KR102311780B1 - Elastomer laminate for improving the properties of the sealing structure, and a sealing structure to which the elastomer laminate is applied - Google Patents

Abstract

In an elastomer laminate disclosed by the present specification, a second adhesive layer, a first adhesive layer, and a perfluorinated elastomer layer comprising a curing site are sequentially stacked, wherein the second adhesive layer comprises polyepoxide and a catalyst, the first adhesive layer comprises a coupling agent and a crosslinking agent, the coupling agent comprises a functional group activating the polyepoxide included in the second adhesive layer, the crosslinking agent forms a crosslink between the first adhesive layer and the perfluorinated elastomer, and a cure site of the perfluorinated elastomer comprises nitrile groups.

Description

An elastomer laminate for improving the properties of a sealing structure, and a sealing structure to which the elastomer laminate is applied

The present invention relates to an elastomer laminate for improving the properties of a sealing structure, and to a sealing structure to which the elastomer laminate is applied, and more particularly, to an elastomer laminate capable of improving plasma resistance of a conventional sealing structure, and the like It relates to a sealing structure characterized in that the elastomer laminate is laminated.

In manufacturing an electronic device, various processes are selectively and/or repeatedly performed. As a representative example of the process, an etching process, a chemical or physical vapor deposition process, a photo process, a diffusion process, etc. may be considered. Typically, the above processes are performed inside a sealed chamber, and sealing each connection part in order to maintain a sealed state becomes an important problem.

In general, it is preferred to use a rubber member such as an O-ring for sealing the chamber. However, the conventional rubber member is damaged or destroyed in severe cases due to severe process conditions, which easily causes an obstacle to maintaining the process environment of the chamber.

For example, in at least some semiconductor manufacturing processes, plasma is induced by injecting a process gas into a vacuum chamber and applying power. The plasma used to etch the wafer simultaneously etches the rubber member. Continuous exposure to plasma may cause plasma leakage through the rubber member, which is exemplified as a key cause of process failure.

In the same vein, the condition of high temperature or high pressure applied to the inside of the chamber is another cause of damage to the rubber member. In particular, high temperature or high pressure conditions and plasma conditions are mixed to promote separation of the rubber member, and in severe cases, a problem in which the damaged portion of the rubber member is attached to the wafer may occur.

In order to solve the above-described problems, the development of a rubber member with improved plasma resistance and chemical resistance has been made. For example, as a rubber member, a fluoroelastomer (eg, FKM) or a perfluoroelastomer (eg, FFKM) has been proposed. Both FKM and FFKM are characterized by increased plasma and chemical resistance by fluorination of the elastomer. However, fluorinated elastomers are unsatisfactory in physical properties, corrosion resistance, and plasma resistance, and perfluoroelastomers have a significant supply cost, which is pointed out as a cause of increasing production costs.

On the other hand, Patent Document 1 discloses that Japanese Patent Application Laid-Open No. 2007-277340 (Patent Document 1) is an adhesive composition having high adhesion between a metal support and a perfluoroelastomer, per 100 parts by weight of a phenol resin, 50 * parts by weight of a silane couple. A vulcanized adhesive composition comprising a ring agent and 50 * parts by weight of an organometallic compound is disclosed.

However, the means of Patent Document 1 contains a fundamental limitation in that it cannot prevent consumption of the perfluorinated elastomer by plasma. Moreover, although the vulcanized adhesive composition disclosed in Patent Document 1 is undesirable in terms of manufacturing cost, the organometallic compound released from the adhesive by plasma may adhere to the wafer or the inside of the chamber, and may cause defects.

Japanese Laid-Open Patent Publication No. 2007-277340

The present invention has been developed to solve the above-described technical problem, and an object of the present invention is to provide a laminate of a perfluorinated elastomer with improved versatility.

In addition, an object of the present invention is to improve the plasma resistance compared to the cost of the sealing structure through the utilization of the elastomer laminate.

The present inventors have devised an invention including the following configuration as a result of research in order to solve the above-described problems. Specifically, the present specification includes a second adhesive layer; a first adhesive layer; and an elastomeric laminate in which a perfluorinated elastomer layer including a curing site is sequentially laminated.

