CN100523080C - Phenolic resin molding material and resin sliding part - Google Patents
Phenolic resin molding material and resin sliding part Download PDFInfo
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- CN100523080C CN100523080C CNB200480023399XA CN200480023399A CN100523080C CN 100523080 C CN100523080 C CN 100523080C CN B200480023399X A CNB200480023399X A CN B200480023399XA CN 200480023399 A CN200480023399 A CN 200480023399A CN 100523080 C CN100523080 C CN 100523080C
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Abstract
A phenolic resin molding material, comprising blending 350 to 900 parts by mass of an inorganic filler with 100 parts by mass of a phenolic novolakin that a total content of a monomeric phenol and a dimeric phenol is 10% or less when measured by the area method of gel filtration chromatography and a degree of dispersion (Mw/Mn) of a weight-average molecular weight (Mw) and a number-average molecular weight (Mn) is 1.1 to 3.0 when measured by gel filtration chromatography, and excelling in moldability, heat resistance, dimensional accuracy and mechanical strength.
Description
Technical field
The present invention relates to be suitable for to replace the phenolic resin molding material of various metal workpieces of auto parts etc.
Background technology
Phenolic resin molding material is the balance excellent material of thermotolerance, size precision, wear resistant, physical strength and expense, is widely used in each field.But, in recent years, especially in automobile industry, day by day strict near the requirement of the plastics replacementization of the part employed transmission mechanism and the engine braking apparatus under the hot environment etc., and in fact, phenolic resin molding material in the past reaches capacity on its performance.
Especially for example in the resinifying of drift stop piston, oil pump for engine, require to improve thermotolerance, size precision and wear resistant with near the metal parts the engine braking apparatus of valve etc., though lowering on the amount of resin is effective means, but because of plasticity is reduced, so the characteristic of plasticity and thermotolerance, size precision, wear resistant, physical strength etc. is satisfied in requirement simultaneously.
In addition, used varnish-type phenolic resin in the known phenolic resin molding material, be generally an acidic catalyst reaction down of phenols and aldehydes in oxalic acid etc., but because of containing many low molecular weight compositions based on unreacted phenolic monomers, so gas easily takes place, and cause that mould hazes and the problem of plasticity such as release property variation when being shaped.
In order to address the above problem, patent documentation 1 motion has and for example uses with hydroxycarboxylic acid as catalyzer, makes the phenolic resin molding material of the varnish-type phenolic resin that the unreacted phenols of gained is few after phenols and the aldehydes condensation reaction.But, though this shaped material has solved the problem that mould hazes, but because of physical strength and stable on heating characteristic are not improved fully, so requirement can be satisfied plasticity and thermotolerance, size precision, physical strength simultaneously and look purposes and the characteristic of different wear resistant etc.
Patent documentation 1: Japanese patent laid-open 8-59769 communique
Summary of the invention
The present invention is because as above-mentioned problem, be purpose so that the good phenolic resin molding material of plasticity, thermotolerance, size precision and physical strength to be provided.
In addition, the present invention is providing plasticity, thermotolerance, size precision and physical strength good, and the also good phenolic resin molding material of wear resistant is a purpose.
People such as present inventor endeavour research in order to overcome above-mentioned problem, found that via making phenolic monomers and phenolic dimer content is few and molecular weight distribution is narrow varnish-type phenolic resin and inorganic filling material with specific ratio allotment, then can obtain the shaped material of purpose, finish the present invention then.
Promptly, being characterized as of phenolic resin molding material of the present invention with respect to varnish-type phenolic resin 100 mass parts, allotment inorganic fibrous packing material 450～900 mass parts, it is below the 10 area % that described varnish-type phenolic resin has with the phenolic monomers of the planimetry mensuration gained of colloid filtration chromatography and the total content of phenolic dimer, and the weight-average molecular weight of measuring with the colloid filtration chromatography is 1.1～3.0 with the dispersion ratio of number-average molecular weight, described inorganic fibrous packing material is the combination of wollastonite and glass fibre, wherein, the combined amount of wollastonite (blending amount) is 350～800 mass parts, and the combined amount of glass fibre is 100～200 mass parts.
Phenolic resin molding material of the present invention is good in plasticity, thermotolerance, size precision and physical strength.Therefore, the formation of parts of shaped material gained is fit to be used in the replacementization of the various metal workpieces such as auto parts that require thermotolerance and size precision thus.
