A wet coating resin composition, a method for preparing the same, and an application thereof

Abstract

The present invention relates to the technical field of compression cushioning, and specifically to a wet-coated resin composition, and methods of making and using the same. The composition includes a polytetrafluoroethylene resin emulsion, an epoxy resin, an isocyanate, water, a filler, and a cellulose. The composition of the present invention has excellent overall performance when used in compression cushioning, such as thickness uniformity, non-absorbency, and flexibility.

Description

Technical Field

[0001] This invention relates to the field of compression cushioning technology, specifically to a wet-coated resin composition, its preparation method, and its application. Background Technology

[0002] A single-layer circuit board consists of a resin substrate covered with a layer of circuitry (copper wires). However, single-layer circuit boards cannot meet the current needs of integrated circuits. Therefore, multi-layer circuit boards have been developed. These multi-layer circuit boards are formed by laminating multiple layers of resin substrates and multiple layers of copper foil together like a sandwich. High pressure is required for heat pressing during the lamination process. However, both the resin substrate and the copper foil are fragile and easily damaged during pressing. Therefore, a soft pad is needed underneath. This pad is called a lamination buffer. Currently, most research on lamination buffers focuses on their high-temperature resistance. However, the lamination buffer comes into contact with the copper foil during use. Under certain circumstances, after repeated contact, it may adhere to the copper foil. Summary of the Invention

[0003] The purpose of this invention is to provide a wet-coating resin composition, its preparation method, and its application.

[0004] The present invention provides a wet coating resin composition comprising a polytetrafluoroethylene resin emulsion, an epoxy resin, an isocyanate, water, a filler, and cellulose.

[0005] In this invention, the various components of the composition work synergistically to give the resin composition excellent overall performance when used in compression cushioning pads.

[0006] In order to improve the overall performance of the resin composition of the present invention when used in compression cushioning pads, as a preferred technical solution of the present invention, the composition comprises, by weight, 100 parts of polytetrafluoroethylene resin emulsion, 15-30 parts of epoxy resin, 5-20 parts of isocyanate, 10-30 parts of water, 5-20 parts of filler and 0.5-5 parts of cellulose.

[0007] In order to improve the overall performance of the resin composition of the present invention when used in compression cushioning pads, as a more preferred technical solution of the present invention, the composition comprises, by weight, 100 parts of polytetrafluoroethylene resin emulsion, 20-25 parts of epoxy resin, 12-15 parts of isocyanate, 15-20 parts of water, 8-10 parts of filler and 1-2 parts of cellulose.

[0008] The polytetrafluoroethylene resin emulsion in this invention is commercially available, such as the polytetrafluoroethylene resin emulsion D30 from DuPont, USA.

[0009] The epoxy resin used in this invention can be obtained commercially, preferably epoxy resin YT-100 purchased from Jiangsu Yatai Chemical Co., Ltd.

[0010] In this invention, the epoxy resin and other components in the composition work synergistically to better increase the adhesion between the composition and the substrate.

[0011] The isocyanate in this invention can be obtained commercially, preferably from Jiangsu Yatai Chemical Co., Ltd.

[0012] In this invention, the epoxy resin, isocyanate and other components in the composition work synergistically to better increase the bonding strength between the composition and the substrate.

[0013] In order to improve the overall performance of the resin composition of the present invention when used in compression cushioning pads, as a technical solution of the present invention, the filler is selected from at least one of graphene, graphene oxide, talc, hydrotalcite, silicon dioxide, calcium carbonate and barium sulfate.

[0014] To enhance the overall performance of the resin composition of the present invention when used in press-fit cushioning pads, as a preferred embodiment of the present invention, the filler is graphene oxide and silicon dioxide. Preferably, the weight ratio of graphene oxide to silicon dioxide is 1:(0.1-1), more preferably 1:(0.3-0.5).

[0015] In order to improve the overall performance of the resin composition of the present invention when used in compression cushioning pads, as a preferred technical solution of the present invention, the graphene oxide has an average thickness of 1-3 nm, a number of layers of 2-5 (e.g., 2, 3, 4 or 5 layers), and a diameter of 4-7 μm.

[0016] The graphene oxide used in this invention can be obtained commercially, preferably multilayer graphene oxide ZM-SM05 from Hangzhou Zheming New Materials Co., Ltd.

[0017] In this invention, experiments have shown that using multilayered graphene oxide can better improve the overall performance of the resin composition when used for press-fit cushioning pads, especially increasing its non-adhesion to steel plates.

[0018] In order to improve the overall performance of the resin composition of the present invention when used in press-fit cushioning pads, as a preferred technical solution of the present invention, the silica is hydrophilic silica.

[0019] The use of hydrophilic silica in this invention can better enhance the overall performance of the resin composition when used for press-fit cushioning pads, especially increasing its non-adhesion to steel plates. This may be because graphene oxide has a layered structure with a certain surface effect, and hydrophilic silica can better enhance the surface effect through synergistic effects.

