JP2003041078A - Chlorinated polyolefin composition, laminate and hose using the same - Google Patents

Abstract

(57) Abstract: An object of the present invention is to provide a chlorinated polyolefin composition capable of firmly vulcanizing and bonding without subjecting a fluoropolymer to a special surface treatment, and a layer comprising the composition. An object of the present invention is to provide a laminate with a layer made of a fluoropolymer. An acid acceptor (5 to 40) is added to 100 parts by weight of a chlorinated polyolefin having a chlorine content of 25 to 50% by weight.
A chlorinated polyolefin composition comprising 0.1 parts by weight, 0.3-15 parts by weight of onium salt, 1-5 parts by weight of a mercaptotriazine compound, 0.1-5.0 parts by weight of a thiuram compound and / or sulfur is produced and used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a chlorinated polyolefin composition having excellent vulcanization adhesion to a fluoropolymer, and excellent adhesion strength between a layer made of the composition and a layer made of the fluoropolymer. The present invention relates to a laminated body and a hose made of the laminated body, and relates to a laminated body and a hose suitable for applications requiring excellent oil resistance, fuel oil resistance, and fuel oil permeation resistance.

[0002]

2. Description of the Related Art In the field of fuel hoses, excellent fuel oil resistance and fuel oil permeation resistance are required, so that rubber materials with high polarity such as nitrile rubber, chlorosulfonated polyethylene, and hydrin rubber are mainly used. Has been applied.

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

Under such circumstances, there is a tendency to use a fluoropolymer having excellent fuel oil resistance and fuel oil permeation resistance as a material for the fuel system hose, but it is more expensive than conventional rubber materials. Therefore, it has been attempted to reduce the cost by thinning the fluoropolymer and forming a laminate with another type of rubber. Among the fluoropolymers, non-elastomeric fluoropolymers are more excellent in fuel oil resistance and fuel oil permeation resistance than elastomeric fluoropolymers. However, the application of non-elastomeric fluoropolymers has been attracting attention from the viewpoint of cost reduction.

On the other hand, an important required characteristic of the laminated fuel system hose is the adhesiveness between the layers. If the adhesion strength between the layers is insufficient, there is a risk of delamination during use, which is a serious defect for fuel system hoses. Especially for non-elastomeric fluoropolymers, the adhesiveness between the respective layers is poor because it does not require compounding agents such as various reinforcing agents and vulcanizing agents unlike the elastomeric fluoropolymers. . Therefore, the non-elastomer fluorine-containing polymer is subjected to a surface treatment such as an etching treatment with a metal sodium complex or the like, a concavo-convex treatment by sputtering, or a reduced-pressure plasma treatment to improve the adhesive strength with other rubbers.

[0006]

However, since the above-mentioned surface treatment complicates the hose manufacturing process and raises the cost of the hose product, there is a demand for a technique capable of performing strong adhesion without performing the surface treatment. There is.

Further, the rubber type laminated with the fluoropolymer is naturally excellent in fuel oil resistance and fuel oil permeation resistance, but the rubber type used in the outer layer is heat resistant,
Weather resistance and ozone resistance are also required, and in order to reduce the manufacturing cost of the hose, it is desirable that the rubber to be applied be low in price. A chlorinated polyolefin is mentioned as a rubber type which satisfies these required physical properties and is relatively inexpensive, but its improvement is strongly desired because of its poor adhesion to a fluoropolymer.

The present invention has been made in view of the above problems, and is a chlorinated polyolefin composition capable of being firmly vulcanized and bonded without subjecting a fluoropolymer to a special surface treatment, and the composition. An object of the present invention is to provide a layered product of a layer composed of and a layer composed of a fluoropolymer.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by applying a specific vulcanization system to chlorinated polyolefin. It was found that the present invention has been completed. That is, the present invention has a chlorine content of 25 to 5
5 to 40 parts by weight of an acid acceptor and 0.3 to 15 parts of an onium salt based on 100 parts by weight of a chlorinated polyolefin which is 0% by weight.
Chlorination excellent in vulcanization adhesiveness with a fluoropolymer characterized by containing 1 to 5 parts by weight, a mercaptotriazine compound, 1 to 5 parts by weight, a thiuram compound and / or 0.1 to 5.0 parts by weight of sulfur. A polyolefin composition, a laminate of a layer made of the chlorinated polyolefin composition and a layer made of a fluoropolymer, and a hose made of the laminate.

