Low-VOC (volatile organic compound) high-temperature-resistant acrylic adhesive tape

Abstract

The low-VOC high-temperature-resistant acrylic adhesive tape comprises release paper, a base material layer and adhesive layers, the adhesive layers comprise a first adhesive layer and a second adhesive layer, and the adhesive tape sequentially comprises the release paper, the first adhesive layer, the base material layer and the second adhesive layer from top to bottom; an adhesive of the adhesive layer is prepared from the following components: ethyl methyl propyl acid, acrylic acid, n-butyl acrylate, vinyl acetate, 1, 3, 5, 7-tetramethylcyclotetrasiloxane, trimethylolpropane triacrylate, propylene imine, a Kastend catalyst, an organic silicon modifier, a modified inorganic filler, a flatting agent, deionized water and a water-based photoinitiator. By using the inorganic filler subjected to high-temperature treatment, the fire resistance of the adhesive can be improved; the inorganic filler also plays a role in thickening the adhesive, and inorganic materials are used for thickening, so that the VOC release amount of the adhesive is greatly reduced; the organic silicon modifier has a good defoaming effect, an adhesive system of an inorganic-acrylic acid adhesive system is formed by adding the organic silicon modifier, and organic silicon does not release VOC.

Description

Technical field:

[0001] The invention relates to the technical field of adhesive tape manufacturing, in particular to a low-VOC high-temperature resistant acrylic adhesive tape. Background technology:

[0002] Acrylic tape is a high-performance adhesive material widely used in automobile manufacturing, electronics, construction and other fields. It is based on acrylate, has excellent weather resistance and adhesion, and can maintain stable performance in different environments. Although acrylic tape has been widely studied, the traditional process of preparing acrylic tape often uses a large amount of deionized water as the medium for the polymerization of acrylic adhesive. Therefore, the product usually has a strong odor and a large amount of VOC volatility. Some processes use biomass emulsion as the raw material to synthesize adhesives, which can effectively reduce the VOC content. However, biomass-based tapes are easy to lose their stickiness and detach from the adherend at high temperatures, and their performance in high temperature resistance is poor. Summary of the invention:

[0003] In order to solve the defects in the prior art, the present invention designs a low-VOC high-temperature resistant acrylic tape.

[0004] A low-VOC high-temperature resistant acrylic tape, comprising a release paper, a substrate layer and an adhesive layer, wherein the adhesive layer comprises a first adhesive layer and a second adhesive layer, and the tape comprises a release paper, a first adhesive layer, a substrate layer and a second adhesive layer from top to bottom; wherein both sides of the substrate layer are subjected to corona treatment;

[0005] The adhesive components used in the adhesive layer and the proportions by weight are: 30-40 parts of ethyl methyl acrylate, 40-60 parts of acrylic acid, 40-60 parts of n-butyl acrylate, 10-20 parts of vinyl acetate, 5-15 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 3-5 parts of trimethylolpropane triacrylate, 2-6 parts of propylene imine, 0.1-0.5 parts of Castide catalyst, 5-10 parts of organosilicon modifier, 6-10 parts of modified inorganic filler, 2-4 parts of leveling agent, 120-150 parts of deionized water, 3-5 parts of sodium dodecyl sulfate, 6-7 parts of ethylene oxide, and 3-5 parts of water-based photoinitiator;

[0006] Wherein, the preparation method of the modified inorganic filler is:

[0007] 2-5 parts of fly ash, 2-5 parts of carbide slag, 1-5 parts of desulfurized gypsum and 6-12 parts of sodium hydroxide are mixed and ground, the ground mixed powder is calcined at high temperature, and the mixed powder calcined at high temperature is placed in a hydrothermal reactor with water according to a certain solid-liquid ratio for hydrothermal reaction, and inorganic filler powder is obtained after the hydrothermal reaction is completed;

[0008] Dissolving 5-15 parts of 1,3,5,7-tetramethylcyclotetrasiloxane in 40-60 parts of ether to obtain an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane;

[0009] The inorganic filler powder is dissolved in an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane, stirred evenly and then ultrasonically dispersed. After the ultrasonic dispersion is completed, the inorganic filler powder is separated from the ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane and the inorganic filler powder is dried. The dried inorganic filler powder is calcined at a high temperature to obtain a modified inorganic filler.

