CN101020779A - Fireproof thermosetting resin composition - Google Patents
Fireproof thermosetting resin composition Download PDFInfo
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- CN101020779A CN101020779A CN 200610007648 CN200610007648A CN101020779A CN 101020779 A CN101020779 A CN 101020779A CN 200610007648 CN200610007648 CN 200610007648 CN 200610007648 A CN200610007648 A CN 200610007648A CN 101020779 A CN101020779 A CN 101020779A
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Abstract
The present invention relates to one kind of thermosetting resin composition containing at least one kind of titanium compound-polymer composition serving as the stuffing. The thermosetting resin composition may be used in sealing electromechanical parts, electronic assembly, semiconductor, etc. It has improved fire retarding performance, heat resistance, excellent forming performance and high reliability.
Description
Technical field
The relevant a kind of thermosetting resin composition of the present invention, it contains the copolymerized body of a kind of titanium compound at least as weighting agent, and can be used as potting resins such as electromechanics, electronics spare part, semi-conductor, and it obtains flame retardant resistance, stable on heating enhancement by adding the copolymerized thing of these titanium compounds, and flame resistivity and reliability are splendid, can resist the be full of cracks, the corrosion of the metal wire under moisture and high temperature that are caused by welding especially.In addition, do not use any other flame resistant material can reach the requirement that meets the UL safety.
Background technology
The packaged material of the electromechanics of present stage, electronics spare part, semiconductor device is in view of economical and productive considering, how based on composition epoxy resin or phenol resin composition.These electromechanics, electronics spare part, semi-conductive electronic package are for guaranteeing safety in utilization, and requirement must reach the specified difficult combustion specification of UL.In order to reach this difficulty combustion specification, all fire auxiliary agent as difficulty at present in materials such as the composition epoxy resin that is used for encapsulating or halogen-containing difficult combustion resin of phenol resin composition interpolation and antimonous oxides.Only auxiliary agent is known that human body and animal are had hazardness for these incombustible agents and difficult combustion.For example antimonous oxide has been listed in carcinogenic substance, and halogen-containing difficult combustion resin such as bromated Resins, epoxy not only can produce acrid bromine radical and hydrogen bromide in combustion processes, and the aryl compound of high bromine content more can produce the bromination furans and the bromination class Dioxins compound of severe toxicity, has a strong impact on HUMAN HEALTH and harm environment.Therefore, the difficulty combustion characteristic resin that a kind of not halogen-containing and antimonous oxide is provided is to know the problem that this skill person seeks to improve electromechanics such as present, electronics spare part, semiconductor sealing material because of the pollution of using halogen-containing Resins, epoxy and antimonous oxide and being caused.
With regard to nonflammable resin, be extensive use of phosphorus system and compound nitrogen series incombustible agent as a new generation.Wherein the most phosphorous, the nitrogenous firing-difficult matter matter of normal use for trimeric cyanamide for example, contain the nitrogenous compound of the non-response types such as cyanate of triazine ring; And for example comprise red phosphorus, triphenyl (triphenyl phosphate, TPP), the trimethylphenyl phosphoric acid ester (tricresyl phosphate, TCP) and the non-response type phosphorus incombustible agent of ammonium polyphosphate; And comprise trimeric cyanamide dipolymer and the nitrogenous incombustible agent of trimeric non-response type, but this type of is phosphorous, nitrogenous compound fires effect in order to reach required difficulty, need heavy addition in resin composition formula, but these compounds are easily moisture absorption or react with minor amount of water all, produce phosphuret-(t)ed hydrogen and corrosive phosphoric acid, thereby moisture resistance is very poor.Therefore, these phosphorous, nitrogenous nonflammable materials and not being suitable for need the encapsulation of the electronic component of splendid moisture resistance.
In addition, also have research use metal hydroxides for example aluminium hydroxide and magnesium hydroxide and boryl (boron-based) compound as nonflammable material, unless but use these metal hydroxidess or boryl compound in a large number in resin combination, otherwise can't bring into play enough difficulty combustion effects.If yet use this type of fire retardant material in a large number, can cause the plasticity-of resin combination to worsen, and cause moulding smoothly.
In recent years, cooperate environmental protection and safety to consider, gradually substitute the incombustible agent that uses at present with the reactive resin incombustible agent, wherein has reactive nitrogenous nonflammable resin because of with the molecular binding of other composition thereby have higher heat-resistant quality, extensively be used to replace halogen-containing resin, for example TOHKEMY 2000-297284 discloses the nitrogenous incombustible agent of a kind of response type, is the reaction product by triaizine compounds and formaldehyde reaction gained.And the special fair 6-31276 of Japan discloses a kind of incombustible agent of organic cyclic phosphorus-containing compound.In addition, EP 0877040A1 discloses and a kind ofly to contain the phenolic aldehyde phenolic resin composition of triazine ring and have difficult combustion characteristic.These response type nitrogenous compounds have been widely used in making in the resin combination of the electronic product that flame retardancy requires as incombustible agent.But the exploitation of the nitrogenous nonflammable resin of response type that uses at present is many based on resol, only for semiconductor packages, based on the resin combination of resol since the resin adding proportion reduce relatively so that difficulty combustion characteristic that can't the boosted tree oil/fat composition.
The inventor is based on the technical disadvantages of existing electromechanics, electronics spare part, semiconductor sealing material, composition epoxy resin and phenol resin composition are carried out broad research, utilize the carbonization of the promotion epoxy of titanium system and resol and cooperate with phosphorous, nitrogenous be the mixture of copolymerization, and then develop to contain height flame retardancy and low moisture-absorption characteristics contain the thermosetting resin composition of the copolymerized body of titaniferous compound as weighting agent, thereby finish the present invention.
