CN104804377B - Halogen-free resin composition, and prepreg and laminated boards which are prepared from halogen-free resin composition - Google Patents

Halogen-free resin composition, and prepreg and laminated boards which are prepared from halogen-free resin composition Download PDF

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CN104804377B
CN104804377B CN201510043255.0A CN201510043255A CN104804377B CN 104804377 B CN104804377 B CN 104804377B CN 201510043255 A CN201510043255 A CN 201510043255A CN 104804377 B CN104804377 B CN 104804377B
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halogen
weight portions
resin composition
resin
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CN104804377A (en
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奚龙
何岳山
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention relates to a halogen-free resin composition, and a prepreg and laminated boards which are prepared from the halogen-free resin composition. The halogen-free resin composition comprises following ingredients, by weight, 5 to 45 parts of epoxy resin, 10 to 80 parts of benzoxazine resin, 0.5 to 25 parts of a curing agent, and 1 to 15 parts of a fire retardant. The invention also provides the prepreg, the laminated boards, and printed circuit-used the laminated boards which are prepared from the halogen-free resin composition. According to a preparation method, two kinds of benzoxazine resins are combined at a certain ratio, so that excellent heat and humidity resistance of the halogen-free resin composition is ensured, and resin composition roughness is increased effectively; and dielectric properties and machining properties of the prepreg, the laminated boards, and the printed circuit-used the laminated boards are excellent.

Description

A kind of halogen-free resin composition and the prepreg and laminate that are made of it
Technical field
The present invention relates to laminate technical field, and in particular to a kind of resin combination, more particularly to a kind of Halogen resin Composition and the prepreg and laminate for printed circuits that are made of it.
Background technology
As the harmful substance of European Union limits the use of instruction (Restriction of Hazardous Substances, RoHS) Implementation and green peace organization promote the greenization of electron trade energetically, electronic material it is non-halogen turn into 2007 after The evaluation emphasis of industry.Relative to brominated flame-retarded resin or fire retardant, phosphorous flame-retardant product pollutes relatively small after burning, Developed faster in recent years.
To realize bromine-free flame-retardant, phosphorous resin or fire retardant are generally used in the industry, coordinate nitrogenous resin or fire retardant Realize phosphorus-bromine collaboration highly effective flame-retardant.Phosphorous epoxy resin shows excellent due to containing P elements in molecular structure at fire-retardant aspect It is different, obtain the favor of developer in the industry.Because P elements cause water absorption rate to raise, the reliability of electronic material has been badly influenced Property.Contain nitrogen in benzoxazine colophony, this problem can be obviously improved, cure shrinkage is low in addition, and chemical resistance is good, It is widely used.However, most of benzoxazine is more due to rigid radical, the molecular radical molecular weight between crosslinking points It is limited, cause that its solidfied material fragility is larger, manufactured goods processability is poor, becomes the difficult point of its application.
On the other hand, with the development of the development of electronic technology, particularly mechanics of communication, printed wiring board (PCB) is to letter Cease the speed more and more higher of processing requirement.It is well known that the dielectric constant (Dk) of printed substrate (CCL) is lower, signal exists The speed transmitted on substrate is faster, and the dielectric loss (Df) of substrate is smaller, and signal wasted power in transmitting procedure is consistent When, allow that the frequency of transmission is higher.That is, dielectric loss is smaller, and distortion of the signal in transmission gets over unobvious.Additionally, with Mobile phone, notebook computer and panel computer are the consumer electronics field of representative, and compact this trend will further develop. To realize thinner design and not reducing arithmetic speed, it is necessary to which exploitation has the substrate compared with low-k/dielectric loss.With base Site server etc. is the high-end field of representative, while having relatively strict demand to Dk/Df, pays special attention to the reliability of material, Seeking substrate has glass transition temperature (Tg) higher, resistance to thermal reliability and lower thermal coefficient of expansion (CTE).
