KR100894110B1 - Perfluoro-elastomer improved stretchflangeability using for insemiconductor device - Google Patents

Abstract

Provided is perfluoro-elastomer which improves elongation properties while maintaining basic properties of existing sealants for high integration and high temperature and density processes of semiconductor devices. Perfluoro-elastomer for sealants of semiconductor devices comprises the 25-65wt% of perfluoro-elastomer, the 15-35wt% of ternary perfluoro-elastomer, the 5-50wt% of filler, the 2-5wt% of cross-linking agent and the 1-5wt% of cross-linking accelerator. The filler consists of the 20-80wt% of barium sulphate(BaSO4), the 7-45wt% of titanium dioxide(TiO2) and the 3-35wt% of zinc oxide(ZnO). The cross-linking accelerator includes one or more compositions selected from the group consisting of cyclohexanone peroxide, t-butylperoxyisopropylcarbonate, t-butylperoxylaurylate, t-butylperoxyacetate, di-t-butyldiperoxyphthalate, t-dibutylperoxymaleic acid, t-butylcumylperoxide, t-butylhydroperoxide, dibenzoylperoxide, dicumylperoxide, 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, alpha,alpha'-bis(t-butylperoxy)diisopropylbenzene, di-(2,4-chlorobenzoyl)-peroxidase(di-(2,4-dichlorobenzoyl)-peroxide), dibenzoyl peroxide, tert-butyl peroxybenzoate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-(2-tert-butyl-peroxyisopropyl)-benzene, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, di-tert-butylperoxide and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3.

Description

PERFLUORO-ELASTOMER IMPROVED STRETCHFLANGEABILITY USING FOR INSEMICONDUCTOR DEVICE}

  The present invention relates to perfluorinated rubber used for sealing semiconductor equipment with improved elongation by mixing perfluorinated rubber and ternary fluorine rubber.

The present invention relates to the improvement of the elongation (Strength) in the physical properties of the perfluorinated rubber used for semiconductor sealing, and to a method of manufacturing the same. In the case of sealing materials, the elongation ranges from 150% up to about 250%, and among the semiconductor processes, perfluorine (Elongation) is required for processes requiring high elongation while maintaining the properties of conventional perfluoro sealing materials. Perfluoro) To apply seailng material, the mixture of perfluoro rubber and ternary fluorine rubber is mixed in a certain ratio to make the most of the advantages of Perfluoro and ternary fluoro, to improve the performance and physical properties of rubber as a sealing material and to reduce the unit cost of the product. Elongation) relates to a mixture of improved perfluorinated rubber and ternary fluorine rubber and a method for producing the same.

Fluoro-elastomer is a hydrocarbon polymer with high degree of fluorination. In general, all polymers with high degree of fluorination are very stable and have very good oxidation resistance, weather resistance, flame retardancy, and chemical resistance.

This stability is due to higher C-F bond strengths compared to C-H bonds. The monomers that form these rubbers are polyvinylidene fluoride (PVF) and nucleated fluoropropylene (HFP), and the chemical structure of fluororubber is as follows.

In addition, there are various products depending on the composition and fluorine content of the fluororubber polymer, and its structure is as follows. In addition, there are various products depending on the composition and fluorine content of the fluororubber polymer, and its structure is as follows.

In general, ternary copolymers (ternary fluorine rubber) are better in oil resistance and chemical resistance than binary copolymers (Fluoro-elastomer). Swelling resistance improves with increasing fluorine content, but low temperature flexibility.

As mentioned above, the characteristics of fluorine rubber are very high heat resistance, ozone resistance, weather resistance, flame retardancy and resistance to oxidizing chemicals, and thus rubber elasticity up to 200 ° C and resistance to various oils, fuels, solvents and various chemicals. There is this.

However, fluorine rubber, which is oil resistant to a wide variety of fluids, is also very severely attacked by some fluids. Examples include polar solvents such as ketones and esters, low molecular organic acids such as formic acid and acetic acid, hot water and steam, methanol, alkyl-aryl phosphate esters, glycols, anhydrous ammonia and amines.

