CN105601886A - Isocyanate modified epoxy resin and application - Google Patents
Isocyanate modified epoxy resin and application Download PDFInfo
- Publication number
- CN105601886A CN105601886A CN201610129824.8A CN201610129824A CN105601886A CN 105601886 A CN105601886 A CN 105601886A CN 201610129824 A CN201610129824 A CN 201610129824A CN 105601886 A CN105601886 A CN 105601886A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- replacement
- unsubstituted
- replace
- alkylene
- 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.)
- Withdrawn
Links
- 0 CC*NC(C)CCCC** Chemical compound CC*NC(C)CCCC** 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Abstract
The invention relates to isocyanate modified epoxy resin of the structure shown in the formula (I). X does not exist or is selected from a sub organic group, R is selected from a sub organic group, R1, R2, R3, R4, R18, R19, R20 and R21 are independently selected from hydrogen atoms or organic groups and are not hydrogen atoms at the same, and n is an integer larger than or equal to 0. Two or more polyisocyanates are used as the raw material of the epoxy resin and react with a resin monomer with an epoxy group, and the purpose of introducing an oxazolidinone group in the epoxy resin monomer is achieved; in addition, the end of the epoxy resin is sealed through the epoxy group, and therefore the composition of the epoxy resin has the high heat resistance and low dielectric performance.
Description
Technical field
The invention belongs to epoxy resin preparation field, relate to a kind of epoxy resin and uses thereof, be specifically related to a kind of isocyanideAcid esters modified epoxy and in the application of pre-impregnated sheet, composite metal substrate and wiring board.
Background technology
Epoxy resin is the organic compound that contains two or more epoxide groups in general reference molecule, except indivedual,Their relative molecular mass is not high. The molecular structure of epoxy resin is to contain active epoxide group in strand as itFeature, epoxide group can be positioned at the end, centre of strand or structure circlewise. Owing to containing active ring in molecular structureOxygen groups, makes them can form with polytype curing agent generation cross-linking reaction the insoluble cancellated height of three-dimensional that hasPolymers. The macromolecular compound that contains epoxide group in all molecular structures is referred to as epoxy resin. Epoxy resin tool after solidifyingHave good physics, chemical property, it has excellent adhesive strength to the surface of metal and nonmetallic materials, and dielectric properties are goodGood, set shrinkage factor is little, product size good stability, and hardness is high, and pliability is better, to alkali and most of solvent-stable, therebyBe widely used in national defence, all fields of national economy, pour into a mould, the purposes such as dipping, lamination material, bonding agent, coating.
Taking mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with air-conditioning, refrigerator, television image, soundThe various products that sound articles for use etc. use for family expenses, office electric equipment products and the other field of representative, for safety, very most ofProduct all require it to possess low-dielectric and heat resistance.
With regard to electrical equipment character, mainly need the factor of considering also to comprise dielectric constant and the dielectric loss of material. Generally, because the square root of the signal transfer rate of substrate and the dielectric constant of baseplate material is inversely proportional to, therefore Jie of baseplate materialElectric constant is conventionally the smaller the better; On the other hand, represent that because dielectric loss is less the loss of signal transmission is fewer, therefore dielectric lossThe transmission quality that less material can provide is also comparatively good.
Therefore, how to develop the material with low-k and low-dielectric loss, and be applied to high frequency sealThe manufacture of printed circuit board is the problem that solution is desired most ardently in present stage printed circuit board material field.
Summary of the invention
The object of the present invention is to provide a kind of isocyanate modified epoxy resin, there is structure shown in formula (I):
Wherein, not there is not or be selected from sub-organic group in X;
R is selected from sub-organic group;
R1、R2、R3、R4、R18、R19、R20、R21Be selected from independently of one another hydrogen atom or organic group; And R1、R2、R3、R4、R18、R19、R20、R21When different, it is hydrogen atom;
N is more than or equal to zero integer, and for example 1,2,3,4,5,6,7,8,9,10 etc.
Preferably, described epoxy resin has structure shown in formula (II):
Wherein, not there is not or be selected from sub-organic group in X;
R is selected from sub-organic group;
Described R1、R2、R3、R4、R18、R19、R20、R21Be selected from independently of one another hydrogen atom or organic group; And R1、R2、R3、R4、R18、R19、R20、R21When different, it is hydrogen atom;
Described n is more than or equal to zero integer.
