CN101003690B - Heat radiation insulation resin composition and printing circuit board using same - Google Patents
Heat radiation insulation resin composition and printing circuit board using same Download PDFInfo
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- CN101003690B CN101003690B CN2007100009877A CN200710000987A CN101003690B CN 101003690 B CN101003690 B CN 101003690B CN 2007100009877 A CN2007100009877 A CN 2007100009877A CN 200710000987 A CN200710000987 A CN 200710000987A CN 101003690 B CN101003690 B CN 101003690B
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Abstract
The present invention provides a heat dissipation insulating resin composition which exhibits heat dissipation useful for encapsulation baseboards, surface installation type light-emitting diodes etc. and exhibits excellent stability in storage, as well as a printed circuit using the same. Said heat dissipation insulating resin composition provided is characterized in that (A) ceramic particles for radiating far infrared rays and (B) solidifying resin compositions are contained therein, wherein the volume occupation rate of (A) is 60 volume% of the total volume of the condensate. There is also provided a printed circuit using said composition.
Description
Technical field
The present invention relates to the insulating resin composition of thermal diffusivity excellence and use its printed circuit board (PCB), in more detail, relate to the heat radiation insulation resin composition of useful thermal diffusivity such as resin insulating barrier of having base plate for packaging, surface mounting luminous diode, excellent storage stability and use its printed circuit board (PCB).
Background technology
In recent years, miniaturization, high performance along with e-machine require semi-conductive densification, multifunction.Therefore, it is small-sized highdensity installing that semi-conductive circuit substrate also requires.Its result, the thermal diffusivity of parts, circuit substrate becomes very big problem recently.
Be directed to this, as the good circuit substrate of thermal diffusivity, enumerated the metal base substrate, it uses metal sheets such as copper or aluminium, forms circuit patterns (reference example such as reference 1) by electric insulation layers such as prepreg or hot curing resin compositions on the single face of this metal sheet or two sides.
But this metal base substrate is because therefore the poor thermal conductivity of electric insulation layer must make the insulation layer attenuation, and its result tends to produce the problem of dielectric voltage withstand.
On the other hand, the main flow of the installation method of high-density semiconductor chip is a surface mounting, and recently, BGA (ball grid array), CSP base plate for packaging such as (chip size packages) begin to climb up stage.Employed solder resist composition in this base plate for packaging (reference example such as patent documentation 2), interlayer dielectic with low-molecular-weight epoxy compounds as matrix, packing material also is good silicon-dioxide of electric insulating quality, resistance to chemical reagents or settleability barium sulfate, lacks thermal diffusivity.In addition, when using aluminum oxide that thermal diffusivity, electric insulating quality, resistance to chemical reagents expect to some extent as filler, the sedimentation of filler is violent, and settled filler is assembled and solidified, and therefore becomes and can not use, and lacks practicality aspect storage stability.
Be directed to this, also considered the method for subsidiary radiating piece on semi-conductor top, but owing to about 50% of the heat that is discharged is accumulated on the base plate for packaging, so the thermal diffusivity of base plate for packaging still becomes problem.
In addition, in a plurality of surface mounting luminous diodes being used for nearest mobile telephone that button shows etc., exist the most of heat that distributes by photodiode to be accumulated in problem on the substrate.Specifically, for example dispose on being formed with the resin insulating barrier of portion of terminal in light-emitting diode chip for backlight unit, the surface mounting luminous diode of its top by the sealing resin encapsulation of the band lens jacket of holding concurrently, the thermal diffusivity of above-mentioned resin insulating barrier becomes problem.
Patent documentation 1: Japanese kokai publication hei 6-224561 communique (claims)
Patent documentation 2: Japanese kokai publication hei 11-288091 communique (claims)
Summary of the invention
The problem that invention will solve
The present invention puts in view of the above problems and carries out, and its main purpose is to provide heat radiation insulation resin composition, and it has the useful thermal diffusivities such as resin insulating barrier to base plate for packaging, surface mounting luminous diode, excellent storage stability.
Its purpose also is to provide printed circuit board (PCB), its following formation: by above-mentioned heat radiation insulation resin composition being carried out active energy beam irradiation or thermofixation, form interlayer insulating film and any one deck at least of solder mask.
