CN106380715A

CN106380715A - Resin composition

Info

Publication number: CN106380715A
Application number: CN201610769395.0A
Authority: CN
Inventors: 殷卫峰; 张记明; 曾耀德; 李莎
Original assignee: SHAANXI SHENGYI SCI TECH Co Ltd
Current assignee: SHAANXI SHENGYI SCI TECH Co Ltd
Priority date: 2016-08-29
Filing date: 2016-08-29
Publication date: 2017-02-08
Anticipated expiration: 2036-08-29
Also published as: CN106380715B

Abstract

The invention discloses a resin composition. The resin composition comprises styrene butadiene resin, epoxy modified unsaturated polybutadiene with a molecular weight less than 50000, a crosslinking agent, and an initiator. The invention also discloses applications of the resin composition in prepreg, laminated board, copper clad laminate, and printed circuit board. The resin composition has excellent comprehensive performances such as good heatproof performance, high peeling strength, little dielectric loss, and the like, and can meet the performance requirements of high frequency sheet.

Description

A kind of resin combination

Technical field

The present invention relates to copper-clad plate field is and in particular to a kind of resin combination, the invention still further relates to this resin combination Application in prepreg, laminate, copper-clad laminate, printed circuit board.

Background technology

In recent years, step on the development of communication apparatus high performance, multifunction and networking with computer, mobile phone, be High-speed transfer and process Large Copacity information, operation signal carries out high frequency, needs one kind to be applied to high frequency signal transmission The high-performance electric insulant of characteristic.

In high-frequency circuit, electric signal transmission loss dielectric loss and conductor losses, radiation loss sum represent, telecommunications Number more high then dielectric loss of frequency, conductor losses, radiation loss are bigger.Because transmission loss makes the signal of telecommunication decay, destroys telecommunications Number reliability, this loss simultaneously, from high frequency circuit radiation, is likely to result in electronic failure.Dielectric therefore must be reduced damage Consumption, conductor losses, radiation loss.It is known that the dielectric loss angle of the insulator of the dielectric loss of the signal of telecommunication and formation circuit The product of tangent and the signal frequency being used is directly proportional.Therefore as insulator, can be by just selecting dielectric loss angle Cut little insulant, the increase of suppression dielectric loss.

Application No. CN200810142665.0 (the applying date：2008.7.28, notification number：CN101328277A, the day for announcing： 2010.7.21 Chinese patent) is disclosed one kind and is more than using epoxide modified polybutadiene, maleic anhydride modified molecular weight 50000 butadiene and cinnamic copolymer, this patent does not provide the epoxide modified scope on modified strand, such as Fruit epoxide group quantity is excessive, the polarity of composite can be led to increase, dielectric constant, dielectric loss increase；If epoxy radicals Group's quantity is too small, and resin system can be led to too small with the peel strength between Copper Foil.Additionally, the MA modification fourth disclosed in this patent Diene is more than 50,000 with cinnamic molecular weight of copolymer, is difficult in a solvent dissolve, subsequent technique is poor.

For problem above, the present invention proposes one kind and has that heat-resist, peel strength is high, dielectric constant is low, dielectric The little baseplate material waiting excellent comprehensive performance of loss.

Content of the invention

It is an object of the invention to provide a kind of resin combination, it has, and heat-resist, peel strength is high, dielectric loss is little Deng excellent comprehensive performance, the performance requirement of high frequency sheet material can be met.

It is a further object to provide a kind of resin combination is in prepreg, laminate, copper-clad laminate, print Application in circuit board processed.

The technical solution adopted in the present invention is that a kind of resin combination, including butadiene styrene resin, molecular weight less than 50000 Epoxide modified unsaturation polybutadiene, cross-linking agent, initiator.

The feature of the present invention also resides in,

The molecular weight of butadiene styrene resin is less than 11000, and the contents of ethylene of butadiene styrene resin is 60～99%, preferably 70～ 95wt%, further preferred 75～93wt%；The styrene-content of butadiene styrene resin is 30～60%, preferably 35～55%, enters one Step preferably 40～50%；The percentage by weight that butadiene styrene resin accounts for resin combination is 45～80wt%, preferably 48～70wt%, enters One step preferably 50～60wt%.

The molecular weight of epoxide modified polybutadiene is 5000～50000, preferably 8000～40000, further preferred 11000 ～30000.

The contents of ethylene 60～99% of epoxide modified polybutadiene, preferably 70～95wt%, preferably 70～95wt%, enter One step preferably 75～93wt%；Epoxide group percent grafting on epoxide modified polybutadiene strand is between 5 to 10.

