JP2006021363A - Chlorosulfonated polyolefin composition for laminate with fluorine-containing polymer, laminate comprising it and hose comprising the laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chlorosulfonated polyolefin composition excellent in the vulcanization adhesiveness with a fluorine-containing polymer, a laminate, and a hose comprising the laminate. <P>SOLUTION: The chlorosulfonated polyolefin composition for the laminate with the fluorine-containing polymer is prepared by adding 0.2-5 pts.wt. of a mercaptotriazine compound and 0.3-10 pts.wt. of an onium salt and/or a tertiary amine salt having a diazabicyclic ring to 100 pts.wt. of a chlorosulfonated polylefin with a sulfur content of 0.05-0.45 wt.%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a chlorosulfonated polyolefin composition for a laminate excellent in vulcanization adhesion to a fluoropolymer, a laminate of the composition and a fluoropolymer, and a hose comprising the laminate. .

  In the field of fuel-based hoses, fuel oil resistance, fuel oil permeability, heat resistance, cold resistance, weather resistance, and ozone resistance are required, so nitrile rubber and other excellent oil resistance rubbers and chlorosulfonated Rubber laminates having excellent heat resistance, cold resistance, weather resistance, and ozone resistance, such as polyethylene, have been mainly applied.

  However, there is a movement to reduce the amount of hydrocarbons released into the atmosphere from the viewpoint of protecting the global environment in recent years, and the fuel oil permeability required for fuel hoses is becoming more severe.

  Under such circumstances, there is a movement to apply a fluorine-containing polymer that is extremely excellent in fuel oil resistance and fuel oil permeability as a material for fuel system hoses, but it is more expensive than conventional rubber materials. Therefore, attempts have been made to reduce the cost by thinning the fluoropolymer to form a laminate with other types of rubber.

  In particular, among the fluoropolymers, the non-elastomeric fluoropolymer is superior in fuel oil resistance and fuel oil permeability compared to the elastomeric fluoropolymer, and therefore the fluoropolymer layer of the fuel hose. From the viewpoint of cost reduction, the application of non-elastomeric fluorine-containing polymers is attracting attention.

  On the other hand, as an important required characteristic of a laminated fuel system hose, adhesion between layers can be mentioned. If the adhesive strength between the layers is insufficient, there is a risk of delamination during use, which becomes a serious defect as a fuel system hose. Especially for non-elastomeric fluorine-containing polymers, since various reinforcing agents and compounding agents such as vulcanizing agents are not required unlike elastomeric fluorine-containing polymers, the adhesion between each layer is inferior. . Therefore, the surface of the non-elastomeric fluorine-containing polymer formed into a layer is bonded to other types of rubber formed into a layer by performing an etching process such as a metal sodium complex, an uneven process by sputtering, or a reduced pressure plasma process. The strength is improved.

  The rubber type laminated with the fluoropolymer is naturally excellent in fuel oil resistance and fuel oil permeability, but the rubber type used in the outer layer also has heat resistance, weather resistance, ozone resistance, etc. In order to reduce the manufacturing cost of the hose that is required, it is desirable that the rubber to be applied is inexpensive. A chlorosulfonated polyolefin is mentioned as a rubber type that satisfies these required physical properties and is relatively inexpensive.

  Patent documents relating to a laminate of a chlorosulfonated polyolefin and a fluorine-containing polymer have been reported (for example, see Patent Document 1 and Patent Document 2).

JP 2001-526972 A Japanese Patent Laid-Open No. 09-505006 describes a method for increasing the adhesion of a first layer containing a vinylidene fluoride-containing fluoropolymer to a second layer containing a curable elastomer. However, although chlorosulfonated polyethylene is defined as a curable elastomer in the claims, there is no specific illustration in the detailed description of the invention, and there is no description of the examples.

  Patent Document 2 describes a laminate of a low swelling elastomer, a non-elastomeric fluoropolymer, and an elastomer. However, Patent Document 2 requires the use of a non-elastomeric fluoropolymer that has been surface-treated as described above (treated to promote adhesion). However, the above-described surface treatment complicates the hose manufacturing process and causes an increase in the cost of the hose product.

