KR101467101B1 - Compound for sealing - Google Patents

Abstract

The present invention relates to a sealing compound for semiconductor/LCD CVD process equipment which is suitable for a high temperature process and is mixed and designed in order to have excellent plasma resistance. The sealing compound is manufactured by mixing 1.75-2.25 parts per hundred resin of vulcanization catalysts in perfluoro-elastomers prepared by mixing raw gum, curing agents and functional additives related to the hardness and crosslink density of materials in order to accelerate the curing reaction of the perfluoro-elastomers.

Description

SEALING COMPOUND {COMPOUND FOR SEALING}

The present invention relates to a compound used as a sealing material, and more particularly, to a sealing compound of a semiconductor / LCD CVD process equipment, which is suitable for a high-temperature process and has a composition designed to have excellent plasma resistance .

Currently, the development of perfluoro-elastomer (FFKM) technology as a sealing material (hereinafter also referred to as seal material or seal material) of a special material in the field of domestic semiconductor equipment parts is continuously under way. FFKM for heat resistance and plasma enhancement is a key technology applied to high-value-added advanced equipment as a seal material widely applied in the most advanced industrial fields such as semiconductor equipment, LCD equipment, solar cell and aerospace industry.

At present, the processing environment of manufacturing equipment due to the high integration of semiconductor process and LCD process, high density process, high plasma process, and process scale is getting worse and more refined. As a result, the properties of the seal material have reached their limits and it is very difficult to find a seal material suitable for use in process equipment. Therefore, it is urgently required to develop a functional seal material that upgrades the performance of existing seal materials.

In other words, the performance of the rubber used as the actual material of the semiconductor equipment needs to be developed as a material applicable to the process conditions, due to the high integration of the existing semiconductor process and the application of the high density process and the high density plasma process.

In addition, it is urgent to develop a material that can withstand high temperatures and can withstand plasma as a reality of equipments required for high manufacturing yield and low consumable replacement of semiconductor manufacturing equipment.

In addition, the semiconductor equipment industry is a high-tech capital goods industry that manufactures various equipment used to produce semiconductor devices by processing wafers. Currently, it has a very important position in terms of size and importance of the market, and the role of reality as its component material is also becoming very important. The role of reality as a critical core component of semiconductor equipment has a direct impact on semiconductor production, and the role of reality is crucial to producing high yield equipment.

In addition, the development of a rubber material which can withstand the harsh environment of the semiconductor manufacturing process, has excellent heat resistance to increase the yield of semiconductor equipment and frequently replace consumables, has excellent resilience (permanent compressive recovery) and plasma resistance There is a desperate need for a technique capable of improving the characteristics.

Accordingly, the present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a plasma display panel which is excellent in heat resistance and plasma resistance, To provide a sealing compound that is superior in compression set.

A sealing compound according to an aspect of the present invention for solving the above-mentioned problems is a sealing compound comprising a raw material (raw gum), a curing agent, and a functional additive relating to hardness and cross- In order to accelerate the curing reaction of the perfluoro-elastomer with a perfluoro-elastomer, a perfluoro-elastomer is impregnated with 1.75 phr (part per hundred resin) to 2.25 phr of a vulcanization accelerator (catalyst).

According to one embodiment, the functional additive may be 1.5 g Aerosil R-972 and 15 g N-550 (carbon classified as ASTM standard).

According to one embodiment, the perfluoroelastomer is blended with 94 g of Raw Gum and 7.5 g of curing agent 'A', which contains 6 g of raw material, .

According to one embodiment, the perfluoro-elastomer comprises 94 grams of Raw Gum and 7.5 grams of vulcanizing agent A, which contains 6 grams of raw material, wherein the perfluoro-elastomer , 2.7 phr of additional vulcanizing agent for the vulcanization reaction, and 2 phr of Aerosil R-972 which is an additional functional additive relating to the hardness and crosslinking density of the material.

A sealing compound according to another aspect of the present invention comprises a perfluoro-elastomer prepared by blending a raw material, a curing agent, and a functional additive relating to the hardness and crosslinking density of the material, (FFKM D) prepared by blending a polyolefin-based elastomer (FFKM B), a raw material, and a functional additive relating to the hardness and crosslinking density of a material, in a ratio of 50:50, And Aerosil R-972, an additional functional additive associated with the hardness and crosslinking density of the material, and a part per hundred resin to 2.25 phr vulcanization accelerator for the mixed perfluoroelastomer catalyst.

According to one embodiment, the FFKM B is a blend of 94 g of Raw Gum and 7.5 g of a curing agent 'A', which contains 6 g of raw material, and the FFKM B 1.5 g of Aerosil R-972 and 15 g of N-550 (carbon classified as ASTM standard) are added to 100 g of raw material, and 1.5 g of Aerosil R-972 , 3.0 g of N-550 and 25 g of N-990, the additional vulcanizing agent is 2.7 phr relative to the mixed perfluoroelastomer and the additional functional additive is added to the mixed perfluoro-elastomer 2 phr of Aerosil R-972.

