CN101845134B - Thermally cured resin composition - Google Patents
Thermally cured resin composition Download PDFInfo
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- CN101845134B CN101845134B CN200910224842.4A CN200910224842A CN101845134B CN 101845134 B CN101845134 B CN 101845134B CN 200910224842 A CN200910224842 A CN 200910224842A CN 101845134 B CN101845134 B CN 101845134B
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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
The invention provides a thermally cured resin composition, a printed circuit board using the same and a reflection plate for luminescent members. The thermally cured resin composition has good storing stability and its cured object has good heat resistance and light resistance. The thermally cured resin composition is characterized by including two components an agent A and an agent B that are mixed, wherein the agent A contains a copolymer of styrene-maleic anhydride and an organic solvent and the agent B contains a multifunctional alicyclic epoxy resin and inorganic fillers.
Description
Technical field
The present invention relates to the hot curing resin composition that contains mineral filler, specifically, relate to its cured article and there is non-discoloring photostabilization, thermotolerance in rayed, thermal history, and can contain the hot curing resin composition of mineral filler, use its printed circuit board (PCB) and luminous element reflector.
Background technology
In recent years, as backlight, the light source of lighting fixtures etc. of the liquid-crystal display of portable terminal, PC, TV etc., with the luminous photodiode of low electric power (hereinafter referred to as " LED ".) etc. luminous element be practical.The briliancy of such luminous element is high, heat dissipation capacity is large, thereby has the variable colors such as the periphery material xanthochromia that causes due to heat or light, loss of transmission problem.
In addition, be formed with the purposes of on the printed circuit board (PCB) of solder resist cured article, these luminous elements being directly installed also in increase in coating.Be equipped with the requirements such as the reflector using in the printed circuit board (PCB), luminous element of the luminous elements such as such LED and guarantee lightness, effectively utilize the light of luminous element and do not reduce the reflection light quantity of luminous element.Therefore, coating is formed on printed circuit board (PCB), for luminous element, the film on reflector (solder resist cured article) needs high reflectivity.
But this film exposes to the open air for a long time and has in the light of light source that xanthochromia that photoconduction causes etc. is deteriorated, reflectivity reduces.In addition, in the heating processes such as the soldering in the time that luminous element is installed to substrate, this film is exposed under 250 DEG C of above high temperature, therefore has the problem that the xanthochromia that causes due to thermal conductance etc. is deteriorated, reflectivity reduces.
Therefore,, in order to obtain and maintain high-reflectivity, mineral filler high titanium oxide isoreflectance need to be coupled to water white transparency and there is photostabilization and fully in the resin combination of solder heat resistance, form film.
As the high heat-stable material of the transparency, can list the composition of acid anhydrides and epoxy resin.But their speed of response is slow, particularly forming film and make in its curing use-pattern as soldering-resistance layer, because acid anhydrides volatilization is difficult to obtain good cured article.In addition, to add when curing catalysts in order promoting to solidify, due to the impact of curing catalysts, to exist and produce painted or the problem of the variable colors such as xanthochromia occurs after heat-resisting, light fastness test.
With respect to this, by the high acid of reactivity or the composition of its acid anhydrides and epoxy-containing yl resin, good cured article can be in the situation that not using catalyzer, just obtained, and thermotolerance, high transparent, photostabilization (for example, with reference to patent documentation 1 etc.) to a certain degree can be obtained.But its existence can not obtain the desired abundant stable on heating problems such as solder resist cured article such as solder heat resistance.
Prior art document
patent documentation
Patent documentation 1: TOHKEMY 2005-36218 communique
Summary of the invention
invent problem to be solved
The present invention completes in order to solve such problem, its object 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.
for the method for dealing with problems
In order to realize aforementioned object, 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 multipolymer that A agent contains phenylethylene-maleic anhydride and organic solvent, B agent contains multifunctional alicyclic epoxy resin and mineral filler.
By using the multipolymer of 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, be the multipolymer that contains phenylethylene-maleic anhydride in the 1st dose (A agent) by making hot curing resin composition, the two-component-type that contains mineral filler in the 2nd dose (B agent), can prevent from reducing because maleic anhydride mixes the storage stability causing with mineral filler.
In the hot curing resin composition forming 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, the solder resist cured article thermofixation that its printed circuit board surface that is formed with circuit by the hot curing resin composition of above-mentioned formation is applied to forms obtains.By hot curing resin composition is applicable to printed circuit board (PCB), can obtain sufficient solder heat resistance.In addition, even in the situation that being equipped with luminous element, also can obtain high photostabilization, and then by using titanium oxide as mineral filler, can improve luminous efficiency.