In each elastomer laminate of the present invention, the second adhesive layer includes polyepoxide and a catalyst, the catalyst capable of promoting crosslinking between the elastomer and the second adhesive layer; the first adhesive layer includes a coupling agent and a crosslinking agent, the coupling agent includes a functional group activating the polyepoxide included in the second adhesive layer, and the crosslinking agent forms a crosslink between the first adhesive layer and the perfluorinated elastomer; The cure site of the perfluorinated elastomer contains nitrile groups.

In each elastomer laminate of the present invention, the polyepoxide is creosol novolac, epichlorohydrin/tetraphenylol ethane, bisphenol A/epichlorohydrin, novolac/bisphenol A, epichlorohydrin/phenol - formaldehyde, 9,9-bis-2,3-epoxypropylphenylfluorene, bisphenol AF/epichlorohydrin, novolac/bisphenol AF, and combinations thereof.

In each elastomer laminate of the present invention, the catalyst is preferably selected from peroxide, perfluoro carboxylic acid salt, triallyl isocyanurate, tri(methyl)allyl isocyanurate, and combinations thereof.

In each elastomer laminate of the present invention, the functional group of the coupling agent is preferably at least one selected from the group consisting of an epoxy group, an amine group, and a mercapto group.

In each elastomer laminate of the present invention, the crosslinking agent is preferably at least one crosslinking agent selected from the group consisting of an oxazole compound, a thiazole-forming compound and an imidazole-forming compound.

In each elastomer laminate of the present invention, the crosslinking agent is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BOAP), 4,4'-sulfonylbis(2-aminophenol) At least one selected from the group consisting of [bis(3-amino-4-hydroxyphenyl)sulfone], 3,3'-diaminobenzidine, and 3,3',4,4'-tetraaminobenzophenone is more preferable. .

On the other hand, the present specification is a fluorinated elastomer; and each of the elastomer laminates of the present invention; as a sealing structure comprising, a second adhesive layer of the elastomer laminate is attached to the fluorinated elastomer.

Through the adoption of the above-described means, the present invention can easily improve the plasma resistance, durability, etc. of the conventional sealing structure by crosslinking the bonding between one or more fluorinated elastomers.

On the other hand, the present invention can enjoy the above-described effects without excessive physical deformation of the sealing structure by providing an elastomer laminate that can be universally applied to the conventional conventional sealing structure.

On the other hand, in the sealing structure of the present invention, by excluding the use of inorganic compounds or organometallic compounds, it is possible to suppress contamination of production equipment by residues separated from the sealing structure.

On the other hand, the present invention additionally discloses a sealing structure having improved durability, plasma resistance, etc. by stably positioning the perfluorinated elastomer on the surface thereof.

The terms used in this application are only used to describe specific examples. Therefore, for example, a singular expression includes a plural expression unless the context clearly requires it to be singular. In addition, terms such as "comprises" or "comprises" used in the present application are used to clearly indicate that there is a feature, step, function, component, or a combination thereof described in the specification, and other features It should be noted that it is not intended to preliminarily exclude the existence of elements, steps, functions, components, or combinations thereof.

Meanwhile, unless otherwise defined, all terms used herein should be regarded as having the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Accordingly, unless explicitly defined herein, certain terms should not be construed in an unduly idealistic or formal sense.

Specifically, the present specification includes a second adhesive layer; a first adhesive layer; and an elastomeric laminate in which a perfluorinated elastomer layer including a curing site is sequentially laminated. In other words, a first adhesive layer is laminated on one surface of the perfluorinated elastomer layer, and the second adhesive layer is laminated on one surface of the first adhesive layer that is not in contact with the perfluorinated elastomer layer. Accordingly, the first adhesive layer may be understood as a layer positioned between the second adhesive layer and the perfluorinated elastomer layer. Hereinafter, each layer included in the elastomer laminate of the present invention will be described in detail.

In each elastomer laminate of the present invention, the second adhesive layer includes polyepoxide and a catalyst, and the catalyst can promote crosslinking between the elastomer and the second adhesive layer.

In each elastomer laminate of the present invention, the polyepoxide is creosol novolac, epichlorohydrin/tetraphenylol ethane, bisphenol A/epichlorohydrin, novolac/bisphenol A, epichlorohydrin/phenol - formaldehyde, 9,9-bis-2,3-epoxypropylphenylfluorene, bisphenol AF/epichlorohydrin, novolac/bisphenol AF, and combinations thereof.

The polyepoxide of the present invention is commercially available, and the use of the following products can be considered preliminary. Those skilled in the art will recognize that readily available epoxides include styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ether of bisphenol A (e.g., Hexion Specialty Chemicals). Trademarks "EPON 828", "EPON 1004F", and "EPON 1001F" from Hexion Specialty Chemicals, and "DER-332" from Dow Chemical Co., Midland, Michigan, USA " and "DER-334", a diglycidyl ether of bisphenol F (e.g., "ARALDITE GY281" from Ciba-Geigy Corp., and Hexion Specialty Chemicals) trade name “EPON 862”), vinylcyclohexane dioxide (eg, “ERL-4206” from UnionCarbide Corp.), 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexene carboxylate (e.g. Union Carbide trade name "ERL-422"), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane (e.g. Union Carbide trade name " ERL-4234"), bis(3,4-epoxycyclohexyl) adipate (eg, Union Carbide trade name "ERL-4299"), dipentene dioxide (eg Union Carbide trade name "ERL-4269"), epoxy polybutadiene (eg, FMC Corp. under the trade name “OXIRON 2001”), flame retardant epoxide resins (eg, Dow Chemical under the trade name “DER-542”), 1,4- Butanediol diglycidyl ether (eg, trade name "Araldite RD-2" from BASF Corp.), diglycidyl ether of hydrogenated bisphenol A-based epoxide resin (eg, Hexion Specialty Chemicals) trade name "EPONEX 1510"), and polyglycidyl ethers of phenol-formaldehyde novolac (e.g., the Dow Chemical trade name "DEN- 431" and "DEN-438") may be considered.

이상의 온도조건에서 분해되지 않는 것을 특징으로 한다. The polyepoxides of the present invention are expected to have stability at relatively high temperatures. In particular, polyepoxide containing a phenol group is known to have stability under high temperature conditions. For example, 200

It is characterized in that it does not decompose under the above temperature conditions.

As a polyepoxide having the above-mentioned characteristics, creosol/novolac, epichlorohydrin/tetraphenylol ethane, bisphenol A/epichlorohydrin, novolac/bisphenol A, epichlorohydrin/phenol-formaldehyde , 9,9 bis-2,3 epoxypropylphenyl fluorene, bisphenol AF/epichlorohydrin, novolac/bisphenol AF, and combinations thereof are contemplated.

In each elastomer laminate of the present invention, the second adhesive layer further includes a catalyst, and the catalyst can promote crosslinking between the elastomer and the second adhesive layer. At this time, it is preferable that the elastomer is a fluorinated elastomer.

As an example of the above-mentioned fluorinated elastomer, TFE (Tetrafluoroethylene) / PAVE (Perfluoro (alkylvinylidene ether) copolymer, TFE / HFP (Hexafluoropropylene) copolymer, TFE / Et (ethylene) copolymer, TFE / HFP / Et copolymer, TFE /HFP/VdF (Vinylidene Fluoride) copolymer, TFE/PAVE/CTFE (Chlorotrifluoroethylene) copolymer, CTFE/Et copolymer, VdF/PMVE (perfluoromethylvinylether)/TFE copolymer, HFP/VdF copolymer, and HFP/VdF/ It may be one selected from the group consisting of TFE, and one copolymer selected from the group consisting of VdF / PMVE / TFE copolymer, HFP / VdF copolymer, and HFP / VdF / TFE in terms of ease of processing and process unit cost desirable.

In each elastomer laminate of the present invention, the catalyst is preferably selected from peroxide, perfluoro carboxylic acid salt, triallyl isocyanurate, tri(methyl)allyl isocyanurate, and combinations thereof.

In particular, as a catalyst for promoting the formation of crosslinks between the present second adhesive layer and the fluorinated elastomer, the use of peroxide is recommended. For example, the use of peroxides capable of generating free radicals at curing temperatures is preferred. Since the second adhesive layer of the present invention can be activated by receiving residual heat from the first adhesive layer, it can be said that the use of peroxide capable of generating free radicals at a temperature of about 50° C. is most preferable.