[0020] As a preferred embodiment of the present invention, the average particle size of the hydrophilic silica is different from the diameter of graphene oxide. Preferably, the average particle size of the hydrophilic silica is 10-50 nm, and more preferably 10-30 nm.

[0021] The hydrophilic silica in this invention can be obtained commercially, such as the hydrophilic silica with product number H10 from Tianxing New Materials.

[0022] In this invention, the inventors discovered through experiments that using hydrophilic silica with a specific average particle size can not only better increase the non-adhesion of the resin composition to the steel plate when used for pressing buffer pads, but also further increase the thickness uniformity of the buffer pads when used for pressing buffer pads.

[0023] As one technical solution of the present invention, the cellulose is selected from at least one of hydroxyethyl cellulose, methyl cellulose and hydroxypropyl methyl cellulose.

[0024] As a preferred embodiment of the present invention, the cellulose is hydroxyethyl cellulose and hydroxypropyl methyl cellulose, and preferably the weight ratio of hydroxyethyl cellulose to hydroxypropyl methyl cellulose is 1:(2-3).

[0025] The hydroxyethyl cellulose used in this invention can be obtained commercially, preferably Dow hydroxyethyl cellulose HEC QP-4400HQP-15000H.

[0026] The hydroxypropyl methylcellulose used in this invention is commercially available, such as Dow METHOCEL. TM E4M Premium Hydroxypropyl Methylcellulose HPMC.

[0027] In this invention, the inventors discovered through experiments that using specific hydroxyethyl cellulose and hydroxypropyl methyl cellulose in a synergistic effect can better increase the toughness of the composition during use. The mechanism is not yet clear, but the inventors speculate that hydroxypropyl methyl cellulose makes the dispersion of each component in the system better. Although the dispersion effect of hydroxyethyl cellulose is not as good as that of hydroxypropyl methyl cellulose, it can better synergize with graphene oxide in the system to improve the toughness of the composition product.

[0028] A second aspect of the present invention provides a method for preparing the wet-coating resin composition described in the first aspect of the present invention, the method comprising:

[0029] S1 mixes water, filler, and cellulose to obtain material A;

[0030] S2 involves a second mixing of polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate, and material A to obtain a wet coating resin composition.

[0031] As a preferred technical solution of the present invention, the conditions for the first mixing include: room temperature, mixing at 500-600 r / min for 0.5-1 h.

[0032] As a preferred technical solution of the present invention, the conditions for the second mixing include: mixing at 40-50℃ and 1200-1500r / min for 1-2 hours.

[0033] The third aspect of the present invention provides the application of the wet-coated resin composition described in the first aspect of the present invention or the wet-coated resin composition prepared by the preparation method of the wet-coated resin composition described in the first aspect of the present invention in a buffer material for hot pressing.

[0034] As a preferred technical solution of the present invention, the specific method for using the wet-coated resin composition as a buffer material for hot pressing includes: (1) impregnating glass fiber cloth in the wet-coated resin composition and then drying it to obtain modified glass fiber cloth; (2) bonding the modified glass fiber cloth to the upper and lower surfaces of the organic fiber woven layer respectively by means of an adhesive.

[0035] As a preferred technical solution of the present invention, the impregnation can be carried out in the glue circulation system of the glue applicator, preferably the glass fiber cloth is impregnated in the glue in step (1) at a speed of 35-45cm / min.

[0036] As a preferred embodiment of the present invention, the coating amount of the composition is 100-140 g / m². 2 In this invention, excess material can be removed by squeezing with a squeezing roller.

[0037] As a preferred embodiment of the present invention, the drying temperature is 210-230℃ and the drying time is 20-30 minutes.

[0038] As a preferred technical solution of the present invention, the product can be cut and rolled into a finished product as needed after drying.

[0039] The glass fiber cloth in this invention can be either plain glass fiber cloth or twill glass fiber cloth.

[0040] The thickness of the glass fiber cloth in this invention can be 0.55-0.65 mm.

[0041] In this invention, the type of adhesive is not particularly limited. In this invention, a polyurethane adhesive and an organosilicon adhesive with a weight ratio of 1:1 are used as the adhesive.

[0042] In this invention, the organic fiber braided layer is Kevlar 1414 fiber or Kevlar 1313 fiber, and the thickness can be 4-8mm. Detailed Implementation

[0043] The present invention will be described in detail below through embodiments. The following embodiments are merely exemplary descriptions of specific technical solutions of the present invention and do not limit the scope of the present invention. That is, it should be understood that non-essential simple corrections, adjustments and combinations made by those skilled in the art based on the inventive concept of the present invention are all within the scope of protection claimed by the present invention.

