CN111518496B - Epoxy resin liquid mixture and UV (ultraviolet) delayed curing solid adhesive film prepared from same - Google Patents
Epoxy resin liquid mixture and UV (ultraviolet) delayed curing solid adhesive film prepared from same Download PDFInfo
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- CN111518496B CN111518496B CN202010230667.6A CN202010230667A CN111518496B CN 111518496 B CN111518496 B CN 111518496B CN 202010230667 A CN202010230667 A CN 202010230667A CN 111518496 B CN111518496 B CN 111518496B
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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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- 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
- C08G59/68—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 catalysts used
- C08G59/688—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 catalysts used containing phosphorus
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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Abstract
The invention relates to an epoxy resin liquid mixture and a UV delayed curing solid adhesive film prepared from the same, which is characterized in that the epoxy resin liquid mixture comprises solid alicyclic epoxy resin, solid phenolic epoxy resin, isocyanate modified alicyclic epoxy resin, a UV delayed curing agent, a toughening agent, a filler and a solvent A. The bonding and curing mechanism mode of the UV delayed curing solid adhesive film prepared from the epoxy resin liquid mixture is that UV is pre-activated, then bonding and bonding are carried out, and finally bonding is realized by utilizing a delayed curing mechanism and a moisture post-curing mechanism in a UV delayed initiator. The UV delayed curing solid adhesive film has the dual advantages of adhesive tapes and glue and the characteristic of UV delayed curing, is particularly suitable for bonding small parts of sensors, does not need high-temperature curing, and has excellent bonding strength and long-term reliability.
Description
Technical Field
The invention relates to an epoxy resin liquid mixture and a UV delayed curing solid adhesive film prepared from the same, and the UV delayed curing solid adhesive film is applied to the field of sensor bonding.
Background
Along with the development of science and technology, more and more intelligent chip or sensor need bond fixedly, like the car, the cell-phone, equipment such as wearing, the fixed requirement of bonding of sensor has very strong bonding strength and reliability, simultaneously because the bonding of these sensors needs lower temperature, consequently, require bonding material to have low temperature curing's characteristic, consequently, the present industry mainly adopts room temperature curing's bi-component structure to glue, low temperature curing's thermosetting glue or anaerobic adhesive bond, but when liquid glue bonded, because the mobility of liquid, the slope and the displacement of chip appear easily, thereby influence the function of sensor. If the adhesive tape is used for bonding, the flowability of the liquid glue can be avoided, but the bonding strength of the conventional adhesive tape is only about one tenth of that of the high-temperature cured liquid glue or anaerobic glue, so that the bonding reliability requirement of the sensor cannot be met.
Aiming at the bonding of the intelligent sensor, a bonding effect similar to an adhesive tape and with controllable thickness and bonding strength similar to double-component structural adhesive and anaerobic adhesive are required to be developed.
As shown in fig. 1, firstly, a high-bonding-strength UV-delayed adhesive film is pasted on the surface of a base material, irradiated with UV for activation, then, a chip is pasted, and then, the adhesive film is placed at room temperature, so that the effects of high bonding strength and controllable thickness similar to that of an adhesive tape can be realized, and the problems of chip inclination, deviation and the like can not be caused.
At present, there are UV-delayed liquid glues in the industry, such as the invention patent with patent number ZL201510006072.1 and the name "UV-initiated curable one-component epoxy adhesive with delayed curing", the invention patent with patent number 201780021968.4 and the name "light-curable composition containing electronic olefin", the invention patent with patent number 201680068589.6 and the name "delayed curing type photocurable resin composition", and the invention patent with patent number ZL201010225303.5 and the name "delayed curing resin composition", which are all UV-delayed liquid glues, and compared with glue, glue films have greater advantages in the bonding process, but there is no UV-delayed epoxy structure glue film with good bonding reliability in the industry, and the need of the above application scenarios cannot be met.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an epoxy resin liquid mixture and a UV delayed curing solid adhesive film prepared from the epoxy resin liquid mixture.
In order to achieve the above-mentioned primary object, the technical solution of the epoxy resin liquid mixture of the present invention is characterized by comprising a solid alicyclic epoxy resin, a solid novolac epoxy resin, an isocyanate-modified alicyclic epoxy resin, a UV delayed curing agent, a filler and a solvent a, wherein the weight ratio of the solid alicyclic epoxy resin, the solid novolac epoxy resin, the isocyanate-modified alicyclic epoxy resin, the UV delayed curing agent, a toughening agent, the filler and the solvent a is: 100: 0-50: 10-30: 20-50: 1-5: 10-200: 200-1500.
