CN105399927A - Epoxy resin curing agent and preparation method and application thereof - Google Patents
Epoxy resin curing agent and preparation method and application thereof Download PDFInfo
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- CN105399927A CN105399927A CN201510934698.9A CN201510934698A CN105399927A CN 105399927 A CN105399927 A CN 105399927A CN 201510934698 A CN201510934698 A CN 201510934698A CN 105399927 A CN105399927 A CN 105399927A
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- epoxy resin
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- curing agent
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—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
- B32B15/04—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention relates to an epoxy resin curing agent and a preparation method and an application thereof. The epoxy resin curing agent has the molecular structure represented by the formula I. Through adopting of the specific-structure epoxy resin curing agent, a resin composition formed by the curing agent has good low-dielectric properties; cured products have low dielectric constant and dielectric loss, have good heat resistance, and are environmental-protection environmental-friendly type low-dielectric materials having greater economic property.
Description
Technical field
The invention belongs to dielectric materials technical field, particularly relate to a kind of epoxy curing agent and its production and use.
Background technology
The electronic product being representative with mobile phone, computer, pick up camera, electronic game machine, the various products used be representative family expenses, office electric equipment products and the other field such as air-conditioning, refrigerator, television image, sound equipment articles for use, in order to safety, very most product all requires that it possesses low-dielectric and thermotolerance.
With regard to electrical properties, the factor mainly need considered also comprises specific inductivity and the dielectric loss of material.Generally speaking, because the square root of the signal transfer rate of substrate and the specific inductivity of baseplate material is inversely proportional to, therefore the specific inductivity of baseplate material is usually the smaller the better; On the other hand, represent the loss that signal transmits because dielectric loss is less fewer, therefore the transmission quality that the less material of dielectric loss can provide is also comparatively good.
Therefore, how developing the material with low-k and low-dielectric loss, and be applied to the manufacture of high frequency printed circuit board, is the problem that solution is desired most ardently in present stage printed circuit board material field.
Summary of the invention
In view of this, first aspect present invention provides a kind of epoxy curing agent, and this epoxy curing agent has low-dielectric, and has good thermotolerance, and this epoxy curing agent has the low advantage of cost.
To achieve these goals, present invention employs following technical scheme:
A kind of epoxy curing agent, it has such as formula the molecular structure shown in I:
In formula I, R is any organic group meeting its chemical environment, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8and R
9independently for meeting any organic group of its chemical environment, n be more than or equal to zero integer.Such as n can be 0,1,2,3,4,5,6,7,8,9,10 etc., is preferably 1-6.
In the present invention, describedly meet its chemical environment and refer to that the atom that can be adjacent is connected, obtain stable chemical connecting key.
In the present invention, in formula I
in segment portion, be connected with oxygen two the position of substitution on phenyl ring can be contraposition, ortho position or a position, position between being preferably.
That is, preferably, described epoxy curing agent has as shown in the formula the molecular structure shown in II:
In formula II, R is any organic group meeting its chemical environment, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8and R
9independently for meeting any organic group of its chemical environment, n be more than or equal to zero integer.
Preferably, R be replace or unsubstituted straight or branched alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted heteroaryl, replacement or unsubstituted alkylaryl, replacement or unsubstituted cycloalkylaryl, replacement or unsubstituted miscellaneous alkyl aryl or replacement or any one in unsubstituted miscellaneous alkyl aryl.
Particularly, R can be but be not limited to-CH
2cH
2-,-CH
2cH
2cH
2-,
Preferably, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8and R
9be H independently, replace or unsubstituted straight or branched alkyl, replace or unsubstituted cycloalkyl, replace or unsubstituted aryl, replace or unsubstituted heteroaryl, replace or unsubstituted alkylaryl, replace or unsubstituted cycloalkylaryl, replace or unsubstituted miscellaneous alkyl aryl, replace or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkoxyl group, replace or unsubstituted cycloalkyloxy, replace or unsubstituted aryloxy, replace or unsubstituted heteroaryl oxygen base, replace or unsubstituted alkoxy aryl, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkyl heteroaryloxy, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, the combination of any one or at least two kinds in substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
In the present invention, described substituting group is not containing any organic group of halogen, such as alkyl, cycloalkyl, alkoxyl group, changes alkoxyl group, aryl, heteroaryl, alkylaryl, heteroarylalkyl, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group.