As preferred examples of the peroxide satisfying the above, 2,5-dimethyl-2,5-di(t-butylperoxy)3-hexyne, and 2,5-dimethyl-2,5-di(t) -Butylperoxy)hexane, dicumyl peroxide, dibenzoyl peroxide, t-butyl perbenzoate, α,α′-bis(t-butylperoxy-diisopropylbenzene), and di[1,3- One or more peroxides selected from the group consisting of dimethyl-3-(t-butylperoxy)-butyl]carbonate are contemplated.

For example, the polyepoxide of the second adhesive layer of the present invention may be used to improve adhesion with the first adhesive layer. On the other hand, the catalyst of the second adhesive layer of the present invention may be used to improve adhesion between the second adhesive layer and the elastomer, preferably the fluorinated elastomer. However, in setting the detailed composition of the second adhesive layer of the present invention, the following matters may be considered. For example, in the second adhesive layer of the present invention, the reaction between the polyepoxide and the catalyst needs to be relatively suppressed. Therefore, the catalyst is preferably a peroxide from the viewpoint of being able to form an epoxide by reacting with alkylene while inhibiting a direct reaction with the epoxide.

On the other hand, when the total weight of the second adhesive layer is 100, the peroxide catalyst as described above is preferably included between 0.01 parts by weight and 5 parts by weight, more preferably between 0.1 parts by weight and 2 parts by weight. , It is most preferably included between 0.2 parts by weight and 1 part by weight.

Meanwhile, in each elastomer laminate of the present invention, the first adhesive layer includes a coupling agent and a crosslinking agent, the coupling agent includes a functional group activating the polyepoxide included in the second adhesive layer, and the crosslinking agent includes the first adhesive layer Cross-links can form between the perfluorinated elastomer and the perfluorinated elastomer.

In particular, in the first adhesive layer of the present invention, the coupling agent is added for the purpose of improving the adhesive force between the first adhesive layer and the second adhesive layer, and the crosslinking agent is added for the purpose of improving the adhesive force between the first adhesive layer and the perfluorinated elastomer is added as As will be described later, both the coupling agent and the crosslinking agent induce the formation of a new covalent bond between the layers, thereby improving the adhesion between the respective layers.

In each elastomer laminate of the present invention, the coupling agent may be either a silane coupling agent containing a silicon atom or an aluminate coupling agent containing an aluminum atom. However, it is preferable that the coupling agent of this invention is a silane coupling agent containing a silicon atom from a viewpoint of being inexpensive and excellent in adhesive strength.

For example, as a silane coupling agent satisfying the above-mentioned conditions, for example, vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl The use of one or more coupling agents selected from the group consisting of )-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like may be contemplated. .

On the other hand, in view of the functional group, the coupling agent of the present invention preferably includes at least one functional group selected from the group consisting of an amide group, a urea group, an alcohol group, an alkoxy group, an epoxy group, an amine group, and a mercapto group. The coupling agent of the first adhesive layer including the above-described functional group may react with the polyepoxide of the second adhesive layer to cure the polyepoxide.

The following compounds may be considered as examples of the coupling agent containing the above-described functional group. For example, benzyldimethylamine, benzylamine, N,N-diethyl aniline, melamine, pyridine, hydrazide, and aromatic polyamines such as o-, m-, and p-phenylene diamines, 4,4 '-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodi Phenyl ether, 4,4′-diaminodiphenyl methane, 1,3-propanediol-bis(4-aminobenzoate), fluorene-containing amines (eg 9,9-bis(4-amino) Phenyl) fluorene, 9,9-bis (3-methyl-4-aminophenyl) fluorene, 9,9-bis (3,5-dimethyl-4-methylaminophenyl) fluorene, 9,9-bis (3,5-dimethyl-4-aminophenyl)fluorene, 9,9-bis(3,5-diisopropyl-4-aminophenyl)fluorene, and 9,9-bis(3-chloro-4 -aminophenyl)fluorene); 1,4-bis[α-(4-aminophenyl)-α-methylethyl]benzene, 1,4-bis[α-(4-amino-3,5-dimethylphenyl)-α-methylethyl]benzene, Bis(4-amino-3-methylphenyl)sulfone, 1,1'-biphenyl-3,3'-dimethyl-4,4'-diamine, 1,1'-biphenyl-3,3'-di Methoxy-4,4'-diamine, 4,7,10-trioxatridecane-1,13-diamine, and diaminonaphthalene are relatively stable from a thermal standpoint, including aromatic rings, and contain one or more The amine group may be substituted to effectively initiate the curing reaction of the polyepoxide.

In a similar sense, poly(ether) amines, guanidines (eg dicyandiamide and tetramethyl guanidine), imidazoles (eg 2-ethyl-4-methyl imidazole), cyclohexylamine, diethylene Triamine, triethylenetetraamine, cyclohexyldiamine, tetramethylpiperamine, N,N-dibutyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1, 2-Diamino-2-methyl-propane, 2,3-diamino-2-methylbutane, 2,3-diamino-2-methylpentane, and 2,4-diamino-2,6-dimethyloctane Silver can contain aliphatic or one or more amine groups to effectively form crosslinks with polyepoxides.

In particular, ketimine, aniline (eg, paramethoxy aniline), o-bis amino including a condensation product of 3-aminopropyl triethoxysilane and methyl isobutyl ketone from the viewpoint that the above-mentioned conditions can be satisfied Phenol AF, and combinations thereof, are preferably used as coupling agents.

In the first adhesive layer of the present invention, the content of the silane coupling agent as described above is based on 100 parts by weight of the first adhesive layer from the viewpoint of effectively promoting crosslinking with the second adhesive layer while suppressing self-polymerization of the coupling agent. It is preferably between about 1 part by weight and 5 parts by weight. For example, if it is less than 1 part by weight, crosslinking and curing with the second adhesive layer may not be effectively induced, so that detachment of the second adhesive layer may be a problem. Conversely, if it exceeds 5 parts by weight, the first adhesive layer and the perfluorinated elastomer The adhesion between them may be weakened.

Meanwhile, in each of the elastomer laminates of the present invention, the curing site of the perfluorinated elastomer may include a nitrile group. In the perfluorinated elastomer of the present invention, since a nitrile group is included in the curing site, a ring-forming reaction between the crosslinking agent and the nitrile group of the first adhesive layer can be induced. The cyclic crosslinking newly generated by the reaction of the crosslinking agent and the nitrile group is the basis for strong chemical adhesion between the first adhesion and the perfluorinated elastomer.

내지 350

사이인 것이 바람직고, 250

내지 300

사이인 것이 더욱 바람직하다. As an example of the perfluorinated elastomer having a nitrile group at the curing site as described above, a perfluorinated elastomer, which is a copolymer of tetrafluoroethylene (TFE) and nitrile perfluoro monomer (NPM), may be considered. As described above, the perfluorinated elastomer has a melting point of 200

to 350

preferably between 250

to 300

It is more preferable that it is between.

In addition, the molar ratio of the TFE unit and the NPM unit is preferably between 80 to 20 to 99 to 1 from the viewpoint of providing sufficient plasma resistance and strong adhesion to the first adhesive layer at the same time, and 90 on the extension line of the same viewpoint It is more preferably between 10 to 95 to 5. For example, when TFE is included below the above-mentioned numerical range, it may be disadvantageous in terms of physical properties. Conversely, when included in excess of the above-described numerical range, moldability may be deteriorated and adhesion with the first adhesive layer may not be easy. The content of each monomer in the above-mentioned copolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescence X-ray diffraction analysis.

In each elastomer laminate of the present invention, the crosslinking agent is preferably at least one crosslinking agent selected from the group consisting of an oxazole-forming compound, a thiazole-forming compound and an imidazole-forming compound. Each crosslinking agent is characterized in that it reacts with the curing site contained in the perfluorinated elastomer to form a cyclic crosslinking. For example, the oxazole-forming compound refers to a compound capable of forming an oxazole ring by reacting with a nitrile group at a curing site. In the same context, the thiazole-forming compound refers to a compound capable of forming a thiazole ring by reacting with a nitrile group at a curing site. The imidazole-forming compound refers to a compound capable of forming an imidazole ring by reacting with a nitrile group at a curing site.

The crosslinking agents of the present invention referred to as oxazole-forming compounds, thiazole-forming compounds, or imidazole-forming compounds are as follows. As an example of an oxazole-forming compound, a bis(aminophenol) compound can be considered. As an example of a thiazole-forming compound, a bis(aminothiophenol) compound can be considered. Specifically, as a crosslinking agent included in the first adhesive layer of the present invention, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BOAP), 4,4'-sulfonylbis(2-amino phenol) [bis(3-amino-4-hydroxyphenyl)sulfone], 3,3'-diaminobenzidine, 3,3',4,4'-tetraaminobenzophenone desirable.

In the first adhesive layer of the present invention, when the total weight of the first adhesive layer is 100, the crosslinking agent as described above is preferably included in an amount of 0.01 to 5 parts by weight. By satisfying the above numerical range, it is possible to prevent embrittlement while improving the adhesion of the first adhesive layer of the present invention. On the extension of the same viewpoint, the content of the crosslinking agent of the present invention is more preferably between 0.1 parts by weight and 2 parts by weight, more preferably 1 part by weight.

On the other hand, in the process of preparing the first adhesive layer of the present invention, the use of a solvent is considered to mix a coupling agent, a crosslinking agent, and the like. A person skilled in the art may use a solvent without limitation in the art in order to effectively disperse the coupling agent and the crosslinking agent. For example, by way of example, an alcohol-based solvent. The use of an ester-based solvent or an ether-based solvent may be considered. The solvent included in the first adhesive layer may be evaporated by heating after the first adhesive layer is sufficiently laminated on the perfluorinated elastomer.

On the other hand, the present specification is a fluorinated elastomer; and each of the elastomer laminates of the present invention; as a sealing structure comprising, a second adhesive layer of the elastomer laminate is attached to the fluorinated elastomer. The elastomer laminate included in the sealing structure of the present invention may be understood by applying the above-described bar in the present specification mutatis mutandis.

On the other hand, the fluorinated elastomer used in the sealing structure is TFE (Tetrafluoroethylene)/PAVE (Perfluoro (alkylvinylidene ether) copolymer, TFE/HFP (Hexafluoropropylene) copolymer, TFE/Et (ethylene) copolymer, TFE/HFP/Et copolymer , TFE/HFP/VdF(Vinylidene Fluoride) copolymer, TFE/PAVE/CTFE(Chlorotrifluoroethylene) copolymer, CTFE/Et copolymer, VdF/PMVE(perfluoromethylvinylether)/TFE copolymer, HFP/VdF copolymer, and HFP/ It may be one selected from the group consisting of VdF / TFE, and one copolymer selected from the group consisting of VdF / PMVE / TFE copolymer, HFP / VdF copolymer, and HFP / VdF / TFE in terms of ease of processing and process unit cost chain is preferred.

The sealing structure of the present invention is resistant to high temperature, high pressure, plasma, and chemicals and can be used as a sealing material. There is no particular limitation on the outer shape of the sealing structure. As an example, the sealing structure of the present invention is formed of an O-ring, a flange seal, a packing, a gasket, a pump diaphragm, a plunger seal, a door seal, a lip seal, a face seal, a plate seal, a barrel seal, etc. may be considered to be used.

In particular, since the outer surface of the sealing structure of the present invention is coated with a perfluorinated elastomer excellent in chemical resistance, heat resistance, and plasma resistance, deterioration of the inside of the sealing structure due to plasma or the like can be effectively suppressed. As a result, even though the overall composition is not a perfluorinated elastomer, it is possible to enjoy the effect of improving the durability of the entire sealing structure.

{Examples and Evaluation}

Hereinafter, with reference to embodiments will be described in more detail with respect to what the present specification claims. However, the examples and comparative examples presented in the present specification may be modified in various ways by those skilled in the art to have various forms, and the description of the present specification does not limit the present invention to specific disclosed forms. It should be regarded as including all equivalents or substitutes included in the spirit and scope of the present invention.

Example 1: Preparation of Elastomer Laminate

A composition for the first adhesive layer was prepared by uniformly mixing 5 parts by weight of a silane coupling agent (ketimine) and 0.1 parts by weight of a crosslinking agent ((2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) As the perfluorinated elastomer, PFE-133TZ (FFKM type) of Dyneon was prepared. The composition for the first adhesive layer was brush-coated on one surface of the perfluorinated elastomer, and dried in an air atmosphere for about 20 minutes.

In addition, separately, as a composition for the second adhesive layer, 5 parts by weight of a creosol novolac epoxide resin (epoxy equivalent is about 220 g/eq) and 2,5-dimethyl-2,5-di(t-butylperoxy) ) was prepared by mixing 0.2 parts by weight of 3-hexine.

Preparation Example 1: Preparation of a silane structure

온도조건에서 브러쉬 도포하였다. As a fluorinated elastomer formed on one surface of the elastomer laminate of the present invention, FKM (Dupont's Viton A) having a thickness of about 3.5 mm was used. The composition for the second adhesive layer was applied to one surface of the fluorinated elastomer in an atmospheric atmosphere and 20

The brush was applied under temperature conditions.

온도조건 및 3 MPa의 가압조건에서 가열함으로써 1차적으로 어닐링하여 접착하였다.After that, about 200 of the perfluorinated elastomer to which the composition for the first adhesive layer of Example 1 was applied was first applied.

It was first annealed and adhered by heating under a temperature condition and a pressure condition of 3 MPa.

온도조건에서 2차적으로 어닐링하여 실링 구조체를 제조하였다.Next, the first adhesive layer and the perfluorinated elastomer in a heated state were placed on the fluorinated elastomer to which the composition for the second adhesive layer was applied on the surface. At this time, one surface of the first adhesive layer and one surface of the composition for the second adhesive layer were bonded to each other. After that, under pressure of 2 MPa and 80

A sealing structure was prepared by secondary annealing under temperature conditions.

Comparative Example 1

The fluorinated elastomer of Example 1 in which the elastomer laminate of the present invention was not laminated was used as Comparative Example 1.

Comparative Example 2

A sealing structure was prepared in the same manner as in Preparation Example 1, except for the second adhesive layer.

Comparative Example 3

A sealing structure was prepared in the same manner as in Preparation Example 1 except for the first adhesive layer.

Experimental Example 1 NF ₃ Weight loss measurement by plasma treatment under atmosphere

In order to examine the plasma resistance of the sealing structures according to Preparation Example 1 and Comparative Examples 1 to 3, additional experiments were performed under the following conditions. The experiment was conducted in the ICP Plasma method, NF ₃ gas was supplied at a flow rate of 200 sccm, RF power was 400 Watt, pressure conditions were 50 mTorr, temperature conditions were 120 °C, and the test time was 2 hours. The experimental results can be summarized in Table 1 below. The detailed value of the measured weight was measured to the third decimal place.

Preparation Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Before plasma treatment (g) 2.545 2.389 2.453 2.468 After plasma treatment (g) 2.531 1.531 2.378 2.381 Loss weight (g) 0.014 0.858 0.075 0.087 Weight loss rate (%) 0.55 35.91 3.05 3.52

As can be seen in Table 1, the sealing structure of the present invention has a significantly lower weight loss rate due to plasma compared to the conventional sealing structure (Comparative Example 1) even though it contains the conventional sealing structure (FKM). In the case of Comparative Example 2 and Comparative Example 3, it was confirmed that improved plasma resistance compared to Comparative Example 1 of the present invention. However, Comparative Examples 2 and 3 have a limitation in that it is easy to peel off the perfluorinated elastomer from the surface, as will be described later.

Experimental Example 2: O ₂ Weight loss measurement by plasma treatment under atmosphere

It proceeded in the same manner as in Experimental Example 1, except that the reaction gas was not _{NF 3 but O 2} and the experiment was carried out. The results are shown in Table 2 below.

Preparation Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Before plasma treatment (g) 2.545 2.389 2.453 2.468 After plasma treatment (g) 2.539 1.835 2.395 2.402 Loss weight (g) 0.006 0.554 0.058 0.066 Weight loss rate (%) 0.23 23.18 2.36 2.67

Referring to Table 2, it can be seen that the overall weight loss rate in Experimental Example 2 is lower than in Experimental Example 1. However, in both Experimental Example 1 and Experimental Example 2, the weight loss rate of the sealing structure of Preparation Example 1 was the smallest.

