CN102453226A - Resin composition, and prepreg and printed circuit board made from same - Google Patents
Resin composition, and prepreg and printed circuit board made from same Download PDFInfo
- Publication number
- CN102453226A CN102453226A CN2010105267716A CN201010526771A CN102453226A CN 102453226 A CN102453226 A CN 102453226A CN 2010105267716 A CN2010105267716 A CN 2010105267716A CN 201010526771 A CN201010526771 A CN 201010526771A CN 102453226 A CN102453226 A CN 102453226A
- Authority
- CN
- China
- Prior art keywords
- temperature
- solvent
- compsn
- nitrogen oxygen
- substituted
- 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.)
- Pending
Links
Images
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a resin composition which comprises an epoxy resin and a polymer solution used as a hardener. The resin composition is prepared by the following steps: (a) dissolving a nitrogen oxygen heterocyclic compound in a first solvent to form a first reaction solution, wherein the nitrogen oxygen heterocyclic compound is disclosed as Formula I or II, and R1 to R3, W1, W2, m, n, p and q are defined in the specification; (b) heating the first reaction solution to a first temperature to carry out ring-opening polymerization reaction; and (c) cooling the first reaction solution to a second temperature to substantially end the ring-opening polymerization reaction, thereby obtaining the polymer solution, wherein the first solvent does not react with the nitrogen oxygen heterocyclic compound, the first temperature is higher than the softening temperature of the nitrogen oxygen heterocyclic compound and lower than the boiling point of the first solvent, the second temperature is lower than the first temperature, and on solid basis, every 100 parts by weight of epoxy resin requires 20-200 parts by weight of epoxy resin.
Description
Technical field
The invention relates to a kind of resin combination; Particular it, the invention relates to a kind of with one by the made polymers soln of nitrogen oxygen helerocyclics as the composition epoxy resin of stiffening agent and by its preimpregnation material (prepreg) processed and printed substrate (printed circuit board).
Background technology
Printed substrate is the circuit substrate of electronic installation, and it carries other electronic components and with these member electrical communication, so that stable circuit working environment to be provided.Common printed circuit board base board is laminated plates (the copper clad laminate of Copper Foil coating; CCL); It mainly is made up of resin, reinforcement material and Copper Foil; Common resin such as epoxy resin, resol, polyamine formaldehyde, silicone and Teflon etc., reinforcement material commonly used is then like glasscloth, glass fibre mats, insulation paper, linen etc.
Generally speaking, printed substrate can be by following method manufacturing: will contain just like the reinforcement material of glass fabric and be dipped in the resin, and the glass fabric that will contain behind the resin pickup is cured to semi-harden state (being B-stage (B-stage)) to obtain a preimpregnation material.Subsequently with the preimpregnation material of certain number of plies range upon range of and at least one outside of this range upon range of preimpregnation material a range upon range of tinsel so that a sandwich to be provided; And this sandwich carried out a hot press operation (being C-stage (C-stage)) and obtain a metal coating laminated plates; Then; On this metal coating laminated plates, dig out several holes; And the plating electro-conductive material is to form through hole (via holes) in these holes, and the tinsel on last etching metal coating laminated plates again surface is accomplished the preparation of printed substrate to form specific circuit pattern (circuit pattern).
Consider rear end electronics work program, printed circuit board base board must reach to a certain degree at aspects such as thermotolerance, dimensional stability, chemicalstability, workability, toughness and physical strengths.Generally speaking, using the printed substrate of epoxy resin preparation can have above-mentioned characteristic concurrently, therefore is the resin that the most often uses in the industry.Epoxy resin is the organic high molecular compound that contains two or two above epoxide groups in molecule of general reference, is a kind of reactive monomeric, and the molecule of high epoxide group number can obtain a highly cross-linked reticulated structure after polymerization.Yet, though this highly cross-linked reticulated structure has quite high hardness and glass transfer temperature and endurance, exist usually to be prone to crisp and shortcoming such as shock-resistance is relatively poor, be unfavorable for that the rear end processes.
To this, at present nitrogen oxygen helerocyclics that comprise
structure that use come the unison ring epoxy resins to use as stiffening agent more.This nitrogen oxygen helerocyclics structurally has a high proportion of phenyl ring and carbon-nitrogen bond knot; Therefore have excellent thermal properties (like thermotolerance, glass tansition temperatures (Tg), flame retardant resistance etc.) and chemistry and mechanical properties; And after this nitrogenous oxygen helerocyclics carries out ring-opening polymerization; Its polymkeric substance structurally has great amount of hydroxy group (hydroxyl group), can further react with epoxy resin, promotes the thermal properties and the mechanical properties of the finished product.
Yet, in the method, the ring-opening polymerization of this nitrogen oxygen helerocyclics and with the polyreaction of epoxy resin be to carry out simultaneously, so extent of polymerization is difficult to grasp, and causes easily that each batch product characteristics differs, quality is difficult to problems such as control.
Given this, the present invention provides a kind of resin combination that is used for printed substrate preparation, and it has and can shorten and the effect of may command hot pressing time-histories, and the product of tool good thermal character and mechanical properties and quality homogeneous can be provided.
