CN114686161B - Organic silicon die bond adhesive and preparation method and application thereof - Google Patents
Organic silicon die bond adhesive and preparation method and application thereof Download PDFInfo
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- CN114686161B CN114686161B CN202210620360.6A CN202210620360A CN114686161B CN 114686161 B CN114686161 B CN 114686161B CN 202210620360 A CN202210620360 A CN 202210620360A CN 114686161 B CN114686161 B CN 114686161B
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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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
Abstract
The invention relates to an organic silicon solid crystal glue and a preparation method and application thereof, wherein the preparation raw materials of the organic silicon solid crystal glue comprise the following components in parts by mass: 100-180 parts of polysiloxane silicone oil, 120-200 parts of polysiloxane resin, 15-30 parts of fumed silica, 15-30 parts of a silicon dioxide coupling agent, 1-5000 ppm of a catalyst, 0.01-0.05 part of a curing inhibitor, 1-5 parts of an adhesion enhancer and 100-200 parts of an aromatic hydrocarbon solvent. The organic silicon die attach adhesive disclosed by the invention has the characteristic of low volatile matter, the cured coating has the advantages of high hardness, high light transmittance, high chip thrust and high shear strength, the yield of a gold wire bonding process is high, and the organic silicon die attach adhesive is suitable for packaging LED chips.
Description
Technical Field
The invention relates to the technical field of organic silicon die attach adhesives, in particular to an organic silicon die attach adhesive as well as a preparation method and application thereof.
Background
In the conventional semiconductor packaging process, the organosilicon material is rarely applied to chip packaging, mainly because the organosilicon material is easy to generate siloxane volatile matters with low molecular weight, the yield of the packaging process is influenced. However, in the LED packaging process, a large amount of organic silicon materials are used for LED chip packaging and die bonding because the organic silicon materials have high light transmittance and excellent high temperature resistance and strong light aging resistance. The content of low molecular weight siloxane volatile in the organic silicon die attach adhesive is particularly important in the LED packaging process, because the gold wire bonding process after die attachment of the chip is seriously affected by the low molecular weight siloxane volatile, which results in a decrease in yield.
The LED package is mainly constructed by SMD or COB techniques. SMD is a short name for Surface Mounted Devices (Surface Mounted Devices), and LED packaging using SMD technology is to fix a bare LED chip on a support with epoxy die attach adhesive or silicone die attach adhesive, electrically connect the chip and the support with gold wires, and protect with package adhesive epoxy resin or a high refractive index silicone elastomer. COB is an abbreviation of Chip on Board, and is formed by directly fixing an LED Chip on a PCB (printed circuit Board) by using epoxy solid crystal glue or organic silicon solid crystal glue or solder, realizing electrical interconnection between the Chip and the PCB by lead (gold wire) bonding, and pouring a low-refractive-index organic silicon elastomer in a range with white organic silicon dam glue to finish COB packaging. Compared with the SMD packaging technology, the COB packaging technology is mainly used for high-power multi-chip integrated packaging, and has the advantages of good heat dissipation performance, high chip packaging density, low packaging cost and the like. The LED packaging material mainly comprises LED packaging glue and LED die bonding glue.
CN103865476A discloses a single-component thermosetting adhesive, in particular to an organic silicon die-bonding insulating adhesive for SMT packaging low-power LEDs, which is prepared by mixing the following raw materials in parts by weight: 48-87.8 parts of methyl vinyl polysiloxane resin, 5-20 parts of methyl hydrogen-containing polysiloxane, 5-20 parts of a linear shrinkage rate control agent, 1-5 parts of an adhesive agent, 1-5 parts of fumed silica, 0.1-1 part of a platinum catalyst and 0.1-1 part of an inhibitor. The conventional adhesive disclosed by the invention does not use epoxy resin, overcomes the defects of poor adhesive force and poor performance after aging of the conventional epoxy type solid crystal adhesive, and has the advantages of larger adhesive force and adhesive strength and lower linear expansion coefficient compared with the prior art.
CN104194716A discloses a low-light-attenuation organic silicon crystal fixing adhesive for high-power COB packaging, which comprises the following raw materials in parts by weight: 65-80 parts of methyl phenyl vinyl polysiloxane resin, 5-10 parts of methyl phenyl vinyl silicone oil, 10-25 parts of a cross-linking agent, 3-6 parts of an adhesive agent, 1-5 parts of nano fumed silica, 5-10 parts of a light decay control agent, 0.3-1 part of a catalyst and 0.2-0.5 part of an inhibitor. The low-light-attenuation organic silicon crystal fixing glue for high-power COB packaging has the advantages of high refractive index, high adhesion strength to a PCB bottom plate and a chip, high reliability, high light efficiency and low light attenuation.
However, the problem faced by the prior art silicone die attach adhesives is that the volatile content is high, which affects the yield of the gold wire bonding process.