Preferably, R is selected from and replaces or unsubstituted straight chain alkylene, replacement or unsubstituted branched alkylene, replacement or unsubstitutedArylene; Preferably C1～C30Replacement or unsubstituted straight chain alkylene, C1～C30Replacement or unsubstituted branched alkylene, C6～C30Replace or unsubstituted arylene; Further preferablyOr
Wherein, described R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R17Be selected from independently of one another hydrogen atom or haveMachine group, preferably from hydrogen atom, replacement or unsubstituted straight-chain alkyl, replacement or unsubstituted branched hydrocarbyl or replacement or do not getThe aromatic radical in generation; Preferably C1～C30Replacement or unsubstituted straight-chain alkyl, C1～C30Replace or unsubstituted branched hydrocarbyl orC6～C30Replace or unsubstituted aromatic radical;
Described R16Be selected from independently of one another organic group, preferably from replacing or unsubstituted straight chain alkylene, replacement or notThe branched alkylene or replacement or the unsubstituted arylene that replace; Preferably C1～C30Replacement or the sub-hydrocarbon of unsubstituted straight chainBase, C1～C30Replace or unsubstituted branched alkylene or C6～C30Replace or unsubstituted arylene;
Described m is more than or equal to zero integer.
Preferably, described R5、R6、R7、R8、R9、R10、R11、R12For hydrogen atom;
Preferably, described R13、R14、R15、R17Be selected from independently of one another and replace or unsubstituted N-oxazolidine ketone group;
Preferably, described R16Be selected from C1～C5Replacement or unsubstituted straight chain alkylene, preferably methylene, ethylidene orIn sub-n-pro-pyl any a kind.
Preferably, described X is selected from and does not exist or replacement or unsubstituted straight chain alkylene, replacement or unsubstituted side chain AsiaAlkyl, replacement or unsubstituted arylene; Preferably do not exist or C1～C30Replacement or unsubstituted straight chain alkylene, C1～C30Replacement or unsubstituted branched alkylene, C6～C30Replace or unsubstituted arylene; Further preferably do not exist or AsiaIn methyl, isopropylidene, isobutylidene, cyclohexylidene, carbonyl any a kind; Particularly preferably do not exist or, or methylene or AsiaIsopropyl;
Preferably, described R is selected from
Preferably, described R1、R2、R3、R4、R18、R19、R20、R21Be selected from independently of one another hydrogen atom, replacement or unsubstitutedStraight-chain alkyl, replacement or unsubstituted branched hydrocarbyl or replacement or unsubstituted aromatic radical; Preferably C1～C30Replacement or do not getThe straight-chain alkyl in generation, C1～C30Replace or unsubstituted branched hydrocarbyl or C6～C30Replace or unsubstituted aromatic radical, be preferablyThe combination of any a kind or at least 2 kinds in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group.
Isocyanate modified epoxy resin of the present invention is typical but non-limiting can be:
Deng.
The typical preparation method of isocyanate modified epoxy resin provided by the invention is: will at least contain 2 cyanic acidThe polyisocyanates of root and the substance reaction with phenolic ether structure, get is Dao oxazolidone ring.
The general formula of the described material with phenolic ether structure is:ItsIn, X has aforesaid range of choice.
Typical but non-limiting hydroquinones epoxy radicals ether, 2-methyl hydroquinone epoxy radicals ether, the bisphenol-A epoxy of comprisingThe combination of any a kind or at least 2 kinds in base ether, Bisphenol F epoxy radicals ether, bisphenol Z epoxy radicals ether.
As nonrestrictive example, the preparation method of described isocyanate modified epoxy resin comprises:
(1) will haveThe epoxy resin of structure drops into reactor, addsHeat, is preferably heated to 60～190 DEG C and is more preferably 120～160 DEG C;
(2) add the polyisocyanates that at least contains 2 cyanate radicals, stir;
(3) add the known catalyst such as imidazoles, amine and salt thereof, triphenylphosphine and derivative thereof, react complete,To isocyanate modified epoxy resin provided by the invention.
