JPS62246938A - Skin material - Google Patents

Abstract

PURPOSE:To obtain skin material excellent in flexibility, lightness, scratch resistance and heat resistance, by embossing a surface of a sheet mainly consisting of a random copolymer of a specified 4-methyl-1-pentene with an alpha-olelfin. CONSTITUTION:4-methyl-1-pentene (A) is copolymerized with a 3-7C alpha-olefin (B) (e.g., 1-hexene) at 20-200 deg.C in the presence of a catalyst (C) comprising a highly active titanium catalyst component containing Mg, Ti, a halogen and a diester, an organoaluminum compound and an organosilicon compound having a bond of the formula to obtain a random copolymer melting point having a component A content of 40-80mol%, a melting point of 140-220 deg.C, a softening point of 90-190 deg.C, a crystallinity by X-ray analysis of 15-35% and an intrinsic viscosity (in decalin at 135 deg.C) of 0.5-6dl/g. 100pts.wt. this copolymer is mixed with, if necessary, at most 100pts.wt. poly (4-methyl-1-pentene) and further mixed with, optionally, a blowing agent (aid), a flame retardant, a dye, etc., and the obtained mixture is molded into a sheet. On surface of this sheet is embossed.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to automobiles, aircraft, furniture, etc., or footwear,
This invention relates to skin materials suitable for clothing, bags, etc.

[Conventional technology]

Conventionally, soft vinyl chloride resin (hereinafter abbreviated as soft PVC) has been mainly used as this type of skin material. This is thought to be because soft ZPVC is flexible and elastic, and has excellent surface appearance, feel, and abrasion resistance. However, since soft ZPVC contains a large amount of plasticizer to impart flexibility, there are various problems such as migration of the plasticizer and scattering during molding. In addition, since hydrogen chloride is generated during disposal, it is desirable to convert them into polyolefins, such as low-density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, etc., or EP to them.
A replacement with synthetic rubber such as R is being considered. However, the above-mentioned polyolefin is soft PvC.
compared to P
When made to be equivalent to vC, the surface abrasion resistance, scratch resistance, heat resistance, and strength were significantly inferior, and the surface felt sticky and sticky, making it unsuitable as a skin material. Furthermore, skin materials are often used with grain patterns on the surface, but these polyolefin materials have poor embossing aptitude, and can be used to prevent grain flow and loss of luster, resulting in molded products with beautiful surface patterns. That was difficult.

[Problem that the invention seeks to solve]

The object of the present invention is to provide a skin material that is flexible and lightweight, which could not be achieved with conventional polyolefin materials, and has good heat resistance with extremely little dimensional change even at high temperatures.

[Means for solving problems]

That is, the present invention has a 4-methyl-1-pentene content of 40 to 80 mol%, a melting point of 140 to 220°C,
4-methyl-1-pentene with a softening point of 90 to 190°C and a crystallinity of 15 to 35% by X-rays and carbon atoms of 3 to 7 (excluding 4-methyl-1-pentene). Random copolymer with α-olefin (
The object of the present invention is to provide a skin material which is made by embossing one side of a sheet containing A) as a main component and is highly flexible, lightweight, and has good scratch resistance and heat resistance.

[For production]

4-methyl-1-pentene/α-olefin random copolymer (A) (hereinafter referred to as random copolymer) used in the present invention
A)) means that the 4-methyl-1-pentene content is 40 to 80 mol%, preferably 50
from 75 mol%, melting point from 140 to 220°C, preferably from 160 to 210"c, softening point from 90 to 1
4-methyl-1-pentene having a crystallinity of 15 to 35%, preferably 20 to 30% at 90°C, preferably 110 to 180°C and X-rays and having 3 to 7 carbon atoms (but 4- (excluding methyl-1-pentene) with α-olefin and usually has an intrinsic viscosity [η] of decalin solvent at 135°C of 0.5 to 6 dl/g, preferably 1 to 5 dl/g! /g range.

Copolymers with a 4-methyl-1-pentene content of less than 40 mol% have low heat resistance and mechanical strength, while copolymers with a 4-methyl-1-pentene content of more than 80 mol% have poor flexibility.