The percentage by weight that epoxide modified polybutadiene accounts for resin combination is 10～50wt%, preferably 15～ 40wt%, further preferred 20～30wt%.

Cross-linking agent account for resin combination percentage by weight be 3～40wt%, cross-linking agent be selected from triallyl isocyanurate, Poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl In base benzene or polyfunctional acrylate any one or at least two mixing.

The percentage by weight that initiator accounts for described resin combination is 1～7wt%, and initiator is selected from a, a '-two (tert-butyl group Isopropylbenzene between peroxidating) benzene, cumyl peroxide, cumyl t-butyl peroxide, double (the tertiary hexyl peroxidating) -3,3 of 1,1-, 5- trimethyl-cyclohexane, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester, perbenzoic acid The tert-butyl ester, three second class amine and its esters, level Four amine salt compound, 2,4,6- tri- (dimethylamino methylamine) phenol, benzyl dimethylamine, Imidazoles, three amylic phenol acid amides, the coordination compound of single or multiple phenolic compounds, boron trifluoride and its Organic substance, phosphoric acid or phosphorous acid three In phenyl ester any one or at least two mixing.

Resin combination also includes fire retardant, and fire retardant is selected from deca-BDE, (adjacent two formyls of tetrabromo-benzene are sub- for ethyl-bis- Amine), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphine, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy - 10 phosphine phenanthrene -10- oxides, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene or 10- phenyl -9,10- dihydro-9-oxy -10- phosphine In phenanthrene -10- oxide any one or at least two mixing.

Resin combination also includes filler, and filler is selected from powdered quartz, unformed silicon dioxide, ball-type dioxy SiClx, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, strontium titanates Barium, calcium Barium metatitanate., lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, niobium Magnesium lead plumbate, barium magnesium niobate, Lithium metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, tantalum In sour bismuth strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate any one or at least two mixing Thing；

In the particle diameter of filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；

The percentage by weight that filler accounts for described resin combination is 0～90wt%, preferably 40～85wt%, further preferably 60～80wt%.

Second technical scheme of the present invention be, above-mentioned resin combination is in prepreg, laminate, copper foil covered Application in pressing plate, printed circuit board.

Compared with prior art, the present invention has the advantages that：

The resin combination that the present invention provides, it has the excellent combination such as heat-resist, peel strength is high, dielectric loss is little Performance, can meet the performance requirement of high frequency sheet material.

Specific embodiment

With reference to specific embodiment, the present invention is described in detail.

Invention resin composition, the epoxide modified unsaturation polybutadiene being less than 50000 including butadiene styrene resin, molecular weight Alkene, cross-linking agent, initiator.

The molecular weight of butadiene styrene resin is less than 11000, and the contents of ethylene of butadiene styrene resin is 60～99%, such as 60%, 65%th, 70%, 75%, 80%, 85%, 90%, 92% or 95%, preferably 70～95wt%, further preferred 75～93wt%.

The styrene-content of butadiene styrene resin be 30～60%, such as 30%, 32%, 38%, 40%, 45%, 48%, 50%th, 55% or 60%, preferably 35～55%, further preferred 40～50%.

Butadiene styrene resin account for resin combination percentage by weight be 45～80wt%, such as 45%, 50%, 55%, 60%, 65%th, 70%, 75%, 78% or 80%, preferably 48～70wt%, further preferred 50～60wt%.

The molecular weight of epoxide modified polybutadiene be 5000～50000, such as 5000,8000,10000,15000, 20000th, 25000,30000,35000,40000,45000 or 50000, preferably 8000～40000, further preferred 11000～ 30000.If molecular weight is more than 50,000, epoxide modified polybutadiene can be led to be difficult in a solvent dissolve, subsequent technique is poor. If molecular weight is less than 5000, during leading to subsequently prepare sheet material, gummosis is excessive, and manufacturability is poor.

The contents of ethylene 60～99% of epoxide modified polybutadiene, such as 60%, 65%, 70%, 75%, 80%, 85%th, 90%, 92% or 95%, preferably 70～95wt%, preferably 70～95wt%, further preferred 75～93wt%；

Epoxide group percent grafting on epoxide modified polybutadiene strand is between 5 to 10；If percent grafting is more than 10, the polarity of composite can be led to increase, dielectric loss increases；If functional group's percent grafting is less than 5, resin system can be led to Too small with the peel strength between Copper Foil.

Epoxide modified polybutadiene account for resin composition weight percentage ratio be 10～50wt%, such as 10%, 15%, 20%th, 25%, 28%, 30%, 33%, 35%, 40%, 43%, 35% or 50%, preferably 15～40wt%, further preferably 20～30wt%.