Be used to solve the method for problem
People of the present invention further investigate to achieve these goals, found that the ceramic particle that contains (A) emitting far infrared ray and (B) the volume occupation rate of the ceramic particle of curable resin composition, described emitting far infrared ray (A) be that composition more than the 60 capacity % does not have sedimentation or accumulative problem with respect to the cured article total volume, excellent storage stability, as used for printed circuit insulating curable resin combination is excellent, and then has finished the present invention.
In addition, as described curable resin composition (B), (B-1) hot curing resin composition or (B-2) any one of Photocurable resin composition all can obtain same effect, the insulating curable composition of Thermocurable and light solidified can be provided.In addition, use, the insulating curable resin combination of the thermofixation photocuring and the type of using also can be provided by mixture heat curable resin composition (B-1) and Photocurable resin composition (B-2).
As other modes, can provide printed circuit board (PCB), its following formation:, form any one deck at least of interlayer insulating film and solder mask by above-mentioned heat radiation insulation resin composition being carried out active energy beam irradiation or thermofixation.
The effect of invention
The ceramic particle of used emitting far infrared ray is spherical among the present invention, therefore can be highly-filled, and can not increase substantially the viscosity of composition, especially have by use and become the spherical particle of the size-grade distribution of close filling, can suppress sedimentation and gathering, the insulating resin composition of storage stability, excellent thermal conductivity can be provided.The insulating resin composition of this thermal diffusivity excellence and excellent storage stability can be suitable in the printed circuit board (PCB) that is equipped with many semi-conductors of thermal value or photodiode, and because excellent thermal conductivity, Miniaturizable, lightweight.
Description of drawings
Fig. 1 is the heat radiation mimic diagram of the substrate of use embodiment 1 and comparative example 1.
Fig. 2 is the heat radiation mimic diagram of the substrate of use embodiment 2 and comparative example 2.
Embodiment
The basic mode of heat radiation insulation resin composition of the present invention is characterised in that, contain the ceramic particle of (A) emitting far infrared ray and (B) the volume occupation rate of the ceramic particle of curable resin composition, described emitting far infrared ray (A) comprise more than the 60 capacity % with respect to the cured article total volume.Especially find, by making chemically also stable and the excellent volume occupation rate of globular aluminum oxide in cured article of insulativity is more than the 60 capacity %, can provide cured article the thermal diffusivity excellence, have insulativity and do not damage the cured article of coating.
Below, each moiety of heat radiation insulation curable resin composition of the present invention is elaborated.
Operable material has the aluminum oxide (Al that is commonly called far-infrared ceramic in the ceramic particle of used at first, in the present invention emitting far infrared ray (A)
2O
3), silicon-dioxide (SiO
2), zirconium white (ZrO
2), titanium oxide (TiO
2), magnesium oxide (MgO), mullite (3Al
2O
32SiO
2), zircon (ZrO especially
2SiO
2), trichroite (2MgO2Al
2O
35SiO
2), silicon nitride (Si
3N
4), silicon carbide (SiC), manganese oxide (MnO
2), ferric oxide (Fe
2O
3), cobalt oxide (CoO) etc.
Wherein, aluminum oxide chemically stable, insulativity is also excellent.Particularly rise by the viscosity of using the globular aluminum oxide can relax when highly-filled.The median size of this alumina particle (A-1) is 0.01 μ m～30 μ m, more preferably 0.01 μ m～20 μ m.Median size is during less than 0.01 μ m, and the viscosity of composition becomes too high, is difficult to disperse, and also is difficult to be applied on the applied thing.On the other hand, median size is exposed to the phenomenon of filming during greater than 30 μ m, and perhaps settling velocity accelerates, and storage stability worsens.In addition, have the aluminum oxide of median size more than 2 kinds of the size-grade distribution that becomes the closeest filling by mixing, can be further highly-filled, consider it is preferred from storage stability, thermal conductivity two aspects.
In addition, in this specification sheets, so-called far infrared rays represents that the wavelength of common notion is the hertzian wave of 4～1000 μ m.In addition, the ceramic particle of so-called emitting far infrared ray (A) is for example to put down in writing like that in TOHKEMY 2003-136618 communique, with respect to perfect black body, has the ceramic particle that is preferably the high far infrared irradiation rate more than 80%.
Commercially available product as described alumina particle (A-1), (Denki Kagaku Kogyo kabushiki produces can to enumerate DAW-05, median size 5 μ m), (Denki Kagaku Kogyo kabushiki produces DAW-10, median size 10 μ m), (clear and electrician company produces AS-40, median size 12 μ m), AS-50 (clear and electrician produces, median size 9 μ m) etc.