Summary of the invention
The present invention's first purpose is relevant a kind of thermosetting resin composition, and it contains the copolymerized body of a kind of titanium compound at least as weighting agent; Wherein the copolymerized body weighting agent of this titanium compound is resultant or its form that coats with this thermosetting resin by titaniferous compound and nitrogenous compound and/or P contained compound copolymerization.
The tool of using the copolymerized body of these titanium compounds among the present invention promote the charing of epoxy and resol and cooperate with phosphorous, nitrogenous be the flame retardant effect that multiplies each other of the mixture of copolymerization, can reach the high flame retardant effect with low usage quantity, with so that develop the thermosetting resin composition that contains the copolymerized body weighting agent of titanium compound that to have height flame resistivity and low moisture-absorption characteristics.
The present invention's second purpose is relevant a kind of thermosetting composition epoxy resin, it comprises Resins, epoxy, stiffening agent, hardening accelerator and as the copolymerized body of the titanium compound of weighting agent, wherein the epoxy equivalent (weight) of this Resins, epoxy is 1: 0.5 to 1: 1.5 to the reactive hydrogens equivalence ratio of stiffening agent, the amount of hardening accelerator accounts for 0.01 to 5 weight % of this Resins, epoxy and stiffening agent gross weight, and the amount of the copolymerized body of this titanium compound accounts for 1 to 25 weight % of this Resins, epoxy and stiffening agent gross weight.
The present invention's the 3rd purpose is relevant a kind of thermosetting phenol resin composition, it comprises the resol of 20 to 60 parts of weight, the stiffening agent of 2 to 12 weight, the hardening accelerator of 1 to 8 weight part and the inorganic filler of 35 to 75 weight parts, and 15 in this inorganic filler is to 30% being the copolymerized body of titanium compound.
In the aforementioned purpose of the present invention, the copolymerized body of this titanium compound is by the titanium compound resultant of the copolymerizations such as P contained compound of nitrogenous compound, the ammonium phosphate of titanic acid ester etc. and nitrogenous compound and/or P contained compound example trimeric cyanamide, melamine cyanurate (Melamine Cyanurate) for example.These complex bodys also can mix through heating with thermosetting resin and be prepared into a kind of copolymerized body of titanium compound that is coated with resin, promoting its compatibility and wet fastness in thermosetting resin composition, but the wet fastness of De Gengjia and reliability.
The copolymerized body of titanium-containing compound of the present invention also can be incorporated in other thermoset and the thermoplastic resin material and be used to make every electronic product as incombustible agent owing to have excellent difficulty combustion effect and thermotolerance.
Embodiment
The copolymerized body of the titanium-containing compound of the aforementioned arbitrary purpose of the present invention has excellent difficulty combustion effect and thermotolerance agent of low hygroscopicity as the thermosetting resin composition of weighting agent, and can be used as electromechanics, electronics spare part, semiconductor sealing material and provide the excellent difficulty of packaged object to fire and heat-resistant quality.Moreover, the copolymerized body of titanium-containing compound of the present invention also can be used as the incombustible agent or the tranquilizer of other resin material beyond Resins, epoxy, the resol, for example as the incombustible agent or the tranquilizer of other thermosetting resin and thermoplastic resin, and can be used for making every electronic product.
Contained Resins, epoxy can use and be generally used for composition epoxy resin and unrestricted in the thermosetting composition epoxy resin of the present invention's second purpose, for example can comprise the phenolic resin varnish type epoxy resin class, the bisphenol-type epoxy resin class, the biphenyl type epoxy resin class, the aromatic series based epoxy resin that contains 3 to 4 functional groups, the united phenol-type epoxy resin class, xylenol type epoxy resin, the dicyclopentadiene-type epoxy resin class, naphthalene type epoxy resin, toluylene type epoxy resin, the epoxy resin of sulfur-bearing, these resins can use or mix two or more uses separately.
One example of above-mentioned phenolic resin varnish type epoxy resin class is the cresol novolak epoxy and the phenol novolac epoxy resins of following formula (a) expression.The example of biphenyl type epoxy resin class is the biphenyl-4 by following formula (b) expression, 4 '-tetraglycidel ether epoxy resin and 3,3 ', 5,5 '-tetramethyl biphenyl-4, the combination of 4 '-tetraglycidel ether epoxy resin.One example of 3 to 4 functional groups' aromatic series based epoxy resin is the tetraphenyl alcohol ethane type Resins, epoxy by following formula (c) expression.One example of united phenol-type epoxy resin class is the phenol biphenyl aralkyl Resins, epoxy by following formula (d) expression.One example of xylenol type epoxy resin is a phenol phenyl aralkyl Resins, epoxy.One example of bisphenol-type epoxy resin class is the bisphenol A type epoxy resin with following formula (e) expression.Bisphenol f type epoxy resin, bisphenol-s epoxy resin and similar compounds thereof also can be used.The naphthols aralkyl-type epoxy resin also can be used.
Resins, epoxy (a)
Resins, epoxy (b)
Resins, epoxy (c)
Resins, epoxy (d)
Resins, epoxy (e)
In the difficult right epoxy resin composition of the present invention's second purpose used stiffening agent can be contain can with the stiffening agent of the active hydrogen of epoxy reaction, can be various not halogen-containing stiffening agents.This stiffening agent can use the known stiffening agent that generally is used for composition epoxy resin and not have special restriction.Example comprises phenolic varnish type phenol resins class, aralkyl-type phenol resins class, dicyclopentadiene-type phenol resins class, biphenyl type phenol resins class, phenol type epoxy resin, triphenyl methane type phenol resins class, bisphenol resin, polyhydroxy phenol resin, phenolic and acid anhydrides, benzene alkyl polyamine class etc.
The mixture that stiffening agent can use separately or they are two or more uses also can.
