CN101077956A - Welding resistant agent composition for flexible substrate, flexible substrate and preparation method for the flexible substrate - Google Patents
Welding resistant agent composition for flexible substrate, flexible substrate and preparation method for the flexible substrate Download PDFInfo
- Publication number
- CN101077956A CN101077956A CNA2007101061106A CN200710106110A CN101077956A CN 101077956 A CN101077956 A CN 101077956A CN A2007101061106 A CNA2007101061106 A CN A2007101061106A CN 200710106110 A CN200710106110 A CN 200710106110A CN 101077956 A CN101077956 A CN 101077956A
- Authority
- CN
- China
- Prior art keywords
- solder resist
- flexible substrate
- epoxy resin
- type epoxy
- resist composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
Abstract
The invention provides a solder resist combination of flexible basal plate with excellent flexibility (softness) and thermal resistance, also provides a solder resist combination of flexible basal plate. Even though crosslinking is performed through adequate curing reaction without residung not-curing part, the solder resist combination is reinforced, soft, and with excellent thermal resistance, furthermore, even though the fill rate of fill is increased to improve therma conductivity, it is not easy to rupture and the softness can be kept. The said solder resist combination of flexible basal plate contains (A)hydrogenated biphenyl epoxy resin, (B) rubber shape compound with functional group reacting with epoxy group, or (C) alumina grain.
Description
Technical field
The present invention relates to a kind of in the flexible substrate that requires the softish flexibility employed welding resistance China ink, for example, as the employed used in flexible substrate solder resist composition of welding resistance China ink of the printed-wiring board (PWB) manufacturing usefulness of miniature electric machines such as mobile notebook computer, mobile phone.
Background technology
As employed solder resist in the manufacturing of flexibility printed circuit board, winding carrier package (Tape CarrierPackaging), following type is arranged: use the mould stamping-out corresponding to be called as the polyimide film of mulch film (coverlay film), the type of sticking then with tackiness agent with pattern; Utilize silk screen printing coating formation to have the ultraviolet hardening of flexible overlay film, the welding resistance China ink of thermohardening type or the type of liquid polyimide China ink; Formation has the type of the liquid photosensitive welding resistance China ink of flexible overlay film.
In mulch film, there is the problem that does not have tracing ability, can't form patterns of high precision with copper platinum.On the other hand, in ultraviolet hardening welding resistance China ink and liquid photosensitive welding resistance China ink, the adaptation of substrate and polyimide is poor, can't obtain flexible fully.In addition, because the cooling after the cure shrinkage of welding resistance China ink and the curing is shunk greatly, therefore there is the problem of generation warpage.In liquid polyimide China ink, use solubility aromatic polyimide (with reference to patent documentation 1), but the price height, generation is oozed out when printing in addition, and existence can't obtain the problem of sufficient operability.
In addition, as present heat curing-type welding resistance China ink, proposed to use the scheme (for example, with reference to patent documentation 2) of melmac etc.Yet these are by dehydration reaction cured coating film surface only, in the inside of filming uncured part are arranged, and obtain flexible thus.Therefore, if carry out solder heat resistance test etc. repeatedly, then completely solidified and filming becomes fragile.In addition, owing to use acid catalyst, therefore also there is the problem of electrical characteristic equal difference as curing catalysts.
Particularly because the recent technology of quick compactization, the also attenuation of core of employed lamination (buld up) substrate in mobile phone etc., the warpage that the cure shrinkage of solder resist causes becomes the problem that solve.
In addition, there is the tendency of the heat storage that is produced by the employed photodiode of the illumination of button, display unit heating in the employed substrate of mobile phone, requires heat dissipation characteristics.
Patent documentation 1: Japanese kokai publication hei 1-121364, claims etc.
Patent documentation 2: Japanese kokai publication sho 50-69563, claims, specification sheets
Summary of the invention
Invent problem to be solved
The present invention carries out in order to solve above-mentioned problem, and its purpose is, the solder resist composition of the flexible substrate of a kind of flexible (pliability) and excellent heat resistance is provided.In addition, a kind of solder resist composition of flexible substrate is provided, even it is undertaken crosslinked and not residual uncured portion by sufficient curing reaction, also tough and soft, thermotolerance is also excellent, and then, even improve the filling ratio of filler in order to improve thermal conductivity, also be difficult for breaking, can keep flexibility.
The method of dealing with problems
People of the present invention further investigate in order to reach above-mentioned purpose, the result, as its first basic form, find a kind of composition, it is characterized in that, it contains (A) hydrogenation biphenyl type epoxy resin, (B) and has rubber-like compound with the functional group of epoxy reaction, the used in flexible substrate solder resist composition of said composition is suitable as flexible (pliability) and excellent heat resistance, thus finished the present invention.In preferred form, the average hydrogenation rate of aforementioned (A) hydrogenation biphenyl type epoxy resin is 5～95%, further preferably, with respect to 1 equivalent epoxy group(ing) of institute's blended Resins, epoxy in the solder resist composition, aforementioned (B) rubber-like compound with functional group epoxy reaction be 0.5～3.0 equivalent.
As second form of the present invention, find a kind of composition, it is characterized in that, it contains (A) hydrogenation biphenyl type epoxy resin, (B) and has rubber-like compound, (C) alumina particle with the functional group of epoxy reaction, even said composition is undertaken crosslinked and not residual uncured portion by sufficient curing reaction, also tough and soft, thermotolerance is also excellent, and then, even improve the filling ratio of filler in order to improve thermal conductivity, also be difficult for breaking, can keep flexibility, be suitable as used in flexible substrate solder resist composition, thereby finished the present invention.In preferred form, the average hydrogenation rate of aforementioned (A) hydrogenation biphenyl type epoxy resin is 5～95%, further preferably, 1 equivalent epoxy group(ing) with respect to institute's blended Resins, epoxy in the solder resist composition, aforementioned (B) rubber-like compound with functional group epoxy reaction be 0.5～3.0 equivalent, and then, in cured article 100 parts by volume of solder resist composition, contain 60～95 parts by volume (C) alumina particle.