Especially allotment has the of the present invention phenolic resin molding material of fibrous packing material as inorganic filling material, even if lower amount of resin, plasticity is still good, and is good on thermotolerance, size precision, physical strength and wear resistant.Especially via making the amount of resin attenuatingization, can make the high fillingization of wear resistant inorganic fibrous packing material, the reinforced effects of improving effect and resin part via the hardness of product surface reaches the wear resistant raising, is suitable for the resinifying of the sliding part under oil lubrication or the water lubricating.
Description of drawings
Fig. 1 is the shape figure of the piston model of demonstration thermal shocking test usefulness.
Embodiment
Used phenolic varnish type resol is for measuring the phenolic monomers of gained with the planimetry of colloid filtration chromatography and the total content of phenolic dimer is below 10% area, is preferably below 5% area among the present invention.
In addition, the used phenolic varnish type resol of the present invention is to be 1.1～3.0 than (Mw/Mn), to be preferably 1.5～2.0 with the weight-average molecular weight (Mw) of colloid filtration chromatography mensuration and the dispersion of number-average molecular weight (Mn).In addition, weight-average molecular weight (Mw) is not particularly limited, and is preferably 800～3700, is more preferred from 900～3500.
The used phenolic varnish type resol of the present invention is not particularly limited, for example, with phenols be aldehydes more than 0.80 mole, below 1.00 moles with respect to 1 mole of phenols, in being under the existence of the phosphoric acid class more than 5 mass parts with respect to phenols 100 mass parts, the preparation method by heterogeneous reaction (heterogeneous reaction) step can prepare.
Particularly, must have as the phenols of raw material and aldehydes, as the phosphoric acid class of acid catalyst, and will be mixed with mechanical stirring, ultrasound etc. by these formed two phase-separated state, for in the inhomogeneous reaction system of gonorrhoea shape of entwining, carry out the reaction of phenols and aldehydes and synthetic condensation agent thing (resin) in two-phase (organic phase and water).Secondly, for example add and mix water-insoluble organic solvent (for example methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.), and stop to mix and leaving standstill, make organic phase (organic solvent phase) separate with water (phosphate aqueous solution phase) with this condenses dissolving.Remove water and recovery thereafter, on the other hand organic phase is given hot water washing and/or neutralization after, organic solvent evaporation is reclaimed, then can prepare.
Use can be enumerated for example phenol, cresols, xylenol, butylphenol, phenyl phenol etc. as the phenols of raw material.On the other hand, aldehydes can be enumerated for example formaldehyde, formalin, Paraformaldehyde 96, acetaldehyde etc.These raw materials are all non-limiting in this, and can be separately or and with two or more.
The proportioning (F/P) of aldehydes (F) and phenols (P) if with the mole be benchmark in the scope more than 0.80 and below 1.00, then can the used phenolic varnish type resol of produced in high yields the present invention.
In addition, use is under the existence of water as the phosphoric acid class of acid catalyst, and forms reaction place that is separated between the phenols and serve as important post, so be preferably use aqueous solution type, for example 89 quality % phosphoric acid, 75 quality % phosphoric acid etc., but optionally also can use Tripyrophosphoric acid, phosphoric anhydride etc.
The allotment amount of phosphoric acid class makes a big impact for the control of the effect that is separated, and generally speaking is more than 5 mass parts, is preferably more than 25 mass parts, is more preferred from more than 50 mass parts with respect to phenols 100 mass parts.If the allotment amount, does not then reduce the generation that low molecular weight compositions ground promotes high molecular weight components less than 5 mass parts, so have the tendency that makes the molecular weight distribution width broaden.In addition, the situation in using the phosphoric acid more than 70 mass parts preferably is fed in the reaction system in batches, the heating at inhibited reaction initial stage and guarantee security.
By the viewpoint that promotes to be separated and to react, using the non-reacted oxygen organic solvent that contains is good as the reaction secondary solvent.It is that ether, ring-type ethers, polyvalent alcohol are that ester, ketone, sulfoxide class are formed select among the group at least a that the reaction secondary solvent preferably uses by alcohols, polyvalent alcohol.
Alcohols can be enumerated the monohydroxy-alcohol as methyl alcohol, ethanol, propyl alcohol etc., the dibasic alcohol of butyleneglycol, pentanediol, hexylene glycol, ethylene glycol, propylene glycol, trimethylene dibasic alcohol, Diethylene Glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyoxyethylene glycol etc., the trivalent alcohol of glycerine etc.