As the combined amount of this alumina particle (A-1), be more than the 60 capacity % with respect to the total volume of cured article.The combined amount of alumina particle (A-1) can't obtain the sufficient thermal conductivity as heat sink material during with respect to the total volume less than 60 capacity % of cured article.
In addition, the proportion of curable resin is about 1.1g/ml usually, and the proportion of aluminum oxide is 4.0g/ml, therefore with respect to curable resin 40 (ml) * 1.1 (g/ml)=44g, aluminum oxide is 60 (ml) * 4.0 (g/ml)=more than the 240g, when being benchmark with the quality, be about more than the 84 quality %.
Employed curable resin composition (B) can be (B-1) hot curing resin composition and (B-2) Photocurable resin composition any among the present invention.
As above-mentioned hot curing resin composition (B-1), can enumerate by heating the composition that shows electric insulating quality takes place to solidify, for example epoxies composition, trimethylene oxide based composition, melamine resin, silicone resin etc. can preferably use any at least a kind hot curing resin composition of any at least a kind and solidifying agent and the curing catalysts that contain epoxy compounds and oxetane compound especially in the present invention.
As above-mentioned epoxy compounds,, then can use known compound commonly used so long as have more than 1 in a part, be preferably the compound of 2 above epoxy group(ing).For example, can enumerate bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, di-toluene phenol-type epoxy resin, trihydroxymethylpropanyltri diglycidyl ether, phenyl-1, the 3-diglycidylether, 1, the 6-hexanediol diglycidyl ether, the diglycidylether of ethylene glycol or propylene glycol, the Sorbitol Powder polyglycidyl ether, three (2, the 3-epoxypropyl) isocyanuric acid ester, has the compound of 2 above epoxy group(ing) etc. in 1 molecules such as triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester.Further, can also in the scope that does not reduce the cured coating film characteristic, add mono-epoxy compounds such as butylglycidyl ether, phenyl glycidyl ether, (methyl) glycidyl acrylate.
These compounds can use the territory combination to use more than 2 kinds separately according to the requirement that coating characteristic improves.
Above-mentioned oxetane compound is shown in following general formula (1), for containing the compound of trimethylene oxide.As concrete compound, can enumerate 3-ethyl-3-methylol trimethylene oxide (the trade(brand)name OXT-101 that East Asia Synesis Company produces), 3-ethyl-3-(phenoxymethyl) trimethylene oxide (the trade(brand)name OXT-211 that East Asia Synesis Company produces), 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (the trade(brand)name OXT-212 that East Asia Synesis Company produces), 1, two { [(3-ethyl-3-oxetanyl) methoxyl group] methyl } benzene of 4-(the trade(brand)name OXT-121 that East Asia Synesis Company produces), two (3-ethyl-3-trimethylene oxide ylmethyl) ether (the trade(brand)name OXT-221 that East Asia Synesis Company produces) etc.Also can enumerate the oxetane compound of phenol phenolic varnish type.
[changing 1]
(in the formula, R
1Expression hydrogen atom or carbonatoms are 1～6 alkyl.)
Above-mentioned oxetane compound can and be used or independent the use with above-mentioned epoxy compounds, but reactive poor owing to comparing with epoxy compounds, so must be noted that raising solidified temperature etc.
Then, as material, can enumerate multifunctional oxybenzene compound, poly carboxylic acid and acid anhydrides thereof, aliphatics or aromatic uncle or secondary amine, polyamide resin, poly-sulfhydryl compound etc. as solidifying agent.Wherein, preferably use multifunctional oxybenzene compound and poly carboxylic acid and acid anhydrides thereof from operability, insulativity aspect.
As multifunctional oxybenzene compound,, then can use known compound commonly used so long as have the compound of 2 above phenolic hydroxyl groups in a part.Specifically, can enumerate novolac resin, vinylphenol copolymer resins of phenol novolac resin, cresols novolac resin, dihydroxyphenyl propane, allylation dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane etc., particularly, the phenol novolac resin is because reactivity is high, the stable on heating effect of raising is also high, and is therefore preferred.This multifunctional oxybenzene compound is in the presence of suitable curing catalysts, also with described epoxy compounds and/or oxetane compound generation addition reaction.
