CN100343302C - Flame-retardant epoxy resin composition and cured product obtained therefrom - Google Patents
Flame-retardant epoxy resin composition and cured product obtained therefrom Download PDFInfo
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- CN100343302C CN100343302C CNB2003801042590A CN200380104259A CN100343302C CN 100343302 C CN100343302 C CN 100343302C CN B2003801042590 A CNB2003801042590 A CN B2003801042590A CN 200380104259 A CN200380104259 A CN 200380104259A CN 100343302 C CN100343302 C CN 100343302C
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Abstract
An epoxy resin composition which comprises (a) an epoxy resin and (b) a polyamide resin containing phenolic hydroxy groups which has a structure represented by the formula (1); a method of curing the composition; a varnish, prepreg, or sheet comprising or obtained with the composition; and an epoxy resin hardener which contains as an active ingredient a polyamide resin represented by the formula (1). The epoxy resin composition gives a cured object which has sufficient flexibility even when it is in a thin film form. The cured object further has flame retardancy although it contains none of flame retardants such as halogenated flame retardants and antimony compounds, and is excellent in heat resistance and adhesiveness. The composition is hence extremely useful in a wide range of applications such as a molding material, casting material, laminating material, coating material, adhesive, and resist.
Description
Technical field
The present invention relates to epoxy curing agent, contain the composition epoxy resin and the cured article thereof of this epoxy curing agent.
Background technology
Resins, epoxy is solidified with all solidifying agent, and becomes the character of common mechanical, water tolerance, and resistance to chemical reagents, thermotolerance, electric superior cured articles such as character can be used in tackiness agent, coating, veneer sheet, shaped material, extensive fields such as injection molded material.In the past, the most widely used Resins, epoxy can be enumerated as bisphenol A type epoxy resin.As curing agent for epoxy resin, well-known have acid anhydrides and an amine compound, but in electric, electronic component field from aspect the reliability of thermotolerance etc., use linear phenolic resin (phenol novolac) more.In addition, fire retardant is to use for the purpose of giving the cured article flame retardant resistance.As fire retardant is well-known tetrabromo-bisphenol and epoxide thereof are arranged, or the compound of tetrabromo-bisphenol and bisphenol A type epoxy resin reaction etc. contains the compound of bromine.
But above-mentioned bromine-containing compound is though flame retardant resistance is superior, at material discarded, that may produce contaminate environment when burning.And worry its toxicity equally as the antimony compounds that the flame retardant resistance auxiliary agent uses.Along with the raising of environmental protection consciousness in recent years also improves requirement not halogen-containing in the composition epoxy resin and antimony.In addition, though good with linear phenolic resin as its reliability of cured article of the Resins, epoxy of solidifying agent, the firm shortage snappiness of its cured article.The form of electric in recent years, electronic component, not only have and use, also developed to use and have the laminal object (shaping thing) that polyimide film, PET (polyethylene terephthalate) film or tinsel etc. have flexible laminal substrate with in the past heavy packages or glass fibre plate object as the firm substrate of base material.This shaping thing normally is coated on composition epoxy resin on the laminal substrate with the state of varnish, remove to desolvate, and will solidify through the composition epoxy resin of coating then and makes.The cured article that obtains in this occasion is required to have abundant snappiness and base materials such as polyimide is had high adherence.In addition, with regard to the reliability of electric, electronic component, also require the thermotolerance of cured article.
In addition, as the composition epoxy resin of modified epoxy resin vulnerability in the past, the composition epoxy resin that TOHKEMY 2000-313787 communique discloses contains the aromatic polyamide resin three of Resins, epoxy, phenol resins and tool phenol hydroxyl, and puts down in writing it and have thermotolerance and obdurability.But not mentioned fully for snappiness and flame retardant resistance that can corresponding laminal substrate, think still to be not enough person at that point.
Summary of the invention
The inventor etc. are because above-mentioned practical situation, can obtain not when obtaining solidifying that fire retardant such as brominated system has flame retardant resistance, and thermotolerance, binding property is good, lamellarly also have abundant flexible cured article and further investigate even be configured as in addition, the result has finished the present invention.
That is, the present invention relates to:
1. composition epoxy resin, it comprises (a) Resins, epoxy and (b) polyamide resin of structure shown in the following formula of tool (1):
(in the formula, l, m are mean value, expression m/ (l+m) 0.05, and l+m is 2 to 200 positive number.Ar
1Aromatic series base, Ar for divalent
2Aromatic series base, Ar for the divalence that contains the phenol hydroxyl
3Expression-ph (R
1) n-or-ph (R
2) n-X-ph (R
3) n-;-ph (R
1) n-,-ph (R
2) n-or-ph (R
3) n-represents R separately
1Replacement, R
2Replace or R
3The phenylene that replaces, or represent the phenylene of non-replacement; N is 0 to 3 integer; R
1, R
2Or R
3Represent C1～C3 alkyl, C1～C3 alkoxyl group independently; X represents O, S, CO, SO
2, or singly-bound.)
2. the composition epoxy resin of above-mentioned 1 record, with respect to epoxy group(ing) 1 equivalent in the composition (a), Ahew is 0.7～1.2 equivalent in the composition (b),
3. the composition epoxy resin of above-mentioned 1 record, for the contained whole solidifying agent of composition, the content ratio of the polyamide resin of composition (b) is more than the 30 weight %,
4. the composition epoxy resin of above-mentioned 1 record, all with respect to composition, contain Resins, epoxy 10～50 weight % of composition (a) and solidifying agent 50～98 weight % of composition (b),
5. the composition epoxy resin of each record, wherein Ar in above-mentioned 1～4
3For-ph (R
1) n-or-ph (R
2) n-O-ph (R
3) n-,
6. the composition epoxy resin of each record in above-mentioned 1～4, wherein the polyamide resin of composition (b) is the compound with following formula (3) structure,
(in the formula, l and m represent with formula (1) in identical implication.)
