JP2002019033A - Resin laminate, coated fabric style sheet and interior finishing material for automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate having a high surface strength and a high adhesive strength of a TPO layer and a polyurethane layer. SOLUTION: In the resin laminate 1 comprising a polyolefin thermoplastic elastomer layer 10, a primer layer 30 laminated on the elastomer layer 10 and a polyurethane layer 20 laminated on the layer 30, the layer 30 contains an organic pigment and a polyolefin thermoplastic elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin laminate, a leather-like sheet, and an interior material for an automobile.

[0002]

2. Description of the Related Art In recent years, resinous leather seats have been frequently used for interior materials and furniture for automobiles. Such resin-like leather-like sheets include paints,
Vinyl chloride resin and urethane-based materials with high adhesion to coatings and adhesives are generally used, and polyolefin-based thermoplastic elastomers with low adhesion (hereinafter, referred to as
TPO) was not used.

[0003] In order to eliminate such disadvantages, various studies have been made on the modification of the surface of TPO.
The following technologies are known. (1) A method in which a photopolymerization initiator having no hydroxyl group and a pigment or dye are applied to a polyolefin to form a film, and then irradiated with ultraviolet rays (Japanese Patent Application Laid-Open Nos. 7-62127 and 7-6).
No. 2128) (hereinafter referred to as Conventional Example 1). (2) A method using a dye and a specific organosilicon compound as a primer (Japanese Patent Publication No. 6-51849) (hereinafter referred to as Conventional Example 2).

[0004]

However, in the method of the prior art 1, it is necessary to irradiate ultraviolet rays to initiate polymerization, and there is a problem that the processing steps become complicated. In addition, there is a problem that a corona treatment or a plasma treatment, which is a general surface treatment method, cannot be performed. On the other hand, in the method of Conventional Example 2, since the organosilicon compound is sensitive to humidity, the interval until the application of a paint, a coating agent, an adhesive, or the like must be extremely short, and a quick operation can be performed. There is a problem that is required.

It is an object of the present invention to provide a high surface strength,
An object of the present invention is to provide a resin laminate, a leather-like sheet, and an interior material for automobiles having a high adhesive strength between a TPO layer and a polyurethane layer.

[0006]

Means for Solving the Problems The resin laminate according to the present invention comprises a polyolefin-based thermoplastic elastomer layer (hereinafter referred to as "polyolefin-based thermoplastic elastomer layer").
A TPO layer), a primer layer laminated on the TPO layer, and a polyurethane layer laminated on the primer layer, wherein the primer layer comprises an organic pigment and a polyolefin-based thermoplastic resin. It is characterized by being formed from an elastomer.

The TPO in the present invention includes (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, and (3) an ethylene-propylene-diene rubber (EPDM). ), (4) ethylene-propylene rubber (EPR), (5) butyl rubber-grafted polyethylene, (6) styrene-based elastomer, (7)
(1) to (6) each elastomer (rubber) blended, (8) organic peroxide added to (1) to (7) and partially crosslinked, (9) unsaturated Those graft-modified with a hydroxy monomer or an unsaturated carboxylic acid derivative can be used.

The organic pigments contained in the primer layer include insoluble azo pigments, condensed azo pigments, phthalocyanine blue, dye lake, isoindolinone, quinacridone,
Dioxane violet, perinone / perylene and the like. The content of the organic pigment in the primer layer is preferably 0.2% by weight or more, and more preferably 0.5% by weight or more, which is an amount intended for ordinary coloring and the like. In order to improve the adhesive strength, the content is preferably as large as possible. However, if the content is too large, the resin laminate itself may become brittle. Even more preferably, it is 0.5 to 50% by weight. Note that it is preferable to add a dispersant in order to improve the dispersion of the organic pigment and the like in the solvent.

When applying the primer, a solvent is generally used, but usable solvents include aromatic hydrocarbons such as benzene, toluene and xylene, trichloroethylene, tetrachloroethylene, methylchloroform and the like. Halogenated hydrocarbons, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane, aliphatic hydrocarbons such as n-hexane and n-heptane, ketones such as acetone and methyl ethyl ketone, ethyl acetate and acetic acid Esters such as butyl, ethers such as ethyl ether and diphenyl ether, and alcohols such as ethanol and isopropanol can be used.

Further, the polyurethane constituting the polyurethane layer is preferably formed from 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. Examples of the polyisocyanate compound include mono-, double-aromatic, aliphatic, and alicyclic di, tri, and tetra polyisocyanate compounds. 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-based 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, a caprolactone derivative, carbonate, or the like can be used.