In addition, as other form of the present invention, provide a kind of flexible substrate, it is formed with the solder resist that is made of above-mentioned solder resist composition, and the manufacture method that a kind of flexible substrate is provided, it is characterized in that the solder resist that coating is made of above-mentioned solder resist composition.
In addition, in the present invention, " average hydrogenation rate " following obtaining: will be in as the aromatic nucleus of the Resins, epoxy of raw material all hydrogenation and the addition amount (M) that becomes cyclohexane ring are as 100%, the value of actual addition be (X), on average hydrogenation rate is (X)/(M).
Hydrogenation rate is obtained by the absorbancy of 276nm with the UV spectrophotometer.
In addition, following the obtaining of average hydrogenation rate in the mixture: will be in as the aromatic nucleus of all Resins, epoxy of raw material all hydrogenation and the addition amount (M) that becomes cyclohexane ring as 100%, the value of actual addition is (X), and the average hydrogenation rate of mixture is (X)/(M).
" median size " expression is to the mixture of primary particle and second particle (aggregated particles), with the median size of transmission type microscope (TEM) at the observed particulate of any range.
" spherical " is meant mineral or synthetics carried out pulverization process, and heat-treat then, shape becomes the spheric state as a result.Be not meant real ball.
The effect of invention
Usually, rubber-like compound (giving the flexible of solder resist cured article) is compatible with liquid bisphenol A type epoxy resin, but poor heat resistance.In addition, biphenyl type epoxy resin (being di-toluene phenol-type epoxy resin definitely) though excellent heat resistance, it is the high powdered epoxy resin of crystallinity, even homodisperse also can not get uniform cured article, the result obtains lacking the cured article of flexibility.
At this point, use the hydrogenation biphenyl type epoxy resin to replace these resins among the present invention.Hydrogenation biphenyl type epoxy resin excellent heat resistance, and crystallinity is low, therefore good with rubber-like compound consistency, can obtain the cured article of flexibility excellence.And then, even improve the filling ratio of filler in order to improve thermal conductivity (raising heat dissipation characteristics), also be difficult for breaking, can keep flexibility.
Embodiment
Composition of the present invention contains (A) hydrogenation biphenyl type epoxy resin, (B) and has rubber-like compound with the functional group of epoxy reaction.In addition, (C) aluminum oxide that requires the composition of heat dissipation characteristics also to contain.In addition, can provide the composition that contains (D) biphenyl type epoxy resin as required.
Below, describe each moiety in detail.
As aforementioned (A) hydrogenation biphenyl type epoxy resin, can use hydrogenation biphenyl type epoxy resin arbitrarily.For example, it is such that Japanese kokai publication hei 11-335439 communique is put down in writing, can use the hydrogenation biphenyl type epoxy resin that obtains by following reaction: with boron trifluoride or boron trifluoride complex as catalyzer, to diphenol compound (xenol, 2,2 '-dimethyl diphenyl phenol, di-cresylol, 2,2 '-diallyl xenol, 2,2 ', 6,6 '-tetraallyl xenol etc.) behind the hydrogenation, obtain the hydrogenation biphenyl type epoxy resin with the epihalohydrin reaction.Yet, when like this tart phenolic hydroxyl group being become the neutral alcoholic extract hydroxyl group, with the reaction of epihalohydrin in, the β cracking not only taking place, the α cracking also takes place, generates the not compound of closed loop of epoxy group(ing), therefore, the reaction product of gained becomes the compound that comprises more halogen atom in the molecule.
At this point, for example, the method of being put down in writing by TOHKEMY 2000-226380 communique, working load has the catalyzer of ruthenium, only the phenyl ring to biphenyl type epoxy resin, di-toluene phenol-type epoxy resin carries out selective hydrogenation, and the Resins, epoxy of gained is different with aforesaid method, and the halogen atom in the molecule is few, the electrical characteristic excellence is preferred.As commercially available product, can list Japan Epoxy Resins Co., the trade(brand)name YL6800 that Ltd. produces etc.
Consideration maintains the hydrogenation biphenyl type epoxy resin state (in other words, keep with the rubber-like compound consistency) of low-crystalline and keeps the average hydrogenation rate that good thermotolerance decides (A) of the present invention hydrogenation biphenyl type epoxy resin.Particularly, average hydrogenation rate is 5～95%, is preferably 25～75%, more preferably 35～65%.If average hydrogenation rate is lower than lower value, crystallinity grow then reduces with the consistency of rubber-like compound.Too, the crystallinity grow reduce with the consistency of rubber-like compound, and thermotolerance reduces when being higher than higher limit.In addition, the hydrogenation biphenyl type epoxy resin of low-crystalline is liquid usually at normal temperatures, is not necessarily must be liquid at normal temperatures but with the rubber-like compound hydrogenation biphenyl type epoxy resin of consistency is arranged.
(A) crystallinity of hydrogenation biphenyl type epoxy resin is not only by this factor decision of hydrogenation rate, the biphenol compound of other condition, for example raw material with substituting group (allyl group etc.) also be the crystalline important factor of decision hydrogenation biphenyl type epoxy resin, therefore to consider suitably to set these factors with the consistency of rubber-like compound.
For example, the number-average molecular weight of hydrogenation biphenyl type epoxy resin is 300～1000, is preferably 380～450 especially.By being controlled in this scope, can reduce crystallinity, and good with the consistency change of rubber-like compound, thermotolerance is also excellent.
