CN102076805A - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- CN102076805A CN102076805A CN2009801253584A CN200980125358A CN102076805A CN 102076805 A CN102076805 A CN 102076805A CN 2009801253584 A CN2009801253584 A CN 2009801253584A CN 200980125358 A CN200980125358 A CN 200980125358A CN 102076805 A CN102076805 A CN 102076805A
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- 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
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/72—Sealings
- F16C33/74—Sealings of sliding-contact bearings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- 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
- C09K3/12—Materials for stopping leaks, e.g. in radiators, in tanks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
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- 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
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
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- 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
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C2370/00—Apparatus relating to physics, e.g. instruments
- F16C2370/12—Hard disk drives or the like
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Conventional curable resin compositions have low chemical resistance against lubricants for fluid bearing motors used in an HDD or the like, and thus suffer from problems such that cured products of the resin compositions are deteriorated due to contact with the lubricants or components of the resin compositions dissolve into the lubricants. Consequently, the conventional curable resin compositions are poorly reliable with respect to sealing performance and/or adhesion. The above-mentioned problems can be solved by using an epoxy resin composition composed of the following components (A)-(C). Component (A): an epoxy resin Component (B): rubber particles Component (C): an imidazole derivative.
Description
Technical field
The present invention relates to a kind of sealing and/or bonding in the composition epoxy resin of use, it is used for making the lubricating fluid that uses in the used fluid bearing type electric motor such as hard disk drive can not leak.
Background technology
In recent years, for hard disk drive (below be called HDD.) electric motor of usefulness, require the raising (with reference to shallow Tian Longwen, flat, great clear, the auxilliary greatly work Matsushita of her the rattan Technical Journal Vol.51 No.1 Feb.2005 of vegetarian rattan of Yamamoto wise man) of high speed and low noise.In order to satisfy these characteristics, use fluid bearing widely.This fluid bearing is following mode, that is, and and at axle (axostylus axostyle: shaft) and bearing (axle sleeve: be full of lubricating fluid sleeve), utilized axle in the lubricating fluid film, to produce pressure (dynamic pressure), come support loading thus with the relative sliding motion of bearing.Under the situation of this bearing, in order to produce dynamic pressure, the cross-sectional shape that is carved with the gap of bearing is the groove that is generally known as chevron-notch of wedge shape, notch cuttype and so on, needs to form nonparallel shape.Under fluid bearing axis immobilized state, do not produce dynamic pressure, therefore can't form can support loading the lubricating fluid film.Thus, be used to situation with the motion of the speed of constant speed or certain limit.Though can obtain high rigidity at an easy rate, yet, therefore when design, need prior clear and definite use range because characteristic depends on relative slip velocity.(following lubricating fluid is called lubricating oil.)
In addition, the demand of the vehicle mounted electronic component of high reliability improves constantly, and requires the reliability of PC or portable phone to improve.Same requirement is also arranged in HDD with it together.As the concrete test method of confirming reliability, the high temperature test of carrying out placing in the high temperature about 100 ℃, be positioned over the humidity test of hot and humid (for example 85 ℃ * 85%RH etc.) down, carry out that the thermal cycling test of (for example-40 ℃ with 80 ℃ switching) is placed with high temperature and placed to low temperature repeatedly or compare the more strict thermal shock test of low temperature pyritous switching condition etc. with thermal cycling test.When utilizing this kind test, when reliabilities such as generation motor characteristic variation reduce, will in HDD, counteract driving.(following so-called reliability is meant the tolerance to high temperature test, humidity test, thermal cycling test and/or thermal shock test.)
In general, bearing is made of transverse bearing and thrust block.Carry out the thrust plate bolster not only of the supporting of thrust block, but also as being used for not making the containment member of oil leak to play a role.As a rule, as the method that thrust plate is fixed on the axle sleeve, the known way (with reference to TOHKEMY 2003-235199 communique) that welding used or curable resin composition are arranged.Like this, just can take into account the bonding of the sealing of lubricating oil and thrust plate.In case oil leak, the lubricant effect of fluid bearing will reduce, the obvious deterioration of running accuracy, and axle or bearing wear, device damages.Moreover, the lubricating oil that leaks out also can cause detrimentally affect to machine itself.In HDD, even be not directly to adhere to the lubricating oil that leaks out, and the gaseous constituent that just produces from lubricating oil is attached on the disk, also might have problems in reading, or magnetic head is broken down.In addition, the gaseous constituent that produces from resin combination itself also might become problem.(the following gaseous constituent that will become problem is generically and collectively referred to as discharge gas.)