Described poly carboxylic acid and acid anhydrides thereof are compound and the acid anhydrides thereof that has 2 above carboxyls in a part, for example can enumerate the multipolymer of (methyl) acrylic acid multipolymer, maleic anhydride, the condenses of diprotic acid etc.As commercially available product, can enumerate poly-nonane diacid acid anhydride that ジ ョ Application Network リ Le (commodity group name) that Johnson Polymer company produces, SMA resin (commodity group name) that ARCO Chemical company produces, new Japanese natural sciences company produce etc.
As above-mentioned curing catalysts, can enumerate in the reaction of epoxy compounds and/or oxetane compound and multifunctional oxybenzene compound and/or poly carboxylic acid and acid anhydrides thereof as the compound of curing catalysts or when not using solidifying agent as the compound of polymerizing catalyst, for example tertiary amine, tertiary ammonium salt, quaternary salt, tertiary phosphine, crown ether complex compound and phosphorus ylide etc., can select arbitrarily from these materials, these can be used alone or in combination of two or more kinds.
In these materials, as preferred material, can enumerate trade(brand)name 2E4MZ, C11Z, C17Z, imidazoles such as 2PZ, trade(brand)name 2MZ-A, the azines of imidazoles such as 2E4MZ-A, trade(brand)name 2MZ-OK, the isocyanurate of imidazoles such as 2PZ-OK, trade(brand)name 2PHZ, imidazoles methylol bodies such as 2P4MHZ (above-mentioned trade(brand)name is four countries and changes into industry (strain) production), dicyanodiamide and derivative thereof, melamine and derivative thereof, diaminomaleonitrile and derivative thereof, diethylenetriamine, Triethylenetetramine (TETA), tetren, two (hexa-methylene) triamine, trolamine, diaminodiphenyl-methane, amines such as organic acid dihydrazide, 1,8-diazacyclo [5,4,0] undecylene-7 (trade(brand)name DBU, SAN-APRO (strain) produces), 3, two (the 3-aminopropyls)-2 of 9-, 4,8,10-four oxygen spiral shell [5,5] undecane (trade(brand)name ATU, aginomoto (strain) is produced) or triphenylphosphine, tricyclohexyl phosphine, tributylphosphine, organic phosphine compounds such as methyldiphenyl base phosphine etc.
The combined amount of these curing catalysts is promptly abundant with the ratio of common amount, for example with respect to the total amount of described epoxy compounds of 100 mass parts and/or oxetane compound, is preferably more than 0.1 mass parts, below 10 mass parts.
As Photocurable resin composition (B-2), get final product so long as the composition with electric insulating quality takes place to solidify by the active energy beam irradiation, contain the compound that has 1 above ethylenic unsaturated bond in a part and the composition of Photoepolymerizationinitiater initiater, excellence aspect thermotolerance, electric insulating quality is preferred.
As the described compound that in a part, has 1 above ethylenic unsaturated bond, can use the oligopolymer of known photopolymerization commonly used and vinyl monomer of photopolymerization etc.
As the oligopolymer of described photopolymerization, can enumerate unsaturated polyester oligoesters, (methyl) acrylate quasi-oligomer etc.As (methyl) acrylate quasi-oligomer, can enumerate epoxy (methyl) acrylate such as phenol phenolic varnish epoxy (methyl) acrylate, cresols phenolic varnish epoxy (methyl) acrylate, bisphenol type epoxy (methyl) acrylate, urethane (methyl) acrylate, epoxy urethane (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate, polybutadiene-modified (methyl) acrylate etc.
In addition, in this specification sheets, (methyl) acrylate is meant the term of general designation acrylate, methacrylic ester and composition thereof, for other similar expression too.
Can enumerate known material commonly used, for example styrene derivativess such as vinylbenzene, chloro-styrene, alpha-methyl styrene as the vinyl monomer of described photopolymerization; Vinyl esters such as vinyl-acetic ester, vinyl butyrate or M-nitro benzoic acid vinyl acetate; Vinyl ethers such as VINYL ISOBUTYL ETHER, vinyl n-butyl ether, vinyl uncle butyl ether, vinyl n-amylether, vinyl isoamyl oxide, vinyl Octadecane ether, vinyl hexamethylene ether, glycol monomethyl butyl vinyl ether, triethylene glycol monomethyl vinyl ether; (methyl) acrylic amides such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-ethoxyl methyl acrylamide, N-butoxymethyl acrylamide; Allylic cpds such as cyanacrylate, Phthalic acid, diallyl ester, diallyl isophthalate; (methyl) acrylic acid ester classes such as (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid phenoxy ethyl; (methyl) acrylic acid hydroxy alkyl ester classes such as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, three (methyl) vinylformic acid pentaerythritol ester; Single (methyl) alkoxyalkyl acrylate such as (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester; Two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid butanediol ester class, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid-1, alkylidene polyol many (methyl) acrylate such as 6-hexylene glycol ester, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate; Polyether polyols many (methyl) esters of acrylic acids such as Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, Macrogol 200 two (methyl) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylation trimethylolpropane tris (methyl) acrylate; Many (methyl) esters of acrylic acids such as hydroxyl trimethylacetic acid DOPCP two (methyl) acrylate; Isocyanuric acid ester type many (methyl) esters of acrylic acids such as three [(methyl) acryloxy ethyl] isocyanuric acid ester etc.