Polyvalent alcohol is that ether can be enumerated for example dibasic alcohol ethers of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, glycol monomethyl amyl ether, glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethyleneglycol monophenylether etc.
The ring-type ethers for example can enumerate 1,3-diox, 1,4-diox etc., polyvalent alcohol are the ester binary alcohol esters class that can enumerate ethyl glycol etc. for example etc., ketone can be enumerated for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc., and the sulfoxide class can be enumerated for example dimethyl sulfoxide (DMSO), diethyl sulfoxide etc.
Wherein, with methyl alcohol, ethylene glycol monomethyl ether, polyoxyethylene glycol, 1,4-diox etc. are special good.
The reaction secondary solvent is not limited to above-mentioned example, if having above-mentioned characteristic and the reaction person that the time presents in liquid, even also can use for solid, and also can distinguish separately or also with two or more.The allotment amount of reaction secondary solvent is not particularly limited, and is more than 5 mass parts, is preferably 10～200 mass parts with respect to phenols 100 mass parts.
In addition, the water yield in the reaction system influences be separated effect, production efficiency, generally is that benchmark is below 40% with the quality.The water yield is if surpass the possibility that 40% production efficiency has reduction.
In addition, the temperature of reaction of phenols and aldehydes is essential condition on raising is separated effect, be generally 40 ℃～reflux temperature, be preferably 80 ℃～reflux temperature, be more preferred from reflux temperature.If temperature of reaction is less than 40 ℃, then the reaction times extremely long, and can't make that low molecular weight compositions is low to simplify.In addition, the reaction times is the allotment amount according to temperature of reaction, phosphoric acid, the water content in the reaction system etc. and different, is generally about 1～10 hour.In addition, reaction environment is more suitable with normal pressure, but if can keep the inhomogeneous reaction of feature of the present invention, then also can in adding to depress or reduce pressure down to react.
In addition, the used inorganic fibrous packing material of the present invention is good from improving wear resistant and stable on heating viewpoint to select wollastonite, and reach the viewpoint that does not reduce wear resistant from improving physical strength and thermotolerance, to select glass fibre and to make up both for good.Its combination also is good by the viewpoint of cost performance.
The allotment amount of inorganic fibrous packing material is to be 450～900 mass parts, to be preferably 600～800 mass parts with respect to phenolic varnish type resol 100 mass parts, wollastonite is 350～800 mass parts, be preferably 450～700 mass parts, and glass fibre is 100～200 mass parts, be preferably 110～150 mass parts.The inorganic fibrous packing material is if be less than 450 mass parts, then the tendency that makes wear resistant reduce is arranged because of amount of resin increases, because of becoming, linear expansivity cause rapid temperature variation to have the tendency that thermal shocking of making (thermotolerance) reduces greatly, if more than 900 mass parts, then because of flowability reduces the problem that can not guarantee stable plasticity, so for not good.
In phenolic resin molding material of the present invention, the various additives of being habitually practised in the optionally adjustable known phenolic resin molding material, for example hardening accelerator of the releasing agent of stiffening agent, calcium stearate and the Zinic stearas etc. of vulkacit H etc., magnesium oxide etc., coupler, solvent etc.
The preparation method of phenolic resin molding material of the present invention is not particularly limited, and the thing working power mill that mixes that mixes with heating such as pressurization kneader, twin-screw extruder, Henshell mixing machine, mixing rolls etc. can be pulverized and prepares.In addition, the shaped material of so handling gained also can be applicable to any one of injection forming, transfer printing shaping and compression molding etc.
Shaped material of the present invention can be speculated as in the good reason of plasticity, thermotolerance, precision size degree, physical strength and wear resistant, via using the phenol monomer and the dipolymer composition is few and disperse than little phenolic varnish type resol, can reduce the melt viscosity of the shaped material when mixing, lower and make the ratio of inorganic filling material increase relatively than the resinous principle ratio in the known shaped material.
Especially via the goods of the fibrous packing material of allotment as the shaped material gained of the present invention of inorganic filling material, the organic composition that cause easily is influenced by heat is few, so size precision is good, and thermal expansivity is also little, so the environment for temperature variation is good, in addition, during actual the slip, owing to cause that the organic composition of abrasion phenomenon is few, so in the good wear resistant of the lubricated demonstration down of profit.