The specific examples of phenolic comprises phenol formaldehyde condensate typical example, cresols phenolic condensation compound, bisphenol-A phenolic condenses or the dicyclo amylene-phenolic condensation compound of for example being represented by following stiffening agent (a) etc.
The example of bisphenol resin for example comprise compound shown in the formula HO-Ph-X-Ph-OH (wherein phenyl is stretched in the Ph representative, the X=chemical bond ,-CH
2-C (CH
3)
2-,-O-,-S-,-CO-or-SO
2-), specific examples is for example tetramethyl-dihydroxyphenyl propane D, tetramethyl-bisphenol S, 4,4 '-xenol, 3,3 '-dimethyl 4,4 '-xenol or 3,3 ', 5,5 '-tetramethyl-4,4 '-xenol etc.Comprise and do not have the example of phenol resins of phenyl derivatives of hydroxyl for comprising phenol biphenyl aralkyl-phenol resin by following formula stiffening agent (c) expression by the phenol benzene alkyl resin of following formula stiffening agent (b) expression, the example of phenol resins of biphenyl derivatives of hydroxyl of not having.
Stiffening agent (a)
Stiffening agent (b)
Stiffening agent (c)
Polyhydroxy phenol resin specific examples comprises as ginseng (4-hydroxy phenyl) methane, ginseng (4-hydroxy phenyl) ethane, ginseng (4-hydroxy phenyl) propane, ginseng (4-hydroxy phenyl) butane, ginseng (3-methyl-4-hydroxy phenyl) methane, ginseng (3,5-methyl-4-hydroxy phenyl) polyhydroxy phenol resins such as methane, four (4-hydroxy phenyl) methane or four (3,5-dimethyl-4-hydroxy phenyl) methane.Comprise in the molecule in the phenol resins of the how fragrant same clan in addition, the naphthols aralkyl-type resin that comprises naphthalene derivatives also can use.
The specific examples of anhydrides for example comprises 3,3 ', 4,4 '-benzophenone tetracarboxylic acid anhydride (3,3 ', 4,4 '-benzophenone-tetracarboxylic dihydride) (BTDA), trimellitic acid 1,2-anhydride (trimellitic acid anhydride) (BTDA) and Pyromellitic Acid dicarboxylic anhydride (pyromellitic acid dihydride) etc.
Used stiffening agent also can be for example hardening of resin agent of the nitrogenous and phosphorus of (1) shown in the following formula in the right epoxy resin composition of difficulty of the present invention:
In the formula, R
2For-NHR
1, C
1-6Alkyl or C
6-10Aryl;
R
1Respectively be respectively hydrogen ,-(CH
2-R
3-)
rThe base of H or following formula:
Wherein r is 0 to 20 integer and R
3For stretching phenyl, stretching the base of naphthyl or following formula:
In the formula A be-O-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-or the following formula base:
And R
4And R
5Independent is hydrogen, C
1-10Alkyl or C
6-10Aryl; Y is-OH ,-NH
2Or-COOH; A is 0 to 2 integer; X is that 0 to 3 integer and a+x are not more than 3;
But condition be above-mentioned at least one R
1Be not hydrogen.
Used hardening accelerator can use the known person that generally is used for composition epoxy resin and unrestricted in the thermosetting composition epoxy resin of the present invention, can comprise ring miaow compound, maleic anhydride or naphtoquinone compounds, tertiary amine class and derivative, imidazoles and derivative thereof, phosphorus compound, tetraphenyl borate salts and derivative example thereof and be for example tertiary amine, three grades of phosphines, quarternary ammonium salt, phosphonium salt, boron trifluoride mixture, lithium compound or imidazolium compounds or its mixtures.
The tertiary amine specific examples comprises for example Trimethylamine 99, triethylamine, diisopropylethylamine, dimethylethanolamine, xylidine, ginseng (N, N-dimethyl amine ylmethyl) phenol or N, N-dimethyl amido methylphenol etc.
Three grades of phosphine specific exampless comprise triphenyl phosphine etc.
The quarternary ammonium salt specific examples comprises for example Tetramethylammonium chloride, tetramethylammonium bromide, chlorination triethylbenzene ammonium methyl, bromination triethylbenzene ammonium methyl or iodate triethylbenzene ammonium methyl etc.
The phosphonium salt specific examples comprises the chlorination 4-butyl-phosphonium, the Xiuization 4-butyl-phosphonium, the iodate 4-butyl-phosphonium, tetrabutyl phosphoric acid salt acetate mixture, tetraphenylphosphonium chloride, the Xiuization tetraphenylphosphoniphenolate, the iodate tetraphenylphosphoniphenolate, the tonsilon triphenyl phosphonium, bromination Yi base triphenyl phosphonium, iodate Yi base triphenyl phosphonium, ethyl triphenyl phosphoric acid salt acetate mixture, ethyl triphenyl phosphoric acid salt phosphoric acid salt mixture, chlorination propyl group triphenyl phosphonium, bromination propyl group triphenyl phosphonium, iodate propyl group triphenyl phosphonium, the chlorinated butyl triphenyl phosphonium, bromination Ding base triphenyl phosphonium or iodate Ding base triphenyl phosphonium etc.
The imidazolium compounds specific examples comprises for example glyoxal ethyline, 2-phenylimidazole or 2-ethyl-4-methylimidazole etc.
These hardening accelerators can multiple alone or in combination use.
In the thermosetting composition epoxy resin of the present invention, the addition of stiffening agent is according to the reactive behavior hydrogen equivalent of the epoxy equivalent (weight) of Resins, epoxy and stiffening agent and decide.Usually the epoxy equivalent (weight) of Resins, epoxy is 1: 0.5 to 1: 1.5 to the reactive hydrogens equivalence ratio of stiffening agent, is preferably 1: 0.6 to 1: 1.4, and the best is 1: 0.7 to 1: 1.3.
