CN1239615C - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
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- CN1239615C CN1239615C CN00819862.4A CN00819862A CN1239615C CN 1239615 C CN1239615 C CN 1239615C CN 00819862 A CN00819862 A CN 00819862A CN 1239615 C CN1239615 C CN 1239615C
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- resin composition
- curable resin
- polyphenylene oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Graft Or Block Polymers (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to curable resin composition, which comprises polyphenylether resin, a crosslinking agent and at least one kind of phosphorus compounds. The latter is selected from melamine polyphosphate ester with a degree of polymerization of 3 or higher and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide derivatives with a reactive substituent. The weight ratio of the polyphenylether resin to the crosslinking agent to the phosphorus compounds is (10 to 98): (90 to 2): (10 to 80), wherein every 100 parts by weight of the composition of the polyphenylether resin and the crosslinking agent comprise 10 to 98 parts by weight of the polyphenylether resin and 2 to 90 parts by weight of the crosslinking agent. The cured products comprises the curable resin composition and the curable composite material of base material. Although the halogen is not contained, the curable resin composition of the present invention can maintain the heat-resistance characteristic of the polyphenylether resin and have sufficient fire resistance.
Description
Technical field
The present invention relates to a kind of curable resin composition, its film and by solidifying the curable resin composition that described curable resin composition obtains with halogen of flame retardant resistance.In addition, the present invention relates to comprise the curable composites of described curable resin composition and strongthener, by solidifying the cured composite material that described curable composites obtains, comprise the laminate of described cured composite material and tinsel and the tinsel of resin-coating.
Curable resin composition of the present invention has excellent chemical resistant properties after solidifying, dielectric properties, and thermotolerance and flame retardant resistance, and can be in electrician's industry, space and aircraft industry wait and are used as dielectric materials in the field, insulating material, and heat-stable material, structured material, etc.It is particularly useful for the single or double multilayer printed circuit board, flexible print circuit board, and the sequential build circuit card, etc.
Background technology
In recent years, be used for telecommunication, be used for the human consumer and be used for obvious trend miniaturization of industrial field of electronic devices and high density interconnect packing, and so further thermotolerance, dimensional stability and electrical property that improves material therefor of requirement.For example,, used the copper-clad laminate, wherein used thermosetting resin such as phenolic resin and Resins, epoxy as material as printed-wiring board (PWB).Although have good balance quality, the shortcoming of these laminates is to have bad electrical property, especially the dielectric properties in high-frequency region.Have been noted that the polyphenylene oxide as new raw material that can overcome the above problems recently, and attempt they are applied to the copper-clad laminate.
For example, JP-A-61-287739 discloses and has a kind ofly comprised the laminate that the resin combination of polyphenylene oxide and triallyl isocyanurate and/or triallyl cyanurate obtains by curing; JP-B-7-37567 discloses a kind of curable resin composition and laminate by using said composition to obtain that comprises by the polyphenylene oxide of modification with unsaturated carboxylic acid or acid anhydrides and triallyl isocyanurate and/or triallyl cyanurate reaction; And JP-A-64-69628, JP-A-64-69629, JP-A-113425 and JP-A-1-113426 disclose and have comprised three or the polyphenylene oxide of two keys and the curable resin composition of cyanacrylate and/or triallyl cyanurate a kind of comprising.
As the material of the combination that comprises polyphenylene oxide and Resins, epoxy, for example JP-B-64-3223 discloses the curable resin composition that comprises polyphenylene oxide and various Resins, epoxy such as bisphenol A epoxide resin and linear phenolic resin varnish and various solidifying agent such as phenol and amine.In addition, JP-A-2-135216 discloses a kind of comprising by with unsaturated carboxylic acid or anhydride reaction and the polyphenylene oxide of modification, the curable resin composition of polyepoxides and epoxy-curing catalysts, a kind of polyphenylene oxide that comprises melt treatment, the curable resin composition of polyepoxides and epoxy-curing catalysts are disclosed with JP-A-2-166115.
These compositions are used for various electronic materials, common copper-clad laminate, and also in these occasions, the flame retardant resistance of resin is an important performance on the safety point of view of product.So far, as the method that is used to make flame retardant resin, organohalogen compound such as aromatics bromide or epoxy bromide have been used.But organohalogen compound might produce strong toxicity dioxin when they burn, and therefore recently applies stricter regulations at its purposes.
Therefore, in order to deal with these situations, attempted providing flame retardant resistance to the curable resin of described polyphenylene oxide by the compound that uses halogen.As the compound of these halogen, for example metal hydroxides has been proposed, phosphoric acid ester, ammonium polyphosphate.For example, if use metal hydroxides,, be difficult to produce enough flame retardant resistances although this resin keeps the high heat resistance characteristic.In addition, if use phosphoric acid ester, be difficult to when enough flame retardant resistances are provided, keep thermotolerance.In addition, if use ammonium polyphosphate, although provide enough flame retardant resistances when keeping enough flame retardant resistances, weight loss takes place and becomes and can not actually use in impregnated in water the time in solidify material.Therefore, so far, if use the compound of halogen, being difficult to provides enough flame retardant resistances to polyphenylene oxide resin, keeps the thermotolerance characteristic of this resin simultaneously.
The present invention overcomes the above problems, therefore an object of the present invention is to provide a kind of curable resin composition, although not halogen-containing, that is, halogen, it is keeping stable on heating enough flame retardant resistances that has simultaneously.
Disclosure of the present invention
The present invention at first provides a kind of curable resin composition, comprise polyphenylene oxide resin (following being called " component (A) "), linking agent (following being called " component (B) "), with at least a phosphorus compound (following being called " component (C) "), the latter is selected to have the polymerization degree 3 or higher melamine poly phosphate and has reactive substituents and be expressed as 9 of following structural formula (1), and the 10-dihydro-9-oxy is assorted-phosphorus phenanthrene-10-oxide derivative:
(R wherein
1Be vinyl, allyl group, methacrylic or 1-butylene base group; And R
2And R
3Be independently selected from hydrogen atom and C
1-C
6Hydrocarbyl group), component (A) wherein, (B) and content ratio (C) be respectively combination 10-98 part weight of per 100 parts of components by weight percent (A) and component (B), 90-2 part weight and 10-80 part weight; Film with described composition.Curable resin composition of the present invention does not have halogen generally.
At curable resin composition of the present invention in a preferred embodiment, be i as the polyphenylene oxide resin of component (A)) comprise the polyphenylene oxide resin of unsaturated group, and/or the ii) reaction product of polyphenylene oxide resin and unsaturated carboxylic acid and/or acid anhydrides.
Another embodiment preferred of curable resin composition of the present invention is that the linking agent that is used as component (B) is a kind of polyfunctional compound or Resins, epoxy that contains unsaturated link(age).
The second, the invention provides a kind of by solidifying the curable resin composition that described curable resin composition (or its film) obtains.
The 3rd, the invention provides a kind of curable composites that comprises foregoing curable resin combination (or its film) and strongthener, the content ratio of described strongthener is a 5-90% weight.
The 4th, the invention provides a kind of by solidifying the cured composite material that described curable composites obtains.
The 5th, the invention provides a kind of laminate that comprises described cured composite material and tinsel.
The 6th, the invention provides a kind of resin-coating tinsel, comprise tinsel and the film of the described curable resin composition that on the one side of tinsel, forms.
Be used to realize best mode of the present invention
Following more detailed description the present invention.
