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CN-122011396-A - Modified organic silicon resin and adhesive using same

CN122011396ACN 122011396 ACN122011396 ACN 122011396ACN-122011396-A

Abstract

According to the preparation method of the modified organic silicon resin, disclosed by the invention, the hydrogen-containing silicon resin, the acrylic ester with the long-chain alkane group and the glycidyl mono-olefin are subjected to addition reaction, the long-chain alkane group and the epoxy group are connected to the hydrogen-containing silicon resin, the prepared modified organic silicon resin is applied to an epoxy resin adhesive system, the characteristics of the two resins can complement and synergistically act, the compatibility of the system is improved, the heat resistance is improved, the permeability and the hydrophobic capacity of the flexible copper-clad copper foil to a base material are improved, the stripping force is improved, the etching rate of an etched liquid is reduced, and the resolution and the accuracy of an electronic circuit prepared by a photoetching process are further improved.

Inventors

  • DING FUCHUAN
  • DAI LONGFEI
  • ZHOU ANMING

Assignees

  • 惠州市振源鑫电子材料有限公司

Dates

Publication Date
20260512
Application Date
20260210

Claims (10)

  1. 1. The preparation method of the modified organic silicon resin is characterized by comprising the following steps: S1, adding hydrogen-containing silicone resin, acrylic ester with long-chain alkane groups and glycidyl mono-olefin monomer into a reaction kettle together, stirring uniformly, dispersing the stirred mixture into a solvent A, adding a platinum catalyst, and stirring uniformly; s2, heating to perform hydrosilylation; after the S3S 2 reaction is completed, cooling, adding an activated carbon adsorption catalyst, filtering, and carrying out reduced pressure distillation on the filtered filtrate to remove the solvent A, thereby obtaining the modified organic silicon resin; the molar ratio of the acrylate with long-chain alkane to the glycidyl vinyl monomer is (2-5) 1, and the ratio of the sum of the molar numbers of the acrylate with long-chain alkane and the glycidyl vinyl monomer to the molar number of the silicon hydride groups in the hydrogen-containing silicon resin is (1.2-1.5) 1.
  2. 2. The method of claim 1, wherein the hydrogen-containing silicone resin is any one of methyl hydrogen-containing silicone resin, phenyl hydrogen-containing silicone resin, methylphenyl hydrogen-containing silicone resin, or a mixture thereof, and the hydrogen content of the hydrogen-containing silicone resin is 0.1 to 1.0%.
  3. 3. The method according to claim 1, wherein the acrylic acid ester having a long chain alkane group is any one of stearyl methacrylate, stearyl acrylate, isooctyl methacrylate, isooctyl acrylate, lauryl methacrylate, lauryl acrylate, or a mixture thereof.
  4. 4. The method of claim 1, wherein the glycidyl mono-olefin monomer is any one of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a mixture thereof.
  5. 5. The preparation method according to claim 1, wherein the solvent A is a toluene and butanone mixed solvent.
  6. 6. The preparation method according to claim 1, wherein in S2, the hydrosilylation reaction temperature is 80-100 ℃ and the reaction time is 3-4 hours.
  7. 7. The method according to claim 1, wherein in S3, activated carbon adsorption is performed by lowering the temperature to 50-60 ℃.
  8. 8. An adhesive comprising the modified silicone resin prepared according to any one of claims 1 to 7.
  9. 9. The adhesive of claim 8, wherein the adhesive comprises: The modified silicone resin comprises, by weight, 1.0-10.0 parts of modified silicone resin, 10.0-50.0 parts of epoxy resin, 5.0-15.0 parts of nitrile rubber, 10.0-20.0 parts of flame retardant, 0.5-3.0 parts of curing agent, 0.02-1.0 parts of imidazole curing accelerator, 0.02-0.06 parts of antioxidant and 30.0-60.0 parts of solvent B.
  10. 10. The adhesive of claim 9 wherein the epoxy resin is a mixture of bisphenol a epoxy resin and dicyclopentadiene epoxy resin, the nitrile rubber is carboxylated nitrile rubber, the curative is 4,4 '-diaminodiphenyl sulfone, the imidazole cure accelerator is 2-ethyl-4-methylimidazole, the flame retardant is a mixture of aluminum hydroxide and aluminum diethylphosphinate, the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-benzamide), and the solvent B is a ketone solvent or an amide solvent.

