CN109851997A - A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it - Google Patents
A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it Download PDFInfo
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Abstract
The present invention provides a kind of compositions of thermosetting resin and use its prepreg, laminate and metal-clad laminate.The compositions of thermosetting resin includes epoxy resin, cyanate ester resin and the esters curing agent with Formulas I structure.The present invention uses the esters curing agent with Formulas I structure to cooperate with cured epoxy resin with cyanate ester resin, secondary hydroxyl isopolarity group is not generated in the curing process, and contain a large amount of hydrophobic groupings in cured product, while guarantee cured product glass transition temperature with higher, its water absorption rate and dielectric loss factor can be substantially reduced.There is good heat resistance, moisture-proof, peel strength, dielectric properties, anti-flammability, processability and chemical resistance using the laminate and metal-clad laminate of compositions of thermosetting resin preparation.
Description
Technical field
The invention belongs to printed circuit board technology fields, and in particular to a kind of compositions of thermosetting resin and use the pre- of its
Leaching material, laminate and metal-clad laminate.
Background technique
The high speed and multifunction handled with electronic product information, applying frequency are continuously improved, it is desirable that dielectric constant
(Dk) and dielectric loss value (Df) is lower and lower, therefore reduce that Dk/Df has become substrate dealer chases hot spot.In order to realize height
Glass transition temperature (Tg) and low Df, various low polar resins such as cyanate ester resin (CE), active ester are widely used.Wherein
For the low-loss material of 0.0060~0.0080 this rank of Df, epoxy resin/cyanate/active ester ternary system by
It is widely used in the industry, has high Tg, high-fire resistance and very excellent dielectric using plate made from the ternary system formula
Performance, but cyanate, active ester have that water absorption rate is high.
In addition, halogen-free flame-retardant copper-clad laminate is developed under the general trend of events that " green " " environmental protection " is strengthened in the whole world
The hot spot of industry, each copper-clad laminate producer all release the halogen-free flameproof copper-clad laminate of oneself one after another.At present in the industry most
Common halogen-free flame retardants is still based on phosphorus flame retardant, and phosphorus flame retardant is easier the moisture absorption compared to bromide fire retardant, therefore
General halogen-free board is more obvious compared to the higher disadvantage of bromine tie-plate material water absorption rate.
High water absorbing capacity will cause plate dielectric properties and obviously deteriorate because of the moisture absorption, it is also possible to will lead to substrate in printed circuit
It is heated due to plate bursting after the moisture absorption when plate (PCB) is processed.Therefore under the premise of guaranteeing high Tg and excellent dielectric properties, how to drop
The water absorption rate of low cyanate Halogen system becomes a technical problem.
Copper-clad plate benzoxazine resin commonly used in the trade reduces solidfied material water absorption rate, however the dielectricity of benzoxazine resin
Can be poor, and polar functionalities in molecular structure, the dielectric properties and heat resistance of meeting severe exacerbation cyanate system.
Therefore, how while guaranteeing that copper-clad plate has higher glass transition temperature, its water absorption rate and dielectric are reduced
Loss is this field urgent problem to be solved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of compositions of thermosetting resin and use
Its prepreg, laminate and metal-clad laminate.Using the compositions of thermosetting resin preparation laminate and cover metal
Foil laminate has high glass-transition temperature, high-peeling strength, low water absorption, low-k, low dielectric loss factor, height
Heat resistance and good chemical resistance.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of compositions of thermosetting resin, which is characterized in that the thermosetting resin combination
Object includes following component: epoxy resin, cyanate ester resin and esters curing agent；
The esters curing agent has Formulas I structure:
Wherein, R1-R8It is each independently selected from hydrogen atom, C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10
One of aromatic hydrocarbyl, and it is not all hydrogen atom；
X is selected from-O- ,-S- ,-CH2Or-C (CH3)2One of；
Y is selected from C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10One of aromatic hydrocarbyl；
N is the integer of 1-10.
Present invention resin based on epoxy resin and cyanate ester resin cooperates the esters with Formulas I structure to solidify dosage form
At compositions of thermosetting resin, which does not generate secondary hydroxyl isopolarity group in the curing process, and
Contain a large amount of hydrophobic groupings in cured product, it, can be bright while guarantee cured product glass transition temperature with higher
It is aobvious to reduce its water absorption rate and dielectric loss factor, so that cured product dielectric constant and dielectric loss factor are more stable.Using
The laminate and metal-clad laminate of compositions of thermosetting resin preparation have high glass-transition temperature, high removing strong
Degree, low water absorption, low-k, low dielectric loss factor, high-fire resistance and good chemical resistance.
