Halogen-free horn drum paper reinforcing glue and preparation method thereof

Abstract

The halogen-free horn drum paper reinforcing adhesive is prepared from the following components in parts by weight: 30 to 60 parts of diluent, 15 to 40 parts of main material resin, 15 to 30 parts of auxiliary material resin, 0.5 to 8 parts of filler and 0 to 8 parts of additive, the auxiliaries comprise a flatting agent, a defoaming agent, a dispersing wetting agent and an antioxidant. In addition, the invention also provides a preparation method of the halogen-free horn drum paper reinforcing adhesive. The reinforcing glue product adopting a brand new formula has a good bonding effect on various different materials, so that the production and processing of a horn drum paper product formed by bonding and splicing various different carcasses and rim charges can be realized, and the market requirements of high strength, high tone quality and high performance of loudspeakers are met; compared with conventional glue, the reinforcing glue is better in stability, moisture resistance and weather resistance and more convenient to transport, store and use, the waterproof performance, the cold resistance and other performance are improved in a leap mode, and the reliability of bonded and spliced products can be greatly improved; the method is high in practicability and has high popularization significance.

Description

Technical Field

[0001] The invention relates to an adhesive, in particular to a halogen-free speaker drum paper reinforcing adhesive and a preparation method thereof. Background Art

[0002] The drum paper is also called the vibration plate or paper cone. It is one of the main parts of the speaker and has a decisive influence on the performance and sound quality of the speaker. Most drum paper product structures are often formed by gluing and splicing the body and the side materials. For various speaker drum papers with different products and functions, the body and side materials used are also different. For example, the body materials include paper, PP plastic, woven glass, fiber, woven carbon fiber, bulletproof cloth, polyester film, phenolic resin film, aluminum, stainless steel and other metal materials; and the side materials include cloth edge, EVA foam material, PU foam material, TPU film and NBR, SBR, butyl rubber, EPDM rubber and Santoprene and other rubber materials. The material combination of the body and side materials used by different drum papers is ever-changing.

[0003] In order to cope with the strong adhesive splicing between various materials, a universal adhesive is needed for drum paper forming. At present, the reinforcing adhesive for the body and edge material of speaker drum paper on the market is mostly solvent-based chloroprene rubber adhesive. The main raw material of this adhesive is chloroprene rubber. Due to the regularity and polarity of the molecular structure, chloroprene rubber limits the thermal motion of molecules, and thermal motion is more difficult at low temperatures. The chloroprene rubber adhesive prepared with chloroprene rubber as the main body is difficult to restore to its original state after stretching and deformation at low temperatures, and is prone to brittle fracture. Therefore, the cold resistance of chloroprene rubber adhesive is not good.

[0004] Moreover, chloroprene rubber contains highly active chlorine atoms, which easily react with other atoms or atomic groups, causing the adhesive to self-crosslink during storage. The linear polymer undergoes irreversible changes and transforms into a network cross-linked structure. Therefore, the storage stability of chloroprene rubber adhesive is poor.

[0005] In addition, chloroprene rubber adhesives are prone to delamination, gelation, and precipitation, and the adhesives themselves have certain disadvantages such as toxicity. Summary of the invention

[0006] Based on this, it is necessary to provide a halogen-free speaker drum paper reinforcing adhesive to address the deficiencies in the prior art.

[0007] A halogen-free speaker drum paper reinforcing adhesive comprises the following components by weight: 30-60 parts of diluent, 15-40 parts of main material resin, 15-30 parts of auxiliary material resin, 0.5-8 parts of filler and 0-8 parts of auxiliary agent. The diluent comprises at least one of dimethyl carbonate, toluene, xylene or cyclohexane. The main material resin comprises at least one of methyl methacrylate-butadiene-styrene terpolymer, styrene-butadiene copolymer and styrene-butadiene-styrene triblock copolymer. The auxiliary material resin comprises at least one of C5 petroleum resin, C5 hydrogenated petroleum resin, C9 petroleum resin, C9 hydrogenated petroleum resin, rosin, hydrogenated rosin, disproportionated rosin and esterified rosin. The filler comprises at least one of fumed silica, modified nano-silicon dioxide, aluminum hydroxide powder, nano-scale carbon black particles and titanium dioxide. The auxiliary agent comprises a leveling agent, a defoaming agent, a dispersing wetting agent and an antioxidant.

[0008] Furthermore, the diluent includes dimethyl carbonate and at least one of toluene, xylene or cyclohexane.

[0009] Furthermore, the leveling agent includes at least one of a polyacrylate leveling agent and a polyether polyester modified polydimethylsiloxane leveling agent containing a hydroxyl functional group.

[0010] Furthermore, the defoamer includes at least one of a polysiloxane defoamer, a polymethylalkylsiloxane defoamer, a defoaming polymer, a polysiloxane mixed defoamer and a modified organic polysiloxane defoamer.

[0011] Furthermore, the dispersing and wetting agent includes at least one of a phosphate ester dispersing and wetting agent, a polyester phosphate ester salt dispersing and wetting agent, a high molecular weight hydroxyalkylaminoamide dispersing and wetting agent, and a high molecular weight block copolymer dispersing and wetting agent containing an acidic group.

[0012] Furthermore, the antioxidant includes at least one of pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) antioxidant, 2,6-di-tert-butyl-4-methylphenol antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline antioxidant and ethoxyquinoline antioxidant.

[0013] In addition, the present invention also provides a method for preparing a halogen-free speaker drum paper reinforcing adhesive.

[0014] A method for preparing a halogen-free speaker drum paper reinforcing adhesive, which is used to prepare the halogen-free speaker drum paper reinforcing adhesive, comprises the following steps:

[0015] Step 1: Prepare a resin solution of component A, dissolve 15 to 30 parts of auxiliary resin in 15 to 30 parts of diluent (i.e., half of the total number of diluents), control the temperature and continue stirring until the auxiliary resin is completely dissolved, and obtain a resin solution of component A;

[0016] Step 2: Prepare the filler slurry of component B, dissolve 0.5 to 8 parts of filler in 15 to 30 parts of diluent (i.e. the other half of the total diluent), and continue stirring until the filler is evenly dispersed to obtain the filler slurry of component B;

[0017] Step 3: Prepare a mixture of components AB, slowly add the filler slurry of component B into the resin solution of component A, fully mix and stir evenly to obtain a mixture of components AB;

[0018] Step 4: Prepare the semi-finished product. After the mixture of components AB is cooled to room temperature, add 15 to 40 parts of the main material resin particles, control the temperature and continue stirring until the main material resin is completely dissolved to obtain the semi-finished product;

[0019] Step 5: Prepare the finished product. Add the formulated amount of leveling agent, defoamer, dispersant and wetting agent to the semi-finished product in sequence, dissolve the antioxidant in the diluent first, then add the semi-finished product and stir thoroughly until it is evenly dispersed to obtain the finished product.

[0020] Furthermore, in step 1, the temperature is controlled within a range of 50°C to 60°C, and in step 4, the temperature is controlled within a range of 20°C to 30°C.

[0021] Furthermore, in step 1, the continuous stirring time is controlled within the range of 20 min to 40 min, and in step 2 and step 4, the continuous stirring time is controlled within the range of 40 min to 60 min.

[0022] To sum up, the beneficial effects of the halogen-free speaker drum paper reinforcing glue and the preparation method thereof of the present invention are: the reinforcing glue product with a new formula has a good bonding effect on a variety of different materials, so that various different carcasses and edge materials can be bonded and spliced ​​into speaker drum paper products to achieve production and processing, meeting the market demand for high strength, high sound quality and high performance of speakers; and compared with conventional glues, the reinforcing glue has better stability and moisture resistance and weather resistance, is more convenient for transportation, storage and use, and has a leap-forward improvement in waterproof and cold resistance properties, which can greatly enhance the reliability of bonded and spliced ​​products; in addition, the reinforcing glue does not contain halogen, fully meets the requirements of various relevant current laws and regulations, its environmental friendliness far exceeds that of ordinary glue, and its harm to human health is also greatly reduced; the present invention is highly practical and has a strong promotional significance. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the invention more clear, the invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the invention and are not used to limit the invention.

[0024] The invention provides a halogen-free speaker drum paper reinforcing adhesive, which comprises the following components in parts by weight: 30-60 parts of a diluent, 15-40 parts of a main material resin, 15-30 parts of an auxiliary material resin, 0.5-8 parts of a filler and 0-8 parts of an auxiliary agent.

[0025] The diluent includes at least one of dimethyl carbonate, toluene, xylene or cyclohexane. Specifically in this embodiment, the diluent includes dimethyl carbonate and at least one of toluene, xylene or cyclohexane. Dimethyl carbonate is a non-toxic, low-pollution, green and environmentally friendly solvent. It can replace toluene and xylene to a certain extent when used as an adhesive solvent. Using a certain proportion of dimethyl carbonate can effectively reduce the toxicity of the adhesive and improve the safety and environmental performance of the adhesive.

[0026] The main material resin includes at least one of methyl methacrylate-butadiene-styrene terpolymer, styrene-butadiene copolymer, and styrene-butadiene-styrene triblock copolymer. The auxiliary material resin includes at least one of C5 petroleum resin, C5 hydrogenated petroleum resin, C9 petroleum resin, C9 hydrogenated petroleum resin, rosin, hydrogenated rosin, disproportionated rosin, and esterified rosin. The auxiliary material resin selected is a small molecule substance, which can effectively improve the initial adhesion and peeling force of the adhesive, so that the speaker drum paper reinforcement glue can reach or even exceed the bonding performance of the common halogen-containing reinforcement glue on the market while meeting the halogen-free requirement.

[0027] The filler includes at least one of fumed silica, modified nano-silicon dioxide, aluminum hydroxide powder, nano-scale carbon black particles, and titanium dioxide. The proper use of nano-scale fillers can enhance the mechanical properties of the adhesive. During processing, the fillers are fully dispersed in the molecular gaps of the main material resin of the polymer chain, which enhances the toughness of the adhesive. At the same time, the porous structure with a high specific surface area can also improve the storage stability of the adhesive and the bonding performance to the object to be attached.

[0028] The auxiliary agent includes a leveling agent, and the leveling agent includes at least one of a polyacrylate leveling agent and a polyether polyester modified polydimethylsiloxane leveling agent containing a hydroxyl functional group. Specifically, in this embodiment, the leveling agent is selected from one or more of BYK-354, BYK-358N, and BYK-375 of German BYK Company.

[0029] The auxiliary agent also includes a defoamer, which includes at least one of a polysiloxane defoamer, a polymethyl alkyl siloxane defoamer, a defoaming polymer and a polysiloxane mixed defoamer and a modified organic polysiloxane defoamer. Specifically, in this embodiment, the defoamer is selected from one or more of BYK-073, BYK-077, BYK-141 of German BYK Company or domestic brand XP-71.

[0030] The auxiliary agent also includes a dispersing wetting agent, which includes at least one of a phosphate dispersing wetting agent, a polyester phosphate salt dispersing wetting agent, a high molecular weight hydroxyalkyl aminoamide dispersing wetting agent, and a polymer block copolymer dispersing wetting agent containing an acidic group. Specifically, in this embodiment, the dispersing wetting agent is selected from one or more of BYK-103, BYK-109, BYK-111 of German BYK Company or domestic brands FS-510, FX-511.

[0031] The auxiliary agent also includes an antioxidant, and the antioxidant includes at least one of pentaerythritol tetra(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) antioxidant, 2,6-di-tert-butyl-4-methylphenol antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline antioxidant and ethoxyquinoline antioxidant. Specifically in this embodiment, the antioxidant is selected from one or more of domestic brand antioxidant 1010, antioxidant 264, antioxidant RD, and antioxidant AW. The main material resin of the halogen-free trumpet drum paper reinforcing adhesive contains a double bond structure, which may be oxidized or cross-linked by moisture, oxygen, acid, alkali and other substances in the natural state, affecting the normal use of the adhesive. The additional addition of antioxidant components can eliminate the adverse effects of the reinforcing adhesive being easily oxidized or cross-linked.

[0032] In addition, the present invention also provides a method for preparing a halogen-free speaker drum paper reinforcing adhesive.

[0033] A method for preparing a halogen-free speaker drum paper reinforcing adhesive, which is used to prepare a halogen-free speaker drum paper reinforcing adhesive, comprises the following steps:

[0034] Step 1: Prepare the resin solution of component A, dissolve 15 to 30 parts of auxiliary resin in 15 to 30 parts of diluent (i.e. half of the total number of diluents), control the temperature range of 50°C to 60°C and continue stirring for 20min to 40min until the auxiliary resin is completely dissolved, and obtain the resin solution of component A. In the temperature range of 50°C to 60°C, the dissolution speed of the resin is significantly accelerated, and the dissolution is more thorough;

[0035] Step 2: Prepare the filler slurry of component B, dissolve 0.5 to 8 parts of filler in 15 to 30 parts of diluent (i.e. the other half of the total diluent), and continue stirring for 40 to 60 minutes until the filler is evenly dispersed to obtain the filler slurry of component B. The resin solution has a high viscosity and a large surface tension, while the particle size of the filler is small. Directly adding the filler powder to the resin solution will make it difficult for the filler to enter the resin system, unable to be evenly dispersed, and easy to float in the air, increasing the processing difficulty and material loss rate. Therefore, the filler needs to be dissolved in the solvent first to prepare the filler slurry of component B;

[0036] Step 3: Prepare a mixture of components AB, slowly add the filler slurry of component B into the resin solution of component A, fully mix and stir evenly to obtain a mixture of components AB;

[0037] Step 4: Prepare the semi-finished product. After the mixture of components AB cools to room temperature, add 15 to 40 parts of the main resin particles, control the temperature range of 20°C to 30°C and continue stirring for 40min to 60min until the main resin is completely dissolved to obtain the semi-finished product. The temperature should not be too high during the preparation of the semi-finished product. Too high a temperature can easily cause a resin reaction, causing the resin to be in a cross-linked or semi-cross-linked state, affecting the dispersion of other components and the use of the subsequent adhesive product. Therefore, it is best to control the temperature at 20°C to 30°C;

[0038] Step 5: Prepare the finished product. Add the formulated amount of leveling agent, defoamer, dispersant and wetting agent to the semi-finished product in sequence, dissolve the antioxidant in the diluent first, then add the semi-finished product and stir thoroughly until it is evenly dispersed to obtain the finished product.

[0039] The finished speaker drum paper reinforcement adhesive has the following advantages:

[0040] ① It has a wide range of bonding and has good bonding effects on a variety of materials, including different body materials, such as paper, PP plastic, woven glass, fiber, woven carbon fiber, bulletproof cloth, polyester film, phenolic resin film and various metal plates such as aluminum and stainless steel; and different edge materials, such as cloth edge, EVA foam material, PU foam material, TPU film and various rubbers such as NBR, SBR, butyl rubber, EPDM rubber and Santoprene, etc.;

[0041] ②Good stability, easy to store, no delamination, gelation, precipitation, etc. will occur even if placed in a cool and dry place for 1500 hours;

[0042] ③Good waterproof performance, saturated water absorption rate is less than 1.0%, no shedding and no dissolution after soaking in water for 720 hours, greatly enhancing the waterproof performance of the product;

[0043] ④Excellent cold resistance. After the glue is completely cured, even if it is placed in a -40℃ environment for 360 hours, the bonding strength still retains more than 80%, and the tensile strength retains more than 80%; after being placed in a -20℃ environment for 720 hours, the bonding strength still retains more than 85%, and the tensile strength retains more than 80%;

[0044] ⑤ Excellent moisture and weather resistance. After the glue is fully cured, the bonding strength decay is less than 20% after high temperature and high humidity of 85℃×85%RH×168h; it can meet the production, transportation and use requirements under different environmental conditions;

[0045] ⑥ The glue component does not contain halogen and complies with the limit requirements of the EU RoHS Directive and halogen-free (HF / Halogen Free) regulations.

[0046] To sum up, the beneficial effects of the halogen-free speaker drum paper reinforcing glue and the preparation method thereof of the present invention are: the reinforcing glue product with a new formula has a good bonding effect on a variety of different materials, so that various different carcasses and edge materials can be bonded and spliced ​​into speaker drum paper products to achieve production and processing, meeting the market demand for high strength, high sound quality and high performance of speakers; and compared with conventional glues, the reinforcing glue has better stability and moisture resistance and weather resistance, is more convenient for transportation, storage and use, and has a leap-forward improvement in waterproof and cold resistance properties, which can greatly enhance the reliability of bonded and spliced ​​products; in addition, the reinforcing glue does not contain halogen, fully meets the requirements of various relevant current laws and regulations, its environmental friendliness far exceeds that of ordinary glue, and its harm to human health is also greatly reduced; the present invention is highly practical and has a strong promotional significance.

[0047] The above-mentioned embodiment only expresses one implementation method of the invention, and its description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the inventive concept, which all belong to the protection scope of the invention. Therefore, the protection scope of the invention patent shall be based on the attached claims.

Claims

1. A halogen-free speaker drum paper reinforcing adhesive, characterized in that: The invention comprises the following components in parts by weight: 30-60 parts of diluent, 15-40 parts of main material resin, 15-30 parts of auxiliary material resin, 0.5-8 parts of filler and 0-8 parts of auxiliary agent; wherein the diluent comprises at least one of dimethyl carbonate, toluene, xylene or cyclohexane; the main material resin comprises at least one of methyl methacrylate-butadiene-styrene terpolymer, styrene-butadiene copolymer and styrene-butadiene-styrene triblock copolymer; the auxiliary material resin comprises at least one of C5 petroleum resin, C5 hydrogenated petroleum resin, C9 petroleum resin, C9 hydrogenated petroleum resin, rosin, hydrogenated rosin, disproportionated rosin and esterified rosin; the filler comprises at least one of fumed silica, modified nano-silicon dioxide, aluminum hydroxide powder, nano-scale carbon black particles and titanium dioxide; the auxiliary agent comprises a leveling agent, a defoaming agent, a dispersing wetting agent and an antioxidant.

2. The halogen-free speaker drum paper reinforcing adhesive according to claim 1, characterized in that: The diluent includes dimethyl carbonate and at least one of toluene, xylene or cyclohexane.

3. The halogen-free speaker drum paper reinforcing adhesive according to claim 1, characterized in that: The leveling agent includes at least one of a polyacrylate leveling agent and a polyether polyester modified polydimethylsiloxane leveling agent containing a hydroxyl functional group.

4. The halogen-free speaker drum paper reinforcing adhesive according to claim 1, characterized in that: The defoamer comprises at least one of a polysiloxane defoamer, a polymethyl alkylsiloxane defoamer, a defoaming polymer, a polysiloxane mixed defoamer and a modified organic polysiloxane defoamer.

5. The halogen-free speaker drum paper reinforcing adhesive according to claim 1, characterized in that: The dispersing and wetting agent includes at least one of a phosphate ester dispersing and wetting agent, a polyester phosphate ester salt dispersing and wetting agent, a high molecular weight hydroxyalkyl amino amide dispersing and wetting agent, and a high molecular weight block copolymer dispersing and wetting agent containing an acidic group.

6. The halogen-free speaker drum paper reinforcing adhesive according to claim 1, characterized in that: The antioxidant includes at least one of pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) antioxidant, 2,6-di-tert-butyl-4-methylphenol antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline antioxidant and ethoxyquinoline antioxidant.

7. A method for preparing a halogen-free speaker drum paper reinforcing adhesive, used for preparing the halogen-free speaker drum paper reinforcing adhesive as claimed in any one of claims 1 to 6, characterized in that: The steps include: Step 1: Prepare a resin solution of component A, dissolve 15 to 30 parts of auxiliary resin in 15 to 30 parts of diluent (i.e., half of the total number of diluents), control the temperature and continue stirring until the auxiliary resin is completely dissolved, and obtain a resin solution of component A; Step 2: Prepare the filler slurry of component B, dissolve 0.5 to 8 parts of filler in 15 to 30 parts of diluent (i.e. the other half of the total diluent), and continue stirring until the filler is evenly dispersed to obtain the filler slurry of component B; Step 3: Prepare a mixture of components AB, slowly add the filler slurry of component B into the resin solution of component A, fully mix and stir evenly to obtain a mixture of components AB; Step 4: Prepare the semi-finished product. After the mixture of components AB is cooled to room temperature, add 15 to 40 parts of the main material resin particles, control the temperature and continue stirring until the main material resin is completely dissolved to obtain the semi-finished product; Step 5: Prepare the finished product. Add the formulated amount of leveling agent, defoamer, dispersant and wetting agent to the semi-finished product in sequence, dissolve the antioxidant in the diluent first, then add the semi-finished product and stir thoroughly until it is evenly dispersed to obtain the finished product.

8. The method for preparing the halogen-free speaker drum paper reinforcing adhesive according to claim 7, characterized in that: In step 1, the temperature is controlled within a range of 50°C to 60°C, and in step 4, the temperature is controlled within a range of 20°C to 30°C.

9. The method for preparing the halogen-free speaker drum paper reinforcing adhesive according to claim 7, characterized in that: In step 1, the continuous stirring time is controlled within the range of 20 min to 40 min. In step 2 and step 4, the continuous stirring time is controlled within the range of 40 min to 60 min.