7. the composition epoxy resin of each record in above-mentioned 1～4, wherein the polyamide resin of composition (b) is the compound with following formula (4) structure,
(in the formula l and m represent with formula (1) in identical implication.)
8. the composition epoxy resin of each record in above-mentioned 1～4, wherein l+m is 2～20 positive number,
9. the composition epoxy resin of each record in above-mentioned 1～4, composition (a) the linear phenol aldehyde type epoxy resin of serving as reasons wherein, the linear phenol aldehyde type epoxy resin that contains the xylylene skeleton, the linear phenol aldehyde type epoxy resin that contains biphenyl backbone, bisphenol A type epoxy resin, more than one that select among the group that bisphenol f type epoxy resin, tetramethyl biphenyl phenol-type epoxy resin and tritane type Resins, epoxy are formed
10. the composition epoxy resin of above-mentioned 8 records, wherein composition (a) is the linear phenol aldehyde type epoxy resin that contains biphenyl backbone shown in the following formula of tool (2),
(in the formula, P represents mean value, is 0.1～10 positive number.)
11. the composition epoxy resin of each record in above-mentioned 1～4, it contains curing catalyst,
12. a varnish is dissolved in the solvent by the composition epoxy resin with each record in above-mentioned 1～11 and gets,
13. a varnish, with respect to varnish generally speaking, solvent is 10～70 weight %, and remaining part is above-mentioned 12 composition epoxy resins of being put down in writing,
14. above-mentioned 13 varnish of being put down in writing, wherein solvent is the aliphatic ketone series solvent of C4～C6,
15. a sheet material, on the two sides of plane support or single face have the layer of each composition epoxy resin of putting down in writing in above-mentioned the 1st～11,
16. a sheet material, on the two sides of plane support or single face have the layer of each composition epoxy resin of putting down in writing in above-mentioned the 1st～11 is solidified and the cured article layer,
17. above-mentioned 15 or 16 sheet materials of being put down in writing, wherein plane support is a polyimide film, tinsel or stripping film,
18. a pre-impregnated article, by with above-mentioned 12 varnish impregnations of being put down in writing in base material, dry and get,
19. the curing of a composition epoxy resin is characterized in that, with each composition epoxy resin of putting down in writing heating in above-mentioned 1～11,
20. an epoxy curing agent is an effective constituent with the polyamide resin of structure with following formula (1) expression,
(in the formula, l, m are mean value, expression m/ (l+m) 〉=0.05, and l+m is 2～200 positive number.Ar
1Aromatic series base, Ar for divalent
2Aromatic series base, Ar for divalence with phenol hydroxyl
3Expression-ph (R
1) n-or-ph (R
2) n-X-ph (R
3) n-;-ph (R
1) n-,-ph (R
2) n-or-ph (R
3) n-represents R separately
1Replacement, R
2Replace or R
3The phenylene that replaces, or represent the phenylene of non-replacement; N is 0～3 integer; R
1, R
2Or R
3C1～C3 alkyl, C1～C3 alkoxyl group respectively do for oneself; X represents O, S, CO, SO
2, or singly-bound.)
21. above-mentioned 20 epoxy curing agents of being put down in writing, wherein Ar
3For-ph (R
1) n-or-ph (R
2) n-O-ph (R
3) the represented group of n-.
Embodiment
Polyamide resin used in the present invention uses the aromatic polyamide resin that contains the phenol hydroxyl that contains structure shown in the above-mentioned formula (1) in the polymer architecture.This contains the aromatic polyamide resin of phenol hydroxyl, for example same with the aromatic polyamide resin that contains the phenol hydroxyl of the concrete record of Japanese kokai publication hei 8-143661 communique, the aromatic dicarboxylic acid that contains the phenol hydroxyl (hereinafter referred to as the aromatic dicarboxylic acid that contains the phenol hydroxyl) by making corresponding above-mentioned formula (1), the aromatic dicarboxylic acid that does not contain the phenol hydroxyl of corresponding above-mentioned formula (1) carry out polycondensation with the aromatic diamine (aftermentioned formula (i) or (ii) represented diamines) of corresponding above-mentioned formula (1) and can make.
When polycondensation; if carrying out as in the presence of the phosphorous acid ester of condensing agent and the pyridine derivate, then functional group's phenol hydroxyl is not protected, and phenol hydroxyl and other reactive group; for example do not react, can make straight catenate aromatic polyamide resin easily with carboxyl or amino.In addition, do not need high temperature when having polycondensation, the promptly about advantage that can carry out polycondensation below 150 ℃.
The aromatic diamine of corresponding above-mentioned formula (1) can be listed below the aromatic diamine of row formula:
(i) H
2N-ph (R
1) n-NH
2Or
(ii)H
2N-ph(R
2)n-X-ph(R
3)n-NH
2
(in the formula ,-ph (R
1) n-,-ph (R
2) n-or-ph (R
3) n-represents R separately
1Replacement, R
2Replace or R
3The phenylene that replaces, or represent the phenylene of non-replacement; N is 0～3 integer; R
1, R
2Or R
3Be C1～C3 alkyl, C1～C3 alkoxyl group independently of one another; X represents O, S, CO, SO
2, or singly-bound).With the phenylenediamine of formula (i) or formula (ii) in the diamino-diphenyl ether of X=O be good.
