JP2006218629A - Fluororubber-metal laminated gasket material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluororubber-metal laminated gasket material causing no adhesion peel even if used in an electrolyte simultaneously with a different kind of a metal in a practical use environment as a gasket and making it possible to evaluate the retention of sufficient adhesiveness even in a method for confirming and evaluating test solution resistance. <P>SOLUTION: The fluororubber-metal laminated gasket material is constituted by successively laminating a surface treatment agent layer, which contains a zirconium element, a phosphorus element and an aluminum element, a silica-containing resinous vulcanized adhesive layer and a fluororubber layer on a stainless steel sheet. The element mass ratio of zirconium to phosphorus in the surface treatment agent layer is 95:5-60:40 and the element mass ratio of zirconium to aluminum is 90:10-10:90. This fluororubber-metal laminated gasket material causes no adhesion peel even if it is used in an electrolyte such as water, an LLC aqueous solution or the like simultaneously with a metal different from stainless steel in kind such as aluminum, iron or the like in the practical use environment as the gasket. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a fluororubber-metal laminated gasket material. More specifically, the present invention relates to a fluororubber-metal laminated gasket material suitably used as an engine cylinder head gasket or the like.

  Stainless steel is used for gaskets for engine cylinder heads that require LLC (long life coolant) resistance. However, even if vulcanized adhesive is applied directly to stainless steel and rubber is vulcanized and bonded, it is resistant. The liquid adhesion durability is poor, and adhesion peeling occurs when the immersion test is performed.

  As a countermeasure against this, as a pretreatment for applying vulcanized adhesive, chromate treatment is applied to the surface of stainless steel to improve resistance to water and LLC aqueous solution, but chromium-free treatment that does not contain hexavalent chromium. The demand for is getting stronger.

The present applicant previously described dihydrobenzoic acid as a phenolic adhesive in a fluororubber-metal laminate comprising a metal plate / alkoxysilane hydrolyzate or partial condensate undercoat adhesive / phenolic resin-based topcoat adhesive / fluororubber. It has been proposed to use a vulcanized adhesive containing a thermosetting resin having an oxazine ring and a resol type phenolic resin. It has been confirmed that this fluororubber-metal laminate can withstand a long time at a considerably high temperature in a simple immersion test in various aqueous solutions such as water and LLC aqueous solution. However, such fluororubber-metal laminates and gaskets using them as a raw material often have different metals in contact with each other in the same liquid in the actual usage environment. There is a phenomenon in which an electric potential is generated between the plate and the dissimilar metal and adhesion peeling is promoted.
JP 2004-202725 A

  When the fluororubber-stainless steel laminate is used in contact with an electrolyte such as water or an LLC aqueous solution, the applicant of the present invention will be able to determine the presence of the laminate metal if there is a corrosive metal such as aluminum or iron in the same solution. There is a phenomenon in which an electric potential is generated between the aluminum and iron, causing a corrosion reaction (anode reaction), and a cathode reaction occurs on the stainless steel surface of the laminate, which causes peeling. I found. A prominent example of this is that when a fluororubber-stainless steel laminate is used as the gasket for an engine cylinder head made of aluminum, the blister and adhesion can be done in a shorter time than when the laminate is subjected to immersion testing under similar temperature conditions. Examples include phenomena such as peeling.

  A method that can reproduce such a phenomenon in the laboratory is necessary. For this purpose, a rubber stainless steel laminate and a metal having a smaller ionization energy than hydrogen, such as an aluminum plate, are immersed in the test solution, and in this case, near the top. In a semi-immersed state so as to be located above the liquid level, the exposed portions of the immersion liquid are brought into contact directly or via a conductive wire, for example, a rubber stainless steel laminate and a metal plate having a smaller ionization energy than hydrogen As a state of being immersed in a test solution so as to be in contact with an inverted V shape, after being immersed for a predetermined time in a state where they are not in contact with each other, the liquid resistance of the test liquid is measured or evaluated for the deterioration of the characteristic value of the laminate A confirmation evaluation method has been proposed previously (Japanese Patent Application No. 2003-282441).

  The object of the present invention is to prevent adhesion peeling even when used in the electrolyte at the same time as a dissimilar metal in an actual use environment as a gasket, and to maintain sufficient adhesion even in the above test liquid resistance confirmation evaluation method. The object is to provide a fluororubber-metal laminated gasket material that can be evaluated as being.

  An object of the present invention is to provide a fluororubber obtained by sequentially laminating a surface treatment agent layer containing a zirconium element, a phosphorus element and an aluminum element, a silica-containing resin-based vulcanized adhesive layer and a fluororubber layer on a metal steel plate. Achieved by metal laminated gasket material. Zirconium and phosphorus in the surface treatment agent layer are used in an element mass ratio of 95: 5 to 60:40, and zirconium and aluminum are used in an element mass ratio of 90:10 to 10:90, respectively.

  The fluororubber-metal laminated gasket material according to the present invention is bonded even if it is used at the same time as a metal different from stainless steel such as aluminum and iron in an electrolyte such as water and LLC aqueous solution in an actual use environment as a gasket. Does not peel off. In addition, in the test liquid resistance confirmation evaluation method, sufficient water resistance and LLC resistance are maintained. Further, even in a fluororubber-metal laminated gasket material in which fluororubber is vulcanized and bonded to chromate-treated stainless steel, peeling occurs when such a test liquid resistance confirmation evaluation method is performed for a long time. This is not the case with the fluororubber-metal laminated gasket material, and it is possible to provide a chromium-free fluororubber-metal laminated gasket material having water resistance higher than that of the chromate-treated rubber metal laminate.

  Therefore, the fluororubber-metal laminated gasket material of the present invention is not only effectively used as an engine cylinder head gasket, but also used as a rubber metal composite part for automobiles, industrial machines, etc. that require water resistance. it can.

  As the metal steel plate, iron, aluminum, copper and the like, alloys thereof, stainless steel plates, and the like are used. Generally, stainless steel plates such as SUS301, SUS301H, SUS304, and SUS430 are used. On these steel plates, a surface treatment agent layer containing each element of zirconium, phosphorus and aluminum is formed.

  In this surface treatment agent layer, the element mass ratio of zirconium and aluminum is 90:10 to 10:90, preferably 70:30 to 30:70, and the element mass ratio of zirconium and phosphorus is 95: 5 to 60:40, Preferably, it is formed at a ratio of 90:10 to 68:32. When the amount of aluminum is larger than this, film formation is poor or the film is easily detached, whereas when it is less than this, heat resistance and water resistance are lowered. On the other hand, if the amount of phosphorus is larger than this, the heat resistance is lowered, while if it is smaller than this, film formation is poor.

  The zirconium component in these films is present in the form of zirconium phosphate or zirconium oxide, but is preferably present in the form of zirconium phosphate. As a component for forming these, a treatment liquid containing zirconium nitrate, zirconium acetate, zirconium sulfate, ammonium zirconium carbonate, zirconium oxide or the like is used, but a treatment liquid containing ammonium zirconium carbonate is preferably used. Aluminum is present in the film by a treatment solution containing aluminum silicate, alumina (aluminum oxide), aluminum hydroxide, aluminum sulfate or the like, but is preferably present in the form of aluminum oxide. The phosphorus component in the film is supplied by adding phosphoric acid, and the amount added is adjusted so that the Zr: P mass ratio is 95: 5 to 60:40.

  In addition, in the surface treatment agent, in order to enhance the effect and ensure the stability of the liquid, inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, organic acids such as formic acid, acetic acid, ammonium hydroxide (ammonia water) Nitrogen-containing alkaline compounds such as ethylenediamine, triethylenetetramine, morpholine and choline can also be added.

The surface treatment agent is a solution in which the above components are dissolved or dispersed in water, and is coated on one side by a method such as spraying, dipping, brushing, or roll coater on a steel plate degreased with alkali or the like, preferably a stainless steel plate. The amount is about 10 to 1000 mg / m ² , preferably about 50 to 500 mg / m ² , dried at room temperature or warm air, and then baked at about 100 to 250 ° C. for about 0.5 to 20 minutes. Is implemented.

  A silica-containing resin-based vulcanized adhesive layer is further formed on the steel sheet that has been subjected to the surface treatment treatment, preferably a stainless steel sheet.

Silica (silicon oxide) is a dispersion of dry or wet silica having a SiO ₂ content of 85% or more in an organic solvent or water, preferably high-purity anhydrous silica fine particles in an organic solvent or water. So-called colloidal silica dispersed in colloidal form is used. The colloidal silica has an average particle diameter of 1 to 50 nm, preferably 10 to 30 nm, and is dispersed in an organic solvent such as methanol, methyl ethyl ketone, or methyl isobutyl ketone, and is a commercially available product, for example. Methanol silica sol (Nissan Chemical Industries product: Dispersed in methanol at a solid concentration of 30% by weight), Snowtex MEK-ST (Company product; Dispersed in methyl ethyl ketone at a solid content of 30% by weight), Snowtex MIBK -ST (Company product; dispersed in methyl isobutyl ketone at a solid content of 30% by weight) is used.

  Such silica is generally used in a state where it is dispersed in a thermosetting phenol resin or in combination with a thermosetting phenol resin.

  As a phenol resin used as one component of the vulcanizing adhesive, a phenol resin having a dihydrobenzoxazine ring is also used in addition to a resol type phenol resin, and together with these phenol resins, a cresol novolac type epoxy resin, a phenol novolac type Other thermosetting resins such as a novolac type epoxy resin such as an epoxy resin can be used in combination, and further, an unvulcanized fluororubber or a compound thereof can be added and used.

  As resol type phenolic resin, two phenolic hydroxyl groups such as phenol, p-cresol, m-cresol, p-tert-butylphenol, p-phenylphenol, bisphenol A, etc. at the o-position and / or p-position Alternatively, it is obtained by subjecting phenols having three substitutable nuclear hydrogen atoms or a mixture thereof and formaldehyde to a condensation reaction in the presence of an alkali catalyst such as sodium hydroxide, sodium carbonate, magnesium hydroxide or ammonia. A resin having a softening point of about 80 to 150 ° C is used, and preferably a resin having a softening point of 100 ° C or higher produced from m-cresol, a p-cresol mixture and formaldehyde is used.

  As the novolak type phenol resin, a product obtained by reacting the above condensation reaction in the presence of an acid catalyst such as hydrochloric acid or oxalic acid is used.

特開２００４−８３６２３号公報 In addition, as the thermosetting phenol resin having a dihydrobenzoxazine ring, any thermosetting phenol resin having a dihydrobenzoxazine ring and being cured by a ring-opening reaction of the dihydrobenzoxazine ring should be used. For example, a dihydro-2H-1,3-benzoxazine derivative is synthesized from a compound having a phenolic hydroxyl group, a primary amine and formaldehyde, as shown in the following formula.

JP 2004-83623 A

  The compound having a phenolic hydroxyl group must have a hydrogen atom bonded to at least one o-position with respect to the phenolic hydroxyl group of the aromatic ring, and preferably a plurality of phenolic hydroxyl groups in the molecule. Existing multifunctional phenols are used. Specifically, phenols such as catechol, resorcinol and hydroquinone, dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene, bisphenols such as bisphenol A and bisphenol F, novolac type or resole type phenol Examples thereof include phenol resins such as resin, melamine phenol resin and alkylphenol resin.

  Examples of primary amines include aromatic amines such as aniline and toluidine, and aliphatic amines such as methylamine and ethylamine.

  Two moles or more of formaldehyde is used for each mole of the compound having a phenolic hydroxyl group and the primary amine, and the reaction temperature is about 70 to 130 ° C., preferably about 90 in the presence of an oxalic acid catalyst. After reacting at ~ 110 ° C for about 1/3 to 4 hours, remove the unreacted phenolic compounds, primary amines, formaldehyde, etc. under reduced pressure at 120 ° C or less, and heat with dihydrobenzoxazine ring A curable resin is obtained.

  The silica and the resin component are used in a proportion of about 5 to 200 parts by weight, preferably about 10 to 100 parts by weight, based on 100 parts by weight of the resin component. When the proportion of silica is larger than this, the initial adhesiveness is lowered, whereas when used at a proportion smaller than this, the water resistance is lowered.

  When an epoxy resin is used in combination with a phenol resin, the epoxy resin is used in an amount of about 500 parts by weight or less, preferably about 20 to 200 parts by weight per 100 parts by weight of the phenol resin. The initial adhesiveness is further improved by the combined use of the epoxy resin, but if it is used in a proportion higher than this, the water resistance is lowered. When an epoxy resin is used in combination, a curing accelerator such as tertiary amine or imidazole can be used at the same time. The fluororubber or compound thereof is added at a rate of about 500 parts by weight or less, preferably about 30 to 200 parts by weight per 100 parts by weight of the phenol resin. Addition of fluororubber (compound) further improves the heat resistance of the vulcanized adhesive layer, but addition in a proportion higher than this decreases the water resistance.

Silica-containing resin-based vulcanized adhesives generally use alcohol-based organic solvents such as methanol, ethanol, and isopropanol, ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, or a mixed solvent thereof. Prepared as a 10 wt% organic solvent solution, applied in the same manner as in the case of the surface treatment agent at a weight per side of about 50 to 2000 mg / m ² , dried at room temperature or warm air, and then about 100 to A baking process is performed at 250 ° C. for about 1 to 20 minutes.

  On the vulcanized adhesive layer thus formed, an unvulcanized fluororubber compound is formed on both sides so that a vulcanizate layer having a thickness of about 5 to 120 μm on one side is formed on both sides. It is applied as an organic solvent solution.

  As the fluororubber, both polyol vulcanizability and peroxide vulcanizability can be used. Examples of the unvulcanized fluororubber compound include the following blending examples.

  As the polyol vulcanizable fluoro rubber, generally vinylidene fluoride and other fluorine-containing olefins such as hexafluoropropene, pentafluoropropene, tetrafluoroethylene, trifluorochloroethylene, vinyl fluoride, perfluoro (methyl vinyl ether), etc. Examples of such a fluororubber include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Polyol is vulcanized with polyhydroxy aromatic compounds such as (hydroxyphenyl) perfluoropropane and hydroquinone.

  Examples of the peroxide vulcanizable fluororubber include fluororubbers having iodine and / or bromine in the molecule, and these fluororubbers are added by organic peroxides generally used for peroxide vulcanization. Sulfurized (crosslinked). In this case, it is preferable to use a polyfunctional unsaturated compound represented by triallyl isocyanurate together with the organic peroxide.

(Formulation example)
Fluoro rubber (DuPont product Viton E45) 100 parts by weight Calcium metasilicate 40 部
MT carbon black 20 〃
Magnesium oxide (Kyowa Chemical Product Magnesia # 150) 6 〃
Calcium hydroxide 3 〃
Vulcanizing agent (DuPont product curative # 30) 2 〃
Vulcanization accelerator (the company's product curative # 20) 1〃

  The applied unvulcanized rubber layer is dried at a temperature of room temperature to about 100 ° C. for about 1 to 15 minutes, and alcohols such as methanol and ethanol used as an organic solvent, and ketones such as methyl ethyl ketone and methyl isobutyl ketone Or after volatilizing these mixed solvents etc., it vulcanizes by heating at about 150-230 degreeC for about 0.5-30 minutes, and pressurizing as needed and vulcanizing. The vulcanized fluoro rubber layer should have a hardness (durometer A) of 80 or more and a compression set (100 ° C, 22 hours) of 50% or less for use as a gasket. Is not to be done.

Moreover, when it is necessary to prevent adhesion, an anti-adhesive agent can be applied to the surface. The anti-sticking agent can be used for the purpose of preventing sticking between rubbers or between rubber and metal, and any anti-sticking agent can be used as long as it can form a film on the vulcanized fluoro rubber layer. , Fluorine-based, graphite-based, amide, paraffin-based wax-based, polyolefin-based or polybutadiene-based materials, etc., preferably liquid 1,2-polybutadiene hydroxyl group-containing materials, 1,2-polybutadiene isocyanate group-containing materials And an anti-adhesive agent comprising an organic solvent dispersion of polyolefin resin.
Japanese Patent Laid-Open No. 7-165953

  Next, the present invention will be described with reference to examples.

Examples 1-5, Comparative Examples 1-7
On an alkali degreased SUS301 stainless steel plate (thickness 0.2 mm), ammonium zirconium carbonate, phosphoric acid and phosphoric acid were added so that the element mass ratio of Zr, P, and Al in the surface treatment agent film was the ratio shown in Table 1. A surface treatment agent with an adjusted amount of alumina was applied so that the amount per unit area of the surface was 200 to 300 mg / m ² , and dried at 200 ° C. for 1 minute. The surface treatment agent was prepared with ammonium hydroxide so as to have a pH of 6 to 10.
Table 1
Element mass ratio
Surface treatment agent component composition ratio Zr: P Zr: Al
Surface treatment agent Zr P Al Zr P Zr Al
[Zr: P]
A (Lower limit) 37 16 47 70 30 44 56
B (upper limit) 30 2 68 94 6 31 69
C (intermediate) 35 10 55 78 22 39 61
[Zr: Al]
D (Lower limit) 10 2 88 82 18 10 90
E (upper limit) 72 20 8 78 22 90 10
F (Al) 4 1 95 80 20 4 96
G [Al low] 67 27 6 71 29 92 8
H (P) 30 30 40 50 50 43 57
I [P less] 52 2 46 96 4 53 47
J (without Al) 80 20 − 80 20 100 −
K (without Zr) − 15 85 − 100 − 100
L (without P) 45 0 55 100 − 45 55
On the steel sheet coated with these surface treatment agents A to E and F to L,
100 parts by weight of resol type phenolic resin (30% methanol solution) Colloidal silica (Nissan Chemicals Snowtex MEK-ST; 40 〃
(Methyl ethyl ketone solution with a solid content of 30% by weight)
Fluororubber compound of the above formulation 80 80
(30 wt% methyl ethyl ketone solution)
Methyl ethyl ketone 1100 〃
The vulcanized adhesive A was applied so that the coating amount was 1500 mg / m ² , dried at room temperature, and then baked at 220 ° C. for 5 minutes.

On this vulcanized adhesive coated steel sheet, a 25 wt% toluene-methyl ethyl ketone (9: 1 weight ratio) mixed solvent solution of the fluororubber compound of the above blending example was applied and dried at 60 ° C. for 15 minutes to have a thickness of one side of 20 μm. After the unvulcanized rubber layer was formed, pressure vulcanization was performed under the conditions of 220 ° C., 60 kgf / cm ² (5.88 MPa) for 2 minutes to prepare a fluororubber-metal laminated gasket material.

The gasket material was subjected to the following various tests.
Water resistance test: A rubber stainless steel laminated gasket material and an aluminum plate are immersed in a 1% by weight sodium hydrogen carbonate aqueous solution, and the immersion liquid is exposed in a semi-immersed state so that the top is located above the liquid level. After being immersed in the liquid without being in contact with each other at 90 ° C for 70 hours or 240 hours, the gasket material was peeled off according to JIS K5600-5-6, and the following Grade 5: The edges of the cuts are completely smooth and no grid eyes peel off. 〃 4: There is a small peeling of the coating film at the intersection of the cuts (peeling area ratio less than 5%)
３ 3: The film is peeled along the edge of the cut and / or at the intersection
(Peeling area ratio 5-15%)
〃 2: A large amount of peeling occurs partially or entirely along the edge of the cut of the coating film.
And / or various parts of the eye are partially or totally peeled off
(Area ratio 15-35%)
１ ： 1: There is large or partial peeling along the edge of the cut of the coating
And / or some of the eyes are partially or totally peeled (peeled area ratio 35%
more than)
LLC resistance test: The above Goban eye tape test was performed on gasket materials after being immersed in a 50% by weight aqueous solution of LLC liquid (Japan Chemical Product JCC310) at 150 ° C for 100 hours or 240 hours. Heat resistance test evaluated based on evaluation criteria: Gasket material is exposed to heat at 220 ° C for 100 hours or 240 hours, and then subjected to a bending resistance test (using a 4mm mandrel) in accordance with JIS K5600-5-1 Rating 5: No cracking or peeling 〃 4: Small cracks on the end face ： 3: Small cracks overall 〃 2: Overall cracks １ ： 1: Completely peeled off Have

Examples 6-10, Comparative Examples 8-14
In Examples 1 to 5 and Comparative Examples 1 to 7, the same amount of the thermosetting resin having a dihydrobenzoxazine ring produced by the method described above was used instead of the resol type phenol resin of the vulcanized adhesive A. Vulcanized adhesive B was used.

