POLYPHENYLENE ETHER MODIFIED PHENOL-BENZALDEHYDE MULTIFUNCTIONAL EPOXY RESIN AND USE

Abstract

The invention provides a polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin with formula (I).

##STR00001##

wherein

A is:

##STR00002##

PPE are:

##STR00003##

Z are:

##STR00004##

Y are:

##STR00005##

Their manufactured is following steps: polyphenylene ether 100 parts is dissolved in solvent, then phenol-benzaldehyde multifunctional epoxy resin 100˜450 parts and catalyst 0.01˜5 parts are added, stirred and mixed at 90˜180□, for 1˜4 hour, to obtain formula (I) solution. Said product is formulated with compositions for laminate, having excellent electrical properties and heat resistance. The dielectric constant is 4.03 (1 GHz), dissipation factor is 0.0046 (1 GHz) and no delamination longer than 60 minutes dipping in 288 soldering test after 2 hours pressure cooking test. Application is insulating materials for highly reliable electronic components such as EMC, PCB substrates, laminate and insulating plates.

Claims

1. A polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin having the formula (I): ##STR00018## wherein A is: ##STR00019## PPE are: ##STR00020## Z are: ##STR00021## Y are: ##STR00022##

2. A manufacturing method of polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin having the formula (I): ##STR00023## wherein A is: ##STR00024## PPE are: ##STR00025## Z are: ##STR00026## Y are: ##STR00027## , comprising the following steps: converting 500 parts of the polyphenylene resin PPE solvent with average molecular mass Mn1500˜6000 into 100 parts of the polyphenylene PPE solid, and adding 100-450 parts of the phenol-benzaldehyde multifunctional epoxy resin (NAN YA PLASTICS CORPORATION'S PRODUCT NAME: NPPN-433) and 0.01-5 parts of the catalyst in the polyphenylene PPE solid, increasing the temperature to 120˜180 to execute the addition reaction for 2-3 hours in order to obtain the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin solvent, wherein the catalyst is the phosphor salt, including triphenyl phosphine, triphenyl butyl phosphonium bromide and ethyl triphenyl phosphonium acetate, etc., or the limidazole, including 2-methylimidazole, 2-phenylimidazole, etc; and the solvent is selected from the group consisting of toluene, xylenes, propylene glycol mono-methyl ether, methyl ethyl ketone or a combination thereof, or other frequently-used solvents of glass fiber laminated plate.

3. The manufacturing method of polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin as claimed in claim 2, wherein the polyphenylene PPE with suitable average molecular mass Mn1500˜6000 is manufactured by the cracking recombination reaction of the polyphenylene PPE with high molecular mass Mn1300˜25000 or the polymerization reaction of 2,6-dimethylphenol with low molecular mass, wherein the structure of the polyphenylene PPE with suitable average molecular mass Mn1500˜6000 is as following formula: ##STR00028## Z are: ##STR00029## Y are: ##STR00030##

4. An epoxy resin varnish composition applicable to glass fiber laminated plate, comprising: (1) the usage amount of the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin according to the present invention is 40-80% of the total resin amount (the total resin amount is equal to the total amount of the content 1˜content 4); (2) the usage amount of the 2,6-dimethylphenol difunctional epoxy is 0-20% of the total resin amount; (3) the hardening agent 1: the usage amount of the phenolic resin hardening agent or bisphenol A type phenolic resin hardening agent is 0-30% of the total resin amount; (4) the flame retartant: the flame retartant includes the phosphorus-containing flame retardant, such as the phosphorus-containing bisphenol A type novolac hardening agent with 9.2-9.5% phosphorus content, and the nitrogen-containing flame retartart, such as the melamine phenolic resin, and the bromine-containing flame retartant, such as the tetrabromobisphenol A; the usage amount is 10-40% of the total resin amount; (5) the filler: the filer may be SiO2, Al(OH)3, etc., and the usage amount 0-45% of the total varnish content; (6) Adding proper the hardening promoter and the solvent, the hardening promoter may be the limidazole, quaternary amine, quaternary phosphor salt; the most frequently-used promoters are 2-methylimidazole, 2-phenylimidazole; the proper usage amount of the promoter is 0.01-0.2 phr (compared with all main epoxy resins, not including the hardening agents); the solvent may be ketone, glycol ether, such as acetone, butanone, cycolhexanone, 2-methoxyethanol (MCS), propylene glycol mono-methyl ether; the proper solid content is 55-70%.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0027] The detailed structure, operating principle and effects of the present invention will now be described in more details hereinafter with reference to the various embodiments of the invention as follows.

[0028] The embodiment 0-1: the synthesis of the polyphenylene ether PPE with proper quantity average molecular mass Mn1500-6000:

[0029] Adding 150 parts of the toluene solvent in 100 parts of the polyphenylene ether PPE (Asahi 5202A) with the quantity average molecular mass Mn1500-6000, and adjusting the solid part to be 40%, and adding 30 parts of the recombination agent “bisphenol A (BRA)”, and adding 30 parts of the perbenzoic acid (BPO) by 2-4 times, and each time is 7.5 parts, and conducting the cracking recombination reaction under 80 for 2 hours, and adding 370 parts of the toluene solvent to create the polyphenylene ether PPE resin solvent with 20% solid content, and adding 100 parts of water to wash which by water, and keeping which standing for 30 minutes to remove the water; using the same step to wash which again by water; finally, filtering the resin solvent to obtain the polyphenylene ether PPE (I) resin solvent with the quantity average molecular mass Mn=3791 and the yield rate is 98%.