In addition, the luminous element of an embodiment of the invention is characterised in that with reflector, and it obtains by the film thermofixation that the hot curing resin composition of above-mentioned formation is applied to form on substrate.By hot curing resin composition being applicable to luminous element reflector, can obtain heat, the sufficient thermotolerance of light, photostabilization that luminous element is produced, and by utilizing titanium oxide as mineral filler, the light that reflection is produced by luminous element, can improve illumination.
invention effect
Hot curing resin composition can obtain good storage stability, and its cured article can be at printed circuit board (PCB) and luminous element with obtaining good thermotolerance, photostabilization in reflector.
Brief description of the drawings
Fig. 1 represents the Heating temperature distribution plan of the feeding type process furnace described in embodiments of the invention.
Embodiment
The 1st of hot curing resin composition of the present invention is characterised in that, use the multipolymer of phenylethylene-maleic anhydride as the solidifying agent of epoxy resin, even if it forms the film as soldering-resistance layer, in its curing operation, also can not volatilize making, the transparency is excellent, and can obtain the cured article with 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, though do not use become the curing catalysts of variable color reason also can make its solidify, its cured article can obtain good thermotolerance, photostabilization.
On the other hand, known while adding mineral filler to such composition, viscosity increases in time, storage stability variation.Therefore, the inventor etc. found that after repeatedly furtheing investigate: storage stability variation is to produce owing to mineral filler being mixed in the multipolymer of phenylethylene-maleic anhydride, thereby has completed 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, wherein, the multipolymer that A agent contains phenylethylene-maleic anhydride, 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, the multipolymer that A agent contains phenylethylene-maleic anhydride and organic solvent, and B agent contains multifunctional alicyclic epoxy resin and mineral filler.
Below, each constituent of the hot curing resin composition to 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 copolymerization ratio (mol ratio) of styrene units and maleic anhydride unit is preferably 1: 1～and 3: 1.When the ratio less than 1 of styrene units, can not form multipolymer; Exceed at 3 o'clock, cross-linking set tails off, and is difficult to obtain solder heat resistance.In addition, the molecular weight of this multipolymer is preferably 800～6000.And then, above-mentioned copolymerization ratio more preferably 1: 1～2: 1.
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 the ketones such as methylethylketone, pimelinketone; Toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based; The alcohol ethers such as methylcyclohexane, ethylene glycol butyl ether, methyl carbitol, ethyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, DPE, Triethylene glycol ethyl ether, Trivalin SF acetic ester; The ester classes such as the acetic ester compound of vinyl acetic monomer, N-BUTYL ACETATE and above-mentioned alcohol ethers; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The organic solvents such as petroleum solvent such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha.Their two or more uses alone or in combination.
The contained multifunctional alicyclic epoxy resin of B agent is the multi-functional epoxy compound with more than two ester ring type epoxy construction, specifically, for example can list, CELLOXIDE 2021P, Epolead GT-301, Epolead GT-403, EHPE-3150 etc. (being Daicel Chemical Industries, Ltd. system).Also can will after these epoxy compounds dilutions, use 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.When this use level less than 30 mass parts, solvent resistance and thermotolerance variation; While exceeding 900 mass parts, thermotolerance variation.This use level is 50～500 mass parts more preferably.
The contained mineral filler of B agent regulates for the proterties of the compositions such as mobility, viscosity adjustment, and the Characteristics Control of the cured article such as the raising of the raising of physical strength, painted, optical characteristics.In the time that load board of luminous element etc. requires high-reflectivity, be suitable for the tinting pigment high to the reflectivity of emission wavelength, for example, the in the situation that of visible ray, preferably use the color white such as zinc oxide, titanium oxide pigment, particularly 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 high at the reflectivity of the low wavelength side of visible region, initial reflectivity can obtain good value, also partially blue in appearance, can obtain and seem whiter film, but because its photolytic activity is high, thereby resin is easily deteriorated, easily produces the variable color that rayed causes, thereby preferably use rutile-type.As Titanium Dioxide (Rutile) Top grade, can use known material.Specifically, can use TIPAQUER-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-680, TIPAQUE R-670, TIPAQUER-680, TIPAQUE R-670, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUE CR-80, TIPAQUECR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUE CR-67, TIPAQUECR-58, TIPAQUE CR-85, TIPAQUE UT771 (Ishihara Sangyo Kaisha, Ltd.'s system), Ti-Pure R-100, Ti-Pure R-101, Ti-Pure R-102, Ti-PureR-103, Ti-Pure R-104, Ti-Pure R-105, Ti-Pure R-108, Ti-PureR-900, Ti-Pure R-902, Ti-Pure R-960, Ti-Pure R-706, Ti-PureR-931 (Du Pont Kabushiki Kaisha system), TITON R-25, TITONR-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, TITOND-918, TITON TCR-29, TITON TCR-52, TITON FTR-700 (Sakai Chemical Industry Co., Ltd.'s 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. system), TIPAQUE A-100, TIPAQUE A-220, TIPAQUE W-10 (Ishihara Sangyo Kaisha, Ltd.'s system), TITANIX JA-1, TITANIX JA-3, TITANIXJA-4, TITANIX JA-5 (TAYCA CORPORATION system), KRONOSKA-10, KRONOS KA-15, KRONOS KA-20, KRONOS KA-30 (Titan Kogyo, Ltd. system), A-100, A-100, A-100, SA-1, SA-1L (Sakai Chemical Industry Co., Ltd.'s system) etc.