In conclusion, it is important to develop a silicone solid crystal glue with low volatile content.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an organic silicon die bond adhesive and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an organosilicon crystal-fixing adhesive, which comprises the following raw materials in parts by mass:
100-180 parts of polysiloxane silicone oil
120-200 parts of polysiloxane resin
15-30 parts of fumed silica
15-30 parts of silica coupling agent
1-5000 ppm of catalyst
0.01 to 0.05 part of curing inhibitor
1-5 parts of adhesion force enhancer
100-200 parts of an aromatic solvent;
according to the invention, polysiloxane silicone oil and polysiloxane resin are used as matrixes, and are matched with inorganic filler gas-phase method silicon dioxide which can increase the colloid strength and reduce the body shrinkage, so that the organic silicon solid crystal glue is formed with a silicon dioxide coupling agent in the environment of an aromatic solvent; the invention solves the problem of high volatile matter of the conventional organic silicon die bond, reduces the pollution of low molecular weight siloxane volatile matter to metal welding spots, and improves the yield of the gold thread bonding process.
In the present invention, the silicone oil is 100 to 180 parts by mass, for example, 105 parts, 110 parts, 115 parts, 120 parts, 125 parts, 130 parts, 135 parts, 140 parts, 145 parts, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, and the like.
The polysiloxane resin is 120-200 parts by mass, such as 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts and the like.
The mass parts of the fumed silica are 15-30 parts, such as 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts and the like.
The silica coupling agent is 15-30 parts by mass, such as 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts and the like.
The mass part of the catalyst is 1-5000 ppm, such as 10 ppm, 50 ppm, 100 ppm, 500 ppm, 1000ppm, 1500 ppm, 2000 ppm, 2500 ppm, 3000 ppm, 3500 ppm, 4000 ppm, 4500 ppm, etc.
The curing inhibitor is 0.01-0.05 part by mass, such as 0.02 part, 0.03 part, 0.04 part, 0.05 part and the like.
The adhesion force enhancer is 1-5 parts by mass, such as 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts and the like.
The mass portion of the aromatic hydrocarbon solvent is 100-200, such as 110, 120, 130, 140, 150, 160, 170, 180, 190 and the like.
The silicone oil comprises a linear silicone oil;
the polysiloxane silicone oil comprises a combination of vinyl polysiloxane silicone oil and hydrogen polysiloxane silicone oil;
the vinyl polysiloxane silicone oil comprises any one of compounds A1-A4 or a combination of at least two of the compounds A1-A4;
wherein R is 1 And R 2 Each independently selected from methyl,Ethyl, propyl, cyclohexyl or phenyl;
k is 0 or a positive integer (e.g., 0, 1, 2,3, etc.), l is a positive integer (e.g., 1, 2,3, etc.);
the viscosity of the vinyl silicone oil is 1 to 100000 cP (for example, 10 cP, 100 cP, 1000 cP, 5000 cP, 10000 cP, 20000 cP, 40000 cP, 60000 cP, 80000 cP, etc.), preferably 5 to 5000 cP, and further preferably 20 to 500 cP;
the hydrogen polysiloxane silicone oil comprises any one of compounds A5-A8 or a combination of at least two of the compounds A5-A8;
wherein R is 3 And R 4 Each independently selected from methyl, ethyl, propyl, cyclohexyl or phenyl;
m is 0 or a positive integer (e.g., 0, 1, 2,3, etc.), n is a positive integer (e.g., 1, 2,3, etc.);
the viscosity of the hydrogen-based polysiloxane silicone oil is 1 to 100000 cP (for example, 10 cP, 100 cP, 1000 cP, 5000 cP, 10000 cP, 20000 cP, 40000 cP, 60000 cP, 80000 cP, etc.), preferably 5 to 5000 cP, and further preferably 50 to 1000 cP;
the polysiloxane resin is three-dimensional reticular resin;
the polysiloxane resin comprises a combination of a vinyl polysiloxane resin and a hydrogen polysiloxane resin;
the molecular formula of the vinyl polysiloxane resin is shown as B1:
((R 5 ) 3 SiO 0.5 ) A ((R 6 ) a (R 7 ) b SiO (4-a-b)/2 ) B (SiO 2 ) C B1；
wherein R is 5 And R 6 Each independently selected from methyl, ethyl, propyl, cyclohexyl or phenyl;
R 7 selected from vinyl or allyl;
a is 0, 1 or 2, b is 1 or 2, a + b is 1, 2 or 3.
The molar ratio of A, B, C is (1-60): (0.1-20): (10-95) based on the total mole number of A, B, C being 100, wherein, 1-60 can be 5, 10, 20, 30, 40, 50, etc., 0.1-20 can be 1, 2, 5, 10, 15, etc., 10-95 can be 20, 30, 40, 50, 60, 70, 80, etc., preferably (1-50): 0.5-15): 40-90;
the vinyl polysiloxane resin has a number average molecular weight of 10000-;
the molecular formula of the hydrogen-based polysiloxane resin is shown as B2:
((R 8 ) 3 SiO 0.5 ) D ((R 9 ) c H d SiO (4-c-d)/2 ) E (SiO 2 ) F B2；
wherein R is 8 And R 9 Each independently selected from methyl, ethyl, propyl, cyclohexyl or phenyl;
c is 0, 1 or 2, d is 1 or 2, and c + d is 1, 2 or 3.
