CN1167728C - Cross-linking polyphenyl ether resin with epoxy group, its composition and making method - Google Patents

Cross-linking polyphenyl ether resin with epoxy group, its composition and making method Download PDF

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CN1167728C
CN1167728C CNB011181087A CN01118108A CN1167728C CN 1167728 C CN1167728 C CN 1167728C CN B011181087 A CNB011181087 A CN B011181087A CN 01118108 A CN01118108 A CN 01118108A CN 1167728 C CN1167728 C CN 1167728C
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group
epoxy
polyphenyl ether
ether resin
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CN1385454A (en
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鄞盟松
林倩婷
康鸿洲
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Industrial Technology Research Institute ITRI
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Abstract

The present invention relates to cross-linking polyphenyl ether PPE resin with an epoxy group, and a composition and a preparation method thereof. The preparation method comprises the following steps: hydroxyl and an ester group in the terminal structure of PPE are modified by a PPE modified technique; a functional group with an epoxy group is introduced to prepare cross-linking thermosetting PPE resin with an epoxy group. Because the modified PPE resin has an epoxy group, the compatibility between the modified PPE resin and epoxy resin can be greatly enhanced.

Description

Cross-linking polyphenyl ether resin, its composition and manufacture method thereof with epoxy group(ing)
The present invention relates to a kind of cross-linking polyphenyl ether resin, its composition and manufacture method thereof, be particularly related to a kind of manufacture method of cross-linking polyphenyl ether resin, it is that end group with polyphenylene oxide resin gives modificationization, the functional group that will have an epoxy group(ing) import and.
Along with information products move towards high speed and high frequencyization, the required baseplate material of future development new generation product, as cableless communication networking, satellite communication device, superpower and wideband product, high-speed computing machine and computer workstation etc. all need to have high glass-transition temperature (Tg), the baseplate material of low-k (Dk) and low loss factors (Df).The present employed copper clad laminate of printed circuit board (PCB) (PCB) no matter be quantitatively or technical, all is the FR-4 sheet material based on the Resins, epoxy made, but electrical propertiess such as the Dk of FR-4 and Df can't meet the demand of high frequency gradually.
Polyphenylene oxide resin (Polyphenylene ether; PPE) have high Tg and good electrical specification, therefore have potential as the high frequency substrate material.Therefore, existing people introduces the PPE resin in the FR-4 substrate of Resins, epoxy made, so that the character of limited Resins, epoxy is improved.Yet, Resins, epoxy and PPE resin are very different on chemical structure, its chemical compatibility generally not good (each other can't be crosslinked), make that having the phenomenon that is separated between PPE and the Resins, epoxy takes place, cause when being applied in the PPE-epoxy resin system on the printed circuit board (PCB), very big difficulty is arranged.Therefore, existing investigator attempts solving PPE and Resins, epoxy mixes the problem that is separated when using.
For example, U.S.Patent No.4,853,423, it is with after PPE and the Resins, epoxy mixing, adds zinc acetylacetonate or Zinic stearas, and these two kinds of metal-salts are as compatilizer, can make and produce coordinate bond (coordination bonding) between PPE and the Resins, epoxy, to solve the problem that is separated between PPE and the Resins, epoxy.But this type of metal-salt regular meeting causes the electrical properties of substrate not good.
Again for example, U.S.Patent No.5,834,565, it is little that it is that molecular weight with the PPE resin changes, and emphasizes that the molecular weight of PPE is littler, then more do not have the generation that is separated between PPE and the Resins, epoxy.But the molecular weight of PPE resin is too little, and especially Mn was less than 3000 o'clock, and the electrical properties of resin is not good, has lost the original idea that adds the PPE resin.
Therefore, still be necessary to develop new method, to solve the problem that consistency between PPE and the Resins, epoxy is not good, be separated.
Purpose of the present invention is and addresses the above problem, and a kind of manufacture method with cross-linking polyphenyl ether resin of epoxy group(ing) is provided, and it is that epoxy group(ing) is imported in the polyphenylene oxide resin;
Another object of the present invention provides a kind of cross-linking polyphenyl ether resin with epoxy group(ing) of novelty, and it has epoxy group(ing), thereby with Resins, epoxy good consistency is arranged;
Another purpose of the present invention provides a kind of polyphenyl ether resin composition of novelty, and it can be in order to make the film and the copper clad laminate of use in printed circuit board;
Another purpose of the present invention provides the application of described polyphenyl ether resin composition aspect making gum Copper Foil;
Another purpose of the present invention provides the application of described polyphenyl ether resin composition aspect the making caking agent;
Another purpose of the present invention provides the application of described polyphenyl ether resin composition aspect making IC packaged material;
Another purpose of the present invention provides the application of described polyphenyl ether resin composition aspect the making powder coating;
Another purpose of the present invention provides the application aspect described polyphenyl ether resin composition has strongthener in making the film;
A further object of the present invention provides the application of described polyphenyl ether resin composition aspect the making copper clad laminate.