Prevent that in order to leak reliably welding is main flow in thrust plate fixing.But,, all be problem aspect productivity therefore because once manageable number is limited in the welding all the time.On the other hand, by in curable resin composition fixing, if use the curing oven etc. of batch processing formula, then can the disposable processing of carrying out a large amount of numbers.But lubricating oil is many to constitute (with reference to TOHKEMY 2008-1886 communique) by dioctyl phthalic acid (DOP), dioctyl sebacic acid ester classes such as (DOS), for the cured article requirement of resin combination and the resistance to chemical reagents under the lubricating oil state of contact.Can not have with the lubricating oil state of contact under resin combination expand, the situation of composition stripping in lubricating oil of adhesive composite.Lubricating oil will become discharge gas under the situation of electric motor external leakage, produce aforesaid problem, will produce cured article under the situation of resin combination stripping in lubricating oil in lubricating oil, might the driving of electric motor be counteracted.(followingly will be called resistance to chemical reagents to the tolerance of lubricating oil.)
As mentioned above, the curable resin composition that generally uses was because low to the resistance to chemical reagents of the lubricating oil of fluid bearing electric motor used among the HDD etc. in the past, therefore exist because of the composition of cured article deterioration, resin combination that makes resin combination with contacting of lubricating oil shortcoming such as stripping in lubricating oil, seal and/or bonding in reliability low.
Summary of the invention
The objective of the invention is to, solve the problem of above-mentioned conventional art, a kind of composition epoxy resin is provided, its lubricating oil for fluid bearing type electric motor has tolerance especially, the sealing and/or bonding in reliability aspect also very excellent.
First mode of the present invention is a kind of composition epoxy resin that is used in the sealing and/or the bonding use of fluid bearing type electric motor, it is characterized in that, as containing (A)～(C) composition by composition.
(A) composition: Resins, epoxy
(B) composition: rubber particles
(C) composition: imdazole derivatives
Second mode of the present invention is following above-mentioned composition epoxy resin, that is, (B) composition is the particle that contains divinyl rubber and/or acrylic rubber.
Third Way of the present invention is following above-mentioned composition epoxy resin, that is, (B) composition is rubber particles or in advance letex polymerization and the rubber particles made in Resins, epoxy that is scattered in advance in the Resins, epoxy.
Cubic formula of the present invention is following above-mentioned composition epoxy resin,, with respect to (A) composition 100 mass parts, contains the rubber particles of conduct (B) composition of 5～50 mass parts that is.
The 5th mode of the present invention is following above-mentioned composition epoxy resin, that is, do not contain in fact as the solidifying agent beyond the imdazole derivatives of (C) composition.
The 6th mode of the present invention is following above-mentioned composition epoxy resin, that is, and and the sealing of fluid bearing type electric motor and/or to be bonded in the fluid bearing type spindle drive motor that is used for hard disk drive be as the sealing in the gap of thrust plate and/or bonding.
The 7th mode of the present invention is following above-mentioned composition epoxy resin,, also contains the pyrogenic silica as (D) composition that is.
All directions of the present invention formula is following above-mentioned composition epoxy resin,, contains the pyrogenic silica of conduct (D) composition of 0.5～5 weight part with respect to (A) composition 100 mass parts that is.
Composition epoxy resin of the present invention is particularly suitable in the fluid bearing type electric motor used in HDD etc., in order not make oil leak with thrust plate and sleeve sealing and/or bonding.
Embodiment
Below details of the present invention is described.