In the thermosetting composition epoxy resin of the present invention, the addition of hardening accelerator accounts for 0.01 to 5 weight % of this thermosetting composition epoxy resin gross weight, is preferably 0.05 to 3 weight %.If hardening accelerator content surpasses 5 weight %,, easily generate by product and electrical properties, moisture resistance, the suction character of using is subsequently had detrimentally affect though can shorten the reaction times; If content is lower than 0.01 weight %, then speed of reaction is crossed slowly and will be caused poor efficiency.
The addition of hardening accelerator should be with reference to the gel time and the viscosity of thermosetting composition epoxy resin of the present invention, usually make the gel time of this thermosetting composition epoxy resin be controlled at 30 to 500 seconds/171 ℃ scope, the preferable scope that is controlled at 20 to 500cps/25 ℃ of viscosity.
Thermosetting composition epoxy resin of the present invention can contain other additive again, for example inorganic filler, coupler, colorant (as carbon black and ferric oxide), releasing agent and the low stress additives beyond the copolymerized body of titanium compound.
In the thermosetting composition epoxy resin of the present invention, the available inorganic filler example except the copolymerized body of titanium compound comprises ball-type and angle type fused silica, crystalline silica, aluminum oxide, zircon, Calucium Silicate powder, lime carbonate, potassium titanate, silicon carbide, silicon nitride, aluminium nitride, boron nitride, beryllium oxide, zirconium white, aluminium peridotites, steatite, spinel, mullite and titanium oxide etc.These weighting agents can use or make up two or more uses separately.Be preferably the mixture of ball-type fused silica, angle type fused silica, crystalline silica and ball-type fused silica, angle type fused silica and crystalline silica.
The median size of copolymerized body weighting agent of these titanium compounds and inorganic filler is preferably the 1-30 micron.Median size will cause resin combination viscosity to rise and mobile the reduction during less than 1 micron; If median size surpasses 30 microns, then resin and weighting agent skewness in the composition will make the hardening thing rerum natura after composition hardens produce variation, the bad situation that resin overflows when causing simultaneously encapsulated moulding to use easily.In addition, the weighting agent maximum particle diameter should be bad to avoid narrow and small running channel or slot to fill less than 150 microns.
It is preferable that the weighting agent addition of the copolymerized body of this titanium compound accounts for the 1-25 weight % of difficult combustible epoxy resin composition gross weight of the present invention.
In the thermosetting composition epoxy resin of the present invention, except the copolymerized body of titanium compound, can contain other weighting agent again, the addition of this other weighting agent is 60 to the 92 weight % that the total amount of this other weighting agent and the copolymerized body of this titanium compound accounts for the composition epoxy resin gross weight, is preferably 65 to 90 weight %.If filling dose is lower than 60 weight % of composition epoxy resin, the Resins, epoxy ratio that then will make resin combination increases relatively and bad phenomenon such as resin overflows takes place when encapsulated moulding; If weighting agent content is higher than 92 weight %, then resin combination viscosity causes mobile decline with rising.
In the thermosetting phenol resin composition of the present invention's the 3rd purpose, contained resol, application is generally used for known person in the phenol resin composition and does not have special restriction, and the example can be given an example as phenolic varnish type phenol resins class, aralkyl-type phenol resins class, dicyclopentadiene-type phenol resins class, biphenyl type phenol resins class, phenol type phenol resins class, triphenyl methane type phenol resins class etc.The usage quantity of these resol is the 20-60 weight part of thermosetting phenol resin composition total amount, is preferably the 25-55 weight part.
In the thermosetting phenol resin composition of the present invention's the 3rd purpose, contained stiffening agent can use the known person who generally is used for phenol resin composition and unrestricted, and the example comprises the hexamethyl tetramine.These stiffening agent additions are preferably the 2.5-11 weight part for the 2-12 weight part of thermosetting phenol resin composition of the present invention.
In the thermosetting phenol resin composition of the present invention's the 3rd purpose, contained hardening accelerator can use the known person who generally is used for phenol resin composition and unrestricted, and the example comprises magnesium oxide, calcium oxide, calcium hydroxide etc.These hardening accelerators can use or make up two or more uses separately.The usage quantity of these hardening accelerators is the 1-8 weight part of thermosetting phenol resin composition total amount.
In the thermosetting phenol resin composition of the present invention's the 3rd purpose, except the copolymerized body of titanium compound, can contain other inorganic filler again, the example can comprise ball-type and angle type fused silica, crystalline silica etc., and fused silica powder, talcum powder, aluminum oxide powder, zinc borate, aluminium hydroxide, magnesium hydroxide, Paris white, aln precipitation, glass sphere, glass fibre etc.These weighting agents can use or make up two or more uses separately.These other weighting agent usage quantitys are that this other weighting agent and the copolymerized body mixture of titanium compound amount are the 35-75 weight part of thermosetting phenol resin composition total amount, be preferably the 40-70 weight part, and this titanium compound interpolymer complex body accounts for 15 to 30% of all weighting agents.
The present invention will be described in detail with following synthesis example, embodiment and comparative example, and only these synthesis examples and embodiment be not in order to limit the scope of the invention.
Epoxy equivalent (weight) described in the present invention (EEW, Epoxy Equivalent Weight), viscosity (Viscosity) and softening point measurement are as follows:
(1) epoxy equivalent (weight):, make Resins, epoxy to be measured be dissolved in chlorobenzene according to ASTM 1652 described methods: in 1: 1 the mixed solvent of chloroform, carry out titration with the HBr/ Glacial acetic acid, and measured with Viola crystallina as indicator.
(2) viscosity: Resins, epoxy to be measured was placed 4 hours in 25 ℃ of thermostatic baths, used Brookfield (Brookfield) viscometer in 25 ℃ of measurements.