Two of object of the present invention is to provide a kind of composition epoxy resin, and described composition epoxy resin comprises epoxy treeFat and curing agent; Described epoxy resin is partly or entirely the described isocyanate modified epoxy resin of one of object;
Preferably, described epoxy resin also comprises liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-stateBisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin, bisphenol-s epoxy resin, acyclic isoprenoid type epoxy resin or connectionThe combination of any a kind or at least 2 kinds in benzene type epoxy resin;
Preferably, described curing agent comprises in preferred amine, polyphenol compound, ester type compound, acids, anhydridesThe combination of any a kind or at least 2 kinds;
Preferably, also comprise curing accelerator in described composition epoxy resin, described curing accelerator is that imidazoles is solidChange in promoter, organic phosphine curing accelerator, tertiary amine curing accelerator or pyridine and its derivatives any one or at leastThe mixture of two kinds;
Preferably, described composition epoxy resin also comprises inorganic filler;
Preferably, described composition epoxy resin also comprises fire retardant;
Preferably, described composition epoxy resin also comprises releasing agent.
Three of the object of the invention is to provide a kind of pre-impregnated sheet, its by object two described in composition epoxy resin impregnation or paintingBeing distributed in base material forms;
Preferably, described base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiberBase material.
Four of the object of the invention is to provide a kind of composite metal substrate, and it comprises an above preimpregnation as described in three of objectPlate carries out surperficial metal-clad successively, overlapping, pressing forms;
Preferably, the material of described surperficial metal-clad is the alloy of aluminium, copper, iron and any combination thereof;
Preferably, described composite metal substrate is that copper is covered in CEM-1 copper-clad plate, CEM-3 copper-clad plate, FR-4 copper-clad plate, FR-5Plate, CEM-1 aluminium base, CEM-3 aluminium base, FR-4 aluminium base or FR-5 aluminium base.
Five of the object of the invention is to provide a kind of wiring board, by object four described in the Surface Machining of composite metal substrateCircuit forms.
Compared with prior art, the present invention has following beneficial effect:
It is raw material preparation that epoxy resin provided by the invention adopts the polyisocyanates more than containing 2, polyisocyanatesReact with the resin monomer with epoxy radicals, reach the object of drawing into oxazolidine ketone group in epoxy monomer, and the present inventionThe epoxy resin providing is with epoxy radicals end-blocking, and the epoxy resin ingredient that makes to provide has the performance of high heat-resisting, low dielectric.
Detailed description of the invention
Further illustrate technical scheme of the present invention below by detailed description of the invention.
Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as thisBright concrete restriction.
Embodiment 1
Compound 1 has following structure:
Preparation method is:
(1) in the glass reactor of three mouthfuls of 1000mL that mixer is housed, dropping into epoxide equivalent is the as follows of 190g/eqEpoxy resin 285g (1.5eq) and tetramethyl ammonium chloride 0.1g shown in structure, passes into nitrogen while stirring and dissolving,Limit is warmed up to 105 DEG C, then evenly splashes into 2 of 26.1g with the 240min time, is warmed up to 130 DEG C of continuation after 4 '-TDI (0.3eq)Reaction 640min, obtaining epoxide equivalent is the epoxy resin 311.1g of 259.3g/eq, by this product epoxy resin called after ringEpoxy resins A.
Performance characterization:
Infrared: epoxy radicals 913～916cm-1; Ether 1230～1010cm-1; Oxazolidine ketone group 1755cm-1；
Nuclear-magnetism 1H-NMR (DMSO-d6, ppm): 1.6～1.7 (s, Ar-C (CH3)2The hydrogen of-Ar); 6.65～6.72 (O-Ar-Hydrogen on C benzene); 7.60～7.65 (m, the hydrogen on N-Ar-N benzene); 2.47～2.52 (m,)；3.00～3.10(m，); 5.05～5.12 (hydrogen of the upper methyl of oxazolidine ketone group);4.03～4.10 (CH that are connected with epoxy radicals2Hydrogen); 4.18 (the CH that are connected with oxazolidine ketone group2Hydrogen).