Embodiment
Below, specify the present invention according to embodiment, but the present invention is not limited to embodiment.In addition, " part " of putting down in writing among the embodiment reaches " % ", does not specialize as long as have, and is that expression " mass parts " reaches " quality % ".
The preparation of phenolic varnish type resol (1)
In the reaction vessel that possesses thermometer, whipping appts, prolong, behind 193 parts in phenol (P), 92% Paraformaldehyde 96 (F) 57 parts (F/P=0.85), 89% phosphatase 11 16 parts (60%/P), the ethylene glycol of packing into 96.5 parts (50%/P), through mixing under the basis that forms gonorrhoea state (biphasic mixture), slowly be warming up to reflux temperature, carry out condensation reaction in 10 hours under synthermal again after stopped reaction.Secondly, mix on one side and add after methyl iso-butyl ketone (MIBK) dissolves condenses, stop to mix and move to content in the separatory flask and leave standstill, make methyl isobutyl ketone solution layer (upper strata) separate with phosphate aqueous solution layer (lower floor).Secondly, remove the phosphate aqueous solution layer, the methyl isobutyl ketone solution washed several times with water is removed phosphoric acid after, again content is put back in the reaction vessel, via underpressure distillation methyl iso-butyl ketone (MIBK) is removed fully, obtain (1) 213.5 part in phenolic varnish type resol.
The preparation of phenolic varnish type resol (2)
In the reaction vessel that possesses thermometer, whipping appts, prolong, pack into behind phenol 193 gram, 37 quality % formalin, 142 grams (F/P=0.85), oxalic acid 0.97 gram (0.5%/P), slowly be warming up to reflux temperature (98～102 ℃) and under synthermal, carry out condensation reaction in 6 hours, carry out concentrating under reduced pressure and obtain phenolic varnish type resol (2) 199 gram (productive rate 103%/P).
The characteristic of phenolic varnish type resol
The characteristic of the phenolic varnish type resol of gained is according to following test method determination.
The results are shown in table 1.
(I) disperse ratio
To the east of the glue body filtration chromatography SC-8020 of shuttle limited-liability company series package system (tubing string: G2000H
X1+ G4000H
X1, detector: UV254nm, carrier: tetrahydrofuran (THF) 1 ml/min, tubing string temperature: 38 ℃) measure, obtain the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) that are converted into polystyrene standard, calculate dispersion than (Mw/Mn).
(II) content of phenolic monomers and phenolic dimer (%)
Measured with the planimetry that the area of phenolic monomers and phenolic dimer is represented with percentage with respect to the gross area of molecular weight distribution.
[table 1]
| Phenolic varnish type resol (1) | Phenolic varnish type resol (2) | |
| Number-average molecular weight (Mn) | 755 | 512 |
| Weight-average molecular weight (Mw) | 1227 | 3842 |
| Dispersion is than (Mw/Mn) | 1.63 | 7.5 |
| The content of phenolic monomers (%) | 0.3 | 9.1 |
| The content of phenolic dimer (%) | 3.3 | 8.4 |
＜embodiment 1 〉
As shown in table 2, allocate (1) 100 part in phenolic varnish type resol, use wollastonite (crust industry system as the inorganic fibrous packing material, NYAD 400, benchmark Fibre diameter: 7 μ m, aspect ratio: 4) 400 parts, glass fibre (day east twist flax fibers and weave (thigh) make, the benchmark Fibre diameter: 11 μ m, average fiber is long: 3mm) 167 parts, 16 parts of vulkacit Hs and releasing agent etc. are 15 parts and uniform mixing.Thereafter, with the hot-rolling even heating slabbing that mixes, the cooling back is broken with the power abrasive dust, obtains granular shaped material.
The shaped material of gained is carried out injection forming according to following condition, obtain JIS contraction test sheet, JIS pliability test sheet (80 * 10 * 4mm), wear test ring test sheet.
Cylinder temperature: 85 ℃ of front portions, 40 ℃ at rear portion
Die temperature: 175 ℃
Setting time: 60 seconds
For the test film of gained, carry out 210 ℃ * 20 hours postcure, and estimate for following characteristic.It the results are shown in table 2.
(1) flexural strength
Measure according to JIS K7203 specification.
