CN113214767B - Low-temperature high-hardness epoxy glue for metallographic cold embedding of heat sensitive element - Google Patents
Low-temperature high-hardness epoxy glue for metallographic cold embedding of heat sensitive element Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
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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
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
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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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Abstract
The invention discloses low-temperature high-hardness epoxy glue for metallographic cold embedding of a heat sensitive element. The invention is composed of the following substances by mass: epoxy resin component: 70-90 parts of bisphenol A epoxy resin (E-51), 5-15 parts of monofunctional reactive diluent and 5-15 parts of difunctional reactive diluent; curing agent component: 30-50 parts of aliphatic amine, 5-15 parts of alicyclic amine, 30-50 parts of polyether amine and 5-20 parts of xylene formaldehyde resin. The epoxy glue for metallographic cold inlay can be cured for 4-8 hours at 25 ℃, the highest temperature of the surface of a glue block in the curing process is not more than 75 ℃, and is far lower than the temperature of about 140 ℃ of the current epoxy glue, so that the volume expansion and size deformation caused by high temperature generated by using the epoxy glue in the metallographic cold inlay process of a heat sensitive element in the prior art are overcome. The epoxy glue disclosed by the invention is safe and environment-friendly, does not contain a volatile solvent, has the highest temperature of a glue block adjustable according to the heat sensitivity of an insert, and is particularly suitable for a metallographic cold embedding process of a heat sensitive element.
Description
Technical Field
The invention belongs to the field of organic polymer packaging materials, relates to application of epoxy glue in the field of metallographic cold embedding, and particularly relates to low-temperature high-hardness epoxy glue for metallographic cold embedding of a heat sensitive element.
Background
The epoxy resin has low volume shrinkage rate, good adhesion and high comprehensive mechanical property in the curing process, so the epoxy resin is widely used in the field of metallographic cold-inlaid materials. However, epoxy resins, particularly bisphenol a epoxy resins, have a rigid structure, high viscous flow activation energy and high bulk viscosity, resulting in poor workability. Even if bisphenol A type epoxy resin E-51 with the lowest molecular weight is adopted, the viscosity is as high as 12000-14000 mPa.s at 25 ℃. To improve workability of epoxy resins, low viscosity epoxy reactive diluents are often added to reduce the viscosity of the cold-setting material, improve its flowability and wettability to the substrate (e.g., printed circuit board) to be set without introducing volatile solvents. Secondly, the metallographic phase cold embedding process requires that the used epoxy glue has good defoaming and defoaming performances, and bubbles generated by stirring in the mixing process of the epoxy component and the curing agent component are eliminated as much as possible. Because the refractive index of the air in the air bubbles and that of the epoxy glue are different, scattering of light occurs at the interface between the two; air bubbles in the epoxy blocks can also interfere with the viewing of printed circuit board quality details. In addition, the metallurgical grade cold-set epoxy resin mass is required to have high hardness (mechanical properties). Because when the microsection is made, the epoxy glue block needs to be cut and ground. When the hardness of the epoxy glue block is low, the section is irregular, and the glue block is stuck with sand paper during polishing, so that the polished surface is not smooth; on the contrary, when the rubber block is too hard or has a large brittleness, the edge of the rubber block is easily cracked during cutting or polishing. Therefore, metallographic cold-set epoxy glues require high transparency, high hardness and no bubbles.
