CN103289283A - Thermosetting resin composition, as well as prepreg and laminated board manufactured by using same - Google Patents
Thermosetting resin composition, as well as prepreg and laminated board manufactured by using same Download PDFInfo
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- CN103289283A CN103289283A CN2013102283301A CN201310228330A CN103289283A CN 103289283 A CN103289283 A CN 103289283A CN 2013102283301 A CN2013102283301 A CN 2013102283301A CN 201310228330 A CN201310228330 A CN 201310228330A CN 103289283 A CN103289283 A CN 103289283A
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Abstract
The invention discloses a thermosetting resin composition. The thermosetting resin composition comprises the following components in parts by solid weight: (a) 5-80 parts of modified epoxy resin; (b) 5-80 parts of cyanate ester resin; (c) 0-50 parts of fire retardant; (d) 0-100 parts of inorganic filler; and (e) 0-5 parts of curing accelerator. A preparation method of the modified epoxy resin comprises the following steps of: adding one or more of unsaturated monomers which have double bonds and in which an initiator is dissolved into the epoxy resin; heating to 30-60 DEG C and stirring uniformly; and then, heating to 60-150 DEG C, and performing a reaction for 2-8 hours. According to the thermosetting resin composition disclosed by the invention, the unsaturated monomers with double bonds are added into the epoxy resin for modification, therefore, compared with the traditional epoxy resin composition prepared by simple blending, the thermosetting resin composition disclosed by the invention has more excellent cohesiveness, thermal stability and wet and heat resistance; and a laminated board manufactured by using cyanate ester as a curing agent has low dielectric constant, low dielectric loss, high heat resistance and good wet and heat resistance.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to a kind of compositions of thermosetting resin and use prepreg and the veneer sheet of its making.
Background technology
For a long time, Resins, epoxy has obtained using in a large number and widely in the FR-4 veneer sheet owing to have comprehensive advantages such as starting material wide material sources, processibility is good, cost is lower.Yet, along with the high-speed high frequencyization of information processing in recent years and information transmission, laminate for printed circuits is had higher requirement aspect the dielectric properties.In simple terms, namely laminate sheet material need possess low specific inductivity and dielectric loss, delay, distortion and the loss of signal during with the minimizing high-speed transfer, and interference between signals.But, specific inductivity and the dielectric loss of the baseplate material of common Resins, epoxy (FR-4 copper-clad plate) higher (specific inductivity is generally 4.4, and dielectric loss is about 0.02), thereby be difficult to satisfy the high frequency requirement.
Chinese invention patent CN101186744 discloses a kind of Resins, epoxy, it adds the monomer of the acrylate that contains one or more unsaturated double-bond reactive functional group bases and methacrylic acid or prepolymer as reaction diluent in Resins, epoxy, thereby has improved the gelation time in the solidify reaction process of Resins, epoxy.Yet, when this type of simple mixing formula is used in the printed substrate, easily produce the excessive phenomenon of gummosis under the High Temperature High Pressure in the pressing process, thereby influence the thickness evenness of sheet material, can't satisfy the manufacture process requirement of high-precision electronic baseplate material.
On the other hand, cyanate ester resin has excellent dielectric properties, thermotolerance and low water absorption, but wet-hot aging performance and toughness are relatively poor, have limited its application in high-performance printed wiring plate substrate.As disclosing employing epoxy resin roughening modified cyanic acid ester resin in the document (progress of epoxy resin modification cyanate ester resin, thermosetting resin, in September, 2007,22(5), P38～44); Yet when improving toughness, ordinary epoxy resin dielectric properties difference and water-intake rate are big, and the humidity resistance that can make cyanate ester resin is deterioration more.
Summary of the invention
The object of the invention provides a kind of compositions of thermosetting resin and uses prepreg and the veneer sheet of its making.