A sealing compound according to another aspect of the present invention comprises 94 g of raw material Gum, 7.5 g of vulcanizing agent A, which contains 6 g of raw material, and a functional additive relating to the hardness and crosslinking density of the material A perfluoro-elastomer (FFKM B) prepared by blending 1.5 g of Aerosil R-972 and 15 g of N-550 (carbon classified in accordance with ASTM standard), and 94 g of raw material, 5.0 g 7.5 g of a vulcanizer consisting of a mixture of E-18412 and 2.5 g of E-18600, which contains 6 g of raw material, and 1.5 g of Aerosil R-972 which is a functional additive relating to the hardness and crosslinking density of the material (FFKM C), and 1.5 g of Aerosil R-972, 3.0 g of N-550 which is a functional additive relating to the hardness and crosslinking density of the material, 100 g of the material, and 25 g of N- (FFKM D) prepared by blending 1090 to 990 in a ratio of 40: X: 60-X (where X is 10 to 30) The combined perfluoro-elastomers were further blended with 2 phr of Aerosil R-972, an additional functional additive relating to the hardness and crosslinking density of the material, 13 phr (part per hundred resin) for the vulcanization reaction and 1.75 phr to 2.25 phr Of a vulcanization accelerator (catalyst).

The present invention relates to a sealing material for a chemical vapor deposition (CVD) process of semiconductors and LCDs, which can withstand harsh environments, has excellent heat resistance, provides excellent compression set recovery and plasma resistance, It is possible to reduce the idle state of the equipment due to the power consumption of the semiconductor device, thereby improving the yield of the semiconductor equipment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view for showing the kind of a polymer chain,
Fig. 2 is a view for explaining the characteristics of the elastomer,
3 is a view for explaining the crystallinity of polymers,
Fig. 4 is a graph of a rheometer in the case of a single combination of FFKM B, Fig. 5 is a graph of a flow system in the case of a mixture of FFKM B and FFKM D, and Fig. And Fig.
FIGS. 7 to 12 show the results of TGA (Thermogravimetric Analysis) and DSC (Differential Scanning Calorimeter) analysis of 'FFKM B' alone, 'FFKM D' alone, Fig.

Outline of Elastomer

Generally, an elastomer is manufactured by mixing a rubber material selected from a plurality of raw rubber materials according to the purpose of use, mixing a compounding agent and various additives for imparting various properties to the mixed rubber, complicating molding and crosslinking processes have.

Therefore, the development of rubber requires a lot of skill and knowledge about selection of raw material, characterization of compounding agent and additive, formulation and design from manufacture to product.

The so-called rubber is the first material to be obtained from a rubber tree, which is today called "cured rubber", "vulcanized rubber" and "elastomer". Generally, rubber is divided into natural rubber and synthetic rubber. Synthetic rubbers are synthesized from low molecular weight monomers and made from long chain polymer. Generally, after a synthetic latex in the form of water emulsion is obtained and solidified, the solids are washed and dried to prepare a solid polymer synthesis raw material rubber.

When the compounding agent and the specific additives are mixed and compounding is performed on the synthesized polymer raw material rubber, a material capable of exhibiting specific characteristics to the existing raw material rubber is produced. It is possible to manufacture a product having a specific shape and elasticity by heating the thus-blended rubber material with a certain pressure and heat.

The process of vulcanization (or curing) is a phenomenon in which main chain molecules are tightly bound to each other at a plurality of points along the length of the chain, and the bond between the chain and chain is linked to the rubber To maintain the elasticity and maintain the shape.

The difference between these crosslinking materials is the greatest difference between the raw rubber and the elastomer, and the elastomer is a material that is sufficiently deformed when energy is received from the outside, and has a property of returning to its original state when the energy is removed. The term elastomer itself is derived from an elastic polymer.

Structure and Analysis of Elastomers

1. macromolecules, macromolecules, monomers

Materials such as fibers, plastics, raw rubber, and elastomers are organic compounds composed of macromolecules that are tens of thousands of times more molecules than low molecular organic compounds.

A macromolecule consists of a large number of simple repeating units linked together in a long chain. For this reason, the macromolecule has been termed a polymer which is a composite of greies (many) and meros (part). As mentioned earlier, a unit molecule that synthesizes such a polymer is called a monomer, which is a low molecular weight organic compound capable of forming a polymer by reacting with similar or different molecules. The chemical reaction of these monomers with each other to form a polymer is called polymerization.

2. Polymerization - Polymerization

There are many polymers already present in nature, but how such natural chain molecules are made is not well known. However, it is possible to produce synthetic rubbers by polymerization with monomers. There are two important polymerization reactions for polymerization: addition polymerization and condensation polymerization.

Addition polymerization refers to attaching a monomer molecule to an initial molecule without loss of atoms. Representative examples of the addition polymerization are a process for producing soft plastic (polyethylene) from ethylene gas (Chemical Formula 1). Ethylene is an unsaturated hydrocarbon having a double bond between two carbon atoms. One of these bonds is opened and easily becomes one with the bonds generated in the same way from adjacent ethylene molecules. In this way, a polymer having a long chain saturated from an unsaturated monomer can be produced.

A more complex form of addition polymerization can be found in unsaturated monomers in the form of dienes. Unlike ethylene monomers, these have two conjugated double bonds. An important representative monomer in the diene form is butadiene. Condensation polymerization involves reactions between these bi-functional reactants where small molecules are removed at each stage of polymer production.

Polymerization to produce a polyamide polymer is a representative example of condensation polymerization. A polymer is formed by condensing a diamine (H ₂ NR-NH ₂ ) with a dicarboxylic acid (HOOC-R'-COOH). The product can produce a polymer having a high molecular weight by a continuous reaction And have reactive groups (Formula 2, 3). The by-product water (H ₂ O) is removed at each stage of polymer production.

3. Polymer molecular weight

The molecular weight of a large molecule is equal to the number of repeating units in the molecule times the molecular weight of the repeating unit. For example, the molecular weight of polyethylene can be calculated from the formula (C ₂ H ₄ ) n, which is equal to 28 x n.

Some biopolymers, such as special proteins, are composed of macromolecules with the same molecular weight. However, most synthetic polymers and natural polymers such as cellulose and natural rubber are composed of macromolecules of various molecular weights.

4. Monomers Polymers, copolymers, terpolymers

Homopolymer refers to a polymer having several repeating units, such as polyethylene. If two different monomers (i.e., A and B) are polymerized, the product is referred to as a copolymer, and the arrangement of monomers A and B may be random or intersecting (Formula 4, 5)

Random copolymer

Cross-copolymer

The copolymer may have a continuous repeating unit in the chain, which is referred to as a block copolymer (Chemical Formula 6)

Block copolymer

A tetrapolymer is a polymer produced by polymerization of three different monomers (A, B, and C) (Formula 7).

Graft copolymer

5. Types of polymer chain

Types of polymer chains include linear, branched and crosslinked groups, as shown in Fig. Polymer properties are mainly affected by the length and configuration of macromolecules, the degree of interaction between them, and the presence of functional groups.

6. Types of Polymers

Polymers are classified into four types according to their deformation characteristics in the solid state: plastomers, elastomers, TPE, themoplastic elastomers, and thermoset resins.

Plastomers, such as polyethylene, polystyrene, and polyvinyl chloride (PVC), are composed of interdigitated linear hornblende macromolecules and are interdigitated by intermolecular forces.

These plastomers are permanently deformed in the solid state and can not be recovered even if the force exerted by the strain is completely removed. It is because the macromolecules of the plastomer are loosened and slip when pressed under pressure (see Fig. 2 (a)).

The elastomer is an elastomeric material having a property of almost completely returning to its initial shape after completely removing the applied force. Moreover, the elastomer is not only insoluble in the solvent but also does not melt. Only benzene swells in certain solvents such as methyl ethyl ketone (MEK) and decomposes when heated above the operating temperature range.

Unlike plastomers, these unique properties are due to the macromolecules of the elastomer being crosslinked by chemical bonding (see Figure 2b)

In addition, the elastomer is made from the raw rubber, and various fillers are mixed with it. The compounded state in this way is called 'uncured rubber', and generally a thermoplastic and strong solvent having a viscosity, .

Once the compounded materials are crosslinked, they have high elastic restoring force and lose their tackiness. They are insoluble in the solvent and do not melt even when heated. In addition, it also has resistance to property deterioration caused by various aging, and scrap or defective products can not be reused unless the crosslinking point is chemically or mechanically destroyed.

7. Polymer Crystals and Amorphous Structures

Some polymers may be completely amorphous under normal conditions, but crystallized when they are stretched or in the low temperature region.

Crystallinity is usually used to describe polymers with both crystalline and amorphous regions, these regions are not mechanically separated phases, and some of the same macromolecules have crystallographic regions in the longitudinal direction And the remaining portion is filled with the amorphous region (see FIG. 3).

Thus, polymers use the term semi-crystallinity and some elastomers, especially crosslinked rubbers, tend to exhibit this type of crystallization when stretched.

By receiving an extension force, the chain molecules are oriented in the direction in which they are pulled.

The physical properties of many polymers, such as hardness, modulus, tensile strength, etc., are affected by the crystallinity of the polymer. Polymers that do not show crystallization during tensile show low tensile strength.

For high temperature process FFKM  Mixing design

For the blending design of a perfluoroelastomer (FFKM) for high-temperature process, four compounds, FFKM A, FFKM B, FFKM C and FFKM D (each of these are sometimes referred to as raw materials in some cases) (See Table 1).

First, FFKM A was prepared by mixing 100 g of Raw Gum and 1.5 g of vulcanizing agent D as a curing agent, 1.5 g of Aerosil.RTM. As a functional additive for improving the hardness and crosslinking density characteristics of the material, -972 and 15 g of N-550 (carbon classified by ASTM standard).