The present invention will be described in detail below.

The chlorinated polyolefin composition of the present invention contains 5 to 40 parts by weight of an acid acceptor and 0.3 to 15 parts by weight of an onium salt based on 100 parts by weight of a chlorinated polyolefin having a chlorine content of 25 to 50% by weight. Parts, 1 to 5 parts by weight of a mercaptotriazine compound, 0.1 to 5.0 parts by weight of a thiuram compound and / or sulfur.

The chlorinated polyolefin used in the present invention is not particularly limited as long as it is a chlorinated polyolefin having a chlorine content of 25 to 50% by weight, which is obtained by chlorinating a raw material polyolefin.
Chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-1-butene copolymer, chlorinated ethylene-1-hexene copolymer, chlorinated ethylene-1
Examples include chlorinated ethylene-α-olefin copolymers such as octene, chlorinated ethylene-α-olefin copolymers, chlorinated ethylene-vinyl acetate copolymers and chlorinated propylene. In addition, these chlorinated polyolefins can be used alone or as a blend of two or more kinds without any problem. In order to obtain appropriate vulcanization properties and processability, the Mooney viscosity (ML _{1 + 4} (100 ° C.)) of the chlorinated polyolefin is preferably in the range of 10 to 150.

The amount of chlorine in the chlorinated polyolefin in the present invention is 25 to 50% by weight. When it is less than 25% by weight, the fuel oil resistance and fuel oil permeation resistance are poor, which is not preferable, and when it exceeds 50% by weight, the adhesiveness is poor, which is not preferable. In order to improve the balance between vulcanization adhesion and desired fuel oil resistance, heat resistance, weather resistance and vulcanization physical properties,
45% by weight is preferred.

The acid acceptors used in the present invention include magnesium oxide, calcium oxide, calcium hydroxide, lead oxide compounds such as lead monoxide and lead trioxide, tribasic lead maleate and dibasic phthalic acid. Organic acid lead compounds such as lead and hydrotalcites can be mentioned. The hydrotalcites referred to here are basic magnesium, aluminum,
It is a hydroxy carbonate hydrate,
The surface-treated product, decrystallized water product, calcined product and the like of this compound are also meant.

These acid acceptors may be used alone or in combination of two or more. The compounding amount of the acid acceptor is 5 to 40 parts by weight with respect to 100 parts by weight of chlorinated polyolefin,
To obtain suitable vulcanization adhesion and vulcanization physical properties, 10 to 3 is required.
0 parts by weight is preferred. If the acid acceptor is less than 5 parts by weight,
It is not preferable because sufficient vulcanization adhesive strength cannot be obtained and vulcanization physical properties become inferior. On the other hand, when the amount of the acid acceptor exceeds 40 parts by weight, the viscosity of the unvulcanized compound becomes high, resulting in poor processability, and the chlorinated polyolefin vulcanizate obtained has heat resistance and compression. It is not preferable because the permanent set is inferior.

The onium salt used in the present invention includes:
Examples thereof include organic ammonium salts and organic phosphonium salts, but are not particularly limited. Examples of organic ammonium salts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate,
Tetrabutylammonium tetrafluoroborate, tetramethylammonium bromide, tetraethylammonium bromide, trimethylphenylammonium bromide, trimethylbenzylammonium bromide, stearyltrimethylammonium bromide, 1,8-diazabicyclo (5,4,4)
0) Carboxylic acid salts of undecene-7, phenol resin salts, and the like. Further, as an example of the organic phosphonium salt,
Tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, tetraphenylphosphonium chloride , Tetraphenylphosphonium bromide, 4-butoxybenzyltriphenylphosphonium bromide, allyltributylphosphonium chloride, 2-bromide
Examples include propynyltriphenylphosphonium, methoxypropyltributylphosphonium chloride, and tetra-n-butylphosphonium benzotriazole. These onium salts may be used alone or in combination of two or more.
The amount of the onium salt is 0.3 to 15 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin, and 1 to 12 parts by weight is preferable in order to obtain suitable vulcanization adhesiveness and vulcanized physical properties. If the amount of the onium salt is less than 0.3 parts by weight, sufficient vulcanization adhesive strength cannot be obtained, and the vulcanized physical properties become inferior, which is not preferable. On the other hand, when the amount of the onium salt exceeds 15 parts by weight, the chlorinated polyolefin vulcanizate obtained is inferior in heat resistance, ozone resistance and compression set, which is not preferable.

The mercaptotriazine compound used in the present invention is not particularly limited as long as it 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. These mercaptotriazine compounds may be used alone or in combination of two or more. The blending amount of the mercaptotriazine compound is 1 to 5 parts by weight with respect to 100 parts by weight of the chlorinated polyolefin, and 1 to 3 parts by weight is preferable in order to obtain suitable vulcanization adhesiveness and vulcanized physical properties. When the amount of the mercaptotriazine compound is less than 1 part by weight, sufficient vulcanization adhesive strength cannot be obtained and the vulcanized physical properties are inferior, which is not preferable. On the other hand, when the mercaptotriazine compound exceeds 5 parts by weight, the storage stability of the obtained chlorinated polyolefin composition is poor,
The problem of premature vulcanization arises. Further, the elongation at break and the fatigue resistance of the obtained vulcanizate are lowered, which is not preferable.

The thiuram compound used in the present invention is not particularly limited as long as it has a polysulfide structure of disulfide or more, and examples thereof include tetramethylthiuram disulfide, tetraethylthiuram disulfide and dipentamethylenethiuram tetrasulfide. These thiuram compounds can be used alone or in combination of two or more. The compounding amount of the thiuram compound is 0.1 to 5.0 with respect to 100 parts by weight of the chlorinated polyolefin.
In order to obtain suitable vulcanization adhesiveness and vulcanization physical properties, 0.2 to 3.0 parts by weight is preferable. If the amount of the thiuram compound is less than 0.1 part by weight, sufficient vulcanization adhesive strength cannot be obtained, which is not preferable. On the other hand, when the amount of the thiuram compound is more than 5 parts by weight, the compression set of the vulcanizate obtained is lowered, which is not preferable.

It is also possible to add sulfur in place of the thiuram compound. The content of sulfur is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of chlorinated polyolefin,
In order to obtain suitable vulcanization adhesiveness and vulcanized physical properties, 0.2 to
3.0 parts by weight is preferred. When the amount of sulfur is less than 0.1 part by weight, sufficient vulcanization adhesive strength cannot be obtained, which is not preferable. On the other hand, when the amount of sulfur exceeds 5 parts by weight, the compression set of the obtained vulcanizate is lowered, which is not preferable. Also,
Sulfur can be used in combination with the thiuram compound.

If necessary, a reinforcing agent, a filler, a processing aid, a softening agent, a plasticizer, an antiaging agent and the like are added to the chlorinated polyolefin composition of the present invention. Reinforcing agent,
Examples of the filler include carbon black, white carbon, calcium carbonate, clay, talc and the like. As the processing aid, for example, low molecular weight polyethylene, metal soap, etc. are used. As the softening agent and the plasticizer, for example, various oils, esters, paraffin chloride and the like are used. As the antiaging agent, for example, an amine antiaging agent, a phenol antiaging agent or the like can be used.

The laminate of the present invention comprises a layer made of a chlorinated polyolefin composition and a layer made of a fluoropolymer.

The fluorine-containing polymer used in the present invention is
Elastomer-based fluoropolymers and non-elastomeric fluoropolymers, such as tetrafluoroethylene-ethylene copolymers, tetrafluoroethylene-propylene copolymers, chlorotrifluoroethylene-ethylene copolymers, polyvinylidene Fluoride, polyvinyl fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-vinylidene fluoride-perfluoroalkyl vinyl ether copolymer, tetra There are fluoroethylene-vinylidene fluoride-propylene copolymer, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer and the like. Strong vulcanization adhesiveness with the chlorinated polyolefin composition, which is an important requirement in the present invention, without performing surface treatment such as etching treatment with a metal sodium complex or the like, uneven treatment by sputtering, or reduced pressure plasma treatment. In order to achieve the above, it is preferable to use vinylidene fluoride as a monomer component of the fluoropolymer, and a fluoropolymer having hexafluoropropylene, for example, tetrafluoroethylene-vinylidene fluoride-hexafluoro. Examples include propylene copolymers. However, subjecting the fluoropolymer to the above-mentioned surface treatment does not cause any problems, and it is possible to achieve strong vulcanization adhesiveness with the chlorinated polyolefin composition.

If desired, a compounding agent such as carbon black or a processing aid may be added to these fluoropolymers. In particular, regarding the elastomeric fluoropolymer, an acid acceptor, a reinforcing agent, a filler, a processing aid, a softening agent, a plasticizer, an antioxidant, a vulcanizing agent, a vulcanization accelerator, etc. are added as necessary. To be

The laminate of the present invention comprises the above-mentioned chlorinated polyolefin composition and a fluoropolymer, which are superposed on each other.
It can be obtained by vulcanizing by a usual vulcanizing method such as press vulcanization, steam vulcanization, electron beam vulcanization, etc., but a layer composed of a chlorinated polyolefin composition and a layer composed of a fluoropolymer has a plurality of laminated structures. May be formed. Further, in a laminate comprising a chlorinated polyolefin composition and a fluoropolymer,
It is also possible to have another polymer layer made of nitrile rubber, hydrin rubber, acrylic rubber, chlorosulfonated polyethylene or the like, or a structure in which reinforcing fibers are laminated.

The laminate with the fluorine-containing polymer using the chlorinated polyolefin composition of the present invention has excellent vulcanization adhesiveness and excellent oil resistance, fuel oil resistance, and fuel oil permeation resistance. It can be used for the required laminates and hoses, especially automotive fuel system hoses.

[0026]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

The materials in Tables 1 to 3 are as follows.

Chlorinated polyolefin (1): Chlorinated polyethylene with chlorine content of 35% Chlorinated polyolefin (2): Chlorinated polyethylene with chlorine content of 40% Chlorinated polyolefin (3): Chlorinated chlorine content of 47% Polyethylene Chlorinated Polyolefin (4): Chlorinated Ethylene-1-butene Copolymer with Chlorine Content = 28% Chlorinated Polyolefin (5): Showa Denko Erasulene 351AE (Chlorine Content = 35%) Chlorinated Polyolefin (6) : Chlorinated polyethylene with chlorine content = 53% Magnesium oxide: Kyowamag 150 (manufactured by Kyowa Chemical Industry Co., Ltd.) Calcium hydroxide: Calbit (manufactured by Omi Chemical Co., Ltd.) Special wax: ACPE 617A (manufactured by Allied Signal Co.) Carbon SRF: Seast S (Tokai Carbon Co.) Calcium Carbonate: Silver W (White NIPSEAL VN3: White carbon (manufactured by Nippon Silica Co., Ltd.) Plasticizer DOS: Sanso Sizer DOS (manufactured by Shin Nippon Rika Co., Ltd.) Restax A-2: Alkylphenol resin (manufactured by Mitsui Mining Chemicals Co., Ltd.) HYPER CH : Hydrogenated rosin (manufactured by Arakawa Chemical Co., Ltd.) Zeonet PB: Tetra-n-butylphosphonium benzotriazolate (manufactured by Nippon Kagaku Kogyo Co., Ltd.) Dynamer FX-5166: Allyltributylphosphonium chloride mixture (40%) (Sumitomo) Nox Cellar TCA: 2,4,6-Trimercapto-S-Triazine (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Nox cellar TT: Tetramethylthiuram disulfide (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) NOXCELLER TRA: dipentamethylene thiuram tetrasulfi (Ouchi Shinko Chemical Industrial Co., Ltd.) Sulfur: Jinhua mark precipitated sulfur (manufactured by Tsurumi Chemical Industry Co., Ltd.) The value used in these examples, and test results are in compliance with the following measurement methods. <Adhesion test> An adhesion test of a laminate of a layer made of a chlorinated polyolefin composition and a layer made of a fluoropolymer is carried out by using an unvulcanized chlorinated polyolefin composition having a thickness of 2 mm and a non-elastomer having a thickness of 0.5 mm. The fluorine-containing polymer or the elastomeric fluorine-containing polymer composition having a thickness of 2 mm was brought into close contact, vulcanized and adhered under predetermined conditions, and left at 23 ° C. for 24 hours. Then, it was punched into a strip 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 using a tensile tester to measure the obtained test piece at 50
It was measured by peeling at a peeling speed of mm / min. <Adhesion Test after Immersion in Fuel Oil-C> A test piece obtained by the same method as described above was immersed in a fuel oil having the following composition for 48 hours in an atmosphere of 23 ° C. and then for 24 hours at 23 ° C. under atmospheric pressure. It was dried and further dried in a vacuum dryer at 23 ° C. for 24 hours to obtain an adhesive test piece after immersion in fuel oil-C.
The peel strength was measured by the same method as described above.

Fuel oil-C 2,2,4-trimethylpentane: 50% by volume Toluene: 50% by volume <Alcohol-added fuel oil-4 adhesion test after immersion> Alcohol-added fuel oil having the following composition The peel strength was measured by the same method as the adhesion test after immersion in fuel oil-C, except that the peel strength was changed to.

Alcohol-added fuel oil-4 2,2,4-trimethylpentane: 42.5% by volume Toluene: 42.5% by volume Methanol: 15.0% by volume Example 1 Chlorinated polyethylene having a chlorine content of 35% by weight Was kneaded with an 8-inch open roll according to the formulation shown in Table 1 and molded into an unvulcanized compound sheet having a thickness of 2 mm. Using this as a fluoropolymer, a 0.5 mm thick tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer (manufactured by DYNEON, T
HV-500G), using a press vulcanizer,
It was vulcanized and adhered by treating at 160 ° C. for 30 minutes to obtain a laminate. The results of the adhesion test of this laminate are shown in Table 1. As a result, fuel oil-C and alcohol-added fuel oil-
4 Although the peeled state after immersion was interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

[0031]

[Table 1] Example 2 A laminate was obtained in the same formulation as in Example 1 except that chlorinated polyethylene having a chlorine content of 40% was used as the chlorinated polyolefin. The results of the peeling test of the obtained laminate are shown in Table 1. Although the peeling state after immersion in alcohol-added fuel oil-4 was partially interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

Example 3 A laminate was prepared in the same manner as in Example 1 except that chlorinated polyethylene having a chlorine content of 47% was used as the chlorinated polyolefin. The results of the peeling test of the obtained laminate are shown in Table 1. Although the peeling state after immersion in alcohol-added fuel oil-4 was partially interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

Example 4 A laminate was prepared in the same manner as in Example 1 except that a chlorinated ethylene-1-butene copolymer having a chlorine content of 28% was used as the chlorinated polyolefin. The results of the peeling test of the obtained laminate are shown in Table 1. Although the peeling state after immersion in fuel oil-C and alcohol-added fuel oil-4 is interfacial peeling, excellent peeling strength is exhibited in any peeling test, and the obtained laminate has sufficient adhesive strength. all right.

Example 5 Erasuren 35 manufactured by Showa Denko as a chlorinated polyolefin
Example 1 except that 1AE (chlorine content 35%) was used
A laminate was obtained with the same formulation. The results of the peeling test of the obtained laminate are shown in Table 1. Although the peeling state after immersion in fuel oil-C was partly interfacial peeling and the peeling state after immersion in alcohol-added fuel oil-4 was interfacial peeling, excellent peeling strength was obtained in any peeling test, and obtained. It was found that the laminated body having sufficient adhesive strength.

Comparative Example 1 A laminate was obtained in the same formulation as in Example 1 except that chlorinated polyethylene having a chlorine content of 53% was used as the chlorinated polyolefin. The results of the peeling test of the obtained laminate are shown in Table 1. It was found that the peeling state in the peeling test was interfacial peeling and the peeling strength was insufficient.

Example 6 Restax A-2 was changed to Hyper CH and 4
10 parts by weight of Dynanet PB
A laminate was obtained by the same formulation as in Example 1 except that FX-5166 was used. The results of the peeling test of the obtained laminate are shown in Table 1. In all of the peeling tests, the peeled state was rubber breakage, and the excellent peeling strength was exhibited. Therefore, it was found that the obtained laminate had sufficient adhesive strength.

Example 7 A laminate was obtained in the same formulation as in Example 6 except that chlorinated polyethylene having a chlorine content of 40% was used as the chlorinated polyolefin. The results of the peeling test of the obtained laminate are shown in Table 1. Although the peeling state after immersion in alcohol-added fuel oil-4 was interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

Example 8 A laminate was prepared in the same manner as in Example 6 except that a chlorinated ethylene-1-butene copolymer having a chlorine content of 28% was used as the chlorinated polyolefin. The results of the peeling test of the obtained laminate are shown in Table 1. In all of the peeling tests, the peeled state was rubber breakage, and the excellent peeling strength was exhibited. Therefore, it was found that the obtained laminate had sufficient adhesive strength.

Example 9 A laminate was obtained by the same formulation as in Example 1 except that 10 parts by weight of Nipseal VN3 was added. The results of the peeling test of the obtained laminate are shown in Table 2. Although the peeling state after immersion in fuel oil-C is partly interfacial peeling, and the peeling state after immersion in alcohol-added fuel oil-4 is interfacial peeling,
Excellent peel strength was shown in all peel tests, and it was found that the obtained laminate had sufficient adhesive strength.

[0040]

[Table 2] Example 10 A laminate was obtained by the same formulation as in Example 9 except that calcium hydroxide was omitted. The results of the peeling test of the obtained laminate are shown in Table 2. Although the peeling state after immersion in alcohol-added fuel oil-4 was interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

Example 11 A laminate was prepared in the same manner as in Example 2 except that the amount of Nocceller TT added was changed to 0.5 part by weight. The results of the peeling test of the obtained laminate are shown in Table 2. Although the peeling state after immersion in fuel oil-C and alcohol-added fuel oil-4 is interfacial peeling, excellent peeling strength is exhibited in any peeling test, and the obtained laminate has sufficient adhesive strength. all right.

Example 12 Nocceller TT was changed to 1 part by weight, except that
A laminate was obtained with the same formulation as in Example 2. The results of the peeling test of the obtained laminate are shown in Table 2. Fuel oil-C
Although the peeled state after immersion in alcohol-added fuel oil-4 was interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

Example 13 Nocceller TT was used, except that the amount added was changed to 3 parts.
A laminate was obtained with the same formulation as in Example 2. The results of the peeling test of the obtained laminate are shown in Table 2. Fuel oil-C
Although the peeled state after immersion was interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

Comparative Example 2 A laminate was obtained in the same formulation as in Example 2 except that Noxcellar TT was omitted. The results of the peeling test of the obtained laminate are shown in Table 2. It was found that the peeling state in each peeling test was interfacial peeling and the peeling strength was insufficient.

Comparative Example 3 A laminate was obtained in the same formulation as in Example 7, except that Noxcellar TT was omitted. The results of the peeling test of the obtained laminate are shown in Table 2. It was found that the peeling state in each peeling test was interfacial peeling and the peeling strength was insufficient.

Comparative Example 4 Table 2 shows the results of vulcanization adhesion with the same formulation as in Example 2 except that Zeonet PB was omitted.
The peel test could not be performed because the chlorinated polyolefin composition was not sufficiently vulcanized.

Comparative Example 5 Table 2 shows the results of vulcanization adhesion with the same formulation as in Example 7, except that Dynamer FX-5166 was omitted. The peel test could not be performed because the chlorinated polyolefin composition was not sufficiently vulcanized.

Example 14 A laminate was obtained by the same formulation as in Example 2 except that Noxcellar TT was changed to Noxcellar TRA. The results of the peeling test of the obtained laminate are shown in Table 3. Although the peeling state after immersion in alcohol-added fuel oil-4 was partially interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

[0049]

[Table 3] Example 15 A laminate was obtained by the same formulation as in Example 2 except that sulfur was used instead of Noxcellar TT. The results of the peeling test of the obtained laminate are shown in Table 3. Although the peeling state after immersion in alcohol-added fuel oil-4 was partially interfacial peeling, excellent peeling strength was exhibited in all peeling tests, and it was found that the obtained laminate had sufficient adhesive strength.

Example 16 3 mm comprising the chlorinated polyolefin composition of Example 2
An unvulcanized compound sheet having a thickness and an unvulcanized compound sheet having a thickness of 3 mm, which is made of a fluororubber composition having the following composition, are closely adhered to each other, and vulcanized and adhered by using a press vulcanizer at 170 ° C for 30 minutes. Then, a laminated body was obtained. As a result of performing an adhesion test in the same manner as in Example 2, the peel strength was 1 for the laminate not subjected to the dipping treatment.
5.5 kg / inch, 11.3 kg / inch for the laminated body after the fuel oil-C immersion treatment, 10.2 kg / inch for the laminated body after the alcohol-added fuel oil-4 immersion treatment, and both peeled states were fluorine. Since the rubber layer was destroyed, it was found that the obtained laminate had sufficient adhesive strength.

Fluorine 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 (Zeon Corporation) ²⁾ 6-dibutylamino-1,3,5-triazine-2,
4-dithiol (manufactured by Zeon Corporation)

[0052]

Industrial Applicability As described above, the chlorinated polyolefin composition of the present invention is excellent in vulcanization adhesion to a fluoropolymer which is not subjected to any special surface treatment, and thus the chlorinated polyolefin composition of the present invention. The laminate of the layer made of the composition and the layer made of the fluoropolymer has a strong adhesive strength.
Therefore, the laminated body of the present invention is required to have excellent fuel oil resistance and fuel oil permeation resistance, is also excellent in heat resistance, weather resistance, ozone resistance, and the like, and is a fuel system for automobiles suitable for reducing the manufacturing cost of a hose. It can be preferably applied to hoses and the like.

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Claims (10)

[Claims] 1. An acid acceptor 5 to 40 relative to 100 parts by weight of a chlorinated polyolefin having a chlorine content of 25 to 50% by weight.
A chlorinated polyolefin composition comprising 1 part by weight, 0.3 to 15 parts by weight of an onium salt, 1 to 5 parts by weight of a mercaptotriazine compound, 0.1 to 5.0 parts by weight of a thiuram compound and / or sulfur. 2. The chlorinated polyolefin is at least one selected from the group consisting of chlorinated polyethylene, chlorinated ethylene-α-olefin copolymer, chlorinated ethylene-vinyl acetate copolymer, and chlorinated propylene. The chlorinated polyolefin composition according to claim 1. 3. The acid acceptor is at least one selected from the group consisting of magnesium oxide, calcium oxide, calcium hydroxide, lead oxide compounds, organic acid lead compounds, and hydrotalcites. Item 3. The chlorinated polyolefin composition according to item 1. 4. The onium salt is an organic ammonium salt and / or
Alternatively, the chlorinated polyolefin composition according to claim 1, which is an organic phosphonium salt. 5. The chlorinated polyolefin composition according to claim 4, wherein the organic phosphonium salt is tetra-n-butylphosphonium benzotriazole and / or allyltributylphosphonium chloride. 6. The mercaptotriazine compound is 2,4.
6-Trimercapto-1,3,5-triazine, 6-dibutylamino-2,4-dimercapto-1,3,5-triazine, and 6-anilino-2,4-dimercapto-
The chlorinated polyolefin composition according to claim 1, which is at least one selected from the group consisting of 1,3,5-triazine. 7. The chlorinated polyolefin composition according to claim 1, wherein the thiuram compound is at least one selected from the group consisting of tetramethylthiuram disulfide, tetraethylthiuram disulfide, and dipentamethylene thiuram tetrasulfide. . 8. A laminate comprising a layer comprising the chlorinated polyolefin composition according to claim 1 and a layer comprising a fluoropolymer. 9. The laminate according to claim 8, wherein the fluorine-containing polymer contains vinylidene fluoride and a hexafluoropropylene component. 10. A hose comprising the laminated body according to claim 8 or 9.