The 4-methyl-1-pentene content in the present invention is “C
- Values measured by NMR method.

A copolymer with a melting point of less than 140°C has low heat resistance and mechanical strength. On the other hand, if the temperature exceeds 220°C, the flexibility is poor. The melting point in the present invention is measured using a differential scanning calorimeter (D SC).
A 10 mmg sample was taken from a 0.1 mm thick press sheet 20 hours after molding, and heated at 10°C/mi.
A heating curve was measured from 0 to 250°C at a heating rate of n, and the maximum endothermic peak was taken as the melting point (Tm).

Copolymers with a softening point of less than 90°C have low heat resistance.

The softening point in the present invention is defined as thermal mechanical a,
A 1 cm square sample was taken from a 1 fl thick press sheet 20 hours after molding using a analyzer (TMA), and a needle with a diameter of 0.025 inch was placed on one side of the sample, weighing 49 g.
Heating at a heating rate of 10°C/n+in with a load of
The temperature when the needle penetrated to a depth of 0.1 mm was read and determined as the softening point.

A copolymer with an X-ray crystallinity of less than 15% has low rigidity and mechanical strength (on the other hand, a copolymer with an X-ray crystallinity of more than 35% has poor flexibility.The crystallinity in the present invention is measured after 20 hours after molding. Thickness of 1, 2X4CI from Omvs press sheet
! 1. Collect the sample, measure the X-ray diffraction curve by X-ray diffraction method, separate it into crystalline part and amorphous bone using reflection angle 2θ: 4 to 30 degrees as the baseline, and measure the area of the crystalline part. was determined as weight %.

For both press sheets, a predetermined amount of the random copolymer (A) was put into molds with thicknesses of 0.1 and 1.0 mm, respectively.
The mold was preheated for 5 minutes using a hydraulic press molding machine heated to 40°C, pressurized for 5 minutes, and then immediately transferred to a cooling press molding machine cooled with water at 20°C and cooled for 5 minutes.

Specifically, the α-olefin having 3 to 7 carbon atoms to be copolymerized with 4-methyl-1-pentene in the random copolymer (A) used in the present invention is propylene, 1-
Examples include butene, 1-pentene, 1-hexene, 1-heptene, etc. Among these α-olefins, 1-butene and 1-hexene are preferred, particularly 1-
Hexene is preferred because it has an excellent balance between flexibility and rigidity. Copolymers with ethylene reduce scratch resistance, while copolymers with a prime number of 8 or more, such as 1-decene or 1-hexadecene, have poor heat resistance and also have low mechanical strength ( , none of them can achieve the purpose of the present invention.

In addition to the above-mentioned properties, the random copolymer (A) used in the present invention has an acetone/n-decane mixed solvent (
The amount of soluble matter in a volume ratio of 1/1) is 4×Cη]-0·l1% by weight or less, and furthermore, 0.2X (η)-0·8 to 3.8
X (η) - 0.8% by weight ([η] is the numerical value of the intrinsic viscosity of the random copolymer (B), excluding the unit) is deposited on the surface during molding. This is preferable because it does not cause stickiness due to bleed-out of low-molecular polymer components.In the present invention, the amount of the copolymer soluble in the mixed solvent is measured and determined by the following method. In a .50 mj2 flask, 1 g of copolymer sample, 0.05 g of 2,6-di-tert-butyl-
Add 4-methylphenol and 50 m# of n-decane,
Dissolve on oil solution at 120°C. After dissolution, the solution is allowed to cool naturally at room temperature for 30 minutes, then 50 m/acetone is added over 30 seconds, and the solution is allowed to cool on a 10° C. water bath for 60 minutes. A solution containing the precipitated copolymer and low molecular weight polymer component was filtered and separated using a glass filter, and the solution was heated at 150° at 101 μHg.
The sample copolymer was dried at C until it reached a constant weight, the weight was measured, and the amount of the copolymer soluble in the mixed solvent was calculated and determined as a percentage of the weight of the sample copolymer. In the above measurement method, stirring was performed continuously from the time of dissolution to immediately before filtration.

The 4-methyl-1-pentene/α-olefin random copolymer (A) having the above-mentioned properties can be made of, for example, (a) a magnesium compound, a titanium compound, a diester, and optionally a halogen compound (magnesium compound). (b) Organoaluminum compound catalyst component, and fc
) an organosilicon compound catalyst component having St-0-C bonds, in the presence of a catalyst formed from about 20 to about 200
4-methyl-1-pentene and 1-butene, 1 at a temperature of °C.
- Obtained by copolymerizing with an α-olefin having 3 to 7 carbon atoms such as hexene.

Copolymerization conditions for producing the random copolymer (A) suitable for use in the present invention as described above are detailed in Japanese Patent Application No. 60-216258 filed by the present applicant.

The skin material of the present invention has the random copolymer (A) as a main component, but in order to adjust the scratch resistance, heat resistance, flexibility, etc., the random copolymer (A)
Up to 100 parts by weight, preferably 70 parts by weight of poly-4-methyl-1-pentene (B) may be added to 100 parts by weight. Poly4-methyl-1-pentene (B)
If the amount exceeds 100 parts by weight, the flexibility decreases, making it unsuitable for use as a skin material.

Such poly-4-methyl-1-pentene (B) is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene.
1-Pentene and other α-olefins, such as ethylene,
Propylene, l-butene, 1-hexene, 1-decene,
4-Methyl-1- is a copolymer with an α-olefin having 2 to 20 carbon atoms such as 1-tetradecene and 1-octadecene, and usually contains 85 mol% or more of 4-methyl-1-pentene.
It is a polymer mainly composed of pentene. Poly 4-methyl-
The melt flow rate (MFR1 load: 5 kg, temperature: 260°C) of 1-pentene (B) is preferably in the range of 0.5 to 200 g/10n+in.

Those with an MFR of less than 0.5 g/10ml have high melt viscosity and poor moldability, and those with an MFR of less than 200 g/1
If it exceeds 0 m1n, the melt viscosity is low and the moldability is poor, and the mechanical strength is also low.

In the present invention, the random copolymer (A) is further added with an antioxidant, an ultraviolet absorber, a foaming agent, a foaming aid, an antistatic agent, a lubricant, an antiblocking agent, a slip agent, and a flame retardant, if necessary. , dyes, pigments, fillers, etc. can be blended to the extent used in ordinary polyolefins. In particular, in the present invention, a mixture obtained by kneading the above-mentioned polymer with a blowing agent and foaming it to a volume of about 2 to 5 times becomes a skin material that is rich in elasticity, has good embossing properties, and has a good texture. Also,
When a filler is added to the random copolymer (A), calendering properties are improved. However, if a large amount of filler is added, the strength and abrasion resistance of the coating will decrease, so the amount is limited to 100 parts by weight or less based on 100 parts by weight of the total resin amount. The skin material of the present invention is made by embossing one side of a sheet containing the above-mentioned random copolymer (A) as a main component. The skin material of the present invention may be made of, for example, paper, woven fabric, stockinette, non-woven fabric, knitted fabric, foamed polyurethane, high Foamed poly 4-methyl-
The backing can be made of 1-pentene, highly expanded polyethylene, highly expanded polypropylene, or the like. These backing materials include
In order to improve adhesion to the skin material, a subbing agent may be applied in advance. Various known adhesives such as urethane adhesives, epoxy adhesives, acrylic adhesives, and chloroprene adhesives can be used as such subbing agents, but unsaturated carboxylic acids such as maleic anhydride or their anhydrides, etc. Modified poly(4-methyl-) graft-modified with a derivative of
1-pentene or propylene content of 55 to 85 mol%, heat of crystal fusion as determined by differential scanning calorimeter thermal analysis of 2
A propylene/1-butene random copolymer having an amount of 0 to 75 Joule/g is preferred because it has the best adhesion to the random copolymer (A).

Various methods can be employed to manufacture the skin material of the present invention. First, the raw materials containing the random copolymer (8) as the main component are mixed, then melted and kneaded using an ordinary extruder for polyolefin resin molding or a kneader such as a mixing roll, and then melted and kneaded using a calender roll or ordinary sheet molding equipment for polyolefin resin. A method of forming a sheet can be adopted.

Another method is to coat the backing material with a melt of the random copolymer (A). As the device, an extrusion laminating device, a calender roll, etc. are used. In addition, the preferable resin temperature of the copolymer during sheet molding is 190 to 270°C in the case of an extruder, and 160 to 240°C in the case of a calender roll. In the present invention, the surface of the sheet obtained by the above method is embossed in order to further improve the feel, aesthetic appearance, and three-dimensional appearance. The embossing process may be performed using an embossing roll that is continuous with the sheet forming process, or may be performed using an embossing machine after the sheet is formed and wound up. When embossing is done on another line, it is necessary to reheat the sheet, but in any case, during embossing,
The resin temperature of the sheet is preferably higher than the softening temperature of the random copolymer (A), usually in the range of 130 to 210°C.

〔Effect of the invention〕

The skin material of the present invention has a specific 4-methyl-1-pentene.
Since it has α-olefin copolymer (A) as its main component, it is flexible and lightweight, and since no plasticizer is used, it does not cause blocking due to plasticizer bleed, clouding of the surface, or staining.

It also has better scratch resistance than conventional soft polyolefins.
It has excellent heat resistance and there is no risk of the surface becoming sticky. The skin material of the present invention makes use of these characteristics to improve the appearance of automobiles, railway vehicles,
It is suitable as an interior material for aircraft, ships, etc., as well as a surface material for furniture, footwear, clothing, bags, building materials, etc.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way unless the gist of the invention is exceeded.

Example 1 [Production of 4-methyl-1-pentene/1-hexene random copolymer] Preparation of titanium catalyst component (a)> Anhydrous magnesium chloride 4.76 g (50 mmol
), 25 ml of decane, 23.4 ml (150 mmol) of 2-ethylhexyl alcohol, 1
After heating the reaction at 30°C for 2 hours to obtain a homogeneous solution, 1.11 g (7.5 mmol) of phthalic anhydride was added to the solution.
is added and stirred for an additional hour at 130°C to dissolve phthalic anhydride into the homogeneous solution. After cooling the homogeneous solution obtained in this way to room temperature, 200 ml (1,8 mmo+) of titanium tetrachloride kept at -20°C was added.
The entire meter was added dropwise over a period of 1 hour. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and then heated to 110°C.
When the temperature reached 0°C, diisobutyl phthalate B, 68
ml (12.5 mmol) was added and the mixture was kept at the same temperature for 2 hours with stirring. After 2 hours of reaction, the solid portion was collected by hot filtration, and this solid portion was poured into 200 ml of TiCj!
After resuspending at step 4, a heating reaction is further carried out at 110° C. for 2 hours. After the reaction is completed, the solid portion is again collected by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound is detected in the washing liquid. The titanium catalyst component (a) prepared by the above production method was stored as a hexane slurry, and a portion of it was dried for the purpose of investigating the catalyst composition. The composition of the titanium catalyst component (a) thus obtained was 3.1% by weight of titanium and 56% by weight of chlorine.
．． 0% by weight, 17.0% by weight of magnesium and 20.9% by weight of diisobutyl phthalate.

1-hexene at 20 f, 4-methyl-1-pentene at 60 β (hereinafter abbreviated as 4MP), 80 mmol of triethylaluminum, 80 mmol of trimethylmethoxysilane,
1.2 mmol of titanium catalyst component (a) in terms of titanium atoms was continuously charged. The hydrogen partial pressure in the gas phase is 1
．． The polymerization temperature was maintained at 5 kg/crA and 70°C.

The polymerization solution was continuously drawn out so that the liquid volume in the reaction vessel was 100%, the polymerization was stopped with a small amount of methanol, and the unreacted hexamer was removed to obtain 7.5 kg of copolymer per hour. Ta. The 4-methyl-1-pentene/1-hexene random copolymer (hereinafter abbreviated as PMH-1) thus obtained had a 4MP content of 55 mol%, a melting point of 168°C,
Softening point is 140°C, crystallinity is 24%, and intrinsic viscosity [η
] was 2.2 dl/g, and the acetone/n-decane soluble content was 1.7% by weight.

[Preparation of sheet]

PMH-1 (however, as a stabilizer, tetrakis[methylene-3 (3,5-jet
ert-butyl-4-hydroxyphenyl)propionate comethane; 0.15 parts by weight, dilauryl-thio-dipropionate 70.25 parts by weight, zinc stearate;
0.03 parts by weight) was melted in a 40 mmφ extruder (molding temperature 240°C), then fed to a T-die (molding temperature 240°C), and the molten sheet was transferred to three upright rolls (roll temperature 60°C).
℃) to continuously obtain a sheet having a thickness of 0.5 mIm and a width of 30 cm at a processing speed of 2.4 m/min.

The surface of the sheet thus obtained was then reheated to 140°C to 150°C with an infrared heater and embossed using an embossing machine with a single-sided embossing roll.

The following items were evaluated for the obtained sheet.

Sheet formability: There are no wrinkles or creases on the sheet surface before embossing.
All ripples (○ those that do not occur, × those that occur significantly)
, and the middle was set as △.

Heat resistance temperature: After stacking the sheets together and applying a load of 100 g/ad and leaving them at a predetermined temperature, the maximum temperature at which the sheets could be easily peeled off was shown. A temperature of 70°C or higher is practically required.

Embossability: Almost no grain flow or curling (,
Those with a high-class appearance were rated as ``Ol'', those with some wrinkles and lost luster, and those with no luxurious feel were rated as △, and those with severe wrinkles and luster, and the appearance was extremely poor, were rated as ×.

Texture: Flexible and soft items are rated ○, hard items are rated ×.

Those with a dry touch were rated as ○, and those with a sticky feel were rated as ×.

The results are shown in Table 1.

Example 2 PMH-I used in Example 1 70% by weight, 4-methyl-1-pentene [1-hexadecene/1-octadecene (weight ratio 1/1) content 6 mol%, MFR: 2
6 g / 10 m 1 n, hereinafter abbreviated as PMP-1] 30 wt. 1%) were mixed in a Henschel mixer,
The mixture was melt-kneaded using an extruder (molding temperature: 260°C) to obtain a composition (2). Next, using this composition I, a T-die sheet (molding temperature 260°C) was obtained in the same manner as in Example 1.
Embossing was carried out at a temperature of 0 to 170°C. The evaluation results are shown in Table 1.

Example 3.4 A 4MP content of 70 was obtained by polymerizing by changing the charging amount of 1-hexene and 4MP instead of PMH-I used in Example 1, and changing the hydrogen partial pressure appropriately. mole%,
4-Methyl-1-pentene 1 with melting point 195°C, softening point 165°C, crystallinity 26%, intrinsic viscosity [η) 2.5 dl/g, and acetone/n-decane soluble content 2.0% by weight.
The same procedure as in Example 1 was carried out except that -hexene random copolymer (hereinafter abbreviated as PMH-II) was used. Results first
Shown in the table.

Comparative Example 1 The same procedure as in Example 1 was conducted except that PMP-1 was used instead of PMH-1 and the molding temperature was 260°C.

Comparative Example 2.3.4 In Example 1, low-density polyethylene (manufactured by DuPont Mitsui Polychemicals, Mirason 41, M F
R (ASTM D 1238.E) 0.9g/
10m1n.

density 0.918 g/c+J) (abbreviated as LDPE), ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemicals, Evaflex P-2505) (E
V A) and ethylene propylene copolymer rubber (abbreviated as V A) and ethylene propylene copolymer rubber (
Ethylene content 80 mol%, Mooney viscosity 76 M L
+-4 (100°C)) (abbreviated as EPR) and the amounts shown in Table 2, the molding temperature was 130 to 170°C, and the embossing temperature was 9°C.
The same procedure as in Example 1 was conducted except that the temperature was 0 to 130°C. The results are shown in Table 1.

Claims (1)

[Claims] (1) 4-methyl-1-pentene content is 40 to 8
0 mol%, melting point 140 to 220°C, softening point 90
Crystallinity at 190°C to 190°C and X-rays is 15 to 3
4-methyl-1-pentene in the range of 5% and 3 carbon atoms
α of 7 to 7 (excluding 4-methyl-1-pentene)
- A skin material formed by embossing one side of a sheet mainly composed of a random copolymer (A) with olefin.