JPH0134788B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a three-layer laminate structure, in particular, the intermediate layer is a composition made of a specific diene polymer, a bituminous substance, and a polyisocyanate, and at least one of the outer layers is made of a metal, which has rigidity and vibration damping properties. This invention relates to a three-layer laminated structure with excellent physical properties such as: In recent years, there has been a strong desire to reduce the weight of structural materials used in vehicles, ships, machinery, building materials, etc. due to demands for energy and resource conservation. The most common method for reducing the weight of such materials is to reduce the thickness of the metal or other material used, but as a result of reducing the thickness, problems such as a decrease in stiffness and increased vibration occur. Therefore, in order to prevent these troubles, many laminated structures in which different materials are sandwiched between metal materials have been proposed. For example, as an intermediate layer, (1) a structure using thermoplastic resin such as polyolefin or various rubbers, (2) a structure using polyurethane resin, or (3) a filler such as calcium carbonate in a bituminous material such as asphalt. Structures using compositions containing a mixture of these are known. However, in the structure of (1) above, the adhesion between each layer is not sufficient and must be bonded using an adhesive, resulting in low productivity and not much vibration damping effect. On the other hand, the structure in (2) above has almost satisfactory adhesion between each layer, but it is not practical due to poor water resistance, and like the structure in (1), it is susceptible to corrosion of the metal material. There is a risk that this will result in vibration, and the damping effect is also low. Further, although the structure of (3) above is inexpensive and has excellent water resistance, it has the disadvantage that it is highly temperature dependent and flows at high temperatures, and becomes brittle and cracks at low temperatures. An object of the present invention is to provide a new and useful laminate structure that eliminates the drawbacks of these known laminate structures. That is, the present invention provides a laminate structure consisting of three layers, in which (A) a liquid diene polymer containing active hydrogen groups;
The object of the present invention is to provide a three-layer laminated structure characterized in that the intermediate layer is a composition consisting of (B) a bituminous substance and (C) an organic polyisocyanate compound, and at least one of the outer layers is made of a metal. The composition constituting the intermediate layer of the laminated structure of the present invention consists of the components (A), (B) and (C) as described above. Here, the active hydrogen group-containing liquid diene polymer that is component (A) refers to a liquid diene polymer that has active hydrogen groups such as hydroxyl group, carboxyl group, amino group, imino group, and mercapto group at the end of the molecule or within the molecule. It is a polymer. There are no particular restrictions on these liquid diene polymers, and for example, the number average molecular weight is 500.
-25,000 diene polymers having 4 to 12 carbon atoms, copolymers thereof, and copolymers of diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. It also includes liquid diene polymers modified by adding an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof to these liquid diene polymers. Specifically, butadiene homopolymer, isoprene homopolymer, chloroprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer,
Examples include butadiene-n-octadecyl acrylate copolymer. Among these, a polymer having a viscosity of 2000 poise or less, more preferably 500 poise or less, and a microstructure containing 50% or more of 1,4 bonds is used. Next, the bituminous substance that is the component (B) of the above composition is not particularly limited, and examples thereof include straight asphalt, semi-brown asphalt, blown asphalt, or a mixture thereof, and preferably a bituminous substance that does not require too high temperature for processing. Straight asphalt or straight asphalt and other asphalt used together. The amount of bituminous material mixed varies depending on various conditions and cannot be determined unambiguously, but it is usually
Component (A) active hydrogen group-containing diene polymer 100
10 to 1000 parts by weight, preferably 20 to 1000 parts by weight
Select within the range of 600 parts by weight. If the blending amount is too small, it will be difficult to maintain stable vibration damping properties, rigidity, etc. over a wide temperature range, and the adhesive strength between each layer will also decrease. On the other hand, if the amount of bituminous material blended is too large, the adhesiveness, heat resistance, and cold resistance will be reduced, and furthermore, the vibration damping properties in low temperature ranges will be significantly reduced. Next, the organic polyisocyanate compound which is component (C) of the above composition is a polyisocyanate, that is, an organic compound having two or more isocyanate groups in one molecule, and is a liquid diene-based polymer containing active hydrogen groups. It has an isocyanate group that is reactive with the active hydrogen-containing functional group of the polymer. Such organic polyisocyanate compounds are well known, and may be in the form of a prepolymer having isocyanate groups at the ends obtained by reacting a polyol and a polyisocyanate in advance. Examples of organic polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, Examples include methylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, and an addition reaction product of polypropylene glycol and tolylene diisocyanate. These organic polyisocyanate compounds act as curing or crosslinking components of the active hydrogen group-containing liquid diene polymer, and in the composition constituting the intermediate layer of the laminated structure of the present invention, the organic polyisocyanate compounds The blending amount is determined so that the isocyanate group is 0.4 to 2.0 (equivalent ratio), preferably 0.6 to 1.0 (equivalent ratio) to the active hydrogen group of the liquid diene polymer as component (A). Ru. If this amount is too small, the curing reaction will be insufficient and the strength and vibration damping effect will decrease. On the other hand, if the amount is too large, the adhesive strength will decrease, which is not preferable. As described above, the composition constituting the intermediate layer of the laminated structure of the present invention basically consists of the above three components (A), (B), and (C), and is usually heated under heating. It is prepared by adding a catalyst as appropriate and carrying out a curing reaction. The catalyst used in this case is
Di-n-butyltin dilaurate, stannath octoate, triethylenediamine, diethylenediamine, triethylamine, naphthenic acid metal salts,
There are urethane catalysts such as octylic acid metal salts. Furthermore, this composition may optionally contain 1,4 butanediol; trimethylolpropane; ethylene glycol; a 3-mole ethylene oxide adduct of bisphenol A; N,N-bis(2-hydroxypropyl)aniline; etc. can be added. In addition, plasticizers such as dioctyl phthalate, aromatic, naphthenic, and paraffinic softeners (process oils) are added as viscosity modifiers, and tackifying resins are added to adjust adhesive strength. Fillers such as carbon black, calcium carbonate, clay, talc, mica, fiber fillers, graphite and vermiculite, and various stabilizers can also be added. Here, examples of the tackifying resin include alkylphenol resin, terpene resin, terpenephenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, coumaron resin, aliphatic and aromatic petroleum resin, and the component (A). It can also be added in an amount of 5 to 200 parts by weight per 100 parts by weight of the liquid diene polymer. The laminated structure of the present invention can be produced by, for example, uniformly mixing a liquid diene polymer as component (A) with a predetermined amount of bituminous material as component (B) using various mixers, and further adding a predetermined amount of (C The above-mentioned composition is obtained by mixing the organic polyisocyanate compound (component), which is used as an intermediate layer, and an outer layer such as a metal plate is laminated from both sides to form a three-layer structure, which is then cured to produce the composition. The outer layer is preferably made of metal, thermoplastic resin, thermosetting resin, or a mixture of these resins with fibers such as long and short glass fibers, and fillers such as talc and calcium carbonate. Ru. Note that in the laminated structure of the present invention, at least one of both layers is made of metal. The laminated structure of the present invention may be manufactured as described above, but it can also be manufactured by laminating both outer layers while the composition of the intermediate layer is not yet cured, and then press-molding it into a predetermined shape, and then curing and curing it. You can also. With this method, it is also possible to obtain a laminate with an uneven surface. Alternatively, first the intermediate layer and one outer layer are laminated, and then the composition of the intermediate layer is cured,
It can also be manufactured by subsequently laminating the remaining outer layers. In addition, when using the latter method, it is preferable to use an intermediate layer composition having an isocyanate group/active hydrogen group ratio of 0.5 to 0.9 (equivalent ratio). The laminated structure of the present invention having the above-mentioned structure has good adhesion between each layer, and has excellent water resistance, corrosion resistance, and heat resistance, and also has good formability. It can be any shape.
Moreover, because of its high rigidity, it can be made thinner.
Weight reduction can be achieved. Furthermore, it exhibits excellent vibration damping performance over a wide temperature range. Therefore, the laminated structure of the present invention can be widely and effectively used in various structural members such as building materials, vehicle materials, and other industrial materials. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Liquid polybutadiene having a hydroxyl group at the end, asphalt, and a catalyst were thoroughly mixed at 100°C according to the amounts shown in Table 1. Then, a predetermined amount of diisocyanate was added and mixed, and then a 1 mm thick film was prepared.
A three-layer laminated structure was obtained by laminating various metal plates and a high-density polyethylene plate with a thickness of 2 mm as an outer layer, and the above mixture as an intermediate layer with a thickness of 3 mm, and then curing at 80°C for 12 hours. Obtained. The adhesive force of the laminated adhesive surface of the laminated structure was evaluated by the following method. That is, first, the above-mentioned mixture was applied to various outer layer boards to a thickness of approximately 0.5 mm, a cotton cloth was layered on top of that, and the material was cured at 80°C for 12 hours, after which the 180 degree peel strength was measured. This was done by doing. The results are shown in Table 1. Example 2 Liquid polybutadiene having a hydroxyl group at the end, asphalt, and a catalyst were thoroughly mixed at 100°C according to the amounts shown in Table 1. Then, a predetermined amount of diisocyanate was added and mixed, and then a 1 mm thick mixture was prepared.
A layer of the above mixture was formed to a thickness of 3 mm on various metal plates, and a two-layer laminate was obtained by curing at room temperature for 24 hours. Note that the surface of the mixture layer in this two-layer laminate was sticky.
Next, on top of this layer, various metal plates with a thickness of 1 mm or various resin plates with a thickness of 2 mm are layered as a third layer.
A three-layer laminate structure was obtained by applying a pressure of 5 kg/cm ² and curing at room temperature for 24 hours. The adhesive strength of the laminated adhesive surfaces of the two-layer laminate described above was measured in the same manner as in Example 1. The results are shown in Table 1. In addition, the adhesive strength of the bonding surface between the intermediate layer and the third layer of the three-layer laminated structure was evaluated by the following method. That is, first, apply the above blended mixture on a cotton cloth and spread it on a cotton cloth.
A sticky cotton cloth was obtained by applying the adhesive to a thickness of 0.5 mm and curing it at room temperature for 24 hours. Next, this adhesive cotton cloth was placed on top of various outer layer materials with the adhesive side facing down, and a 5 kg roll was run three times to apply a load and press down, and 24 hours later, the 180 degree peel strength was measured. Ta. The results are shown in Table 1.

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Claims (1)

[Scope of Claims] 1. A laminate structure consisting of three layers, including (A) a liquid diene polymer containing active hydrogen groups, (B) a bituminous substance, and
(C) A three-layer laminate structure, characterized in that the intermediate layer is a composition made of an organic polyisocyanate compound, and at least one of the outer layers is made of a metal. 2. The structure according to claim 1, wherein the other layer of the outer layer is made of a material selected from metal, thermoplastic resin, and thermosetting resin. 3. 10 to 1000 parts by weight of (B) a bituminous substance is blended with 100 parts by weight of (A) liquid diene-based polymer containing active hydrogen groups, and (C) an organic polyisocyanate compound is added to 100 parts by weight of the liquid diene-based polymer containing isocyanate groups Claim 1: The intermediate layer is a composition in which the active hydrogen groups (equivalent ratio) in the polymer are blended in an amount of 0.4 to 2.0.
Structures described in Section.