Based on the total mole number of D, E, F being 100, the mole ratio of D, E, F is (0.1-30): (0.1-30): (10-95), wherein, 0.1-3 can be 1, 2, 5, 10, 15, 20, 25, etc., 10-95 can be 20, 30, 40, 50, 60, 70, 80, etc., the numerical values of D and E can be equal or unequal, and preferably (0.5-25): (0.5-25): (40-90);
the hydrogen-based polysiloxane resin has a number average molecular weight of 10000-.
In the present invention, silicone oil and silicone resin of specific structures are employed, wherein vinyl silicone oil and hydrogen-based silicone oil are selected because a linear cross-linking reaction structure is provided; the reason for selecting the vinyl polysiloxane resin and the hydrogen-based polysiloxane resin is to provide a three-dimensional network cross-linking reaction structure. The matching of the linear chain cross-linking reaction structure and the three-dimensional network cross-linking reaction structure determines the hardness, toughness, shrinkage rate and colloid strength of the solid crystal glue.
Preferably, the fumed silica comprises hydrophilic silica that has not been surface treated.
In the present invention, the fumed silica includes hydrophilic silica which has not been surface-treated, and the hydrophilic silica is easily reacted with a silica coupling agent, as compared with hydrophobic silica, to generate reactive functional groups, such as vinyl functional groups, on the surface of the fumed silica.
Exemplary non-surface treated hydrophilic silicas include Wacker V15, N20, T30, T40, or AEROSIL 200, AEROSIL 300, AEROSIL 380, or CAB-O-SIL M-5, which are Degussa. N20 and T40 in Wacker form and AEROSIL 380 in Degussa are preferred.
Preferably, the silica coupling agent comprises any one or a combination of at least two of methyltrimethoxysilane, methyltriethoxysilane, n-octyltriethoxysilane, hexadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltris (2-methoxyethoxy) silane, with typical but non-limiting combinations including: combinations of methyltrimethoxysilane and methyltriethoxysilane, hexadecyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, methyltriethoxysilane, n-octyltriethoxysilane, hexadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane, and the like.
Preferably, the catalyst comprises any one of a platinum catalyst, a palladium catalyst or a rhodium catalyst or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of a platinum catalyst and a palladium catalyst, a combination of a platinum catalyst, a palladium catalyst, and a rhodium catalyst, and the like, and a platinum catalyst is more preferable.
Illustratively, in the present invention, the platinum catalyst comprises platinum black and/or chloroplatinic acid, such as H 2 PtCl 6 •(H 2 O)x、K 2 PtCl 4 、K 2 PtCl 4 •(H 2 O)x、K 2 PtCl 6 、K2PtCl 6 •(H 2 O) x, and PtO 2 •(H 2 O) x, where x is a positive integer (e.g., 1, 2,3, 4, 5, 6, 8, 10, etc.), preferably chloroplatinic acid (H) 2 PtCl 6 •(H 2 O) 6 ) Vinyl-mixed polysiloxanes.
In the present invention, the weight parts of the catalyst are calculated according to the active ingredients of the catalyst, for example, the active ingredient in chloroplatinic acid mixed vinyl polysiloxane is platinum.
Preferably, the cure inhibitor comprises an acetylenic alcohol cure inhibitor.
Preferably, the cure inhibitor comprises 3-methyl-1-pentyn-3-ol and/or 3, 5-dimethyl-1-hexyn-3-ol.
Preferably, the adhesion enhancer comprises any one or a combination of at least two of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, wherein typical but non-limiting combinations include: a combination of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and 3- (2, 3-glycidoxy) propyltrimethoxysilane, a combination of 3-aminopropyltriethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, a combination of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane and 3-aminopropyltriethoxysilane, and the like.
Preferably, the aromatic hydrocarbon solvent comprises toluene and/or xylene.
In a second aspect, the present invention provides a method for preparing the silicone die bond adhesive according to the first aspect, wherein the method comprises the following steps:
mixing polysiloxane silicone oil and polysiloxane resin, sequentially mixing with an aromatic solvent, fumed silica and a silica coupling agent, removing the aromatic solvent, and mixing with a catalyst, a curing inhibitor and an adhesion enhancer to obtain the organic silicon solid crystal glue.