For achieving the above object, the technical solution used in the present invention is: a kind of compositions of thermosetting resin with solid weight meter, comprising:
(a) modified epoxy: 5～80 parts;
(b) cyanate ester resin: 5～80 parts;
(c) fire retardant: 0～50 part;
(d) mineral filler: 0～100 part;
(e) curing catalyst: 0～5 part;
The preparation method of described modified epoxy is as follows: one or more unsaturated monomers that contain two keys that will be dissolved with initiator add in the Resins, epoxy, are heated to 30～60 ℃, stir; Then, be warming up to 60～150 ℃, reacted 2～8 hours;
By weight, the unsaturated monomer that contains two keys: Resins, epoxy=1:0.1～10;
The described unsaturated monomer that contains two keys is styrenic, butadiene type, vinylformic acid and ester class, methacrylic acid and ester class, unsaturated dibasic acid, unsaturated dicarboxylic acid anhydride, double bond containing epoxy resin polymerisable monomer; Described styrenic polymerisable monomer is vinylbenzene, vinyl toluene or Vinyl toluene; Described butadiene type polymerisable monomer is 1,3-butadiene or 2-methyl isophthalic acid, the 3-divinyl; Described vinylformic acid and ester class polymerisable monomer are vinylformic acid, methyl acrylate, butyl acrylate or glycidyl acrylate; Described methacrylic acid and ester class polymerisable monomer are methacrylic acid, methyl methacrylate, butyl methacrylate or glycidyl methacrylate; Described unsaturated dibasic acid and unsaturated dicarboxylic acid anhydride polymerisable monomer are maleic anhydride, FUMARIC ACID TECH GRADE or methylene-succinic acid; The structural formula of described double bond containing epoxy resin polymerisable monomer is as follows:
Wherein, R
1Be selected from A1 :-H or A2 :-CH
3
R
2Be selected from B1:
B2:
B3:
Or B4:
In the technique scheme, the number-average molecular weight of described modified epoxy is 200～50000g/mol, and epoxy equivalent (weight) is 100～25000g/eq.
In the technique scheme, described Resins, epoxy is selected from one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic Resins, epoxy, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane Resins, epoxy, biphenyl type epoxy resin, naphthalene nucleus type Resins, epoxy, dicyclopentadiene type Resins, epoxy, isocyanate-based Resins, epoxy, aralkyl novolac epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, the glycidyl ester type epoxy resin.
In the technique scheme, the initiator that adopts among the preparation method of described modified epoxy is selected from benzoyl peroxide, dicumyl peroxide, Diisopropyl azodicarboxylate, benzoyl peroxide/N, in the accelerine one or more, its consumption be contain two keys the unsaturated monomer total mass 0.1%～10%.
In the technique scheme, described fire retardant is bromine-containing compound or P contained compound.
Described bromine-containing compound is selected from the two tetrabromos of decabromodiphynly oxide, TDE or ethylene and contains in the Phthalimide one or more; Described P contained compound is selected from three (2, the 6-3,5-dimethylphenyl) phosphorus, 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO), 10-(2, the 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ), 10-(2,9-dihydroxyl naphthyl)-9, the 10-dihydro-9-oxy is assorted-in 10-phospho hetero phenanthrene-10-oxide compound, phosphoric acid ester and the luxuriant and rich with fragrance class of compound, phenoxy phosphazene compound or phosphine and the derivative thereof one or more.
In the technique scheme, described mineral filler is selected from one or more in silicon-dioxide, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide, the zinc borate.
In the technique scheme, described curing catalyst is selected from a kind of or its mixture in imidazoles, the organic metal salt.
In the technique scheme, described cyanate ester resin is selected from one or more in the performed polymer of bisphenol A cyanate ester, Bisphenol F type cyanate, dicyclopentadiene type ethylene rhodanate, phenol aldehyde type cyanate, tetramethyl-Bisphenol F type cyanate, bis-phenol M type cyanate, bisphenol E-type cyanate, phosphorous cyanate and above-mentioned cyanate.
The present invention asks for protection the prepreg that adopts above-mentioned resin combination to make simultaneously, and above-mentioned resin combination is made glue with dissolution with solvents, strongthener is immersed in the above-mentioned glue then; The back strongthener will be flooded through 80～170 ℃ of bakings 1～10 minute, described prepreg can be obtained.
Described solvent is selected from one or more in acetone, butanone, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether.Described strongthener can adopt natural fiber, organic synthetic fibers, organic fabric or not have woven fabrics.