The printed circuit board is also called a PCB, and is a core part of an electronic product. In industry, the quality reliability of a rigid PCB is checked by a common metallographic cold embedding mode, namely, when the current PCB is detected, metallographic cold embedding glue is needed to be used for firstly cold embedding the PCB in a transparent epoxy resin curing block, and then a magnifier or a calibrated microscope is used for checking whether the quality of the circuit board is qualified or not and determining whether each parameter of a PCB production line needs to be corrected or not. The PCB is a heat-sensitive element, and generally consists of four layers, namely a silk screen printing layer, a solder mask layer, copper foil and a substrate. The substrate is a framework layer of the PCB and plays a physical supporting role for the screen printing layer, the solder mask layer and the copper foil. The substrate is mainly obtained by crosslinking and curing phenolic resin or epoxy resin, but as the thermal deformation temperature of the phenolic resin or the epoxy resin is 160-180 ℃, when the ambient temperature is close to the range, the free volume of the substrate can be rapidly expanded and large-size deformation can occur; and shear force and stress concentration will occur at the interface of the substrate and the copper foil due to the difference in the amount of deformation between the substrate and the copper foil. When the shear stress at the interface of the two is sufficiently large, the copper foil will be directly delaminated from the substrate. Therefore, when the PCB is detected, the heat effect of the curing reaction of the epoxy glue for the cold metal embedding cannot be too large, or the heat release of the curing reaction of the epoxy glue cannot be too concentrated, otherwise the PCB is directly deformed and loses efficacy, and even burnt damage occurs. Because the epoxy glue for the metallographic cold embedding of the heat sensitive element has the problem of concentrated heat release (the highest temperature of the surface of a glue block reaches more than 120 ℃ and damage to a PCB (printed circuit board) can occur), the metallographic cold embedding detection process for the heat sensitive element PCB generally adopts a physical method for cooling, such as means of reducing the temperature of a working room or cooling through other auxiliary equipment. Moreover, no relevant report of researching on the epoxy glue for metallographic cold embedding of the heat sensitive element is found by researchers from the epoxy glue.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the low-temperature high-hardness epoxy glue for the metallographic phase cold embedding of the heat sensitive element. The low-temperature high-hardness epoxy glue for cold embedding of the metallographic phase of the heat sensitive element can be cured within 4-8 hours at 25 ℃, the highest temperature of the surface of an epoxy glue block can be controlled not to exceed 75 ℃ in the reaction process, the highest temperature is far lower than the curing temperature of the epoxy glue for cold embedding of the metallographic phase of the current heat sensitive element, and the reaction speed/heat effect of the low-temperature high-hardness epoxy glue can be regulated and controlled.
In order to achieve the aim of improving the eyesight, the invention adopts the following technical scheme:
a low-temperature high-hardness epoxy glue for metallographic cold embedding of a thermosensitive element comprises an epoxy resin component and a curing agent component, wherein the molar ratio of epoxy groups in the epoxy resin component to active hydrogen of amino compounds in the curing agent component is 1.95-1.05,
the epoxy resin comprises the following components in parts by mass:
70-90 parts of bisphenol A epoxy resin (E-51);
5-15 parts of monofunctional reactive diluent;
5-15 parts of bi/multifunctional reactive diluent;
the curing agent comprises the following components in parts by mass:
30-50 parts of fatty amine;
5-15 parts of alicyclic amine;
30-50 parts of polyether amine;
5-20 parts of xylene formaldehyde resin;
wherein the monofunctional reactive diluent is any one or a mixture of at least two of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, 2-ethylhexyl glycidyl ether, o-cresol glycidyl ether, p-tert-butylphenyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and C12-14 alkyl glycidyl ether;
the bi/multi-functional reactive diluent is any one or a mixture of at least two of ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether, propoxyglycerol triglycidyl ether and sorbitol polyglycidyl ether;
the aliphatic amine is any one or a mixture of at least two of divinyltriamine, triethylene tetramine, tetraethylene pentamine, m-xylylenediamine, 1, 3-cyclohexyldimethylamine, 1, 6-hexamethylene diamine and ethylene diamine;
the alicyclic amine is any one or a mixture of at least two of isophorone diamine, methyl cyclohexane diamine, 4' -diaminodicyclohexyl methane and amino ethyl piperazine;
the polyether amine is any one or a mixture of at least two of polyether amine D230, polyether amine D400 and polyether amine T403.
Moreover, for the low-temperature high-hardness epoxy glue for the metallographic cold inlay of the heat sensitive element, a person skilled in the art is advised to add a part of defoaming agent in the epoxy resin component, and the selected defoaming agent can be non-silicon organic polymer solution. For example, the epoxy resin component also comprises polyacrylate solution with mass concentration of less than or equal to 50% as a defoaming agent, wherein the number average molecular weight of the polyacrylate is less than or equal to 3000g/mol. Further, the polyacrylate solution in the epoxy resin component is 0.1-0.6 part by mass.
