Layer-adding adhesive film for packaging substrate as well as preparation method and application of layer-adding adhesive film
By introducing multifunctional resins into the laminated film and using acrylate-modified PET release film, the problem of PET shedding during the pre-curing process of the laminated film was solved, thereby improving film stability and processability.
Patent Information
- Application Number
- CN202511753291.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-26
- Publication Date
- 2026-01-23
AI Technical Summary
Existing laminated films are prone to PET peeling during the pre-curing process, which affects the film formation stability and processability in subsequent processing.
A multifunctional resin, including epoxy and acrylate functional groups, is introduced into the laminated film. The surface of the PET release film is modified using acrylate to improve its compatibility and adhesion with the laminated film.
This achieved film-forming stability and good processability of the laminated film, avoided PET peeling, and ensured the smooth progress of subsequent processing.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of resin composite materials, in particular to a build-up adhesive film for packaging substrates and a preparation method and application thereof. BACKGROUND
[0002] BOPET (biaxially oriented polyester film) release polyester film is widely used in the industrial field, and its uses include process protection in the fields of automobiles, electronics and semiconductor industry, ion exchange film in battery materials, and sheet-shaped structure components and molding materials such as ceramic green sheets. At present, most manufacturers use silicon oil and fluorine-based release agents. Although silicon oil and fluorine-based release agents have outstanding advantages, such as high light transmittance, good isolation performance, adjustable peeling force in a wide range, and repeated use effect. However, there is an inevitable problem of silicon element transfer in the use process, which pollutes the semi-finished products and finished products of downstream customers, and the waste after use is difficult to handle, and toxic gases are generated.
[0003] Non-silicon release polyester film refers to a layer of non-silicon release coating on the surface of a polyester film substrate, forming a release film with good mechanical properties, low surface energy, high environmental protection, and easy peeling. Due to its good environmental protection, it can be widely used in various bearing films, protective films, and fields requiring non-silicon and non-fluorine elements. In the field of microelectronic manufacturing, non-silicon release polyester film can be used in the processing technology of semiconductor materials to meet the material pre-treatment and laser drilling requirements, thereby improving the efficiency of fine processing.
[0004] The build-up adhesive film is applied in the processing and manufacturing process of packaging substrates, and needs to be carried with a PET release film substrate for pre-solidification treatment. Some resin systems carried with specific PET release films are prone to PET peeling during pre-solidification, which is not conducive to subsequent processing and manufacturing.
[0005] Therefore, the prior art needs to be improved. SUMMARY
[0006] In view of the deficiencies of the prior art, the present application provides a build-up adhesive film for packaging substrates and a preparation method and application thereof, aiming to solve the problem of meeting the film stability of the build-up adhesive film and ensuring good processability during use.
[0007] To achieve this purpose, the present application adopts the following technical solutions: In a first aspect, the present application provides a build-up film for packaging substrate, comprising a substrate and a film layer disposed on the substrate, wherein the film layer comprises the following components by weight: 70-100 parts of epoxy resin, 2-8 parts of multifunctional group resin, 40-70 parts of curing agent, 340-380 parts of silica, 4-10 parts of toughening resin, 0.6-1.2 parts of curing accelerator and 500-600 parts of solvent. The multifunctional group resin contains at least one epoxy functional group and at least one acrylate functional group. The substrate is a PET release film subjected to surface modification treatment using acrylate.
[0008] Optionally, the multifunctional group resin has a viscosity of 3500-4000 cps, a color of 35-40, a turbidity of 1.45-1.55, a refractive index of 1.50-1.55 and an epoxy value of 460-500 g / eq.
[0009] Optionally, the curing agent is an active ester curing agent. Preferably, the active ester curing agent is any one of EXB9451 of DIC Corporation, HPC-8000-65T of DIC Corporation, EXB-8150-65T of DIC Corporation, EXB9416-70BK of DIC Corporation and DC808 of Mitsubishi Chemical Corporation, or a combination of at least two thereof.
[0010] Optionally, the epoxy resin is selected from any one of biphenyl type epoxy resin, naphthalene type epoxy resin and dicyclopentadiene type epoxy resin, or a combination of at least two thereof.
[0011] Optionally, the toughening resin is phenoxy resin.
[0012] Optionally, the curing accelerator is selected from any one of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine, or a combination of at least two thereof. The solvent is selected from any one of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate or N,N-dimethylformamide, or a combination of at least two thereof.