Further, as the polyoxyalkylene ether diol, for example, polytetramethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polypropylene-ethylene glycol and the like can be employed. As the chain extender, an alkyl diol such as 1,4-butanediol and 1,6-hexanediol, and a primary or secondary aliphatic diamine can be employed. As the solvent, various solvents that dissolve the polyurethane elastomer can be used.
N-dimethylformamide (DMF), methyl ethyl ketone (MEK), ethyl acetate and the like can be employed.

According to the present invention, TPO is contained in the primer layer.
, The compatibility between the primer layer and the TPO layer is improved, and the adhesive strength can be strengthened. Also,
Since the primer layer contains the organic pigment, the adhesive strength with the polyurethane layer laminated on the primer layer can be improved, and the adhesive strength of the resin laminate can be improved. That is, it is considered that the adhesive force (compatibility) with the polyurethane layer is improved by the reactive groups such as amino group and hydroxyl group of the organic pigment.

Further, when a reactive urethane primer is used as a constituent component of the polyurethane layer, the primer layer and the reactive urethane primer are firmly bonded, and the reactive urethane primer and the thermoplastic polyurethane are firmly bonded. Therefore, the adhesive strength can be further improved. In addition, 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 even during incineration, and has high environmental adaptability.

[0015] In the above, it is preferable that the surface of the primer layer is subjected to a corona discharge treatment. Here, the wettability index of the primer layer surface after the corona discharge treatment was 400 μN / cm (40 dyn / cm
(Value converted to I unit). The wetting index is a value measured by a method based on JIS K-6768. By performing the corona discharge treatment and improving the surface wetting index, the surface of the primer layer is oxidized, and the adhesion strength with the polyurethane layer laminated on the surface is further improved.

The leather-like sheet according to the present invention is described in claim 1.
A resin laminate according to any one of claims 1 to 3, and a base material. The substrate in the present invention,
It is a cloth (base cloth), and as the yarn quality, a blend of polyester and rayon, a blend of woolen, polypropylene, polyester, a blend of polyester and woofer, a polypropylene foam nonwoven fabric, a polyurethane foam nonwoven fabric, and the like can be used.
Further, as the structure of the base material, one-side knitting, double-sided knitting, special knitting, twill weaving, plain weaving, Russell knitting, sheet knitting, or the like can be adopted. According to the present invention, since it is a leather-like sheet using the above-mentioned resin laminate, a leather-like sheet having high adhesive strength and high surface strength of each layer of the resin laminate can be obtained.

The above-mentioned leather-like sheet is preferably used as an interior material for automobiles because of the high adhesion strength of the laminate. 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.

[0018]

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 polyolefin-based thermoplastic elastomer layer (hereinafter referred to as a TPO layer) 10, a primer layer 30 laminated on the TPO layer 10, and a polyurethane layer 20 laminated on the primer layer 30. And Here, the primer layer 30 is formed by applying a mixture of an organic pigment, TPO, and toluene to the surface of the TPO layer 10, and the wettability index of the surface of the primer layer 30 is determined by corona discharge. It is set to 400 μN / cm or more by processing. The polyurethane layer 20 is formed from a layer (hereinafter, referred to as a urethane primer layer) 20B made of a reactive urethane primer and a thermoplastic polyurethane layer 20A laminated thereon.

The resin laminate 1 constructed as described above is
It is manufactured as follows. First, calendar processing, T
The TPO raw material is formed into a sheet by die extrusion or the like.
On the PO layer 10, an organic pigment, TPO,
A mixed solution of toluene is applied and dried to form a primer layer 30.
Is formed, the surface is subjected to a corona discharge treatment. Subsequently, a reactive urethane primer is applied with a gravure roll and dried to form a urethane primer layer 20B.
Further, a thermoplastic polyurethane layer 20A is applied thereon 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) Since TPO is contained in the primer layer 30, the compatibility between the primer layer 30 and the TPO layer 10 is improved, and the adhesion can be strengthened. (2) Since the primer layer 30 contains the organic pigment in an amount of 0.5 to 50% by weight, the adhesive strength with the polyurethane layer 20 laminated on the primer layer 30 can be improved,
Thereby, the adhesive strength of the resin laminate 1 can be increased. That is, the adhesive strength (compatibility) with the polyurethane layer is improved by the reactive groups such as amino groups and hydroxyl groups of the organic pigment.

(3) Since the primer layer 30 contains an organic pigment, the effect can be exerted with a small amount as compared with the case where the organic pigment is added to the TPO layer. (4) Since the polyurethane layer 20 is provided on the TPO layer 10, the surface strength of the resin laminate 1 can be improved, and the resin laminate 1 can be used for applications requiring high surface strength. (5) Since a reactive urethane primer is used as a constituent component of the polyurethane layer 20, the primer layer 30 and the urethane primer layer 20B are firmly adhered to each other, and the urethane primer layer and the thermoplastic polyurethane layer 2
Since OA is strongly bonded, the bonding strength can be further improved.

(6) The surface of the primer layer 30 is subjected to a corona discharge treatment to have a surface wetting index of 400 μN / cm or more.
And the adhesive strength with the adhesive can be further improved. (7) Since the resin laminate of the present invention is composed 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 the base material 50 made of polyester 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 tone sheet 2 configured as described above can be manufactured by attaching the base material 50 to the resin laminate 1 by calendering.

According to the second embodiment described above, the same effects as (1) to (7) of the first embodiment can be obtained, and the following effects can be obtained. (8) Since the leather-like sheet 2 includes the resin laminate 1 and the base material 50, 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.

It should be noted that the present invention is not limited to the above embodiment, and modifications and improvements as long as the object of the present invention can be achieved are included in the present invention. For example, in each of the above embodiments, the resin laminate 1 employs a four-layer structure including the TPO layer 10, the primer layer 30, the urethane primer layer 20B, and the thermoplastic polyurethane layer 20A, but is not limited thereto. . In short, it suffices if it has a configuration in which a TPO layer, a primer layer containing an organic pigment, and a polyurethane layer are stacked, and may have a layer made of another resin. Further, a structure in which the thermoplastic polyurethane layer is directly laminated on the primer layer without providing the reactive urethane premer layer 20B may be employed. Furthermore, TPO layer 2
The amount of the organic pigment contained in 0 was 0.5 to 50% by weight, but is not limited thereto, and can be appropriately changed within a range that does not impair the adhesiveness.

In each of the above embodiments, toluene was used as the solvent. However, the present invention is not limited to this. Other aromatic hydrocarbons, halogenated hydrocarbons, alicyclic hydrocarbons,
Various solvents such as ketones, esters, ethers, and alcohols may be used. The wetting index of the surface of the primer layer 30 is 400 due to the corona discharge treatment.
μN / cm or more, but not limited thereto, as long as the adhesive strength with the primer layer 30 can be maintained.
It can be any value. The surface of the primer layer may not be subjected to the corona discharge treatment.

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 adopted.For example, doctor knife, application by a coater such as an over-roll coater, or after a polyurethane film is previously formed on release paper, by a transfer method. A lamination method or the like can be adopted. In addition, although the primer layer 30 is applied with a bar coater, the present invention is not limited to this, and another coater such as a doctor knife, a gravure roll, or an offset coater may be employed. Further, the reactive urethane primer layer 40 is coated with a gravure roll. However, the present invention is not limited to this, and another coater such as a doctor knife or an offset coater may be employed.

In the second embodiment, as the base material 50,
Although polyester is used, the invention is not limited to this, and a blend of polyester and rayon, a staple, a polypropylene, a blend of a polyester and a staple, a polypropylene foam nonwoven fabric, a polyurethane foam nonwoven fabric, or the like may be employed. 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.

[0029]

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 were thoroughly mixed with a 3-inch two-roll roll set at a roll temperature of 160 ° C., and a 1.0 mm thick TPO
A sheet (TPO layer 10) was obtained.

The above TPO (E) was added to the obtained TPO sheet.
2640) A primer obtained by mixing 5 parts by weight, 2.5 parts by weight of a condensed azo pigment as an organic pigment (Chromophtal Yellow 3G, manufactured by Ciba Specialty Chemicals KK) and 100 parts by weight of xylene, and sufficiently dispersing the pigment. Is applied with a bar coater, dried at 110 ° C., and has a thickness of about 5
A μm primer layer 30 was formed. Subsequently, the surface of the primer layer 30 was subjected to a corona discharge treatment. The surface wetting index after corona discharge treatment was 510 μN / cm (51 dy).
n / cm converted to SI units). The wetting index is a value measured by a method based on JIS K-6768.

After the corona discharge treatment, polycarbonate-based 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. The reactive urethane primer solution mixed with the above was applied to the above-mentioned primer layer 30 with a gravure roll, and dried at 100 ° C. for 30 seconds to form a urethane primer layer 20B having a thickness of about 5 μm. Furthermore, a polyurethane elastomer which is a thermoplastic polyurethane (Rezamine ME44,
A solution composed of 100 parts by weight of Dainichi Seika Co., Ltd., 30 parts by weight of DMF, and 30 parts by weight of MEK is applied onto the urethane primer layer 20B with a gravure roll.
The resin was dried at 00 ° C. for 30 seconds to form a thermoplastic polyurethane layer 20A having a thickness of 15 μm. Thus, a resin laminate 1 was obtained.

Example 2 A TPO sheet (TPO layer 10) obtained in the same manner as in Example 1
0) A primer obtained by mixing 5 parts by weight, 2.5 parts by weight of diketopyrrolopyrrole (Chromophthal Red BP, manufactured by Ciba Specialty Chemicals Co., Ltd.) as an organic pigment, and 100 parts by weight of xylene was applied by a bar coater. , 11
After drying at 0 ° C., a primer layer 30 having a thickness of about 5 μm was formed. Subsequently, the surface of the primer layer 30 was subjected to a corona discharge treatment. The wetting index after corona discharge treatment was 490.
μN / cm (a value obtained by converting 49 dyn / cm into SI units).

After the corona discharge treatment, the same reactive urethane primer solution as in Example 1 was applied to the above-mentioned primer layer 30 by using a gravure roll, dried at 100 ° C. for 30 seconds, and a urethane primer layer having a thickness of about 5 μm was obtained. 20B was formed. Further, 100 parts by weight of a polyurethane elastomer (Resamine ME44, manufactured by Dainichi Seika Co., Ltd.) and DMF
A solution consisting of 30 parts by weight of MEK and 30 parts by weight of MEK is applied onto the primer layer 30 with a gravure roll.
The resin was dried at 00 ° C. for 30 seconds to form a thermoplastic polyurethane layer 20A having a thickness of 15 μm. Thus, a resin laminate 1 was obtained.

Comparative Example A resin laminate was obtained in the same manner as in Example 1 except that no organic pigment was used.

The resin laminate obtained in each of the above Examples and Comparative Examples was subjected to a peel test and a surface strength (wear resistance).
And the results are summarized in Table 1. The peel test was conducted at room temperature at a tensile speed of 200 mm / min.
This was performed by peeling off the O layer and the polyurethane layer. The surface strength test is performed by a friction tester specified in 3.2 of JIS L-0823 (a friction tester for a color fastness test).
Using a type II, JIS L-3102 cotton canvas No. 6 was attached to the friction element, and the force was measured by repeatedly applying a force of 9.8 N (a value obtained by converting an actually measured value of 1 kgf into SI units) 10,000 times.

[0036]

[Table 1]

Here, the criteria used to determine the grade are as follows. 5th grade: no change 4th grade: slight change 3rd grade: change is clearly seen 2nd grade: slight change 1st grade: change

As shown in Table 1, the resin laminates obtained in Examples 1 and 2 each have a primer layer containing an organic pigment, so that the adhesive strength between the TPO layer and the polyurethane layer is deteriorated by material destruction. And the surface strength was high, and no change was observed in the abrasion resistance test (grade 5). On the other hand, in the comparative example, since no organic pigment was added to the primer layer, the adhesive strength was low, and as a result, the surface strength was significantly reduced (grade 1).

[0039]

According to the present invention, TP is contained in the primer layer.
Since it contains O, the compatibility between the primer layer and the TPO layer is improved, and the adhesive strength can be strengthened. Further, since the primer layer contains an organic pigment, the adhesive strength with the polyurethane layer laminated on the primer layer can be improved, and the adhesive strength of the resin laminate can be improved. That is, the amino group of the organic pigment,
It is considered that a reactive group such as a hydroxyl group improves adhesion (compatibility) with the polyurethane layer.

Further, when a reactive urethane primer is used as a constituent component of the polyurethane layer, the primer layer and the reactive urethane primer are firmly adhered to each other, and the reactive urethane primer and the thermoplastic polyurethane are firmly adhered to each other. Therefore, the adhesive strength can be further improved. In addition, 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 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 tone sheet 10 Polyolefin thermoplastic elastomer layer 20 Polyurethane layer 20A Thermoplastic polyurethane layer 20B Reactive urethane primer layer 30 Primer layer 50 Base material

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06N 3/08 D06N 3/08 3/14 3/14 F term (Reference) 4F055 AA18 AA23 AA24 AA25 BA13 EA04 EA07 EA22 EA24 FA05 FA15 GA02 4F100 AH00B AK03A AK03B AK45 AK51C AK51D AL09A AL09B AT00E BA03 BA04 BA05 BA07 BA10A BA10C BA10D BA13 CA13B EH46 EJ55 EJ65B EJ65C GB08 GB33 GB81 JB16BJBJ JB16B12 JB16B01B12

Claims (5)

[Claims] 1. A resin laminate comprising a polyolefin-based thermoplastic elastomer layer, a primer layer laminated on the polyolefin-based thermoplastic elastomer layer, and a polyurethane layer laminated on the primer layer, A resin laminate, wherein the primer layer is formed from an organic pigment and a polyolefin-based thermoplastic elastomer. 2. The resin laminate according to claim 1, wherein the content of the organic pigment in the primer layer is 0.5
A resin laminate characterized in that the amount is from 50 to 50% by weight. 3. The resin laminate according to claim 1, wherein the polyurethane layer comprises a reactive urethane primer layer and a thermoplastic polyurethane layer. 4. A leather sheet comprising the resin laminate according to claim 1 and a substrate. 5. An interior material for an automobile, wherein the leather-like sheet according to claim 4 is used.