Experimental Example 3: Peeling test of elastomer laminate

In order to test the adhesive strength of the elastomer laminates of Preparation Example 1 and Comparative Examples 2 to 3, a cross-cut test was performed in accordance with ISO 2409. In the cross-cut test, incisions are formed on the upper part of the coating at intervals of 1 mm, and incisions are again formed at intervals of 1 mm in the direction perpendicular to the incision to form a rectangular grid pattern, and then peeled off with tape to peel the coating. How to check if this is happening. For the test, it was applied to one side of the composition tape for the first adhesive layer prepared in Example 1 and utilized. The evaluation criteria are as follows.

A: The coating layer is not separated at all when the tape is peeled off

B: The coating pieces are separated at the vertices of the grid pattern, and the separated area is less than 5%

C: The coating pieces are separated at the vertices and corners of the grid pattern, and the separated area is between 5% and 15%

D: A piece of coating is separated from the edge of the grid, and a part of the square is separated. The separated area is between 15% and 35%.

E: The coating pieces are largely separated along the edges, and a large number of squares are separated. The separated area is between 35% and 65%.

F: The separated area exceeds 65%.

The evaluation results are shown in Table 3 below.

Preparation Example 1 Comparative Example 2 Comparative Example 3 Experiment result A C D

Referring to Table 3, it can be seen that the adhesive strength of the elastomer laminate of Preparation Example 1 is the best, followed by Comparative Example 3 and Comparative Example 2 in the order. According to the above-described experimental results, the elastomer laminate of the present invention includes both the first adhesive layer and the second adhesive layer, and thus has more improved adhesion compared to the elastomer laminate including only the first adhesive layer or only the second adhesive layer. Able to know.

Summarizing the above experimental results, it can be confirmed that the sealing structure to which the elastomer laminate of the present invention is applied has improved properties such as plasma resistance and has advantages over the conventional sealing structure in terms of durability. In addition, it can be confirmed that it is more preferable that the sealing structure of the present invention includes both the first adhesive layer and the second adhesive layer, assuming a situation in which a physical external force acts on the sealing structure of the present invention.

Claims (7)

a second adhesive layer; a first adhesive layer; and a perfluorinated elastomer layer including a curing site, in which the elastomer laminate is sequentially laminated,
The second adhesive layer includes polyepoxide and a catalyst,
The first adhesive layer includes a coupling agent and a crosslinking agent,
The coupling agent is 1 part by weight to 5 parts by weight based on 100 parts by weight of the first adhesive layer, and at least one selected from the group consisting of an epoxy group, an amine group, and a mercapto group, which is a functional group for activating the polyepoxide included in the second adhesive layer. includes,
the crosslinking agent forms a crosslink between the first adhesive layer and the perfluorinated elastomer;
The cured site of the perfluorinated elastomer comprises a nitrile group.
According to claim 1,
The polyepoxide is creosol novolac, epichlorohydrin/tetraphenylol ethane, bisphenol A/epichlorohydrin, novolac/bisphenol A, epichlorohydrin/phenol-formaldehyde, 9,9-bis -2,3-epoxypropylphenylfluorene, bisphenol AF/epichlorohydrin, novolac/bisphenol AF, and combinations thereof.
3. The method of claim 2,
wherein the catalyst is selected from peroxide, perfluoro carboxylic acid salt, triallyl isocyanurate, tri(methyl)allyl isocyanurate, and combinations thereof.
delete According to claim 1,
wherein the crosslinking agent is at least one crosslinking agent selected from the group consisting of an oxazole-forming compound, a thiazole-forming compound and an imidazole-forming compound.
6. The method of claim 5,
The crosslinking agent is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BOAP), 4,4'-sulfonylbis(2-aminophenol)[bis(3-amino-4- hydroxyphenyl)sulfone], 3,3'-diaminobenzidine, and at least one selected from the group consisting of 3,3',4,4'-tetraaminobenzophenone, an elastomer laminate.
fluorinated elastomers; and the elastomer laminate of claim 6, wherein the second adhesive layer of the elastomer laminate is adhered to the fluorinated elastomer.