[0044] In the following embodiments:

[0045] The polytetrafluoroethylene resin emulsion is DuPont's D30 polytetrafluoroethylene resin emulsion.

[0046] The epoxy resin was purchased from Jiangsu Yatai Chemical Co., Ltd. as epoxy resin YT-100.

[0047] The isocyanate was purchased from Jiangsu Yatai Chemical Co., Ltd.

[0048] The graphene oxide is ZM-SM05 multilayer graphene oxide from Hangzhou Zheming New Materials Co., Ltd., with an average thickness of 2nm, 3 layers, and a diameter of 5μm.

[0049] The silica is hydrophilic silica with product number H10 from Tianxing New Materials, and the average particle size is 20nm.

[0050] The hydroxyethyl cellulose is Dow hydroxyethyl cellulose HEC QP-4400H QP-15000H.

[0051] Hydroxypropyl methylcellulose is a product of Dow METHOCEL. TM E4M Premium Hydroxypropyl Methylcellulose HPMC.

[0052] Example 1

[0053] (1) Prepare 100 parts of polytetrafluoroethylene resin emulsion, 20 parts of epoxy resin, 13 parts of isocyanate, 15 parts of water, 6 parts of graphene oxide, 3 parts of silicon dioxide, 0.5 parts of hydroxyethyl cellulose, and 1 part of hydroxypropyl methyl cellulose by weight, for later use.

[0054] (2) Water, graphene oxide, silicon dioxide, hydroxyethyl cellulose and hydroxypropyl methyl cellulose were mixed at room temperature and 500 r / min for 1 h to obtain material A;

[0055] (3) The polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate and material A are mixed at 50°C and 1200r / min for 1h to obtain a wet coating resin composition.

[0056] Example 2

[0057] (1) Prepare 100 parts of polytetrafluoroethylene resin emulsion, 25 parts of epoxy resin, 15 parts of isocyanate, 20 parts of water, 6.5 parts of graphene oxide, 2 parts of silicon dioxide, 0.5 parts of hydroxyethyl cellulose, and 1.5 parts of hydroxypropyl methyl cellulose by weight for later use.

[0058] (2) Water, graphene oxide, silicon dioxide, hydroxyethyl cellulose and hydroxypropyl methyl cellulose were mixed at room temperature and 600 r / min for 0.5 h to obtain material A;

[0059] (3) The polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate and material A are mixed at 50°C and 1200r / min for 1h to obtain a wet coating resin composition.

[0060] Example 3

[0061] (1) Prepare 100 parts of polytetrafluoroethylene resin emulsion, 20 parts of epoxy resin, 13 parts of isocyanate, 18 parts of water, 6 parts of graphene oxide, 3 parts of silicon dioxide, 0.5 parts of hydroxyethyl cellulose, and 1.5 parts of hydroxypropyl methylcellulose by weight for later use.

[0062] (2) Water, graphene oxide, silicon dioxide, hydroxyethyl cellulose and hydroxypropyl methyl cellulose were mixed at room temperature and 500 r / min for 1 h to obtain material A;

[0063] (3) The polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate and material A are mixed at 50°C and 1200r / min for 1h to obtain a wet coating resin composition.

[0064] Example 4

[0065] (1) Prepare 100 parts of polytetrafluoroethylene resin emulsion, 20 parts of epoxy resin, 13 parts of isocyanate, 15 parts of water, 9 parts of silica, 0.5 parts of hydroxyethyl cellulose, and 1 part of hydroxypropyl methylcellulose by weight, for later use.

[0066] (2) Water, silica, hydroxyethyl cellulose and hydroxypropyl methyl cellulose were mixed at room temperature and 500 r / min for 1 h to obtain material A;

[0067] (3) The polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate and material A are mixed at 50°C and 1200r / min for 1h to obtain a wet coating resin composition.

[0068] Example 5

[0069] (1) Prepare 100 parts of polytetrafluoroethylene resin emulsion, 20 parts of epoxy resin, 13 parts of isocyanate, 15 parts of water, 6 parts of graphene oxide, 3 parts of silicon dioxide, and 1.5 parts of hydroxypropyl methylcellulose by weight for later use.

[0070] (2) Water, graphene oxide, silicon dioxide and hydroxypropyl methylcellulose were mixed at room temperature and 500 r / min for 1 h to obtain material A;

[0071] (3) The polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate and material A are mixed at 50°C and 1200r / min for 1h to obtain a wet coating resin composition.

[0072] Example 6

[0073] (1) Prepare 100 parts of polytetrafluoroethylene resin emulsion, 20 parts of epoxy resin, 13 parts of isocyanate, 15 parts of water, 6 parts of graphene oxide, 3 parts of silicon dioxide, and 1.5 parts of hydroxyethyl cellulose by weight for later use.

