JP3031630B2 - Polychloroprene adhesive composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel polychloroprene-based adhesive composition, and more particularly, to a polychloroprene compounded with a metal chlorohydrocarbon resin as a tackifying resin. The present invention relates to a system adhesive composition.

(Prior art and problems to be solved) Among various rubber-based adhesives, chloroprene rubber-based polychloroprene adhesives are used for a wide range of applications. Generally, an alkylphenol resin metal-chlorinated with magnesium oxide is used as a tackifying resin for the purpose of imparting adhesive force and cohesive force at a high temperature as a polychloroprene adhesive. However, although the metal alkyl chloride phenol resin has excellent adhesive strength and cohesive strength at a high temperature, it has a drawback that the adhesive strength is extremely reduced in a few days when placed in a high-temperature atmosphere of 80 ° C. or higher. On the other hand, it is known to use a terpene phenol resin, a general petroleum resin, a coumarone indene resin, etc. for adjusting the holding time of the tack and for imparting heat aging resistance. The force and cohesion, especially at high temperatures, are significantly lower than with metal alkyl phenolic resins. Further, the terpene phenol resin, like the metal alkyl phenol resin, has an extremely low adhesive strength in a few days in a high-temperature atmosphere.

An object of the present invention is to obtain a polychloroprene-based adhesive composition having excellent adhesive strength and cohesive strength at high temperatures and excellent heat aging resistance.

(Means for Solving the Problem) The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific metal chlorohydrocarbon resin is used as a tackifying resin for a polychloroprene-based adhesive. Has achieved that objective.

That is, the present invention is characterized in that it contains (a) polychloroprene and (b) a metal chlorinated hydrocarbon resin which is a reaction product of an acid anhydride group-containing hydrocarbon resin and a divalent metal compound as main components. To provide a polychloroprene-based adhesive composition.

The polychloroprene (a) used in the present invention is not particularly limited, and general polychloroprene obtained by polymerizing chloroprene and modified products thereof are also used.

The metal chlorohydrocarbon resin (b) used in the present invention is a reaction product of an acid anhydride hydrocarbon resin and a divalent metal compound, and is prepared by a known method, for example, at 100 to 250 ° C. in the absence of a solvent.
Or a solvent method in which metal salification is carried out at a temperature of 40 ° C. to 150 ° C. in the presence of a solvent and water.

Acid anhydride group-containing hydrocarbon resin, the unsaturated dicarboxylic acid to the hydrocarbon resin in a known manner, for example, diluent, gelling inhibitor, in the presence or absence of a reaction accelerator, 50 ° C. ~
It is obtained by performing an addition reaction at a temperature of 250 ° C. for 10 minutes to 10 hours.

Examples of the hydrocarbon resin include hydrocarbon resins selected from petroleum-based hydrocarbon resins and coal-based hydrocarbon resins.

Petroleum hydrocarbon resin is a resin obtained by polymerizing a fraction having a boiling point of 20 ° C. to 280 ° C. obtained by pyrolyzing petroleum and steam cracking using a Friedel-Crafts type catalyst. C ₅ fraction polymerization to obtained aliphatic petroleum resins, aromatic petroleum resins obtained by polymerizing C ₉ fraction, C ₅ fraction and aliphatic obtained a C ₉ fraction copolymerizing -Aromatic copolymer-based petroleum resins.

Coal-based hydrocarbon resin is obtained, for example, by polymerizing a tar obtained by coal dry distillation in a coke oven or a fraction having a boiling point of 140 ° C to 240 ° C obtained by these fractions using a Friedel-Crafts type catalyst. Resin.

Examples of the unsaturated dicarboxylic acid include maleic anhydride, citraconic anhydride, tetrahydrophthalic anhydride and the like, and maleic anhydride is most desirable particularly from the viewpoint of reactivity and economy. The amount of the unsaturated dicarboxylic acid added is not particularly limited, but the reaction rate and other factors indicate that the hydrocarbon resin 100
1 to 10 parts per part is desirable.

Examples of the divalent metal compound used in the present invention include at least one metal compound selected from calcium, zinc and magnesium compounds, and calcium and zinc compounds are preferred from the viewpoint of suppressing intermolecular metal chloride reaction. . The form of the metal compound is preferably an oxide, a hydroxide, or a carbonate.

Metal chloride rate is to improve the high temperature properties of the adhesive,
It is preferable to metallize at least 50% of the added acid anhydride groups. If it is less than 50%, the high-temperature characteristics will deteriorate.

Here, the metal salification ratio is a value calculated from a change in the absorption amount of an acid anhydride group at 1780 cm ⁻¹ based on an IR spectrum.

The amount of the metal chlorohydrocarbon resin (b) used in the present invention is the amount of the tackifying resin added to the ordinary polychloroprene adhesive, that is, 10 to 100 parts by weight based on 100 parts by weight of polychloroprene. Appropriate.

If the amount of the metal chlorinated hydrocarbon resin (b) is less than 10 parts by weight, sufficient adhesive strength cannot be obtained, and adhesive strength and cohesive strength in a high-temperature atmosphere decrease.

On the other hand, if it exceeds 100 parts by weight, the holding time of the tack becomes short, so that the workability decreases and the adhesive loses its elasticity and becomes brittle.

The adhesive of the present invention, magnesium oxide used for ordinary polychloroprene adhesive if necessary, metal oxides such as zinc oxide, an antioxidant generally used for rubber,
A vulcanization accelerator such as carbanilide can be blended.

If necessary, a known alkyl phenol resin and a tackifier resin such as a metal chloride thereof, a terpene phenol resin, a coumarone indene resin, and a petroleum resin may be used in combination. In this case, from 0 to 50% of the metal chlorinated hydrocarbon resin according to the invention can be replaced by known tackifying resins. If the amount is more than 50%, the adhesive strength at high temperatures, cohesive strength and aging resistance are undesirably deteriorated.

The adhesive composition of the present invention is usually used by dissolving it in an organic solvent. The organic solvent is not particularly limited, and includes, for example, toluene, acetone, hexane, ethyl acetate, and the like, which are used for ordinary polychloroprene adhesives.

 These solvents may be used in combination of two or more.

Further, the composition of the present invention is not limited to a one-pack type, but can be used as a two-pack type using a crosslinking agent such as isocyanate.

Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto.

(Reference Example-1) 100 g of Nisseki Neopolymer 150 (manufactured by Nippon Petrochemical: softening point 150 ° C) as a petroleum hydrocarbon resin was heated and melted at 230 ° C under N ₂ . Next, 6 g of maleic anhydride was added and an addition reaction was carried out at the same temperature for 5 hours to obtain an acid anhydride group-containing resin (I). The softening point of this resin was 160 ° C.

(Reference Example-2) An acid anhydride group-containing resin (II) was obtained in the same manner as in Reference Example except that Nisseki Uniresin 760 (manufactured by Nippon Petrochemical: softening point: 160 ° C) was used as the coal-based hydrogen resin. . The softening point of this resin was 164 ° C.

(Reference Example-3) After dissolving 40 g of the resin (I) obtained in Reference Example 1 in 60 g of toluene, 2 g of zinc oxide and 5 g of water were added as metal compounds, and metal salification was performed at 80 ° C for 7 hours. Next, after removing unreacted zinc oxide by filtration, distillation was performed under reduced pressure to remove toluene, and a metal chloride resin (A) was obtained. The metal salt ratio of this resin was 80%, and the softening point was 198 ° C. The molecular weight distribution was exactly the same as that of the resin (I).

(Reference Example-4) A metal chloride resin (B) was obtained in the same manner as in Reference Example 3, except that the resin (II) obtained in Reference Example 2 was used. The metal salt ratio of this resin was 85%, and the softening point was 205 ° C. The molecular weight distribution was exactly the same as that of the resin (II).

(Comparative Reference Example-1) A metal chloride resin (C) was obtained in the same manner as in Reference Example 3 except that the amount of zinc oxide was changed to 1 g. The metal chloride rate of this resin is 32
%, Softening point was 180 ° C. The molecular weight distribution was exactly the same as that of the resin (I).

(Examples and Comparative Examples) (1) Chloroprene rubber adhesive 1) Chloroprene rubber ¹⁾ 100 parts by weight Magnesium oxide 8 Zinc oxide 4.8 Antioxidant (non-staining) ²⁾ 1.6 Tackifying resin 44.8 Solvent ³⁾ 640 1) Showa Neoprene AD 2) Ouchi Shinko Notuku Crack NS-6 3) Toluene: acetone: n-hexane = 1: 1: 1 (2) Adhesive test (coating amount: 300 g / m ² ) Normal adhesive strength: applied to No. 10 canvas, One hour later, the can baths were stuck together, and after curing at 23 ° C. for 1 day and 6 days, the adhesive strength at 23 ° C. was measured.

Shearing force: applied to No. 10 canvas and stainless steel plate, bonded together after 1 hour, at 23 ° C for 1 day and 6 days
After curing on a day, the shearing force at 60 ° C. was measured.

Heat-resistant creep: applied to No. 10 canvas, bonded one hour later, cured at 23 ° C for 1 day and 6 days, and then measured for heat-resistant creep at 80 ° C.

Heat aging test: applied to No. 10 canvas and stainless steel plate, and after 1 hour, bonded to each other and between canvas and stainless steel plate, cured at 23 ° C for 1 day, heat-aged in 105 ° C atmosphere, and 15 days After 30 days and 45 days, the adhesive force at 23 ° C., the shear force at 60 ° C., and the heat creep were measured.

(Example-1) Using the metal chloride resin (A) obtained in Reference Example 3 as a tackifying resin, a polychloroprene adhesive was prepared at the mixing ratio of (1), and the adhesive test of (2) was performed. Was done.

(Example 2) The same operation as in Example 1 was performed except that the metal chloride resin (B) obtained in Reference Example 4 was used as a tackifier resin.

(Comparative Example-1) The same operation as in Example 1 was performed except that the metal chloride resin (C) obtained in Comparative Reference Example 1 was used as a tackifier resin.

(Comparative Example 2) The same operation as in Example 1 was performed except that Nisseki Neopolymer 150 was used as a tackifier resin.

(Comparative Example-3) Terpene phenol resin (Yasuhara Yushi: YS Polystar 2)
Example 13 was carried out in the same manner as in Example 1 except that 130) was used as a tackifier resin.

(Comparative Example-4) Alkylphenol resin (Arakawa Chemical: Tamanol 52)
Example 1 was carried out in the same manner as in Example 1 except that 1) was changed to a metal chloride resin of magnesium oxide as a tackifying resin.

The test results in Examples and Comparative Examples are shown in Tables 1 and 2.

(Effects of the Invention) As shown by the test results in Tables 1 and 2, the metal chloride of the petroleum-based hydrocarbon resin and the metal chloride of the coal-based hydrocarbon resin according to the present invention are tackified with a polychloroprene adhesive. When used for a resin, it has the same adhesive strength and shearing power as a metal alkyl phenol resin and can provide high-temperature creep properties superior to those of a metal alkyl phenol resin. Furthermore, low heat aging resistance, which is the greatest drawback when using a metal alkyl phenol resin, could be greatly improved.

Continuation of the front page (56) References JP-A-52-93445 (JP, A) JP-A-49-128035 (JP, A) JP-A-49-114644 (JP, A) JP-A-56-74167 (JP, A) JP-A-1-118585 (JP, A) JP-A-61-268778 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 111/00 G08F 157/00 C09J 1/00-201/10 C08L 1/00-101/14 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A reaction product of (b) an acid anhydride group-containing hydrocarbon resin and a divalent metal compound with respect to (a) 100 parts by weight of polychloroprene. %
A polychloroprene-based adhesive composition comprising 10 to 100 parts by weight of the above-mentioned metal chlorohydrocarbon resin. 2. The adhesive composition according to claim 1, wherein the hydrocarbon resin is a resin selected from petroleum hydrocarbon resins and coal hydrocarbon resins. 3. The adhesive composition according to claim 1, wherein the divalent metal compound is at least one metal compound selected from calcium and zinc compounds.