With respect to 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 if the use level of titanium oxide exceedes 80 mass parts, do not observe the raising of reflectivity yet, and disperse to become difficulty.On the other hand, when this 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 silicon-dioxide for improving liquidity, barium sulfate, for obtaining the pigment extenders such as thixotropic wilkinite.
In addition,, in the situation that electroconductibility can also be there is, 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, with respect to multipolymer and the multifunctional alicyclic epoxy resin of total amount 100 mass parts phenylethylene-maleic anhydrides, preferably add 10～60 mass parts metallic particles.When this use level less than 10 mass parts, can not obtain electroconductibility, when this use level exceedes 60 mass parts, electroconductibility not improves along with the increase of addition, and uneconomical.
In present embodiment, for reducing the object that is subject to the caused film variable color of thermal degradation when due to film, can coordinate antioxidant.Such antioxidant is not particularly limited, preferably hindered phenol based compound.As hindered phenol based compound, can list for example NOCRAC 200, NOCRAC M-17, NOCRAC SP, NOCRACSP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC 300, NOCRAC NS-7, NOCRAC DAH (being above the emerging chemical industry of imperial palace (strain) system); MARK AO-30, MARK AO-40, MARK AO-50, MARKA O-60, MARK AO616, MARK AO-635, MARK AO-658, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (being above (strain) ADEKA system); Irganox 245, Irganox259, Irganox 565, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1081, Irganox 1098, Irganox 1222, Irganox 1330, Irganox1425WL (being above Ciba Japan K.K. system) 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.When this use level less than 0.4 mass parts, prevent because film is subject to the effect of the caused film variable color of thermal degradation when little; When this use level exceedes 25 mass parts, be difficult to obtain thermotolerance, storage stability.
And then, be photostabilizer by contain hindered amine in the composition of present embodiment, can reduce light deteriorated.
Be photostabilizer as hindered amine, can list for example TINUVIN 622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB 119FL (being above Ciba Specialty Chemicals Corporation system); MARKLA-57, LA-62, LA-67, LA-63, LA-68 (being above (strain) ADEKA system); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (being above SANKYO LIFETECH CO., 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 contain dispersion agent in the thermotolerance heat-curable composition of present embodiment, can improve dispersiveness, the settleability of the 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 (following, be called " Bi Ke chemical company system ".)), DISPARLON2150, DISPARLON1210, DISPARLON KS-860, DISPARLONKS-873N, DISPARLON7004, DISPARLON1830, DISPARLON1860, DISPARLON1850, DISPARLON DA-400N, DISPARLON PW-36, DISPARLON DA-703-50 (nanmu originally changes into Co., Ltd.'s system), FLOWLEN G-450, FLOWLEN G-600, FLOWLENG-820, FLOWLEN G-700, FLOWLEN DOPA-44, FLOWLENDOPA-17 (Kyoeisha Chemical Co., Ltd.'s system).
In order effectively to realize above-mentioned purpose, 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 as required the fire retardants such as the defoamer, flow agent, phosphoric acid ester of silicon-type, fluorine system, copolymer resins system etc., the known thickening material such as polyamide resin, organobentonite, coupling agent, the curing catalyst of silane system, titanic acid ester system, Aluminate 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
500g Sartomer Company Inc. SMA-1000P processed (copolymer resins that the mol ratio of vinylbenzene and maleic anhydride is 1: 1) and 500g Trivalin SF acetic ester are put into the airtight still stirring with reflux tower, at 120 DEG C, make its heating for dissolving 3 hours, obtaining nonvolatile component is the resin solution 1 of 50wt%.