In the technical scheme, the synthetic route of the isocyanate modified alicyclic epoxy resin is shown as the following formula:
wherein R is1Is R1Is H or CH3-，R2Is- (CH)2)m-or- (CH)2-O-CH2)m-, x is 20 to 100, y is 5 to 100, n is 20 to 200, m is 1 to 10;
adding an acrylic monomer with double-bond alicyclic epoxy and an acrylic monomer with isocyanic acid into a solvent B, adding an initiator A, reacting for 2-5 hours at the temperature of 40-80 ℃, adding a polymerization inhibitor, and purifying to obtain the solid isocyanic acid modified alicyclic epoxy resin.
In the technical scheme, the solid alicyclic epoxy resin is poly [ (2-ethylene oxide) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1)/CAS number 244772-00-7.
In the technical scheme, the solid novolac epoxy resin is one or a mixture of more of o-cresol novolac epoxy resin, BPA novolac epoxy resin, dicyclopentadiene phenol novolac epoxy resin, trifunctional novolac epoxy resin and phenol novolac epoxy resin, and the number average molecular weight (Mn) is 10000-200000.
In the technical scheme, the acrylic monomer of the alicyclic epoxy with the double bond comprises 3, 4-epoxy cyclohexyl methyl acrylate, 3, 4-epoxy cyclohexyl methyl acrylate and 1, 2-epoxy-4-vinyl cyclohexane.
In the technical scheme, the initiator A is one or a mixture of more of benzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and azobisisobutyric acid dimethyl ester.
In the technical scheme, the solvent B is one or a mixture of cyclohexanone, toluene, tetrahydrofuran, acetone, trichloromethane and dioxane.
In the technical scheme, the polymerization inhibitor is one or a mixture of more of 2,4, 6-trinitrophenol, 1, 4-benzoquinone, benzenediol, phenothiazine, beta-phenyl naphthylamine and p-tert-butyl catechol.
In the technical scheme, the UV delay curing agent is one or a mixture of more of (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate, triallyl sulfonium hexafluorophosphate, triallyl hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, triphenyl sulfonium antimonate, diphenyl iodonium hexafluoroantimonate and diphenyl-4-sulfonium phenoxyphenyl sulfonium hexafluoroantimonate.
In the technical scheme, the toughening agent is a butadiene elastomer system, an organic silicon modified system or a rubber system; the butadiene elastomer systems are commercially available as MX137, MX154, MX127, MX451, and MX533 series (KANEKA, Japan); the silicone modification system is commercially available MX965 (KANEKA, Japan), KMP-605 (Beacon), and GENIOPERL P-52; the rubber system is ATBN or CTBN (a product of Japan department of Japan).
In the technical scheme, the filler is one or a mixture of more of calcium carbonate, talcum powder, silicon dioxide, aluminum oxide and magnesium oxide, and the particle size distribution is 0.1-10 mu m.
In the technical scheme, the solvent A is one or a mixture of more of tetrahydrofuran, acetone, trichloromethane, dichloromethane, ethyl acetate, dioxane and ethylene oxide.
In the technical scheme, the UV delayed curing solid adhesive film prepared from the epoxy resin liquid mixture is characterized in that the obtained epoxy resin liquid mixture is coated on black release paper in a workshop environment with the wavelength of more than 500nm visible light and the humidity of less than 30%, the black release paper is baked in an oven for 20-100min, the temperature of the oven is 40-60 ℃, and then another layer of black release paper is covered to prepare the UV delayed curing solid adhesive film with the thickness of 10-500 mu m.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the solid resin, the curing agent, the toughening agent and the filler are dispersed in the low-boiling-point solvent, then coated on the release paper, and the solvent is removed through low-temperature drying to prepare the solid adhesive film;
2. according to the invention, a UV delay initiator is adopted to develop a glue film capable of being subjected to UV activation and then subjected to room temperature delay curing, namely, the glue film is activated by UV light irradiation, then a component is attached, and the room temperature delay curing is performed, so that the glue film has the advantages of controllable thickness and convenience in die cutting like a common glue tape, has the same bonding strength as glue, and is not easy to overflow like glue;
3. the application of the invention mentions that two UV delay curing mechanisms are provided, one is a UV delay special type that iodonium and sulfonium salt UV delay curing agents initiate alicyclic epoxy resin to cure, and the other is that NCO and water in air are easy to generate cross-linking reaction.