(3) softening temperature: Resins, epoxy places on the O-type ring, places ball more thereon, and the temperature that ball falls into this O-type ring is measured in heating gradually.
Details are as follows for used each composition in following synthesis example, embodiment and the comparative example:
Resins, epoxy (a): for Changchun Artificial Resin Factory Co. Ltd. makes, polyglycidyl ether with the serial cresols-phenolic condensation compound sold of trade(brand)name CNE200EL/CNE195, its epoxy equivalent (weight) is between 190 to 220 gram/equivalents, and hydrolyzable chlorine is below the 500ppm.
Resins, epoxy (b): by Japanese Yuka Shell epoxy Co., Ltd. is produced, with trade(brand)name YX4000H sell 3,3 ', 5,5 '-tetramethyl--4,4 '-bis-phenol, its epoxy equivalent (weight) is about 195 gram/equivalents.
Resins, epoxy (c): for Changchun Artificial Resin Factory Co. Ltd. makes, with the tetraphenyl alcohol ethane type Resins, epoxy that trade(brand)name TNE190 series is sold, its epoxy equivalent (weight) is between 180 to 210 gram/equivalents, and hydrolyzable chlorine is below the 500ppm.
Resins, epoxy (d): by Nippon Kayaku K. K is produced, with the phenol biphenyl aralkyl Resins, epoxy that trade(brand)name NC3000 sells, its epoxy equivalent (weight) is about 260-290 gram/equivalent.
Resins, epoxy (e): for Changchun Artificial Resin Factory Co. Ltd. makes, with the diglycidylether of the serial dihydroxyphenyl propane of selling of trade(brand)name BE500, its epoxy equivalent (weight) is between 450 to 1000 gram/equivalents.
Resins, epoxy (f): be that Changchun Artificial Resin Factory Co. Ltd. makes, the diglycidylether of the tetrabromo-bisphenol of selling with trade(brand)name BEB350, its epoxy equivalent (weight) is between 350 to 370 gram/equivalents, and bromine content is between 23 to 26 weight %.
Stiffening agent (a): for Changchun Artificial Resin Factory Co. Ltd. makes, sell with trade(brand)name PF-5110, Ahew is between 105 to 110 gram/equivalents.
Stiffening agent (b): bright and change into Co., Ltd. and produced by Japan, with the phenol benzene aralkyl resin of trade(brand)name MEH7800S sale, its equivalent is about 176 gram/equivalents.
Stiffening agent (c): bright and change into Co., Ltd. and produced by Japan, with the phenol biphenyl aralkyl-phenol resin of trade(brand)name MEH7851 sale, its equivalent is about 195 gram/equivalents.
Hardening accelerator a: triphenyl phosphine.
Hardening accelerator b:2-Methylimidazole (hereinafter being called 2MI).
The copolymerized body of titanium-containing compound: produced by the Taiwan first industry of person of outstanding talent, sell with trade(brand)name GY-series product.
[synthesis example 1] is through the preparation of the copolymerized body of titanium compound of resin coating
Place container after agitator fully stirs with 2: 1 ratio of weight ratio the copolymerized body of titanium compound and Resins, epoxy or resol, after 95 ℃ following fully mixes with twin axle cylinder or twin shaft extruder, after cooling, pulverized again, respectively the copolymerized body of the titanium compound through the Resins, epoxy coating of Huo Deing and through the copolymerized body of the titanium compound of resol coating.
[embodiment and comparative example]
The preparation of the difficult combustion of embodiment 1-thermosetting composition epoxy resin.
Prepare flame retardancy thermosetting epoxy resin composition of the present invention according to the listed composition of table 1:
Resins, epoxy (a) 15.4 weight parts
Stiffening agent (a) 7.80 weight parts
Hardening accelerator (a) 0.3 weight part
Copolymerized body 5.00 weight parts of titaniferous compound
Silane coupling agent 0.50 weight part
Silicon-dioxide 70.00 weight parts
Carbon black 0.40 weight part
0.60 heavy part of carnauba wax
After agitator fully stirs, after 95 ℃ twin axle cylinders are fully mixing, after cooling, pulverized again in above-mentioned each container that becomes to be placed in, obtained can be used for the composition epoxy resin of semiconductor packages.
[embodiment 2 to 10 and comparative example 1 to 6]
According to each composition and ratio shown in the table 1, prepare the composition epoxy resin of embodiment 2 to 9 and comparative example 1 to 5 and the phenol resin composition of embodiment 10 and comparative example 6 as same way as described in the embodiment 1.
Table 1
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Resins, epoxy a | - | 10.8 | - | 10.2 | 15.8 | 15.8 | 15.8 | - | 15.8 | 15.8 | 15.8 | 15.8 | 15.8 | - | |
| Resins, epoxy b | 15.8- | - | - | - | - | - | - | - | - | - | |||||
| Resins, epoxy c | - | - | 15.8- | - | - | - | - | - | - | - | - | - | |||
| Resins, epoxy d | 5. | 16.4 | - | - | - | - | - | - | |||||||
| Resins, epoxy e | 4.5 | ||||||||||||||
| Resol | 38 | 38 | |||||||||||||
| Titanium/nitride multipolymer | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 25 | - | 1 | 30 | ||||
| Titanium/nitrogen phosphide multipolymer | - | - | - | - | - | - | - | - | 10 | ||||||
| Titanic acid ester | 5 | ||||||||||||||
| Aluminium hydroxide | 5 | 10 | |||||||||||||
| Antimonous oxide | - | - | - | - | - | - | - | - | - | - | - | - | - | 2 | - |
| Resins, epoxy (f) | - | - | - | - | - | - | - | - | - | - | - | - | - | 3 | - |
| Stiffening agent a | 7.8 | 6.8 | 7.8 | 7.2 | 6.8 | - | - | 7.8 | 7.8 | 7.8 | 7.8 | 7.8 | 7.8 | - | |
| Stiffening agent b | - | 1.0 | - | - | 7.8 | - | - | - | - | - | - | - | - | - | |
| Stiffening agent c | - | - | - | - | - | - | 7.8 | ||||||||
| Hardening accelerator a | 0.3 | 0.15 | 0.3 | 0.3 | 0.15 | 0.3 | 0.3 | - | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | - | |
| Hardening accelerator b | - | 0.15 | - | - | 0.15 | 0.3 | - | - | - | - | - | - | - | - | |
| Calcium hydroxide | 1.9 | 1.9 | |||||||||||||
| Hexamethyl tetramine (Hexamine) | 5 | 5 | |||||||||||||
| Fused silica | 70.0 | 70.0 | 70.0 | 70.0 | 70.0 | 70.0 | 50.0 | 50.0 | 9 | 74.0 | 45.0 | 60.0 | 70.0 | 70.0 | 9 |
| Glass fibre | 35 | 35 | |||||||||||||
| Front three is supported the base silane coupler | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Carnauba wax | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6- | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6- |
According to following method, measure embodiment 2 to 10 and the flame retardancy thermosetting epoxy resin of comparative example 1 to 6 gained or the characteristic of phenol resin composition, the results are shown in table 2 and 3.