Solder resist composition of the present invention is not hindering the flexible etc. of cured article, do not give to film and bring in the dysgenic scope, can mix known Resins, epoxy commonly used, for example bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, brominated bisphenol a type epoxy resin, bisphenol-A epoxy resin, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, the bromination phenol novolak type epoxy resin, glycidyl ether compounds such as the phenolic resin varnish type epoxy resin of dihydroxyphenyl propane; Epihydric alcohol ester compounds such as terephthalic acid diglycidyl ester, hexahydrophthalic acid 2-glycidyl ester, dimeracid 2-glycidyl ester; Triglycidyl group isocyanuric acid ester, N, N, N ', N '-four glycidyl group m-xylene diamine, N, N, N ', the two amino methyl hexanaphthenes of N '-four glycidyl group, N, glycidyl amine compound such as N-diglycidylaniline, alicyclic epoxy compound, epoxidized polybutadiene etc.
As aforementioned (D) biphenyl type epoxy resin (general names of united phenol-type epoxy resin, di-toluene phenol-type epoxy resin etc.), can list for example Japan EpoxyResins Co., the trade(brand)name YX4000 that Ltd. produces.
When mixing aforementioned (D) biphenyl type epoxy resin, about with (A) hydrogenation biphenyl type epoxy resin and (D) the average hydrogenation rate of the summation of biphenyl type epoxy resin ((A)+(D)) when being benchmark, from the state that the hydrogenation biphenyl type epoxy resin the maintained low-crystalline state of the consistency excellence of rubber-like compound (that is, with) with keep good thermotolerance to consider and determine above-mentioned average hydrogenation rate.Particularly, average hydrogenation rate is 5～95%, is preferably 25～75%, more preferably 35～65%.If average hydrogenation rate is lower than lower value, crystallinity grow then, liquefaction difficulty.When being higher than higher limit too, crystallinity grow, liquefaction difficulty.Thermotolerance reduces in addition.
From stable on heating raising and crystalline viewpoint, be preferably: with respect to 50 weight part hydrogenation biphenyl type epoxy resins, (D) blending ratio of biphenyl type epoxy resin is 2.5～950 weight parts, is preferably 10～300 weight parts, is preferably 30～100 weight parts especially.That is, with respect to 50 weight part hydrogenation biphenyl type epoxy resins, when (D) blending ratio of biphenyl type epoxy resin is less than 2.5 weight parts, the stable on heating effect that can't be improved, not preferred.On the other hand,, when (D) blending ratio of biphenyl type epoxy resin surpasses 950 weight parts,, the crystallinity of biphenyl type epoxy resin is difficult to make printing ink owing to becoming with respect to 50 weight part hydrogenation biphenyl type epoxy resins, and not preferred.
(D) number-average molecular weight of biphenyl type epoxy resin is preferably 300～1000, especially is 380～450.By being controlled in this scope, can reduce crystallinity, and good with the consistency change of rubber-like compound, thermotolerance is also excellent.
The rubber-like compound that (B) that uses among the present invention has with the functional group of epoxy reaction is a composition of the solder resist cured article being given flexibility.
As with the functional group of epoxy reaction, can list for example carboxyl, anhydride group, hydroxyl, amino etc.As rubber-like compound with these functional groups, for example can list, the maleation polyhutadiene that the reaction of polyhutadiene and maleic anhydride obtains and this maleation polyhutadiene and primary alconol react the maleation polyhutadiene half ester, the carboxy terminated polybutadiene vinyl cyanide that obtain having free carboxy, contain amino Polybutadiene Acrylonitrile etc.
In the middle of these, especially preferably be called as the carboxy terminated polybutadiene vinyl cyanide of CTBN.The molecular weight of carboxy terminated polybutadiene vinyl cyanide is 2000～5000th, and is suitable.As commercially available product, can list Hycar CTBN2000 * 162 that the emerging product of space portion (strain) produces, CTBN1300 * 31, CTBN1300 * 8, CTBN1300 * 13, CTBNX1300 * 9 etc.
From the electrical insulating property of cured article, the viewpoint of flexibility, the blending ratio of these (B) rubber-like compounds is with respect to 1 equivalent epoxy group(ing) of institute's blended Resins, epoxy in the solder resist composition (summation of hydrogenation biphenyl type epoxy resin and other Resins, epoxy of adding as required), mixes 0.5～3.0 equivalent, to be preferably 0.8～2.0 normal functional group's (being carboxyl during the carboxy terminated polybutadiene vinyl cyanide) with epoxy reaction better.
With respect to 1 equivalent epoxy group(ing), (B) during combined amount less than 0.5 equivalent of rubber-like compound, give cured article flexible effect step-down, not preferred.On the other hand, with respect to 1 equivalent epoxy group(ing), when (B) combined amount of rubber-like compound surpassed 3.0 equivalents, excessive (B) rubber-like compound unreacted and residue is arranged makes reductions such as thermotolerance, and was therefore not preferred.
(C) used in the present invention alumina particle can use known aluminum oxide powder commonly used, and preferred thermal conductivity is more than the 15W/mK, and particle diameter is below the 30 μ m, is preferably below the 20 μ m, more preferably below the 10 μ m.The lower limit of particle diameter is preferably 0.01 μ m.If less than 0.01 μ m, the viscosity of composition becomes too high, is difficult to disperse, and is difficult to applied thing coating.If greater than 30 μ m, can expose to filming, settling velocity accelerates, and storage stability worsens.
By control purity is more than 92%, and can obtain thermal conductivity is above (C) alumina particle of 15W/mK.