For reaching above-mentioned purpose of the present invention, the manufacture method with cross-linking polyphenyl ether resin of epoxy group(ing) of the present invention comprises:
One polyphenylene oxide resin of (I) structure that has chemical formula and the compound that a highly basic and one contains leaving group and epoxy group(ing) are reacted, and the cross-linking polyphenyl ether resin of (II) structure that obtains having chemical formula,
Wherein the structure of chemical formula (I) is:
Figure C0111810800081
R wherein 1Can be identical or different, and for be selected from by the alkyl of H, carbon number 1 to 3 and
Figure C0111810800082
The group that is formed, wherein R 11Be the alkylidene group of carbon number 1 to 3, R 12Be aromatic base;
Z 1Can be identical or different, and for be selected from by H, OH and
In the group that is formed, and at least one Z 1For OH or
Figure C0111810800084
R wherein 13Be aromatic base;
P is 2 to 165,
The wherein said compound that contains leaving group and epoxy group(ing) has the structure shown in the chemical formula (A):
Wherein
X is a leaving group that is selected from the group that is made up of halogen and sulphonate;
N is 1～6 integer,
Wherein the structure of chemical formula (II) is:
Figure C0111810800091
Wherein
R 2Can be identical or different, and for be selected from by the alkyl of H, carbon number 1 to 3,
The group that is formed, wherein
R 11Alkylidene group for carbon number 1 to 3;
R 12Be aromatic base;
N is 1～6 integer; And
S is 0 or 1～6 integer;
Z 2Can be identical or different, and for select free H, OH,
Figure C0111810800093
The group that is formed, and at least one Z 2Be the group shown in the chemical formula (i), wherein R 13Be aromatic base, the definition of n and s as mentioned above;
P is 2 to 165.
The present invention mainly provides the manufacture method of a kind of crosslinkable polyphenyl ether (PPE) resin, and it is to make hydroxyl in the PPE end structure (OH) and ester group [O-(C=O)-R 13, R 13Be aromatic base], give modification via modification technology, the functional group that will have epoxy group(ing) imports, and obtains the crosslinkable solidity PPE resin hot in nature that end has epoxy group(ing).Because the MODIFIED PP E resin that makes has epoxy group(ing), so have good consistency between itself and the Resins, epoxy, and can be used for producing copper clad laminate with advantageous property.
According to the present invention, the manufacture method of cross-linking polyphenyl ether resin is: one polyphenylene oxide resin of (I) structure that has chemical formula and the compound that a highly basic and one contains leaving group and epoxy group(ing) are reacted, and the cross-linking polyphenyl ether resin of (II) structure that obtains having chemical formula.
The structure of chemical formula (I) is:
R wherein 1Can be identical or different, and for be selected from by the alkyl of H, carbon number 1 to 3 and
Figure C0111810800102
The group that is formed, wherein R 11Be the alkylidene group of carbon number 1 to 3, R 12Be aromatic base;
Z 1Can be identical or different, and for be selected from by H, OH and
The group that is formed, and at least one Z 1For OH or
R wherein 13Be aromatic base;
P is 2 to 165.
The compound that contains leaving group and epoxy group(ing) has the structure shown in the chemical formula (A):
Wherein X is a leaving group that is selected from the group that is made up of halogen and sulphonate;
N is 1～6 integer.
The structure of chemical formula (II) is:
Figure C0111810800113
R wherein 2Can be identical or different, and for be selected from by the alkyl of H, carbon number 1 to 3,
Figure C0111810800114
The group that is formed, wherein
R 11Alkylidene group for carbon number 1 to 3;
R 12Be aromatic base;
N is 1～6 integer; And
S is 0 or 1～6 integer;
Z 2Can be identical or different, and for be selected from by H, OH,
Figure C0111810800121
The group that is formed, and at least one Z 2Be the group shown in the chemical formula (i), wherein R 13Be aromatic base, the definition of n and s as mentioned above;
P is 2 to 165.