(resin combination after curable resin composition and the curing)
＜polyphenylene oxide resin 〉
As component (A), promptly, be used for polyphenylene oxide resin of the present invention, for example can mention deriving from 2,6-xylenol homopolymerization poly-(2,6-dimethyl-1, the 4-phenylene ether), the phenylethene grafted copolymer of poly-(2,6-dimethyl-1,4-phenylene ether), 2,6-xylenol and 2,3, the multipolymer of 6-pseudocuminol, 2, the multipolymer of 6-xylenol and 2-methyl-6-phenylphenol, by polymerization 2 in the presence of multifunctional oxybenzene compound, 6-xylenol and the multifunctional polyphenylene oxide resin that obtains, for example, by polymerization 2 in the presence of aniline that replaces or aliphatic secondary amine, 6-xylenol and the nitrogenous polyphenylene oxide resin that obtains for example is disclosed in JP-A-63-301222 and JP-A-1-297428.
About the molecular weight of above-mentioned polyphenylene oxide resin, preferably use in the 0.5g/dl chloroformic solution at 30 ℃ of viscosity number η sp/C those resins in the 0.1-1.0 scope of measuring down.
The polyphenylene oxide resin of mentioning in the present invention comprises the modification of modification, and as the modification of these modifications, can mention i) comprise the polyphenylene oxide resin of unsaturated group (referring to JP-A-64-69628, JP-A-1-113425 and JP-A-1-113426) and the ii) reaction product of polyphenylene oxide resin and unsaturated carboxylic acid and/or acid anhydrides.
In the present invention, in order to improve the consistency with component (B), the especially preferred product i that uses above-mentioned modification) and/or ii), for example, allylation polyphenylene oxide, maleic anhydride modified polyphenylene oxide and analogue are as polyphenylene oxide resin (A).
In the present invention, the content ratio of component (A) is 10-98 part weight preferably, preferred 10-80 part weight, more preferably 20-75 part weight, the combination of per 100 parts of components by weight percent (A) and component (B).Be lower than 10 parts of weight as fruit component (A), cured product, promptly the problem that shock-resistance descends appears in curable resin composition, and surpasses 98 parts of weight as fruit component (A), and the problem that chemical resistant properties descends appears in curable resin composition.
＜linking agent 〉
As component (B), that is, be used for linking agent of the present invention; can mention the compound such as the diallyl phthalate that comprise multifunctional unsaturated link(age), Vinylstyrene, multifunctional acryl compound; multifunctional methacryloyl based compound, polyfunctional isocyanate, multifunctional maleimide; unsaturated polyester, triallyl isocyanurate, triallyl cyanurate; polyhutadiene; styrene butadiene, styrene butadiene-vinylbenzene, etc.These compounds can be separately or are used with two or more mixture.
Resins, epoxy also can be used as component (B).Can use any Resins, epoxy that in molecule, comprises two or more epoxide groups, and known Resins, epoxy can be separately or two or more be used in combination.Can also be used in combination Resins, epoxy and the aforementioned compound that comprises multifunctional unsaturated link(age).
Representative instance as these Resins, epoxy, derive from the glycidyl ether epoxy of the reaction of phenol or pure and mild Epicholorohydrin, derive from the glycidyl epoxies of the reaction of amine or cyanuric acid and Epicholorohydrin, derive from the interior Resins, epoxy of two key oxidations, and analogue.[about the details of these Resins, epoxy, referring to for example, Masaki Shinho: Resins, epoxy handbook, Nikkan KogyoShimbun, Ltd., 1987].
These Resins, epoxy can use with solidifying agent.As solidifying agent, can mention the compound that is usually used in cured epoxy resin, for example, the linear novolac resin of amine type such as Dyhard RU 100 and aromatic amine and phenol type such as phenol, the linear novolac resin of cresols, dihydroxyphenyl propane, with the phenolic resin of nitrogen modification as the aniline modification, melamine-modified, the guanidine modification and polyamide modified phenolic resin.These compounds can be separately or are used with two or more mixture.
Curing catalyst can use with the solidifying agent that is used for component (A) and component (B).As curing catalyst, can mention those and the group initiator that generally are used for Resins, epoxy, the former comprises, for example, imidazolium compounds and the latter comprises, for example, conventional superoxide such as Perhexyne25B.
In the present invention, comprise the compound of multifunctional unsaturated link(age) by use, for example, triallyl isocyanurate and/or triallyl cyanurate can obtain having excellent dielectric properties and stable on heating cured product as component (B).In addition, by using Resins, epoxy, for example, bisphenol A epoxide resin can obtain having the curable resin composition of excellent molding workability as component (B) when solidifying.
In the present invention, the content ratio of component (B) is 90-2 part weight preferably, preferred 90-20 part weight, more preferably 80-25 part weight, the combination of per 100 parts of components by weight percent (A) and component (B).Be lower than 2 parts of weight as fruit component (B), the problem that chemical resistant properties descends appears in curable resin composition, and surpasses 90 parts of weight as fruit component (B), and the problem that shock-resistance descends appears in curable resin composition.
＜phosphorus compound 〉
Being used for component of the present invention (C) is at least a phosphorus compound, is selected to have the polymerization degree 3 or higher melamine poly phosphate and have reactive substituents and be expressed as 9 of following structural formula (1), the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide derivative
(R wherein
1Be vinyl, allyl group, methacrylic or 1-butylene base group, and R
2And R
3Be independently selected from hydrogen atom and C
1-C
6Hydrocarbyl group).
The polymerization degree with the polymerization degree 3 or higher melamine poly phosphate is passed through
31P-NMR determines.
31During P-NMR measures, near the monomer peak that appears on the phosphoric acid standard 0ppm, near the polymer ends peak-10ppm and-near the 20ppm peak, polymkeric substance inside.The intensity of supposing them is respectively X, Y and Z, and the polymerization degree is expressed as (X+Y+Z)/(X+Y/2).Even the modular construction of phosphoric acid can not 100% be keyed on the melamine and may be partly by other nitrogenous compound such as ammonia, acid amides, ethylene diamine, melam, melem, Deng, or metal such as aluminium, magnesium, calcium, Deng replacement, if be keyed to half that part on the melamine surpasses this structure, compound is called the melamine poly phosphate.
In the present invention, do not have the polymerization degree 3 or higher if do not use, preferred 5 or higher melamine poly phosphate, mass loss appears when curable resin composition or laminate are immersed in the water.That is, in the present invention, have the polymerization degree 3 or higher, preferred 5 or higher melamine poly phosphate can be separately or use with two or more mixture.
As can be used for melamine poly phosphate of the present invention, can mention with trade(brand)name PMP-100 (by Nissan Chemical Industries, Ltd. produce), melapur 200 (registered trademark/produce) by DSM Corp., Deng buy those, and these materials can be separately or use with two or more mixture.
Then, about having reactive substituents and being expressed as 9 of said structure formula (1), the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide derivative, can for example mention following material: 9, the 10-dihydro-9-oxy is mixed-10-(allyl group phosphorus) phenanthrene-10-oxide compound, 9, the 10-dihydro-9-oxy is mixed-10-(methacrylic phosphorus)-Fei-10-oxide compound, and 9, the 10-dihydro-9-oxy is mixed-10-(1-butylene base phosphorus) phenanthrene-10-oxide compound, 9, the 10-dihydro-9-oxy is mixed-10-(allyl group phosphorus) (2, the 7-dimethylphenanthrene)-10-oxide compound, 9, the 10-dihydro-9-oxy is mixed-10-(allyl group phosphorus) (1,3,6,8-tetramethyl-phenanthrene)-the 10-oxide compound, with 9, the 10-dihydro-9-oxy is mixed-10-(allyl group phosphorus) (6,8-two-tert-butyl phenanthrene)-10-oxide compound.These can be separately or use with two or more mixture.
It may be noted that if use separately and have the described 9 of reactive substituents at this, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide derivative is as component (C), and preferred the use comprises the compound of multifunctional unsaturated link(age) as component (B).