Particularly, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8and R
9can be independently but be not limited to-CH
3,-CH
2cH
3,-OCH
3,-OCH
2cH
3,
or-OOCCH
3in the combination of any one or at least two kinds.
Preferably, R
6, R
7, R
8and R
9be asynchronously H, preferred R further
6, R
7, R
8and R
9in be H when at least both are different.
In the present invention, substituted or unsubstituted straight or branched alkyl is preferably substituted or unsubstituted C1 ~ C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight or branched alkyl, preferred C1 ~ C8 straight chained alkyl or branched-chain alkyl further, methyl is when carbonatoms is 1, when carbonatoms is 2, be ethyl.
Substituted or unsubstituted cycloalkyl is preferably the cycloalkyl of substituted or unsubstituted C3 ~ C12 (such as C4, C5, C6, C7, C8, C9, C10 or C11).
Replace or unsubstituted alkoxyl group is preferably the alkoxyl group of substituted or unsubstituted C1 ~ C12 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11).
Replace or unsubstituted cycloalkyloxy is preferably the cycloalkyloxy of substituted or unsubstituted C3 ~ C12 (such as C4, C5, C6, C7, C8, C9, C10 or C11).
Substituted or unsubstituted aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylaryl.Be preferably phenyl, naphthyl,
deng.The example of phenyl comprises xenyl, terphenyl, phenmethyl, styroyl or hydrocinnamyl etc.
Substituted or unsubstituted heteroaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaralkyl, is preferably five yuan or six membered heteroaryl, that more preferably replace or unsubstituted furyl or pyridyl.
Substituted or unsubstituted miscellaneous alkyl aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) miscellaneous alkyl aryl.
Substituted or unsubstituted aryloxy is preferably C7-C13 (such as C8, C9, C10, C11 or C12) aryloxy.
Substituted or unsubstituted heteroaryl oxygen base is preferably C5-C13 (such as C6, C7, C8, C9, C10, C11 or C12) heteroaryl oxygen base.
Replace or unsubstituted alkoxy aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkoxy aryl.
Substituted or unsubstituted alkyl-aryloxy is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12) alkyl-aryloxy.
Substituted or unsubstituted alkyl heteroaryloxy is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12) alkyl heteroaryloxy.
Term used in the present invention " replacement " refers to that any one or more hydrogen atoms on specified atom are selected from the substituting group replacement of designated groups, and condition is that described specified atom is no more than normal valency, and the result replaced produces stable compound.When substituting group be oxo group or ketone group (namely=O) time, 2 hydrogen atoms so on atom are substituted.Ketone substituting group does not exist on aromatic nucleus." stable compound " refers to and can from reaction mixture, be separated to effective purity enough con vigore and be mixed with compounds effective.
Preferably, epoxy curing agent of the present invention is the combination with a kind of in the compound of following structure or at least two kinds:
n be more than or equal to zero integer.Such as n can be 0,1,2,3,4,5,6,7,8,9,10 etc., is preferably 1-6.
On the other hand, the invention provides a kind of preparation method of described epoxy curing agent, the epoxy curing agent prepared by the method has low-dielectric, and has good heat resistance and mechanical property.
Prepare the method that above-mentioned ester class states epoxy curing agent, phenolic compound and polybasic acid compound or polynary chloride compounds are reacted and prepares described epoxy curing agent.
Polynary chloride compounds refers to binary acyl chlorides or the above chloride compounds of binary in the present invention, and described polybasic acid compound refers to diprotic acid or the above acid compound of binary.Such as typical, in the present invention, utilize phenolic compound and diacid compound to carry out esterification, with the vitriol oil or solid acid as catalyst, be obtained by reacting corresponding esters.Phenolic compound and acyl chloride reaction can also be utilized to remove hydrogenchloride to obtain corresponding esters.
The manufacture method of ester based epoxy resin curing agent of the present invention is the manufacture method of known ester class, the present invention is to this and not specially provided for, such as, in diprotic acid under melting or dissolved state or polybasic acid compound, use sulfuric acid, phosphoric acid, catalyzer is used as by the dewatering agent that solid acidifying compound etc. are conventional, or replace diprotic acid or polyprotonic acid with the polynary chloride compounds of binary acyl chlorides, use known dehydrochlorination catalyzer under certain temperature condition, while stir, while add aldehydes matter, after dehydration polymerization has reacted, desolventizing is gone out by physical method, by product or other impurity, new rule ester based epoxy resin compound of the present invention can be obtained.
