CN107227015B - Low dielectric material - Google Patents

Low dielectric material Download PDF

Info

Publication number
CN107227015B
CN107227015B CN201610167700.9A CN201610167700A CN107227015B CN 107227015 B CN107227015 B CN 107227015B CN 201610167700 A CN201610167700 A CN 201610167700A CN 107227015 B CN107227015 B CN 107227015B
Authority
CN
China
Prior art keywords
dielectric material
low dielectric
group
weight
ppe
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610167700.9A
Other languages
Chinese (zh)
Other versions
CN107227015A (en
Inventor
鄞盟松
陈礼君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ITEQ Corp
Original Assignee
ITEQ Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ITEQ Corp filed Critical ITEQ Corp
Priority to CN201610167700.9A priority Critical patent/CN107227015B/en
Priority to CN201910318441.9A priority patent/CN109971154A/en
Publication of CN107227015A publication Critical patent/CN107227015A/en
Application granted granted Critical
Publication of CN107227015B publication Critical patent/CN107227015B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a low dielectric material, comprising: (i)5 to 50 parts by weight of polyphenylene ether, number average molecular weight (Mn) = 1000-; and (ii)10-90 parts by weight of a liquid crystal polymer having allyl groups, Mn =1000-4000, Mw =1000-5000, and Mw/Mn =1.0-1.8, wherein the Dk value of the low dielectric material is 3.4-4.0, and the Df value is 0.0025-0.0050. The low dielectric material can be applied to a prepreg or a circuit substrate insulating layer, and has the characteristics of high Tg, low thermal expansion coefficient, low water absorption and excellent dielectric properties such as dielectric constant (Dk) and dielectric loss (Df).