[0013] In a second aspect, the present application provides a preparation method of build-up film for packaging substrate, comprising the following steps: uniformly mixing 70-100 parts of epoxy resin, 2-8 parts of multifunctional group resin, 40-70 parts of curing agent, 340-380 parts of silica, 4-10 parts of toughening resin, 0.6-1.2 parts of curing accelerator and 500-600 parts of solvent, and disposing the mixture on a substrate to obtain a film layer, thereby obtaining the build-up film for packaging substrate.
[0014] In a third aspect, the present application provides a use of a build-up adhesive film for packaging substrates in packaging substrates.
[0015] Compared with the prior art, the present application has the following beneficial effects: (1) The present application introduces a multifunctional group resin (containing at least one epoxy functional group and at least one acrylate functional group) into the build-up adhesive film on the basis of components such as epoxy resin, silica, toughening resin, curing accelerator, etc., and uses acrylate to perform surface modification treatment on the PET release film, thereby preparing a build-up adhesive film product with good processability and pre-cured morphology, which not only ensures film stability, but also avoids the phenomenon of PET peeling in the subsequent processing process.
[0016] (2) The multifunctional group resin introduced into the build-up adhesive film contains an acrylate functional group, and the PET release film is also surface modified with acrylate. The same functional groups can enhance compatibility through hydrogen bonds or covalent bonds, thereby improving the bonding between the acrylate surface modified PET release film and the build-up adhesive film, and thus avoiding the phenomenon of PET peeling in the pre-curing process.
[0017] (3) The multifunctional group resin introduced into the build-up adhesive film contains at least one epoxy functional group and at least one acrylate functional group. The epoxy functional group has good compatibility with the epoxy resin, and the acrylate functional group contains an ester functional group that increases the compatibility with the active ester. The multifunctional group resin is used as a bridge to link the main resin and the curing agent, thereby improving the film stability of the epoxy resin and active ester system build-up adhesive film and avoiding adverse effects such as phase separation. DETAILED DESCRIPTION
[0018] The present application provides a build-up adhesive film for packaging substrates, a preparation method and application thereof. In order to make the purpose, technical scheme and effects of the present application more clear and explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.
[0019] The build-up adhesive film is used in the processing and manufacturing process of packaging substrates, and needs to be pre-cured with a PET release film substrate. Some resin systems with specific PET release film are prone to PET peeling during pre-curing, which is not conducive to subsequent processing and manufacturing.
[0020] Therefore, how to design the components of the build-up adhesive film and select a suitable PET release film substrate, and how to reasonably match the two to meet the film stability of the build-up adhesive film and ensure good processability during use, have become urgent problems to be solved.
[0021] Based on this, the embodiment provides a build-up adhesive film for packaging substrates, comprising a substrate and an adhesive film layer arranged on the substrate, wherein the adhesive film layer comprises components in parts by weight: 70-100 parts of epoxy resin, 2-8 parts of multifunctional group resin, 40-70 parts of curing agent, 340-380 parts of silica, 4-10 parts of toughening resin, 0.6-1.2 parts of curing accelerator and 500-600 parts of solvent. The multifunctional group resin contains at least one epoxy functional group and at least one acrylate functional group. The substrate is a PET release film subjected to surface modification treatment using acrylate.
[0022] The present application introduces multifunctional group resin (multifunctional group resin containing at least one epoxy functional group and at least one acrylate functional group) into the build-up adhesive film on the basis of components such as epoxy resin, silica, toughening resin and curing accelerator, to prepare a build-up adhesive film product with good processability and pre-cured appearance. The multifunctional group resin can be well matched with the PET release film subjected to specific surface modification treatment, which is conducive to ensuring the subsequent laser drilling process and smoothly peeling off the PET release film after laser drilling. In addition, the multifunctional group resin has good compatibility with other components in the build-up adhesive film, which can effectively avoid phase separation.
[0023] The multifunctional group resin introduced into the build-up adhesive film contains at least one epoxy functional group and at least one acrylate functional group, wherein the epoxy functional group has good compatibility with the epoxy resin, and the acrylate functional group contains an ester functional group to increase the compatibility with active ester. The multifunctional group resin is used as a bridge to link the main resin and the curing agent, to improve the film stability of the epoxy resin and active ester system build-up adhesive film and avoid adverse effects such as phase separation.
[0024] The multifunctional group resin introduced into the build-up adhesive film contains an acrylate functional group, and the PET release film is also subjected to surface modification treatment using acrylate. The same functional groups can enhance the compatibility through hydrogen bond or covalent bond, improve the bonding between the acrylate surface modified PET release film and the build-up adhesive film, and thus avoid the phenomenon of PET peeling off during pre-curing. Therefore, the adhesive film layer prepared by using the multifunctional group resin containing at least one epoxy functional group and at least one acrylate functional group, in combination with the PET release film subjected to surface modification treatment using acrylate, can not only ensure the film stability, but also avoid the phenomenon of PET peeling off during the subsequent process.