Used (A) composition is the compound that has the epoxy group(ing) more than 2 at 1 intramolecularly that is generally known as Resins, epoxy among the present invention.Resins, epoxy both can only use a kind, also can be mixed with two or more.Concrete example as the Resins, epoxy that is suitable for using, be the resin that utilizes the condensation of polyatomic phenol such as Epicholorohydrin and bisphenols or polyvalent alcohol to obtain, for example can bisphenol A-type, brominated bisphenol A type, hydrogenation bisphenol A-type, Bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorenes type, novolac-type, linear novolac type, linear phenolic varnish type, three (hydroxy phenyl) methane of ortho-cresol type, four hydroxyphenyl ethane type Racemic glycidol ether type epoxies such as (tetraphenylolethane type) be shown example.In addition, the glycidyl group amine type Resins, epoxy that can also enumerate glycidyl ester type epoxy resin that the condensation that utilizes Epicholorohydrin and carboxylic acids such as phthalic acid derivatives or lipid acid obtains, utilize Epicholorohydrin and amine, the reaction of cyanuric acid class, hydantoins obtains and utilize the whole bag of tricks modification Resins, epoxy, yet be not limited to them.
As commercially available Resins, epoxy, can enumerate EPICLON830, the EXA-835LV etc. of Japan Epoxy Resin Co., Ltd. system 827,828EL etc., big Japanese ink Industrial Co., Ltd system.Can enumerate the system EPOTOTO YD-128 of Toto Kasei KK, YDF-170 etc., yet be not limited to them.Then preferably has the Resins, epoxy of dihydroxyphenyl propane skeleton, Bisphenol F skeleton in price if consider.
(B) composition used among the present invention is a rubber particles.The rubber particles that is suitable for using is the particle that contains divinyl rubber and/or acrylic rubber.As the median size of rubber particles, be preferably 0.05～0.5 μ m.Change if consider the viscosity that causes by expansion, then the rubber particles of core-shell-type most preferably.By adding divinyl rubber and/or acrylic rubber, aspect reliability, just have trend to the tolerance raising of lubricating oil.Particularly, bonding strength is not easy to reduce.
In addition, also can use the rubber particles that is scattered in advance in the Resins, epoxy.Specifically, utilize mixed stirring devices such as super homogenizer (hyper) or homogenizer to be scattered in the interior rubber particles of Resins, epoxy, to utilize letex polymerization synthetic rubber particles in Resins, epoxy suitable with it.The median size of the final rubber particles that forms is preferably 0.05～0.5 μ m in utilizing method of emulsion polymerization.By using the rubber particles that is scattered in advance in the Resins, epoxy, the disposal that will have a composition when the manufacturing of the resin combination simple advantage that becomes.In addition, owing to Resins, epoxy soaks into to rubber particles fully, so the variation of the viscosity behind the effluxion has the trend that diminishes.
As the concrete example of above-mentioned divinyl rubber particle, can enumerate the system Metablen of Mitsubishi Rayon Co. Ltd. E series and Metablen C series etc.As the concrete example of aforesaid propylene acid rubber particles, can enumerate the system MX of Soken Chemical ﹠ Engineering Co., Ltd. series, the system Metablen W of Mitsubishi Rayon Co. Ltd. series, Zeon and change into the system Zefiac of Co., Ltd. series etc.As the concrete example of the Resins, epoxy that is dispersed with rubber particles in advance, can enumerate Resinous and change into the system RKB of Co., Ltd. series etc.As the concrete example of the Resins, epoxy that uses letex polymerization, can enumerate the system Acryset BP of Nippon Shokubai Co., Ltd series etc., yet be not limited to them.
With respect to (A) composition 100 mass parts, (B) addition of composition is preferably 5～50 mass parts.Most preferably with respect to (A) composition 100 mass parts, (B) addition of composition is 5～40 weight parts.If (B) addition of composition is more than 50 mass parts, then bonding force has the trend of reduction, if be less than 1 mass parts, then reliability has the trend of reduction.
(C) composition used among the present invention is an imdazole derivatives, plays a role as solidifying agent with respect to Resins, epoxy.
