KR100907491B1 - Fluororubber composion for encapsulating semiconductor parts - Google Patents

Abstract

The present invention relates to fluorine rubber with improved heat resistance used for sealing semiconductor equipment, and more particularly, to silicon fluorine rubber (SiO ₂ ), titanium dioxide (TiO ₂ ), aluminum hydroxide (Al (OH) ₃ ). Fluorine used in the semiconductor high temperature process equipment having improved heat resistance by using a filler composed of a mixture of zinc oxide (ZnO) and especially adding an aluminum hydroxide (Al (OH) ₃ ) -based flame retardant at an optimum ratio. It is about rubber.

Semiconductor, Fluorine, Rubber, Heat Resistant, Sealing, Polymer, High Temperature, Filler, Vulcanizer

Description

Fluorine rubber for sealing semiconductor equipment with improved heat resistance {FLUORORUBBER COMPOSION FOR ENCAPSULATING SEMICONDUCTOR PARTS}

The present invention relates to a fluorine rubber having improved heat resistance by adding a flame retardant to the fluorine rubber used for sealing semiconductor equipment.

Perfluoro-elastomer is a terpolymer copolymer of monomers such as tetrafluroethylene (TFE), perfluoromethylvinyl ether (PFMVE) and CSM (Cure Site Monomer). Has a structure.

The curing vulcanization of the above fluorine rubber uses three vulcanization methods such as bisphenol curing, peroxide curing, and triazine curing. Mold the ash.

Peroxide curing during the vulcanization process is to vulcanize the link between the polymer and the polymer in the CSM (Cure Site Monomer) of the perfluorine raw material using a compound of the peroxide. Say how.

However, the biggest disadvantage of the peroxide curing is that the bonding structure between the polymer and the polymer is easily broken at a high temperature of 300 ° C. or higher, and the performance of the rubber itself used as a sealing material is lost. .

This problem requires that the current semiconductor process should be usable at high temperature, plasma resistance and chemical resistance due to the high integration, high temperature, high density process and high plasma process. In combination with the present invention, many problems are generated in the semiconductor process.

Flame retardants are materials that slow down the ignition and prevent the expansion of combustion by adding compounds with high flame retardant effects such as halogen, phosphorus, nitrogen, and metal compounds to polymer materials having easy burning properties. This is achieved by interfering with certain combustion stages such as heating, decomposition, and heat generation. Recently, products that combine low-toxicity, low-smoke, and low-corrosiveness as well as simple flame retardant effects have been developed.

Flame retardants are divided into additive type and reactive type, and the additive type is divided into organic and inorganic flame retardant. Inorganic systems (additives) account for the largest portion of the flame retardant market because of their low cost and synergism with halogenated organic compounds and their use as fillers. The organic type (addition type) has the advantage of easy compounding with the polymer, the reaction type is excellent in flame retardant effect, but it is expensive and expensive to manufacture because it actually acts as a copolymer.

The inorganic flame retardant is not volatilized by heat and decomposes to release incombustible gases such as water, carbon dioxide, sulfur dioxide, and hydrogen chloride, and undergoes endothermic reaction. In the gas phase, the flammable gas is diluted to coat the plastic surface to prevent the access of oxygen, and at the same time, there is an effect of reducing the generation of plastic cooling and pyrolysis products through endothermic reactions on the solid phase surface. There are aluminum hydroxide, magnesium hydroxide, antimony oxide, tin hydroxide, tin oxide, molybdenum oxide, zirconium compound, borate, calcium salt, etc. Among them, the demand for aluminum hydroxide, antimony oxide, magnesium hydroxide is the highest.

In the present invention, a conventional mixing ratio of a filler composed of silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), aluminum hydroxide (Al (OH) ₃ ), and zinc oxide (ZnO) in fluorine rubber, in particular, aluminum hydroxide (Al) It is an object of the present invention to provide fluorine rubber having improved heat resistance characteristics used for sealing semiconductor equipment by using an optimum ratio of (OH) ₃ ) flame retardants.