  The present invention has been made in view of the above problems, and is a chlorosulfonated polyolefin composition for laminates excellent in vulcanization adhesion with a fluorine-containing polymer, and the composition and the fluorine-containing polymer. It is providing the laminated body and the hose which consists of the laminated body.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by applying a specific vulcanization system to a specific chlorosulfonated polyolefin, leading to the present invention. Is. That is, in the present invention, 0.2 to 5 parts by weight of a mercaptotriazine compound, onium salt and / or diazabicyclo is added to 100 parts by weight of a chlorosulfonated polyolefin having a sulfur content of 0.05 to 0.45% by weight. A chlorosulfonated polyolefin composition for a laminate with a fluoropolymer, comprising 0.3 to 10 parts by weight of a tertiary amine salt having a ring, and a laminate of the composition and the fluoropolymer The hose which consists of a body and its laminated body.

  Hereinafter, the present invention will be described in detail.

  The chlorosulfonated polyolefin used in the chlorosulfonated polyolefin composition for laminates with the fluoropolymer of the present invention is a chlorinated and chlorosulfonated polyolefin. The polyolefin is not particularly limited. For example, polyethylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-α-ethylene such as ethylene-1-octene, and the like. Examples thereof include olefin copolymers, ethylene-vinyl acetate copolymers, and propylene. Moreover, these polyolefins can be used without any problems even if they are used alone or as a blend of two or more. In order to obtain appropriate vulcanization properties and processability, polyethylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene, etc. An ethylene-α-olefin copolymer is preferred.

  The sulfur content of the chlorosulfonated polyolefin used in the present invention is 0.05 to 0.45% by weight. If it is less than 0.05% by weight, it cannot be said to be a chlorosulfonated polyolefin, and if it exceeds 0.45% by weight, gelation proceeds during kneading of the compounding agent, and molding processing becomes impossible. In consideration of the flowability of the blend, 0.05 to 0.40% by weight is preferable, and 0.05 to 0.35% by weight is more preferable.

  The chlorine content in the chlorosulfonated polyolefin used in the present invention is not particularly limited, but is preferably 15 to 50% by weight in order to maintain vulcanization adhesion with the fluoropolymer, and vulcanization adhesion. 30 to 45% by weight is more preferable in order to improve the balance between the properties and the desired fuel oil resistance, heat resistance, weather resistance and vulcanized physical properties.

  The Mooney viscosity (ML (1 + 4) 100 ° C.) of the chlorosulfonated polyolefin used in the present invention is not particularly limited, but is preferably in the range of 10 to 150 in consideration of the balance between processability and physical properties. .

  The chlorosulfonated polyolefin composition for laminates with the fluoropolymer of the present invention comprises 0.2 to 5 parts by weight of mercaptotriazine compound, onium salt and / or diazabicyclo ring with respect to 100 parts by weight of chlorosulfonated polyolefin. It contains 0.3 to 10 parts by weight of a tertiary amine salt having

  The mercaptotriazine compound used in the present invention is used as a vulcanizing agent and has two or more mercapto groups in the molecule. For example, 2,4,6-trimercapto-1,3,5-triazine, 6-dibutylamino-2,4-dimercapto-1,3,5-triazine, 6-anilino-2,4-dimercapto-1, 3,5-triazine and the like can be mentioned. The compounding amount of the mercaptotriazine compound is 0.2 to 5 parts by weight with respect to 100 parts by weight of the chlorosulfonated polyolefin. When the blending amount is less than 0.2 parts by weight, a vulcanized product cannot be obtained. On the other hand, when it exceeds 5 parts by weight, the flexibility of the vulcanized product is impaired. In order to obtain suitable vulcanization adhesiveness and vulcanized physical properties, 0.5 to 4 parts by weight is preferable.

  The onium salt and / or tertiary amine salt having a diazabicyclo ring used in the present invention is used as a vulcanization accelerator for further promoting the effect of the mercaptotriazine compound.

  The onium salt used in the present invention is not particularly limited as long as it is a salt composed of an element having a bond number one larger than the reference bond number. Examples of onium salts include organic ammonium salts and organic phosphonium salts.

  The organic ammonium salt used in the present invention is not particularly limited. For example, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium tetrafluoroborate, tetramethylammonium bromide, Examples include tetraethylammonium bromide, trimethylphenylammonium bromide, trimethylbenzylammonium bromide, stearyltrimethylammonium bromide, and the like.

  The organic phosphonium salt used in the present invention is not particularly limited, and examples thereof include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, and butyltriphenylphosphonium bromide. Hexyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, 4-butoxybenzyltriphenylphosphonium bromide, allyltributylphosphonium chloride, 2-propynyltriphenylphosphonium bromide, Examples thereof include methoxypropyltributylphosphonium chloride and tetra-n-butylphosphonium benzotriazole. Of these, tetra-n-butylphosphonium benzotriazole and allyltributylphosphonium chloride, which are easily available, are preferably used.

