阅读说明：本技术 玻璃纤维处理剂及其在玻璃纤维的处理工艺及导热硅胶布 (Glass fiber treating agent, treatment process of glass fiber treating agent on glass fiber and heat-conducting silicon adhesive tape ) 是由 宋先均 杨晓青 于 2020-05-25 设计创作，主要内容包括：本发明公开了一种玻璃纤维处理剂及其在玻璃纤维的处理工艺及导热硅胶布,具体属于硅胶材料的技术领域,玻璃纤维处理剂包含以下重量份的组分：硅橡胶8-12份、分散剂55-70份、硅烷偶联剂0.8-1.2份、高含氢硅油0.5-0.9份、铂金催化剂0.5-0.9份；还提供了一种玻璃纤维处理工艺及导热硅胶布,明显改善玻璃纤维与硅橡胶之间结合的附着力,增强玻璃纤维与硅胶混炼胶粘结性的优点。(The invention discloses a glass fiber treating agent, a treatment process of glass fiber by using the glass fiber treating agent and heat-conducting silica gel cloth, and particularly belongs to the technical field of silica gel materials, wherein the glass fiber treating agent comprises the following components in parts by weight: 8-12 parts of silicon rubber, 55-70 parts of dispersing agent, 0.8-1.2 parts of silane coupling agent, 0.5-0.9 part of high hydrogen-containing silicone oil and 0.5-0.9 part of platinum catalyst; also provides a glass fiber treatment process and a heat-conducting silicon adhesive tape, which obviously improve the adhesive force of the combination between the glass fiber and the silicon rubber and enhance the adhesive property of the glass fiber and the silicon rubber compound.)

1. A glass fiber treatment agent characterized by: the glass fiber treating agent comprises the following components in parts by weight: 8-12 parts of silicon rubber, 55-70 parts of dispersing agent, 0.8-1.2 parts of silane coupling agent, 0.5-0.9 part of high hydrogen-containing silicone oil and 0.5-0.9 part of platinum catalyst.

2. A glass fiber treatment agent according to claim 1, characterized in that: the silane coupling agent comprises one of gamma-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.

3. A glass fiber treatment agent according to claim 1, characterized in that: the mass ratio of the platinum catalyst to the silicone rubber is 1: (13-15).

4. A glass fiber treatment agent according to claim 1, characterized in that: the total mass ratio of the silane coupling agent to the mixed raw materials is 1: (71-73).

5. A glass fiber treatment agent according to claim 1, characterized in that: the silicone rubber comprises one or two of methyl vinyl silicone rubber and methyl silicone rubber.

6. A glass fiber treatment agent according to claim 1, characterized in that: the dispersing agent is xylene or white gasoline.

7. A glass fiber treatment agent according to claim 1, characterized in that: the glass fiber treating agent is prepared by the following steps:

step (1): adding a dispersing agent into the silicon rubber raw material for multiple times, fully stirring and mixing, and obtaining a mixed solution A when the viscosity reaches 900-1100mPa & s;

step (2): and adding a silane coupling agent, high-hydrogen-content silicone oil and a platinum catalyst into the mixed solution A, and uniformly mixing and stirring to obtain the glass fiber treating agent.

8. A glass fiber treatment process for treating glass fibers with the glass fiber treatment agent according to any one of claims 1 to 7, comprising the following treatment steps:

1) completely dipping and coating the glass fiber in the glass fiber treating agent, and rolling and adhering 70-90g of glass fiber treating agent per square meter on the surface of the glass fiber;

2) the glass fiber dipped with the glass fiber treating agent is heated to 150-160 ℃ in a gradual heating mode, and is kept warm for 1min, so that the treated glass fiber cloth is the prefabricated product A.

9. A heat conductive silicon tape, which is a glass fiber obtained by processing the glass fiber-processing agent according to any one of claims 1 to 7, characterized in that: pressing the silica gel rubber compound on one surface of the prefabricated product A by calendering, and gradually heating to 130-180 ℃ in a heating manner to form a silica gel sulfide layer; and rolling the silica gel rubber compound on the other surface of the prefabricated product A to respectively form a silica gel vulcanized layer and an unvulcanized silica gel layer on the two surfaces of the prefabricated product A.

10. The thermally conductive silicone adhesive tape of claim 9, wherein: the temperature gradient is set as follows: keeping the temperature at 60-80 ℃ for 60-90 s, then keeping the temperature at 80-100 ℃ for 60-90 s, and finally keeping the temperature at 100-180 ℃ for 60-90 s.