In the present invention, the C1-C10Aliphatic alkyl refer to containing 1-10 (such as 1,2,3,4,5,6,
7,8,9 or 10) aliphatic alkyl of carbon atom；Such as can be methyl, ethyl, propyl, butyl, amyl, hexyl,
Heptyl, octyl, nonyl or decyl etc..
The C3-C10Alicyclic alkyl refers to containing 3-10 (such as 3,4,5,6,7,8,9 or 10
It is a) alicyclic alkyl of carbon atom；Such as can be cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl etc..
The C6-C10Aromatic hydrocarbyl refers to the rouge containing 6-10 (such as 6,7,8,9 or 10) carbon atoms
Fat race alkyl；Such as can be phenyl, benzyl, phenethyl or phenylpropyl etc..
N can be 1,2,3,4,5,6,7,8,9 or 10 in Formulas I.
As the preferred technical solution of the present invention, with the gross weight of the epoxy resin, cyanate ester resin and esters curing agent
Measure number be 100 parts meter, the compositions of thermosetting resin include: 40-70 parts of epoxy resin, 10-35 parts of cyanate ester resins and
5-25 parts of esters curing agent.
Unless otherwise specified, heretofore described " esters curing agent " each means the esters curing agent with Formulas I structure.
In the present invention, the parts by weight of the epoxy resin can be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55
Part, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts or 70 parts etc..
The parts by weight of the cyanate ester resin can be 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22
Part, 23 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 33 parts or 35 parts etc..
The parts by weight of the esters curing agent can be 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18
Part, 20 parts, 22 parts, 23 parts or 25 parts etc..
The present invention is cooperated under above-mentioned specific ratio by epoxy resin, cyanate ester resin and esters curing agent,
The comprehensive performance of its cured product and laminate prepared therefrom can further be promoted.If the content of epoxy resin is very few, meeting
Cause the processing performance of laminate poor；If the additive amount of epoxy resin is excessive, the glass of cured product and laminate will lead to
Glass transition temperature is lower, and dielectric properties are poor.If the content of cyanate ester resin is very few, the vitrifying that will lead to cured product turns
Temperature is lower, and dielectric properties are poor；If the content of cyanate ester resin is excessive, the brittleness of obtained cured product and laminate
Greatly, poor in processability.It is unknown to the improvement result of cured product water absorption rate and dielectric properties if the content of esters curing agent is very few
Aobvious, if the content of esters curing agent is excessive, the brittleness that will lead to cured product and laminate is larger, poor processability.
As the preferred technical solution of the present invention, the epoxy resin is halogen-free epoxy resin.
Preferably, the halogen-free epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol phenolic aldehyde
Epoxy resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type
One of novolac epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin or at least two group
It closes.
Preferably, the halogen-free epoxy resin has Formula II structure:
Wherein, X1、X2And X3It is each independentlyR9Selected from hydrogen atom, replace or
Unsubstituted C1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl；
Y1And Y2It is each independently selected from singly-bound ,-CH2-、 One of, R10Selected from hydrogen original
Sub, substituted or unsubstituted C1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl；
M is the integer of 1-10；Such as it can be 1,2,3,4,5,6,7,8,9 or 10.
In the present invention, the C1-C5Straight chained alkyl refers to former containing 1-5 (such as 1,2,3,4 or 5) carbon
The straight chained alkyl of son；Such as it can be methyl, ethyl, propyl, butyl or amyl.
The C3-C5Branched alkyl refers to the branched alkyl containing 3-5 (such as 3,4 or 5) carbon atoms；Such as
It can be isopropyl, isobutyl group, tert-butyl or isopentyl etc..
Halogen-free epoxy resin degree of functionality with higher and good dielectric properties with Formula II structure, facilitate into one
Step improves the glass transition temperature of cured product, reduces dielectric loss and water absorption rate.
As the preferred technical solution of the present invention, the cyanate ester resin is selected from bisphenol A cyanate ester resin, bisphenol-f type
Cyanate ester resin, tetramethyl bisphenol F cyanate resin, bis-phenol M type cyanate ester resin, bisphenol S type cyanate ester resin, bis-phenol E
Type cyanate ester resin, bis-phenol p-type cyanate ester resin, novolac type cyanate ester resin, cresol novolak type cyanate ester resin, naphthols
Type cyanate ester resin, Naphthol phenolic cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, phenolphthalein type cyanate ester resin, virtue
Alkyl type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, bisphenol A cyanate ester prepolymer, bisphenol-f type cyanate pre-polymerization
Object, tetramethyl bisphenol-f type cyanate prepolymer, bis-phenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer, bisphenol E-type
Cyanate prepolymer, bis-phenol p-type cyanate prepolymer, novolac type cyanate prepolymer, cresol novolak type cyanate pre-polymerization
Object, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type
In cyanate prepolymer, aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer any one or extremely
Few two kinds of mixture, preferably novolac type cyanate ester resin, naphthol type cyanate ester resin, naphthol novolac type cyanate resin
Rouge, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, novolac type cyanic acid
Ester prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, phenolphthalein type cyanate prepolymer, aralkyl
In type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer any one or at least two mixture, into one
Walk preferred novolac type cyanate ester resin, Naphthol phenolic cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, linear phenol
Any one in aldehyde type cyanate prepolymer, naphthol novolac type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer
Or at least two mixture.