In the invention, during preparation, the polysiloxane silicone oil and the polysiloxane resin are mixed firstly, and then the mixture is sequentially mixed with the aromatic solvent, the fumed silica and the silica coupling agent, because the silica coupling agent reacts with (hydrophilic) surface hydroxyl groups of the fumed silica in the aromatic solvent environment, so that the required silica functional groups generated on the surface of the fumed silica can improve the affinity with the polysiloxane silicone oil and the polysiloxane resin, and further increase the mixing amount of the fumed silica. Another advantage of using this method is that unreacted low molecular weight silane compounds are removed during the aromatic hydrocarbon solvent removal process after the reaction, so that the solid crystal glue produced thereafter has very low siloxane volatile:
as a preferable technical scheme, the preparation method comprises the following steps:
(1) uniformly mixing polysiloxane silicone oil and polysiloxane resin;
(2) mixing the mixed solution obtained in step (1) with aromatic hydrocarbon solvent at 20 deg.C above (such as 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, etc.);
(3) mixing the mixed solution obtained in step (2) with fumed silica at 50-70 deg.C (such as 52 deg.C, 54 deg.C, 56 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 64 deg.C, 66 deg.C, 68 deg.C, etc.) for 0.5-3 h (such as 1h, 2h, 2.5 h, etc.);
(4) mixing the mixed solution obtained in the step (3) with a silica coupling agent at 90-120 ℃ for 1-3 h (such as 1.5 h, 2h, 2.5 h and the like);
(5) removing the solvent from the mixed solution obtained in the step (4) at the temperature of 120-130 ℃ (such as 122 ℃, 124 ℃, 126 ℃, 128 ℃ and the like) to form a pre-reactant;
(6) and (3) mixing the pre-reactant obtained in the step (5) with a catalyst, a curing inhibitor and an adhesion enhancer in sequence at 10-40 ℃ (such as 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ and the like), and defoaming to obtain the organic silicon solid crystal glue.
In a third aspect, the invention provides an application of the silicone die bond adhesive of the first aspect in chip packaging.
Compared with the prior art, the invention has the following beneficial effects:
(1) the organic silicon die attach adhesive disclosed by the invention has the characteristic of low volatile matter, the cured coating has the advantages of high hardness, high light transmittance, high chip thrust and high shear strength, the yield of a gold wire bonding process is high, and the organic silicon die attach adhesive is suitable for packaging LED chips.
(2) The organic silicon solid crystal glue has the volatile content within 0.5 percent, the hardness after curing is more than 56 Shore D, the light transmittance is more than 81 percent, and the chip thrust (1 mm) 2 ) Above 2000 g, the shearing strength is above 3.3 MPa, and the yield of the gold wire bonding process is above 99.6%.
Drawings
Fig. 1 is a schematic structural diagram of an application of the silicone die bond adhesive described in embodiment 1 to an LED package structure;
1-LED chip; 2-organic silicon die bond; 3-gold thread; 4-packaging adhesive; 5-a silver-plated copper layer; 6-insulating layer.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an organic silicon crystal-fixing adhesive, which is prepared from the following raw materials in parts by mass:
50 parts of vinyl polysiloxane silicone oil
Hydrogen-based polysiloxane silicone oil 100 parts
Vinyl polysiloxane resin 150 parts
Hydrogen radical polysiloxane resin 30 parts
Fumed silica 23 parts
19 parts of silica coupling agent
Catalyst 9 parts
0.02 portion of curing inhibitor
150 parts of toluene
In the embodiment, the raw materials are specifically:
vinyl silicone oil: the viscosity is 350 cP, and the structure is shown as formula A1;
hydrogen-based polysiloxane silicone oil: the viscosity is 50 cP, and the structure is shown as formula A5;
vinyl polysiloxane resin: the structure is shown as B1, wherein R 5 And R 6 Is methyl, R 7 Is vinyl, with a =1, b =1, A, B, C in a molar ratio of 43:7: 50;
hydrogen-based polysiloxane resin: the structure is shown as B2, wherein R 8 And R 9 Is methyl, c =2, d =1, D, E, F in a molar ratio of 23:22: 50;
gas phase process silica: wacker N20;
silica coupling agent: vinyltriethoxysilane purchased from Sigma-Aldrich under the trademark 175560-;
catalyst: chloroplatinic acid H 2 PtCl 6 •(H 2 O) 6 Mixing vinyl polysiloxane solution (platinum content is 1000 ppm);
curing inhibitor: 3-methyl-1-pentyn-3-ol;
adhesion force enhancer: 2- (3, 4-Oxocyclohexane) ethyltrimethoxysilane, available from Sigma-Aldrich, under the designation 413321-25mL, Trimethoxy [2- (7-oxoacyclo [4.1.0] het-3-yl) ethyl ] silane;
the organic silicon die bond adhesive is prepared by the following method, and the method comprises the following steps:
(1) uniformly mixing polysiloxane silicone oil and polysiloxane resin;
(2) adding toluene into the mixed solution obtained in the step (1), and uniformly mixing at 25 ℃;
(3) adding the gas-phase method silicon dioxide into the mixed liquid obtained in the step (2), heating to 60 ℃, stirring and mixing for 1 h;
(4) adding a silicon dioxide coupling agent into the mixed solution obtained in the step (3), heating to 105 ℃, and stirring and mixing for 2 hours;
(5) rotationally evaporating the mixed solution obtained in the step (4) at 125 ℃ for 2h to remove the toluene solvent to form a pre-reactant;
(6) and (3) mixing the pre-reactant obtained in the step (5) with a catalyst, a curing inhibitor and an adhesion enhancer at 25 ℃ in sequence, and defoaming in vacuum to obtain the organic silicon solid crystal glue.
