CN114716952B - Efficient structural adhesive for temporary bonding and application thereof - Google Patents

Efficient structural adhesive for temporary bonding and application thereof Download PDF

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CN114716952B
CN114716952B CN202210456638.0A CN202210456638A CN114716952B CN 114716952 B CN114716952 B CN 114716952B CN 202210456638 A CN202210456638 A CN 202210456638A CN 114716952 B CN114716952 B CN 114716952B
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acid
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CN114716952A (en
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袁彦超
井长友
李丽珍
刘述梅
赵建青
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South China University of Technology SCUT
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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
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06—Amines
    • 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
    • C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
    • 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
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
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    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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    • C11D7/5013—Organic solvents containing nitrogen
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    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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    • C11D7/5022—Organic solvents containing oxygen
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    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
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    • C08G2170/00—Compositions for adhesives
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    • 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
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    • C08K3/20—Oxides; Hydroxides
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    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention belongs to the field of adhesives, and discloses a high-efficiency structural adhesive for temporary bonding and application thereof. The adhesive comprises a component A and a component B, wherein the component A comprises, by weight, 35% -100% of aromatic aldehyde epoxy prepolymer, 0% -10% of reactive diluent, 0% -30% of inorganic filler, 0% -5% of thixotropic agent and 0% -20% of toughening agent; the component B comprises 30 to 100 weight percent of amine curing agent, 0 to 5 weight percent of accelerator, 0 to 40 weight percent of inorganic filler, 0 to 5 weight percent of thixotropic agent and 0 to 20 weight percent of toughening agent. The temporary bonding adhesive disclosed by the invention does not contain volatile solvents, is high in bonding speed, high in bonding strength, high in thermal stability of a bonding layer, good in solvent resistance of the bonding layer, high in degumming speed, thorough in degumming, simple in operation process, simple in adhesive preparation process, adjustable in structure and wide in application prospect.

Description

Efficient structural adhesive for temporary bonding and application thereof
Technical Field
The invention belongs to the field of adhesives, and is used for temporarily fixing various workpieces or components, such as wafer processing, hard material cutting and the like, and particularly relates to an efficient structural adhesive for temporary bonding, and a preparation method and a use method thereof.
Background
In the fields of semiconductors, solar energy, electronic industry, machining and the like, a plurality of working procedures relate to the process operation of temporarily fixing components, the process requires that various components are temporarily bonded or bonded by using an adhesive so as to facilitate the machining, the components are required to be quickly and completely separated from the adhesive after the machining is finished, and the temporary bonding of the adhesive is the key of whether the process can be successfully implemented. Chinese patent CN104204126a discloses a wafer processing film adhesive composition comprising an acrylic polymer and a photosensitive gas generator, the adhesive layer being debonded using ultraviolet light. Chinese patent CN104804682a discloses a temporary bonding adhesive for wafer thinning, which is prepared by reacting diamine compound and aliphatic aldehyde in solvent to generate hexahydrotriazine resin, bonding wafer and carrier by solvent volatilization and resin curing at 120-180 ℃, and then bonding by strong acid after wafer thinning. Chinese patent ZL201510800691.8 discloses a bi-component epoxy resin temporary adhesive, which adopts a pure physical method of adding microsphere foaming agent and super absorbent resin, and the defoaming process is completed by physical foaming and water absorption degumming. The prior art has the limitations that the adhesive contains volatile solvents, has low bonding speed, low bonding strength, low thermal stability of the bonding layer, low degumming speed, incomplete degumming and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an efficient structural adhesive for temporary bonding. The high-activity aromatic aldehyde epoxy prepolymer containing aldehyde groups and epoxy groups is reacted with amine to prepare the temporary bonding adhesive which does not contain volatile solvents, is high in bonding speed, high in bonding strength, high in thermal stability of a bonding layer, good in solvent resistance of the bonding layer, high in degumming speed, thorough in degumming and simple in operation process, has the characteristics of the epoxy adhesive, and can obtain a degradable function through imine dynamic covalent bonds.