If use component (C) as powder, powder surface can scribble thermosetting resin such as melamine resin or Resins, epoxy, coupling agent such as silane coupling agent, titanate coupling agent, aluminate coupling agent or zircoaluminate coupling agent, or aerosil such as hydrophobic silicon dioxide aerogel.In addition, carrier such as unsaturated polyester resin or Resins, epoxy can add powder to form paste.In addition, powder can be added with auxiliary flame retardant in advance, foam materials agent or tinting material, for example, melamine, benzoguanamine, acetylguanamine, quadrol, melamine cyanurate, melam, melem, tetramethylolmethane, Dipentaerythritol, talcum, silica, lime carbonate, titanium oxide, aluminium hydroxide, magnesium hydroxide, low-fusing point glass or analogue are to form composite particles.
In the present invention, the content of component (C) is preferably in the combination of per 100 parts of components by weight percent (A) and component (B), 10-80 part weight, and preferred 15-60 part weight is more preferably in the scope of 20-50 part weight.Add-on as fruit component (C) is lower than 10 parts of weight, the obtained flame-retardant deficiency, and surpass 80 parts of weight as the amount of fruit component (C), be difficult to produce matrix material, because for example, curable resin composition obviously raises as the viscosity of varnish, makes varnish not to be infiltrated up in the strongthener.Under the situation in conjunction with two or more components (C), this combination is not limited to any ad hoc fashion and can uses any combination.
＜other component 〉
In curable resin composition of the present invention, except described component (A)-(C), can blend its amount do not damage the filler and the additive of the fundamental property of said composition, purpose is to provide desired properties according to its purposes to said composition.
As these fillers, can mention carbon black, silica, titanium oxide, barium titanate, glass beads, hollow glass ball, etc.As additive, can mention antioxidant, thermo-stabilizer, static inhibitor, softening agent, pigment, dyestuff, tinting material, etc.In addition, can blend one or more non-component (A) and thermoplastic resin (B) or thermosetting resins, for example, and styrene resin such as polystyrene, ABS, SBS, Hydrogenated SBS, etc.
The preparation of＜curable resin composition and curable resin composition 〉
As the method for mixing described component (A)-(C), can use wherein with three kinds of component uniform dissolution or be dispersed in the solvent the solution blending means and wherein component by forcing machine or the melt blended method of alternate manner heating blended.As being used for solution blended solvent, can be separately or two or more be used in combination aromatic solvent such as benzene, toluene and dimethylbenzene, or tetrahydrofuran (THF).
Curable resin composition of the present invention can be made desired form in advance, and this depends on the purposes of said composition.Manufacture method does not specifically limit.Usually, can use the casting method that wherein resin combination is dissolved in for example above-mentioned solvent and makes desired form, or wherein with the resin combination heat fused and make the hot melt method of desired form.
Curable resin composition of the present invention can advantageously use with the form of film.The method of producing this film does not specifically limit; For example, can use a kind of like this method, wherein with component (A)-(C) and other component fusing or uniform dissolution or be dispersed in the solvent if desired, and with melt, on solution or dispersion paint PET film or the analogue, subsequent drying.
Curable resin composition of the present invention can obtain by solidifying above-mentioned curable resin composition.Curing can optionally be selected; For example, can use heat, light, the method for electron rays or analogue of adopting.Undertaken by heating if solidify, temperature is selected from 80-300 ℃ so, and preferred 120-250 ℃, although can change according to the kind of used group initiator.Be about 1 minute-Yue 10 hours heat-up time, preferred 1 minute-5 hours.
This curable resin composition can use by it is laminated on tinsel and/or the metal sheet, as the cured composite material of describing after a while.
(curable composites and cured composite material)
Then, explain that curable composites t of the present invention and its solidify modification, that is, and cured composite material.
＜curable composites 〉
Curable composites of the present invention is characterised in that it comprises curable resin composition of the present invention and strongthener.
As strongthener used herein, various woven fiber glass such as Coarse Mesh Gauze, cloth, cutting mat and paving pad; Woven asbesto, metal fiber cloth and other synthetic or natural inorganic fiber cloth; Derive from the system of knitting or the non-woven fabrics such as the completely aromatic-polyamide-fiber of liquid crystal fiber, Wholly aromatic polyester fiber and polybenzoxazole fibers; Derive from the system of knitting or the non-woven fabrics such as the polyvinyl alcohol fiber of synthon, trevira and acrylic fibre; Natural fiber cloth such as cotton, linen and felt; Natural cellulose type cloth such as carbon cloth, hand-made paper, cotton paper and paper-glass blend tissue paper; Polytetrafluoroethylporous porous membrane and analogue can be used in combination separately or with two or more.
The ratio of strongthener in curable composites is per 100 parts of weight curable composites 5-90 part weight, preferred 10-80 part weight, more preferably 20-70 part weight.If the ratio of strongthener is lower than 5 parts of weight, dimensional stability and intensity after the cured composite material are unsatisfactory, and if the strongthener ratio is higher than 90 parts of weight, the dielectric properties variation of matrix material.
In curable composites of the present invention, can use coupling agent as required to improve the adhesivity on the interface between resin and the strongthener.As this coupling agent, can use commonly used those as silane coupling agent, the titanate coupling agent, aluminium-Ji coupling agent and zircoaluminate coupling agent can be to use.
The production of＜curable composites 〉
Method as production curable composites of the present invention, for example can mention, wherein with component of the present invention (A)-(C) and if desired other component such as above-mentioned coupling agent uniform dissolution be dispersed in aromatic ketone or the mixed solvent of the solvent of other type or these types in, and solution or dispersion is infiltrated up to strongthener, subsequent drying.Component (A)-(C) can then and be infiltrated up in the strongthener.Infiltration is by dipping, coating or alternate manner and realize.If desired, infiltration can repeat repeatedly, and in this case, infiltration can use the multiple solution with different compositions and/or concentration to repeat required resin combination of so final acquisition and resin content.
＜cured composite material 〉
Cured composite material of the present invention can solidify the curable composites that so obtains by heating or alternate manner and obtain.Its production method does not specifically limit; For example, a plurality of sheet materials that can be by the described curable composites of lamination, and they are carried out hot pressing to carry out interlaminar bonding under pressure carry out thermofixation simultaneously and obtain having the cured composite material of desired thickness.Also can be by the cured composite material that will once bond and the combination of solidified matrix material and curable composites obtains having new layer structure.Laminate manufacturing and curing use thermocompressor or alternate manner to carry out simultaneously usually, but they can carry out independently of each other.That is, non-curing or the half-cured composite material that obtains in advance by the laminate manufacturing can solidify by thermal treatment or other processing mode.
If carry out laminate manufacturing and curing simultaneously, can select following operational condition: temperature=80-300 ℃, preferred 150-250 ℃; Pressure=0.1-1,000kg/cm
2, preferred 1-500kg/cm
2Time=1 minutes-10 hours, preferred 1 minute-5 hours.
(laminate)
Laminate of the present invention comprises cured composite material of the present invention and tinsel.As tinsel used herein, can mention Copper Foil and aluminium foil as an example.Its thickness does not specifically limit, but it is preferably at 3-200 μ m, more preferably in the scope of 3-105 μ m.
Method as production laminate of the present invention, for example can mention a kind of like this method, wherein the curable composites of above explanation and tinsel and/or sheet-metal layers are pressed into a kind of layer structure that satisfies the desired use of laminate, under pressure, carry out hot pressing then to carry out interlaminar bonding, carry out the method for thermofixation simultaneously.In laminate of the present invention, curable composites and tinsel can be laminated into any layer of structure.Tinsel can be used as upper layer or middle layer.Except above operation, lamination and curing can repeat repeatedly to form multilayered structure.