Drawings
FIG. 1 is a flow chart of the application of a UV-delayed curing adhesive film according to the prior art;
fig. 2 is a schematic structural diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example one
(1) Preparation of isocyanate-modified cycloaliphatic epoxy resin:
the synthetic route of the isocyanate modified alicyclic epoxy resin is shown as the following formula:
wherein R is1Is H, R2Is- (CH)2)m-, x is 20, y is 5, n is 20, m is 1;
adding an acrylic monomer with double-bond alicyclic epoxy and an acrylic monomer with isocyanic acid into a solvent B, adding an initiator A, reacting for 2 hours at the temperature of 40 ℃, adding a polymerization inhibitor, and purifying to obtain the solid isocyanic acid modified alicyclic epoxy resin.
The acrylic monomer of the alicyclic epoxy with double bonds is 3, 4-epoxy cyclohexyl methacrylate; the acrylic monomer with isocyanate is isocyano ethyl methacrylate; the initiator A is benzoyl peroxide; the solvent B is cyclohexanone; the polymerization inhibitor is 2,4, 6-Trinitrophenol (TNP).
(2) Preparation of epoxy resin liquid mixture:
mixing solid alicyclic epoxy resin, solid novolac epoxy resin, isocyanate modified alicyclic epoxy resin, UV delayed curing agent, toughening agent, filler and solvent A to obtain a required epoxy resin liquid mixture; the weight ratio of the solid alicyclic epoxy resin, the solid novolac epoxy resin, the isocyanic acid modified alicyclic epoxy resin, the UV delayed curing agent, the toughening agent, the filler and the solvent A is as follows: 100: 0: 10: 20: 1: 10: 200 of a carrier;
the solid alicyclic epoxy resin is poly [ (2-ethylene oxide) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1)/CAS number 244772-00-7; the solid phenolic epoxy resin is o-cresol formaldehyde epoxy resin, and the molecular weight of the solid phenolic epoxy resin is 10000; the UV delayed curing agent is (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate; the toughening agent is MX 137; the filler is calcium carbonate, and the particle size distribution is 200 nm; the solvent A is tetrahydrofuran.
(3) Preparation of UV delayed curing solid adhesive film
Coating the obtained epoxy resin liquid mixture on black release paper in a workshop environment with visible light with wavelength of more than 500nm and humidity of less than 30%, baking at 40 deg.C for 20min in an oven, and covering with another layer of black release paper to obtain UV delayed curing solid adhesive film with thickness of 10 μm, as shown in FIG. 2.
(4) Method for bonding sensor at room temperature by UV delay
The UV delayed curing solid adhesive film is pasted on the surface of a substrate, then UV light is irradiated, the wavelength of the UV light is 300nm, the energy is 200mW/S, the irradiation time is 1S, a sensor is pasted in 20S after the UV light is irradiated, and the UV delayed curing adhesive film is stood for 2 hours, so that the full curing can be realized, the high bonding strength is achieved, the thickness is controllable, and the inclination and the deviation cannot be generated. The adhesive tape can be replaced to achieve better adhesive strength and is used for adhering small parts of a sensor type.
Example two
(1) Preparation of isocyanate-modified cycloaliphatic epoxy resin:
the synthetic route of the isocyanate modified alicyclic epoxy resin is shown as the following formula:
wherein R is1Is CH3-，R2Is- (CH)2-O-CH2) m-, x is 100, y is 100, n is 200, m is 10;
adding an acrylic monomer with double-bond alicyclic epoxy and an acrylic monomer with isocyanic acid into a solvent B, adding an initiator A, reacting for 2 hours at the temperature of 40 ℃, adding a polymerization inhibitor, and purifying to obtain solid isocyanic acid modified alicyclic epoxy resin;
the acrylic monomer of the alicyclic epoxy with double bonds is 3, 4-epoxy cyclohexyl methyl methacrylate; the acrylic monomer with isocyanate is 2- (2-isocyanatoethoxy) ethyl methacrylate; the initiator A is azobisisoheptonitrile; the solvent B is dioxane, and the polymerization inhibitor is 1, 4-Benzoquinone (BQ).