The invention further aims to provide a using method of the high-efficiency structural adhesive for temporary bonding.
The aim of the invention is achieved by the following technical scheme:
the high-efficiency structural adhesive for temporary bonding comprises a raw material including a component A and a component B, wherein the component A comprises the following components in percentage by weight:
aromatic aldehyde epoxy prepolymer: 35 to 100 percent
Reactive diluent: 0 to 10 percent
Inorganic filler: 0 to 30 percent
Thixotropic agent: 0 to 5 percent
Toughening agent: 0 to 20 percent
The component B comprises the following components in percentage by weight:
an amine curing agent: 30 to 100 percent
And (3) an accelerator: 0 to 5 percent
Inorganic filler: 0 to 40 percent
Thixotropic agent: 0 to 5 percent
Toughening agent: 0 to 20 percent
The aromatic aldehyde epoxy prepolymer contains 1 epoxy group and at least 1 aromatic aldehyde group.
Preferably, the aromatic aldehyde epoxy prepolymer is any one or more of the following structures:
preferably, the amine curing agent is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, m-xylylenediamine, isophoronediamine, menthanediamine, 1, 3-bis (aminomethyl) cyclohexane, bis (4-amino-3-methylcyclohexyl) methane, 1, 3-bis (gamma-aminopropyl) -5, 5-dimethylhydantoin.
Preferably, the reactive diluent is one or more than two of benzaldehyde, p-methoxybenzaldehyde, n-butyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, tolyl glycidyl ether and benzoic acid glycidyl ester.
Preferably, the inorganic filler is one or more than two of quartz powder, alumina powder, titanium dioxide, ferric oxide powder, zinc oxide powder, talcum powder, calcium carbonate powder, kaolin powder, barite powder, iron powder, copper powder, aluminum powder and zinc powder.
Preferably, the thixotropic agent is one or a mixture of more than two of fumed silica, organic bentonite, hydrogenated castor oil and polyethylene wax.
Preferably, the toughening agent is one or a mixture of more than two of polyphenyl ether, polysulfone, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyamide and polyvinyl butyral.
Preferably, the accelerator is one or more than two of 2,4, 6-tri (dimethylaminomethyl) phenol, triethylamine, triethanolamine, benzyl dimethylamine, o-hydroxybenzyl dimethylamine, 2-ethyl-4-methylimidazole, 1-benzyl-2-ethylimidazole and 1-aminoethyl-2-methylimidazole.
Preferably, the A component comprises the following components in percentage by weight:
aromatic aldehyde epoxy prepolymer: 35 to 96 percent
Reactive diluent: 1 to 10 percent of
Inorganic filler: 1 to 30 percent
Thixotropic agent: 1 to 5 percent
Toughening agent: 1 to 20 percent
The component B comprises the following components in percentage by weight:
an amine curing agent: 30 to 96 percent
And (3) an accelerator: 1 to 5 percent
Inorganic filler: 1 to 40 percent of
Thixotropic agent: 1 to 5 percent
Toughening agent: 1 to 20 percent.
The application of the high-efficiency structural adhesive for temporary bonding comprises the steps of uniformly mixing the component A and the component B, and then performing bonding operation, wherein the curing temperature is 0-100 ℃, and the curing time is 2 min-24 h.
Preferably, the mass ratio of the component A to the component B is 10: (5-10).
Preferably, the curing temperature is 20-30 ℃ and the curing time is 10 min-2 h.
The degumming method of the high-efficiency structural adhesive for temporary bonding adopts an acid solution to degrade an adhesive layer, wherein the solute of the acid solution is one or a mixture of more than two of hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, citric acid, malic acid, formic acid, lactic acid, benzoic acid, acetic acid and propionic acid; the solvent of the acid solution is one or more than two of water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, xylene, ethanol, butanol, isobutanol, cyclohexanone, methylcyclohexanone, acetone, butanone, ethyl acetate, butyl acetate and cellosolve.
Preferably, the degumming temperature is 0-100 ℃ and the degumming time is 5-30 min.