Above-mentioned formula (i) or aromatic diamine (ii) can be enumerated as mphenylenediamine Ursol D, phenylenediamine derivatives such as toluylenediamine; 4,4 '-diaminodiphenyl oxide, 3,3 '-dimethyl-4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4, diaminodiphenyl oxide derivatives such as 4 '-diaminodiphenyl sulfide; 3,3 '-dimethyl-4,4 '-diaminodiphenyl sulfide, 3,3 '-diethoxy-4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenyl sulfide, 3,3 '-dimethoxy-4 ', diaminodiphenyl sulfide derivatives such as 4 '-diaminodiphenyl sulfide; 4,4 '-diaminobenzophenone, 3,3 '-dimethyl-4, diaminobenzophenone derivatives such as 4 '-diaminobenzophenone; 4,4 '-diamino thionyl benzene, 4, diaminodiphenylsulfone(DDS) derivatives such as 4 '-diaminodiphenylsulfone(DDS); P-diaminodiphenyl, 3,3 '-tolidine, 3, benzidine derivatives such as 3 '-dimethoxy benzidine; 3,3 '-benzidine; The p dimethylamine, m-xylene diamine, benzene dimethylamine derivatives such as O-phthalic amine are good with phenylenediamine derivative or diaminodiphenyl oxide derivative, and 3,4 '-diaminodiphenyl oxide is with solvent solubility, and the flame retardant resistance aspect is preferred especially.Above-mentioned mix to use more than a kind or 2 kinds also good.
The above-mentioned aromatic carboxylic acid that contains the phenol hydroxyl used in the present invention, as long as aromatic ring is the structure with 1 carboxyl and 1 above hydroxyl, there is not special restriction, for example can enumerate 5-hydroxyl m-phthalic acid, 4 hydroxyisophthalic acid, 2-hydroxyl m-phthalic acid, 3-hydroxyl m-phthalic acid, the dicarboxylic acid of 1 and 2 carboxyl of tool on the phenyl ring such as 2-hydroxyl terephthalic acid.
The above-mentioned aromatic dicarboxylic acid that does not contain the phenol hydroxyl that polyamide resin used in the present invention is used can be enumerated as phthalic acid m-phthalic acid, terephthalic acid, 4,4 '-oxygen, two M-nitro benzoic acids, 4,4 '-diphenyl dicarboxylic acid, 3,3 '-methylene radical, two M-nitro benzoic acids, 4,4 '-methylene radical, two M-nitro benzoic acids, 4,4 '-sulphur, two M-nitro benzoic acids, 3,3 '-carbonyl diurethane M-nitro benzoic acid, 4,4 '-carbonyl diurethane M-nitro benzoic acid, 4,4 '-sulphonyl, two M-nitro benzoic acids, 1, the 5-naphthalene dicarboxylic acids, 1, the 4-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 1,2-naphthalene dicarboxylic acids etc., but be not to be defined in these persons.The dicarboxylic acid that 2 carboxyls are arranged on the usually preferred phenyl ring.
The ratio that this does not contain the aromatic dicarboxylic acid of phenol hydroxyl and contains the aromatic dicarboxylic acid of phenol hydroxyl, the aromatic dicarboxylic acid that preferably contains the phenol hydroxyl more preferably contains 10 moles more than the % all accounting for 5 moles more than the % in the dicarboxylic acid.When using two kinds of dicarboxylic acid with this ratio, the polyamide resin that obtains is generally m/ (l+m) 〉=0.05 in formula (1), preferred m/ (l+m) 〉=0.1.In addition, can measure the value of m and 1 according to gel permeation chromatography or NMR etc.
Above-mentioned phosphorous acid ester as the condensing agent use, can enumerate as triphenyl phosphite phosphorous acid diphenyl ester, tricresyl phosphite o-toluene ester, the phosphorous acid di-o-tolyl, the tricresyl phosphite m-tolyl ester, tri-p-cresyl phosphite, two pairs of toluene esters of phosphorous acid, two pairs of chlorobenzene esters of phosphorous acid, tricresyl phosphite is to the chlorobenzene ester, two pairs of chlorobenzene esters of phosphorous acid etc., but be not to be defined as these persons.
In addition, can enumerate as pyridine 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine etc. with the pyridine derivate that phosphorous acid ester uses.
The above-mentioned pyridine derivate that uses as condensing agent adds in the organic solvent usually and uses.This organic solvent with phosphorous acid ester generation essence reaction, and have the character of above-mentioned aromatic diamine of excellent dissolution and above-mentioned aromatic dicarboxylic acid, and be that good solvent is advisable the aromatic polyamide resin that resultant of reaction contains the phenol hydroxyl.This organic solvent can be enumerated the acid amides series solvent as N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE etc., preferred N-N-methyl-2-2-pyrrolidone N-.Usually, in the mixture of pyridine derivate and solvent, the normal mixture that uses the pyridine derivate that adds to account for 5～30 weight %.
In addition, for obtaining the high polyamide resin of the polymerization degree, except above-mentioned phosphorous acid ester and pyridine derivate, to add lithium chloride, inorganic salts such as calcium chloride are good.
Hereinafter, the manufacture method of the polyamide resin of Ming Dynasty style (1) specifically.
At first, in mixed solvent, add phosphorous acid ester by the organic solvent that contains pyridine derivate, add again aromatic dicarboxylic acid and, be 0.5～2 mole aromatic diamine with respect to 1 mole of this dicarboxylic acid, heated and stirred under inert atmospheres such as nitrogen then.After reaction finishes, reaction mixture is thrown in the lean solvents such as methyl alcohol and hexane and after separating the polymkeric substance of purifying, purified, remove secondary resultant and inorganic salts etc., and acquire the target polyamide resin by reprecipitation method.
