CN102108068A - Polymer material and application thereof - Google Patents
Polymer material and application thereof Download PDFInfo
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- CN102108068A CN102108068A CN2009102655083A CN200910265508A CN102108068A CN 102108068 A CN102108068 A CN 102108068A CN 2009102655083 A CN2009102655083 A CN 2009102655083A CN 200910265508 A CN200910265508 A CN 200910265508A CN 102108068 A CN102108068 A CN 102108068A
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- 0 CCc1c(*=CC*=C)cc(C)c(C=*)c1 Chemical compound CCc1c(*=CC*=C)cc(C)c(C=*)c1 0.000 description 10
- HRDXJKGNWSUIBT-UHFFFAOYSA-N C=[O]c1ccccc1 Chemical compound C=[O]c1ccccc1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- RINOYHWVBUKAQE-UHFFFAOYSA-N Cc1ccccc1I Chemical compound Cc1ccccc1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a polymer material. The polymer material is a long-chain nitrogen-oxygen heterocyclic benzo compound and comprises a plurality of nitrogen-oxygen heterocyclic benzo structures, wherein, the plurality of nitrogen-oxygen heterocyclic benzo structures are connected with each other through at least one structure among covalent bonds, methylene and isopropylidene. The invention further relates to the application of the polymer material.
Description
Technical field
The present invention discloses a kind of macromolecular material, and it is in particular a resin material, and it can be applicable to the insulation layer and the semicure film of circuit substrate.
Background technology
Have the molecular structure of nitrogen oxygen heterocyclic benzopyran compound and synthetic method such as Hitachi in the prior art and change into disclosed Benzoxazine (benzoxazine colophony) in the TaiWan, China patent of delivering 308566, it is by being synthesized by resol, formaldehyde and primary amine, shown in reaction formula 1.The benzoxazine that this patent discloses is that phenyl ring adds a nitrogen oxa-ring structure, yet by the synthesis material of this benzoxazine--resol, formaldehyde and primary amine can't synthesize the long-chain and the nitrogen oxa-toroidal molecule structure of bond continuously.
R：-CH
3or-Ph-
(reaction formula 1)
TaiWan, China patent I243834 proposes the constructional variant derivative of benzoxazine, shown in reaction formula 2.Yet it still adds the reaction product of primary amine and formaldehyde for phenolic aldehyde, or polyphenol adds the reaction product of primary amine and formaldehyde.Have only four nitrogen oxa-rings at most in the molecular structural formula of the benzo-oxazine derivative that this patent proposes, can't produce the molecule that comprises more nitrogen oxa-ring structures, also can't produce the long-chain polymer of continuous a plurality of nitrogen oxa-ring key knots.
(reaction formula 2)
Summary of the invention
Main purpose of the present invention is to disclose a kind of macromolecular material, and this macromolecular material is the nitrogen oxa-ring benzopyran compound of a long-chain and continuous bond.
Based on above-mentioned purpose of the present invention, the present invention discloses a macromolecular material, this macromolecular material is to comprise two or more nitrogen oxa-ring benzo structures, form a long-chain and the nitrogen oxa-ring benzopyran compound of bond continuously by covalent linkage, methylene radical or isopropylidene bond between one nitrogen oxa-ring benzo structure of this macromolecular material and adjacent another nitrogen oxa-ring benzo structure, see also formula one to shown in the formula six.
(formula one)
Wherein, n is any positive integer, and R1 can be a covalent linkage, at least one methylene radical (CH2-) or at least one isopropylidene (C (CH3) 2-).See also formula two, it equals 5 and the macromolecular compound structural formula of R1 when being a covalent linkage for n in formula one structure.
(formula two)
In addition, the disclosed macromolecular compound of the present invention also can be down the compound of array structure, sees also formula three and formula four.
(formula three)
Wherein, n is any positive integer, and R1 can be a covalent linkage, at least one methylene radical (CH2-) or at least one isopropylidene (C (CH3) 2-).See also formula four, its for n equal 3 and R1 be the structural formula of a covalent linkage.
(formula four)
See also formula five and formula six, it is two kinds of structural formulas again of the disclosed macromolecular compound of the present invention.
(formula five)
(formula six)
Wherein, n and m are any positive integer, and R1, R2 can be a covalent linkage, at least one methylene radical (CH2-) and at least one isopropylidene structures such as (C (CH3) 2-).
Macromolecular material of the present invention is the nitrogen oxa-ring benzopyran compound of continuous bond, and it has long-chain and multiple nitrogen oxa-ring structure.Nitrogen oxa-ring in this macromolecular material structure can act on linking agent (crosslinking agent), reaches the compound that the bond reaction forms high crosslink density by open loop again.Macromolecular material of the present invention can be applicable to the resin industry, as the insulating layer material, semicure film etc. of common Resins, epoxy application industry such as solid and tinsel substrate.