In the PPE shown in the chemical formula (I), terminal group Z 1At least one be hydroxyl (OH) or ester group [O-(C=O)-R 13, R 13Be aromatic base], after reacting with highly basic, the compound that contains leaving group and epoxy group(ing), terminal group Z 1Be modified as Z 2, at least one Z wherein 2Be the group shown in the chemical formula (i):
In other words, the present invention is the thermoplasticity PPE resin that end is not contained epoxy group(ing), and the functional group that will have epoxy group(ing) via modification technology imports, and obtains the thermoset PPE resin with bridging property that end has epoxy group(ing).
In above-mentioned modification reaction, topmost reaction is that the functional group who contains epoxy group(ing) is imported into end.In addition, the functional group who contains epoxy group(ing) also might be imported into the side chain of PPE.For example, at least one side chain R in the PPE of chemical formula (I) 1For-R 11-O-(C=O)-R 12(R 11Be the alkylidene group of carbon number 1 to 3, R 12Be aromatic base) time (, side chain contains ester group), then after carrying out the modification reaction with highly basic, the compound that contains leaving group and epoxy group(ing), epoxy group(ing) also can be imported in the side chain, and forms
Figure C0111810800131
R 2Group, wherein R 11Definition the same; N is 1～6 integer; And s is 0 or 1～6 integer.
Be applicable to that highly basic of the present invention can be alkali metal hydroxide, alkalimetal hydride or alkaline earth metal hydride, concrete example such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydride, hydrolith etc.
Contain in the compound of leaving group and epoxy group(ing) in the present invention, leaving group can be halogen leaving group or sulphonate leaving group, and wherein halogen can be chlorine, bromine, iodine etc., and sulphonate can be tosylate, methanesulfonates etc.This object lesson that contains the compound of leaving group and epoxy group(ing) can be epoxy bromopropane (epibromohydrin), and 2,3-epoxypropyl-p-toluenesulfonic esters (glycidyl tosylate), or epoxy chloropropane (epichlorohydrin).
The present invention makes the method for cross-linking polyphenyl ether resin and preferably carries out in the presence of a phase-transfer catalyst.The phase-transfer catalyst that is suitable for for example can be NR 3 4 +Y -, R wherein 3Be the alkyl of carbon number 1～6, Y -For being selected from by Br -, I -, OH -, and HSO 4 -The group that (hydrogen sulfate) formed.Object lesson comprises hydrogen sulfate tetra-n-butyl ammonium [(n-Bu) 4NHSO 4], hydroxide tetra-n-butyl ammonium [(n-Bu) 4NOH], bromination tetra-n-butyl ammonium [(n-Bu) 4NBr], iodate tetra-n-butyl ammonium [(n-Bu) 4NI], hydrogen sulfate four n-propyl ammoniums and iodate four n-propyl ammoniums etc.
The present invention also provides a kind of cross-linking polyphenyl ether resin with epoxy group(ing), and it has the structure of chemical formula (II):
Figure C0111810800141
R wherein 2Can be identical or different, and for be selected from by the alkyl of H, carbon number 1 to 3,
The group that is formed, wherein
R 11Alkylidene group for carbon number 1 to 3;
R 12Be aromatic base;
N is 1～6 integer; And
S is 0 or 1～6 integer;
Z 2Can be identical or different, and for be selected from by H, OH,
Figure C0111810800143
The group that is formed, and at least one Z 2Be the group shown in the chemical formula (i), wherein R 13Be aromatic base, the definition of n and s as mentioned above;
P is 2 to 165.
Z 2Object lesson as
Wherein s is 0 or 1～6 integer.
The present invention also provides a kind of polyphenyl ether resin composition, and it comprises: (a) cross-linking polyphenyl ether resin with epoxy group(ing), and this resin has the structure of above-mentioned chemical formula (II); And (b) epoxy crosslinking agent of 0.1～95wt%, wherein the content of composition (b) is benchmark with the gross weight of said composition.