The preparation method of the high-efficiency structural adhesive for temporary bonding comprises the following steps:
(1) And (3) a component A: adding the aromatic aldehyde epoxy prepolymer, the diluent, the inorganic filler, the thixotropic agent and the toughening agent into a stirrer at normal temperature, stirring for 5-30 min until the mixture is uniform, and vacuum degassing for 5-10 min. If only the aromatic aldehyde epoxy prepolymer is included in the component, it can be used directly;
(2) And the component B comprises the following components: adding the amine curing agent, the accelerator, the inorganic filler, the thixotropic agent and the toughening agent into a stirrer at normal temperature, stirring for 5-30 min until the mixture is uniform, and vacuum degassing for 5-10 min. If only an amine curing agent is included in the component, it may be used as such.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts the high-activity aromatic aldehyde epoxy prepolymer which contains 1 epoxy group and 1-n aromatic aldehyde groups in the molecular structure to react with an amine curing agent, the epoxy group can endow the adhesive with higher bonding strength, and the imine dynamic covalent bond structure generated after the reaction of the aromatic aldehyde groups and primary amine groups endows the adhesive with degradable function. The prepared temporary bonding adhesive does not contain volatile solvents, has high bonding speed, high bonding strength, high thermal stability of a bonding layer, good solvent resistance of the bonding layer, high degumming speed, thorough degumming and simple operation process.
(2) The temporary bonding adhesive prepared by the invention has an arbitrarily adjustable structure, and the preparation method is simple and easy for large-scale production.
Drawings
FIG. 1 is an aromatic aldehyde epoxy prepolymer used in the examples of the present invention: (a) A m-benzaldehyde glycidyl ether, (b) a p-benzaldehyde glycidyl ether.
FIG. 2 is an infrared spectrum of the adhesive in the reaction process of example 3 of the present invention: (a) reaction starts and (b) reaction ends.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the content of the present invention is not limited to the following examples.
Meta-hydroxybenzaldehyde glycidyl etherAnd (3) synthesis: 50g of m-hydroxybenzaldehyde and 3.2g of tetrabutylammonium bromide are added into a three-neck flask with a thermometer and a condenser, 152g of epichlorohydrin is poured into the flask, and the mixture is stirred at normal temperature for 10min until the system is uniformly mixed. Introducing nitrogen, reacting for 2 hours at 80 ℃, and cooling to 15 ℃. 82g of 50wt% aqueous sodium hydroxide solution was added dropwise to the mixture over 15 minutes using a constant pressure dropping funnel, the mixture was allowed to react at 15℃for 3 hours, and the temperature was raised at 40℃for 3 hours. Extracted with 80ml dichloromethane and washed with 100ml water. After removal of unreacted epichlorohydrin and solvent by rotary evaporation, 69g of a yellow oily liquid product (viscosity about 0.35 Pa.S at 25 ℃ C., see FIG. 1) was obtained in a yield of about 95.1%. Other types of aromatic aldehyde epoxy prepolymers are prepared in a similar manner.
Example 1
The A component only comprises m-hydroxybenzaldehyde glycidyl ether, and the B component only comprises tetraethylenepentamine. The adhesive tensile shear strength was tested according to the national standard GB/T7124-2008 adhesive tensile shear strength determination (rigid material to rigid material) method. 10.0g of m-hydroxybenzaldehyde glycidyl ether and 7.0g of tetraethylenepentamine are quickly and evenly mixed, the mixture is smeared on the bonding part of a stainless steel test piece, the steel piece is tightly attached, the redundant sizing material at the edge is removed, the steel piece is fixed by a reverse tail clamp, 5 samples are tested in each group, and the average value is obtained. Curing for 10min, 1h, 2h and 24h at normal temperature, and respectively reaching the tensile shear strength of 0.5, 8.0, 12.1 and 16.3MPa. And (3) soaking the sample solidified at normal temperature for 24 hours in an aqueous solution of ethanol, methanol, acetone, butanone, toluene, ethyl acetate, N-methylpyrrolidone, N-dimethylformamide, hydrogen peroxide and sodium hydroxide for 24 hours at normal temperature, so that the adhesive is not degraded completely and has no degumming phenomenon. The 5wt% thermal decomposition temperature of the sample bonding layer cured at normal temperature for 24 hours is 295 ℃. And (3) soaking the sample cured at normal temperature for 24 hours in 1mol/L acetic acid aqueous solution at normal temperature, and completely degrading the adhesive for about 8 minutes to finish degumming.