The nitrogen oxa-ring benzopyran compound of long-chain of the present invention and repeating structure, it is to add that three kinds of raw materials such as primary amine and formaldehyde synthesize by phenol (or phenolic aldehyde).Also reach, be used for synthesizing the phenolic aldehyde of benzoxazine and the structure that raw materials such as primary amine and formaldehyde can't be produced the disclosed macromolecular compound of the present invention in the prior art.
Provide a method of obviously differentiating difference on the macromolecular compound structure that the described benzoxazine of prior art and the present invention create at this.The structural nitrogen oxa-of nitrogen oxygen heterocyclic benzopyran compound is looked around to head, phenyl ring (or naphthalene nucleus) are considered as afterbody, and then can obviously determine the described benzoxazine or derivatives thereof of prior art all is that a link head, tail link tail or the structure two ends of a part group (can be an alkyl, phenyl, naphthyl, dihydroxyphenyl propane base or Bisphenol F base) link a stature respectively or link a tail respectively.Then be the continuous structure that head links tail on the macromolecular compound structure of the present invention, therefore can obviously distinguish the difference of described benzoxazine or derivatives thereof of the technology of having and the disclosed macromolecular compound of the present invention.The described benzoxazine or derivatives thereof of prior art connects the structure that head or tail connects tail for head, therefore can't link down continuously, and it is the structure of head-to-tail the macromolecular compound structure that the present invention created, and therefore can link the compound structure of long-chain continuously.
In addition, this macromolecular material has long-chain and multiple nitrogen oxygen heterocyclic structure because of it, wherein the structural nitrogen oxa-of benzopyran compound ring can provide the reactivity of planting compound open loop bond with it, and this macromolecular material has characteristics such as low-k and low-dielectric loss, flame retardant resistance, long-chain and repeating structure can provide high crosslink density, high glass transition temp, high mechanical strength and stability of material, if have a naphthalene nucleus, naphthalene nucleus can have high molecular and can improve effect such as thermotolerance in the benzopyran compound structure.Further in the molecular structure of the benzo-oxazine derivative of improvement, generally have only two nitrogen oxa-rings compared to the benzoxazine of Prior Art or its in the molecule, at most also have only four nitrogen oxa-rings (as I243834).Macromolecular material of the present invention is the macromolecular material that a plurality of nitrogen oxa-ring benzopyran compounds are polymerized, it is to have a plurality of nitrogen oxa-rings (can greater than four nitrogen oxa-rings) and the cascaded structure of bond mutually, higher reactivity and stability of material can be provided, more a plurality of nitrogen oxa-rings have more reactive functional group base, can increase W-response.In sum, macromolecular compound of the present invention has obvious improvement.
Therefore, the macromolecular material (nitrogen oxa-ring benzopyran compound) of the present invention's creation has industry applications, novelty and progressive.
Another object of the present invention is to disclose the making method of aforementioned macromolecular material, benzoxazine in prior art is to use three kinds of main raw materials to synthesize, macromolecular material of the present invention is to use two kinds of main raw materials to synthesize, and can reach effects such as reducing by product generation and raising transformation efficiency.
Based on above-mentioned purpose of the present invention, the present invention discloses a kind of making method of macromolecular material, and it is synthesized by phenol amine (Aminophenol) and formaldehyde two kinds of main raw materials such as (Methanal).Described phenol amine can comprise following any one structural formula:
Wherein, R can be hydrocarbon or aromatic series.
Described phenol amine be have on the phenyl ring monohydroxy (OH) and an amido (compound NH2), wherein this amido can be ortho position (ortho), a position (meta), contraposition (para) equipotential to (orientation) with respect to this hydroxyl.Wherein, position and contraposition between this amido is preferably with respect to this hydroxyl.Wherein, this phenyl ring can pass through structures such as naphthalene nucleus, anthracene nucleus or phenanthrene ring and substitutes it.Described phenol amine is and another adjacent phenol amine bond, and formaldehyde provides the carbon atom in the nitrogen oxa-ring structure, forms bond each other between a plurality of phenol amine molecules, can form high molecular long-chain compound, that is have a plurality of nitrogen oxygen heterocyclic benzopyran compounds.Described phenol amine be can with another phenol amine bond of same structure, in addition, described phenol amine also can with another phenol amine bond of dissimilar structure.
Disclosed benzoxazine is by three kinds of basic raw materials in the prior art: phenol, primary amine and formaldehyde are formed, shown in reaction formula 1.The dihydro of mentioning in the method for making as disclosed laminated plates in the TaiWan, China patent 308566-1, the 3-benzoxazine colophony, so these three kinds of raw materials can't produce a plurality of repetitions and long-chain banded nitrogen oxa-ring benzopyran compound.In addition, also can't synthesize a plurality of repetitions and long-chain banded nitrogen oxa-ring benzopyran compound via raw materials such as resin modified phenol resin and primary amine and formaldehyde, shown in reaction formula 2, three phenol molecules and three aniline molecules add that six formaldehyde molecules form three benzoxazine molecules, the nitrogen oxa-ring benzo molecular structure of the non-long-chain bond of this benzoxazine molecule.