Embodiment 2
Compound 2 has following structure:
Preparation method is:
(1) in the glass reactor of three mouthfuls of 1000ml that mixer is housed, dropping into epoxide equivalent is the as follows of 195g/eqEpoxy resin 273g (1.4eq) and glyoxal ethyline 0.2g shown in structure, passes into nitrogen while stirring and dissolving, on one sideBe warmed up to 105 DEG C, then evenly splash into 4 of 62.5g with the 240min time, after 4 '-MDI (0.5eq), be warmed up to 130 DEG C and continue anti-Answer 640min, obtaining epoxide equivalent is the epoxy resin 335.5g of 373g/eq, by this product epoxy resin called after epoxy treeFat B.
Performance characterization:
Infrared: epoxy radicals 913～916cm-1; Ether 1230～1010cm-1; Oxazolidine ketone group 1755cm-1；
After measured, n is 10;
Nuclear-magnetism 1H-NMR (DMSO-d6, ppm): 7.0～7.1 (hydrogen on N-Ar-C benzene); 7.50～7.55 (N-Ar-C benzeneOn hydrogen); 6.90～7.02 (hydrogen on biphenyl); 2.47～2.52 (m, )；3.00～3.10(m，); 5.05～5.12 (hydrogen of the upper methyl of oxazolidine ketone group); 4.03～4.10 (the CH that are connected with epoxy radicals2Hydrogen); 4.18 (the CH that are connected with oxazolidine ketone group2Hydrogen); 2.32～2.38 (on phenyl ringThe hydrogen of methyl).
Embodiment 3
Get the epoxy resin A100g that embodiment 1 obtains, adding phenolic hydroxyl group equivalent is the linear phenol-aldehyde resin of 105g/eqThe 2-phenylimidazole of 25.0g and 0.1g, becomes solution with suitable acetone solution, with the gluing of standard fiber glass cloth, is pressed into and coversCopper coin, by this copper-clad plate called after copper-clad plate a. Record the performance of copper-clad plate a as shown in table-1.
Embodiment 4
Get the epoxy resin B100g that embodiment 2 obtains, add the resin compound 63.7g with following structure, ester is worked asAmount is 220, and the pyridine of 0.2g, becomes solution with suitable acetone solution, with the gluing of standard fiber glass cloth, is pressed into and covers copperPlate, by this copper-clad plate called after copper-clad plate b. Record the performance of copper-clad plate b as shown in table-1.
Wherein, R is ethyl, and f is 5.
Comparative example 1
The MDI modified epoxy 100g that the epoxide equivalent of getting market sale is 380.0g/eq, adds phenolic hydroxyl group equivalent to beThe linear phenol-aldehyde resin 27.3g of 105g/eq and the 2-phenylimidazole of 0.1g, become solution with suitable acetone solution, uses standard glassThe gluing of glass fiber cloth, is pressed into copper-clad plate, by this copper-clad plate called after copper-clad plate c. Record the performance of copper-clad plate c as-1, tableShow.
Comparative example 2
The MDI modified epoxy 100g that the epoxide equivalent of getting market sale is 380.0g/eq, adds and has following structureResin compound 57.9g, ester equivalent is 220, and the pyridine of 0.2g, becomes solution with suitable acetone solution, uses normal glassFiber cloth gluing, is pressed into copper-clad plate, by this copper-clad plate called after copper-clad plate d. Record the performance of copper-clad plate d as shown in table-1.
Wherein, R is ethyl, and f is 5.
Performance test
Copper-clad plate a, copper-clad plate b, copper-clad plate c and copper-clad plate d are carried out to following performance test:
(1) dielectric constant/dielectric loss
Preparation size is the sample of 50mm × 50mm, and on specimen surface evaporation, thickness is aboutCopper layer, afterwards willSample is placed between two test slab electrodes, measures its dielectric constant in designated frequency range.
(2) water absorption rate
100mm × 100mm × 1.6mm sheet material is placed in to the dry 1h of baking oven of 105 DEG C, weighs and be placed on after coolingBoiling 120min under the vapour pressure of 105kPa, finally dries and weighs and calculate water absorption rate.
(3) glass transition temperature
The width of preparation test sample is about 8-12mm, and length is 60mm, measures glass transition temperature Tg.
