JPS5825954A - Three-layer laminated structure - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a three-layer laminated structure, and more specifically, the present invention relates to a three-layer laminated structure that has rigidity, vibration damping properties, etc., using a composition consisting of a specific chlorine-based polymer, 11 blue material, and polyisocyanate as an intermediate layer. This invention relates to a three-layer laminated structure with excellent physical properties.

In recent years, there has been a strong desire to reduce the weight of structural materials used in vehicles, marine machinery, building materials, etc. due to demands for energy and resource conservation.

The most common way to reduce the weight of such materials is to make the metals and other materials used thinner, but as a result of thinner walls, problems such as reduced rigidity 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 thermosetting resin such as polyolefin or various rubbers, (2)
Structures using a polycrethane resin or (2) structures using a composition in which a dark blue substance such as asphalt is mixed with a filler such as calcium carbonate 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 distribution effect. On the other hand, although the structure in (2) above has satisfactory adhesion between each layer, it is poor in practicality due to poor water resistance, and like the structure in (1), it is made of metal materials. The structures mentioned above are inexpensive and have excellent water resistance, but they are highly temperature dependent and flow at high temperatures and are brittle at low temperatures. The disadvantage is that cracks can occur.

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 laminated structure consisting of three layers,
(People) Liquid diene polymer containing active hydrogen groups.

The present invention provides a three-layer laminated structure characterized in that an intermediate layer is a composition comprising a blue substance (CB) III and an organic polyisocyanate compound (C).

The composition constituting the intermediate layer of the laminated structure of the present invention comprises the components (A), CB) and (C) as described above. Here, the active wood group-containing liquid diene polymer, which is the component (mu), refers to active hydrogen containing hydroxyl groups, carboxyl groups, amino groups, imino groups, mercapto groups, etc. in the molecule at the end of the molecule. It is a liquid diene-based polymer having a group.

These wavy diene polymers are not particularly limited, and for example, those having a number average molecular weight of 500 to zs, oo
of) a diene polymer having 4 to 12 carbon atoms, a copolymer thereof,
Furthermore, K is a combination of these diene monomers and α- having 2 to 22 carbon atoms.
Olefinic addition polymerizable material! There is a copolymer with -.

Furthermore, when an unsorated carboxylic acid such as maleic anhydride or a derivative thereof is added to these liquid diene polymers, the term also includes modified liquid diene polymers. Specifically, butadiene polymer, imprene copolymer, 4-crylene polymer, butadiene-styrene copolymer, butadiene/
- Inprene copolymer.

Butadiene-acrynitrile copoly! -, butadiene-2-ethylhexyl acrylate polyester. Examples include butadiene-n-octadecyl acrylate copolymer. Among these, a polymer having a viscosity of 2.000 poise or less, preferably 500 poise or less, and a microstructure of 50 or more 1.4 bonds is used.

Next, the (B) component of the above composition, ① the blue substance, is not particularly limited and may be straight asphalt.

Examples include asphalt, straight asphalt, and mixtures thereof. Preferably, straight asphalt, which does not require very high temperatures for processing, or straight asphalt and other asphalt are used in combination.

The amount of this bituminous material varies depending on various conditions and cannot be determined unequivocally, but it is usually based on 100 parts by weight of the active hydrogen group-containing diene polymer, which is the component.
CIG to 1000 parts by weight, preferably 20 to 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 vibration damping properties, etc. in low temperature ranges will further deteriorate significantly.

Next, the organic polyinocyanate compound which is component (C) of the above composition is a polyisocyanate, that is, an organic compound having two or more incyanate groups in one molecule, and is 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 are compounds in the form of prepolymers having isocyanate groups at the terminals obtained by reacting a polyol and a polyisocyanate in advance.
Examples of suitable organic polyisocyanate compounds include the usual aromatic, aliphatic and alicyclic compounds, such as tolylene diisocyanate, hequinamethylene diisocyanate, diphenylmethane diisocyanate, liquid Modified diphenylmethane diisocyanate, polymethylene poly7-elisocyanate, xylylene diisocyanate, Schiff's hexyl diinocyanate, hekynanphenylene diisocyanate, naphthalene-1,5-diisocyanate-F.

Examples include isoprevir benzene-2,4-diisocyanate and addition reaction products of polypropylene glycol and tolylene diisocyanate.

These organic polyinocyanate compounds act as a curing or crosslinking component 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 compounding amount is such that the isocyanate group is 0.4 to zo based on the active hydrogen group of the liquid diene polymer as component (A)
(6 quantitative ratio), preferably 0.6 to 1. o (equivalence ratio). If this amount is too small, the curing reaction will be insufficient and the strength-9 distribution effect will be reduced. 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 as necessary. It is prepared by carrying out a curing reaction by adding a catalyst accordingly.

Catalysts used in this case include di-n-butyltin diworate, stannath octoate, triethylene cyanocarbon, diethylene cyanocarbon, doryethyl chloride, and naphthenic monomer.

There are urethane catalysts such as metal octylate. Kirak,
If necessary, this composition may have a quantity of akl, 4 to improve physical properties.
Pumendiol; triftm-#fttpan; ethylene glycol; ethylene oxide 3 mole adduct of bisphenols; N,N-bis(2-human tetraxypropyl)aniline, etc. can be added.

In addition, we add lubricants such as dioctyl phthalate as viscosity modifiers, softeners (press oil) such as aa'v, s7ten, and paraffin, and tackifying resins to adjust adhesive strength. or add carbon black, charcoal II and sium.

clay, yuzuri, mica, fiber filler, grabite,
Fillers such as vermiculite and various stabilizers can also be added. Here, the tackifying resin is an alkylphenol resin, a terpene resin, a terpenephenol resin, or a xylene formaldehyde resin.

cash register/. Hydrogenated rosin, Ri! Examples thereof include carbon resins, aliphatic and aromatic petroleum resins, and they can be added in an amount of 5 to 200 parts by weight per 100 parts by weight of the liquid diene polymer as component (1).

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) Component organic polyisocyanate compound is mixed to obtain the above composition, and this is used as an intermediate layer, and outer layers such as metal plates are laminated from both sides to form three layers, and this is cured.
Manufacture more.

Here, the outer layer is preferably made of a material such as metal, thermogenic 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. used. In the laminated structure of the present invention, it is desirable that at least one of the five layers is made of metal.

The laminated structure of the present invention may be manufactured as described above, but the twist is that both outer layers are laminated while the composition of the intermediate layer is not cured, and then press molded to a predetermined shape, and then cured and cured. It can also be manufactured by With this method, it is also possible to obtain a laminate having an am uneven shape. It can also be produced by first laminating a busy intermediate layer and one outer layer, then curing the composition of the intermediate layer, and then laminating the remaining outer layer. In addition, when using the latter method, it is preferable to use a composition in which the isocyanate group/active hydrogen group in the intermediate layer composition is 0.5 to 0.9 (equivalent ratio).

The laminated structure of the present invention having the above structure has good adhesion between each layer, and has excellent water resistance, corrosion resistance, and heat resistance, and has good formability. It can be of any shape. In addition, since it has high rigidity, it can be made thinner and lighter. Furthermore, it exhibits excellent allocation performance over a wide temperature range.

Therefore, the laminated structure of the present invention can be widely and effectively used in various structural members for building materials, vehicle materials, and other industrial materials.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 11th! According to the blending amounts shown in
After mixing thoroughly at 00°C, and then adding a predetermined amount of diisocyanate and mixing, the above mixture was mixed into a 3 m thick intermediate layer using various metal plates with a thickness of 1 dew and high-strength polyethylene plates with a thickness of 2 dew as outer layers. After laminating them into layers, they were cured at 80° C. for 12 hours to obtain a three-layer laminated structure.

The adhesive force of the laminated adhesive surface of the laminated structure was evaluated by the following method. That is, first, the above-mentioned blended mixture was applied to the outer layer board of each food so that it would have a thickness of about 0.5 knits, and then a cotton cloth was layered on top of it and cured at 80°C for 12 hours.
The 0 degree beer strength was measured. The results are shown in Table 1.

Example 2 According to the blending amounts shown in Table 1, 10% of liquid polybutadiene having a hydroxyl group at the end, asphalt, and a catalyst were mixed.
After mixing thoroughly at 0"e, a predetermined amount of diisocyanate was added and mixed. After that, a layer of the above mixture was formed to a thickness of 3 m on various metal plates with a thickness of lsw+, and was heated at room temperature for 24 hours. After curing for a period of time, a two-layer laminate was obtained.

Note that both surfaces of the mixture layer in this two-layer laminate had adhesiveness.

Next, various metal plates with a thickness of 1 cm or various resin plates with a thickness of 2 cm are stacked as the upper II third layer on this layer, and a 5 kI/-
A three-layer laminate structure was obtained by pressurizing the mixture at a pressure of 100 mL and curing it 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, the above blended mixture was coated on a cotton cloth to a thickness of approximately 0, sm.
After drying and curing at room temperature for 24 hours, a sticky cotton cloth was obtained. Next, this adhesive cotton cloth was placed on top of the various outer layer materials with the adhesive side facing down, and it was run 3 times on 5J9+ and pressed under a load. After 24 hours, the beer strength was measured at 180 degrees. I did it more. The results are shown in Table 1.

Rice 1 Liquid polybutadiene with a hydroxyl group at the end (number average molecular weight 2800, viscosity 50 voids (30°C), hydroxyl group content 083 milliequivalents/2. Microstructure Nidoran-1,
460th.

(Cis-1,420%, Vinyl-1,220%) *2 Isocyanate content 30.6vt% rice 3 The adhesive force measurement sample was left at the specified temperature for 1 hour with the adhesive surface kept vertical, and the adhesive surface was kept vertical and the sample was left at the specified temperature to check for displacement and peeling. The presence or absence of was investigated. Here, ○ indicates that there is no dislocation or peeling.

Rice 4 Electroplated steel plate rice 5 Sandblasted steel plate rice 6 High-density polyethylene plate rice 7 Polypropylene rice with glass fiber content of 4owi% 8 Polypropylene plate with talc content of 40wt%*9
Modified Polypropylene Plate Containing 15wt% Maleic Anhydride Content 2vt% Polypropylene Plate Patent Applicant Idemitsu Kosan Co., Ltd. Representative Patent Attorney Fujibe Kubota

Claims (2)

[Claims] (1) In a laminate structure consisting of three layers, a composition consisting of (a) a liquid diene polymer containing active hydrogen groups, (B) a II blue substance, and (C) an organic polyisocyanate compound is used as an intermediate layer. Features a three-layer laminated structure. (Claim 1 in which the outer layer is made of a material selected from metal, thermosetting resin, and thermosetting resin)
Structures described in Section. (2) (A) Active hydrogen group-containing liquid diene polymer 10
0 parts by weight [, (B) II blue substance 10 to 100
0 parts by weight, and (C) an organic polyisocyanate compound in an amount such that the incyanate group/active hydrogen group in the diene polymer (equivalent ratio) is 0.4 to 2-0. The structure according to claim 1, characterized in that the structure is a product.