In order to achieve the above object, the present invention

Fluorine rubber raw material 40 ~ 90% by weight,

Filler 5-50% by weight,

2-5 wt% of triallyl isocyanurate (Taic) as a crosslinking agent

Cyclohexanone peroxide, t-butylperoxyisopropylcarbonate, t-butylperoxylaurylate, t-butylperoxyacetate, di-t-butyldiperoxyphthalate, t-dibutylperoxymaleic acid, t- Butyl cumyl peroxide, t-butyl hydroperoxide, dibenzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, methylethylketone peroxide, di- (2,4- Dichlorobenzoyl) peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, n-butyl-4,4-bis (t-butylperoxy) valerate and α, α'-bis (t-butylperoxy) diisopropylbenzene, di- (2,4-dichlorobenzoyl) -peroxidase (Di- (2,4-dichlorobenzoyl) -peroxide), dibenzoyl peroxide Tert-Butyl peroxate ybenzoate), 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane (1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane), di- (2-tert-butyl-peroxyisopropyl) -benzene (di- (2-tert-butyl-peroxyisopropyl) -benzene), 2,5-dimethyl-2,5-di- (tert-butylperoxy) -Hexane (2,5-Dimethyl-2,5-di- (tert-butylperoxy) -hexane), Di-tert-butylperoxide, 2,5-dimethyl-2,5 Vulcanizing agent composed of any one or a mixture of two or more selected from -di (tert-butylperoxy-hexane-3 (2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3) The main technical configuration is fluorine rubber, which is used for sealing semiconductor equipment with improved heat resistance, which is formed by mixing 10 wt%.

In addition, the filler is 20 to 86% by weight of silicon dioxide (SiO ₂ ), 7 to 30% by weight of titanium dioxide (TiO ₂ ), 3 to 30% by weight of aluminum hydroxide (Al (OH) ₃ ), zinc oxide (ZnO) 4 Characterized in that the composition is ~ 20% by weight.

The fluorine rubber having improved heat resistance according to the present invention is formed by adding a filler, a cross linking agent, and a vulcanizing agent to a fluorine rubber raw material.

The fluorine rubber raw material (Raw material) is used in the range of 40 to 90% by weight relative to the total mixing ratio of the fluorine rubber with improved heat resistance,

If it is used below 40% by weight, there is a problem of poor moldability, and if it is used above 90% by weight, a problem of low heat resistance occurs, so that 40% of the total mixing ratio of the raw material of fluorine rubber It is preferable to use in the range of -90 weight%.

The filler includes aluminum hydroxide (Al (OH) ₃ ) and has a very important function in improving the heat resistance characteristics of the sealing material fluorine rubber. In the case of the conventional filler, the physical properties and the rubber properties are related according to mutual additives. There is a problem in that the characteristics of one part is lowered when the characteristics of one part are improved. For this reason, the optimal formulation of the fillers applied is a very important issue.

Looking at the configuration of the filler used in the present invention, 20 to 86% by weight of silicon dioxide (SiO ₂ ), 7 to 30% by weight of titanium dioxide (TiO ₂ ), aluminum hydroxide (Al (OH) ₃ ) 3 to 30% by weight, Zinc oxide (ZnO) is composed of 4 to 20% by weight.

The silicon dioxide (SiO ₂ ) is purely a filler, it is used in 20 to 86% by weight relative to the total filler. In this case, when silicon dioxide is used at less than 20% by weight, a problem of price of compound occurs, and when used in excess of 86% by weight, a problem of compound hardness is increased. The silicon dioxide is preferably used in the range of 20 to 86% by weight based on the total amount of the filler.

The titanium dioxide (TiO ₂ ) is to have a great effect on the gloss and durability of the compound (compound), 7 to 30% by weight based on the total weight of the filler. In this case, when titanium dioxide is used at less than 7% by weight, a problem of compound durability decreases, and when it is used in excess of 30% by weight, a problem occurs in forming a compound. , The titanium dioxide is preferably used in the range of 7 to 30% by weight based on the total weight of the filler.