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

As shown in the above chemical structure, perfluoro-elastomer has only a fluorine atom F instead of a hydrogen atom, and thus has a much higher binding energy than fluoro-elastomer due to the high electronegativity of fluorine. This shows excellent properties such as heat resistance, chemical resistance, oxidation resistance, weather resistance, etc. than the existing fluorine rubber, and perfluorinated rubber also tends to increase such properties rapidly as the content of fluorine increases.

In general, perfluoro-elastomer combines the resilience and sealing properties of rubber with the thermal stability and chemical resistance of polytetrafluoroethylene (PTFE) resin. These products maintain elastic properties for a long time at high temperature of 260 ℃ and can be used up to 320 ℃ in a short time. In addition, it has good resistance to chemicals that affect other rubbers, including fluorine rubber.

Such perfluorine rubber demands that the performance of rubber materials used as sealing materials for semiconductor equipment should also be available at high temperature, plasma resistance, and chemical resistance due to the high integration, high temperature, high density, and high plasma processes. It is engaged in continuous growth.

In the present invention, while maintaining the basic physical properties of the conventional sealing material, while improving the elongation characteristics of the conventional sealing (Sealing) material, while applying to the high integration of the semiconductor process and the equipment of high temperature, high density process and high plasma process, the existing low elongation is To improve the elongation of perfluorinated rubber, which is a disadvantage, to impart functionality,

Overcharge with improved elongation characteristics used for semiconductor sealing by blending fillers that have an additional effect on the characteristics of raw materials and other fillers, and adding ternary fluororubbers with excellent elongation properties with basic sealing properties It is intended to provide a mixture of bovine rubber and ternary fluorine rubber and a method of manufacturing the same.

In order to achieve the above object, in the present invention, 25 to 65% by weight of the raw material of fluorine rubber (raw material), 15 to 35% by weight of ternary fluorine rubber raw material (raw material), 5 to 50% by weight of the filler, crosslinking agent 2 ~ 5% by weight, cyclohexanone peroxide, t-butylperoxyisopropylcarbonate, t-butylperoxylaurylate, t-butylperoxyacetate, di-t-butyldiperoxyphthalate, t-dibutyl peroxy Maleic 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-butylperox Diisopropylbenzene, di- (2,4-dichlorobenzoyl) -peroxidase (Di- (2,4-dichlorobenzoyl) -peroxide), dibenzoyl peroxide, tert-butyl peroxy Tert-Butyl peroxybenzoate, 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- Any one or two or more selected from dimethyl-2,5-di (tert-butylperoxy) hexane-3 (2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3) The main technical configuration of the perfluororubber for elongation of the semiconductor sealing is improved by the composition of 1 to 5% by weight of the crosslinking accelerator, Is characterized in that the composition of a mixture of barium sulfate (BaSO ₄₎ 20 ~ 80% by weight, titanium dioxide (TiO ₂₎ 7 ~ 45% by weight of zinc oxide (ZnO) 3 ~ 35% by weight.

Hereinafter, the technical configuration will be described in more detail.

The perfluorinated rubber having improved elongation characteristics according to the present invention is formed by adding a filler, a cross linking agent, and a crosslinking accelerator to a perfluorine rubber raw material and a ternary fluorine rubber raw material (Raw material) at a predetermined ratio.

The perfluorinated rubber raw material and ternary fluorine rubber raw material (Raw material) are used in the range of 25 to 65% by weight, 15 to 35% by weight relative to the total mixing ratio of perfluororubber with improved elongation characteristics, respectively, two raw materials If the total weight percentage of the mixture is used less than 40% by weight, there is a problem of poor moldability, and if the total weight percentage of the two raw materials mixture is used in excess of 95% by weight two rubber raw materials (Raw material) Since it is difficult to blend the blending (Blending) of the mixture (perfluororubber raw material and fluorine rubber raw material (Raw material) is preferably used in the range of 25 to 65% by weight, 15 to 35% by weight, respectively.

The filler is related to the physical properties and rubber properties of the perfluorinated rubber with elongation characteristics improved according to the amount of the component, the mixing ratio and the total ratio thereof, so that the optimum blending of the filler is a very important problem, the composition of the filler used in the present invention Silver mixed with barium sulfate (BaSO ₄ ) 20 to 80% by weight, titanium dioxide (TiO ₂ ) 7 to 45% by weight, zinc oxide (ZnO) 3 to 35% by weight is used.

The barium sulfate (BaSO ₄ ) has a great effect on the heat resistance and chemical resistance of the compound (compound), 20 to 80% by weight based on the total weight of the filler. In this case, when the barium sulfate (BaSO ₄ ) is used in less than 20% by weight of the compound (compound) cost problem, and when used in excess of 80% by weight of the compound (compound) formability problem occurs Barium sulfate (BaSO ₄ ) is preferably used in the range of 20 to 80% by weight based on the total weight of the filler.

The titanium dioxide (TiO ₂ ) is used to affect the gloss and durability of the compound (compound) product, it is used in 7 to 45% by weight relative to the total weight of the filler. In this case, when titanium dioxide (TiO ₂ ) is used at less than 7% by weight, a problem in that the durability of the compound is reduced, and when used in excess of 45% by weight, there is a problem of compound formability. Since it occurs, titanium dioxide (TiO ₂ ) is preferably used in the range of 7 to 45% by weight based on the total amount of the filler.

The zinc oxide (ZnO) is a factor affecting the heat resistance during compound milling, and 3 to 35% by weight based on the total weight of the filler is used. At this time, when using zinc oxide (ZnO) less than 3% by weight compounding (compounding) a problem occurs, and when using more than 35% by weight zinc oxide (ZnO) because the problem of poor formability occurs ) Is preferably used in the range of 3 to 35% by weight based on the total weight of the filler.

The filler added to the preparation of such a mixture of perfluorinated rubber and fluorine rubber does not contribute significantly to the improvement of elongation, but the weight percent ratio is important because the properties and rubber properties are related to the additives. Affinity with) is important above all.

The filler having the composition ratio as described above is used in 5 to 50% by weight based on the total blending ratio, when the filler is used in less than 5% by weight, there is a problem in the price competitiveness of the compound (Compound), When used in excess of 50% by weight, heat, chemical resistance and molding problems and compounding (Compounding) problems occur, so the filler is preferably used in the range of 5 to 50% by weight based on the total blending ratio.

Next, the crosslinking agent and the crosslinking accelerator used in the preparation of the perfluoro rubber for semiconductor sealing with improved elongation will be described.

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, and when used in an amount less than 2% by weight, there is a problem in that crosslinking cannot occur during compound vulcanization. Since a problem occurs in the reverse reaction and compounding, the crosslinking agent is preferably used in an amount of 2 to 5% by weight based on the total blending ratio of the perfluoro rubber for semiconductor sealing with improved elongation.

In addition, the crosslinking accelerator is used in an amount of 1 to 5% by weight based on the total blending ratio of the perfluoro rubber for elongation of the semiconductor sealing, elongation of less than 1% by weight does not properly crosslinking of the product to cause product defects As the probability increases and when used in excess of 5% by weight, problems occur in reverse reaction and compounding of the crosslinking agent. Therefore, it is recommended to use the crosslinking accelerator in the range of 1 to 5% by weight based on the total mixture ratio of the perfluorinated rubber and the fluorine rubber mixture desirable.

Hereinafter, the manufacturing method of perfluoro rubber for semiconductor sealing with improved elongation with improved elongation characteristics for semiconductor sealing is as follows.

First, let's look at compounding.

The perfluororubber and ternary fluororubber raw materials are sufficiently rotated on the rolls to allow the filler to penetrate to form a thin mixture (less than 1T thick). 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.

In this case, the filler used is used in a blending ratio of 20 to 80% by weight of barium sulfate (BaSO ₄ ), 7 to 45% by weight of titanium dioxide (TiO ₂ ), and 3 to 35% by weight of zinc oxide (ZnO).

Among the fillers, the filler to be put first is zinc oxide (ZnO), and in order to prevent agglomeration of zinc oxide (ZnO) in the compound, it is added first.

Next, barium sulfate (BaSO ₄ ) and titanium dioxide (TiO ₂ ) are sequentially added, and finally a crosslinking accelerator is added.

When the crosslinking accelerator is added, the compound hardens as the compound is cured, and thus, a sufficiently cured part must be compounded to be mixed and mixed with the compound evenly.

The addition time of the filler, crosslinking agent and vulcanizing agent of the raw material fluorine rubber (Raw material) should be made before 30 minutes to 1 hour, the temperature of the compounding (compounding) material should be less than 60 ℃.

If the temperature is higher than 70 ℃ because the material is vulcanized during the compounding (Compounding) proceeds may cause problems such as mold failure such as scorch during molding.

Finally, in molding a mixture of perfluorinated rubber and ternary fluorine rubber with improved elongation characteristics, it is important to first extruding and to adjust the length and size of the molded article to be manufactured, and to control the molding conditions of the press. Control conditions are temperature, time, and pressure, and because they are the most influential factors in forming the material, there is a big difference for each compound. With this in mind, the optimum molding conditions are carried out by design molding.

As described above, the perfluorinated rubber for semiconductor sealing with improved elongation according to the present invention basically improves the elongation characteristics of the conventional sealing material while maintaining the basic physical properties of the existing sealing material, thereby increasing the integration and high temperature of the semiconductor process. It is applied to the equipment of high density process and high plasma process, and it improves the elongation of perfluorinated rubber, which is the disadvantage of the existing low elongation, and gives the functionality to maintain the performance of perfluorinated rubber, the optimal sealing agent of the conventional semiconductor process. By combining the excellent elongation of raw fluorine rubber, it is possible to meet the requirements of functional sealing agent for processes that require elongation in semiconductor, LCD and various high integration processes.

Hereinafter, the specific technical configuration of the perfluorinated rubber for semiconductor sealing and the perfluorinated rubber having improved elongation using ternary fluorine rubber with improved elongation characteristics is improved.

First, the elongation of the perfluorinated rubber and ternary fluorine rubber according to the conventional blending ratio (Comparative Example 1, Comparative Example 2), and then, the compounding ratio (Compound) of the compound according to the present invention (Example 1) and perfluorinated rubber Let's take a look at the elongation of the ternary fluororubber mixture.

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

                                                           Content (Phr) Perfluorinated Rubber Raw Material RAW MATERIAL 100  Filler TiO ₂ 10 BaSO ₄ 10 ZnO 5 Cross linking Taic 3 Vulcanizing agent Peroxide compound One

Comparative Example 2: Conventional White Series Ternary  Fluorine rubber Compound ( Compound Formulation design

                                                             Content (phr) Ternary Fluorine Rubber Raw Material RAW MATERIAL 100  Filler TiO ₂ 10 BaSO ₄ 20 ZnO 5 Cross linking Taic 3 Vulcanizing agent Peroxide compound One

An elongation characteristic of each of the perfluororubber and the fluororubber prepared at the same compounding ratio as in Comparative Example 1 and Comparative Example 2 will be described with reference to FIGS. 1 and 2. 1 and 2 are graphs showing elongation characteristics of perfluorinated rubber and ternary fluorine rubber according to a conventional compound compounding ratio.

Each specimen was measured three times, and elongation is closely related to hardness, and thus the content of BaSO ₄ in the compounds of Comparative Example 1 and Comparative Example 2 is different. This is to match the hardness of raw fluorine rubber.

The elongation behavior according to the hardness change of the same material tends to decrease the elongation (%) as the hardness increases, and the tensile strength (Tb) and the modulus value generally tend to increase accordingly. Therefore, in the present invention, in forming the respective measurement specimens of ternary fluorine rubber, perfluorinated rubber, mixture of ternary fluorine rubber and perfluorinated rubber, the hardness of each specimen obtained through press curing and the final post-curing is the same. Mixing design and molding were performed, and elongation was measured with each specimen having the same hardness.

As shown in Figure 1, the conventional fluorine rubber according to the ratio of the elongation can be seen that the elongation is not close to 40mm at the final break. Based on the initial 20mm, it can be seen that no elongation of 200%. In addition, the graph slope shows that although the elongation is low, the tensile strength is quite high due to the high stress value.

As described above, since the elongation of the conventional fluorine rubber is very low, it can be confirmed that it is difficult to use as a sealing material for semiconductor equipment used in a semiconductor process requiring a specific elongation.

Figure 2 shows the elongation behavior of ternary fluorine rubber according to the conventional compounding ratio. The elongation exceeded 70mm at the time of final fracture, indicating that the elongation exceeded 350%.

In summary, the blending ratios of Comparative Example 1 and Comparative Example 2 were applied to prepare three specimens of perfluororubber and ternary fluorine rubber, respectively, and the elongation was measured. ) Showed Avg 186%, and the ternary fluorine rubber according to the conventional compounding ratio showed an elongation at break (%) of Avg 367% at the time of final breaking, so that the current perfluorinated rubber has a significantly lower elongation characteristic than the ternary fluorine rubber. It can be seen that it hardly plays a role as a sealing material for semiconductor equipment requiring elongation.

In consideration of this point, in order to apply the semiconductor and LCD process equipment requiring the elongation by improving the elongation characteristics, the compound compound design according to the present invention which can improve the elongation is as follows.

Example 1 According to the Invention Compound ( Compound Formulation design

                                                             Content (phr) Perfluorinated Rubber Raw Material RAW MATERIAL 70 Ternary Fluorine Rubber Raw Material RAW MATERIAL 30  Filler TiO ₂ 10 BaSO ₄ 15 ZnO 5 Cross linking Taic 3 Crosslinking accelerator Peroxide compound One

As described above through Comparative Example 1 and Comparative Example 2, in order to improve the problem of the elongation of the perfluororubber, the compounding ratio as in Example 1, in order to improve the elongation of the perfluoro rubber and the tertiary fluorine rubber To present.

It is suggested that the raw gum used perfluoro rubber and tertiary fluorine rubber 70 phr and 30 phr, respectively, and the elongation characteristics of the perfluorinated rubber are sharply increased due to the addition of the ternary fluorine rubber at a constant mixing ratio. .

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

Three specimens were measured, and elongation was closely related to hardness, and as a result, the elongation was measured with a specimen having the same hardness as the specimen prepared in Comparative Example 1 and Comparative Example 2, and the elongation at the final fracture. This 60mm is shown and the elongation value represents Avg 290%.

As a result, by adding 30 phr of ternary fluorine resin, it imparts functionality to the characteristics of the sealing material of semiconductor equipment used in the existing semiconductor process, thereby improving the elongation characteristics, which were weak in the past, and requiring high elongation. The elongation (%) has been improved for use in process equipment.

Figure 1 is a graph showing the elongation of conventional perfluoro rubber (Perfluoro) rubber.

Figure 2 is a graph showing the elongation of the conventional ternary fluorine rubber compound (Compound)

Figure 3 is a graph showing the elongation of the compound (Compound) in accordance with the present invention.

Claims (2)

Perfluorinated rubber raw material 25 ~ 65% by weight, 15 to 35% by weight of ternary fluorine rubber raw material (raw material), 5 to 50% by weight of a filler formed by mixing barium sulfate (BaSO ₄ ), titanium dioxide (TiO ₂ ) and zinc oxide (ZnO), 2 to 5% by weight of 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 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 Crosslinking accelerator 1 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 of the mixture of -5% by weight, The filler is an improved elongation semiconductor, characterized in that the composition is composed of a mixture of barium sulfate (BaSO ₄ ) 20 to 80% by weight, titanium dioxide (TiO ₂ ) 7 to 45% by weight, zinc oxide (ZnO) 3 to 35% by weight Perfluoro rubber for sealing. delete

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