[0010] Preferably, the preparation method of the adhesive is:

[0011] Place sodium dodecyl sulfate, ethylene oxide and deionized water in a beaker, place the beaker on a magnetic stirrer and heat to 40-60°C while stirring;

[0012] Ethyl methyl acrylate, acrylic acid, n-butyl acrylate, vinyl acetate, trimethylolpropane triacrylate and propylene imine are placed in the beaker, stirred evenly, and then the mixture is transferred to a round-bottom flask, and stirred for 30 minutes to obtain an acrylic-based adhesive;

[0013] When the temperature of the acrylic-based adhesive reaches 70-90° C., add an organosilicon modifier and an aqueous photoinitiator, and at the same time add a Custard catalyst dropwise while stirring, heat to 80-100° C. and react for 20-60 minutes, add a modified inorganic filler and a leveling agent, and react for 1-5 hours to obtain an adhesive.

[0014] Preferably, the aqueous photoinitiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.

[0015] Preferably, the deionized water is one of ethyl acetate, ethyl ether, acetone and ethanol.

[0016] Preferably, the release paper is silicone release paper; and the substrate layer is PET film.

[0017] The invention discloses a low-VOC high-temperature resistant acrylic adhesive tape. A modified inorganic filler is added to an acrylic adhesive. The modified inorganic filler performs alkaline surface treatment on fly ash, carbide slag and desulfurized gypsum, so that the structure of the amorphous phase is reconstructed into aluminosilicate crystals with a tetrahedral structure. The aluminosilicate crystals have multi-level pores. When the aluminosilicate crystals are immersed in 1,3,5,7-tetramethylcyclotetrasiloxane, the 1,3,5,7-tetramethylcyclotetrasiloxane can be more fully immersed in the pores of the inorganic filler. Therefore, when an acrylic adhesive is prepared in the later stage, the 1,3,5,7-tetramethylcyclotetrasiloxane on the surface and in the pores of the modified inorganic filler can promote the modified inorganic filler and the organic phase. At the same time, the inorganic filler after high temperature treatment has a high ignition point, which can improve the fire resistance of the adhesive and the high temperature resistance of the adhesive; the inorganic filler also plays the role of thickening the adhesive, and the use of inorganic materials for thickening can greatly reduce the VOC release of the adhesive; the silicone modifier has a good defoaming effect, and the addition of the silicone modifier forms an inorganic-acrylic adhesive system, and the silicone modifier does not release VOC; finally, in the present invention, the acrylate-based polymer is dispersed in deionized water with an emulsifier prepared by sodium dodecyl sulfate and ethylene oxide as a medium, so as to reduce the addition of organic solvents from the source and minimize the VOC content of the adhesive. Specific implementation method:

[0018] A low-VOC, high-temperature-resistant acrylic tape is described below in conjunction with specific embodiments.

[0019] Embodiment 1:

[0020] A low-VOC, high-temperature-resistant acrylic tape comprises a release paper, a substrate layer and an adhesive layer, wherein the adhesive layer comprises a first adhesive layer and a second adhesive layer, and the tape comprises a release paper, a first adhesive layer, a substrate layer and a second adhesive layer from top to bottom; wherein both sides of the substrate layer are subjected to corona treatment; the release paper is a silicone release paper, and the substrate layer is a PET film.

[0021] The adhesive components used in the adhesive layer and the ratio by weight are: 30 parts of ethyl methyl acrylate, 40 parts of acrylic acid, 40 parts of n-butyl acrylate, 10 parts of vinyl acetate, 5 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 3 parts of trimethylolpropane triacrylate, 2 parts of propylene imine, 0.1 parts of Castide catalyst, 5 parts of silicone modifier, 5 parts of modified inorganic filler, 2 parts of leveling agent, 120 parts of ethanol solution, 3 parts of azobisisobutyronitrile, and the leveling agent selected in this embodiment is polyacrylate.

[0022] Wherein, the preparation method of the adhesive is:

[0023] Step 1: preparing a modified inorganic filler: mixing 2 parts of fly ash, 2 parts of carbide slag, 1 part of desulfurized gypsum and 6 parts of sodium hydroxide and grinding them, calcining the ground mixed powder at high temperature, and placing the calcined mixed powder in a hydrothermal reactor with water at a certain solid-liquid ratio (1:5) for hydrothermal reaction, and obtaining inorganic filler powder after the hydrothermal reaction;

[0024] Dissolving 5 parts of 1,3,5,7-tetramethylcyclotetrasiloxane in 40 parts of ether to obtain an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane;

[0025] The inorganic filler powder is dissolved in an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane, stirred evenly and then ultrasonically dispersed. After the ultrasonic dispersion is completed, the inorganic filler powder is separated from the ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane and the inorganic filler powder is dried. The dried inorganic filler powder is calcined at 550° C. to obtain a modified inorganic filler.

[0026] Step 2: Place 3 parts of sodium dodecyl sulfate, 6 parts of ethylene oxide, and 120 parts of deionized water in a beaker, place the beaker on a magnetic stirrer, and heat to 40° C. while stirring;

[0027] 30 parts of ethyl methyl acrylate, 40 parts of acrylic acid, 40 parts of n-butyl acrylate, 10 parts of vinyl acetate, 3 parts of trimethylolpropane triacrylate, and 2 parts of propylene imine were placed in a beaker, stirred evenly, and then the mixture was transferred to a round-bottom flask, and stirred for 30 minutes to obtain an acrylic-based adhesive;

[0028] Step 3: When the temperature of the acrylic-based adhesive reaches 70°C, add 5 parts of silicone modifier (2 parts of hydroxy silicone oil and 3 parts of γ-methacryloxypropyltrimethoxysilane) and 3 parts of potassium persulfate, add 0.1 parts of Casted catalyst drop by drop while stirring, heat to 80°C and react for 20 minutes, add 5 parts of modified inorganic filler and 2 parts of leveling agent, and react for 1 hour to obtain the adhesive.

[0029] Embodiment 2:

[0030] A low-VOC, high-temperature-resistant acrylic tape comprises a release paper, a substrate layer and an adhesive layer, wherein the adhesive layer comprises a first adhesive layer and a second adhesive layer, and the tape comprises a release paper, a first adhesive layer, a substrate layer and a second adhesive layer from top to bottom; wherein both sides of the substrate layer are subjected to corona treatment; the release paper is a silicone release paper, and the substrate layer is a PET film.

[0031] The adhesive components used in the adhesive layer and the ratio by weight are: 35 parts of ethyl methyl acrylate, 50 parts of acrylic acid, 50 parts of n-butyl acrylate, 15 parts of vinyl acetate, 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 4 parts of trimethylolpropane triacrylate, 4 parts of propylene imine, 0.3 parts of Casted catalyst, 8 parts of silicone modifier, 8 parts of modified inorganic filler, 3 parts of leveling agent, 135 parts of ethyl acetate solution, 4 parts of azobisisobutyronitrile. The leveling agent selected in this embodiment is polyacrylate.

[0032] Wherein, the preparation method of the adhesive is:

[0033] Step 1: preparing a modified inorganic filler: mixing 2 parts of fly ash, 3 parts of carbide slag, 3 parts of desulfurized gypsum and 8 parts of sodium hydroxide and grinding them, calcining the ground mixed powder at high temperature, and placing the calcined mixed powder in a hydrothermal reactor with water at a certain solid-liquid ratio (1:5) for hydrothermal reaction, and obtaining inorganic filler powder after the hydrothermal reaction;

[0034] Dissolving 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane in 50 parts of ether to obtain an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane;

[0035] The inorganic filler powder is dissolved in an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane, stirred evenly and then ultrasonically dispersed. After the ultrasonic dispersion is completed, the inorganic filler powder is separated from the ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane and the inorganic filler powder is dried. The dried inorganic filler powder is calcined at 550° C. to obtain a modified inorganic filler.

[0036] Step 2: Place 4 parts of sodium dodecyl sulfate, 6.5 parts of ethylene oxide, and 135 parts of deionized water in a beaker, place the beaker on a magnetic stirrer, and heat to 50° C. while stirring;

[0037] 35 parts of ethyl methyl acrylate, 50 parts of acrylic acid, 50 parts of n-butyl acrylate, 15 parts of vinyl acetate, 4 parts of trimethylolpropane triacrylate, and 4 parts of propylene imine were placed in the beaker, and after stirring evenly, the mixture was transferred to a round-bottom flask, and stirred for 30 minutes to obtain an acrylic-based adhesive;

[0038] Step 3: When the temperature of the acrylic-based adhesive reaches 80°C, add 8 parts of silicone modifier (4 parts of hydroxy silicone oil and 4 parts of γ-methacryloxypropyltrimethoxysilane) and 4 parts of potassium persulfate, add 0.3 parts of Casted catalyst drop by drop while stirring, heat to 90°C and react for 40 minutes, add 8 parts of modified inorganic filler and 3 parts of leveling agent, and react for 3 hours to obtain the adhesive.

[0039] Embodiment 3:

[0040] A low-VOC, high-temperature-resistant acrylic tape comprises a release paper, a substrate layer and an adhesive layer, wherein the adhesive layer comprises a first adhesive layer and a second adhesive layer, and the tape comprises a release paper, a first adhesive layer, a substrate layer and a second adhesive layer from top to bottom; wherein both sides of the substrate layer are subjected to corona treatment; the release paper is a silicone release paper, and the substrate layer is a PET film.

[0041] The adhesive components used in the adhesive layer and the ratio by weight are: 40 parts of ethyl acrylate, 60 parts of olefinic acid, 60 parts of n-butyl olefinic acid, 20 parts of vinyl ester, 15 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 5 parts of trimethylolpropane triacrylate, 6 parts of propylene imine, 0.5 parts of Castide catalyst, 10 parts of silicone modifier, 10 parts of modified inorganic filler, 4 parts of leveling agent, 150 parts of acetone solution, 5 parts of azobisisobutyronitrile. The leveling agent selected in this embodiment is polyacrylate.

[0042] Wherein, the preparation method of the adhesive is:

[0043] Step 1: preparing a modified inorganic filler: mixing 4 parts of fly ash, 4 parts of carbide slag, 2 parts of desulfurized gypsum and 12 parts of sodium hydroxide and grinding them, calcining the ground mixed powder at high temperature, and placing the calcined mixed powder in a hydrothermal reactor with water at a certain solid-liquid ratio (1:5) for hydrothermal reaction, and obtaining inorganic filler powder after the hydrothermal reaction;

[0044] Dissolving 15 parts of 1,3,5,7-tetramethylcyclotetrasiloxane in 60 parts of ether to obtain an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane;

[0045] The inorganic filler powder is dissolved in an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane, stirred evenly and then ultrasonically dispersed. After the ultrasonic dispersion is completed, the inorganic filler powder is separated from the ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane and the inorganic filler powder is dried. The dried inorganic filler powder is calcined at 550° C. to obtain a modified inorganic filler.

[0046] Step 2: Place 5 parts of sodium dodecyl sulfate, 7 parts of ethylene oxide, and 150 parts of deionized water in a beaker, place the beaker on a magnetic stirrer, and heat to 50° C. while stirring;

[0047] 40 parts of ethyl methyl acrylate, 60 parts of acrylic acid, 60 parts of n-butyl acrylate, 20 parts of vinyl acetate, 5 parts of trimethylolpropane triacrylate, and 6 parts of propylene imine are placed in the beaker, stirred evenly, and then the mixture is transferred to a round-bottom flask, and heated for 30 minutes to obtain an acrylic-based adhesive;

[0048] Step 3: When the temperature of the acrylic-based adhesive reaches 90°C, add 10 parts of silicone modifier (6 parts of hydroxy silicone oil and 4 parts of γ-methacryloxypropyltrimethoxysilane) and 5 parts of potassium persulfate, add 0.5 parts of Casted catalyst drop by drop while stirring, heat to 100°C and react for 60 minutes, add 10 parts of modified inorganic filler and 4 parts of leveling agent, and react for 5 hours to obtain the adhesive.

[0049] Comparative Example 1:

[0050] Compared with the low-VOC high-temperature resistant acrylic tape provided in Example 2, the structure is consistent, including a release paper, a substrate layer and an adhesive layer, the release paper is a silicone release paper, and the substrate layer is a PET film.

[0051] Compared with Example 2, the components of Comparative Example 1 do not add modified inorganic filler, and use styrene as a thickener.

[0052] Comparative Example 2:

[0053] Compared with the low-VOC high-temperature resistant acrylic tape provided in Example 2, the structure is consistent, including a release paper, a substrate layer and an adhesive layer, the release paper is a silicone release paper, and the substrate layer is a PET film.

[0054] Compared with Example 2, the components of Comparative Example 2 are as follows: ethyl acetate solution is used instead of deionized water as the solvent in the adhesive preparation process.

[0055] Comparative Example 3:

[0056] Compared with the low-VOC high-temperature resistant acrylic tape provided in Example 2, the structure is consistent, including a release paper, a substrate layer and an adhesive layer, the release paper is a silicone release paper, and the substrate layer is a PET film.

[0057] Compared with Example 2, the components of Comparative Example 3 are as follows: ethyl acetate solution is used instead of deionized water as the solvent in the adhesive preparation process, no modified inorganic filler is added, and styrene is used as a thickener.

[0058] The VOC volatilization amount and the adhesion at different temperatures of the adhesive tapes in Example 2 and Comparative Examples 1, 2, and 3 were measured. The results are shown in Table 1.

[0059] Table 1 Comparative Examples and Examples Adhesive Tape Performance Test Results

[0060]

[0061] It can be seen from Table 1 that after the aging test, the 180° peel strength of Comparative Examples 1 and 3 decayed significantly; the VOC release of Comparative Examples 2 and 3 was significantly higher than that of Example 2. Therefore, it can be seen from the experimental results that the tape of the present invention uses deionized water instead of organic solvents to effectively reduce the VOC release of the tape, and the use of modified inorganic fillers to modify the acrylic tape can effectively improve the high temperature and humidity resistance of the tape.

[0062] The above description is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements, substitutions, modifications and embellishments can be made without departing from the principle and purpose of the present invention. These improvements, substitutions, modifications and embellishments should also be regarded as the scope of protection of the present invention.

Claims

1. A low VOC high temperature resistant acrylic tape, characterized in that: The adhesive tape comprises a release paper, a substrate layer and an adhesive layer, wherein the adhesive layer comprises a first adhesive layer and a second adhesive layer, and the adhesive tape comprises a release paper, a first adhesive layer, a substrate layer and a second adhesive layer from top to bottom; wherein both sides of the substrate layer are subjected to corona treatment; The adhesive components used in the adhesive layer and the proportions by weight are: 30-40 parts of ethyl methyl acrylate, 40-60 parts of acrylic acid, 40-60 parts of n-butyl acrylate, 10-20 parts of vinyl acetate, 5-15 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 3-5 parts of trimethylolpropane triacrylate, 2-6 parts of propylene imine, 0.1-0.5 parts of Castide catalyst, 5-10 parts of organosilicon modifier, 6-10 parts of modified inorganic filler, 2-4 parts of leveling agent, 120-150 parts of deionized water, 3-5 parts of sodium dodecyl sulfate, 6-7 parts of ethylene oxide, and 3-5 parts of water-based photoinitiator; Wherein, the preparation method of the modified inorganic filler is: 2-5 parts of fly ash, 2-5 parts of carbide slag, 1-5 parts of desulfurized gypsum and 6-12 parts of sodium hydroxide are mixed and ground, the ground mixed powder is calcined at high temperature, and the mixed powder calcined at high temperature is placed in a hydrothermal reactor with water according to a certain solid-liquid ratio for hydrothermal reaction, and inorganic filler powder is obtained after the hydrothermal reaction is completed; Dissolving 5-15 parts of 1,3,5,7-tetramethylcyclotetrasiloxane in 40-60 parts of ether to obtain an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane; The inorganic filler powder is dissolved in an ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane, stirred evenly and then ultrasonically dispersed. After the ultrasonic dispersion is completed, the inorganic filler powder is separated from the ether solution of 1,3,5,7-tetramethylcyclotetrasiloxane and the inorganic filler powder is dried. The dried inorganic filler powder is calcined at a high temperature to obtain a modified inorganic filler.

2. The heat-reducing adhesive tape for semiconductor dicing according to claim 1, characterized in that: The preparation method of the adhesive is: Place sodium dodecyl sulfate, ethylene oxide and deionized water in a beaker, place the beaker on a magnetic stirrer and heat to 40-60°C while stirring; Ethyl methyl acrylate, acrylic acid, n-butyl acrylate, vinyl acetate, trimethylolpropane triacrylate and propylene imine are placed in the beaker, stirred evenly, and then the mixture is transferred to a round-bottom flask, and stirred for 30 minutes to obtain an acrylic-based adhesive; When the temperature of the acrylic-based adhesive reaches 70-90° C., add an organosilicon modifier and an aqueous photoinitiator, and at the same time add a Custard catalyst dropwise while stirring, heat to 80-100° C. and react for 20-60 minutes, add a modified inorganic filler and a leveling agent, and react for 1-5 hours to obtain an adhesive.

3. The heat-reducing adhesive tape for semiconductor dicing according to claim 2, characterized in that: The organic silicon modifier includes gamma-methacryloxypropyltrimethoxysilane and hydroxy silicone oil.

4. The heat-reducing adhesive tape for semiconductor dicing according to claim 2, characterized in that: The water-based photoinitiator is one of sodium persulfate, potassium persulfate and ammonium persulfate.

5. The heat-reducing adhesive tape for semiconductor dicing according to claim 1, characterized in that: The release paper is silicone release paper; the substrate layer is PET film.

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