The making raw material of the disclosed nitrogen oxygen of the present invention heterocyclic benzopyran compound only needs phenol amine and two kinds of basic raw materials of formaldehyde, wherein this phenol amine be a benzene ring structure and have at least one hydroxyl (OH) and at least one amido (NH2), this phenol amine can form bond with another phenol amine.Concrete, amido on the hydroxyl on the first phenol amine and the second phenol amine and two formaldehyde reactions form first six nitrogen oxa-ring key knot molecular structure (seeing also reaction formula 3) that encircles, hydroxyl on the second phenol amine and the amido on the triphenol amine and two formaldehyde reactions form second nitrogen oxa-ring key knot, wherein formaldehyde is as the carbon source in the above-mentioned bond process, that is required carbon atom when providing this nitrogen oxa-ring benzopyran compound structure to form.Shown in reaction formula 4, three phenol amine and four formaldehyde can form the nitrogen oxa-ring benzo molecular structure of a long-chain bond.Relatively reaction formula 2 and reaction formula 4 can be distinguished the difference of the present invention and prior art easily.In like manner, provide carbon atom can form a long-chain macromolecular compound by formaldehyde between a plurality of phenol amine with a plurality of nitrogen oxa-ring key knots.
(reaction formula 3)
(reaction formula 4)
Another aspect of the disclosed nitrogen oxygen of the present invention heterocyclic benzopyran compound is as follows, the carbon atom that amido on hydroxyl on the one phenol amine and another phenol amine adds a formaldehyde to be provided can act on the nitrogen oxygen heterocyclic benzene ring structure (seeing also reaction formula 5) that forms five rings in the nitrogen oxa-ring benzopyran compound, can be by the carbon atom on the hydroxyl between a plurality of phenol amine and amido and the formaldehyde in conjunction with the phenyl ring molecular structure that forms long-chain bond and multiple nitrogen oxa-ring (five rings), that is nitrogen oxa-ring benzopyran compound of the present invention (formula four).In addition, the nitrogen oxa-ring benzopyran compound that the present invention discloses is the high-molecular weight compound, it has a plurality of nitrogen oxygen heterocyclic benzene ring structures that are connected, nitrogen oxa-ring on this benzene ring structure can be planted linking agent or Resins, epoxy effect with it, because of it has the structure of long-chain, therefore has stronger cross-linking density and stronger physical strength, in addition, because of having a plurality of nitrogen oxa-ring structures in its a part, have more reactive functional group base, therefore have preferable reactivity.
(reaction formula 5)
The disclosed nitrogen oxa-of the present invention ring benzopyran compound can make phenol amine and formaldehyde effect form nitrogen oxa-ring benzopyran compound in manufacturing processed under cold condition.In addition, in order to promote can also heat up heating or add the transformation efficiency that modes such as catalyzer promote reactant phenol amine and formaldehyde of transformation efficiency, wherein this catalyzer can be selected an acidic catalyst and basic catalyst for use.
Nitrogen oxa-ring benzopyran compound of the present invention has following advantage:
(1) have the nitrogen oxygen heterocyclic benzo structure of long-chain and repeating structure, its a plurality of nitrogen oxa-ring structures have further bonding interaction, can plant linking agent with it or Resins, epoxy is done further reaction;
(2) have good low-k and low-dielectric loss characteristic;
(3) has agent of low hygroscopicity;
(4) has thermotolerance.
(5) has high crosslink density.
(6) has high mechanical strength.
(7) has more reactive functional group base.
(8) has preferable reactivity.
Another purpose of the present invention is to disclose a kind of resin to be formed, and this resin has low-k and characteristics such as low-dielectric loss, agent of low hygroscopicity and halogen element.This resin is formed various kenels such as can be liquid resin solution (Varnish), the film (film) of semicure, solid-state insulation layer.
Based on above-mentioned purpose of the present invention, the present invention discloses a resin, and it comprises macromolecular material of the present invention and at least a linking agent (crosslinking agent).
Described linking agent is to act on and this macromolecular material forms bond, be preferably with this macromolecular material on the effect of nitrogen oxa-ring make its open loop and bond each other.
Described linking agent can be cyanate (Cyanate ester), isocyanic ester (Isocyanate ester), resol (Phenol Novolac resin), amino-complex, anhydride compound, poly-phenolic group ether (Polyphenylether), polyphenylene oxide (Polyphenylene oxide).Wherein said amino-complex can be acid amides, two cyanogen diamide (Dicyandiamide; DICY), diaminodiphenylsulfone(DDS) (Diaminodiphenylsulfone, DDS), MDA etc.Described resol can be DCPD-type phenolic resin.Described anhydride compound can be MTHPA, PA, NMA, styrene-maleic anhydride (styrene-maleic-anhydride; SMA) etc.Wherein, described linking agent for have-C=N-or-the isostructural compound of C ≡ N (as cyanate and isocyanic ester etc.), can do open loop and bond reaction again with the nitrogen oxa-ring on the nitrogen oxa-ring benzopyran compound of the present invention, the resin composition that its reaction back forms has characteristics such as low-k and low-dielectric loss, and this resin composition has more a spot of hydroxyl (OH), make it have lower water absorbability, can improve the stability of material that this resin is formed.
