CN103214656A - Thermosetting resin composition - Google Patents
Thermosetting resin composition Download PDFInfo
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- CN103214656A CN103214656A CN2013101362217A CN201310136221A CN103214656A CN 103214656 A CN103214656 A CN 103214656A CN 2013101362217 A CN2013101362217 A CN 2013101362217A CN 201310136221 A CN201310136221 A CN 201310136221A CN 103214656 A CN103214656 A CN 103214656A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
Abstract
A thermosetting resin composition is provided to secure the proper preserving stability, and to form a cured product with the improved light resistance at a reflector for a printed circuit board and a light emitting device. A thermosetting resin composition contains the following: a material A including a styrene-maleic anhydride copolymer and an organic solvent; and a material B containing a polyfunctional alicyclic epoxy resin, and an inorganic filler. The material A and the material B are stored separately and mixed when using. The inorganic filler includes a titanium oxide. A solder resist cured material is formed by thermosetting the thermosetting resin composition spread on a printed circuit board including a circuit.
Description
The application is dividing an application of China's application 200910224842.4, and the applying date of original application CN200910224842.4 is on November 26th, 2009, and its title is " hot curing resin composition ".
Technical field
The present invention relates to contain the hot curing resin composition of mineral filler, specifically, relate to its cured article and have non-discoloring photostabilization, thermotolerance in rayed, thermal history, and the hot curing resin composition that can contain mineral filler uses its printed circuit board (PCB) and luminous element reflector.
Background technology
In recent years, as the backlight liquid crystal display lamp of portable terminal, PC, TV etc., the light source of lighting fixtures etc., to hang down the luminous photodiode of electric power (hereinafter referred to as " LED ".) wait luminous element to be practical.The briliancy height of such luminous element, heat dissipation capacity are big, thereby exist because heat or the variable colors such as periphery material xanthochromia that light caused, loss of transmission problem.
In addition, being formed with the purposes that these luminous elements directly are installed on the printed circuit board (PCB) of solder resist cured article in lining is also increasing.Be equipped with the requirements of using in the printed circuit board (PCB), luminous element of such luminous elements such as LED such as reflector and guarantee lightness, effectively utilize the light of luminous element and do not reduce the reflection light quantity of luminous element.Therefore, lining is formed on printed circuit board (PCB), luminous element needs high reflectivity with the film on the reflector (solder resist cured article).
Yet this film exposes the deteriorations such as xanthochromia, the reflectivity that have photoconduction and cause in the light of light source for a long time to the open air to be reduced.In addition, because in the heating processes such as soldering when luminous element is installed to substrate, this film is exposed under the high temperature more than 250 ℃, therefore exist because the problem that the deteriorations such as xanthochromia that thermal conductance causes, reflectivity reduce.
Therefore, in order to obtain and keep high-reflectivity, need the mineral filler that the titanium oxide isoreflectance is high be coupled to water white transparency and have photostabilization and form film in the resin combination of solder heat resistance fully.
As the high heat-stable material of the transparency, can list the composition of acid anhydrides and Resins, epoxy.Yet their speed of response is slow, is particularly forming film and make in its solidified use-pattern as soldering-resistance layer, owing to the acid anhydrides volatilization is difficult to obtain good cured article.In addition, when adding curing catalysts, because the influence of curing catalysts, exist to produce painted or the problem of variable colors such as xanthochromia takes place behind heat-resisting, light fastness test in order to promote to solidify.
With respect to this, composition by high sour or its acid anhydrides and epoxy-containing yl resin of reactivity, good cured article can be under the situation of not using catalyzer, just obtained, and to a certain degree thermotolerance, high transparent, photostabilization (for example with reference to patent documentation 1 etc.) can be obtained.Yet its existence can not obtain desired abundant stable on heating problems such as solder resist cured article such as solder heat resistance.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-36218 communique
Summary of the invention
Invent problem to be solved
The present invention finishes in order to solve such problem, its purpose is, hot curing resin composition is provided, uses its printed circuit board (PCB) and luminous element reflector, wherein said hot curing resin composition can obtain good storage stability, and its cured article can obtain good thermotolerance, photostabilization.