In general, as solidifying agent used in the Resins, epoxy, known have polyamino compound (comprising Dyhard RU 100 or hydrazide compound etc.), phenolic compound, poly-thiol compound, an acid anhydrides etc.In order to promote the reactivity of solidifying agent, also tertiary amine compound etc. is used as curing catalyst sometimes.In general curing catalyst at room temperature is the solid material, use will to solid have addition tertiary amine in the compound of imidazoles skeleton or the Resins, epoxy and halfway the epoxy addition compound of stopped reaction pulverize and micropowder etc.As commercially available epoxy addition based compound, Amicure series, the Fuji that can enumerate aginomoto Fine Techno Co., Ltd. system change into the Fujicure series of Industrial Co., Ltd's system or the Novacure series of Chemicals Co., Ltd. of Asahi Chemical Industry system etc.In addition, as being aqueous curing catalyst under the room temperature, known have organophosphorus based compound, organic amine based compound, an imdazole derivatives based compound etc.In addition, knownly also can according to circumstances curing catalyst be used as solidifying agent.
Among the present invention, to being used to seal in order to make the lubricating fluid of the fluid bearing type electric motor that uses in the hard disk drive etc. not leak and/or bonding caking agent is furtherd investigate, found that, with Resins, epoxy and rubber particles, the imdazole derivatives that has the imidazoles key in main framing optionally demonstrates excellent effect as (C) composition.Preferred especially normal temperature (20 ℃) is the aqueous imdazole derivatives that begins to react in the temperature below 100 ℃.
Because the solidifying agent and/or the curing catalyst of the solid (powder) that will generally use add in the resin combination, can cause high viscosityization or give thixotropy, it is difficult that the disposal when therefore brushing becomes.In addition, if use the aqueous solidifying agent that generally uses, then have reactive low and solidified situation or reactive on the contrary too fast and produce the situation of problems such as work-ing life is extremely short not.Under the low situation of solidified nature, can produce secondary problems such as the discharge of discharging gas or bonding force reduction.
Confirm among the present invention, most preferably use aqueous imdazole derivatives, do not contain imdazole derivatives solidifying agent in addition in fact as (C) composition.As the concrete example of this kind (C) composition, the Curezol series of Shikoku Chem's system is arranged, can enumerate 1B2MZ, 2E4MZ etc., yet be not limited thereto.Above-mentioned so-called " not containing imdazole derivatives solidifying agent in addition in fact " is meant, do not contain and do not determine that in fact reactive compound is not to be the such compound of imdazole derivatives, in the manufacturing process of raw material the situation of remaining impurities, wittingly add very micro-ly the situation of solidifying agent beyond the imdazole derivatives and/or curing catalyst, substantially determine reactive situation for above-mentioned these compounds etc. also to be contained in the above-mentioned statement.
With respect to (A) composition 100 mass parts, (C) addition of composition is preferably 0.5～5 mass parts.Under the situation that is less than 0.5 mass parts and under the situation more than 5 mass parts, solidified nature can reduce.
Among the present invention, add pyrogenic silica by conduct (D) composition, and will seal and/or the adhesiveproperties raising, help the raising of reliability in addition.Possess hydrophilic property and hydrophobicity in pyrogenic silica, as the concrete example of commercially available product, the AEROSIL series of Japanese Aerosil Co., Ltd. system that corresponding is etc., however be not limited to them.Preferred median size is 5～50nm's.
The addition of above-mentioned (D) composition is so long as in the scope of not damaging purport of the present invention, just be not particularly limited, yet preferably with respect to (A) composition 100 mass parts, adds (D) composition of 0.5～5 mass parts.If more than 5 mass parts, then viscosity uprises, therefore mobile the disappearance can counteract when the coating resin composition.
Composition epoxy resin of the present invention can all mix (A)～(C) composition and be made as 1 liquid type.Perhaps, also can be made as with host that constitutes by (A) composition and (B) mixture of ingredients and the 2 liquid types of forming by the solidifying agent that (C) composition constitutes.
In composition epoxy resin of the present invention, also can in the scope of not damaging desired effect of the present invention, cooperate additives such as inorganic fillers such as tinting materials such as pigment, dyestuff, metal powder, lime carbonate, talcum, silicon-dioxide, aluminum oxide, aluminium hydroxide, fire retardant, organic filler, softening agent, antioxidant, defoamer, silane series coupling agent, leveling agent, rheology control agent in right amount.Utilize their interpolation, can obtain excellent composition and cured articles thereof such as mechanical strength of resin bonding strength operation keeping quality.