[0025] In a preferred embodiment, the thickness of the substrate layer is 20-50 μm.
[0026] In a preferred embodiment, the thickness of the adhesive film layer is 20-100 μm.
[0027] In some preferred embodiments, the viscosity of the multifunctional group resin is 3500-4000 cps, the color is 35-40, the turbidity is 1.45-1.55, the refractive index is 1.50-1.55, and the epoxy value is 460-500 g / eq.
[0028] In a preferred embodiment, the multifunctional group resin is PRO33184 of Sartomer, the viscosity is 3800 cps, the color is 36, the turbidity is 1.49, the refractive index is 1.51, and the epoxy value is 488 g / eq.
[0029] In an embodiment, the curing agent is an active ester curing agent.
[0030] It should be noted that the active ester of the present embodiment can make the network structure of the cured epoxy resin dense and low in polarity, so that the cured epoxy resin can still maintain very stable electrical insulation performance in high temperature and high frequency environment, thereby making the obtained build-up film suitable for high frequency communication, semiconductor packaging, high performance electronic components, and the like.
[0031] In some preferred embodiments, the present embodiment is not intended to limit the types of active ester curing agents, and as an example, the active ester curing agent is any one or a combination of at least two of EXB9451 of DIC Corporation, HPC-8000-65T of DIC Corporation, EXB-8150-65T of DIC Corporation, EXB9416-70BK of DIC Corporation, and DC808 of Mitsubishi Chemical Corporation.
[0032] In some preferred embodiments, the present embodiment is not intended to limit the types of epoxy resins, and as an example, the epoxy resin is selected from any one or a combination of at least two of a biphenyl type epoxy resin, a naphthalene type epoxy resin, and a dicyclopentadiene type epoxy resin.
[0033] In an embodiment, the toughening resin is a phenoxy resin.
[0034] It should be noted that the phenoxy resin of the present embodiment has a similar chemical structure to the epoxy resin, so that it has good compatibility with the epoxy resin; in the curing process, it can form a homogeneous system with the epoxy resin, or form a very fine and stable microphase separation structure; such fine microstructure is the key to efficiently initiate silver streaks and shear bands and absorb impact energy, thereby achieving efficient toughening.
[0035] In some preferred embodiments, the present embodiments are not intended to limit the curing accelerator, for example, the curing accelerator is selected from any one or a combination of at least two of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, and 4-dimethylaminopyridine.
[0036] In some preferred embodiments, the present embodiments are not intended to limit the solvent, for example, the solvent is selected from any one or a combination of at least two of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate, or N,N-dimethylformamide.
[0037] The present embodiments also provide a preparation method of the build-up film for packaging substrates, which comprises the following steps: uniformly mixing 70-100 parts of epoxy resin, 2-8 parts of multifunctional group resin, 40-70 parts of curing agent, 340-380 parts of silicon dioxide, 4-10 parts of toughening resin, 0.6-1.2 parts of curing accelerator, and 500-600 parts of solvent, and setting the mixture on a substrate to obtain a film layer, thereby obtaining the build-up film for packaging substrates.
[0038] It should be noted that when setting, the uniformly mixed 70-100 parts of epoxy resin, 2-8 parts of multifunctional group resin, 40-70 parts of curing agent, 340-380 parts of silicon dioxide, 4-10 parts of toughening resin, 0.6-1.2 parts of curing accelerator, and 500-600 parts of solvent can be set on the substrate in a coating manner. After coating, the film layer needs to be dried, dried at 70-90°C for 5-10 min, and then a protective film is covered on the dried film layer.
[0039] The present embodiments also provide an application of the build-up film for packaging substrates in packaging substrates. The build-up film for packaging substrates of the present embodiments solves the problem of meeting the film forming stability of the build-up film and ensuring good processability during use.
[0040] The present application is further described below in conjunction with specific embodiments.
[0041] The sources of some components in the examples and comparative examples are as follows: Epoxy resin: biphenyl type epoxy resin, model NC 3000 L, Japan Chemical Company; Multifunctional group resin: model PRO33184, containing three acrylate functional groups and two epoxy functional groups, Sartomer Company; model MY0500, containing three epoxy functional groups, Araldite Company; Curing agent: active ester, model HPC-8000-65T, DIC Company; Silica: Model SO-C2, Yamanaka Chemical Industry Co., Ltd. Toughening resin: Phenoxy resin, Model YX6954BH30, Mitsubishi Chemical Corporation Curing accelerator: 1 Benzyl 2 Phenylimidazole, 1B2PZ, Shikoku Chemicals Corporation Solvent: Cyclohexanone
[0042] Example 1 The present example provides a preparation method of a build-up adhesive film for packaging substrates, comprising the following steps: mixing 100 parts of epoxy resin, 8 parts of multifunctional group resin (Model PRO33184), 70 parts of curing agent, 380 parts of silica, 10 parts of toughening resin, 1.2 parts of curing accelerator and 600 parts of solvent in equal parts by weight, coating on the substrate to obtain an adhesive film layer, drying, covering a protective film, and obtaining a build-up adhesive film for packaging substrates.