Summary of the invention
A purpose of the present invention is to provide a kind of resin combination, comprises:
One epoxy resin;
One polymers soln as stiffening agent, it is obtained with following steps:
(a) a nitrogen oxygen helerocyclics is dissolved in one first solvent to form one first reaction soln, this nitrogen oxygen helerocyclics is tool following formula I or II;
[formula I]
[formula II]
Wherein,
R1 to R3 be the group that independently is selected from following group separately: H, halogen, warp or without substituted C1 to C10 alkyl, warp or without substituted C1 to C10 naphthenic base, and through or without substituted C6 to C20 aryl;
W1 and W2 be the group that independently is selected from following group separately: H, halogen, ether, thioether group, alkylsulfonyl, sulfinyl, carbonyl, warp or without substituted C1 to C10 alkyl, warp or without substituted C1 to C10 naphthenic base, and through or without substituted C6 to C20 aryl;
M and n are independently to be 1 to 4 integer separately;
P is 1 to 3 integer; And
Q is 1 to 4 integer;
(b) heat this first reaction soln to, first temperature, to carry out ring-opening polymerization; And
(c) cool off this first reaction soln to, second temperature,, obtain this polymers soln to stop this ring-opening polymerization in fact.
Wherein, this first solvent is not react with this nitrogen oxygen helerocyclics; This first temperature is the boiling point that is higher than the softening temperature of this nitrogen oxygen helerocyclics and is lower than this first solvent; And this second temperature is to be lower than this first temperature.
Wherein, in solid substance, the content of this stiffening agent is per 100 weight part epoxy resin, 20 weight part to 200 weight parts.
Another object of the present invention is to provide a kind of preimpregnation material, it is by with the above-mentioned resin combination of a base material impregnation, carries out drying and makes.
A purpose more of the present invention is to provide a kind of printed substrate; It is to make by following mode: range upon range of several layers above-mentioned preimpregnation material and at least one outside of this range upon range of preimpregnation material a range upon range of tinsel so that a sandwich to be provided; And this sandwich carried out a hot press operation and obtain a metal coating laminated plates, this tinsel of patterning thereafter.
For letting above-mentioned purpose of the present invention, technical characterictic and the advantage can be more obviously understandable, hereinafter be to be elaborated with part practical implementation form.
Description of drawings
Shown in Figure 1 is the infrared spectrum of the prepared laminate of resin combination of embodiment 1.
Embodiment
Below will describe particularly according to part practical implementation form of the present invention; Just, do not deviating under the spirit of the present invention, the present invention still can multiple multi-form form put into practice, and should protection domain of the present invention be interpreted as to be limited to the representor of specification sheets institute.In addition, only if Wen Zhongyou explains that in addition (especially in claims) employed " one ", " being somebody's turn to do " and similar term are interpreted as comprising odd number and number form formula in this specification sheets.Only and if Wen Zhongyou explains in addition, when in this specification sheets, describing composition contained in solution, mixture or the compsn, be that the solid substance with each composition is a base of calculation.
Use the nitrogen oxygen helerocyclics as stiffening agent compared to known techniques, characteristics of resin combination of the present invention are, be with by the prepared polymers soln of nitrogen oxygen helerocyclics as stiffening agent, thereby can shorten hot pressing time-histories and effective control product property.Wherein, Be a nitrogen oxygen helerocyclics to be dissolved in form a reaction soln in the solvent; Under the situation of the use that does not relate to catalyzer, the mixture of gained is warming up to the softening temperature that is higher than this nitrogen oxygen helerocyclics carries out ring-opening polymerization, comprise the solution of the polymkeric substance of tool great amount of hydroxy group with formation; Thereby the rapid reaction through hydroxyl and epoxy resin in heat pressing process is reaching the hardened effect, and can effectively shorten the hot pressing time-histories.Further, can with the length of control hot pressing time-histories, improve the applicability of resulting polymers solution by the polymerization degree of the polymkeric substance in this stable state solution of control.
In specific words, resin combination of the present invention is to comprise an epoxy resin and a polymers soln as stiffening agent, and wherein, this polymers soln is obtained with the method that comprises following steps:
(a) a nitrogen oxygen helerocyclics is dissolved in one first solvent to form one first reaction soln;
(b) heat this first reaction soln to, first temperature, to carry out ring-opening polymerization; And
(c) cool off this first reaction soln to, second temperature,, obtain this polymers soln to stop this ring-opening polymerization in fact,
Wherein, this first solvent is not react with this nitrogen oxygen helerocyclics; This first temperature is the boiling point that is higher than the softening temperature of this nitrogen oxygen helerocyclics and is lower than this first solvent; And this second temperature is to be lower than this first temperature.
In step (a), used nitrogen oxygen helerocyclics is the structure of tool following formula I or II,
[formula I]
[formula II]
Wherein, R1 to R3 be independent separately for be selected from the group of following group: H, halogen, warp or without substituted C1 to C10 alkyl, warp or without substituted C1 to C10 naphthenic base, reach warp or without substituted C6 to C20 aryl; W1 and W2 be independent separately for be selected from the group of following group: H, halogen, ether, thioether group, alkylsulfonyl, sulfinyl, carbonyl, warp or without substituted C1 to C10 alkyl, warp or without substituted C1 to C10 naphthenic base, reach warp or without substituted C6 to C20 aryl; M and n are independently to be 1 to 4 integer separately; P is 1 to 3 integer; And q is 1 to 4 integer.