According to the requirement on the coating characteristic, these materials can be used alone or in combination of two or more kinds.
As described Photoepolymerizationinitiater initiater, can enumerate st-yrax compound and alkyl ethers thereof such as st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzoyl dimethyl acetal; Methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, diethoxy acetophenone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-acetophenones such as 1-ketone; Anthraquinone classes such as tectoquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone; Thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-two clopenthixal ketones, 2-methyl thioxanthone, 2, thioxanthene ketones such as 4-di-isopropyl thioxanthone; Ketal classes such as methyl phenyl ketone dimethyl ketal, benzil dimethyl ketal; Benzophenone, 4, benzophenones such as the two methylamino benzophenone of 4-etc.These materials can use separately, also can mix more than 2 kinds and to use, and can also be used in combination with light-initiated auxiliary agent etc. in addition, as tertiary amines such as trolamine, methyldiethanolamines; M-nitro benzoic acid derivatives such as 2-dimethyl aminoethyl M-nitro benzoic acid, 4-dimethylamino ethyl benzoate etc.
Highly-filled in order easily to carry out as required, can in insulating curable resin combination of the present invention, add Ricinate.As this Ricinate, can use have carboxyl, the compound or the macromolecular compound of hydroxyl, acid esters isopolarity group, for example phosphoric acid ester etc. contains acid compound, contains the salt etc. of polycarboxylate, polysiloxane, long-chain polyaminoamide and acid esters of multipolymer, the hydroxyl of acidic group.In commercially available Ricinate, as the material that can especially preferably use can enumerate Disperbyk (registered trademark)-101 ,-103 ,-110 ,-111 ,-160 ,-171 ,-174 ,-190 ,-300, Bykumen (registered trademark), BYK-P105 ,-P104 ,-P104S ,-240 (being PVC ッ Network ケ ミ one ジ ャ パ Application company produces), EFKA-polymkeric substance 150, EFKA-44 ,-63 ,-64 ,-65 ,-66 ,-71 ,-764 ,-766, N (being EFCA company produces).
For modulation group compound, adjustment viscosity, insulating curable resin combination of the present invention can add organic solvent.As described organic solvent, can use for example ketone such as methylethylketone, pimelinketone; Toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methylcyclohexane, ethylene glycol butyl ether, Trivalin SF, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; Ester classes such as ethyl acetate, butylacetate, n-Butyl lactate, cellosolve acetic ester, ethylene glycol butyl ether acetic ester, carbitol acetate, diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; Aliphatic hydrocarbon such as octane, decane; Organic solvents such as petroleum-type solvent such as sherwood oil, petroleum naphtha, solvent naphtha.These organic solvents can use use more than 2 kinds also capable of being combined separately.
As required, insulating curable resin combination of the present invention can also mix known additive kind commonly used, as phthalocyanine blue, phthalocyanine green, iodine is green, dual-azo yellow, Viola crystallina, titanium oxide, carbon black, known tinting materials commonly used such as naphthalene is black, quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, known hot stopper commonly used such as phenothiazine, fine particle silica, organobentonite, known thickening material commonly used such as montmorillonite, silicone, the fluorine class, the defoamer and/or the flow agent of high score subclass etc., imidazoles, thiazoles, the silane coupling agent of triazole species etc. etc.
Insulating curable resin combination of the present invention is adjusted to the viscosity that is suitable for coating process by described organic solvent, is applied on the base material by methods such as silk screen print methods.
When described insulating curable resin combination is hot curing resin composition (B-1), after coating, make its thermofixation, can obtain cured coating film by being heated to about 140 ℃～180 ℃ temperature.