Example 2
The embodiment provides an organic silicon crystal-fixing adhesive, which is prepared from the following raw materials in parts by mass:
50 parts of vinyl polysiloxane silicone oil
115 parts of hydrogen-based polysiloxane silicone oil
150 parts of vinyl polysiloxane resin
30 parts of hydrogen-based polysiloxane resin
Fumed silica 23 parts
19 parts of silica coupling agent
Catalyst 9 parts
0.02 portion of curing inhibitor
150 parts of toluene
In the embodiment, the raw materials are specifically:
vinyl silicone oil: the viscosity is 500 cP, and the structure is shown as formula A3;
hydrogen-based polysiloxane silicone oil: a first part: 70 parts of a polymer, the viscosity of the polymer is 50 cP, and the structure of the polymer is shown as A5; a second part: 45 parts of a mixture, wherein the viscosity is 35 cP, and the structure is shown as a formula A7;
vinyl polysiloxane resin: the structure is shown as B1, wherein R 5 And R 6 Is methyl, R 7 Is vinyl, with a =1, b =1, A, B, C in a molar ratio of 43:7: 50;
hydrogen-based polysiloxane resin: the structure is shown as B2, wherein R 8 And R 9 Is methyl, c =2, d =1, D, E, F in a molar ratio of 23:22: 50;
gas phase process silica: wacker N20;
silica coupling agent: vinyltriethoxysilane purchased from Sigma-Aldrich under the trademark 175560-;
catalyst: chloroplatinic acid H 2 PtCl 6 •(H 2 O) 6 Mixing vinyl polysiloxane solution (platinum content is 1000 ppm);
curing inhibitor: 3-methyl-1-pentyn-3-ol;
adhesion force enhancer: 2- (3, 4-Oxocyclohexane) ethyltrimethoxysilane, available from Sigma-Aldrich, under the designation 413321-25mL, Trimethoxy [2- (7-oxoacyclo [4.1.0] het-3-yl) ethyl ] silane;
the organic silicon die bond adhesive is prepared by the following method, and the method comprises the following steps:
(1) uniformly mixing polysiloxane silicone oil and polysiloxane resin;
(2) adding toluene into the mixed solution obtained in the step (1), and uniformly mixing at 25 ℃;
(3) adding the gas-phase method silicon dioxide into the mixed liquid obtained in the step (2), heating to 60 ℃, stirring and mixing for 1 h;
(4) adding a silicon dioxide coupling agent into the mixed solution obtained in the step (3), heating to 105 ℃, and stirring and mixing for 2 hours;
(5) carrying out rotary evaporation on the mixed solution obtained in the step (4) at 125 ℃ for 2h to remove a toluene solvent to form a pre-reactant;
(6) and (3) mixing the pre-reactant obtained in the step (5) with a catalyst, a curing inhibitor and an adhesion enhancer at 25 ℃ in sequence, and defoaming in vacuum to obtain the organic silicon solid crystal glue.
Example 3
The embodiment provides an organic silicon crystal-fixing adhesive, which is prepared from the following raw materials in parts by mass:
50 parts of vinyl polysiloxane silicone oil
Hydrogen-based polysiloxane silicone oil 100 parts
Vinyl polysiloxane resin 150 parts
Hydrogen radical polysiloxane resin 30 parts
Fumed silica 23 parts
19 parts of silica coupling agent
Catalyst 9 parts
0.02 part of curing inhibitor
150 parts of toluene
In the embodiment, the raw materials are specifically:
vinyl polysiloxane silicone oil: the viscosity is 350 cP, and the structure is shown as formula A1;
hydrogen-based polysiloxane silicone oil: the viscosity is 50 cP, and the structure is shown as formula A5;
vinyl polysiloxane resin: the structure is shown as B1, wherein R 5 And R 6 Is methyl, R 7 Is vinyl, with a =1, b =1, A, B, C in a molar ratio of 43:7: 50;
hydrogen-based polysiloxane resin: the structure is shown as B2, wherein R 8 And R 9 Is methyl, c =2, d =1, D, E, F in a molar ratio of 23:22: 50;
gas phase process silica: wacker N20;
silica coupling agent: vinyltrimethoxysilane, purchased from Sigma-Aldrich, having a trade name of 235768-500mL, Vinyltrimethoxysilane;
catalyst: chloroplatinic acid H 2 PtCl 6 •(H 2 O) 6 Mixing vinyl polysiloxane solution (platinum content is 1000 ppm);
curing inhibitor: 3-methyl-1-pentyn-3-ol;
adhesion force enhancer: 3- (2, 3-glycidoxy) propyltrimethoxysilane, purchased from Sigma-Aldrich, trade name 440167-;
the organic silicon die bond adhesive is prepared by the following method, and the method comprises the following steps:
(1) uniformly mixing polysiloxane silicone oil and polysiloxane resin;
(2) adding toluene into the mixed solution obtained in the step (1), and uniformly mixing at 25 ℃;
(3) adding the gas-phase method silicon dioxide into the mixed liquid obtained in the step (2), heating to 60 ℃, stirring and mixing for 1 h;
(4) adding a silicon dioxide coupling agent into the mixed solution obtained in the step (3), heating to 105 ℃, and stirring and mixing for 2 hours;
(5) carrying out rotary evaporation on the mixed solution obtained in the step (4) at 125 ℃ for 2h to remove a toluene solvent to form a pre-reactant;
(6) and (3) mixing the pre-reactant obtained in the step (5) with a catalyst, a curing inhibitor and an adhesion enhancer at 25 ℃ in sequence, and defoaming in vacuum to obtain the organic silicon solid crystal glue.