Phenolic compound refers to and has R in formula I
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8or R
9phenolic compound corresponding to substituent phenyl ring, such as, with R
1or R
2phenolic compound corresponding to substituent phenyl ring is dihydroxy-benzene, such as, work as R
1during for methyl, with R
1phenolic compound corresponding to substituent phenyl ring can be Resorcinol, pyrocatechol or Resorcinol.With R
3or R
4phenolic compound corresponding to substituent phenyl ring is
described diprotic acid refers to and the diprotic acid corresponding to the carboxylic acid ester groups with R substituent in formula I, HOOC-R-COOH can be expressed as, described binary chloride compounds refers to and the binary acyl chlorides corresponding to the carboxylic acid ester groups with R substituent in formula I, be ClOC-R-COCl, described phenolic compound and diprotic acid or binary chloride compounds generation condensation reaction, generate ester, thus obtain epoxy curing agent shown in formula I.Described reaction and the required condition of reaction are well-known to those skilled in the art.
On the other hand, the invention provides a kind of composition epoxy resin with low-dielectric, good heat resistance, good mechanical property.
This composition epoxy resin comprises epoxy resin and above-described epoxy curing agent.
Preferably, described epoxy resin is the combination of a kind of in liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin, bisphenol-s epoxy resin, acyclic isoprenoid type epoxy resin or biphenyl type epoxy resin or at least two kinds.
Preferably, described composition epoxy resin also comprises curing catalyst.
Preferably, described curing catalyst is the mixture of any one or at least two kinds in imidazoles curing catalyst, organic phosphine curing catalyst or tertiary amine curing catalyst.
Preferably, described composition epoxy resin also comprises mineral filler.
Preferably, described mineral filler is selected from the mixture of any one or at least two kinds in aluminium hydroxide, boehmite, silicon-dioxide, talcum powder, mica, barium sulfate, zinc sulfide white, calcium carbonate, wollastonite, kaolin, brucite, diatomite, wilkinite or pumice sand.
Preferably, described composition epoxy resin also comprises fire retardant.The organic fire-retardant that described fire retardant is known in the art and/or inorganic combustion inhibitor.
Above-mentioned epoxy curing agent can make plastic cement and pre-impregnated sheet according to actual needs.
A kind of plastic cement, it comprises composition epoxy resin of the present invention.
A kind of pre-impregnated sheet, it is by composition epoxy resin impregnation described above or coat base material and form.
Base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material etc.
Here, the concrete technology condition of its impregnation or coating is not particularly limited." bonding sheet " that " pre-impregnated sheet " is also well known to those skilled in the art.
A kind of composite metal substrate, it comprises more than one as above-mentioned pre-impregnated sheet carries out surperficial metal-clad overlap successively, pressing forms.
Here, the material of surperficial metal-clad is the alloy of aluminium, copper, iron and arbitrary combination thereof.
The specific examples of composite metal substrate has CEM-1 copper-clad plate, CEM-3 copper-clad plate, FR-4 copper-clad plate, FR-5 copper-clad plate, CEM-1 aluminium base, CEM-3 aluminium base, FR-4 aluminium base or FR-5 aluminium base.
A kind of wiring board, the surface working circuit in above-mentioned composite metal substrate forms.
The raw material of composition epoxy resin is by being solidificated in coating composite metal substrate being formed and has good low-dielectric energy, can wiring board be improved, such as electronic industry, electrically, Electric Industrial, communications and transportation, aerospace, toy industry etc. need the widespread use of the industry such as machine, equipment, instrument, instrument of wiring board.
Above-mentioned term " ××× base or group " refers to slough in ××× molecular structure of compounds remaining part after one or more hydrogen atom or other atom or atomic group.
The present invention is by adopting the epoxy curing agent of ad hoc structure, make consisting of resin combination there is good low-dielectric energy, its cured article has low specific inductivity and dielectric loss, good thermotolerance and mechanical property are a kind of dielectric materials also with larger economy and environmental protection friendly.The specific inductivity (1GHz) of the copper-clad plate adopting this resin combination to obtain is 3.28-3.31, dielectric loss (1GHz) for 0.005-0.006, Tg can reach 158 DEG C and more than, T-stripping strength can reach 1.96kg/mm
2and more than, interlaminar strength can reach 1.63kg/mm
2and more than, saturated water absorption can reach less than 0.34%.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
In the examples below, raw materials used all purchase by business obtains.
Embodiment 1
The epoxy curing agent of the present embodiment has following structure:
Preparation method is as follows:
2 are added in the 1000mL glass reactor of agitator, 6-dimethyl Resorcinol 1mol, take methylene dichloride as solvent, stirring and dissolving, the vitriol oil of instillation 3mL98% is as catalyzer, then slowly drip the dichloromethane solution of terephthalic acid (1.1mol), dropwise, at room temperature stirring reaction 10 hours, then add the adjacent xylenol of 1.1mol, continue stirring reaction 8 hours, with by product in the method removing system of physics, evaporating solvent, obtain the object 100g that ester equivalent is 100g/eq, by this object called after epoxy curing agent A.
Characterized the epoxy curing agent A obtained by proton nmr spectra, result is as follows:
1hNMR (CDCl
3, 500MHz): δ ppm6.92-6.96 (m,
hydrogen on phenyl ring), 6.81-6.83 (m,
hydrogen on phenyl ring), 2.32 (s, CH
3).
The position of infrared spectrum characteristic peak: ester carbonyl group 1730-1740cm
-1, the C-O-C1200cm of ester group
-1, ortho position substituted benzene ring 750cm
-1, para-orientation phenyl ring 860-790cm
-1, the absorption peak 2995cm of methyl
-1.
Utilize this epoxy curing agent and other component component epoxy compositions, and make copper-clad plate, step is as follows:
Epoxy equivalent (weight) 187g/eq bisphenol A epoxide resin 100g, epoxy equivalent (weight) are the o-cresol formaldehyde epoxy resin 100g of 120g/eq, add above-mentioned epoxy curing agent 136g, curing catalyst DBU0.1g.Adopt this composition epoxy resin to obtain the standard copper-clad plate sample meeting the standard such as GB, UL according to general copper-clad plate production process, called after a copper-clad plate, the performance of test a copper-clad plate, its result represents in table-1.
Embodiment 2
The epoxy curing agent of the present embodiment has following structure:
Preparation method is as follows:
2 are added in the 1000mL glass reactor of agitator, 3-dimethyl Resorcinol 1mol, stirring and dissolving, the vitriol oil of instillation 3mL98% is as catalyzer, then slowly drip 2,3-dimethyl terephthaldehyde formic acid 1.1mol, dropwise, at room temperature stirring reaction 15 hours, then add the adjacent xylenol of 1.2mol, continue stirring reaction 6 hours, with by product, evaporating solvent in the method removing system of physics, obtain the object 180g that ester equivalent is 180g/eq, by this object called after epoxy curing agent B.
Characterized the epoxy curing agent B obtained by proton nmr spectra, result is as follows:
1hNMR (CDCl
3, 500MHz): δ ppm7.7-7.9 (m,
hydrogen on middle phenyl ring), 6.91-6.94 (m,
with
hydrogen on middle phenyl ring), 2.32 (s, CH
3).
The position of infrared spectrum characteristic peak: ester carbonyl group 1730-1740cm
-1, the C-O-C1200cm of ester group
-1, ortho position substituted benzene ring 750cm
-1, para-orientation phenyl ring 860-790cm
-1, the absorption peak 2995cm of methyl
-1.
Utilize this epoxy curing agent and other component component epoxy compositions, and make copper-clad plate, step is as follows:
Epoxy equivalent (weight) 187g/eq bisphenol A epoxide resin 100g, epoxy equivalent (weight) are the o-cresol formaldehyde epoxy resin 100g of 120g/eq, add above-mentioned epoxy curing agent 245g, curing catalyst DBU0.1g.Adopt this composition epoxy resin to obtain the standard copper-clad plate sample meeting the standard such as GB, UL according to general copper-clad plate production process, called after b copper-clad plate, the performance of test b copper-clad plate, its result represents in table-1.
Embodiment 3
The epoxy curing agent of the present embodiment has following structure:
Preparation method is as follows:
2 are added in the 1000mL glass reactor of agitator, 6-2-methoxyhydroquinone 1mol, stirring and dissolving, the vitriol oil of instillation 3mL98% is as catalyzer, then under ice-water bath, slowly drip 2,3-dimethyl p-phthaloyl chloride 1.1mol, dropwise, at room temperature stirring reaction 10 hours, then adds 1.1mol3,5-xylenol, continue stirring reaction 6 hours, with by product, evaporating solvent in the method removing system of physics, obtain the object 200g that ester equivalent is 200g/eq, by this object called after epoxy curing agent C.