Resin of the present invention can further comprise compositions such as Resins, epoxy, fire-retardant compound, catalyzer, inorganic filler, toughner, solvent, tensio-active agent.
Described Resins, epoxy comprises dihydroxyphenyl propane (bisphenol-A) Resins, epoxy, Bisphenol F (bisphenol-F) Resins, epoxy, bisphenol S (bisphenol-S) Resins, epoxy, phenolic aldehyde (phenol novolac) Resins, epoxy, bisphenol-A phenolic (bisphenol-A novolac) Resins, epoxy, ortho-cresol (O-cresol novolac) Resins, epoxy, trifunctional base (trifunctional) Resins, epoxy, four functional groups (tetrafunctional) Resins, epoxy, multiple functional radical (multifunctional) Resins, epoxy, Dicyclopentadiene (DCPD) Resins, epoxy (Dicyclopendiene epoxy resin; DCPD), phosphorous epoxy resin, p-Xylol Resins, epoxy (P-xylene epoxy resin), naphthalene epoxy resins (Naphthalene epoxy resin), benzopyrone-type Resins, epoxy.
Described fire-retardant compound is the compound with flame retardant resistance element or flame retardant resistance functional group, its can with epoxy or stiffening agent bond.This fire-retardant compound can be P contained compound, nitrogenous compound, bromine-containing compound.Wherein, P contained compound system can be triphenylphosphate (Tri-phenyl phosphate), bis-phenol diphenyl phosphoester (Bisphenol diphenyl phosphate), ammonium polyphosphate (Ammoniumpoly phosphate), Resorcinol two (diphenyl phosphoester) (Hydroquinone bis-(diphenylphosphate), three (2-carbonic acid ethyl) phosphine (Tris (2-carboxyethyl) phosphine, TCEP), tricresyl phosphate (2-chloropropyl) ester (TCPP), trimethyl phosphite 99 (Trimethyl phosphate, TMP), dimethyl methyl phosphonate (Dimethyl methylphosphonate, DMMP), Resorcinol xylyl phosphoric acid ester (resorcinol dixylenylphosphate, RDXP), 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) etc.
Wherein, preferable P contained compound has following structural person:
J=wherein
Or J=
This P contained compound has following advantage, preferable heat-resistant stability and lower water absorbability.General known technology uses DOPO directly to combine with Resins, epoxy as additive, understands the residual hydroxyl functional group, this hydroxyl-functional base also with water molecules bond, the water absorbability of increase Resins, epoxy.P contained compound of the present invention is to engage with PN, BPAN or resol phenolic aldehyde such as (resol) earlier, and this P contained compound has more a spot of hydroxyl-functional base, that is has more a spot of active hydrogen atom, is difficult for absorbing moisture water-absorbent is reduced.In addition, add the thermo-cracking temperature that this fire-retardant compound can improve described semicure film, the stiffening agent of planting compared to it has preferable thermotolerance.
Described nitrogenous compound can be aminotriazine resol (Amino triazine novolac, ATN), melamine cyanurate (Melamine cyanurate), trihydroxy-ethyl isocyanate (Tri-hydroxyethylisocyanurate).
In addition, this resin is formed also can comprise the environmental regulation bromine compounds of the halogen-containing element of forbidding not as yet, as contain the stiffening agent of small amount of bromine atom or bromine group, this bromated compound can be tetrabromo third diphenol (TBBPA), tetrabromo hexanaphthene, hexabromo cyclodecane and 2,4,6-three (tribromophenoxy)-1,3, the 5-triazine.Because some discover halogen-containing Resins, epoxy under temperature of combustion (＜1,000 ℃) improperly, may produce deleterious dioxin (dioxin) and furans (furane) etc. and be harmful to carcinogenic gas, cause the pollution of environment.Therefore the preferable implementation condition of resin of the present invention is not bromated fire-retardant compound.
Fire-retardant compound of the present invention provides described resin to have flame retardant resistance element or functional group, and it is nonflammable that this resin groups is formed under the high temperature.Macromolecular material of the present invention itself has flame retardant resistance, but still not enough, and this resin needs further to add fire-retardant compound makes this resin increase flame retardant resistance and heat-resisting flame retardancy.So, epoxy of the present invention can have flame retardant resistance element or functional group, this epoxy also can not have flame retardant resistance element or functional group.Extra interpolation fire-retardant compound is incorporated into epoxy and the aromatic ester stiffening agent can guarantee that this resin has stable thermotolerance and flame retardant resistance.
Described hardening accelerator (or claiming catalyst, catalyzer) is to comprise imidazoles (imidazole), boron trifluoride amine compound, tonsilon triphenylphosphine (ethyltriphenyl phosphonium chloride), methylimidazole (2-methylimidazole; 2MI), diphenyl-imidazole (2-phenyl-1H-imidazole; 2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole; 2E4MZ), triphenylphosphine (triphenylphosphine; TPP) with 4-dimethyl amine yl pyridines (4-dimethylaminopyridine; DMAP) wherein a kind of or its composition.