In formula I and formula II, m and n assist mutually with the key footing of W1 and W2 respectively to join.With formula I is example, and under the situation of bound by theory not, when m was 1, W1 was the group (like H, halogen, methyl etc.) of the single key knot of tool, and this moment, the nitrogen oxygen helerocyclics was the compound of the single nitrogen oxa-of tool ring structure; When m was 2, W1 was the linking group of the two key knots of tool, and this moment, the nitrogen oxygen helerocyclics was the compound of tool dinitrogen oxa-ring structure, by that analogy.After this specification sheets, attaching the chemical synthesis that is to use phenolic compound, aldehyde cpd and amine compound among the embodiment provides the nitrogen of being desired oxygen helerocyclics, detailed as after to attach embodiment said.
Consider the character of nitrogen oxygen helerocyclics polymeric complexity and resulting polymers; It independently is 2 or 3 separately that m and n are preferably; At this moment, W1 and W2 are can be separately independent of being selected from the group of following group: ether, thioether group, alkylsulfonyl, sulfinyl, carbonyl, warp or without the alkyl of the C1 to C10 of ether, thioether group, alkylsulfonyl, sulfinyl or carbonyl substituted; Through or without the naphthenic base of the C1 to C10 of ether, thioether group, alkylsulfonyl, sulfinyl or carbonyl substituted; And through or without the aryl of the C6 to C20 of ether, thioether group, alkylsulfonyl, sulfinyl or carbonyl substituted; More preferably, m and n are 2, and W1 and W2 are separately independently for being selected from the group of following group:
[formula I ']
[formula II ']
In after attach among the embodiment, be to use
and
In (a) step, be that the nitrogen oxygen helerocyclics is dissolved in first solvent so that first reaction soln to be provided, and can be through heating or the mode that stirs to improve dissolution rate.First solvent can be the inert solvent of the used nitrogen oxygen helerocyclics of any solubilized, and be one not with the inert solvent of used nitrogen oxygen helerocyclics reaction.The boiling point of first solvent should be higher than the polymers soln desired related maximum operating temperature (being the temperature of ring-opening polymerization usually) in the preparation process at least; Change the concentration of first reaction soln to avoid first solvent in operating process, to escape, cause difficulty (can't stir) that subsequent technique carries out or the quality that influences prepared polymers soln (uneven) like extent of polymerization like the solution retrogradation.Select for use under the condition in bound by theory not and without prejudice to above-mentioned, first solvent can be for example for being selected from the solvent of following group: pimelinketone, toluene, YLENE, acetone, butanone, MIBK, N, dinethylformamide (N; N-dimethyl formamide; DMF), DMAC N,N (N, N '-dimethyl acetamide; DMAc), N-Methyl pyrrolidone (N-methyl-pyrolidone, NMP) and aforesaid combination.In after attach among the embodiment, be to use pimelinketone or N, dinethylformamide is as first solvent.
The usage quantity of first solvent only need be enough to dissolve used nitrogen oxygen helerocyclics and get final product.Generally speaking, consider down at cost, the nitrogen oxygen helerocyclics of normally per 100 weight parts of the usage quantity of this first solvent uses about 5 weight parts to about 60 weight parts, is preferably about 20 weight parts to about 40 weight parts.In after to attach among the embodiment be first solvent that uses 25 weight parts in the nitrogen oxygen helerocyclics of per 100 weight parts.
In step (b); Be in nitrogen oxygen helerocyclics uniform dissolution forms first reaction soln in first solvent after; Provide an energy first reaction soln is warming up to one first temperature, this first temperature is the softening temperature that is higher than the nitrogen oxygen helerocyclics at least, in order to do under the situation of not using expensive and environmentally harmful catalyzer; Carry out the ring-opening polymerization of nitrogen oxygen helerocyclics, contain the polymers soln of being desired to make.In addition, this first temperature should be lower than the boiling point of first solvent, changes the concentration of first reaction soln to avoid first solvent in operating process, to escape, and causes the difficulty that subsequent technique carries out or influences the quality of prepared polymers soln.In after attach among the embodiment, consider the nitrogen oxygen helerocyclics and the solvent of use, first temperature be the boundary in about 110 ℃ to about 160 ℃ scope.In the present invention, be that behind ring-opening polymerization, polymkeric substance contains the structure of Formula Il I and formula IV respectively so that the nitrogen oxygen helerocyclics of apparatus formula I ' and formula II ' is an example:
[formula III]
[formula IV]
Wherein, Can for example pass through heat energy (like water-bath, oil bath, electric heater, heat exchanger tube), radiating capacity (like UV-irradiation, gammairradiation) or its combination; This first reaction soln energy is provided; Promoting its temperature to the first temperature, and consider that heat passes and the reaction homogeneity, be preferably and in temperature-rise period, stir first reaction soln simultaneously.
According to the present invention; Can be by the condition (like temperature of reaction, time etc.) of control ring-opening polymerization; Adjust the extent of polymerization of resulting polymers, thereby can effectively control the hot pressing time-histories length of applied heat pressing process, improve the applicability of resin combination of the present invention.But mat is in the ring-opening polymerization process, and the gel time of sampling amount test sample article is realized the adjustment of the extent of polymerization of above-mentioned polymkeric substance.And when first reaction soln reaches the gel time of being desired, can carry out step (c).