(2) thermal shocking
The piston model of size shape shown in Figure 1 is carried out 300 ℃ * 30 minutes heating, drop into immediately after the taking-up in 23 ℃ the water, the outward appearance of validation test sheet, and recirculation 5 times.After recirculation 5 times, flawless is good.
(3) hot water resistance
JIS contraction test sheet was flooded 500 hours in 80 ℃ of hot water, and the size changing rate before mensuration and the dipping.
(4) wear resistant
To test under the following condition, measure the wear loss of wear test with loop test sheet and subject material.
Testing load: 60kg/cm
2
Trial speed: 0.1m/s
Test period: 2 hours
Object material: FCD450
Testing circumstance: in the brake solution (normal temperature)
＜embodiment 2, comparative example 1～3 〉
Except make mixing ratio as shown in table 2 as the change, implement with embodiment 1, make shaped material, and estimate.The results are shown in table 2.In addition, the cylinder operation of comparative example 2 is poor, can't obtain shaped material.
[table 2]
Can learn obviously that by table 2 phenolic resin molding material of embodiment gained shows the equilibrium response of good thermotolerance (resistance to sudden heating), wear resistant, size precision, physical strength.
Claims (4)
1. phenolic resin molding material, it is characterized in that: with respect to varnish-type phenolic resin 100 mass parts, it is below the 10 area % that described varnish-type phenolic resin has with the phenolic monomers of the planimetry mensuration gained of colloid filtration chromatography and the total content of phenolic dimer, and the weight-average molecular weight of measuring with the colloid filtration chromatography is 1.1～3.0 with the dispersion ratio of number-average molecular weight, allotment inorganic fibrous packing material 450～900 mass parts, described inorganic fibrous packing material is the combination of wollastonite and glass fibre, wherein, the combined amount of wollastonite is 350～800 mass parts, and the combined amount of glass fibre is 100～200 mass parts.
2. phenolic resin molding material as claimed in claim 1 is characterized in that: the total content of phenolic monomers and phenolic dimer is below the 5 area %.
3. phenolic resin molding material as claimed in claim 1 or 2, it is characterized in that: above-mentioned phenolic varnish type resol is to make phenols and is aldehydes more than 0.80 mole, below 1.00 moles with respect to 1 mole of phenols, under the existence that with respect to phenols 100 mass parts is the phosphoric acid class more than 5 mass parts, carry out heterogeneous reaction and obtain, the phosphoric acid that wherein said phosphoric acid class is 75 quality %, phosphoric acid, Tripyrophosphoric acid or the phosphoric anhydride of 89 quality %.
4. a resin sliding part is to use down or under the water lubricating in oil lubrication, it is characterized in that: be to use according to each described phenolic resin molding material shaping in the claim 1 to 3 to form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003298117 | 2003-08-22 | ||
| JP298117/2003 | 2003-08-22 | ||
| JP176348/2004 | 2004-06-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1930239A CN1930239A (en) | 2007-03-14 |
| CN100523080C true CN100523080C (en) | 2009-08-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200480023399XA Expired - Fee Related CN100523080C (en) | 2003-08-22 | 2004-08-19 | Phenolic resin molding material and resin sliding part |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014024992A1 (en) * | 2012-08-10 | 2014-02-13 | 旭有機材工業株式会社 | Sliding member molding material and sliding member |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000219796A (en) * | 1999-02-02 | 2000-08-08 | Fudow Co Ltd | Impact-resistant phenolic resin molding material composition |
| JP3167248B2 (en) * | 1994-09-30 | 2001-05-21 | 積水化学工業株式会社 | Manufacturing method of retardation plate |
| CN1412241A (en) * | 2001-10-16 | 2003-04-23 | 上海欧亚合成材料有限公司 | High temp. resistant inorganic fibre reinforced injection type phenolic moulding plastics |
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2004
- 2004-08-19 CN CNB200480023399XA patent/CN100523080C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3167248B2 (en) * | 1994-09-30 | 2001-05-21 | 積水化学工業株式会社 | Manufacturing method of retardation plate |
| JP2000219796A (en) * | 1999-02-02 | 2000-08-08 | Fudow Co Ltd | Impact-resistant phenolic resin molding material composition |
| CN1412241A (en) * | 2001-10-16 | 2003-04-23 | 上海欧亚合成材料有限公司 | High temp. resistant inorganic fibre reinforced injection type phenolic moulding plastics |
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| CN1930239A (en) | 2007-03-14 |
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