Characterized the epoxy curing agent obtained by proton nmr spectra, result is as follows:
1hNMR (CDCl
3, 500MHz): δ ppm7.7-7.9 (m,
hydrogen on middle phenyl ring), 6.8-7.0 (m,
hydrogen on phenyl ring in group), 6.29 (m,
benzene ring hydrogen in group), 3.74 (m,
hydrogen in group on methyl), 2.35 (s,
with
hydrogen on methyl in group).
The position of infrared spectrum characteristic peak: ester carbonyl group 1730-1740cm
-1, the C-O-C1200cm of ester group
-1, ortho position substituted benzene ring 750cm
-1, para-orientation phenyl ring 860-790cm
-1, the absorption peak 2995cm of methyl
-1.
Utilize this epoxy curing agent and other component component epoxy compositions, and make copper-clad plate, step is as follows:
Epoxy equivalent (weight) 187g/eq bisphenol A epoxide resin 100g, epoxy equivalent (weight) are the o-cresol formaldehyde epoxy resin 100g of 120g/eq, add above-mentioned epoxy curing agent 272g, curing catalyst DBU0.1g.Adopt this composition epoxy resin to obtain the standard copper-clad plate sample meeting the standard such as GB, UL according to general copper-clad plate production process, called after c copper-clad plate, the performance of test c copper-clad plate, its result represents in table-1.
Comparative example 1
In this comparative example, utilize the linear phenolic resin of conventional phenolic hydroxyl equivalent 105g/eq to carry out alternative epoxy curing agent of the present invention as solidifying agent, method identical in embodiment 1 is utilized to prepare copper-clad plate d, the performance of test d copper-clad plate, its result represents in table-1.
Comparative example 2
The epoxy equivalent (weight) getting market sale is the MDI modified epoxy 100g of 380.0g/eq, add the resin compound 57.9g had such as formula (1) structure, ester equivalent is 220, with the pyridine of 0.2g, solution is become with suitable acetone solution, with staple glass fiber cloth, make copper-clad plate in a known manner, by this copper-clad plate called after copper-clad plate e.Record the performance of copper-clad plate e as shown in Table-1.
The test result of embodiment and comparative example is as shown in following table-1 (in view of concrete testing method is well known to those skilled in the art, no longer describing in detail method at this).
Table-1
As can be seen from Table 1, the resin combination that the present invention adopts the compound containing the molecular structure shown in formula I to prepare as solidifying agent, the specific inductivity (1GHz) making the copper-clad plate prepared by it is 3.28-3.31, dielectric loss (1GHz) is 0.005-0.006, Tg can reach 158 DEG C and more than, T-stripping strength can reach 1.96kg/mm
2and more than, interlaminar strength can reach 1.63kg/mm
2and more than, saturated water absorption can reach less than 0.34%, is obviously better than the performance of comparative example copper-clad plate.
Applicant states, the present invention illustrates epoxy curing agent of the present invention and its production and use by above-described embodiment, but the present invention is not limited to above-described embodiment, does not namely mean that the present invention must rely on above-described embodiment and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. an epoxy curing agent, is characterized in that, it has such as formula the molecular structure shown in I:
In formula I, R is any organic group meeting its chemical environment, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8and R
9independently for H or meet any organic group of its chemical environment, n be more than or equal to zero integer.
2. epoxy curing agent according to claim 1, is characterized in that, described epoxy curing agent has as shown in the formula the molecular structure shown in II:
In formula II, R is any organic group meeting its chemical environment, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8and R
9independently for H or meet any organic group of its chemical environment, n be more than or equal to zero integer.
