CN1350026A - Phenol curing agent for epoxy resin and epoxy resin composition using said curing agent - Google Patents
Phenol curing agent for epoxy resin and epoxy resin composition using said curing agent Download PDFInfo
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- CN1350026A CN1350026A CN01125222A CN01125222A CN1350026A CN 1350026 A CN1350026 A CN 1350026A CN 01125222 A CN01125222 A CN 01125222A CN 01125222 A CN01125222 A CN 01125222A CN 1350026 A CN1350026 A CN 1350026A
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- curing agent
- epoxy resin
- resins
- phenols curing
- epoxy
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 50
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 title claims description 85
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 61
- 239000011347 resin Substances 0.000 claims description 61
- 239000004593 Epoxy Substances 0.000 claims description 46
- 150000002989 phenols Chemical class 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 30
- 239000002966 varnish Substances 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 15
- 238000010030 laminating Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 5
- 239000012764 mineral filler Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 9
- 239000011147 inorganic material Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000004848 polyfunctional curative Substances 0.000 abstract 5
- 125000003277 amino group Chemical group 0.000 abstract 3
- 150000002739 metals Chemical class 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 229910000077 silane Inorganic materials 0.000 description 15
- 239000004922 lacquer Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- -1 organic acid salt Chemical class 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 239000012776 electronic material Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical class CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000013212 metal-organic material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Paints Or Removers (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Die Bonding (AREA)
Abstract
Provided is a hardener for an epoxy resin excellent in adhesion with inorganic materials or metals, and an epoxy resin composition. The hardener contains a phenol hardener and a silane coupling agent having a tertiary or quaternary amino group. The amino group may be desirably an imidazole group, a dimethyl amino group or their salts. The hardener may be a mixture of above two or be a modification obtained by stiring and mixing the silane coupling agent having the tertiary or quaternary amino group with the phenol hardener melt, and is effective in improvement of adhesive property with inorganic materials and metals.
Description
Background of invention
Invention field
The present invention relates to be used for that metal and inorganic materials are had the phenols curing agent of the Resins, epoxy of excellent adhesiveness, and relate to the composition epoxy resin that uses this phenols curing agent.Phenols curing agent and composition epoxy resin can be used for fields such as electronic material, paint, priming paint, tackiness agent, are specially adapted to sealing agent, laminating material and are used for the material for sealing of electronic material.
The description of prior art
In recent years, the development trend in the field of electronic materials is microminiaturized and reduces material weight and prevent the pollution of the environment halogen and no antimony material, unleaded solder etc.Present situation is to comply with these trend, needs the performance that further improves sealing agent, laminating material, material for sealing and be used for the analogous material of electronic material.
For example, composition epoxy resin (wherein novolac epoxy solidifies with lacquer resins) is usually used in semiconductor sealing resin.But,, strict all the more to the littler thinner requirement of packing for semi-conductor satisfies the needs of Highgrade integration.On the other hand, consider environmental problem, same necessary is the trend of complying with unleaded solder, and necessary in addition is satisfies the development of lead frame PPFs (precoated plate framework) etc.Owing to these reasons,, and be difficult to guarantee the reliability (this depends primarily on the mechanical strength of sealing resin) of conventional epoxies composition to the various performance demands increasingly stringents of sealing resin.The example of required specific performance is more effective bonding to semi-conductor chip and lead frame.Even particularly require sealing resin immersing under the situation of solder flux after the moisture absorption, sealing resin phenomenons such as be full of cracks, interface peel can not occur yet.
In addition, based on the most frequently used insulating material of making printed circuit board (PCB) of the epoxy laminate material of glass baseplate.Dyhard RU 100 is used as the curing agent for epoxy resin of laminating material usually, but owing to require thermotolerance when using unleaded solder, so people have begun to pay close attention to a kind of like this method, wherein lacquer resins is used as solidifying agent.But, use lacquer resins to be binding property to Copper Foil as the shortcoming of solidifying agent, particularly to the binding property of the internal layer Copper Foil in the multi-ply wood far below the effect of using Dyhard RU 100.
