JPH054905B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a foamed sheet for leather-like vacuum forming, more specifically, a sheet consisting of six layers, which is particularly useful as a surface material for automobile interiors, and which has a luxurious feel and softness similar to natural leather. This invention relates to a foam sheet for leather-like vacuum forming that has a warm touch. Conventional technology and problems to be solved As skin materials for automobile interiors, for example, PVC (polyvinyl chloride) sheets with leather binding or
A laminate product of PVC/ABS (acrylonitrile-butadiene-styrene) sheet (thickness 0.3 to 1.0 mm) and PVC foam or PO (polyolefin) foam is used. However, the problems are that (i) it does not have the luxurious feel of natural leather, (ii) it lacks natural color, and (iii) the appearance and touch after vacuum forming is cold and lacks softness. . As a result of intensive research to provide a skin material that solves these problems, the present inventors have developed a polyurethane elastomer film layer consisting of two layers and a thermoplastic resin layer consisting of three layers including a foam layer. It was discovered that a laminated foam sheet useful as a skin material for the intended purpose could be obtained by laminating the sheets through an adhesive layer,
The present invention has now been completed. Structure and Effects of the Invention That is, the present invention provides a transparent to translucent colored polyurethane elastomer film layer, a colored polyurethane elastomer film layer, a polyurethane adhesive layer, a thermoplastic resin foam layer, a thermoplastic resin sheet layer, and a thermoplastic resin foam layer. Consisting of layers,
The present invention provides a foamed sheet for leather-like vacuum forming, characterized in that each layer is laminated in the order of . The transparent to translucent colored polyurethane elastomer film layer (hereinafter referred to as transparent colored layer) in the present invention is made of, for example, polyester diol (adipate, caprolactone, carbonate, etc.) or polyoxyalkylene ether diol (polyoxyalkylene ether diol) having an average molecular weight of 500 to 3000. tetramethylene glycol (PTMG), polypropylene glycol, polyethylene propylene glycol, etc.) and chain extenders (1,4-butanediol, 1,6
A polyurethane elastomer (especially durable carbonate-based polyester urethane elastomer is preferred). The above polyurethane elastomer is dissolved in a suitable solvent (DMF, MEK, toluene, ethyl acetate, etc.) to make a 10-20% (wt%) solution, and 3% as a coloring agent is added to this solution.
~15% pigments (carbon black, titanium white, azo organic pigments, phthalocyanine organic pigments, etc.)
to mix and disperse, and then to make it transparent or translucent.
The composition is prepared by adding up to 20% silica powder. In addition, upon use, a polyisocyanate compound (HMDI, IPDI, etc.) may be combined with the polyurethane elastomer solution as a crosslinking agent. Use of this crosslinking agent results in a tough film and improved durability. Such a composition is usually applied in an amount of 20 to 150 g/m ² and then dried at 80 to 130°C for several minutes to a thickness of 3 to 20 μm (preferably 5 to 10 μm).
A transparent colored layer is obtained. If the thickness is less than 3μ, this layer will break during molding, and if it exceeds 20μ, the texture will be hard, impairing the feel and softness, and it tends to be uneconomical. In addition, the physical properties of the urethane film include elongation at break of 200 to 600%, 100%
% modulus 100-300Kg/ ^cm2 (high hysteresis), thermal softening point 150-220℃ (preferably 190-200℃)
℃). The colored polyurethane elastomer film layer (hereinafter referred to as colored layer) in the present invention can be formed from a composition containing the same polyurethane elastomer as used for the transparent colored layer,
In this case, the molecular weight of the elastomer is 100,000~
300000, film physical properties are elongation at break of 200-600%, 100%
Modulus 30-200Kg/ ^cm2 (preferably 60-120
Kg/cm ² ). 10 to 40 of such polyurethane elastomer (preferably carbonate-based polyester urethane elastomer)
A composition is prepared by mixing and dispersing coloring agents (pigments, dyes) in a % solvent solution, and after applying this in an amount of 100 to 250 g/ ^m2 , drying at 80 to 130 °C for several minutes makes the thickness A colored layer of 20-100μ (preferably 20-35μ) is obtained. If the thickness is less than 20μ, the film thickness will become even thinner after molding, the surface strength will decrease, and
If it exceeds 100μ, the texture will be hard and it is also economically unfavorable. The polyurethane adhesive layer (hereinafter referred to as adhesive layer) in the present invention is made of the carbonate-based polyester urethane elastomer (with a molecular weight of 30,000 to 100,000 and a film physical property of 200 to 100,000 yen).