The present invention asks for protection the veneer sheet that adopts above-mentioned resin combination to make simultaneously; be covered with tinsel at a single or double by above-mentioned prepreg; perhaps incite somebody to action at least 2 by after the above-mentioned prepreg stack; be covered with tinsel at its single or double; 0.2～2MPa pressure and 180～250 ℃ of temperatures systems 2～4 hours, can obtain described veneer sheet.
The quantity of described prepreg is to determine available one or more according to the veneer sheet thickness of customer requirement.Described tinsel can be Copper Foil, also can be aluminium foil, and their thickness is not particularly limited.
Because technique scheme is used, the present invention compared with prior art has following advantage:
1. the present invention has designed a kind of new compositions of thermosetting resin, with carrying out modification in the unsaturated monomer adding Resins, epoxy that contains two keys, compare with the composition epoxy resin of traditional simple blend gained, the present invention has more excellent cohesiveness, thermostability and humidity resistance.
2. can participate in the curing reaction of Resins, epoxy because contain the polymkeric substance of the unsaturated double-bond structure of low polarity in the molecular structure as properties-correcting agent in the composition epoxy resin of the present invention, make its have low-k, low-dielectric loss, thermotolerance, humidity resistance and and the good characteristics of cohesiveness of Copper Foil; Use prepreg and the veneer sheet of the preparation of this resin combination, its have simultaneously low-k, low-dielectric loss, thermotolerance, humidity resistance and and the good characteristics of cohesiveness of Copper Foil, can be used as the electronic machine printed circuit board.
3. the present invention is based on modified epoxy, and the employing cyanate ester resin is solidifying agent, has effectively improved the humidity resistance of cyanate ester resin and the dielectric properties of system, has obtained prepreg and the veneer sheet of excellent property.
Embodiment
Be further described below in conjunction with the present invention of embodiment:
Synthesis example one:
Press mass ratio, get 100 parts of biphenyl type epoxy resins (NC-3000, Japanese chemical drug) and it is dissolved in 100 parts of butanone (MEK), the mol ratio of maleic anhydride and styrene monomer is 0.3:1, and the total mass of maleic anhydride and styrene monomer is 50 parts.Elder generation is dissolved in 0.5 part benzoyl peroxide (BPO) in the vinylbenzene, then maleic anhydride and the styrene monomer that is dissolved with BPO is added in the MEK solution of biphenyl type epoxy resin NC-3000, is stirred to maleic anhydride and dissolves fully under 40 ℃; At last, be warming up to the modified epoxy that 90 ℃ of reactions namely obtained containing styrene-maleic anhydride copolymer in 4 hours.
Synthesis example two:
Press mass ratio, get dicyclopentadiene type Resins, epoxy (XD-1000, Japan's chemical drug) 100 part and it is dissolved in 100 parts of butanone (MEK), the mol ratio of glycidyl methacrylate and styrene monomer is 0.2:1, and the total mass of glycidyl methacrylate and styrene monomer is 100 parts.Elder generation is dissolved in 2 parts dicumyl peroxide (DCP) in the vinylbenzene, then glycidyl methacrylate and the styrene monomer that is dissolved with DCP is added in the MEK solution of dicyclopentadiene type Resins, epoxy XD-1000, stirs under 60 ℃; At last, be warming up to the modified epoxy that 120 ℃ of reactions namely obtained containing vinylbenzene-glycidyl methacrylate copolymer in 6 hours.
Synthesis example three:
Press mass ratio, get 100 parts of adjacent sylvan formaldehyde epoxy resins (N-695, Japanese DIC) and it is dissolved in 100 parts of butanone (MEK), the mol ratio of methacrylic acid and styrene monomer is 1:1, and the total mass of methacrylic acid and styrene monomer is 130 parts.Elder generation is dissolved in 5 parts Diisopropyl azodicarboxylate (AIBN) in the vinylbenzene, then methacrylic acid and the styrene monomer that is dissolved with AIBN is added in the MEK solution of adjacent sylvan formaldehyde epoxy resin N-695, stirs under 50 ℃; At last, be warming up to the modified epoxy that 80 ℃ of reactions namely obtained containing vinylbenzene-Sipacril 2739OF in 8 hours.