Cross-linking agent account for resin combination percentage by weight be 3～40wt%, such as 3%, 5%, 15%, 20%, 22%, 25%th, 28%, 30%, 33%, 35%, 38% or 40%, preferably 10～38wt%, further preferred 20～35wt%.Crosslinked Agent is sour, adjacent selected from triallyl isocyanurate, poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate In dially phthalate, divinylbenzene or polyfunctional acrylate any one or at least two mixing.

Initiator account for resin combination percentage by weight be 1～7wt%, such as 1%, 1.3%, 1.5%, 1.7%, 2%th, 2.3%, 2.5%, 3%, 3.5%, 4%, 5%, 6% or 7%, preferably 1.5～5%, further preferred 2～4wt%.Draw Send out agent be selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, 1, Double (the tertiary hexyl peroxidating) -3 of 1-, 3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, Octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate, three second class amine and its esters, level Four amine salt compound, 2,4,6- tri- (dimethylamine Base methylamine) phenol, benzyl dimethylamine, imidazoles, three amylic phenol acid amides, single or multiple phenolic compounds, boron trifluoride and its Organic substance Coordination compound, in phosphoric acid or triphenyl phosphite any one or at least two mixing.

This resin combination also includes fire retardant, and fire retardant is selected from deca-BDE, ethyl-bis- (tetrabromo-benzene neighbour's two formyls Imines), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphine, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy Change -10 phosphine phenanthrene -10- oxides, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene or 10- phenyl -9,10- dihydro-9-oxy - In 10- phosphine phenanthrene -10- oxide any one or at least two mixing.

This resin combination also includes filler, and filler is selected from powdered quartz, unformed silicon dioxide, ball-type two Silicon oxide, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, metatitanic acid Strontium barium, calcium Barium metatitanate., lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, Lead magnesio-niobate, barium magnesium niobate, Lithium metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, In bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate any one or at least two mixing Thing.

In the particle diameter of filler, angle value is 0.5～20uM, such as 0.5,1.0,2.0,4.0,6.0,10,12,15,20,25,28 Or 30, preferably 1～15uM, further preferred 4～10uM；

Filler account for resin combination percentage by weight be 0～90wt%, such as 0%, 10%, 25%, 35%, 45%, 55%th, 65%, 70%, 75%, 78%, 80%, 85% or 90%, preferably 40～85wt%, further preferred 60～80wt%.

According to information in the public domain, different molecular weight, different contents of ethylene, the polybutadiene of different epoxy percent grafting can be prepared Resin, as follows.

16L is dried hexamethylene, 1600g is dried butadiene and puts into four mouthfuls of glass reaction bottles of 4L (at overbaking drying Reason) in, it is passed through drying nitrogen protection, 40 DEG C～80 DEG C of constant temperature, then sequentially add following catalytic component：4ml～9ml tri- The hexane solution of [di-(2-ethylhexyl)phosphoric acid] ferrum (0.4mmol～0.9mmol), 16ml～36ml triisobutyl aluminium (8mmol) hexane solution, the hexane solution of 12ml～27ml triphenyl phosphate (1.2mmol～2.7mmol), 17mmol～ The tetrahydrofurfuryl alcohol ethylether of 38mmol, PMDETA 7mmol～17mmol, are warming up to 65 DEG C～90 DEG C, are polymerized 1～9 hour.So After add ethanol terminating reaction and separate out glue sample, sucking filtration, with acetone extraction 12～18h, put into 25 DEG C of baking ovens vacuum drying 12h, Obtain white solid product polybutadiene.

By 1000g polybutadiene, 2.5L ethyl acetate is put in four mouthfuls of glass reaction bottles of 4L, 65 DEG C～75 DEG C of constant temperature, After polybutadiene is completely dissolved, be passed through drying nitrogen, be warming up to 80 DEG C～95 DEG C, be slowly added to in system containing 50g～ 200g formic acid, 5g～42g Polyethylene Glycol, stirring reaction 2～4 hours after completion of dropping, then by the hydrogen peroxide of 30g～215g Interior in 30min be slowly dropped in four-hole bottle, reactant is slowly warmed up to 120 DEG C, continues reaction 3～5 hours at a constant temperature, After reaction terminates, product is poured out, add dehydrated alcohol precipitation, sedimentation a period of time, sucking filtration, with sodium bicarbonate solution and distillation Water washing at least 12 times, puts into 25 DEG C of baking oven vacuum drying 12h, obtains white solid product.

Different molecular weight, different contents of ethylene, different epoxy percent grafting polybutadiene as shown in table 1.