Further, the xylene formaldehyde resin in the present invention has a number average molecular weight of 250 to 700g/mol, which is a product of Mitsubishi gas corporation of Japan.
Compared with the prior art, the invention has the beneficial effects that:
1. the epoxy glue disclosed by the invention is moderate in viscosity, good in fluidity, easy to defoam and good in wetting property on a substrate.
2. The epoxy glue has high curing speed (can be completely cured within 4-8 hours at 25 ℃), and the maximum temperature of the surface of an epoxy glue block does not exceed 75 ℃ in the curing reaction process and is far lower than the temperature of the current epoxy glue about 140 ℃; and the reaction of the epoxy component and the curing agent component is stable in heat release, the problem of centralized heat release is avoided, and the problems of volume expansion and size deformation of the substrate caused by high temperature due to the heat release generated by the reaction of epoxy glue in the metallographic phase cold embedding process of the heat sensitive element in the prior art are solved. Therefore, the characteristics of the low-temperature high-hardness epoxy glue disclosed by the invention enable the low-temperature high-hardness epoxy glue to be suitable for a metallographic cold embedding process, and are particularly suitable for the quality detection application of a PCB (printed circuit board) of a heat-sensitive substrate.
3. The reaction speed/thermal effect of the low-temperature high-hardness epoxy glue can be regulated, namely the reaction speed and the heat release rate of the epoxy glue can be controlled by properly regulating the proportion of the relevant components.
4. The epoxy glue disclosed by the invention is safe and environment-friendly, does not contain a volatile solvent, has the highest temperature of a glue block adjustable according to the heat sensitivity of an insert, and is particularly suitable for a metallographic cold embedding process of a heat sensitive element.
The curing agent component of the low-temperature high-hardness epoxy glue for metallographic cold inlay of the thermosensitive element consists of three organic amine compounds with different reaction activities, namely fatty amine, alicyclic amine and polyether amine, wherein the reaction activation energy of the organic amine compounds is that of the fatty amine, the alicyclic amine and the polyether amine in sequence from low to high (the reaction difficulty degree). Based on the difference of the reaction activation energy of the organic amine compound and the epoxy component, the invention has the design idea that the ring-opening addition reaction of the aliphatic amine, the alicyclic amine and the polyether amine is activated successively by a chain, specifically, the aliphatic amine with higher reaction activity in the initial stage of the curing reaction (at 25 ℃) preferentially performs the ring-opening addition reaction with the epoxy group and releases reaction heat, the temperature of the epoxy glue is gradually increased by the heat effect of the reaction to sequentially excite the alicyclic amine and the polyether amine which need higher reaction activation energy to react with the epoxy component, and the one-time ring-opening addition reaction (concentrated reaction) of the traditional epoxy resin component and curing agent component is decomposed into the chain type step-by-step activation reaction for releasing heat, so that the heat released by the reaction of the epoxy resin component and the curing agent component is uniform and stable, the accumulation of the reaction heat in the glue/glue block is effectively avoided, and the problems of the overlarge heat effect of the existing epoxy glue for metal cold inlay and the deformation of a substrate caused by concentrated reaction heat release are solved, and the low-temperature high-hardness epoxy glue suitable for metal cold inlay is obtained.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a graph of the reaction time of the epoxy glue obtained in example 1 versus the temperature of the glue block.
FIG. 2 is a photograph of a sample block obtained in example 1 after the epoxy glue is cured.
FIG. 3 is a graph of the reaction time of the epoxy glue obtained in example 2 versus the temperature of the glue block.
FIG. 4 is a photograph of a sample block obtained in example 2 after the epoxy glue is cured.
FIG. 5 is a graph of the reaction time versus the block temperature of the epoxy glue obtained in example 3.
FIG. 6 reaction time-block temperature curve of epoxy glue obtained in example 4.