In step (c), be to utilize fast cooling means so that first reaction soln is lower than second temperature of this first temperature from first greenhouse cooling to, to stop ring-opening polymerization in fact, obtain the stable state solution of being desired.The palpus exponent; Here indication " stop in fact " be meant through between the compound of open loop, between the polymkeric substance and through the compound of open loop and the polyreaction between the polymkeric substance by the negative catalysis of certain degree ground, in order to do making the result of use of prepared product can meet user's requirement.Wherein, second temperature is low more, and then negative catalysis effect is more obvious, otherwise then negative catalysis effect is more not obvious; And the rate of temperature fall of first reaction soln is fast more, and then the variation of the gel time of first reaction soln between cooldown period is more little.In theory, may command second temperature is about room temperature, and avoiding the variation a little of polymers soln its gel time when second temperature is reduced to room temperature, but this need expend higher cooling cost (using more a large amount of low-temperature solvents like need).Therefore, the gel time in guaranteeing temperature-fall period is changed under the prerequisite of acceptable scope, and normally controlling second temperature is the softening temperature that is lower than the nitrogen oxygen helerocyclics, preferablely is lower than at least 30 ℃ of first temperature, goodly is lower than at least 50 ℃ of first temperature.
The cooling means that can be used for step (c) do not have particular restriction; For example; Can be under the situation that optionally stirs first reaction soln; Be selected from the operation of following group: add one second solvent to this first reaction soln, this first reaction soln is placed an atmosphere surrounding, this first reaction soln is placed a water-bath, and aforesaid combination, wherein, the temperature of this second solvent, this atmosphere surrounding and this water-bath should be lower than this second temperature at least.Desired cooling-down effect by obtaining fast; Be preferably with the mode of adding one second solvent (separately or and with other cooling means) and lower the temperature; This mode decapacitation directly contacts with first reaction soln and reaches outside the fast cooling; More can reach the effect of diluted polymer concentration, prevent that further polymeric nitrogen oxygen helerocyclics is separated out because of supersaturation in temperature-fall period and under the storing temp.In after attach among the embodiment, be to reach the purpose of fast cooling to the mode of this first reaction soln to add one second solvent.
In step (c) use to be added in one second solvent to this first reaction soln with the form that stops ring-opening polymerization, second solvent can be identical or different with first solvent, and can be any not with the solvent of ring-opening polymerization polymer reaction.For example, this second solvent can be the polar solvent that is selected from following group: toluene, YLENE, acetone, butanone, MIBK, pimelinketone, N, dinethylformamide and aforesaid combination.Behind this specification sheets, attach among the embodiment, be to use acetone and butanone as second solvent that stops ring-opening polymerization.The addition and the temperature of second solvent are not limited to them, as long as second temperature of being desired can be provided, reach the effect that stops ring-opening polymerization and get final product.
The polymers soln of resin combination of the present invention promptly makes through above-mentioned steps, stores even this solution is long-time separately, also can not produce the phenomenon that polymkeric substance is separated out.In addition; Because the nitrogen oxygen helerocyclics in this polymers soln is through aggregating into the polymkeric substance of tool hydroxyl in advance, therefore, compared to without the nitrogen oxygen helerocyclics (like benzoxazine) of ring-opening polymerization known techniques as stiffening agent; Resin combination of the present invention is owing to use this polymers soln as stiffening agent; Therefore required hot pressing time-histories is shorter, and also visual user needs the gel time (promptly adjusting the polymerization degree of polymkeric substance) of change polymers soln; And then the hot pressing time-histories of adjustment resin combination, have more practicality.
Used epoxy resin is the resin that a part contains at least two cycloalkyl groups in resin combination of the present invention, like novolac epoxy, phosphorous epoxy resin etc.Behind this specification sheets, attaching among the embodiment, be to use 9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthrene-10-oxide compound (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) or novolac epoxy.
In resin combination of the present invention, the consumption of stiffening agent can optionally be adjusted by the user.Generally speaking, consider based on cost, in solid substance, the content of this stiffening agent is preferably per 100 weight part epoxy resin, 20 weight part to 200 weight parts, is more preferred from per 100 weight part epoxy resin, 70 weight part to 90 weight parts, but not as limit.In addition, under the situation of bound by theory not, but also other stiffening agent of blending of resin combination of the present invention, to obtain the special efficacy of different stiffening agents.One example it; As after attach embodiment institute illustration; Resin combination of the present invention also can be shared with the benzoxazine (benzoxazine) of not open loop, and consumption looks closely user's demand and decide, and for example can be the arrange in pairs or groups benzoxazine of 10 weight part to 50 weight parts of per 100 weight part epoxy resin.
Resin combination of the present invention can further comprise other additives.One example it; Can add the hardening accelerator that is selected from following group, so that the hardening effect of improvement to be provided, but not as limit: glyoxal ethyline (2-methyl-imidazole; 2MI), 2-ethyl-4-methylimidazole (2-ethyl-4-methyl-imidazole; 2E4MI), (2-phenyl-imidazole, 2PI) and aforesaid combination, the content of hardening accelerator is generally per 100 weight part epoxy resin, 0.01 weight part to 1 weight part to the 2-phenylimidazole.Perhaps; Can add the weighting agent that is selected from following group; With characteristics such as the workability of modified epoxy resin, flame retardant resistance, thermotolerance, wet fastnesss; But not as limit: silicon-dioxide, glass powder, talcum, kaolin, white mountain range soil, mica and aforesaid combination, the content of weighting agent is generally per 100 weight part epoxy resin, 0.01 weight part to 80 weight part.