There is no particular restriction for epoxy crosslinking agent in the polyphenylene ether resin combination of the present invention, can comprise the linking agent that general Resins, epoxy is commonly used.For example, amine linking agent, concrete example such as Dyhard RU 100 (dicyandiamide), diethylenetriamine (diethylene triamine), boron triflouride-mono aminoethane mixture (BF 3-MEA), melamine, guanamines (guanamine), biguanides (biguanide) etc.; The phenols linking agent, concrete example such as phenolic varnish, the cresols phenolic varnish, the Resorcinol phenolic varnish, bisphenol-A phenolic varnish, and three (dimethyl amine ylmethyl) phenol [tris (dimethyl aminomethyl) phenol] etc.; The anhydrides linking agent, concrete example such as phthalate anhydride (phthalic anhydride) etc.The consumption of employed amine linking agent among the present invention, the equivalence ratio that is preferably amine active hydrogen and epoxy group(ing) is 0.5～3.0; The consumption of phenols linking agent, the equivalence ratio that is preferably hydroxyl and epoxy group(ing) is 0.5～2.0, more preferably 0.6～1.3; The consumption of anhydrides linking agent, the equivalence ratio that is preferably acid anhydrides and epoxy group(ing) is 0.5～3.0.
One Resins, epoxy that also can comprise 0.5～90wt% in the polyphenyl ether resin composition of the present invention is benchmark with the gross weight of said composition.It is Resins, epoxy or its mixture that Resins, epoxy can be dicyclopentadienyl Resins, epoxy, xenyl (biphenyl) Resins, epoxy, phenolic resin varnish, bis-phenol (bisphenol) Resins, epoxy, terpenes (terpene) Resins, epoxy, aralkyl (aralkyl) Resins, epoxy, polyfunctional epoxy resin, naphthalene.
Polyphenyl ether resin composition of the present invention further can comprise the crosslinking accelerator of 0.1～10wt%, is benchmark with the gross weight of said composition.Kind to this crosslinking accelerator is not particularly limited, and general Resins, epoxy crosslinking accelerator commonly used gets final product.Concrete example such as triphenyl Three (2, the 6-Dimethoxyphenyl)
Figure C0111810800162
Three (contraposition-tolyls)
Figure C0111810800163
The phosphorus compound of tricresyl phosphite phenyl etc.; The imidazoles of glyoxal ethyline, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-ethyl-4-methylimidazole etc.; The tertiary amine class of 2-dimethyl amido sylvan, benzyl dimethyl amine etc.; 2,5-azo dicyclo [4,3,0]-5-nonene, 1,4-azo dicyclo [2,2,2] octane, 1, the organic salt base class of 8-azo dicyclo [5,4,0]-7-hendecene etc.
Polyphenyl ether resin composition of the present invention can further comprise the fire retardant of 0.1～50wt%, is benchmark with the gross weight of said composition.Fire retardant can be phosphonium flame retardant, chlorine-containing flame retardant, brominated flame-retardant, contains nitrogen combustion inhibitor, antimony oxygen compound, aluminium hydroxide, magnesium hydroxide or its mixture.The wherein object lesson of brominated flame-retardant such as N1; N1-diallyl-2-[2; 6-two bromo-4-(2-{3; 5-two bromo-4-[(diallyl formamyls) methoxyl group] phenyl }-1; the 1-dimethyl ethyl)-and phenoxy group] ethanamide (N1, N1-diallyl-2-[2,6-dibromo-4-(2-{3; 5-dibromo-4-[(diallylcarbamoyl) methoxy] phenyl}-1,1-dimethylethyl)-and phenoxy] acetamide).
Polyphenyl ether resin composition of the present invention can be applicable on gum Copper Foil (resin coated copper), caking agent, IC packaged material or the powder body coating.
In the present invention, the composition in the above-mentioned resin combination is added thorough mixing in the solvent, be dissolved into colloidal solution (varnish; Be commonly called as polish) after, with the strongthener impregnation wherein, oven dry back film (pre-preg), wherein strongthener for example is paper, glasscloth etc.
Substrate with Copper Foil and above-mentioned film pressing form is copper clad laminate.When this copper clad laminate is applied to the preparation of printed circuit board (PCB), have superior electrical properties, it meets the demand of high speed and high frequencyization.
Below, will be for several embodiment so that method of the present invention, feature, and advantage to be described, but be not in order to limiting scope of the present invention, scope of the present invention should be as the criterion with accompanying claims.
Fig. 1 has the NMR collection of illustrative plates of the rPPE product of epoxy group(ing) for the end of the embodiment of the invention 2;
Fig. 2 is the DSC collection of illustrative plates of the resin combination of the embodiment of the invention 3.