Can use tackiness agent to be bonded to tinsel curable or cured composite material on.
As these tackiness agents, can mention epoxy, vinylformic acid, phenol and cyanoacrylate type, but the tackiness agent that can be used for this paper is not limited to these.
Above laminate manufacturing can be carried out under the condition identical with curable composites of the present invention with solidifying.
(resin-coating tinsel)
Curable resin composition of the present invention can be used for forming the resin-coating tinsel.The curable resin composition of the present invention that " resin-coating tinsel " of the present invention forms by tinsel with on the one side of described tinsel is formed.As tinsel used herein, can for example mention Copper Foil and aluminium foil.Its thickness is not particularly limited, but it is preferably at 3-200 μ m, more preferably in the scope of 3-105 μ m.
The method of production resin-coating Copper Foil of the present invention is not particularly limited; For example, can use a kind of like this method, wherein component (A)-(C) and if desired other component uniform dissolution be dispersed in aromatic ketone or the solvent of other type or its mixed solvent in, and with on solution or the dispersion paint tinsel and dry.
Apply and to repeat repeatedly as required.In addition, use can repeat by the multiple solution with various combination and/or concentration, and the required resin of so final acquisition is formed and resin content.
Embodiment
Then, according to embodiment embodiment of the present invention are described.In the following Examples and Comparative Examples, unless otherwise mentioned, all " parts " all is the weight meter.
Embodiment 1
With 50 parts of poly-(2,6-dimethyl-1,4-phenylene ether) with viscosity number η sp/C (in the 0.5g/dl chloroformic solution 30 ℃ measure down) 0.54 as component (A); 46 parts of triallyl isocyanurates (by Nippon Kasei Chemical Co., Ltd. produces) are as component (B); 4 parts of polystyrene (GPPS, weight-average molecular weight: 270,000); 30 parts of melamine poly phosphates (melapur 200 (registered trademark) is produced by DSM Corp.) with polymerization degree 10 are as component (C); Be dissolved in the toluene varnish with 6 parts of Perhexyne 25B (producing) as curing catalyst with the preparation curable resin composition by NOF Corporation, and with 107g/m
2Woven fiber glass be immersed in make woven fiber glass infiltration that varnish is arranged in this varnish and in air furnace drying obtain curable composites.
Then, 6 described curable composites are piled up mutually, laminate has the about 0.8mm of thickness after solidifying like this, and will this stores use press that has the thick Copper Foil of 35 μ m on its two sides under 180 ℃ at pressure 40kg/cm
2Under make and solidify 90 minutes to obtain laminate.
The gained laminate carries out flammability test according to the UL94 standard, obtains grade V-0.The second-order transition temperature of this laminate of being determined by the flex point of the linear expansivity of unit temperature by TMA (TMA-10 type, Seiko Instruments Inc.) is 180 ℃.In addition, this laminate is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 2
＜maleic anhydride modified polyphenylene oxide synthetic 〉
The synthetic of maleic anhydride modified polyphenylene oxide carries out according to the method described in the reference example 3 of JP-B-7-37567.Promptly, polyphenylene oxide with 100 parts of weight embodiment 1,2 parts of weight maleic anhydrides and 1 weight part Perhexa 25B (being produced by NOF Corporation) at room temperature mix by using the drum blender to do as modification promotor, and blend extruded from twin screw extruder under the condition of cylinder temperature=300 ℃ and screw speed 230rpm obtain maleic anhydride modified polyphenylene oxide.
The production of＜laminate and assessment 〉
Curable composites and laminate only are to use described maleic anhydride modified polyphenylene oxide as polyphenylene oxide according to the same way as production of embodiment 1.Flammable mensuration is carried out according to embodiment 1, and the result is V-0.The second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 176 ℃.In addition, this laminate is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 3
Synthesizing of＜allylation polyphenylene oxide 〉
The synthetic of allylation polyphenylene oxide carries out according to the method described in the embodiment 2 of JP-B-5-8931.Promptly, the 2g polyphenylene oxide that will be used for embodiment 1 is dissolved among the 100ml dehydration distillatory THF at three-necked flask, subsequently under nitrogen gas stream to wherein adding 2.2ml n-butyllithium (1.55mol/l, hexane solution), and with this mixture reflux 1 hour under nitrogen atmosphere.
After mixture is cooled to room temperature, adds the 0.40g allyl bromide 98 and also this mixture was at room temperature stirred 30 minutes.The content of flask is poured in a large amount of methyl alcohol with precipitation polymers, and throw out is filtered, subsequently with methanol wash three times to obtain white powdered product.By
1The substitution value of the allyl group that H-NMR is fixed is 4%.
The production of＜laminate and assessment 〉
With 60 parts of described allylation polyphenylene oxide as component (A); 40 parts of triallyl isocyanurates are as component (B); 4 parts of polystyrene (GPPS, weight-average molecular weight: 270,000); 30 parts of melamine poly phosphates (Melapur 200 (registered trademark) is produced by DSM Corp.) with polymerization degree 10 are as component (C); Be dissolved in the toluene to prepare the varnish of curable resin composition as curing catalyst with 6 parts of Perhexyne 25B (producing) by NOF Corporation, produce curable composites and laminate then and carry out flammability test, obtain flammability rating V-0 according to the same way as of embodiment 1.The second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 175 ℃.In addition, this laminate is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 4 and 5
Curable composites and laminate are according to the same way as production of embodiment 1, and just as described in Table 1 variation of prescription of curable resin composition, and mensuration is flammable, second-order transition temperature and the laminate weight loss after water retting.
The measurement result of embodiment 1-5 provides in table 1.
Table 1
(the unit of component: weight part)
| Embodiment № | 1 | 2 | 3 | 4 | 5 |
| Polyphenylene oxide | 50 | ||||
| Maleic anhydride modified polyphenylene oxide | 50 | 55 | 66 | ||
| Allylation polyphenylene oxide | 60 | ||||
| Triallyl isocyanurate 1) | 46 | 46 | 40 | 45 | 30 |
| GPPS 2) | 4 | 4 | 4 | 4 | |
| PH25B 3) | 6 | 6 | 6 | 6 | |
| PBP 4) | 2 | ||||
| SEBS 5) | 10 | ||||
| Silica 6) | 42 | ||||
| melapur200 7) | 30 | 30 | 30 | 30 | 20 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 180 | 176 | 175 | 183 | 169 |
| Weight loss % after water retting | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
1) triallyl isocyanurate, by Nippon Kasei Chemical Co., Ltd. produces
2) polystyrene has weight-average molecular weight 270,000
3) Perhexyne 25B is produced by NOF Corporation
4) Perbutyl P is produced by NOF Corporation
5) Tuftec H1041 is produced by ASAHI KASEI KABUSHIKI KAISHA
6) Fuselex E-2 is produced by Tatsumori Ltd.
7) melamine poly phosphate (polymerization degree is 10) is produced by DSM Corp.
Therefore, in embodiment 1-5, the melamine poly phosphate that has the polymerization degree 10 by use is as component (C), and the polyphenylene oxide resin and the multifunctional product that contains any prescription of compound of unsaturated link(age) that comprise any prescription are keeping the stable on heating flammability rating V-0 that has simultaneously.
Embodiment 6-10
Curable composites and laminate are made according to the same way as of embodiment 1, and just as described in Table 2 variation of prescription of curable resin composition, and mensuration is flammable, second-order transition temperature and the laminate weight loss after water retting.The measurement result of embodiment 6-10 provides in table 2.