[0043] The thickness of the substrate of the present example is 38 μm. The thickness of the adhesive film layer is 40 μm.
[0044] Example 2 The present example provides a preparation method of a build-up adhesive film for packaging substrates, comprising the following steps: mixing 70 parts of epoxy resin, 2 parts of multifunctional group resin (Model PRO33184), 40 parts of curing agent, 340 parts of silica, 4 parts of toughening resin, 0.6 parts of curing accelerator and 500 parts of solvent in equal parts by weight, coating on the substrate to obtain an adhesive film layer, drying, covering a protective film, and obtaining a build-up adhesive film for packaging substrates.
[0045] The thickness of the substrate of the present example is 50 μm. The thickness of the adhesive film layer is 100 μm.
[0046] Example 3 The present example provides a preparation method of a build-up adhesive film for packaging substrates, comprising the following steps: mixing 80 parts of epoxy resin, 4 parts of multifunctional group resin (Model PRO33184), 50 parts of curing agent, 360 parts of silica, 6 parts of toughening resin, 0.8 parts of curing accelerator and 550 parts of solvent in equal parts by weight, coating on the substrate to obtain an adhesive film layer, drying, covering a protective film, and obtaining a build-up adhesive film for packaging substrates.
[0047] The thickness of the substrate of the present example is 20 μm. The thickness of the adhesive film layer is 20 μm.
[0048] Example 4 The embodiment provides a preparation method of a build-up adhesive film for a packaging substrate, and the method comprises the following steps: uniformly mixing 90 parts of an epoxy resin, 6 parts of a multifunctional group resin (model PRO33184), 60 parts of a curing agent, 370 parts of silicon dioxide, 8 parts of a toughening resin, 1.1 parts of a curing accelerator and 580 parts of a solvent, and then coating the mixture on a substrate to obtain an adhesive film layer, drying the adhesive film layer, covering a protective film, and obtaining the build-up adhesive film for the packaging substrate.
[0049] The substrate thickness of the embodiment is 38 μm. The thickness of the adhesive film layer is 35 μm.
[0050] Example 5 The embodiment provides a preparation method of a build-up adhesive film for a packaging substrate, and the method comprises the following steps: uniformly mixing 75 parts of an epoxy resin, 3 parts of a multifunctional group resin (model PRO33184), 50 parts of a curing agent, 350 parts of silicon dioxide, 5 parts of a toughening resin, 0.7 parts of a curing accelerator and 520 parts of a solvent, and then coating the mixture on a substrate to obtain an adhesive film layer, drying the adhesive film layer, covering a protective film, and obtaining the build-up adhesive film for the packaging substrate.
[0051] The substrate thickness of the embodiment is 38 μm. The thickness of the adhesive film layer is 37.5 μm.
[0052] Comparative Example 1 The difference between the comparative example and the embodiment 1 is that a polyolefin surface modified PET release film is used instead of an acrylate surface modified PET release film.
[0053] Comparative Example 2 The difference between the comparative example and the embodiment 1 is that a non-surface modified PET release film is used instead of an acrylate surface modified PET release film.
[0054] Comparative Example 3 The difference between the comparative example and the embodiment 1 is that no multifunctional group resin is added.
[0055] Comparative Example 4 The difference between the comparative example and the embodiment 1 is that a multifunctional group resin MY0500 is used instead of a multifunctional group resin PRO33184.
[0056] The performance of the build-up adhesive film provided by the above embodiment and comparative examples is tested, and the testing method is as follows: The protective film of the build-up adhesive film is removed, the build-up adhesive film with a PET release film is pressed on a core plate by using a vacuum film sticking machine, and the test sample is obtained by pre-curing at 180 ℃ for 30 min.
[0057] (1) Test of peelability of the PET release film: The PET release film is peeled off, and the case that the PET release film can be peeled off from the adhesive film layer smoothly is evaluated as "good", and the case that part or all of the PET release film is attached to the adhesive film layer and cannot be peeled off smoothly is evaluated as "poor"; whether the PET residue exists on the surface of the adhesive film layer and whether the PET release film has cracks are confirmed by visual observation.
[0058] (2) Pre-cured appearance: After the PET release film is peeled off, whether the phase separation, color unevenness and the like occur on the adhesive film layer is observed visually.
[0059] Table 1,
[0060] As can be seen from Table 1, the build-up adhesive film for packaging substrates obtained by each embodiment of the present application has good peelability, no PET cracks and no PET residue, the adhesive film layer has no phase separation and uniform color.
[0061] In summary, the present application provides a build-up adhesive film for packaging substrates and a preparation method and application thereof.
[0062] (1) On the basis of components such as epoxy resin, silica, toughening resin, curing accelerator and the like, a build-up adhesive film product with good processability and pre-cured appearance is prepared by introducing a multifunctional group resin (containing at least one epoxy functional group and at least one acrylate functional group) into the build-up adhesive film, and using an acrylate surface-modified PET release film, which not only ensures the film stability, but also avoids the phenomenon of PET falling off in the subsequent processing process.
[0063] (2) The multifunctional group resin introduced into the build-up adhesive film contains an acrylate functional group, and the PET release film is also surface-modified with acrylate, and the same functional groups can enhance the compatibility through hydrogen bond or covalent bond, thereby improving the combination between the acrylate surface-modified PET release film and the build-up adhesive film, so as to avoid the phenomenon of PET falling off in the pre-curing process.
[0064] (3) The multifunctional group resin introduced into the build-up adhesive film contains at least one epoxy functional group and at least one acrylate functional group, wherein the epoxy functional group has good compatibility with the epoxy resin, and the acrylate functional group contains an ester functional group to increase the compatibility with the active ester, and the multifunctional group resin is used as a bridge to link the main resin and the curing agent, thereby improving the film stability of the epoxy resin and the active ester system build-up adhesive film, and avoiding the adverse effects such as phase separation.
[0065] Applicant states that the detailed process flow of the present application is illustrated by the above-mentioned examples, but the present application is not limited to the above-mentioned detailed process flow, i.e. it does not mean that the present application must rely on the above-mentioned detailed process flow to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.
Claims
1. A build-up film for a package substrate, characterized by, The adhesive film layer comprises components in parts by weight: 70-100 parts of epoxy resin, 2-8 parts of multifunctional group resin, 40-70 parts of curing agent, 340-380 parts of silica, 4-10 parts of toughening resin, 0.6-1.2 parts of curing accelerator and 500-600 parts of solvent; The multifunctional group resin contains at least one epoxy functional group and at least one acrylate functional group; The substrate is a PET release film subjected to surface modification treatment using acrylate.
2. The build-up film for a package substrate according to claim 1, wherein The multifunctional group resin has a viscosity of 3500-4000 cps, a colority of 35-40, a turbidity of 1.45-1.55, a refractive index of 1.50-1.55 and an epoxy value of 460-500 g / eq.
3. The build-up film for a package substrate according to claim 1, wherein The curing agent is an active ester curing agent.
4. The build-up film for a package substrate according to claim 3, wherein The active ester curing agent is any one or a combination of at least two of EXB9451 of DIC Corporation, HPC-8000-65T of DIC Corporation, EXB-8150-65T of DIC Corporation, EXB9416-70BK of DIC Corporation and DC808 of Mitsubishi Chemical Corporation.
5. The build-up film for a package substrate according to claim 1, wherein The epoxy resin is selected from any one or a combination of at least two of biphenyl type epoxy resin, naphthalene type epoxy resin and dicyclopentadiene type epoxy resin.
6. The build-up film for a package substrate according to claim 1, wherein The toughening resin is phenoxy resin.
7. The build-up film for a package substrate according to claim 1, wherein The curing accelerator is selected from any one or a combination of at least two of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole and 4-dimethylaminopyridine.
8. The build-up film for a package substrate according to claim 1, wherein The solvent is selected from any one or a combination of at least two of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate and N,N-dimethylformamide.
9. A method for producing a build-up film for a package substrate according to any one of claims 1 to 8, characterized by, The method comprises the following steps: uniformly mixing 70-100 parts of epoxy resin, 2-8 parts of multifunctional group resin, 40-70 parts of curing agent, 340-380 parts of silica, 4-10 parts of toughening resin, 0.6-1.2 parts of curing accelerator and 500-600 parts of solvent, and setting on a substrate to obtain an adhesive film layer, thereby obtaining the adhesive film for increasing layers of packaging substrates.
10. Use of the adhesive film for increasing layers of packaging substrates according to any one of claims 1-8 in packaging substrates.