(1) helicoidal flow:, make resin combination to be measured in 175 ℃ and 70kg/cm according to the method for EMMI-1-66
2Under measure its helicoidal flow, the result is as shown in table 2.
(2) flame resistivity: resin combination was made long 5 o'clock, wide 0.5 o'clock and the test piece during thickness 1/16, tested its flame retardancy according to the UL94 specification.The made test piece of same combination is got 5, every burning twice, adds up to 10 burning sum total time if be no more than 50 seconds and the every single burning i.e. expression that is no more than 10 seconds by testing.The result is as shown in table 2.And calculate average single combustion time and be shown in table 3.
(3) water absorbability: the circular test piece that makes resin combination make 5 millimeters of 25 millimeters thickness of diameter takes by weighing weight, in 100 ℃ boiling water or pressure cooker boiling after 24 hours, takes by weighing test piece weight once again, calculates the suction weight percent.
(4) reflow thermotolerance: the double pin of moulding 18 pin uses composition epoxy resin in 175 ℃ of encapsulated mouldings (18LD-PDIP), and through 175 ℃ the sclerosis 4 hours after, after handling 72 hours under 85 ℃/85% relative humidity condition, whether continuously heat treated re-treatment in 10 seconds 3 times in 240 ℃ solder furnace is inspected outward appearance with vision and is chapped.
Table 2
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Implement 10 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Helicoidal flow (centimetre) | 75 | 75 | 82 | 70 | 75 | 75 | 75 | 78 | 78 | 72 | 80 | 75 | 70 | 75 | 65 |
| Flame resistivity UL-94 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 | V-0 | V-0 | V-0 |
| Water absorbability (%) | 0.23 | 0.24 | 0.23 | 0.22 | 0.23 | 0.23 | 0.25 | 0.24 | 0.24 | 0.25 | 0.25 | 0.30 | 0.28 | 0.28 | 0.28 |
| PCT reliability yield | ＞90 ％ | ＞90 ％ | ＞90 ％ | ＞90 ％ | ＞90 ％ | ＞90 ％ | ＞90 ％ | ＞90 ％ | ＞90 ％ | 80％ | 80％ | 85％ | 80％ | 80％ | 80％ |
| Annotate | Anti-combustion is not good | Reliability is not good | Anti-combustion is not good | Anti-combustion is not good | Brominated prescription | Anti-combustion is not good |
Table 3
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Implement 10 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Average single combustion time (second) | 2 to 3 | 2 to 3 | 1 to 2 | 2 to 3 | 1 to 2 | 1 to 2 | 2 to 3 | 1 to 2 | 1 to 2 | More than 10 | 1-2 | More than 10 | More than 10 | 1 to 2 | More than 10 |
[embodiment 11 to 12]
According to each composition and ratio shown in the table 4, prepare the composition epoxy resin of embodiment 11 to 12 as same way as described in the embodiment 1.
Table 4
| Embodiment 11 | Embodiment 12 | |
| Resins, epoxy a | 13.3 | 15.8 |
| Resins, epoxy b | -- | -- |
| Resins, epoxy c | -- | -- |
| Resins, epoxy d | -- | -- |
| Resins, epoxy e | -- | -- |
| Resol | -- | -- |
| Titanium compound multipolymer through the Resins, epoxy lining | 7.5 | -- |
| Titanium compound multipolymer through the resol lining | -- | 7.5 |
| Titanic acid ester | -- | -- |
| Aluminium hydroxide | -- | -- |
| Antimonous oxide | -- | -- |
| Resins, epoxy (f) | -- | -- |
| Stiffening agent a | 7.8 | 5.3 |
| Stiffening agent b | -- | -- |
| Stiffening agent c | -- | -- |
| Hardening accelerator a | 0.3 | 0.3 |
| Hardening accelerator b | -- | -- |
| Calcium hydroxide | -- | -- |
| Hexamethyl tetramine (Hexamine) | ||
| Fused silica | 70.0 | 70.0 |
| Glass fibre | ||
| Front three is supported the base silane coupler | 0.5 | 0.5 |
| Carnauba wax | 0.6 | 0.6 |
According to preceding method, measure the characteristic of the flame retardancy thermosetting epoxy resin composition of embodiment 11 to 12 gained, the results are shown in table 5.