Comparative example 1
This comparative example differs from example 1 in that a silica coupling agent is not included, and the rest is the same as example 1.
Comparative example 2
This comparative example differs from example 1 in that no aromatic hydrocarbon solvent is included, no aromatic hydrocarbon solvent is used for the prepolymerization in the preparation, and the rest is the same as in example 1.
Performance testing
The silicone solid crystal glue described in examples 1-3 and comparative examples 1-2 were tested as follows:
(1) viscosity (25 ℃): according to ASTM D4287.
(2) Volatile matter (100 ℃/1 h +150 ℃/2 h): taking 1 g of the organic silicon die-bonding adhesive, curing the organic silicon die-bonding adhesive by using a die with the thickness of 2mm for a test piece, curing the organic silicon die-bonding adhesive at the curing temperature of 100 ℃ for 1 hour, then heating the organic silicon die-bonding adhesive to 150 ℃ for curing for 2 hours, measuring the weight of the cured organic silicon die-bonding adhesive, calculating the difference before and after curing, and dividing the difference by 1 g of the initial weight to obtain the volatile matter percentage.
The following tests were carried out after curing the silicone die-bond adhesives described in examples 1-3 and comparative examples 1-2 (curing conditions were 1h at 100 ℃ and 2h at 150 ℃):
(1) hardness (shore D): according to ASTM D2240.
(2) Light transmittance (400 nm/2 mm): taking 1 g of the organic silicon die bond adhesive, curing the organic silicon die bond adhesive by using a die with the thickness of 2mm for a test piece, curing the organic silicon die bond adhesive at the curing temperature of 100 ℃ for 1 hour, then heating to 150 ℃ for curing for 2 hours, and measuring the light transmittance at the wavelength of 400 nm.
(3) Chip thrust (1 mm) 2 Si/Ag): using a dispensing needle head on a die bonder (Xinyichang GT836M) to pick out a proper amount of die bonder for fixing a 1W blue light chip (with an area of 1 mm) 2 ) On a silver-plated copper wire SMD support, the support is placed in an oven to be cured, the curing temperature is 100 ℃, the curing time is 1 hour, then the temperature is raised to 150 ℃, the curing time is 2 hours, then the support with the fixed chip is used for testing the chip thrust by using a chip thrust tester (Dage4000), and 16 samples prepared in each embodiment or comparative example are tested and averaged.
(4) Shear strength (Al/Al): according to ASTM D1002.
(5) Yield of the gold wire bonding process: using a dispensing needle head on a die bonder (Xinyichang GT836M) to take a proper amount of die bonder glue to fix a 1W blue light chip (with an area of 1 mm) 2 ) On a silver-plated copper wire SMD support, the support is placed in an oven to be cured, the curing temperature is 100 ℃, the curing time is 1 hour, then the temperature is raised to 150 ℃, the curing time is 2 hours, then the support with the fixed chip is bonded by using an automatic wire bonding machine (KS8028), 512 samples are manufactured in each embodiment or comparative embodiment, and a gold wire tensile testing machine (Dage4000) is used for testing whether the bonding of the gold wire is successful.
The test results are summarized in table 1.
TABLE 1
The data in table 1 show that the volatile matter of the organosilicon die bond adhesive is within 0.5%, the hardness after curing is more than 56 Shore D, the light transmittance is more than 81%, the chip thrust is more than 2000 g, the shear strength is more than 3.3 MPa, and the yield of the gold thread bonding process is more than 99.6%. The organic silicon die attach adhesive disclosed by the invention has the characteristic of low volatile matter, the cured coating has the advantages of high hardness, high light transmittance, high chip thrust and high shear strength, the yield of a gold wire bonding process is high, and the organic silicon die attach adhesive is suitable for packaging LED chips.