Embodiment
To enumerate embodiment below the present invention is further elaborated, yet the present invention not only is defined in these embodiment.
＜embodiment 1～14 〉
Prepared following compositions in order to prepare composition epoxy resin.
(A) composition: Resins, epoxy
● have the Resins, epoxy and mixture (the big Japanese ink of Epiclon EXA-835LV Industrial Co., Ltd system) of dihydroxyphenyl propane skeleton with Resins, epoxy of Bisphenol F skeleton
(B) composition: rubber particles
● acrylic rubber particle (Zefiac F340 Zeon changes into Co., Ltd.'s system)
● divinyl rubber particle (Metablen E-901 Mitsubishi Rayon Co. Ltd. system)
● contain the Resins, epoxy (rubber particles that contains 20 quality %) (Acryset BPF-307 Nippon Shokubai Co., Ltd system) of acrylic rubber particle
● contain the Resins, epoxy (rubber particles that contains 15 quality %) (Resibond RKB-1003 Resinous changes into Co., Ltd.'s system) of divinyl rubber particle
(C) composition: imdazole derivatives
● 1 benzyl 2 methyl imidazole (Curezol 1B2MZ Shikoku Chem system)
● 2-ethyl-4-methylimidazole (Curezol 2E4MZ Shikoku Chem system)
(D) composition: pyrogenic silica
● hydrophilic fumed silica (AEROSIL200 Japan Aerosil Co., Ltd. system)
(A) composition and (B) composition were stirred 1 hour.Add (D) composition restir 30 minute thereafter.At last, adding (C) composition stirred 15 minutes.Concrete amount of preparation is with reference to table 1, and numerical value is all with the mass parts souvenir.
＜comparative example 1～9 〉
Prepared following compositions in order to prepare composition epoxy resin.
(A) composition: Resins, epoxy
● have the Resins, epoxy and mixture (the big Japanese ink of Epiclon EXA-835LV Industrial Co., Ltd system) of dihydroxyphenyl propane skeleton with Resins, epoxy of Bisphenol F skeleton
(B) composition: rubber particles
● acrylic rubber particle (Zefiac F340 Zeon changes into Co., Ltd.'s system)
● divinyl rubber particle (Metablen E-901 Mitsubishi Rayon Co. Ltd. system)
(C) composition: imdazole derivatives
● 1 benzyl 2 methyl imidazole (Curezol 1B2MZ Shikoku Chem system)
(C ') composition: polyamino compound
● hetero ring type diamines modifier (Epomate B002 Japan Epoxy Resin Co., Ltd. system)
(D) composition: pyrogenic silica
● hydrophilic fumed silica (AEROSIL200 Japan Aerosil Co., Ltd. system)
(A) composition and (B) composition were stirred 1 hour.Add (D) composition restir 30 minute thereafter.At last, add (C) composition and/or (C ') composition stirred 15 minutes.Concrete amount of preparation is with reference to table 2, and numerical value is all with the mass parts souvenir.
To the composition epoxy resin that obtains in embodiment 1～14 and the comparative example 1～9, carried out each test as follows and confirmed.It is the results are summarized in the table 3.
[chimeric bonding strength test]
Use the axle collar of the 15 φ * 15mm in the pin of stainless steel (SUS304) system 6 φ * 40mm and the hole that internal diameter 6 φ that can insert pin were made and offered to stainless steel (SUS304).Clearance during insertion is 0.01mm.Behind the resin combination of coating 1mg on the pin, extend equably on adhesive portion, by 90 ℃ of heating 1 hour, make specimen.Mensuration so that the compression speed of 10mm/min carries out maximum loading calculates bonding strength according to following formula (1).
The evaluation of chimeric bonding strength (Pa) is as follows, is summarized in the table 3.