In addition, when described insulating curable resin combination is Photocurable resin composition (B-2), after coating, utilize high pressure mercury vapour lamp, metal halide lamp, xenon lamp etc. to carry out uviolizing, can obtain cured coating film.
Embodiment
Then provide embodiments of the invention and comparative example specifies the present invention, certainly, the present invention is not subjected to the qualification of following examples.In addition, following " part " and " % " represent " mass parts " and " quality % " unless otherwise specified.
Mixing element with mixing following table 1 illustrated embodiment 1,2 of 3 roll-type roller mills and comparative example 1,2 obtains curable resin composition.The evaluation result of the storage stability of gained curable resin composition is shown in Table 2, and its evaluating characteristics the results are shown in the table 3, and temperature simulation the results are shown in Fig. 1, Fig. 2.
Table 1
Annotate: the volume occupation rate of filler composition is by the volume V that removes the composition outside the filler composition
0With the volume V behind the interpolation filler
1Following trying to achieve.
The volume occupation rate of filler composition (capacity %)=(V
1-V
0)/V
1* 100
Table 2
| Embodiment 1 | |
Comparative example 1 | Comparative example 2 | |
| After 2 days | ◎ | ◎ | ○ | ○ |
| After 7 days | ◎ | ◎ | × | ○ |
| After 30 days | ◎ | ○ | × | × |
| After 90 days | ○ | ○ | × | × |
Table 3
| Embodiment 1 | |
Comparative example 1 | Comparative example 2 | |
| Solvent resistance | ○ | ○ | ○ | ○ |
| Thermotolerance | ○ | ○ | ○ | ○ |
| Pencil hardness | 9H | 4H | 7H | 3H |
| Insulating resistance value | 9×10 11Ω | 3×10 10Ω | 1×1012Ω | 1×10 12Ω |
| Heat radiation test (temperature after 10 minutes) | 102.5℃ | 104.6℃ | 117.3℃ | 118.3℃ |
In addition, the evaluation method of above-mentioned table 3 and table 4 is as follows.
Storage stability is estimated:
The heat-curable composition of embodiment 1 and comparative example 1 is packed in the sealing black container of polyethylene system, preserve down at 5 ℃.Sedimentation state after 2 days, after 7 days, after 30 days, after 90 days is estimated.
In addition, the Photocurable composition of embodiment 2 and comparative example 2 is packed in the sealing black container of polyethylene system, preserve 20 ℃ dark places.Sedimentation state after 2 days, after 7 days, after 30 days, after 90 days is estimated.
◎: not sedimentation
Zero: though there are some sedimentations not assemble, no problem in the use after the stirring
*: sedimentation, gathering.Also become piece even if stir, can not use.
Evaluating characteristics:
(1) solvent resistance
According to dry coating is that about 30 μ m are thick, utilizes silk screen printing, and the heat-curable composition pattern of embodiment 1 and comparative example 1 is printed onto on the FR-4 substrate that is formed with circuit, solidifies 60 minutes down at 150 ℃.
In addition, be that about 30 μ m are thick according to dry coating, utilize silk screen printing, the Photocurable composition pattern of embodiment 2 and comparative example 2 is printed onto on the FR-4 substrate that is formed with circuit, use metal halide lamp under the wavelength of 350nm, to shine 2J/cm
2The accumulation light quantity make its curing.The gained substrate is immersed in the propylene glycol monomethyl ether acetate 30 minutes, after the drying, utilizes the glassine paper adhesive tape to carry out stripping test, estimate the variable color of peeling off of filming.
Zero: do not peel off, variable color
*: peel off, variable color
(2) thermotolerance
Use embodiment 1 and the heat-curable composition of comparative example 1 and the Photocurable composition of embodiment 2 and comparative example 2, utilize the method identical to solidify with solvent resistance.Coating rosin based solder flux flow through for 10 seconds in 260 ℃ of weld grooves on the gained substrate, utilize propylene glycol monomethyl ether acetate washing, drying after, utilize the glassine paper adhesive tape to carry out stripping test, estimate peeling off of filming.
Zero: do not peel off
*: peel off
(3) pencil hardness
Use embodiment 1 and the heat-curable composition of comparative example 1 and the Photocurable composition of embodiment 2 and comparative example 2, utilize the method identical to solidify with solvent resistance.B is polished to the nib of the pencil-lead of 9H, scratch the gained substrate, the hardness of the pencil that writing down films does not peel off with about 45 ° angle.