Table 5
| Embodiment 11 | Embodiment 12 | |
| Helicoidal flow (centimetre) | 76 | 77 |
| Flame resistivity UL-94 | V-0 | V-0 |
| Water absorbability (%) | 0.21 | 0.21 |
| PCT reliability yield | ＞90％ | ＞90％ |
| Average single combustion time (second) | 1 to 2 | 1 to 2 |
By The above results as can be known, use is of the present invention among the embodiment 2 to 10 contains the copolymerized body weighting agent of titaniferous compound, and uses different rings epoxy resins and hardening accelerator to prepare difficult combustible epoxy resin composition among each embodiment.The titanium compound polymkeric substance weighting agent of the present invention that comparative example 1 uses in a small amount, comparative example 2 uses relatively large titanium compound polymkeric substance weighting agent of the present invention, comparative example 3 uses the common pure titanium compound, comparative example 4 uses common metal oxyhydroxide, and comparative example 5 uses bromated Resins, epoxy and stibiated incombustible agent.These embodiment and comparative example all have flame retardancy, therefore have suitable flame resistivity matter, and do not influence under the situation of helicoidal flow, can test by UL94V-0; But aspect the reflow thermotolerance, the embodiment 2 to 9 that adds nitrogenous difficult combustible epoxy resin of the present invention manifests preferable flame resistivity and PCT reliability.
Though comparative example 1 also uses the copolymerized body weighting agent of titaniferous compound that contains of the present invention, because content accounts for 1 weight % of composition epoxy resin total amount, can't be by the anti-combustion test of UL94V-0.Though it is copolymerized powder weighting agent that comparative example 2 also uses titaniferous of the present invention, because content accounts for more than the 25 weight % of composition epoxy resin total amount, though by the anti-combustion test of UL94 V-0, reliability worsens relatively.
Comparative example 3 uses pure titaniferous compound, and prepared composition epoxy resin can't be by the anti-combustion test of 94ULV-0, and water absorbability and PCT reliability aspect are all relatively poor.
Comparative example 4 uses metal hydroxidess (aluminium hydroxide), and prepared composition epoxy resin can't be by the anti-combustion test of 94ULV-0, and water absorbability and PCT reliability aspect are all relatively poor.
Comparative example 5 uses known brominated Resins, epoxy and stibiated incombustible agent, and the Resins, epoxy relative content is reduced, mobile variation after reaching flame retardancy, and also to contain the embodiment of difficult combustible epoxy resin composition of the present invention poor water absorbability and PCT reliability aspect.
[industry applications]
The difficult combustible epoxy resin composition of the copolymerized body filler of titanium-containing compound of the present invention has excellent flame retardancy and high-fire resistance, agent of low hygroscopicity and moisture-proof reliability, therefore not needing to add in addition incombustible agent namely has good flame retardancy matter and high-fire resistance, and can be used as electromechanics, electronic components, semiconductor sealing material, and prepared hardening thing can obtain good mouldability and good reliability.
Moreover, because these excellent flame retardancy and heat resistances of the present invention, and can be used for making electrical appliance, appliance and electronic, Automobile Products and the mechanical implement articles for use etc. of resin strengthening material preimpregnation thing (prepreg), laminate (laminate), printed circuit board (PCB), electronic package material, semiconductor sealing material, connector, transformer, power switch, relay, sheathing material, coil method etc.
Claims (18)
1. thermosetting resin composition, it contains the copolymerized body of a kind of titanium compound at least as weighting agent and thermosetting resin.
2. thermosetting resin composition as claimed in claim 1, wherein the copolymerized body weighting agent of this titanium compound is the resultant by titaniferous compound and nitrogenous compound and/or P contained compound copolymerization.
3. thermosetting resin composition as claimed in claim 1, wherein the copolymerized body weighting agent of this titanium compound is to be contained in the said composition with the form that this thermosetting resin coats.
4. thermosetting composition epoxy resin, it comprises Resins, epoxy, stiffening agent, hardening accelerator and as the copolymerized body of the titanium compound of weighting agent, wherein the epoxy equivalent (weight) of this Resins, epoxy is 1: 0.5 to 1: 1.5 to the reactive hydrogens equivalence ratio of stiffening agent, the amount of hardening accelerator accounts for 0.01 to 5 weight % of this Resins, epoxy and stiffening agent gross weight, and the amount of the copolymerized body of this titanium compound accounts for 1 to 25 weight % of this Resins, epoxy and stiffening agent gross weight.
5. thermosetting composition epoxy resin as claimed in claim 4, wherein the copolymerized body weighting agent of this titanium compound is the resultant by titaniferous compound and nitrogenous compound and/or P contained compound copolymerization.
6. thermosetting composition epoxy resin as claimed in claim 4, wherein the copolymerized body weighting agent of this titanium compound is to be contained in the said composition with the form that this thermosetting resin coats.
7. thermosetting composition epoxy resin as claimed in claim 4, wherein this thermosetting resin is a Resins, epoxy, and is to be selected from by one or more of the cohort that epoxy resin is formed of phenolic resin varnish type epoxy resin class, bisphenol-type epoxy resin class, biphenyl type epoxy resin class, united phenol-type epoxy resin class, xylenol type epoxy resin, dicyclopentadiene-type epoxy resin class, naphthalene type epoxy resin, toluylene type epoxy resin, sulfur atom-containing.
8. thermosetting composition epoxy resin as claimed in claim 4, wherein this stiffening agent is to be selected from one or more of the phosphorous and cohort that nitrogen compound is formed shown in phenolic varnish type phenol resins class, aralkyl-type phenol resins class, dicyclopentadiene-type phenol resins class, biphenyl type phenol resins class, phenol type epoxy resin, triphenyl methane type phenol resins class and the following formula:
In the formula, R
2For-NHR
1, C
1-6Alkyl or C
6-10Aryl;
R
1Respectively be respectively hydrogen ,-(CH
2-R
3-)
rH or be the base of following formula:
Wherein r is 0 to 20 integer and R
3For stretching phenyl, stretching the base of naphthyl or following formula:
In the formula A be-O-,-S-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-or the following formula base:
And R
4And R
5Independent is hydrogen, C
1-10Alkyl or C
6-10Aryl; Y is-OH ,-NH
2Or-COOH; A is 0 to 2 integer; X is that 0 to 3 integer and a+x are not more than 3;
But condition be above-mentioned at least one R
1Be not hydrogen.