More than the 55MPa: ◎ (the best)
50～54MPa: zero (well)
45～49MPa: △ (common)
Less than 45MPa: * (bad)
[resistance to chemical reagents test]
Use DOS to carry out the dip test of cured article as lubricating oil.Each composition is filled in the container of 10 φ * 10mm, makes cured article 90 ℃ of heating 1 hour.Cured article is taken out from container, measure " quality at initial stage " of cured article.This cured article be impregnated among the DOS and placed 1000 hours at 100 ℃.Dipping finishes the back and takes out cured article, fully removes lubricating oil, and quality measurement is made as this quality " quality behind the dipping " once more.According to following formula (2), " mass change (%) " after calculating the initial stage and flooding.
The evaluation of mass change (%) is as follows, is summarized in the table 3.
-0.09～+ 0.09%: zero (very)
Less than-0.1% or+more than 0.1%: * (bad)
[total vent gas scale of construction is measured]
(unit: what mensuration ppm) was used is that the gas chromatography mass analyser (is generally known as GC-MS to total vent gas scale of construction.)。In the aluminium cup, gather each resin combination of about 30mg, make it to solidify 90 ℃ of following heating 1 hour.After getting back to room temperature, under 85 ℃ * 3 hours extraction condition, extract out and discharge gas, utilize gas-chromatography various discharge gas component separating.N-hexadecane as standard model, is obtained the quality of various discharge gaseous constituents.The total of the quality of various discharge gaseous constituents is equivalent to total vent gas scale of construction.The evaluation of total vent gas scale of construction (ppm) is as follows, is summarized in the table 3.
Less than 5ppm: ◎ (the best)
5～9ppm: zero (well)
More than the 10ppm: * (bad)
[reliability test (reduced rate of chimeric bonding strength)]
Used the specimen of using the method identical to make with chimeric bonding strength test.Use the part of solidified specimen side by side, measure the bonding strength at initial stage, it is made as " the chimeric bonding strength at initial stage ".Under the state of remaining specimen in impregnated in DOS, placed 400 hours at 100 ℃.After lubricating oil after will flooding end removes fully, measure chimeric bonding strength, it is made as " the chimeric bonding strength behind the dipping ".Result behind initial stage and the dipping is calculated " reduced rate (%) " of bonding strength according to following formula (3).
The evaluation of the reduced rate of chimeric bonding strength (%) is as follows, is summarized in the table 3.
Less than 1%: ◎ (the best)
1～3%: zero (well)
4～9%: △ (common)
More than 10%: * (bad)
[work-ing life]
Just made the back at resin combination and measured initial stage viscosity according to following use.
The specification of viscometer
Producer: the TV-33 of Toki Sangyo Co., Ltd. type viscometer (EHD type)
Condition determination
Cone rotor: 3 ° * R14
Rotating speed: 0.5rpm
Minute: 5 minutes
Measure higher limit: 1024Pas
Measure temperature: 25 ℃
Gathering above-mentioned resin combination 50g in plastic containers is positioned under 25 ℃.Measured viscosity with identical specification in per 1 hour, the time that will reach 2 times viscosity of initial stage viscosity was confirmed as " work-ing life (hour) ".Work-ing life (hour) evaluation as follows, be summarized in the table 3.
More than 12 hours: zero (well)
1～12 hour: △ (common)
Less than 1 hour: * (bad)
[comprehensive judgement]
In order synthetically to judge the characteristic of composition epoxy resin, chimeric bonding strength test, resistance to chemical reagents test, total vent gas scale of construction mensuration, reliability test, the score in work-ing life have been carried out.Evaluation method is carried out as followsly, and it be the results are summarized in the table 3.
3 minutes: ◎
2 minutes: zero
1 minute: △
0 minute: *
What the comprehensive numerical value of judging was high in the table 3 is exactly to be suitable for the sealing of fluid bearing type electric motor and/or bonding resin combination.If comparing embodiment 1～6,11,12 and comparative example 5～9, then by adding rubber particles, characteristic is equal or improves in all tests, and particularly reliability improves.In addition, if relatively all embodiment and comparative example 1～4, then by in amine compound, only would using imdazole derivatives, for resistance to chemical reagents, reliability, can see the raising of characteristic work-ing life.According to these results, by side by side using rubber particles and imdazole derivatives, will embody for the sealing of fluid bearing type electric motor and/or bonding essential characteristic.