Except that above-mentioned should changing promotor and the weighting agent, resin of the present invention also can add other additives commonly used to desire characteristic, and like dispersion agent (like silane coupling agent), releasing agent, fire retardant, toughner etc., and these additives can be used alone or in combination.
Resin combination of the present invention can by with epoxy resin, as the polymers soln of stiffening agent and the weighting agent that optionally adds with the whisking appliance uniform mixing, and be dissolved or dispersed in and process the varnish shape in the solvent, supply the following process utilization.
The present invention provides a kind of preimpregnation material in addition, is a base material (reinforcement material) is contained in the varnish that is immersed in above-mentioned resin combination, and carries out drying by suitable drying conditions and obtain.Reinforcement material commonly used comprises: glasscloth (glass fabric, zellglas, glassmat etc.), kraft paper, short flannel cotton paper, natural fiber cloth, organic fibre cloth etc.Behind this specification sheets, attach among the embodiment, be to use 7628 glasscloths, and, make the preimpregnation material of semi-harden state by this in 2 to 10 minutes (the B-stage) of 180 ℃ of following heat dryings as the reinforcement material.
In addition; The present invention provides a kind of printed substrate in addition; It is with several layers above-mentioned preimpregnation material range upon range of and in the range upon range of tinsel at least one outside of this range upon range of preimpregnation material (like Copper Foil) so that a sandwich to be provided; And this sandwich carried out a hot press operation and obtain a metal coating laminated plates, this tinsel of patterning and making thereafter.
Now with following practical implementation form further to illustrate the present invention, wherein, the measuring instrument that is adopted and method respectively as follows:
[gel time]
Choose 0.2 gram as the polymers soln of stiffening agent as sample; And on the about 200 ℃ heat dish of a temperature, form the disk of 2 square centimeters of sizes; Calculating continue to be stirred to draw with stirring rod and is tried required time when sample no longer adheres to stirring rod or be about to solidify, and this promptly is decided to be its gel time.
[water-absorbent test]
Carry out the pressure cooker cooking test (pressure cooker test, PCT) test places pressurized vessel with laminated plates, under the environment of 121 ℃, saturated humidity (100%R.H.) and 2 air pressure 1 hour, the anti-high humidity ability of test laminated plates.
[property testing of anti-immersed solder]
Whether the laminated plates that drying is crossed behind the immersion certain hour, is observed defective and occurred in 288 ℃ soldering is bathed, for example confirm with the layering or the puff of laminated plates.
[tearing strength test]
Tearing strength is meant the sticking power of tinsel as far as base material, and the Copper Foil with per inch (25.4 millimeters) width vertically tears up on the plate face usually, expresses the power of sticking power with the size of its required strength.MIL-P-55110E stipulates that its qualifying standard of substrate of 1 ounce copper foil is 4 pounds/inch.
[glass transfer temperature test]
(dynamic mechanical analyzer DMA) measures glass tansition temperatures (Tg) to utilize the dynamic mechanical analysis appearance.The test specification of glass tansition temperatures is interconnected and encapsulation association (The Institute for Interconnecting and Packaging Electronic Circuits, IPC-TM-650.2.4.25C IPC) and a 24C detection method of electronic circuit.
[heat decomposition temperature test]
(thermogravimetric analyzer TGA) measures and to compare with the initial stage quality, and the temperature when quality reduces 5% is heat decomposition temperature to utilize thermogravimetric analyzer.
[flame retardancy test]
Utilize UL94V: the vertical combustion testing method, laminated plates is fixed with the vertical position, with the Bunsen burner burning, relatively its spontaneous combustion is extinguished and combustion-supporting characteristic, and its result's report is divided into UL94V-0 (the best) to the difficult combustion of UL94V-2 grade.
[toughness test]
Basal plate is lain against on the tool of plane, vertically contact, grant vertical pressure again with the laminated plates surface with cross metal fixture; After remove this cross tool; Observe cross shape vestige on the substrate, inspect this laminate surface, do not have white scrimp and take place then to be judged to be good; Show slightly lineae ablicantes for general, it is bad that crackle or fracture person are taken place.
[specific inductivity and the dissipation factor measure]
According to ASTM D150 standard, under operating frequency 1 meps (GHz), calculate specific inductivity (dielectric constant, Dk) with the dissipation factor (dissipation factor, Df).
Embodiment
[preparation nitrogen oxygen helerocyclics]
With 784 g dihydroxyphenyl propanes (bisphenol A), 458 g aniline and 600 g toluene; Adding one is equiped with heating unit, TM, stirrer, cooling tube, splashes in 3 liters the detachable reaction flask of four-hole of device and reclaim under reduced pressure device; To form a resulting solution, be warming up to about 40 ℃ and stir.Under stirring state; The toluene solution of 44 weight % formaldehyde that in 20 minutes, dropwise adds 819 g is to this resulting solution; This moment, the temperature of this resulting solution rose to about 90 ℃, heated and kept this resulting solution in about 90 ℃ temperature and reacted 3 hours, and its reaction formula is following.
Stop heating subsequently and stir and left standstill about 20 minutes; After treating that this resulting solution is divided into two layers; Remove the water on upper strata and the emulsification of trace; Soon reheat to about 90 ℃ and with the decompression (being lower than about 90 mmhg) mode reclaim solvent, treat temperature to about 130 ℃ and reclaim whole solvents after, promptly obtain the about 1380 g nitrogen oxygen helerocyclics 1 of weight.
