JPS6261056B2 - - Google Patents

Description

[Detailed description of the invention]

[] Object of the Invention The present invention relates to a method of adhering a metal surface to a chlorinated polyethylene composition. More specifically,
After applying and drying an adhesive containing a thermosetting phenolic resin as a main component to the surface of the metal, and bonding a composition containing a chlorine-containing polymer as a main component and a dried or molded product thereof to the coated surface, Then, a composition containing crosslinkable chlorinated polyethylene is applied to the surface of this mixture or a molded product thereof, and the composition is dried, or the molded product is bonded together to simultaneously perform crosslinking and adhesion. The object of the present invention is to provide a method for producing an adhesive with excellent adhesion between a chlorinated polyethylene composition and a chlorinated polyethylene composition. [] Background of the Invention Methods for bonding a metal surface to a composition containing a polymeric substance as a main component or a molded product thereof have been proposed for quite some time. In particular, bonding a composition based on chlorinated polyethylene or a molded product of the composition to a metal surface is difficult because chlorinated polyethylene, especially amorphous chlorinated polyethylene rubber, is chemically saturated. Based on the fact that it is not only a structure but also a chlorine-containing polymeric material, the adhesive that adheres it to the metal surface can be used to attach compositions based on other polymeric articles or molded products thereof to the metal surface. Weather resistant, flame retardant,
Because of its good physical properties such as chemical resistance, oil resistance, electrical properties, and heat resistance, it is used in many industrial fields, being molded into wire coatings, appliance parts, hoses, building materials, automatic parts, packing, sheets, etc. has been done. This method of manufacturing an adhesive by bonding a metal surface and a chlorinated polyethylene composition or a molded product thereof involves crosslinking and adhesion when bonding the metal surface and the composition or molded product thereof. There are two main types of bonding methods: simultaneous bonding and bonding using special adhesive properties. However, with these methods, even if the initial adhesion is good, the adhesion may deteriorate over time, or even if the adhesion is excellent, the crosslinking agent may be chlorinated due to the influence of the adhesive. Due to foaming of the polyethylene composition, there are disadvantages such as not only unstable adhesive properties but also unsatisfactory mechanical properties (eg, releasability). As mentioned above, because chlorinated polyethylene has a chemically saturated structure, unlike other general-purpose rubbers (e.g., chloroprene rubber, butyl rubber), crosslinking methods using sulfur or sulfur-containing compounds are rarely used; A commonly used method is to complete the crosslinking reaction within a mold using an oxide. without using adhesive
When a chlorinated polyethylene composition and a metal surface are bonded by this method, the adhesion is poor (sometimes the bond does not adhere). Furthermore, when bonding is performed using a special adhesive, there are drawbacks such as the fact that the adhesive prevents crosslinking and may cause foaming. [] Structure of the Invention Based on the above, the present inventors have searched various methods for bonding the metal surface and the chlorinated polyethylene composition, which have almost no of these drawbacks, and have found that An adhesive whose main component is a curable phenolic resin is applied and dried (hereinafter referred to as the "first adhesion step"), and a chlorine-containing polymer and an organic filter are further applied to the coated surface obtained in the first adhesion step. After applying and drying a composition containing an oxide and a crosslinking aid as main components or bonding the molded product together (hereinafter referred to as the "second adhesion step"), a crosslinkable adhesive is then applied to the surface of this mixture or molded product. By applying and drying a composition containing chlorinated polyethylene, or by bonding the molded products together to perform crosslinking and adhesion at the same time (hereinafter referred to as the "third adhesion step"), an adhesive with excellent adhesiveness can be obtained. The present invention has been achieved based on the discovery that the present invention can be obtained. [] Effects of the Invention When a metal molded article and a chlorinated polyethylene composition or a molded article thereof are bonded together according to the present invention, not only the adhesion is excellent, but also the adhesion is excellent.
