JP2002317082A - Polyolefin resin composition for surface skin material, surface skin material and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin resin composition for a surface skin material composed of an olefin resin and having excellent surface strength and whitening resistance in folding, and provide a surface skin material composed of the composition. SOLUTION: The surface skin material is composed of a polyolefin resin composition for surface skin material containing (A) 40-95 wt.% polypropylene resin containing (A1) a propylene homopolymer resin having a melt flow rate(MFR) of 0.1-30 g/10 min measured in conformity to ASTM D 1238 at 230 deg.C under a load of 2.16 kg and (A2) a propylene/α-olefin random copolymer having a melting point of 120-155 deg.C measured by a differential scanning calorimeter and an MFR of 0.1-30 g/10 min measured in conformity to ASTM D 1238 at 230 deg.C under a load of 2.16 kg at an (A1)/(A2) blending ratio of 10/90 to 90/10 and (B) 5-60 wt.% poly-1-butene having an MFR of 0.1-25 g/10 min measured in conformity to ASTM D 1238 at 190 deg.C under a load of 2.16 kg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition for a skin material comprising a polyolefin resin, a skin material comprising the resin composition, and a laminate obtained by laminating the skin materials.

[0002]

2. Description of the Related Art Conventionally, a skin material is laminated on a base material made of metal plate, wood, plywood, resin, foam, leather, cloth, or the like to protect the surface of a molded product, or to impart durability or design. Has been done. Conventionally, polyvinyl chloride is mainly used as a raw material of such a skin material.
However, the skin material made of polyvinyl chloride has the following problems. 1) Poor heat and cold resistance. 2) The temperature dependence of rigidity is large. 3) Transfer of the plasticizer compounded occurs, and cracks and poor appearance are likely to occur on the surface. 4) The compounded plasticizer is vaporized, and the glass or the like is easily clouded. 5) Noxious gas is generated during combustion.

[0003] On the other hand, polyolefin resins have the following characteristics as compared with polyvinyl chloride. Therefore, replacement with polyolefin resins as raw materials for skin materials is desired. 1) Excellent heat resistance and cold resistance. 2) The temperature dependence of rigidity is small. 3) Since the compounding of the plasticizer is unnecessary, cracks and poor appearance are unlikely to occur on the surface. 4) Since no plasticizer is required, fogging does not occur on glass or the like. 5) No harmful gas is generated during combustion.

However, when a polyolefin resin is used as a skin material, it is necessary to use a flexible material. At this time, however, there is a problem that the surface strength is reduced and the scratch resistance is remarkably deteriorated.

Japanese Patent Application Laid-Open No. Hei 7-179624 describes a skin sheet comprising crystalline poly-1-butene and an ethylene / α-olefin copolymer. However, the resin composition disclosed in the above publication has a relatively small amount of crystal components, so that the surface strength is weak, and as a result, a sheet having poor scratch resistance is obtained.

JP-A-2000-143902 describes a skin material comprising a polypropylene resin, an ethylene / α-olefin copolymer, and a 1-butene / α-olefin copolymer. The skin material of the above publication is excellent in surface strength and flexibility, but uses a polypropylene resin and an ethylene-based copolymer that are incompatible with each other. Cracks tend to occur at the interface with the system copolymer phase, and as a result, whitening tends to occur.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin resin composition for a skin material, comprising a olefin resin, capable of obtaining a skin material having excellent surface strength and bending whitening resistance. An object of the present invention is to provide a skin material comprising a composition and a laminate in which the skin material is laminated.