Table 2
(the unit of component: weight part)
| Embodiment № | 6 | 7 | 8 | 9 | 10 |
| Polyphenylene oxide | 30 | 30 | 30 | ||
| Maleic anhydride modified polyphenylene oxide | 30 | 30 | |||
| Triallyl isocyanurate | 10 | 10 | 20 | ||
| Bisphenol A epoxide resin | 20 | 20 | 20 | 20 | 20 |
| Linear phenolic resin varnish | 20 | 20 | 20 | 20 | 20 |
| Phenolic resin | 20 | 20 | 20 | 20 | 20 |
| Imidazoles | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| pH25B | 2 | 2 | 2 | ||
| melapur200 | 40 | 40 | 40 | 40 | 40 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 168 | 167 | 160 | 171 | 160 |
| Weight loss % after water retting | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
Therefore, in embodiment 6-10, the melamine poly phosphate that has the polymerization degree 10 by use comprises the polyphenylene oxide resin of any prescription and the product of Resins, epoxy and is keeping the stable on heating flammability rating V-0 that has simultaneously as component (C).
Embodiment 11 and 12
Curable composites and laminate are made according to the same way as of embodiment 1 and 2, use has the melamine poly phosphate (PMP-100 of the polymerization degree 3.9, by Nissan ChemicalIndustries, Ltd. produce) as component (C), and mensuration is flammable, second-order transition temperature and the laminate weight loss after water carries out.Embodiment 11 and 12 measurement result provide in table 3.
Table 3
(the unit of component: weight part)
| Embodiment № | 11 | 12 |
| Polyphenylene oxide | 50 | |
| Maleic anhydride modified polyphenylene oxide | 50 | |
| Triallyl isocyanurate | 46 | 46 |
| GPPS | 4 | 4 |
| PH25B | 6 | 6 |
| PMP-100 8) | 30 | 30 |
| The result of flammability test (UL94) | V-0 | V-0 |
| Second-order transition temperature ℃ | 181 | 180 |
| Weight loss % after water retting | 0.0 | 0.0 |
8) melamine poly phosphate (polymerization degree is 3.9), by Nissan ChemicalIndustries, Ltd. produces
Therefore, by the result of embodiment 11 and 12 as can be seen, the product that comprises polyphenylene oxide resin and the multifunctional compound that contains unsaturated link(age) can have the melamine poly phosphate of the polymerization degree 3.9 as component (C) even use keeping the stable on heating grade V-0 that has simultaneously.
Embodiment 13 and 14
Curable composites and laminate are made according to the same way as of embodiment 1, and just as described in Table 4 variation of prescription of curable resin composition, and mensuration is flammable, second-order transition temperature and the laminate weight loss after water retting.Embodiment 13 and 14 measurement result provide in table 4.
Table 4
(the unit of component: weight part)
| Embodiment № | 13 | 14 |
| Polyphenylene oxide | 90 | |
| Maleic anhydride modified polyphenylene oxide | 10 | |
| Triallyl isocyanurate | 10 | 90 |
| GPPS | ||
| PH25B | 3 | 10 |
| melapur200 | 20 | 50 |
| The result of flammability test (UL94) | V-0 | V-0 |
| Second-order transition temperature ℃ | 160 | 195 |
| Weight loss % after water retting | 0.0 | 0.0 |
Embodiment 13 and 14 compares with embodiment 1 on resin combination and greatly changes, but uses the melamine poly phosphate with polymerization degree 10 identical with embodiment 1 as component (C), and therefore product is keeping the stable on heating test-results V-0 that has simultaneously respectively.
Embodiment 15
The varnish of curable resin composition is made according to the same way as of embodiment 2, and it was descended dry 3 hours at 60 ℃, and dry toluene is to obtain curable resin composition like this.
This curable resin composition heated 90 minutes in nitrogen gas stream in vacuum press at 180 ℃, obtained cured product, or curable resin composition.The result of the flammability test of this cured product is V-0.In addition, the second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 176 ℃.In addition, this curable resin composition is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 16
The varnish of curable resin composition is made according to the same way as of embodiment 2, and will descend dry 3 hours on its paint PET film and at 60 ℃, and dry toluene is to obtain membranaceous curable resin composition like this.
This film of curable resin composition heats 90 minutes to obtain cured film in nitrogen gas stream in vacuum press under 180 ℃.The result of the flammability test of this cured film is V-0.In addition, the second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 175 ℃.In addition, this cured film is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 17
The varnish of curable resin composition is made according to the same way as of embodiment 2, and by the bar spreader with on the one side of the thick Copper Foil of its paint 18 μ m to have resin layer thickness 50 μ m and under 60 ℃ in air furnace dry 3 hours subsequently, obtain the resin-coating Copper Foil.
2 these resin-coating Copper Foils are stacked mutually and use press under 180 ℃ at pressure 40kg/cm
2Under make and solidified 90 minutes.The result of the flammability test of the laminate that so obtains is V-0.In addition, the second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 176 ℃.In addition, this laminate is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
The result of the foregoing description 15-17 gathers in table 5.
Table 5
(the unit of component: weight part)
| Embodiment № | 15 | 16 | 17 |
| Maleic anhydride modified polyphenylene oxide | 50 | 50 | 50 |
| Triallyl isocyanurate | 46 | 46 | 46 |
| GPPS | 4 | 4 | 4 |
| PH25B | 6 | 6 | 6 |
| melapur200 | 30 | 30 | 30 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 176 | 175 | 176 |
| Weight loss % after water retting | 0.0 | 0.0 | 0.0 |
Therefore, even wherein not adding the curable resin composition of glass, the laminate of cured film and resin-coating Copper Foil is also because use the melamine poly phosphate with polymerization degree 10 keeping the stable on heating flammability test V-0 as a result that obtains simultaneously as component (C).
Embodiment 18
＜9, the 10-dihydro-9-oxy is assorted-10-(allyl group phosphorus) phenanthrene-10-oxide compound (being called for short the HCA-allyl group) synthetic 〉
With 54.1g 9, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound (trade(brand)name: HCA, by Sanko Co., Ltd. produce), 35g allyl bromide 98 (particular stage, by Wako PureChemical Industries Co., Ltd. produce), 300g methyl alcohol (particular stage, by WakoPure Chemical Industries Co., Ltd. produces) and 30g triethylamine (particular stage, by Wako Pure Chemical Industries Co., Ltd. produce) add the 500ml three-necked flask of being furnished with reflux exchanger, and with mixture heating up to methyl alcohol gentle reflux in reflux exchanger, and reacted 8 hours.Subsequently flask is cooled to room temperature, methyl alcohol is under reduced pressure by using rotatory evaporator to distill, and with resistates the decompression (0.1mmHg, 140 ℃) descend distillation to obtain about 45g 9, the 10-dihydro-9-oxy is mixed-10-(allyl group phosphorus) phenanthrene-10-oxide compound (being called for short the HCA-allyl group), it is a kind of 9 of reactive substituents that has, and the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide derivative.
The production of＜laminate and assessment 〉
Is that 0.54 poly-(2,6-dimethyl-1,4-phenylene ether) as component (A) at 30 ℃ of its viscosity number η sp/C that measure down with 50 parts in the 0.5g/dl chloroformic solution; 46 parts of triallyl isocyanurates are as component (B); 4 parts of polystyrene (GPPS, weight-average molecular weight: 270,000); 30 parts of HCA allyl groups are as component (C); Be dissolved in the varnish of toluene with 6 parts of Perhexyne 25B (producing) as curing catalyst, and produce laminate and carry out flammability test according to the same way as of embodiment 1 with the preparation curable resin composition by NOF Corporation.The result of the flammability test of this laminate is V-0.In addition, the second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 170 ℃.In addition, this laminate is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 19-22
Curable composites and laminate are made according to the same way as of embodiment 18, and just as described in Table 6 variation of prescription of curable resin composition, and mensuration is flammable, second-order transition temperature and the laminate weight loss after water retting.