(2) Preparation of epoxy resin liquid mixture:
mixing solid alicyclic epoxy resin, solid novolac epoxy resin, isocyanate modified alicyclic epoxy resin, UV delayed curing agent, toughening agent, filler and solvent A to obtain a required epoxy resin liquid mixture; wherein the weight ratio of the solid alicyclic epoxy resin, the solid novolac epoxy resin, the isocyanic acid modified alicyclic epoxy resin, the UV delayed curing agent, the flexibilizer, the filler and the solvent A is as follows: 100: 50: 30: 50: 5: 200: 1500;
the solid alicyclic epoxy resin is poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1)/CAS number 244772-00-7; the solid-state novolac epoxy resin is trifunctional novolac epoxy resin, and the molecular weight is 200000; the UV delay curing agent is benzenediazonium hexafluorophosphate; the toughening agent is KMP-605 (Xinyue); the filler is silicon dioxide, and the particle size distribution is 4000 micrometers; the solvent A is ethyl acetate.
(3) Preparation of UV delayed curing solid adhesive film
Coating the obtained epoxy resin liquid mixture on black release paper in a workshop environment with visible light with a wavelength of more than 500nm and humidity of less than 30%, baking at 60 ℃ in an oven for 100min, and covering with another layer of black release paper to obtain the UV delayed curing solid adhesive film with the thickness of 500 microns.
(4) Method for bonding sensor at room temperature by UV delay
The UV delayed curing solid adhesive film is attached to the surface of a base, then UV light is irradiated, the wavelength of the UV light is 500nm, the energy is 2000mW/S, the irradiation time is 10S, a sensor needing to be bonded is attached to the interior of 200S after the UV light is irradiated, standing is carried out for 24 hours, sufficient curing can be achieved, high bonding strength is achieved, the thickness is controllable, and inclination and deviation cannot be generated. The adhesive tape can be replaced to achieve better adhesive strength and is used for adhering small parts of a sensor type.
EXAMPLE III
(1) Preparation of isocyanate-modified cycloaliphatic epoxy resin:
the synthetic route of the isocyanate modified alicyclic epoxy resin is shown as the following formula:
wherein R is1Is CH3-，R2Is- (CH)2-O-CH2)m-, x is 50, y is 60, n is 100, m is 8;
adding an acrylic monomer with double-bond alicyclic epoxy and an acrylic monomer with isocyanic acid into a solvent B, adding an initiator A, reacting for 4 hours at the temperature of 60 ℃, adding a polymerization inhibitor, and purifying to obtain solid isocyanic acid modified alicyclic epoxy resin;
the acrylic monomer of the alicyclic epoxy with double bonds is 3, 4-epoxy cyclohexyl methyl methacrylate; the acrylic monomer with isocyanate is isocyano ethyl acrylate; the initiator A is dimethyl azodiisobutyrate; the solvent B is trichloromethane; the polymerization inhibitor is beta-phenyl naphthylamine.
(2) Preparation of epoxy resin liquid mixture:
mixing solid alicyclic epoxy resin, solid novolac epoxy resin, isocyanate modified alicyclic epoxy resin, UV delayed curing agent, toughening agent, filler and solvent A to obtain a required epoxy resin liquid mixture; the weight ratio of the solid alicyclic epoxy resin, the solid novolac epoxy resin, the isocyanic acid modified alicyclic epoxy resin, the UV delayed curing agent, the toughening agent, the filler and the solvent A is as follows: 100: 10: 20: 40: 3: 100: 1000, parts by weight;
the solid alicyclic epoxy resin is poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1)/CAS number 244772-00-7; the solid novolac epoxy resin is phenol novolac epoxy resin, and the molecular weight is 100000; the UV delayed curing agent is (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate; the toughening agent is GENIOPERL P-52; the filler is magnesium oxide; the solvent A is dioxane.
(3) Preparation of UV delayed curing solid adhesive film
Coating the obtained epoxy resin liquid mixture on black release paper in a workshop environment with the humidity of less than 30% in a yellow room (visible light with the wavelength of more than 500 nm), baking for 50min at the temperature of 50 ℃ by an oven, and covering with another layer of black release paper to obtain the UV delayed curing solid adhesive film with the thickness of 100 microns.