The method that is used to deal with problems
In order to realize aforementioned purpose, the hot curing resin composition of an embodiment of the invention is characterised in that, it is the hot curing resin composition that mixes the two-component-type that uses A agent and B agent, the A agent contains the multipolymer and the organic solvent of phenylethylene-maleic anhydride, and the B agent contains multifunctional alicyclic epoxy resin and mineral filler.
By the multipolymer of use phenylethylene-maleic anhydride and the composition of multifunctional alicyclic epoxy resin, can obtain good reactivity, and its cured article can obtain good thermotolerance, photostabilization.And then, by making hot curing resin composition is the multipolymer that contains phenylethylene-maleic anhydride in the 1st dose (A agent), the two-component-type that contains mineral filler in the 2nd dose (B agent) can prevent because maleic anhydride mixes the storage stability reduction that causes with mineral filler.
In the hot curing resin composition that constitutes like this, can contain titanium oxide as mineral filler.By containing titanium oxide, the cured article of hot curing resin composition can obtain high reflectivity.
In addition, the printed circuit board (PCB) of an embodiment of the invention is characterised in that, it is applied to the solder resist cured article thermofixation that the printed circuit board surface that is formed with circuit forms by the hot curing resin composition that makes above-mentioned formation and obtains.By hot curing resin composition is applicable to printed circuit board (PCB), can obtain sufficient solder heat resistance.In addition, even, also can obtain high photostabilization, and then, can improve luminous efficiency by using titanium oxide as mineral filler being equipped with under the situation of luminous element.
In addition, the luminous element of an embodiment of the invention is characterised in that with reflector it is applied to the thermofixation of filming that forms on the substrate by the hot curing resin composition that makes above-mentioned formation and obtains.By hot curing resin composition being applicable to the luminous element reflector, can obtain heat, the sufficient thermotolerance of light, photostabilization to the luminous element generation, and by utilizing titanium oxide as mineral filler, reflection can improve illumination by the light that luminous element produces.
The invention effect
Hot curing resin composition can obtain good storage stability, and its cured article can obtain good thermotolerance, photostabilization in printed circuit board (PCB) and luminous element usefulness reflector.
Description of drawings
Fig. 1 represents the Heating temperature distribution plan of the described feeding type process furnace of embodiments of the invention.
Embodiment
The 1st of hot curing resin composition of the present invention is characterised in that, the multipolymer that uses phenylethylene-maleic anhydride is as curing agent for epoxy resin, even it forms the film as soldering-resistance layer, in making its solidified operation, can not volatilize yet, the transparency is excellent, and can obtain to have the cured article of the such high heat resistance of solder heat resistance.
The 2nd of hot curing resin composition of the present invention is characterised in that, the curing system that it forms for the copolymer in combination of multifunctional alicyclic epoxy resin and phenylethylene-maleic anhydride.Thus, even do not use the curing catalysts that becomes the variable color reason that it is solidified, its cured article can obtain good thermotolerance, photostabilization.
On the other hand, known when adding mineral filler to such composition, viscosity increases in time, the storage stability variation.Therefore, the inventor etc. found that after furtheing investigate repeatedly: the storage stability variation is owing to producing in the multipolymer that mineral filler is mixed into phenylethylene-maleic anhydride, thereby has finished the present invention.That is, the 3rd of hot curing resin composition of the present invention is characterised in that, it has the two-component-type that mixes use A agent and B agent, and wherein, the A agent contains the multipolymer of phenylethylene-maleic anhydride, and the B agent contains mineral filler.
Therefore, the hot curing resin composition of present embodiment is characterised in that, it is the heat-curable composition that mixes the two-component-type that uses A agent and B agent, and the A agent contains the multipolymer and the organic solvent of phenylethylene-maleic anhydride, and the B agent contains multifunctional alicyclic epoxy resin and mineral filler.
Below, each constituent of the hot curing resin composition of present embodiment is elaborated.