Synthesis example four:
Press mass ratio, get biphenyl type epoxy resin (NC-3000, Japan's chemical drug) 100 part and it is dissolved in 100 parts of butanone (MEK), double bond containing epoxy monomer is (in the structural formula, R1=A1, R2=B2) and the mol ratio of styrene monomer be 0.5:1, the total mass of double bond containing epoxy monomer and styrene monomer is 100 parts.Elder generation is dissolved in 2 parts benzoyl peroxide (BPO) in the vinylbenzene, then double bond containing epoxy monomer and the styrene monomer that is dissolved with BPO is added in the MEK solution of biphenyl type epoxy resin NC-3000, stirs under 30 ℃; At last, be warming up to 90 ℃ of reactions and namely obtained containing vinylbenzene-the contain modified epoxy of two key epoxy resin copolymers in 6 hours.
Embodiment one:
Modified epoxy 50g with gained in the synthesis example one, add 40g bisphenol A cyanate ester resin (BA-3000S, Lonza), 10g phosphorus containing phenolic resin (XZ92741, DOW Chemical), 0.2g2-ethyl-4-methylimidazole and 0.2g zinc octoate and an amount of butanone solvent, mix and obtain glue.
With this glue dipping and be coated on E glass cloth (2116, substance is 104g/m
2) on, and baking 5min makes prepreg in 160 ℃ of baking ovens.
With this prepreg that makes, respectively put a Copper Foil up and down, place the compacting of vacuum hotpressing machine to obtain copper-clad plate.Concrete process for pressing is at 1.5Mpa pressure, and 220 ℃ of temperatures were closed 2 hours.
The copper clad laminate performance that obtains is as shown in table 1.
Embodiment two:
Modified epoxy 50g with gained in the synthesis example two, add 40g dicyclopentadiene type ethylene rhodanate resin (CY-3, Jiangdu Fructus Hordei Germinatus chemical industry company limited), 10g phosphonitrile (SPB-100, Ri Ben Otsuka Chemical Co., Ltd), 0.2g2-ethyl-4-methylimidazole and 0.2g zinc naphthenate and an amount of butanone solvent, mix and obtain glue.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance that obtains is as shown in table 1.
Embodiment three:
Modified epoxy 40g with gained in the synthesis example three, add 50g bisphenol E-type cyanate resin (CY-9, Jiangdu Fructus Hordei Germinatus chemical industry company limited), 10g phosphorus containing phenolic resin (XZ92741, DOW Chemical), 0.2g2-ethyl-4-methylimidazole and 0.3g acetylacetone cobalt and an amount of butanone solvent, mix and obtain glue.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance that obtains is as shown in table 1.
Embodiment four:
Modified epoxy 60g with gained in the synthesis example four, add 30g phenol aldehyde type cyanate ester resin (CY-5, Jiangdu Fructus Hordei Germinatus chemical industry company limited), 10g phosphonitrile (SPB-100, Ri Ben Otsuka Chemical Co., Ltd), 15g fused silica, 0.3g2-ethyl-4-methylimidazole and 0.2g aluminium acetylacetonate and an amount of butanone solvent, mix and obtain glue.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance that obtains is as shown in table 1.
Comparative Examples one:
70g biphenyl type polyfunctional epoxy resin (NC-3000, Japanese chemical drug) is joined in the 70g butanone, and stirring is dissolved it fully.After treating that it dissolves fully, add 30gSMA resin (EF40, U.S.'s Sartomer), 0.2g2-ethyl-4-methylimidazole and an amount of butanone solvent, mix and obtain glue.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance that obtains is as shown in table 1.
Comparative Examples two:
With the modified epoxy 70g of gained in the synthesis example one, add 30g linear phenolic resin, 0.2g2-ethyl-4-methylimidazole and an amount of butanone solvent, mix and obtain glue.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance that obtains is as shown in table 1.
Comparative Examples three:
(BA-3000S Lonza), 0.5g zinc octoate and an amount of butanone solvent, mixes and obtains glue with the 100g bisphenol A cyanate ester resin.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance that obtains is as shown in table 1.