As the preferred technical solution of the present invention, the compositions of thermosetting resin further includes fire retardant.
Preferably, the fire retardant is phosphonium flame retardant.
It preferably, is institute in terms of 100 parts by the total weight number of the epoxy resin, cyanate ester resin and esters curing agent
The additive amount for stating phosphonium flame retardant is 1-50 parts, such as can be 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20
Part, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts etc.；Further preferably 1-30 parts.
Preferably, the phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,
Miscellaneous -10- phosphine phenanthrene -10- the oxide of 10- dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- two
Hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxide, phenoxy phosphazene compound, phosphate, polyphosphate, phosphonate ester or polyphosphonates
One of or at least two combination.
As the preferred technical solution of the present invention, the compositions of thermosetting resin further includes curing accelerator, makes resin
Composition solidifies and accelerates the curing rate of resin combination.
It preferably, is institute in terms of 100 parts by the total weight number of the epoxy resin, cyanate ester resin and esters curing agent
The additive amount for stating curing accelerator is 0.05-1 parts；Such as it can be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5
Part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part etc..
Preferably, the curing accelerator is selected from glyoxaline compound, triphenylphosphine, dimethylamino naphthyridine, boron trifluoride
One of mono aminoethane or zinc octoate or at least two combination.
Preferably, the glyoxaline compound be selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or
One of 2- undecyl imidazole or at least two combination.
Preferably, the compositions of thermosetting resin further includes filler, to further decrease cured product and laminate
Thermal expansion coefficient (CTE) and water absorption rate improve thermal conductivity.
It preferably, is institute in terms of 100 parts by the total weight number of the epoxy resin, cyanate ester resin and esters curing agent
The additive amount for stating filler is 1-150 parts, such as can be 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35
Part, 40 parts, 45 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts etc.；
Further preferably 1-100 parts.
Preferably, the filler is organic filler and/or inorganic filler.
Preferably, the inorganic filler be selected from silica, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride,
One of silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, mica, glass fiber powder or at least two
Combination.
Preferably, the organic filler be selected from one of polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder or
At least two combination.
In the present invention, the filler is most preferably silica, such as can be fused silica, crystal type titanium dioxide
Silicon, spherical silica or hollow silicon dioxide etc.；In partial size angle value be 1-15 μm, such as can be 1 μm, 2 μm, 3 μm, 5 μm,
6 μm, 8 μm, 10 μm, 12 μm, 13 μm or 15 μm etc.；Further preferably 1-10 μm.The filler of particle diameter distribution within the above range
There is preferably dispersibility in compositions of thermosetting resin.
Second aspect, the present invention provide a kind of resin adhesive liquid, and the resin adhesive liquid is to provide first aspect present invention
Compositions of thermosetting resin is dissolved or dispersed in solvent and obtains.
The third aspect, the present invention provide a kind of prepreg, including reinforcing material, and described by being attached to after impregnation drying
The compositions of thermosetting resin that first aspect present invention on reinforcing material provides.
In the present invention, prepreg can be prepared with the following method:
Compositions of thermosetting resin is dissolved in solvent, resin adhesive liquid is formed, being then impregnated with the resin adhesive liquid enhances
Material obtains prepreg after dry.
Wherein, the solvent is preferably butanone (MEK), and the solid content of the glue is preferably 60-70%, the strengthening material
Material is preferably glass cloth, and glue impregnation amount is preferably 200-230g/m2, the temperature of the drying is preferably 155 DEG C, and the time is preferred
For 5-10min.
Fourth aspect, the present invention provide a kind of laminate, including one or at least two overlapping third aspect present invention
The prepreg of offer.
5th aspect, the present invention provides a kind of metal-clad laminate, including one or the present invention of at least two overlappings
The metal foil of prepreg and the one or both sides being overlying on the outside of the prepreg that the third aspect provides.
The metal-clad laminate be by first by one or at least two Prepreg Lays, then again prepreg most
The one or both sides in outside paste metal foil, and the method for finally heated cure under pressure is prepared.
The operation of the heating pressurization can be carried out by laminating machine, and lamination must meet claimed below: the heating being 1. laminated
Rate should usually be controlled at 80-120 DEG C of material temperature in 1.5-2.5 DEG C/min；2. the pressure setting being laminated, outer layer material temperature is in 120-
150 DEG C apply full pressure, and full pressure pressure is 350psi or so；3. solidify, material temperature is controlled at 180-220 DEG C, and keep the temperature 60-
120min。
The metal foil can be copper foil, nickel foil, aluminium foil or SUS foil (stainless steel foil) etc..
6th aspect, the present invention provide a kind of printed circuit board, provide including an at least third aspect present invention pre-
Leaching material.
Compared with prior art, the invention has the following advantages:
Present invention resin based on epoxy resin and cyanate ester resin cooperates the esters with Formulas I structure to solidify dosage form
At compositions of thermosetting resin, which does not generate secondary hydroxyl isopolarity group in the curing process, and
Contain a large amount of hydrophobic groupings in cured product, the glass transition temperature of cured product can be effectively improved, and reduce its water suction
Rate and dielectric loss factor.The glass transition temperature for the laminate for using the compositions of thermosetting resin to be prepared is 178-
235 DEG C, thermal expansion coefficient 1.8%-2.4%, water absorption rate 0.20%-0.38%, dielectric constant (1GHz) is 3.42-
3.76, dielectric loss factor (1GHz) is 0.0070-0.0092, and dielectric constant is 3.5-3.94 after humidity, and dielectric is damaged after humidity
The consumption factor is 0.0077-0.0103,288 DEG C of layering cream time ﹥ 120s, peel strength 1.34-1.46N/mm, drop impact
Slight crack area is 231-362mm2, difficult to burn reaches V-0 grade, with good heat resistance, moisture-proof, peel strength, Jie
Electrical property, anti-flammability, processability and chemical resistance.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
The source of material involved in the embodiment of the present invention and comparative example/the preparation method is as follows:
(A) halogen-free epoxy resin
(A-1) dicyclopentadiene novolac epoxy resin HP-7200H (big Japanese ink trade name)；
(A-2) biphenyl type novolac epoxy resin NC-3000 (the Japanization pharmacist name of an article)；
(A-3) HP-9900 containing naphthalene epoxy resins (big Japanese ink trade name).
(B) cyanate ester resin
(B-1) bisphenol A cyanate ester prepolymer CE01PS (Yangzhou apocalypse trade name)；
(B-2) novolac type cyanate ester resin PT-30 (Switzerland's Lonza trade name)；
(B-3) DCPD Novolac Cyanate Ester Resins CY-40 (Jiangsu Wuqiao trade name).
(C) curing agent
(C-1) with the esters curing agent of Formulas I structure, structure are as follows:
Wherein average repeat unit n is 1.25；
Preparation method is as follows:
In the flask for being equipped with thermometer, dropping funel, blender put into 2mol (568.78g) bisphenol-A and
1500g tetrahydrofuran, is passed through nitrogen, and stirring is to being completely dissolved.Then, investment 1mol (203.02g) paraphthaloyl chloride stirring
Then dissolution controls system temperature at 20 DEG C hereinafter, being slowly added dropwise and (being greater than 0.5 hour) 2mol (202.38g) triethylamine
(triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%).Then, continue to be stirred to react 2~3 hours at 20 DEG C or less.It connects
, 2mol (381.25g) 2- naphthoyl chloride is put into, system temperature is controlled at 15 DEG C hereinafter, 2mol is then slowly added dropwise
(202.38g) triethylamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%), continues to be stirred to react 2 at 15 DEG C or less
~5 hours.It stands after the reaction was completed, is filtered to remove triethylamine hydrochloride solid, carries out vacuum distillation concentration in solution, then again
Methanol is added, resin product is precipitated, filtering, being washed with water to the pH value of final water layer is 7, and again with methanol washing is then so dry that produce
Object.The ester equivalent of prepared active ester resin is 252g/eq according to feed ratio.
(C-2) with the esters curing agent of Formulas I structure, structure are as follows:
Wherein average repeat unit n is 1.25；
Preparation method is as follows:
In the flask for being equipped with thermometer, dropping funel, blender put into 2mol (568.78g) bisphenol-A and
1500g tetrahydrofuran, is passed through nitrogen, and stirring is to being completely dissolved.Then, investment 1mol (203.02g) paraphthaloyl chloride stirring
Then dissolution controls system temperature at 20 DEG C hereinafter, being slowly added dropwise and (being greater than 0.5 hour) 2mol (202.38g) triethylamine
(triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%).Then, continue to be stirred to react 2~3 hours at 20 DEG C or less.It connects
, 2mol (281.14g) chlorobenzoyl chloride is put into, system temperature is controlled at 15 DEG C hereinafter, 2mol is then slowly added dropwise
(202.38g) triethylamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%), continues to be stirred to react 2 at 15 DEG C or less
~5 hours.It stands after the reaction was completed, is filtered to remove triethylamine hydrochloride solid, carries out vacuum distillation concentration in solution, then again
Methanol is added, resin product is precipitated, filtering, being washed with water to the pH value of final water layer is 7, and again with methanol washing is then so dry that produce
Object.The ester equivalent of prepared active ester resin is 226g/eq according to feed ratio.
(C-3) with the esters curing agent of Formulas I structure, structure are as follows:
Wherein average repeat unit n is 1.25；
Preparation method is as follows:
In the flask for being equipped with thermometer, dropping funel, blender put into 2mol (512.66g) tetramethyl Bisphenol F and
1500g tetrahydrofuran, is passed through nitrogen, and stirring is to being completely dissolved.Then, investment 1mol (203.02g) paraphthaloyl chloride stirring
Then dissolution controls system temperature at 20 DEG C hereinafter, being slowly added dropwise and (being greater than 0.5 hour) 2mol (202.38g) triethylamine
(triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%).Then, continue to be stirred to react 2~3 hours at 20 DEG C or less.It connects
, 2mol (157g) chloroacetic chloride is put into, system temperature is controlled at 15 DEG C hereinafter, 2mol (202.38g) three is then slowly added dropwise
Ethamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%), continues to be stirred to react 2~5 hours at 15 DEG C or less.Reaction
It stands after the completion, is filtered to remove triethylamine hydrochloride solid, carries out vacuum distillation concentration in solution, then add methanol precipitation
Resin product, filtering, being washed with water to the pH value of final water layer is 7, again with methanol washing, then dry product.Prepared
The ester equivalent of active ester resin is 181g/eq according to feed ratio.
(C-4) a kind of esters curing agent V-575 (Japanese UNITIKA trade name), structure is as follows:
Wherein average repeat unit n is 1.25；
(C-5) dicyclopentadiene phenolic active ester HPC-8000T65 (big Japanese ink trade name)；
(C-6) dicyclopentadiene type benzoxazine LZ 8260N70 (HUNTSMAN trade name).
(D) fire retardant
(D-1) phosphorus-containing phenolic aldehyde XZ92741 (U.S.'s DOW trade name)；
(D-2) phenoxy phosphazene compound SPB-100 (Mitsubishi trade name).
(E) curing accelerator
(E-1) zinc Isoocatanoate (the leading commodity chemical name in Shanghai)；
(E-2) 4-dimethylaminopyridine (the wide flourish commodity chemical name of Japan).
(F) filler
(F-1) ball-type silicon powder (average grain diameter is 1-10 μm, 99% or more purity)
(F-2) aluminium oxide (average grain diameter is 1-10 μm, 99% or more purity).
Embodiment 1-16
Embodiment 1-16 provides compositions of thermosetting resin glue, the prepreg using it and copper-clad plate, and preparation method is such as
Under:
(1) preparation of compositions of thermosetting resin glue:
With MEK solvent by component (B) cyanate ester resin, (C) curing agent and (D-2) phenoxy phosphazene compound SPB-100
It is configured to the solution that solid content is 60%, 50% and 25% respectively, is added sequentially in 1000mL beaker, sequentially adds (A)
Appropriate (E) curing accelerator is added, when adjusting gelation in halogen-free epoxy resin, (D-1) phosphorus-containing phenolic aldehyde XZ92741 and (F) filler
Between (GT) to 200-300s, it is 65% that MEK solvent, which is added, by solid content control, continues to stir 2h curing, obtains thermosetting property tree
Oil/fat composition glue；
Wherein, the type and dosage (based on parts by weight) of each component are as shown in Table 1 and Table 2.
(2) preparation of prepreg:
It is ready to 6 2116 glass cloth (manufacturer: stopping Bell Co. in Taiwan), size: 320mm × 380mm, it first will be upper
It states compositions of thermosetting resin glue to be coated on every glass cloth, make glue Sized glass cloth and is stained with resin on two surfaces, so
Two surfaces are struck off and are removed part glue by the folder axis of roll-in by the glass cloth after infiltration afterwards, by glass cloth and removal solvent
The sum of resin composition weight afterwards is controlled in 200-230g/m2, the glass cloth presoaked is obtained, puts it into 155 DEG C later
6-8min is toasted in baking oven, obtains prepreg.
(3) production of copper-clad plate:
Prepare 2 with a thickness of 35 μm, the electrolytic copper foil having a size of 410mm × 410mm (manufacturer: Suzhou Feitian), by 6
Zhang Shangshu prepreg gathers into folds, and keeps 4 angle alignments, and respectively cover the electrolysis being ready in the prepreg upper and lower surface folded
Copper foil is put into laminating machine, and lamination is carried out as follows: the heating rate being 1. laminated should be controlled at 80-120 DEG C of material temperature
1.5-2.5℃/min；2. the pressure setting being laminated, outer layer material temperature applies full pressure at 120-150 DEG C, and full pressure pressure is 350psi；
3. solidify, material temperature is controlled at 200 DEG C, and keep the temperature 90min, obtain copper-clad plate.
Comparative example 1-3
Comparative example 1-3 the difference from example 2 is that, the type of component (C) curing agent is different, shown in table 3 specific as follows.
Comparative example 4-6
Comparative example 4-6 and the difference of embodiment 16 are that the type of component (C) curing agent is different, 3 institute of table specific as follows
Show.
The performance of the copper-clad plate provided respectively above-described embodiment and comparative example is tested, and testing standard/method is as follows:
(a) glass transition temperature (Tg): according to differential scanning calorimetry (DSC), according to IPC-TM-6502.4.25 institute
Defined DSC method is measured.
(b) thermal expansion coefficient (CTE)
It is measured according to the Z-direction CTE test method of IPC-TM-650 2.4.24 defined.
(c) water imbibition
100mm × 100mm sample is placed in the climatic chamber of 85 DEG C of temperature, humidity 85% after handling 168h, test
The water absorption rate of sample after processing.
(d) dielectric constant, dielectric loss factor
According to the resonance method for using stripline runs, the dielectric loss under 1GHz is measured according to IPC-TM-650 2.5.5.5, is situated between
The electrical loss factor.
(e) dielectric constant, dielectric loss factor (after moist)
Sample is placed in the climatic chamber of 85 DEG C of temperature, humidity 85% after handling 168h, according still further to IPC-TM-650
2.5.5.5 the dielectric loss under measurement 1GHz, dielectric loss factor.
(f) resistance to dip solderability
Layering cream time is observed according to IPC-TM-650 2.4.13.1.
(g) peel strength
According to the experiment condition of " after thermal stress " in IPC-TM-650 2.4.8 method, the removing for testing metallic cover layer is strong
Degree.
(h) drop impact slight crack area
Tested using drop hammer impact testing machine, test method: height of the fall 1m, weight of dropping hammer are 0.75kg, and release is fallen
Hammer, test plate torn surface product.Plate slight crack size can tentatively reflect the toughness superiority and inferiority of plate, it is, in general, that slight crack
Area is smaller to show that plate toughness is better.
(i) difficult to burn
It is measured according to 94 vertical combustion of UL.
The performance for the copper-clad plate that the various embodiments described above and comparative example provide is as shown in following table 1-3:
Table 1
Table 2
Table 3
It was found from the performance data of table 1-3: embodiment 1-10 using 5-25 part with Formulas I structure esters curing agent and
40-70 parts of halogen-free epoxy resins of 10-35 parts of cyanate composite curings, obtained plate have high Tg, low CTE, low water absorption,
Excellent dielectric properties, high-fire resistance and peel strength and excellent toughness, while being also able to achieve V-0 grades of halogen-free flameproof.
It is compound using the esters curing agent and bisphenol A cyanate ester prepolymer CE01PS with Formulas I structure in embodiment 11
Solidify 75 parts of dicyclopentadiene novolac epoxy resin HP-7200H, plate has high Tg, low CTE, but due to dicyclopentadiene phenol
Formaldehyde epoxy resin HP-7200H excessively leads to solidification not exclusively, final plate water absorption rate is high, dielectric properties are poor and heat resistance not
It is ideal.
Esters curing agent and bisphenol A cyanate ester prepolymer CE01PS in embodiment 12 using 27 parts with Formulas I structure
Solidify 38 parts of dicyclopentadiene novolac epoxy resin HP-7200H, plate has high Tg, low CTE, low water absorption and excellent Jie
Electrical property, but heat resistance is undesirable, and the drop impact test slight crack area for being used to characterize toughness is big, and plate poor toughness is unfavorable
PCB in downstream is processed.
Esters curing agent and bisphenol A cyanate ester prepolymer CE01PS in embodiment 13 using 3 parts with Formulas I structure is multiple
Solidification dicyclopentadiene novolac epoxy resin HP-7200H is closed, plate has high Tg, low CTE, excellent heat resistance and toughness, but
Water absorption rate is high, and plate dielectric properties deteriorate serious after the moisture absorption.
Using 40 parts of bisphenol A cyanate ester prepolymer CE01PS and with the esters curing agent of Formulas I structure in embodiment 14
Composite curing dicyclopentadiene novolac epoxy resin HP-7200H, plate have high Tg, low CTE, low water absorption and excellent Jie
Electrical property, but cause plate toughness poor because CE01PS additive amount is too high, it is unfavorable for the PCB processing in downstream.
It is multiple with the esters curing agent with Formulas I structure using 8 parts of bisphenol A cyanate ester prepolymer CE01PS in embodiment 15
Close solidification dicyclopentadiene novolac epoxy resin HP-7200H, plate have low CTE, low water absorption, excellent dielectric loss because
Son, but plate Tg is lower, dielectric constant is higher and heat resistance is undesirable.
It is compound using the esters curing agent and bisphenol A cyanate ester prepolymer CE01PS with Formulas I structure in embodiment 16
Solidifying dicyclopentadiene novolac epoxy resin HP-7200H, does not add filler, the CTE and water absorption rate of plate are increased, but still
It is maintained at comparatively ideal level, while plate has high Tg, excellent dielectric properties, heat resistance and toughness.
As described above, being prepared compared with general Halogen laminate using compositions of thermosetting resin provided by the invention
Laminate there is higher Tg, lower CTE, lower water absorption rate, superior dielectric properties and peel strength, heat-resisting
Property, toughness, be suitable for high-speed applications field.In addition content of halogen of the present invention can reach difficult within the scope of JPCA Halogen standard requirements
V-0 standard in combustion property test UL94, there is environmental protection.
Esters curing agent V-575 and bisphenol A cyanate ester prepolymer CE01PS composite curing bicyclic penta are used in comparative example 1
Diene novolac epoxy resin HP-7200H, plate has high Tg, low CTE, excellent dielectric properties and heat resistance, but water absorption rate is high
And the dielectric properties after the plate moisture absorption are poor.
Dicyclopentadiene phenolic active ester HPC-8000T65 and bisphenol A cyanate ester prepolymer are used in comparative example 2
CE01PS composite curing dicyclopentadiene novolac epoxy resin HP-7200H, plate have high Tg, low CTE, excellent dielectricity
Energy and heat resistance, but the dielectric properties after water absorption rate height and the plate moisture absorption are poor.
Dicyclopentadiene type benzoxazine LZ 8260N70 and bisphenol A cyanate ester prepolymer are used in comparative example 3
CE01PS composite curing dicyclopentadiene novolac epoxy resin HP-7200H, plate have higher Tg, lower CTE, low water absorption,
Excellent dielectric constant, but plate dielectric loss factor is higher and heat resistance is undesirable.
Esters curing agent V-575 and bisphenol A cyanate ester prepolymer CE01PS composite curing bicyclic penta are used in comparative example 4
Diene novolac epoxy resin HP-7200H, does not add filler, and plate has a high Tg and excellent dielectric properties, but water absorption rate it is high and
Dielectric properties after the plate moisture absorption are poor, and heat resistance is also undesirable.
Dicyclopentadiene phenolic active ester HPC-8000T65 and bisphenol A cyanate ester prepolymer are used in comparative example 5
CE01PS composite curing dicyclopentadiene novolac epoxy resin HP-7200H, does not add filler, and plate has high Tg and excellent
Dielectric properties, but the dielectric properties after water absorption rate height and the plate moisture absorption are poor, and heat resistance is also undesirable.
Dicyclopentadiene type benzoxazine LZ 8260N70 and bisphenol A cyanate ester prepolymer are used in comparative example 6
CE01PS composite curing dicyclopentadiene novolac epoxy resin HP-7200H, does not add filler, and plate has higher Tg, low water suction
Rate, excellent dielectric constant, but plate dielectric loss factor is higher and heat resistance is undesirable.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of compositions of thermosetting resin, which is characterized in that the compositions of thermosetting resin includes following component: asphalt mixtures modified by epoxy resin
Rouge, cyanate ester resin and esters curing agent；
The esters curing agent has Formulas I structure:
Wherein, R1-R8It is each independently selected from hydrogen atom, C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10Fragrance
One of race's alkyl, and it is not all hydrogen atom；
X is selected from-O- ,-S- ,-CH2Or-C (CH3)2One of；
Y is selected from C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10One of aromatic hydrocarbyl；
N is the integer of 1-10.
2. compositions of thermosetting resin according to claim 1, which is characterized in that with the epoxy resin, cyanate resin
The total weight number of rouge and esters curing agent be 100 parts meter, the compositions of thermosetting resin include: 40-70 parts of epoxy resin,
10-35 parts of cyanate ester resins and 5-25 parts of esters curing agent.
3. compositions of thermosetting resin according to claim 1 or 2, which is characterized in that the epoxy resin is Halogen ring
Oxygen resin；
Preferably, the halogen-free epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol epoxy novolac
Resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type phenolic aldehyde
One of epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin or at least two combination；
Preferably, the halogen-free epoxy resin has Formula II structure:
Wherein, X1、X2And X3It is each independentlyR9Selected from hydrogen atom, replaces or do not take
The C in generation1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl, Y1And Y2It is each independently selected from list
Key ,-CH2-、 One of, R10Selected from hydrogen original
Sub, substituted or unsubstituted C1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl, m 1-10
Integer.
4. compositions of thermosetting resin according to claim 1-3, which is characterized in that the cyanate ester resin choosing
From bisphenol A cyanate ester resin, bisphenol-f type cyanate ester resin, tetramethyl bisphenol F cyanate resin, bis-phenol M type cyanate resin
Rouge, bisphenol S type cyanate ester resin, bisphenol E-type cyanate resin, bis-phenol p-type cyanate ester resin, novolac type cyanate resin
Rouge, cresol novolak type cyanate ester resin, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, dicyclopentadiene type cyanogen
Acid ester resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, bisphenol A-type cyanogen
Acid esters prepolymer, bisphenol-f type cyanate prepolymer, tetramethyl bisphenol-f type cyanate prepolymer, bis-phenol M type cyanate prepolymer,
Bisphenol S type cyanate prepolymer, bisphenol E-type cyanate prepolymer, bis-phenol p-type cyanate prepolymer, novolac type cyanate
It is prepolymer, cresol novolak type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, bicyclic
Pentadiene type cyanate prepolymer, phenolphthalein type cyanate prepolymer, aralkyl-type cyanate prepolymer or aralkyl phenol aldehyde type cyanogen
In acid esters prepolymer any one or at least two mixture, preferably novolac type cyanate ester resin, naphthol type cyanogen
Acid ester resin, Naphthol phenolic cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl phenolic aldehyde
Type cyanate ester resin, novolac type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate pre-polymerization
It is any in object, phenolphthalein type cyanate prepolymer, aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer
It is a kind of or at least two mixture, further preferred novolac type cyanate ester resin, Naphthol phenolic cyanate ester resin,
Aralkyl Novolac Cyanate Ester Resins, novolac type cyanate prepolymer, naphthol novolac type cyanate prepolymer or aralkyl
In Novolac Cyanate Eater Resin prepolymer any one or at least two mixture；
Preferably, the compositions of thermosetting resin further includes fire retardant；
Preferably, the fire retardant is phosphonium flame retardant；
Preferably, described to contain in terms of by the total weight number of the epoxy resin, cyanate ester resin and esters curing agent for 100 parts
The additive amount of phosphorus fire retardant is 1-50 parts, further preferably 1-30 parts；
Preferably, the phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- bis-
Hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxide, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- dihydro -9-
In oxa- -10- phosphine phenanthrene -10- oxide, phenoxy phosphazene compound, phosphate, polyphosphate, phosphonate ester or polyphosphonates
It is a kind of or at least two combination.
5. compositions of thermosetting resin according to claim 1-4, which is characterized in that the thermosetting resin group
Closing object further includes curing accelerator；
Preferably, described solid in terms of by the total weight number of the epoxy resin, cyanate ester resin and esters curing agent for 100 parts
The additive amount for changing promotor is 0.05-1 parts；
Preferably, the curing accelerator is selected from glyoxaline compound, triphenylphosphine, dimethylamino naphthyridine, boron trifluoride list second
One of amine or zinc octoate or at least two combination；
Preferably, the glyoxaline compound is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or 2- ten
One of one alkyl imidazole or at least two combination；
Preferably, the compositions of thermosetting resin further includes filler；
Preferably, described to fill out in terms of by the total weight number of the epoxy resin, cyanate ester resin and esters curing agent for 100 parts
The additive amount of material is 1-150 parts, further preferably 1-100 parts；
Preferably, the filler is organic filler and/or inorganic filler；
Preferably, the inorganic filler is selected from silica, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, carbonization
One of silicon, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, mica, glass fiber powder or at least two group
It closes；
Preferably, the organic filler is selected from one of polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder or at least
Two kinds of combination；
Preferably, the filler is silica, and angle value is 1-15 μm, further preferably 1-10 μm in partial size.
6. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by thermosetting property as described in any one in claim 1-5
Resin combination is dissolved or dispersed in solvent and obtains.
7. a kind of prepreg, which is characterized in that the prepreg includes reinforcing material, and described by being attached to after impregnation drying
Compositions of thermosetting resin as described in any one in claim 1-5 on reinforcing material.
8. a kind of laminate, which is characterized in that the laminate includes the as claimed in claim 7 of one or at least two overlapping
Prepreg.
9. a kind of metal-clad laminate, which is characterized in that the metal-clad laminate includes one or at least two overlapping
Prepreg as claimed in claim 7 and the metal foil of one or both sides that is overlying on the outside of the prepreg.
10. a kind of printed circuit board, which is characterized in that the printed circuit board includes at least one as claimed in claim 7
Prepreg.
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| CN115322336A (en) * | 2022-08-12 | 2022-11-11 | 中国地质大学（北京） | Heat latent curing accelerator and preparation method thereof, epoxy laminated film and preparation method and application thereof |
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