The measurement result of the foregoing description 18-22 provides in table 6.
Table 6
(the unit of component: weight part)
| Embodiment № | 18 | 19 | 20 | 21 | 22 |
| Polyphenylene oxide | 50 | ||||
| Maleic anhydride modified polyphenylene oxide | 50 | 55 | 66 | ||
| Allylation polyphenylene oxide | 60 | ||||
| Triallyl isocyanurate | 46 | 46 | 40 | 45 | 30 |
| GPPS | 4 | 4 | 4 | 4 | |
| PH25B | 6 | 6 | 6 | 6 | |
| PBP | 2 | ||||
| SEBS | 10 | ||||
| Silica | 42 | ||||
| The HCA-allyl group | 30 | 30 | 30 | 30 | 20 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 170 | 168 | 168 | 174 | 161 |
| Weight loss % after water retting | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
Therefore, in embodiment 18-22, by using the HCA allyl group, or has 9 of a reactive substituents, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide derivative is as component (C), and the polyphenylene oxide resin and the multifunctional product that contains the compound of unsaturated link(age) that comprise any prescription are keeping the stable on heating flammability test V-0 as a result that has simultaneously.
Embodiment 23-25
Curable composites and laminate are made according to the same way as of embodiment 18, and just as described in Table 7 variation of prescription of curable resin composition, and mensuration is flammable, second-order transition temperature and the laminate weight loss after water retting.The measurement result of embodiment 23-25 provides in table 7.
Table 7
(the unit of component: weight part)
| Embodiment № | 23 | 24 | 25 |
| Polyphenylene oxide | 30 | 30 | |
| Maleic anhydride modified polyphenylene oxide | 30 | ||
| Triallyl isocyanurate | 10 | 10 | 20 |
| Bisphenol A epoxide resin | 20 | 20 | 20 |
| Linear phenolic resin varnish | 20 | 20 | 20 |
| Phenolic resin | 20 | 20 | 20 |
| Imidazoles | 0.5 | 0.5 | 0.5 |
| pH25B | 2 | 2 | 2 |
| The HCA-allyl group | 30 | 30 | 30 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 162 | 161 | 166 |
| Weight loss % after water retting | 0.0 | 0.0 | 0.0 |
At embodiment 23-25, by using the HCA-allyl group, or has 9 of a reactive substituents, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide derivative is as component (C), and comprise the polyphenylene oxide resin of any prescription and the product of Resins, epoxy and keeping the stable on heating flammability rating V-0 that has simultaneously.
Embodiment 26
The varnish of curable resin composition is made according to the same way as of embodiment 19, and it was descended dry 3 hours at 60 ℃, and dry toluene is to obtain curable resin composition like this.
This curable resin composition heated 90 minutes in nitrogen gas stream in vacuum press at 180 ℃, obtained cured product, i.e. curable resin composition.The flammability test of carrying out at this cured product obtains V-0 as a result.In addition, the second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 171 ℃.In addition, this curable resin composition is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 27
The varnish of curable resin composition is made according to the same way as of embodiment 19, and will descend dry 3 hours on its paint PET film and at 60 ℃, and dry toluene is to obtain membranaceous curable resin composition like this.The film of this curable resin composition heats 90 minutes to obtain cured film in nitrogen gas stream in vacuum press under 180 ℃.This cured film is carried out flammability test, obtains V-0 as a result.In addition, the second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 170 ℃.In addition, this cured film is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 28
The varnish of curable resin composition is made according to the same way as of embodiment 19, and by the bar spreader with on the one side of the thick Copper Foil of its paint 18 μ m to have resin layer thickness 50 μ m and under 60 ℃ in air furnace dry 3 hours subsequently, obtain the resin-coating Copper Foil.
Then, 2 these resin-coating Copper Foils are stacked mutually and by use press under 180 ℃ at pressure 40kg/cm
2Under make and solidified 90 minutes.The gained laminate carries out flammability test like this.The result of flammability test is V-0.In addition, the second-order transition temperature of measuring according to the same way as of embodiment 1 by TMA is 170 ℃.In addition, this laminate is 0.0% in the weight loss after 24-hour water retting under 25 ℃.
Embodiment 26-28 is above-mentioned the results are summarized in table 8.
Table 8
(the unit of component: weight part)
| Embodiment № | 26 | 27 | 28 |
| Maleic anhydride modified polyphenylene oxide | 50 | 50 | 50 |
| Triallyl isocyanurate | 46 | 46 | 46 |
| GPPS | 4 | 4 | 4 |
| PH25B | 6 | 6 | 6 |
| The HCA-allyl group | 30 | 30 | 30 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 171 | 170 | 170 |
| Weight loss % after water retting | 0.0 | 0.0 | 0.0 |
Therefore, even wherein do not add the curable resin composition of woven fiber glass, the laminate of cured film and resin-coating Copper Foil is also because use the HCA-allyl group, or 9, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide derivative keeping the stable on heating flammability test V-0 as a result that obtains simultaneously as component (C).
Comparative Examples 1-5
Curable composites and laminate are made according to the same way as of embodiment 1-5, only be to use the melamine poly phosphate (MPP-A with polymerization degree 2.6 of equal parts, by SanwaChemical Co., Ltd. production) alternative have the melamine poly phosphate (melapur 200 (registered trademark) is produced by DSM Corp.) of the polymerization degree 10 as component (C).Carry out flammability test and measure second-order transition temperature and the weight loss of laminate after water retting.These measurement results of Comparative Examples 1-5 provide in table 9.
Table 9
(the unit of component: weight part)
| Comparative Examples № | 1 | 2 | 3 | 4 | 5 |
| Polyphenylene oxide | 50 | ||||
| Maleic anhydride modified polyphenylene oxide | 50 | 55 | 66 | ||
| Allylation polyphenylene oxide | 60 | ||||
| Triallyl isocyanurate | 46 | 46 | 40 | 45 | 30 |
| GPPS | 4 | 4 | 4 | 4 | |
| PH25B | 6 | 6 | 6 | 6 | |
| PBP | 2 | ||||
| SEBS | 10 | ||||
| Silica | 42 | ||||
| MPP-A 9) | 30 | 30 | 30 | 30 | 20 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 180 | 178 | 177 | 184 | 163 |
| Weight loss % after water retting | 0.2 | 0.2 | 0.2 | 0.2 | 0.3 |
9) melamine poly phosphate (polymerization degree is 2.6), by Sanwa Chemical Co., Ltd. produces
Therefore, if use the melamine poly phosphate with polymerization degree 2.6, keep thermotolerance simultaneously although combustibility is V-0, laminate is 0.2-0.3% in the weight loss after 24-hour water retting under 25 ℃, so product can not actual use.
Comparative Examples 6 and 7
Curable composites and laminate are made according to the same way as of embodiment 1 and 2, only be to use melamine poly phosphate (the Pranelon NP with polymerization degree 1.5 of equal parts, by Mitsui Kagaku Fine Chemicals, Inc.) alternative have the melamine poly phosphate (melapur 200 (registered trademark) is produced by DSM Corp.) of the polymerization degree 10 as component (C).Carry out flammability test and measure second-order transition temperature and the weight loss of laminate after water retting.Comparative Examples 6 and these measurement results of 7 provide in table 10.
Table 10
(the unit of component: weight part)
| Comparative Examples № | 6 | 7 |
| Polyphenylene oxide | 50 | |
| Maleic anhydride modified polyphenylene oxide | 50 | |
| Triallyl isocyanurate | 46 | 46 |
| GPPS | 4 | 4 |
| PH25B | 6 | 6 |
| Pranelon NP 10) | 30 | 30 |
| The result of flammability test (UL94) | V-0 | V-0 |
| Second-order transition temperature ℃ | 179 | 178 |
| Weight loss % after water retting | 0.4 | 0.4 |
10) melamine poly phosphate (polymerization degree is 1.5), by Mitsui Kagaku FineChemicals, Inc. produces
Therefore, if even use melamine poly phosphate with polymerization degree 1.5, although keeping the stable on heating flammable V-0 that obtains simultaneously, laminate is 0.4% in the weight loss after 24-hour water retting under 25 ℃, so product can not actual use.
Comparative Examples 8-10
Curable resin composition, the laminate of cured film and resin-coating Copper Foil is made according to the same way as of embodiment 15-17, only be to use the melamine poly phosphate (MPP-A with polymerization degree 2.6 of equal parts, by Sanwa Chemical Co., Ltd. production) alternative have the melamine poly phosphate (melapur 200 (registered trademark) is produced by DSM Corp.) of the polymerization degree 10 as component (C).Carry out flammability test and measure second-order transition temperature and the weight loss of laminate after water retting.These measurement results of Comparative Examples 8-10 provide in table 11.
Table 11
(the unit of component: weight part)
| Comparative Examples № | 8 | 9 | 10 |
| Maleic anhydride modified polyphenylene oxide | 50 | 50 | 50 |
| Triallyl isocyanurate | 46 | 46 | 46 |
| GPPS | 4 | 4 | 4 |
| PH25B | 6 | 6 | 6 |
| MPP-A | 30 | 30 | 30 |
| The result of flammability test (UL94) | V-0 | V-0 | V-0 |
| Second-order transition temperature ℃ | 176 | 176 | 175 |
| Weight loss % after water retting | 0.2 | 0.2 | 0.2 |
Therefore, even do not add the curable resin composition of woven fiber glass therein, under the situation of the laminate of cured film and resin-coating Copper Foil, if use melamine poly phosphate with polymerization degree 2.6, although can keep the stable on heating flammable V-0 that obtains simultaneously, but laminate is 0.2% in the weight loss after 24-hour water retting under 25 ℃, so product can not actually use.
Comparative Examples 11-15
Curable composites and laminate are made according to the same way as of embodiment 1-5, it is component (C), that is, have the melamine poly phosphate (melapur 200 (registered trademark), by DSM Corp. produce) of the polymerization degree 10 or in embodiment 18 the allylic umber of synthetic HCA-change into 5.In flammability test, all product burnings (table 12).At this, " burning " is meant that product can not reach grade V-0 in flammability test.
Table 12
(the unit of component: weight part)
| Comparative Examples № | 11 | 12 | 13 | 14 | 15 |
| Polyphenylene oxide | 50 | ||||
| Maleic anhydride modified polyphenylene oxide | 50 | 55 | 66 | ||
| Allylation polyphenylene oxide | 60 | ||||
| Triallyl isocyanurate | 46 | 46 | 40 | 45 | 30 |
| GPPS | 4 | 4 | 4 | 4 | |
| PH25B | 6 | 6 | 6 | 6 | |
| PBP | 2 | ||||
| SEBS | 10 | ||||
| Silica | 42 | ||||
| melapur200 | 5 | 5 | 5 | 5 | |
| The HCA-allyl group | 5 | ||||
| The result of flammability test (UL94) | Burning * | Burning * | Burning * | Burning * | Burning * |
* can not reach V-0
Therefore, if even use and to have the polymerization degree 3 or higher melamine poly phosphate or to have 9 of reactive substituents, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide derivative is as component (C), be lower than the combination of 10/ per 100 parts of components by weight percent (A) and component (B) as the umber of fruit component (C), can not obtain gratifying flame retardant resistance.
Comparative Examples 16 and 17
Curable composites and laminate are made according to the same way as of embodiment 2, it is component (C), that is, have the melamine poly phosphate (melapur 200 (registered trademark), by DSM Corp. produce) of the polymerization degree 10 or in embodiment 18 the allylic umber of synthetic HCA-change into 85.In flammability test, the varnish of curable resin composition can not flood, because the varnish viscosity (table 13) under every kind of situation is too high.
Table 13
(the unit of component: weight part)
| Comparative Examples № | 16 | 17 |
| Maleic anhydride modified polyphenylene oxide | 50 | 50 |
| Triallyl isocyanurate | 46 | 46 |
| GPPS | 4 | 4 |
| PH25B | 6 | 6 |
| melapur200 | 85 | |
| The HCA-allyl group | 85 | |
| The result of flammability test (UL94) | * | * |
* base material can not infiltrate varnish, because viscosity is too high.
Therefore, if even use and to have the polymerization degree 3 or higher melamine poly phosphate or to have 9 of reactive substituents, the 10-dihydro-9-oxy is assorted-and 10-phosphorus phenanthrene-10-oxide derivative is as component (C), surpass the combination of 80/ per 100 parts of components by weight percent (A) and component (B) as the umber of fruit component (C), become Tai Gao and varnish of the varnish viscosity of curable resin composition can not be infiltrated up in the strongthener.
Comparative Examples 18-20
Curable resin composition, the laminate of cured film and resin-coating Copper Foil is made according to the same way as of embodiment 15-17, is component (C), promptly, number with melamine poly phosphate (melapur 200 (registered trademark) is produced by DSM Corp.) of the polymerization degree 10 changes into 5.In flammability test, all in flammability test, all curable resin compositions, cured film and laminate burning (table 14).At this, " burning " is meant that product can not reach grade V-0 in flammability test.
Table 14
(the unit of component: weight part)
| Embodiment № | 18 | 19 | 20 |
| Maleic anhydride modified polyphenylene oxide | 50 | 50 | 50 |
| Triallyl isocyanurate | 46 | 46 | 46 |
| GPPS | 4 | 4 | 4 |
| PH25B | 6 | 6 | 6 |
| melapur200 | 5 | 5 | 5 |
| The result of flammability test (UL94) | Burning * | Burning * | Burning * |
* can not reach V-0
Therefore, the curable resin composition that does not add woven fiber glass therein, in the laminate of cured film and resin-coating Copper Foil, if even use has the polymerization degree 3 or higher melamine poly phosphate, if the umber of used melamine poly phosphate is lower than the combination of 10/ per 100 parts of components by weight percent (A) and component (B), can not obtain gratifying flame retardant resistance.
Industrial applicibility
The present invention can provide the curable resin composition that does not have halogen but keep the heat resistance characteristic of polyphenylene oxide resin and have gratifying anti-flammability (for example, the grade V-0 in the UL94 test).
Claims (13)
1. curable resin composition, comprise polyphenylene oxide resin, linking agent, with at least a phosphorus compound, the latter is selected to have the polymerization degree 3 or higher melamine poly phosphate and has reactive substituents and be expressed as 9 of following structural formula (1), and the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide derivative:
R wherein
1Be vinyl, allyl group, methacrylic or 1-butylene base group; And R
2And R
3Be independently selected from hydrogen atom and C
1-C
6Hydrocarbyl group, wherein said polyphenylene oxide resin, the content ratio of described linking agent and described phosphorus compound is respectively combination 10-98 part weight, 90-2 part weight and 10-80 part weight of per 100 parts of described polyphenylene oxide resins of weight and described linking agent.
2. according to the curable resin composition of claim 1, wherein said phosphorus compound is the melamine poly phosphate with polymerization degree 3.