The main effect of described resin interpolation catalyzer is to accelerate the reactivity of each composition in the resin.
Described inorganic filler is the person of one at least who comprises silicon-dioxide, molten state silicon-dioxide, aluminum oxide, magnesium oxide, magnesium hydroxide, lime carbonate, talcum powder (talc), clay (clay), aluminium nitride, boron nitride, aluminium hydroxide, aluminum silicon carbide, silicon carbide, yellow soda ash, titanium dioxide, zinc oxide, zirconium white, quartz, diamond dust, class diamond dust, graphite, calcined kaolin.This inorganic filler can be ball-type inorganic filler or non-regular pattern composite inorganic filler, and this inorganic filler particle diameter can be the following particle powder of 100 μ m, and it is preferably the particle powder of 1～20 μ m, and the best is the particle powder of the following nano-scale of 1 μ m.
The main effect that described resin adds inorganic filler be to increase thermal conductivity, this resin of modulation of this resin thermal expansivity, improve the characteristics such as physical strength of this resin.
Described solvent is to comprise toluene, acetone, methyl ethyl ketone (MEK), pimelinketone (SC) and propylene glycol monomethyl ether (propylene glycol monomethyl ether; PM), dimethyl formamide (N, N-dimethylformamide, DMF), N,N-DIMETHYLACETAMIDE (Dimethylacetamide, DMAC) etc.
Described tensio-active agent is to comprise silane coupling agent, siloxanes coupler, titanate coupler, amino containing silane coupler etc., and this tensio-active agent is to be used for promoting described inorganic filler uniformly dispersed in solution.
A further object of the present invention is to disclose a kind of resin, and it is made up of macromolecular material of the present invention and hardening accelerator.
Based on above-mentioned purpose of the present invention, the present invention discloses another resin, and it is to comprise macromolecular material of the present invention and at least a hardening accelerator, that is makes the ring open loop of nitrogen oxa-and the self-polymerization of this macromolecular material by hardening accelerator.
A further object of the present invention is to disclose a semicure film, and this semicure film is to have low-k and characteristics such as low-dielectric loss, agent of low hygroscopicity and halogen element.
Based on above-mentioned purpose of the present invention, the present invention discloses a kind of semicure film, and it comprises a resin.
Described resin can be thermosetting resin or thermoplastic resin.This thermosetting resin is to comprise macromolecular material of the present invention.
This resin places on a polyethylene terephthalate (PET, the polyethylene terephthalate) film and is heated and forms the semicure film.
Another purpose of the present invention is to disclose a laminated wood, and the insulation layer of this laminated wood has characteristics such as low-k and low-dielectric loss, is applicable to the circuit card of high-speed high frequency rate signal transmission.
Based on above-mentioned purpose of the present invention, the invention provides a kind of laminated wood, it comprises at least one tinsel laminate and at least one insulation layer.Described tinsel laminate can be the tinsel laminate of metal such as copper, aluminium, nickel, platinum, silver, gold or its alloy, and is right, with regard to material behavior and cost for considering that this tinsel laminate is preferably copper foil plate.This insulation layer is to be fitted at least one tinsel laminate and removed described PET film by the disclosed semicure film of the present invention, and with this semicure film and at least one tinsel laminate the semicure film on this tinsel laminate that is heating and curing under the High Temperature High Pressure makes it form insulation layer, this insulation layer and described tinsel laminate tight joint.
Laminated wood of the present invention has following advantage: good heat-resisting flame retardancy, agent of low hygroscopicity, low-k and low-dielectric loss, higher thermal conductivity, preferable thermal expansivity, preferable physical strength and the feature of environmental protection of halogen element.This laminated wood further can form a circuit card after making processing procedure processing such as circuit, this circuit card with can operate under the harsh environment such as high temperature, high humidity after electronic component engages, and do not influence its quality.
A further object of the present invention is to disclose a semicure film, and this semicure film has characteristics such as high mechanical strength, low-k and low-dielectric loss, agent of low hygroscopicity and halogen element.
Based on above-mentioned purpose of the present invention, the present invention discloses a kind of semicure film again, and it comprises a reinforcement material and a resin.
Described resin can be thermosetting resin or thermoplastic resin.This thermosetting resin comprises macromolecular material of the present invention.
Described reinforcement material can be filamentary material, weaves cotton cloth and tNonwovens, and as glasscloth etc., it can increase the physical strength of this semicure film.Further, this reinforcement material can comprise silane coupling agent or siloxanes coupler preprocessing process, as the pretreated glasscloth of silane coupling agent.
Described semicure film forms a curing film or a solid-state insulation layer via adding heat solidifiable under heat or high temperature and the high pressure, if contain solvent, this solvent can volatilize in the heat program and remove in the wherein said resin.
Another purpose of the present invention is to disclose a laminated wood, and the insulation layer of this laminated wood has characteristics such as low-k and low-dielectric loss, is applicable to the circuit card of high-speed high frequency rate signal transmission.