the making of resin solution 2
500g Sartomer Company Inc. SMA-2000P processed (copolymer resins that the mol ratio of vinylbenzene and maleic anhydride is 2: 1) and 500g Trivalin SF acetic ester are put into the airtight still stirring with reflux tower, at 120 DEG C, make its heating for dissolving 3 hours, 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 composition shown in table 1, in addition, and as a comparative example 1～8, make A agent and B agent according to the composition shown in table 2.In addition, at gradation composition be multiple in the situation that, make mixing each gradation composition of 3 roll-type mixing rolls.In addition, the numeral mass parts in table 1, 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 of the rotation of per minute at 25 DEG C 5 times.Preserved after 30 days, again similarly measured viscosity, obtained viscosity rise.The results are shown in table 3.In addition, viscosity ratio initial viscosity is risen below 10% be designated as zero, by viscosity rise 10～50% be designated as △, being designated as by viscosity rise more than 50% ×, by being designated as of gelation × ×.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
|
| Storage stability (A agent) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Storage stability (A agent) | × | × | ×× | ○ | ○ | ○ | ○ | ○ |
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 containing mineral filler, and viscosity rises in time, and storage stability declines.
(2) Evaluation of Heat Tolerance
The hot curing resin composition that mixes respectively A agent and B agent and obtain is printed onto on the FR-4 substrate of full version copper by screen printed pattern, and making dry coating is approximately 20 μ m, it is heated at 150 DEG C within 60 minutes, make it curing, obtains test film.Rosin series solder flux is applied on each test film, in the solder bath of 260 DEG C, flow through for 30 seconds.Then, with propylene glycol methyl ether acetate washing, after making it dry, use glassine paper self adhesive tape to carry out stripping test, evaluate peeling off of film.The results are shown in table 4.In addition, by there is no that film peels off be designated as zero, by being designated as of having that film peels off ×.
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
|
| Thermotolerance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Thermotolerance | ○ | ○ | ○ | × | × | ○ | ○ | ○ |
As shown in table 4, the hot curing resin composition of embodiment 1～8 has obtained good thermotolerance.On the other hand, because the epoxy resin of the A agent of comparative example 4,5 does not have 2 above ester ring type epoxy constructions, thereby can not obtain sufficient thermotolerance.
(3) fast light Evaluation of Heat Tolerance 1
By the A agent of mix embodiment 1～4,7 and comparative example 6 respectively and B agent and the hot curing resin composition obtaining be printed onto on the sheet glass that thickness is 1mm by screen printed pattern, making dry coating is approximately 20 μ m, it is heated and makes it curing in 60 minutes at 150 DEG C, obtain test film.Use transmissivity determinator (JASCO V-570: integrating sphere I SN-470), be determined at the transmissivity that wavelength is 400nm place, set it as initial value.Use conveying type UV irradiating machine QRM-2082-E-01 (ORCMANUFACTURING CO., 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 repeatedly carry out 20 UV and irradiate.Then, use feeding type process furnace repeatedly to heat 2 times.Make the transmissivity using the same method after the each test film test of mensuration.Fig. 1 represents that the Heating temperature of the feeding type process furnace now using distributes.As shown in Figure 1, being up to Da Wendu is 260 DEG C that drop into after 250 seconds.The results are shown in table 5.In addition, in visual valuation, by indiscriminately the tone after initial and test being designated as zero, being designated as of visible hue difference ×.
Table 5
| Transmissivity (%T) 400nm | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 7 | Comparative example 6 |
| Initial value | 95.00 | 95.20 | 94.88 | 95.11 | 94.78 | 90.00 |
| After heat-resisting light fastness test | 91.90 | 92.22 | 91.85 | 92.38 | 91.23 | 54.22 |
| Poor (Δ) | 3.10 | 2.98 | 3.03 | 2.73 | 3.55 | 35.78 |
| Visual valuation | ○ | ○ | ○ | ○ | ○ | × |
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 not containing multifunctional alicyclic epoxy resin in comparative example 6, thereby the poor change of transmissivity is large, and in visual valuation, also finds variable color, can not obtain sufficient fast light thermotolerance.
(4) fast light Evaluation of Heat Tolerance 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, adopt the method same with (2) to make test film, as initial value, use color colour-difference meter CR-400 (Konica MinoltaSensing, Inc. system) to measure Y value and the L of XYZ colour system
*a
*b
*each value of colour system.Use conveying type UV irradiating machine QRM-2082-E-01 (ORCMANUFAC TURING CO., 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, repeatedly carry out 20 UV and irradiate.Then, use the feeding type process furnace using in fast light Evaluation of Heat Tolerance 1 repeatedly to heat after 2 times, 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, L
*represent L
*a
*b
*the lightness of colour system.Δ E
*ab is to L
*a
*b
*each value get value after test and initial value difference square and by the summation of these squares value that root obtains of making even.A
*represent red direction ,-a
*represent green direction, b
*represent yellow direction ,-b
*represent blue direction, more approaching null representation does not more have colourity.Δ E
*ab represents the variation of color.The variation of the less expression color of this value is less.In visual valuation project, by almost do not have being designated as zero, having being designated as of obvious variable color 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 not containing multifunctional alicyclic epoxy resin in comparative example 7,8, thereby the variation of color is large, and in visual valuation, finds that there is variable color, can not obtain sufficient fast light thermotolerance.Below, whether embodiment 1～8 is obtained the confirmation evaluation of the characteristic of regulation.