Example 2
The adhesive composition and test method were the same as in example 1, with different curing conditions. Curing at 100 ℃ for 3min, 5min, 10min and 1h, and respectively reaching the tensile shear strength of 1.5, 5.1, 11.8 and 22.1MPa. The sample solidified for 1h at 100 ℃ is soaked in aqueous solution of ethanol, methanol, acetone, butanone, toluene, ethyl acetate, N-methyl pyrrolidone, N-dimethylformamide, hydrogen peroxide and sodium hydroxide for 24h at normal temperature, and the adhesive is not degraded and degummed completely. The sample adhesive layer was cured at 100℃for 1 hour at a 5wt% thermal decomposition temperature of 309 ℃. And (3) soaking the sample cured at 100 ℃ for 1h in 1mol/L acetic acid aqueous solution at normal temperature, and completely degrading the adhesive for about 10min to finish degumming.
Example 3
The adhesive A component only comprises parahydroxyben-zaldehyde glycidyl etherSee fig. 2), other components and test methods are the same as in example 1. Curing for 30min, 1h, 2h and 24h at normal temperature, and respectively reaching the tensile shear strength of 0.4, 7.9, 11.5 and 15.7MPa. The reaction process and reaction mechanism (aldehyde group and epoxy group in the structure of the parahydroxyben-zaldehyde glycidyl ether respectively react with amino group in the structure of tetraethylenepentamine to generate imine bond and cross-linking structure) of the adhesive are shown in an infrared spectrogram 2. Soaking the sample cured at normal temperature for 24 hours in ethanol, methanol, acetone, butanone, toluene, ethyl acetate, N-methylpyrrolidone,N,N-
And the adhesive is completely not degraded and has no degumming phenomenon in dimethylformamide, hydrogen peroxide and sodium hydroxide aqueous solution for 24 hours. The 5wt% thermal decomposition temperature of the sample bonding layer cured at normal temperature for 24 hours is 302 ℃. And (3) soaking the sample cured at normal temperature for 24 hours in 1mol/L acetic acid aqueous solution at normal temperature, and completely degrading the adhesive for about 9 minutes to finish degumming.
Example 4
30.0g of m-hydroxybenzaldehyde glycidyl ether, 23.0g of p-hydroxybenzaldehyde glycidyl ether, 5.0g of benzaldehyde, 30.0g of alumina powder, 2.0g of nano silica and 10.0g of polyvinyl butyral powder are added into a stirrer, stirred for 10min and degassed under vacuum for 5min to obtain a component A. 45.0g of tetraethylenepentamine, 3.0g of 2,4, 6-tris (dimethylaminomethyl) phenol, 40.0g of alumina powder, 2.0g of nano silica and 10.0g of polyvinyl butyral powder are added into a stirrer, stirred for 10min and degassed in vacuo for 5min to obtain component B. The adhesive was tested for tensile shear strength according to national standard GB/T7124-2008. And (3) rapidly and uniformly mixing 10.0g of A component and 10.0g of B component, smearing the mixture on a bonding part of a stainless steel test piece, tightly attaching the steel piece, removing excessive sizing materials at the edge, fixing the steel piece by a reverse tail clamp, testing 5 samples in each group, and taking an average value. Curing for 10min, 1h, 2h and 24h at normal temperature, and respectively reaching the tensile shear strength of 0.8, 10.7, 15.8 and 20.7MPa. And (3) soaking the sample solidified at normal temperature for 24 hours in an aqueous solution of ethanol, methanol, acetone, butanone, toluene, ethyl acetate, N-methylpyrrolidone, N-dimethylformamide, hydrogen peroxide and sodium hydroxide for 24 hours at normal temperature, so that the adhesive is not degraded completely and has no degumming phenomenon. The 5wt% thermal decomposition temperature of the sample bonding layer cured at normal temperature for 24 hours is 326 ℃. And (3) soaking the sample cured at normal temperature for 24 hours in 1mol/L acetic acid aqueous solution at normal temperature, and completely degrading the adhesive for about 6 minutes to finish degumming.