Based on above-mentioned purpose of the present invention, the invention provides a kind of laminated wood, it comprises two or more tinsel laminates and at least one insulation layer.Described tinsel laminate can be the tinsel laminate of metals such as copper, aluminium, nickel, platinum, silver, gold or its alloy, this insulation layer is to be solidified under High Temperature High Pressure by the disclosed semicure film of the present invention to form, and this insulation layer generation type can be this semicure film and coincides and form in pressing between two tinsel laminates and under by high temperature and high pressure.So, be consideration with regard to material behavior and cost, this tinsel laminate is preferably copper foil plate.
Laminated wood of the present invention has following advantage: good heat-resisting flame retardancy, agent of low hygroscopicity, low-k and low-dielectric loss, higher thermal conductivity, preferable thermal expansivity, preferable physical strength and the feature of environmental protection of halogen element.This laminated wood further can form a circuit card after making processing procedure processing such as circuit, this circuit card with can operate under the harsh environment such as high temperature, high humidity after electronic component engages, and do not influence its quality.
Embodiment of the present invention will be further described by following embodiment.
Embodiment
The macromolecular material of first embodiment of the present invention (nitrogen oxa-ring benzopyran compound) sees also formula seven:
(formula seven)
This macromolecular material is to have the bond polyphone formation to each other of a plurality of nitrogen oxygen heterocyclic benzopyran compound monomers, and these a plurality of nitrogen oxa-rings can be done further open loop bond reaction again with linking agent.Wherein, the nitrogen oxa-ring structure of this macromolecular material is the hexagonal ring, and it is Sauerstoffatom of bond, a nitrogen-atoms and two carbon atoms again on the phenyl ring main structure, and this nitrogen-atoms is another phenyl ring main structure of bond again.
The macromolecular material of second embodiment of the invention, see also formula eight, it is similar to the described macromolecular material of first embodiment (formula seven) basically, difference is in the nitrogen oxa-ring that has the five rings in the described macromolecular material of present embodiment (formula eight), that is in formula one structural formula when R1 be the structural formula that a covalent linkage and n equal five.In like manner, the n value equals 10 in formula one structural formula, and its structural formula promptly has 10 nitrogen oxa-ring structures.Therefore, the disclosed macromolecular material of the present invention can be the benzopyran compound structure with a plurality of nitrogen oxa-ring key knots, (TaiWan, China patent I243834) has only four nitrogen oxa-rings at most in prior art, the macromolecular material that the macromolecular material that the present invention discloses can have more nitrogen oxa-ring and be bonded into by bond to each other.
(formula eight)
The macromolecular material of the 3rd embodiment of the present invention sees also formula nine,
(formula nine)
Wherein, the nitrogen oxa-ring structure of this macromolecular material is the five rings structure, and it is Sauerstoffatom of bond, a nitrogen-atoms and carbon atom again on the phenyl ring main structure, and this nitrogen-atoms is another phenyl ring main structure of bond again.
The macromolecular material of the 4th embodiment of the present invention sees also formula ten.
(formula ten)
The macromolecular material of the 5th embodiment of the present invention sees also formula 11,
(formula 11)
The macromolecular material manufacture method of the 6th embodiment of the present invention, it is by being synthesized by a plurality of first phenol amine and a plurality of second phenol amine and a plurality of formaldehyde.The described first phenol amine is 2-hydroxyl-4-amido-phenol (formula 12), and the described second phenol amine is a 4-phenol amine (formula 13), the first phenol amine and the second phenol amine and formaldehyde is added to mix in the solution to stir can form a macromolecular compound (formula 14).
(formula 12)
(formula 14)
The macromolecular material of the 7th embodiment of the present invention please see formula 15 for details.
(formula 15)
The resin of the 8th embodiment of the present invention, it comprises embodiment one described macromolecular material (formula seven) and cyanate, polyfunctional epoxy resin, phosphorous stiffening agent, spherical silica and diphenyl-imidazole.
The semicure film of the 9th embodiment of the present invention comprises the described resin of the 8th embodiment, and this resin is to place on the PET film and be heated into the semicure film.
The laminated wood of the tenth embodiment of the present invention, it comprises two-layer copper foil plate and one deck semicure film, and wherein this semicure film is the described semicure film of the 9th embodiment.Wherein, the one side that this semicure film does not contain the PET film is to fit in one first copper foil plate, remove this PET film and this semicure film is fitted in one second copper foil plate again, make the semicure film between this first copper foil plate and second copper foil plate solidify to form insulation layer via high temperature and highly compressed pressing plate processing procedure, combining closely between this insulation layer and first copper foil plate and second copper foil plate forms described laminated wood.The described laminated wood of present embodiment is not limited to two above-mentioned copper foil plates and does with a semicure film and combine, and also a plurality of copper foil plates and a plurality of semicure film can be made joint.
The described laminated wood of present embodiment can further be made into circuit card, can reach with the procedure for processing circuit board of prior art, seldom does at this and gives unnecessary details.