Examples 11-15, Comparative Examples 15-21
In Examples 1 to 5 and Comparative Examples 1 to 7, a vulcanized adhesive C having the following composition was used in place of the vulcanized adhesive A.
100 parts by weight of resol type phenolic resin (30% by weight methanol solution) Thermosetting resin with dihydrobenzoxazine ring 100 部
(30 wt% methyl ethyl ketone solution)
Colloidal silica (Snowtex MEK-ST) 80 〃
Fluororubber compound of the above example 160 〃
(30 wt% methyl ethyl ketone solution)
Methyl ethyl ketone 2200 〃

Examples 16-20, Comparative Examples 22-28
In Examples 1 to 5 and Comparative Examples 1 to 7, a vulcanized adhesive D having the following composition was used in place of the vulcanized adhesive A.
100 parts by weight of resol type phenolic resin (30% by weight methanol solution)
o-Cresol novolac epoxy resin 18 〃
(Japan Epoxy Resin Product Epicoat 180S)
2-ethyl-4-methylimidazole 0.9 〃
Colloidal silica (Snowtex MEK-ST) 40 〃
Fluororubber compound of the above formulation 80 80
(30 wt% methyl ethyl ketone solution)
Methyl ethyl ketone 1459 〃

Examples 21-25, Comparative Examples 29-35
In Examples 1 to 5 and Comparative Examples 1 to 7, a vulcanized adhesive E having the following composition was used in place of the vulcanized adhesive A.
100 parts by weight of resol type phenolic resin (30% by weight methanol solution) Thermosetting resin with dihydrobenzoxazine ring 100 部
(30 wt% methyl ethyl ketone solution)
o-Cresol novolac epoxy resin (Epicoat 180S) 36 〃
2-Ethyl-4-methylimidazole 1.8〃
Colloidal silica (Snowtex MEK-ST) 128 〃
Fluororubber compound of the above example 160 〃
(30 wt% methyl ethyl ketone solution)
Methyl ethyl ketone 3158 〃

Comparative Example 36
In Example 3, a vulcanized adhesive F having the following composition was used in place of the vulcanized adhesive A.
100 parts by weight of resol type phenolic resin (30% by weight methanol solution) Thermosetting resin with dihydrobenzoxazine ring 100 部
(30 wt% methyl ethyl ketone solution)
Fluororubber compound of the above example 160 〃
(30 wt% methyl ethyl ketone solution)
Methyl ethyl ketone 1800 〃

Comparative Example 37
In Example 3, a vulcanized adhesive G having the following composition was used in place of the vulcanized adhesive A.
100 parts by weight of resol type phenolic resin (30% by weight methanol solution) Thermosetting resin with dihydrobenzoxazine ring 100 部
(30 wt% methyl ethyl ketone solution)
o-Cresol novolac epoxy resin (Epicoat 180S) 36 〃
2-Ethyl-4-methylimidazole 1.8〃
Fluororubber compound of the above example 160 〃
(30 wt% methyl ethyl ketone solution)
Methyl ethyl ketone 2518 〃

Comparative Example 38
In Example 3, a vulcanized adhesive H having the following composition was used in place of the vulcanized adhesive A.
100 parts by weight of novolac type phenolic resin
o-Cresol novolac epoxy resin (Epicoat 180S) 60 〃
2-Ethyl-4-methylimidazole 3
Colloidal silica (Snowtex MEK-ST) 210 〃
Fluororubber compound of the above formulation 80 80
(30 wt% methyl ethyl ketone solution)
Methyl ethyl ketone 4547 〃

Comparative Examples 39-41
In Comparative Examples 36 to 38, surface treatment agent E was used in place of surface treatment agent C.

Comparative Examples 42-49
In Example 1, instead of the surface treatment agent A, a chromate treatment agent (Nippon Paint Product Surf Coat NRC350) was used, and vulcanized adhesives A to H were used.