Example 5
20.0g of m-hydroxybenzaldehyde glycidyl ester23.0g 6-hydroxy-2-naphthaldehyde glycidyl ether +.>10.0g of phenyl glycidyl ether, 25.0g of quartz powder, 2.0g of organic bentonite and 20.0g of polycarbonate powder are added into a stirrer, stirred for 10min and vacuum degassed for 10min to obtain a component A. 52.0g g N-aminoethylpiperazine, 2.0g triethanolamine, 23.0g calcium carbonate powder, 3.0g organobentonite, 20.0g polycarbonate powder were added to a stirrer, stirred for 10min, and vacuum degassed for 10min to obtain component B. The adhesive was tested for tensile shear strength according to national standard GB/T7124-2008. And (3) rapidly and uniformly mixing 10.0g of A component and 5.0g of B component, smearing the mixture on a bonding part of a stainless steel test piece, tightly attaching the steel piece, removing excessive sizing materials at the edge, fixing the steel piece by a reverse tail clamp, testing 5 samples in each group, and taking an average value. Curing for 10min, 1h, 2h and 24h at normal temperature, and respectively reaching the tensile shear strength of 1.0, 11.2, 16.3 and 19.8MPa. And (3) soaking the sample solidified at normal temperature for 24 hours in an aqueous solution of ethanol, methanol, acetone, butanone, toluene, ethyl acetate, N-methylpyrrolidone, N-dimethylformamide, hydrogen peroxide and sodium hydroxide for 24 hours at normal temperature, so that the adhesive is not degraded completely and has no degumming phenomenon. The 5wt% thermal decomposition temperature of the sample bonding layer cured at normal temperature for 24 hours is 332 ℃. And (3) soaking the sample cured at normal temperature for 24 hours in 1mol/L acetic acid aqueous solution at normal temperature, and completely degrading the adhesive for about 13 minutes to finish degumming.
Comparative example
The A component comprises bisphenol A glycidyl ether NPEL-128 only, and the B component comprises tetraethylenepentamine only. The adhesive was tested for tensile shear strength according to national standard GB/T7124-2008. 17.6g of NPEL-128 and 2.4g of tetraethylenepentamine are quickly and evenly mixed, the mixture is smeared on the bonding part of a stainless steel test piece, the steel piece is tightly attached, excessive sizing materials at the edge are removed, the steel piece is fixed by a reverse tail clamp, 5 samples are tested in each group, and the average value is obtained. Curing for 2h, 4h, 10h and 24h at normal temperature, and respectively reaching tensile shear strength of 0, 5.1, 11.5 and 12.4MPa. The sample solidified for 24 hours at normal temperature is soaked in 1mol/L acetic acid or hydrochloric acid aqueous solution, ethanol, methanol, acetone, butanone, toluene, ethyl acetate, N-methylpyrrolidone, N-dimethylformamide, hydrogen peroxide and sodium hydroxide aqueous solution for 24 hours, and the adhesive is not degraded and degummed at all.
TABLE 1 high efficiency structural adhesive for temporary bonding
* Remarks: degumming time, namely the time for the adhesive to be completely degraded after being soaked in 1mol/L acetic acid aqueous solution, wherein the sample is cured for 1h at 100 ℃ in the example 2, and the samples are cured for 24h at normal temperature; the sample of the control sample is not degraded at all and cannot be degummed; normal temperature means 23+ -1deg.C.