[0030] The embodiment 0-2:

[0031] Converting 500 parts of the polyphenylene ether PPE (I) resin solvent of Step (1) to 100 parts of the solid polyphenylene ether PPE, and adding 400 parts of the phenol-benzaldehyde multifunctional epoxy resin (NAN YA PLASTICS CORPORATION′S PRODUCT NAME: NPPN-433), and adding 0.5 part (0.1%) of the triphenyl phosphine (TPP), and increase the temperature to 170 to conduct the addition reaction for 2 hours; then, the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin solvent can be obtained; the yield rate is 100%; the quantity average molecular mass Mn of the obtained polyphenylene ether PPE modified phenol-benzaldehyde multifunctional epoxy resin I (20% PPE) is 997 and its weight average molecular mass Mw is 3851, and its epoxy equivalent weight is 309.5 g/eq.

[0032] The embodiment 0-3:

[0033] Dissolving 100 parts of the solid polyphenylene ether PPE (Sabic MX-90) in 150 parts of the toluene, and adding 369 parts of the phenol-benzaldehyde multifunctional epoxy resin (NAN YA PLASTICS CORPORATION'S PRODUCT NAME: NPPN-433), and adding 0.5 part (0.1%) of the triphenyl phosphine (TPP), and increase the temperature to 170 to conduct the addition reaction for 2 hours; then, the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin solvent can be obtained; the yield rate is 100%; the quantity average molecular mass Mn of the obtained polyphenylene ether PPE modified phenol-benzaldehyde multifunctional epoxy resin II (21.3% PPE) is 1258 and its weight average molecular mass Mw is 5937, and its epoxy equivalent weight is 343 g/eq.

[0034] The embodiment 0-4:

[0035] Converting 500 parts of the polyphenylene ether PPE (I) resin solvent of Step (1) to 100 parts of the solid polyphenylene ether PPE, and adding 233 parts of the phenol-benzaldehyde multifunctional epoxy resin (NAN YA PLASTICS CORPORATION'S PRODUCT NAME: NPPN-433), and adding 0.33 part (0.1%) of the triphenyl phosphine (TPP), and increase the temperature to 170 to conduct the addition reaction for 2 hours; then, the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin solvent can be obtained; the yield rate is 100%; the quantity average molecular mass Mn of the obtained polyphenylene ether PPE modified phenol-benzaldehyde multifunctional epoxy resin III (30% PPE) is 1152 and its weight average molecular mass Mw is 5928, and its epoxy equivalent weight is 354.5 g/eq.

[0036] The embodiment 1-3:

[0037] The polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin according to the present invention is applied to the glass fiber laminated plate, and the formula composition is as shown in Table (1), which adopts the solvent, such as the propylene glycol mono-methyl ether (PM), methyl ethyl ketone, acetone, or the resin varnish formula composition with 65% adjusted solid part; using the conventional method to manufacturing the glass fiber laminated plate and immersing the 7268 glass fiber fabric into the above resin liquid, and then drying which under 170 for several minutes; afterward, the lowest melt viscosity of the pre-impregnated body after dried can be adjusted to be 4000-10000poise by controlling the drying time; finally, putting 8 pre-impregnated bodies between two the copper foils with 35-um thickness, and then controlling the heating program under 25 kg/cm2 preasure:

##STR00017##

[0038] The copper foil substrate with 1.6 mm thickness can be obtained by hot pressing.

[0039] The comparison example 1-2:

[0040] If the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin according to the present invention is not applied and using other multifunctional epoxy resins as the comparison examples, the comparison example 1 is the phenol-benzaldehyde multifunctional epoxy resin NPPN-433, and the comparison example 2 is the bisphenol A type phenolic epoxy resin; its formula composition is as shown in Table (2).

[0041] The embodiments of Table (1)—The varnish composition and the physical characteristics of the glass fiber laminated plate