Consider heat dissipation characteristics and flexibility, when being benchmark with the solder resist cured article, in 100 parts by volume solder resist cured articles, the combined amount of (C) of the present invention alumina particle is preferably 60～95 parts by volume, is preferably 70～90 parts by volume.When (C) combined amount of alumina particle is with respect to cured article cumulative volume less than 60 parts by volume, can't obtain sufficient thermal conductivity as heat sink material.On the other hand, when (C) combined amount of alumina particle surpassed 95 parts by volume with respect to the cured article cumulative volume, becoming was difficult to make solder resist, not preferred.
In addition, have the material of median size more than 2 kinds of the size-grade distribution that can reach the closeest filling by mixing, (C) alumina particle can be further highly-filled, considers it is preferred from storage stability, thermal conductivity two aspects.If can reach the size-grade distribution of close filling for example, with respect to first alumina particle of 100 weight part particle diameters in the scope of 5～20 μ m, mix second alumina particle of 20～100 weight part particle diameters in 1/2～1/10 scope of the median size of this first alumina particle.
As the representative commercially available product of globular used in the present invention (C) alumina particle, can list DAW-05 (Denki Kagaku Kogyo kabushiki produce, median size 5 μ m), DAW-10 (Denki Kagaku Kogyo kabushiki produces, median size 10 μ m), AS-40 (clear and electrician company produces, median size 12 μ m), AS-50 (clear and electrician company produces, median size 9 μ m) etc.
For modulation group compound, adjustment viscosity, can add organic solvent in the used in flexible substrate solder resist composition of the present invention.As organic solvent, can use following organic solvent: ketone such as methylethylketone, pimelinketone for example; 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; Petroleum-type solvents such as sherwood oil, petroleum naphtha, solvent naphtha etc.These organic solvents can be used alone or in combination of two or more kinds.
The combined amount of these organic solvents is not particularly limited, and in order to ensure the thickness of coating, cured coating film, the ratio in composition is below the 50 weight %, is preferably below the 30 weight %.Combined amount is during more than above-mentioned scope, and so therefore the thickness attenuation of the cured coating film that is obtained by one-step print must repeatedly print curing, repeatedly not preferred.
Do not bringing filming in the dysgenic scope, used in flexible substrate solder resist composition of the present invention can use known mineral filler commonly used or organic filler.
If these fillers of illustration can example illustrate organic fillers such as mineral fillers such as barium sulfate, talcum, silica, aluminum oxide, aluminium hydroxide and benzoguanamine resin.From keeping the viewpoint of electrical characteristic well, the particle diameter of such filler is preferably below the 20 μ m, is preferably below the 10 μ m.If particle diameter is greater than above-mentioned scope, the filler that protrudes from filming causes the condition of surface variation of filming, and moisture content etc. enter by the filler interface, and electrical characteristic are reduced, and are therefore not preferred.
As the combined amount of these fillers, in composition, be preferably below the 50 weight %, be preferably the scope below the 30 weight %.If more than above-mentioned scope, though can reduce the warpage that causes by the cure shrinkage of filming etc., damage flexible, so not preferred.
Known tinting materials commonly used such as used in flexible substrate solder resist composition of the present invention can also mix known additive kind commonly used as required, and, dual-azo yellow green as phthalocyanine blue, phthalocyanine green, iodine, Viola crystallina, titanium oxide, carbon black, naphthalene are black; Known hot stoppers commonly used such as quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, thiodiphenylamine; Known thickening materials commonly used such as fine particle silica, organobentonite, montmorillonite; The defoamer and/or the flow agent of silicone, fluorine class, high score subclass etc.; The silane coupling agent of imidazoles, thiazoles, triazole species etc. etc.
More than such used in flexible substrate solder resist composition of the present invention, use 80～250 purpose screen printings usually, be applied on the flexibility printed circuit board that is formed with circuit by silk screen print method.Substrate after the coating is heated to for example 120～200 ℃ temperature, thermofixation 20～120 minutes.As required, can change temperature, time and carry out two stage solidification.
The cured coating film that obtains does not like this have cure shrinkage and cooling to shrink caused warpage, to excellences such as the adaptation of base material, anti-warpage properties, folding resistance, flexibility, anti-plating, PCT patience, solder heat resistance, electrical insulating properties.
Embodiment
Below, specify the present invention by embodiment, but the present invention is not limited to these embodiment.In addition, below short of special explanation, " part " is meant weight part.
Utilize silk screen printing, the heat-curing composition pattern of embodiment and comparative example is printed onto on the FR-4 substrate that is formed with circuit, and makes dry coating become about 30 μ m, solidified 60 minutes down at 170 ℃.
Estimate
(1) solvent resistance
The substrate of gained was flooded in propylene glycol monomethyl ether acetate 30 minutes, after the drying, utilize cellophane tape to carry out stripping test, peel off variable color evaluation what film.
Zero: do not peel off or variable color
*: peel off or variable color
(2) thermotolerance
The heat-curing composition that uses embodiment and comparative example with the same resulting substrate of method of solvent resistance on coating rosin series solder flux, in 260 ℃ weld groove, flooded for 30 seconds, after propylene glycol monomethyl ether acetate washing drying, utilize cellophane tape to carry out stripping test, the maximum times of peeling off that record is not filmed.
(3) pencil hardness
The heat-curing composition that uses embodiment and comparative example polishes B to obtain substrate with the same method of solvent resistance to the nib of the pencil-lead of 9H, get substrate with about 45 ° angle by the detention office, writes down the highest hardness of pencil that cannot see the Copper Foil under filming.
(4) electrical insulating property
On the FR-4 substrate of the comb-type electrode that is formed with IPC specification B pattern, with the heat-curing composition of screen printed pattern printing embodiment and comparative example, and make dry coating become about 30 μ m, solidified 60 minutes down at 170 ℃.To apply the interelectrode insulating resistance value that voltage 500V measures the gained substrate.