Detailed Description
The present invention will now be described in more detail, wherein preferred embodiments of the invention are shown, it being understood that one skilled in the art could modify the invention herein described while still achieving the beneficial results of the present invention. Accordingly, the following description should be construed as broadly as possible to those skilled in the art and not as limiting the invention.
Example 1
Epoxy resin component: 70 parts of bisphenol A epoxy resin (E-51), 5 parts of phenyl glycidyl ether, 10 parts of benzyl glycidyl ether, 10 parts of 1, 4-butanediol diglycidyl ether, 5 parts of cyclohexyl dimethanol diglycidyl ether and 0.10 part of non-silicon defoaming agent BYK A530;
curing agent component: 40 parts of diethylenetriamine, 10 parts of m-xylylenediamine, 5 parts of aminoethylpiperazine, 10 parts of polyetheramine D230, 15 parts of polyetheramine T403 and 20 parts of xylene formaldehyde resin.
The two components are respectively prepared in two containers, stirred evenly and then kept stand for degassing. After the air introduced by mixing is completely discharged, uniformly mixing the epoxy group and the active hydrogen in the amino compound according to the equimolar amount. Then, the mixture was poured into a special mold (thermoplastic polypropylene) having a diameter of 32 mm. The quality of the epoxy glue poured into the mould is controlled to be 17.5 +/-0.1 g.
The mixed epoxy glue reacts at 25 ℃, the surface temperature of the glue block is measured by a Fluke MT4 type hand-held infrared thermometer (the temperature measurement precision is 0.1 ℃), and the obtained reaction time-glue block temperature curve is shown in figure 1. When the reaction time of the epoxy glue is 91 minutes, the surface temperature of the system reaches the highest value, namely 69 ℃. The highest temperature of the central part of the glue block is tested to be 104 ℃ by using a thermocouple, which shows that the epoxy glue disclosed by the invention has the curing temperature far lower than the thermal deformation temperature (160-180 ℃) of a phenolic resin or epoxy resin substrate, cannot cause the deformation of the board, and is suitable for the curing application of the phase-cooling embedding process of a thermal sensitive element gold PCB.
After reacting for 6 hours at ambient temperature, the average hardness of the rubber block is measured by a Shore D hardness tester to be as high as 81D, which shows that the epoxy glue disclosed by the invention has excellent mechanical properties after being cured, has higher hardness and can be completely suitable for subsequent polishing procedures. Moreover, as can be seen from fig. 2, the epoxy glue block has good transparency, few bubbles, smooth surface and no defects of whitening and stickiness, and meets the process requirements of metallographic cold mosaic on high transparency, high hardness and no bubbles in PCB detection.
Example 2
Epoxy resin component: 90 parts of bisphenol A epoxy resin (E-51), 5 parts of butyl glycidyl ether, 5 parts of ethylene glycol glycidyl ether and 0.60 part of non-silicon defoamer BYK 051N;
the curing agent component: 30 parts of trivinyl tetramine, 10 parts of isophorone diamine, 5 parts of aminoethylpiperazine, 400 parts of polyether amine D, 30 parts of polyether amine T403 and 5 parts of xylene formaldehyde resin.
The two components are prepared in two containers respectively, stirred evenly and then kept stand for degassing. After the air introduced by mixing is completely discharged, weighing the epoxy group and the active hydrogen in the amino compound according to the molar ratio of 1.05, and uniformly mixing the epoxy group and the active hydrogen in the amino compound. Then, the mixture was poured into a special mold (made of thermoplastic polypropylene) having a diameter of 32 mm. The quality of the epoxy glue poured into the mould is controlled to be 17.5 +/-0.1 g.
The mixed epoxy glue reacts at 25 ℃, the surface temperature of the glue block is measured by a Fluke MT4 type hand-held infrared thermometer (the temperature measurement precision is 0.1 ℃), and the obtained reaction time-glue block temperature curve is shown in figure 3. When the reaction time of the epoxy glue is 83 minutes, the surface temperature of the system reaches the maximum value of 72.5 ℃. The highest temperature of the central part of the glue block is 114 ℃ by using a thermocouple test, which shows that the epoxy glue of the invention has the curing temperature far lower than the thermal deformation temperature (160-180 ℃) of a phenolic resin or epoxy resin substrate, can not cause the deformation of the board, has stable heat release process and no phenomenon of concentrated heat release, and is suitable for the curing application of the phase-cooling embedding process of a thermal sensitive element gold PCB.
