JP4696568B2 - Primer composition - Google Patents

Description

The present invention relates to a primer composition. More specifically, the present invention relates to a primer composition used as a primer in the production of fluororubber / adhesive / primer / metal laminate.

  Fuel cell gaskets, since the water resistance and acid resistance are required, and plating the plate surface with gold or the like. When wearing such a plated steel sheet and unvulcanized rubber pressure and vulcanization is be adhered rubber by using conventional vulcanization adhesive can not be obtained a stable initial adhesion.

  For low plated steel sheet chemically active, as pretreatment for applying a vulcanization adhesive, by applying a primer mainly composed of a silane coupling agent, the initial adhesion is greatly improved that is, there is a problem of poor water resistance. The electronic storage device, in particular a gasket for use in a hard disk drive (HDD), have a low outgassing, Si, S, and it is required that does not contain Cl or the like, therefore silane coupling use of a primer composed mainly of coupling agent is not preferred.

With regard to water resistance, it can be improved by using a vulcanization adhesion primer containing a copolymer oligomer of an amino group-containing alkoxysilane and a vinyl group-containing alkoxysilane and an organometallic compound. But there is still room for improvement.
JP 2004-26848 A

  Further, in the case of bonding by the post-applied to the plated steel sheet and vulcanized rubber, waterproof as an adhesive, in applications where oxidation resistance is required, the thermosetting resin is applied such as a phenol resin and an epoxy resin but these adhesives also poor adhesion to chemical lower plated steel sheet active, the liquid-resistance test for acid, peeling of an adhesive interlayer between the steel sheet occurs.

Primer object of the present invention, when applied to a bonding adhesive after the vulcanization bonding or plated steel sheets and vulcanized fluoro rubber and plated steel sheets and unvulcanized fluoro rubber is also water resistance, excellent acid resistance It is to provide a composition.

The object of the present invention is to provide a primer composition used as a primer in the production of fluororubber / adhesive / primer / metal laminate, comprising 5 to 120 parts by weight of an organometallic compound per 100 parts by weight of phenol resin. Achieved by:

Primer compositions according to the present invention, when using this as a primer during fluorine rubber / adhesive / primer / metal laminate production, vulcanization of the lower plated steel sheet and unvulcanized rubber active or Even when used for post-bonding of plated steel sheets and vulcanized rubber, they have excellent water resistance and acid resistance, so rubber and metal integrated gaskets, especially fuel cell gaskets and HDD cover gaskets (metal separators) It can be effectively applied to the production of an integrated gasket).

  The phenol resin used as a component of a primer, other resol, novolak type phenolic resins, phenol resins used having a dihydrobenzoxazine ring, other thermosetting resins such as epoxy resin together with these phenolic resins It can be used in combination, and as much as possible the reactive groups of the phenolic resin, in order to increase the adhesion between the top coat adhesives and plated steel sheet, it is preferable to use a resol-type phenolic resin alone.

  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 phenolic resin, the condensation reaction of hydrochloric acid, is obtained by reacting in the presence of an acid catalyst such as oxalic acid used.

特開２００４−８３６２３号公報 Furthermore, as a thermosetting phenol resin having a dihydrobenzoxazine ring, any thermosetting phenol resin having a dihydrobenzoxazine ring and curing 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 needs to 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 resins, melamine phenol resins and alkylphenol resins.

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

  For each one mole of compound with a primary amine having these phenolic hydroxyl groups, 2 moles or more of formaldehyde are used, the presence of such oxalic acid catalyst, the reaction temperature of about 70 to 130 ° C., preferably about 90 110 after about 1 / 3-4 hours approximately reacted at ° C., the phenolic compound, unreacted under reduced pressure at 120 ° C. or less, primary amines, by removing the formaldehyde or the like, the heat having a dihydrobenzoxazine ring curable resin is obtained.

R：CH₃、C₂H₅、n-C₃H₇ 、i-C₃H₇、n-C₄H₉、i-C₄H₉、i-C₈H₁₇ などのア
ルキル基
R´：CH₃基またはOR
M₁：Ti、Zr、Sn
M₂：Al
n：0〜3の整数
m：0〜2の整数
で表される少くとも１個のアルコキシル基または少くとも１個のキレート環およびアルコキシル基を有する有機金属化合物、あるいは少くとも１個のキレート環を有する化合物と金属アルコキシドとの混合物が用いられる。有機金属化合物の中では、好ましくは有機アルミニウム化合物が用いられ、有機金属化合物は１種または２種以上の混合物としても用いられる。ただし、有機金属化合物は、適用溶剤の範囲が限定されてしまうため、比較的溶剤選定に自由度のある少くとも1個のキレート環を有する化合物を用いることが好ましい。 Examples of organometallic compounds added to these phenolic resins include triisopropoxyaluminum, mono-sec-butoxydipropoxyaluminum, tri-sec-butoxyaluminum, tri (2-ethylhexyl) aluminum, diisopropoxyaluminum mono ( Methyl acetoacetate), diisopropoxy aluminum mono (ethyl acetoacetate), diisopropoxy aluminum mono (propyl acetoacetate), diisopropoxy aluminum mono (butyl acetoacetate), diisopropoxy aluminum mono (hexyl acetoacetate), di n-propoxy aluminum mono (methyl acetoacetate), di n-propoxy aluminum mono (ethyl acetoacetate), di n-propoxy aluminum mono (propyl acetoacetate), di n-pro Xi aluminum mono (butyl acetoacetate), di-n-propoxy aluminum mono (hexyl acetoacetate), dibutoxy aluminum mono (methyl acetoacetate), dibutoxy aluminum mono (ethyl acetoacetate), dibutoxy aluminum mono (propyl acetoacetate) , Dibutoxy aluminum mono (butyl acetoacetate), dibutoxy aluminum mono (hexyl acetoacetate), aluminum tris (acetyl acetate), aluminum tris (ethyl acetoacetate), aluminum tris (propyl acetoacetate), aluminum tris (butyl acetoacetate) ), Aluminum tris (hexyl acetoacetate), aluminum-monoacetylacetonate-bis (ethyl acetoacetate), aluminum tris ( Cetylacetonate), diisopropoxyaluminum mono (acetylacetonate), ethylacetoacetate aluminum diisopropyrate and other organoaluminum compounds, tetra i-propoxy titanium, tetra n-propoxy titanium, tetra n-butoxy titanium, tetra (2 -Ethylhexyl) titanate, diisopropoxy titanium bis (methyl acetoacetate), diisopropoxy titanium bis (ethyl acetoacetate), diisopropoxy titanium bis (propyl acetoacetate), diisopropoxy titanium bis (butyl acetoacetate), diisopropoxy titanium bis ( Hexyl acetoacetate), di-n-propoxytitanium bis (methylacetoacetate), di-n-propoxytitanium bis (ethylacetoacetate), di-n-propoxytitanium bis (propylacetoacetate) Tate), di n-propoxy titanium bis (butyl acetoacetate), di n-propoxy titanium bis (hexyl acetoacetate), di n-butoxy titanium bis (methyl acetoacetate), di n-butoxy titanium bis (ethyl acetoacetate), di n- Butoxytitanium bis (propyl acetoacetate), di-n-butoxytitanium bis (butylacetoacetate), di-n-butoxytitanium bis (hexylacetoacetate), 1,3-propanedioxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (acetyl) Acetonate), di-n-propoxytitanium bis (acetylacetonate), di-n-butoxytitanium bis (acetylacetonate), titanium tetraacetylacetonate, titanium tetraethyl acetoacetate, titanium tetrapropyl acetoacetate, titanium tetrabutyl Organic titanium compounds such as acetoacetate, tetra i-propoxy zirconium, tetra n-propoxy zirconium, tetra n-butoxy zirconium, diisopropoxy zirconium bis (methyl acetoacetate), diisopropoxy zirconium bis (ethyl acetoacetate), diiso Propoxyzirconium bis (propylacetoacetate), diisopropoxyzirconium bis (butylacetoacetate), diisopropoxyzirconium bis (hexylacetoacetate), di-n-propoxyzirconium bis (methylacetoacetate), di-n-propoxyzirconium bis ( Ethyl acetoacetate), di-n-propoxyzirconium bis (propylacetoacetate), di-n-propoxyzirconium bis (butylacetoacetate), di-n-propoxyzirconium Mubis (hexyl acetoacetate), di n-butoxyzirconium bis (methyl acetoacetate), di n-butoxyzirconium bis (ethyl acetoacetate), di n-butoxyzirconium bis (propyl acetoacetate), di n-butoxyzirconium bis ( Butyl acetoacetate), di-n-butoxyzirconium bis (hexylacetoacetate), 1,3-propanedioxyzirconium bis (ethylacetoacetate), diisopropoxyzirconium bis (acetylacetonate), di-n-propoxyzirconium bis ( Acetylacetonate), di-n-butoxyzirconium bis (acetylacetonate), zirconium tetraacetylacetonate, zirconium tetraethylacetoacetate, zirconium tetrapropylacetoacetate, zirconium tetrabutyl Organic zirconium compounds such as ruacetoacetate, tetra i-propoxy tin, tetra n-propoxy tin, tetra n-butoxy tin, diisopropoxy tin bis (methyl acetoacetate), diisopropoxy tin bis (ethyl acetoacetate), di Isopropoxytin bis (propylacetoacetate), diisopropoxytin bis (butylacetoacetate), diisopropoxytin bis (hexylacetoacetate), di-n-propoxytin bis (methylacetoacetate), di-n-propoxytin bis (Ethyl acetoacetate), di-n-propoxytin bis (propylacetoacetate), di-n-propoxytin bis (butylacetoacetate), di-n-propoxytin bis (hexylacetoacetate), di-n-butoxytin bis (methyl Acetoacetate), di-n-butoxytin bis (ethylacetoacetate), di-n -Butoxytin bis (propylacetoacetate), di-n-butoxytin bis (butylacetoacetate), di-n-butoxytin bis (hexylacetoacetate), 1,3-propanedioxytin bis (ethylacetoacetate), di Isopropoxytin bis (acetylacetonate), di-n-propoxytin bis (acetylacetonate), di-n-butoxytin bis (acetylacetonate), tin tetraacetylacetonate, tin tetraethylacetoacetate, tin tetrapropylacetoacetate , Organic tin compounds such as tin tetrabutyl acetoacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, and the like, preferably the following two general formulas

R: CH ₃ , C ₂ H ₅ , nC ₃ H ₇ , iC ₃ H ₇ , nC ₄ H ₉ , iC ₄ H ₉ , iC ₈ H _17, etc.
Rukyl group
R´: CH ₃ group or OR
M ₁ : Ti, Zr, Sn
M ₂ : Al
n: Integer from 0 to 3
m: at least one alkoxyl group represented by an integer of 0 to 2 or an organometallic compound having at least one chelate ring and an alkoxyl group, or a compound having at least one chelate ring and a metal alkoxide; A mixture of Among the organometallic compounds, organoaluminum compounds are preferably used, and the organometallic compounds are also used as one kind or a mixture of two or more kinds. However, since the range of applicable solvents is limited for the organometallic compound, it is preferable to use a compound having at least one chelate ring with a relatively high degree of freedom in solvent selection.

  These organometallic compounds, from about 5 to 250 parts by weight per 100 parts by weight of phenolic resin, preferably used in a ratio of about 50 to 150 parts by weight. In addition the rate of which the following is an organometallic compound, in particular reduces the adhesion between the plated steel sheet, whereas above ratio, inevitably lowering the liquid-resistance to acid.

  Primer composition as an essential component or components are used as solution diluted with an organic solvent such that each of these components the total amount concentration becomes about 0.5 to 15 wt%. As the organic solvent, generally methanol, ethanol, isopropanol, 2-ethoxyethanol (ethylene glycol monoethyl ether) alcohol-based organic solvent or acetone, etc., methyl ethyl ketone, ketone-based organic solvents such as methyl isobutyl ketone is used.

  Primer solution is a metal, generally stainless steel sheet, as the steel sheet on the coating film of aluminum steel plate is about 1 to 30 [mu] m, spraying, dipping, applied by any method such as a roll coater method, at room temperature or after drying warm air, about 0.5 to 2 hours baking process is performed at about 100 to 250 ° C.. The stainless steel plate, for example SUS301, SUS301H, SUS304, SUS430, etc. are used. Gold for surface to impart corrosion resistance, such as those of stainless steel or aluminum steel sheets, it is preferable to use those plated with nickel or the like.

On the primer layer formed in this manner, a vulcanized adhesive corresponding to the type of fluororubber to be vulcanized and bonded is applied. Examples of the vulcanized adhesive to be used include those having the following composition, and various commercially available vulcanized adhesives for fluororubber can be used as they are.
(For peroxide crosslinkable rubber)
・ Γ-methacryloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, organic titanium compound, water and organic solvent (for fluoro rubber)
・ Novolak type epoxy resin, novolak type phenolic resin derived from p-substituted phenol, imidazole compound curing catalyst and fluorine rubber compound ・ Vinyltrialkoxysilane, γ-aminopropyltrialkoxysilane, organoaluminum compound and organic solvent ・ γ -Aqueous liquid containing aminopropyltrihydroxysilane, methacrylic acid and acetic acid at pH 5-7-Aqueous liquid containing γ-methacryloxypropyltrialkoxysilane, amino group-containing trihydroxysilane and lower saturated carboxylic acid or inorganic acid γ-glycidoxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, organotitanium compound, alcohol-based organic solvent and water
JP 2001-226642 A JP-A-6-88062 JP 7-34054 A JP-A-8-209102 Japanese Patent Laid-Open No. 9-3432 Japanese Patent Laid-Open No. 10-8021 JP-A-6-306340 JP 7-216309 A JP-A-8-302323 JP-A-9-132758 JP-A-10-121020 JP 2000-1658 A JP 2000-17247 A JP 2003-147314 A JP 2003-261850 A JP 2004-277435 A

  These vulcanization adhesive is sprayed onto primed steel, dipping, brushing, applied by a method such as a roll coater, dried and baking treatment is carried out in dry conditions and baking conditions suitable for each.

On the vulcanized adhesive layer thus formed, an unvulcanized rubber compound in which a vulcanizing agent , a reinforcing agent, and other necessary compounding agents are blended with fluororubber, preferably water-resistant and acid-resistant. From the point of view, a gasket is molded by a pressure molding method such as compression molding or injection molding using an unvulcanized fluororubber compound. In molding, for example, in press compression molding, molding conditions of about 150 to 220 ° C. and about 5 to 20 minutes are taken.

  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 I)
Fluoro rubber (DuPont product Viton E45) 100 parts by weight
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〃
(Composition Example II)
Fluoro rubber (DuPont Viton E60C) 100 parts by weight Vulcanizing agent (DuPont Diac No. 3) 3 〃
Magnesium oxide (Kyowa Chemical Product Magnesia # 30) 10 〃
MT carbon black 20 〃
(Formulation example III)
Fluoro rubber (Daikin product Daiel G901) 100 parts by weight
MT carbon black 20 〃
Magnesium oxide (magnesia # 150) 6 〃
Calcium hydroxide 3 〃
Triallyl isocyanurate 1.8 〃
Organic peroxide (NIPPON OIL & PRODUCTS PERHEXA 25B) 0.8 〃

  Fluororubber layer which is press-molded, restrictions on use as a gasket, hardness (durometer A) of 70 or less, a compression set (0.99 ° C., 22 hours) is desirably 20% or less, in particular by compounding components not intended to be.

  Laminated and composite rubber layer of the primer coating a steel sheet is thus carried out by vulcanization bonding with vulcanization adhesive, vulcanized rubber sheets on the primer coating steel sheet, for example in the case of the gasket applications It can also be post-bonded via an adhesive vulcanized rubber sheet having a lip portion of any shape and size to the sheet-like material having a thickness of about of about 0.2 to 2 mm. As the adhesive in this case, it is possible to use any commercially available adhesives according to the type of rubber, but in the case of water resistance and acid resistance required applications, epoxy resin, heat of phenolic resin, etc. it is preferable to use a curable resin system. Adhesion thereto superimposed vulcanized rubber after the adhesive is applied over the primer coating a steel sheet, depending on the kind of the vulcanized rubber, is about generally about 150 to 220 ° C. effected by pressure heating.

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

Example 1
Primer A having the following composition on a degreased gold-plated stainless steel plate
Resole-type phenolic resin (Gunei Chemicals product cash register top PL-2208; 159 parts by weight
(Solid content 63% by weight)
Ethyl acetoacetate aluminum diisopropylate 10 〃
2-Ethoxyethanol 2031 〃
Was applied at a thickness of 10 μm, dried at room temperature, and then baked at 200 ° C. for 15 minutes.

On this primer, a commercially available phenol / epoxy resin vulcanized adhesive for fluororubber A
Rohm and Haas Product Sixon 300 100 parts by weight Rohm and Haas Product Sixon 311 100 〃
Methyl ethyl ketone 1360 〃
Was applied at a thickness of 10 μm and dried at room temperature, followed by baking at 200 ° C. for 15 minutes. On top of that, the unvulcanized fluororubber compound of Formulation Example I was placed, and after press vulcanization at 180 ° C. for 6 minutes, secondary vulcanization at 200 ° C. for 24 hours was performed to prepare an adhesion test piece. .

  This adhesion test piece in conformity with JIS K6256 90 ° peel test method, initial, 140 hours or 280 hours after immersion in 0.5 wt% sulfuric acid in a 80 ° C. warm water for 140 hours or 280 hours after dipping and 80 ° C. measurements and peeling of the rubber residual area ratio Re was visually observed for the state of the interface. For peeling the interface state, display the rubber breakage R, RC peeling of rubber and the topcoat adhesive interface, the peeling at the interface of the topcoat adhesive and primer CP, the peeling at the interface between the metal and the primer as M did.

Example 2
In the primer A of Example 1, primer B was used in which the amount of the organoaluminum compound was changed to 100 parts by weight and the amount of 2-ethoxyethanol was changed to 3741 parts by weight.

Example 3
In primer A of Example 1, primer C was used in which the amount of organoaluminum compound was changed to 200 parts by weight and the amount of 2-ethoxyethanol was changed to 5641 parts by weight.

Comparative Example 1
In Example 1, a silane coupling agent-based surface treatment agent (product of Road Far East Co., Ltd. AP-133) was used as a primer.

Comparative Example 2
In Example 1, a primer for vulcanization adhesion consisting of an alkoxysilane copolymer oligomer described in Example 1 of Patent Document 1, titanium tetra (acetylacetonate), methanol, and water was used as a primer.

Comparative Example 3
In Example 1, Primer A was not used.

The results obtained in Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1 below.
Table 1
Example Comparative Example
Measurement conditions 1 2 3 1 2 3
Initial rubber residual area ratio (%) 100 100 100 100 100 20
Peeling interface R R R R R M
After immersion for 140 hours in 80 ° C hot water Rubber remaining area ratio (%) 100 100 100 40 100-
Peeling interface R R R M R −
After immersion in 80 ° C hot water for 280 hours Rubber remaining area ratio (%) 100 100 100 20 100-
Peeling interface R R R M R −
After immersion in sulfuric acid at 80 ° C for 140 hours Rubber remaining area ratio (%) 100 100 100 0 20-
Peeling interface R R R M M −
After immersion in sulfuric acid at 80 ° C for 280 hours Rubber remaining area ratio (%) 70 100 80-0-
Peeling interface MRCP-M-

Examples 4-6, Comparative Examples 4-6
In Examples 1 to 3 and Comparative Examples 1 to 3, post-adhesive adhesive B was used in place of vulcanized adhesive A.
Epoxy resin (Asahi Denki products EP-4100) 100 parts by weight Dicyandiamide (Company EH-3636AS) 8 〃
Post-adhesion adhesion using this adhesive was performed by applying post-adhesion adhesive B on a primer-treated gold-plated stainless steel plate to a thickness of 10 μm, and then vulcanized rubber (unvulcanized fluororubber compound of Formulation Example I). The film was press vulcanized at 180 ° C. for 6 minutes and then subjected to secondary vulcanization at 200 ° C. for 24 hours, and a 1 mm-thick sheet) was attached, and cured at 150 ° C. for 1 hour.

The results shown in Examples 4 to 6 and Comparative Examples 4 to 6 are shown in Table 2 below.
Table 2
Example Comparative Example
Measurement conditions 4 5 6 4 5 6
Initial rubber residual area ratio (%) 100 100 100 100 100 100
Peeling interface R R R R R R
After immersion for 140 hours at 80 ° C in warm water Rubber area ratio (%) 100 100 100 80 100 0
Peeling interface R R R M R M
After immersion in 80 ° C hot water for 280 hours Rubber remaining area ratio (%) 100 100 100 40 100-
Peeling interface R R R M R −
After dipping in sulfuric acid at 80 ° C for 140 hours Rubber remaining area ratio (%) 100 100 100 0 40 0
Peeling interface R R R M M M
After immersion in sulfuric acid at 80 ° C for 280 hours Rubber remaining area ratio (%) 70 100 90-0-
Peeling interface MRRC-M-

Examples 7-9, Comparative Examples 7-9
In Examples 1 to 3 and Comparative Examples 1 to 3, a vulcanized fluoro rubber sheet (thickness 0.1 mm, width 2 mm) having a semicircular cross-section (radius 0.5 mm) lip on a primer-treated gold-plated stainless steel plate is vulcanized For the bonded ones, the measurement of the rubber residual area ratio and the visual observation of the peeling interface were similarly performed. The water resistance test was also performed on 50% compressed product, and the acid resistance test was also performed on 0.3% by weight hydrofluoric acid.

The results obtained in Examples 7-9 and Comparative Examples 7-9 are shown in Table 3 below.
Table 3
Example Comparative Example
Measurement conditions 7 8 9 7 8 9
〔initial〕
Rubber remaining area ratio (%) 100 100 100 100 100 20
Peeling interface R R R R R M
[Water resistance test 1]
After immersion for 140 hours in 80 ° C hot water Rubber remaining area ratio (%) 100 100 100 40 100-
Peeling interface R R R M R −
After immersion in 80 ° C hot water for 280 hours Rubber remaining area ratio (%) 100 100 100 20 100-
Peeling interface R R R M R −
[Water resistance test 2; 50% compression]
After immersion for 140 hours in 80 ° C hot water Rubber remaining area ratio (%) 100 100 100 20 100-
Peeling interface R R R M R −
After immersion in 80 ° C hot water for 280 hours Rubber remaining area ratio (%) 95 100 100 0 90-
Peel interface M R R M M −
[ Acid resistance test 1 ; 0.5% sulfuric acid]
After immersion in sulfuric acid at 80 ° C for 140 hours Rubber remaining area ratio (%) 100 100 100 0 20-
Peeling interface R R R M M −
After immersion in sulfuric acid at 80 ° C for 280 hours Rubber remaining area ratio (%) 70 100 80-0-
Peeling interface MRCP-M-
[ Acid resistance test 2 ; 0.3% hydrofluoric acid]
After immersion for 140 hours at 80 ° C in hydrofluoric acid Rubber remaining area ratio (%) 90 100 95 0 0 0
Peeling interface M R CP M M M
After dipping in 80 ° C hydrofluoric acid for 280 hours Rubber residual area ratio (%) 60 100 60---
Peeling interface MRCP − − −

Examples 10-12, Comparative Examples 10-12
In Examples 4 to 6 and Comparative Examples 4 to 6, on the primer-treated gold-plated stainless steel plate, a vulcanized fluorine sheet having a semicircular cross-section (radius 0.5 mm) lip portion was post-bonded and bonded, similarly, the remaining rubber area Measurement of the rate and visual observation of the peeled interface were performed. The water resistance test was also performed on 50% compression-fixed material in the thickness direction, and the acid resistance test was also performed on 0.3% by weight hydrofluoric acid.

The results obtained in Examples 10 to 12 and Comparative Examples 10 to 12 are shown in Table 4 below.
Table 4
Example Comparative Example
Measurement conditions 10 11 12 10 11 12
〔initial〕
Rubber remaining area ratio (%) 100 100 100 100 100 100
Peeling interface R R R R R R
[Water resistance test 1]
After immersion for 140 hours at 80 ° C in warm water Rubber area ratio (%) 100 100 100 80 100 0
Peeling interface R R R M R M
After immersion in 80 ° C hot water for 280 hours Rubber remaining area ratio (%) 100 100 100 40 100-
Peeling interface R R R M R −
[Water resistance test 2; 50% compression]
After 140 hours of warm water at 80 ° C, rubber remaining area ratio (%) 100 100 100 50 100 0
Peeling interface R R R M R M
After immersion in 80 ° C hot water for 280 hours Rubber remaining area ratio (%) 100 100 100 10 100-
Peeling interface M R R M R −
[ Acid resistance test 1 ; 0.5% sulfuric acid]
After dipping in sulfuric acid at 80 ° C for 140 hours Rubber remaining area ratio (%) 100 100 100 0 40 0
Peeling interface R R R M M M
After immersion in sulfuric acid at 80 ° C for 280 hours Rubber remaining area ratio (%) 70 100 90-0-
Peeling interface MRRC-M-
[ Acid resistance test 2 ; 0.3% hydrofluoric acid]
After immersion for 140 hours at 80 ° C in hydrofluoric acid Rubber remaining area ratio (%) 90 100 95 0 0 0
Peel interface M R M M M M
After dipping in 80 ° C hydrofluoric acid for 280 hours Rubber remaining area ratio (%) 60 100 70---
Peel interface M, RC RM, RC − − −

Claims (9)

A primer composition used as a primer in producing a fluororubber / adhesive / primer / metal laminate, comprising 5 to 250 parts by weight of an organometallic compound per 100 parts by weight of a phenol resin.   The primer composition of claim 1, wherein the resol type phenol resin is used as the phenolic resin.   Organometallic compound is at least a compound in which claim 1 or 2 primer composition according having one chelate ring and / or alkoxyl group. The primer composition according to claim 1, 2 or 3, which is used as a primer for vulcanization adhesion between a steel plate and unvulcanized fluororubber . The primer composition according to claim 1, 2 or 3, which is used as a primer for adhesion between a steel plate and vulcanized fluoro rubber.   Claim 4 or 5 primer composition according steel sheet is plated steel sheet. A fluororubber / adhesive / primer / metal laminate produced using the primer composition according to claim 1, 2, 3, 4, 5 or 6 as a primer. The fluororubber / adhesive / primer / metal laminate according to claim 7, which is used as a rubber / metal integrated gasket.   Rubber-metal integrated gasket according to claim 8, wherein for use as a gasket for a fuel cell.