CN111471420B - Packaging adhesive and preparation method and application thereof - Google Patents

Packaging adhesive and preparation method and application thereof Download PDF

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Publication number
CN111471420B
CN111471420B CN202010275710.0A CN202010275710A CN111471420B CN 111471420 B CN111471420 B CN 111471420B CN 202010275710 A CN202010275710 A CN 202010275710A CN 111471420 B CN111471420 B CN 111471420B
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epoxy resin
anhydride
weight
minutes
byk
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CN111471420A (en
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庞凯敏
马晨阳
刘聪
刘新平
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Beijing Kmt Technology Co ltd
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Beijing Kmt Technology Co ltd
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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
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a packaging adhesive and a preparation method and application thereof. The raw materials for preparing the packaging adhesive comprise: the gel time difference between the epoxy resin and the two acid anhydrides is delta T1Said Δ T110-50 minutes; alternatively, it comprises: acid anhydride, at least two epoxy resins and optional auxiliary agent, wherein the difference of the gel time of the acid anhydride and the gel time of the two epoxy resins is delta T2Said Δ T2Is 10-50 minutes. The packaging adhesive disclosed by the invention has a good matte effect, high shear strength and low viscosity.

Description

Packaging adhesive and preparation method and application thereof
Technical Field
The invention relates to packaging adhesive and a preparation method and application thereof.
Background
The LED is widely used at present due to the characteristics of low power, high brightness, simple process, environmental protection and the like. Especially many electronic backlit displays in many indoor and outdoor locations. However, there are some problems with current LED epoxy packages. The mirror surface LED screen in the current market reflects light easily, stimulates eyes, and some outdoor screens reflect light easily to form light pollution. Because different indoor environments and outdoor environments put higher requirements on the matte epoxy encapsulation, the common matte epoxy encapsulation adhesive is easy to have the problems of poor mechanical properties and the like.
CN104804688B discloses a matte epoxy resin packaging adhesive for outdoor LED packaging and a preparation method thereof. Specifically, the packaging adhesive comprises a component A and a component B, wherein the component A comprises 100 parts of alicyclic epoxy resin, 0.05-2 parts of antioxidant, 0.1-5 parts of accelerator A, 5-25 parts of matte powder and 0.1-1 part of defoaming agent, the component B comprises 60-150 parts of anhydride, 0.05-2 parts of antioxidant, 0.1-5 parts of accelerator B and 0.1-1 part of defoaming agent, the molar ratio of epoxy in the component A to anhydride in the component B is 1: 1; the accelerator A is N- (2-cyanoethyl) caprolactam or beta diketone metal complex, and the accelerator B is ethyl triphenyl phosphonium iodide, triphenylphosphine, tetramethyl ammonium bromide, tetraethyl ammonium bromide or tetrabutyl ammonium bromide;
the matte powder is prepared by the following steps: (1') mixing fumed silica powder with spherical methyl solid silicone powder according to a ratio of 1: (0.5-3) uniformly mixing in a weight ratio to obtain mixed powder; (2') dissolving gamma-glycidyl ether oxypropyl trimethoxysilane in ethanol to prepare a solution with the weight percentage concentration of 5-15%, adding organic acid into the solution, and adjusting the pH value to 4-5; (3 ') adding the mixed powder obtained in the step (1 ') into the solution obtained in the step (2 '), and performing high-speed dispersion to obtain a mixed material; (4 ') filtering the mixed material obtained in the step (3') to remove filtrate, and drying the solid obtained by filtering to obtain the matte powder.
The packaging glue for realizing the matte packaging effect is realized by adding the matte powder, but the use of the matte powder mainly has the following defects: 1) higher filling amount is needed, namely, the using amount of the matte powder is larger, so that the problem of uneven matte degree and level occurs at the moment, and the matte effect is poor. 2) The packaging adhesive adopting the matte powder has low shear strength, has an infirm structure when applied to LED packaging, cannot effectively block air, moisture and the like for a long time, and further cannot achieve the effect of protecting an LED chip for a long time. 3) The viscosity is high, usually 3000-5000 mPas, which brings inconvenience to the construction. 4) After the matte powder is added, the colloid becomes fogged, and the light-emitting efficiency is reduced.
In conclusion, the existing packaging adhesive has the problems of poor matte effect, low shear strength and high viscosity.
Disclosure of Invention
Aiming at the technical problems, the invention provides the packaging adhesive which has a good matte effect, high shear strength and low viscosity.
The invention provides a packaging adhesive in a first aspect, and a raw material for preparing the packaging adhesive
The method comprises the following steps: the gel time difference between the epoxy resin and the two acid anhydrides is delta T1Said Δ T110-50 minutes; or,
the method comprises the following steps: acid anhydride, at least two epoxy resins and optional auxiliary agent, wherein the difference of the gel time of the acid anhydride and the gel time of the two epoxy resins is delta T2Said Δ T2Is 10-50 minutes.
In some specific embodiment modes of the invention, the packaging adhesive can be a combination of the following components, as long as the difference of the gel time of the epoxy resin and the gel time of the two anhydrides is delta T1(10-50 minutes, preferably 12-40 minutes, more preferably 10-30 minutes), or the difference in gel time of the acid anhydride and one of the two epoxy resins, respectively, is Δ T2(10-50 minutes, preferably 12-40 minutes, more preferably 10-30 minutes) of:
combination 1) encapsulation is glued and is included: an epoxy resin, at least two anhydrides, and optionally an auxiliary agent.
Combination 2) encapsulation is glued and is included: an acid anhydride, at least two epoxy resins, and optionally an auxiliary agent.