Table 1 adopts the copper clad laminate performance of different embodiment gained
Annotate: the relevant test data chamber is based on the veneer sheet sample of RC=50% in the table.
The testing method of characteristic is as follows in the table:
(1) flame retardant resistance (resistance to flame): measure according to the UL94 method.
(2) the wicking time (minute): the time that wicking to layering is bubbled in 288 ℃ tin stove.
(3) specific inductivity: use flat band method according to IPC-TM-6502.5.5.9, measure the specific inductivity under the 1GHz.
(4) tangent of the dielectric loss angle: use flat band method according to IPC-TM-6502.5.5.9, measure the dielectric loss factor under the 1GHz.
(5) second-order transition temperature (Tg, ℃): according to differential scanning calorimetric (DSC) method, measure according to the DSC method of IPC-TM-6502.4.25 defined.
(6) stripping strength (PS, N/mm): according to " after the thermal stresses " experiment condition in the IPC-TM-6502.4.8 method, the stripping strength of test metal cap rock.
(7) wicking thermotolerance (PCT) after the wet heat treatment: getting 3 10cm * 10cm, thickness is the sample that tinsel is removed on 0.80mm, two sides, 100 ℃ of dryings 2 hours, pressure-cook test (Pressure Cooker test) machine then, after handling 1 hour under 121 ℃, 2 normal atmosphere, wicking 20s in 288 ℃ tin stove, whether visual observations has demixing phenomenon.If any 0,1,2,3 demixing phenomenons are designated as 0/3,1/3,2/3,3/3 respectively in 3.
As seen from Table 1, Comparative Examples one adopts macromolecule polymkeric substance and the simple blend of Resins, epoxy of preparation in advance, because its sheet material thermotolerance deficiency of dispersed official post, cohesive strength is low, and humidity resistance is poor; Comparative Examples two adopts linear phenolic resin to solidify the modified epoxy that is synthesized, and its dielectric properties have deterioration to a certain degree; Comparative Examples three adopts pure ethylene rhodanate resin curing, and its dielectric properties are quite excellent, but wet-hot aging performance is bad; And embodiments of the invention have low-k, low-dielectric loss angle tangent, thermotolerance, humidity resistance and and the good characteristics of cohesiveness of Copper Foil.
Claims (10)
1. a compositions of thermosetting resin is characterized in that, with solid weight meter, comprising:
(a) modified epoxy: 5～80 parts;
(b) cyanate ester resin: 5～80 parts;
(c) fire retardant: 0～50 part;
(d) mineral filler: 0～100 part;
(e) curing catalyst: 0～5 part;
The preparation method of described modified epoxy is as follows: one or more unsaturated monomers that contain two keys that will be dissolved with initiator add in the Resins, epoxy, are heated to 30～60 ℃, stir; Then, be warming up to 60～150 ℃, reacted 2～8 hours;
By weight, the unsaturated monomer that contains two keys: Resins, epoxy=1:0.1～10;
The described unsaturated monomer that contains two keys is styrenic, butadiene type, vinylformic acid and ester class, methacrylic acid and ester class, unsaturated dibasic acid, unsaturated dicarboxylic acid anhydride, double bond containing epoxy resin polymerisable monomer; Described styrenic polymerisable monomer is vinylbenzene, vinyl toluene or Vinyl toluene; Described butadiene type polymerisable monomer is 1,3-butadiene or 2-methyl isophthalic acid, the 3-divinyl; Described vinylformic acid and ester class polymerisable monomer are vinylformic acid, methyl acrylate, butyl acrylate or glycidyl acrylate; Described methacrylic acid and ester class polymerisable monomer are methacrylic acid, methyl methacrylate, butyl methacrylate or glycidyl methacrylate; Described unsaturated dibasic acid and unsaturated dicarboxylic acid anhydride polymerisable monomer are maleic anhydride, FUMARIC ACID TECH GRADE or methylene-succinic acid; The structural formula of described double bond containing epoxy resin polymerisable monomer is as follows:
Wherein, R
1Be selected from A1 :-H or A2 :-CH
3
R
2Be selected from B1:
B2:
B3:
Or B4:
2. resin combination according to claim 1, it is characterized in that: the number-average molecular weight of described modified epoxy is 200～50000g/mol, epoxy equivalent (weight) is 100～25000g/eq.