The epoxide modified polybutadiene of table 1

	Molecular weight	Contents of ethylene	Epoxy percent grafting
				PB-5000	5000	60%	5
PB-7000	7000	85%	7
				PB-10000	10000	90%	8
PB-50000	50000	99%	10
				PB-5000-2	5000	60%	2
PB-5000-15	5000	60%	15
				PB-5000-30	5000	30%	5

According to information in the public domain, the butadiene styrene resin of different molecular weight, different contents of ethylene can be prepared, specific as follows.

4L is dried hexamethylene, 0.05ml～0.48ml tetrahydrofurfuryl alcohol ethylether, puts into four mouthfuls of glass reaction bottle (warps of 4L Overbaking dried) in, it is passed through drying nitrogen protection, 40 DEG C～60 DEG C of constant temperature, be then simultaneously introduced with the following group in 60min Point：25g～200g styrene (S), the mix monomer of 30～210g butadiene (B), 0.4mol/L butyl lithium 0.02mL～ 0.1mL, is subsequently adding the cyclohexane solution of the 0.2mol/L mono- chlorine trimethyl silane of 1.0mL～16.65mL, reacts 30min, plus Enter isopropanol terminating reaction and separate out glue sample, sucking filtration, use acetone extraction 12h, put into 25 DEG C of baking oven vacuum drying 12h, obtain white Solid product.

Different molecular weight, different contents of ethylene, different styrene-content butadiene styrene resin as shown in table 2.

Table 2 butadiene styrene resin

	Molecular weight	Contents of ethylene	Styrene-content
				PBS-1000	1000	60%	30%
PBS-5000	5000	85%	40%
				PBS-7000	7000	90%	50%
PBS-11000	11000	99%	60%
				PBS-1000-05	1000	60%	5%
PBS-1000-30	1000	30%	30%

For the present invention is better described, readily appreciate technical scheme, the present invention's is typical but non-limiting Embodiment is as follows：

Embodiment

Embodiment 1-8 and the manufacture method of comparative example 1-4 copper-clad laminate：Design parameter is as shown in Table 3 and Table 4.

Butadiene styrene resin, epoxide modified polybutadiene, cross-linking agent, initiator are dissolved in toluene, after fully dissolving, add The filler of angle value, different quality containing in different-grain diameter, is then mixed to get glue at room temperature.Impregnated above-mentioned using glass cloth Glue, then in 155 DEG C of baking oven, baking is cured as B-stage for 5 minutes, and control obtains prepreg.

Then, the prepreg of making is placed between Copper Foil, is laminated and solidifies in 210 DEG C in press, obtain solidfied material Measuring Dielectric Constant afterwards, Tg, peel strength, DK, Df.Specific performance is shown in Table 3, table 4.

In above-described embodiment and comparative example, used material is specific as follows：

Triallyl isocyanurate：Nippon Kasei Chemical Company TAIC M-60

Poly- triallyl isocyanurate：Nippon Kasei Chemical Company

Triallyl cyanurate：Nippon Kasei Chemical Company

BPO：Great river oils and fatss Co., Ltd.

BIPB：Great river oils and fatss Co., Ltd.

DCP：Shanghai Fang Rui reaches chemical industry

Barium titanate/strontium titanate/barium strontium titanate：Shanghai allusion quotation raises science and technology

Lead titanates：Hubei Prunus persica f. compressa culminant star electronics.

Table 3 embodiment 1～8 formula and test result

Table 4 comparative example 1～4 formula and test result

The method of testing of above characteristic is as follows：

1st, glass transition temperature (Tg)：DMA method according to IPC-TM-650 2.4.24 defined is measured.

2nd, peel strength (PS)：According to " after thermal stress " experiment condition in IPC-TM-650 2.4.8 method, test sheet material Peel strength.

3rd, dielectric properties：SPDR (splite post dielectric resonator) method is tested, test condition For A state, 10GHz.

From table 3 and table 4, can be seen that what embodiment 1 was prepared to embodiment 8 from the contrast of embodiment and comparative example Sheet material, the combination property such as its dielectric loss, dielectric constant, peel strength, glass transition temperature preferably, uses in comparative example 1 The polybutadiene of low percent grafting, the dielectric loss ratio of sheet material is relatively low, but peel strength is low；Using high percent grafting in comparative example 2 Polybutadiene, the peel strength of sheet material is high, but the dielectric loss of sheet material is high；Comparative example 3 uses the little fourth of styrene-content Benzene resin, the Tg of sheet material is low；Comparative example 4 uses the little butadiene styrene resin of contents of ethylene, butadiene resin, and the Tg of sheet material is low.