Combination 3) packaging glue includes: two or more epoxy resins, two or more acid anhydrides, and optionally an auxiliary.
In the present invention, the gel time of the epoxy resin and the acid anhydride can be measured according to GB 12007.7-1989, method for measuring gel time of epoxy resin.
According to some embodiments of the encapsulant of the present invention, the Δ T is1And Δ T2Each independently of the other for 12 to 40 minutes, preferably 15 to 30 minutes. In the invention, when the difference of the gel time is less than 10 minutes, no matte effect is generated; when the difference of the gel time is 10-50 minutes, the matte effect can be generated, the shear strength is higher, the viscosity is lower, and the matte effect is optimal, the shear strength is maximum and the viscosity is minimum when the optimal time is 15-30 minutes; when gelledWhen the difference is more than 50 minutes, the surface of the colloid becomes rough and wrinkled, resulting in uneven light emission.
According to some embodiments of the encapsulant of the present invention, the weight ratio of epoxy resin to anhydride is 100:15 to 150, preferably 100:20 to 125, such as 100:20, 100:30, 100:40, 100:50, 100:60, 100:70, 100:80, 100:90, 100:100, 100:110, 100:120, 100:125, and any value therebetween.
In the present invention, when the encapsulation adhesive includes at least two anhydrides, the weight ratio of the epoxy resin to the anhydride refers to the weight ratio of the epoxy resin to the total anhydride weight.
In the present invention, when the encapsulation paste includes at least two kinds of epoxy resins, the weight ratio of the epoxy resin to the acid anhydride refers to the weight ratio of the total epoxy resin weight to the acid anhydride.
In the present invention, when the encapsulant includes two or more epoxy resins and two or more acid anhydrides, the weight ratio of the epoxy resin to the acid anhydride refers to the weight ratio of the total epoxy resin to the total acid anhydride.
According to some embodiments of the present invention, the packaging adhesive comprises: the weight ratio of epoxy resin to first and second anhydrides is 100: 5-145: 145-5 and the weight ratio of epoxy resin to anhydride is 100:15-150, preferably 100: 20-125.
According to some embodiments of the present invention, the packaging adhesive comprises: an acid anhydride, at least two epoxy resins, and optionally an auxiliary agent, the weight ratio of the first epoxy resin, the second epoxy resin, and the acid anhydride being from 10 to 90: 90-10: 15-150, preferably 10-90: 90-10: 20-125.
According to some embodiments of the present invention, the packaging adhesive comprises: two or more epoxy resins, two or more acid anhydrides, and optionally an auxiliary agent, as long as the weight ratio of the total epoxy resin to the total acid anhydride is 100:15 to 150, preferably 100:20 to 125.
According to some embodiments of the encapsulant of the present invention, the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2, 3-epoxypropyl acrylate, bis (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxycyclohexanecarboxylic acid-3 ',4' -epoxycyclohexanemethyl ester, 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ',4' -epoxy-6 '-methylcyclohexanemethyl ester, dicyclopentadiene diepoxy, cis-bis- (2, 3-epoxycyclopentyl) -ether, trans-bis- (2, 3-epoxycyclopentyl) -ether, 3, 4-epoxycyclohexylmethyl-2', 3 '-epoxycyclohexyl ether, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A epoxy resin, bisphenol B epoxy resin, bisphenol A epoxy resin, bis (3, 4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxy-6' -epoxy resin, dicyclopentadiene diepoxy ester, cis-6-bis- (2, dicyclopentadiene) ether, bis- (2, 3-epoxycyclopentyl) -ether, trans-3, trans-epoxycyclopentyl) -ether, trans-6-cyclopentyl) -ether, trans-cyclohexyl ether, or a, Bis- (2, 3-epoxycyclohexane), 1, 2-bis- (2, 3-epoxycyclohexyloxy) -ethane, bis- (2, 3-epoxycyclohexyl) ether and 1, 1-bis (2',3' -epoxycyclohexyloxymethyl) -3, 4-epoxycyclohexane.
In the present invention, 3, 4-epoxycyclohexanecarboxylic acid-3 ',4' -epoxycyclohexanemethyl ester, 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ',4' -epoxy-6 '-methylcyclohexanemethyl ester, dicyclopentadiene diepoxy, cis-bis- (2, 3-epoxycyclopentyl) -ether, trans-bis- (2, 3-epoxycyclopentyl) -ether, 3, 4-epoxycyclohexylmethyl-2', 3 '-epoxycyclohexyl ether, bis- (2, 3-epoxycyclohexane), 1, 2-bis- (2, 3-epoxycyclohexyloxy) -ethane, bis- (2, 3-epoxycyclohexyl) ether and 1, 1-bis (2', the structural formula of 3' -epoxycyclohexyloxymethyl) -3, 4-epoxycyclohexane can be referred to "molecular design and synthesis research progress of high-performance alicyclic epoxy resin", Wangzaigang, etc. (high molecular materials system of chemical industry institute of university, Dalian, 116024).
According to some embodiments of the encapsulant of the present invention, the bisphenol a epoxy resin is selected from bisphenol a epoxy resin E44, bisphenol a epoxy resin E51, and bisphenol a epoxy resin E55.
According to some embodiments of the encapsulant of the present invention, the bisphenol F epoxy resin is bisphenol F epoxy resin NPEF-170.
According to some embodiments of the encapsulant of the present invention, the bisphenol S type epoxy resin is bisphenol S diglycidyl ether.
According to some embodiments of the encapsulant of the present invention, the acid anhydride is selected from phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, eleostearic anhydride, chlorendic anhydride, methylnadic anhydride, glutaric anhydride, polyazelaic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrabromophthalic anhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, and succinic anhydride.