After the reaction is carried out for 8 hours at the ambient temperature, the average hardness of the glue block is as high as 83D (measured by a Shore D hardness meter), which shows that the epoxy glue has excellent mechanical properties after being cured. Moreover, as can be seen from fig. 4, the epoxy glue block has good transparency, few bubbles, smooth surface, no whitening and stickiness, and meets the process requirements of metallographic cold mosaic for PCB detection on high transparency, high hardness and no bubbles.
Example 3
Epoxy resin component: 80 parts of bisphenol A epoxy resin (E-51), 6 parts of 2-ethylhexyl glycidyl ether, 4 parts of o-cresol glycidyl ether, 3 parts of 1, 6-hexanediol diglycidyl ether, 4 parts of neopentyl glycol diglycidyl ether, 3 parts of cyclohexyl dimethanol diglycidyl ether and 0.40 part of non-silicon defoamer EFKA-2720;
curing agent component: 20 parts of divinyltriamine, 20 parts of tetravinyl pentamine, 10 parts of 4,4' -diaminodicyclohexylmethane, 40 parts of polyetheramine D and 10 parts of xylene formaldehyde resin.
The two components are respectively prepared in two containers, stirred evenly and then kept stand for degassing. After the air introduced by mixing is completely discharged, uniformly mixing the epoxy group and the active hydrogen in the amino compound according to the molar ratio of 1. Then, the mixture was poured into a special mold (made of thermoplastic polypropylene) having a diameter of 32 mm. The quality of the epoxy glue poured into the mould is controlled to be 17.5 +/-0.1 g.
The mixed epoxy glue reacts at 25 ℃, the surface temperature of the glue block is measured by a Fluke MT4 type hand-held infrared thermometer (the temperature measurement precision is 0.1 ℃), and the obtained reaction time-glue block temperature curve is shown in FIG. 5. When the reaction time of the epoxy glue is 93 minutes, the surface temperature of the system reaches a maximum value of 74.1 ℃. The highest temperature of the central part of the glue block is tested by a thermocouple to be 112 ℃, which shows that the curing temperature of the epoxy glue is far lower than the thermal deformation temperature of a phenolic resin or epoxy resin substrate, and the heat release process is stable without the phenomenon of concentrated heat release, so that the epoxy glue is suitable for curing application of a phase-cooling embedding process of a thermal sensitive element gold PCB.
After the reaction is carried out for 4 hours at the ambient temperature, the average hardness of the glue block is as high as 80D (measured by a Shore D hardness tester), which shows that the epoxy glue disclosed by the invention has excellent mechanical properties and high hardness after being cured.
Example 4
Epoxy resin component: 80 parts of bisphenol A epoxy resin (E-51), 5 parts of allyl glycidyl ether, 10 parts of C12-14 alkyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether and 0.20 part of non-silicon defoamer TEGO-Airex 920;
the curing agent component: 25 parts of trivinyl tetramine, 20 parts of 1, 3-cyclohexanediamine, 10 parts of methylcyclohexanediamine, 10 parts of polyetheramine D, 20 parts of polyetheramine T403 and 15 parts of xylene formaldehyde resin.
The two components are respectively prepared in two containers, stirred evenly and then kept stand for degassing. After the air introduced by mixing is completely discharged, uniformly mixing the epoxy group and the active hydrogen in the amino compound according to the molar ratio of 1.05. Then, the mixture was poured into a special mold (thermoplastic polypropylene) having a diameter of 32 mm. The quality of the epoxy glue poured into the mould is controlled to be 17.5 +/-0.1 g.
The mixed epoxy glue reacts in an environment of 25 ℃, the surface temperature of a glue block is measured by a Fluke MT4 type handheld infrared thermometer (the temperature measurement precision is 0.1 ℃), when the temperature reaches the highest peak within 78 minutes, the highest value of the measured surface temperature of a system is 72.2 ℃, and the method indicates that the curing temperature of the epoxy glue is far lower than the thermal deformation temperature of a phenolic resin or epoxy resin substrate, and the heat release process is stable without the phenomenon of centralized heat release, so that the method is suitable for curing application of a phase-cooling embedding process of a heat sensitive element gold PCB.
After the reaction is carried out for 5 hours at the ambient temperature, the average hardness of the glue block is as high as 81D (measured by a Shore D hardness meter), which shows that the epoxy glue has excellent mechanical properties after being cured, and the high hardness can completely adapt to the subsequent polishing process.
Example 5
Epoxy resin component: 85 parts of bisphenol A epoxy resin (E-51), 5 parts of p-tert-butylphenyl glycidyl ether, 5 parts of 1, 4-butanediol diglycidyl ether, 5 parts of propoxyglycerol triglycidyl ether, and 0.50 part of non-silicon antifoaming agent, basken Perenol E8;
the curing agent component: 20 parts of tetravinyl pentamine, 10 parts of 1, 6-hexamethylene diamine, 10 parts of isophorone diamine, 5 parts of aminoethyl piperazine, 45 parts of polyether amine T403 and 10 parts of xylene formaldehyde resin.
The two components are respectively prepared in two containers, stirred evenly and then kept stand for degassing. After the air introduced by mixing is completely discharged, the epoxy group and the active hydrogen in the amino compound are uniformly mixed according to the equal molar weight. Then, the mixture was poured into a special mold (made of thermoplastic polypropylene) having a diameter of 32 mm. The quality of the epoxy glue poured into the mould is controlled to be 17.5 +/-0.1 g.
The mixed epoxy glue reacts in an environment of 25 ℃, the surface temperature of the glue block is measured by a Fluke MT4 type handheld infrared thermometer (the temperature measurement precision is 0.1 ℃), the highest value of the measured surface temperature of the system is 71 ℃, and the epoxy glue curing temperature is far lower than the thermal deformation temperature of a phenolic resin or epoxy resin substrate, and the heat release process is stable and does not have the phenomenon of concentrated heat release, so that the epoxy glue curing process is suitable for curing application of the phase-cooling inlaying process of a heat sensitive element gold PCB. After the reaction is carried out for 6.5 hours at the ambient temperature, the average hardness of the rubber block is as high as 80D (measured by a Shore D hardness tester), which shows that the epoxy glue has excellent mechanical properties after being cured, and the high hardness can be completely suitable for the subsequent polishing process.
The above embodiments show that the epoxy glue of the present invention has a fast curing speed (can be completely cured within 4-8 hours at 25 ℃), and the maximum temperature of the epoxy glue block surface does not exceed 75 ℃ in the curing reaction process, which is far lower than the temperature of the current epoxy glue about 160 ℃, and the reaction of the epoxy component and the curing agent component releases heat linearly and stably, and there is no problem of concentrated heat release. Based on the difference of the reaction activation energy of the organic amine compound and the epoxy component, the curing agent component (organic amine compound) of the low-temperature high-hardness epoxy glue for the metallographic cold inlay of the heat sensitive element adopts a strategy of chain-type stepwise activation of three organic amines according to the condition of activation energy, the reaction heat of ring-opening addition reaction of aliphatic amine and epoxy group is used for exciting alicyclic amine and polyether amine which need higher reaction activation energy to react with the epoxy component, so that the heat of reaction heat release of the epoxy resin component and the curing agent component is linear and stable, the accumulation of the reaction heat in the glue/glue block is effectively reduced, the highest temperature of the glue block/glue is finally reduced, and the problems of overlarge heat effect and substrate deformation caused by concentrated reaction heat release of the existing epoxy glue for the metallographic cold inlay are solved. Meanwhile, tests show that the solidified rubber block has the advantages of good transparency, few bubbles, smooth surface, no defects of whitening and stickiness, and average hardness of more than 80D, and meets the process requirements of low-temperature heat release, high transparency, high hardness and no bubbles in metallographic cold embedding of a heat sensitive element gold PCB.
In addition, the mass composition of the aliphatic amine, the alicyclic amine and the polyether amine in the curing agent component can be conveniently adjusted according to the ambient temperature. When the temperature of the gluing environment is low (such as winter), the heat dissipation efficiency of the glue to the environment is high, the proportion of the aliphatic amine can be properly increased, so that the reaction of the organic amine and the epoxy resin can be started as soon as possible, the temperature of the glue/glue block is raised to sequentially excite the reaction conditions of the alicyclic amine, the polyether amine and the epoxy, and the total curing time (4-8 hours) is ensured to be unchanged. On the contrary, when the temperature of the sizing environment is higher, the proportion of the aliphatic amine can be properly reduced, and the reaction of the alicyclic amine, the polyether amine and the epoxy can be delayed.
In addition, the xylene formaldehyde resin in the curing agent composition does not participate in the reaction, but can absorb part of the reaction heat, and the highest reaction temperature of the epoxy glue block/glue is regulated and controlled through catalysis. Meanwhile, compared with solvents such as benzyl alcohol and the like, the xylene formaldehyde resin has the advantages of higher molecular weight (250-700 g/mol), small irritation, difficult volatilization and vaporization, and small smell and high environmental safety. Moreover, the xylene formaldehyde resin has low polarity and good compatibility with the epoxy glue, can relieve the defects of whitening and stickiness on the surface of the epoxy glue block caused by the reaction of organic amine and carbon dioxide in the air, eliminate partial internal stress formed in the reaction process, increase the toughness of the epoxy glue block and improve the polishing performance during detection.
Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the details of the embodiments, and various equivalent modifications can be made within the technical spirit of the present invention, and the scope of the present invention is also within the scope of the present invention. It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (4)
1. The application of the composition as low-temperature high-hardness epoxy glue for metallographic cold inlay of a heat sensitive element is characterized in that the composition comprises an epoxy resin component and a curing agent component, wherein the molar ratio of epoxy groups in the epoxy resin component to active hydrogen of amino compounds in the curing agent component is (1) 0.95-1.05,
the epoxy resin comprises the following components in parts by mass:
bisphenol A epoxy resin E-5170-90 parts;
5-15 parts of monofunctional reactive diluent;
5-15 parts of bi/multifunctional reactive diluent;
the curing agent comprises the following components in parts by mass:
30-50 parts of fatty amine;
5-15 parts of alicyclic amine;
30-50 parts of polyether amine;
5-20 parts of xylene formaldehyde resin;
wherein the monofunctional reactive diluent is any one or a mixture of at least two of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, 2-ethylhexyl glycidyl ether, o-cresol glycidyl ether, p-tert-butylphenyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and C12-14 alkyl glycidyl ether;
the bi/multi-functional reactive diluent is any one or a mixture of at least two of ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether, propoxyglycerol triglycidyl ether and sorbitol polyglycidyl ether;
the aliphatic amine is any one or a mixture of at least two of divinyltriamine, triethylene tetramine, tetraethylene pentamine, m-xylylenediamine, 1, 3-cyclohexyldimethylamine, 1, 6-hexamethylene diamine and ethylene diamine;
the alicyclic amine is any one or a mixture of at least two of isophorone diamine, methyl cyclohexane diamine, 4' -diaminodicyclohexyl methane and amino ethyl piperazine;
the polyether amine is any one or a mixture of at least two of polyether amine D230, polyether amine D400 and polyether amine T403.
2. The use according to claim 1, characterized in that the epoxy resin component further comprises a polyacrylate solution having a mass concentration of 50% or less, wherein the polyacrylate has a number average molecular weight of 3000g/mol or less.
3. Use according to claim 2, characterized in that the polyacrylate solution in the epoxy resin component is 0.1 to 0.6 parts by mass.
4. Use according to claim 1, characterized in that the xylene formaldehyde resin has a number average molecular weight of 250-700g/mol.
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