(4) electric insulating quality
According to dry coating is that about 30 μ m are thick, utilizes silk screen printing, and the heat-curable composition pattern of embodiment 1 and comparative example 1 is printed onto on the FR-4 substrate of the comb poles that is formed with IPC specification B pattern, solidifies 60 minutes down at 150 ℃.In addition, according to dry coating is that about 30 μ m are thick, utilize silk screen printing, the Photocurable composition pattern of embodiment 2 and comparative example 2 is printed onto on the FR-4 substrate of the comb poles that is formed with IPC specification B pattern, use metal halide lamp under the wavelength of 350nm, to shine 2J/cm
2The accumulation light quantity make its curing.Applying the interelectrode insulating resistance value of measuring the gained substrate under the voltage 500V.
(5) heat radiation test
According to dry coating is that about 30 μ m are thick, utilizes silk screen printing, the heat-curable composition pattern of embodiment 1 and comparative example 1 is printed onto covers on the copper FR-4 substrate, solidifies 60 minutes down at 150 ℃.In addition, be that about 30 μ m are thick according to dry coating, utilize silk screen printing, the Photocurable composition pattern of embodiment 2 and comparative example 2 is printed onto covers on the copper FR-4 substrate, use metal halide lamp under the wavelength of 350nm, to shine 2J/cm
2The accumulation light quantity make its curing.At this moment, one jiao of state that exposes Copper Foil with substrate prints.On this jiao by on become the well heater of the 60W of thermal source, heated 10 minutes, then, dispelled the heat 10 minutes.Utilization sticks on the K type thermocouple measurement substrate temperature at this moment apart from well heater 3mm position.The results are shown among Fig. 1 and Fig. 2.
In addition, the temperature of the substrate of heating in the time of 10 minutes is shown in table 2 and table 3.
By result shown in table 2 and the table 3 as can be known, by heat radiation insulation resin composition of the present invention, no matter be Thermocurable or light solidified, it is excellent and as the cured article of the required abundant characteristic of use in printed circuit board heat-resistant insulation material to obtain thermal diffusivity.
In addition, by Fig. 1 and Fig. 2 as can be known, used the substrate of the heat radiation insulation resin composition of embodiment 1,2 to compare with the substrate that has used the comparative example composition, thermal diffusivity excellence, temperature rise few.
Claims (7)
1. the purposes of heat radiation insulation resin composition in solder resist, it is characterized in that, described heat radiation insulation resin composition contains spherical alumina particle and (B) curable resin composition that (A) median size is the emitting far infrared ray of 0.01 μ m～30 μ m, and described median size is that the volume occupation rate of spherical alumina particle (A) of the emitting far infrared ray of 0.01 μ m～30 μ m is more than the 60 capacity % with respect to the total volume of cured article.
2. purposes according to claim 1 is characterized in that, described curable resin composition (B) is (B-1) hot curing resin composition.
3. purposes according to claim 2 is characterized in that, described hot curing resin composition (B-1) contains any at least a kind that is selected from epoxy compounds and the oxetane compound.
4. purposes according to claim 2 is characterized in that, described hot curing resin composition (B-1) contains and is selected from any at least a in solidifying agent and the curing catalysts.
5. purposes according to claim 1 is characterized in that, described curable resin composition (B) is (B-2) Photocurable resin composition.
6. purposes according to claim 5 is characterized in that, described Photocurable resin composition (B-2) contains compound and the Photoepolymerizationinitiater initiater that has 1 above ethylenic unsaturated bond in 1 molecule.