According to some embodiments of the encapsulant of the present invention, the auxiliary agent comprises one or more of a defoamer, an antioxidant, an accelerator, a leveling agent, a toughening agent, and an ultraviolet absorber.
According to some embodiments of the encapsulant of the present invention, the content of the defoaming agent is 0 to 5 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight of the epoxy resin.
According to some embodiments of the encapsulant of the present invention, the antioxidant is contained in an amount of 0 to 5 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight of the epoxy resin.
According to some embodiments of the encapsulant of the present invention, the accelerator is included in an amount of 0 to 5 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the epoxy resin.
According to some embodiments of the encapsulant of the present invention, the content of the leveling agent is 0 to 5 parts by weight, preferably 0.001 to 5 parts by weight, with respect to 100 parts by weight of the epoxy resin.
According to some embodiments of the encapsulant of the present invention, the toughening agent is included in an amount of 0 to 70 parts by weight, preferably 0.1 to 70 parts by weight, with respect to 100 parts by weight of the epoxy resin.
According to some embodiments of the encapsulant of the present invention, the ultraviolet absorber is contained in an amount of 0 to 0.5 parts by weight, preferably 0.1 to 0.5 parts by weight, with respect to 100 parts by weight of the epoxy resin.
According to some embodiments of the encapsulant of the present invention, the defoamer is an organosiloxane and/or polyether; further preferably, the antifoaming agent is selected from one or more of BYK-025, BYK-028, BYK-093, BYK-1610, BYK-1615, BYK-530, BYK-072, BYK-141, and Tego 910.
According to some embodiments of the encapsulant of the present invention, the antioxidant is selected from one or more of pentaerythritol tetrakis (. beta. - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (4-nonylphenyl) phosphite, 2, 6-di-tert-butyl-4-methylphenol, and triphenylphosphine.
According to some embodiments of the encapsulant of the present invention, the accelerator is selected from one or more of the group consisting of fatty amines, substituted ureas, imidazoles and their salts, acetylacetone metal salts, triphenylphosphine and its salts, carboxylic acid metal salts and its complexes, phenols, quaternary ammonium salts, thiourea and its derivatives, organic guanidines, peroxides, and boron trifluoride complexes, preferably diethylenetriamine, triethylenetetramine, polyethylene polyamines, N-p-chlorophenyl-N ', N' -dimethylurea, dimethylimidazole urea, 2-ethyl-4-methylimidazole, zinc acetylacetonate, copper acetylacetonate, neodymium acetylacetonate, aluminum acetylacetonate, triphenylphosphine, zinc naphthenate, cobalt naphthenate, manganese naphthenate, phenol, o-cresol, m-cresol, resorcinol, benzyltriethylammonium chloride, propenyl thiourea, ethylenethiourea, One or more of tetramethylguanidine, benzoyl peroxide and boron trifluoride complex.
According to some embodiments of the encapsulant of the present invention, the leveling agent is selected from an organosiloxane and/or an acrylate; further preferably, the leveling agent is selected from one or more of BYK-320, BYK-310, BYK-307, BYK-301, BYK-333, BYK-300 and BYK-S706.
According to some embodiments of the encapsulant of the present invention, the weight average molecular weight of the toughening agent is 200-.
According to some embodiments of the encapsulant of the present invention, the polyester polyol may be a polyester polyol conventional in the art, such as selected from, but not limited to: one or more of polyethylene glycol adipate, polybutylene adipate, polyethylene glycol phthalate and polycarbonate 1, 6-hexanediol glycol ester.
According to some embodiments of the encapsulant of the present invention, the polyether polyol may be a polyether polyol conventional in the art, such as one or more selected from polytetrahydrofuran ether glycol, polyethylene glycol, and polypropylene glycol.
According to some embodiments of the encapsulant of the present invention, the uv absorber is selected from one or more of 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) -benzotriazole, 2-hydroxy-4-methoxybenzophenone, and 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole.
In the present invention, the epoxy resin, the acid anhydride, the defoaming agent, the antioxidant, the accelerator, the leveling agent, the toughening agent and the ultraviolet absorber are all commercially available.
According to some embodiments of the potting compound according to the invention, the potting compound has a shear strength of more than 8MPa, preferably 12 to 19 MPa. In the present invention, the shear strength can be measured according to GB 7124-86 "method for testing tensile Strength of adhesive".
According to some embodiments of the potting compound according to the invention, the potting compound has a gloss value of 40 to 70 GU. In the present invention, the method for measuring the gloss value may be: and (4) defining the matte degree of the glass according to the gloss value by using a gloss meter. Gloss value definition: the high gloss is more than or equal to 70GU, the flat gloss is 40-70GU, the matte is 5-40GU, and the dark is less than or equal to 5 GU.
According to some embodiments of the encapsulant of the present invention, the viscosity of the encapsulant is 800-1800 mPa.s, preferably 800-1500 mPa.s, more preferably 800-1000 mPa.s. In the present invention, the viscosity measurement method is: the viscosity of the product is tested by an Anton Paar rheometer, the testing temperature is 25 ℃, a DPP25 rotor is adopted, the rotating speed is 10/s, and after 3min of testing, the average value of the viscosity is taken as the viscosity data.
The invention provides a preparation method of the packaging adhesive,
the method comprises the following steps: mixing and curing an epoxy resin, at least two acid anhydrides and an optional auxiliary agent, wherein the difference of the gel time of the epoxy resin and the gel time of the two acid anhydrides is delta T1Said Δ T110-50 minutes; or,
the method comprises the following steps: mixing and curing acid anhydride, at least two epoxy resins and optional auxiliary agent, wherein the gel time difference between the acid anhydride and the two epoxy resins is delta T1Said Δ T2Is 10-50 minutes.