The test results obtained in the above examples and comparative examples are shown in Table 2 below.
Table 2
Water resistance test LLC resistance test Heat resistance test
Examples 70hr 240hr 100hr 240hr 100hr 240hr
Example 1 5 5 5 5 5 4
〃 2 5 5 5 5 5 4
３ 3 5 5 5 5 5 4
４ 4 5 5 5 5 5 4
〃 5 5 4 5 5 5 3
Comparative Example 1 2 1 2 1 1 1
〃 2 1 1 3 2 4 3
３ 3 3 2 4 3 1 1
４ 4 2 1 2 1 2 2
〃 5 1 1 2 1 3 2
６ 6 1 1 1 1 1 1
７ 7 1 1 1 1 2 1
Example 6 5 4 5 5 5 5
７ 7 5 4 5 5 5 5
８ 8 5 4 5 5 5 5
９ 9 5 4 5 5 5 5
〃 10 5 3 5 5 5 4
Comparative Example 8 1 1 1 1 1 1 1
９ 9 1 1 2 1 4 3
〃 10 2 1 3 2 2 1
〃 11 1 1 2 1 3 2
〃 12 1 1 2 1 4 3
〃 13 1 1 1 1 1 1
〃 14 1 1 1 1 2 1
Example 11 5 5 5 5 5 5
〃 12 5 5 5 5 5 5
〃 13 5 5 5 5 5 5
〃 14 5 5 5 5 5 5
〃 15 5 5 5 5 5 5
Comparative Example 15 3 1 2 1 2 1
〃 16 2 1 3 2 4 3
〃 17 4 2 4 3 2 1
〃 18 3 1 2 1 3 2
〃 19 1 1 2 1 3 2
〃 20 1 1 1 1 1 1
〃 21 1 1 1 1 2 1
Example 16 5 4 5 4 5 3
〃 17 5 4 5 4 5 4
〃 18 5 4 5 4 5 4
〃 19 5 3 5 3 5 4
〃 20 5 3 5 5 5 3
Comparative Example 22 1 1 1 1 2 2 1
〃 23 1 1 2 1 4 3
〃 24 3 1 3 2 2 1
〃 25 2 1 2 1 3 2
〃 26 1 1 1 1 3 2
〃 27 1 1 1 1 1 1
〃 28 1 1 1 1 2 1
Example 21 5 5 5 5 5 5
〃 22 5 4 5 4 5 5
〃 23 5 5 5 5 5 5
〃 24 5 3 5 4 5 5
〃 25 5 4 5 4 5 5
Comparative Example 29 3 1 2 1 2 1
〃 30 2 1 3 2 4 3
〃 31 4 2 4 3 2 1
〃 32 3 1 2 1 3 2
〃 33 1 1 2 1 3 2
〃 34 1 1 1 1 1 1
〃 35 1 1 1 1 2 1
〃 36 2 1 2 1 5 5
〃 37 1 1 1 1 5 5
〃 38 1 1 1 1 4 3
〃 39 1 1 1 1 4 3
〃 40 1 1 1 1 4 3
〃 41 1 1 1 1 3 3
〃 42 3 2 5 4 5 5
〃 43 4 2 5 3 5 5
〃 44 4 2 5 4 5 5
〃 45 4 2 5 3 5 5
〃 46 4 2 5 4 5 5
〃 47 2 1 5 3 6 3
〃 48 2 1 5 2 6 5
〃 49 3 1 5 4 6 5

Claims (10)

  A fluororubber-metal laminated gasket material obtained by sequentially laminating a surface treatment agent layer containing a zirconium element, a phosphorus element and an aluminum element, a silica-containing resin-based vulcanized adhesive layer, and a fluororubber layer on a metal steel plate.   The fluororubber-metal laminated gasket material according to claim 1, wherein a surface treatment agent having an element mass ratio of zirconium and phosphorus of 95: 5 to 60:40 is used.   The fluororubber-metal laminated gasket material according to claim 1 or 2, wherein a surface treatment agent having an element mass ratio of zirconium and aluminum of 90:10 to 10:90 is used.   The fluororubber-metal laminated gasket material according to claim 1, 2 or 3, wherein the metal steel plate is a stainless steel plate.   The fluororubber-metal laminated gasket material according to claim 1, wherein the silica-containing resin-based vulcanized adhesive is a silica-containing thermosetting phenol resin-based vulcanized adhesive.   6. The fluororubber-metal laminated gasket material according to claim 5, wherein the phenol resin is a resol type phenol resin or a thermosetting resin having a dihydrobenzoxazine ring.   6. The fluororubber-metal laminated gasket material according to claim 5, wherein a layer of a silica-containing resin-based vulcanized adhesive further containing a cresol novolac type epoxy resin or a phenol novolac type epoxy resin is formed.   6. The fluororubber-metal laminated gasket material according to claim 5, wherein a layer of a silica-containing resin-based vulcanized adhesive further containing unvulcanized fluororubber or a compound thereof is formed.   2. The fluororubber-metal laminated gasket material according to claim 1, wherein an anti-blocking agent layer is formed on the fluororubber layer. The fluororubber-metal laminated gasket material according to any one of claims 1 to 9, which is used as an engine cylinder head gasket.