Next, FFKM B was prepared by mixing 94 g of raw material (Raw Gum), 7.5 g of vulcanizing agent 'A' (containing 6 g of raw material) as a liquid vulcanizing agent, 1.5 as a functional additive for improving the hardness and cross- g of Aerosil R-972 and 15 g of N-550.

Next, FFKM C is a compound raw material compounded with 94 g of raw material (Raw Gum), 5.0 g of FKM A and 2.5 g of FKM B as vulcanizing agents, and 1.5 g of Aerosil R-972 as a functional additive.

Finally, FFKM D is a mixture of 100 grams of raw material (Raw Gum), 1.5 grams of Aerosil R-972, 3.0 grams of N-550 and 25 grams of N-990 (ASTM standardized carbon) to be.

The crosslinking densities of FFKM A, B, C and D were 0.8, 1.3, 1.3 and 1.9 (mol%), respectively.

Compound FFKME FFKM B FFKM C FFKM D Raw Gum 100 94 94 100 The vulcanizing agent 'A' 7.5 The vulcanizing agent 'D' 1.5 Aerosil R-972 1.5 1.5 1.5 1.5 N-550 15 15 3.0 N-990 25 TiO2 5.0 FKMA 5.0 FKM B 2.5 Polymer fluorine content % F (by NMR) 73.1 Crosslink density Density (mol%) 0.8 1.3 1.3 1.9 Polymer Mooney Viscosity
(121 ° C for 1 '+ 10') Viscosity (MU) 109 MDR (12 minutes) Temperature (℃) 188 188 188 177 MH (in-lb) 9.1 14.7 13.9 23.8 ML (in-ib) 0.8 1.03 1.2 0.8 Ts2 (minute) 3.4 2.9 2.4 4.1 T'50 (minutes) 4.5 4.4 3.4 7.6 T'90 (min) 8.1 8.1 6.4 16.2 Properties (ASTM D412 - Die D) Hardness (Shore A) 73 77 77 78 Tensile Strength (psi) 1690 1910 1755 1750 Elongation (%) 270 155 225 130 Modulus 100% (psi) 715 1210 685 1490 Permanent compression set (compression set)
(%, ASTM D395-Method B) 230 < 0 > C @ 70 hours -25% 43 18 18 230 ° C @ 168 hours - 25% Deformation 51 35 300 < 0 > C @ 70 hours -18% 81 43 300 < 0 > C @ 168 h -18% 85 52

(Comparison of characteristics by raw materials)

As shown in Table 1, it can be seen that the mechanical properties of 'FFKM D' are the best (ie, in the case of 'FFKM D', hardness (Shore hardness) is 78, tensile strength is 1750, elongation is 130 and modulus is 1490). However, since T '90 (time elapsed from the start of the reaction to the point at which 90% of the reaction is completed, as measured by the rheometer) is very slow as 16.2 minutes, the formulation into this state is not suitable . Therefore, it is aimed to find an optimum blend that can impart functionalities by adding an optimal vulcanizing agent, a vulcanization accelerator, and a functional additive.

In addition, since the crosslinking density of 'FFKM D' is designed to be very high at 1.9 mol%, it is necessary to lower the crosslinking density because it is deteriorated in thermal stability when used alone. Therefore, in order to improve the thermal stability, we tried to find the optimum crosslink density by mixing with 'FFKM A', 'FFKM B', and 'FFKM C'.

FFKM Vulcanizing agent  And vulcanization accelerator formulation design

First, the prepared compound raw material FFKM B was compounded while varying the amount of a vulcanization accelerator (catalyst). As a result, in the case where the vulcanization accelerator is not added (the first sample), when the vulcanization accelerator is added in the amount of 0.15 g (the second sample), and when 1 g of the vulcanization accelerator is added (third and fifth samples) (See Table 2).

Compound Primary Secondary Third Fourth 5th FFKM B 100 100 100 100 100 Vulcanizing agent accelerant 0.15 One 2 One Characteristics (ASTM D412 - Die D) Hardness (Shore A) 55 58 65 64 67 Tensile strength (kgf / cm2) 80.8 95.0 89.7 93.9 101.5 Elongation (%) 223.2 239.9 235.4 226.9 213.9 Modulus 100% (kgf / cm2) 18.7 17.9 19.3 18.5 20.7 Permanent compression set (compression set)
(%, ASTM D395-Method B) 300 [deg.] C @ 72 hours -25% Crack Crack Crack 22.7 Crack

(Comparison of Properties of FFKM B with Vulcanizing Agent and Accelerator Mixture)

Example  One

As shown in Table 2, as a result of blending the curing agent and the catalyst with respect to 'FFKM B', the promoter was found to be approximately 2 phr (part per hundred resin) (within the range of 2 phr ± 12.5% And showed the best characteristics when used. On the other hand, when the amount of catalyst used is small (less than 1.75 phr), the result of compression set measurement shows that the sample is cracked due to thermal expansion. In addition, when the amount of the accelerator is more than 2.25 phr, it is confirmed that the supersaturated state has little effect on the improvement of properties as the amount of use increases.

FFKM  Of D The curing agent and  accelerant( catalyst ) Characteristics according to formulation

Table 3 below shows the characteristics of the prepared compound raw material FFKM D as a result of blending a curing agent and a catalyst.

Compound Primary Secondary Third Fourth FFKM D 100 100 100 100 Vulcanizing agent One accelerant 0.15 0.15 One Characteristics (ASTM D412 - Die D) Hardness (Shore A) 67 67 67 67 Tensile strength (kgf / cm2) 87.8 95.4 93.5 83.2 Elongation (%) 171.5 156.1 156.7 141.6 Modulus 100% (kgf / cm2) 26.3 32.2 30.9 33.9 Permanent Compression Set
(%, ASTM D395 - Method B) 300 [deg.] C @ 72 hours -25% crack crack crack crack

(Comparative Example 1)

Comparative Example 1

As shown in Table 3, when both the vulcanizing agent and the vulcanization accelerator were not added (the first sample) and the addition of the vulcanization accelerator was added to the FFKM D, only 0.15 phr of the vulcanization accelerator was added And the addition of 1phr of the vulcanized firstphr and the vulcanization accelerator at the same time, the result of the compression set measurement shows that the sample is cracked due to the thermal expansion. This is due to the high crosslinking density (1.9 mol%) and thermal expansion of 'FFKM D'. In order to improve this, it is necessary to design the optimum crosslinking density by blending the raw materials.

FFKM of Crosslink density  Designed to improve functionality through optimization

For the optimization of cross - linking density, a comparison test was carried out for the single use of each of 'FFMB B' and 'FFKM D' and for mixing blends. In this test, the same vulcanizing agent and vulcanization accelerator compounding ratio were applied.

Compound The primary (Example 2) Secondary (Comparative Example 2) Tertiary (Example 3) FFKM B 100 50 FFKM D 100 50 Vulcanizing agent 2.7 2.7 2.7 Aerosil R-972 2 2 2 accelerant 2 2 2 Characteristics (ASTM D412 - Die D) Hardness (Shore A) 71 75 74 Tensile strength (kgf / cm2) 111.9 111.8 139.8 Elongation (%) 214.1 148.8 213.2 Modulus 100% (kgf / cm2) 26.1 43.5 28.4 Permanent Compression Set
(%, ASTM D395 - Method B) 300 [deg.] C @ 72 hours -25% 22.7 crack 21.96

(Table 4: Comparison of characteristics according to the mixing ratio of 'FFKM B' and 'FFKM D')

Comparative Example 2

As shown in Table 4 above, using 'FFKM D' alone, using 2.7 phr of an additional vulcanizing agent and 2 phr of a vulcanization accelerator, Aerosil® R-972, a functional additive relating to the material crosslinking density and hardness, is used at 2 phr (1.9 mol%) of 'FFKM D' (Comparative Example 2 as a secondary sample), the samples were destroyed by thermal expansion as a result of measurement of permanent compressive recovery, It is very unsuitable for equipment sealing.

Example  2

As shown in Table 4, when compared to Comparative Example 2, the addition amount of 2.7 phr of an additional vulcanizing agent and 2 phr of Aerosil R-972 as an additional functional additive were added to 100 g of 'FFKM B' as shown in Table 4, Generally, when used at a level of 2 phr (part per hundred resin) (within the range of 2 phr ± 12.5% of the test), it was not cracked even at a high temperature of 300 ° C. or higher.

Example  3

In addition, as shown in Table 4, when FFKM B and FFKM D were mixed (50 to 50) and when 100 g of the mixed FFKM was used as a reference, 2.7 phr of an additional vulcanizing agent, 2 phr of an additive additive When Aerosil® R-972 was blended and the accelerator was used in a proportion of 2 phr (part per hundred resin) (in the range of 2 phr ± 12.5% as a result of experiments), it was not cracked even at high temperature of 300 ° C or higher. This Example 3 exhibited better tensile strength characteristics (111.9 vs 139.8 kgf / cm ² ) than the FFKM B alone composition (Example 2) 22.7 vs 21.96) and is suitable for sealing semiconductor equipment which is placed in high temperature and high pressure environment.