Demonstrates the following effects (characteristics). (1) Not only is the initial adhesion good, but there is almost no deterioration in adhesion over time. (2) The mechanical strength (for example, releasability) of the adhesive is significantly improved. (3) Unlike when these are bonded using the above-mentioned special adhesive, cross-linking is not prevented due to the influence of the adhesive, so a perfect adhesive without foaming can be obtained. . (4) Excellent adhesion (i.e., even when bonding metals (e.g., stainless steel) that are difficult to bond with commonly used adhesives or conventional bonding methods (i.e.,
(can be easily glued). [] Detailed Description of the Invention (A) First Adhesion Process The first adhesion process of the present invention involves applying and drying an adhesive whose main component is a thermosetting phenolic resin on the surface of a metal that is an object to be adhered. This can be achieved by (1) Thermosetting phenolic resin The thermosetting phenolic resin used in the present invention is obtained by addition condensation of phenols and aldehydes. The addition condensates include resols obtained by addition condensation of phenols (e.g., phenol, cresol, xylenol, resorcinol) and aldehydes (e.g., formaldehyde, paraformaldehyde) using an alkali catalyst, and the above phenols and aldehydes. Novolacs are broadly classified into novolaks obtained by addition condensation using acid catalysts. In addition to these addition condensates, the present invention also includes those obtained by etherification and esterification reactions, those obtained by epoxy etherification reactions, and amine- or amide-modified products (e.g. , aniline modification, melamine modification)
Those obtained by such methods can also be used. These addition condensates or modified products thereof are thermally or catalytically hardened and cannot be made soft again even when heated to a fairly high temperature (for example, 200° C.). In the present invention, these addition condensates or modified products thereof may be used as they are, but fillers commonly used for phenolic resins (for example, wood flour, pulp flour, mica, natural or synthetic fibers),
Additional additives such as plasticizers, colorants, pigments and flame retardants (heat resistance aids) may also be added. Regarding the types of phenols and aldehydes mentioned above, the production conditions and methods for resols and novolacs, their reaction mechanisms, the types of modified addition condensates, the modification methods, and the types of additives, etc. [15] “Phenol Resin” (1970, published by Nikkan Kogyo Shimbun), edited by Japan Adhesive Association, “Adhesive Handbook” (1976, published by Nikkan Kogyo Shimbun), pp. 247 to
It is described in detail on page 250 and on pages 123 to 152 of "Plastic Handbook" edited by Murahashi et al. (published by Asakura Shoten in 1962). (2) Bonding method, etc. Before carrying out the first bonding process, the surface of the metal to be bonded has been degreased, surface roughened,
Perform pretreatment such as bubbling. Next, the above-mentioned thermosetting phenolic resin is applied to the surface of the pretreated metal to a uniform thickness of 20 to 50 microns, and then left or heated (generally at 100°C or less). This purpose can be achieved by drying. These coating and drying procedures may be carried out by methods commonly used when adhering to other metal molded articles using an adhesive containing a phenolic resin as a main component. (B) Second bonding process A chlorine-containing polymer, an organic peroxide, and a crosslinking agent are applied to the surface of the metal obtained as described above and the adhesive whose main component is a thermosetting resin phenolic resin. The second adhesion step of the present invention can be achieved by applying and drying a mixture containing the agent as a main component, or by bonding molded products thereof. (1) Chlorine-containing polymer The chlorine-containing polymer used in this process generally contains 20 to 70% by weight of chlorine.
Typical examples of this polymer include chlorinated butyl rubber, chlorinated polyethylene obtained by chlorinating polyethylene, chloroprene rubber, and chlorosulfonated polyethylene (generally, the sulfur content is 1.0 to 1.5% by weight). %, chlorine content 25
~50% by weight) and chlorinated rubber obtained by chlorinating natural rubber (generally, the chlorine content is 50 to 70% by weight), as well as vinyl chloride homopolymers and vinyl chloride. Chlorinated polypropylene (generally, the chlorine content is 20 to 50% by weight). Regarding these rubber-like and resin-like substances, please refer to "Synthetic Rubber Handbook" edited by Kambara et al.
It is widely known as a book published by Asakura Shoten in 1942. (2) Organic peroxide and crosslinking aid In obtaining the adhesive used in the second adhesion step, the organic peroxide used crosslinks the rubbery and resinous materials mentioned above at a temperature range of 100 to 200°C. There are no special limitations as long as it is possible, but
Decomposition temperature (temperature at which half-life is 1 minute) is 100℃