[0074] (2) Water, graphene oxide, silicon dioxide and hydroxyethyl cellulose were mixed at room temperature and 500 r / min for 1 h to obtain material A;

[0075] (3) The polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate and material A are mixed at 50°C and 1200r / min for 1h to obtain a wet coating resin composition.

[0076] Comparative Example 1

[0077] (1) Prepare 100 parts of polytetrafluoroethylene resin emulsion, 20 parts of epoxy resin, 13 parts of isocyanate, 15 parts of water, 6 parts of graphene oxide, and 3 parts of silicon dioxide by weight, for later use.

[0078] (2) Water, graphene oxide and silicon dioxide were mixed at room temperature and 500 r / min for 1 h to obtain material A;

[0079] (3) The polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate and material A are mixed at 50°C and 1200r / min for 1h to obtain a wet coating resin composition.

[0080] Test case

[0081] (1) In the adhesive circulation system of the glue applicator, the composition is conveyed;

[0082] (2) The coating machine impregnates electronic-grade glass fiber bisque fabric into the composition at a speed of 35 cm / min. Excess adhesive is removed by the extrusion rollers, resulting in a coating amount of 140 g / m. 2 ;

[0083] (3) The impregnated electronic-grade glass fiber plain weave fabric is dried in an oven at 220°C for 30 minutes, and then cut into rolls to obtain modified electronic-grade glass fiber twill fabric.

[0084] (4) Prepare a Kevlar aramid 1313 fiber layer with a thickness of 8mm. Coat the upper and lower sides of the Kevlar aramid 1313 fiber layer with a high-temperature resistant adhesive (a 1:1 weight ratio of polyurethane adhesive and silicone adhesive). Then bond the modified electronic-grade glass fiber slant cloth to the upper and lower sides of the Kevlar aramid 1313 fiber layer to form a compression buffer pad.

[0085] Non-adhesion test: The number of times the press-fit buffer pad does not adhere to the steel plate after multiple cycles at 220℃ is used as the non-adhesion index.

[0086] Flexibility test: Cut the pressed cushioning pad into strips of 60*300mm and perform a bending test on a support with an included angle of 30°. The angle at which cracks or fissures occur is used as the flexibility index.

[0087] Thickness test: The thickness of the modified electronic-grade glass fiber twill fabric at different locations was measured (a1, a2, a3, and a4 are the thicknesses at the two corners on the two diagonals, and a5 is the thickness at the center of the plain weave fabric).

[0088] The test results are shown in Table 1.

[0089] Table 1

[0090] a1 a2 a3 a4 a5 Non-adsorption (times) Flexibility Example 1 0.62 0.63 0.62 0.62 0.62 1724 133 Example 2 0.62 0.63 0.62 0.63 0.62 1692 128 Example 3 0.61 0.63 0.62 0.62 0.62 1705 131 Example 4 0.61 0.65 0.59 0.62 0.6 1356 121 Example 5 0.61 0.65 0.62 0.63 0.63 1463 118 Example 6 0.61 0.63 0.61 0.63 0.65 1474 112 Comparative Example 1 0.62 0.65 0.62 0.63 0.58 1443 100

[0091] The above examples illustrate that the compositions of the present invention have excellent overall performance when used in press-fit cushioning pads, such as thickness uniformity, non-absorbency, and flexibility.

Claims

1. A wet-coating resin composition, characterized in that, The composition comprises, by weight, 100 parts of polytetrafluoroethylene resin emulsion, 15-30 parts of epoxy resin, 5-20 parts of isocyanate, 10-30 parts of water, 5-20 parts of filler and 0.5-5 parts of cellulose. The filler is graphene oxide and silicon dioxide, with a weight ratio of graphene oxide to silicon dioxide of 1:(0.1-1); the cellulose is hydroxyethyl cellulose and hydroxypropyl methyl cellulose, with a weight ratio of hydroxyethyl cellulose to hydroxypropyl methyl cellulose of 1:(2-3).

2. The composition according to claim 1, characterized in that, The graphene oxide has an average thickness of 1-3 nm, 2-5 layers, and a diameter of 4-7 μm.

3. A method for preparing the wet-coating resin composition according to claim 1 or 2, characterized in that, The preparation method includes: S1. Water, filler, and cellulose are mixed in a first step to obtain material A; S2 involves a second mixing of polytetrafluoroethylene resin emulsion, epoxy resin, isocyanate, and material A to obtain a wet coating resin composition.

4. The preparation method according to claim 3, characterized in that, The conditions for the first mixing include: room temperature, mixing at 500-600 r / min for 0.5-1 h.

5. The preparation method according to claim 3 or 4, characterized in that, The conditions for the second mixing include: mixing at 40-50℃ and 1200-1500r / min for 1-2 hours.

6. The application of the wet-coated resin composition prepared by the method of claim 1 or 2 or any one of claims 3-5 in a hot-pressing buffer material.