Description

Modified organic silicon resin and adhesive using same Technical Field The invention relates to the technical field of flexible copper-clad plate adhesives, in particular to a modified organic silicon resin and an adhesive using the same. Background In the field of flexible copper-clad plates, the epoxy resin adhesive has the remarkable advantages of strong adhesive force, good insulating property and small curing shrinkage, and is an adhesive type widely applied at present. However, on the one hand, the epoxy resin adhesive has high polarity and high hydrophilicity, so that the epoxy resin adhesive has high water absorption, and can possibly contact chemical substances such as an etchant and the like in the production and use processes of the flexible copper-clad plate, the high water absorption can enable the etching resistance of the epoxy resin adhesive to be low, the performance and service life of the copper-clad plate are affected, and on the other hand, the epoxy resin adhesive has high crosslinking density after being cured, so that the material is brittle, easy to crack and insufficient in flexibility, and in the flexible electronic field, the material needs to have good flexibility to adapt to various bending, folding and other deformation conditions. The methods for improving the defects of the epoxy resin adhesive which are commonly used at present mainly comprise two methods, namely adding rubber or modified rubber and directly modifying the epoxy resin. Because of the difference between the chemical structure and the polarity of the rubber and the epoxy resin, the rubber and the epoxy resin have poor compatibility, in an adhesive system, the rubber can be dispersed in an epoxy resin matrix in an independent phase, a phase separation structure is easy to form during curing to influence the integral heat resistance of the adhesive and the mechanical property at high temperature, the compactness of the epoxy resin matrix can be damaged, a plurality of tiny pores and channels are formed, a path for permeation and adsorption is provided for water molecules, so that the water molecules can enter the adhesive more easily, the water absorption rate is improved, the epoxy resin is directly modified, and the improvement of a plurality of performance indexes is difficult to be simultaneously considered, for example, the flexibility of the epoxy resin can be increased through long-chain modification, the water absorption rate of the epoxy resin can be reduced, but the bonding strength and the heat resistance of the adhesive can be reduced, and the requirement of the flexible electronic field on the flexibility of materials can not be met. Disclosure of Invention The invention aims to overcome the defects in the prior art and provides a preparation method of modified organic silicon resin capable of synergistically enhancing the comprehensive performance of an epoxy resin adhesive. The aim of the invention is realized by the following technical scheme: A preparation method of modified organic silicon resin comprises the following steps: S1, adding hydrogen-containing silicone resin, acrylic ester with long-chain alkane groups and glycidyl mono-olefin monomer into a reaction kettle together, stirring uniformly, dispersing the stirred mixture into a solvent A, adding a platinum catalyst, and stirring uniformly; s2, heating to perform hydrosilylation; after the S3S 2 reaction is completed, cooling, adding an activated carbon adsorption catalyst, filtering, and carrying out reduced pressure distillation on the filtered filtrate to remove the solvent to obtain the modified organic silicon resin; The ratio of the sum of the mole numbers of the long-chain alkane-carrying acrylate and the glycidyl vinyl monomer to the mole number of the silicon hydride groups in the hydrogen-containing silicon resin is (1.2-1.5): 1, and the mole ratio of the long-chain alkane-carrying acrylate and the glycidyl vinyl monomer is (2-5): 1. In a preferred scheme, the hydrogen-containing silicone resin is any one of methyl hydrogen-containing silicone resin, phenyl hydrogen-containing silicone resin and methylphenyl hydrogen-containing silicone resin or a mixture thereof, and the mass fraction of active hydrogen of the hydrogen-containing silicone resin is 0.1-1.0%. In a preferred embodiment, the acrylate with long chain alkane group is any one of stearyl methacrylate, stearyl acrylate, isooctyl methacrylate, isooctyl acrylate, lauryl methacrylate, lauryl acrylate or a mixture thereof. In a preferred embodiment, the glycidyl mono-olefin monomer is any one of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, or a mixture thereof. In a preferred scheme, the solvent A is toluene and butanone mixed solvent. In a preferred scheme, in S2, the hydrosilylation reaction temperature is 80-100 ℃ and the reaction time is 3-4 h. In a preferred scheme, in S3, the temperature is reduced to 50-60 ℃ for activated carbon adsorption. The i