The aluminum hydroxide (Al (OH) ₃ ) has a great effect on the flame retardancy and heat resistance of the compound (compound), 3 to 30% by weight based on the total weight of the filler. In this case, when the aluminum hydroxide used is out of the above range, there is a problem that the heat resistance of the compound (compound) is inferior, it is preferable to use the aluminum hydroxide in the range of 3 to 30% by weight based on the total weight of the filler.

The zinc oxide (ZnO) is a factor affecting the heat resistance during compound milling, and 4 to 20% by weight based on the total weight of the filler is used. In this case, when zinc oxide is used at less than 4% by weight, problems occur during compounding, and when used in excess of 20% by weight, poor moldability occurs, so zinc oxide (ZnO) is It is preferable to use in the range of 4-20 weight% with respect to the total weight of a filler.

Since the filler added in the production of such fluorine rubber is added with aluminum hydroxide (Al (OH) ₃ ) -based oxide in the ratio as described above, the heat resistance characteristics of the sealing material, which was not previously expected, are greatly improved. Will have

As described above, the filler having the composition ratio is used in an amount of 5 to 50% by weight based on the total blending ratio of fluorine rubber, and when the filler is used in an amount less than 5% by weight, the heat resistance, chemical resistance and There is a problem in price competitiveness, and even when used in excess of 50% by weight, heat, chemical resistance and molding problems and compounding problems occur, so the filler is 5 to 50% by weight of the total compounding ratio of fluorine rubber It is preferable to use it in% range.

Next, look at the crosslinking agent and vulcanizing agent used in the production of fluororubber.

The crosslinking agent has a function of affecting crosslinking during compound vulcanization, and uses triallyl isocyanurate (Taic).

The crosslinking agent is used in an amount of 2 to 5% by weight based on the total blending ratio of fluorine rubber, and when used at less than 2% by weight, crosslinking does not occur in compound vulcanization. Since a problem occurs in the reverse reaction and compounding of the crosslinking, it is preferable to use the crosslinking agent in the range of 2 to 5% by weight based on the total blending ratio of fluorine rubber.

In addition, the vulcanizing agent has an important function for the crosslinking of the molded article when the product is molded, and is used in the range of 3 to 10% by weight based on the total fluorine rubber compounding ratio, and when used less than 3% by weight, the vulcanizing agent does not occur in the crosslinking of the product. Since many problems occur in the physical properties of the product, the vulcanizing agent is preferably used in the range of 3 to 10% by weight based on the total fluorine rubber compounding ratio.

Hereinafter, a method of manufacturing fluorine rubber used for sealing semiconductor equipment having improved heat resistance will be described.

First, a raw material of fluorine rubber is made thin (less than 1T thickness) by turning it sufficiently in a roll so that filler can penetrate therein. The reason for the thinning is that the fluorine rubber raw material (Raw material) in the roll (Roll) is easy to penetrate the filler (Filler) must be wound on the roll (Roll) with sufficient shear force.

The filler used at this time, as described above, 20 to 86% by weight of silicon dioxide (SiO ₂ ), 7 to 30% by weight of titanium dioxide (TiO ₂ ), aluminum hydroxide (Al (OH) ₃ ) 3 to 30% by weight, oxidation Zinc (ZnO) 4 to 20% by weight is used.

The filler is added in order of zinc oxide (ZnO) in order to prevent the aggregation of ZnO in the compounded compound, which helps solve the problem of particles in the product during the molding of the product, and the remaining filler SiO ₂ , TiO ₂ and Al (OH) ₃ do not have a special reaction and bonding in the raw materials, but rather reinforce the heat resistance characteristics of the product, so the order of loading is to check the filler particle size and to add from the larger particle filler. Easy to proceed

In addition, as described above, raw material is applied to both binary FKM and ternary FKM materials, and basic additives are specified in specific FKM. Binary system: binary copolymer polymer compound, ternary system: terpolymer copolymer polymer compound)

As described above, the fluororubber (Perfluoro-elastomer) semiconductor sealing O-ring according to the present invention is a conventional fluorine rubber, silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), aluminum hydroxide (Al (OH) ₃ ), Heat resistance used for sealing semiconductor equipment by using the optimum ratio of the flame retardant greatly improved flame retardancy by the mixing ratio of zinc oxide (ZnO), in particular, the optimum ratio of aluminum hydroxide (Al (OH) ₃ ), a flame retardant. As the fluorine rubber with improved properties can be provided, the performance of rubber materials used as sealing materials for semiconductor equipment is also high and high due to the high integration, high temperature, high density and high plasma processes in semiconductor processes. It is now possible to meet the need to meet plasma and chemical resistance.

Hereinafter, the specific content of the blending ratio of the fluorine rubber having improved heat resistance characteristics used for sealing the semiconductor high-temperature process equipment will be confirmed through the examples.

First, the heat resistance behavior of the fluorine rubber according to the conventional compounding ratio (Comparative Example 1), and then look at the compounding ratio (Compound 1) and the heat resistance behavior of the fluorine rubber according to the present invention. .

Comparative Example 1: Conventional White Series Compound ( Compound Formulation design

ingredient content(%) Fluorine rubber raw material RAW MATERIAL 100  Filler SiO ₂ 20 TiO ₂ 10 ZnO 5 Cross linking Taic 3 Vulcanizing agent Peroxide compound One

The heat resistance characteristics of the fluorine rubber formed at the same compounding ratio as in Comparative Example 1 will be described with reference to FIG. 1. 1 is a graph illustrating heat resistance characteristics of fluorine rubber according to a compound compounding ratio.

As shown in Figure 1, the fluorine rubber according to the conventional compounding ratio was maintained in a state that almost the surface is not melted below 250 ℃, but gradually melted up to 300 ℃ while slowly starting to melt from 250 ℃ after passing the 250 ℃ at 320 ℃ Surface melting behavior is almost 100%.

As such, the fluorine rubber according to the conventional compounding ratio is very inferior in heat resistance, and thus, it may be confirmed that the fluorine rubber is not suitable for use as a sealing material for semiconductor equipment used at high temperature and high pressure.

In summary, the compounding ratio of Example 1 is applied so that the service temperature of the fluorine rubber of peroxide vulcanization reaches almost 300 ° C., and at 300 ° C. or more, the rubber properties of the sealing material are almost lost, thereby almost no role as a sealing material. This results in lower equipment application cycles.

Compound compound design according to the present invention that can overcome these disadvantages and improve the heat resistance characteristics to overcome the high temperature process equipment application limitations, and improve the application cycle (cycle) life is as follows.

Example 1 According to the Invention Compound ( Compound Formulation design

ingredient Content (phr) Fluorine rubber raw material RAW MATERIAL 100  Filler SiO ₂ 20 TiO ₂ 5 Al (OH) ₃ 5 ZnO 5 Cross linking Taic 3 Vulcanizing agent Peroxide compound One

As described above through Comparative Example 1, in order to improve the problem of fluorine rubber that starts to melt at 250 ° C. or more and then melts at 320 ° C., a compounding ratio as in Example 1 is presented.

It is suggested that the aluminum hydroxide (Al (OH) ₃ ) is used 5phr as the filler, it can be seen that the heat resistance of the fluorine rubber is rapidly increased due to the addition of such aluminum hydroxide in a certain ratio.

For this reason, it will be described through the drawings shown in FIG.

First, the graph shown in FIG. 2 shows that the heat resistance characteristics of aluminum hydroxide (Al (OH) ₃ ) added 5 phr, 10 phr, and 15 phr as fillers were examined. Looking at the fluororubber according to the present invention the aluminum hydroxide (Al (OH) ₃₎ are each added to the conventional fluorine-containing rubber is not added at all, 5phr, 10phr, aluminum hydroxide at a ratio of 15phr (Al (OH) ₃₎ as a filler, First, as described above, the conventional fluorine rubber starts to melt at 250 ° C. and almost melts at a point of 320 ° C., thus making it difficult to use a high temperature and high pressure semiconductor equipment sealing material.