In recent years, it is big that the capacity of HDD constantly becomes, and miniaturization is in continuous propelling, thereby require the high precision int of part.Thus, in physical properties such as welding or riveted joint are bonding, can see the limit.On the other hand, by the bonding counter stress height of curable resin composition, and in production line, can help the raising of throughput at part change.In addition, require the reliability of temperature or humidity is improved in vehicle mounted HDD, require the raising of various performances such as shock-resistance raising at subnotebook PC in HDD, the present invention is the composition epoxy resin that can tackle these reliability tests.Owing to the resistance to chemical reagents and the reliability height of lubricating oil, therefore be not limited only to the HDD spindle drive motor, can also be used for the sealing of various fluid dynamic bearing structures and/or bonding purposes.
Claims (8)
1. composition epoxy resin, it is used for the sealing of fluid bearing type electric motor and/or bonding, it is characterized in that, as must containing (A)～(C) composition by composition,
(A) composition: Resins, epoxy
(B) composition: rubber particles
(C) composition: imdazole derivatives.
2. composition epoxy resin according to claim 1, wherein, (B) composition is the particle that contains divinyl rubber and/or acrylic rubber.
3. composition epoxy resin according to claim 1 and 2, wherein, (B) composition is rubber particles or in advance letex polymerization and the rubber particles made in Resins, epoxy that is scattered in advance in the Resins, epoxy.
4. according to any described composition epoxy resin in the claim 1～3, wherein,, contain the rubber particles of conduct (B) composition of 5～50 mass parts with respect to (A) composition 100 mass parts.
5. according to any described composition epoxy resin in the claim 1～4, wherein, do not contain in fact as the solidifying agent beyond the imdazole derivatives of (C) composition.
6. according to any described composition epoxy resin in the claim 1～5, wherein, the sealing of fluid bearing type electric motor and/or bonding is the sealing in gap of thrust plate and axle sleeve and/or bonding in being used for the fluid bearing type spindle drive motor of hard disk drive.
7. according to any described composition epoxy resin in the claim 1～6, wherein, also contain pyrogenic silica as (D) composition.
8. according to any described composition epoxy resin in the claim 1～7, wherein, contain the pyrogenic silica of conduct (D) composition of 0.5～5 weight part with respect to (A) composition 100 mass parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008171939A JP5263496B2 (en) | 2008-07-01 | 2008-07-01 | Epoxy resin composition |
| JP2008-171939 | 2008-07-01 | ||
| PCT/JP2009/062234 WO2010002007A1 (en) | 2008-07-01 | 2009-06-29 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102076805A true CN102076805A (en) | 2011-05-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801253584A Pending CN102076805A (en) | 2008-07-01 | 2009-06-29 | Epoxy resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5263496B2 (en) |
| CN (1) | CN102076805A (en) |
| WO (1) | WO2010002007A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173174A (en) * | 2011-12-22 | 2013-06-26 | 三星电机株式会社 | Adhesive resin composition for HDD motor and HDD motor fabricated using the same |
| CN105764985A (en) * | 2013-12-05 | 2016-07-13 | 三键有限公司 | Heat-curable resin composition |
| CN106543941A (en) * | 2015-09-17 | 2017-03-29 | (株)利来化学商社 | Automobile epoxy bond compositionss and the adhesive method using this |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101400724B1 (en) | 2008-01-15 | 2014-05-29 | 연세대학교 산학협력단 | Method and device for communicating using network coding scheme |
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| KR101300460B1 (en) * | 2011-09-21 | 2013-08-27 | 삼성전기주식회사 | Adhesive resin composition for HDD motor and HDD motor fabricated by using the same |