In the above-mentioned manufacture method as the addition of the phosphorous acid ester of condensing agent, usually with respect to carboxyl for waiting more than the mole, but 30 times of above and inefficiencies of mole.Though the amount of pyridine derivate is necessary with respect to carboxyl for waiting more than the mole, in fact because double as is a reaction solvent usefulness, so the situation of big excessive use is more.The usage quantity of the above-mentioned mixture of forming by pyridine derivate and organic solvent for polyamide resin 100 weight parts of gained in theory, the scope of preferred 5～30 weight parts.Temperature of reaction is generally 60～180 ℃.Reaction times is subjected to big influence because of temperature of reaction.No matter in any case to present high viscosity (the highest polymerization degree) up to reaction solution be preferred to the stirring reaction system, is generally several minutes～20 hours.
Above-mentioned, the inherent viscosity of the aromatic polyamide resin that contains the phenol hydroxyl with preferred mean polymerisation degree is (at 30 ℃, 0.5g/dl N, measure in the N-dimethylacetamide solution) be in 0.1～4.0dl/g scope, be generally 0.2～2.0dl/g, preferred 0.35～0.70dl/g, more preferably 0.40～0.60dl/g.Generally speaking whether have preferred mean polymerisation degree, judge with reference to particular viscosity.When limiting viscosity during less than 0.1dl/g, because film-forming properties and insufficient as the character performance of aromatic polyamide resin, so not preferred.On the contrary, when limiting viscosity during greater than 4.0dl/g, because the too high not only solvent solubility of the polymerization degree is not good, and the problem of shaping processability variation takes place.
Regulate the short-cut method of the polyamide resin polymerization degree, can enumerate the superfluous method of using as either party in aromatic diamine and the aromatic dicarboxylic acid.Generally speaking, the either party uses big excessive use then to obtain molecular weight to diminish, and obtains having the corresponding superfluous polyamide resin that uses the end of raw material.Preferably wait mole for obtaining the high-molecular weight polyamide resin as far as possible, but from the viewpoint of binding property etc., preferred two end be amino (the right terminal bonding of formula (1) hydrogen atom, the left-end point bonding H
2N-Ar
3The compound of-NH-) polyamide resin.This polyamide resin is when with respect to the about 0.1～about 20 moles of % of aromatic dicarboxylic acid, preferred about 0.2～about 15 moles of %, more preferably from about can obtain during the excessive use aromatic diamine of 0.5～about 15 moles of %.According to circumstances, most preferably with superfluous 1～5 mole of %.
The total (mean polymerisation degree) of l+m changes according to polymerizing condition, starting compound etc. in the polyamide resin of the above-mentioned formula that obtains (1), cannot treat different things as the same, but is generally the scope of l+m=2～200.Operation aspect under the low viscosity, preferred about 2～about 40.In addition, but 10 obtain the cured article of membranization when above, 20 become the cured article that is fit to become film when above, and 30 obtain being more suitable for the cured article of membranization when above, obtain being rich in flexible cured article at about 50～about 200 o'clock.Have flexible cured article, use to good composition epoxy resin of the present invention is processed into membranaceous back.Polyamide resin so of the present invention preferably according to the purposes of cured article of the composition that contains these, and is selected its mean polymerisation degree aptly.Considering the purposes of membranization etc., serve as preferred with the snappiness and operation (low viscosity) person of having both of cured article, the value of this mean polymerisation degree be about 10～about 60, preferably about 20～about 55,40 front and back most preferably, that is, 35～about 45 mean polymerisation degree most preferably from about.Preferred viscosity is index with above-mentioned limiting viscosity preferably.
The polyamide resin of the above-mentioned formula that obtains (1) is suitable for as epoxy curing agent, and can be used as with it is the epoxy curing agent use of effective constituent.
The content of this polyamide resin in the composition epoxy resin of the present invention, be generally more than 30% all (weight :) of said composition hereinafter if no special note is then identical, preferred more than 40%, more preferably more than 50%, the upper limit is generally below 98%, and is preferred about below 95%.
The Resins, epoxy that is used in the composition epoxy resin of the present invention has various.Can be used in electric, electronic component and get final product with the person, there is no particular restriction.For example can use alicyclic epoxy resin, fragrant family Resins, epoxy; Sorbitol polyglycidylether, Polyglycerine polyglycidyl ether, two glycerine polyglycidyl ethers, tetramethylolmethane polyglycidyl ether, glycerine polyglycidyl ether, trimethylolpropane polyglycidylether, neopentylglycol diglycidyl ether, 1, the reactant of polyalcohols such as 6-hexanediol diglycidyl ether and epoxy chloropropane; Ester ring type that two keys are obtained after with oxidations such as superoxide or straight catenate Resins, epoxy etc.Its epoxy equivalent (weight) of Resins, epoxy that the present invention uses (measuring according to JIS-K-7236) is generally about 50g/eq～about 600g/eq, preferably about 100g/eq～about 450g/eq, more preferably from about 120g/eq～about 350g/eq.
In the above-mentioned Resins, epoxy, serve as preferred with fragrant family Resins, epoxy from the flame retardant resistance aspect of cured article.As long as preferred fragrant family Resins, epoxy is for having aromatic rings such as phenyl ring, cyclohexyl biphenyl, naphthalene nucleus, and contains 2 above epoxy group(ing) persons in 1 molecule and get final product, and there is no specific qualification.Particularly can enumerate as linear phenol aldehyde type epoxy resin, the linear phenol aldehyde type epoxy resin that contains the xylylene skeleton contains the linear phenol aldehyde type epoxy resin of biphenyl backbone, bisphenol A type epoxy resin, bisphenol f type epoxy resin, tetramethyl biphenyl phenol-type epoxy resin etc.