9. thermosetting composition epoxy resin as claimed in claim 4, wherein this hardening accelerator is to be selected from one or more that encircles miaow compound, maleic anhydride, naphtoquinone compounds, tertiary amine and derivative, imidazoles and derivative thereof, phosphorus compound, tetraphenyl borate salts and cohort that derivative is formed thereof.
10. thermosetting composition epoxy resin as claimed in claim 4, wherein the copolymerized body of this titaniferous compound can part be selected from the following at least a weighting agent displacement of forming cohort again: fused silica, crystalline silica, aluminum oxide, zircon, Calucium Silicate powder, lime carbonate, potassium titanate, silicon carbide, silicon nitride, aluminium nitride, boron nitride, beryllium oxide, zirconium white, aluminium peridotites, steatite, spinel, mullite and titanium oxide.
11. thermosetting composition epoxy resin as claimed in claim 4, it can comprise one or more additive that is selected from inorganic filler, coupler, colorant, releasing agent and low stress additives again.
12. thermosetting phenol resin composition, it comprises the resol of 20 to 60 weight parts, the stiffening agent of 2 to 12 weight parts, the hardening accelerator of 1 to 8 weight part and the inorganic filler of 35 to 75 weight parts, and the 15-30% in this inorganic filler is the copolymerized body of titanium compound.
13. thermosetting phenol resin composition as claimed in claim 12, wherein the copolymerized body weighting agent of this titanium compound is the resultant by titaniferous compound and nitrogenous compound and/or P contained compound copolymerization.
14. thermosetting phenol resin composition as claimed in claim 12, wherein the copolymerized body weighting agent of this titanium compound is to be contained in the said composition with the form that this thermosetting resin coats.
15. thermosetting phenol resin composition as claimed in claim 12, wherein this resol is to be selected from one or more of phenolic varnish type phenol resins class, aralkyl-type phenol resins class, dicyclopentadiene-type phenol resins class, biphenyl type phenol resins class, phenol type phenol resins class, triphenyl methane type phenol resins cohort that class is formed.
16. thermosetting phenol resin composition as claimed in claim 12, wherein this stiffening agent is a vulkacit H.
17. thermosetting phenol resin composition as claimed in claim 12, wherein this hardening accelerator is be selected from magnesium oxide, calcium oxide, cohort that calcium hydroxide is formed at least a.
18. thermosetting phenol resin composition as claimed in claim 12, wherein the copolymerized body part of this this titanium compound can be replaced through being selected from following extra weighting agent: one or more of ball-type and angle type fused silica, crystalline silica, fused silica powder, talcum powder, aluminum oxide powder, zinc borate, aluminium hydroxide, magnesium hydroxide, Paris white, aln precipitation, glass sphere and cohort that glass fibre is formed.
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|---|---|---|---|
| CN 200610007648 CN101020779A (en) | 2006-02-15 | 2006-02-15 | Fireproof thermosetting resin composition |
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| CN101906236A (en) * | 2009-06-04 | 2010-12-08 | 日东电工株式会社 | Epoxy resin composition for semiconductor encapsulation and the semiconductor device that uses described composition |
| CN101974140A (en) * | 2010-10-15 | 2011-02-16 | 山东圣泉化工股份有限公司 | Preparation method for phenolic resin |
| CN101376665B (en) * | 2008-09-29 | 2012-01-25 | 四川东材科技集团股份有限公司 | Phosphaphenanthrene flame-retardant compound containing s-triazine structure, and preparation and use thereof |
| CN104788910A (en) * | 2015-04-29 | 2015-07-22 | 海太半导体（无锡）有限公司 | Environment-friendly semiconductor plastic packaging material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376665B (en) * | 2008-09-29 | 2012-01-25 | 四川东材科技集团股份有限公司 | Phosphaphenanthrene flame-retardant compound containing s-triazine structure, and preparation and use thereof |
| CN101906236A (en) * | 2009-06-04 | 2010-12-08 | 日东电工株式会社 | Epoxy resin composition for semiconductor encapsulation and the semiconductor device that uses described composition |
| CN101906236B (en) * | 2009-06-04 | 2014-03-12 | 日东电工株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device using same |
| CN101974140A (en) * | 2010-10-15 | 2011-02-16 | 山东圣泉化工股份有限公司 | Preparation method for phenolic resin |
| CN101974140B (en) * | 2010-10-15 | 2012-08-15 | 山东圣泉化工股份有限公司 | Preparation method for phenolic resin |
| TWI583668B (en) * | 2012-11-28 | 2017-05-21 | Dainippon Ink & Chemicals | A composition containing a phenolic hydroxyl group, a resin containing a (meth) acryloyl group, a hardened composition, a hardened product and a |
| CN104788910A (en) * | 2015-04-29 | 2015-07-22 | 海太半导体（无锡）有限公司 | Environment-friendly semiconductor plastic packaging material |
| CN106543638A (en) * | 2016-10-27 | 2017-03-29 | 苏州富通高新材料科技股份有限公司 | A kind of nanometer phenolic aldehyde resin section bar and preparation method thereof |
| CN106751509A (en) * | 2016-12-15 | 2017-05-31 | 南京市消防工程有限公司宜兴安装分公司 | A kind of organic nonflammable material |
| CN109370148A (en) * | 2018-09-29 | 2019-02-22 | 武汉理工大学 | A kind of high-densit high temperature suitable for RFI moulding process can porcelain phenolic resin infiltration film and preparation method thereof |
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