3. epoxy curing agent according to claim 1 and 2, it is characterized in that, R be replace or unsubstituted straight or branched alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted heteroaryl, replacement or unsubstituted alkylaryl, replacement or unsubstituted cycloalkylaryl, replacement or unsubstituted miscellaneous alkyl aryl or replacement or any one in unsubstituted miscellaneous alkyl aryl;
Preferably, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8and R
9be H independently, replace or unsubstituted straight or branched alkyl, replace or unsubstituted cycloalkyl, replace or unsubstituted aryl, replace or unsubstituted heteroaryl, replace or unsubstituted alkylaryl, replace or unsubstituted cycloalkylaryl, replace or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkoxyl group, replace or unsubstituted cycloalkyloxy, replace or unsubstituted aryloxy, replace or unsubstituted heteroaryl oxygen base, replace or unsubstituted alkoxy aryl, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkyl heteroaryloxy, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, the combination of any one or at least two kinds in substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group,
Preferably, R
6, R
7, R
8and R
9be asynchronously H, preferred R further
6, R
7, R
8and R
9in be H when at least both are different.
4. the epoxy curing agent according to any one of claim 1-3, is characterized in that, described epoxy curing agent is the combination with a kind of in the compound of following structure or at least two kinds:
n be more than or equal to zero integer.
5. a composition epoxy resin, is characterized in that, described composition epoxy resin comprises epoxy resin and the epoxy curing agent according to any one of claim 1-4;
Preferably, described epoxy resin is the combination of a kind of in liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol f type epoxy resin, bisphenol-s epoxy resin, acyclic isoprenoid type epoxy resin or biphenyl type epoxy resin or at least two kinds;
Preferably, described composition epoxy resin also comprises curing catalyst;
Preferably, described curing catalyst is the mixture of any one or at least two kinds in imidazoles curing catalyst, organic phosphine curing catalyst or tertiary amine curing catalyst;
Preferably, described composition epoxy resin also comprises mineral filler;
Preferably, described composition epoxy resin also comprises fire retardant.
6. a pre-impregnated sheet, is characterized in that, it is by composition epoxy resin impregnation as claimed in claim 5 or coat base material and form.
7. pre-impregnated sheet according to claim 6, is characterized in that, described base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material.
8. a composite metal substrate, is characterized in that, it comprises more than one, and pre-impregnated sheet carries out surperficial metal-clad successively as claimed in claims 6 or 7, overlap, pressing form.
9. composite metal substrate according to claim 8, is characterized in that, the material of described surperficial metal-clad is the alloy of aluminium, copper, iron and arbitrary combination thereof;
Preferably, described composite metal substrate is CEM-1 copper-clad plate, CEM-3 copper-clad plate, FR-4 copper-clad plate, FR-5 copper-clad plate, CEM-1 aluminium base, CEM-3 aluminium base, FR-4 aluminium base or FR-5 aluminium base.
10. a wiring board, is characterized in that, the surface working circuit in the composite metal substrate described in claim 8 or 9 forms.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510934698.9A CN105399927A (en) | 2015-12-15 | 2015-12-15 | Epoxy resin curing agent and preparation method and application thereof |
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| CN201510934698.9A CN105399927A (en) | 2015-12-15 | 2015-12-15 | Epoxy resin curing agent and preparation method and application thereof |
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| CN105399927A true CN105399927A (en) | 2016-03-16 |
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| CN201510934698.9A Pending CN105399927A (en) | 2015-12-15 | 2015-12-15 | Epoxy resin curing agent and preparation method and application thereof |
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| CN105542128A (en) * | 2015-12-15 | 2016-05-04 | 广东广山新材料有限公司 | Curing agent for epoxy resin as well as preparation method and application thereof |
| CN109608828A (en) * | 2018-12-20 | 2019-04-12 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it |
| CN109651763A (en) * | 2018-12-25 | 2019-04-19 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it |
| CN109694462A (en) * | 2018-12-26 | 2019-04-30 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, metal-clad laminate and printed circuit board using it |
| CN109851997A (en) * | 2018-12-25 | 2019-06-07 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it |
| JP2019112557A (en) * | 2017-12-25 | 2019-07-11 | 積水化学工業株式会社 | Resin material and multilayer printed board |
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| CN109651763A (en) * | 2018-12-25 | 2019-04-19 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it |
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| CN109851997B (en) * | 2018-12-25 | 2020-10-27 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same |
| CN109694462A (en) * | 2018-12-26 | 2019-04-30 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, metal-clad laminate and printed circuit board using it |
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Address after: 523000 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building on the third floor Applicant after: Guangdong Guang Shan new materials Limited by Share Ltd Address before: 523990 Dongguan Port Road, Guangdong (Sha Tianduan) Humen port service center, Humen port service building 3F Applicant before: GUANG SHAN NEW MATERIALS CO., LTD. |
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