| CN102925092B (en) * | 2012-11-14 | 2014-01-29 | 杭州师范大学 | Epoxy resin nano composite adhesive film and preparation method thereof |
| US9762445B2 (en) * | 2013-05-20 | 2017-09-12 | Trane International Inc. | Device and method for automatic switching of communication protocol of network devices based on user action |
| DE102013111120A1 (en) | 2013-10-08 | 2015-04-09 | Osram Opto Semiconductors Gmbh | Semiconductor chip and method for separating a composite in semiconductor chips |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004115650A (en) * | 2002-09-26 | 2004-04-15 | Three Bond Co Ltd | Adhesive composition |
| CN1803916A (en) * | 2005-01-13 | 2006-07-19 | 三菱瓦斯化学株式会社 | Resin composite and prepreg and laminate materials used thereof |
| CN1886479A (en) * | 2003-12-01 | 2006-12-27 | 德古萨股份公司 | Adhesive and sealant systems |
| WO2007066763A1 (en) * | 2005-12-08 | 2007-06-14 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic element and electronic element device |
| CN101006135A (en) * | 2004-08-18 | 2007-07-25 | 株式会社钟化 | Epoxy resin composition for semiconductor sealing agents and epoxy resin molding material |
| CN101165076A (en) * | 2006-10-17 | 2008-04-23 | 比亚迪股份有限公司 | Anti-flaming phosphorus-containing epoxy resin, preparation method thereof and composition containing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08283687A (en) * | 1995-04-14 | 1996-10-29 | Hitachi Kasei Polymer Co Ltd | Epoxy-based single liquid-type adhesive composition for fixing magnet for motors |
| WO1998003047A1 (en) * | 1996-07-15 | 1998-01-22 | Hitachi Chemical Company, Ltd. | Film-like adhesive for connecting circuit and circuit board |
| JP3931207B2 (en) * | 2000-05-10 | 2007-06-13 | 日本電産株式会社 | Hydrodynamic bearing device |
| JP2006165094A (en) * | 2004-12-03 | 2006-06-22 | Hitachi Chem Co Ltd | Insulating adhesive sheet for printed wiring board and method of manufacturing printed wiring board |
| JP4826729B2 (en) * | 2005-10-17 | 2011-11-30 | 株式会社スリーボンド | Heat-expandable sheet adhesive composition |
-
2008
- 2008-07-01 JP JP2008171939A patent/JP5263496B2/en not_active Expired - Fee Related
-
2009
- 2009-06-29 CN CN2009801253584A patent/CN102076805A/en active Pending
- 2009-06-29 WO PCT/JP2009/062234 patent/WO2010002007A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004115650A (en) * | 2002-09-26 | 2004-04-15 | Three Bond Co Ltd | Adhesive composition |
| CN1886479A (en) * | 2003-12-01 | 2006-12-27 | 德古萨股份公司 | Adhesive and sealant systems |
| CN101006135A (en) * | 2004-08-18 | 2007-07-25 | 株式会社钟化 | Epoxy resin composition for semiconductor sealing agents and epoxy resin molding material |
| CN1803916A (en) * | 2005-01-13 | 2006-07-19 | 三菱瓦斯化学株式会社 | Resin composite and prepreg and laminate materials used thereof |
| WO2007066763A1 (en) * | 2005-12-08 | 2007-06-14 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic element and electronic element device |
| CN101165076A (en) * | 2006-10-17 | 2008-04-23 | 比亚迪股份有限公司 | Anti-flaming phosphorus-containing epoxy resin, preparation method thereof and composition containing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173174A (en) * | 2011-12-22 | 2013-06-26 | 三星电机株式会社 | Adhesive resin composition for HDD motor and HDD motor fabricated using the same |
| CN103173174B (en) * | 2011-12-22 | 2015-05-27 | 三星电机株式会社 | Adhesive resin composition for HDD motor and HDD motor fabricated using the same |
| CN105764985A (en) * | 2013-12-05 | 2016-07-13 | 三键有限公司 | Heat-curable resin composition |
| CN105764985B (en) * | 2013-12-05 | 2018-07-03 | 三键有限公司 | Compositions of thermosetting resin |
| CN106543941A (en) * | 2015-09-17 | 2017-03-29 | (株)利来化学商社 | Automobile epoxy bond compositionss and the adhesive method using this |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010002007A1 (en) | 2010-01-07 |
| JP5263496B2 (en) | 2013-08-14 |
| JP2010013493A (en) | 2010-01-21 |
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Application publication date: 20110525 |