As the multipolymer of the contained phenylethylene-maleic anhydride of A agent, specifically, for example can list SMA-1000P, SMA-2000P, (Sartomer Company, Inc. system).In the multipolymer of such phenylethylene-maleic anhydride, the unitary copolymerization ratio of styrene units and maleic anhydride (mol ratio) is preferably 1:1～3:1.In addition, the molecular weight of this multipolymer is preferably 800～6000.And then above-mentioned copolymerization ratio is 1:1～2:1 more preferably.
As the contained organic solvent of A agent, it is normally for the multipolymer of the phenylethylene-maleic anhydride of dissolved solids and carry out viscosity adjustment and use.Specifically, for example can list ketones such as methylethylketone, pimelinketone; Toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based; Pure ethers such as methylcyclohexane, ethylene glycol butyl ether, methyl carbitol, ethyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol list ether, Triethylene glycol ethyl ether, Trivalin SF acetic ester; Ester classes such as the acetic acid carboxylate of vinyl acetic monomer, N-BUTYL ACETATE and above-mentioned pure ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Organic solvents such as oil series solvent such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha.They can two or more alone or in combination uses.
The contained multifunctional alicyclic epoxy resin of B agent is the multi-functional epoxy compound with two above ester ring type epoxy constructions, specifically, for example can list, CELLOXIDE2021P, Epolead GT-301, (being Daicel Chemical Industries, the Ltd. system) such as Epolead GT-403, EHPE-3150.Also can these epoxy compounds dilution backs be used with organic solvent.With respect to the multipolymer of 100 mass parts phenylethylene-maleic anhydrides, preferably add the so multifunctional alicyclic epoxy resin of 30～900 mass parts.This use level is 50～500 mass parts more preferably.
The contained mineral filler of B agent is used for the proterties of compositions such as flowability, viscosity adjustment to be regulated, and the Characteristics Control of the cured articles such as raising of the raising of physical strength, painted, optical characteristics.When load board of luminous element etc. requires high-reflectivity, be suitable for the tinting pigment high to the reflectivity of emission wavelength, for example under the situation of visible light, preferably use color white pigment, particularly titanium oxide such as zinc oxide, titanium oxide can obtain high reflectivity.According to crystalline structure, titanium oxide is divided into rutile-type and Detitanium-ore-type.Detitanium-ore-type is at the reflectivity height of the low wavelength side of visible region, initial reflectivity can obtain good value, also blue partially in appearance, can obtain to seem whiter filming, but because its photolytic activity height, thereby the easy deterioration of resin, be easy to generate the variable color that rayed causes, thereby preferably use rutile-type.As Titanium Dioxide (Rutile) Top grade, can use known material.Specifically, can use TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-680, TIPAQUE R-670, TIPAQUE R-680, TIPAQUE R-670, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUE CR-80, TIPAQUE CR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUE CR-67, TIPAQUE CR-58, TIPAQUE CR-85, TIPAQUE UT771(Ishihara Sangyo Kaisha, Ltd. system), Ti-Pure R-100, Ti-Pure R-101, Ti-Pure R-102, Ti-Pure R-103, Ti-Pure R-104, Ti-Pure R-105, Ti-Pure R-108, Ti-Pure R-900, Ti-Pure R-902, Ti-Pure R-960, Ti-Pure R-706, Ti-Pure R-931(Du Pont Kabushiki Kaisha system), TITON R-25, TITON R-21, TITON R-32, TITON R-7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D-918, TITON TCR-29, TITON TCR-52, TITON FTR-700(Sakai Chemical Industry Co., Ltd. system) etc.
In addition, as anatase-type titanium oxide, can list TA-100, TA-200, TA-300, TA-400, TA-500(FUJI TITANIUM INDUSTRY CO., LTD. make), TIPAQUE A-100, TIPAQUE A-220, TIPAQUE W-10(Ishihara Sangyo Kaisha, Ltd. system), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5(TAYCA CORPORATION system), KRONOS KA-10, KRONOS KA-15, KRONOS KA-20, KRONOS KA-30(Titan Kogyo, the Ltd. system), A-100, A-100, A-100, SA-1, SA-1L(Sakai Chemical Industry Co., Ltd. system) etc.