According to some embodiments of the method of the invention, the Δ Τ1And Δ T2Each independently of the other for 12 to 40 minutes, preferably 15 to 30 minutes.
According to some embodiments of the preparation method of the present invention, the preparation method of the packaging adhesive comprises: mixing the required epoxy resin, anhydride and optional auxiliary agent, then curing, and ensuring that the gel time difference between the epoxy resin and the two anhydrides is delta T1(10-50 minutes, preferably 12-40 minutes, more preferably 10-30 minutes), or the difference in gel time between the anhydride and the two epoxy resins is Δ T2(10 to 50 minutes, preferably 12 to 40 minutes, more preferably 10 to 30 minutes) to obtain a powdery compound.
According to some embodiments of the preparation method of the present invention, when the epoxy resin and/or the acid anhydride is in a solid state, it may be mixed after being melted by heating. For example, bisphenol a epoxy resin E55 and methylnadic anhydride are solid and heated to melt them for use.
According to some embodiments of the method of manufacturing of the present invention, the curing conditions comprise: the temperature is 100-180 ℃, and the preferred temperature is 120-160 ℃; the time is 2 to 8 hours, preferably 4 to 6 hours.
According to some preferred embodiments of the production method of the present invention, the curing comprises a stage a) and a stage b),
the conditions of the stage a) include: the temperature is 100-140 ℃, preferably 120-130 ℃; the time is 0.5 to 2 hours, preferably 1 to 2 hours;
the conditions of the stage b) include: a temperature greater than 140 ℃ and not greater than 180 ℃, preferably greater than 130 ℃ and not greater than 160 ℃; the time is 1.5 to 6 hours, preferably 3 to 4 hours.
The third aspect of the invention provides the application of the packaging adhesive and/or the packaging adhesive prepared by the method in the field of LEDs.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention easier to understand, the present invention will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, the test methods involved are as follows:
1. the gel time of epoxy resins with anhydrides was tested according to GB 12007.7-1989 method for determining gel time of epoxy resins.
2. The shear strength was measured according to GB 7124-86 "method for testing tensile Strength of Adhesives".
3. The gloss value was determined by the following method: the matte degree of the sample is defined according to the gloss value by adopting a gloss meter (model NHG60M 60 micro-pore precision gloss meter purchased from Shenzhen Shenshi science and technology Limited company, Sanchenshi, Shenzhen). Gloss value definition: the high gloss is more than or equal to 70GU, the flat gloss is 40-70GU, the matte is 5-40GU, and the dark is less than or equal to 5 GU.
4. The viscosity measurement method comprises the following steps: the viscosity of the product is tested by an Anton Paar rheometer, the testing temperature is 25 ℃, a DPP25 rotor is adopted, the rotating speed is 10/s, and after 3min of testing, the average value of the viscosity is taken as the viscosity data.
In the following examples of the present invention,
bis (3, 4-epoxycyclohexylmethyl) adipate was obtained from sigma-aldrich under CAS number 3130-19-6.
3, 4-Epoxycyclohexanecarboxylic acid-3 ',4' -epoxycyclohexanemethyl ester is available from sigma-aldrich under CAS number 2386-87-0.
Bisphenol A epoxy resin E55 was obtained from south Asia epoxy resins (Kunshan) Inc. under CAS number 25085-99-8, with an epoxy value of 0.52-0.56.
Bisphenol A epoxy resin E51 was obtained from south Asia epoxy resins (Kunshan) Inc. under CAS number 25085-99-8, with an epoxy value of 0.48-0.54.
Bisphenol A epoxy resin E44 was obtained from south Asia epoxy resins (Kunshan) Inc. under CAS number 25085-99-8, with an epoxy value of 0.41-0.47.
Dicyclopentadiene diepoxy was purchased from Jiangsu Taiter New materials technology Inc. under CAS number 81-21-0.
2, 3-epoxypropyl acrylate was purchased from Shanghai Allantin Biotech, Inc. under CAS number 106-90-1.
Bisphenol S diglycidyl ether was purchased from wuhan, a pioneer science and technology limited.
Methylhexahydrophthalic anhydride was purchased from national pharmaceutical group chemical reagent Beijing, Inc., CAS number 25550-51-0.
Phthalic anhydride was purchased from Beijing, Inc., national pharmaceutical group Chemicals, CAS number 85-44-9.
Trimellitic anhydride was purchased from Beijing, Inc., a chemical reagent of the national drug group, under CAS number 552-30-7.
Tetrabromobenzoic anhydride was purchased from Beijing, Inc., a national pharmaceutical group chemical reagent, CAS number 632-79-1.
Tetrahydrophthalic anhydride was purchased from Beijing, Inc., national pharmaceutical group Chemicals, CAS number 935-79-5.
Chlorineanhydride was purchased from Jiangsu Aikang biomedical research and development Co., Ltd, and its CAS number was 115-27-5.
3,3',4,4' -Benzophenone tetracarboxylic dianhydride available from Sigma-aldrich under CAS number 2421-28-5
Aluminum acetylacetonate was purchased from Beijing, Inc., a national pharmaceutical group chemical reagent, having a CAS number of 13963-57-0.
Polybutylene adipate was obtained from Shanghai Yiqing trade, Inc. and had a weight average molecular weight of 2000.
The carboxyl-terminated liquid nitrile rubber is obtained from CVC company of America, and has the weight-average molecular weight of 3150.
[ example 1 ]
The components and the amounts of the packaging adhesive are shown in the table 1.