In the invention, fig. 1 exemplarily shows a schematic structural diagram of the application of the silicone die bond adhesive described in embodiment 1 to an LED package structure; the method comprises the following steps of coating a silver-plated copper layer 5 on a support with an insulating layer 6 with organic silicon die attach adhesive 2, arranging an LED chip 1 on the organic silicon die attach adhesive, arranging a gold wire 3 on the LED chip, and then arranging packaging adhesive 4.
Analysis of comparative example 1 and example 1 shows that comparative example 1 is inferior to example 1 in performance, and proves that the cured silicone solid crystal glue without the silica coupling agent has low chip pushing force and shear strength and low light transmittance, although the volatile matter is low, and is not suitable for packaging LED chips.
As can be seen from the analysis of comparative example 2 and example 1, the performance of comparative example 2 is inferior to that of example 1, and the results prove that the organic silicon solid crystal glue formed by prepolymerization without using an aromatic hydrocarbon solvent has high volatile matter content, low chip pushing force and shearing strength after curing, low light transmittance and is not suitable for packaging LED chips.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (7)
1. The organic silicon crystal-fixing adhesive is characterized by comprising the following raw materials in parts by mass:
100-180 parts of polysiloxane silicone oil
120-200 parts of polysiloxane resin
15-30 parts of fumed silica
15-30 parts of silica coupling agent
1-5000 ppm of catalyst
0.01 to 0.05 part of curing inhibitor
1-5 parts of adhesion force enhancer
100-200 parts of an aromatic solvent;
the silicone oil comprises a linear silicone oil;
the polysiloxane silicone oil comprises a combination of vinyl polysiloxane silicone oil and hydrogen polysiloxane silicone oil;
the vinyl polysiloxane silicone oil comprises any one of compounds A1-A4 or a combination of at least two of the compounds A1-A4;
wherein R is 1 And R 2 Each independently selected from methyl, ethyl, propyl, cyclohexyl or phenyl;
k is a positive integer, and l is a positive integer;
the viscosity of the vinyl polysiloxane silicone oil is 1-100000 cP;
the hydrogen polysiloxane silicone oil comprises any one of compounds A5-A8 or a combination of at least two of the compounds A5-A8;
wherein R is 3 And R 4 Each independently selected from methyl, ethyl, propyl, cyclohexyl or phenyl;
m is a positive integer, n is a positive integer;
the viscosity of the hydrogen-based polysiloxane silicone oil is 1-100000 cP;
the polysiloxane resin is three-dimensional reticular resin;
the polysiloxane resin comprises a combination of a vinyl polysiloxane resin and a hydrogen-based polysiloxane resin;
the molecular formula of the vinyl polysiloxane resin is shown as B1:
((R 5 ) 3 SiO 0.5 ) A ((R 6 ) a (R 7 ) b SiO (4-a-b)/2 ) B (SiO 2 ) C B1；
wherein R is 5 And R 6 Each independently selected from methyl, ethyl, propyl, cyclohexyl or phenyl;
R 7 selected from vinyl or allyl;
a is 0, 1 or 2, b is 1 or 2, a + b is 1, 2 or 3;
based on the total mole number of A, B, C as 100, the molar ratio of A, B, C is (1-60): (0.1-20): 10-95);
the number average molecular weight of the vinyl polysiloxane resin is 10000-100000;
the molecular formula of the hydrogen-based polysiloxane resin is shown as B2:
((R 8 ) 3 SiO 0.5 ) D ((R 9 ) c H d SiO (4-c-d)/2 ) E (SiO 2 ) F B2；
wherein R is 8 And R 9 Each independently selected from methyl, ethyl, propyl, cyclohexyl or phenyl;
c is 0, 1 or 2, d is 1 or 2, c + d is 1, 2 or 3;
the total mole number of D, E, F is 100, the mole ratio of D, E, F is (0.1-30): (0.1-30): 10-95);
the number average molecular weight of the hydrogen polysiloxane resin is 10000-100000;
the fumed silica comprises an untreated hydrophilic silica;
the volatile matter of the organic silicon solid crystal glue is within 0.5%, the hardness after curing is more than 56 Shore D, the light transmittance is more than 81%, and the chip thrust is 1mm 2 The Si/Ag is more than 2000 g, the shearing strength is more than 3.3 MPa, and the yield of the gold thread bonding process is more than 99.6 percent;
the organic silicon die bond adhesive is prepared by the following preparation method, and the preparation method comprises the following steps:
mixing polysiloxane silicone oil and polysiloxane resin, sequentially mixing with an aromatic solvent, fumed silica and a silica coupling agent, removing the aromatic solvent, and mixing with a catalyst, a curing inhibitor and an adhesion enhancer to obtain the organic silicon solid crystal glue.
2. The silicone die bond paste of claim 1, wherein the silica coupling agent comprises any one of methyltrimethoxysilane, methyltriethoxysilane, n-octyltriethoxysilane, hexadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltris (2-methoxyethoxy) silane, or a combination of at least two thereof.
3. The silicone die bond gel of claim 1, wherein the catalyst comprises any one of a platinum catalyst, a palladium catalyst, or a rhodium catalyst, or a combination of at least two thereof.
4. The silicone die bond paste of claim 1, wherein the cure inhibitor comprises an acetylenic alcohol cure inhibitor;
the adhesion force enhancer comprises any one or the combination of at least two of 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-aminopropyl triethoxy silane or N- (2-aminoethyl) -3-aminopropyl trimethoxy silane.
5. The preparation method of the organic silicon die-bonding adhesive according to any one of claims 1 to 4, which is characterized by comprising the following steps:
mixing polysiloxane silicone oil and polysiloxane resin, sequentially mixing with an aromatic solvent, fumed silica and a silica coupling agent, removing the aromatic solvent, and mixing with a catalyst, a curing inhibitor and an adhesion enhancer to obtain the organic silicon solid crystal glue.
6. The method of claim 5, comprising the steps of:
(1) uniformly mixing polysiloxane silicone oil and polysiloxane resin;
(2) uniformly mixing the mixed solution obtained in the step (1) with an aromatic hydrocarbon solvent at the temperature of more than 20 ℃;
(3) mixing the mixed solution obtained in the step (2) with fumed silica at 50-70 ℃ for 0.5-3 h;
(4) mixing the mixed solution obtained in the step (3) with a silicon dioxide coupling agent at the temperature of 90-120 ℃ for 1-3 h;
(5) removing the aromatic hydrocarbon solvent from the mixed solution obtained in the step (4) at the temperature of 120-130 ℃ to form a pre-reactant;
(6) and (3) mixing the pre-reactant obtained in the step (5) with a catalyst, a curing inhibitor and an adhesion enhancer at the temperature of 10-40 ℃ in sequence, and defoaming to obtain the organic silicon solid crystal glue.
7. Use of the silicone die bond adhesive of any one of claims 1-4 in LED chip packaging.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073215A (en) * | 2014-06-30 | 2014-10-01 | 江苏华程光电科技有限公司 | Preparation method for nano silicon dioxide modified organic silicon sealant for packaging of light emitting diode (LED) |
| CN106065317A (en) * | 2016-07-13 | 2016-11-02 | 东莞市和天新材料有限公司 | Fast setting non-volatile LEDbulb lamp adhesive glue and preparation method thereof |
| CN109294514A (en) * | 2018-09-29 | 2019-02-01 | 烟台德邦先进硅材料有限公司 | A kind of LED chip organosilicon crystal-bonding adhesive |
| CN109554159A (en) * | 2018-11-13 | 2019-04-02 | 汕头市骏码凯撒有限公司 | A kind of LED silicone insulation crystal-bonding adhesive and preparation method thereof |
| CN109628037A (en) * | 2018-12-14 | 2019-04-16 | 烟台德邦科技有限公司 | A kind of LED chip hydridization crystal-bonding adhesive |
| CN110637074A (en) * | 2017-05-17 | 2019-12-31 | 株式会社大赛璐 | Curable composition for adhesive, adhesive sheet, cured product, laminate, and device |
| CN113969132A (en) * | 2021-11-05 | 2022-01-25 | 南京科矽新材料科技有限公司 | Organic silicon die bonding adhesive suitable for high-speed die bonding of LED |
| CN114045152A (en) * | 2021-11-05 | 2022-02-15 | 南京科矽新材料科技有限公司 | Organic silicon die bonding adhesive for die bonding of LED |
-
2022
- 2022-06-02 CN CN202210620360.6A patent/CN114686161B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073215A (en) * | 2014-06-30 | 2014-10-01 | 江苏华程光电科技有限公司 | Preparation method for nano silicon dioxide modified organic silicon sealant for packaging of light emitting diode (LED) |
| CN106065317A (en) * | 2016-07-13 | 2016-11-02 | 东莞市和天新材料有限公司 | Fast setting non-volatile LEDbulb lamp adhesive glue and preparation method thereof |
| CN110637074A (en) * | 2017-05-17 | 2019-12-31 | 株式会社大赛璐 | Curable composition for adhesive, adhesive sheet, cured product, laminate, and device |
| CN109294514A (en) * | 2018-09-29 | 2019-02-01 | 烟台德邦先进硅材料有限公司 | A kind of LED chip organosilicon crystal-bonding adhesive |
| CN109554159A (en) * | 2018-11-13 | 2019-04-02 | 汕头市骏码凯撒有限公司 | A kind of LED silicone insulation crystal-bonding adhesive and preparation method thereof |
| CN109628037A (en) * | 2018-12-14 | 2019-04-16 | 烟台德邦科技有限公司 | A kind of LED chip hydridization crystal-bonding adhesive |
| CN113969132A (en) * | 2021-11-05 | 2022-01-25 | 南京科矽新材料科技有限公司 | Organic silicon die bonding adhesive suitable for high-speed die bonding of LED |
| CN114045152A (en) * | 2021-11-05 | 2022-02-15 | 南京科矽新材料科技有限公司 | Organic silicon die bonding adhesive for die bonding of LED |
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