Be usually used in improving that fusible method is to handle its surface with silane coupling agent between resin and metal or the inorganic materials, or silane coupling agent is added in the resin.Commercially available epoxy type and amino-type silane coupling agent can improve binding property effectively and use for many years, but present case is that with regard to processing environment problem and above-mentioned microminiaturized in recent years trend, they can not satisfy required performance day by day.So the present inventor has developed the silane coupling agent (not examining open H05-186479, H09-012683 and H09-295988 referring to for example Japanese patent application) with imidazole group or dimethylamino.Proved with commercially available silane coupling agent and compared that these silane coupling agents can significantly improve bonding between resin and metal or the inorganic materials.
But above-mentioned shortcoming with silane coupling agent of imidazole group or dimethylamino is that they are difficult to handle under the situation of overall blend, because its viscosity height and hydrolysis rate are fast.In addition, these silane coupling agents cause short shortcoming of shelf lives when being used for varnish, so the application of these silane coupling agents is restricted solvent poorly soluble in the ketone for example.
Summary of the invention
First purpose of the present invention provides and a kind ofly is used to prepare the epoxy curing agent that metal and inorganic materials is had the composition epoxy resin of excellent adhesiveness, and corresponding composition epoxy resin and solidify material thereof.In addition, another object of the present invention provide a kind of easy-to-handle, in ketone solvent, have high-dissolvability and be applicable to the various uses epoxy curing agent of (comprising varnish), and the composition epoxy resin and the solidifying product thereof that use this solidifying agent.
The present inventor finishes above-mentioned target by deep research, found that if phenols curing agent commonly used is mixed with the silane coupling agent with three replacements or senior amino, and this mixture or its reaction product be as solidifying agent, then can significantly improve bonding between Resins, epoxy and metal or the inorganic materials.In addition, even also find to use the silane coupling agent with three replacements or senior amino, solidifying agent also is easy to handle, and can both dissolve in all common solvent.
So, the invention provides a kind of phenols curing agent that is used for Resins, epoxy, comprise:
A kind of phenols curing agent; With
A kind of silane coupling agent with three replacements or senior amino.
Think that resin that uses solidifying agent of the present invention and the mechanism that the bond strength between metal or the inorganic materials is improved are, the hydroxyl of contained phenols curing agent and contained alkoxysilyl interreaction in solidifying agent in solidifying agent with silane coupling agent of three replacements or senior amino, thereby the functional group of solidifying agent and curing catalyst makes up in individual molecule, makes the curing reaction of Resins, epoxy carry out smoothly.
Be used for phenols curing agent of the present invention and can be each intramolecularly and have 2 or more any phenols curing agent of polyphenol hydroxyl, for example dihydroxyphenyl propane, Bisphenol F, polyvinylphenol, lacquer resins, cresols novolac resin, bisphenol-A phenolic varnish resin, bisphenol F phenolic varnish resin, aralkyl-phenol resin or analogue.Wherein, the phenol resins solidifying agent is particularly preferred.
Silane coupling agent with three replacements or senior amino preferably has the silane coupling agent of imidazolyl or its salt or dimethylamino or its salt, thereby as curing catalyst.Example comprises that for example being disclosed in Japanese patent application examines disclosed silane coupling agent among open H05-186479, H09-295988, H05-039295, H06-279458, H09-296135, H09-295989, H09-295992, H10-273492, H11-092482, H12-226757 and the H11-108246, or its salt, wherein these have in the silane coupling agent of imidazolyl or dimethylamino with the addings such as organic acid salt of acetate.
In above-mentioned silane coupling agent, below be particularly preferred.The first, Japanese patent application is not examined disclosed 3 kinds of imidazoles-silane compounds among the open H05-186479, or its mixture.As described in the careful open H05-186479 of Japanese patent application, these imidazoles-silane compounds obtain (this mixture only is called " imidazoles-silane " hereinafter) as the mixture of 3 kinds of compounds by imidazolium compounds and 3-epoxypropoxy silane compound are reacted down in 80-200 ℃.The second, the silicoorganic compound with dimethylamino of the active ingredient of formation surface treatment agent are disclosed in Japanese patent application and examine open H09-296135 (these compounds only are called " dimethylamino base silane " hereinafter).It is disclosed to examine open H09-296135 as Japanese patent application, and these dimethylamino base silanes are by being heated to 20-80 ℃ with dimethyl amine and epoxy radicals silicone hydride, removes non-reactive dimethyl amine then and obtains.