With respect to the multipolymer and the multifunctional alicyclic epoxy resin of total amount 100 mass parts phenylethylene-maleic anhydrides, the use level of such titanium oxide is 30～80 mass parts.Even the use level of titanium oxide surpasses 80 mass parts, do not observe the raising of reflectivity yet, and disperse the difficulty that becomes.On the other hand, during these use level less than 30 mass parts, the power of covering diminishes, and is difficult to obtain the cured article of high-reflectivity.
In addition, can also use the silicon-dioxide, the barium sulfate that are used to improve liquidity, be used to obtain pigment extenders such as thixotropic wilkinite.
In addition, under the situation that can also have electroconductibility, can use metallic particles.And its shape can be that for example median size is that spherical or offset flat shape or the length of 0.5～10 μ m is the fibrous of 0.5～100 μ m.And multipolymer and multifunctional alicyclic epoxy resin with respect to total amount 100 mass parts phenylethylene-maleic anhydrides preferably add 10～60 mass parts metallic particles.During these use level less than 10 mass parts, can not obtain electroconductibility, when this use level surpassed 60 mass parts, electroconductibility not improved along with the increase of addition, and uneconomical.
In the present embodiment, be subjected to the purpose of the caused variable color of filming of thermal degradation when, can cooperate antioxidant for reducing owing to film.Such antioxidant is not particularly limited, preferred hindered phenol based compound.As the hindered phenol based compound, for example can list NOCRAC200, NOCRAC M-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC300, NOCRAC NS-7, be the emerging chemical industry of imperial palace (strain) system more than the NOCRAC DAH(); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO616, MARK AO-635, MARK AO-658, MARK AO-15, MARK AO-18, MARK328, be (strain) ADEKA system more than the MARK AO-37(); Irganox245, Irganox259, Irganox565, Irganox1010, Irganox1035, Irganox1076, Irganox1081, Irganox1098, Irganox1222, Irganox1330, be Ciba Japan K.K. system more than the Irganox1425WL() etc.
With respect to the multipolymer of 100 mass parts phenylethylene-maleic anhydrides, the use level of antioxidant is preferably 0.4～25 mass parts, 0.8～15 mass parts more preferably.
And then, be photostabilizer by in the composition of present embodiment, containing hindered amine, can reduce the light deterioration.
As hindered amine is photostabilizer, can list for example TINUVIN622LD, TINUVIN144; CHIMASSORB944LD, be Ciba Specialty Chemicals Corporation system more than the CHIMASSORB119FL(); MARK LA-57, LA-62, LA-67, LA-63, be (strain) ADEKA system more than the LA-68(); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, be SANKYO LIFETECH CO. more than the LS-744(, LTD., system) etc.
With respect to the multipolymer of 100 mass parts phenylethylene-maleic anhydrides, preferably add the such photostabilizer of 0.1～10 mass parts.
By in the thermotolerance heat-curable composition of present embodiment, containing dispersion agent, can improve dispersiveness, the settleability of inorganic filler components such as titanium oxide.For example can list, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S(Bi Ke chemistry (Japan) (strain) system (below, be called " Bi Ke chemistry corporate system ".)), DISPARLON2150, DISPARLON1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON7004, DISPARLON1830, DISPARLON1860, DISPARLON1850, DISPARLON DA-400N, DISPARLON PW-36, DISPARLON DA-703-50(nanmu originally change into Co., Ltd.'s system), FLOWLEN G-450, FLOWLEN G-600, FLOWLEN G-820, FLOWLEN G-700, FLOWLEN DOPA-44, FLOWLEN DOPA-17(Kyoeisha Chemical Co., Ltd. system).
In order to realize above-mentioned purpose effectively, with respect to 100 mass parts mineral fillers, the content of dispersion agent is preferably 0.1～10 mass parts.This use level is 0.5～5 mass parts more preferably.