(5) solvent resistance
Each test film of making same with (2) is flooded 30 minutes in propylene glycol methyl ether acetate, after making it to be dried, use glassine paper self adhesive tape to carry out stripping test, evaluate peeling off and variable color of film.The results are shown in table 7.In addition, film is not peeled off, 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 core tip is polished is pressed onto with the angle of approximately 45 ° on each test film of making same with (2), and record does not produce the pencil hardness that film is peeled off.The results are shown in table 7.As shown in table 7, the hot curing resin composition of embodiment 1～8 has obtained good pencil hardness more than 4～5H.
(7) insulation resistance test
Except the comb-type electrode B sample that uses IPC B-25 test pattern replaces FR-4 copper clad laminate, under the condition same with (2), make test film.This test film is applied to 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 resistance.
Table 7
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
|
| Solvent resistance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Pencil hardness | More than 4H | More than 4H | More than 4H | More than 4H | More than 5H | More than 5H | More than 4H | More than 5H |
| Insulation resistance test (Ω) | 1×10 13 | 1×10 13 | 1×10 13 | 1×10 13 | 1×10 13 | 1×10 13 | 1×10 13 | 1×10 13 |
Claims (4)
1. a hot curing resin composition, is characterized in that, it comprises A agent and B agent, multipolymer and organic solvent that described A agent contains phenylethylene-maleic anhydride, described B agent contains multifunctional alicyclic epoxy resin and mineral filler, and described mineral filler contains titanium oxide
Described A agent and described B agent bulk segregation, mix described A agent when use with described B agent,
In the multipolymer of described phenylethylene-maleic anhydride, the copolymerization ratio of styrene units and maleic anhydride unit is taking molar ratio computing as 1:1～3:1,
With respect to the multipolymer of 100 mass parts phenylethylene-maleic anhydrides, described multifunctional alicyclic epoxy resin is 30～900 mass parts.
2. hot curing resin composition according to claim 1, is characterized in that, with respect to 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.
3. a solder resist cured article, it forms by the hot curing resin composition thermofixation that makes to be applied to described in the claim 1 or 2 on the printed circuit board (PCB) that is formed with circuit.
4. a luminous element reflector, is characterized in that, it has the hot curing resin composition thermofixation described in the claim 1 or 2 that makes to be applied on 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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| CN2013101362217A Division CN103214656A (en) | 2009-03-26 | 2009-11-26 | Thermosetting resin composition |
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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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009141A (en) * | 1972-07-07 | 1977-02-22 | General Electric Company | Electrical insulating compositions of epoxy resins, zirconium silicate and alumina |
| CN1935896A (en) * | 2006-10-23 | 2007-03-28 | 江苏科技大学 | Epoxy vesin complex and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06112606A (en) * | 1992-09-28 | 1994-04-22 | Hitachi Chem Co Ltd | Epoxy resin composite for printed wiring board |
| CN1129648C (en) * | 1997-01-21 | 2003-12-03 | 陶氏环球技术公司 | Latent catalysts for epoxy curing systems |
| JP4536437B2 (en) * | 2003-06-30 | 2010-09-01 | 三菱瓦斯化学株式会社 | Thermosetting resin composition and use thereof |
| JP4683933B2 (en) * | 2005-01-19 | 2011-05-18 | ダイセル化学工業株式会社 | Curable resin composition and interlayer insulating film |
| 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 |
|---|---|---|---|---|
| US4009141A (en) * | 1972-07-07 | 1977-02-22 | General Electric Company | Electrical insulating compositions of epoxy resins, zirconium silicate and alumina |
| CN1935896A (en) * | 2006-10-23 | 2007-03-28 | 江苏科技大学 | Epoxy vesin complex and its use |
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| JP2010229221A (en) | 2010-10-14 |
| JP5144572B2 (en) | 2013-02-13 |
| CN103214656A (en) | 2013-07-24 |
| KR101692551B1 (en) | 2017-01-03 |
| CN101845134A (en) | 2010-09-29 |
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