(4) bending strength and bending modulus
The sample of preparation 25mm × 65m, uses its thickness of vernier caliper measurement, by the test pattern of material universal testing machineBe adjusted to crooked test pattern, measure bending strength and bending modulus.
(5) hot strength
The sample of preparation 250mm × 25m, uses its thickness of vernier caliper measurement, by the test mould of material universal testing machineFormula is adjusted to extension test pattern, measures hot strength.
(6) peel strength is measured
Copper-clad laminated board is cut into the test film of 100mm × 3mm, uses anti-stripping instrument experimental rig, with speed 50.8mm/Min peels off layering to Copper Foil, the peel strength of test Copper Foil and resin.
The performance test results of copper clad laminate prepared by embodiment is as shown in table 1;
The performance test results of copper clad laminate prepared by table 1 embodiment
Applicant's statement, the present invention illustrates process of the present invention by above-described embodiment, but not office of the present inventionBe limited to above-mentioned processing step, do not mean that the present invention must rely on above-mentioned processing step and could implement. Affiliated technical fieldTechnical staff should understand, any improvement in the present invention, the equivalence replacement to the selected raw material of the present invention and auxiliary elementThe selections of interpolation, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (9)
1. an isocyanate modified epoxy resin, has structure shown in formula (I):
Wherein, not there is not or be selected from sub-organic group in X;
R is selected from sub-organic group;
R1、R2、R3、R4、R18、R19、R20、R21Be selected from independently of one another hydrogen atom or organic group; And R1、R2、R3、R4、R18、R19、R20、R21When different, it is hydrogen atom;
N is more than or equal to zero integer.
2. epoxy resin as claimed in claim 1, is characterized in that, described epoxy resin has structure shown in formula (II):
Wherein, not there is not or be selected from sub-organic group in X;
R is selected from sub-organic group;
Described R1、R2、R3、R4、R18、R19、R20、R21Be selected from independently of one another hydrogen atom or organic group; And R1、R2、R3、R4、R18、R19、R20、R21When different, it is hydrogen atom;
Described n is more than or equal to zero integer.
3. epoxy resin as claimed in claim 1 or 2, is characterized in that, R be selected from replace or unsubstituted straight chain alkylene,Replace or unsubstituted branched alkylene, replacement or unsubstituted arylene; Preferably C1～C30Replacement or unsubstituted straightChain alkylene, C1～C30Replacement or unsubstituted branched alkylene, C6～C30Replace or unsubstituted arylene; Further excellentChoosing
Wherein, described R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R17Be selected from independently of one another hydrogen atom or organic groupGroup, preferably from hydrogen atom, replacement or unsubstituted straight-chain alkyl, replacement or unsubstituted branched hydrocarbyl or replacement or unsubstitutedAromatic radical; Preferably C1～C30Replacement or unsubstituted straight-chain alkyl, C1～C30Replace or unsubstituted branched hydrocarbyl or C6～C30Replace or unsubstituted aromatic radical;
Described R16Be selected from independently of one another organic group, preferably from replacing or unsubstituted straight chain alkylene, replacement or not replacementBranched alkylene or replacement or unsubstituted arylene; Preferably C1～C30Replacement or unsubstituted straight chain alkylene, C1～C30Replace or unsubstituted branched alkylene or C6～C30Replace or unsubstituted arylene;
Described m is more than or equal to zero integer.
4. epoxy resin as claimed in claim 3, is characterized in that, described R5、R6、R7、R8、R9、R10、R11、R12For hydrogen formerSon;
Preferably, described R13、R14、R15、R17Be selected from independently of one another and replace or unsubstituted N-oxazolidine ketone group;
Preferably, described R16Be selected from C1～C5Replacement or unsubstituted straight chain alkylene, preferably methylene, ethylidene or Asia are justIn propyl group any a kind.