The results of the above examples and Table 1 show that the high-efficiency structural adhesive for temporary bonding of the present invention has the advantages of high bonding speed, high bonding strength, high degumming speed, thorough degumming and simple operation process.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (8)

1. The high-efficiency structural adhesive for temporary bonding is characterized by comprising a component A and a component B, wherein the component A comprises the following components in percentage by weight:
aromatic aldehyde epoxy prepolymer: 35 to 100 percent
Reactive diluent: 0 to 10 percent
Inorganic filler: 0 to 30 percent
Thixotropic agent: 0 to 5 percent
Toughening agent: 0 to 20 percent
The component B consists of the following components in percentage by weight:
an amine curing agent: 30 to 100 percent
And (3) an accelerator: 0 to 5 percent
Inorganic filler: 0 to 40 percent
Thixotropic agent: 0 to 5 percent
Toughening agent: 0 to 20 percent
The aromatic aldehyde epoxy prepolymer is any one or more of the following structures:
the amine curing agent is one or more than two of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, m-xylylenediamine, isophoronediamine, menthanediamine, 1, 3-bis (aminomethyl) cyclohexane, bis (4-amino-3-methylcyclohexyl) methane and 1, 3-bis (gamma-aminopropyl) -5, 5-dimethylhydantoin.
2. The efficient structural adhesive for temporary bonding according to claim 1, wherein the reactive diluent is one or a mixture of more than two of benzaldehyde, p-methoxybenzaldehyde, n-butyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, tolyl glycidyl ether and glycidyl benzoate;
the inorganic filler is one or more than two of quartz powder, alumina powder, titanium dioxide, ferric oxide powder, zinc oxide powder, talcum powder, calcium carbonate powder, kaolin powder, barite powder, iron powder, copper powder, aluminum powder and zinc powder;
the thixotropic agent is one or a mixture of more than two of fumed silica, organic bentonite, hydrogenated castor oil and polyethylene wax;
the toughening agent is one or a mixture of more than two of polyphenyl ether, polysulfone, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyamide and polyvinyl butyral;
the promoter is one or more than two of 2,4, 6-tri (dimethylaminomethyl) phenol, triethylamine, triethanolamine, benzyl dimethylamine, o-hydroxybenzyl dimethylamine, 2-ethyl-4-methylimidazole, 1-benzyl-2-ethylimidazole and 1-aminoethyl-2-methylimidazole.
3. The efficient structural adhesive for temporary bonding according to claim 1 or 2, wherein the A component comprises the following components in percentage by weight:
aromatic aldehyde epoxy prepolymer: 35 to 96 percent
Reactive diluent: 1 to 10 percent of
Inorganic filler: 1 to 30 percent
Thixotropic agent: 1 to 5 percent
Toughening agent: 1 to 20 percent
The component B consists of the following components in percentage by weight:
an amine curing agent: 30 to 96 percent
And (3) an accelerator: 1 to 5 percent
Inorganic filler: 1 to 40 percent of
Thixotropic agent: 1 to 5 percent
Toughening agent: 1 to 20 percent.
4. The use of the high-efficiency structural adhesive for temporary bonding according to claim 1, 2 or 3, wherein the component A and the component B are uniformly mixed and then subjected to bonding operation, and the curing temperature is 0-100 ℃ and the curing time is 2 min-24 h.
5. The use according to claim 4, wherein the mass ratio of the a component to the B component is 10: (5-10).
6. The use according to claim 4 or 5, wherein the curing temperature is 20-30 ℃ and the curing time is 10 min-2 h.
7. The degumming method of the high-efficiency structural adhesive for temporary bonding according to claim 1, 2 or 3, wherein an acid solution is adopted to degrade the bonding layer, and the solute of the acid solution is one or a mixture of more than two of hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, citric acid, malic acid, formic acid, lactic acid, benzoic acid, acetic acid and propionic acid; the solvent of the acid solution is one or more than two of water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, xylene, ethanol, butanol, isobutanol, cyclohexanone, methylcyclohexanone, acetone, butanone, ethyl acetate, butyl acetate and cellosolve.
8. The degumming process according to claim 7, wherein the degumming temperature is between 0 and 100 ℃ and the degumming time is between 5 and 30 minutes.
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