JP2002137335A - Resin laminate and sheet having leather appearance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate wherein each of laminated layers is strongly bonded. SOLUTION: The resin laminate 1 has a polyolefin based thermoplastic elastomer (TPO) layer 10 and a polyurethane layer 20 laminated on the TPO layer 10, wherein an adhesion force improver having a functional group containing an activated hydrogen is added to the TPO layer 10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin laminate and a leather-like sheet.

[0002]

2. Description of the Related Art In recent years, resinous leather seats have been frequently used for interior materials and furniture for automobiles. As such a leather-like sheet made of resin, a vinyl chloride resin-based material or a urethane-based material having relatively high surface strength is generally used, and a polyolefin-based thermoplastic elastomer (hereinafter, referred to as TPO) having low surface strength is used. Had not been.

[0003] However, vinyl chloride resin has problems of low environmental adaptability such as generation of harmful substances such as chlorine-based gas upon incineration, and urethane is expensive.
The appearance of a resin-made leather-like sheet mainly composed of PO has been desired. In response to such demands, TPO-based leather-like sheets comprising a TPO layer and a urethane-based surface treatment layer have been developed, and are now mainly used for furniture.

[0004]

However, in the above-mentioned TPO-based leather-like sheet, since the adhesion between the TPO layer and the polyurethane layer is weak, the surface strength (abrasion resistance) is lower than that of the TPO itself. There is a problem that it has not been improved so much. For this reason, it is difficult to use the above-mentioned TPO-based leather-like sheet for applications requiring high surface strength, and it is desired to develop a TPO-based leather-like sheet having high surface strength and using TPO as a main material. It is rare.

[0005] It is an object of the present invention to provide a resin laminate and a leather-like sheet in which the laminated layers are firmly bonded.

[0006]

Means for Solving the Problems The resin laminate according to the present invention is made of a polyolefin thermoplastic elastomer (hereinafter referred to as T).
PO) and a polyurethane layer laminated on the polyolefin-based thermoplastic elastomer layer, wherein the polyolefin-based thermoplastic elastomer layer has an adhesiveness improver having an active hydrogen-containing functional group. Is added.

In the above, the TPO constituting the TPO layer
Examples of (1) an elastomer having polypropylene as a hard segment and polyethylene as a soft segment, (2) an elastomer having ethylene and a small amount of a diene component, (3) ethylene-propylene-diene rubber (EPDM), (4) ethylene- Propylene rubber (EP
R), (5) butyl rubber-grafted polyethylene, (6) styrene-based elastomer, (7) a blend of each of the elastomers (rubbers) (1) to (6), (8) an organic peroxide as (1) ~
A partially crosslinked product obtained by adding (7), a product (9) graft-modified with an unsaturated hydroxy monomer or an unsaturated carboxylic acid derivative, and the like can be used. Note that a foamed TPO may be used.

[0008] The active hydrogen-containing functional group is not particularly limited as long as it has active hydrogen, but an amino group is ideal. Further, as the adhesive strength improver, if the compound having the active hydrogen-containing functional group,
There is no particular limitation, and an aliphatic, alicyclic, or aromatic amine compound having an active hydrogen-containing functional group containing at least one amino group can be used.

The amine compounds include aliphatic chain polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine and polyoxypropylenetriamine, mensendiamine, isophoronediamine, and the like. Bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,
Aliphatic cyclic amines such as 4,8,10-tetraoxaspiro (5,5) undecane, m-xylenediamine, α-
Aliphatic aromatic amines such as (m / p-aminophenyl) ethylamine and the like, aromatic diamines such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and diethyldimethyldiaminodiphenylmethane can be employed. Preferred amine compounds are those having high reactivity with the NCO group in urethane, low toxicity, low volatility, and low odor.

[0010] The content of the adhesion promoter is 0.00
Preferably it is 1 to 50% by weight. If the content is less than 0.001% by weight, a sufficient effect of improving the adhesive strength cannot be obtained, which is not preferable. On the other hand, if it exceeds 50% by weight, the adhesive strength may be reduced. More preferably, it is 0.01 to 40% by weight, and still more preferably 0.1 to 30% by weight. The surface of the TPO layer may be subjected to a corona discharge treatment. By applying corona discharge treatment, more TPO
The adhesion between the layer and the polyurethane layer can be further improved. At this time, the surface wetting index of the TPO layer (JIS K
The value measured by a method according to −6768 is not particularly limited, but the value is preferably 350 μN / cm or more.