5. the epoxy resin as described in one of claim 1～4, is characterized in that, described X does not exist or is selected from and replaces or do not getStraight chain alkylene, replacement or unsubstituted branched alkylene, replacement or the unsubstituted arylene in generation; Preferably do not exist or C1～C30Replacement or unsubstituted straight chain alkylene, C1～C30Replacement or unsubstituted branched alkylene, C6～C30Replace or notThe arylene replacing; Further preferably do not exist or methylene, isopropylidene, isobutylidene, cyclohexylidene, carbonyl in appointAnticipate a kind; Particularly preferably do not exist, or methylene or isopropylidene;
Preferably, described R is selected from
Preferably, described R1、R2、R3、R4、R18、R19、R20、R21Be selected from independently of one another hydrogen atom, replacement or unsubstituted straight chainAlkyl, replacement or unsubstituted branched hydrocarbyl or replacement or unsubstituted aromatic radical; Preferably C1～C30Replacement or unsubstitutedStraight-chain alkyl, C1～C30Replace or unsubstituted branched hydrocarbyl or C6～C30Replace or unsubstituted aromatic radical, be preferably methyl,The combination of any a kind or at least 2 kinds in ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group.
6. a composition epoxy resin, is characterized in that, described composition epoxy resin comprises epoxy resin and curing agent; InstituteStating epoxy resin is partly or entirely the described isocyanate modified epoxy resin of one of claim 1～5;
Preferably, described epoxy resin also comprises liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bis-phenolA type epoxy resin, solid-state bisphenol f type epoxy resin, bisphenol-s epoxy resin, acyclic isoprenoid type epoxy resin or biphenyl typeThe combination of any a kind or at least 2 kinds in epoxy resin;
Preferably, described curing agent comprise in preferred amine, polyphenol compound, ester type compound, acids, anhydrides arbitrarilyThe combination of a kind or at least 2 kinds;
Preferably, also comprise curing accelerator in described composition epoxy resin, described curing accelerator is that imidazoles is curing shortEnter any one or at least two kinds in agent, organic phosphine curing accelerator, tertiary amine curing accelerator or pyridine and its derivativesMixture;
Preferably, described composition epoxy resin also comprises inorganic filler;
Preferably, described composition epoxy resin also comprises fire retardant;
Preferably, described composition epoxy resin also comprises releasing agent.
7. a pre-impregnated sheet, is characterized in that, it is by composition epoxy resin impregnation as claimed in claim 6 or coat base materialForm;
Preferably, described base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material.
8. a composite metal substrate, is characterized in that, it comprise one above as claimed in claim 7 pre-impregnated sheet carry out successivelySurface metal-clad, overlapping, pressing form;
Preferably, the material of described surperficial metal-clad is the alloy of aluminium, copper, iron and any combination thereof;
Preferably, described composite metal substrate be CEM-1 copper-clad plate, CEM-3 copper-clad plate, FR-4 copper-clad plate, FR-5 copper-clad plate,CEM-1 aluminium base, CEM-3 aluminium base, FR-4 aluminium base or FR-5 aluminium base.
9. a wiring board, is characterized in that, is formed by the Surface Machining circuit of composite metal substrate claimed in claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610129824.8A CN105601886A (en) | 2016-03-08 | 2016-03-08 | Isocyanate modified epoxy resin and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610129824.8A CN105601886A (en) | 2016-03-08 | 2016-03-08 | Isocyanate modified epoxy resin and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105601886A true CN105601886A (en) | 2016-05-25 |
Family
ID=55982285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610129824.8A Withdrawn CN105601886A (en) | 2016-03-08 | 2016-03-08 | Isocyanate modified epoxy resin and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105601886A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020189912A (en) * | 2019-05-21 | 2020-11-26 | 日鉄ケミカル＆マテリアル株式会社 | Oxazolidone ring-containing epoxy resin, method for producing the same, epoxy resin composition and cured product thereof |
| CN112538155A (en) * | 2020-11-02 | 2021-03-23 | 建滔（江苏）化工有限公司 | Phosphorus-containing halogen-free epoxy resin and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497271A (en) * | 2014-12-24 | 2015-04-08 | 济南圣泉集团股份有限公司 | Modified epoxy resin and modified epoxy resin composition |