And then, can use the fire retardant such as defoamer, flow agent, phosphoric acid ester of silicon-type, fluorine system, copolymer resins system etc. as required, known thickening material such as polyamide resin, organobentonite, coupling agent, the curing catalyst of silane system, titanic acid ester system, aluminic acid ester system etc., hot stopper etc.
Embodiment
Below, embodiment and comparative example are shown, present embodiment is specifically described, certainly, the present invention is not limited to these embodiment.
The making of resin solution 1
With the mol ratio of 500g Sartomer Company Inc. system SMA-1000P(vinylbenzene and maleic anhydride is the copolymer resins of 1:1) and 500g Trivalin SF acetic ester put into the airtight still that stirs that has reflux tower, make its heating for dissolving 3 hours under 120 ℃, obtaining nonvolatile component is the resin solution 1 of 50wt%.
The making of resin solution 2
With the mol ratio of 500g Sartomer Company Inc. system SMA-2000P(vinylbenzene and maleic anhydride is the copolymer resins of 2:1) and 500g Trivalin SF acetic ester put into the airtight still that stirs that has reflux tower, make its heating for dissolving 3 hours under 120 ℃, obtaining nonvolatile component is the resin solution 2 of 50wt%.
The making of A agent, B agent
As embodiment 1～8, make A agent and B agent according to the composition shown in the table 1, in addition, and as a comparative example 1～8, make A agent and B agent according to the composition shown in the table 2.In addition, under gradation composition is a plurality of situation, use 3 roll-type mixing rolls to make each gradation composition is mixing.In addition, the numeral mass parts in table 1, the table 2.
Table 1
Table 2
Use A agent, the B agent made like this to carry out following evaluation.
(1) storage stability evaluation
For the A agent of embodiment 1～8, comparative example 1～8, use rotational viscosimeter (eastern machine industry VISCOMETER TV-33), be determined at the initial viscosity that 25 ℃ of following per minutes rotate 5 times.Its preservation after 30 days, is similarly measured viscosity once more, obtain viscosity and rise.The results are shown in table 3.In addition, the viscosity ratio initial viscosity is risen 10% below be designated as zero, with viscosity rise 10～50% be designated as △, with viscosity rising being designated as more than 50% *, with being designated as of gelation * *.
Table 3
As shown in table 3, the A agent of embodiment 1～8 has obtained good storage stability.On the other hand, the A agent of comparative example 1～3 is owing to contain mineral filler, and viscosity rises in time, and storage stability descends.
(2) thermotolerance evaluation
The hot curing resin composition that mixes A agent and B agent respectively and obtain is printed onto on the FR-4 substrate of full version copper by screen printed pattern, makes that dry coating is about 20 μ m, its heating under 150 ℃ was made it to solidify in 60 minutes, obtain test film.The rosin series solder flux is applied on each test film, in 260 ℃ solder bath, flow through for 30 seconds.Then, with propylene glycol methyl ether acetate washing, make its drying after, use the glassine paper self adhesive tape to carry out stripping test, estimate peeling off of filming.The results are shown in table 4.In addition, will not film peel off be designated as zero, being designated as of peeling off of filming will be arranged *.
Table 4
As shown in table 4, the hot curing resin composition of embodiment 1～8 has obtained good thermotolerance.On the other hand, because the Resins, epoxy of the A agent of comparative example 4,5 does not have the ester ring type epoxy construction more than 2, thereby can not obtain sufficient thermotolerance.