Description

Low dielectric material
Technical Field
The present invention relates to a low dielectric material, and more particularly to a resin composition.
Background
With the rapid development of wireless transmission products and the leap forward of high frequency transmission technology, the materials of the existing epoxy resin and phenolic resin systems have been unable to meet the requirements of advanced applications, especially high frequency printed circuit boards.
The substrate material of the printed circuit board with low dielectric loss is fluorine-based resin, but the resin has high cost and is difficult to process, and the application is limited to military and aerospace applications. In addition, polyphenylene ether (PPE) resin is a preferred resin material for substrates of high frequency printed circuit boards because of its good mechanical properties and excellent dielectric properties, such as dielectric constant (Dk) and dielectric loss (Df).
However, polyphenylene ether is a thermoplastic resin, and its direct use in a copper foil substrate has the following disadvantages: the melt viscosity is high, and the processing and the forming are difficult; the solvent resistance is poor, and the lead is easy to be attached or fall off in the environment of solvent cleaning in the manufacturing process of the printed circuit board; and a melting point close to the glass transition temperature (Tg), which makes it difficult to withstand soldering operations above 250 ℃ in printed circuit board processes. Therefore, PPE is thermoset modified to meet the requirements of printed circuit board applications.
Thermosetting modification of PPE is generally done in two ways: introducing crosslinkable active groups into the molecular structure of PPE to make it become thermosetting resin. Alternatively, other thermosetting resins are introduced by blending modification or interpenetrating network (IPN) techniques to form blended thermosetting composites. However, due to the difference in polarity of the chemical structure, the PPE is often incompatible with the reactive groups or thermosetting resin, and is not easily processed or loses the original excellent properties of PPE, which is limited.
Therefore, how to develop a material with excellent dielectric properties and meeting the requirements of other characteristics of printed circuit boards, such as high Tg, low thermal expansion coefficient and low water absorption, and apply it to the manufacture of high frequency printed circuit boards is a problem that printed circuit board material suppliers are demanding to solve at present.
Disclosure of Invention
Accordingly, the present invention is directed to a low dielectric material having excellent dielectric properties, a low thermal expansion coefficient and low water absorption.
In order to achieve the above object, the present invention provides a low dielectric material, comprising: (i)5 to 50 parts by weight of polyphenylene ether, having a number average molecular weight (Mn) of 1000-4000, a weight average molecular weight (Mw) of 1000-7000 and Mw/Mn of 1.0 to 1.8; and (ii)10 to 90 parts by weight of a liquid crystal polymer having an allyl group, Mn 1000-4000, Mw 1000-5000, and Mw/Mn 1.0 to 1.8. The Dk value of the low dielectric material is 3.4-4.0, and the Df value is 0.0025-0.0050. In the low dielectric material of the present invention, the low dielectric material further comprises 0.01 to 15 parts by weight of Bismaleimide (BMI) resin. In the low dielectric material of the present invention, the low dielectric material further comprises 0.01 to 10 parts by weight of a polymer additive.
In the low dielectric material of the present invention, the structural formula of polyphenylene ether is as follows:
it is composed of
Figure BDA0000947973120000021
In the low dielectric material of the present invention, the bismaleimide is selected from at least one of the following groups:
phenyl methane maleimide (phenyl methane maleimide)
Figure BDA0000947973120000022
Wherein n ≧ 1;
bisphenol A diphenyl ether bismaleimide (Bisphenol A diphenyl ether bismalimide)
Figure BDA0000947973120000031
3,3 '-dimethyl-5, 5' -diethyl-4,4 '-diphenylethane bismaleimide (3, 3' -dimethyl-5,5 '-diethyl-4, 4' -diphenylethane bismaleimide)
Figure BDA0000947973120000032
1,6-bismaleimide- (2,2,4-trimethyl) hexane (1,6-bismaleimide- (2,2, 4-trimethy) hexane)
Figure BDA0000947973120000033
In the dielectric material, the polymer additive may be at least one selected from the following group:
butadiene homopolymer (homo polymers of Butadiene)
Figure BDA0000947973120000034
Wherein y is 70%, x + z is 30%;
butadiene and styrene Random copolymers (Random copolymers of butadiene and styrene)
Figure BDA0000947973120000041
Wherein y is 30%, x + z is 70%, w is ≧ 1, and styrene content is 25 wt%;
maleated Polybutadiene (Maleinized polybutadienee)
Figure BDA0000947973120000042
Wherein y is 28%, x + z is 72%, Maleic Anhydride (MA) content is 8 wt%;
copolymers of butadiene, styrene and divinylbenzene; and
Styrene-Maleic Anhydride copolymer (Styrene Maleic Anhydride copolymer)
Figure BDA0000947973120000043
Wherein X is 1-8, and n is ≧ 1.
Preferably, a crosslinking agent (crosslinking linker) is optionally added to the low dielectric material of the invention to further increase the crosslinking density of the resin, wherein the crosslinking agent is selected from at least one of the following groups in an amount of 40 to 80 parts by weight:
triallyl isocyanate (TAIC)
Figure BDA0000947973120000051
Triallyl cyanate (TAC)
Figure BDA0000947973120000052
4-tert-butyl
Figure BDA0000947973120000053
The low dielectric material of the present invention may have added thereto a suitable amount of a peroxide having a 10-hour half-life and a temperature in the range of 116 ℃ to 128 ℃ as a catalyst (or crosslinking promoter) for effectively bonding the crosslinking agent to other resins, and suitable peroxides of the present invention, such as dicumyl peroxide, α' -bis (t-butylperoxy) diisopropylbenzene, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3.
The low dielectric material of the present invention may further contain inorganic filler (filler) to increase the thermal conductivity of the dielectric material and improve the thermal expansion and mechanical strength of the dielectric material. Suitable inorganic fillers of the present invention are, for example, fused silica, spherical silica, talc, aluminum silicate and soft silica, such as siliesof, wherein the soft silica can be used to reduce drill pin wear during PCB drilling. The soft silica has a particle size in the range of 0.5 μm to 10 μm.
In order to improve the flame retardancy of the low dielectric material of the invention, a halogen flame retardant or a non-halogen flame retardant can be added. The halogen-based flame retardant includes, for example, decabromodiphenylethane. The non-halogen flame retardant includes, for example, phosphorus-containing flame retardants and phosphoric acid esters available from Albemarle corporation. Phosphoric acid esters such as resorcinol bis [ bis (2,6-dimethylphenyl) phosphate ], HCA derivatives (I), HCA derivatives (II) and HCA derivatives (III). A compound wherein resorcinol bis [ bis (2,6 dimethylphenyl) phosphate ] has the formula:
〔OC6H3(CH3)22P(O)OC6H4OP(O)〔OC6H3(CH3)22
the HCA derivative (I) has a structure of p-diphenylphosphonyl dibenzyl
Figure BDA0000947973120000061
The HCA derivative (II) has the following structure:
Figure BDA0000947973120000062
Figure BDA0000947973120000071
when the B structure is-CH 2-or-CH (CH3) -, m ═ 1 and n ═ 1-3; when the structure of B is CHCH, m is 2 and n is 0.
The HCA derivative (III) has the following structure (XP-7866, Albemarle):
Figure BDA0000947973120000072
wherein A is a direct bond, C6-C12Aryl radical, C3-C12Cycloalkyl, or C3-C12Cycloalkenyl, wherein the cycloalkyl or cycloalkenyl can be substituted by C1-C6Alkyl is optionally substituted; each R1、R2、R3And R4Independently of one another is hydrogen, C1-C15Alkyl radical, C6-C12Aryl radical, C7-C15Aralkyl or C7-C15An alkaryl group; or R1And R2Or R3And R4Taken together, may form a saturated or unsaturated cyclic ring, wherein the saturated or unsaturated ring may be substituted with C1-C6Alkyl is optionally substituted; each m is independently 1, 2, 3 or 4; each R5And R6Independently is hydrogen or C1-C6An alkyl group; and each n is independently 0, 1, 2, 3, 4, or 5; provided that when a is aryl or a direct bond, n cannot be 0.
The low dielectric material has the advantages of excellent dielectric property, low thermal expansion coefficient and low water absorption.
Drawings
FIG. 1 shows an FTIR spectrum of a liquid crystal polymer according to an embodiment of the present invention.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, several embodiments accompanied with figures are described in detail below:
examples 4-1 to 4-7 below are prepregs made in a continuous process using the thermosetting compositions of the present invention. Usually, a glass fiber cloth is used as a substrate. The fiberglass cloth in roll form is continuously passed through a series of rollers into a sizing trough which contains the thermosetting composition of the present invention. And fully soaking the glass fiber cloth in the gluing tank by resin, scraping redundant resin by a metering roller, baking the glass fiber cloth in a gluing furnace for a certain time to evaporate a solvent and solidify the resin to a certain degree, cooling and rolling to form a prepreg.
And (2) laminating and aligning prepregs prepared by soaking a certain number of electronic grade 2116 glass fiber cloth in the resin, arranging loz electrolytic copper foils on the upper and lower sides of the prepregs respectively, heating the prepregs to 200 ℃ from 80 ℃ within 30min under the pressure of 40-900psi in a vacuum press, then hot-pressing the prepregs for 120min at 200 ℃, and cooling the prepregs to room temperature within 30min to prepare the double-sided copper-clad plate with a certain thickness. Generally, 1.0mm thickness requires 4 2116 prepregs, 0.8mm requires 4 2116 prepregs, and 2.0mm requires 10 21160 prepregs.
The invention provides a thermosetting resin composition which forms stable homogeneous solution in a low boiling point solvent, a copper-clad plate manufactured by the thermosetting resin composition is subjected to glass transition temperature, thermal decomposition temperature, thermal layering time, soldering tin heat resistance (288 ℃), thermal expansion coefficient, water absorption, thermal conductivity, dielectric constant, dielectric loss factor and flame resistance index detection according to IPC-TM-650, and the detection result shows that: has the characteristics of high glass transition temperature (Tg), excellent dielectric property, low thermal expansion coefficient, low water absorption rate, high thermal shock resistance, high thermal conductivity and the like, and is suitable for being used as a substrate material for electronic components and Integrated Circuit (IC) packages.
(examples)
TABLE 1-1 influence of PPE resin content
Figure BDA0000947973120000081
Figure BDA0000947973120000091
Comparing Tg and the usage ratio of Dk, Df to PPE, too high or too low amount of PPE will result in too low Tg, while the amount of PPE will also affect Dk, Df, when the amount of PPE is high, Dk, Df are both high, and when the amount of PPE is low, Dk, Df are both low. Preferably, Dk and Df are both low. In addition, the thermal expansion coefficient is increased by adding PPE, so that the thermal expansion coefficient is decreased by adding BMI. In Table 1-1, PPE type SA9000 is available from Sabic corporation under the chemical name of poly-2, 6-dimethyl-1, 4-phenylene oxide (PPO) or PPE (polyphenylene ether), also known as polyphenylene oxide or polyphenylene ether.
TABLE 1-2 influence of LCP content
Figure BDA0000947973120000092
Figure BDA0000947973120000101
Liquid Crystal Polymers (LCP) generally exhibit good chemical, moisture and heat resistance, and good mechanical strength, and are capable of forming thin films with a high degree of structural integrity. However, the cost and/or dielectric constant of films made using LCP alone may be too high for some cushion applications.
The LCP's of the invention are selected from a liquid crystalline polymer (or a thermoplastic polymer capable of forming a selectively anisotropic dissolved phase) that can be processed in the melt. The chemical formula of the LCP is not particularly limited as long as it can dissolve the processed liquid crystalline polymer, and examples thereof may include a vinyl type thermoplastic liquid crystal polymer, an aramid thermoplastic liquid crystal polymer, or an aromatic polyester thermoplastic liquid crystal polymer, and it is preferable to introduce allyl group modification due to the terminal and/or side ends. The LCP of the invention can perform radical reaction by allyl to form interpenetrating polymer networks. Example C13 in tables 1-2 used low Dk glass fibers and example C8 and example C9 used E-glass fibers.
The vinyl type thermoplastic liquid crystal polymer has the following structure:
Figure BDA0000947973120000102
the aramid thermoplastic liquid crystalline polymer has the following structure:
Figure BDA0000947973120000111
FIG. 1 shows an FTIR spectrum of a liquid crystal polymer according to an embodiment of the present invention. The absorption peaks of FTIR are illustrated belowPeak at 3472cm-1With regard to-OH or-NH stretching. Peak 3097cm-1With respect to the asymmetric stretching of the vinyl group or-CH 2. Peak 2950cm-1、2919cm-1、2874cm-1And 2842cm-1Related to-C ≡ C-H, -C ≡ CH2, -C-CH3 or
Figure BDA0000947973120000112
Peak 1730cm-1And 1715cm-1Aromatic esters, C ═ O stretching, saturated C ═ O stretching, or aromatic C ═ O. Wave crest 1640cm-1And 1605cm-1Related to-C ═ C or cyclic C ═ C. Wave crest 1640cm-1、1570cm-1And 1482cm-1concerning-NH bending or asymmetry
Figure BDA0000947973120000113
And (5) stretching. Peak 1459cm-1And 1377cm-1To a
Figure BDA0000947973120000114
And (4) symmetrically stretching. Peak 1299cm-1、1244cm-1、1188cm-1、1153cm-1、1043cm-1And 1023cm-1With respect to-C-O-, -C-O-C-or-C-. Peak 1377cm-1To 1023cm-1Regarding amide, imide, -CN stretching. Peak 827cm-1to 691cm-1With respect to-C ═ C-phenyl substituted on the phenyl ring, at the para or meta position, or-NH out of the plane or singly. From the FTIR spectrum of FIG. 1, the absorption peak signals of the structures of the vinyl type thermoplastic liquid crystal polymer and the aramid thermoplastic liquid crystal polymer can be found.
TABLE 2 influence of the differences in the structure and ratio of BMI resins
Figure BDA0000947973120000115
Figure BDA0000947973120000121
TABLE 2-continuation
Figure BDA0000947973120000122
Figure BDA0000947973120000131
Comparing the use ratio of the coefficient of thermal expansion to the BMI, the higher the ratio of the BMI, the lower the reduction in the coefficient of thermal expansion. In this example, BMI comparisons were divided into three parts, A1-A5 for BMI resins of the same type at different ratios, A6-A8 for BMI resins of the same type but different types, and A9-A15 for comparison of mixed BMI resins. BMI models 2300, 4000, 5100, TMH are produced by Daiwakasei Industry CO., LTD, and the chemical names are in the following comparison table.
Figure BDA0000947973120000132
From A1 to A5, different ratios of BMI of the same species were effective in reducing the coefficient of thermal expansion, but also in improving the water absorption rate. From A6-A8, different BMI's are effective at reducing the coefficient of thermal expansion, but also have an effect on water absorption. From A9-A15, different combinations of BMI were also effective in reducing the coefficient of thermal expansion and at the same time achieving water absorption. The purpose of adding BMI in the invention is to reduce the thermal expansion coefficient, but the water absorption rate is also increased according to the use ratio and combination of BMI, so that the water absorption rate is reduced by adding a polymer additive.
TABLE 3 Effect of Polymer additive Structure and ratio Difference
Figure BDA0000947973120000133
Figure BDA0000947973120000141
TABLE 3-run
Figure BDA0000947973120000142
Figure BDA0000947973120000151
Comparing the ratio of water absorption to the use of polymer additives, the use of Polybutadiene (polybutadienes) and styrene-maleic anhydride copolymer (SMA) results in lower water absorption but higher thermal expansion coefficient when the same Polybutadiene is used. When different kinds of polybutadiene are used and SMA is matched for use, the SMA is more effective in reducing the water absorption rate and can also reduce the thermal expansion coefficient, but the performance of the SMA in the Df part is poor, and the defect of the SMA in the Df part can be overcome by using the polybutadiene. Butadiene models Ricon100, Ricon130MA8, Ricon150, Ricon257 from Sartomer are listed in the Table, with chemical names as follows.
Figure BDA0000947973120000152
In the table, SMA is listed as S: M ═ 3:1, which represents the ratio of Styrene (Styrene) to Maleic Anhydride (Maleic Anhydride), and the ratio is generally in the range of 1:1 to 12: 1.
TABLE 4 influence of the differences in the type of crosslinking agent
Figure BDA0000947973120000153
Figure BDA0000947973120000161
The low dielectric material of the present invention further comprises 40 to 80 parts by weight of at least one crosslinking agent selected from the following group: triallyl cyanate, triallyl isocyanate, 4-t-butyl styrene and trimethallyl allyl isocyanate (TMAIC). Compared with the influence of different crosslinking agents (crosslinking agents) on the physical properties of the invention, the Tg and the thermal expansion coefficient of the triallyl cyanate (TAC) are poor, and the Dk, the Df and the water absorption are common. Physical properties are more average when triallyl isocyanate (TAIC) is used. However, one disadvantage of using TAIC is that it is volatile during hot pressing. The use of TMAIC is effective in improving the high volatility of TAIC because TMAIC has a high melting point and is not easily evaporated, while maintaining its properties at a normal level. The use of 4-t-butylstyrene (TBS) is preferred in view of thermal expansion coefficient, water absorption and Df, but the Dk value is low.
TABLE 5 influence of differences in flame retardant types
Figure BDA0000947973120000162
Figure BDA0000947973120000171
The flame retardant can be matched with different flame retardants according to physical requirements. The halogen-containing flame retardant part may be added with 7 to 15phr (calculated by the sum of PPE, LCP, BMI, polymer additive and crosslinking agent) of decabromodiphenylethane (decabromodiphenylethane), and the halogen-free flame retardant part may be added with 12 to 14phr (calculated by the sum of PPE, LCP, BMI, polymer additive and crosslinking agent) of at least one selected from the following groups: phosphorus-containing flame retardants and phosphoric acid esters from ALBEMARLE corporation. Phosphoric acid esters such as resorcinol bis [ bis (2,6-dimethylphenyl) phosphate ] (Tetrakis (2,6-dimethylphenyl)1,3-phenylene bisphophate), HCA derivative (I), HCA derivative (II) and HCA derivative (III), wherein HCA derivative (III) having a product name XP7866 comprises an organic filler, 10-15% phosphorus. XP7866 has a particle size in the range of 0.5 μm to 60 μm.
TABLE 6 influence of the differences in the type and proportion of the inorganic fillers
Figure BDA0000947973120000172
Figure BDA0000947973120000181
TABLE 6-run
Figure BDA0000947973120000182
As for the inorganic filler, depending on physical requirements, 8 to 50phr (calculated by the sum of PPE, LCP, BMI, polymer additive and cross-linking agent) of different inorganic fillers may be added, such as fused silica, spherical silica and soft silica, such as Siliesof, wherein the soft silica may be used to reduce drill point abrasion during PCB drilling, compare examples F1-F3 with F8-F9. The soft silica has a particle size in the range of 0.5 μm to 10 μm. In the case of the same proportion of fused silica and spherical silica, the spherical silica is used, and both Dk and Df are lower than those of the fused silica.
TABLE 7 influence of the type and ratio differences of the crosslinking promoters
Figure BDA0000947973120000191
TABLE 7-run
Figure BDA0000947973120000192
Figure BDA0000947973120000201
The low dielectric material of the present invention further comprises 2 to 8phr (calculated as the sum of PPE, LCP, BMI, polymer additive and crosslinking agent) of peroxide having a 10-hour half-life temperature range of 116 ℃ to 128 ℃. The crosslinking accelerators (catalysts) may be used in combination with different crosslinking accelerators depending on the physical requirements. The invention can use peroxide with 10-hour half-life and temperature range of 116-128 ℃, preferably uses peroxide with 10-hour half-life and temperature of 119 ℃.
The low dielectric material of the invention uses PPE but does not add epoxy resin, because the addition of epoxy resin can cause Dk/Df to not reach the expected value, because the epoxy resin can generate too many OH groups after ring opening, and further causes Dk and Df value to not be reduced.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.

Claims (10)

1. A low dielectric material, comprising:
(i)5 to 50 parts by weight of a polyphenylene ether resin having a number average molecular weight (Mn) of 1000-4000, a weight average molecular weight (Mw) of 1000-7000 and Mw/Mn of 1.0 to 1.8, wherein the polyphenylene ether resin has the following structural formula:
Figure FDA0002340259590000011
y is at least one carbon, at least one oxygen, at least one benzene ring, or a combination thereof; and
(ii)10 to 90 parts by weight of a liquid crystal polymer having an allyl group, Mn 1000-4000, Mw 1000-5000, Mw/Mn 1.0 to 1.8,
wherein the Dk value of the low dielectric material is 3.4-4.0, and the Df value is 0.0025-0.0050.
2. The low dielectric material of claim 1, further comprising a bismaleimide resin selected from at least one of the group consisting of:
phenyl methane maleimide (phenyl methane maleimide)
Figure FDA0002340259590000012
Wherein n is ≧ 1;
bisphenol A diphenyl ether bismaleimide
Figure FDA0002340259590000013
3,3 ' -dimethyl-5,5 ' -diethyl-4,4 ' -diphenylethane bismaleimide
Figure FDA0002340259590000021
1,6-bismaleimide- (2,2,4-trimethyl) hexane
Figure FDA0002340259590000022
3. The low dielectric material of claim 2, further comprising a polymer additive selected from at least one of the following groups:
butadiene homopolymer
Figure FDA0002340259590000023
Wherein y is 70%, x + z is 30%;
butadiene and styrene random copolymer
Figure FDA0002340259590000024
Wherein y is 30%, x + z is 70%, w is ≧ 1, and styrene content is 25 wt%;
maleated polybutadienes
Figure FDA0002340259590000031
Wherein y is 28%, x + z is 72%, and the maleic anhydride content is 8 wt%;
copolymers of butadiene, styrene and divinylbenzene; and
styrene-maleic anhydride copolymer
Figure FDA0002340259590000032
Wherein X is 1-8, and n is ≧ 1.
4. The low dielectric material of claim 3, further comprising 40 to 80 parts by weight of at least one crosslinking agent selected from the group consisting of:
TAIC
Figure FDA0002340259590000033
TAC
Figure FDA0002340259590000041
4-tert-butylstyrene, 3-tert-butylstyrene and 2-tert-butylstyrene
Figure FDA0002340259590000042
And
trimethallyl isocyanate (TMAIC)
Figure FDA0002340259590000043
5. The low dielectric material of claim 4, further comprising 2 to 8phr of a peroxide having a 10 hour half-life temperature in a range of 116 ℃ to 128 ℃, wherein 2 to 8phr is based on the sum of the PPE, the LCP, the BMI, the polymeric additive, and the crosslinking agent.
6. The low dielectric material of claim 5, wherein the peroxide is at least one crosslinking promoter selected from the group consisting of dicumyl peroxide, α' -bis (t-butylperoxy) diisopropylbenzene, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3.
7. The low dielectric material of claim 4, further comprising 8 to 50phr of at least one inorganic filler selected from the group consisting of: fused silica, spherical silica, talc, aluminum silicate, and soft silica; wherein 8 to 50phr is calculated by the sum of PPE, LCP, BMI, polymer additive and cross-linking agent.
8. The low dielectric material of claim 7, wherein the soft silica has a particle size in a range of 0.5 μm to 10 μm.
9. The low dielectric material of claim 4, further comprising 12 to 14phr of at least one selected from the group consisting of: a phosphorus-containing flame retardant and a phosphate ester; wherein 12-14 phr is calculated by the sum of PPE, LCP, BMI, polymer additive and cross-linking agent.
10. The low dielectric material of claim 9, wherein the phosphorus-containing flame retardant is selected from the group consisting of HCA derivative (I), HCA derivative (II), and HCA derivative (III),
the HCA derivative (I) has a structure of p-diphenylphosphonyl dibenzyl:
Figure FDA0002340259590000051
the HCA derivative (II) has the following structure:
Figure FDA0002340259590000052
when the structure of B is-CH2-or-CH (CH)3) -where m is 1 and n is 1-3; when B has the structure of
Figure FDA0002340259590000053
When m is 2 and n is 0; and
the HCA derivative (III) has the following structure:
Figure FDA0002340259590000061
wherein A is a direct bond, C6-C12Arylene radical、C3-C12Cycloalkylene, or C3-C12Cycloalkenylene, wherein the cycloalkylene or cycloalkenylene may be substituted by C1-C6Alkyl is optionally substituted; each R1、R2、R3And R4Independently of one another is hydrogen, C1-C15Alkyl radical, C6-C12Aryl radical, C7-C15Aralkyl or C7-C15An alkaryl group; or R1And R2Or R3And R4Taken together, may form a saturated or unsaturated cyclic ring, wherein the saturated or unsaturated ring may be substituted with C1-C6Alkyl is optionally substituted; each m is independently 1, 2, 3 or 4; each R5And R6Independently is hydrogen or C1-C6An alkyl group; and each n is independently 0, 1, 2, 3, 4, or 5; provided that when a is aryl or a direct bond, n cannot be 0.
CN201610167700.9A 2016-03-23 2016-03-23 Low dielectric material Active CN107227015B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201610167700.9A CN107227015B (en) 2016-03-23 2016-03-23 Low dielectric material
CN201910318441.9A CN109971154A (en) 2016-03-23 2016-03-23 Dielectric materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610167700.9A CN107227015B (en) 2016-03-23 2016-03-23 Low dielectric material

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201910318441.9A Division CN109971154A (en) 2016-03-23 2016-03-23 Dielectric materials

Publications (2)

Publication Number Publication Date
CN107227015A CN107227015A (en) 2017-10-03
CN107227015B true CN107227015B (en) 2020-04-24

Family

ID=59931649

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201910318441.9A Pending CN109971154A (en) 2016-03-23 2016-03-23 Dielectric materials
CN201610167700.9A Active CN107227015B (en) 2016-03-23 2016-03-23 Low dielectric material

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201910318441.9A Pending CN109971154A (en) 2016-03-23 2016-03-23 Dielectric materials

Country Status (1)

Country Link
CN (2) CN109971154A (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108727800A (en) * 2018-05-21 2018-11-02 高斯贝尔数码科技股份有限公司 A kind of composition of high-frequency microwave copper-clad plate
CN110876230B (en) * 2018-09-03 2020-09-15 昆山雅森电子材料科技有限公司 Composite laminated LCP substrate and preparation method thereof
CN109777123B (en) * 2018-12-25 2021-07-30 广东生益科技股份有限公司 Resin composition, prepreg for printed circuit, and metal-clad laminate
CN109971175B (en) * 2019-03-18 2021-09-21 苏州生益科技有限公司 Modified maleimide resin composition, prepreg and laminated board prepared from same
CN110724261B (en) * 2019-09-30 2022-03-01 艾蒙特成都新材料科技有限公司 High-heat-resistance low-dielectric polyphenylene ether type bismaleimide resin, laminated board and preparation method thereof
JPWO2021166649A1 (en) * 2020-02-20 2021-08-26
JPWO2023276379A1 (en) * 2021-06-29 2023-01-05
TW202321372A (en) 2021-11-26 2023-06-01 南亞塑膠工業股份有限公司 Resin composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1336944A (en) * 1999-01-08 2002-02-20 纳幕尔杜邦公司 High arc tracking-index poly(phenylene oxide)-liquid crystalline polymer blend compositions
JP2005057000A (en) * 2003-08-01 2005-03-03 Asahi Kasei Chemicals Corp Film for flexible printed circuit board
CN102876002A (en) * 2011-07-11 2013-01-16 苍南县慧丰塑料有限公司 Rapid molding high heat-resistant polyamide-polyphenyl ether alloy and preparation method thereof
CN103965606A (en) * 2013-02-04 2014-08-06 联茂电子股份有限公司 Low dielectric material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6759460B2 (en) * 2001-03-08 2004-07-06 Asahi Kasei Kabushiki Kaisha Resin composition
JP4007828B2 (en) * 2002-03-08 2007-11-14 旭化成ケミカルズ株式会社 Method for producing low molecular weight polyphenylene ether

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1336944A (en) * 1999-01-08 2002-02-20 纳幕尔杜邦公司 High arc tracking-index poly(phenylene oxide)-liquid crystalline polymer blend compositions
JP2005057000A (en) * 2003-08-01 2005-03-03 Asahi Kasei Chemicals Corp Film for flexible printed circuit board
CN102876002A (en) * 2011-07-11 2013-01-16 苍南县慧丰塑料有限公司 Rapid molding high heat-resistant polyamide-polyphenyl ether alloy and preparation method thereof
CN103965606A (en) * 2013-02-04 2014-08-06 联茂电子股份有限公司 Low dielectric material

Also Published As

Publication number Publication date
CN107227015A (en) 2017-10-03
CN109971154A (en) 2019-07-05

Similar Documents

Publication Publication Date Title
CN107227015B (en) Low dielectric material
EP2407503B1 (en) Thermosetting resin composition of semi-ipn composite, and varnish, prepreg and metal clad laminated board using the same
KR101716990B1 (en) Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite
EP2291061B1 (en) Composite material, high frequency circuit substrate made therefrom and making method thereof
CN112724640B (en) Thermosetting resin composition, prepreg using same and copper-clad laminate
CN103965606A (en) Low dielectric material
TW201702311A (en) Resin composition, prepreg, laminate and multilayer printed wiring board
EP2595460A1 (en) Composite material and high frequency circuit substrate manufactured with the composite material and the manufacturing method thereof
CN109777123B (en) Resin composition, prepreg for printed circuit, and metal-clad laminate
CN113773632B (en) Composition containing curable polyphenyl ether resin and application thereof
JP6384711B2 (en) Insulating resin composition, prepreg using the same, and laminate for printed wiring board
TWI593749B (en) Dielectric material with low dielectric loss
CN113121981B (en) Resin composition, prepreg and insulating plate using same
KR20170086558A (en) Resin composition, prepreg, metal-clad laminate, and wiring board
KR20220024148A (en) Resin composition, prepreg, resin-added film, resin-added metal foil, metal clad laminate, and wiring board
JPH01121356A (en) Thermosetting resin composition and prepreg and laminated board produced by using same
TWI618097B (en) Low dielectric material
KR20220117913A (en) Resin composition, prepreg, metal-clad laminate and wiring board
JP4852292B2 (en) Copper-clad laminate
JP6575151B2 (en) Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same
JPH04258658A (en) Flame-retardant thermosetting resin composition
JPH0579686B2 (en)
JP4255759B2 (en) Polyphenylene ether resin composition, prepreg containing the same, laminate, copper-clad laminate and printed wiring board
JPS6356548A (en) Thermosetting resin composition, laminated sheet produced by using same and production thereof
CN112824451B (en) Low dielectric resin composition, prepreg, and copper-clad laminate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant