CN103664834B - Epoxy monomer of a kind of thermal destruction and preparation method thereof and underfill material - Google Patents
Epoxy monomer of a kind of thermal destruction and preparation method thereof and underfill material Download PDFInfo
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- CN103664834B CN103664834B CN201310574404.7A CN201310574404A CN103664834B CN 103664834 B CN103664834 B CN 103664834B CN 201310574404 A CN201310574404 A CN 201310574404A CN 103664834 B CN103664834 B CN 103664834B
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- 0 CCC1NC1*C(C)(C)OC(*C(OC(C)(C)C(C1)C1C1C(C)*1)=N)=C Chemical compound CCC1NC1*C(C)(C)OC(*C(OC(C)(C)C(C1)C1C1C(C)*1)=N)=C 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
Abstract
The present invention relates to epoxy monomer of a kind of thermal destruction and preparation method thereof and underfill material.The structural formula of the epoxy monomer of this thermal destruction is
r be carbonatoms be less than 10 alkyl, alkylene, phenyl, naphthyl and anthryl; R ˊ is structural formula
group, carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10, R ˊ ˊ is hydrogen, phenyl, carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10.The epoxy monomer of this thermal destruction at high temperature can decomposes, when using the underfill material temperature of the epoxy monomer of this thermal destruction to be elevated to 200 ~ 240 DEG C, the epoxy monomer decomposes of thermal destruction, underfill material cohesive strength significantly declines, thus chip can be extractd from substrate, realize Rework Technics.Thus, going back unmodified resin and can preparing the underfill material with reworkable characteristic of this thermal destruction is used.
Description
Technical field
The present invention relates to electronic package material technology, particularly relate to epoxy monomer of a kind of thermal destruction and preparation method thereof and underfill material.
Background technology
In modern electronic product, Electronic Encapsulating Technology is the bridge between large-scale integrated circuit and electronic devices and components.For realizing higher Electronic Performance and packaging density in limited space, flip chip technology (fct) should need as an indispensable encapsulation technology and give birth to, and become hyundai electronics encapsulate in focus technology.Compared with the Wire Bonding Technology that conventional speed is slower, flip chip technology (fct) is more suitable for being applied in the product of high pin number, miniaturization, multi-functional, high-speed trend unicircuit.And the use of flip chip technology (fct), one of its emphasis is the research and preparation of underfill material.Underfill material is the key material of connection substrate and electronic devices and components.
To the research and preparation of underfill material be in recent years electronic package material research in an emphasis.In the underfill material of routine, epoxy resin is an important component part.Epoxy resin has preferably processing and use properties, as good thermostability, lower molding shrinkage, extremely low rate of moisture absorption, preferably erosion resistance and good cohesive strength etc.
But, in industrial manufacturing process, in order to ensure the reliability of large-scale integrated circuit further, on the one hand higher requirement being proposed to the good article rate of electronic devices and components, then new challenge---a reworkable characteristic being proposed to underfill material on the other hand.One piece of work in-process circuit card, often discard because of the inefficacy of certain electronic devices and components, if by reprocessing processing, the electronic devices and components lost efficacy can be extractd, again change good electronic devices and components, then can improve the reliability of large-scale integrated circuit greatly.In existing Industrial products, most epoxy resin is all do not possess so reworkable characteristic, the not melting of ordinary epoxy resin and undissolved characteristic, make the excision technique of inactive electronic components and parts very complicated, and be easy to damage whole circuit card.
The epoxy resin that research and preparation has reworkable characteristic is a project with extensive market using value, also has some to report in recent years.StephenL.Buchwalter etc. have synthesized a series of alicyclic epoxide compound with degradable acetal group.This epoxy resin can use cyclic acid anhydride to solidify, and the material after solidification can be degraded in mixed acid solution.But the directional property of this degradation method is clear and definite not, this technology, also due to the limitation of degradation technique method, is difficult to be applied in actual industrial.
Summary of the invention
Based on this, be necessary the epoxy monomer that a kind of thermal destruction is provided, to prepare the underfill material with reworkable characteristic.
An epoxy monomer for thermal destruction, structural formula is as follows:
Wherein, R be carbonatoms be less than 10 alkyl, alkylene, phenyl, naphthyl or anthryl; R' and R " be structural formula and be
group, carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10, R " for hydrogen, phenyl, carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10.
Wherein in an embodiment, described R is
-CH=CH-or-CH=CH-CH=CH-.
A preparation method for the epoxy monomer of thermal destruction, comprises the steps:
Structural formula is by 2:1 in molar ratio
compound and structural formula be
compound be dissolved in alkali organic solvent, in 0 DEG C of reaction after 3 hours, then in 70 DEG C of reactions reaction of 24 hours, obtain containing structural formula be
the solution of epoxy presoma; Wherein, R be carbonatoms be less than 10 alkyl, alkylene, phenyl, naphthyl or anthryl; R' to be carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10.
To described containing structural formula be
epoxy presoma solution in add metachloroperbenzoic acid, in 0 DEG C reaction 3 hours after, then in 50 DEG C reaction 48 hours, after separation and purification, obtaining structural formula is
the epoxy monomer of thermal destruction, wherein, R " for carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10.
A kind of underfill material, by mass percentage, comprising:
Wherein in an embodiment, described epoxy hardener is acid anhydride type curing agent.
Wherein in an embodiment, described acid anhydride type curing agent is Tetra hydro Phthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, pyromellitic dianhydride or Benzophenone acid dianhydride.
Wherein in an embodiment, described Epoxy curing accelerators is the curing catalyst of acid anhydride type curing agent.
Wherein in an embodiment, the curing catalyst of described acid anhydride type curing agent is amine type accelerator, imidazoles promotor or acetylacetonate promotor.
Wherein in an embodiment, described mineral filler is spherical silica particle.
Wherein in an embodiment, the particle diameter of described spherical silica particle is 20 nanometer ~ 5000 nanometers.
Wherein in an embodiment, described processing aid is selected from least one in defoamer, glidant and coupling agent.
The experiment proved that, when using the underfill material temperature of the epoxy monomer of above-mentioned thermal destruction to be elevated to 200 ~ 240 DEG C, the epoxy monomer decomposes of thermal destruction, underfill material cohesive strength significantly declines, thus chip can be extractd from substrate, realize Rework Technics.Thus, going back unmodified resin and can preparing the underfill material with reworkable characteristic of this thermal destruction is used.
Accompanying drawing explanation
Fig. 1 is the use schematic diagram of controlled collapsible chip connec-tion and underfill material;
The DSC curve of the solidification process of the underfill material of Fig. 2 embodiment 2;
The DSC curve of the degradation process of the underfill material of Fig. 3 embodiment 2;
The TGA curve of the degradation process of the underfill material of Fig. 4 embodiment 2.
Embodiment
The epoxy monomer of the thermal destruction of one embodiment, structural formula is as follows:
This epoxy monomer is tertiary ester class epoxy monomer, and refer to the epoxy compounds with tertiary ester groups structure, epoxy group(ing) and tertiary ester groups do not exist conjugative effect.
Wherein, R be carbonatoms be less than 10 alkyl, alkylene, phenyl, naphthyl or anthryl; R' is structural formula
group, phenyl, carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10, R " for hydrogen, phenyl, carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10.
Carbonatoms be less than 10 alkyl can for straight chained alkyl or branched-chain alkyl.Preferably, R is
-CH=CH-or-CH=CH-CH=CH-.
Carbonatoms be 1 ~ 10 alkyl can straight chained alkyl or branched-chain alkyl.
Carbonatoms is that the non-conjugated substituted radical of the alkyl of 1 ~ 10 refers to Cl-, Br-, SO
4-wait group alternate c atoms number be the alkyl of 1 ~ 10 part hydrogen atom formed group.Such as,
deng.
Such as, a specific embodiment of the epoxy monomer of above-mentioned thermal destruction can be
wherein, R be phenyl (
), R' is
r " be methyl.
And for example, another specific embodiment of the epoxy monomer of above-mentioned thermal destruction can be
wherein, R be phenyl (
), R' is-CH
2-, R " be methyl.
The epoxy monomer of thermal destruction at high temperature can decomposes, makes to use the epoxy monomer of above-mentioned thermal destruction can prepare the underfill material with reworkable characteristic.Our experiments show that, when temperature is elevated to 200 ~ 240 DEG C, the tertiary ester groups decomposes in the epoxy resin of thermal destruction, makes the cohesive strength of underfill material significantly decline, thus chip can be extractd from substrate, realize Rework Technics.
Therefore, the underfill material of the epoxy monomer of this thermal destruction is used to have reworkable characteristic.The reliability of the large-scale integrated circuit of this underfill material is used greatly to improve.
The preparation method of the epoxy monomer of the thermal destruction of one embodiment, comprises the steps:
Step S110: structural formula is by 2:1 in molar ratio
compound and structural formula be
compound be dissolved in alkali organic solvent, in 0 DEG C reaction 3 hours after, then in 70 DEG C reaction 24 hours, obtain containing structural formula be
the solution of epoxy presoma.
Wherein, R be carbonatoms be less than 10 alkyl, alkylene, phenyl, naphthyl or anthryl; R' to be carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10.
Alkali organic solvent is pyridine and methylene dichloride mixed solvent.Basic solvent is selected to be conducive to the carrying out reacted.The volume ratio of pyridine and methylene dichloride is 1:5.
Preferably, in order to what obtain purifying containing structural formula be
the solution of epoxy presoma, be conducive to subsequent reactions, after reaction terminates, also comprise deacidification, dewater and the step of removal of impurities.
Reaction formula is as follows:
Structural formula is
compound can be Terpineol 350, structural formula is
compound can be p-phthaloyl chloride.
Step S120: be to containing structural formula
epoxy presoma solution in add metachloroperbenzoic acid, in 0 DEG C reaction 3 hours after, then in 50 DEG C reaction 48 hours, after separation and purification, obtaining structural formula is
the epoxy monomer of thermal destruction, wherein, R " for carbonatoms be 1 ~ 10 alkyl or carbonatoms be the non-conjugated substituted radical of the alkyl of 1 ~ 10.
Preferably, metachloroperbenzoic acid and structural formula are
the mol ratio of compound be 1:1.
The step that the method for separation and purification comprises deacidification, dewaters and filter.
Reaction formula is as follows:
Preparation method's technique of the epoxy monomer of above-mentioned thermal destruction is simple, and reaction conditions is gentle, and energy consumption is low, and preparation cost is lower.
The underfill material of one embodiment, by mass percentage, comprising:
Wherein, epoxy hardener is acid anhydride type curing agent.Anhydride curing agent is preferably Tetra hydro Phthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, pyromellitic dianhydride or Benzophenone acid dianhydride.
Epoxy curing accelerators is the curing catalyst of acid anhydride type curing agent, for promoting that acid anhydride type curing agent solidifies.The curing catalyst of acid anhydride type curing agent is preferably amine type accelerator, imidazoles promotor or acetylacetonate promotor.
Amine type accelerator can be DMP-30.Imidazoles promotor can be 2-ethyl-4-methyl-imidazoles.Acetylacetonate promotor can be chromium acetylacetonate.
Mineral filler is preferably spherical silica particle, is more preferably the spherical silica particle that particle diameter is 20 nanometer ~ 5000 nanometers.
Preferably, spherical silica particle is 20 nanometers, 50 nanometers, 100 nanometers, 200 nanometers, 400 nanometers, 600 nanometers, 800 nanometers, 1000 nanometers, 3000 nanometers, the spherical silica particle of 5000 nanometer equidimensions or the wherein composition of at least two kinds.
Select spherical silica particle as mineral filler, to control the working process parameter of underfill material.In practical application in industry, by changing different mineral fillers and adding proportion, the underfill material with different working process parameter may be obtained, to be applicable to different applied environments.Under processing performance meets the requirements of prerequisite, other fillers can be used to reduce costs.Such as, in other embodiments, zinc oxide or talcum powder etc. can be selected as mineral filler.
Processing aid is for improving the processing characteristics of underfill material.Processing aid is selected from least one in defoamer, glidant and coupling agent.
By certain proportioning, the epoxy monomer of above-mentioned thermal destruction, epoxy hardener, Epoxy curing accelerators, mineral filler and processing aid high-speed stirring are reached dispersed, obtain the paste mixture of stable homogeneous, namely obtain this underfill material.
Above-mentioned underfill material comprises the epoxy monomer of thermal destruction.The results showed, this underfill material solidifies under 80 ~ 150 DEG C of conditions, has higher cohesive strength and less thermal expansivity after solidification.And when temperature is elevated to 200 ~ 240 DEG C, the epoxy monomer decomposes of thermal destruction, the cohesive strength of underfill material significantly declines, thus chip can be extractd from substrate, realizes Rework Technics.
Be heated to 200 ~ 240 DEG C can significantly reduce the cohesive strength of underfill material and chip can be extractd from substrate, technique be simple, and is not easy to damage whole circuit card, safe and reliable.
Refer to Fig. 1, will by solder mask 30 by after printed circuit board (PCB) 10 and silicon chip 20 welding assembly, then be coated on printed circuit board (PCB) 10 by above-mentioned underfill material, be heated to 80 ~ 150 DEG C, namely underfill material solidify to form the Underfill layer 40 connecting silicon chip 20 and printed circuit board (PCB) 10.
In practical application in industry, segment length or the substituting group of the functional functional group of the epoxy monomer of the thermal destruction in above-mentioned underfill material can be changed, to meet the specific requirement to underfill material.
Such as, wishing to get the slightly better underfill material of resistance to elevated temperatures (as high 5 ~ 10 DEG C in required), R group can be selected to contain the raw material of more phenyl ring, as naphthyl substituted; Now solidification value also influenced corresponding raising, and by being regulated at the Epoxy curing accelerators of original increase by 0.5% substantially.
And for example, wish to get good fluidity and quick-setting underfill material, the raw material that the basic steric hindrance of R is less can be selected, as vinylidene replaces; And by the Epoxy curing accelerators in original increase by 0.5% substantially, solidification rate can be accelerated, or improve solidification value, solidification rate can be made to meet the demands.
Set forth further below by way of specific embodiment.
Embodiment 1
The epoxy monomer of preparation thermal destruction
1, phthalyl chloride and Terpineol 350 are dissolved in the mixed solvent of pyridine and methylene dichloride 1:5 mixing by volume, in 0 DEG C of reaction after 3 hours, again in 70 DEG C of reactions reaction of 24 hours, generate the solution containing the epoxy presoma with tertiary ester groups structure, deacidification should be passed through, dewaters and removal of impurities by solution containing the epoxy presoma with tertiary ester groups structure, obtain homogeneous containing have tertiary ester groups structure epoxy presoma clear solution wherein, the mol ratio of Terpineol 350 and phthalyl chloride is 2:1;
2, upwards add metachloroperbenzoic acid in clear solution and epoxidation is carried out to double bond, react after 3 hours at 0 DEG C, then react 48 hours at 50 DEG C, obtain the reworkable epoxy compounds of tertiary ester class.Product is by deacidification, and dewater, the steps such as removal of impurities, obtain homogeneous clear solution, and after filtering and purifying, obtain the epoxy monomer of the structural formula of purifying thermal destruction as follows, wherein, the mol ratio of metachloroperbenzoic acid and phthalyl chloride is 1:1:
The reaction formula of the epoxy monomer of above-mentioned preparation thermal destruction is as follows:
Embodiment 2