Then; What change resulting solution consists of 564 g phenol, 594 g two amido ditane (diaminodiphenylmethane; And to prepare nitrogen oxygen helerocyclics 2 with the identical in fact mode of preceding method, reaction formula is following MDA) and 600 g toluene.Obtain the about 1288 g nitrogen oxygen helerocyclics 2 of weight.
[polymers soln of preparation nitrogen oxygen helerocyclics]
With 450 g nitrogen oxygen helerocyclics 1 and 115 g pimelinketone; Adding is equiped with heating unit, TM, stirrer, cooling tube, splashes in one 1 liters the four-hole reaction flask of device and reclaim under reduced pressure device; Under condition of stirring; Be heated to 70 ℃ and keep 70 ℃ to dissolve fully, subsequently the gained mixture be warming up to 150 ℃ to carry out ring-opening polymerization until nitrogen oxygen helerocyclics 1, last 300 minutes after; 25 ℃ the butanone (185 g) that adds; Make solution temperature reduce to about 94 ℃ rapidly, and to naturally cool to normal temperature be 200 seconds polymers soln 1-1 (the about 60 weight % of polymer content) to stop ring-opening polymerization, to obtain 200 ℃ of gel times.
Then with same procedure; Adjusting the cyclopolymerization reaction times respectively is 315 and 330 minutes, makes polymers soln 1-2 (the about 60 weight % of polymer content) and polymers soln 1-3 (the about 60 weight % of polymer content) that 200 ℃ of gel times are respectively 170 seconds and 150 seconds.
Prepare polymers soln 2 subsequently in a similar fashion.With 1293 g nitrogen oxygen helerocyclics 2 and 322 g N, dinethylformamide, add be equiped with heating unit, TM, stirrer, cooling tube, splash into device and reclaim under reduced pressure device in one 1 liters four-hole reaction flask; Under condition of stirring; Be heated to nitrogen oxygen helerocyclics 2 and dissolve fully, subsequently the gained mixture is warming up to 110 ℃ to carry out ring-opening polymerization, last 250 minutes after; The acetone (about 540 g) that adds 25 ℃; Make temperature reduce to about 78 ℃ rapidly, being cooled to normal temperature subsequently is 200 seconds polymers soln 2 (the about 60 weight % of polymer content) to stop ring-opening polymerization, to obtain 200 ℃ of gel times.
[preparation resin combination]
< embodiment 1 >
Ratio as shown in table 1; With the DOPO epoxy resin (Kolon5138) of 100 weight parts, the glyoxal ethyline of 0.5 weight part, epoxy radicals silicone hydride coupler (SHIN-ETSU HANTOTAI's chemistry of 0.5 weight part; KBM-403), the phosphonitrile fire retardant of 20 weight parts (big tomb chemistry; SBP-100), the talcum of 50 weight parts and the polymers soln 1-1 (in solid substance) of 80 weight parts, under room temperature, use whisking appliance to mix 60 minutes, add the butanone of 80 weight parts subsequently again.Above-mentioned mixture after stirring 120 minutes under the room temperature, is made resin combination 1.
< embodiment 2 >
To prepare resin combination 2 with embodiment 1 identical mode, polymers soln 1-2 (in solid substance) the substituted polymer solution 1-1 that just is to use 80 weight parts is as stiffening agent, and is as shown in table 1.
< embodiment 3 >
To prepare resin combination 3 with embodiment 1 identical mode, polymers soln 1-3 (in solid substance) the substituted polymer solution 1-1 that just is to use 80 weight parts is as stiffening agent, and is as shown in table 1.
< embodiment 4 >
To prepare resin combination 4 with embodiment 1 identical mode, polymers soln 2 (in solid substance) the substituted polymer solution 1-1 that just is to use 80 weight parts is as stiffening agent, and is as shown in table 1.
< embodiment 5 >
To prepare resin combination 5 with embodiment 1 identical mode, the benzoxazine of polymers soln 1-1 (in solid substance) and 40 weight parts that just is to use 40 weight parts is as stiffening agent, and is as shown in table 1.
< embodiment 6 >
To prepare resin combination 6 with embodiment 1 identical mode, only be to use the novolac epoxy (Kolon 1138) of 100 weight parts to replace DOPO epoxy resin, as shown in table 1.Wherein, consider the novolac epoxy flame retardancy, so add the phosphonitrile fire retardant of relative volume (40 weight part) not as DOPO epoxy resin.
< comparing embodiment 1 >
To prepare control resin compsn 1 with embodiment 1 identical mode, the benzoxazine substituted polymer solution 1-1 that just is to use 80 weight parts is as stiffening agent, and is as shown in table 1.
[preparation printed substrate]
Use the resin combination of embodiment 1 to 6 and comparing embodiment 1 to make printed substrate respectively.Utilize roll coater; Resin combination with embodiment 1 to 6 and comparing embodiment 1 is coated on 7628 (resin/glass cloth: 43%) on the glasscloth respectively; Then; Be placed in the drying machine, and, produce the preimpregnation material of semi-harden state by this 180 ℃ of following heat dryings 2 to 10 minutes.Then four preimpregnation material layers are closed, and open 1 ounce Copper Foil in each layer of outermost layer unification of its two side.Then it is carried out hot pressing; Obtain the laminated plates of Copper Foil coating by this; Wherein hot pressing condition is: be warming up to 190 ℃ with 2.0 ℃/minute heat-up rates, and under 190 ℃, with the pressure hot pressing of 15 kilograms/square centimeter of total heads (8 kilograms/square centimeter of first pressing) 60 minutes.Then, the Copper Foil by etched pattern coating laminated plates surface forms circuit pattern by this, so far accomplishes the preparation of printed substrate.Shown in Figure 1 is infrared spectrum analysis result with the resin combination 1 prepared laminate of embodiment 1.
Using the analytical resultss such as water-absorbent, anti-immersed solder property (solder floating), tearing strength (peeling strength), glass tansition temperatures (Tg), heat decomposition temperature, flame retardant resistance, toughness, specific inductivity, the dissipation factor and hot pressing time-histories of the prepared printed substrate of composition epoxy resin of embodiment 1 to 6 and comparing embodiment 1 is to be shown in the table 1.
Table 1
*The hot pressing time-histories of indication means in 190 ℃ of following hot pressing times in the table 1
Can know by table 1; Compared to the convention resin combination that uses benzoxazine as stiffening agent (comparing embodiment 1); Resin combination of the present invention (embodiment 1 to 6) can significantly shorten the hot pressing time-histories; And can see through the adjustment stiffening agent and become to assign to further control hot pressing time-histories length (embodiment 1 to 3), significantly promote the elasticity on using.In addition; Using the prepared printed substrate of resin combination of the present invention to have with using benzoxazine transfers character such as temperature, heat decomposition temperature and flame retardancy, and has preferable toughness and electrical specification (the Df value is lower) as the suitable water-absorbent of stiffening agent person, anti-immersed solder property, tearing strength, glass.
The foregoing description is merely illustrative principle of the present invention and effect thereof, and sets forth technical characterictic of the present invention, but not is used to limit protection category of the present invention.Anyly be familiar with present technique person under know-why of the present invention and spirit, can unlabored change or arrangement, the scope that all belongs to the present invention and advocated.Therefore, rights protection scope of the present invention is that claim is listed.
Claims (15)
1. resin combination is characterized in that it comprises:
One epoxy resin;
One polymers soln as stiffening agent is obtained with following steps:
(a) a nitrogen oxygen helerocyclics is dissolved in one first solvent to form one first reaction soln, this nitrogen oxygen helerocyclics tool following formula I or II;
[formula I]
[formula II]
Wherein,
R1 to R3 be the group that independently is selected from following group separately: H, halogen, warp or without substituted C1 to C10 alkyl, warp or without substituted C1 to C10 naphthenic base, and through or without substituted C6 to C20 aryl;
W1 and W2 be the group that independently is selected from following group separately: H, halogen, ether, thioether group, alkylsulfonyl, sulfinyl, carbonyl, warp or without substituted C1 to C10 alkyl, warp or without substituted C1 to C10 naphthenic base, and through or without substituted C6 to C20 aryl;
M and n are independently to be 1 to 4 integer separately;
P is 1 to 3 integer; And
Q is 1 to 4 integer;
(b) heat this first reaction soln to, first temperature, to carry out ring-opening polymerization; And
(c) cool off this first reaction soln to, second temperature,, obtain this polymers soln to stop this ring-opening polymerization in fact,
Wherein, this first solvent does not react with this nitrogen oxygen helerocyclics; This first temperature is the boiling point that is higher than the softening temperature of this nitrogen oxygen helerocyclics and is lower than this first solvent; And this second temperature is to be lower than this first temperature,
Wherein, in solid substance, the content of this stiffening agent is per 100 weight part epoxy resin, 20 weight part to 200 weight parts.
2. according to the compsn of claim 1, it is characterized in that m and n are independently to be 2 or 3 separately, and W1 and W2 are the groups that independently is selected from following group separately: ether; Thioether group; Alkylsulfonyl; Sulfinyl; Carbonyl; Through or without the alkyl of the C1 to C10 of ether, thioether group, alkylsulfonyl, sulfinyl or carbonyl substituted; Through or without the naphthenic base of the C1 to C10 of ether, thioether group, alkylsulfonyl, sulfinyl or carbonyl substituted; And through or without the aryl of the C6 to C20 of ether, thioether group, alkylsulfonyl, sulfinyl or carbonyl substituted.
3. according to the compsn of claim 2, it is characterized in that m and n are 2, and W1 and W2 are independent of separately being selected from the group of following group:
4. according to the compsn of claim 1, it is characterized in that in step (a), the consumption of this first solvent is that this nitrogen oxygen helerocyclics of per 100 weight parts uses 5 to 60 weight parts.
5. according to the compsn of claim 1, it is characterized in that this first solvent is to be selected from following group: pimelinketone, toluene, YLENE, acetone, butanone, MIBK, N; Dinethylformamide (N, N-dimethyl formamide, DMF), N; N-N,N-DIMETHYLACETAMIDE (N; N ' dimethyl acetamide, DMAc), N-Methyl pyrrolidone (N-methyl-pyrolidone, NMP) and aforesaid combination.
6. according to the compsn of claim 1; It is characterized in that; In step (c), be selected from the operation of following group: add one second solvent to this first reaction soln, this first reaction soln is placed an atmosphere surrounding, this first reaction soln placed a water-bath, and aforesaid combination, wherein; The temperature of this second solvent, this atmosphere surrounding and this water-bath is to be lower than this second temperature, and this second solvent not with this polymer reaction.