(3) fast light thermotolerance estimates 1
With the A agent of mix embodiment 1～4,7 and comparative example 6 respectively and B agent and the hot curing resin composition that obtains be printed onto on the sheet glass that thickness is 1mm by screen printed pattern, make that dry coating is about 20 μ m, its heating under 150 ℃ was made it to solidify in 60 minutes, obtain test film.Use the transmissivity determinator (JASCO V-570: integrating sphere I SN-470), be determined at the transmissivity that wavelength is the 400nm place, with it as initial value.Use conveying type UV irradiating machine QRM-2082-E-01(ORCMANUFACTURING CO., the LTD. system), at metal halide lamp, cold mirror, 80W/cm
2* 3 lamps, transfer rate 6.5m/ minute (accumulative total light quantity 1000mJ/cm
2) condition under carry out 20 UV irradiation repeatedly.Then, use the feeding type process furnace to heat repeatedly 2 times.Making the transmissivity after each test film of mensuration that uses the same method is tested.Fig. 1 represents that the Heating temperature of the feeding type process furnace that use this moment distributes.As shown in Figure 1, being up to Da Wendu is 260 ℃ that drop into after 250 seconds.The results are shown in table 5.In addition, in the visual valuation, with the tone after initial and the test indiscriminately be designated as zero, being designated as of visible hue difference *.
Table 5
As shown in table 5, the hot curing resin composition of embodiment 1～4,7 has obtained good fast light thermotolerance.On the other hand, owing to do not contain multifunctional alicyclic epoxy resin in the comparative example 6, thereby the difference change of transmissivity is big, and also find variable color in the visual valuation, can not obtain sufficient fast light thermotolerance.
(4) fast light thermotolerance estimates 2
The hot curing resin composition that uses the A agent of mix embodiment 5,6,8 respectively and comparative example 7,8 and B agent and obtain, the same method in employing and (2) is made test film, as initial value, use color colour-difference meter CR-400(Konica Minolta Sensing, the Inc. system) the Y value of mensuration XYZ colour system and each value of L*a*b* colour system.Use conveying type UV irradiating machine QRM-2082-E-01(ORC MANUFACTURING CO., the LTD. system), at metal halide lamp, cold mirror, 80W/cm
2* 3 lamps, transfer rate 6.5m/ minute (accumulative total light quantity 1000mJ/cm
2) condition under, carry out 20 UV irradiation repeatedly.Then, after the feeding type process furnace that use is used in fast light thermotolerance evaluation 1 heats 2 times repeatedly, with same method determination test sheet.The results are shown in table 6.
In addition, in table 6, Y represents the reflectivity of XYZ colour system, and L* represents the lightness of L*a*b* colour system.Δ E*ab be to each value of L*a*b* get value after the test and initial value difference square and with the make even value of root acquisition of the summation of these squares.A* represent red direction ,-a* represent green direction, b* represent yellow direction ,-b* represents blue direction, do not have colourity more near null representation more.Δ E*ab represents change in color.The more little expression change in color of this value is more little.In the visual valuation project, with almost do not have being designated as zero, being designated as of obvious variable color arranged of variable color *.
Table 6
As shown in table 6, the hot curing resin composition of embodiment 5,6,8 has obtained good fast light thermotolerance.On the other hand, owing to do not contain multifunctional alicyclic epoxy resin in the comparative example 7,8, thereby change in color is big, and find that in visual valuation variable color is arranged, can not obtain sufficient fast light thermotolerance.
Below, the affirmation evaluation of the characteristic whether embodiment 1～8 is obtained to stipulate.
(5) solvent resistance
To in propylene glycol methyl ether acetate, flood 30 minutes with (2) same each test film of making, make it drying after, use the glassine paper self adhesive tape to carry out stripping test, what evaluation was filmed peels off and variable color.The results are shown in table 7.In addition, do not peel off filming, variable color be designated as zero.As shown in table 7, the hot curing resin composition of embodiment 1～8 has obtained good solvent resistance.
(6) pencil hardness test
The pencil of the B to 9H that the core tip is polished with about 45 ° angle be pressed onto with (2) same each test film of making on, the pencil hardness that record not have generation to film and peel off.The results are shown in table 7.As shown in table 7, the hot curing resin composition of embodiment 1～8 has obtained the above good pencil hardness of 4～5H.
(7) insulation resistance test
Except the comb-type electrode B sample that uses IPC B-25 test pattern replaces the FR-4 copper clad laminate, with (2) same condition under make test film.This test film is applied the bias voltage of DC500V, measure insulating resistance value.The results are shown in table 7.
