount of the base catalyst used is appropriately determined according to the types of phenols and aldehydes, and is preferably 10 to 100 parts by mass with respect to 1000 parts by mass of the phenols, for example.
  • the pH condition of the mixed solution of the phenols, aldehydes and base catalyst is preferably pH 6.0 to 8.5, more preferably pH 6.5 to 8.0. is there.
  • the temperature condition for reacting phenols with aldehydes is preferably 80 to 110 ° C., more preferably 90 to 100 ° C., and the reaction time is preferably 0.5 to 6 hours, more preferably 1 to 4 hours.
  • the pH condition of the mixed solution means the pH of the mixed solution at the temperature (reaction temperature) when the phenols and aldehydes are reacted.
  • An ether group (—R 3 —O—R 4 —) is generated by dehydration condensation between the phenol and the aldehyde.
  • the target resol type phenol resin which has a structural unit represented by general formula (r1) and a structural unit represented by general formula (r2) is obtained.
  • the reaction product (resol type phenol resin) may be diluted with an organic solvent.
  • the organic solvent used for the dilution is not particularly limited, and examples thereof include alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; toluene, ethylbenzene, and the like.
  • Aromatic hydrocarbon solvents or mixtures thereof.
  • a dehydration treatment such as decompression may be performed before the reaction product is diluted.
  • the resol type phenol resin may be used alone or in combination of two or more.
  • the resin composition for a friction material of the present embodiment may contain, for example, a curing agent, a powder filler, a solvent, and the like, as necessary, in addition to the resol type phenol resin.
  • curing agent suitably according to the kind etc. of a resole type phenol resin, for example, hexamethylenetetramine, an isocyanate resin, an epoxy resin, hexamethoxymethylol melamine etc. are mentioned.
  • the powder filler include inorganic fillers such as diatomaceous earth, activated carbon, and graphite; and organic fillers such as cashew dust.
  • the resin composition for a friction material may use the above-mentioned resol type phenol resin as it is, or may be a mixture of the above resol type phenol resin, other components and a solvent.
  • This solvent can be selected as appropriate, and among them, those capable of dissolving each component are preferable.
  • the solvent include alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbon solvents such as toluene and ethylbenzene, or mixtures thereof. It is done.
  • the resin concentration of the resin composition for a friction material is preferably 10 to 50% by mass, more preferably 15 to 40% by mass.
  • the resin composition for a friction material of the present embodiment include those containing a base material containing an aramid fiber in addition to the above-mentioned resol type phenol resin.
  • the base material containing an aramid fiber is exemplified in a state before or after curing impregnated with a resol type phenol resin.
  • the base material here is a base material containing an aramid fiber, and a fiber base material mainly composed of an aramid fiber is preferable.
  • An aramid fiber refers to a polyamide (aromatic polyamide) fiber having an aromatic ring in the main chain.
  • the aramid resin constituting the aramid fiber may have either a meta-type structure (meta-type aramid) or a para-type structure (para-type aramid).
  • the base material containing an aramid fiber may be composed of an aramid fiber alone, or may be a mixture of an aramid fiber and other fibers.
  • Other fibers are not particularly limited, and examples thereof include metal fibers, glass fibers, carbon fibers, natural fibers, and synthetic resin fibers.
  • the base material may be filled with a friction modifier such as cashew dust and a filler such as diatomaceous earth in addition to the aramid fiber.
  • the wet paper friction material of this embodiment is a resol type phenol having a base material containing the aramid fiber, a structural unit represented by the general formula (r1), and a structural unit represented by the general formula (r2).
  • a resin, and the resol type phenolic resin is cured in a state of being impregnated into a base material containing an aramid fiber.
  • the wet paper friction material of the present embodiment can be produced, for example, by impregnating a base material containing aramid fibers with the above-described resin composition for friction material and curing.
  • the temperature condition at the time of curing is preferably 120 to 280 ° C, more preferably 150 to 250 ° C.
  • the curing time is preferably from 0.1 to 3 hours, more preferably from 0.25 to 1 hour.
  • resol-type phenol resin in the embodiment described above at least a part of —R 2 —OH which is a polar group in the resin is etherified by dehydration condensation.
  • a resol type phenol resin in which at least a part of —R 2 —OH is etherified has a lower polarity than a conventional product and has a high affinity with an aramid fiber. For this reason, the resol type phenol resin is easily impregnated into the aramid fiber, and the resol type phenol resin and the base material are more integrated.
  • the wet paper friction material in which the resin composition for a friction material of the present embodiment is cured in a state in which the base material containing aramid fibers is impregnated has higher mechanical properties (tensile strength, tensile elongation at break, etc.). ing.
  • resol type phenol resin had a weight average molecular weight (Mw) of 250.
  • Mw of the resol type phenol resin obtained in Production Examples 1 to 5 represents a value in terms of polystyrene measured by gel permeation chromatography (GPC).
  • Example 1 The resol type phenol resin obtained in Production Example 1 and acetone were mixed to prepare a resin composition having a resin concentration of 30% by mass. The resin composition was impregnated into the base material (1) and then cured in an oven at 190 ° C. for 30 minutes to obtain a wet paper friction material.
  • Examples 2 and 3 Comparative Examples 1 and 2
  • the resin composition was prepared in the same manner as in Example 1 except that the resol type phenol resin obtained in Production Example 1 was changed to the resol type phenol resin obtained in Production Examples 2 to 5. And then cured in an oven at 190 ° C. for 30 minutes to obtain a wet paper friction material.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Braking Arrangements (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne : une composition de résine pour matériaux de friction, qui contient une résine phénolique de type résol ayant une unité constitutive représentée par la formule générale (r1) (dans laquelle chacun de R1 et R2 représente indépendamment un groupe hydrocarboné divalent facultativement substitué) et un motif constitutif représenté par la formule générale (r2) (où chacun de R3 et R4 représente indépendamment un groupe hydrocarboné divalent facultativement substitué), et le rapport des groupes éther (-R3-O-R4-) dans la résine phénolique de type résol étant de 0,2 à 1,0 mole pour 1 mole de cycles de benzène ; et analogue.
PCT/JP2017/027180 2016-08-09 2017-07-27 Composition de résine pour matériaux de friction et matériau de friction de papier humide Ceased WO2018030162A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-156415 2016-08-09
JP2016156415A JP2019167386A (ja) 2016-08-09 2016-08-09 摩擦材用樹脂組成物及び湿式ペーパー摩擦材

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WO2018030162A1 true WO2018030162A1 (fr) 2018-02-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111620989A (zh) * 2019-02-27 2020-09-04 Nsk沃纳株式会社 湿式摩擦材料用酚醛树脂、酚醛树脂组合物和湿式摩擦材料
WO2021241245A1 (fr) * 2020-05-29 2021-12-02 住友ベークライト株式会社 Feuille de composition de résine phénolique, feuille de composition de résine phénolique avec film antiadhésif, procédé de production de feuille composite de résine phénolique en phase b, procédé de production de feuille composite de résine phénolique durcie et procédé de production de feuille composite de résine phénolique carbonisée

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5645916A (en) * 1979-07-19 1981-04-25 Hooker Chemicals Plastics Corp Phenol resin abrasive grain* its manufacture and abrasive material containing it
JPH03111447A (ja) * 1989-09-26 1991-05-13 Hitachi Chem Co Ltd 摩擦材組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5645916A (en) * 1979-07-19 1981-04-25 Hooker Chemicals Plastics Corp Phenol resin abrasive grain* its manufacture and abrasive material containing it
JPH03111447A (ja) * 1989-09-26 1991-05-13 Hitachi Chem Co Ltd 摩擦材組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111620989A (zh) * 2019-02-27 2020-09-04 Nsk沃纳株式会社 湿式摩擦材料用酚醛树脂、酚醛树脂组合物和湿式摩擦材料
WO2021241245A1 (fr) * 2020-05-29 2021-12-02 住友ベークライト株式会社 Feuille de composition de résine phénolique, feuille de composition de résine phénolique avec film antiadhésif, procédé de production de feuille composite de résine phénolique en phase b, procédé de production de feuille composite de résine phénolique durcie et procédé de production de feuille composite de résine phénolique carbonisée

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