[0008]

The present invention provides the following polyolefin resin composition for skin material, skin material and laminate. (1) (A) ASTM D 1238, 230 ° C,
2. The melt flow rate measured at a load of 16 kg is 0.
1 to 30 g / 10 min homopolypropylene resin (A
1) and the melting point measured by a differential scanning calorimeter is 120 to 1
55 ° C, ASTM D1238, 230 ° C, 2.16k
Melt flow rate measured under a load of 0.1 g to 30 g
/ 10 min of a propylene / α-olefin random copolymer (A2), and the blend ratio thereof is from 10/90 by weight ratio of homopolypropylene resin (A1) / propylene / α-olefin random copolymer (A2). 90 /
40-95% by weight of a polypropylene resin which is 10 and (B) ASTM D 1238, 190 ° C, 2.16
The melt flow rate measured under a kg load is 0.1 to 25
A polyolefin-based resin composition for a skin material, comprising 5 to 60% by weight of poly-1-butene of g / 10 min. (2) When the homopolypropylene resin (A1) is ¹³ C-N
Isotactic pentad fraction (m
The polyolefin resin composition for a skin material according to the above (1), which is a highly crystalline polypropylene resin having an mmm fraction of 0.960 to 0.995. (3) The polyolefin resin composition for a skin material according to (1) or (2), wherein the propylene content of the propylene / α-olefin random copolymer (A2) is 90 to 99.5 mol%. (4) The poly 1-butene (B) is a homopolymer of 1-butene or a copolymer of 1-butene and an α-olefin having 2 to 10 carbon atoms (excluding 1-butene), (1) to (3) above, wherein the content of butene is 60 to 100 mol% and the content of α-olefin is 0 to 40 mol%.
The polyolefin resin composition for a skin material according to any one of the above. (5) A skin material comprising the polyolefin resin composition for skin material according to any one of (1) to (4). (6) The skin material according to (5), wherein the thickness is 50 to 500 µm. (7) Metal plate, wood, plywood, resin, foam, leather,
The skin material according to the above (5) or (6), which is a skin material for a cloth or a composite thereof. (8) A laminate in which the skin material according to any of (5) to (7) is laminated on a metal plate, wood, plywood, resin, foam, leather, cloth, or a composite thereof.

Homopolypropylene resin (A1) As the homopolypropylene resin (A1) used in the present invention, ASTM D 1238, 230 ° C., 2.16 kg
Melt flow rate (MFR) measured by load is 0.1
３０30 g / 10 min, preferably 0.5-20 g / 1
0 min propylene homopolymer can be used without limitation. Since the MFR is in the range of 0.1 to 30 g / 10 min, a sheet can be easily formed with high productivity by a molding method such as cast molding, sheet molding, or extrusion lamination.

As the homopolypropylene resin (A1),
A crystalline polypropylene resin having an isotactic pentad fraction (mmmm fraction) of 0.900 or more, preferably 0.940 to 0.995, as measured by ¹³ C-NMR,
More preferably, a highly crystalline polypropylene resin of 0.960 to 0.995 is desirable. By increasing the stereoregularity of the homopolypropylene resin (A1) used, the crystallinity of the polypropylene resin (A) is improved, and as a result, a skin material having excellent scratch resistance is obtained.

The homopolypropylene resin (A1) has a flexural modulus of 1 as measured by ASTM D790.
000-3000 MPa, preferably 1500-250
A high crystalline polypropylene resin having 0 MPa is desirable.
When the homopolypropylene resin (A1) having a flexural modulus of 1000 to 3000 MPa is used, a skin material excellent in scratch resistance can be obtained.

The isotactic pentad fraction (m
(mmm fraction) is an isotactic chain in a pentad unit in a polypropylene resin molecular chain measured using ¹³ C-NMR, and is 5 units in a propylene monomer unit.
It is the fraction of propylene monomer units at the center of a chain of meso-bonds that are consecutively formed. Actually, it can be determined as a fraction occupied by the mmmm peak in all the absorption peaks in the methyl carbon region measured in the ¹³ C-NMR spectrum.

Propylene / α-olefin random copolymer (A2) As the propylene / α-olefin random copolymer (A2) used in the present invention, propylene and C 2-10
Is a random copolymer with an α-olefin (excluding propylene) having a melting point (hereinafter, referred to as DSC melting point) of 120 to 1 measured by a differential scanning calorimeter (DSC).
55 ° C, preferably 120-145 ° C, ASTM D
1238, 230 ° C., melt flow rate (MFR) measured under a load of 2.16 kg is 0.1 to 30 g / 10 mi
n, preferably 0.5 to 20 g / 10 min can be used without limitation.

Since the DSC melting point is in the range of 120 to 155 ° C., the compatibility between the homopolypropylene resin (A1) and the poly-1-butene (B) is improved, and a skin material excellent in bending whitening resistance is obtained. Can be. MFR is 0.1 to 30
Since it is within the range of g / 10 min, the sheet can be easily formed with high productivity by a molding method such as cast molding, sheet molding, or extrusion lamination.

In the propylene / α-olefin random copolymer (A2), ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1 -Pentene, 1-hexene, 1-octene, 1-decene and the like. Among them, ethylene, 1-butene and the like are preferable. The α-olefin can be used alone or in combination of two or more. Propylene / α-olefin random copolymer (A
2) as a propylene / ethylene random copolymer,
Preferred are propylene / 1-butene random copolymer, propylene / ethylene / 1-butene random copolymer and the like.

The propylene / α-olefin random copolymer (A2) desirably has a propylene content of 90 to 99.5 mol%, preferably 92 to 99 mol%. When the propylene content is in the range of 90 to 99.5 mol%, the compatibility between the homopolypropylene resin (A1) and the poly-1-butene (B) is further improved, and a skin material having more excellent bending whitening resistance is obtained. Can be.

The method for producing the homopolypropylene resin (A1) and the propylene / α-olefin random copolymer (A2) used in the present invention is not particularly limited, and can be produced by a known method. For example, in the presence of a known catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst, a highly stereoregular olefin polymerization catalyst, propylene can be produced by polymerization in the presence of a comonomer, if necessary. . For example, the following (a)
It can be produced by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method and a slurry method in the presence of a catalyst system composed of components (c) to (c). (A) a solid titanium catalyst component containing magnesium, titanium and an electron donor (b) an organoaluminum compound (c) an electron donor

The solid titanium catalyst component (a) contains a tetravalent titanium compound such as titanium tetrahalide or halogenated alkoxy titanium, alcohol, phenol, ketone, aldehyde, ester, ether, amine or nitrile acid. It can be prepared by contacting an electron donor selected from oxygen, a nitrogen-containing compound, and a halogen-containing magnesium compound.

The organoaluminum compound (b) is
It can be used by appropriately selecting from trialkylaluminum, alkylaluminum halide, alkylalkoxyaluminum, alkoxyaluminum halide and the like. As the electron donor (c), an alkoxysilane compound, a polyether compound, or the like can be used.

When the propylene / α-olefin random copolymer (A2) is produced, a process is adopted in which the branched olefin polymer is first prepolymerized prior to the main polymerization of propylene, and then the process is shifted to the main polymerization of propylene. You may. The polymerization may be performed by any method such as gas phase polymerization, solution polymerization, and slurry polymerization. The polymerization of propylene may be carried out in one step or in multiple steps, whereby a copolymer having a changed molecular weight distribution or monomer composition can be obtained.

Polypropylene resin (A) The polypropylene resin (A) used in the present invention contains the homopolypropylene resin (A1) and the polypropylene resin random copolymer (A2), and the blend ratio thereof is homopolypropylene resin (A1) / propylene. · 10/90 by weight ratio of α-olefin random copolymer (A2)
90/10, preferably 20/80 to 80/20 polypropylene resin.

In the present invention, the homopolypropylene resin (A) having the above-mentioned specific properties is used as the polypropylene resin (A).
1) and a polypropylene resin random copolymer (A
Since 2) is used in the above blend ratio, a skin material having excellent bending whitening resistance (the property of not causing whitening even when bent), excellent surface hardness, and excellent balance between both is obtained.

Poly 1-butene (B) The poly 1-butene (B) used in the present invention includes 1
-Butene homopolymer or 1-butene and carbon number of 2-1
A random copolymer with an α-olefin of 0 (but excluding 1-butene);
MFR measured at 90 ° C. under a load of 2.16 kg is 0.1 to
25 g / 10 min, preferably 0.5 to 10 g / 10
min poly 1-butene can be used without restriction. MFR
Is in the range of 0.1 to 25 g / 10 min, so that a sheet can be easily formed with high productivity by a molding method such as cast molding, sheet molding, or extrusion lamination.

In the poly-1-butene (B), the α-olefin copolymerized with 1-butene is ethylene, propylene, 1-pentene, 3-methyl-1-butene,
Methyl-1-pentene, 1-hexene, 1-octene,
1-decene and the like. Among them, ethylene, propylene and the like are preferable. The α-olefin can be used alone or in combination of two or more.

The 1-butene content of poly 1-butene (B) is 60 to 100 mol%, and the α-olefin content is 0 to 100 mol%.
40 mol%, preferably the 1-butene content is 70 to 10
The content of 0 mol% and the content of α-olefin is desirably 0 to 30 mol%. DSC of poly 1-butene (B)
The melting point is desirably 60 to 130 ° C, preferably 70 to 130 ° C. The crystallinity of poly 1-butene (B) determined by diffraction X-ray is 5 to 60%, preferably 20 to 60%.
Desirably, it is 50%.

When the 1-butene content, DSC melting point and crystallinity of poly 1-butene (B) are within the above ranges,
It is possible to obtain a skin material which makes the polypropylene resin (A) flexible and which is excellent in bending whitening resistance.

The poly-1-butene (B) is obtained by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method, and a slurry method in the presence of a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It can be manufactured by doing.

Polyolefin resin composition for skin material The content of each component of the resin composition of the present invention is from 40 to 95% by weight, preferably from 60 to 9% by weight of the polypropylene resin (A).
0% by weight, 5-60% by weight of poly 1-butene (B), preferably 10-40% by weight. Since the content of both components is within the above range, a skin material having an excellent balance between scratch resistance and bending whitening resistance can be obtained.

The resin composition of the present invention contains other resins, tackifiers, weather stabilizers, heat stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, as long as the object of the present invention is not impaired. Additives such as a lubricant, a pigment, a dye, a plasticizer, an antioxidant, a hydrochloric acid absorbent, and an antioxidant can be added as necessary.

The resin composition of the present invention can be produced by a known method. For example, the components (A) and (B) and, if necessary, additives to be compounded are melted using an extruder, a kneader or the like. It can be produced by a method such as kneading.

The sheet or film made of the resin composition of the present invention has excellent surface hardness while maintaining the characteristics inherent to the polyolefin resin (A), and therefore has a low surface scratch resistance and a low surface scratch resistance. Are better. Moreover, since whitening does not occur even when bent, the appearance does not deteriorate. For this reason, the resin composition of the present invention is used as a raw material for a skin material.

Skin material and laminate The skin material of the present invention comprises the above-mentioned polyolefin resin composition for skin material, and is used by being laminated on a base material. Although the shape of the skin material of the present invention is not particularly limited, it is usually a sheet or film shape, and the thickness is usually 5 μm to 1 mm, preferably 50 to 500 μm, and more preferably 100 to 200 μm.

The type and shape of the substrate on which the skin material of the present invention is laminated are not particularly limited, and examples thereof include a metal plate, wood, plywood, resin, foam, leather, cloth, and a composite thereof. Among these, a metal plate, particularly a steel plate is preferable. By laminating the skin material of the present invention on these substrates, the surface of the laminate can be protected, durability can be imparted, and design can be imparted. In this case, since the skin material of the present invention is composed of the polyolefin resin composition for the skin material, the skin material is excellent in surface hardness and bending whitening resistance, so that the surface is hardly damaged and has excellent surface scratch resistance. In addition, it has excellent appearance.

The laminate of the present invention is a laminate in which the skin material is laminated on a metal plate, wood, plywood, resin, foam, leather, cloth, or a composite thereof. The laminate is preferably a metal plate, particularly a laminate of a steel plate and a skin material.

The method of laminating the skin material of the present invention on a substrate is not particularly limited, and a known method such as an extrusion lamination method or a dry lamination method can be adopted according to the type and shape of the substrate. When the substrate is a resin or a foam, for example, the following method is exemplified. (1) A skin material and a base material which have been formed into a sheet shape in advance,
A method of thermocompression bonding or heat fusion using a means such as a calender molding machine. (2) in which either a method in which one is a substrate or skin material is sheet shaped, thermocompression bonding or heat sealing to the other layer that extrusion molding or calender molding. (3) A method in which a base material and a skin material are simultaneously extruded by a multilayer extruder and thermocompression-bonded or heat-fused (co-extrusion).

When the base material is a metal, for example, the following method is exemplified. (1) A method in which a skin material is pressure-bonded to the surface of a metal plate coated with an adhesive. (2) A method in which an adhesive resin and a skin material are co-extruded to laminate the skin material on the surface of the metal plate.

Concrete materials obtained by laminating the skin material of the present invention on a metal plate include: building materials such as interior equipment; electric equipment such as audio equipment, office equipment, kitchen products, air conditioning equipment, and other home appliances; Transportation equipment such as ships; other household goods, miscellaneous goods, furniture and the like. Further, as the concrete material of the skin material of the present invention laminated on wood, plywood or resin,
Building materials such as interior equipment; and miscellaneous goods such as bags and cases. Specific examples laminated on a foam include an automobile interior part. For automotive interior parts,
As the substrate, polyethylene foam, polypropylene foam, urethane foam and the like are usually used. Specific items laminated on cloth include household goods, miscellaneous goods and the like. As concrete thing laminated on leather,
Menstrual goods, miscellaneous goods, etc. are given.

[0038]

The polyolefin resin composition for a skin material of the present invention comprises a polypropylene resin containing a specific homopolypropylene resin and a propylene / α-olefin random copolymer in a specific ratio, and a specific poly-1-butene. Because it contains a specific amount of, it is excellent in surface strength and bending whitening resistance despite having a polyolefin resin as a main component, so that the surface is hardly damaged and has excellent surface scratch resistance In addition, a skin material excellent in appearance can be easily obtained. Since the skin material of the present invention is composed of the above-mentioned polyolefin resin composition for skin material, despite having a polyolefin resin as a main component, it is excellent in surface strength and bending whitening resistance. The surface is not easily scratched, has excellent surface scratch resistance, and has excellent appearance. Since the laminate of the present invention has the skin material laminated on the substrate, it has excellent surface strength and bending whitening resistance,
For this reason, the surface is hardly damaged and has excellent surface scratch resistance and excellent appearance.

[0039]

Next, an embodiment of the present invention will be described.

Examples 1 to 3 and Comparative Examples 1 to 3 Each component having the composition shown in Table 1 was mixed with a Henschel mixer, and then mixed with a cast molding machine at a set temperature of 230 ° C.
A 50 μm sheet was prepared.

[0041]

[Table 1]

* 1 PP-1: homopolypropylene resin (A1) MFR (230 ° C.) = 10 g / min, flexural modulus = 2
200MPa, isotactic pentad fraction (mm
mm fraction) = 0.980 * 2 PP-2: homopolypropylene resin (A1) MFR (230 ° C.) 2.4 g / min, flexural modulus = 1
750MPa, isotactic pentad fraction (mm
mm fraction) = 0.945 * 3 PP-3: propylene / α-olefin random copolymer (A2) propylene / ethylene / 1-butene random copolymer, MFR (230 ° C) = 7.0 g / 10
min, DSC melting point = 138 ° C., propylene content = 9
5 mol% * 4 PB-1: poly 1-butene (B) 1-butene-ethylene random copolymer, 1-butene content = 95 mol%, MFR (190 ° C) = 4.0 g / 1
0 min, density = 900 kg / m ³ , DSC melting point = 10
Crystallinity determined by diffraction X-ray at 4 ° C. = 45% * 5 EO-1: ethylene / 1-octene copolymer, ethylene content = 85 mol%, density = 870 kg / m ³ ,
MFR (190 ° C.) = 4 g / 10 min

* 6 Ultra-micro hardness: Test load: 9.8 m
N, holding time: 5 seconds, loading speed: 1.42 mN / sec, indenter: triangular pyramid indenter hardness = 3.858 × test load / (indentation depth) ² * 7 Bending whitening resistance: adhesive applied A laminate was prepared by thermocompression bonding a formed sheet to the surface of a steel sheet.
The state of the laminate when bent at 180 ° at 180 ° C. was visually evaluated. ；: No whitening observed ×: whitening observed

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Naoto Yasaka, Inventor 3rd Chikusa Beach, Ichihara-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Norihide Inoue 580-30 Nagaura, Sodegaura-shi, Chiba Within Grand Polymer (72) Inventor Takashi Kimura 580-30 Nagaura, Sodegaura-shi, Chiba Prefecture Within Grand Polymer Co., Ltd. (72) Inventor Kazuhiro Tani 148-27 Takano, Hitachinaka-shi, Ibaraki F-term (reference) 4F100 AB01B AJ10B AK01B AK07A AK09A AK66A AL03A AL05A AP02B BA02 DG12B DJ01B GB08 GB32 GB48 GB81 JA04A JA06A JA11A JK01 JK04 JK16 YY00A 4J002 BB12W BB14X BB15X BB171 GF00

Claims (8)

[Claims] (A) ASTM D 1238, 230
A homopolypropylene resin (A1) having a melt flow rate of 0.1 to 30 g / 10 min measured at 2.degree. C. under a load of 2.16 kg and a melting point of 120 measured by a differential scanning calorimeter.
１５155 ° C., ASTM D 1238, 230 ° C., 2.
Melt flow rate measured at 16 kg load is 0.1 ~
30 g / 10 min of propylene / α-olefin random copolymer (A2), and the blend ratio is 10/90 by weight ratio of homopolypropylene resin (A1) / propylene / α-olefin random copolymer (A2). ~
40-95% by weight of a polypropylene resin which is 90/10, and (B) ASTM D 1238, 190 ° C,
2. The melt flow rate measured at a load of 16 kg is 0.
A polyolefin resin composition for a skin material, comprising 5 to 60% by weight of poly 1-butene of 1 to 25 g / 10 min. 2. The method according to claim 1, wherein the homopolypropylene resin (A1) comprises ¹³
The polyolefin resin composition for a skin material according to claim 1, which is a highly crystalline polypropylene resin having an isotactic pentad fraction (mmmm fraction) of 0.960 to 0.995 measured by C-NMR. 3. The polyolefin resin composition for a skin material according to claim 1, wherein the propylene content of the propylene / α-olefin random copolymer (A2) is 90 to 99.5 mol%. 4. The poly-1-butene (B) is a homopolymer of 1-butene or a copolymer of 1-butene and an α-olefin having 2 to 10 carbon atoms (excluding 1-butene). ,
The content of 1-butene is 60 to 100 mol%, and the content of α-olefin is 0 to 40 mol%.
The polyolefin resin composition for a skin material according to any one of the above. 5. A skin material comprising the polyolefin resin composition for a skin material according to any one of claims 1 to 4. 6. The method according to claim 5, wherein the thickness is 50 to 500 μm.
The described skin material. 7. The skin material according to claim 5, which is a skin material for a metal plate, wood, plywood, resin, foam, leather, cloth, or a composite thereof. 8. A laminate in which the skin material according to claim 5 is laminated on a metal plate, wood, plywood, resin, foam, leather, cloth, or a composite thereof.