Therefore, practitioner has made various effort to this in the industry.Proposed using preferred in Chinese patent CN102504532A Epoxy resin and benzoxazine be applied in combination and can realize excellent electrical property, while moisture-proof is thermally relieved etc., and performance is taken into account； But the benzoxazine fragility in said composition is larger, and bad influence is generated to processability.Chinese patent Disclosed in CN103724997A realized using the benzoxazine and trifunctional epoxy resin of special construction it is preferably comprehensive Can, but because trifunctional epoxy resin is readily burned, water absorption rate is higher, and in view of the characteristic of its benzoxazine colophony, its combination Thing has some limitations at aspects such as glass transition temperature, moisture-proof thermal reliabilities.
Therefore, find a kind of while ensureing to have excellent humidity resistance, can effectively lift the toughness of resin combination And make prepreg, laminate and laminate for printed circuits have the halogen-free resin composition of superior dielectric performance be at present urgently The problem of solution.
The content of the invention
It is an object of the invention to provide a kind of halogen-free resin composition, particularly a kind of halogen-free resin composition and it is used The prepreg and laminate for printed circuits of making.
To reach this goal of the invention, the present invention uses following technical scheme：
In a first aspect, the invention provides a kind of halogen-free resin composition, the composition, with solid constituent weight portion Meter, including following component：
(A) epoxy resin：5 to 45 weight portions；
(B) benzoxazine colophonies：10 to 80 weight portions；
(C) curing agent：0.5 to 25 weight portion；
(D) fire retardant：1 to 15 weight portion；
Wherein, described benzoxazine colophony includes two kinds of components of B1 and B2, and the structural formula of B1 components is as follows：
Wherein, n is 1~10 integer；R1, R6Independently selected from alkyl or aryl；R3, R4Independently selected from substitution or not Substituted carbon atom is the straight chained alkyl or branched alkyl of 4-8, preferably normal-butyl or n-octyl；R2, R5Independently selected from substitution Or unsubstituted carbon atom is the straight chained alkyl or branched alkyl of 4-8, or selected from hydrogen atom, preferably hydrogen atom；
B2 components are selected from bisphenol A-type benzoxazine colophony, dicyclopentadiene type benzoxazine colophony, bisphenol-f type Ben Bing Evil In piperazine resin, phenolphthalein type benzoxazine resin or MDA type benzoxazine colophonies any one or at least two mixing.
B1 components in benzoxazine colophony of the present invention, or the compound with Er hydrogen benzoxazine rings, be It is a kind of benzo 6-membered heterocyclic compound of Material synthesis by phenol, primary amine and formaldehyde, can produces nitrogenous and similar through ring-opening polymerisation The network structure of phenolic resin.
Bisphenol A-type benzoxazine colophony monomer and bisphenol-f type benzoxazine colophony monomer, phenolphthalein type benzo in the present invention Shown in the structure of oxazine resin monomer such as formula (α)：
Wherein, R3ForR4For-CH2- orIn any one.
Work as R4ForWhen, structural formula (α) is bisphenol A-type benzoxazine colophony monomer；Work as R4For-CH2- when, Structural formula (α) is bisphenol-f type benzoxazine colophony monomer；Work as R4ForWhen, structural formula (α) is phenolphthalein type benzoxazine Resin monomer.
MDA type benzoxazine colophonies in the present invention, also known as (4,4 '-two amido diphenyl-methane) type benzoxazine colophony, Shown in its structure such as formula (β)：
The structural formula of the dicyclopentadiene benzoxazine colophony monomer in the present invention is such as shown in (γ)：
Halogen-free resin composition of the invention uses the benzoxazine colophony with B1 structures as the solidification of epoxy resin Agent, and it is used cooperatively with B2 components, efficiently solve the problems, such as that resin combination toughness is not good, improve resin group The machining property of compound, i.e., in the present invention, benzoxazine colophony can improve halogen-free resin composition and by the tree The required fire resistance such as prepreg, laminate that fat is obtained, moisture-proof, heat resistance, mechanical property and Glass Transition higher Temperature (Tg)；Further, since the presence of the part alkyl segment in B1 components, polar group obtains " dilution ", improves resin The dielectric properties of composition.