3. according to the curable resin composition of claim 1, wherein said phosphorus compound is to have reactive substituents and be expressed as 9 of following structural formula (1), and the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide derivative:
R wherein
1Be vinyl, allyl group, methacrylic or 1-butylene base group, and R
2And R
3Be independently selected from hydrogen atom and C
1-C
6Hydrocarbyl group.
4. according to the curable resin composition of any one claim 1-3, wherein said linking agent is the compound that comprises multifunctional unsaturated link(age).
5. according to the curable resin composition of claim 1 or 2, wherein said linking agent is a Resins, epoxy.
6. according to the curable resin composition of any one claim 1-3, wherein said polyphenylene oxide resin is i) comprise the polyphenylene oxide resin of unsaturated group, and/or the ii) reaction product of polyphenylene oxide resin and unsaturated carboxylic acid and/or acid anhydrides.
7. by the film of each curable resin composition preparation among the claim 1-6.
8. by being solidificated in the curable resin composition that the curable resin composition that proposes among any one claim 1-7 obtains.
9. a curable composites is included in the curable resin composition and the strongthener that propose among any one claim 1-7, and the content ratio of described strongthener is a 5-90% weight.
10. one kind by being solidificated in the claim 9 cured composite material that the curable composites that proposes obtains.
11. a laminate is included in the cured composite material and the tinsel that propose in the claim 10.
12. a resin-coating tinsel comprises tinsel and the film of the curable resin composition that proposes in any one claim 1-6, described film forms on the one side of described tinsel.
13. film by each described curable resin composition preparation among the claim 1-3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2000/005883 WO2002018493A1 (en) | 2000-08-30 | 2000-08-30 | Curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1454240A CN1454240A (en) | 2003-11-05 |
| CN1239615C true CN1239615C (en) | 2006-02-01 |
Family
ID=11736411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00819862.4A Expired - Lifetime CN1239615C (en) | 2000-08-30 | 2000-08-30 | Curable resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4007911B2 (en) |
| CN (1) | CN1239615C (en) |
| WO (1) | WO2002018493A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7413791B2 (en) | 2003-01-28 | 2008-08-19 | Matsushita Electric Works, Ltd. | Poly (phenylene ether) resin composition, prepreg, and laminated sheet |
| JP3923441B2 (en) * | 2003-03-25 | 2007-05-30 | 三光株式会社 | Flame retardant synthetic resin composition |
| WO2004111121A1 (en) * | 2003-06-12 | 2004-12-23 | Fuji Electric Holdings Co., Ltd. | Reactive flame retardants and flame-retarded resin products |
| WO2005033179A1 (en) * | 2003-10-03 | 2005-04-14 | General Electric Company | Flame-retardant thermoset composition, method, and article |
| US7488766B2 (en) | 2005-10-06 | 2009-02-10 | Sabic Innovative Plastics Ip B.V. | Polymer composition, method, and article |
| US7495047B2 (en) | 2005-10-06 | 2009-02-24 | At&T Intellectual Property, I, L.P. | Poly(arylene ether) composition, method, and article |
| WO2009125623A1 (en) * | 2008-04-09 | 2009-10-15 | 住友電気工業株式会社 | Flame-retardant tube and heat-shrinkable tube made by using the same |
| JP5165639B2 (en) * | 2009-05-26 | 2013-03-21 | パナソニック株式会社 | Polyphenylene ether resin composition, prepreg, metal-clad laminate, and printed wiring board |
| DE102010035103A1 (en) * | 2010-08-23 | 2012-02-23 | Catena Additives Gmbh & Co. Kg | Flame retardant compositions containing triazine-intercalated metal phosphates |
| JP6219112B2 (en) * | 2013-09-27 | 2017-10-25 | 旭化成株式会社 | PPE-containing resin composition |
| US10047224B2 (en) | 2013-11-20 | 2018-08-14 | Asahi Kasei Kabushiki Kaisha | Cured product of polyphenylene ether-containing resin composition |
| DE102014014098A1 (en) * | 2014-09-30 | 2016-03-31 | Mankiewicz Gebr. & Co. Gmbh & Co. Kg | Barrier layer and its use in coating systems on plastic substrates |
| DE102017215780A1 (en) * | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Synergistic flame retardant combinations for polymer compositions and their use |
| US20190127576A1 (en) * | 2017-10-27 | 2019-05-02 | Frx Polymers, Inc. | Phosphonate based halogen-free compositions for printed circuit board applications |
| CN112969749B (en) * | 2018-11-08 | 2024-02-02 | 株式会社力森诺科 | Resin composition, prepreg, laminate, resin film, multilayer printed wiring board, and multilayer printed wiring board for millimeter wave radar |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900768A (en) * | 1983-08-23 | 1990-02-13 | General Electric Company | Crosslinkable flame retardant composition of polyphenylene ether and elastomers |
| JPH0726014B2 (en) * | 1989-03-08 | 1995-03-22 | 旭化成工業株式会社 | Flame retardant resin composition |
| JP2796145B2 (en) * | 1989-11-15 | 1998-09-10 | 旭化成工業株式会社 | Resin composition |
| JPH03185058A (en) * | 1989-12-14 | 1991-08-13 | Asahi Chem Ind Co Ltd | Thermoplastic resin composition |
| JPH03275761A (en) * | 1990-03-26 | 1991-12-06 | Matsushita Electric Works Ltd | Polyphenylene oxide resin composition and metal-plated laminate board |
| JPH04117452A (en) * | 1990-09-06 | 1992-04-17 | Mitsubishi Kasei Polytec Co | Polyphenylene ether resin composition |
| JPH04370134A (en) * | 1991-06-19 | 1992-12-22 | Asahi Chem Ind Co Ltd | Halogen-free flame-retarding resin composition |
| DE4130488A1 (en) * | 1991-09-13 | 1993-03-18 | Bayer Ag | New phosphorus-contg. thermoplastic polymers of vinyl] cpds. used for mouldings with improved flame resistance - prepd. by polymerisation in presence of 9,10-di:hydro-9-oxa-10-phospha-phenanthrene-10-oxide as mol. wt. regulator |
| JPH07316415A (en) * | 1994-05-23 | 1995-12-05 | Sumitomo Bakelite Co Ltd | Flame-retardant polyphenylene ether resin composition and production thereof |
| JPH08176450A (en) * | 1994-12-21 | 1996-07-09 | Sumitomo Bakelite Co Ltd | Thermoplastic resin composition |
| JP2000129263A (en) * | 1998-10-27 | 2000-05-09 | Rin Kagaku Kogyo Kk | Low-smoke-generation flame retardant composition and low-smoke-generation flame-retardant resin composition |
| JP2000248169A (en) * | 1999-03-01 | 2000-09-12 | Asahi Chem Ind Co Ltd | Flame-retardant, curable resin composition |
| JP2000336261A (en) * | 1999-03-24 | 2000-12-05 | Asahi Chem Ind Co Ltd | Curable resin composition |
| JP2000290490A (en) * | 1999-04-01 | 2000-10-17 | Asahi Chem Ind Co Ltd | Flame retardant curable resin composition |
| JP3403987B2 (en) * | 1999-12-27 | 2003-05-06 | 京セラケミカル株式会社 | Build-up type multilayer printed wiring board, resin composition and resin film used therefor |
-
2000
- 2000-08-30 CN CN00819862.4A patent/CN1239615C/en not_active Expired - Lifetime
- 2000-08-30 WO PCT/JP2000/005883 patent/WO2002018493A1/en active Application Filing
- 2000-08-30 JP JP2002524003A patent/JP4007911B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP4007911B2 (en) | 2007-11-14 |
| CN1454240A (en) | 2003-11-05 |
| WO2002018493A1 (en) | 2002-03-07 |
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