The semicure film of the 11 embodiment of the present invention, it comprises a glasscloth and the described resin of the 8th embodiment, and this resin forms the semicure attitude by heated baking and combines with this glasscloth.
The laminated wood of the 12 embodiment of the present invention, it comprises two-layer copper foil plate and three layers of semicure film, and wherein this semicure film is the described semicure film of the 9th embodiment.Wherein, this semicure film is between two copper foil plates, also reach the three layers of semicure film that coincide on the copper foil plate, the copper foil plate that coincides again on these three layers of semicure films makes these three layers of semicure films solidify and combines with copper foil plate via high temperature and highly compressed pressing plate processing procedure to form described laminated wood.
The described laminated wood of present embodiment can further be made into circuit card, can reach with the procedure for processing circuit board of prior art, seldom does at this and gives unnecessary details.
By the above detailed description of preferred embodiments, be to wish to know more to describe feature of the present invention and spirit, and be not to come category of the present invention is limited with above-mentioned disclosed preferred embodiment.On the contrary, its objective is that hope can contain in the category of the claim that is arranged in institute of the present invention desire application of disclosed various possible changes of content of the present invention and tool equality.
Claims (20)
1. macromolecular material, it is the nitrogen oxa-ring benzopyran compound of a long-chain, and it comprises a plurality of nitrogen oxa-ring benzo structures, and the above-mentioned at least a structure by covalent linkage, methylene radical and isopropylidene between these a plurality of nitrogen oxa-ring benzo structures interlinks.
2. macromolecular material as claimed in claim 1, it is the reaction product of phenol amine and formaldehyde.
3. macromolecular material as claimed in claim 1, wherein, described macromolecular material is at least one in the following structural:
Wherein, n and m are any positive integer, R1, R2 be a covalent linkage ,-CH2-or-C (CH3) 2-functional group.
4. macromolecular material as claimed in claim 2, wherein, described phenol amine is at least one in the following structural:
5. macromolecular material as claimed in claim 3, wherein, described macromolecular material is one in the following structural:
6. resin, it comprises the described macromolecular material of claim 1 and at least one linking agent.
7. resin as claimed in claim 6, wherein, described linking agent is cyanate, isocyanic ester, resol, amino-complex, anhydride compound, poly-phenolic group ether, polyphenylene oxide; Wherein said amino-complex is acid amides, two cyanogen diamide, DDS or MDA; Described resol is DCPD-type resol; Described anhydride compound is the person of one at least of MTHPA, PA, NMA, styrene-maleic anhydride.
8. resin as claimed in claim 6, this resin further comprise the person of one at least of Resins, epoxy, fire-retardant compound, hardening accelerator, inorganic filler, toughner, solvent.
9. resin as claimed in claim 8 is formed, wherein, described Resins, epoxy is the person of one at least in bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-s epoxy resin, novolac epoxy, bisphenol-A phenolic Resins, epoxy, o-cresol epoxy resin, trifunctional basic ring epoxy resins, four functional group's Resins, epoxy, polyfunctional epoxy resin, Dicyclopentadiene (DCPD) Resins, epoxy, phosphorous epoxy resin, p-Xylol Resins, epoxy, naphthalene epoxy resins, the benzopyrone-type Resins, epoxy.
10. resin as claimed in claim 8 is formed, wherein, described fire-retardant compound is triphenylphosphate, bis-phenol diphenyl phosphoester, ammonium polyphosphate, Resorcinol two (diphenyl phosphoester), three (2-carbonic acid ethyl) phosphine, tricresyl phosphate (2-chloropropyl) ester, trimethyl phosphite 99, dimethyl methyl phosphonate, Resorcinol xylyl phosphoric acid ester, 9, the 10-dihydro-9-oxy is assorted-and the person of one at least in the 10-phospho hetero phenanthrene-10-oxide compound, aminotriazine resol, melamine cyanurate, trihydroxy-ethyl isocyanate.
11. resin as claimed in claim 8, wherein, described hardening accelerator comprises the person of one at least in imidazoles, boron trifluoride amine compound, tonsilon triphenylphosphine, methylimidazole, diphenyl-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine and the 4-dimethyl amine yl pyridines.
12. resin as claimed in claim 8, wherein, described inorganic filler is the person of one at least in silicon-dioxide, molten state silicon-dioxide, aluminum oxide, magnesium oxide, magnesium hydroxide, lime carbonate, talcum powder, clay, aluminium nitride, boron nitride, aluminium hydroxide, aluminum silicon carbide, silicon carbide, yellow soda ash, titanium dioxide, zinc oxide, zirconium white, quartz, diamond dust, class diamond dust, graphite, calcined kaolin, spherical silica, the ball-type aluminum oxide.
13. resin as claimed in claim 8, wherein, described toughner is rubber particles.
14. as the resin as described in the claim 8, wherein, described solvent is the person of one at least in toluene, acetone, methyl ethyl ketone, pimelinketone and propylene glycol monomethyl ether, dimethyl formamide, the N,N-DIMETHYLACETAMIDE.