TABLE-US-00001 Embodiment Embodiment Embodiment 1 2 3 Resin varnish Polyphenylene ether modified Embodiment Embodiment Embodiment formula phenol-benzaldehyde multifunctional 0-2 0-3 0-4 composition epoxy resin I, Π,    according to the 33 33.7 33.9 present invention 2,6-dimethylphenol difunctional epoxy resin 8.2 8.4 8.5 NAN YA PLASTICS CORPORATION NPPN-260 BPA-PN phenolic resin hardening agent 11.8 10.9 10.7 NAN YA PLASTICS CORPORATION NPEH-720H Phosphorus-containing bisphenol A type 16.9 16.9 16.9 phenolic resin hardening agent SHIN-A LC-950, the phosphorus content is 9.5%. Filler SiO2 30 30 30 Hardening promoter − 2-methylimidazole 2MI 0.08 0.08 0.08 Acetone solvent + PM 66 66 66 Gel Varnish gel time second/170□ 240 245 200 time Prepreg gel time second/170□ 120 121 115 The physical Phosphorus content % 2.3 2.3 2.3 characteristics Flame retardance UL-94V0 UL-94V0 UL-94V0 of the glass Temperature of glass transition Tg□ 158 159 158 fiber laminated Water absorption rate % 0.24 0.28 0.26 plate (by PCT for 2 hours) 288□ dipped soldering heat resistance >60 minutes >60 minutes >60 minutes (By PCT for 2 hours) No No No delamination delamination delamination takes place. takes place. takes place. Dielectric constant Dk (1 GHz) 4.07 4.03 4.09 Dissipation factor Df (1 GHz) 0.0049 0.0046 0.0048

[0042] The comparison examples of Table (1)—The varnish composition and the physical characteristics of the glass fiber laminated plate

TABLE-US-00002 Comparison Comparison example 1 example 2 Resin varnish Phenol-benzaidehyde multifunctional epoxy resin 30.8 — formula NPPN-433 composition Bisphenol A type phenolic epoxy resin NPPN-438 — 29 2,6-dimethylphenol difunctional epoxy resin 7.7 7.3 NAN YA PLASTICS CORPORATION NPPN-260 BPA-PN phenolic resin hardening agent NPEH-720H 14.5 16.8 Phosphorus-containing bisphenol A type phenolic resin 17 17 hardening agent SHIN-A LC-950, the phosphorus content is 9.5%. Filler SiO2 30 30 Hardening promoter − 2-methylimidazole 2MI 0.05 0.04 Acetone solvent + PM 66 66 The physical Phosphorus content % 2.3 2.3 characteristics Flame retardance UL-94V0 UL-94V0 of the glass Temperature of glass transition Tg□ 166 164 fiber laminated Water absorption rate % (by PCT for 2 hours) 0.3 0.3 plate 288□ dipped soldering heat resistance >10 minutes >10 minutes (by PCT for 2 hours) No delamination No delamination takes place. takes place. Dielectric constant Dk (1 GHz) 4.4 4.6 Dissipation factor Df (1 GHz) 0.011 0.016

[0043] According to the above test results, the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin according to the present invention is formulated to manufacture the glass fiber laminated plate; the dielectric constant Dk can be reduced up to 4.03; compared with comparison example, the dielectric constant can be reduced from 4.6 to 4.03, which shows the polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin can effectively reduce the dielectric constant and very suitable for the circuit board for high-frequent signal transmission.

[0044] 1. Varnish Gel Time

[0045] The varnish reaction test is to use the epoxy resin solvent, hardening agent “dicydiamide solvent” (dissolved in the solvent DMF; the solvent concentration-13.3%) and the promoter “2-phenyl imidazole” or “2-methyl imidazole” (dissolved in the solvent DMF; the solvent concentration=14.28%) to prepare the varnish mixture liquid; adding 0.3 ml of the varnish mixture liquid on the heat plate and the temperature of the heat plate is 170; afterward, recording the gel time.

[0046] 2. Prepreg Gel Time

[0047] The test method of the pre-impregnated body is to put 0.2 mg of the pre-impregnated body powder on the heat plate and the temperature of the heat plate is 170; afterward, recording the gel time.

[0048] 3. Water absorption rate test (2 hours by the pressure cooking test PCT)

[0049] The test method of the water absorption rate is to cut the etched substrate into 5 cm.sup.2 square test plate and put which in 105 oven to bake for 2 hours, and then put the test plate in the pressure cooker; the condition of the pressure cooker is 2 atm×120; after 120 minutes, recording the weight difference before/after processed by the pressure cooker and divide which by the initial weight of the test plate, and the water absorption rate is obtained.

[0050] 4. 288 soldering heat resistance (by POT for 2 hours)

[0051] The test method is to dip the above test plate processed by the pressure cooker into 288 soldering stove, and the record the time for the delamination of the test plate.

[0052] 5. Dielectric Constant Test:

[0053] The test method is to remove the cooper foil of the 5 cm×5 cm square test plate of the glass fiber laminated plate and then put which in 105 oven to bake for 2 hours; afterward, using the thickness measurer to measure the thickness and then putting the test plate in the dielectric constant measurer to measure the data of the three points; finally, calculating the average value of which.

[0054] 6. Dissipation Factor Test:

[0055] The test method is to remove the cooper foil of the 5 cm×5 cm square test plate of the glass fiber laminated plate and then put which in 105 oven to bake for 2 hours; afterward, using the thickness measurer to measure the thickness and then putting the test plate in the dielectric constant measurer to measure the data of the three points; finally, calculating the average value of which.

[0056] 7. Temperature of Glass Transition Test:

[0057] Using the differential scaning calorimeter (DSC) and the heating speed is 20/min.

[0058] 8. Flame Retardance

[0059] Test the flame retardance of the sample according to the UL-94 standard method.