Technical Field

The invention relates to the technical field of silica gel materials, in particular to a glass fiber treating agent, a treatment process of the glass fiber treating agent on glass fibers and heat-conducting silica gel cloth.

Background

The heat-conducting silicon adhesive tape is an organic silicon high-molecular polymer elastomer which is reinforced by taking glass fiber as a base material. The heat-conducting silica gel cloth can effectively reduce the thermal resistance between the electronic component and the radiator, resists the high voltage and the piercing of metal pieces, avoids the phenomenon of short circuit of a circuit, and is an excellent heat-conducting insulating material. The existing heat-conducting silica gel cloth is mainly applied to switching power supplies, communication equipment, computers, flat-panel televisions, mobile equipment, video equipment, network products, household appliances and the like.

Electric automobile adopts the electric heating mode at battery power usually today, directly at the battery on the surface installation electric heating plate, makes the circular telegram of electric heating plate, and the electric heating plate makes the battery keep the constant temperature state through heat-conduction, even at cold north weather, the battery of electric automobile or electric motor car all can keep efficient battery conversion efficiency. When the electric heating plate is used, the electric heating plate is in direct contact with the battery, and in the preparation of the electric heating plate, a material with good insulating property, ageing resistance and high temperature resistance is required to be selected to wrap the electric heating wire, and a heat-conducting silicon adhesive tape is generally adopted to be tightly attached to the electric heating wire to form a structure for sealing the electric heating plate. If the insulation of the heat-conducting silicon adhesive tape is poor, the problem that the heating wire is easy to be short-circuited exists.

Disclosure of Invention

Aiming at the defects in the prior art, the first object of the invention is to provide a glass fiber treating agent which has the advantages of obviously improving the adhesive force of the combination between glass fibers and silicon rubber and enhancing the adhesive property of the glass fibers and the silicon rubber compound.

In order to achieve the first object, the invention provides the following technical scheme: a glass fiber treating agent comprises the following components in parts by weight: 8-12 parts of silicon rubber, 55-70 parts of dispersing agent, 0.8-1.2 parts of silane coupling agent, 0.5-0.9 part of high hydrogen-containing silicone oil and 0.5-0.9 part of platinum catalyst.

By adopting the technical scheme, the main component of the glass fiber is inorganic salt, the silicon rubber is high-molecular organic siloxane with a linear molecular structure, and the silicon rubber contains alkyl or hydroxyl; under the action of the dispersing agent, the silane coupling agent, the high hydrogen-containing silicone oil and the platinum catalyst, the silicone rubber promotes physical adsorption or chemical reaction between the silicone rubber and the glass fiber in the glass fiber treating agent, further improves the adhesive force between the silicone rubber and the glass fiber in the glass fiber treating agent, and can greatly enhance the adhesive property between the silicone rubber and the glass fiber. The silicon rubber on the surface of the glass fiber treated by the treating agent and the silica gel rubber compound are vulcanized at high temperature, and the silicon rubber in the treated glass fiber reacts with the cross-linking agent and the curing agent in the silica gel rubber compound under the high-temperature condition, so that the compatibility of the silicon rubber in the glass fiber and the silica gel rubber compound is improved, and the caking property between the glass fiber and the silica gel rubber compound is further enhanced.

In the scheme, organic siloxane molecules in the silicon rubber can react with each other, and when the silicon rubber is combined with the glass fiber, in order to reduce the acting force between the organic siloxane molecules in the silicon rubber, the dispersing agent is added, so that the mutual action between the organic siloxane molecules in the silicon rubber can be effectively reduced, and on the other hand, the dispersing agent can also enable the organic siloxane in the silicon rubber to be dispersed more uniformly, improve the adhesive force between the silicon rubber and the glass fiber in the treating agent, and enable the treating agent to be compounded with the glass fiber more tightly.

The silane coupling agent forms a layer of interlayer on the surface of the glass fiber and the surface of the treating agent, so that the silane coupling agent can be bonded with the glass fiber on one hand, and the structure of the silicon rubber in the treating agent is restrained on the other hand, so that the glass fiber and the treating agent are not easy to delaminate.

Under the action of platinum catalyst, the high hydrogen-containing silicone oil makes the silicone rubber in the treating agent form a three-dimensional network structure with stable structure, and the interlayer is solidified on the surface of the glass fiber and the surface of the treating agent, so that the glass fiber and the treating agent are bonded together.