A temperature above 120°C is preferable, and a temperature above 140°C is most suitable. Representative examples of suitable organic peroxides include ketone peroxides such as 1,1-bis-tertiary-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5 - hydroperoxides such as dihydroperoxy, peroxy esters such as 2,5-dimethyl-2,5-di-tertiary-butylperoxyhexane, diacyl peroxides such as benzoyl peroxide, and dicumyl peroxide. Dialkyl peroxides such as: (3) Crosslinking aid The crosslinking aid may be any polymeric crosslinking aid that promotes crosslinking of the rubbery material and resinous material with the organic peroxide. This crosslinking aid has a double bond, and those having a double bond in the side chain (for example, 1,2-polybutadiene) are excellent. Furthermore, divinyl compounds with a short number of carbon atoms between double bonds give better results than those with a long number of carbon atoms. The crosslinking aids include dimaleimide-based (e.g., maleimide, N,N'-m-phenylenebismaleimide, phenylmaleimide), dimethacrylic-based (e.g., trimethylolpropene trimethacrylate, lauryl acrylate),
They are roughly classified into allyl type (for example, triaryl cyanurate, diaryl fumarate) and quinone dioxime type (for example, p-quinone dioxime). These organic peroxides and crosslinking aids are described in "Handbook, Rubber/Plastic Compounded Chemicals" edited by Rubber Digest Co., Ltd. (1971, published by Rubber Digest Co., Ltd.), pages 1 to 18, and in "Plastic Materials" edited by Goto et al. and Rubber Additives Practical Handbook” (Showa 47
It is described in detail on pages 871 to 916 (published by Kagaku Kogyo Co., Ltd.). (4) Manufacture of the composition When manufacturing the adhesive used in the second adhesion step, the ratio of organic peroxide and crosslinking aid to the chlorine-containing polymer is determined depending on the chlorine-containing polymer and organic peroxide used. The proportion of organic peroxide to 100 parts by weight of chlorine-containing polymer is generally 0.1-
20 parts by weight, particularly preferably 1.0 to 10 parts by weight. In addition, the blending ratio of the crosslinking aid is generally 1.0
~10 parts by weight, particularly preferably 3.0 to 5.0 parts by weight. The composition is mainly composed of a chlorine-containing polymer, an organic peroxide, and a crosslinking coagent, and contains stabilizers against oxygen, heat, or light (ultraviolet light) that are commonly used in the chlorine-containing polymer; Additives such as dehydrochlorination inhibitors, fillers and plasticizers may also be added to the extent that the adhesion of the composition is not substantially impaired. A chlorine-containing polymer, an organic peroxide, a crosslinking aid, or a composition obtained by further blending these with the above-mentioned additives is generally used after being dissolved or suspended in an organic solvent or water.
In this case, the total ratio of the chlorine-containing polymer, organic peroxide, crosslinking aid, and other additives to one organic solvent is 100 to 500 g. (5) Manufacture of molded article When performing the second adhesion step, the composition used in this step may be molded in advance. Prior to molding, a composition is prepared by uniformly mixing the chlorine-containing polymer, organic peroxide, and crosslinking aid or other additives. Methods for producing this composition include dry blending using mixers such as ribbon mixers and tumblers, and kneading using mixers such as open rolls, extruders, and Banbury mixers. Among these mixing methods, the kneading method is preferable because it is relatively easy to obtain a homogeneous composition and the operation is relatively simple.
In order to obtain a more uniform composition, two or more of these mixing methods may be applied (eg, mixing with a ribbon mixer and then kneading the mixture using an open mixer). The composition obtained as described above is molded into a desired shape using a molding machine such as an extrusion molding machine, an injection molding machine, a compression molding machine and a calender molding machine which are commonly used in the respective fields of chlorine-containing polymers. Just mold it into something. Examples of the shape of this molded product include a sheet, a tube, a rod, and a mold. It goes without saying that the production of the above-mentioned compositions and molded articles must be carried out within a temperature range in which the chlorine-containing polymer used does not completely crosslink. (6) Bonding method, etc. The composition obtained in the above manner is applied to the coated surface of the adhesive obtained in the first bonding step and dried, or the second bonding method is applied by bonding the molded product. The gluing process can be completed. Drying of the applied composition and bonding of the molded product may be carried out at room temperature or may be heated. The heating temperature varies depending on the types of chlorine-containing polymer, organic peroxide, crosslinking aid, and other additives used, as well as their blending ratio, but is generally at most 100°C. At this time,