Comprehensive the above results understand, the material of the present invention can reach that heat-resist, peel strength is high, dielectric constant is low, be situated between Electrical loss is little to wait excellent comprehensive performance, and performance has obtained larger improvement, can meet the performance requirement of high dielectric material.

Above example, not imposes any restrictions to the content of the compositionss of the present invention, every technology according to the present invention Any trickle amendment, equivalent variations and modification that essence or compositionss composition or content are made to above example, all still fall within In the range of technical solution of the present invention.

Applicant states, the present invention illustrates the detailed composition of the present invention by above-described embodiment, but the present invention not office It is limited to above-mentioned detailed composition, that is, do not mean that the present invention has to rely on above-mentioned detailed composition and could implement.Art Technical staff is it will be clearly understood that any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and auxiliary element Interpolation, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims

1. a kind of resin combination is it is characterised in that include butadiene styrene resin, the epoxide modified unsaturation less than 50000 for the molecular weight Polybutadiene, cross-linking agent, initiator.

2. resin combination according to claim 1 it is characterised in that described butadiene styrene resin molecular weight be less than 11000, The contents of ethylene of described butadiene styrene resin is 60～99%, preferably 70～95wt%, further preferred 75～93wt%；Described fourth The styrene-content of benzene resin is 30～60%, preferably 35～55%, further preferred 40～50%；Described butadiene styrene resin accounts for tree The percentage by weight of oil/fat composition is 45～80wt%, preferably 48～70wt%, further preferred 50～60wt%.

3. resin combination according to claim 1 is it is characterised in that the molecular weight of described epoxide modified polybutadiene is 5000～50000, preferably 8000～40000, further preferred 11000～30000.

4. resin combination according to claim 1 is it is characterised in that the vinyl of described epoxide modified polybutadiene contains Amount 60～99%, preferably 70～95wt%, preferably 70～95wt%, further preferred 75～93wt%；Described epoxide modified poly- Epoxide group percent grafting on butadiene molecule chain is between 5 to 10.

5. according to the arbitrary described resin combination of claim 1,3,4 it is characterised in that described epoxide modified polybutadiene tree The percentage by weight that fat accounts for resin combination is 10～50wt%, preferably 15～40wt%, further preferred 20～30wt%.

6. resin combination according to claim 1 is it is characterised in that described cross-linking agent accounts for the weight hundred of resin combination Divide than being 3～40wt%, described cross-linking agent is selected from triallyl isocyanurate, poly- triallyl isocyanurate, triallyl three Any in polycyanate ester, trimethacrylate acid, diallyl phthalate, divinylbenzene or polyfunctional acrylate A kind of or at least two mixing.

7. resin combination according to claim 1 is it is characterised in that described initiator accounts for the weight of described resin combination Amount percentage ratio is 1～7wt%, and described initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, peroxidating diisopropyl Double (the tertiary hexyl peroxidating) -3 of benzene, cumyl t-butyl peroxide, 1,1-, 3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5- Two (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate, three second class amine and its esters, quaternary ammonium compound Salt compound, 2,4,6- tri- (dimethylamino methylamine) phenol, benzyl dimethylamine, imidazoles, three amylic phenol acid amides, single or multiple phenolate Any one in the coordination compound of compound, boron trifluoride and its Organic substance, phosphoric acid or triphenyl phosphite or at least two Mixing.

8. resin combination according to claim 1 is it is characterised in that this resin combination also includes fire retardant, fire-retardant Agent is selected from deca-BDE, ethyl-bis- (tetrabromo phthalimide), decabromodiphenylethane, three (2,6- dimethyl benzenes Base) phosphine, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy -10 phosphine phenanthrene -10- oxide, 2,6- bis- (2,6- dimethyl Phenyl) in phosphino- benzene or 10- phenyl -9,10- dihydro-9-oxy -10- phosphine phenanthrene -10- oxide any one or at least two The mixing planted.

9. it is characterised in that this resin combination also includes filler, filler selects resin combination according to claim 1 From powdered quartz, unformed silicon dioxide, spherical silica, titanium dioxide, boron nitride, aluminium nitride, carborundum, Aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium Barium metatitanate., lead titanates, lead zirconate titanate, zirconium lanthanium titanate Lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, Lithium metaniobate, potassium niobate, tantalic acid aluminum Strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, metatitanic acid In lead-lead magnesio-niobate any one or at least two mixture；

In the particle diameter of described filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；

The percentage by weight that described filler accounts for described resin combination is 0～90wt%, preferably 40～85wt%, further preferably 60～80wt%.

10. described resin combination as arbitrary in claim 1～9 is in prepreg, laminate, copper-clad laminate, printing electricity Application in the plate of road.