On the other hand, the fluorine rubber according to the present invention, when aluminum hydroxide (Al (OH) ₃ ) is blended with 15phr, hardly melts up to 270 ° C, and surface melting behavior does not reach 40% even at a high temperature of 300 ° C, Compared with the conventional fluorine rubber showing almost 100% surface melting behavior at 300 ℃ it can be seen that the heat resistance is very excellent.

When the aluminum hydroxide (Al (OH) ₃ ) is blended with 10 phr, the alumina (Al ₂ O ₃ ) is blended with 15 phr, although it exhibits similar behavior to that of aluminum hydroxide (Al (OH) ₃ ) with 15 phr. It can be seen that the heat resistance is higher than the case.

When aluminum hydroxide (Al (OH) ₃ ) is blended at 5 phr, it exhibits the highest heat resistance and hardly dissolves up to 320 ° C., which is almost 50 to about fluorine rubber according to the conventional compounding ratios identified in Comparative Example 1 described above. It can be confirmed that it can be used as a sealing material even at a temperature difference of more than ℃.

As confirmed through Example 1, the optimum amount of aluminum hydroxide (Al (OH) ₃ ) showed the best heat resistance at about 5 phr, the heat resistance was lowered as the addition amount was increased, the mechanical properties or elastic force of the basic physical properties of rubber This resulted in a decrease in part.

When the content of the aluminum hydroxide is increased, the content of other additives must be reduced to maintain hardness in accordance with the existing use conditions, and a certain portion or more of the amount of addition may result in deterioration of the rubber properties. Therefore, it was confirmed that 5 phr of aluminum hydroxide-based oxide exhibited optimal characteristics as described above.

As a result, the addition of aluminum hydroxide at 5 phr improves the properties of materials in which vulcanized rubbers, which are difficult to use by the conventional peroxide method, are more than 300 ° C. Improved heat resistance properties so that can be used.

1 is a graph showing the heat resistance characteristics of a conventional compound (Compound).

Figure 2 is a graph showing the heat resistance characteristics of the compound (Compound) according to the present invention.

Claims (2)

Fluorine rubber raw material 40 ~ 90% by weight, Filler 5-50% by weight, Triallyl isocyanurate (Taic) 2 to 5% by weight Cyclohexanone peroxide, t-butylperoxyisopropylcarbonate, t-butylperoxylaurylate, t-butylperoxyacetate, di-t-butyldiperoxyphthalate, t-dibutylperoxymaleic acid, t- Butyl cumyl peroxide, t-butyl hydroperoxide, dibenzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, methylethylketone peroxide, di- (2,4- Dichlorobenzoyl) peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, n-butyl-4,4-bis (t-butylperoxy) valerate and α, α'-bis (t-butylperoxy) diisopropylbenzene, di- (2,4-dichlorobenzoyl) -peroxidase (Di- (2,4-dichlorobenzoyl) -peroxide), dibenzoyl peroxide Tert-Butyl peroxybenzoate benzoate), 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane (1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane), di- (2-tert-butyl-peroxyisopropyl) -benzene (di- (2-tert-butyl-peroxyisopropyl) -benzene), 2,5-dimethyl-2,5-di- (tert-butylperoxy) -Hexane (2,5-Dimethyl-2,5-di- (tert-butylperoxy) -hexane), Di-tert-butylperoxide, 2,5-dimethyl-2,5 Vulcanizing agent composed of any one or a mixture of two or more selected from -di (tert-butylperoxy-hexane-3 (2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3) In the composition by mixing ~ 10% by weight, The filler is 20 to 86% by weight of silicon dioxide (SiO ₂ ), 7 to 30% by weight of titanium dioxide (TiO ₂ ), 3 to 30% by weight of aluminum hydroxide (Al (OH) ₃ ), zinc oxide (ZnO) 4 to 20 Fluorine rubber for sealing semiconductor equipment with improved heat resistance, characterized in that it is formulated in weight percent. delete

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