Under high-temperature treatment, the silicon rubber in the treated glass fiber reacts with the platinum catalyst and the high-hydrogen-content silicon oil in the silica gel rubber compound, so that the bonding property of the vulcanized silicon rubber and the glass fiber can be improved, and when the silicon rubber is applied to the heat-conducting silica gel cloth, the glass fiber and the vulcanized silicon rubber are not easy to tear, so that the durability of the heat-conducting silicon adhesive tape is improved.

Further, the silane coupling agent comprises one of gamma-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.

By adopting the technical scheme, the silane coupling agents all contain organic functional groups and silane oxygen groups, wherein the organic functional groups of the methacryloxy groups, the glyceryl ether oxypropyl groups and the aminopropyl groups can be subjected to coupling reaction with methyl vinyl groups of silicon rubber in the treating agent, so that the compatibility between the silicon rubber and glass fibers in the treating agent is improved, a bonding layer of an organic matrix, the silane coupling agent and an inorganic matrix is formed between the silicon rubber and the glass fibers in the treating agent, and the bonding effect of the silicon rubber and the glass fibers in the treating agent can be improved.

Further, the mass ratio of the platinum catalyst to the silicone rubber is 1: (13-15).

Through the technical scheme, when the glass fiber treating agent is prepared by adopting the platinum catalyst, through test tests, when the mass ratio of the platinum catalyst to the silicon rubber is more than 1: 13, the effect of catalytic reaction can be achieved, but the cost of the platinum catalyst is high, and the production cost is increased by the redundant platinum catalyst; when the content of the platinum catalyst is less than 1: 15, when the glass fiber treating agent is prepared, the speed of promoting the silicon rubber to form stable net structure strength by the high-hydrogen-containing silicone oil is reduced, the time for treating the glass fiber by the glass fiber treating agent is increased, and the production cost is increased.

Further, the total mass ratio of the coupling agent to the mixed raw materials is 1: (71-73).

By adopting the technical scheme, through tests, when the content ratio of the coupling agent to the total mass of the mixed raw materials is more than 1: 71, the bonding property between the glass fiber and the silicon rubber is reduced by the redundant coupling agent, and the reinforcing effect of the glass fiber is reduced; when the content ratio of the coupling agent to the total mass of the mixed raw materials is less than 1: 73, when the content of the coupling agent is less, and the acting force between organic siloxane molecules in the silicon rubber is greater than the adsorption acting force of the silicon rubber on the glass fiber, the cohesiveness of the silicon rubber and the glass fiber is reduced, so that the prepared heat-conducting silicon adhesive tape is easy to delaminate.

Further, the silicone rubber comprises one or two of methyl vinyl silicone rubber and methyl silicone rubber.

By adopting the technical scheme, the unsaturated bond vinyl in the methyl vinyl silicone rubber can improve the aging resistance and the high-temperature compression deformation resistance of the glass fiber after high-temperature treatment, and improve the reinforcing effect of the glass fiber; the organic siloxane molecules in the methyl silicone rubber improve the bonding property of the methyl silicone rubber and the glass fiber under the synergistic action of the platinum catalyst, the high-hydrogen silicone oil and the siloxane coupling agent, and can also improve the weather resistance of the glass fiber.

Further, the dispersing agent is xylene or white gasoline.

By adopting the technical scheme, the silicon rubber raw material is dissolved in the dimethylbenzene or the white gasoline, so that the silicon rubber can be dissolved and dispersed in the solution, the acting force between organic siloxane molecules in the silicon rubber is reduced, the reaction of the organic siloxane and the glass fiber is better promoted by the silane coupling agent, the high-hydrogen-content silicon oil and the platinum catalyst, the wettability between the silicon rubber and the glass fiber in the treating agent can be improved, and the adhesive force between the silicon rubber and the glass fiber is further increased.

Further, the glass fiber treating agent is prepared by the following steps:

step (1): adding a dispersing agent into the silicon rubber raw material for multiple times, fully stirring and mixing, and obtaining a mixed solution A when the viscosity reaches 900-1100mPa & s;

step (2): and adding a silane coupling agent, high-hydrogen-content silicone oil and a platinum catalyst into the mixed solution A, and uniformly mixing and stirring to obtain the glass fiber treating agent.

By adopting the technical scheme, the dispersing agent is added into the silicon rubber raw material to completely dissolve the silicon rubber, the dispersing agent is continuously added to dissolve the silicon rubber, and the acting force between organic siloxane molecules in the silicon rubber is gradually reduced, so that the silicon rubber is more fully dissolved until the viscosity of the solution is 900-1100mPa & s, and tests show that the roller sticking phenomenon occurs in the production when the viscosity is more than 1100mPa & s; when the solution viscosity is less than 900 mPas, the adhesiveness of the silicone rubber on the surface of the glass fiber is reduced in production.

And in the proper viscosity range, adding a silane coupling agent, high-hydrogen silicone oil and a platinum catalyst to prepare the glass fiber treating agent for the existing preparation, and immersing the glass fibers into the glass fiber treating agent to improve the reinforcing effect of the glass fibers.

The second purpose of the invention is to provide a glass fiber treatment process, which comprises the following treatment steps:

1) completely dipping and coating the glass fiber in the glass fiber treating agent, and rolling and adhering 70-90g of glass fiber treating agent per square meter on the surface of the glass fiber;

2) the glass fiber dipped with the glass fiber treating agent is heated to 150-160 ℃ in a gradual heating mode, and is kept warm for 1min, so that the treated glass fiber cloth is the prefabricated product A.

By adopting the technical scheme, a layer of glass fiber treating agent is calendered on the surface of the glass fiber, so that the glass fiber is completely dipped and coated in the glass fiber treating agent, and through test tests, when the coating amount of the glass fiber is 70-90g, the adhesive force and the adhesive property of the glass fiber and the silicon rubber are better, and when the coating amount per square meter of the glass fiber is less than 70g, the glass fiber treating agent compounded on the prepared glass fiber (the prefabricated product A) is less, so that when the prefabricated product A is compounded with the silicon rubber compound, the silicon rubber and the silicon rubber compound on the surface of the glass fiber have poorer adhesive property and lower adhesive strength; when the coating amount per square meter of the glass fiber is more than 90g, the prepared prefabricated product A has higher hardness, the caking property of the prefabricated product A and the silica gel rubber compound is reduced, and the delamination is easy to occur.

In the temperature rising treatment process of the glass fiber coated with the glass fiber treating agent, the dispersing agent in the glass fiber treating agent is gradually volatilized through temperature rising, so that bubbles generated in silicon rubber on the surface of the glass fiber when the glass fiber is directly placed at high temperature are avoided, and the bonding property between the glass fiber and the silicon rubber is reduced.

The third purpose of the invention is to provide a heat-conducting silica gel cloth, and the invention provides the following technical scheme: pressing the silica gel rubber compound on one surface of the prefabricated product A by calendering, and gradually heating to 120-180 ℃ in a heating manner to form a silica gel sulfide layer; and rolling the silica gel rubber compound on the other surface of the prefabricated product A to respectively form a silica gel vulcanized layer and an unvulcanized silica gel layer on the two surfaces of the prefabricated product A.

By adopting the technical scheme, the glass fiber treating agent is coated on the surface of the prefabricated product A, the silica gel rubber compound is rolled on the prefabricated product A and is combined with the silica gel rubber compound of the prefabricated product A to form a firm vulcanized silica rubber layer, and the cohesiveness of the silica gel rubber compound and the glass fiber is improved.

Further, the ramp gradient is set to: keeping the temperature at 60-80 ℃ for 60-90 s, then keeping the temperature at 80-100 ℃ for 60-90 s, and finally keeping the temperature at 100-180 ℃ for 60-90 s.

By adopting the technical scheme, the silica gel rubber compound is pressed on one surface of the prefabricated product A, the dispersing agent in the silica gel rubber compound can be gradually discharged in the step heating process at the temperature of between 60 and 80 ℃ and between 80 and 100 ℃ in a step heating mode, the heat preservation process at the temperature of between 100 and 180 ℃ is avoided, and the dispersing agent is volatilized when the prefabricated product A and the silica gel rubber compound are vulcanized, so that bubbles are generated in a vulcanized silica rubber layer, and the reinforcing effect of glass fibers and the bonding strength of the heat-conducting silica adhesive tape and the glass fibers are influenced.