| CN104892898A (en) * | 2015-05-12 | 2015-09-09 | 广东广山新材料有限公司 | Phosphorus-nitrogen epoxy resin with bisphenol S radicals, flame-retardant composition, composite metal substrate |
| CN105482076A (en) * | 2015-12-15 | 2016-04-13 | 广东广山新材料有限公司 | Isocyanate modified epoxy resin and application |
| CN105566613A (en) * | 2016-03-08 | 2016-05-11 | 广东广山新材料有限公司 | Isocyanate modified epoxy resin and application |
-
2016
- 2016-03-08 CN CN201610129824.8A patent/CN105601886A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497271A (en) * | 2014-12-24 | 2015-04-08 | 济南圣泉集团股份有限公司 | Modified epoxy resin and modified epoxy resin composition |
| CN104892898A (en) * | 2015-05-12 | 2015-09-09 | 广东广山新材料有限公司 | Phosphorus-nitrogen epoxy resin with bisphenol S radicals, flame-retardant composition, composite metal substrate |
| CN105482076A (en) * | 2015-12-15 | 2016-04-13 | 广东广山新材料有限公司 | Isocyanate modified epoxy resin and application |
| CN105566613A (en) * | 2016-03-08 | 2016-05-11 | 广东广山新材料有限公司 | Isocyanate modified epoxy resin and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020189912A (en) * | 2019-05-21 | 2020-11-26 | 日鉄ケミカル＆マテリアル株式会社 | Oxazolidone ring-containing epoxy resin, method for producing the same, epoxy resin composition and cured product thereof |
| JP7296781B2 (en) | 2019-05-21 | 2023-06-23 | 日鉄ケミカル＆マテリアル株式会社 | Oxazolidone ring-containing epoxy resin, method for producing the same, epoxy resin composition and cured product thereof |
| CN112538155A (en) * | 2020-11-02 | 2021-03-23 | 建滔（江苏）化工有限公司 | Phosphorus-containing halogen-free epoxy resin and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105566613A (en) | Isocyanate modified epoxy resin and application | |
| CN105936745B (en) | A kind of resin combination | |
| US9872382B2 (en) | Low dielectric composite material and laminate and printed circuit board thereof | |
| CN105482076A (en) | Isocyanate modified epoxy resin and application | |
| CN107868188B (en) | Phosphorus-containing ethylene polyphenylene ether, resin composition containing the same, and product thereof | |
| EP3066148B1 (en) | Ultra low loss dielectric thermosetting resin compositions and high preformance laminates manufactured therefrom | |
| CN105440645A (en) | Phosphorus-containing flame retardant low-dielectric resin composition and preparation method and application thereof | |
| TWI675063B (en) | Halogen-free epoxy resin composition, laminated substrate and printed circuit board thereof | |
| CN105778414B (en) | A kind of composition epoxy resin and use its prepreg and laminate | |
| CN105778430A (en) | Epoxy resin composition, and prepreg and laminated board with epoxy resin composition | |
| TW201249922A (en) | Trimethyl borate in epoxy resins | |
| CN109535715A (en) | A kind of flame resistance resin composite and prepreg and laminate using its preparation | |
| IE58759B1 (en) | Curable compositions containing a polyepoxide and a halogenated dihydric phenol and impregnated substrates and laminates prepared therefrom | |
| JP2013536287A (en) | Copolymer | |
| TW201905015A (en) | Vinyl-modified maleimide, combination and preparation thereof | |
| CN105601886A (en) | Isocyanate modified epoxy resin and application | |
| JPH01501156A (en) | homogeneous thermosetting copolymer | |
| KR101381506B1 (en) | Oligomeric halogenated chain extenders for preparing epoxy resins | |
| CN105482075A (en) | Isocyanate modified epoxy resin and application | |
| CN105778049A (en) | Isocyanate modified epoxide resin and application thereof | |
| CN113292852A (en) | Resin composition containing phosphorus-containing phenyl bisphenol polymer and preparation method and application thereof | |
| TWI733256B (en) | Resin composition and products made therefrom | |
| CN106433124B (en) | A kind of halogen-free resin composition of high frequency, High-Speed Printed Circuit Board curing agent containing esters | |
| US9006377B2 (en) | Resin composition and uses of the same | |
| CN105524253A (en) | Isocyanate modified epoxy resin and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 523000 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building on the third floor Applicant after: Guangdong Guang Shan new materials Limited by Share Ltd Address before: 523990 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building 3F Applicant before: GUANG SHAN NEW MATERIALS CO., LTD. |
|
| CB02 | Change of applicant information | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20160525 |
|
| WW01 | Invention patent application withdrawn after publication |