TABLE 1
Composition (I) Name (R) Parts by weight
Epoxy resin 1 Bis (3, 4-epoxycyclohexylmethyl) adipate 50
Epoxy resin 2 Bisphenol A epoxy resin E55 50
Acid anhydrides Methyl hexahydrophthalic anhydride 100
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bisphenol A epoxy resin E55 with 100 parts by weight of methylhexahydrophthalic anhydride was 20 minutes. Therefore, the difference in gel time was 15 minutes.
The compositions shown in Table 1 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 2 ]
The components and the amounts of a packaging adhesive are shown in Table 2.
TABLE 2
Figure BDA0002444701680000091
Figure BDA0002444701680000101
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bisphenol A epoxy resin E51 with 100 parts by weight of methylhexahydrophthalic anhydride was 25 minutes. Therefore, the difference in gel time was 20 minutes.
The compositions shown in Table 2 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 3 ]
The components and the amounts of a packaging adhesive are shown in Table 3.
TABLE 3
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl) adipate 100
Acid anhydrides 1 Methyl hexahydrophthalic anhydride 50
Acid anhydride 2 Trimellitic anhydride 50
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of trimellitic anhydride was 20 minutes. Therefore, the difference in gel time was 15 minutes.
The materials were weighed in accordance with the compositions shown in Table 3, and after stirring and mixing in vacuo, they were cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 4 ]
The components and the amounts of a packaging adhesive are shown in Table 4.
TABLE 4
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl) adipate 100
Acid anhydrides 1 Methyl hexahydrophthalic anhydride 50
Acid anhydride 2 Tetrabromobenzene anhydride 50
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time was 30 minutes for 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate and 100 parts by weight of tetrabromobenzoic anhydride. Therefore, the difference in gel time was 25 minutes.
The compositions shown in Table 4 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 5 ]
The components and the amounts of the packaging adhesive are shown in Table 5.
TABLE 5
Composition (I) Name (R) Parts by weight
Epoxy resin 1 Bis (3, 4-epoxycyclohexylmethyl) adipate 50
Epoxy resin 2 Bisphenol A epoxy resin E44 50
Acid anhydrides Methyl hexahydrophthalic anhydride 100
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bisphenol A epoxy resin E44 with 100 parts by weight of methylhexahydrophthalic anhydride was 35 minutes. Therefore, the difference in gel time was 30 minutes.
The compositions shown in Table 5 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 6 ]
The components and the amounts of a packaging adhesive are shown in Table 6.
TABLE 6
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl) adipate 100
Acid anhydrides 1 Methyl hexahydrophthalic anhydride 50
Acid anhydride 2 Tetrahydrophthalic anhydride 50
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of tetrahydrophthalic anhydride was 35 minutes. Therefore, the difference in gel time was 30 minutes.
The compositions shown in Table 6 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 7 ]
The components and the amounts of a packaging adhesive are shown in Table 7.
TABLE 7
Composition (I) Name (R) Parts by weight
Epoxy resin 1 Dicyclopentadiene diepoxy 50
Epoxy resin 2 Bisphenol A epoxy resin E55 50
Acid anhydrides Methyl hexahydrophthalic anhydride 100
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of dicyclopentadiene diepoxide with 100 parts by weight of methylhexahydrophthalic anhydride was 10 minutes.
The gel time of 100 parts by weight of bisphenol A epoxy resin E55 with 100 parts by weight of methylhexahydrophthalic anhydride was 20 minutes. Therefore, the difference in gel time was 10 minutes.
The compositions shown in Table 7 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 8 ]
The components and the amounts of a packaging adhesive are shown in Table 8.
TABLE 8
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl) adipate 50
Acid anhydrides 1 Trimellitic anhydride 50
Acid anhydride 2 Tetrabromobenzene anhydride 100
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of trimellitic anhydride was 20 minutes.
The gel time was 30 minutes for 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate and 100 parts by weight of tetrabromobenzoic anhydride. Therefore, the difference in gel time was 10 minutes.
The compositions shown in Table 8 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 9 ]
The components and the amounts of the packaging adhesive are shown in Table 9.
TABLE 9
Composition (I) Name (R) Parts by weight
Epoxy resin 1 3, 4-Epoxycyclohexanecarboxylic acid-3 ',4' -epoxycyclohexanemethyl ester 50
Epoxy resin 2 Bisphenol S diglycidyl ether 50
Acid anhydrides Methyl hexahydrophthalic anhydride 100
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of 3, 4-epoxycyclohexanecarboxylic acid-3 ',4' -epoxycyclohexanemethyl ester and 100 parts by weight of methylhexahydrophthalic anhydride was 3 minutes.
The gel time of 100 parts by weight of bisphenol S diglycidyl ether with 100 parts by weight of methylhexahydrophthalic anhydride was 55 minutes. Therefore, the difference in gel time was 52 minutes.
The compositions shown in Table 9 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 10 ]
The components and the amounts of a packaging adhesive are shown in table 10.
Watch 10
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl) adipate 100
Acid anhydrides 1 Methyl hexahydrophthalic anhydride 50
Acid anhydride 2 Chlorineanhydride 50
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butylButyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of chlorendic anhydride was 55 minutes. Therefore, the difference in gel time was 50 minutes.
The compositions shown in Table 10 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 11 ]
The components and the amounts of a packaging adhesive are shown in Table 11.
TABLE 11
Composition (I) Name (R) Parts by weight
Epoxy resin 1 Bis (3, 4-epoxycyclohexylmethyl group)) Adipic acid ester 50
Epoxy resin 2 Bisphenol A epoxy resin E55 50
Acid anhydrides Methyl hexahydrophthalic anhydride 100
Accelerator Diethylenetriamine 6
Defoaming agent BYK-025 1
Toughening agent Carboxyl-terminated liquid nitrile rubber 1
Antioxidant agent Bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite 1
Ultraviolet absorber 2-hydroxy-4-n-octoxy benzophenone 0.1
Leveling agent BYK-320 0.05
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bisphenol A epoxy resin E55 with 100 parts by weight of methylhexahydrophthalic anhydride was 20 minutes. Therefore, the difference in gel time was 15 minutes.
The compositions shown in Table 11 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 12 ]
The components and the amounts of a packaging adhesive are shown in table 12.
TABLE 12
Composition (I) Name (R) Parts by weight
Epoxy resin 1 Bis (3, 4-epoxycyclohexylmethyl) adipate 50
Epoxy resin 2 Bisphenol A epoxy resin E55 50
Acid anhydrides Methyl hexahydrophthalic anhydride 20
Accelerator Neodymium acetylacetonate 8
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bisphenol A epoxy resin E55 with 100 parts by weight of methylhexahydrophthalic anhydride was 20 minutes. Therefore, the difference in gel time was 15 minutes.
The compositions shown in Table 12 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
[ example 13 ]
The components and the amounts of a packaging adhesive are shown in Table 13.
Watch 13
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl)Alkyl) adipate 100
Acid anhydrides 1 Methyl hexahydrophthalic anhydride 60
Acid anhydride 2 Trimellitic anhydride 65
Accelerator Neodymium acetylacetonate 2
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of trimellitic anhydride was 20 minutes. Therefore, the difference in gel time was 15 minutes.
Weighed in accordance with the composition shown in Table 13, and after stirring and mixing in vacuo, cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
Comparative example 1
The components and the amounts of a packaging adhesive are shown in Table 14.
TABLE 14
Figure BDA0002444701680000171
Figure BDA0002444701680000181
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of 3, 4-epoxycyclohexanecarboxylic acid-3 ',4' -epoxycyclohexanemethyl ester and 100 parts by weight of methylhexahydrophthalic anhydride was 3 minutes. Therefore, the difference in gel time was 2 minutes.
The compositions shown in Table 14 were weighed, mixed uniformly under vacuum with stirring, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
Comparative example 2
The components and the amounts of a packaging adhesive are shown in table 15.
Watch 15
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl) adipate 100
Acid anhydrides 1 Methyl hexahydrophthalic anhydride 50
Acid anhydride 2 Phthalic anhydride 50
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of phthalic anhydride was 8 minutes. Therefore, the difference in gel time was 3 minutes.
Weighed in accordance with the composition shown in Table 15, and after stirring and mixing in vacuo, cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
Comparative example 3
The components and amounts of a packaging adhesive are shown in Table 16.
TABLE 16
Composition (I) Name (R) Parts by weight
Epoxy resin 1 Bis (3, 4-epoxycyclohexylmethyl) adipate 50
Epoxy resin 2 Acrylic acid 2, 3-epoxypropyl ester 50
Acid anhydrides Methyl hexahydrophthalic anhydride 100
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time between the anhydride of the encapsulant and epoxy resin 1 and epoxy resin 2, respectively, was tested.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of 2, 3-epoxypropyl acrylate and 100 parts by weight of methylhexahydrophthalic anhydride was 60 minutes. Therefore, the difference in gel time was 55 minutes.
Weighed in accordance with the composition shown in Table 16, and after stirring and mixing in vacuo, cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
Comparative example 4
The components and the amounts of a packaging adhesive are shown in table 17.
TABLE 17
Composition (I) Name (R) Parts by weight
Epoxy resin Bis (3, 4-epoxycyclohexylmethyl) adipate 100
Acid anhydrides 1 Methyl hexahydrophthalic anhydride 50
Acid anhydride 2 3,3',4,4' -benzophenone tetracarboxylic dianhydride 50
Accelerator Aluminium acetylacetonate 3
Defoaming agent BYK-530 1
Toughening agent Polybutylene adipate 1
Antioxidant agent 2, 6-di-tert-butyl-4-methylphenol 1
Ultraviolet absorber 2-hydroxy-4-methoxybenzophenone 0.1
The difference in gel time of the epoxy resin of the encapsulant was tested with anhydride 1 and anhydride 2, respectively.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate with 100 parts by weight of methylhexahydrophthalic anhydride was 5 minutes.
The gel time of 100 parts by weight of bis (3, 4-epoxycyclohexylmethyl) adipate and 100 parts by weight of 3,3',4,4' -benzophenonetetracarboxylic dianhydride was 60 minutes. Therefore, the difference in gel time was 55 minutes.
The compositions shown in Table 17 were weighed, mixed uniformly under vacuum, and then cured. Curing conditions are as follows: curing was carried out at 130 ℃ for 1 hour and then at 150 ℃ for 4 hours. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
Comparative example 5
The preparation of the packaging adhesive according to the method of example 1 of CN104804688B specifically comprises:
firstly, preparing matte powder according to the following steps: (1') fumed silica powder (average particle size of fumed silica powder is 5 μm) and spherical methyl solid silicone powder (average particle size of spherical methyl solid silicone powder is 9 μm)) were mixed in a ratio of 3: 2, uniformly mixing the components in a weight ratio to obtain mixed powder; (2') dissolving gamma-glycidoxypropyltrimethoxysilane in ethanol to prepare a solution with the weight percentage concentration of 10%, adding acetic acid into the solution, and adjusting the pH value to 4.5; (3 ') adding the mixed powder obtained in the step (1 ') into the solution obtained in the step (2 '), and performing high-speed dispersion to obtain a mixed material; (4 ') filtering the mixed material obtained in the step (3') to remove filtrate, and drying the solid obtained by filtering to obtain the matte powder.