The phenols curing agent that the present invention is used for Resins, epoxy can be used simply as mixture, but if, also be effective by with above-mentioned phenols curing agent fusion, have three and replace or the silane-cure agent of senior amino mixes the modification phenols curing agent that obtains with above-mentioned then.
In addition, the present invention also provides a kind of composition epoxy resin, comprises (a) Resins, epoxy and the phenols curing agent that (b) is used for Resins, epoxy according to the present invention.
The Resins, epoxy that is used for composition epoxy resin of the present invention can be any Resins, epoxy, but preferably is widely used in the Resins, epoxy in sealing agent and the laminating material.Example comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A phenolic varnish type Resins, epoxy, line style phenol aldehyde type epoxy resin, cresols phenolic resin varnish type epoxy resin, have the Resins, epoxy of xenyl skeleton, have the naphthalene skeleton Resins, epoxy, have the Resins, epoxy of triphenyl methane skeleton and wherein in these epoxy resin structurals some hydrogen atoms by halogen alternate Resins, epoxy.In addition, the Resins, epoxy in composition epoxy resin of the present invention preferably makes mixture ratio (hydroxyl/epoxy group(ing)) in the 0.2-1.2 scope with the content that is used for the phenols curing agent of Resins, epoxy.
Composition epoxy resin of the present invention can contain mineral filler in addition.Can use any mineral filler that is usually used in sealing agent, but impurity concentration is low and median size to be not more than 30 microns SiO 2 powder be preferred.The ratio of mineral filler is preferably based on the 25-90 weight % of resin combination total amount.
If desired, can in composition epoxy resin of the present invention, suitably add releasing agent for example metal-salt, sour acid amides, ester and the paraffin of natural wax, synthetic wax, straight chain fatty acid; Fire retardant is ANTIMONY TRIOXIDE SB 203 99.8 PCT for example; Tinting material is carbon black for example; Silane coupling agent; Various curing catalysts; Reagent with low-stress is rubber and siloxanes etc. for example.
Composition epoxy resin of the present invention is applicable to the varnish of laminating material.In addition, composition epoxy resin of the present invention also can be impregnated in the matrix, and as prepreg, maybe can be used for the laminating material that forms by this prepreg lamination.In addition, with the also suitable semi-conductor chip material for sealing of doing of the composition epoxy resin of the present invention of metal-powder kneading.In this way, composition epoxy resin of the present invention has many purposes.
By heating composition epoxy resin of the present invention, also can provide solidified Resins, epoxy.This solidify material is applicable to the encapsulating semiconductor element, wherein uses the solidify material sealing semiconductor chips.
On the other hand, the invention provides the method that a kind of preparation is used for the phenols curing agent of Resins, epoxy, comprising:
With the phenols curing agent fusion; With
It is mixed with the silane coupling agent with three replacements or senior amino, obtain a kind of modification phenols curing agent.
The present invention is used for the method for the phenols curing agent of Resins, epoxy in preparation, has three and replaces or the ratio of the silane coupling agent of senior amino preferably 0.001-1, more preferably 0.01-0.5 weight part/1 weight part phenols curing agent.If have three replace or the amount of the silane coupling agent of senior amino too high, gel then appears, and if should amount too low, then can not improve binding property.
If this phenols curing agent is a solid, then with phenols curing agent with have three and replace or the silane coupling agent blended preferred method of senior amino is earlier with the phenols curing agent fusion, progressively add silane coupling agent then, stir this melt simultaneously well.The reaction of the alkoxysilyl of the hydroxyl of phenol resins and silane obtains alcohol then.
The accompanying drawing summary
Fig. 1 is the detection method synoptic diagram with the shearing resistance of the resin bond of making in embodiment of the invention copper alloy plate together.
