CN109265654A - Resin combination and its manufactured prepreg, laminate - Google Patents
Resin combination and its manufactured prepreg, laminate Download PDFInfo
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- CN109265654A CN109265654A CN201811023022.4A CN201811023022A CN109265654A CN 109265654 A CN109265654 A CN 109265654A CN 201811023022 A CN201811023022 A CN 201811023022A CN 109265654 A CN109265654 A CN 109265654A
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- epoxy resin
- resin
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- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/04—Epoxynovolacs
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
Abstract
The present invention provides a kind of resin combination and its manufactured prepregs, laminate, it is related to technical field of polymer materials, the resin combination includes 10-90 parts and 1-50 parts of active ester curing agent of epoxy resin, alleviate the technical issues of existing resin is unable to satisfy electronic circuit substrate high-frequency high-speed requirement, resin combination provided by the invention uses epoxy resin as matrix resin, so that resin combination has good machining property；Using the small-molecule substance with naphthalene nucleus and polyfunctionality ester bond structure as active ester curing agent, so that the resin combination dielectric loss after solidifying is low, glass transition temperature is high, also have the function of UV-blocking simultaneously, can satisfy the PCB use demand of baseplate material high speed and high frequency.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly, to a kind of resin combination and its manufactured preimpregnation
Material, laminate.
Background technique
In recent years, with the communication apparatus such as computer, mobile phone high performance, multifunction and the development of networking, it is
High-speed transfer and processing large capacity information, operation signal are carrying out high frequency, meanwhile, with the continuous high-tech of human lives
Skill and height informationization, information processing and information communication have become the pith of human lives, and the mankind constantly pursue information
The high speed of processing, the high integrality of phonotape and videotape transmitting, the micromation of tech electronic product and multifunction etc., with catenet work
Stand, mobile phone wireless communication, automobile satellite navigation and Bluetooth technology be representative new technique applying frequency is continuously improved, become
In high frequency or hyperfrequency field, signal transmission high frequency and high speed have the electronic circuit substrate proposition transmitted for signal
The requirement of high-frequency high-speed characteristic.Currently, PCB (printed circuit board) is copper-clad plate industry with the high speed of baseplate material, high frequency
Developing cutting edge technology, it has become for the production of raw material used in whole world PCB substrate material producer and baseplate material
The important topic of factory.
In view of this, the present invention is specifically proposed.
Summary of the invention
One of the objects of the present invention is to provide a kind of resin combinations, are unable to satisfy electronic circuit to alleviate existing resin
The technical issues of substrate high-frequency high-speed requires.
Resin combination provided by the invention, by organic solid content based on 100 parts by weight, including epoxy resin 10-90
Part and 1-50 parts of active ester curing agent；Wherein, the molecular structural formula of the active ester curing agent is as follows:
Wherein, R1、R2、R3And R4It is independently selected from alicyclic ring hydrocarbons and their derivates, the carbon atom of carbon atom number 3~20
The fatty hydrocarbons and their derivates of number 1~20, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its derivative, carbon atom number 6~20
Fragrant hydrocarbons and their derivates.
Further, the molecular structural formula of the active ester curing agent is as follows:
Wherein, the R5、R6、R7And R8Be independently selected from hydrogen atom, carbon atom number 3~20 alicyclic and its spread out
Biology, the fatty hydrocarbons and their derivates of carbon atom number 1~20, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its derivative or
The fragrant hydrocarbons and their derivates of carbon atom number 6~20.
Further, the resin combination further includes benzoxazine resin by organic solid content based on 100 parts by weight
10-90 parts.
Further, the molecular structural formula of the benzoxazine resin monomer is as follows:
The R9And R10It is independently selected from alicyclic ring hydrocarbons and their derivates, the carbon atom number 1~20 of carbon atom number 3~20
Fatty hydrocarbons and their derivates, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its fragrance of derivative, carbon atom number 6~20
Hydrocarbons and their derivates.
Further, the epoxy resin is selected from bifunctional epoxy resin, novolac epoxy resin, brominated epoxy resin and contains
At least one of phosphorus epoxy resin；
Preferably, the bifunctional epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin and cyclohexyl biphenyl
At least one of oxygen resin；
Preferably, the novolac epoxy resin is selected from phenol novolak type epoxy, o-cresol formaldehyde type epoxy resin, bis-phenol
At least one of A type novolac epoxy resin and dicyclopentadiene phenol epoxy resin；
Preferably, the phosphorous epoxy resin is DOPO and its derivative modified epoxy resin；
Preferably, the brominated epoxy resin is TBBA modified epoxy.
Further, the resin combination further includes at least one of fire retardant, curing accelerator and filler；
Preferably, by organic solid content based on 100 parts by weight, flame retardant agent content is 5-50 parts, preferably 15-30 parts；
It preferably, is phosphonium flame retardant and/or brominated flame-retardant；
Preferably, the brominated flame-retardant is selected from deca-BDE, ethyl-bis- (tetrabromo phthalimides) and ten bromines
At least one of diphenylethane；
Preferably, the phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,
- 10 phosphine phenanthrene -10- oxide of 10- dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- two
At least one of hydrogen -9- oxidation -10- phosphine phenanthrene -10- oxide, phosphate and phosphorus containing phenolic resin；
Preferably, by organic solid content based on 100 parts by weight, curing accelerator content is 0.01-1 parts, preferably
0.1-0.5 parts；
Preferably, the curing accelerator is aminated compounds；
Preferably, the aminated compounds is selected from 2-methylimidazole, 1- methylimidazole, 2-ethyl-4-methylimidazole, 2- benzene
Base imidazoles, 2- undecyl imidazole, in 2- phenyl -4-methylimidazole, 4-dimethylaminopyridine and benzyl dimethylamine at least one
Kind；
Preferably, by organic solid content based on 100 parts by weight, filer content is 10-100 parts, preferably 15-50 parts；
Preferably, the filler is selected from inorganic filler and/or organic filler；
Preferably, the inorganic filler be selected from aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia,
At least one of calcium silicates, calcium carbonate, clay, fossil and mica；
Preferably, the organic filler is nitrogenous organic filler；
Preferably, the nitrogenous organic filler is selected from least one of melamine and/or melamine cyanurate.
The second object of the present invention is to provide a kind of prepreg, including resin combination provided by the invention and base-material,
It is attached on the base-material after the resin combination impregnation is dry；
Preferably, the base-material is fabric；
Preferably, the fabric is adhesive-bonded fabric, woven or knitted fabric.
The third object of the present invention is to provide a kind of laminate, including an at least prepreg provided by the invention.
The fourth object of the present invention is to provide a kind of metal-clad laminate, including at least one provided by the invention pre-
Leaching material and the metal foil for being overlying on prepreg one or both sides.
The fifth object of the present invention is to provide a kind of printed circuit board, including resin combination provided by the invention, pre-
Leaching material, laminate or metal-clad laminate.
Resin combination provided by the invention uses epoxy resin as matrix resin, so that resin combination has well
Machining property；Using the small-molecule substance with naphthalene nucleus and multifunctional ester bond structure as active ester curing agent, so that
Resin combination dielectric loss after solidification is low, and glass transition temperature is high, while also having the function of UV-blocking, can
Meet the PCB use demand of baseplate material high speed and high frequency.
Prepreg provided by the invention is prepared using resin combination provided by the invention, not only has good machine
Tool processing performance, and dielectric loss is low, and glass transition temperature is high, while also having the function of UV-blocking, can satisfy
The use demand of PCB baseplate material high speed and high frequency.
Laminate provided by the invention is prepared using resin combination provided by the invention, not only has good machine
Tool processing performance, and dielectric loss is low, and glass transition temperature is high, while also having the function of UV-blocking, can satisfy
The use demand of PCB baseplate material high speed and high frequency.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to an aspect of the present invention, the present invention provides a kind of resin combinations, press 100 weight with organic solid content
Number meter, including 10-90 parts and 1-50 parts of active ester curing agent of epoxy resin, wherein the molecule knot of the active ester curing agent
Structure formula is as follows:
Wherein, R1、R2、R3And R4It is independently selected from alicyclic ring hydrocarbons and their derivates, the carbon atom of carbon atom number 3~20
The fatty hydrocarbons and their derivates of number 1~20, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its derivative, carbon atom number 6~20
Fragrant hydrocarbons and their derivates.
In the present invention, organic solid content refers to resin dried object, does not include auxiliary agent and filler.
In resin combination of the invention, in terms of 100 parts of organic solid content, the typical but non-limiting matter of epoxy resin
For example 10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85 or 90 parts of number of amount.
In the present invention, the usage amount of epoxy resin is 10-90 parts, if the additive amount of epoxy resin is less than 10 parts, is set
The flame retardant property and dielectric properties of oil/fat composition solidfied material are poor, if additive amount is higher than 90 parts, the water suction of resin combination solidfied material
Rate is excessively high, and humidity resistance is poor, especially when the additive amount of epoxy resin is 20-45 parts, the synthesis of resin combination solidfied material
Performance is more preferably.
Epoxy resin makes resin combination after solidification have good mechanical performance and heat resistance.
In resin combination provided by the invention, the typical but non-limiting mass fraction of active ester curing agent is for example
1,5,10,15,20,25,30,35,40,45 or 50 parts.If the additive amount of active ester curing agent less than 1 part, reduces dielectric damage
The effect of consumption is unobvious, if the additive amount of active ester curing agent is excessively more than 50 parts, active ester curing agent excessively has residual,
Resin combination Solidified enzyme can be deteriorated, especially when the additive amount of active ester curing agent is 5-20 parts, resin combination
The comprehensive performance of object solidfied material is more preferably.
The present invention uses the small-molecule substance with naphthalene nucleus and polyfunctionality ester bond structure as active ester curing agent, so that
Resin combination dielectric loss is low, and glass transition temperature is high, while also having the function of UV-blocking.
Resin combination provided by the invention uses epoxy resin as matrix resin, so that resin combination is machined
Performance；Using the small-molecule substance with naphthalene nucleus and multifunctional ester bond structure as active ester curing agent, so that the tree after solidifying
Oil/fat composition dielectric loss is low, and glass transition temperature is high, while also having the function of UV-blocking, can satisfy PCB base
The use demand of plate material high speed and high frequency.
In the preferred embodiment of the present invention, the molecular structural formula for stating active ester curing agent is as follows:
Wherein, R5、R6、R7And R8Be independently selected from hydrogen atom, carbon atom number 3~20 alicyclic ring hydrocarbons and their derivates,
The fatty hydrocarbons and their derivates of carbon atom number 1~20, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its derivative or carbon atom
The fragrant hydrocarbons and their derivates of number 6~20.
In present invention further optimization embodiment, R5、R6、R7And R8It is independently selected from hydrogen atom, carbon atom
The insatiable hunger of the alicyclic ring hydrocarbons and their derivates, the fatty hydrocarbons and their derivates, carbon atom number 2~10 of carbon atom number 1~6 of number 3~10
With the fragrant hydrocarbons and their derivates of fatty hydrocarbons and their derivates or carbon atom number 6~12.
In one embodiment of the present invention, active ester curing agent by four p-hydroxybenzene ethane and α-naphthoicacid and its
Derivative synthesis.
In the preferred embodiment of the present invention, resin combination is also wrapped by organic solid content based on 100 parts by weight
Include 10-90 parts of benzoxazine resin.
In a preferred embodiment of the invention, in resin combination, in terms of 100 parts of organic solid content, benzoxazine tree
The typical but non-limiting mass fraction for example 10 of rouge, 15,20,25,30,35,40,45,50,55,60,65,70,75,80,
85 or 90 parts.
The resistance to of resin combination solidfied material can be further increased by the way that benzoxazine resin is added in resin combination
It is hot, reduce water absorption rate.
In a preferred embodiment of the invention, the usage amount of benzoxazine resin is 10-90 parts, and additive amount is lower than 10
Part, then the water absorption rate of resin combination solidfied material is slightly higher, and heat resistance is slightly worse, if additive amount is higher than 90 parts, resin combination
Solidfied material brittleness is larger, poor in processability；Especially when the additive amount of benzoxazine resin is 15-30 parts, resin combination is solid
The processing performance of compound is more preferably.In the preferred embodiment of the present invention, the molecular structural formula of benzoxazine resin monomer
It is as follows:
The R9And R10It is independently selected from alicyclic ring hydrocarbons and their derivates, the carbon atom number 1~20 of carbon atom number 3~20
Fatty hydrocarbons and their derivates, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its fragrance of derivative, carbon atom number 6~20
Hydrocarbons and their derivates.
In the preferred embodiment of the present invention, epoxy resin is selected from difunctional epoxy resin, epoxy novolac tree
Rouge, brominated epoxy resin and at least one of with phosphorous epoxy resin.
In one embodiment of the present invention, bifunctional epoxy resin is selected from from bisphenol A type epoxy resin, Bisphenol F type ring
One or more of oxygen resin and biphenyl epoxy resin.
In one embodiment of the present invention, formaldehyde epoxy resin is selected from phenol novolak type epoxy, o-cresol formaldehyde type
One or more of epoxy resin, bisphenol A-type novolac epoxy resin and dicyclopentadiene phenol epoxy resin.
In one embodiment of the present invention, phosphorous epoxy resin is DOPO (miscellaneous -10 phospha of 9,10- dihydro-9-oxies
Luxuriant and rich with fragrance -10 oxides) and its derivative modified linear phenolic resin.In the preferred embodiment of the present invention, brominated epoxy
Resin is TBBA (tetrabromobisphenol) modified epoxy.In the preferred embodiment of the present invention, resin combination also wraps
Include at least one of fire retardant, curing accelerator and filler.
By the way that fire retardant is added in resin combination, to further increase the flame retardant effect of resin combination solidfied material.
By curing agent promotor being added in resin combination to further speed up solidification rate, curing efficiency is improved.
It can be improved the physical property effect of resin combination solidfied material by the way that filler is added in resin combination on the one hand, such as
The coefficient of expansion is reduced, reduce water absorption rate and improve thermal conductivity etc., it on the other hand also can reduce the cost of resin combination.
In the preferred embodiment of the present invention, resin combination by organic solid content based on 100 parts by weight, it is fire-retardant
Agent content is 5-50 parts, preferably 15-30 parts.
In a preferred embodiment of the invention, resin combination by organic solid content based on 100 parts by weight, fire retardant
Typical but non-limiting parts by weight for example 5,8,10,12,15,18,20,22,25,28,30,32,35,38,40,42,45,
48 or 50 parts.
In present invention further optimization embodiment, fire retardant is phosphonium flame retardant and/or brominated flame-retardant.
Brominated flame-retardant is selected from deca-BDE, ethyl-bis- (tetrabromo phthalimides) and decabromodiphenylethane
One or more of.
Phosphorus-containing composition is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy
Change -10 phosphine phenanthrene -10- oxides, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- dihydro-9-oxy -10-
One or more of phosphine phenanthrene -10- oxide, phosphate and phosphorus containing phenolic resin.In a kind of preferred embodiment of the invention, tree
For oil/fat composition by organic solid content based on 100 parts by weight, curing accelerator content is 0.01-1 parts.
In the preferred embodiment of the present invention, in resin combination, curing accelerator it is typical but non-limiting
For example 0.01,0.02,0.05,0.08,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or 1 part of mass fraction, most
Good is 0.1-0.5 parts.
In the preferred embodiment of the present invention, curing accelerator is aminated compounds.
Aminated compounds includes but is not limited to 2-methylimidazole, 1- methylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl
One of imidazoles, 2- undecyl imidazole, 2- phenyl -4-methylimidazole, 4-dimethylaminopyridine, benzyl dimethylamine are several
Kind.
In a kind of preferred embodiment of the invention, by organic solid content based on 100 parts by weight, filler contains resin combination
Amount is 10-100 parts.
In the preferred embodiment of the invention, in resin combination, the typical but non-limiting mass fraction of filler
For example 10,15,20,25,30,35,40,45,50,55,60,6,70,75,80,85,90,95 or 100 parts, most preferably 15-50
Part.
Inorganic filler is selected from aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, calcium silicates, carbonic acid
One or more of calcium, clay, fossil and mica.
Organic filler is nitrogenous organic filler, and nitrogenous organic filler is selected from melamine and/or melamine cyanurate
One or more of.
Resin combination provided by the invention can also contain various additives, as concrete example, can enumerate antioxidant,
Heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These various additives can individually make
With two or more can also being used in mixed way.
Solid content: being first put into container by the conventional production method of resin combination of the invention, and it is molten that liquid is then added
Agent adds optional filler and optional promotor, continues to stir evenly, most after stirring is completely dissolved to solid content
Glue is made to 60-80% with solvent adjustment solution solids content afterwards, especially when solid content is 65%-75%, glue
It is more advantageous to the production of subsequent prepreg.
In the preferred embodiment of the present invention, solvent is selected from acetone, butanone, cyclohexanone, ethylene glycol monomethyl ether, the third two
One or more of alcohol methyl ether, propylene glycol monomethyl ether vinegar ester etc..
According to the second aspect of the invention, the present invention provides a kind of prepregs, including resin group provided by the invention
Object and base-material are closed, is attached on base-material after resin combination impregnation is dry.
Prepreg provided by the invention is prepared using resin combination provided by the invention, not only has good machine
Tool processing performance, and dielectric loss is low, and glass transition temperature is high, while also having the function of UV-blocking, can satisfy
The use demand of PCB baseplate material high speed and high frequency.
In the preferred embodiment of the present invention, base-material is fabric.
In a more step preferred embodiment of the invention, fabric is one of adhesive-bonded fabric, woven and knitted fabric
Or it is several.
Fabric is prepared by natural fiber, synthetic fibers and inorfil.
In the preferred embodiment of the present invention, the preparation method of prepreg includes the following steps: for base-material to be impregnated with
In the glue made of resin combination, then it will be placed in heat drying in baking oven containing the base-material for being soaked with glue, can be obtained pre-
Leaching material.
According to the third aspect of the present invention, the present invention provides a kind of laminates, including at least anticipatory remark invention provides
Prepreg.
Laminate provided by the invention is prepared using resin combination provided by the invention, not only has good machine
Tool processing performance, and dielectric loss is low, and glass transition temperature is high, while also having the function of UV-blocking, can satisfy
The use demand of PCB baseplate material high speed and high frequency.
According to the fourth aspect of the present invention, the present invention provides a kind of metal-clad laminates, including an at least anticipatory remark
The prepreg provided and the metal foil for being overlying on prepreg one or both sides are provided.
Metal-clad laminate provided by the invention is prepared using resin combination provided by the invention, is not only had
Good machining property, and dielectric loss is low, and glass transition temperature is high, while also having the function of UV-blocking,
It can satisfy the PCB use demand of baseplate material high speed and high frequency.
In the preferred embodiment of the present invention, metal foil is copper foil, nickel foil, aluminium foil and SUS foil etc., and material is not
Limit.
In a kind of typical scenario of the invention, metal-clad laminate is copper-clad laminate, and preparation method includes
Following steps: first at least two panels it will be bonded together using glass fabric as prepreg made of base-material laminate is made, in layer
Pressing plate one or both sides place copper foil, then put laminate and the copper foil placed into laminating machine, by being heated and pressurizeed solidification
Molding, makes to be bonded together between prepreg and copper foil between prepreg, so that copper-clad laminate be made.
Lamination is as follows:
(1) heating rate of the heating rate being laminated usually at 80-160 degrees Celsius of material temperature should be controlled 1.0~3.0
℃/min；
(2) the pressure setting being laminated, outer layer material temperature apply full pressure at 80~100 DEG C, and full pressure pressure is 300psi or so；
(3) when solidifying, material temperature is controlled at 185 DEG C, and keep the temperature 90min.
According to the fifth aspect of the present invention, the present invention provides a kind of printed circuit boards, including tree provided by the invention
Oil/fat composition, prepreg, laminate or metal-clad laminate.
Printed circuit board provided by the invention is prepared using resin combination provided by the invention, has high-vitrification
Transition temperature, high-modulus, low-dielectric loss factor, high humidity resistance, low water absorption and good anti-flammability, processing performance and
Chemical-resistance.
Technical solution provided by the invention is further described below with reference to embodiment and comparative example.
Details are as follows for each component used in Examples and Comparative Examples:
(A) benzoxazine resin, monomer have the following structure:
(B) poly epoxy resin
(B-1) (marque TER530K75, epoxide equivalent 300g/eq, Guangdong has phosphorous epoxy resin with space new material
Limit company production)
(B-2) Study On O-cresol Epoxy Resin (marque NC-3000, epoxide equivalent 280g-eq, Japanese chemical drug company
Production)
(C) curing agent
(C-1) active ester curing agent has the following structure:
(C-2) active ester curing agent has the following structure:
(C-3) phenylethylene-maleic anhydride oligomer (marque: SMA-EF40, the production of U.S.'s Sartomer Company)
(D) fire retardant
(D-1) deca-BDE (production of Albemarle Corporation of the U.S.)
(D-2) PX-200 (the big eight chemical companies production of Japan)
(E) curing accelerator
2-methylimidazole (Japanese four countries' chemical conversion)
(F) filler
Ball-shaped silicon micro powder (average grain diameter is 1 to 10 μm, 99% or more purity)
The concrete composition of embodiment 1-8 and comparative example 1-3 are as shown in table 1, and hereinafter without special instruction, part represents weight
Part, % represents " wt% ".
The composition data table of 1 resin combination of table
Embodiment 9
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R1、R2、R3And R4It is ethyl.
Embodiment 10
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R1、R2、R3And R4It is allyl.
Embodiment 11
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R1、R2、R3And R4It is phenyl.
Embodiment 12
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R5、R6、R7And R8It is cyclopropyl.
Embodiment 13
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R5、R6、R7And R8It is diisoamyl.
Embodiment 14
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R5、R6、R7And R8It is pentenyl.
Embodiment 15
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R5、R6、R7And R8It is benzene butyl.
Embodiment 16
Present embodiments provide a kind of resin combination, the present embodiment and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R5、R6、R7And R8It is naphthylethyl.
Comparative example
This comparative example provides a kind of resin combination, this comparative example and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, R is methyl, n 2.
Comparative example 5
This comparative example provides a kind of resin combination, this comparative example and embodiment 8 the difference is that, active ester is solid
Agent has the following structure:
Wherein, X is phenyl ring, and k and j are 1, n 2.
Embodiment 1-16 and comparative example the 1-5 resin combination provided are prepared into copper-clad laminate, specifically include as
Lower step:
(1) resin combination is dissolved in acetone, resin adhesive liquid is made；
(2) glass fabric is immersed in resin adhesive liquid, obtains putting it into containing the glass fabric for being soaked with resin adhesive liquid
It is dried in baking oven, obtains prepreg；
(3) laminate is made in two prepreg bondings；
(4) eight laminates and two copper foils are overlapped, is laminated by hot press, so that two-sided copper foil covered lamination be made
Plate.
Test example 1
The obtained copper-clad laminate of embodiment 1-16 and comparative example 1-5 is subjected to glass transition temperature, removing by force
Degree, flammability, thermally stratified layer time, thermal expansion coefficient, thermal decomposition temperature, dielectric loss and punching test, as a result such as 2 institute of table
Show.
2 copper-clad laminate performance data table of table
The test method of above-mentioned copper-clad laminate characteristic is as follows:
(1) glass transition temperature (Tg): according to differential scanning calorimetry (DSC), according to IPC-TM-6502.4.25 institute
Defined DSC method is measured.
(2) it flammability: is measured according to 94 vertical combustion of UL.(3) thermally stratified layer time T-300: according to IPC-TM-
6502.4.24.1 method is measured.
(4) it thermal expansion coefficient Z axis CTE (TMA): is measured according to IPC-TM-6502.4.24. method.
(5) it thermal decomposition temperature Td: is measured according to IPC-TM-6502.4.26 method.
(6) it dielectric constant and dielectric loss factor: is measured under 1GHz according to IPC-TM-6502.5.5.9.
(7) it UV transmitance: is measured according to IEC1189-2C11 method.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of resin combination, which is characterized in that by organic solid content based on 100 parts by weight, including epoxy resin 10-90
Part and 1-50 parts of active ester curing agent；Wherein, the molecular structural formula of the active ester curing agent is as follows:
Wherein, R1、R2、R3And R4Be independently selected from the alicyclic ring hydrocarbons and their derivates of carbon atom number 3~20, carbon atom number 1~
The virtue of 20 fatty hydrocarbons and their derivates, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its derivative, carbon atom number 6~20
Fragrant hydrocarbons and their derivates.