In the step (3 '), the weight ratio of the mixed powder obtained in the step (1 ') to the solution obtained in the step (2 ') is 1: 1.
then, preparing the matte epoxy resin packaging adhesive for packaging the outdoor LED according to the following steps:
(1) preparing a component A: mixing 100 parts by weight of alicyclic epoxy resin (3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate), 0.2 part by weight of antioxidant (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate), 0.6 part by weight of accelerator A (N- (2-cyanoethyl) caprolactam), 10 parts by weight of matte powder (namely the matte powder prepared above) and 0.1 part by weight of defoamer (the main component of the defoamer is polydimethylsiloxane), and stirring until the mixture is uniform (stirring can be carried out by using a double-planet stirrer at 25 ℃, the stirring speed is 60 revolutions per minute, and the stirring time is 30 minutes), so as to obtain a component A;
(2) preparing a component B: mixing 85 parts of anhydride (all methyl hexahydrophthalic anhydride), 0.5 part of antioxidant (all 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate), 0.3 part of accelerator B (all tetrabutylammonium bromide) and 0.1 part of defoamer (the main component of the defoamer is polydimethylsiloxane) by weight, and stirring until the mixture is uniformly mixed (stirring can be carried out by using a double-planet stirrer at 25 ℃, the stirring speed is 40 r/min, and the stirring time is 25 min) to obtain a component B;
(3) respectively storing the component A and the component B;
(4) preparing epoxy resin packaging adhesive: when encapsulation is needed, according to the molar ratio of epoxy in the component A to anhydride in the component B of 1: 1, mixing the component A and the component B, and stirring until the components are uniformly mixed to obtain the required epoxy resin packaging adhesive. The obtained epoxy resin encapsulating adhesive is cured within 2.5 hours at 150 ℃. The gloss values, matte level, shear strength and viscosity were measured and the results are given in Table 18.
Watch 18
Figure BDA0002444701680000211
Figure BDA0002444701680000221
As can be seen from the above examples and table 18, the change of the epoxy resin and the curing agent both affect the matte effect, and when the difference of the gel time is between 10 minutes and 52 minutes, the gel surface has the matte effect, higher shear strength and lower viscosity, and preferably the difference of the gel time is between 25 minutes and 30 minutes, the matte effect is optimal; the shear strength also increased with the increase in matte effect when the difference in gel time was between 15 minutes and 30 minutes and reached a maximum when the difference in reaction rate time was 25 minutes.
Moreover, it can be seen from examples 12 and 13 of the present invention and comparative example 5 that the shear strength of the encapsulant of the present invention can be greatly improved even without using a toughening agent, compared to the encapsulant of example 5 using a matte powder.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.

Claims (33)

1. Packaging adhesive and raw material for preparing packaging adhesive
The method comprises the following steps: the gel time difference between the epoxy resin and the two acid anhydrides is delta T1Said Δ T1Is 10-50 minutes, wherein the weight ratio of the epoxy resin to the first anhydride to the second anhydride is 100: 5-145: 145-5, and the weight ratio of the epoxy resin to the acid anhydride is 100: 15-150; or,
the method comprises the following steps: acid anhydride, at least two epoxy resins and optional auxiliary agent, wherein the difference of the gel time of the acid anhydride and the gel time of the two epoxy resins is delta T2Said Δ T210-50 minutes, wherein the weight ratio of the first epoxy resin, the second epoxy resin and the anhydride is 10-90: 90-10: 15-150;
the acid anhydride is selected from phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, eleostearic anhydride, chlorendic anhydride, methyl nadic anhydride, glutaric anhydride, polyazelaic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrabromophthalic anhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, and succinic anhydride.
2. The packaging adhesive of claim 1, wherein Δ T is greater than Δ T1And Δ T2Each independently for 12-40 minutes.
3. The packaging adhesive of claim 2, wherein the Δ T is1And Δ T2Each independently for 15-30 minutes.
4. The packaging adhesive according to claim 1, wherein the weight ratio of the epoxy resin to the acid anhydride is 100: 20-125.
5. The encapsulant of any one of claims 1-3, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2, 3-epoxypropyl acrylate, bis (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxycyclohexanecarboxylic acid-3 ',4' -epoxycyclohexanemethyl ester, 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ',4' -epoxy-6 '-methylcyclohexanemethyl ester, dicyclopentadiene diepoxy, cis-bis- (2, 3-epoxycyclopentyl) -ether, trans-bis- (2, 3-epoxycyclopentyl) -ether, 3, 4-epoxycyclohexylmethyl-2', 3' -epoxycyclohexyl ether, bis- (2, 3-epoxycyclohexane), 1, 2-bis- (2, 3-epoxycyclohexyloxy) -ethane, bis- (2, 3-epoxycyclohexyl) ether and 1, 1-bis (2',3' -epoxycyclohexyloxymethyl) -3, 4-epoxycyclohexane.
6. The encapsulant of claim 5, wherein the bisphenol A epoxy resin is selected from bisphenol A epoxy resin E44, bisphenol A epoxy resin E51, and bisphenol A epoxy resin E55.
7. The packaging adhesive according to claim 5, wherein the bisphenol F epoxy resin is bisphenol F epoxy resin NPEF-170.
8. The packaging adhesive according to claim 5, wherein the bisphenol S type epoxy resin is bisphenol S diglycidyl ether.
9. The encapsulant of any of claims 1-3, wherein the additive comprises one or more of a defoamer, an antioxidant, an accelerator, a leveling agent, a toughening agent, and an ultraviolet absorber.
10. The potting adhesive of claim 9, wherein the content of the defoaming agent is 0.01 to 5 parts by weight relative to 100 parts by weight of the epoxy resin; the content of the antioxidant is 0.01-5 parts by weight; the content of the accelerant is 0.05 to 5 weight parts; the content of the flatting agent is 0.001-5 parts by weight; the content of the toughening agent is 0.1-70 parts by weight; the content of the ultraviolet absorbent is 0.1-0.5 weight part.
11. The packaging adhesive according to claim 9, wherein the defoaming agent is an organosiloxane and/or polyether.
12. The potting adhesive of claim 11, wherein the anti-foaming agent is selected from one or more of BYK-025, BYK-028, BYK-093, BYK-1610, BYK-1615, BYK-530, BYK-072, BYK-141, and Tego 910.
13. The packaging adhesive according to claim 9, wherein the antioxidant is selected from one or more of pentaerythritol tetrakis (. beta. - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (4-nonylphenyl) phosphite, 2, 6-di-tert-butyl-4-methylphenol and triphenylphosphine.
14. The package adhesive of claim 9, wherein the accelerator is selected from one or more of fatty amine, substituted urea, imidazole and its salt, acetylacetone metal salt, triphenylphosphine and its salt, carboxylic acid metal salt and its complex, phenol, quaternary ammonium salt, thiourea and its derivative, organic guanidine, peroxide and boron trifluoride complex.
15. The encapsulant of claim 14, wherein the accelerator is selected from one or more of diethylenetriamine, triethylenetetramine, polyethylene polyamine, N-p-chlorophenyl-N ', N' -dimethylurea, dimethylimidazolium urea, 2-ethyl-4-methylimidazole, zinc acetylacetonate, copper acetylacetonate, neodymium acetylacetonate, aluminum acetylacetonate, triphenylphosphine, zinc naphthenate, cobalt naphthenate, manganese naphthenate, phenol, o-cresol, m-cresol, resorcinol, benzyltriethylammonium chloride, propenyl thiourea, ethylenethiourea, tetramethylguanidine, benzoyl peroxide, and boron trifluoride complex.
16. The encapsulating glue according to claim 9, wherein the leveling agent is selected from an organosiloxane and/or an acrylate.
17. The encapsulant of claim 16, wherein the leveling agent is selected from one or more of BYK-320, BYK-310, BYK-307, BYK-301, BYK-333, BYK-300, and BYK-S706.
18. The encapsulant of claim 9, wherein the weight average molecular weight of the toughening agent is 200-200000.
19. The encapsulant of claim 18, wherein the toughening agent is selected from one or more of carboxyl-terminated liquid nitrile rubber, polyester polyol, polyether polyol, polyamide resin 650, polypropylene oxide rubber, polybutadiene, isocyanate-terminated polyether, polysiloxane, dibutyl phthalate, dioctyl phthalate, nonyl phenol, and polypropylene glycol diglycidyl ether.
20. The potting adhesive of claim 19, wherein the polyester polyol is selected from one or more of polyethylene adipate, polybutylene adipate, polyethylene glycol phthalate, and polycarbonate.
21. The potting compound of claim 19, wherein the polyether polyol is selected from one or more of polytetrahydrofuran ether glycol, polyethylene glycol and polypropylene glycol.
22. The encapsulant of claim 9, wherein the uv absorber is selected from one or more of 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) -benzotriazole, 2-hydroxy-4-methoxybenzophenone, and 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole.
23. The encapsulating glue of any one of claims 1-3, characterized in that the shear strength of the encapsulating glue is larger than 8 MPa.
24. The packaging adhesive of claim 23, wherein the shear strength of the packaging adhesive is 12-19 MPa.
25. The method for producing an encapsulating adhesive according to any of claims 1 to 24,
the method comprises the following steps: mixing and curing an epoxy resin, at least two acid anhydrides and an optional auxiliary agent, wherein the difference of the gel time of the epoxy resin and the gel time of the two acid anhydrides is delta T1Said Δ T110-50 minutes; or,
the method comprises the following steps: mixing and curing acid anhydride, at least two epoxy resins and optional auxiliary agent, wherein the gel time difference between the acid anhydride and the two epoxy resins is delta T2Said Δ T2Is 10-50 minutes.
26. According to the rightThe method of claim 25, wherein Δ T is1And Δ T2Each independently for 12-40 minutes.
27. The method of claim 26, wherein Δ T is the maximum value of Δ T1And Δ T2Each independently for 15-30 minutes.
28. The method of any one of claims 25-27, wherein the curing conditions comprise: the temperature is 100-180 ℃; the time is 2-8 hours.
29. The method of claim 28, wherein the curing conditions comprise: the temperature is 120-160 ℃; the time is 4-6 hours.
30. The method of claim 28, wherein the curing comprises stage a) and stage b),
the conditions of the stage a) include: the temperature is 100-140 ℃; the time is 0.5 to 2 hours;
the conditions of the stage b) include: the temperature is higher than 130 ℃ and not higher than 180 ℃ for 1.5-6 hours.
31. The method of claim 30, wherein the conditions of stage a) comprise: the temperature is 120-130 ℃; the time is 1-2 hours.
32. The method of claim 30, wherein the conditions of stage b) comprise: the temperature is more than 140 ℃ and not more than 160 ℃; the time is 3-4 hours.
33. Use of an encapsulant according to any of claims 1-24 and/or an encapsulant prepared according to the method of any of claims 25-32 in the field of LEDs.
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