Next, FIG. 4 is a graph of a rheometer in the case of a single combination of FFKM B (Example 2), and FIG. 5 is a graph of rheometer in the case of a mixture of FFKM B and FFKM D (Example 3) And FIG. 6 is a graph of a flow system in the case of a single combination of FFKM D (Comparative Example 2). 4 and 6 with reference to Table 5 below, the results of Comparative Example 2 and Comparative Example 2 were compared with those of Example 2 and Example 3, The result of the mixed formulation of 'FFKM B' and 'FFMK D' (Example 3) is the most stable, and in the case of 'FFKM D' alone (Comparative Example 2), the crosslinking reaction is continuously observed.

contents ML MH ts1 tc10 tc50 tc90 S ML S MH TDML TDMH FFKM B
Solo blend 3.1 17.1 0:36 0:38 1:05 3:56 1.4 2.4 0.522 0.140 FFKM B, FFKM D
Blending 2.7 19.3 0:36 0:39 1:12 4:30 1.2 2.9 0.556 0.150 FFKM D
Solo blend 2.7 24.3 0:43 0:39 1:16 4:50 1.3 4.0 0.532 0.164

(The rheometer measurement result of the compounding ratio of FFKM B and FFKM D, the comparison table of Example 2, Example 3 and Comparative Example 2)

In Table 5, ML and MH represent the lowest and highest values, respectively, when the vulcanization torque is expressed as rheometer (red graph in FIGS. 4 to 6), and ts1, ts10, tc10, tc50, Represents the elapsed time up to the point at which the 1% starting point, 10%, 50%, and 90% of the vulcanization reactions occurred.

My Plasma ( Plasma resistance ) Test

Plasma tests were carried out using NF ₃ , O ₂ , CF ₄ and SF ₆ gas, which are mainly used in semiconductor processing, to investigate the chemical characteristics according to the formulation as in Example 2, Example 3 and Comparative Example 2. The plasma test conditions were as follows: the chamber temperature was 200 ° C, the RF power was 1200W, the feed gas was 200sccm, and the process pressure was 150mmTorr. (plasma resistance). For each specimen, three specimens were measured and their average values were shown (see Table 6)

Item
FFKM B alone formulation FFKM D alone formulation FFKM B and FFKM D
Blending NF3 CF4 SF6 O2 NF3 CF4 SF6 O2 NF3 CF4 SF6 O2 Before Weight
(g) 0.810 0.840 0.860 0.810 0.825 0.830 0.830 0.870 0.860 0.840 0.800 0.840 After Weight
(g) 0.225 0.730 0.790 0.760 0.700 0.730 0.790 0.840 0.700 0.730 0.760 0.810 Δ
Weight 0.585 0.110 0.070 0.050 0.125 0.100 0.040 0.040 0.160 0.110 0.040 0.030 Δ Weight ratio
(%) 72.2 13.1 8.1 6.2 15.5 12.0 4.8 4.6 18.6 13.1 5.0 3.6

(A result of the plasma resistance test according to the mixing ratio of FFKM B and FFKM D)

As shown in Table 6, as a result of the plasma plasma test, the sole compounding of 'FFKM D' (Comparative Example 2) showed the highest resistance to plasma, and the single compounding of 'FFKM B' (Example 2) It can be seen that the result is the worst. On the other hand, in the case of the combination of 'FFKM B' and 'FFKM D' (Example 3), resistance to plasma is slightly lower than that of 'FFKM D' alone (Comparative Example 2), but generally similar results are obtained.

Therefore, it can be confirmed that the mixture of FFKM B and FFKM D having the best compression set and excellent resistance to plasma resistance (Example 3) is the optimum combination.

Optimization of thermal expansion through optimization of materials seal Product development

Most seal products used in high-temperature and high-pressure semiconductor and LCD processes are designed to have a thread deformation of 25% or less. Therefore, it is common to measure the permanent compressive recovery rate under the condition of 25% or less. However, in some processes, if the process has a compression ratio of 25% or more and the thermal expansion is not optimized, the yarn breaks down due to the expansion at a certain temperature and pressure, thereby failing to perform the function of the seal.

Therefore, we sought to optimize the composition to achieve the role of yarn even at a compression ratio of over 35% by optimizing the thermal expansion.

Compound Primary Secondary
(Comparative Example 3) Third Fourth FFKME 87.5 87.5 FFKM B 40 40 FFKM C 10 10 FFKM D 50 50 Vulcanizing agent 12.5 12.5 13 6.5 R-972 2 2 accelerant 2 2 2 Properties (ASTM D412 - Die D) Hardness (Shore A) 61 64 71 68 Tensile strength (kgf / cm2) 117.9 152.9 122.6 161.0 Elongation (%) 305.2 333.3 206.3 244.7 Modulus 100% (kgf / cm2) 19.9 19.8 31.5 25.7 Permanent Compression Set
(%, ASTM D395-Method B) 300 [deg.] C @ 72 hours -25% 47.94 20.48 300 DEG C @ 9 hours -35% crack 27.00 crack crack 300 ° C @ 9 hours -40% Deformation 28.10 crack

Comparative Example 3

As shown in Table 7, when 87.5 g of 'FFKM A' having a low crosslinking density of 0.8 mol%, 12.5 g of a vulcanizing agent, and a vulcanization accelerator of 2 phr were mixed with the mixture of the vulcanizing agent and FFKM Secondary sample, Comparative Example 3), even at a compression ratio of 35% or more (deformation), the thermal expansion was reduced and the shape of the yarn was maintained without being broken. However, the 'FFKM A' formulation is not suitable because the permanent compressive decomposition rate at 300 ° C and 25% compression ratio is not good at 47.94% and thus the object of improving the characteristics for high temperature characteristics above 300 ° C is not satisfied.

However, as a result of the test, 'FFKM A' having a crosslinking density as low as 0.8 mol% maintains the shape of the yarn even at a high compression ratio of 35% or more, indicating that there is a correlation between the crosslink density and thermal expansion. We tried to develop an optimal seal product by optimizing the crosslink density and thermal expansion by adding 'FFKM C' formulations to the mixture of 'FFKM B' and 'FFKM D' which showed good results in terms of recovery and resistance to plasma.

Compound Primary Secondary Third FFKM B 40 40 40 FFKM C 10 20 30 FFKM D 50 40 30 Cross-linking agent 13 13 13 R-972 2 2 2 accelerant 2 2 2 Characteristics (ASTM D412 - Die D) Hardness (Shore A) 71 73 76 Tensile strength (kgf / cm2) 122.6 157.2 139.9 Elongation (%) 206.3 227.0 194.6 Modulus 100% (kgf / cm2) 31.5 32.7 46.4 Permanent Compression Set
(%, ASTM D395 - Method B) 300 ° C @ 70 hours - 25% Deformation 20.48 - 26.17 300 ° C @ 24 hours - 35% Deformation crack crack crack

(Comparison of characteristics according to the mixing ratio of FFKM B, FFKM C, FFKM D)

Example  4

The mixing ratio of 'FFKM B', 'FFKM C' and 'FFKM D' was proceeded as shown in Table 8 (the mixing ratio of the first sample: 40 to 10:50, the second sample: 40 to 20:40, The third sample: the ratio of 40 to 30 to 30). 13 phr of the crosslinking agent, 2 phr of the functional additive Aerosil R-972, and 2 phr of the crosslinking accelerator were added in the same manner.

Among these samples, FFKM B was fixed at 40, FFKM C was increased from 10 to 30, and FFKM D was decreased from 50 to 30 in the mixing ratio of FFKM B, FFKM C and FFKM D, Respectively. As a result, the results of permanent compressive decompression rate measurement were relatively good at a compression ratio of 25%.

However, in all of these cases, under the condition of compression ratio of more than 35%, permanent compressive decompression ratio measurement results in destruction of the sample in thermal expansion (all cracks are shown for the 35% deformation in Table 8).

In particular, the higher the content of 'FFKM D' having a high crosslinking density of 1.9 mol% (the primary, secondary and tertiary samples in high order), the permanent compressive decomposition is excellent but the high thermal expansion due to the high crosslink density is optimized It is considered that a combination of 'FFKM A', 'FFKM B', and 'FFKM C' having a lower crosslink density is essential. On the other hand, the lower the crosslink density, the lower the compression set and the lower the mechanical properties such as hardness and tensile strength. Also, the resistance to plasma was decreased as the crosslinking density was lowered.

As a result, FFKM having a low cross-linking density of 1.6 mol% or less is considered unsuitable for use as a sealant structure for high-temperature and high-pressure semiconductor and LCD processes.

Optimized mixing design technology for heat resistance improvement

(Example 2, Figs. 7 and 8), 'FFKM D' alone (Comparative Example 2, Figs. 9 and 10), and 'FFKM B' TGA (Thermogravimetric Analysis) and DSC (Differential Scanning Calorimeter) analysis of the mixture of these compounds (Examples 3, 11 and 12) were carried out. As a result, it was confirmed that decomposition started at 330 ° C there was. As a result, the heat resistance of the raw gum used in this study is considered to be the same.

Conclusion and Application Areas

As a result of blending of the curing agent and the catalyst in the blending design of the compound as the sealing material according to the present invention, the vulcanization accelerator showed the best characteristics when 1.75 to 2.25 phr of the vulcanization accelerator was used.

When the amount of accelerator used is less than that, the result of permanent compressive restoration measurement shows that the sample is destroyed by thermal expansion.

The higher the vulcanization density of the raw gum, the better the mechanical properties such as hareness, modulus and compression set.

When the vulcanization density is less than 1.3 mole%, it is confirmed that the permanent compression recovery ratio is not good enough to be applied to the high temperature and high pressure semiconductor and LCD processes.

The optimum vulcanization density with excellent mechanical properties and chemical resistance is preferably 1.6 to 1.9 mole%.

The TGA (Thermogravimetric Analysis) analysis of the raw materials used in this study confirmed that decomposition started at the same temperature of 330 ° C. As a result, the heat resistance characteristics of the raw materials used in this study are considered to be the same.

Therefore, the heat resistance limit of the raw materials used in this study is suitable for use in high-temperature semiconductor and LCD processes at 330 ° C.

The sealing compound according to the present invention can be applied to o-ring products and yarn products for semiconductors and LCD equipment parts, and further applicable to future special equipment, chemical plant industry, and poor process equipment.