In the present invention, described epoxy resin is selected from the modified ring of DCPD-containing epoxy resin, phosphorous epoxy resin, MDI Oxygen tree fat, biphenyl epoxy resin, bisphenol A type epoxy resin, phenol type novolac epoxy resin, o-cresol formaldehyde type epoxy resin or ring Oxidation polybutadiene in any one or at least two mixing.
In halogen-free resin composition of the present invention, the epoxide equivalent of all types of epoxy resin is 150~800.
Heretofore described epoxy resin content is 5 to 45 weight portions, for example, can be 5 weight portions, 8 weight portions, 10 Weight portion, 12 weight portions, 15 weight portions, 20 weight portions, 22 weight portions, 25 weight portions, 30 weight portions, 32 weight portions, 35 weight Part, preferably 38 weight portions, 40 weight portions, 42 weight portions, 45 weight portions, 10 to 35 weight portions.
Heretofore described benzoxazine colophony content is 10 to 80 weight portions, for example, can be 10 weight portions, 15 weights Amount part, 20 weight portions, 25 weight portions, 30 weight portions, 35 weight portions, 40 weight portions, 45 weight portions, 50 weight portions, 55 weight portions, 60 weight portions, 65 weight portions, 70 weight portions, 75 weight portions, 80 weight portions, preferably 30 to 65 weight portions.
In benzoxazine colophony of the present invention, the weight ratio of two kinds of components of B1 and B2 is 5:1 to 1:5, for example can be with It is 5:1、5:2、5:3、5:4、5:5、1:5、2:5、3:5、4:5.
Relative to B2 components, the molecule segment of B1 components benzoxazine colophony of the invention is more long, good containing flexible Alkyl segment, with more excellent toughness；And B2 components then have glass transition temperature (Tg) higher, heat resistance is good. When the weight ratio of the two is 5:1-1:When between 5, resin combination obtains balance in terms of humidity resistance and toughness, with preferable Combination property.
Heretofore described curing agent is selected from dicyandiamide, 4,4- DADPSs, diaminodiphenyl ether, diaminourea two Any one in diphenyl sulfide, phenol type phenolic resin, orthoresol type phenolic resin or bisphenol A type phenolic resin or at least two Mixing.
Curing agent content of the invention is 0.5 to 25 weight portion, for example, can be 0.5 weight portion, 1 weight portion, 2 weight Part, 4 weight portions, 6 weight portions, 8 weight portions, 10 weight portions, 12 weight portions, 14 weight portions, 15 weight portions, 16 weight portions, 18 weights Amount part, 20 weight portions, 22 weight portions, 24 weight portions, preferably 25 weight portions, 1 to 15 weight portion.
Curing agent in the present invention is favorably improved the crosslink density between resin, improves glass transition temperature (Tg), Improve the resistance to thermal reliability of substrate.If content is less than 0.5 part, the glass transition temperature (Tg) of resin combination is relatively low, substrate Heat resistance is not enough, is easily caused PCB plate burstings failure；If content is more than 25 parts, resin combination water absorption rate will be caused to be substantially increased, can Substantially deteriorated by property.
Heretofore described fire retardant be selected from resorcinol-bis- (diphenyl phosphates), bisphenol-A-bis- (diphenyl phosphate), In resorcinol-bis- (2,6- dixylenyl phosphates), methyl-phosphoric acid dimethyl ester or phosphazene compound any one or at least Two kinds of mixing, preferably phosphazene compound.
Flame retardant agent content of the invention is 1 to 15 weight portion, for example, can be 1 weight portion, 2 weight portions, 3 weight portions, 4 weights Amount part, 5 weight portions, 6 weight portions, 7 weight portions, 8 weight portions, 9 weight portions, 10 weight portions, 11 weight portions, 12 weight portions, 13 weights Amount part, 14 weight portions, preferably 15 weight portions, 3 to 12 weight portions.
In halogen-free resin composition of the invention, due to having used fire retardant, the use of phosphorous resin can be effectively reduced, dropped The low water absorption rate of resin combination.
Composition of the present invention also includes (E) curing accelerator：0.1 to 1 weight portion, for example, can be 0.1 weight Part, 0.2 weight portion, 0.3 weight portion, 0.4 weight portion, 0.5 weight portion, 0.6 weight portion, 0.7 weight portion, 0.8 weight portion, 0.9 Weight portion, 1 weight portion.
Curing accelerator of the present invention is selected from imidazoles accelerator and its derivative, pyridines or Louis's acids Any one or at least two mixing.
Curing accelerator of the invention is beneficial to epoxy resin and benzoxazine colophony and curing agent carries out curing reaction, Uniform three-dimensional netted molecular structure is formed, preferably physical property is reached；And the radical concentrations such as hydroxyl (- OH) and epoxy radicals can be promoted Decline, help resin combination to realize preferably dielectric properties, reduce dielectric constant and dielectric loss.
Composition of the present invention also includes (F) filler：5 to 80 weight portions, for example, can be 5 weight portions, 8 weight Part, 10 weight portions, 12 weight portions, 15 weight portions, 20 weight portions, 22 weight portions, 25 weight portions, 30 weight portions, 35 weight portions, 40 Weight portion, 45 weight portions, 50 weight portions, 55 weight portions, 60 weight portions, 65 weight portions, 70 weight portions, 75 weight portions, 80 weight Part, preferably 25 to 60 weight portions；
Filler of the present invention is selected from inorganic filler and/or organic filler.
Preferably, described inorganic filler be selected from aluminium hydroxide, silica, talcum powder, boehmite, zeolite, wollastonite, In magnesia, calcium silicates, calcium carbonate, clay or mica any one or at least two mixing.
Preferably, described organic filler is selected from melamine and/or melamine cyanurate.
At 50nm-50 μm, its physical aspect can be sheet, bar-shaped, spherical, hollow to the particle diameter of inorganic filler of the present invention Spherical, granular, fibrous or tabular etc., it is alternative to be processed with silane coupler.Uniform filling of the invention is dispersed in resin In composition, the mechanical strength its role is to further improve resin combination, heat conductivity reduces water absorption rate, reduces swollen Swollen coefficient and improvement processability.
The preparation method of halogen-free flame resistance resin composite of the present invention, those skilled in the art may be referred to existing Resin combination preparation method, selected with reference to actual conditions, the present invention do not do particular determination.
As optimal technical scheme, halogen-free resin composition of the present invention, in terms of solid constituent weight portion, including such as Lower component：
(A) epoxy resin：5 to 45 weight portions；
(B) benzoxazine colophonies：10 to 80 weight portions；
(C) curing agent：0.5 to 25 weight portion；
(D) fire retardant：1 to 15 weight portion；
(E) curing accelerator：0.1 to 1 weight portion；
(F) filler：5 to 80 weight portions.
As further preferred technical scheme, halogen-free resin composition of the present invention, with solid constituent weight portion Meter, including following component：
(A) epoxy resin：10 to 35 weight portions；
(B) benzoxazine colophonies：30 to 65 weight portions；
(C) curing agent：1 to 15 weight portion；
(D) fire retardant：3 to 12 weight portions；
(E) curing accelerator：0.1 to 1 weight portion；
(F) filler：25 to 60 weight portions.
Second aspect, present invention also offers a kind of prepreg, it includes Halogen tree as described in the first aspect of the invention Oil/fat composition.
Prepreg be with resin matrix under conditions of strict control impregnating continuous fibres or fabric, be made resin matrix with The composition of reinforcement, is the intermediate materials for manufacturing composite.
Preferably, described prepreg includes base-material and by Halogen resin combination attached thereto after impregnation drying Thing.
Base-material of the present invention be adhesive-bonded fabric or other fabrics, it is typical but non-limiting including natural fiber, have Machine synthetic fibers or inorfil etc..
Preferably, described base-material is nonwoven or has spinning glass fabric.
The preparation method of prepreg of the present invention, those skilled in the art may be referred to the preparation of existing prepreg Method, the present invention is not specifically limited, and the preparation method of the typical but non-limiting prepreg comprises the following steps：
The glue of the halogen-free resin composition provided using the present invention is impregnated with base-material, the glass cloth that will be impregnated with 140~ Heat drying is made for 3~8 minutes in 200 DEG C of baking oven.
The third aspect, present invention also offers a kind of laminate, it includes prepreg as described in respect of the second aspect of the invention.
Laminate is one kind of laminated product, is the fiber or fabric (i.e. prepreg) that resin is soaked with by two-layer or multilayer, Through overlapping, hot binding into entirety.
Fourth aspect, the invention provides a kind of printed circuit board (PCB), it includes the lamination as described in third aspect present invention Plate.
Compared with prior art, the present invention at least has the advantages that：
(1) as asphalt mixtures modified by epoxy resin after the present invention is used and matches the benzoxazine colophony of two kinds of components of B1 and B2 by a certain percentage The curing agent of fat, it is ensured that resin combination has excellent heat resistance, while compared with low water absorption, overcomes resin combination fragility Greatly, the defect of machining property difference；
(2) benzoxazine colophony that the present invention is used, is controlled by its functional group, can improve resin combination Toughness, while humidity resistance, reliability is increased, with relatively low dielectric constant, relatively low dielectric loss；
(3) use of phosphorous resin can be reduced in the present invention using fire retardant, water absorption rate is relatively low, good reliability；
(4) prepreg of present invention offer, copper-clad laminate have excellent dielectric properties, while also having glass high Change transition temperature (Tg), high-fire resistance, high reliability, low water absorbable, low thermal coefficient of expansion (CTE), fire-retardant and excellent machine Tool processing characteristics etc., is conducive to industrialization promotion to implement.
Specific embodiment
For the present invention is better described, technical scheme is readily appreciated, it is of the invention typical but non-limiting Embodiment is as follows：
The synthesis of preparation example B1 component benzoxazine colophonies
(1) 4-TBP and 4- tert-octyl phenols are chosen with mol ratio 1:1 adds in reactor, is heated to 100 DEG C, Appropriate oxalic acid and formalin are slowly added to, flow back 3-6h.Then by product in water precipitating, after normal pressure, vacuum distillation To solid；
(2) mol ratio with phenolic hydroxyl group, amido, aldehyde functions is 1:1:2, sequentially add the product of step (1), benzene Amine, paraformaldehyde adjusts pH value to 8-10 with NaOH；After stirring, temperature rising reflux, cooling device after reacting 3 hours obtains shallow The translucent viscous body of yellow, after washing, purifying, drying, that is, obtains the benzoxazine B1 components with following structural formula, produces Rate is 81%.
Wherein R1, R6 are
In the embodiment and comparative example, unless otherwise instructed, wherein " part " representative " weight portion ", wherein " % " is represented " weight % ".
The formula difference of the halogen-free resin composition that embodiment 1-8 and comparative example 1-8 is provided is as shown in Table 1 and Table 2.
Table 1
Table 2
In Tables 1 and 2, each component code name and its corresponding ingredient names used by embodiment 1-8 and comparative example 1-8 are such as Shown in lower：
A is the DCPD-containing epoxy resin for being purchased from Japanese DIC companies, trade name HP-7200H；
B is benzoxazine colophony；
B-1 is the B1 component benzoxazine colophonies of synthesis in preparation example；
B-2 is the product of the model D125 for being purchased from Sichuan Dongcai Technology Group Co., Ltd；
The structural formula of B-3 is：
Wherein n is the positive integer of 1-9；
C is curing agent；
C-1 is linear phenolic resin, the model EPONOL 6635M65 of momentive companies of South Korea；
C-2 is the DICY for being purchased from Ningxia Daiei；
D is the product of the model SPB-100 for being purchased from Ben Otsuka Chemical Co., Ltd；
E is the 2E4MI for being purchased from Japanese four countries' chemical conversion；
F is filler；
F-1 is the refined precious aluminium hydroxide in the U.S.；
F-2 is the silica of Chongqing brocade skill.
Performance test：
The halogen-free resin composition that embodiment 1-8 and comparative example 1-8 is provided, is prepared as follows printed circuit use Laminate, and laminate to preparing carries out performance test.
The preparation method of the laminate for printed circuits includes：
(1) make one by heating and pressurization or the prepreg of more than is bonded together, be made laminate；
(2) the bonding metal paper tinsel on the one or both sides of laminate obtained in step (1)；
(3) it is laminated in laminating machine.
During step (2), it is superimposed together using the metal foil of 8 prepregs and 2 one ounce (35 μ m-thick)；
During step (3), the operating condition of lamination is：During 80~140 DEG C of material temperature, it is 1.5 to control heating rate ~2.5 DEG C/min；During 80-100 DEG C of outer layer material temperature, apply full pressure, full pressure pressure is 350psi or so；During solidification, material temperature is controlled At 195 DEG C, and it is incubated more than 60min.
The project and specific method of performance test be：
(a) glass transition temperature：
According to differential scanning calorimetry, it is measured according to the DSC method of 2.4.25 defineds in IPC-TM-650.
(b) flame resistance：
Determined according to UL94 methods.
(c) resistance to immersed solder time：
Pressure cooking first by sample (laminate for printed circuits of 100 × 100mm) in 121 DEG C, 105kPa is processed Kept for 2 hours in device；The solder bath that sample is immersed in 260 DEG C is recorded into its layering bubble time afterwards.
(d) water imbibition：
Method according to the 2.6.2.1 defineds in IPC-TM-650 is measured.
(e) dielectric constant and dielectric loss factors
According to the resonance method using stripline runs, 1GHz is determined according to the method for the 2.5.5.5 defineds in IPC-TM-650 Under dielectric constant and dielectric loss factors.
(f) bending strength
Method according to the 2.4.4 defineds in IPC-TM-650 is tested.
(g) drop impact area
Thickness 1.60mm, the base material of 100 × 100mm are horizontally placed on stand, the circle for having diameter 8cm inside stand is led to Road will choose the cross face hammer of 1Kg weights through lower section on stand, and tup is placed in 1m highly, alignment tool by tup diameter 10mm Frame circular section, Vertical Free falls within sheet material, and the area for occurring lineae ablicantes to sheet material is calculated.
H () PP is apparent
Whether range estimation PP surfaces are uniform and smooth, if smooth.
The performance test results of laminate for printed circuits prepared by the halogen-free resin composition provided by embodiment 1~8 As shown in table 3；The performance test knot of laminate for printed circuits prepared by the halogen-free resin composition provided by comparative example 1~8 Fruit is as shown in table 4.
Table 3
Table 4
From the data of table 3 and table 4 can be seen that it is following some：
(1) can be seen that the epoxy resin content in embodiment 1-6 by embodiment 1-6 to successively decrease, in embodiment 1 Epoxy resin content it is minimum, its glass transition temperature highest, bending strength preferably, but drop impact area is larger, it is tough Property is poor；Illustrate, when the epoxy resin content in halogen-free resin composition is less, to raise glass transition temperature, bending is strong Degree improves, but drop impact area is larger, and toughness can be deteriorated；
(2) embodiment 2 and embodiment 3 show that the benzoxazine of B1 components is effectively reducing resin combination dielectric constant While with dielectric loss, toughness is greatly improved.Embodiment 3 and embodiment 4 show, when phenolic aldehyde ratio is higher in curing agent, Easily cause the increase of fragility, amine curing agent can increase toughness；Embodiment 5 and embodiment 6 show, two kinds of components of B1 and B2 Benzoxazine weight ratio can be 1:5~5:Adjusted between 1, can obtain preferable performance；
(3) embodiment 1-8 shows that resin combination of the invention has performance more in a balanced way；
(4) it is compared from embodiment 1-6 and comparative example 1, the glass transition temperature in comparative example 1 is relatively low, resistance to Hot not good, toughness is very poor, illustrate when epoxy resin content not within the scope of the present invention when, its heat resistance and toughness can be deteriorated；
(5) from comparative example 2, benzoxazine content is too low, and the dielectric constant of resin combination is relatively low, but Tg is low, resistance Combustion can only achieve V-1 ranks.Found out by comparative example 3, while the benzoxazine of B1 components can be effectively increased sheet material toughness, dielectric Excellent performance, but heat resistance is not good.Be can be seen that by comparative example 4, the benzoxazine of B2 components has Tg higher, but dielectric is normal Number and dielectric loss are all higher, and tough sex expression is general；
(6) from comparative example 5, the sample properties not comprising phosphonium flame retardant preferably, but can not reach V-0 ranks It is fire-retardant；
(7) from comparative example 3 and comparative example 6, two kinds of benzoxazines of component of B1 and B3 can be effectively increased resin group The toughness of compound, but the use of the benzoxazine of B3 components can cause dielectric properties to deteriorate；Comparative example 5 and comparative example 7 are carried out Compare and understand, the benzoxazine of B3 components can substantially reduce the dielectric properties of resin system, improvement of the B1 to resin system toughness It is better than B3；Embodiment 4 is compared with comparative example 8 and is shown, the benzoxazine part by weight of two kinds of components of B1 and B2 exceedes 5：When 1, the increase of B1 usage amounts will not produce actively impact to key indexs such as Tg and heat resistances.
It should be noted that and understand, in the feelings for not departing from the spirit and scope of the present invention required by appended claims Under condition, various modifications and improvements can be made to the present invention of foregoing detailed description.It is therefore desirable to the model of the technical scheme of protection Enclose and do not limited by given any specific exemplary teachings.
Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the present invention not office It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (23)

1. a kind of halogen-free resin composition, it is characterised in that the composition, in terms of solid constituent weight portion, including such as the following group Point：
(A) epoxy resin：5 to 45 weight portions；
(B) benzoxazine colophonies：10 to 80 weight portions；
(C) curing agent：0.5 to 25 weight portion；
(D) fire retardant：1 to 15 weight portion；
Wherein, described benzoxazine colophony includes two kinds of components of B1 and B2, and the structural formula of B1 components is as follows：
Wherein, n is 1~10 integer；R1, R6Independently selected from alkyl or aryl；R3, R4Independently selected from substituted or unsubstituted Carbon atom is the straight chained alkyl or branched alkyl of 4-8；R2, R5It is the straight chain of 4-8 independently selected from substituted or unsubstituted carbon atom Alkyl or branched alkyl, or selected from hydrogen atom；
B2 components are selected from bisphenol A-type benzoxazine colophony, dicyclopentadiene type benzoxazine colophony, bisphenol-f type benzoxazine tree In fat, phenolphthalein type benzoxazine resin or MDA type benzoxazine colophonies any one or at least two mixing；
The weight ratio of described two kinds of components of B1 and B2 is 5:1 to 1:5.
2. composition as claimed in claim 1, it is characterised in that the R3, R4It independently is normal-butyl or n-octyl.
3. composition as claimed in claim 1 or 2, it is characterised in that the R2, R5It independently is hydrogen atom.
4. composition as claimed in claim 1, it is characterised in that described epoxy resin is selected from dicyclopentadiene asphalt mixtures modified by epoxy resin Fat, phosphorous epoxy resin, MDI modified epoxies, biphenyl epoxy resin, bisphenol A type epoxy resin, phenol type epoxy novolac tree In fat, o-cresol formaldehyde type epoxy resin or POLYBUTADIENE EPOXY RESIN any one or at least two mixing.
5. composition as claimed in claim 1, it is characterised in that in described halogen-free resin composition, epoxy resin contains It is 10 to 35 weight portions to measure.
6. composition as claimed in claim 1, it is characterised in that in described halogen-free resin composition, benzoxazine colophony Content be 30 to 65 weight portions.
7. composition as claimed in claim 1, it is characterised in that described curing agent is selected from dicyandiamide, 4,4- diaminourea two Benzene sulfone, diaminodiphenyl ether, diaminodiphenyl sulfide, phenol type phenolic resin, orthoresol type phenolic resin or bisphenol A-type phenolic aldehyde In resin any one or at least two mixing.
8. composition as claimed in claim 1, it is characterised in that in described halogen-free resin composition, the content of curing agent It is 1 to 15 weight portion.
9. composition as claimed in claim 1, it is characterised in that described fire retardant is selected from resorcinol-bis- (phosphoric acid hexichol Ester), bisphenol-A-bis- (diphenyl phosphate), resorcinol-bis- (2,6- dixylenyl phosphates), methyl-phosphoric acid dimethyl ester or phosphonitrile In compound any one or at least two mixing.
10. composition as claimed in claim 9, it is characterised in that described fire retardant is phosphazene compound.
11. compositions as claimed in claim 1, it is characterised in that in described halogen-free resin composition, the content of fire retardant It is 3 to 12 weight portions.
12. compositions as claimed in claim 1, it is characterised in that described composition also includes (E) curing accelerator：0.1 To 1 weight portion.
13. compositions as claimed in claim 12, it is characterised in that described curing accelerator be selected from imidazoles accelerator and In its derivative, pyridines or Louis's acids any one or at least two mixing.
14. compositions as claimed in claim 1, it is characterised in that described composition also includes (F) filler：5 to 80 weight Part.
15. compositions as claimed in claim 14, it is characterised in that the content of described filler is 25 to 60 weight portions.
16. compositions as claimed in claim 14, it is characterised in that described filler is selected from inorganic filler and/or organic fills out Material.
17. compositions as claimed in claim 16, it is characterised in that described inorganic filler is selected from aluminium hydroxide, titanium dioxide Silicon, talcum powder, boehmite, in zeolite, wollastonite, magnesia, calcium silicates, calcium carbonate, clay or mica any one or extremely Few two kinds mixing.
18. compositions as claimed in claim 16, it is characterised in that described organic filler is selected from melamine and/or three Poly cyanamid cyanurate.
19. a kind of prepregs, it is characterised in that described prepreg includes the Halogen tree as described in claim any one of 1-18 Oil/fat composition.
20. prepregs as claimed in claim 19, it is characterised in that described prepreg includes base-material and by impregnation drying Halogen-free resin composition attached thereto afterwards.
21. prepregs as claimed in claim 20, it is characterised in that described base-material is nonwoven or has spinning glass fabric.
22. a kind of laminates, it is characterised in that it includes prepreg as claimed in claim 19.
23. a kind of printed circuit board (PCB)s, it is characterised in that it includes laminate as claimed in claim 22.
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CN107151308B (en) * 2016-03-04 2019-06-14 广东生益科技股份有限公司 A kind of halogen-free thermosetting resin composite and prepreg, laminate for printed circuits using it
CN106166874B (en) * 2016-06-29 2018-07-20 南亚新材料科技股份有限公司 halogen-free copper-clad plate and preparation method thereof
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