The description of preferred embodiment
Specifically describe the present invention by the following examples.But the present invention is not subjected to the restriction of these embodiment.The first, before preparation the present invention is used for the phenols curing agent of Resins, epoxy, preparation imidazoles-silane or dimethylamino base silane; This is described among following synthetic embodiment 1 and the synthetic embodiment 2.The unit that note that blending ratio mentioned among the embodiment by weight.Synthetic embodiment 1
As described in the careful open H05-186479 of Japanese patent application, prepare imidazoles-silane earlier.In 95 ℃ of preparations, 3.4 gram (0.05 mole) imidazoles melts, in 30 minutes, 11.8 gram (0.05 mole) 3-glycidoxy-propyltrimethoxy silanes are added in the imidazoles, under argon gas atmosphere, stir simultaneously.After adding is finished, continue reaction 1 hour in 95 ℃.Imidazoles-the silane of gained is the mixture of 3 components.Synthetic embodiment 2
Examine preparation dimethylamino base silane as described in the open H09-296135 as Japanese patent application.The mixtures of 13.5 gram (0.3 mole) dimethyl amines and 17.3 gram (0.07 mole) 3-glycidoxy-propyltrimethoxy silanes are placed autoclave nitrogen atmosphere under, reacted two kinds of components in 1 hour by heating in 150 ℃.After the reaction, from reaction mixture, remove excessive dimethyl amine, obtain 19.9 gram dimethylamino base silanes with vaporizer.
Embodiment 1
Use imidazoles-silane of synthetic embodiment 1 to be prepared as follows the phenols curing agent that is used for Resins, epoxy according to the present invention.Be heated to 100 ℃ of preparations, 35 gram lacquer resins (hydroxyl equivalent is 104) melts.1 gram imidazoles-silane to wherein progressively adding from synthetic embodiment 1 stirs the gained mixture 5 minutes after the interpolation, then cooling.After cooling, the gained solid is clayed into power, obtain imidazoles-silane-modified lacquer resins (solidifying agent 1), it is the phenols curing agent that is used for Resins, epoxy.
Embodiment 2
Carry out the step identical with embodiment 1, different is the 1 gram imidazoles-silane that replaces synthetic embodiment 1 with the 1 gram dimethylamino base silane of synthetic embodiment 2, obtain dimethylamino-silane-modified lacquer resins (solidifying agent 2), it is the phenols curing agent that is used for Resins, epoxy.
Embodiment 3-14
In embodiment 3-14, use from the solidifying agent 1 of embodiment 1 or from the solidifying agent 2 of embodiment 2 and be prepared as follows composition epoxy resin.With neighbour-cresols phenol aldehyde type epoxy resin (epoxy equivalent (weight) is 210) and other material according to the ratio shown in the table 1 in mixed at room temperature.As shown in table 1, pyrogenic silica powder (14 microns of median sizes), 2-ethyl-4-methylimidazole and 3-glycidoxy-propyltrimethoxy silane are included as suitable additive.The gained mixture is further mediated in 90-100 ℃, and cooling is clayed into power then, obtains composition epoxy resin.
With the above-mentioned corresponding composition epoxy resin that obtains two copper alloy plates (C-7025,50 millimeters * 25 millimeters of sizes) are bonded together as shown in Figure 1, composition epoxy resin was solidified 8 hours in 175 ℃.Structure as shown in Figure 1 according to the stretching detector tension specimen of the direction of arrow among Fig. 1, and detects shearing resistance as sample.Used draw speed is 1 mm/min.The result is as shown in table 2.Comparative Examples 1-3
In Comparative Examples 1-3, lacquer resins replaces the present invention to be used for the phenols curing agent of Resins, epoxy as solidifying agent.That is, use material and the blending ratio shown in the table 1, but different be, composition epoxy resin is as preparation as described in the embodiment 3-14.In addition, use the epoxy resin composition that so obtains, detect the shearing resistance of embodiment 3-14.Detected result is as shown in table 2.