Claims (7)

As a sealing compound,
94 g raw raw material (Raw Gum) composed of perfluoro organic polymer, 7.5 g curing agent for perfluoro organic polymer for vulcanization reaction of the raw rubber raw material, vulcanized organic polymer vulcanizing agent Containing 6 g of the raw rubber raw material and a functional additive consisting of 1.5 g of Aerosil R-972 and 15 g of N-550 (carbon classified according to ASTM standard) to control the hardness and crosslinking density of the material (Part per hundred resin) to 2.25 (parts per hundred resin) per perfluoro-elastomer to promote the curing reaction of the perfluoro-elastomer in a perfluoro-elastomer prepared by blending the perfluoro- by weight of a perfluoro-elastomer vulcanization accelerator (catalyst). delete delete As a sealing compound,
94 g raw raw material (Raw Gum) composed of perfluoro organic polymer, 7.5 g curing agent for perfluoro organic polymer for vulcanization reaction of the raw rubber raw material, vulcanized organic polymer vulcanizing agent Containing 6 g of the raw rubber raw material and a functional additive consisting of 1.5 g of Aerosil R-972 and 15 g of N-550 (carbon classified according to ASTM standard) to control the hardness and crosslinking density of the material (Part per hundred resin) to 2.25 (parts per hundred resin) per perfluoro-elastomer to promote the curing reaction of the perfluoro-elastomer in a perfluoro-elastomer prepared by blending the perfluoro- phr of a vulcanization accelerator for a perfluoro-elastomer,
For the vulcanization reaction of the perfluoro-elastomer, 2.7 phr of perfluoro-elastomer vulcanizing agent is added to the perfluoro-elastomer,
Characterized in that it is prepared by adding 2 phr of Aerosil R-972 to the perfluoroelastomer as an additional functional additive to control hardness and crosslinking density of the material. As a sealing compound,
94 g raw raw material (Raw Gum) composed of perfluoro organic polymer, 7.5 g curing agent for perfluoro organic polymer for vulcanization reaction of the raw rubber raw material, vulcanized organic polymer vulcanizing agent Containing 6 g of the raw rubber raw material and a functional additive consisting of 1.5 g of Aerosil R-972 and 15 g of N-550 (carbon classified according to ASTM standard) to control the hardness and crosslinking density of the material 100 g of the raw rubber raw material composed of the perfluoro organic polymer and 1.5 g of Aerosil R-972 and 3.0 (trade name) were added to adjust the hardness and crosslinking density of the material, and the perfluoro-elastomer g of N-550, and 25 g of N-990 were added to a mixed perfluoro-elastomer prepared by mixing perfluoro-elastomer in a ratio of 50 to 50,
For the vulcanization reaction of the mixed perfluoro-elastomer, 2.7 phr of perfluoro-elastomer vulcanizing agent is further added to the mixed perfluoro-elastomer,
To control the hardness and crosslinking density of the material, 2 phr of Aerosil R-972 was added as an additional functional additive to the perfluoroelastomer,
Wherein the perfluoro-elastomer is prepared by blending 1.75 phr (part per hundred resin) to 2.25 phr of a perfluoro-elastomer vulcanization accelerator with respect to the mixed perfluoroelastomer. delete As a sealing compound,
94 g raw raw material (Raw Gum) composed of perfluoro organic polymer, 7.5 g curing agent for perfluoro organic polymer for vulcanization reaction of the raw rubber raw material, vulcanized organic polymer vulcanizing agent Containing 6 g of the raw rubber raw material and a functional additive consisting of 1.5 g of Aerosil R-972 and 15 g of N-550 (carbon classified according to ASTM standard) to control the hardness and crosslinking density of the material A perfluoro-elastomer prepared by blending a perfluoro-elastomer,
94 g of raw rubber raw material composed of the perfluoro organic polymer, 7.5 g of a vulcanization organic polymer vulcanizing agent for vulcanization reaction of the raw rubber raw material, 5.0 g of a fluoro elastomer vulcanizing agent for perfluoro organic polymer And 2.5 g of a fluoroelastomer different from that of the fluoroelastomer. The mixture contains 6 g of the raw rubber raw material. To control the hardness and crosslinking density of the material, 1.5 g Of a perfluoro-elastomer prepared by blending a functional additive made of Aerosil R-972,
100 g of the raw rubber raw material composed of the perfluoro organic polymer and a functional additive composed of 1.5 g of Aerosil R-972, 3.0 g of N-550 and 25 g of N-990 were added to control the hardness and crosslinking density of the material, To prepare a perfluoro-elastomer,
To a mixed perfluoro-elastomer mixed at a ratio of X: 60-X (where X is 10 to 30)
For the vulcanization reaction of the mixed perfluoro-elastomer, 13 phr of perfluoro-elastomer vulcanizing agent is further added to the mixed perfluoro-elastomer,
To control the hardness and crosslinking density of the material, 2 phr of Aerosil R-972 was added as an additional functional additive to the perfluoroelastomer,
Wherein the perfluoro-elastomer is prepared by blending 1.75 phr (part per hundred resin) to 2.25 phr of a perfluoro-elastomer vulcanization accelerator with respect to the mixed perfluoroelastomer.

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