(4) Method for bonding sensor at room temperature by UV delay
The UV delayed curing solid adhesive film is attached to the surface of a base, then UV light is irradiated, the wavelength of the UV light is 500nm, the energy is 1000mW/S, the irradiation time is 10S, small parts of sensors needing to be bonded are attached to the inside of 100S after the UV light is irradiated, standing is carried out for 10 hours, sufficient curing can be achieved, high bonding strength is achieved, the thickness is controllable, and inclination and deviation cannot be generated. The adhesive tape can be replaced to achieve better adhesive strength and is used for adhering small parts of a sensor type.
Example four
(1) Preparation of isocyanate-modified cycloaliphatic epoxy resin:
the synthetic route of the isocyanate modified alicyclic epoxy resin is shown as the following formula:
wherein R is1Is H, R2Is composed of(-CH2)m-, x is 50, y is 60, n is 100, m is 5;
adding an acrylic monomer with double bond alicyclic epoxy and an acrylic monomer with isocyanic acid into a solvent B, adding an initiator A, reacting for 3 hours at the temperature of 70 ℃, adding a polymerization inhibitor, and purifying to obtain solid isocyanic acid modified alicyclic epoxy resin;
the acrylic monomer of the alicyclic epoxy with double bonds is 3, 4-epoxy cyclohexyl methacrylate; the acrylic monomer with isocyanate is 2- (2-isocyanatoethoxy) ethyl acrylate; the initiator A is benzoyl peroxide tert-butyl ester; the solvent B is cyclohexanone; the polymerization inhibitor is p-tert-butyl catechol.
(2) Preparation of epoxy resin liquid mixture:
mixing solid alicyclic epoxy resin, solid novolac epoxy resin, isocyanic acid modified alicyclic epoxy resin, a UV (ultraviolet) delayed curing agent, a toughening agent, a filler and a solvent A to obtain a required epoxy resin liquid mixture; wherein the weight ratio of the solid alicyclic epoxy resin, the solid novolac epoxy resin, the isocyanic acid modified alicyclic epoxy resin, the UV delayed curing agent, the flexibilizer, the filler and the solvent A is as follows: 100: 30: 20: 40: 4: 100: 800;
the solid alicyclic epoxy resin is poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1)/CAS number 244772-00-7; the solid novolac epoxy resin is dicyclopentadiene phenol novolac epoxy resin, and the molecular weight is 150000; the UV delay curing agent is triallyl hexafluoroantimonate; the toughening agent is ENIOPERL P-52; the filler is magnesium oxide; the solvent A is ethylene oxide.
(3) Preparation of UV delayed curing solid adhesive film
Coating the obtained epoxy resin liquid mixture on black release paper in a workshop environment with visible light with a wavelength of more than 500nm and humidity of less than 30%, baking for 60min at 55 ℃ by an oven, and covering with another layer of black release paper to obtain the UV delayed curing solid adhesive film with the thickness of 400 mu m.
(4) Method for bonding sensor at room temperature by UV delay
The UV delayed curing solid adhesive film is attached to the surface of a base, then UV light is irradiated, the wavelength of the UV light is 400nm, the energy is 1200mW/S, the irradiation time is 8S, small parts of sensors needing to be bonded are attached within 100S after the UV light is irradiated, standing is carried out for 20 hours, full curing can be achieved, high bonding strength is achieved, the thickness is controllable, and inclination and deviation cannot be generated. The adhesive tape can be replaced to achieve better adhesive strength and is used for adhering small parts of a sensor type.
EXAMPLE five
(1) Preparation of isocyanate-modified cycloaliphatic epoxy resin:
the synthetic route of the isocyanate modified alicyclic epoxy resin is shown as the following formula:
wherein R is1Is CH3-，R2Is- (CH)2)m-, x is 90, y is 90, n is 100, m is 6;
adding an acrylic monomer with double bond alicyclic epoxy and an acrylic monomer with isocyanic acid into a solvent B, adding an initiator A, reacting for 3 hours at the temperature of 70 ℃, adding a polymerization inhibitor, and purifying to obtain solid isocyanic acid modified alicyclic epoxy resin;
the acrylic monomer of the alicyclic epoxy with double bonds is 3, 4-epoxy cyclohexyl methyl methacrylate;
the acrylic monomer with the isocyanate group is isocyano ethyl methacrylate; the initiator is azobisisobutyronitrile; the solvent B is dioxane; the polymerization inhibitor is benzenediol.
(2) Preparation of epoxy resin liquid mixture:
mixing solid alicyclic epoxy resin, solid novolac epoxy resin, isocyanic acid modified alicyclic epoxy resin, UV delayed curing agent, toughening agent, filler and solvent A to obtain a required epoxy resin liquid mixture; wherein the weight ratio of the solid alicyclic epoxy resin, the solid novolac epoxy resin, the isocyanic acid modified alicyclic epoxy resin, the UV delayed curing agent, the flexibilizer, the filler and the solvent A is as follows: 100: 20: 10: 45: 4: 100: 900;
the solid alicyclic epoxy resin is poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3:1)/CAS number 244772-00-7; the solid novolac epoxy resin is BPA novolac epoxy resin, and the molecular weight is 60000; the UV delayed curing agent is benzenediazonium hexafluorophosphate; the toughening agent is MX 533; the filler is silicon dioxide, and the particle size distribution is 1000 microns; the solvent A is ethylene oxide.
(3) Preparation of UV delayed curing solid adhesive film
Coating the obtained epoxy resin liquid mixture on black release paper in a workshop environment with visible light with a wavelength of more than 500nm and humidity of less than 30%, baking for 60min at 50 ℃ by an oven, and covering with another layer of black release paper to obtain the UV delayed curing solid adhesive film with the thickness of 100 microns.
(4) Method for bonding sensor at room temperature by UV delay
The UV delayed curing solid adhesive film is attached to the surface of a base, then UV light is irradiated, the wavelength of the UV light is 400nm, the energy is 1300mW/S, the irradiation time is 6S, small parts of sensors needing to be adhered are attached to the inside of 100S after the UV light is irradiated, standing is carried out for 14 hours, full curing can be achieved, high adhesion strength is achieved, the thickness is controllable, and inclination and deviation cannot be generated. The adhesive tape can be replaced to achieve better adhesive strength and is used for adhering small parts of a sensor type.
Test data
The performance of the UV delayed room temperature adhesion sensor prepared in examples one through five was tested for performance, as shown in table 1:
table 1 comparison of parameters of UV-delayed curing solid adhesive films prepared in examples one to five
Testing of adhesive strength: and testing the thrust of the cured chip on the embodiment by adopting DAGE3800 after curing, wherein the thrust speed is 300mm/min, and the bonding strength can be obtained after testing.
And (3) testing the glass transition temperature Tg by adopting a DSC method, putting 0.5mg of a sample into equipment, controlling the temperature to be 20-200 ℃ and the temperature rise speed to be 10 ℃/min, and analyzing the obtained curve to obtain Tg data.
The CTE test method refers to a standard JISK7197 method, the detection temperature range is-50-600 ℃, the temperature is controlled to be 0.01-100 min, and the TMA range (sensitivity) is as follows: 5mm-0.02m, style size: 100mm 25 mm. The test instrument references two data of CTE obtained from the curve obtained using TMA 4000 SE, one above and one below the Tg point.
The modulus testing method adopts a DMA8000 dynamic thermomechanical analyzer and a stretching method, the frequency is set to be 500HZ, the temperature rising speed is 20-200 ℃, and the modulus data at 25 ℃ can be obtained by analyzing and testing the curve.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. An epoxy resin liquid mixture is characterized by comprising solid alicyclic epoxy resin, solid phenolic epoxy resin, isocyanic acid modified alicyclic epoxy resin, a UV delayed curing agent, a toughening agent, a filler and a solvent A; the weight ratio of the solid alicyclic epoxy resin, the solid novolac epoxy resin, the isocyanic acid modified alicyclic epoxy resin, the UV delayed curing agent, the toughening agent, the filler and the solvent A is as follows: 100: 0-50: 10-30: 20-50: 1-5: 10-200: 200-1500;
adding an acrylic monomer with double bond alicyclic epoxy and an acrylic monomer with isocyanic acid into a solvent B, adding an initiator A, reacting for 2-5 hours at the temperature of 40-80 ℃, adding a polymerization inhibitor, and purifying to obtain solid isocyanic acid modified alicyclic epoxy resin, wherein the synthetic route of the isocyanic acid modified alicyclic epoxy resin is shown as the following formula:
wherein R is1Is H or CH3-，R2Is- (CH)2)m-or- (CH)2-O-CH2)m-, x is 20 to 100, y is 5 to 100, n is 20 to 200, m is 1 to 10;
the solvent A is one or a mixture of more of tetrahydrofuran, acetone, trichloromethane, dichloromethane, ethyl acetate, dioxane and ethylene oxide;
the solvent B is one or a mixture of cyclohexanone, toluene, tetrahydrofuran, acetone, trichloromethane and dioxane;
the initiator A is one or a mixture of more of benzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and azobisisobutyric acid dimethyl ester.
2. The epoxy resin liquid mixture according to claim 1, characterized in that the solid cycloaliphatic epoxy resin is poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1)/CAS number 244772-00-7.
3. The epoxy resin liquid mixture according to claim 1, wherein the solid novolac epoxy resin is one or more of o-cresol novolac epoxy resin, BPA novolac epoxy resin, dicyclopentadiene phenol novolac epoxy resin, trifunctional novolac epoxy resin and phenol novolac epoxy resin, and the number average molecular weight (Mn) is 10000-.
4. The epoxy resin liquid mixture according to claim 1, wherein the acrylic monomer of the alicyclic epoxy having a double bond is 3, 4-epoxycyclohexyl methyl methacrylate, 3, 4-epoxycyclohexyl methyl acrylate.
5. The epoxy resin liquid mixture according to claim 1, wherein the polymerization inhibitor is one or more of 2,4, 6-trinitrophenol, 1, 4-benzoquinone, hydroquinone, phenothiazine, β -phenylnaphthylamine and p-tert-butylcatechol.
6. The liquid epoxy resin mixture according to claim 1, wherein the UV-retarding curing agent is one or more selected from the group consisting of (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate, triallylsulfonium hexafluorophosphate, triallylhexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, triphenylsulfonium antimonate, diphenyliodonium hexafluoroantimonate and diphenyl-4-sulfonium phenoxyphenylsulfonium hexafluoroantimonate.
7. The epoxy resin liquid mixture according to claim 1, characterized in that the toughening agent is a butadiene elastomer system, a silicone modified system or a rubber system; the butadiene elastomer systems are the commercial MX137, MX154, MX127, MX451, and MX533 series; the organosilicon modified systems are commercialized MX965, KMP-605 and GENIOPERLP-52; the rubber system is ATBN or CTBN.
8. The epoxy resin liquid mixture according to claim 1, wherein the filler is one or more of calcium carbonate, talc, silica, alumina and magnesium oxide, and has a particle size distribution of 0.1-10 μm.
9. A UV delayed curing solid glue film prepared from an epoxy resin liquid mixture is characterized in that the epoxy resin liquid mixture obtained in the claim 1 is coated on black release paper in a workshop environment with visible light with the wavelength of more than 500nm and the humidity of less than 30%, the black release paper is baked in an oven for 20-100min, the temperature of the oven is 40-60 ℃, and then another layer of black release paper is covered to prepare the UV delayed curing solid glue film with the thickness of 10-500 microns.
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| CN105925145A (en) * | 2016-07-07 | 2016-09-07 | 天津瑞远粉末涂料有限公司 | High-performance anti-corrosion epoxy powder coating |
| CN110330919A (en) * | 2019-07-03 | 2019-10-15 | 昆山博益鑫成高分子材料有限公司 | A kind of UV visbreaking glue |
| CN110484177A (en) * | 2018-05-15 | 2019-11-22 | 上海本诺电子材料有限公司 | A kind of dual cure epoxy adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105925145A (en) * | 2016-07-07 | 2016-09-07 | 天津瑞远粉末涂料有限公司 | High-performance anti-corrosion epoxy powder coating |
| CN110484177A (en) * | 2018-05-15 | 2019-11-22 | 上海本诺电子材料有限公司 | A kind of dual cure epoxy adhesive and preparation method thereof |
| CN110330919A (en) * | 2019-07-03 | 2019-10-15 | 昆山博益鑫成高分子材料有限公司 | A kind of UV visbreaking glue |
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