3. resin combination according to claim 1, it is characterized in that: described Resins, epoxy is selected from bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic Resins, epoxy, phenol novolac epoxy resins, the trifunctional phenol-type epoxy resin, tetraphenyl ethane Resins, epoxy, biphenyl type epoxy resin, naphthalene nucleus type Resins, epoxy, dicyclopentadiene type Resins, epoxy, isocyanate-based Resins, epoxy, the aralkyl novolac epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, in the glycidyl ester type epoxy resin one or more.
4. resin combination according to claim 1, it is characterized in that: the initiator that adopts among the preparation method of described modified epoxy is selected from benzoyl peroxide, dicumyl peroxide, Diisopropyl azodicarboxylate, benzoyl peroxide/N, in the accelerine one or more, its consumption be contain two keys the unsaturated monomer total mass 0.1%～10%.
5. resin combination according to claim 1, it is characterized in that: described fire retardant is bromine-containing compound or P contained compound.
6. resin combination according to claim 1, it is characterized in that: described mineral filler is selected from one or more in silicon-dioxide, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide, the zinc borate.
7. resin combination according to claim 1, it is characterized in that: described curing catalyst is selected from a kind of or its mixture in imidazoles, the organic metal salt.
8. resin combination according to claim 1 is characterized in that: described cyanate ester resin is selected from one or more in the performed polymer of bisphenol A cyanate ester, Bisphenol F type cyanate, dicyclopentadiene type ethylene rhodanate, phenol aldehyde type cyanate, tetramethyl-Bisphenol F type cyanate, bis-phenol M type cyanate, bisphenol E-type cyanate, phosphorous cyanate and above-mentioned cyanate.
9. a prepreg that adopts resin combination as claimed in claim 1 to make is characterized in that: the described resin combination of claim 1 is made glue with dissolution with solvents, strongthener is immersed in the above-mentioned glue then; The back strongthener will be flooded through 80～170 ℃ of bakings 1～10 minute, described prepreg can be obtained.
10. veneer sheet that adopts resin combination as claimed in claim 1 to make, it is characterized in that: be covered with tinsel at a single or double by the described prepreg of claim 9, perhaps incite somebody to action at least 2 by after the described prepreg stack of claim 9, be covered with tinsel at its single or double, 0.2～2MPa pressure and 180～250 ℃ of temperatures systems 2～4 hours, can obtain described veneer sheet.
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| CN103554811A (en) * | 2013-11-05 | 2014-02-05 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board made from thermosetting resin composition |
| CN104002525A (en) * | 2014-04-18 | 2014-08-27 | 南通诺德电子有限公司 | Making method for high TG halogen-free LOW Dk/Df copper-clad plate |
| CN104194262A (en) * | 2014-08-18 | 2014-12-10 | 苏州生益科技有限公司 | Thermosetting resin composition as well as semi-cured piece and laminated plate manufactured by using thermosetting resin composition |
| CN105085973A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Preparation method for electron beam-cured double-bond phenolic foam material |
| CN108192264A (en) * | 2017-12-29 | 2018-06-22 | 广东正业科技股份有限公司 | A kind of resin combination for high frequency flexible circuit board |
| CN108342160A (en) * | 2018-02-05 | 2018-07-31 | 合肥市大卓电力有限责任公司 | A kind of Environment-friendlyadhesive adhesive and preparation method thereof |
| CN109563222A (en) * | 2016-09-30 | 2019-04-02 | 太阳油墨制造株式会社 | Photocurable resin composition, dry film, solidfied material and printed circuit board |
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| CN111925628A (en) * | 2020-06-30 | 2020-11-13 | 上海复合材料科技有限公司 | Solvent-free epoxy resin system for winding composite material pipe structure and preparation method thereof |
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| CN103554811A (en) * | 2013-11-05 | 2014-02-05 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board made from thermosetting resin composition |
| CN103554811B (en) * | 2013-11-05 | 2016-06-15 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use prepreg and the laminate of its making |
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Application publication date: 20130911 |