In summary, the invention has at least one of the following advantages:

firstly, the invention adopts methyl vinyl silicone rubber, dimethylbenzene, gamma-methacryloxypropyl trimethoxysilane, high hydrogen-containing silicone oil and a platinum catalyst, under the action of the platinum catalyst, the gamma-methacryloxypropyl trimethoxysilane can realize the reinforcement effect on glass fibers, and simultaneously, the gamma-methacryloxypropyl trimethoxysilane forms a bonding layer of an organic matrix-gamma-methacryloxypropyl trimethoxysilane-inorganic matrix between the methyl vinyl silicone rubber and the glass fibers, thereby improving the bonding effect of the silicone rubber and the glass fibers.

Secondly, a certain amount of glass fiber treating agent is compounded on the surface of the glass fiber to obtain a prefabricated product A, the tensile strength of the glass fiber treated by the treating agent is improved by 30% to the maximum extent, and the reinforcing effect of the glass fiber on the heat-conducting silica gel cloth is good.

Thirdly, the glass fiber treating agent is prepared from raw materials such as methyl vinyl silicone rubber and gamma-methacryloxypropyl trimethoxy silane, the glass fiber is treated by the glass fiber treating agent and then is rolled on the surface of the glass fiber to obtain a prefabricated product A, and the silicone rubber in the prefabricated product A is combined with the cross-linking agent and the curing agent in the silicone rubber compound, so that the cohesiveness of the glass fiber and the silicone rubber compound is further improved, and the vulcanized silicone rubber and the glass fiber are not easy to delaminate.

Fourthly, when the glass fiber treating agent is coated on the prefabricated product A, a step-type heating mode is adopted, the dispersing agent in the silica gel rubber compound can be gradually discharged in the process, in the gradual high-temperature vulcanization process of the heat-conducting silica rubber cloth, the dispersing agent is gradually volatilized through the step-type heating mode of the tunnel oven when the heating temperature is lower, in the gradual heating process of the tunnel oven, the bubbles generated by volatilization of the dispersing agent are gradually discharged, when the vulcanized silica rubber layer is under the high-temperature vulcanization condition, the dispersing agent is discharged, no obvious bubbles can be generated, and the reinforcing effect of the glass fiber on the heat-conducting silica rubber cloth and the bonding strength of the heat-conducting silica rubber cloth and the glass fiber are improved.

Fifthly, the bonding strength of the glass fiber and the silicon rubber in the heat-conducting silicon adhesive tape prepared by the invention is high, and the heat-conducting silicon adhesive tape can be applied to a PCB (printed circuit board), and can also be widely applied to battery heating, motors, communication equipment, household appliances and other aspects.

Sixth, through testing the bonding strength between the vulcanized silicone rubber layer and the glass fiber in the heat-conducting silicone rubber cloth prepared by the invention, the increase rate of the bonding strength reaches more than 450%, so that the adhesive force between the glass fiber and the vulcanized silicone rubber layer in the heat-conducting silicone rubber cloth is greatly increased.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the tables in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, other embodiments obtained by persons of ordinary skill in the art with the understanding of the inventive concept of the present invention are within the scope of the present invention.

The present invention is further illustrated by the following examples.

TABLE 1 type and manufacturer of the raw materials of the present invention

After the glass fiber is treated, the tensile strength of the glass fiber changes, and the tensile strength refers to the stress which generates the maximum uniform plastic deformation of the material. In the tensile test of the glass fiber, the maximum tensile stress applied to the treated glass fiber sample until the glass fiber sample is broken is the tensile strength, and the tensile strength enhancement rate is the increase rate of the tensile strength of the glass fiber treated by the glass fiber treating agent to the tensile strength of the untreated glass fiber. The size of tensile strength can influence the toughness of prefab A, if the tensile strength increase back of prefab A, not only can prolong heat conduction silicon rubber cloth's life, simultaneously, also can enlarge heat conduction silicon rubber cloth's range of application, if prefab A's tensile strength is not enough, can break easily in the in-process of using, and then influence the performance that silica gel cloth cladding electric heating wire is to electric heating wire heat conduction of insulation, consequently, prefab A's tensile strength's change is very important to heat conduction silicon rubber cloth's application.

The tensile strength growth rate of preform a was calculated as follows: a. obtaining the difference between the tensile strength of the preform A and the tensile strength of the untreated glass fiber; b. the ratio of the tensile strength difference to the tensile strength of the untreated glass fiber, i.e., the rate of increase in the tensile strength of preform A. In the present invention, the preforms A obtained in examples 1 to 16 and comparative examples 1 to 8 were subjected to the test of tensile strength. The tensile strength of preform A was tested using ASTM D-2343 standard.