  These organic ammonium salts and organic phosphonium salts can be used alone or in combination of two or more.

  The tertiary amine salt containing a diazabicyclo ring used in the present invention is, for example, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) -nonene-5. And a salt comprising a tertiary amine containing a diazabicyclo ring such as 6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7 and an acidic component such as a compound containing carbonic acid, phenols or carboxylic acid Is mentioned. Of these, preferred are salts of acidic components such as phenols of 1,8-diazabicyclo (5,4,0) undecene-7, compounds containing carboxylic acid, and the like because of their availability.

  These onium salts and tertiary amine salts containing a diazabicyclo ring can be used alone or in combination of two or more. The amount of tertiary amine salt containing an onium salt and a diazabicyclo ring is 0 with respect to 100 parts by weight of chlorosulfonated polyolefin in consideration of sufficient vulcanization adhesive strength, heat resistance, ozone resistance and compression set. 3 to 10 parts by weight. When the blending amount is less than 0.3 parts by weight, a vulcanized product cannot be obtained, while when it exceeds 10 parts by weight, the flexibility of the vulcanized product is impaired. In order to obtain suitable vulcanized physical properties, 0.5 to 7 parts by weight is preferable, and 1 to 5 parts by weight is more preferable.

  In the present invention, it is preferable to add sodium acetate trihydrate to improve vulcanization adhesion. The amount of sodium acetate trihydrate added is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of chlorosulfonated polyolefin in view of sufficient adhesion, workability, flexibility, etc., and suitable vulcanization In order to obtain an adhesion improvement effect, 0.5 to 15 parts by weight is more preferable.

  The chlorosulfonated polyolefin composition for laminates with the fluoropolymer of the present invention additionally requires an acid acceptor, a reinforcing agent, a filler, a processing aid, a softener, a plasticizer, an anti-aging agent, and the like. Added accordingly. Examples of the acid acceptor include lead oxide compounds such as magnesium oxide, calcium oxide, calcium hydroxide, lead monoxide and lead trioxide, and organic acid lead such as tribasic lead maleate and dibasic lead phthalate. Examples thereof include compounds and hydrotalcites. Examples of the reinforcing agent and filler include carbon black, white carbon, calcium carbonate, clay, and talc. As the processing aid, for example, low molecular weight polyethylene, polyethylene glycol, metal soap and the like are used. As the softener and plasticizer, for example, various oils, esters, chlorinated paraffin and the like are used. As an anti-aging agent, for example, a phenol-based anti-aging agent can be used.

  The fluoropolymer referred to in the present invention is a polymer having a fluorine atom, and examples thereof include an elastomeric fluoropolymer and a non-elastomeric fluoropolymer. Examples of the elastomeric fluorine-containing polymer include vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoromethyl vinyl ether copolymer, three Examples thereof include a fluorinated ethylene chloride-vinylidene fluoride copolymer and a tetrafluoroethylene-propylene copolymer. Non-elastomeric fluoropolymers include, for example, tetrafluoroethylene polymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer. Polymer, ethylene trifluorochloride polymer, chlorotrifluoroethylene-ethylene copolymer, polyvinylidene fluoride, vinyl fluoride polymer, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer (for example, DYNEON) Manufactured, THV (trade name)) and the like. Among these, non-elastomeric fluorine-containing polymers are preferable from the viewpoint of reducing the thickness and reducing the cost.

  Among fluoropolymers, in order to achieve strong vulcanization adhesion with the chlorosulfonated polyolefin composition, etching treatment with a metal sodium complex or the like, uneven treatment by sputtering, or reduced pressure plasma treatment, etc. In order to achieve strong vulcanization adhesion with the chlorosulfonated polyolefin composition without subjecting to surface treatment, those having a vinylidene fluoride structure are preferred. Examples of those having a vinylidene fluoride structure include polyvinylidene fluoride, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer (for example, THV (trade name) manufactured by DYNEON) and the like. Among these, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer (for example, THV (trade name) manufactured by DYNEON) is preferable.

  In addition, these fluoropolymers may contain acid acceptors, reinforcing agents, fillers, processing aids, softeners, plasticizers, anti-aging agents, vulcanizing agents, vulcanization accelerators, etc., as necessary. It is also possible to add an agent.

  The laminate in the present invention is a laminate comprising the chlorosulfonated polyolefin composition of the present invention and a fluorine-containing polymer, and examples thereof include films, sheets, hoses, tubes and the like. The laminate of the present invention includes, for example, a chlorosulfonated polyolefin composition of the present invention formed into a film or sheet by press molding or the like, and a fluorinated polymer formed into a film or sheet by press molding or the like. It is obtained by overlapping and vulcanizing by a normal vulcanization method such as press vulcanization, steam vulcanization, electron beam vulcanization and the like. In addition, the chlorosulfonated polyolefin composition of the present invention and a fluoropolymer laminated in a cylindrical shape by an extrusion apparatus are vulcanized by a normal vulcanization method such as press vulcanization, steam vulcanization, and electron beam vulcanization. Can also be obtained. Further, a chlorosulfonated polyolefin composition formed into a sheet or film and a fluoropolymer made into a film or sheet and wound in a cylindrical shape are laminated in a usual manner such as press vulcanization, steam vulcanization, and electron beam vulcanization. It can also be obtained by vulcanization by a vulcanization method.

  The laminated body of the present invention can also have a structure in which reinforcing fibers are further stacked.

  The laminated body thus obtained is used as a hose, a sheet or the like. In particular, it is suitable as a fuel system hose for automobiles.

  As described above, according to the present invention, it is clear that a chlorosulfonated polyolefin composition excellent in vulcanization adhesion with a fluorine-containing polymer can be obtained, and can be preferably applied to an automotive fuel hose or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited by these.

The values and test results used in these examples are based on the following measurement method.
<Adhesion test>
The adhesion test of a laminate composed of an elastomer composition and a fluoropolymer was made by molding an unvulcanized elastomer to a thickness of 2 mm and a non-elastomeric fluoropolymer to a thickness of 0.5 mm. They were adhered, vulcanized and bonded under predetermined conditions, and left at 23 ° C. for 24 hours. Then, it was punched into a strip shape having a width of 1 inch and a length of 150 mm to prepare a test piece for an adhesion test. The peel strength was measured by peeling the obtained test piece using a tensile tester at a peel rate of 50 mm / min.
<Hardness of vulcanizate>
After kneading according to the formulation of Table 1, steam vulcanization was performed at a predetermined temperature time. This sample was measured according to JIS K6253 (1997 edition).
<Tensile properties of vulcanizates>
After kneading according to the formulation of Table 1, steam vulcanization was performed at a predetermined temperature time. This sample was evaluated according to JIS K6251 (1993 version) using a dumbbell-shaped No. 3 type test piece at a tensile speed of 500 mm / min (breaking strength, breaking elongation, 100% stress).

Example 1
Chlorosulfonated polyethylene 1 was used as the chlorosulfonated polyolefin, and kneaded with an 8-inch open roll according to the formulation shown in Table 1 to form an unvulcanized compound sheet to a thickness of 2 mm. This unvulcanized compound sheet and a non-elastomeric fluorine-containing polymer obtained by molding a tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer (DYNON, THV-500G) to a thickness of 0.5 mm The laminated sheet in intimate contact with the sulfonated polyolefin unvulcanized sheet was treated at 160 ° C. for 40 minutes using a steam vulcanizer, and vulcanized physical properties evaluation and vulcanization adhesion test were performed. As a result, sufficient vulcanized physical properties were obtained, the adhesive strength was 5.0 kg / inch, the peeled state showed rubber breakage, and excellent vulcanized adhesiveness was exhibited. The test results are shown in Table 1.

実施例２
クロロスルホン化ポリオレフィンとしてクロロスルホン化ポリエチレン２を用いた以外は、実施例１と同様の方法にて１６０℃で４０分間処理することにより、加硫物性評価及び加硫接着試験を行った。その結果、十分な加硫物性が得られ、接着強度４．１ｋｇ／ｉｎｃｈ，剥離状態がゴム破壊を示し、優れた加硫接着性を示した。試験結果を表１に示す。

Example 2
Except for using chlorosulfonated polyethylene 2 as the chlorosulfonated polyolefin, a vulcanized physical property evaluation and a vulcanization adhesion test were performed by treating at 160 ° C. for 40 minutes in the same manner as in Example 1. As a result, sufficient vulcanized physical properties were obtained, the adhesive strength was 4.1 kg / inch, the peeled state showed rubber breakage, and excellent vulcanized adhesion was exhibited. The test results are shown in Table 1.

Example 3
Instead of 2.5 parts by weight of the DBU phenol salt, 40 parts at 160 ° C. in the same manner as in Example 1 except that 2 parts by weight of DBU formate was added as a tertiary amine salt having a diazabicyclo ring. The vulcanization physical property evaluation and the vulcanization adhesion test were performed by processing for a minute. As a result, sufficient vulcanized physical properties were obtained, the adhesive strength was 5.8 kg / inch, the peeled state showed rubber breakage, and excellent vulcanized adhesiveness was exhibited. The test results are shown in Table 1.

Example 4
Treated at 160 ° C. for 40 minutes in the same manner as in Example 1 except that 2 parts by weight of Zeonet PB (trade name) was added as an onium salt (organic phosphonium salt) instead of 2.5 parts by weight of the phenol salt of DBU. As a result, a vulcanized physical property evaluation and a vulcanization adhesion test were performed. As a result, sufficient vulcanized physical properties were obtained, the adhesive strength was 4.6 kg / inch, the peeled state showed rubber breakage, and excellent vulcanized adhesiveness was exhibited. The test results are shown in Table 1.

Example 5
Instead of 2.5 parts by weight of DBU phenol salt, 1.5 parts by weight of DBU phenol salt as a tertiary amine salt having a diazabicyclo ring and 1 part by weight of Zeonet PB (trade name) as onium salt (organic phosphonium salt) Except for the addition of a part, a vulcanized physical property evaluation and a vulcanization adhesion test were conducted by treating at 160 ° C. for 40 minutes in the same manner as in Example 1. As a result, sufficient vulcanized physical properties were obtained, the adhesive strength was 5.2 kg / inch, the peeled state showed rubber breakage, and excellent vulcanized adhesiveness was exhibited. The test results are shown in Table 1.

Example 6
A layer made of the chlorinated polyolefin composition of Example 1 (3 mm-thick unvulcanized compound sheet) and a layer made of a fluororubber composition having the following composition (3 mm-thick unvulcanized compound sheet) were brought into close contact with each other and pressed. Using a vulcanizer, vulcanization adhesion was performed by treating at 160 ° C. for 40 minutes to obtain a laminate. An adhesion test was performed in the same manner as in Example 1. As a result, the vulcanized adhesive strength was 9.5 kg / inch, the peeled state showed rubber breakage, and excellent vulcanized adhesiveness was exhibited. The test results are shown in Table 1.

Fluoro rubber (* 1): 100 parts by weight Magnesium oxide: 5 parts by weight Calcium hydroxide: 2.6 parts by weight Carbon MT: 20 parts by weight Zisnet DB (* 2): 2 parts by weight Dynamer FX-5166: 5 parts by weight
(* 1) Technoflon TN50S (Nippon Zeon Corporation)
(* 2) 6-dibutylamino-1,3,5-triazine-2,4-
Dithiol (made by Nippon Zeon)
Example 7
The layer made of the chlorinated polyolefin composition of Example 2 (3 mm-thick unvulcanized compound sheet) and the layer made of the fluororubber composition described in Example 6 (3 mm-thick unvulcanized compound sheet) were adhered, Using a press vulcanizer, vulcanization was performed by treating at 160 ° C. for 40 minutes to obtain a laminate. An adhesion test was performed in the same manner as in Example 1. As a result, the vulcanized adhesive strength was 8.8 kg / inch, the peeled state showed rubber breakage, and excellent vulcanized adhesiveness was exhibited. The test results are shown in Table 1.

Comparative Example 1
Except for using chlorosulfonated polyethylene 3 as the chlorosulfonated polyolefin, a vulcanized physical property evaluation and a vulcanization adhesion test were performed by treating at 160 ° C. for 40 minutes in the same manner as in Example 1. As a result, sufficient vulcanized physical properties were obtained, but the adhesive strength was 1.7 kg / inch, the peeled state was interfacial peeling, and the vulcanized adhesiveness was very poor. The test results are shown in Table 2.

比較例２
ＤＢＵのフェノール塩を添加しない以外は、実施例１と同様の方法にて１６０℃で４０分間処理することにより、加硫物性評価及び加硫接着試験を行った。その結果、加硫物が得られず、接着強度０ｋｇ／ｉｎｃｈ，剥離状態が界面剥離であり、加硫接着性を示さなかった。試験結果を表２に示す。

Comparative Example 2
A vulcanized physical property evaluation and a vulcanization adhesion test were performed by treating at 160 ° C. for 40 minutes in the same manner as in Example 1 except that the DBU phenol salt was not added. As a result, a vulcanized product was not obtained, the adhesive strength was 0 kg / inch, the peeled state was interfacial peeling, and no vulcanization adhesion was exhibited. The test results are shown in Table 2.

Comparative Example 3
It knead | mixed with the 8-inch open roll by the method similar to Example 1 except having changed the addition amount of the phenol salt of DBU from 2.5 weight part to 15 weight part. As a result, gelation progressed during kneading and could not be formed into a 2 mm thick sheet. Therefore, vulcanization physical property evaluation and vulcanization adhesion evaluation could not be performed.

Comparative Example 4
A vulcanized physical property evaluation and a vulcanization adhesion test were performed by treating at 160 ° C. for 40 minutes in the same manner as in Example 1 except that noxeller TCA (trade name) as a mercaptotriazine compound was not added. As a result, a vulcanized product was not obtained, the adhesive strength was 0 kg / inch, the peeled state was interfacial peeling, and no vulcanization adhesion was exhibited. The test results are shown in Table 2.

Comparative Example 5
By treating for 40 minutes at 160 ° C. in the same manner as in Example 1 except that the addition amount of Noxeller TCA (trade name) as a mercaptotriazine compound was changed from 2 parts by weight to 10 parts by weight, vulcanized physical properties evaluation and addition A sulfur adhesion test was conducted. As a result, sufficient vulcanized physical properties were obtained, but the adhesive strength was 0 kg / inch, the peeled state was interfacial peeling, and the vulcanized adhesiveness was very poor. The test results are shown in Table 2.

Claims (11)

Tertiary having 0.2 to 5 parts by weight of mercaptotriazine compound, onium salt and / or diazabicyclo ring with respect to 100 parts by weight of chlorosulfonated polyolefin having a sulfur content of 0.05 to 0.45% by weight A chlorosulfonated polyolefin composition for laminates with a fluoropolymer, comprising 0.3 to 10 parts by weight of an amine salt. The chlorosulfonated polyolefin composition for a laminate with a fluoropolymer according to claim 1, wherein the chlorosulfonated polyolefin is a chlorosulfonated polyethylene and / or a chlorosulfonated ethylene-α-olefin copolymer. object. The chlorosulfonated polyolefin composition for laminates with a fluoropolymer according to claim 1 or 2, wherein the chlorine content of the chlorosulfonated polyolefin is 15 to 50% by weight. The mercaptotriazine compound is 2,4,6-trimercapto-1,3,5-triazine, for a laminate with a fluoropolymer according to any one of claims 1 to 3. Chlorosulfonated polyolefin composition. The chlorosulfonated polyolefin composition for laminates with a fluorine-containing polymer according to any one of claims 1 to 4, wherein the onium salt is an organic ammonium salt and / or an organic phosphonium salt. . The organic phosphonium salt is tetra-n-butylphosphonium benzotriazole and / or allyltributylphosphonium chloride, The chlorosulfonated polyolefin composition for laminates with a fluorine-containing polymer according to claim 5. A tertiary amine salt having a diazabicyclo ring is a salt of 1,8-diazabicyclo (5,4,0) undecene-7 with a phenol, 1,8-diazabicyclo (5,4,0) undecene-7 The chlorosulfonated polyolefin composition for laminates with a fluorine-containing polymer according to any one of claims 1 to 6, wherein the composition is a salt with a compound containing an acid. The chlorosulfonated polyolefin composition for laminates with the fluoropolymer according to any one of claims 1 to 7, further comprising 0.1 to 30 parts by weight of sodium acetate trihydrate A chlorosulfonated polyolefin composition for laminates with a fluorine-containing polymer. A chlorosulfonated polyolefin composition for laminates with a fluoropolymer according to any one of claims 1 to 8 and a fluoropolymer are overlaid and vulcanized. A laminate comprising a fluoropolymer and a chlorosulfonated polyolefin composition. The laminate comprising a fluoropolymer and a chlorosulfonated polyolefin composition according to claim 9, wherein the fluoropolymer contains a vinylidene fluoride structure. A hose comprising a laminate comprising the fluoropolymer according to claim 9 or 10 and a chlorosulfonated polyolefin composition.