Table 1
| Embodiment | Comparative Examples | ||||||||||||||
| ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ??9 | ??10 | ??11 | ??12 | ??13 | ??14 | ????1 | ????2 | ????3 | |
| Ortho-cresol line style phenol aldehyde type epoxy resin | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ????100 | ????100 | ????100 |
| Solidifying agent 1 | ????55 | ????55 | ????55 | ????55 | ????55 | ????55 | ??- | ??- | ??- | ??- | ??- | ??- | ????- | ????- | ????- |
| Solidifying agent 2 | ????- | ????- | ????- | ????- | ????- | ????- | ??55 | ??55 | ??55 | ??55 | ??55 | ??55 | ????- | ????- | ????- |
| Lacquer resins | ????- | ????- | ????- | ????- | ????- | ????- | ??- | ??- | ??- | ??- | ??- | ??- | ????54 | ????54 | ????54 |
| The pyrogenic silica powder | ????- | ????600 | ????600 | ????- | ????600 | ????600 | ??- | ??600 | ??600 | ??- | ??600 | ??600 | ????- | ????600 | ????600 |
| 2-ethyl-4-methylimidazole | ????- | ????- | ????1.5 | ????1.5 | ????- | ????1.5 | ??- | ??- | ??1.5 | ??1.5 | ??- | ??1.5 | ????1.5 | ????1.5 | ????1.5 |
| The 3-glycidoxy-propyltrimethoxy silane | ????- | ????- | ????- | ????- | ????1.5 | ????1.5 | ??- | ??- | ??- | ??- | ??1.5 | ??1.5 | ????1.5 | ????1.5 | ????1.5 |
| Imidazoles-silane | ????- | ????- | ????- | ????- | ????- | ????- | ??- | ??- | ??- | ??- | ??- | ??- | ????- | ????- | ????1.5 |
Table 2
| Embodiment | Comparative Examples | ||||||||||||||
| ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 | ??11 | ???12 | ??13 | ??14 | ????1 | ????2 | ????3 | |
| Bonding shearing resistance (kg/cm 2) | ??82 | ??34 | ??35 | ??86 | ??37 | ??38 | ??80 | ??32 | ??36 | ???81 | ??35 | ??37 | ????60 | ????25 | Form aggregate |
Embodiment 3-14 has shown competent bonding shearing resistance, wherein uses according to solidifying agent of the present invention.For embodiment 3,6,9 and 12, do not comprise that the pyrogenic silica powder as additive, demonstrates 80 kg/cm
2Or higher high bonding shearing resistance.By contrast, Comparative Examples 1 is not wherein used solidifying agent of the present invention and is not comprised the pyrogenic silica powder, and intensity is in 60 kg/cm
2Be insufficient.Then, embodiment 4,5,7,8,10,11,13 and 14, and comprising the pyrogenic silica powder, demonstrating bonding shearing resistance is 32 kg/cm
2Or it is higher.By contrast, Comparative Examples 2 and 3 comprising similar pyrogenic silica powder, but is not used solidifying agent of the present invention, demonstrates 25 kg/cm
2Low strength, or form aggregate, can not be bonding.
Embodiment 15 and 16
In embodiment 15 and 16, use solidifying agent 1 preparation varnish from embodiment 1, obtain prepreg and copper-plated laminating material with these varnish.First, with brominated bisphenol a type epoxy resin (Br content 21.5%, epoxy equivalent (weight) 480), ortho-cresol line style phenol aldehyde type epoxy resin (epoxy equivalent (weight) 210), from the solidifying agent 1 (imidazoles-silane-modified novolac resin) of embodiment 1 and the material shown in other table 3 mixed according to table 3.Then acetone is added in each mixture and prepare varnish.
Then, each varnish impregnation is gone into 7628 specific type glass fabric matrix (non-alkaline plain weave woven fiber glass is used for laminating material),, carry out drying and obtain prepreg so that resin content is about 50%.Maximum 8 prepregs are superimposed, place then (35 microns of thickness) on Copper Foil one side, then with 40 kg/cm
2Suppressed 90 minutes, and be heated to 175 ℃ simultaneously, obtain copper-plated laminating material.In order to estimate the binding property of each copper facing laminating material, detect stripping strength with 1 centimetre wide copper wire.The result is as shown in table 4 below.Comparative Examples 4 and 5
In Comparative Examples 4 and 5, the material shown in the table 3 uses according to the ratio shown in the table 3, and lacquer resins (hydroxyl equivalent 104) replaces solidifying agent of the present invention.In addition, obtain copper-plated laminating material, and detect its stripping strength according to embodiment 15 and 16.Detected result is as shown in table 4.Comparative Examples 6
In Comparative Examples 6, the material shown in the table 3 uses according to the ratio shown in the table 3, does not wherein use solidifying agent of the present invention.Among the embodiment in front, preparation is only used acetone during varnish, but in Comparative Examples 6 in order to prepare varnish, also necessary use dimethyl formamide and methylcyclohexane except that acetone.In addition, obtain copper-plated laminating material, and detect its stripping strength according to embodiment 15 and 16.Detected result is as shown in table 4.