The redistribution reaction of embodiment 1 PPE
With 360 grams poly-(2,6-dimethyl-1,4-phenylate) (a kind of PPE, the number molecular-weight average is about 19772 gram/moles) is dissolved in 100 ℃ the 360 gram toluene, after treating that it dissolves fully, add 36 grams 2 again, and two (4-hydroxyphenyl) propane of 2-(bisphenol A, BPA), after treating its dissolving, slowly add 48 gram dibenzoyl peroxide (BPO, 75% the aqueous solution) again, reacted about 2 hours down at 100 ℃.After treating that it is back to room temperature, add about 800 milliliters methyl alcohol,, clean repeatedly more than twice, about 360 grams of the PPE that can reallocate after the drying (rPPE) product with methyl alcohol then with the solid that precipitates.Show that by the GPC measurement result number molecular-weight average of this rPPE product is about 3512 gram/moles.
The terminal-modified reaction of embodiment 2 rPPE
The rPPE products of about 50 gram embodiment 1 gained are dissolved in 150 milliliters the toluene, are heated to 65 ℃.The KOH of 6.73 grams is dissolved in the methyl alcohol of 20.2 grams.Then, the methanol solution of KOH is poured in the toluene solution of rPPE, W-response was carried out under 65 ℃ 4 hours, be cooled to the epoxy chloropropane that adds 6.94 grams after 35 ℃ again, at room temperature reacted 14 hours.
Then, reaction mixture is extracted solvent to surplus 50 milliliters approximately with the concentrating under reduced pressure method, pour in 200 ml methanol, resin precipitated is come out.The resin of gained is taken out remaining solvent with vacuum pump again with washed with methanol twice, can obtain the rPPE product that end has epoxy group(ing).
By can see in the NMR collection of illustrative plates (Fig. 1) successfully connected epoxy group(ing) (δ=2.88ppm, 2.77ppm).
Embodiment 3 preparation crosslinkable PPE resin combination and colloidal solutions
Get the rPPE that 8.9 ends that restrain embodiment 2 gained have epoxy group(ing), add 17.8 gram toluene, after being stirred to fully dissolving, getting the tetrabromo Resins, epoxy (BEB-530A80 of Changchun petro-chemical corporation) that 11.13 grams contain 20% acetone again and add wherein, continue to be stirred to and be dissolved into A liquid fully.In addition, get 1.06 gram Dyhard RU 100 (DICY; Dicyandiamide) (linking agent) and 0.2 gram glyoxal ethyline (2-MI) (crosslinking accelerator) add 5.3 gram N again, and dinethylformamide (DMF) stirring and dissolving together becomes B liquid.At last B liquid is added in the A liquid, stirs and form colloidal solution.Through dsc analysis, crosslinking reaction can take place between provable terminal-modified rPPE and Resins, epoxy in the existence of exothermic peak from collection of illustrative plates (Fig. 2).
Embodiment 4 preparation films
At first cut glass cloth and become 8 centimeters * 8 centimeters areas.The colloidal solution that utilizes the foregoing description 3 to prepare comes impregnation glass cloth, and the glass cloth after the impregnation is with the oven dry of 120 ℃ in baking oven after 5 minutes, film.
Embodiment 5 preparation substrates
Film with embodiment 4 prepares need pile up certain No. of film according to thickness, puts into mould, sends in 200 ℃ of vacuum mold press mold pressing again and takes out after 1 hour, get final product substrate.The electrical properties that records substrate is as follows: Dk (1MHz)=3.8, Df (1MHz)=0.0144.
The above only is preferred embodiment of the present invention, be not in order to limiting scope of the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention, any change and the retouching done all should be included within the claim scope of the present invention.

Claims (18)

1. manufacture method with cross-linking polyphenyl ether resin of epoxy group(ing), it comprises:
One polyphenylene oxide resin of (I) structure that has chemical formula and the compound of a highly basic and a halogen-containing leaving group and epoxy group(ing) are reacted, and the cross-linking polyphenyl ether resin of (II) structure that obtains having chemical formula,
Wherein the structure of chemical formula (I) is:
Figure C011181080002C1
R wherein 1Can be identical or different, and for being selected from the alkyl of H and carbon number 1 to 3;
Z 1Can be identical or different, and for being selected from H, OH and at least one Z 1Be OH
P is 2 to 165,
The compound of wherein said halogen-containing leaving group and epoxy group(ing) has the structure shown in the chemical formula (A):
Figure C011181080002C2
Wherein X is the halogen leaving group that is selected from fluorine, chlorine, bromine or iodine;
N is 1～6 integer,
Wherein the structure of chemical formula (II) is:
Figure C011181080002C3
R wherein 2Can be identical or different, and for be selected from H, carbon number 1 to 3 alkyl,
Figure C011181080003C1
The cohort of being formed;
R 11Alkylidene group for carbon number 1 to 3;
N is 1～6 integer; And
S is 0 or 1～6 integer;
Z 2Can be identical or different, and for be selected from OH,
The group that is formed, and at least one Z 2Be the group shown in the chemical formula (i), wherein n is 1～6 integer, and s is 0 or 1～6 integer;
P is 2 to 165.