7. according to the compsn of claim 6; It is characterized in that; Be to carry out in step (c), to add one second solvent to the mode of this first reaction soln; And this second solvent is to be selected from following group: toluene, YLENE, acetone, butanone, MIBK, pimelinketone, N, dinethylformamide and aforesaid combination.
8. according to the compsn of claim 1, it is characterized in that this second temperature is to be lower than at least 30 ℃ of this first temperature.
9. according to the compsn of claim 1, it is characterized in that this second temperature is to be about room temperature.
10. according to the compsn of claim 1, it is characterized in that the content of this stiffening agent is 70 weight part to 90 weight parts.
11. the compsn according to claim 1 is characterized in that, more comprises benzoxazine (benzoxazine).
12. compsn according to claim 1; It is characterized in that; More comprise one be selected from following group hardening accelerator: glyoxal ethyline (2-methyl-imidazole, 2MI), 2-ethyl-4-methylimidazole (2-ethyl-4-methyl-imidazole, 2E4MI), 2-phenylimidazole (2-phenyl-imidazole; 2PI) and aforesaid combination, wherein the content of this hardening accelerator is per 100 weight part epoxy resin, 0.01 weight part to 1 weight part.
13. compsn according to claim 1; It is characterized in that; More comprise one be selected from following group weighting agent: silicon-dioxide, glass powder, talcum, kaolin, white mountain range soil, mica and aforesaid combination, wherein the content of this weighting agent is per 100 weight part epoxy resin, 0.01 weight part to 80 weight part.
14. a preimpregnation material is characterized in that, its be by with a base material impregnation according to arbitrary described compsn in the claim 1 to 13, and carry out drying and the preimpregnation material that makes.
15. printed substrate; It is characterized in that; It is the printed substrate that makes by following mode: the described preimpregnation material of range upon range of several layers of claim 14 and at least one outside of this range upon range of preimpregnation material a range upon range of tinsel so that a sandwich to be provided; And this sandwich carried out a hot press operation and obtain a metal coating laminated plates, this tinsel of patterning thereafter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105267716A CN102453226A (en) | 2010-11-01 | 2010-11-01 | Resin composition, and prepreg and printed circuit board made from same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105267716A CN102453226A (en) | 2010-11-01 | 2010-11-01 | Resin composition, and prepreg and printed circuit board made from same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102453226A true CN102453226A (en) | 2012-05-16 |
Family
ID=46036944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105267716A Pending CN102453226A (en) | 2010-11-01 | 2010-11-01 | Resin composition, and prepreg and printed circuit board made from same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102453226A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775728A (en) * | 2011-05-11 | 2012-11-14 | 台燿科技股份有限公司 | Resin composition, prepreg prepared by same and printed circuit board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490318A (en) * | 2002-10-17 | 2004-04-21 | 长春人造树脂厂股份有限公司 | Oxynitride helerocyclic compounds and preparation thereof |
| CN101643570A (en) * | 2009-08-24 | 2010-02-10 | 广东生益科技股份有限公司 | Halogen-free flame resistance resin composite and prepreg, laminate and laminate for printed circuit prepared from same |
-
2010
- 2010-11-01 CN CN2010105267716A patent/CN102453226A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490318A (en) * | 2002-10-17 | 2004-04-21 | 长春人造树脂厂股份有限公司 | Oxynitride helerocyclic compounds and preparation thereof |
| CN101643570A (en) * | 2009-08-24 | 2010-02-10 | 广东生益科技股份有限公司 | Halogen-free flame resistance resin composite and prepreg, laminate and laminate for printed circuit prepared from same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775728A (en) * | 2011-05-11 | 2012-11-14 | 台燿科技股份有限公司 | Resin composition, prepreg prepared by same and printed circuit board |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103319877B (en) | Resin composition and use thereof | |
| CN106147195B (en) | Resin composition and use thereof | |
| TWI678393B (en) | Resin composition, and pre-preg, metal-clad laminate and printed circuit board prepared using the same | |
| TWI445727B (en) | A resin composition, and prepreg and printed circuit board prepared using the same | |
| US10081728B2 (en) | Resin composition and uses of the same | |
| CN102372900B (en) | Epoxy resin composition, and prepreg material and printed circuit board prepared from the same | |
| TWI475040B (en) | Resin composition and uses of the same | |
| CN102746616B (en) | Resin composition and use thereof | |
| CN102453226A (en) | Resin composition, and prepreg and printed circuit board made from same | |
| TWI454528B (en) | Resin composition, and prepreg and printed circuit board prepared using the same | |
| CN102775728B (en) | Resin combination and the prepreg be made up of it and printed circuit board (PCB) | |
| CN103665756B (en) | Resin composition and use thereof | |
| CN103059308B (en) | Steady state solution of ring-opening polymer and application thereof | |
| TWI449722B (en) | Resin composition and uses of the same | |
| CN102295742B (en) | Epoxy resin composition and prepreg material as well as printed circuit board prepared by same | |
| TWI422610B (en) | Resin composition, and prepreg and laminate prepared using the same | |
| CN103059309B (en) | Resin composition and use thereof | |
| CN105219079B (en) | Resin composition and use thereof | |
| CN102234409B (en) | Composition epoxy resin and the prepreg made thereof and printed circuit board (PCB) | |
| TW201144350A (en) | Epoxy resin composition, and prepreg and printed wiring board using the same | |
| CN102838729B (en) | Resin composition and prepreg and laminated board prepared from same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120516 |