Table 3
| Embodiment | Comparative Examples | ||||
| ????15 | ????16 | ????4 | ????5 | ????6 | |
| Brominated bisphenol a type epoxy resin | ????90 | ????90 | ????90 | ????90 | ????90 |
| Ortho-cresol line style phenol aldehyde type epoxy resin | ????10 | ????10 | ????10 | ????10 | ????10 |
| Solidifying agent 1 | ????27 | ????27 | ????- | ????- | ????- |
| Lacquer resins | ????- | ????- | ????27 | ????27 | ????- |
| Dyhard RU 100 | ????- | ????- | ????- | ????- | ????3 |
| 2-ethyl-4-methyl-imidazoles | ????- | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Imidazoles-silane | ????- | ????- | ????- | ????0.4 | ????- |
Table 4
| Embodiment | Comparative Examples | ||||
| ????15 | ????16 | ????4 | ????5 | ????6 | |
| Stripping strength (kg/cm) | ????2.0 | ????1.9 | ????1.7 | In varnish, form aggregate | ????2.0 |
As shown in table 4, in the embodiment 15 and 16 that uses solidifying agent of the present invention,, also have competent stripping strength even only use acetone as solvent.By contrast, not using solidifying agent of the present invention and only using in the Comparative Examples 4 and 5 of acetone as solvent, obtain low strength or in varnish, form aggregate.In addition, find in embodiment 15 and 16, to demonstrate the competent stripping strength that equates with dicy-curing agent (Comparative Examples 6).
The application of the invention is used for the phenols curing agent of Resins, epoxy, after composition epoxy resin solidifies, and bonding being improved between Resins, epoxy and metal or the inorganic materials.In addition, the phenols curing agent that the present invention is used for Resins, epoxy also has high-dissolvability at ketone solvent, thereby can be used for various uses, for example varnish and prepreg.Owing to these reasons, the composition epoxy resin of solidifying agent of the present invention and this solidifying agent of use is used for field of electronic materials ideally.
Claims (13)
1. phenols curing agent that is used for Resins, epoxy, contain:
Phenols curing agent; With
Silane coupling agent with three replacements or senior amino.
2. according to the phenols curing agent that is used for Resins, epoxy of claim 1, wherein said phenols curing agent is a kind of modification phenols curing agent, obtains by the phenols curing agent fusion also being made then it under agitation mix with described silane coupling agent with three replacements or senior amino.
3. according to the phenols curing agent that is used for Resins, epoxy of claim 1 or 2, wherein said three replacements or senior amino are imidazolyl or its salt, or dimethylamino or its salt.
4. composition epoxy resin, contain:
(a) Resins, epoxy; With
(b) according to each the phenols curing agent that is used for Resins, epoxy among the claim 1-3.
5. according to the composition epoxy resin of claim 4, contain mineral filler in addition.
6. a use is according to the varnish that is used for laminating material of the composition epoxy resin of claim 4 or 5.
7. a prepreg wherein will be impregnated in the matrix of this prepreg according to the composition epoxy resin of claim 4 or 5.
8. laminating material that forms by superimposed prepreg according to claim 7.
9. a semi-conductor chip material for sealing contains the composition epoxy resin of mediating with metal-powder according to claim 4 or 5.
10. cured epoxy resin that obtains according to the composition epoxy resin of claim 4 or 5 by heating.
11. an encapsulating semiconductor equipment is wherein used the cured epoxy resin sealing semiconductor chips according to claim 10.
12. a method for preparing the phenols curing agent that is used for Resins, epoxy comprises:
With the phenols curing agent fusion; With
It is under agitation mixed with the silane coupling agent with three replacements or senior amino, thereby obtain the modification phenols curing agent.