1, by 4-methyl-4-hydroxyl-1-alkene and 2,7-dimethyl chloride naphthalene is dissolved in the mixed solvent of pyridine and methylene dichloride 1:5 mixing by volume, in 0 DEG C of reaction after 3 hours, again in 70 DEG C of reactions reaction of 24 hours, generate the solution containing the epoxy presoma with tertiary ester groups structure, deacidification should be passed through, dewaters and removal of impurities by solution containing the epoxy presoma with tertiary ester groups structure, obtain homogeneous containing have tertiary ester groups structure epoxy presoma clear solution wherein, the mol ratio of 4-methyl-4-hydroxyl-1-alkene and 2,7-dimethyl chloride naphthalene is 2:1;
2, upwards add metachloroperbenzoic acid in clear solution and epoxidation is carried out to double bond, react after 3 hours at 0 DEG C, then react 48 hours at 50 DEG C, obtain the reworkable epoxy compounds of tertiary ester class.Product, by deacidification, dewaters, the steps such as removal of impurities, obtain homogeneous clear solution, after filtering and purifying, obtain the epoxy monomer of the structural formula of purifying thermal destruction as follows, wherein, the mol ratio of metachloroperbenzoic acid and 2,7-dimethyl chloride naphthalene is 1:1:
The reaction formula of the epoxy monomer of above-mentioned preparation thermal destruction is as follows:
Embodiment 3
1,5-methyl-5-hydroxyl-2-alkene and phthalyl chloride is dissolved in the mixed solvent of pyridine and methylene dichloride 1:5 mixing by volume, in 0 DEG C of reaction after 3 hours, again in 70 DEG C of reactions reaction of 24 hours, generate the solution containing the epoxy presoma with tertiary ester groups structure, deacidification should be passed through, dewaters and removal of impurities by solution containing the epoxy presoma with tertiary ester groups structure, obtain homogeneous containing have tertiary ester groups structure epoxy presoma clear solution wherein, the mol ratio of 5-methyl-5-hydroxyl-2-alkene and phthalyl chloride is 2:1;
2, upwards add metachloroperbenzoic acid in clear solution and epoxidation is carried out to double bond, react after 3 hours at 0 DEG C, then react 48 hours at 50 DEG C, obtain the reworkable epoxy compounds of tertiary ester class.Product is by deacidification, and dewater, the steps such as removal of impurities, obtain homogeneous clear solution, and after filtering and purifying, obtain the epoxy monomer of the structural formula of purifying thermal destruction as follows, wherein, the mol ratio of metachloroperbenzoic acid and phthalyl chloride is 1:1:
The reaction formula of the epoxy monomer of above-mentioned preparation thermal destruction is as follows:
Embodiment 4
A kind of underfill material, by mass percentage, comprising:
The epoxy monomer 50% of thermal destruction, epoxy hardener 32.5%, Epoxy curing accelerators 1.5%, mineral filler 15% and processing aid 1%.
Wherein, the structural formula of the epoxy monomer of thermal destruction is
Epoxy hardener is methylhexahydrophthalic anhydride, and Epoxy curing accelerators is 2-ethyl-4-methyl-imidazoles, and the preparing spherical SiO 2 of mineral filler to be particle diameter be 20 nanometers, processing aid comprises the dispersion agent and defoamer that mass ratio is 1:0.5.
As seen from Figure 2, the underfill material of embodiment 4 has good curing exothermic peak at 121 DEG C, illustrates that this underfill material is 121 DEG C of solidifications.
Can be found out by Fig. 3 and Fig. 4, the underfill material of embodiment 4 can realize degraded under the condition of being heated.When temperature is elevated to 206 DEG C, the underfill material of 5% decomposes, and when temperature is elevated to 246 DEG C, the underfill material of 50% decomposes.
Embodiment 5
A kind of underfill material, by mass percentage, comprising:
The epoxy monomer 60% of thermal destruction, epoxy hardener 20%, Epoxy curing accelerators 2.5%, mineral filler 16% and processing aid 1.5%.
Wherein, the structural formula of the epoxy monomer of thermal destruction is
Epoxy hardener is Tetra hydro Phthalic anhydride, and Epoxy curing accelerators is chromium acetylacetonate, and the preparing spherical SiO 2 of mineral filler to be particle diameter be 200 nanometers, processing aid comprises the dispersion agent and defoamer that mass ratio is 1:0.5.
Embodiment 6
A kind of underfill material, by mass percentage, comprising:
The epoxy monomer 30% of thermal destruction, epoxy hardener 35%, Epoxy curing accelerators 7.5%, mineral filler 25% and processing aid 2.5%.
Wherein, the structural formula of the epoxy monomer of thermal destruction is
Epoxy hardener is Tetra hydro Phthalic anhydride, and Epoxy curing accelerators is 2-ethyl-4-methyl-imidazoles, and the preparing spherical SiO 2 of mineral filler to be particle diameter be 300 nanometers, processing aid comprises dispersion agent, defoamer and the coupling agent that mass ratio is 1:0.5:1.
The working process parameter of the underfill material of embodiment 4 and embodiment 5 sees the following form 1.
The underfill material working process parameter of table 1 embodiment 4 ~ embodiment 5
As seen from Table 1, the underfill material of embodiment 4 ~ embodiment 5 has higher cohesive strength and less thermal expansivity after solidifying.Further, when the temperature increases, the viscosity of the underfill material of embodiment 4 ~ embodiment 5 significantly reduces, and is conducive to electronic devices and components to be extractd from substrate, realizes Rework Technics.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an epoxy monomer for thermal destruction, is characterized in that, structural formula is as follows:
2. a preparation method for the epoxy monomer of thermal destruction, comprises the steps:
(1), by 4-methyl-4-hydroxyl-1-alkene and 2,7-dimethyl chloride naphthalene is dissolved in the mixed solvent of pyridine and methylene dichloride 1:5 mixing by volume, in 0 DEG C of reaction after 3 hours, again in 70 DEG C of reactions 24 hours, generate the solution containing the epoxy presoma with tertiary ester groups structure, deacidification should be passed through, dewaters and removal of impurities by solution containing the epoxy presoma with tertiary ester groups structure, obtain homogeneous containing have tertiary ester groups structure epoxy presoma clear solution wherein, the mol ratio of 4-methyl-4-hydroxyl-1-alkene and 2,7-dimethyl chloride naphthalene is 2:1;
(2), upwards add metachloroperbenzoic acid in clear solution epoxidation is carried out to double bond, react after 3 hours at 0 DEG C, then react 48 hours at 50 DEG C, obtain the reworkable epoxy compounds of tertiary ester class; Product, by deacidification, dewaters, the step of removal of impurities, obtain homogeneous clear solution, after filtering and purifying, obtain the epoxy monomer of the structural formula of purifying thermal destruction as follows, wherein, the mol ratio of metachloroperbenzoic acid and 2,7-dimethyl chloride naphthalene is 1:1:
The reaction formula of the epoxy monomer of above-mentioned preparation thermal destruction is as follows:
3. a underfill material, is characterized in that, by mass percentage, comprising:
4. underfill material according to claim 3, is characterized in that, described epoxy hardener is acid anhydride type curing agent.
5. underfill material according to claim 4, is characterized in that, described acid anhydride type curing agent is Tetra hydro Phthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, pyromellitic dianhydride or Benzophenone acid dianhydride.
6. underfill material according to claim 3, is characterized in that, described Epoxy curing accelerators is the curing catalyst of acid anhydride type curing agent.
7. underfill material according to claim 6, is characterized in that, the curing catalyst of described acid anhydride type curing agent is amine type accelerator, imidazoles promotor or acetylacetonate promotor.
8. underfill material according to claim 3, is characterized in that, described mineral filler is spherical silica particle.
9. underfill material according to claim 8, is characterized in that, the particle diameter of described spherical silica particle is 20 nanometer ~ 5000 nanometers.
10. underfill material according to claim 3, is characterized in that, described processing aid is selected from least one in defoamer, glidant and coupling agent.
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| CN108484533A (en) * | 2018-04-24 | 2018-09-04 | 中科广化（重庆）新材料研究院有限公司 | A kind of epoxy monomer of the mesomorphic unit containing arylate structural and preparation method thereof |
| CN113667097B (en) * | 2021-03-26 | 2024-01-23 | 蓝赛夫(上海)电子材料有限公司 | Intermediate compound of epoxy resin monomer, preparation method and application thereof |
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| CN103664834A (en) | 2014-03-26 |
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