2. manufacture method as claimed in claim 1, wherein said highly basic are to be selected from the group that is made up of alkali metal hydroxide, alkalimetal hydride and alkaline earth metal hydride.
3. manufacture method as claimed in claim 2, wherein said highly basic are to be selected from the group that is made up of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydride and hydrolith.
4. manufacture method as claimed in claim 1, the leaving group in the compound of wherein said halogen-containing leaving group and epoxy group(ing) is a chlorine.
5. manufacture method as claimed in claim 4, wherein n is 3.
6. as claim 4 or 5 described manufacture method, the wherein said compound that contains leaving group and epoxy group(ing) is for being selected from: epoxy bromopropane and epoxy chloropropane.
7. cross-linking polyphenyl ether resin with epoxy group(ing), it has the structure of chemical formula (II):
R wherein 2Can be identical or different, and for be selected from by the alkyl of H, carbon number 1 to 3,
The group that is formed, wherein
R 11Alkylidene group for carbon number 1 to 3;
N is 1～6 integer; And
S is 0 or 1～6 integer;
Z 2Can be identical or different, and for be selected from OH,
The group that is formed, and at least one Z 2Be the group shown in the chemical formula (i), wherein n is 1～6 integer, and s is 0 or 1～6 integer;
P is 2 to 165.
8. the cross-linking polyphenyl ether resin with epoxy group(ing) as claimed in claim 7, wherein at least one Z 2For
S is 0 or 1～6 integer.
9. polyphenyl ether resin composition, it comprises:
(a) claim 7 or 8 cross-linking polyphenyl ether resin with epoxy group(ing),
(b) amine epoxy linking agent, wherein the equivalence ratio of the epoxy group(ing) of the active hydrogen of component (b) amine linking agent and component (a) is 0.5-3.0.
10. polyphenyl ether resin composition as claimed in claim 9, wherein said amine epoxy linking agent is a Dyhard RU 100.
11. polyphenyl ether resin composition as claimed in claim 10, the content of wherein said Dyhard RU 100 are the 2.39wt% based on composition weight.
12. polyphenyl ether resin composition as claimed in claim 9 is a benchmark with the weight of composition, it further comprises the halogenated epoxy resin of 25wt%.
13. polyphenyl ether resin composition as claimed in claim 12, wherein said halogenated epoxy resin are tetrabromo Resins, epoxy.
14. polyphenyl ether resin composition as claimed in claim 9 is a benchmark with the weight of composition, it further comprises the crosslinking accelerator of 0.45wt%.
15. polyphenyl ether resin composition as claimed in claim 14, wherein said crosslinking accelerator is a glyoxal ethyline.
16. the described polyphenyl ether resin composition of one of claim 9-12 has the application aspect the film of strongthener in making.
17. application as claimed in claim 16, wherein said strongthener are paper or glasscloth.
18. the application of the described polyphenyl ether resin composition of one of claim 9-12 aspect the making copper clad laminate.
CNB011181087A 2001-05-16 2001-05-16 Cross-linking polyphenyl ether resin with epoxy group, its composition and making method Expired - Lifetime CN1167728C (en)

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CN101747854B (en) * 2008-12-04 2012-11-21 比亚迪股份有限公司 Adhesive combination, covering film and flexible circuit board
CN102516530B (en) * 2011-12-08 2014-03-12 中山台光电子材料有限公司 Epoxy modified polyphenylene ether resin, resin composition and its application
CN102516532B (en) * 2011-12-27 2013-06-05 四川东材科技集团股份有限公司 Preparation method for amination polyphenyl ether
CN102786664B (en) * 2012-07-17 2014-07-23 常州大学 Low dielectric and high heat-resistant epoxy resin composition and its preparation method
CN111500046A (en) * 2020-05-25 2020-08-07 常州中英科技股份有限公司 Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and thermosetting copper-clad plate prepared from polyarylether base composition
CN114714708B (en) * 2022-05-09 2023-09-19 江苏耀鸿电子有限公司 High-frequency copper-clad plate with PPO resin substrate and preparation method thereof

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