7. the purposes of heat radiation insulation resin composition in printed circuit board (PCB), the following formation of this printed circuit board (PCB):, form solder mask by each described heat radiation insulation resin composition of described claim 1 to 6 being carried out active energy beam irradiation or thermofixation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006009196 | 2006-01-17 | ||
| JP2006009196A JP5089885B2 (en) | 2006-01-17 | 2006-01-17 | Thermal insulation resin composition and printed wiring board using the same |
| JP2006-009196 | 2006-01-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003690A CN101003690A (en) | 2007-07-25 |
| CN101003690B true CN101003690B (en) | 2010-04-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007100009877A Active CN101003690B (en) | 2006-01-17 | 2007-01-17 | Heat radiation insulation resin composition and printing circuit board using same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5089885B2 (en) |
| KR (1) | KR100849585B1 (en) |
| CN (1) | CN101003690B (en) |
| TW (1) | TW200746935A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130158167A1 (en) * | 2010-12-20 | 2013-06-20 | Daicel Corporation | Curable epoxy resin composition and optical semiconductor device using said resin composition |
| JP6024265B2 (en) * | 2011-10-14 | 2016-11-16 | Jnc株式会社 | Thermal radiation coating composition and thermal radiation member using the same |
| JP6149498B2 (en) * | 2013-05-10 | 2017-06-21 | パナソニックＩｐマネジメント株式会社 | UV curable sheet material, UV curable dry film, UV curable insulating material for build-up |
| KR101687394B1 (en) | 2013-06-17 | 2016-12-16 | 주식회사 엘지화학 | Photo-curable and thermo-curable resin composition and dry film solder resist |
| JP6349543B2 (en) * | 2013-12-25 | 2018-07-04 | パナソニックＩｐマネジメント株式会社 | COOLING STRUCTURE AND METHOD FOR MANUFACTURING COOLING STRUCTURE |
| CN107075258B (en) * | 2014-10-01 | 2020-03-06 | 纳美仕有限公司 | Resin composition |
| KR101792755B1 (en) | 2014-10-28 | 2017-11-01 | 주식회사 엘지화학 | Photo-curable and thermo-curable resin composition and dry film solder resist |
| JP6941810B2 (en) * | 2017-04-19 | 2021-09-29 | パナソニックＩｐマネジメント株式会社 | Resin composition and electronic components and electronic devices using it |
| JP7142453B2 (en) * | 2018-03-30 | 2022-09-27 | 太陽インキ製造株式会社 | Heat dissipation insulating resin composition and printed wiring board using the same |
| CN112823188B (en) * | 2018-11-20 | 2023-08-11 | 太阳控股株式会社 | High withstand voltage heat radiation insulating resin composition and electronic component using the same |
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| JPH01109753A (en) * | 1987-10-23 | 1989-04-26 | Hitachi Ltd | Semiconductor device |
| JPH0362844A (en) * | 1989-02-27 | 1991-03-18 | Shin Etsu Chem Co Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device |
| JPH06167806A (en) * | 1992-11-30 | 1994-06-14 | Sony Corp | Solder resist ink composition and printed circuit board formed by suing the same |
| JPH0841294A (en) * | 1994-07-27 | 1996-02-13 | Shin Etsu Chem Co Ltd | Insulating resin paste and semiconductor apparatus |
| KR100201223B1 (en) | 1996-09-16 | 1999-06-15 | 조규삼 | Far-infrared radiating thermosetting resin compositions |
| JP2002179763A (en) | 2000-11-28 | 2002-06-26 | Sumitomo Bakelite Singapore Pte Ltd | Epoxy resin composition |
| JP2004027004A (en) * | 2002-06-25 | 2004-01-29 | Matsushita Electric Works Ltd | Semiconductor-sealing epoxy resin composition and semiconductor device |
| JP2004217861A (en) * | 2003-01-17 | 2004-08-05 | Hitachi Chem Co Ltd | Heat-resistant adhesive, laminate using this adhesive, heat sink with adhesive, and metal foil with adhesive |
| JP2004256687A (en) * | 2003-02-26 | 2004-09-16 | Polymatech Co Ltd | Thermally conductive reaction-curing resin molding and its manufacturing method |
| JP4250996B2 (en) * | 2003-03-28 | 2009-04-08 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
| JP2005002283A (en) * | 2003-06-13 | 2005-01-06 | Sekisui Chem Co Ltd | Thermally conductive composition and plasma display device |
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2006
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Non-Patent Citations (3)
| Title |
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| JP特开2001-348488A 2001.12.18 * |
| JP特开2003-268076A 2003.09.25 * |
| JP特开平9-207270A 1997.08.12 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI357783B (en) | 2012-02-01 |
| CN101003690A (en) | 2007-07-25 |
| KR20070076506A (en) | 2007-07-24 |
| TW200746935A (en) | 2007-12-16 |
| KR100849585B1 (en) | 2008-07-31 |
| JP2007191519A (en) | 2007-08-02 |
| JP5089885B2 (en) | 2012-12-05 |
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Application publication date: 20070725 Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Holding Co., Ltd. Contract record no.: 2011990000116 Denomination of invention: Heat radiation insulation resin composition and printing circuit board using same Granted publication date: 20100407 License type: Common License Record date: 20110302 |
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