Further, it is preferable that the polyurethane constituting the polyurethane layer is formed of a reactive urethane primer layer and a thermoplastic polyurethane layer. Here, the reactive urethane primer refers to a mixture of a mixture of a polyisocyanate compound and a polyhydroxyl compound, which react to form a polyurethane polymer. Specifically, compounds dissolved in different solvents are mixed, applied with a gravure roll or the like, and dried to obtain a polyurethane polymer.

As the polyisocyanate compound, simple
Double aromatic ring, aliphatic and alicyclic di-, tri-, and tetra-based polyisocyanate compounds are exemplified. On the other hand, examples of the polyhydroxyl compound include polyester polyol (from diol to polyol) and polyether polyol (from diol to polyol).

The polyurethane constituting the thermoplastic polyurethane layer is a polymer of a polycarbonate polyol, polyester diol, or polyoxyalkylene ether diol, a polyisocyanate, and a chain extender, which is dissolved in a solvent. What was done can be adopted. As a polycarbonate-based polyol,
A polyalkylene polycarbonate-based polyol, a mixture partially substituted with a polyoxyalkylene-modified polycarbonate, or the like can be used.

As the polyester diol, for example, adipate having a diol, caprolactone derivative, carbonate and the like can be used. As the polyoxyalkylene ether diol, for example, polytetramethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polypropylene-ethylene glycol and the like can be employed.

Examples of the chain extender include alkyldiols such as 1,4-butanediol and 1,6-hexanediol;
Primary or secondary aliphatic diamines can be employed. As the solvent, various solvents capable of dissolving the polyurethane elastomer can be used. For example, N, N-dimethylformamide (DMF), methyl ethyl ketone (M
EK), ethyl acetate and the like.

The polyurethane constituting the polyurethane layer may be an acrylic-urethane resin. As the acrylic-urethane resin, a resin obtained by dissolving a polymer of acrylic polyol and polyisocyanate in a solvent can be used. Here, the polyurethane layer preferably has a thickness of 1 to 300 μm, a rubber hardness of 50 ° or more in JIS-A display and / or a flexibility of 1
It is preferable that the modulus is 00 MPa or more and 1 MPa or more. More preferably, the thickness is 3 to 100 μm and the rubber hardness is 55 to 10
0 ° and / or flexibility is 2 to 30 MPa or more.

Further, a polyurethane elastomer may be used for the polyurethane layer. Further, the polyurethane layer may have a multilayer structure as required. Specifically, for example, a structure according to the application is adopted, such as a structure in which a surface layer is provided with a layer for improving the touch feeling, a structure in which a lower layer is provided with a layer having strength, or a structure opposite thereto. can do.

The polyurethane layer may contain natural organic fine powder. As the natural organic substance fine powder, silk, cellulose, collagen, wool, keratin, hemp, cotton, chitin, chitosan, betaine, eggshell membrane and the like can be adopted. Further, a plurality of these may be used in combination.

The amount of the finely divided natural organic matter is usually 1 to 9
0 wt%, preferably 3 to 60 wt%, particularly preferably 5 to 30 wt%. Natural organic matter fine powder addition amount is 9
If it exceeds 0 wt%, the flexibility of the resin may be impaired. Also, as the average particle size of the natural organic matter fine powder,
The value measured with a laser diffraction / scattering particle size distribution analyzer (LMS-24) manufactured by Seishin Enterprise Co., Ltd. is 300 μm.
m, preferably 1 to 100 μm, more preferably 3 to 30 μm. If it exceeds 300 μm, a good touch may not be obtained.

According to the present invention, since the TPO layer contains an adhesion promoter having an active hydrogen-containing functional group, the TP
The adhesive strength between the O layer and the polyurethane layer can be improved. That is, an active hydrogen-containing functional group such as an amino group of the adhesive strength improving agent improves the adhesion (compatibility) between the TPO layer and the polyurethane layer, and as a result, the TPO layer and the polyurethane layer are firmly bonded. it is conceivable that. Thereby, the surface strength of the resin laminate can also be improved.

Further, when a reactive urethane primer is used as a component of the polyurethane layer, the TPO layer and the reactive urethane primer layer are firmly adhered to each other, and the reactive urethane primer layer and the thermoplastic polyurethane layer are strongly bonded. Therefore, the bonding strength can be further improved. Since the resin laminate of the present invention is made of a material mainly composed of polyolefin, it does not generate chlorine-based harmful gas or the like even during incineration, and has high environmental adaptability.

Such a resin laminate can be obtained by various methods of coating a polyurethane layer on a TPO layer obtained by previously forming a TPO raw material to which an amine compound has been added into a sheet by calendering, T-die molding or the like. For example, a method of directly applying a polyurethane layer on a TPO layer with a gravure roll, a comma coater, a doctor knife, an over roll coater, or the like, or a method of forming a polyurethane film (polyurethane layer) on release paper,
It can be manufactured by a method such as sticking on a TPO layer by a transfer method.

A leather-like sheet according to the present invention is characterized by including the above-mentioned resin laminate and a base material. Here, the substrate is a cloth (base cloth), and the yarn quality is
Blends of polyester and rayon, soup, polypropylene, polyester, blends of polyester and soup, polypropylene foam non-woven fabric, polyurethane foam non-woven fabric, and the like can be used.

As the structure of the base material, one side knitting, two sided knitting, special knitting, twill weaving, plain weaving, Russell knitting, sheet knitting and the like can be adopted. Such a leather-like sheet can be produced, for example, by applying an adhesive on a base material and laminating a resin laminate thereon by T-die extrusion, calendering, or the like.

According to this, since it is a leather-like sheet provided with the above-mentioned resin laminate and the base material, a TPO-based leather-like sheet having high surface strength can be provided. Further, the obtained leather-like sheet has a high surface strength, and thus can be suitably used as an interior material for automobiles. As interior materials for automobiles, for example, leather for seats, leather for door trims, leather for instrument panels, leather for sun visors, leather for ceilings and the like can be used.

[0026]

Embodiments of the present invention will be described below with reference to the drawings. [First Embodiment] FIG. 1 shows a resin laminate 1 according to a first embodiment of the present invention. The resin laminate 1 includes a TPO layer 10 containing an amine compound as an adhesion enhancer having an amino group which is an active hydrogen-containing functional group, and a TP
A polyurethane layer 20 laminated on the O layer 10. The amine compound is contained in the TPO layer in an amount of 0.00%.
1 to 50% by weight. Here, the polyurethane layer 20 is formed of a layer (hereinafter, referred to as a urethane primer layer) 20B composed of a reactive primer layer, and a thermoplastic polyurethane layer 20A laminated thereon.

The resin laminate 1 configured as described above is
It is manufactured as follows. First, calendar processing, T
The TPO material containing the amine compound is formed into a sheet by die extrusion or the like to obtain the TPO layer 10. Then, the urethane primer layer 20B is gravure rolled to the TPO layer 1.
0, dried, and further, a thermoplastic polyurethane layer 20A is applied thereon by using a gravure roll and laminated to obtain a resin laminate 1.

According to the above-described embodiment, the following effects can be obtained. (1) 0.001 to 5 amine compounds in the TPO layer 10
Since it contains 0% by weight, the adhesive strength with the polyurethane layer 20 can be improved, and thereby the adhesive strength of the resin laminate 1 can be increased. That is, the adhesion (compatibility) between the TPO layer 10 and the polyurethane layer 20 is improved by the amino group of the amine compound. (2) Since the polyurethane layer 20 is firmly bonded on the TPO layer 10, the surface strength of the resin laminate 1 can be improved.

(3) Since a reactive urethane primer is used as a constituent of the polyurethane layer 20, the TPO layer 10 and the urethane primer layer 20B are firmly adhered to each other, and the thermoplastic layer laminated on the urethane primer layer 20B Since the adhesive is firmly bonded to the polyurethane layer 20A, the adhesive strength of the resin laminate 1 can be further improved. (4) Since the resin laminate 1 is made of a material mainly composed of polyolefin, it does not generate chlorine-based harmful gas even during incineration, and has high environmental adaptability.

[Second Embodiment] FIG. 2 shows a second embodiment of the present invention.
The leather tone sheet 2 according to the embodiment is shown. The leather-like sheet 2 has the same configuration as that of the first embodiment, except that a polyester base material 30 is attached to the surface of the TPO layer 10 of the resin laminate 1 shown in the first embodiment. Therefore, the detailed description is omitted. The leather-like sheet 2 configured as described above can be manufactured by attaching the base material 30 to the resin laminate 1 by calendering.

According to the above-described second embodiment, the following effects can be obtained in addition to the same effects as (1) to (4) of the first embodiment. (5) Since the leather-like sheet 2 includes the resin laminate 1 and the base material 30, the TPO-based leather-like sheet 2 having a high adhesive strength between the TPO layer 10 and the polyurethane layer 20 and a high surface strength. It can be suitably used for furniture such as sofas, automobile seats, and the like.

The present invention is not limited to the above embodiments, but includes modifications and improvements as long as the object of the present invention can be achieved. For example, in each of the above embodiments, the resin laminate 1 has a three-layer structure, but is not limited thereto. In short, a TPO layer, a TPO layer containing an adhesion promoter having an active hydrogen-containing functional group, and a polyurethane layer may be provided, and the thermoplastic polyurethane layer may be directly provided without a urethane primer layer. A stacked configuration may be used. Further, a layer made of another resin may be provided.

In each of the above embodiments, the amine-based compound is used as the adhesive force improver. However, the present invention is not limited to this, and other compounds having an active hydrogen-containing functional group can also be used. In addition, the amount of the adhesive strength improver contained in the TPO layer 30 is 0.001 to 50% by weight, but is not limited thereto, and can be appropriately changed as long as the adhesiveness is not impaired. In addition, it is also possible to perform a corona discharge treatment on the surface of the TPO layer. At this time, TPO
The surface wetting index of the layer (a value measured by a method based on JIS K-6768) is not particularly limited, but by setting the value to 350 μN / cm or more, the adhesiveness can be further improved.

In the first embodiment, the method of applying the thermoplastic polyurethane layer 20A using a gravure roll is employed, but the present invention is not limited to this. That is, various devices and methods capable of laminating a polyurethane layer can be employed.For example, doctor knife, application by a coater such as an over-roll coater, or a polyurethane film formed on release paper in advance, followed by a transfer method A lamination method or the like may be employed. Also, the apparatus for applying the urethane primer layer 20B is not limited to the gravure roll, and another coater such as an offset coater may be employed.

In the second embodiment, as the substrate 30,
Although polyester is used, the invention is not limited to this, and a blend of polyester and rayon, a blend of polypropylene, a blend of polyester and fabric, a polypropylene foam nonwoven fabric, a polyurethane foam nonwoven fabric, or the like may be used. In addition, the specific structure, shape, and the like at the time of carrying out the present invention may be other structures and the like as long as the object of the present invention can be achieved.

[0036]

The present invention will now be described more specifically with reference to examples and comparative examples. [Example 1] 10 parts by weight of process oil (PW90, Idemitsu Kosan Co., Ltd.) and polyolefin-based thermoplastic elastomer (E2640, manufactured by Idemitsu Petrochemical Co., Ltd.) 1
00 parts by weight and 0.5 parts by weight of a polyamidoamine (Sunmide 305, manufactured by Sanwa Chemical Industry Co., Ltd.) as an adhesive strength improver were sufficiently mixed with a three-inch two-roller set at a roll temperature of 160 ° C. Thus, a TPO sheet (TPO layer 10) having a thickness of 1.0 mm was obtained.

Subsequently, the output 0. 0 is placed on the surface of the TPO layer 10.
Corona discharge treatment was performed at 3 kW, a table speed of 6.2 m / min, and two reciprocating treatments. T after corona discharge treatment
The surface wetting index of the PO sheet is 390 μN / cm (55 d
yn / cm converted to SI units). In addition,
The wetting index is a value measured by a method based on JIS K-6768.

After the corona discharge treatment, a polycarbonate urethane (a product obtained by reacting Duracarb 140 with hexamethylene diisocyanate to form an OH group at the end) is dissolved in a DMF / MEK mixed solvent, and hexamethylene diisocyanate is dissolved in MEK. A reactive urethane primer solution mixed with the above is coated on the above-mentioned TPO sheet with a gravure roll,
After drying for 2 seconds, a urethane primer layer 20B having a thickness of about 5 μm was formed.

Further, 100 parts by weight of a polyurethane elastomer which is a thermoplastic polyurethane (Resamine ME44, manufactured by Dainichi Seika Co., Ltd.), 30 parts by weight of DMF,
A solution consisting of 30 parts by weight of K was applied onto the urethane primer layer 20B with a gravure roll and dried at 100 ° C. for 30 seconds to form a thermoplastic polyurethane layer 20A having a thickness of 15 μm. Obtained.

Example 2 The procedure of Example 1 was repeated, except that 0.3 parts by weight of polyoxypropylenediamine (Jeffamine D-200, manufactured by San Techno Chemical Co., Ltd.) was used as an adhesion enhancer. A resin laminate 1 was obtained.

Example 3 Diaminodicyclohexylmethane (Wandamine, Shin Nippon Science Co., Ltd.)
Resin laminate 1 was obtained in the same manner as in Example 1 except for using 1.0 part by weight of Co., Ltd.).

Example 4 As an adhesion promoter, 3, 9
-Bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane (epomate 8.
002, manufactured by Yuka Shell Epoxy Co., Ltd.), and a resin laminate 1 was obtained in the same manner as in Example 1 except that 1.0 part by weight was used.

Example 5 A resin was prepared in the same manner as in Example 1 except that 0.5 part by weight of an aliphatic cyclic polyamine (Gaskamin 328, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used as an adhesion enhancer. The laminate 1 was obtained.

Comparative Example 1 A resin laminate was obtained in the same manner as in Example 1 except that no adhesive strength improving agent was used.

The adhesive strength between the TPO layer and the polyurethane layer in the resin laminate obtained in each of the above Examples and Comparative Examples was measured, and the results are summarized in Table 1. The adhesive strength is
At room temperature, the TPO layer and the polyurethane layer were peeled off at a tensile speed of 200 mm / min.

[0046]

[Table 1]

As shown in Table 1, the resin laminate obtained in each of Examples 1 to 5 has a T
Since the PO layer and the polyurethane layer are laminated, it is understood that the adhesive strength of each layer is high. On the other hand, in Comparative Example 1,
Since no adhesion enhancer was added to the primer layer, the adhesion was found to be low.

[0048]

According to the present invention, the TPO layer contains an adhesiveness improving agent having an active hydrogen-containing functional group.
The adhesive strength between the PO layer and the polyurethane layer can be improved. That is, an active hydrogen-containing functional group such as an amino group of the adhesive strength improving agent improves the adhesion (compatibility) between the TPO layer and the polyurethane layer, and as a result, the TPO layer and the polyurethane layer are firmly bonded. it is conceivable that. Thereby, the surface strength of the resin laminate can also be improved.

Further, when a reactive urethane primer is used as a constituent of the polyurethane layer, the TPO layer and the reactive urethane primer layer are firmly adhered to each other, and the reactive urethane primer layer and the thermoplastic polyurethane layer are strongly bonded. Therefore, the bonding strength can be further improved. Since the resin laminate of the present invention is made of a material mainly composed of polyolefin, it does not generate chlorine-based harmful gas or the like even during incineration, and has high environmental adaptability.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view illustrating a resin laminate according to a first embodiment of the present invention.

FIG. 2 is a partial cross-sectional view illustrating a leather-like sheet according to a second embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Resin laminated body 2 Leather-like sheet 10 Polyolefin thermoplastic elastomer layer 20 Polyurethane layer 20A Thermoplastic polyurethane layer 20B Reactive urethane primer layer 30 Substrate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06N 3/18 D06N 3/18 F-term (Reference) 4F055 AA03 BA13 EA02 EA03 EA22 EA23 EA24 FA04 FA05 FA06 FA15 FA39 GA32 4F100 AK03A AK45 AK51B AK51C AL09A AT00D BA02 BA03 BA04 BA10A BA10D BA13 BA16 CA16A EH46 EJ65B JB04A JB16A JB16B JB16C JK06 JK14 JL11A YY00A 4J002 BB151 BC021 BN031 BN201 EN0

Claims (5)

[Claims] 1. A resin laminate comprising a polyolefin-based thermoplastic elastomer layer and a polyurethane layer laminated on the polyolefin-based thermoplastic elastomer layer, wherein the polyolefin-based thermoplastic elastomer layer has an active hydrogen-containing functional group. A resin laminate, wherein an adhesive strength improving agent having a group is added. 2. The resin laminate according to claim 1, wherein said active hydrogen-containing functional group is an amino group. 3. The resin laminate according to claim 1, wherein the content of the adhesion promoter in the polyolefin-based thermoplastic elastomer layer is 0.001 to 50% by weight. Resin laminate. 4. The resin laminate according to claim 1, wherein said polyurethane layer comprises a reactive urethane primer layer and a thermoplastic polyurethane layer. 5. A leather sheet comprising the resin laminate according to any one of claims 1 to 4 and a base material.