15. a semicure film, it comprises one of them person of the described resin of claim 6 to 14, and this resin is to be baked into the semicure attitude via heat.
16. a laminated wood, it comprises at least one tinsel laminate and at least one insulation layer, and this at least one tinsel laminate and this at least one insulation layer are staggered repeatedly to be put, and wherein, this insulation layer is to be solidified by the described semicure film of claim 15 to form.
17. a circuit card, it comprises the described laminated wood of claim 16.
18. semicure film, it is one of them person who comprises a reinforcement material and the described resin of claim 6 to 14, this reinforcement material be weave cotton cloth, the person of one at least of tNonwovens, glasscloth, wherein this resin is attached to this reinforcement material, and this reinforcement material and resin are baked into the semicure attitude via heat.
19. a laminated wood, it comprises a plurality of tinsel laminates and at least one insulation layer, and these a plurality of tinsel laminates and this at least one insulation layer are staggered repeatedly to be put, and wherein, this insulation layer is to be solidified by the described semicure film of claim 18 to form.
20. a circuit card, it comprises the described laminated wood of claim 19.
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| CN2009102655083A CN102108068A (en) | 2009-12-25 | 2009-12-25 | Polymer material and application thereof |
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Cited By (8)
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| JP2012171971A (en) * | 2011-02-17 | 2012-09-10 | Jfe Chemical Corp | Thermosetting resin composition and cured product thereof |
| WO2013033955A1 (en) * | 2011-09-09 | 2013-03-14 | 复旦大学 | Benzoxazine monomer comprising benzocyclobutenyl functional group, synthetic method therefor and use thereof |
| CN103131007A (en) * | 2011-11-22 | 2013-06-05 | 台光电子材料股份有限公司 | Thermosetting resin composition and laminated plate and circuit board employing same |
| CN103635532A (en) * | 2011-07-14 | 2014-03-12 | 积水化学工业株式会社 | White curable composition for optical semiconductor device, molded object for optical semiconductor device, and optical semiconductor device |
| CN105061417A (en) * | 2015-07-30 | 2015-11-18 | 哈尔滨工程大学 | Monoamine-bisphenol type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof |
| CN105111222A (en) * | 2015-07-30 | 2015-12-02 | 哈尔滨工程大学 | Triphenol quinoxalinyl benzoxazine monomer and preparation method therefor |
| JP2018177718A (en) * | 2017-04-17 | 2018-11-15 | 学校法人近畿大学 | Benzoxazine compound and benzoxazine resin |
| CN108102072B (en) * | 2017-12-21 | 2021-03-02 | 淮北绿洲新材料有限责任公司 | Castor oil modified benzoxazine resin and preparation method thereof |
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2009
- 2009-12-25 CN CN2009102655083A patent/CN102108068A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012171971A (en) * | 2011-02-17 | 2012-09-10 | Jfe Chemical Corp | Thermosetting resin composition and cured product thereof |
| CN103635532A (en) * | 2011-07-14 | 2014-03-12 | 积水化学工业株式会社 | White curable composition for optical semiconductor device, molded object for optical semiconductor device, and optical semiconductor device |
| CN103635532B (en) * | 2011-07-14 | 2016-01-06 | 积水化学工业株式会社 | Optical semiconductor device white hardening composition, optical semiconductor device molding and optical semiconductor device |
| WO2013033955A1 (en) * | 2011-09-09 | 2013-03-14 | 复旦大学 | Benzoxazine monomer comprising benzocyclobutenyl functional group, synthetic method therefor and use thereof |
| CN103131007A (en) * | 2011-11-22 | 2013-06-05 | 台光电子材料股份有限公司 | Thermosetting resin composition and laminated plate and circuit board employing same |
| CN103131007B (en) * | 2011-11-22 | 2015-06-17 | 台光电子材料股份有限公司 | Thermosetting resin composition and laminated plate and circuit board employing same |
| CN105061417A (en) * | 2015-07-30 | 2015-11-18 | 哈尔滨工程大学 | Monoamine-bisphenol type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof |
| CN105111222A (en) * | 2015-07-30 | 2015-12-02 | 哈尔滨工程大学 | Triphenol quinoxalinyl benzoxazine monomer and preparation method therefor |
| CN105061417B (en) * | 2015-07-30 | 2017-11-21 | 哈尔滨工程大学 | Monoamine bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine and preparation method thereof |
| CN105111222B (en) * | 2015-07-30 | 2017-11-21 | 哈尔滨工程大学 | Three phenolic quinoxalinyl benzoxazine monomers and preparation method thereof |
| JP2018177718A (en) * | 2017-04-17 | 2018-11-15 | 学校法人近畿大学 | Benzoxazine compound and benzoxazine resin |
| CN108102072B (en) * | 2017-12-21 | 2021-03-02 | 淮北绿洲新材料有限责任公司 | Castor oil modified benzoxazine resin and preparation method thereof |
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Application publication date: 20110629 |