13. be used for the method for the phenols curing agent of Resins, epoxy according to the preparation of claim 12, wherein said three replace or senior amino is imidazolyl or its salt, or dimethylamino or its salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP320792/2000 | 2000-10-20 | ||
| JP2000320792A JP3708423B2 (en) | 2000-10-20 | 2000-10-20 | Phenolic curing agent for epoxy resin and epoxy resin composition using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1350026A true CN1350026A (en) | 2002-05-22 |
| CN1175037C CN1175037C (en) | 2004-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011252227A Expired - Lifetime CN1175037C (en) | 2000-10-20 | 2001-08-31 | Phenol curing agent for epoxy resin and epoxy resin composition using said curing agent |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3708423B2 (en) |
| KR (1) | KR100456348B1 (en) |
| CN (1) | CN1175037C (en) |
| TW (1) | TW572926B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357333C (en) * | 2002-10-28 | 2007-12-26 | 日矿金属株式会社 | Solid silane coupling agent compsn., method for mfg. the same, and resin compsn. contg the same |
| CN102803333A (en) * | 2009-06-05 | 2012-11-28 | 日本化药株式会社 | Epoxy resin composition, prepreg and cured products thereof |
| CN103703047A (en) * | 2011-07-26 | 2014-04-02 | 日本化药株式会社 | Epoxy resin, epoxy resin composition, prepreg, and curing product of each |
| CN107629194A (en) * | 2017-10-16 | 2018-01-26 | 六安捷通达新材料有限公司 | A kind of epoxide powder coating heat resistance phenols curing agent and preparation method thereof |
| CN107987254A (en) * | 2017-11-03 | 2018-05-04 | 福建师范大学 | A kind of adjustable silicon substrate thiazole epoxy curing agent of structure and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG119379A1 (en) | 2004-08-06 | 2006-02-28 | Nippon Catalytic Chem Ind | Resin composition method of its composition and cured formulation |
| KR101249479B1 (en) * | 2007-06-25 | 2013-03-29 | 미쓰이 긴조꾸 고교 가부시키가이샤 | Resin composition and copper foil with resin obtained by using the resin composition |
| WO2010024391A1 (en) * | 2008-09-01 | 2010-03-04 | 積水化学工業株式会社 | Laminate and method for producing laminate |
| TWI490266B (en) * | 2009-12-02 | 2015-07-01 | Mitsui Mining & Smelting Co | A resin composition for forming a bonding layer of a multilayer flexible printed circuit board, a resin varnish, a porous flexible printed circuit board, and a multilayer flexible printed circuit board |
| JP5885331B2 (en) * | 2011-07-27 | 2016-03-15 | 日本化薬株式会社 | Epoxy resin mixture, epoxy resin composition, prepreg and cured products thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212661A (en) * | 1989-10-16 | 1993-05-18 | Matsushita Electric Industrial Co., Ltd. | Apparatus for performing floating point arithmetic operation and rounding the result thereof |
-
2000
- 2000-10-20 JP JP2000320792A patent/JP3708423B2/en not_active Expired - Lifetime
-
2001
- 2001-07-18 TW TW90117504A patent/TW572926B/en not_active IP Right Cessation
- 2001-08-10 KR KR10-2001-0048238A patent/KR100456348B1/en active IP Right Grant
- 2001-08-31 CN CNB011252227A patent/CN1175037C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357333C (en) * | 2002-10-28 | 2007-12-26 | 日矿金属株式会社 | Solid silane coupling agent compsn., method for mfg. the same, and resin compsn. contg the same |
| CN102803333A (en) * | 2009-06-05 | 2012-11-28 | 日本化药株式会社 | Epoxy resin composition, prepreg and cured products thereof |
| CN103703047A (en) * | 2011-07-26 | 2014-04-02 | 日本化药株式会社 | Epoxy resin, epoxy resin composition, prepreg, and curing product of each |
| CN107629194A (en) * | 2017-10-16 | 2018-01-26 | 六安捷通达新材料有限公司 | A kind of epoxide powder coating heat resistance phenols curing agent and preparation method thereof |
| CN107987254A (en) * | 2017-11-03 | 2018-05-04 | 福建师范大学 | A kind of adjustable silicon substrate thiazole epoxy curing agent of structure and preparation method thereof |
| CN107987254B (en) * | 2017-11-03 | 2019-11-26 | 福建师范大学 | A kind of adjustable silicon substrate thiazole epoxy curing agent of structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1175037C (en) | 2004-11-10 |
| TW572926B (en) | 2004-01-21 |
| KR100456348B1 (en) | 2004-11-09 |
| KR20020031031A (en) | 2002-04-26 |
| JP2002128867A (en) | 2002-05-09 |
| JP3708423B2 (en) | 2005-10-19 |
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