JPS623943A - 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 Field of Industrial Application The present invention relates to a laminated structure, more specifically, an aluminum plate (hereinafter referred to as "triclean finish system (TFS)") treated with a special coating process.

The present invention relates to a laminated structure consisting of a special painted or TFS treated aluminum plate) and a polyvinyl chloride decorative material laminated and bonded using a specific combination of primer and adhesive.

Aluminum plates have recently been widely used as various building materials, but they suffer from problems such as corrosion over time, so they are coated with special paints as described above to improve their durability. However, from a design point of view, if desired, this specially painted aluminum plate is laminated with a decorative polyvinyl chloride material (sheet or film) with a woodgrain pattern and used as a building material. There is a problem with sexuality.

The present inventors have carried out extensive research in order to provide a laminated structure in which such a specially coated aluminum plate and a polyvinyl chloride decorative material are well bonded. The present inventors have discovered that a desired laminated structure can be obtained by applying a polyurethane adhesive in combination with a polyurethane adhesive, and have completed the present invention.

Structure and Effects of the Invention: 1 The present invention provides a laminated structure in which a specially coated aluminum plate and a polyvinyl chloride decorative material are bonded together. The present invention provides a laminated structure characterized in that polyvinyl chloride decorative materials are bonded together with a polyurethane adhesive comprising thermoplastic polyester urethane rubber and a polyisocyanate compound as a crosslinking agent.

The primer used in the present invention is composed of a system in which chlorinated rubber is dissolved in a suitable organic solvent to a concentration of usually 10 to 40% (heavy equipment %, hereinafter the same).

The above-mentioned chlorinated rubber refers to natural rubber or synthetic rubber that has been reacted with chlorine.
γdeca chloride rubber CR-5J, [CR-10J, [C
R-20J, r CR-40J, r CR-90J, r
CR-150j is commercially available, and examples of synthetic rubbers include chlorinated polyethylene and chlorinated polypropylene obtained by chlorinating polyethylene and polypropylene, and chlorinated polyvinyl chloride made of polyvinyl chloride and chlorinated polyethylene.

The organic solvent mentioned above is aromatic (toluene, etc.).

xylene, benzene, etc.), esters (ethyl acetate,
butyl acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, gamma setone f, jr) '4? can be mentioned.

The polyurethane adhesive used in the present invention is composed of a two-component type consisting of a thermoplastic polyester urethane rubber (referred to as urethane rubber under U) as a main ingredient and an IJ isocyanate compound as a crosslinking agent.

The urethane rubber mentioned above is an elastomer having a urethane bond in one molecule chain, and usually contains polybasic acids (terephthalic acid,
isophthalic acid, phthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, etc.) and dihydric alcohols (ethylene chloride:l) L=, L4-butanediol, 1
．． 5-bentanediol, 1,6-hexanediol,
Diethylene glycol, triethylene glycol, polyethylene glycol.

Propylene glycol, etc.) are subjected to a condensation reaction, and the resulting saturated polyester resin having wood end hydroxyl groups is combined with active hydrogen groups and diisocyanate compounds (tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate).

cyclohexylmethanediisonanate), ketone type (methyl ethyl ketone, cyclohexanone, acetone, etc.), aromatic type (toluene, xylene, benzene, etc.), chlorine type ( Trichloride, methylene chloride, etc.) before use.

In addition, a radically reactive alkoxysilyl compound having an unsaturated bond (for example, r-methacryloxyprobyltrimethoxysilane) is added to the urethane rubber.

r-methacryloxypropylmethyldimethoxysilane,
r-methacryloxyalkylalkoxysilanes such as r-acryloxypropyltrimethoxysilane, r-acryloxypropylmethyldimethoxysilane, 2-styrylethyltrimethoxysilane, r-acryloxyalkylalkoxysilanes, vinyltrimethoxy Vinyl alkoxysilanes such as silane, vinyltriethoxysilane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, vinyldimethylethoxysilane, vinylmethyljethoxysilane, allyltriethoxysilane, vinyltris[β-methoxyethoxy]silane, or allyl Alkoxysilanes, alkoxysilanes having a mercapto group such as r-mercaptopropylmethyldimethoxysilane, r-mercaptopropyltrimethoxysilane, β-mercaptoethyltriethoxysilane], and other polymerizable monomers [e.g. acrylic acid, acrylic Acid ester (methyl acrylate.

Ethyl acrylate, butyl acrylate, acrylic acid 2
-Ethylhexyl, isobutyl acrylate.

2-Ethoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, 2-acrylate
Hydroxyethyl, 2-hydroxypropyl acrylate% 1.4-butanediol diacrylate, 16-hexanediol diacrylate, pentaerythritol triacrylate, etc.), methacrylic acid and methacrylic acid esters (methyl methacrylate, ethyl methacrylate, methacrylate) butyl methacrylate, isobutyl methacrylate, [-butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate,
Lauryl methacrylate, tridecyl lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate
Stearyl, stearyl methacrylate, cyclohexyl methacrylate.

Benzyl methacrylate, 2-hydroxyethyl methacrylate Jlz, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylminoethyl methacrylate, monobutylaminoethyl methacrylate,
glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.), acrylamide, acrylonitrile, acrolein, vinyl acetate, styrene, N-methylolacrylamide, vinylpyridine, maleic anhydride.

[vinylpyrrolidone, butadiene, etc.] may be used. This allows the adhesive force to be further improved. The graft reaction is carried out using a polymerization initiator (benzoyl peroxide, azobisisobutyronitrile) in a reaction solvent (the above-mentioned organic solvent).

60-b in the presence of cumene hydroperoxide, [-butyl/X hydroperoxide, potassium persulfate, ammonium persulfate, etc.].

The above crosslinking agent is a polyisocyanate compound that is used as a crosslinking agent for ordinary chlorprene solvent-based adhesives and urethane rubber adhesives, and has a high vapor pressure, low toxicity to the human body, and is easy to handle. For example, triphenylmethane triisocyanate (Bay
r)esmodurR920% methylene chloride solution (manufactured by Er), triisocyanate phenylthiophosphate (Desmodur RF, manufactured by Bayer, 2
0% methylene chloride solution), an incyanate compound prepared by adding trimethylolpropane to tolylene diisocyanate (Coronate manufactured by Nippon Polyurethane Co., Ltd., 75%
ethyl acetate solution).

Examples include special grade MDI (Millione MR manufactured by Nippon Polyurethane Co., Ltd.). In such a polyisocyanate compound, the active hydrogen group of the hydroxyl group in the molecular chain of the urethane rubber reacts with the incyanate group, resulting in crosslinking, so it contributes to improving the adhesive strength, and its consumption is equivalent to 100 parts of the urethane rubber. The amount may be selected to be 2 to 100 parts, preferably 5 to 50 parts, based on the heavy collapsed portion (the same applies hereinafter).

Such a two-component polyurethane adhesive may contain a tackifier resin (for example, a rosin resin or a rosin derivative (pentaerythritol ester of rosin resin, glycerol ester, hydrogenated rosin resin, hydrogen Methyl ester of added rosin resin, triethylene glycol ester, pentaerythritol ester, rosin ester, polymerized rosin resin 1 glycerol ester fx of polymerized rosin resin)] may be blended in appropriate amounts.

The laminated structure according to the present invention can be manufactured by the following procedure.

First, the above-described primer is applied to a specially coated aluminum plate (painted side) using a brush, roller coater, spray, etc. to a thickness of usually 30 to 50 μm, and dried at room temperature. Next, the polyvinyl chloride decorative material was layered with the above polyurethane adhesive interposed therebetween.

Tighten with a roller. polyurethane adhesive.

It can be applied to either the primer surface or the PVC decorative material surface, in which case a bar coater.

Usually 50 for roll coater, spatula, brush, roller, etc.
After coating to a thickness of ~150μ.

Layer them together and dry at 30-80°C for 1-3 minutes.

By applying the primer and adhesive as described above, it is possible to solve the problem of insufficient adhesive strength, which has been a problem in the past, and a laminated structure with good adhesive quality can be obtained.

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

Examples 1 to 4 Preparation of primer Chlorinated rubber (Asahi Denka Kogyo Co., Ltd.'s "γ" in the number of parts shown in Table 1)
Deka Chlorinated Rubber CR-5J, rDeka Chlorinated Rubber CR-4
04 or (Toyo Kasei Co., Ltd.) “Birdren 15 T-
Prepare a primer by dissolving J) in toluene.

Urethane rubber (manufactured by Dainippon Ink and Chemicals Co., Ltd.).

A main component was prepared by stirring and mixing 15 parts of Bandex T5205), 40 parts of toluene and 40 parts of methyl ethyl ketone, and this was mixed with a crosslinking agent (manufactured by Bayer "d").

5 parts of Desmodur R) was mixed and the polyurethane adhesive tread force was measured). The results are shown in Table 2.

Prepare the agent.

The primer of each of the above-mentioned Examples was brushed onto a TFSfi aluminum plate (its painted surface) to a thickness of 30 to 50 μm, and dried for 5 minutes at room temperature. Next, the above polyurethane adhesive was applied to one side of the semi-rigid polyvinyl chloride sheet using a bar coater to a thickness of 100μ, dried at 40°C for 1 minute, and superimposed on the TFS-treated aluminum plate described in L.
A laminated structure is produced by compacting by making one reciprocation with a kg roller.

Comparative Example 1 A laminated structure is manufactured in the same manner as in Examples 1 to 4, except that the primer coating is omitted.

Adhesion test Examples 1-4. For the laminated structure of Comparative Example 1.

Peeling force after 3 minutes of lamination (initial adhesive strength), lamination 24
Peeling force after hours (normal adhesive strength) and 500 at 60℃
peeling length after 1 hour under a load of
(Note:

Adhesive strength is tensile speed 200/min, 180° peeling surface 2

Claims (1)

[Claims] 1. In a laminated structure in which a specially coated aluminum plate and a polyvinyl chloride decorative material are bonded together, a primer consisting of an organic solvent solution of chlorinated rubber is applied to the specially coated aluminum plate, and then a thermoplastic polyester urethane rubber and a crosslinking agent are applied. A laminated structure characterized by stacking and bonding polyvinyl chloride decorative materials with a polyurethane adhesive made of a polyisocyanate compound.