In order to ensure the abundant flame retardant resistance of cured article, snappiness serves as preferred with the linear phenol aldehyde type epoxy resin that contains biphenyl backbone in above-mentioned Resins, epoxy, the Resins, epoxy of preferred especially above-mentioned formula (2) expression.The Resins, epoxy of formula (2) for example is easy to obtain as NC-3000, NC-3000-H commercially available products such as (being Japanese chemical drug (strain) system).
Other solidifying agent gone back and uses by solidifying agent in the composition epoxy resin of the present invention except the polyamide resin of structure shown in the tool formula (1).Also the solidifying agent of usefulness can specifically be enumerated as diaminodiphenylmethane diethylenetriamine, Triethylenetetramine (TETA), diaminodiphenylsulfone(DDS), isophorone diamine, Dyhard RU 100, by linolenic acid dipolymer and quadrol synthetic polyamide resin, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid acid anhydride, maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methyl-5-norbornylene-2,3 dicarboxylic anhydrides (methyl Nadic acidanhydride, the methyl carbic anhydride), hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, linear phenolic resin, tritane and these modifier, imidazoles, BF
3-amine complex, guanidine derivative etc., but be not to be defined in these.The represented polyamide resin of formula (1) shared ratio in whole solidifying agent is generally more than 20%, and is preferred more than 30%, and more preferably 40%～100%.
The usage quantity of solidifying agent in the composition epoxy resin of the present invention with respect to epoxy group(ing) 1 equivalent of Resins, epoxy, can be generally 0.4～1.5 with the equivalent of the active group of the epoxy reaction of solidifying agent, serves as preferred with 0.6～1.3, and 0.7～1.2 equivalent is for most preferably.Under the situation of the polymeric amide of above-mentioned formula of the present invention (1), for can with the phenol hydroxyl equivalent (Ahew) of epoxy reaction.This Ahew can be by mensuration such as NMR, but represent for convenient using from the calculated value of the Intake Quantity of diamines with phenol hydroxyl in an embodiment.
Also can when in addition, using above-mentioned solidifying agent and with curing catalyst.Curing catalyst can specifically be enumerated as glyoxal ethyline, 2-ethyl imidazol(e), imidazoles such as 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl) phenol, 1,8-diaza-dicyclo (5,4,0) tertiary amines such as hendecene-7, phosphine classes such as triphenyl phosphine, metallic compounds such as stannous octoate etc.As required, Resins, epoxy can use 0.1～5.0 part of curing catalyst for 100 parts relatively.
Composition epoxy resin of the present invention optionally can contain inorganic filling material.Inorganic filling material can specifically be enumerated as silica, alumina, talcum etc.Inorganic filling material accounts for 0～90 weight % in composition epoxy resin of the present invention.Can add silane coupling agent in the composition epoxy resin of the present invention, stearic acid, palmitinic acid, Zinic stearas, releasing agents such as calcium stearate, the various Synergist S-421 95s of pigment etc.
Preferred epoxy composition of the present invention is for containing Ar in the formula (1)
1Be phenylene, Ar
2Phenylene, Ar for the hydroxyl replacement
3Serve as reasons-ph (R
1) n-or-ph (R
2) n-O-ph (R
3) polyamide resin of the represented group of n-, those of the Resins, epoxy of formula (2) expression and curing catalyst optionally.
Composition epoxy resin of the present invention is by getting above-mentioned each composition uniform mixing.For example, with Resins, epoxy and the solidifying agent that contains formula (1) polyamide resin, and curing catalyst optionally and inorganic filling material, Synergist S-421 95, be fully mixed to evenly with forcing machine, kneader, roller etc. as required, can obtain composition epoxy resin of the present invention.After this resin combination optionally is shaped, available and the same method of institute's perception method in the past, for example method such as thermofixation obtains its cured article easily.Particularly optionally with this resin combination via fusion injection molding or transfer molding method or method moulding such as spray up moulding, compressed moulding method after, again in 80～200 ℃ of down heating 2～10 hours and obtain cured article.This cured article serves as preferred with the high person of second-order transition temperature with regard to thermotolerance, and for example the second-order transition temperature of measuring with the DMA method is to be advisable more than 200 ℃, more preferably more than 220 ℃.Though do not have the special upper limit,, therefore be generally about below 300 ℃ because of needs have snappiness.
Varnish of the present invention gets by composition epoxy resin of the present invention is dissolved in the solvent.This solvent can be enumerated as the gamma-butyrolactone class; N-Methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N,N-dimethylacetamide, N, acid amides series solvents such as N-methylimidazole alkane ketone; Sulfone classes such as tetramethylene sulfone; Ether series solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether-acetic ester, propylene glycol single-butyl ether; Ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone; Aromatic series such as toluene, dimethylbenzene series solvent.Wherein, be suitable for uniform mixing resin combination of the present invention with the aliphatic ketone series solvent of ketone series solvent, particularly C4～C6.Solid shape branch concentration is generally 10～80 weight % in the varnish that obtains, and serves as preferred with 10～70 weight %.
Sheet material with composition epoxy resin layer of the present invention normally is coated on the plane support by above-mentioned varnish is coated in support, gets via drying.At this moment, support uses peel plate (Bao From シ one ト usually) situation more.
Have the sheet material of the cured article layer that composition epoxy resin layer curing of the present invention is got,, normally be coated on the plane support, carry out drying, the layer that obtains can be obtained through thermofixation again by above-mentioned varnish being coated on the support (base material).Be about to above-mentioned varnish with various coating processes such as various known intaglio plate coating methods own, silk screen print method, metal mask method, method of spin coating, on plane support, be coated with, make that dried thickness is desirable thickness, 5～100 μ m for example, dry then, obtain the layer of this resin combination.Use which kind of coating method can be, shape, size, the film thickness of filming and suitable the selection according to the kind of base material.Base material is for example polymeric amide, polyimide, polyamidoimide, polyarylester (polyarylate), polyethylene terephthalate, polybutylene terephthalate, polyether-ether-ketone, polyetherimide, polyetherketone, polyketone, polyethylene, the film that various polymers such as polypropylene and/or its multipolymer make, or tinsel such as Copper Foil serve as preferred with polyimide or tinsel wherein.The sheet material of this resin combination layer of tool of gained like this; but being used in to former state following curing uses; in addition, according to purposes, support can use stripping film; the protection thin plate can be covered the surface in case of necessity; peel the protection thin plate during use, on other support, paste and pay this resin combination layer, peel stripping film; after processing according to necessity, carry out following solidification treatment and also can.
Then, above-mentioned this resin combination layer heating that obtains can be obtained having the sheet material of cured article layer.The preferable use of sheet material of the present invention can be enumerated as flexographic printing (flexoprinting) wiring flexographic printing running board materials such as substrate, covering layer material, bonding thin plate, and composition epoxy resin of the present invention works as the tackiness agent that constitutes these.
In addition, for obtaining to use the pre-impregnated article of composition epoxy resin of the present invention, this resin combination is dissolved in the above-mentioned solvent obtains varnish, make varnish impregnation at glass fibre, carbon fiber, trevira, tynex, alumina fiber gets in the base materials such as paper and through heat drying.The pre-impregnated article that obtains forms via hot compacting etc. and solidifies, and obtains cured article.At this moment solvent is generally about 10～about 70%, preferred about 15～about 70% with respect to the total amount of this resin combination and this solvent.
Embodiment
Hereinafter with embodiment, comparative example the present invention is described more specifically, hereinafter " part " is not weight part as long as there is special instruction.
Embodiment 1
In the flask that thermometer, cooling tube, agitator are installed, lead to nitrogen purge on one side, add 45.5 parts of 5-hydroxyl m-phthalic acids on one side, 41.5 parts of m-phthalic acids, 55.1 parts of mphenylenediamines, 3.4 parts of lithium chlorides, 344 parts of N-N-methyl-2-2-pyrrolidone N-s are after 115.7 parts of pyridines and the stirring and dissolving, 251 parts of triphenyl phosphites of adding also reacted 4 hours under 90 ℃, obtained containing the polyamide resin lipoprotein solution of phenol hydroxyl.This reaction solution room temperature to cooling, is put in 500 parts of the methyl alcohol, separated out the resin of following formula (3) expression.
With behind this resin of separating out of 500 parts of washings of methyl alcohol, carry out methanol eddy, purification once more, obtain 120 parts polyamide resin (A).The limiting viscosity of the polyamide resin that obtains (A) is 0.49dl/g (dimethylacetamide solution, 30 ℃), and in formula (3), the value of l is about 6, and the value of m is about 6, can be 417g/eq with the Ahew of epoxy reaction.
Embodiment 2
Remove and to change the mphenylenediamine among the embodiment 1 into 3 for 55.1 parts, carry out same reaction beyond 102 parts of 4 '-diaminodiphenyl oxides, obtain 166 parts of the polyamide resins (B) of following formula (4) expression:
The limiting viscosity of the polyamide resin that obtains (B) is 0.56dl/g (dimethylacetamide solution, 30 ℃), and in formula (4), the value of l is about 20, and the value of m is about 20, can be 633g/eq with the Ahew of epoxy reaction.
Embodiment 3
Except the usage quantity with the 5-hydroxyl m-phthalic acid among the embodiment 2 changes 13.0 parts into, beyond changing 71.1 parts into, the usage quantity of m-phthalic acid carries out reaction similarly to Example 2, separate out the resin of following formula (4) expression.This resin of separating out with after 500 parts of washings of methyl alcohol, carries out methanol eddy, purification again, obtains 163 parts polyamide resin (C).The limiting viscosity of the polyamide resin that obtains (C) is 0.54dl/g (dimethylacetamide solution, 30 ℃), and in formula (4), the value of l is about 34, and the value of m is about 6, can be 1868g/eq with the Ahew of epoxy reaction.
Application Example 1 to 4
To the polyamide resin (A) that obtains among the embodiment 1,2 or (B), will be according to the weight ratio shown in the table 1 as above-mentioned (2) of Resins, epoxy represented Resins, epoxy NC-3000 (Nippon Kayaku K. K's system, epoxy equivalent (weight) is 275g/eq, softening temperature is 58 ℃, p=2.5) (being NC-3000 in the table), and aqueous bisphenol A type epoxy resin RE-310S (Nippon Kayaku K. K's system, epoxy equivalent (weight) is 184g/eq) (in the table for RE-310), as the triphenyl phosphine (TPP) of curing catalyst, mix as the cyclopentanone of solvent, obtain varnish of the present invention.