The adhesive obtained in the first adhesion step and the composition or the molded product thereof are completely adhered. However, it is of course necessary to carry out the process in such a way that the chlorine-containing polymer does not deteriorate due to heat. When applying and drying the composition, the pretreatment, application method, and drying of the applied surface obtained in the first adhesion step are generally performed using the chlorine-containing polymer used in the same manner as in the first adhesion step. Just apply the method you have. In addition, when bonding molded products together, pressure may be applied using a pressure machine, although this depends on the shape of the bonded product obtained in the first bonding step and the molded product. (C) Third adhesion step The present invention is achieved by simultaneously performing crosslinking and adhesion by bonding the coated surface of the adhesive obtained in the second adhesion step and a crosslinkable chlorinated polyethylene composition. can do. (1) Chlorinated polyethylene The chlorinated polyethylene used in this third bonding step is obtained by chlorinating the polyethylene powder or particles in an aqueous suspension or in an organic solvent (e.g., carbon tetrachloride) capable of dissolving the polyethylene. It is obtained by chlorinating polyethylene dissolved in This chlorinated polyethylene is widely produced industrially and is commonly used. Generally, it is amorphous or crystalline chlorinated polyethylene whose chlorine content is 20 to 50% by weight,
In particular, those having a chlorine content of 25 to 45% by weight and being amorphous are preferred. Polyethylene, which is the starting material for this chlorinated polyethylene, generally has a density of 0.910~
0.970 g/cc, particularly preferably 0.930 to 0.960 g/cc. In addition, the molecular weight is generally 50,000~
500,000, and 100,000 to 400,000 is especially desirable. (2) Other mixed components When producing a composition containing this chlorinated polyethylene, only chlorinated polyethylene may be used as the polymer substance, but other types of polymer substances that are miscible with chlorinated polyethylene may be used. may also be blended. The polymeric substances include ethylene-propylene-diene ternary copolymer rubber (EPDM), natural rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, styrene-butadiene copolymer rubber (SBR), Rubbers such as acrylonitrile-butadiene copolymer rubber (NBR) and butadiene homopolymer rubber [generally,
Mooney viscosity (ML ₁₊₄ ) is 10 to 150]. In addition, other polymeric substances include the above-mentioned polyethylene, vinyl chloride resin containing vinyl chloride as the main component (degree of polymerization, 400-1800), methyl methacrylate resin containing methyl methacrylate as the main component, and acrylonitrile-styrene copolymer resin. Examples include resin-like substances such as. These rubber-like materials and resin-like materials are well known from the aforementioned "synthetic rubber handbook" and "plastic handbook." When these polymeric substances are blended, the blending ratio is at most 50 parts by weight based on the chlorinated polyethylene. Additionally, oxygen, light and heat stabilizers, dehydrochlorination inhibitors, fillers, flame retardants, plasticizers and processability modifiers commonly used in chlorinated polyethylene and their rubbery and resinous products. Additives such as the following may be added or used. Furthermore, a crosslinking agent (organic peroxide and crosslinking aid) is added to crosslink this chlorinated polyethylene composition. As these organic peroxides and crosslinking aids, the organic peroxides and crosslinking aids used in the second adhesion step may be used (they may be the same or different from those in the second adhesion step). These compounding ratios are chlorinated polyethylene,
100 parts by weight of chlorine, depending on the type of rubbery material (if used) and resinous material (if used), their blending ratio to chlorinated polyethylene, and the type of organic peroxide and crosslinking aid. The blending ratio of organic peroxide to polyethylene, other rubber-like materials, and resin-like materials is generally 0.1 to 20 parts by weight, particularly preferably 1.0 to 10 parts by weight. Further, the blending ratio of the crosslinking aid is generally 1.0 to 10 parts by weight, and particularly preferably 3.0 to 5.0 parts by weight. The organic peroxide used in this process has a decomposition temperature (temperature at which the half-life is 1 minute).
A temperature of 110°C or higher is preferred, a temperature of 130°C or higher is suitable, and a temperature of 140 to 190°C is particularly optimal. (3) Manufacture of compositions and molded products Compositions containing chlorinated polyethylene are composed of chlorinated polyethylene, an organic peroxide, a crosslinking aid, or at least one of the above-mentioned rubber-like substances, resin-like substances, and additives. It is manufactured by uniformly mixing. In this case, as in the case of the composition containing the chlorine-containing polymer as a main component, it is generally used after being dissolved or suspended in an organic solvent or water. Further, the molded product is also manufactured in the same manner as in the case of manufacturing the molded product of the composition containing the chlorine-containing polymer as a main component. (4) Adhesion method, etc. The mixture obtained in the above manner is applied and dried on the applied surface of the adhesive obtained in the second adhesion process, or the third adhesion is performed by bonding the molded product together. The process can be completed. This bonding method may be performed in the same manner as in the second bonding step. At this time, crosslinking and adhesion are performed simultaneously. The crosslinking time is usually 5 to 100 minutes, particularly 5 to 40 minutes. In addition, the crosslinking temperature varies depending on the types of the chlorinated polyethylene, other rubbery substances, resinous substances, organic peroxides, crosslinking aids, etc., and their blending ratios, but generally it is 140°C or higher. , especially 160