As shown in table 7, the hot curing resin composition of embodiment 1～8 has obtained 1 * 10
13Above good insulation performance resistance.
Table 7
Claims (7)
1. a hot curing resin composition is characterized in that, it comprises A agent and B agent, and described A agent contains the multipolymer and the organic solvent of phenylethylene-maleic anhydride, and described B agent contains multifunctional alicyclic epoxy resin and mineral filler,
Described A agent and described B agent bulk segregation mix described A agent during use with described B agent.
2. hot curing resin composition according to claim 1 is characterized in that, in the multipolymer of described phenylethylene-maleic anhydride, the unitary copolymerization ratio of styrene units and maleic anhydride is 1:1～3:1 with the molar ratio computing.
3. hot curing resin composition according to claim 1 is characterized in that, with respect to the multipolymer of 100 mass parts phenylethylene-maleic anhydrides, described multifunctional alicyclic epoxy resin is 30～900 mass parts.
4. hot curing resin composition according to claim 1, described mineral filler contains titanium oxide.
5. hot curing resin composition according to claim 4 is characterized in that, with respect to the multipolymer and the multifunctional alicyclic epoxy resin of total amount 100 mass parts phenylethylene-maleic anhydrides, the use level of described titanium oxide is 30～80 mass parts.
6. solder resist cured article, it forms by making each the described hot curing resin composition thermofixation of claim 1～5 that is applied on the printed circuit board (PCB) that is formed with circuit.
7. a luminous element reflector is characterized in that, it has makes each the described hot curing resin composition thermofixation of claim 1～5 that is applied on the base material and the cured article that forms.
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| JP2009076209A JP5144572B2 (en) | 2009-03-26 | 2009-03-26 | Thermosetting resin composition |
| JP2009-076209 | 2009-03-26 |
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| WO2016063506A1 (en) | 2014-10-22 | 2016-04-28 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, metal foil with resin, metal-clad laminated plate, and printed wiring board |
| WO2016145652A1 (en) * | 2015-03-19 | 2016-09-22 | Ablestik (Shanghai) Ltd. | A method for manufacturing an optical semiconductor device, a thermosetting resin composition therefor and an optical semiconductor obtained therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1249772A (en) * | 1997-01-21 | 2000-04-05 | 陶氏化学公司 | Latent catalysts for epoxy curing systems |
| CN101103062A (en) * | 2005-01-19 | 2008-01-09 | 大赛璐化学工业株式会社 | Curable resin composition and interlayer insulating film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4009141A (en) * | 1972-07-07 | 1977-02-22 | General Electric Company | Electrical insulating compositions of epoxy resins, zirconium silicate and alumina |
| JPH06112606A (en) * | 1992-09-28 | 1994-04-22 | Hitachi Chem Co Ltd | Epoxy resin composite for printed wiring board |
| JP4536437B2 (en) * | 2003-06-30 | 2010-09-01 | 三菱瓦斯化学株式会社 | Thermosetting resin composition and use thereof |
| CN1935896A (en) * | 2006-10-23 | 2007-03-28 | 江苏科技大学 | Epoxy vesin complex and its use |
| JP2009004592A (en) * | 2007-06-22 | 2009-01-08 | Idemitsu Kosan Co Ltd | Reflector for polystyrene-based light emitting diode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249772A (en) * | 1997-01-21 | 2000-04-05 | 陶氏化学公司 | Latent catalysts for epoxy curing systems |
| CN101103062A (en) * | 2005-01-19 | 2008-01-09 | 大赛璐化学工业株式会社 | Curable resin composition and interlayer insulating film |
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| KR20100108181A (en) | 2010-10-06 |
| JP2010229221A (en) | 2010-10-14 |
| JP5144572B2 (en) | 2013-02-13 |
| CN101845134B (en) | 2014-06-04 |
| KR101692551B1 (en) | 2017-01-03 |
| CN101845134A (en) | 2010-09-29 |
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