Table 1
| Application Example | ||||
| 1 | 2 | 3 | 4 | |
| NC-3000 | 100 | 100 | 100 | |
| RE-310 | 100 | |||
| Polyamide resin (A) | 136 | 203 | ||
| Polyamide resin (B) | 188 | 281 | ||
| TPP | 2 | 2 | 2 | 2 |
| Cyclopentanone | 238 | 290 | 305 | 383 |
4 kinds of varnish of the invention described above are coated to make dried thickness on the PET film be 50 μ m, and heating makes its curing in 1 hour under 180 ℃ temperature, obtain tabular sample (thickness is 12.5 μ m) after removing the PET film.Any one all can not break the sample that obtains through bending yet, has sufficient film and forms ability.This cured article carries out the test of flame retardant resistance according to UL94-VTM.In addition, these samples are measured second-order transition temperature via DMA (dynamic mechanical analysis, Dynamic MechanicalAnalysis).Re-using spreader is the last varnish coating with gained of polyimide film (Upilex 25SGA Ube Industries, Ltd system) of 25 μ m at thickness, and making dried thickness is 10 μ m.100 ℃ removed in dry 10 minutes down desolvate after, overlapping with same polyimide film on resin layer again, under 180 ℃, carry out 1 hour curing reaction.Observe the degree of peeling off (90 degree are peeled off) of various samples.The results are shown in table 2.
Table 2
| Application Example |
| 1 | 2 | 3 | 4 | |
| Flame retardant test | V-0 | V-0 | V-0 | V-0 |
| Second-order transition temperature (℃) | 245 | 234 | 232 | 228 |
| Stripping test | Aggegation destroys | Aggegation destroys | Aggegation destroys | Aggegation destroys |
In addition, the described V-0 of fire retardancy test item in the table is the evaluation of difficult to burn in the flame retardant of plastic degree.
Stripping test is that fixedly the adherent film is pulled to right angle (90 degree) at leisure to a slice in 2 films of adherent, checks the degree of peeling off.It is not that 2 films are peeled off fully that aggegation in the table destroys expression, but film destroy.
Application Example 5 to 8
To embodiment 2, the polyamide resin that obtains in 3 (B) or (C), will be as tritane type epoxy resin PN-502H (Nippon Kayaku K. K's system of Resins, epoxy, epoxy equivalent (weight) is 170g/eq, softening temperature is 65 ℃) (in table, being EPPN-502H) or aqueous bisphenol f type epoxy resin RE-304S (Nippon Kayaku K. K's system, epoxy equivalent (weight) is 170g/eq) (in table, being RE-304S), 2-phenyl-4 as curing catalyst, 5-dihydroxyl Methylimidazole (2PHZ), cyclopentanone as solvent, press the represented weight ratio of table 3 and mix, obtain varnish of the present invention.
Table 3
| Application Example | ||||
| 5 | 6 | 7 | 8 | |
| RE-304S | 100 | 100 | ||
| EPPN-502H | 100 | 100 | ||
| Polyamide resin (B) | 372 | 372 | ||
| Polyamide resin (C) | 1098 | 1098 | ||
| 2PHZ | 2 | 2 | 2 | 2 |
| Cyclopentanone | 474 | 1200 | 474 | 1200 |
Above-mentioned 4 kinds of varnish of the present invention are coated to make dried thickness on the PET film be 50 μ m, and heating makes curing in 1 hour under 180 ℃ temperature, obtain tabular sample after removing the PET film.Any one all can not break resulting sample through bending yet, has sufficient film and forms ability.Cured article carries out flame retardant test according to the UL94-VTM method.These samples are measured second-order transition temperature via DMA.In addition, the varnish that obtains is coated on the polyimide that thickness is 25 μ m (Upilex 25SGA Ube Industries, Ltd system) with spreader, and thickness is that making dried thickness is 10 μ m on the asperities of surface treatment copper foil of 18 μ.100 ℃ removed in dry 10 minutes down desolvate after, the overlapping more same polyimide film or the asperities of surface treatment copper foil on resin layer carry out 1 hour curing reaction under 180 ℃ with the hot plate pressing unit.Observe the degree that various samples are peeled off.The result is shown in table 4.
Table 4
| Application Example | ||||
| 5 | 6 | 7 | 8 | |
| Flame retardant test | V-0 | V-0 | V-0 | V-0 |
| Second-order transition temperature (℃) | 235 | 242 | 260 | 272 |
| Stripping test (polyimide) | Aggegation destroys | Aggegation destroys | Aggegation destroys | Aggegation destroys |
| Stripping test (Copper Foil) | Aggegation destroys | Aggegation destroys | Aggegation destroys | Aggegation destroys |
(utilizing on the industry possibility)
The solidfied material of composition epoxy resin of the present invention, also has sufficient pliability when membranaceous being configured as, although and its solidfied material do not contain halogenated flame retardant or antimonial etc. and still have anti-flammability, and heat resistance, cohesive is superior, therefore at moulding material, the injection molding material, laminated material, coating, adhesive, exceedingly useful in the purposes of the broad range such as resist.
Claims (21)
1. composition epoxy resin, it comprises (a) Resins, epoxy and (b) polyamide resin of the following formula of tool (1) structure:
In the formula, l, m are mean value, expression m/ (l+m) 〉=0.05, and l+m is 2～200 positive number; Ar
1Aromatic series base, Ar for divalent
2Aromatic series base, Ar for the divalence that contains the phenol hydroxyl
3Expression-ph (R
1) n-or-ph (R
2) n-X-ph (R
3) n-;-ph (R
1) n-,-ph (R
2) n-or-ph (R
3) n-represents R separately
1Replacement, R
2Replace or R
3The phenylene that replaces, or represent the phenylene of non-replacement; N is 0～3 integer; R
1, R
2Or R
3Represent C1～C3 alkyl, C1～C3 alkoxyl group independently; X represents O, S, CO, SO
2, or singly-bound.
2. composition epoxy resin as claimed in claim 1, wherein, with respect to epoxy group(ing) 1 equivalent in the composition (a), the Ahew in the composition (b) is 0.7～1.2 equivalent.
3. composition epoxy resin as claimed in claim 1, wherein, for whole solidifying agent contained in the composition, the content ratio of the polyamide resin of composition (b) is more than the 30 weight %.
4. composition epoxy resin as claimed in claim 1, wherein all with respect to composition, contain the Resins, epoxy of 2～50 weight % compositions (a) and the solidifying agent of 50 to 98 weight % compositions (b).
5. as each described composition epoxy resin, wherein Ar in the claim 1～4
3For-ph (R
1) n-or-ph (R
2) n-O-ph (R
3) n-.
6. as each described composition epoxy resin in the claim 1～4, wherein the polyamide resin of composition (b) is the compound with structure shown in the following formula (3):
In the formula, l and m represent with formula (1) in identical implication.
7. as each described composition epoxy resin in the claim 1～4, wherein the polyamide resin of composition (b) is the compound with structure shown in the following formula (4):
In the formula, l and m represent with formula (1) in identical implication.
8. as each described composition epoxy resin in the claim 1～4, wherein, l+m is 2～20 positive number.
9. as each described composition epoxy resin in the claim the 1～4, wherein, composition (a) for be selected from by linear phenol aldehyde type epoxy resin, contain the xylylene skeleton linear phenol aldehyde type epoxy resin, contain linear phenol aldehyde type epoxy resin, the bisphenol A type epoxy resin of biphenyl backbone, at least a in the group that bisphenol f type epoxy resin, tetramethyl biphenyl phenol-type epoxy resin and tritane type Resins, epoxy are formed.
10. composition epoxy resin as claimed in claim 8, wherein, the linear phenol aldehyde type epoxy resin of composition (a) for having biphenyl backbone shown in the following formula (2):
In the formula, P is expressed as mean value, is 0.1～10 positive number.
11. as each described composition epoxy resin in the claim 1～4, it contains curing catalyst.
12. a varnish obtains by each described composition epoxy resin in the claim 1～11 is dissolved in the solvent.
13. a varnish, solvent is 10～70 weight % for varnish is all, and rest part is the described composition epoxy resin of claim 12.
14. varnish as claimed in claim 13, wherein, solvent is the aliphatic ketone series solvent of C4～C6.
15. a sheet material has the layer as each described composition epoxy resin in the claim 1～11 on the two sides of plane support or single face.
16. a sheet material, on the two sides of plane support or single face, have the layer of each described composition epoxy resin in the claim 1～11 is solidified and the cured article layer.
17. as claim 15 or 16 described sheet materials, wherein, plane support is polyimide film, tinsel or stripping film.
18. a pre-impregnated article is by making the described varnish impregnation of claim 12 in base material, dry and obtain.
19. the curing of a composition epoxy resin is characterized in that, with each described composition epoxy resin heating in the claim 1～11.
20. an epoxy curing agent is an effective constituent with the polyamide resin with structure shown in the following formula (1):
In the formula, l, m are mean value, expression m/ (l+m) 〉=0.05, and l+m is 2～200 positive number; Ar
1Aromatic series base, Ar for divalent
2Aromatic series base, Ar for divalence with phenol hydroxyl
3Expression-ph (R
1) n-or-ph (R
2) n-X-ph (R
3) n-;-ph (R
1) n-,-ph (R
2) n-or-ph (R
3) n-represents R separately
1Replacement, R
2Replace or R
3The phenylene that replaces, or represent the phenylene of non-replacement; N is 0～3 integer; R
1, R
2Or R
3Represent C1～C3 alkyl, C1～C3 alkoxyl group independently; X represents O, S, CO, SO
2, or singly-bound.
21. epoxy curing agent as claimed in claim 20, wherein, Ar
3For-ph (R
1) n-or-ph (R
2) n-O-ph (R
3) group shown in the n-.
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| CN106715579A (en) * | 2014-09-22 | 2017-05-24 | 赫克塞尔合成有限公司 | Fast curing compositions |
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| CN101208373B (en) | 2005-07-21 | 2010-12-01 | 日本化药株式会社 | Polyamide resin, epoxy resin compositions, and cured articles thereof |
| WO2008072630A1 (en) * | 2006-12-13 | 2008-06-19 | Nipponkayaku Kabushikikaisha | Polyamide resin, epoxy resin composition using the same, and use of the composition |
| CN101343403B (en) * | 2007-07-12 | 2010-11-17 | 比亚迪股份有限公司 | Halogen-free flame retardant epoxy resin composition and preparation thereof |
| KR20120135217A (en) * | 2010-03-15 | 2012-12-12 | 니폰 가야꾸 가부시끼가이샤 | Heat-resistant adhesive |
| CN105612190B (en) * | 2013-10-09 | 2017-11-10 | 日本化药株式会社 | Phenol resin, epoxy resin, composition epoxy resin, prepreg and their solidfied material |
| CN110452533A (en) * | 2019-09-25 | 2019-11-15 | 常州市宏发纵横新材料科技股份有限公司 | A kind of norbornene end-sealed type Wholly aromatic polyamide prepreg composition and its preparation method and application method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686557A (en) * | 1994-09-21 | 1997-11-11 | Tomoegawa Paper Co., Ltd. | Polyamide resin which can be dissolved in alcohol solvent, composition thereof, and method of use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686557A (en) * | 1994-09-21 | 1997-11-11 | Tomoegawa Paper Co., Ltd. | Polyamide resin which can be dissolved in alcohol solvent, composition thereof, and method of use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106715579A (en) * | 2014-09-22 | 2017-05-24 | 赫克塞尔合成有限公司 | Fast curing compositions |
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