~200℃ is desirable. Further, the crosslinking density can be determined by setting the optimum values of the crosslinking temperature and crosslinking time by using the torque obtained from a kyurometer, rheometer, JSR chilastometer, etc. (D) Adhesive product The adhesive product obtained by the method of the present invention not only has the excellent characteristics described above, but also has the ability to bond iron, aluminum, copper, tin, zinc, nickel, and chromium. It not only has good initial adhesion to the surfaces of metals such as metals and alloys containing these metals as main components, but also has excellent long-term adhesion. Furthermore, the mechanical properties are also significantly improved. From these points, the adhesive obtained by the method of the present invention can be used for adhesion of rubber and metal, which is widely used in the industrial parts field and the automobile field, for example, rubber diaphragm valves,
It is extremely useful as rubber rolls, bumper parts, bonnets, vibration damping materials, etc. [] Examples and Comparative Examples The present invention will be explained in more detail below using Examples. In addition, in Examples and Comparative Examples, "parts" are based on weight. Adhesive strength is ASTM D-903-49
Measured according to. The length of the metal plate used as a test piece was 120 mm, the width was 25 mm, and the thickness was 2 mm. An adhesive is created between a metal plate and an adhesive whose main component is a thermosetting phenolic resin, an adhesive whose main component is a chlorine-containing polymer, etc. is bonded to this adhesive, and the resulting adhesive is fixed. , most of the sheet obtained from chlorinated polyethylene or the like as described below is completely adhered to the adhesive, and this sheet is pulled at a pulling speed of 50 mm/min.
It was created using a peel test method that allows it to be bent 180 degrees. Examples 1 to 53, Comparative Examples 1 to 24 [(A) Production of thermosetting phenolic resin adhesives and production of adhesives with molded articles of various metals As the thermosetting phenolic resin, phenol and formaldehyde were used. Resol (resol type, alkylphenol resin, melting point 75-95) obtained by addition condensation in the presence of an alkali catalyst
°C, specific gravity 1.25) 10 parts titanium oxide (rutile type, average particle size, 0.3-0.5 microns, specific gravity 3.9-
4.3), Part 2 Furnace Black (SRF, Specific Gravity)
1.8, average particle size 58~94 mm, surface area 25~
30m ² /g, oil absorption 0.7-0.9cc/g), 2 parts of sodium disulfonate (anionic,
An adhesive (hereinafter referred to as "Adhesive 1") consisting of a specific gravity of 1.62) and 76 parts of isopropyl alcohol was prepared. In addition, adhesive 1 was prepared in the same manner as Adhesive 1, except that the amount of resol used was changed to 15 parts and the amount of isopropyl alcohol was changed to 71 parts. It was created. Furthermore, instead of the resol used to create the adhesive 1, Novolak (manufactured by Novolak Co., Ltd., modified phenolic resin, specific gravity 1.03) obtained by addition condensation of phenol and formaldehyde in the presence of an acid catalyst. ~1.06, softening point 75
An adhesive (hereinafter referred to as "Adhesive 3") was prepared in the same manner as Adhesive 1, except that the adhesive (hereinafter referred to as "Adhesive 3") was used. In addition, 5 parts of the resol used to create adhesive 1, 15 parts of chlorinated rubber (chlorine content 68% by weight, apparent density, 0.5 kg/), emulsifier (sodium disulfonate (anionic type, specific gravity 1.62)) 1
An adhesive (hereinafter referred to as "Adhesive 4") was prepared from 45 parts of xylene and 22 parts of isopropyl alcohol. On the other hand, the length is 120mm, the width is 25mm and the thickness is 2
A steel plate, an aluminum plate, a copper plate, and a stainless steel (suspension #2) plate of mm were each polished with sandpaper (#80). The polished surface of each metal plate was degreased with toluene and then dried. After applying the adhesive prepared above to a thickness of approximately 30 microns on these surfaces by dipping, the adhesive was left at 70°C for 30 minutes to completely dry and remove the adhesive. Created. Table 1-1 shows the types of metal plates used as adherends and the types of adhesives used. In Table 1-1, the abbreviations of the adhesives are the abbreviations of the adhesives obtained by bonding the metal plates, which are the respective adherends, and the adhesive as described above.

[(B) Production of adhesives mainly composed of chlorine-containing polymers, etc. and adhesion of these to various adhesives]

10 parts of the chlorinated rubber used in producing adhesive 4 in (A) above, 2 parts of furnace black, 5 parts of triallyl cyanurate, 1 part of 10 parts,
1-bis(tertiary-butyl-peroxy)3,
An adhesive (hereinafter referred to as "adhesive A") consisting of 3,5-trimethylcyclohexane, 45 parts of xylene, and 28 parts of toluene was prepared. In addition, the same adhesive as Adhesive A [hereinafter referred to as "Adhesive B ”) was created. When preparing the above adhesive B, the 1,1-bis(tertiary-butyl-peroxy)-3,35-trimethylhexane used as the organic peroxide was not used, and the amount of toluene was changed to 33 parts. , an adhesive similar to adhesive B [hereinafter referred to as "adhesive C"]
was manufactured. Furthermore, the 1,1-bis(tertiary-butyl-peroxy)-
Adhesive B [hereinafter referred to as "Adhesive D"] was used in the same manner as Adhesive B, except that the amount of 3,3,5-trimethylcyclohexane was changed to 15 parts, and triallyl cyanurate, which was used as a crosslinking aid, was not used. ”]
was manufactured. In place of the chlorinated rubber used in making Adhesive A above, 10 parts of chlorosulfonated polyethylene (chlorine content 29.1% by weight, sulfur content 1.25%) was added.
Adhesive (hereinafter referred to as "Adhesive E") was used in the same manner as Adhesive A, except that weight% and Mooney viscosity (30) were used.
It was created. In addition, in the same manner as Adhesive E, the adhesive [hereinafter 1,1-bis-(tertiary-butyl-peroxy)-3,3,5-trimethyl used as an organic peroxide in preparing the adhesive F. An adhesive (hereinafter referred to as "Adhesive G") was prepared in the same manner as Adhesive F, except that cyclohexane was not used and the amount of toluene was changed to 33 parts. Furthermore, when creating adhesive F, the amount of 1,1-bis-(tertiary-butyl-peroxy)-3,3,5-trimethylcyclohexane used as the organic peroxide was changed to 15 parts. Further, an adhesive (hereinafter referred to as "Adhesive H") was produced in the same manner as Adhesive F, except that triallyl cyanurate prepared as a crosslinking aid was not used. Adhesive A [hereinafter referred to as "Adhesive"] was used in the same manner as Adhesive A, except that 10 parts of chlorinated polypropylene (chlorine content: 45.2% by weight) was used instead of the chlorinated rubber used in making Adhesive A. "Agent I"]
It was created. In addition, the same adhesive as Adhesive I was used, except that the amount of chlorinated polypropylene used in making Adhesive I was changed to 15 parts, and the amount of toluene was changed to 23 parts. It's called "Adhesive J"]
was manufactured. In producing the above adhesive J, 1,1-bis(tertiary-butyl-peroxy)-3,3,5-trimethylcyclohexane, which was used as an organic peroxide, was not used, and the amount of toluene was reduced to 33%. An adhesive [hereinafter referred to as "Adhesive K"] was prepared in the same manner as Adhesive J, except that the adhesive was changed to "Adhesive K". Furthermore, 1,1-bis(tertiary-butyl-
Adhesive J [hereinafter referred to as ""AdhesiveL" was manufactured. Adhesives A to L obtained in the above manner are applied to the surface to which Adhesives 1 to 4 of adhesives (1-1) to (1-10) obtained in the above (A) are adhered. was applied to a thickness of about 20 microns using a dipping method, and then left at a temperature of 70°C for 30 minutes to completely dry, creating an adhesive. Table 2 shows the types of adhesives and adhesives used. In Table 2, the abbreviations of the adhesives are the abbreviations of each of the adhesives obtained as described above.

【table】

[(C) Production of chlorinated polyethylene compositions and adhesion of them to various adhesives]

Amorphous polyethylene obtained by chlorinating with an aqueous suspension polyethylene having a density of 0.930 g/cc and a melt index of 2.0 g/10 min at a temperature of 190°C and a load of 21.6 kg. Chlorinated polyethylene [chlorine content 37.0% by weight, Mooney viscosity (MS ₁₊₄ @100℃ 70)] 100 parts, 40 parts of Furnace Black (manufactured by Asahi Carbon Co., Ltd., product name)
SRF Asahi No. 50, average particle size 77 microns, specific surface area 28
m ² /g), 10 parts of thermal black (manufactured by Asahi Carbon Co., Ltd., trade name FT Asahi Thermal, average particle size 90 mm, specific surface area 19 m ² /g), 25 parts of lead oxide (average particle size 20 mm) micron, specific gravity 9.2-9.5), 10 parts chlorinated paraffin (chlorine content 45% by weight, specific gravity
1.15-1.19, viscosity 1.0-3.0 poise), 3 parts triallylisocyanurate and 6.3 parts 2.5-di-
Methyl-2,5-di-tert-butyl-peroxyhexane was thoroughly kneaded for 20 minutes using a roll whose surface was set at 50°C. A sheet with a thickness of 2.5 mm was produced from the obtained composition using this roll. Adhesives (2-1) to (2-42) obtained in (B) above, containing the surfaces adhered with adhesives A to L and the chlorinated polyethylene obtained in the above manner. The sheets were pressed together at a temperature of 180° C. and a surface pressure of 100 Kg/cm ² for 10 minutes using a hot press, and the adhesive was bonded while crosslinking. Table 3 shows the adhesive strength of each of the obtained adhesives measured immediately after adhesion and the adhesive strength after the adhesives were left at room temperature for 60 days.

【table】

[(D) Production of chlorinated polyethylene compositions and adhesion of them to various adhesives]

Instead of 100 parts of the chlorinated polyethylene used in producing the mixture in (C) above, 70 parts of the chlorinated polyethylene and 30 parts of ethylene-propylene-diene terpolymer rubber (Mooney viscosity
The mixture was thoroughly kneaded for 20 minutes using a roll under the same conditions as in (C) above, except that the mixture had an iodine value of 20, an iodine value of 24, and a diene compound (ethylene norbornene). A sheet having a thickness of 2.5 mm was prepared from the obtained mixture in the same manner as in (C) above. The surfaces of adhesives (2-1) to (2-42) obtained in (B) above to which adhesives A to L were adhered, and the chlorinated polyethylene and ethylene- A composition sheet containing a propylene-diene ternary copolymer rubber was pressed using a hot press at a temperature of 180° C. and a surface pressure of 100 kg/cm ² for 10 minutes, and bonding was performed while crosslinking. Table 4 shows the adhesive strength of each of the obtained adhesives measured immediately after adhesion and the adhesive strength after the adhesives were left at room temperature for 60 days.

[(E) Production of chlorinated polyethylene compositions and adhesion of them to various adhesives]

In place of the 100 parts of chlorinated polyethylene used in producing the composition in (C) above, 50 parts of the chlorinated polyethylene and 50 parts of polyvinyl chloride (homopolymer, average degree of polymerization of about 1100) were used. 20 using the roll under the same conditions as in (C) above, except that
Thoroughly kneaded for a minute. Then, the surface of the roll
3 parts triallylisocyanurate and 6.3 parts 2,5-di-methyl-2,
5-di-tert-butyl-peroxyhexane was added and thoroughly kneaded for 10 minutes. Using this roll, roll the resulting mixture to a thickness similar to (C) above.
A 2.5mm sheet was created. The surfaces of the adhesives (2-1) to (2-42) obtained in (B) above to which adhesives A to L were adhered, and the chlorinated polyethylene and polychloride obtained in the above manner. The sheets of the composition containing vinyl were pressed together at a temperature of 180° C. and a surface pressure of 100 kg/cm ² for 10 minutes using a hot press, and the adhesive was bonded while crosslinking. After adhesion of each adhesive obtained, the adhesion strength was immediately measured and the adhesive strength of these adhesives was measured at room temperature for 60°C.
Table 5 shows the adhesive strength after standing for minutes.

【table】

【table】

[Table] From the above Examples and Comparative Examples, it is clear that the adhesives with metals obtained by the present invention not only have superior adhesive strength than the adhesives with metals obtained by Comparative Examples. It is clear that even if left for a long time, it will withstand the same initial adhesive strength.

Claims (1)

[Claims] 1. Applying and drying an adhesive mainly composed of a thermosetting phenolic resin to the surface of the metal, and further applying a composition mainly containing a chlorine-containing polymer, an organic peroxide, and a crosslinking aid to the coated surface. After drying or bonding the molded product, a composition containing crosslinkable chlorinated polyethylene is applied to the surface of this composition or the molding, and drying or bonding the molded product to simultaneously perform crosslinking and adhesion. A method for bonding a metal surface and a chlorinated polyethylene composition, the method comprising: