JP2001347617A - Laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet having excellent formability, excellent flexibility and fitness to a floor surface of an automobile and formable to a floor mat for the automobile. SOLUTION: In the laminated sheet comprising a polyolefin resin crosslinked foamed sheet and a polyolefin resin sheet laminated on and integrated with one surface of the foamed sheet, the resin sheet has a weight-average molecular weight of 80,000 to 600,000, a resin elution amount measured according to a cross fractionating method at 0 deg.C of 40 to 70 wt.% of the total polyolefin resin amount and of 10 to 30 wt.% of the total polyolefin resin amount at >0 to <=70 deg. C, and contains the polyolefin resin of 20 to 40 wt.% at a temperature exceeding 70 deg.C of 50 to 90 wt.%, a vinyl aromatic elastomer of 5 to 40 wt.% and an inorganic filler of 5 to 40 wt.%. Accordingly, the laminated sheet has excellent tear strength, excellent formability, and excellent flexibility and excellent fitness to a floor surface of the automobile in the case of molding to the floor mat for the automobile.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sheet which can be formed into an automobile floor mat which is excellent in secondary workability, excellent in flexibility and excellent in fitting to a floor of an automobile.

[0002]

2. Description of the Related Art Polyvinyl chloride resin mats have been conventionally provided as floor mats for automobiles.
The polyvinyl chloride resin mat has a problem that dioxin is generated during incineration.

Therefore, instead of the above-mentioned polyvinyl chloride resin mat, a laminated sheet in which a polyolefin-based elastomer sheet is laminated and integrated on one surface of a polyolefin-based resin foam has been proposed. Lack of fit to the mat, it cannot be a substitute for the polyvinyl chloride resin mat described above, and an automotive floor mat formed from a polyolefin resin having excellent flexibility and fit to the floor of an automobile has been developed. Was desired.

[0004]

SUMMARY OF THE INVENTION The present invention provides a laminated sheet which can be formed into an automobile floor mat which is excellent in secondary formability, excellent in flexibility and excellent in fitting to an automobile floor.

[0005]

Means for Solving the Problems The laminated sheet of the present invention comprises:
A polyolefin-based resin sheet is a laminated sheet obtained by laminating and integrating a polyolefin-based resin sheet on one surface of a cross-linked foamed polyolefin-based resin sheet. The polyolefin-based resin sheet has a weight-average molecular weight of 80,000 to 600,000 and is subjected to a cross separation method. The measured resin elution amount is 40 to 70% by weight of the total polyolefin resin amount at a temperature of 0 ° C or less, and 10 to 30% by weight of the total polyolefin resin amount at a temperature exceeding 0 ° C and 70 ° C or less. From 50 to 90% by weight of a polyolefin resin which is 20 to 40% by weight of the total amount of the polyolefin resin at a temperature exceeding 70 ° C., 5 to 40% by weight of a vinyl aromatic elastomer and 5 to 40% by weight of an inorganic filler. It is characterized by becoming.

The polyolefin resin is not particularly limited as long as the weight average molecular weight and the resin elution amount by the cross fractionation method are within the above ranges, and examples thereof include those produced by the following method. Can be.

That is, in the presence of a titanium compound and an aluminum compound, propylene is first polymerized to form a titanium-containing polypropylene resin, and then, in the second and subsequent polymerizations, the titanium compound and the aluminum compound are mixed. Propylene-α-olefin copolymer obtained by copolymerizing titanium-containing polypropylene-based resin produced in the first stage with propylene and α-olefin in the presence of a long-lived catalyst and multi-stage gas phase reaction A polypropylene-based resin such as a gas-phase copolymerized ethylene-propylene copolymer that directly polymerizes an olefin-based polymer alloy from the gas phase using a vessel, from the viewpoint that the obtained laminated sheet is excellent in flexibility, Gas-phase copolymerization that polymerizes olefin-based polymer alloys directly from the gas phase using a long-life catalyst and a multi-stage gas-phase reactor. Tylene-propylene copolymers are preferred. The propylene-α-olefin copolymer is commercially available from Montelues Decay Sunrise under the trade name “Cataroy” and from Tokuyama under the trade name “PER”. The polymer is commercially available from Montelues Decay Sunrise under the trade name "Cataroy KS Series".

If the weight-average molecular weight of the polyolefin resin is large, the flexibility of the obtained laminated sheet is reduced, and if it is small, the mechanical strength of the obtained laminated sheet is reduced. It is limited to 600,000, preferably 170,000 to 440,000.

When the polyolefin resin is measured by the cross-fractionation method at a temperature of 0 ° C. or less, the resin elution amount is large, and the heat resistance of the obtained laminated sheet is reduced. 40 to 70% by weight of the total polyolefin-based resin
And 45 to 60% by weight of the total polyolefin resin is preferable.

Further, when the above polyolefin resin is measured by the cross fractionation method, it exceeds 0 ° C. and 70 ° C.
When the resin elution amount below is large, the flexibility of the obtained laminated sheet is reduced, and when it is small, the mechanical strength of the obtained laminated sheet is reduced. And preferably 15 to 25% by weight of the total polyolefin resin.

In addition, when the polyolefin resin is measured by the cross fractionation method at a temperature exceeding 70 ° C., the resin elution amount is large, and the flexibility of the obtained laminated sheet is reduced. Since the strength of the obtained laminated sheet is reduced, the total polyolefin-based resin may have a strength of 20 to 40.
% By weight, 25 to 4% of the total polyolefin resin
0% by weight is preferred.

In the present invention, the cross fractionation method is performed in the following manner. That is, the polyolefin-based resin is first dissolved in o-dichlorobenzene at 140 ° C. or a temperature at which the polyolefin-based resin is completely dissolved, and the solution in which the polyolefin-based resin is dissolved is cooled at a constant rate to prepare a previously prepared polyolefin-based resin. A thin polymer layer is formed on the surface of the active carrier in order of crystallinity and molecular weight. Next, the temperature is raised continuously or stepwise, and the concentration of the sequentially eluted components is detected to measure the composition distribution (crystallinity distribution). This is eluted by temperature separation (T
REF = Temperature Rising El
Ution Fractionation).

Along with the temperature-rise elution fractionation, the weight-average molecular weight of the sequentially eluted components is measured by high-temperature GPC. In the present invention, the temperature rising elution fractionation part and the high temperature GPC (SEC = Size Exclusion C)
(CFC-T150A) from Mitsubishi Yuka Company, which has a
A cross-separation chromatograph device sold under "type" was used.

The weight average molecular weight of the polyolefin resin of the present invention is a value measured by the above-mentioned cross fractionation method.

When the content of the polyolefin resin in the polyolefin resin sheet is large,
The content of the vinyl aromatic elastomer described below decreases, and the flexibility of the obtained laminated sheet decreases, or the content of the inorganic filler described below decreases, and the heat resistance of the obtained laminated sheet decreases. On the other hand, if the amount is too small, the mechanical strength such as the tear strength of the obtained laminated sheet is reduced. Therefore, the amount is limited to 50 to 90% by weight, and preferably 60 to 85% by weight.

The above-mentioned polyolefin resin has the following properties so long as the physical properties of the obtained laminated sheet are not impaired.
Polyolefin resins other than the above polyolefin resins such as low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, polypropylene and polybutene are added. Is also good. As the α-olefin, propylene, 1-butene, 1-hexene, 4-
Methyl-1-pentene and the like.

As the vinyl aromatic elastomer, for example, A- (BA) m (m is a natural number) or (AB) n obtained by copolymerizing a vinyl aromatic compound A and a conjugated diene compound B is used. (N is a natural number), such as a block copolymer or a random copolymer or a hydrogenated product thereof, and ABA (m = 1) or a hydrogenated product thereof, AB
(N = 1) -type block copolymers, hydrogenated products thereof, and hydrogenated styrene-butadiene random copolymers are preferred.

The vinyl aromatic compound A includes, for example, styrene, α-methylstyrene, t-butylstyrene, p-methylstyrene, divinylstyrene,
1,1-diphenylstyrene and the like, styrene,
α-Methylstyrene is preferred. Further, as the conjugated diene compound B, 1,3-butadiene, isoprene,
Examples thereof include 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 2-methyl-1,3-pentadiene, and 1,3-butadiene and isoprene are preferred.

The AB type block copolymer of the vinyl aromatic compound A and the conjugated diene compound B may be a styrene-butadiene block copolymer or a hydrogenated product thereof.
A styrene-isoprene block copolymer or a hydrogenated product thereof is preferred, and a hydrogenated styrene-butadiene block copolymer and a hydrogenated styrene-isoprene block copolymer are more preferred. A hydrogenated styrene-isoprene block copolymer obtained by such 3,4 addition polymerization is more preferred.

[0020]

Embedded image

Further, as the ABA type block copolymer of the vinyl aromatic compound A and the conjugated diene compound B, a styrene-butadiene-styrene block copolymer or a hydrogenated product thereof, styrene-isoprene- Styrene block copolymers or hydrogenated products thereof are preferred, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers are more preferred, and the isoprene monomer is The hydrogenated styrene-isoprene-styrene block copolymer obtained by the 3,4 addition polymerization as shown is more preferred.

[0022]

Embedded image

If the content of the vinyl aromatic elastomer in the polyolefin resin sheet is large, the heat resistance and mechanical strength of the laminated sheet decrease, and if the content is small, the flexibility of the resulting laminated sheet and the automobile The fitting to the floor of an automobile when formed into a floor mat for use is reduced, so that it is limited to 5 to 40% by weight.

The inorganic filler is not particularly limited as long as it can be dispersed in the polyolefin resin or the aromatic elastomer, and examples thereof include calcium carbonate and talc.

When the particle size of the inorganic filler is large,
Since it cannot be uniformly dispersed in the polyolefin-based resin or the aromatic-based elastomer, and the uniformity of the quality of the obtained laminated sheet may be impaired,
m or less is preferable.

When the content of the inorganic filler in the polyolefin resin sheet is large, the flexibility of the obtained laminated sheet is reduced, and when the content is small, the heat resistance of the obtained laminated sheet is reduced. So, 5-40% by weight
Is limited to

If the thickness of the polyolefin resin sheet is large, the fit and flexibility of the polyolefin resin sheet to the floor of an automobile may be reduced when molded into a floor mat for an automobile. Since the mechanical strength such as the tear strength of the sheet may decrease, the thickness is preferably 0.1 to 1 mm.

Further, the polyolefin resin constituting the crosslinked foamed polyolefin resin sheet is not particularly limited as long as it has been conventionally used for a foam. For example, low density polyethylene, medium density polyethylene, Polyethylene resins such as linear low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, and ethylene-α-olefin copolymer; homopolypropylene;
Examples include polypropylene-based resins such as propylene-α-olefin copolymers, and preferred are polyethylene-based resins and polyolefin-based resins having a specific weight-average molecular weight and a specific resin elution amount in a cross fractionation method as described below. Chain low-density polyethylene and low-density polyethylene are more preferred.

The α-olefin of the ethylene-α-olefin copolymer in the polyethylene resin is propylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1-pentene. , 1
-Heptene and the like, and the propylene-α-olefin copolymer α-
As the olefin, ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1-
Pentene, 1-heptene and the like.

The polyolefin resin having a specific weight-average molecular weight and a specific resin elution amount in the above-mentioned cross-fractionation method, specifically, has a weight-average molecular weight of 80,000 to 600,000 and a cross-fractionation method. The measured resin elution amount is 40 to 70% by weight of the total polyolefin resin amount at a temperature of 0 ° C or less, and 10 to 30% by weight of the total polyolefin resin amount at a temperature exceeding 0 ° C and 70 ° C or less. And a polyolefin resin at a temperature exceeding 70 ° C. and 20 to 40% by weight of the total amount of the polyolefin resin.

As the polyolefin resin, for example, in the presence of a titanium compound and an aluminum compound,
First, propylene is polymerized to produce a titanium-containing polypropylene-based resin, and then, in the second and subsequent stages of polymerization, in the presence of the titanium compound and the aluminum compound, the titanium-containing polypropylene-based resin produced in the first stage Propylene-α-olefin copolymer obtained by copolymerizing resin, propylene and α-olefin; polymerizing olefin-based polymer alloy directly from gas phase using long-life catalyst and multi-stage gas phase reactor Gas phase copolymerized ethylene
A propylene-based resin such as a propylene copolymer is mentioned, and from the viewpoint that the obtained laminated sheet has excellent flexibility, an olefin-based polymer is directly obtained from the gas phase using a long-life catalyst and a multi-stage gas phase reactor. A gas phase copolymerized ethylene-propylene copolymer which polymerizes an alloy is preferred. The propylene-α-olefin copolymer is commercially available from Montelues Decay Sunrise under the trade name “Cataroy” and from Tokuyama under the trade name “PER”.
The above-mentioned gas-phase copolymerized ethylene-propylene copolymer is commercially available from Montelues Decay Sunrise under the trade name “Cataroy KS Series”.

When the weight average molecular weight of the polyolefin resin is large, the flexibility of the obtained laminated sheet is reduced, and when the weight average molecular weight is small, the mechanical strength of the obtained laminated sheet is reduced. 600,000 is preferable, and 170,000 to 440,000 is more preferable.

Further, when the polyolefin resin is measured by the cross fractionation method at a temperature of 0 ° C. or lower, the resin elution amount at a temperature of 0 ° C. or less is high, and the heat resistance of the obtained laminated sheet is low. 40 to 70% by weight of the total polyolefin-based resin
And more preferably 45 to 60% by weight of the total polyolefin resin.

Further, when the above polyolefin resin is measured by the cross fractionation method, it exceeds 0 ° C. and 70 ° C.
In the following, the resin elution amount is large, the flexibility of the obtained laminated sheet is reduced, and if the amount is small, the strength of the obtained laminated sheet is reduced.
30% by weight is preferable, and 15% by weight of the total polyolefin resin.
-25% by weight is more preferred.

In addition, when the above polyolefin-based resin is measured by a cross fractionation method, the resin elution amount at a temperature exceeding 70 ° C. is large, and the flexibility of the obtained laminated sheet is reduced. Since the strength of the obtained laminated sheet is reduced, the total polyolefin-based resin may have a strength of 20 to 40.
% By weight, preferably 25 to 4% of the total polyolefin resin.
0% by weight is more preferred.

The crosslinked foamed polyolefin resin sheet is provided with 2,6-di-olefin within a range that does not impair the physical properties.
Phenols such as t-butyl-p-cresol, phosphorus-based, amine-based, antioxidants such as sulfur-based such as dilaurylthiodipropionate, metal harm inhibitor such as methylbenzotriazole, phosphorus-based, nitrogen-based, Additives such as halogen-based and antimony-based flame retardants, fillers, antistatic agents, stabilizers, and pigments may be added, and these may be used alone or in combination.

Next, a method for producing the above-mentioned polyolefin resin crosslinked foamed sheet will be described. The method for producing the crosslinked polyolefin-based resin foam sheet is a conventional production method, for example, a pyrolytic foaming agent and a crosslinking aid and, if necessary, the polyolefin-based resin component are added to the polyolefin-based resin component. After the foamable resin composition comprising the additive is supplied to an extruder and melt-kneaded at a temperature lower than the thermal decomposition temperature of the pyrolytic foaming agent to extrude a foamable molded article having a desired shape such as a sheet shape, Irradiating the obtained expandable molded article with ionizing radiation to crosslink the expandable molded article, and then heating the expandable molded article to a temperature equal to or higher than the decomposition temperature of the pyrolytic foaming agent. A method for producing a crosslinked resin foam sheet is given.

The pyrolytic foaming agent is not particularly limited as long as it has been conventionally used for producing a foam. For example, azodicarbonamide, azobisisobutyronitrile, N, N ' -Dinitrosopentamethylenetetramine, P, P'-dinitrosopentamethylenetetramine, P, P'-oxybisbenzenesulfonylhydrazide, barium azodicarboxylate, trihydrazinotriazine, toluenesulfonylhydrazide, benzenesulfonylhydrazide, 4,4 -Oxybis (benzenesulfonyl hydrazide) and other thermal decomposition type foaming agents, and azodicarbonamide is used because it is easy to adjust the decomposition rate and decomposition temperature, generates a large amount of gas, and is excellent in hygiene. Is preferred.

When the amount of the pyrolytic foaming agent is large,
In some cases, the foamed molded article breaks and a crosslinked polyolefin-based resin sheet having uniform quality cannot be obtained. When the amount is small, the foamed molded article may not foam. System resin component 10
1 to 50 parts by weight relative to 0 parts by weight, preferably 5 to 20 parts by weight.
Parts by weight are more preferred.

The crosslinking assistant is not particularly limited as long as it has been conventionally used for producing a foam.
For example, divinylbenzene, trimethylolpropane trimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate,
Examples include triallylic acid triallyl ester, triallyl isocyanurate, ethylvinylbenzene, and the like. These may be used alone or in combination.

If the amount of the crosslinking aid is too large, the crosslink density of the expandable molded article may be too high and the moldability of the crosslinked polyolefin resin foam sheet obtained may be reduced. Since the cross-linking density of the expandable molded article may be lowered and a cross-linked polyolefin-based resin sheet having uniform quality may not be obtained, 0.5 to 10 parts by weight based on 100 parts by weight of the polyolefin-based resin component is used. And more preferably 0.8 to 6 parts by weight.

The ionizing radiation is not particularly limited as long as it has been conventionally used for crosslinking an expandable molded article, and examples thereof include α-rays, β-rays, γ-rays, and electron beams. When the irradiation dose is small, the crosslink density of the expandable molded article may be insufficient and a crosslinked polyolefin resin sheet having uniform quality may not be obtained. Since the flexibility of the polyolefin-based resin crosslinked foamed sheet obtained by becoming too high may decrease, 1 to 20 Mrad is preferable.

Further, if the foaming ratio of the crosslinked foamed polyolefin resin foam sheet is low, the flexibility of the laminated sheet to be obtained may be reduced, so that it is preferably 25 times or more.
The expansion ratio of the crosslinked polyolefin resin foam sheet is the reciprocal of the apparent density (g / cm ³ ) measured using “Electron Densitometer ED120T” manufactured by Mirage.

The laminated sheet of the present invention is obtained by laminating and integrating the polyolefin resin sheet on one surface of the crosslinked foamed polyolefin resin sheet. As a method of laminating and integrating the sheets, a general-purpose method is used, and is not particularly limited.
A method of laminating and integrating the above-mentioned polyolefin-based resin sheet on one side of the cross-linked polyolefin-based resin foam sheet by heat lamination or via an adhesive, and laminating the polyolefin-based resin sheet on one side of the cross-linked polyolefin-based resin sheet by melt extrusion. Method and the like. At this time, if the thickness of the laminated sheet is large, when the laminated sheet is formed into an automobile floor mat, the fit or lightness of the obtained automobile floor mat to the floor of the automobile may be reduced. 3-6mm
It is preferable to adjust so that

[0045]

The laminated sheet of the present invention is characterized in that the polyolefin resin sheet has a specific weight-average molecular weight and a specific resin elution amount in a cross-separation method, and a heat-resistant polyolefin resin having excellent flexibility. The aromatic elastomer is added at a specific ratio, and an inorganic filler for improving heat resistance, tear strength and heat shrinkage (dimensional stability) is also added at a specific ratio, so that the tear strength and The molded article obtained by molding the laminated sheet has excellent flexibility, heat resistance and heat shrinkage while having excellent secondary workability.

[0046]

(Example 1) The weight-average molecular weight was 440,000, and the resin elution amount at a temperature of 0 ° C. or less when measured by the cross fractionation method was 55% by weight of the entire polypropylene resin. The resin elution amount at a temperature exceeding 0 ° C. and 70 ° C. or less is 18% by weight of the total polypropylene resin amount, and the resin elution amount at a temperature exceeding 70 ° C. is 27% by weight of the total polypropylene resin amount. 67 parts by weight of a polypropylene-based resin (trade name “Cataroy KS353P” manufactured by Montelus d'Sunrise Co., Ltd.), 10 parts by weight of a hydrogenated styrene-isoprene-styrene block copolymer (trade name “Hibler 7125” manufactured by Kuraray Co., Ltd.), carbonic acid Calcium masterbatch (polyethylene base, manufactured by Calp Industries, calcium carbonate content = 80% by weight) 20
A resin composition composed of 3 parts by weight and 3 parts by weight of a color master batch (polyethylene base, gray) is supplied to a single screw extruder, melted and kneaded at a resin temperature of 230 ° C., and the thickness is 0.55 mm using a T-die mold. Extruded into a polypropylene resin sheet at the same time as this polyethylene resin sheet was separately prepared in a molten state, and a polyethylene resin crosslinked foam sheet (trade name: SOFTRON IF35 manufactured by Sekisui Chemical Co., Ltd.)
05, foaming ratio = 35 times, thickness = 3.5 mm) to obtain a laminated sheet having a thickness of 3.6 mm.

Example 2 The weight-average molecular weight was 440,000, and the resin elution amount at a temperature of 0 ° C. or less when measured by the cross fractionation method was 55% by weight of the total polypropylene resin. Polypropylene in which the resin elution amount at a temperature exceeding 70 ° C. and 70 ° C. or less is 18% by weight of the total polypropylene resin amount, and the resin elution amount at a temperature exceeding 70 ° C. is 27% by weight of the total polypropylene resin amount. 100 parts by weight of a resin (trade name “CATAROY KS353P”, manufactured by Montelues Decay Sunrise Co., Ltd.), 2.0 parts by weight of 1,9-nonanediol dimethacrylate, 1.0 part by weight of trimethylolpropane trimethacrylate, 15 parts by weight of azodicarbonamide Part, 2,6-di-t-butyl-p
0.3 parts by weight of cresol, 0.3 parts by weight of dilaurylthiodipropionate and 0.1 part by weight of methylbenzotriazole.
Five parts by weight were supplied to a twin-screw extruder, melt-kneaded at 180 ° C., and a 0.8 mm-thick sheet-like foamed molded product was extruded from a T-die.

Then, 750 is applied to both sides of the foamed molded article.
The foamable molded article was crosslinked by irradiating it with an electron beam of 2 Mrad at a kv intensity. Next, the foamed molded body was heated at 260 ° C.
And heated and foamed in a vertical oven furnace held by the above to obtain a cross-linked foamed polypropylene resin sheet. In addition, the expansion ratio of the obtained crosslinked foamed polypropylene resin sheet was 35 times, and the thickness was 3.5 mm.

On the other hand, the weight average molecular weight is 440,000, and the resin elution amount at a temperature of 0 ° C. or less when measured by the cross fractionation method is 55% by weight of the total polypropylene resin, and exceeds 0 ° C. And the resin elution amount at a temperature of 70 ° C. or less is 18% by weight of the total amount of the polypropylene resin,
Polypropylene resin having a resin elution amount of 27% by weight of the total amount of the polypropylene resin at a temperature exceeding ℃ (Cataroy K manufactured by Montelues Decay Sunrise Co., Ltd.)
S353P ") 67 parts by weight, hydrogenated styrene-isoprene-styrene block copolymer (trade name" Hibler 7125 "manufactured by Kuraray Co., Ltd.) 10 parts by weight, calcium carbonate masterbatch (polyethylene base manufactured by Calp Industries, containing calcium carbonate) (Amount = 80% by weight) A resin composition composed of 20 parts by weight and 3 parts by weight of a color master batch (polyethylene base, gray) is supplied to a single screw extruder and melt-kneaded at a resin temperature of 230 ° C. to form a T-die mold. This was extruded into a 0.55 mm-thick polypropylene resin sheet, and at the same time, this polypropylene resin sheet was laminated on one side of a cross-linked foamed polypropylene resin sheet to obtain a laminated sheet having a thickness of 3.6 mm.

Comparative Example 1 The weight-average molecular weight was 440,000, and the resin elution amount at a temperature of 0 ° C. or less when measured by the cross fractionation method was 55% by weight of the total polypropylene resin. Polypropylene in which the resin elution amount at a temperature exceeding 70 ° C. and 70 ° C. or less is 18% by weight of the total polypropylene resin amount, and the resin elution amount at a temperature exceeding 70 ° C. is 27% by weight of the total polypropylene resin amount. Except that a polypropylene-based resin sheet was prepared using a resin composition consisting of 97 parts by weight of a base resin (trade name “CATAROY KS353P” manufactured by Montelus Decay Sunrise Co., Ltd.) and 3 parts by weight of a color masterbatch (polyethylene base, gray). A laminated sheet was obtained in the same manner as in Example 1.

Comparative Example 2 The weight-average molecular weight was 440,000, and the resin elution amount at a temperature of 0 ° C. or less when measured by the cross fractionation method was 55% by weight of the total polypropylene resin. Polypropylene in which the resin elution amount at a temperature exceeding 70 ° C. and 70 ° C. or less is 18% by weight of the total polypropylene resin amount, and the resin elution amount at a temperature exceeding 70 ° C. is 27% by weight of the total polypropylene resin amount. 87 parts by weight of a base resin (trade name “CATAROY KS353P” manufactured by Montelues Decay Sunrise Co., Ltd.), 10 parts by weight of a hydrogenated styrene-isoprene-styrene block copolymer (trade name “Hibler 7125” manufactured by Kuraray Co., Ltd.) and a color master Batch (polyethylene base, gray) 3
A laminated sheet was obtained in the same manner as in Example 1, except that a polypropylene-based resin sheet was prepared using a resin composition composed of parts by weight.

(Comparative Example 3) The weight average molecular weight was 440,000, and the resin elution amount at a temperature of 0 ° C. or less when measured by the cross fractionation method was 55% by weight of the total polypropylene resin. Polypropylene in which the resin elution amount at a temperature exceeding 70 ° C. and 70 ° C. or less is 18% by weight of the total polypropylene resin amount, and the resin elution amount at a temperature exceeding 70 ° C. is 27% by weight of the total polypropylene resin amount. 67 parts by weight of a system resin (trade name “CATAROY KS353P” manufactured by Montelues Decay Sunrise Co., Ltd.), calcium carbonate masterbatch (polyethylene base manufactured by Calp Industries, Ltd.)
20 parts by weight of calcium carbonate content = 80% by weight) and color masterbatch (polyethylene base, gray) 3
A laminated sheet was obtained in the same manner as in Example 1, except that a polypropylene-based resin sheet was prepared using a resin composition composed of parts by weight.

The tear strength, sagging amount and heat shrinkage of the obtained laminated sheet were measured by the following methods, and the results are shown in Table 1.

(Tear Strength) The tear strength of the laminated sheet was measured by JI.
It was measured using a B-type dumbbell according to SK6301.

(Amount of sag) 30 m vertically from the laminated sheet
A test piece of a horizontal oblong rectangular shape of mx 200 mm in width was cut out, and this test piece was placed on a desk between one end edge of the test piece and a portion 50 mm from one side edge to the other side and was placed on the desk. A 50 g weight was placed on the positioned test piece portion, and the other side portion of the test piece other than the portion was disposed so as to protrude from the desk and hang downward. After one hour from this state, the difference in height between the upper surface of the desk and the other end of the test piece was measured, and the difference in height was defined as the amount of sag. The larger the amount of sag, the more excellent the laminated sheet is in flexibility and fit to the floor of an automobile when molded into an automobile floor mat.

(Heating shrinkage) 100 m vertically from the laminated sheet
Cut out a square square test piece of mx 100 mm wide,
This test piece was left in an oven at 100 ° C. for 10 hours,
Furthermore, the longitudinal dimension L after being left at 25 ° C. for 2 hours was measured,
The heat shrinkage was calculated by the following equation.

[Heating shrinkage (%)] = 100 × (100
-L) / 100

[0058]

[Table 1]

[0059]

Since the laminated sheet of the present invention has the above-described structure, it has excellent tear strength, excellent secondary workability, flexibility, and flexibility when molded into an automobile floor mat. Also has excellent fit to the floor.

Moreover, since the laminated sheet is formed from a polyolefin resin, even when incinerated, no toxic gas such as dioxin is generated, and the laminated sheet is excellent in environmental aspects.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/00 C08L 23/00 // B60N 3/04 B60N 3/04 C (C08L 23/00 (C08L 23 / 00 53:02) 53:02) F-term (reference) 3B088 HA02 4F071 AA12X AA15X AA20X AA22X AA75 AA81 AB21 AE17 AF05 AH11 BB06 BC01 4F074 AA17 AA24 AB01 BA13 BB02 CA22 CC04X CC04Y CC05Z CC06A CE02 CE02 A AK03B AK04A AK07 AK11B AK28B AK73B AL02B AL09B BA02 BA16 CA23B DJ01A EH23 EJ02 EJ05A GB33 JA07A JA07B JB07A JB07B JK03 JK13 JK17 JL01 YY00A YY00B 4J002 BB141 BB151 046012

Claims (5)

[Claims] 1. A laminated sheet in which a polyolefin-based resin sheet is laminated and integrated on one surface of a cross-linked foamed polyolefin-based resin sheet, wherein the polyolefin-based resin sheet has a weight average molecular weight of 80,000 to 600,000. The resin eluted amount measured by the cross fractionation method is 40 to 70% by weight of the total amount of the polyolefin resin at a temperature of 0 ° C. or less.
And a polyolefin resin having a temperature of more than 0 ° C. and 70 ° C. or less, which accounts for 10 to 30% by weight of the total polyolefin resin, and a temperature exceeding 70 ° C., 20 to 40% by weight of the total polyolefin resin. 50 to 90% by weight, 5 to 40% by weight of vinyl aromatic elastomer and inorganic filler 5
To 40% by weight. 2. The method according to claim 1, wherein the vinyl aromatic elastomer is a hydrogenated styrene-butadiene-styrene block copolymer or a hydrogenated styrene-isoprene-styrene block copolymer. The laminated sheet according to the above. 3. The hydrogenated styrene-isoprene-styrene block copolymer is obtained by subjecting an isoprene monomer to 3,4 addition polymerization as shown in Chemical formula 1. The laminated sheet according to the above. Embedded image 4. The laminated sheet according to claim 1, wherein the polyolefin resin crosslinked foam sheet is a polyethylene resin crosslinked foam sheet. 5. The polyolefin resin constituting the crosslinked polyolefin resin foamed sheet has a weight average molecular weight of 8
The resin elution amount measured by the cross fractionation method is 40 to 70% by weight of the total amount of the polyolefin resin at a temperature of 0 ° C. or less, and exceeds 0 ° C. and 70 ° C.
The amount of the polyolefin resin is 10 to 30% by weight of the total amount of the polyolefin resin at the following temperature, and 20 to 40% by weight of the total amount of the polyolefin resin at a temperature exceeding 70C. The laminated sheet according to any one of the above.