2. resin combination according to claim 1, which is characterized in that the molecular structural formula of the active ester curing agent is such as
Under:
Wherein, the R5、R6、R7And R8Be independently selected from hydrogen atom, carbon atom number 3~20 alicyclic ring hydrocarbons and their derivates,
The fatty hydrocarbons and their derivates of carbon atom number 1~20, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its derivative or carbon atom
The fragrant hydrocarbons and their derivates of number 6~20.
3. resin combination according to claim 1, which is characterized in that by organic solid content based on 100 parts by weight, also
Including 10-90 parts of benzoxazine resin.
4. resin combination according to claim 3, which is characterized in that the molecular structure of the benzoxazine resin monomer
Formula is as follows:
The R9And R10It is independently selected from the alicyclic ring hydrocarbons and their derivates of carbon atom number 3~20, the rouge of carbon atom number 1~20
Fat hydrocarbons and their derivates, the unsaturated aliphatic hydrocarbon of carbon atom number 2~20 and its derivative, carbon atom number 6~20 aromatic hydrocarbon and
Its derivative.
5. resin combination according to claim 1-4, which is characterized in that the epoxy resin is selected from difunctionality
At least one of epoxy resin, novolac epoxy resin, brominated epoxy resin and phosphorous epoxy resin；
Preferably, the bifunctional epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin and biphenyl epoxy
At least one of rouge；
Preferably, the novolac epoxy resin is selected from phenol novolak type epoxy, o-cresol formaldehyde type epoxy resin, bisphenol A-type
At least one of novolac epoxy resin and dicyclopentadiene phenol epoxy resin；
Preferably, the phosphorous epoxy resin is selected from DOPO and its derivative modified epoxy resin；
Preferably, the brominated epoxy resin is TBBA modified epoxy.
6. resin combination according to claim 1-4, which is characterized in that further include fire retardant, solidification promotion
At least one of agent and filler；
Preferably, by organic solid content based on 100 parts by weight, flame retardant agent content is 5-50 parts, preferably 15-30 parts；It is preferred that
Ground, fire retardant are phosphonium flame retardant and/or brominated flame-retardant；Preferably, the brominated flame-retardant is selected from deca-BDE, second
At least one of base-bis- (tetrabromo phthalimides) and decabromodiphenylethane；
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- aoxidizes -10 phosphine phenanthrene -10- oxides, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- dihydro -9-
At least one of oxidation -10- phosphine phenanthrene -10- oxide, phosphate and phosphorus containing phenolic resin；
Preferably, by organic solid content based on 100 parts by weight, curing accelerator content is 0.01-1 parts, preferably 0.1-0.5
Part；
Preferably, the curing accelerator is aminated compounds；
Preferably, the aminated compounds is selected from 2-methylimidazole, 1- methylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl miaow
At least one of azoles, 2- undecyl imidazole, 2- phenyl -4-methylimidazole, 4-dimethylaminopyridine and benzyl dimethylamine；
Preferably, by organic solid content based on 100 parts by weight, filer content is 10-100 parts, preferably 15-50 parts；
Preferably, the filler is selected from inorganic filler and/or organic filler；
Preferably, the inorganic filler is selected from aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, silicic acid
At least one of calcium, calcium carbonate, clay, fossil and mica；
Preferably, the organic filler is nitrogenous organic filler；
Preferably, the nitrogenous organic filler is selected from least one of melamine and/or melamine cyanurate.
7. a kind of prepreg, which is characterized in that described including resin combination described in any one of claims 1-6 and base-material
It is attached on the base-material after resin combination impregnation is dry；
Preferably, the base-material is fabric；
Preferably, the fabric is adhesive-bonded fabric, woven or knitted fabric.
8. a kind of laminate, which is characterized in that including an at least prepreg as claimed in claim 7.
9. a kind of metal-clad laminate, which is characterized in that including an at least prepreg as claimed in claim 7 and be overlying on pre-
The metal foil of leaching material one or both sides.
10. a kind of printed circuit board, which is characterized in that wanted including resin combination described in any one of claims 1-6, right
Prepreg described in asking 7, laminate according to any one of claims 8 or metal-clad laminate as claimed in claim 9.
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| WO2020155291A1 (en) * | 2019-01-30 | 2020-08-06 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg containing same, metal foil-clad laminate and printed circuit board |
| US20230212038A1 (en) * | 2022-01-05 | 2023-07-06 | Access Business Group International Llc | Water treatment system |
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