300%, 100% modulus set to 20 to 100Kg/ ^cm2 )
A 30-70% solvent solution of
100 to 200 of a two-component mixture composition of
g/ ^m2 and then dried at 80-130℃ for several minutes to a thickness of 30-100μ (preferably
It is formed in a layer of 40-50μ). If the thickness is less than 30μ, the skin layer tends to break during molding, and if it exceeds 100μ, the texture tends to be hard and the feel to the touch is impaired. The thermoplastic resin foam layer (hereinafter referred to as foam layer or foam layer) in the present invention is:
The foam sheet of the present invention is given appropriate thickness and cushioning properties, and exhibits good moldability and a soft cushioning feeling. As such a foam layer or foam layer, PVC foam or PO [polypropylene (PP), cross-linked polyethylene (PE), etc.]
PVC foam is preferred.
For example, PVC, blowing agents (azodicarbonamide, dinitrosopentamethylenetetramine, diethyl azodicarpoxylate, azobisisobutyronitrile, etc.), plasticizers (DOP, DBP, DUP,
Phthalate esters such as BBP, glycol esters such as diethylene glycol dibenzoate and pentaerythol ester, fatty acid esters such as butyl oleate and methyl acetyl ricinoleate, phosphoric acids such as tricresyl phosphate, trioctyl phosphate, and octyl diphenyl phosphate. esters, epoxidized soybean oil, chlorinated paraffin, etc.),
Stabilizers or catalysts (dibutyltin dilaurate,
Dibutyltin maleate, dibutyltin phthalate,
dibutyltin laurate, Ba-Zn stabilizers, etc.),
PVC foam can be formed from plastisol containing appropriate amounts of fillers (calcium carbonate, bentonite, titanium oxide, ferric oxide, talc, etc.). In this case, the foam layer should have a foaming ratio of 1.5 to 3.0 times, a density of 0.6 g/ ^cm2 or less, a cell size of 50 to 150 μ, and a 100% modulus of 20 to 3.0.
100Kg/ ^cm2 soft PVC sheet physical properties, thickness 0.2~1.5
mm (preferably 0.4 to 0.8 mm). If the thickness is less than 0.2 mm, a suitable cushioned feel cannot be obtained after molding, and if it exceeds 1.5 mm, waving or wrinkles occur during molding, and the surface strength of the molded product tends to decrease. For the foam layer, the foaming ratio should be 1.5 to 3.0 times, and the thickness should be 0.5 to 4 mm.
(preferably 0.5 to 1.0 mm). If the thickness is less than 0.5 mm, it will feel uncomfortable with the backing part material and good cushioning properties will not be obtained, and if it exceeds 4 mm, it will be difficult to mold, especially when molding along a sharp shape. Processing tends to be difficult. The thermoplastic resin sheet layer (hereinafter referred to as sheet layer) in the present invention is a thermoplastic resin.
Formed from a composition that includes PVC, in this case
Plasticizer per 100 parts (by weight, same below) of PVC
A PVC plastisol containing 50 to 150 parts (preferably 65 to 100 parts) is heated at 130 to 250°C,
gelatinized to a thickness of 0.3 to 1 mm (preferably 0.4 to 0.8
Obtain the sheet layer which is a soft PVC sheet of mm).
If the thickness is less than 0.3 mm, it tends to cause breakage during vacuum forming, and if it exceeds 1 mm, it tends to result in a decrease in tactile feel and cushioning feeling. Note that the sheet layer can also be formed from a composition containing the carbonate-based polyester urethane elastomer having a 100% modulus of 50 to 120 kg/cm ² . In this case, the sheet thickness is
It is sufficient if it is set to 0.05 to 0.2 mm. The foamed sheet of the present invention includes the above-mentioned transparent colored layer,
It is constructed by laminating a colored layer, an adhesive layer, a foam layer, a sheet layer, and a foam layer, and can be manufactured, for example, by the following procedure. First, a composition for a transparent colored layer is applied on a release paper with a squeezing pattern and dried, then a composition for a colored layer is applied thereto and dried, and a two-component mixed composition for an adhesive layer is applied. Dry to form three layers. Separately, a plastisol for a foam layer is applied on a release paper, heated and foamed, a composition for a sheet layer is applied thereto, heated and gelled, and a plastisol for a foam layer is further applied, heated and foamed to form three layers. . Next, the coating layers formed on the release paper are bonded together via an adhesive layer. After lamination, a long roll is obtained by peeling off the release paper on both sides, and cured in this state at 30 to 60°C for several days. The foamed sheet of the present invention having the above-mentioned structure has the following advantages: (1) There is almost no throttling flow after vacuum forming, there is no loss of throttling at the corner convex parts, and small wrinkles are left behind;
It gives a high-quality appearance, () has an excellent soft feel, high surface strength, has a heat insulating effect, and has a warm taste (in particular, the appearance, color and feel are similar to those formed by pasting and molding natural leather). gives a soft feel). The foamed sheet of the present invention is particularly useful as a skin material for automobiles (instrument consoles, door trims, etc.), and can also be applied to furniture, miscellaneous goods (cases, bag skins), and the like. Next, the present invention will be explained in more detail with reference to Examples. Example 1 A foam made of PVC [average degree of polymerization (hereinafter expressed as) = 1700], TOTM (trioctyl trimellitate, plasticizer), stabilizer, carbon black, blowing agent, and filler was placed on flat silicone paper. Apply the sol to a wet thickness of 0.2 mm and foam at 200°C for 1 minute (double foaming). On top of that, PVC (=3500),
Plastisol consisting of TOTM, stabilizer, filler and carbon black is applied to a dry thickness of 0.5 mm and gelled at 200°C for 1 minute. Furthermore, the first foaming sol was applied to a wet thickness of 0.3 mm, and 220
Gel and foam at ℃ x 2.5 minutes (double foaming). After cooling, the silicon paper is peeled off to obtain a PVC foam with a total thickness of 1.5 mm, with foam layers on both sides and a solid layer in the center. Separately, carbonate-based polyester urethane elastomer (100%
A colored solution prepared by adding a coloring agent and silica powder to a solution with a modulus of 300 kg/cm ² and a thermal softening point of 180° C. is applied to a dry thickness of 7 μm, and dried at 100° C. for 1 minute. Next, a coloring solution made by adding a coloring agent to a solution of carbonate-based polyester urethane elastomer (100% modulus 60 kg/cm ² , heat softening point 160°C) was applied on top to a dry thickness of 30μ, and the coating was applied at 100°C for 2 minutes. Dry with. Furthermore, a two-component mixed composition of carbonate-based polyester urethane elastomer (100% modulus 30Kg/cm ² )/polyisyanate compound was applied as an adhesive layer on top of it to a dry thickness of 60μ, and the mixture was heated at 90°C.
The solvent was evaporated in 2 minutes, and before curing was completed, the first layer of PVC foam applied was layered on the adhesive surface, laminated, rolled up, and then heated at 50°C x 72°C. After curing for a period of time to complete the curing reaction, the PP laminated paper is peeled off to obtain the desired laminated foam sheet. Using this foam sheet as a skin agent, the surface temperature
By vacuum forming at 160-180℃, injecting urethane and foaming, we created instrument pads and consoles with a high-quality appearance, excellent soft feel, and cushioning, as well as the required high degree of durability. Comparative Example 1 Regarding the PVC foam of Example 1, the coating thickness (wet) of the first foaming sol was 0.4 mm and the coating thickness (wet) of the subsequent foaming sol was 0.2 mm, both of which were 3 times larger. A laminated foam sheet is obtained in accordance with the manufacturing method of Example 1, except that foaming is employed. When this was simultaneously applied as a skin material, wrinkles occurred in the surface urethane layer during vacuum forming, and the mechanical strength of the surface decreased (scratches, etc.). Example 2 According to the manufacturing method of Example 1, PVC shown below was produced.
A laminated foam sheet consisting of three layers of foam and urethane is obtained. PVC foam Same as Example 1, 3-layer urethane transparent colored layer: 7μ thick, carbonate (100
% modulus 150Kg/cm ² , heat softening point 190℃) Colored layer: thickness 30μ, carbonate type (100% modulus 100Kg/cm ² , heat softening point 170℃) Adhesive layer: thickness 50μ, carbonate type (100%)
Modulus: 30 Kg/cm ² ) Using this foam sheet, vacuum forming and urethane injection foaming were performed at a surface temperature of 160 to 190°C to create an excellent full instrument pad. Next, Table 1 below shows a performance comparison between the skin material of the present invention (Example 1) and other companies' products currently used for instrument pads.

【table】

[Table] From the comparison results in Table 1, it is recognized that the skin material of the present invention has excellent moldability and durability, and furthermore, by using this material, a luxurious You can get a good instrumentation.

Claims (1)

[Scope of Claims] 1 Consisting of: a transparent to translucent colored polyurethane elastomer film layer, a colored polyurethane elastomer film layer, a polyurethane adhesive layer, a thermoplastic resin foam layer, a thermoplastic resin sheet layer, and a thermoplastic resin foam layer, A foam sheet for leather-like vacuum forming, characterized in that each layer is laminated in the order of . 2 The thickness of each layer is 3 to 20μ, 20 to
The foamed sheet according to item 1 above, which has a diameter of 100μ, 30 to 100μ, 0.2 to 1.5 mm, 0.3 to 1 mm, and 0.5 to 4 mm.