(5) resistance to flexing
Go up with whole heat-curing composition that prints embodiment and comparative example of silk screen printing at Kapton material (thick 50 μ m) respectively, solidify 60 minutes (dry film thickness 20 μ m) down at 170 ℃.According to IPC-SM-849B TM2.4.29 with 1/8 inch of diameter, 10 round-robin conditions, with the resistance to flexing of following its cured coating film of benchmark evaluation.
Zero: cured coating film does not have the crack
△: cured coating film has a little crack
*: cured coating film has the crack
Synthesis example 1
In the flask that possesses thermometer, agitator, dropping funnel and reflux exchanger, add 214.3 parts of carbitol acetates, 24.0 parts of Diisopropyl azodicarboxylates, under nitrogen atmosphere, be heated to 70 ℃.To wherein with the mix monomer that dripped 18.0 parts of vinylformic acid, 162.5 parts of Propenoic acid, 2-methyl, isobutyl esters and 319.5 parts of methacrylic acid 2-ethylhexyls in 3 hours.Thereafter restir, reaction 4 hours obtains polycarboxylic acid resin solution, and wherein, nonvolatile component is 70%, the solids component acid number is that 28.1mgKOH/g, weight-average molecular weight are 16000, calculated value=9.7 of the Tg that obtained by the FOX formula ℃.Below, claim that this polycarboxylic acid resin solution is A varnish.
The composition and the evaluation result of each composition are summarized in the following table 1.
Table 1
| Embodiment | Comparative example | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
| Hycar X1300 1) | 50 | 50 | 75 | 5 | 7 | 50 | 50 | 50 | 50 | - | 5 | - | - |
| YL6800 2) | 50 | 50 | 50 | 5 | 5 | - | - | - | - | - | - | - | - |
| YX4000 3) | 25 | 25 | 2 | 50 | - | - | - | - | 5 | - | - | ||
| YX8000 4) | - | - | - | - | 50 | - | - | - | - | - | - | ||
| YL6753 5) | - | - | - | - | - | 50 | - | - | - | - | - | ||
| EPIKOTE 1001 6) | - | - | - | - | - | - | 50 | - | - | - | - | ||
| DAW-05 7) | - | 20 | 20 | - | - | - | - | - | 20 | 15 | 20 | ||
| DAW-10 8) | - | 80 | 80 | - | - | - | - | - | 80 | 60 | 80 | ||
| Carbitol acetate | 5 | 5 | 7 | 9 | 5 | - | - | 25 | 10 | 9 | 14 | 14 | |
| A varnish 9) | - | - | - | - | - | - | - | 100 | - | 10 | 10 | ||
| Phthalocyanine green | - | 2 | 2 | - | - | - | - | 2 | 2 | 2 | |||
| DICY 10) | - | - | - | - | - | - | - | 1 | - | 0.1 | 0.1 | ||
| TEPIC-H 11) | - | - | - | - | - | - | - | 10 | - | 1 | 1 | ||
| Silicone KS-66 12) | - | 0.1 | 0.1 | - | - | - | - | 1 | 0.1 | 0.1 | 0.1 | ||
| Barium sulfate | - | - | - | - | - | - | - | 20 | - | - | - | ||
| The micro mist silica 13) | - | 0.5 | 0.5 | - | - | - | - | 5 | 0.5 | 0.5 | 0.5 | ||
| Amount to | 100 | 130 | 155 | 119.6 | 125.6 | 105 | 100 | 100 | 125 | 147 | 121.6 | 102.7 | 127.7 |
| Solvent resistance | ○ | ○ | ○ | ○ | ○ | Mix bad | ○ | ○ | Gelation during stirring | × | Can't make printing ink | × | Can't make printing ink |
| Thermotolerance | 2 times | 3 times | 2 times | 1 time | 1 time | × | × | × | × | ||||
| Pencil hardness | 6H | 6H | 6H | 6H | 6H | 6H | 6H | 6H | 6H | ||||
| Electrical insulating property | 1.00 E+13 | 1.10 E+13 | 1.80 E+13 | 1.00 E+13 | 2.10 E+12 | 1.30 E+13 | 1.40 E+13 | 1.30 E+13 | 5.30 E+12 | ||||
| Flexibility | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ||||
1) (the liquid CTBN rubber that the emerging product of space portion (strain) is produced)
2) (Japan Epoxy Resins Co., the hydrogenation biphenyl type epoxy resin that Ltd. produces)
3) (Japan Epoxy Resins Co., the biphenyl type epoxy resin that Ltd. produces)
4) (Japan Epoxy Resins Co., the bisphenol-A epoxy resin that Ltd. produces)
5) (Japan Epoxy Resins Co., the A Hydrogenated Bisphenol A F type Resins, epoxy that Ltd. produces)
6) (Japan Epoxy Resins Co., the bisphenol A type epoxy resin that Ltd. produces)
7) (alumina particle that electrochemical industry (strain) is produced)
8) (alumina particle that electrochemical industry (strain) is produced)
9) synthesis example of putting down in writing in the test method
10) (Japan Epoxy Resins Co., the Dyhard RU 100 that Ltd. produces
11) (daily output chemical industry (strain) main component is β-triglycidyl group isocyanuric acid ester)
12) (Shin-Etsu Silicones Co., the silicone defoamer that Ltd. produces)
13) (NIPPON AEROSIL CO., the R974 that LTD. produces)
As shown in Table 1, the solder resist of embodiment 1～3, its flexibility, solvent resistance, pencil hardness, electrical insulating property excellence, and thermotolerance is also excellent, has the characteristic as flexible substrate purposes excellence.
In addition we know, mixed the solder resist of the embodiment 4,5 of (C) aluminum oxide, its flexibility, solvent resistance, thermotolerance, pencil hardness, electrical insulating property excellence, and thermal diffusivity is also excellent, has the characteristic as flexible substrate purposes excellence.
In addition, relative therewith, comparative example 1 is not mix the hydrogenation biphenyl type epoxy resin and the example that mixes biphenyl type epoxy resin and liquid CTBN.Owing to biphenyl type epoxy resin has crystallinity to become to mix bad.
Comparative example 2 is to use bisphenol-A epoxy resin to replace the hydrogenation biphenyl type epoxy resin and makes it and liquid CTBN blended example.As can be known, the solder resist of comparative example 2, its flexibility, solvent resistance, pencil hardness, electrical insulating property excellence, but poor heat resistance.
Comparative example 3 is to use A Hydrogenated Bisphenol A F type Resins, epoxy to replace the hydrogenation biphenyl type epoxy resin and makes it and liquid CTBN blended example.As can be known, the solder resist of comparative example 3, its flexibility, solvent resistance, pencil hardness, electrical insulating property excellence, but poor heat resistance.
Comparative example 4 is to use bisphenol A type epoxy resin to replace the hydrogenation biphenyl type epoxy resin and makes it and liquid CTBN blended example.The gelation when stirring of this example.
Comparative example 5 is all unmixed examples of hydrogenation biphenyl type epoxy resin, biphenyl type epoxy resin, bisphenol-type epoxy resin, rubber.As can be known, the flexibility of this example, pencil hardness, electrical insulating property excellence, but solvent resistance, poor heat resistance.
In addition, mixed the comparative example 6 of (C) aluminum oxide, owing to biphenyl type epoxy resin has crystallinity to become to mix bad.
In addition, comparative example 7 is mixed aluminium oxides and hydrogenation biphenyl type epoxy resin, biphenyl type epoxy resin, all unmixed example of rubber.As can be known, the flexibility of this example, solvent resistance, poor heat resistance.
The mixing element of comparative example 8 is identical with comparative example 7, but the combined amount of aluminum oxide is than comparative example more than 7.In this example, can't make printing ink.
Claims (13)
1. a used in flexible substrate solder resist composition is characterized in that, it contains (A) hydrogenation biphenyl type epoxy resin, (B) and has rubber-like compound with the functional group of epoxy reaction.
2. a used in flexible substrate solder resist composition is characterized in that, it contains (A) hydrogenation biphenyl type epoxy resin, (B) and has rubber-like compound, (C) alumina particle with the functional group of epoxy reaction.
3. used in flexible substrate solder resist composition according to claim 1 and 2 is characterized in that, the average hydrogenation rate of described (A) hydrogenation biphenyl type epoxy resin is 5～95%.
4. used in flexible substrate solder resist composition according to claim 1 and 2, it is characterized in that, it also contains (D) biphenyl type epoxy resin, with (A) hydrogenation biphenyl type epoxy resin and (D) the average hydrogenation rate of the summation of biphenyl type epoxy resin ((A)+(D)) when being benchmark be 5～95%.
5. used in flexible substrate solder resist composition according to claim 4 is characterized in that, with respect to 50 weight parts described (A) hydrogenation biphenyl type epoxy resin, contains 2.5～950 weight parts (D) biphenyl type epoxy resin.
6. used in flexible substrate solder resist composition according to claim 1 and 2 is characterized in that, described (B) rubber-like compound is the carboxy terminated polybutadiene vinyl cyanide.
7. used in flexible substrate solder resist composition, it is characterized in that, with respect to 1 equivalent epoxy group(ing) of institute's blended Resins, epoxy in the solder resist of claim 1 or 2, being that 0.5～3.0 normal amount is mixed described (B) rubber-like compound with the functional group of epoxy reaction.
8. used in flexible substrate solder resist composition according to claim 2 is characterized in that, in cured article 100 parts by volume of solder resist composition, contains 60～95 parts by volume (C) alumina particle.
9. used in flexible substrate solder resist composition according to claim 2 is characterized in that, (C) alumina particle is the globular alumina particle that thermal conductivity 15W/mK is above, particle diameter 30 μ m are following.
10. used in flexible substrate solder resist composition according to claim 2, it is characterized in that, (C) alumina particle is with respect to first alumina particle of 100 weight part particle diameters in 20～5 mu m ranges, mixes second alumina particle of 20～100 weight part particle diameters in 1/2～1/10 scope of the median size of this first alumina particle.
11. a flexible substrate is characterized in that, it forms the solder resist that is made of claim 1 or 2 described solder resist compositions and forms on substrate.
12. a flexible substrate is characterized in that, it forms the solder resist that is made of the described solder resist composition of claim 2 and forms on substrate, in cured article 100 parts by volume of this solder resist, contains 60～95 parts by volume alumina particles.
13. the manufacture method of a flexible substrate is characterized in that, the solder resist that coating is made of each described solder resist composition of claim 1～10 on substrate.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006146993A JP4871646B2 (en) | 2006-05-26 | 2006-05-26 | Thermosetting solder resist composition for flexible substrate, flexible substrate and method for producing flexible substrate |
| JP2006146993 | 2006-05-26 | ||
| JP2006-146993 | 2006-05-26 | ||
| JP2006146994 | 2006-05-26 | ||
| JP2006-146994 | 2006-05-26 | ||
| JP2006146994A JP4864545B2 (en) | 2006-05-26 | 2006-05-26 | Thermosetting solder resist composition for flexible substrate, flexible substrate and method for producing flexible substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101077956A true CN101077956A (en) | 2007-11-28 |
| CN101077956B CN101077956B (en) | 2010-12-08 |
Family
ID=39091704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101061106A Active CN101077956B (en) | 2006-05-26 | 2007-05-25 | Welding resistant agent composition for flexible substrate, flexible substrate and preparation method for the flexible substrate |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JP4871646B2 (en) |
| KR (1) | KR100830810B1 (en) |
| CN (1) | CN101077956B (en) |
| TW (1) | TW200811236A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205472A (en) * | 2010-03-30 | 2011-10-05 | 荒川化学工业株式会社 | Soldering flux and solder composition |
| CN102714032A (en) * | 2010-01-29 | 2012-10-03 | 西门子公司 | Attenuating mass for an ultrasonic sensor, use of an epoxy resin |
| CN102933033A (en) * | 2012-10-31 | 2013-02-13 | 金鹏源康(广州)精密电路有限公司 | Using method of polyimide (PI) ink |
| CN105820646A (en) * | 2015-01-04 | 2016-08-03 | 赖中平 | Solder mask and manufacturing method thereof |
| CN111454537A (en) * | 2019-01-21 | 2020-07-28 | 信越化学工业株式会社 | Resin composition, resin film, semiconductor laminate, method for producing semiconductor laminate, and method for producing semiconductor device |
| CN112106450A (en) * | 2018-05-11 | 2020-12-18 | 昭和电工材料株式会社 | Conductor substrate, stretchable wiring substrate, and stretchable resin film for wiring substrate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101451568B1 (en) | 2013-03-27 | 2014-10-22 | 주식회사 엘 앤 에프 | Printed circuit board having heat sink structure |
| KR101687394B1 (en) | 2013-06-17 | 2016-12-16 | 주식회사 엘지화학 | Photo-curable and thermo-curable resin composition and dry film solder resist |
| KR101792755B1 (en) | 2014-10-28 | 2017-11-01 | 주식회사 엘지화학 | Photo-curable and thermo-curable resin composition and dry film solder resist |
| JP7336881B2 (en) * | 2019-06-06 | 2023-09-01 | 太陽ホールディングス株式会社 | Coated substrate having thermosetting composition and its cured coating |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0747682B2 (en) * | 1990-05-10 | 1995-05-24 | 信越化学工業株式会社 | Epoxy resin composition and cured product thereof |
| JPH0415272A (en) * | 1990-05-10 | 1992-01-20 | Tonen Corp | Solder resist ink |
| JPH0415273A (en) * | 1990-05-10 | 1992-01-20 | Tonen Corp | Solder resist ink |
| JP2002171050A (en) * | 1997-04-11 | 2002-06-14 | Ibiden Co Ltd | Printed wiring board |
| JP3346263B2 (en) * | 1997-04-11 | 2002-11-18 | イビデン株式会社 | Printed wiring board and manufacturing method thereof |
| JP3537119B2 (en) * | 1998-01-16 | 2004-06-14 | ジャパンエポキシレジン株式会社 | Epoxy resin composition |
| JP3415047B2 (en) * | 1998-11-18 | 2003-06-09 | ジャパンエポキシレジン株式会社 | Curable epoxy resin composition |
| JP2000171973A (en) * | 1998-12-08 | 2000-06-23 | Ngk Spark Plug Co Ltd | Photosensitive resin composition and photosensitive resin composition for solder resist |
| JP4435342B2 (en) * | 1999-10-19 | 2010-03-17 | ジャパンエポキシレジン株式会社 | Epoxy resin composition and epoxy resin composition for semiconductor encapsulation |
| DE10057111C1 (en) * | 2000-11-16 | 2002-04-11 | Bosch Gmbh Robert | Casting composition for removing thermal energy from electrical or electronic device, comprises epoxide resin, silicone, filler and initiator and cures by chemical reaction, has specified thermal conductivity |
| JP4845274B2 (en) * | 2001-02-27 | 2011-12-28 | 京セラ株式会社 | Wiring board and manufacturing method thereof |
| JP2002256063A (en) | 2001-02-28 | 2002-09-11 | Ootex Kk | Photocuring resist composition |
| WO2002077058A1 (en) * | 2001-03-23 | 2002-10-03 | Taiyo Ink Manufacturing Co., Ltd. | Resin curable with actinic energy ray, photocurable/thermosetting resin composition containing the same, and cured article obtained therefrom |
| JP4442131B2 (en) * | 2002-07-12 | 2010-03-31 | 住友化学株式会社 | Curable resin composition |
| JP2005036092A (en) * | 2002-09-19 | 2005-02-10 | Sumitomo Chemical Co Ltd | Curable resin composition and protective film |
| 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 |
| JP4576794B2 (en) * | 2003-02-18 | 2010-11-10 | 日立化成工業株式会社 | Insulating resin composition and use thereof |
| JP4554170B2 (en) | 2003-06-03 | 2010-09-29 | 株式会社タムラ製作所 | UV curable alkali-soluble resin, UV curable resin for solder resist film and printed wiring board |
| JP4999254B2 (en) * | 2003-07-29 | 2012-08-15 | 住友化学株式会社 | Curable resin composition and protective film |
| JP4479882B2 (en) * | 2003-11-20 | 2010-06-09 | 信越化学工業株式会社 | Cannonball type light emitting semiconductor device |
| TW200519535A (en) * | 2003-11-27 | 2005-06-16 | Taiyo Ink Mfg Co Ltd | Hardenable resin composition, hardened body thereof, and printed circuit board |
| JP4345554B2 (en) | 2004-04-12 | 2009-10-14 | 日立化成工業株式会社 | Printed wiring board having an auxiliary adhesion layer between insulating layers and method for manufacturing the same |
| CN100519630C (en) * | 2004-03-31 | 2009-07-29 | 太阳油墨制造株式会社 | Active energy line cured resin, optical solidified and thermosetting resin composition containing the resin and condensate thereof |
| JP2006008867A (en) * | 2004-06-25 | 2006-01-12 | Matsushita Electric Works Ltd | Vinyl ester resin composition and molded article of the same |
-
2006
- 2006-05-26 JP JP2006146993A patent/JP4871646B2/en active Active
- 2006-05-26 JP JP2006146994A patent/JP4864545B2/en active Active
-
2007
- 2007-05-04 TW TW096115966A patent/TW200811236A/en unknown
- 2007-05-25 KR KR1020070050656A patent/KR100830810B1/en active IP Right Grant
- 2007-05-25 CN CN2007101061106A patent/CN101077956B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102714032A (en) * | 2010-01-29 | 2012-10-03 | 西门子公司 | Attenuating mass for an ultrasonic sensor, use of an epoxy resin |
| CN102714032B (en) * | 2010-01-29 | 2014-07-30 | 大陆汽车有限公司 | Attenuating mass for an ultrasonic sensor, use of an epoxy resin |
| US8947981B2 (en) | 2010-01-29 | 2015-02-03 | Continental Automotive Gmbh | Attenuating mass for an ultrasonic sensor, use of epoxy resin |
| KR101731467B1 (en) | 2010-01-29 | 2017-04-28 | 콘티넨탈 오토모티브 게엠베하 | Attenuating mass for an ultrasonic sensor use of an epoxy resin |
| CN102205472A (en) * | 2010-03-30 | 2011-10-05 | 荒川化学工业株式会社 | Soldering flux and solder composition |
| CN102205472B (en) * | 2010-03-30 | 2014-10-15 | 荒川化学工业株式会社 | Soldering flux and solder composition |
| CN102933033A (en) * | 2012-10-31 | 2013-02-13 | 金鹏源康(广州)精密电路有限公司 | Using method of polyimide (PI) ink |
| CN102933033B (en) * | 2012-10-31 | 2015-04-22 | 广州金鹏源康精密电路股份有限公司 | Using method of polyimide (PI) ink |
| CN105820646A (en) * | 2015-01-04 | 2016-08-03 | 赖中平 | Solder mask and manufacturing method thereof |
| CN112106450A (en) * | 2018-05-11 | 2020-12-18 | 昭和电工材料株式会社 | Conductor substrate, stretchable wiring substrate, and stretchable resin film for wiring substrate |
| CN111454537A (en) * | 2019-01-21 | 2020-07-28 | 信越化学工业株式会社 | Resin composition, resin film, semiconductor laminate, method for producing semiconductor laminate, and method for producing semiconductor device |
| CN111454537B (en) * | 2019-01-21 | 2023-09-05 | 信越化学工业株式会社 | Resin composition, resin film, semiconductor laminate, method for producing semiconductor laminate, and method for producing semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4871646B2 (en) | 2012-02-08 |
| JP2007317945A (en) | 2007-12-06 |
| JP2007314695A (en) | 2007-12-06 |
| KR20070114027A (en) | 2007-11-29 |
| JP4864545B2 (en) | 2012-02-01 |
| KR100830810B1 (en) | 2008-05-19 |
| TWI379865B (en) | 2012-12-21 |
| TW200811236A (en) | 2008-03-01 |
| CN101077956B (en) | 2010-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101077956B (en) | Welding resistant agent composition for flexible substrate, flexible substrate and preparation method for the flexible substrate | |
| US9029438B2 (en) | Thermosetting resin composition, B-stage heat conductive sheet, and power module | |
| CN1250663C (en) | Anisotropic conductive adhesives having enhanced viscosity and bondng methods and integrated circuit packages using same | |
| JP5899022B2 (en) | Conductive paste, method of forming conductive pattern, and conductive pattern | |
| CN106459718B (en) | Thermally and electrically conductive adhesive composition | |
| CN101003690B (en) | Heat radiation insulation resin composition and printing circuit board using same | |
| JP7185289B2 (en) | Electromagnetic wave shielding spray coating agent | |
| CN101238760A (en) | Insulating curable composition, cured product thereof, and printed wiring board using same | |
| CN1651510A (en) | Thermo setting resin composition and its setting coating film | |
| JP5278386B2 (en) | Mounting sealing material and semiconductor device sealed using the same | |
| TW201641565A (en) | Polytetrafluoroethylene oil-based solvent type dispersion, epoxy resin composition containing polytetrafluoroethylene and the cured material thereof | |
| CN116367997A (en) | Resin composition, resin-equipped metal foil, cured product, metal base substrate, and electronic component | |
| JP7394782B2 (en) | High voltage withstand heat dissipating insulating resin composition and electronic components using the same | |
| CN1831074A (en) | Gooey composition of flexible printing wiring plate and adhibit thin film using thereof | |
| CN1680470A (en) | Curable resin comosition and coating film thereof | |
| JP6461627B2 (en) | Polytetrafluoroethylene-containing epoxy resin composition | |
| JP7142453B2 (en) | Heat dissipation insulating resin composition and printed wiring board using the same | |
| CN1246412C (en) | Flexible printing circuit board adhesive | |
| JP2006233078A (en) | Method for modifying epoxy resin | |
| JP7281246B1 (en) | Maleimide resin mixture for sealing material, maleimide resin composition and cured product thereof | |
| CN1289352A (en) | Adhesive composition and precursor thereof | |
| JP2020059818A (en) | Heat conductive adhesive | |
| TW202328265A (en) | Conductive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20071128 Assignee: Taiyo Ink Mfg.Co., Ltd. Assignor: Taiyo Holding Co., Ltd. Contract record no.: 2011990000116 Denomination of invention: Welding resistant agent composition for flexible substrate, flexible substrate and preparation method for the flexible substrate Granted publication date: 20101208 License type: Common License Record date: 20110302 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |