WO2020174792A1

WO2020174792A1 - Laminated foamed sheet, and molded body thereof

Info

Publication number: WO2020174792A1
Application number: PCT/JP2019/046369
Authority: WO
Inventors: 博章北出; 阿南　伸一; 卓正山岸
Original assignee: 積水化成品工業株式会社
Priority date: 2019-02-28
Filing date: 2019-11-27
Publication date: 2020-09-03
Also published as: JP7132153B2; JP2020138402A

Abstract

This laminated foamed sheet comprises a foamed layer and a first non-foamed layer located on one side of the foamed layer surface. The foamed layer has a closed-cell percentage of at least 70%, and a density of 50-1,000 kg/m³. The maximum load obtained according to JIS K7125 for the first non-foamed layer is 10-50N. The cell (A) percentage is at least 50% in a region from the interface between the foamed layer and the first non-foamed layer to, in the thickness direction of the foamed layer, a depth corresponding to 15% of the thickness of the foamed layer.

Description

\\0 2020/174792 1 卩 (: 17 2019/046369 Clarification

Title of invention: Laminated foam sheet and molded article thereof

Technical field

The present invention relates to a laminated foam sheet and a molded body thereof.

The present application claims priority on the basis of Japanese Patent Application No. 2019-9-035111, filed in Japan on February 28, 2019, the content of which is incorporated herein by reference.

Background technology

[0002] Conventionally, there is known a laminated foam sheet including a foamed layer using a thermoplastic resin as a base resin and a non-foamed layer using a thermoplastic resin as a base resin. Since the laminated foam sheet has excellent heat resistance and light weight, it is used as a raw material for food packaging containers, vehicle floor mats, and the like.

[0003] Food packaging containers, vehicle floor mats, and the like are required to have a property of not slipping when installed (grip property).

Patent Document 1 proposes a foam laminated body having a foam layer and a pressure-sensitive adhesive layer containing a synthetic rubber. Further, Patent Document 2 proposes a laminated foam sheet having a foam layer and a thermoplastic elastomer layer. According to the foam laminates of Patent Documents 1 and 2, grip performance can be realized.

Prior art documents

Patent literature

[0004] Patent Document 1: Japanese Patent Laid-Open No. 20 1 4 _ 1 8 0 8 1 8

Patent Document 2: JP 2 0 0 9 _ 1 8 4 1 8 1 Publication

Summary of the invention

Problems to be Solved by the Invention

[0005] By the way, the laminated foam sheet is required to have gripping properties, as well as the property of being easily formed into a predetermined shape by heating (thermoformability) and the property of resisting frictional force on the surface (wear resistance). To be In particular, when the thickness of the laminated foam sheet is reduced, the surface layer is easily peeled off, and the wear resistance is likely to decrease. \¥0 2020/174792 2 卩 (: 17 2019/046369

It

However, in Patent Documents 1 and 2, thermoformability and wear resistance are not examined.

[0006] The present invention has been made in view of the above circumstances. The purpose is to provide.

Means for solving the problem

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a laminated foam sheet having at least two layers.

[0008] The present invention has the following aspects.

[1] A foamed layer and a first non-foamed layer located on one surface of the foamed layer,

The foamed layer has a closed cell ratio of 70% or more and a density of

And

The first non-foamed layer has a maximum load of 10

~ 5 0 1\1,

A laminated foam sheet in which the proportion of air bubbles (eight) calculated by the following method is 50% or more.

The laminated foamed sheet was cut along the thickness direction, and a photograph of the cut surface was taken with a scanning electron microscope at a magnification of 30 times. In the obtained photograph, the foamed layer and the first non-foamed layer were taken. From the interface of the foam layer, in the thickness direction of the foam layer, measure the major axis and minor axis of the bubbles in the region up to a depth of 15% of the thickness of the foam layer, and calculate the ratio expressed by major axis/minor axis. The number of bubbles () and the number of all bubbles contained in the region are counted as the number of bubbles (/\), and the ratio of the bubbles to the total number of bubbles contained in the region is Calculate the ratio of bubbles ().

[2] The thickness of the foam layer is 0.1 to 3.

The laminated foam sheet according to [1]. 20/174792 3 卩 (: 171?2019/046369

[3] The laminated foam sheet according to [1] or [2], wherein the first non-foamed layer contains a non-crosslinked olefin elastomer.

[4] Laminate according to any one of [1] to [3], wherein the first non-foamed layer has a Duro 8 hardness of 70 or less, which is determined by 3 <6 2 5 3-3. Foam sheet.

[5] The first non-foamed layer] [3] [Elongation at break as determined by <6 2 5 1 is 900% or more, [1] to [4] Laminated foam sheet.

[6] The thickness of the first non-foamed layer is 0.05 to 〇.

Is, [1]

~ The laminated foam sheet according to any one of [5].

[7] The density is

The laminated foam sheet according to any one of [1] to [6].

[8] The laminate according to any one of [1] to [7], wherein the first non-foamed layer contains a non-crosslinked olefin-based elastomer and a resin other than the non-crosslinked olefin-based elastomer. Foam sheet.

[9] The mass ratio expressed by [content of non-crosslinking olefin-based elastomer]: [content of resin other than non-crosslinking olefin-based elastomer] is from 10:900 to 90:10. The laminated foam sheet according to [8], wherein 20:80 to 80:20 is more preferable, and 30:70 to 70:30 is further preferable.

[10] The resin other than the non-crosslinked olefin elastomer is at least one resin selected from the group consisting of polyolefin resin, polystyrene resin, and polyester resin, [8] or [ 9] The laminated foam sheet according to [9].

[11] The laminated foam sheet according to any one of [1] to [10], further including a second non-foam layer located on the other surface of the foam layer.

[12] The gel fraction of the non-crosslinked olefin elastomer is preferably 3.0% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less, and 0.3% by mass. It is particularly preferable that the content is not more than mass%, [1] to [11] 〇 2020/174792 4 卩 (：171?2019/046369

The laminated foam sheet according to any one of 1.

[1 3] Density of the foam layer is preferably 90 to 9001 ^<9/3, more preferably 1 00-5001 <9/3,

Is more preferable, The laminated foam sheet as described in any one of [1]-[12].

[14] The proportion of the bubbles (8) is preferably 50 to 75%, more preferably 60 to 70%, further preferably 65 to 70%, and any one of [1] to [13]. The laminated foam sheet according to.

[15] The ratio of air bubbles (Minami) calculated by the following method is preferably 50 to 75%, more preferably 60 to 70%, further preferably 65 to 70%, as described in [11] Laminated foam sheet.

The laminated foam sheet was cut along the thickness direction, and a photograph of the cut surface was taken with a scanning electron microscope at a magnification of 30 times. In the obtained photograph, a foam layer and a second non-foam layer were formed. From the interface of the foam layer, in the thickness direction of the foam layer, measure the major axis and minor axis of the bubbles in the region up to a depth of 15% of the thickness of the foam layer, and calculate the ratio expressed by major axis/minor axis. Then, the bubbles having the ratio of 4.0 or more are defined as bubbles (Mitsumi), and the number of bubbles (Mitsumi) and the number of all the bubbles contained in the region are counted, and the total number of bubbles contained in the region is calculated. Calculate the percentage of air bubbles.

[16] The thickness of the foamed layer is 0.1 to 3.

Is preferred.

3 to 2.

More preferably, the laminated foam sheet according to any one of [1] to [15].

[17] The thickness of the first non-foamed layer 2 is 0.05 to 0.

Is more preferable, and 0.1 to 0.4 is more preferable, and 0.15 to 0.

The laminated foam sheet according to any one of [1] to [16], which is preferable.

[18] The ratio of the thickness of the first non-foaming layer 2 to the thickness of the foaming layer 1 is represented by Ding 2 /Ding 1, preferably 0.01 to 1, and 0.05 to 0. The laminated foam sheet according to any one of [1] to [17], wherein 5 is more preferable.

[0009] [1 9] [1] to the laminated foam sheet according to any one of [1 8] 〇 2020/174792 5 卩 (：171?2019/046369

A molded body formed by.

[20] The molded product according to [19], which is a floor mat of a vehicle.

[2 1] The molded product according to [1 9], which is an undercover of a vehicle.

[22] The molded article according to [19], which is a luggage tray for a vehicle.

[2 3] A method for producing a laminated foam sheet according to any one of [1] to [18],

A first laminating step of fusing the resin constituting the first non-foamed layer at 200 to 240° on one surface of the foamed sheet constituting the foamed layer, Foam sheet manufacturing method.

Effect of the invention

[001 0] According to the present invention, it is possible to provide a laminated foam sheet having a surface that is hard to slip, and excellent in thermoformability and abrasion resistance, and a molded product thereof.

Brief description of the drawings

[001 1] [Fig. 1] Fig. 1 is a cross-sectional view showing an example of a laminated foam sheet of the present invention.

[Fig. 2] Fig. 2 is a schematic view showing an example of an apparatus for manufacturing a foamed sheet.

[FIG. 3] A cross-sectional photograph of an example of the laminated foam sheet of the present invention.

FIG. 4 is a schematic view showing an example of an apparatus for manufacturing a laminated foam sheet of the present invention.

FIG. 5 is a schematic view showing an example of a floor mat of a vehicle of the present invention.

FIG. 6 is a schematic view showing an example of an undercover of the vehicle of the present invention.

FIG. 7 is a schematic view showing an example of a luggage tray of the vehicle of the present invention.

FIG. 8 is a schematic view showing another example of the luggage tray of the vehicle of the present invention.

MODE FOR CARRYING OUT THE INVENTION

[0012] <<Laminated foam sheet>>

The laminated foam sheet of the present invention has a foam layer and a first non-foam layer located on one surface of the foam layer. The laminated foam sheet of the present invention may further have a second non-foamed layer located on the other surface of the foamed layer.

An example of the laminated foam sheet will be described with reference to FIG.

The laminated foam sheet shown in Fig. 1 is provided on one side of the foam layer 10 and the foam layer 10 The first non-foamed layer 20 and the second non-foamed layer 30 provided on the other surface of the foamed layer 10 are provided.

The laminated foam sheet 1 has a three-layer structure.

Note that FIG. 1 is illustrated in an enlarged manner in the thickness direction.

[0013] <Foam layer>

The foam layer is formed by foaming the resin composition. The resin composition contains a polyolefin resin and a foaming agent.

[0014] Examples of the polyolefin-based resin include homopolymers of olefin-based monomers such as ethylene and propylene or copolymers thereof, and olefin-based monomers as main components, and olefin-based monomers and vinyl monomers that can be polymerized therewith. And a copolymer thereof. These polyolefin resins may be used alone or in combination of two or more. Among them, polyethylene resin and polypropylene resin are preferable, and polypropylene resin is more preferable.

[0015] Examples of the polyethylene-based resin include, for example, low-density polyethylene resin (L D PE) in which ethylene is polymerized under high pressure to form long chain branches in the molecule.

A high-density polyethylene resin (HDPE) with a density of 0.942 g/cm ³ or more obtained by polymerizing ethylene using a Ziegler-Natta catalyst or a metallocene catalyst under medium and low pressure, 1-butene in the HDPE polymerization process, Linear low-density polyethylene resin (LLDPE) with a density of less than 0.942 g/cm ³ is formed by adding a small amount of olefins such as 1-hexene and 1-octene to form short-chain branches in the molecule. Can be mentioned.

[0016] As the polypropylene resin, a high melt tension polypropylene (HMS-PP) resin is preferable. High melt tension polypropylene resin is a polypropylene whose tension in the molten state is increased by mixing a high molecular weight component or a component having a branched structure into polypropylene resin or by copolymerizing polypropylene with a long chain branched component. It is a resin. High melt tension polypropylene resin is commercially available, for example, WB 1 30 HMS and WB 1 35 manufactured by Borealis. 〇 2020/174792 7 卩 (：171?2019/046369

"\^/Mimi 1 401 ^~ 11\/13";"Made in 336 1 I Company""○-dried 3 X 81 4"; Made in Japan Polypro "Mimi 33 1 2", "Min 5 100" , "Minami 7200", "Minami 9100", "1\/1 侂8", "1\/1 乂6", etc.

Whether or not the polypropylene resin is a high melt tension polypropylene resin can be judged not only by the difference in polymer structure but also by the magnitude of its melt tension (melt tension). For example, if the melt tension is 50 or more, it can be judged that it is a high melt tension polypropylene resin.

The melt tension of the high melting tension polypropylene resin is, for example, preferably 100 or more and 3001\! or less. When it is at least the above lower limit, the strength of the foamed layer will be more easily increased. When it is at most the above upper limit, thermoformability will be more easily improved. The melt tension of the resin can be measured using the measuring device “CAYPYROgraph 1\/10-〇” manufactured by Toyo Seiki Co., Ltd. as follows. First, in a state where the sample resin is heated to 230 ^° 〇 and melted, the piston drop from the cavity (caliber 2.095 ○ 101, length 801 〇 0) of the piston extrusion type plastometer of the above equipment. Keep the speed at a constant speed of 1 001111/111 and extrude into a string shape.

After passing through the tension detection pulley located at, use the take-up port to change the take-up speed from the initial speed of 5 / I

Wind it while increasing it with the acceleration of ² . Then, when the test is conducted until the string-like object is cut, the maximum tension immediately before breaking detected by the tension detection pulley is taken as the melt tension of the sample resin.

[0018] Melt mass flow rate of polyolefin resin

Is, 5.0 _9/1 0_Rei! Preferably equal to or less than丨, 〇. 1 9/1 0_Rei_1丨1 ^ 5 or more.

|1^ or less is more preferable, and 0.52 / ^ 0 ^ \ 〇 or more and 4.02 /} 0 ^ \ 〇 or less is further preferable. When IV! is at least the above lower limit, it is easy to make the independent bubble ratio of the foam layer 70% or more. When IV! is less than or equal to the above upper limit, the strength of the foam layer can be more easily increased. 〇2020/174792 8 卩(：171?2019/046369

1\/1 [¾ is a numerical value representing the fluidity of the thermoplastic resin when melted. 1\/1 [In case of ¾, the resin melted in the cylinder is extruded by the piston under constant temperature and load conditions from the die with the specified bore installed at the bottom of the cylinder per 10 minutes. It is represented by the amount of resin.

In this specification, 1\/1 [¾ is 230. 〇, 0.

Is the numerical value in.

[0019] The melting point of the polyolefin-based resin is preferably 150°° or more and 170°° or less,

More preferably, it is not less than 155 ^° ○ and not more than 165 ^° ○. When the melting point of the polyolefin-based resin is equal to or higher than the above lower limit value, the strength of the foam layer can be more easily increased. When the melting point of the polyolefin resin is not more than the above upper limit, the thermoformability is likely to be improved. The melting point of the polyolefin resin is measured by the method described in "3 <7 1 2 1 :1 9 8 7 "Measurement method of plastic transition temperature".

[0020] The content of the polyolefin-based resin is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass, based on 100% by mass of the resin constituting the foamed layer. ..

[0021] The resin composition may include other resins. Examples of other resins include polystyrene resins and polyester resins.

[0022] Examples of the polystyrene resin include, for example, homopolymers or copolymers of styrene monomers, copolymers of styrene monomers with other vinyl monomers, or these resins. A mixture etc. are mentioned. The polystyrene resin may be used alone or in combination of two or more.

The polystyrene-based resin preferably contains a structural unit based on a styrene-based monomer in an amount of 50% by mass or more, and more preferably 70% by mass or more, based on the total structural units of the polystyrene-based resin. It is more preferable that the content of 80% by mass or more is more preferable.

The mass average molecular weight of the polystyrene resin is preferably 200,000 to 400,000, more preferably 240,000 to 400,000. The mass average molecular weight is the value measured by 〇〇 (gel permeation chromatography), and is 〇 2020/174792 9 卩(：171?2019/046369

It is a value converted based on a calibration curve by Ren.

[0023] Examples of the homopolymers or copolymers of the above-mentioned styrene-based monomers include styrene, <<_methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, propylpropylstyrene, dimethylstyrene, bromostyrene, etc. Examples thereof include homopolymers or copolymers of the styrene-based monomer. Among these, those having a structural unit based on styrene of 50% by mass or more based on all structural units are preferable, and polystyrene (homopolymer) is more preferable.

High impact polystyrene containing a rubber component may be used as the polystyrene resin.

[0024] Examples of copolymers of styrene-based monomers and other vinyl-based monomers include styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid ester copolymers, styrene-chlorides. Vinyl Copolymer, Styrene-Butadiene Copolymer, Styrene-Acrylonitrile Copolymer, Styrene-Maleic Anhydride Copolymer, Styrene-Maleic Ester Copolymer, Styrene-Fumaric Acid Ester Copolymer, Styrene-Divinylbenzene Copolymer Examples thereof include polymers, styrene-alkylene glycol dimethacrylate copolymers, (meth)ester acrylate butadiene-styrene copolymers (for example, IV!3 resin). In addition, in this specification, (meth)acrylic acid means acrylic acid or methacrylic acid.

[0025] As a copolymer of a styrene-based monomer and another vinyl-based monomer, a structural unit based on a styrene-based monomer is added in an amount of 50% by mass based on all the structural units of the copolymer. The above content is preferable, the one containing 70% by mass or more is more preferable, and the one containing 80% by mass or more is further preferable.

As the copolymer of the styrene-based monomer and the other vinyl-based monomer, a styrene-(meth)acrylic acid copolymer and a styrene-butadiene copolymer are preferable. Examples of the styrene-(meth)acrylic acid copolymer include a styrene-acrylic acid copolymer and a styrene-methacrylic acid copolymer.

[0027] The content of the structural unit based on (meth) acrylic acid in the polystyrene resin is 〇 2020/174792 10 卩 (：171?2019/046369

, 0.5 to 6.8% by mass is preferable with respect to all the constitutional units constituting the polystyrene resin. It is more preferable that the content is .0 to 5.0% by mass, and! More preferably, it is 0.3 to 3.0 mass %. By setting it within the above numerical range, excellent toughness and heat resistance can be exhibited.

The content of the structural unit based on (meth)acrylic acid in the polystyrene resin can be calculated from the charged amount of styrene-(meth)acrylic acid.

[0028] The content of the butadiene-based structural unit in the polystyrene-based resin is preferably 0.5 to 6.8 mass% with respect to all the structural units constituting the polystyrene-based resin. It is more preferable that the content is .0 to 5.0% by mass, and! More preferably, it is from 0.3 to 3.0% by mass. Within the above numerical range, excellent toughness and heat resistance can be exhibited.

The content of the constitutional unit based on butadiene in the polystyrene resin can be calculated from the charged amount of styrene-diene.

[0029] In the polystyrene-based resin, the content of the styrene-(meth)acrylic acid copolymer is preferably 10% by mass or more based on the total mass of the polystyrene-based resin. When the content of the styrene-(meth)acrylic acid copolymer is at least the above lower limit value, it is easy to improve the fusion property.

The content of the styrene-(meth)acrylic acid copolymer in the polystyrene resin is not particularly limited, and may be 100% by mass with respect to the total mass of the polystyrene resin.

[0030] In the polystyrene resin, the content of the styrene-butadiene copolymer is preferably 10% by mass or more based on the total mass of the polystyrene resin. When the content of the styrene-butadiene copolymer is at least the lower limit value described above, it is easy to increase the fusion property. The content of the styrene-butadiene copolymer in the polystyrene resin is not particularly limited, and the total content of the polystyrene resin is not limited. It may be 100% by mass relative to the mass.

[0031] Examples of the polystyrene-based resin include a commercially available polystyrene-based resin, a polystyrene-based resin synthesized by a suspension polymerization method, etc., and a polystyrene that is not a recycled raw material. 〇 2020/174792 1 1 卩(：171?2019/046369

In addition to the use of resin (virgin polystyrene), it is possible to use recycled raw materials obtained by recycling used polystyrene foam, polystyrene resin foam moldings (food packaging trays, etc.). Examples of the recycled raw material include a recycled raw material obtained by collecting a used polystyrene foam and a polystyrene resin foam molded product and regenerating it by a limonene dissolution method or a heat volume reduction method.

[0032] Examples of the polyester-based resin include polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene furanoate resin, polyethylene terephthalate resin, terephthalic acid/ethylene glycol/cyclohexanedimethanol copolymer, And mixtures of these and mixtures of these with other resins. In addition, a plant-derived polyethylene terephthalate resin or a polyethylene furanoate resin may be used. The polyester resins may be used alone or in combination of two or more.

Further, a (meth)acrylic resin, an acrylonitrile-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, a polyphenylene ether resin, or the like may be contained.

[0034] The resin composition contains a foaming agent.

Examples of the foaming agent include baking soda-citric acid-based foaming agents, ammonium carbonate, sodium bicarbonate, ammonium bicarbonate, ammonium nitrite, calcium azide, sodium azide, sodium borohydride, and other inorganic decomposable foaming agents; azodicarboxylic amine. Azo compounds such as azo, azobissulfolumamide, azobisisobutyronitrile and diazoaminobenzene; 1\1, 1\1'-dinitrosopentanemethylenetetramine, 1\], 1\1'-dimethyl-1\1 ,1\1'-Dinitrosoterephthalamide and other ditroso compounds; benzenesulfonyl hydrazide, 1-toluenesulfonyl hydrazide, ,'-oxybisbenze sulfonylsemicarbazide, _toluenesulfonyl semicarbazide, trihydrazinotriazine, barium azodicarboxylate, etc. To be Gas blowing agent 〇 2020/174792 12 卩 (：171?2019/046369

Examples thereof include air, nitrogen, carbon dioxide, propane, neopentane, methyl ether, fluoromethane dichloride, 1·!-butane, and isobutane. Here, the gas means that it is a gas at room temperature (15 ^° 〇 to 25 ^° 〇). On the other hand, examples of the volatile blowing agent include ether, petroleum ether, acetone, pentane, hexane, isohexane, heptane, isoheptane, benzene, and toluene.

Of the above foaming agents,

Butane and nitrogen are particularly preferred.

[0035] The content of the foaming agent in the resin composition is appropriately determined in consideration of the type of the foaming agent, the specific gravity, etc., and, for example, 0.5 to 20 parts by mass relative to 100 parts by mass of the resin. Parts are preferred, and 0.8 to 5.5 parts by mass are more preferred.

The content of the foaming agent in the foam layer (so-called residual gas amount) is preferably 0.3 to 3.6 mass%, more preferably 0.5 to 3.3 mass%, based on the total mass of the foam layer. ..

[0036] The resin composition includes a surfactant, a cell regulator, a cross-linking agent, a filler, a flame retardant, a flame retardant aid, and a lubricant (hydrocarbon, fatty acid, fatty acid amide, ester, alcohol, Additives such as metal soap, silicone oil, waxes such as low molecular weight polyethylene), spreading agents (liquid paraffin, polyethylene glycol, polybutene, etc.), colorants, heat stabilizers, UV absorbers, antioxidants, etc. May be done.

Examples of the cell regulator include inorganic powder such as talc and silica; acidic salt of polyvalent carboxylic acid; reaction mixture of polyvalent carboxylic acid and sodium carbonate or sodium bicarbonate. Among them, the reaction mixture is preferable because the closed cell ratio is maintained and the thermoformability is easily improved.

The cell regulator may be used alone or in combination of two or more.

The addition amount of the bubble control agent is preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the resin.

[0038] The closed cell content of the foam layer is 70% or more, preferably 75% or more, and more preferably 80% or more. The upper limit is not particularly limited. For example, 99% or less is preferable. 〇 2020/174792 13 卩 (：171?2019/046369

Good When the closed cell ratio of the foam layer is within the above numerical range, the impact resistance is excellent and the thermoformability is more likely to be improved.

The closed cell rate of the foam layer is measured by the method described in "3 <71 38: 2006 "Rigid foamed plastic-determination of open cell rate and closed cell rate"".

[0039] The thickness of the foam layer 1 is preferably from 0.1 to 3.0, and from 0.3 to 2.

Is more preferable. When the thickness of the foam layer is at least the above lower limit, the shape retention is excellent. When the thickness of the foam layer is not more than the above upper limit, the thermoformability can be further improved.

In the present specification, the thickness is a value obtained by measuring the 20 points of the measurement object at equal intervals in the width direction (the horizontal direction) with a macro gauge and calculating the arithmetic mean value thereof.

[0040] The basis weight of the foam layer is 250 to 700.

Is preferred, 400-600

2 is more preferable. When the basis weight of the foam layer is within the above numerical range, it is easy to handle.

The basis weight can be measured by the following method.

Both ends of the foam layer in the width direction 2

1 0001X 1 at equal intervals in the width direction

Cut out 10 pieces of 0 ○ and measure the mass (9) of each piece up to 0.001 9 units. The value obtained by converting the average value in mass per ^second mass (9) in each section, the basis weight of the foam layer | and (9/11 ^2).

[0041] The density of the foam layer is 50 ~ 1 000 / 〇! ³ and 90 ~ 900

^3, more preferably 1 00-500 ^9/3,

9/○! ³ is even more preferable. When the density of the foam layer is within the above numerical range, the handleability is excellent.

The foamed sheet forming the foamed layer is manufactured according to a conventionally known manufacturing method.

As a method for producing a foamed sheet, a resin composition is prepared, and the resin composition is sealed. 〇2020/174792 14 卩(：171?2019/046369

A method of extruding into a square shape and foaming (primary foaming) can be mentioned (extrusion foaming method). An example of the method for manufacturing the foamed sheet will be described with reference to FIG. The foamed sheet manufacturing apparatus 200 shown in Fig. 2 is an apparatus for obtaining a foamed sheet by inflation molding, and includes an extruder 200, a foaming agent supply source 208, a circular die 210, and a mandrel. The extruder 20 2 provided with 2 20 and two winding machines 2 4 0 is a so-called tandem type extruder, and the extruder 2 0 2 ₃ and the extruder 2 0 2 It is configured to be connected in 6. First push out section 2 0 2 ₃ is provided with a hopper 2 0 4, in an extruder eight 2 0 2 _3, blowing agent supply 2 0 8 is connected.

The extruder die 210 is connected to the circle die 210, and the mandrel 220 is provided downstream of the circle die 210. The mandrel 220 is equipped with a cutter _2 22.

[0043] First, turning on the material constituting the resin composition in an extruder eight 2 0 2 ₃ from the hopper 2 0 4.

The raw materials charged from the hopper 204 are the resin that constitutes the foamed sheet, and additives that are added as necessary.

[0044] In an extruder 2 0 2 _3, raw materials are mixed while heating to any temperature a resin dissolved Torubutsu, supplies blowing agent to an extruder 2 0 2 ₃ blowing agent supply 2 0 8, A resin composition is prepared by mixing a resin melt with a foaming agent.

The heating temperature is appropriately determined in consideration of the type of resin and the like within a range in which the resin melts and the additive does not denature.

[0045] The resin composition is fed to an extruder snake 2 0 2 spoon via a pipe 2 0 6 from the extruder 2 0 2 _3, are further mixed, after being cooled to any temperature, Sakiyurada Lee 2 1 0 Supplied to. The temperature of the resin composition when it is extruded from the circular die 210 is 1400-1900 ^° , more preferably 1500-1900 ^° .

The resin composition was extruded from the circular die 210 and the foaming agent foamed. 〇 2020/174792 1 5 卩 (：171?2019/046369

To form a cylindrical foam sheet 1103. The foamed sheet 1 0 1 3 extruded from the circular die 210 is blown with cooling air 2 11 and then supplied to the mandrel 2 20. The cooling rate of the foamed sheet 1103 can be adjusted by combining the temperature, amount, and blowing position of the cooling air 211.

The cylindrical foam sheet 1013 is heated to an arbitrary temperature by the mandrel 220, sized, and cut into two by the cutter 2222 to form the foam sheet 1101. The foamed sheet 1 0 1 is wound around a guide roll 2 4 2 and a guide roll 2 4 4 respectively, and wound up by a winding machine 2 4 0 to form a foamed sheet roll 1 0 2.

The foaming factor of the foamed sheet is, for example, 2 to 20 times.

The foamed sheet may be manufactured by a method other than inflation molding.

[First non-foamed layer]

The first non-foamed layer is a layer located on one surface of the foamed layer.

In the present specification, “non-foaming” means a state in which the raw material resin is not foamed, and means a case where the foaming multiple is 1.0 times.

The first non-foamed layer preferably contains a non-crosslinked olefinic elastomer.

In the present specification, “non-crosslinked” means that the gel fraction is 3.0% by mass or less, more preferably 1.0% by mass or less. The gel fraction is the value measured as follows.

[0047] The mass 1 of the resin is measured. The resin is then heated to reflux in 80 milliliters of boiling xylene for 3 hours. Next, the residue in xylene was filtered using a 200-mesh wire net, the residue remaining on the wire net was co-washed with new xylene, then dried naturally for 1 day, then to 120 ° 〇. After drying for 2 hours with a dryer, measure the mass of residue left on the wire net \^/2. Then, calculate the gel fraction of the resin based on the following formula (1).

Gel fraction (mass %) = 100/1 (1) 〇2020/174792 16 卩(：171?2019/046369

[0048] Examples of the non-crosslinking olefin elastomer include homopolymers of propylene, propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene. A copolymer or the like selected from one or more kinds of reffins is preferable.

[0049] The content of the non-crosslinked olefin elastomer is preferably 10% by mass or more and more preferably 20% by mass or more with respect to 100% by mass of the resin constituting the first non-foamed layer. Further, the content of the non-crosslinking olefin-based elastomer is preferably 90% by mass or less, and more preferably 80% by mass or less, relative to 100% by mass of the resin constituting the first non-foamed layer. Specifically, the content of the non-crosslinking olefinic elastomer is 100% by mass with respect to 100% by mass of the resin constituting the first non-foaming layer.

10 to 90 mass% is preferable, and 20 to 80 mass% is more preferable.

The first non-foaming layer may contain, as a resin other than the non-crosslinking olefin-based elastomer, the polyolefin-based resin, the polystyrene-based resin, the polyester-based resin and the like described in the above <foaming layer>.

[0050] When the first non-foamed layer contains a non-crosslinking olefin-based elastomer and a resin other than the non-crosslinking olefin-based elastomer, [content of non-crosslinking olefin elastomer]: [non-crosslinking Content of resin other than type olefin-based elastomer] is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, 0:70 to 70:30 is more preferable. When the above mass ratio is within the above range, abrasion resistance is likely to be improved.

[0051] The maximum load required for the first non-foamed layer" 3 <7 1 25 is 10 to 50 1\1, preferably 15 to 4 5 1\1, and 20 to 40 1\1 is more preferable, and 20 to 3 5 1\1 is further preferable. When the maximum load of the first non-foamed layer is within the above range, it becomes easy to improve wear resistance.

[0052] The first coefficient of static friction determined by 3 <71 25 of the first non-foamed layer is

It is preferably 1.0 or higher, more preferably 2.0 or higher, even more preferably 2.5 or higher, and particularly preferably 3.0 or higher. The maximum static friction coefficient of the first non-foamed layer is preferably 5.0 or less, more preferably 4.5 or less. In particular, 〇 2020/174792 17 卩(: 171?2019/046369

The maximum static friction coefficient of the first non-foamed layer is preferably from 1.0 to 5.0, more preferably from 2.0 to 4.5, even more preferably from 2.5 to 4.0. When the maximum coefficient of static friction of the first non-foamed layer is within the above range, it can be made slippery.

It is preferable to use a mirror-finished aluminum material as the mating material for measuring the maximum static friction coefficient in order to clarify the slipperiness.

[0053] The basis weight 3 of the first non-foamed layer is

Is preferred, and 130 ~

Is more preferable. When the basis weight 3 of the first non-foamed layer is within the above numerical range, the handleability is excellent.

The basis weight can be measured by the following method.

Both ends in the width direction of the first non-foamed layer 2

At equal intervals in the width direction,

Cut out 10 pieces of ◯100 and measure the mass (9) of each piece up to the unit of 0.0001. The mass value obtained by conversion calculation of 1 ² per an average value of the mass (9) in each section, the basis weight of the first non-foamed layer 3 (9 / 〇! ^2).

[0054] The thickness of the first non-foamed layer 2 is appropriately determined according to the required strength and the like, and is, for example, 0. 05 to 0.

Is preferred, and 0.01 to 0.4 is more preferred, and 0.15 to 0.3

Is more preferable. If it is at least the above lower limit value, sufficient strength is likely to be obtained. If it is at most the above upper limit, the molding process will be easy.

[0055] The ratio of the thickness of the first non-foamed layer to the thickness of the foamed layer is expressed as D 2 /D 1, and is preferably 0.01-1 and more preferably 0.05-5.

[0056] The hardness of the first non-foaming layer" is 3 <6 2 5 3-3 and the Duro 8 hardness is 7

0 or less is preferable. Further, the Duro 8 hardness of the first non-foamed layer is preferably 30 or more, and more preferably 40 or more. Specifically, the Duro 8 hardness of the first non-foamed layer is preferably from 30 to 70, more preferably from 40 to 70. When the Duro 8 hardness of the first non-foamed layer is within the above range, the grip property is excellent.

[0057] The elongation percentage at break as determined by "3 [< 6 2 5 1 of the first non-foamed layer] is preferably 900% or more, and more preferably 10000 to 1500%. Elongation at break 〇 2020/174792 18 卩 (：171?2019/046369

Within the above range, the thermoformability is excellent.

[0058] An additive may be contained in the first non-foamed layer. Examples of the additives include flame retardants, flame retardant aids, lubricants, spreading agents, colorants, antistatic agents, antifogging agents, antiblocking agents, antioxidants, light stabilizers, crystal nucleating agents, surfactants. , Filler, etc.

When the first non-foamed layer contains the additive, the content thereof is preferably more than 0 parts by mass and 30 parts by mass or less with respect to 100 parts by mass of the resin.

The second non-foamed layer is a layer located on the other surface of the foamed layer.

As the second non-foamed layer, the same one as the above-mentioned <third non-foamed layer> can be used.

The second non-foamed layer may include a filler. By including a filler, it is easier to improve the strength.

The filler is preferably an inorganic filler, and examples thereof include plate-like mineral particles such as talc, kaolin, calcined kaolin, bentonite, mica group minerals (sericite, muscovite, phlogopite, biotite). Of these, talc is preferred.

The content of the filler is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, based on the total mass of the second non-foamed layer. When the content of the inorganic filler is within the above numerical range, the strength is excellent.

The average particle size of the filler is preferably 1 to 50, more preferably 3 to 30. When the average particle size of the filler is within the above numerical range, the strength is excellent. In the present specification, the average particle size can be measured by a laser diffraction method.

[0060] The maximum load required for the second non-foamed layer" 3 <71 25 is 10 to 5

0 1\1 is preferable, 15 to 4 5 1\1 is more preferable, 20 to 4 0 1\1 is further preferable, and 20 to 3 5 1\1 is particularly preferable. When the maximum load of the first non-foamed layer is within the above range, it becomes easy to improve wear resistance. 〇 2020/174792 19 卩 (: 171?2019/046369

[0061] The maximum coefficient of static friction obtained by the second non-foaming layer"

It is preferably 1.0 or higher, more preferably 2.0 or higher, even more preferably 2.5 or higher, and particularly preferably 3.0 or higher. Further, the maximum static friction coefficient of the second non-foamed layer is preferably 5.0 or less, more preferably 4.5 or less. Specifically, the maximum static friction coefficient of the second non-foamed layer is preferably 1.0 to 5.0, more preferably 2.0 to 4.5, and even more preferably 2.5 to 4.0. When the maximum coefficient of static friction of the second non-foamed layer is within the above range, the stickiness and the feeling of being caught can be reduced.

[0062] The basis weight of the second non-foamed layer is

Is preferred, 1 to 30 ~

3009

² is more preferable. When the basis weight of the second non-foamed layer is within the above numerical range, the handleability is excellent.

The basis weight can be measured by the following method.

Both ends in the width direction of the second non-foamed layer 2

At equal intervals in the width direction,

Cut out 10 pieces of 〇 100 pieces and measure the mass (9) of each piece up to 0.001 9 units. The mass value obtained by conversion calculation of 1 ² per an average value of the mass (9) in each section, the basis weight of the second non-foamed layer spoon

And

[0063] The thickness of the second non-foamed layer 3 is appropriately determined according to the required strength and the like.

Is preferred, and 0.01 to 0.4 is more preferred, and 0.15 to 0.3

[0064] The second non-foamed layer" has a Duro 8 hardness of 7 determined by 3 <6253-3.

0 or less is preferable. Further, the Duro 8 hardness of the first non-foamed layer, which is determined by "3 [< 6253-3", is preferably 30 or more, and more preferably 40 or more. Specifically, the Duro 8 hardness of the second non-foamed layer is preferably 30 to 70, more preferably 40 to 70. When the Duroha hardness is within the above range, the handleability is excellent.

[0065] The second elongation of the non-foamed layer is 900 [< 625 1 \¥0 2020/174792 20 20 (: 17 2019/046369

% Or more is preferable, and 100 to 150% is more preferable. When the elongation at break is within the above range, the thermoformability is excellent.

[0066] The second non-foamed layer may contain an additive. Examples of the additives include flame retardants, flame retardant aids, lubricants, spreading agents, colorants, antistatic agents, antifogging agents, antiblocking agents, antioxidants, light stabilizers, crystal nucleating agents, surfactants. When the additive is contained in the second non-foamed layer, the content thereof is preferably more than 0 parts by mass and 30 parts by mass or less with respect to 100 parts by mass of the resin.

[0067] In the laminated foam sheet, the ratio of bubbles (eight) calculated by the following method was 5

It is 0% or more, preferably 60% or more, and more preferably 65% or more. The proportion of the bubbles (8) is preferably 75% or less, more preferably 70% or less. Specifically, the proportion of the bubbles (8) is preferably from 50 to 75%, more preferably from 60 to 70%, even more preferably from 65 to 70%. When the ratio of the bubbles (8) is within the above range, abrasion resistance is easily improved.

The laminated foam sheet was cut along the thickness direction, and a photograph of the cut surface was taken with a scanning electron microscope at a magnification of 30 times. In the obtained photograph, among the bubbles in the foam layer, the first Select three or more bubbles located on the non-foaming layer side of, and draw a tangent line to the first non-foaming layer side of the selected bubbles in the direction perpendicular to the thickness direction. The tangent line is the interface between the foam layer and the first non-foam layer. From the interface, in the thickness direction of the foam layer, measure the major axis and minor axis of the bubbles in the region up to a depth of 15% with respect to the thickness of the foam layer, and obtain the ratio of major axis/minor axis. Then, the bubbles with the ratio of 4.0 or more are defined as bubbles (). Voids having a minor axis of 1% or more with respect to the thickness of the foam layer included in the region are regarded as bubbles. The number of all bubbles and the number of bubbles (8) are counted, and the ratio of bubbles () to the total number of bubbles contained in the region is calculated. The maximum value of the bubble diameter in the direction perpendicular to the thickness direction of the foam layer is the major axis, and the maximum value of the bubble diameter in the thickness direction of the foam layer is the minor axis.

Also, in the thickness direction of the foam layer, up to a depth of 15% with respect to the thickness of the foam layer. 〇2020/174792 21 卩(：171?2019/046369

A bubble in which at least a part of the bubble is included in the region is regarded as a bubble in the region.

[0068] In the laminated foam sheet, the ratio of air bubbles (Mi) calculated by the following method was 5

0% or more is preferable, 60% or more is more preferable, and 65% or more is further preferable. In addition, the proportion of the bubbles (Mi) is preferably 75% or less, more preferably 70% or less. Specifically, the proportion of the bubbles (Mi) is preferably 50 to 75%, more preferably 60 to 70%, further preferably 65 to 70%. When the ratio of the bubbles (Mitsumi) is within the above range, the wear resistance is likely to be improved. <Calculation method of the ratio of bubbles (Mitsumi)>

The laminated foam sheet was cut along the thickness direction, and a photograph of the cut surface was taken with a scanning electron microscope at a magnification of 30 times. In the obtained photograph, a foam layer and a second non-foam layer were formed. From the interface of the foam layer, in the thickness direction of the foam layer, measure the major axis and minor axis of the bubbles in the region up to a depth of 15% of the thickness of the foam layer, and calculate the ratio expressed by major axis/minor axis. Then, the bubbles having the ratio of 4.0 or more are defined as bubbles (Mitsu), and the number of bubbles (Mitsu) and the number of all the bubbles included in the region are counted, and the total number of bubbles included in the region is calculated. Calculate the percentage of air bubbles.

A method of calculating the ratio of bubbles (8) will be described with reference to FIG.

In FIG. 3, a laminated foam sheet 11 having three layers is cut along the thickness direction, and a cut surface is photographed with a scanning electron microscope at a magnification of 30 times. The laminated foam sheet 11 of FIG. 3 has a first non-foamed layer, a foamed layer, and a second non-foamed layer laminated in that order from the bottom. In the photograph of the obtained laminated foam sheet 11, the position of the interface 21 between the foam layer and the first non-foam layer is determined. Here, the “interface” is selected by selecting three or more bubbles located on the first non-foaming layer side among the bubbles in the foaming layer, and selecting the bubbles in the direction perpendicular to the thickness direction. Is determined by drawing a tangent line on the side of the first non-foaming layer of, and using the tangent line as an interface. Next, the line 2 2 parallel to the interface 21 is located at a position from the interface 21 in the thickness direction of the foam layer to a depth of 15% with respect to the thickness of the foam layer. Subtract 2. Further, the major axis and minor axis of the bubbles contained in the region from the interface 21 to the line 22 are measured. Here, the major axis and the minor axis of the cell are the cell diameter in the direction perpendicular to the thickness direction of the foam layer. 〇2020/174792 22 卩(：171?2019/046369

The maximum value is the major axis, and the maximum value of the bubble diameter in the thickness direction of the foam layer is the minor axis. Then, the ratio of the long diameter/short diameter of the bubbles is calculated, and the bubbles having the ratio of 4.0 or more are defined as bubbles (8). Count the number of bubbles () and the total number of bubbles contained in the region. Regarding the number of bubbles, cavities with a minor axis of 1% or more with respect to the thickness of the foam layer are regarded as bubbles, and bubbles are formed in the thickness direction of the foam layer up to a depth of 15% with respect to the thickness of the foam layer. The bubbles including at least a part of the above are counted as bubbles in the region. The ratio of bubbles () to the total number of bubbles contained in the region is calculated.

The proportion of bubbles (Mitsumi) can also be calculated in the same manner as for bubbles (8).

[0070] The thickness of the laminated foam sheet 1 is appropriately determined in consideration of the application and the like.

〇-5~4.

Is preferred, and! .0-3.

More preferable. When the thickness of the laminated foam sheet is at least the above lower limit, sufficient strength can be easily obtained. If it is at most the above upper limit, the molding process will be easy.

[0071] The basis weight of the laminated foam sheet is

Is preferred, 200 to 5

More preferably _509/012, more preferably 300 to 5,009 / _012. When the basis weight of the laminated foam sheet is within the above numerical range, the handleability is excellent.

The basis weight can be measured by the following method.

Both ends of the laminated foam sheet in the width direction 2

At equal intervals in the width direction,

Cut out 10 pieces of 〇 100 pieces and measure the mass (9) of each piece up to 0.001 9 units. The mass value obtained by conversion calculation of 1 ² per an average value of the mass (9) in each section, the basis weight of the laminated foam sheet

And

[0072] The density of the laminated foam sheet is

1 50

Is more preferable. When the density of the laminated foam sheet is within the above numerical range, the handleability is excellent.

An example of a method for manufacturing the laminated foam sheet 1 will be described.

The method for manufacturing the laminated foam sheet 1 includes, for example, a foam sheet forming step of obtaining a foam sheet and a resin forming the first non-foam layer on one surface of the foam sheet by extrusion extrusion. 〇 2020/174792 23 卩 (：171?2019/046369

It is preferable to include a first laminating step of fusing with a minate, and a second laminating step of fusing the resin forming the second non-foamed layer to the other surface of the foamed sheet by extrusion laminating.

The foamed sheet forming step is the same as the method for manufacturing the foamed sheet described above.

[0075] The first laminating step is a step of fusion-bonding the resin forming the first non-foamed layer to one surface of the foamed sheet by extrusion lamination.

DETAILED DESCRIPTION ^_ example of the ^_ laminating step, and a second lamination step will be described with reference to FIG.

[0076] The foamed sheet 1 0 1 is fed from the foamed sheet roll 10 2 to form the foamed sheet 1

The resin 1 0 3 melted by the first extruder 1 1 1 is supplied to one surface of 0 1 from a die 1 1 0. After that, they are pressure-bonded and fused by a pair of cooling ports 1 1 2.

In this way, a laminated foam sheet 10 4 including two layers including the foam layer 10 and the first non-foam layer 20 is obtained. The heating temperature in the laminating step is appropriately determined according to the material of each layer and the like.

[0077] In the first laminating step, the temperature at which the resin constituting the first non-foamed layer 20 is fused to one surface of the foamed sheet 101 is 200 to 240° O is preferable, and 210 to 240 ^° is more preferable. When the temperature at the time of fusing is within the above range, it becomes easy to improve the wear resistance of the obtained laminated foam sheet.

[0078] The second laminating step is a step of fusion-bonding the resin constituting the second non-foamed layer to the other surface of the foamed sheet by extrusion laminating.

The laminated foamed sheet 10 2 consisting of two layers obtained in the ^_th laminating step was spun around the mouth 1 13 and the resin 1 melted by the second extruder 1 15 was applied to the other surface of the foamed sheet. 0 5 is supplied from die 1 1 4. After that, they are pressure-bonded and fused by a pair of cooling ports 1116.

In this way, the laminated foam sheet 1 is formed of three layers including the foam layer 10, the first non-foam layer 20 and the second non-foam layer 30.

[0079] In the second laminating step, the temperature at which the resin forming the second non-foaming layer 30 is fused to the other surface of the foamed sheet 101 is 200 to 240° ◯ is preferred 〇 2020/174792 24 卩 (：171?2019/046369

More preferably, 210 to 240 ^° is more preferable. When the temperature at the time of fusing is within the above range, it becomes easy to improve the wear resistance of the obtained laminated foam sheet.

The two laminating steps may be performed in the order of the second laminating step and the first laminating step. Further, the laminated foam sheet of the present invention is not limited to the above production method (extrusion laminating method). The foamed layer and the non-foamed layer may be laminated by coextrusion or a heat laminating method.

[0081] <<Molded body>>

The molded product of the present invention is obtained by molding a laminated foam sheet. As a method for molding the laminated foam sheet, for example, the laminated foam sheet is heated to an arbitrary temperature for secondary foaming, and then the laminated foam sheet is sandwiched between a male mold and a female mold of an arbitrary shape and molded. Is mentioned.

It is preferable that the first non-foamed layer is formed so that the surface thereof faces downward in the vertical direction.

The molded article of the present invention can be used for a floor mat of a vehicle, a luggage tray, and an under cover of a vehicle.

The floor mat of a vehicle is removably placed on the floor of the vehicle. It is used to replenish the dirt caused by dirt and sand brought in by passengers from the outside of the vehicle, and wash it outside the passenger compartment for repeated use. In the floor mat of the vehicle, it is preferable that the first non-foamed layer is arranged so that the first non-foamed layer faces downward in the vertical direction when the floor mat is used. As a result, it is possible to prevent the floor mat of the vehicle from being displaced from the predetermined position.

FIG. 5 is a schematic diagram showing an example of the floor mat of the vehicle of the present invention. The vehicle floor mat 2 in Fig. 5 has notches so that it can be placed at the foot of the seat in front of the vehicle, and has an uneven structure on the surface to prevent slipping. The notch may be formed according to the shape of the vehicle. The concavo-convex structure may have any shape and may or may not be rough.

The undercover of a vehicle covers and protects the lower part of the vehicle body. In a vehicle undercover, the first non-foaming layer is 〇 2020/174792 25 卩 (：171?2019/046369

It is preferable to arrange it so that the surface thereof faces downward in the vertical direction. As a result, the vehicle can be protected from dirt and the like that jumps from the ground to the vehicle while the vehicle is traveling.

FIG. 6 is a schematic diagram showing an example of the undercover of the vehicle of the present invention. The undercover of the vehicle shown in Fig. 6 has a concavo-convex structure to reduce air resistance and improve fuel efficiency. The concavo-convex structure may have any shape and may or may not be present.

The luggage tray of a vehicle is a tray for loading items that is installed at the bottom of the vehicle's luggage compartment. In the luggage tray of the vehicle, it is preferable to arrange the first non-foamed layer so that the first non-foamed layer is a surface that faces downward in the vertical direction when the luggage tray of the vehicle is used. As a result, it is possible to prevent the luggage tray of the vehicle from being displaced in a predetermined position.

FIG. 7 is a schematic view showing an example of the luggage tray of the vehicle of the present invention. The luggage tray 4 of the vehicle in FIG. 7 is rectangular in plan view, but may have any shape.

FIG. 8 is a schematic view showing another example of the luggage tray of the vehicle of the present invention. The luggage tray 5 of the vehicle shown in FIG. 8 has a notch so that it can be placed in the trunk, and has an uneven structure on the surface to prevent slipping. The notch may be formed according to the shape of the vehicle. The concavo-convex structure may have any shape, and may or may not have one.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]

As polypropylene-based resin, made of 3 〇 r _& a \ \ 3 companies

3” (melt tension: 2 3 0 1\1, melt flow rate: ··· 7 9/10 min) 40 parts by mass, as the block polypropylene, the product name “Mix 0 60” manufactured by Nippon Polypro Co., Ltd. 50 parts by mass, polyolefin-based thermoplastic elastomer ( 20/174792 26 卩 (: 171?2019/046369

As a sample, a polymer component was prepared by mixing the product name "○1100" manufactured by Sun Allomer Co., Ltd. at a ratio of 10 parts by mass. A baking soda-citric acid-based foaming agent (Masterbatch manufactured by Dainichiseika Co., Ltd., trade name "FINECELL MASTER 〇410") in which the ratio to the polymer component of 100 mass parts is 0.2 mass part was blended. To give a mixture. A tandem extruder was prepared in which a second extruder with a diameter of 115 was connected to the tip of a first extruder with a diameter of 90. The mixture was melt-kneaded at a temperature of about 200 to 210 ^° by feeding a first extruder. Then, butane (normal butane:isobutane = 65:35 (mass ratio)) as a foaming agent was press-fitted into the first extruder at a ratio of 1.0 parts by mass to 100 parts by mass of the polymer component. Melted and kneaded. After that, it is cooled to about 1750 ^° and supplied to an annular die that is connected to the tip of the second extruder and extruded into a cylindrical shape at an extrusion rate of 1500!<9/hour. It was

The obtained cylindrical foam was cooled by blowing air on its inner surface. After that, the inner surface was solidified along the cooling mandrel plug, and air was also blown on the outer surface of the plug to cool and solidify. Then, the cylindrical foam was cut in the direction of extrusion and cut open, wound into a continuous sheet as a continuous sheet, with a thickness of 2.

To obtain a foam sheet.

Non-crosslinking type olefin elastomer resin () manufactured by 3 companies, trade name “340M”, gel fraction 0.3 mass% 60 parts by mass, and polypropylene resin (manufactured by San Allomer Co., trade name “ The resin mixture obtained by mixing 40 parts by mass was fed to the third extruder and the fourth extruder. The sheet was extruded from a die attached to the tip of the third extruder, and a sheet in a molten state immediately after extrusion was laminated on one surface of the foamed sheet and fused. Subsequently, the sheet was extruded from a die attached to the tip of the fourth extruder, and the sheet in a molten state immediately after extrusion was laminated on the other surface of the foamed sheet and fused. Thus, a laminated foam sheet having non-foamed layers on both sides was obtained. The extrusion conditions of the third extruder and the fourth extruder were the same. In all the die, the temperature of the parts other than both ends is set so that the temperature of both ends in the width direction of the resin flow path becomes 260 ^° 〇. 〇 2020/174792 27 卩 (：171?2019/046369

It was adjusted to be 280 ^° 〇. The temperature of the sheet in the molten state at the time of fusing was 220°°.

[0085] [Example 2]

Non-cross-linking olefin elastomer resin ("3 companies, trade name "3400 跳", gel fraction 0.3 mass%) 80 parts by mass, and polypropylene resin (San Allomer Co., trade name "01 00") A laminated foam sheet was obtained in the same manner as in Example 1 except that a resin mixture prepared by mixing 20 parts by mass was used.

[0086] [Example 3]

Non-crosslinking olefin elastomer resin (" 3 companies, trade name "3400 Mitsumi", gel fraction 0.3 mass%) 20 parts by mass, and polypropylene resin (San Allomer Co., trade name "01 00") A laminated foam sheet was obtained in the same manner as in Example 1 except that a resin mixture obtained by mixing 80 parts by mass was used, and the temperature of the sheet in a molten state at the time of fusing was changed to 230 ^° .

[0087] [Example 4]

Non-crosslinkable olefin elastomer resin (", manufactured by 3 companies, trade name "3700", gel fraction: 0.2 mass%) 70 parts by mass, and polypropylene resin (manufactured by San Allomer Co., trade name "01 00") A laminated foam sheet was obtained in the same manner as in Example 1 except that a resin mixture obtained by mixing 30 parts by mass was used, and the temperature of the sheet in a molten state at the time of fusing was changed to 225 ^° .

[0088] [Example 5]

Non-cross-linking olefin elastomer resin (", manufactured by 3 companies, trade name "3400", gel fraction: 0.3% by mass) 70 parts by mass, and polypropylene resin (manufactured by San Allomer Co., trade name "0300") 30 A laminated foam sheet was obtained in the same manner as in Example 1 except that a resin mixture in which parts by weight were mixed was used, and the temperature of the sheet in the molten state at the time of fusing was changed to 2 15° 〇. ..

[0089] [Example 6]

Non-cross-linking olefin elastomer resin () manufactured by 3 companies, trade name "3400", gel fraction 0.3 mass% 60 parts by mass, polypropylene resin (d 〇2020/174792 28 卩(：171?2019/046369

(Chemicals, trade name "Engage 1_Choen 8677") A resin mixture containing 40 parts by mass was used, and the temperature of the molten sheet when fusing was changed to 240 ^° 〇. A laminated foam sheet was obtained in the same manner as in Example 1 except for the above.

[0090] [Example 7]

Non-crosslinkable olefin elastomer resin (", manufactured by 3 companies, trade name "3400", gel fraction 0.3 mass%) 60 parts by mass, and polystyrene resin (Aron Kasei Co., trade name "[¾_885 (3)) Laminated foaming in the same manner as in Example 1 except that a resin mixture in which 40 parts by mass was mixed was used, and the temperature of the sheet in the molten state at the time of fusing was changed to 235 ^° Got the sheet.

[0091] [Example 8]

A thickness of 3.0111111, as in Example 1, except that the amount of the foaming agent was 1.5 parts by mass.

To obtain a foam sheet.

Using the obtained foamed sheet, 50 parts by mass of a non-crosslinked olefinic elastomer resin (manufactured by the company, trade name "3400", gel fraction 0.3% by mass), and polypropylene resin (manufactured by San Allomer Co., Ltd. Name “01 00 ”) Except that a resin mixture in which 50 parts by mass was mixed was used, and the temperature of the sheet in the molten state at the time of fusing was changed to 210° 〇 A laminated foam sheet was obtained in the same manner.

[0092] [Example 9]

The thickness was the same as in Example 1 except that the amount of the foaming agent was 0.3 part by mass.

To obtain a foam sheet.

A laminated foam sheet was obtained in the same manner as in Example 1 except that the obtained foam sheet was used.

[Example 10]

A foam sheet having a thickness of 2.0111111 and a density of 270 was obtained in the same manner as in Example 1 except that the amount of the foaming agent was 1.5 parts by mass.

Using the resulting foamed sheet, a non-crosslinked olefin elastomer resin ( 〇2020/174792 29 卩(：171?2019/046369

Manufactured by the company, trade name "340,000", gel fraction 0.3 mass%) 70 parts by mass, and polypropylene resin (manufactured by Sun Allomer Co., trade name "0100") 30 parts by mass. A laminated foam sheet was obtained in the same manner as in Example 1 except that the mixed resin mixture was used, and the temperature of the sheet in the molten state at the time of fusion bonding was changed to 2 15 °C.

[Example 1 1]

Non-crosslinking olefin elastomer resin (" 3 companies, trade name "340 MIN", gel fraction 0.3 mass%) 70 parts by mass, and polypropylene resin (San Allomer Co., trade name " 0 1 0 0 ”) 30 parts by mass of a resin mixture was used, the temperature of the sheet in the molten state at the time of fusing was changed to 230 ^° 〇, and the first non-foaming layer Thickness 0.3

A laminated foam sheet was obtained in the same manner as in Example 1 except that the above was adopted.

[0095] [Example 12]

A thickness of 1% was obtained in the same manner as in Example 1 except that the amount of the foaming agent was 0.8 parts by mass.

To obtain a foam sheet.

Using the obtained foamed sheet, 50 parts by mass of a non-crosslinked olefin elastomer resin (manufactured by the company, trade name "340M", gel fraction: 0.3% by mass), and a polypropylene resin (Sun Allomer Manufactured by the company, trade name "0100") 5 0 parts by weight of a resin mixture was used, and the temperature of the sheet in the molten state at the time of fusing was changed to 230 ^° 〇, A laminated foam sheet was obtained in the same manner as in Example 1 except that the second extruder was not operated.

[0096] [Example 13]

Polyethylene terephthalate resin as a polyester resin (Mita, manufactured by Mitsui Chemicals, Inc.

Product name "3/8 1 3 5", glass transition temperature 9: 7 9 ° 〇, melting point: 2 4 7.1 ° 〇, V value: 0.86) 100 parts by mass, talc 0. 7 A thermoplastic polyester resin composition containing 2 parts by mass and 0.2 parts by mass of pyromellitic dianhydride is supplied to a single-screw extruder with a diameter of 6500 and a 1/0 ratio of 35. Melt at 290 ° 〇 2020/174792 30 卩(：171?2019/046369

Melted and kneaded. Then, butane (normal butane:isobutane = 65:35 (mass ratio)) as a foaming agent was press-fitted into the single-screw extruder in an amount of 1.0 part by mass with respect to 100 parts by mass of the polymer component. Melted and kneaded. After that, it was cooled to about 220 ^° 〇, and a cylindrical die was extruded and foamed into a cylindrical shape from a circular die connected to the tip of a single-screw extruder to produce a cylindrical body, and this cylindrical body was gradually expanded in diameter. After supplying it to the cooling mandrel above and cooling the cylindrical body so that the surface temperature becomes 25 ° 〇, the cylindrical body is continuously cut in the extrusion direction between the inner and outer peripheral surfaces and cut open. By deploying it, the thickness is 2.

To obtain a foam sheet.

Using the obtained foamed sheet, a laminated foamed sheet was obtained in the same manner as in Example 1 except that the temperature of the sheet in a molten state at the time of fusing was changed to 235 ^° .

[Example 14]

Extrusion rate is 50

Same as Example 1 except that the thickness is 2.0 111 111,

To obtain a foam sheet.

Using the obtained foamed sheet, a laminated foamed sheet was obtained in the same manner as in Example 1 except that the temperature of the sheet in a molten state at the time of fusion bonding was changed to 230 ^° .

[0098] [Comparative Example 1]

As the resin that constitutes the first non-foamed layer, non-crosslinked olefin elastomer

A laminated foam sheet was obtained in the same manner as in Example 1 except that a resin having a trade name of “340,000” and a gel fraction of 0.3% by mass) was used.

[0099] [Comparative Example 2]

A laminated foam sheet was obtained in the same manner as in Example 1 except that the foaming agent was press-fitted so as to be 1.1 parts by mass and then cooled to about 185 ^° . Using the obtained foamed sheet, a laminated foamed sheet was obtained in the same manner as in Example 1 except that the temperature of the sheet in a molten state at the time of fusion bonding was changed to 210 ^°. 〇2020/174792 31 卩(：171?2019/046369

It was

[0100] [Comparative Example 3]

A thickness of 3.00!, similar to Example 1, except that the amount of the foaming agent was press-fitted to be 0.2 parts by mass.

To obtain a foam sheet.

[0101] [Comparative Example 4]

Amount of foaming agent! .Thickness of 3.000!, in the same manner as in Example 1 except that press-fitting was performed so that the amount became 5 parts by mass.

To obtain a foam sheet. A laminated foam sheet was obtained in the same manner as in Example 1 except that the temperature of the sheet in the molten state at the time of fusing was changed to 180 ^° .

[0102] [Comparative Example 5]

As the resin forming the first non-foamed layer, a resin made of polypropylene resin (manufactured by Nippon Polypropylene Corporation, trade name "Min 060") was used, and the sheet in a molten state at the time of fusing A laminated foam sheet was obtained in the same manner as in Example 1 except that the temperature of 2 was changed to 215°.

[0103] [Comparative Example 6]

As the resin that constitutes the first non-foamed layer, polypropylene resin (manufactured by Nippon Polypro Co., Ltd., trade name “Min 060”) 100 parts by mass contains talpet 70 (Nitto) which contains 70% by mass of inorganic filler. Same as Example 1, except that a resin mixture containing 43 parts by mass was used, and the temperature of the sheet in the molten state at the time of fusing was changed to 2 25 ^° 〇. To obtain a laminated foam sheet

[0104] [Comparative Example 7]

A foamed sheet was obtained in the same manner as in Example 1. The obtained foamed sheet was directly used for evaluation.

[0105] [Comparative Example 8]

As a resin that constitutes the first non-foamed layer, a cross-linking olefin elastomer 〇 2020/174792 32 卩 (：171?2019/046369

A resin made of a company, trade name "1300 1", gel fraction 40% by mass) was used, and the temperature of the sheet in the molten state at the time of fusing was changed to 2 3 5 ^° A laminated foam sheet was obtained in the same manner as in Example 1 except for the above.

[0106] [Comparative Example 9]

As the resin constituting the first non-foamed layer, a resin made of a cross-linkable olefin-based elastomer, having a trade name of "1703" and a gel fraction of 39.5 mass%) was used. A laminated foam sheet was obtained in the same manner as in Example 1 except that the temperature of the molten sheet when it was attached was changed to 220°.

[0107] [Comparative Example 1 0]

Styrene elastomer as the resin that constitutes the first non-foamed layer

Except that a resin made by the company, trade name "Cha[¾200") was used, and that the temperature of the molten sheet during fusion was changed to 230 ^° 〇 The same procedure as in Example 1 was performed, but a laminated foam sheet could not be obtained.

[0108] [Comparative Example 1 1]

A laminated foam sheet was obtained in the same manner as in Example 1 except that the temperature of the sheet in the molten state at the time of fusing was changed to 180 ^° .

[0109] With respect to the obtained laminated foam sheet, the thickness of foam layer, the density, the closed cell ratio, the melting point of the resin contained in the foam layer, the thickness of the non-foam layer, the basis weight, the Duro hardness, the elongation at break, and the The melting point of the resin contained in the foam layer, the total thickness of the laminated foam sheet, the basis weight, the density, the maximum coefficient of static friction, the maximum load, the ratio of bubbles (8), and the wear resistance were measured. Further, the thermoformability of the laminated foam sheet was evaluated. The results obtained are shown in Tables!

For the laminated foamed sheet of Example 12 having no second non-foamed layer, the other surface of the foamed sheet was regarded as the surface of the second non-foamed layer, and the maximum static friction coefficient, the maximum load, and Abrasion resistance was measured.

Further, regarding the foam sheet of Comparative Example 7 having neither the first non-foaming layer nor the second non-foaming layer, one surface of the foaming sheet was used as the surface of the first non-foaming layer, and the foaming sheet The other surface of the is considered as the surface of the second non-foamed layer 〇 2020/174792 33 卩 (：171?2019/046369

, Maximum load, and wear resistance were measured.

[0110] <Basis weight>

Except for both ends 200101 in the width direction of the foamed sheet, the first non-foamed layer sheet, the second non-foamed layer sheet, or the laminated foamed sheet, 10 pieces of 1 0001X 100 ○ are equally spaced in the width direction. Was cut out and the mass (9) of each section was measured up to 0.001 9 units. A value converted to a mass per 1 ² the average value of the mass (9) in each section, the basis weight IV!

And

[0111] Thickness ñ

Both ends in the width direction of the foam sheet, the first non-foam layer sheet, the second non-foam layer sheet, or the laminated foam sheet 2

Widthwise, excluding 50

2 1 points at intervals were used as measurement points. About this measuring point, dial thickness gauge

1 1 2 (manufactured by Teclock Co.) was used to measure the thickness to the minimum unit of 0.01. The average of these measured values was used as the thickness (111111).

[0112] <Density>

Thickness () and basis weight IV!

Then, the density _| 〇 (

I asked for 1 <9/01 ³ ).

ø = |\/|/ Ding-(2)

[0113] <Ratio of closed cells>

The closed cell ratio was measured by the method described in “3 <7 1 38: 2006 “Rigid foamed plastic-Method of determining open cell ratio and closed cell ratio””.

[0114] <Duro hardness>

Duro hardness 8 was measured according to 13 <6253-3.

[0115] <Elongation at break>

The elongation at break was measured according to “3 [< 625 1”.

[0116] <Melting point>

The melting point was measured by the method described in “Method of measuring transition temperature of plastic” 3 [< 7 1 2 1 = 1 987].

[0117] <Maximum coefficient of static friction> 〇 2020/174792 34 卩 (：171?2019/046369

The maximum coefficient of static friction was measured according to I 3 <71 25.

[0118] <Maximum load>

The maximum load was measured according to “3 <71 25”.

[0119] <Ratio of air bubbles (eight)>

The ratio of bubbles () was calculated by the following method.

The laminated foam sheet was cut along the thickness direction, and a photograph of the cut surface was taken with a scanning electron microscope at a magnification of 30 times. In the obtained photograph, the major axis and the minor axis of bubbles in the region from the interface between the foamed layer and the first non-foamed layer to the depth of 15% of the thickness of the foamed layer in the thickness direction of the foamed layer. The diameter was measured. The ratio expressed by the major axis/minor axis was calculated, and the bubbles having the ratio of 4.0 or more were regarded as bubbles (/\). The number of bubbles () and the number of all bubbles contained in the region were counted, and the ratio of bubbles () to the total number of bubbles contained in the region was calculated.

[0120] <Thermoformability>

For thermoforming, a single-shot molding machine Model 3_500 (manufactured by Wakisaka Engineering Co., Ltd.) was used to obtain a cylindrical foam laminated thermoformed body having a heating temperature of 295° (:, a heating time of 223 and a bore of 1 55 ¢).

At this time, the maximum depth at which a foamed laminated thermoformed body having a smooth surface, sufficient container strength, no peeling, and good thermoformability was obtained was determined.

[0121] <Measurement of wear resistance>

The abrasion resistance was measured as follows.

The measurement is ”3

I went according to. Specimen size is diameter

The product is a laminated foam sheet with a thickness of 6 mm in the center.

I used the one with a hole in it. Using tapered wear test apparatus (tapered Inc. 1 \ / 1_Rei ₆丨503), using the worn wheel 1 ^to 1_38, load 5009, the rotational speed of 60 rev / min, the appearance after the test carried out at a rotation number of 1 000 rotation Was evaluated according to the following evaluation criteria.

[Evaluation criteria]

Eight: The surface diaphragm remains slightly

Mami: There is a marked step \¥02020/174792 35 卩(: 17 2019/046369

〇: A hole opens

[0122] [Table 1]

[0123]

1

(谢_-4

〇 2020/174792 39 卩 (：171?2019/046369

Was inferior in.

Comparative Example 2 in which the closed cell ratio was less than 70% and the ratio of the cells () was less than 50% was inferior in thermoformability.

Foam layer density 50

Comparative Example is less than 4.5 / ³ 3 had poor Tsu thermoformability.

Comparative Example 4 in which the proportion of bubbles () was less than 50% was inferior in thermoformability and wear resistance.

Comparative Examples 5 and 6 in which the maximum load in the first non-foamed layer was less than 10 1\1 were inferior in grip properties and wear resistance.

Comparative Example 7 in which the maximum load in the first non-foamed layer was less than 10 1\! and the proportion of bubbles (8) was less than 50% was inferior in grip property and wear resistance.

Comparative Examples 8 and 9 in which the maximum load in the first non-foamed layer was less than 10\1\1 were inferior in grip property, thermoformability, and wear resistance.

In Comparative Example 10, sufficient adhesive strength between the foamed layer and the non-foamed layer could not be obtained, and a measurable laminated sheet could not be obtained.

Comparative Example 11 in which the ratio of bubbles () was less than 50% was inferior in thermoformability and abrasion resistance.

Industrial availability

[0127] According to the present invention, it is possible to provide a laminated foam sheet having a non-slip surface, which is excellent in thermoformability and abrasion resistance, and a molded body thereof.

Explanation of symbols

[0128] 1--Laminated foam sheet

1 0-foam layer

1 1-laminated foam sheet

20-first non-foamed layer

2 1 ··· Interface between the foam layer and the first non-foam layer

2 2 ··· From the interface between the foam layer and the first non-foam layer, 20/174792 40 卩 (: 171?2019/046369

Line drawn to a depth of 15% of the foam layer thickness

30 ···Second non-foamed layer

3 1 ··· Interface between the foam layer and the second non-foam layer

32.. A line drawn from the interface between the foam layer and the second non-foam layer in the thickness direction of the foam layer to a depth of 15% of the thickness of the foam layer.

2 Vehicle floor mat

3 Vehicle undercover

4 Vehicle luggage tray

5 Vehicle luggage tray

Claims

\¥0 2020/174792 41 卩(: 17 2019/046369 Claims

[Claim 1] comprising a foam layer and a first non-foam layer located on one surface of the foam layer,

The foamed layer has a closed cell ratio of 70% or more and a density of 50 to 10

The first non-foamed layer has a maximum load of 10 to 5 0 1\1, which is obtained by ``'' 3 <7 1 25.

A laminated foam sheet in which the proportion of bubbles (eight) calculated by the following method is 50% or more.

The laminated foam sheet was cut along the thickness direction, and a photograph of the cut surface was taken at a magnification of 30 times using a scanning electron microscope.In the obtained photograph, the foam layer and the first non-foam layer were From the interface of the foam layer to the depth direction of the foam layer in the thickness direction of the foam layer, measure the major axis and minor axis of the bubbles in the area up to a depth of 15%, and calculate the ratio of major axis/minor axis Calculate the number of bubbles () and the number of all bubbles included in the region, and calculate the number of bubbles in the region as the bubble (). Calculate the percentage of bubbles (eight).

[Claim 2] The thickness of the foam layer is from 0.1 to 3.

The laminated foam sheet according to claim 1, wherein

[Claim 3] The first non-foamed layer contains a non-crosslinked olefin elastomer

The laminated foam sheet according to claim 1 or 2.

[Claim 4] The laminate according to any one of claims 1 to 3, wherein the first non-foamed layer has a Duro 8 hardness of 70 or less, which is determined by "3 <6 2 5 3-3". Foam sheet.

[Claim 5] The elongation percentage at break obtained in the first non-foamed layer" 3 [< 6 2 5 1 is 900% or more, The method according to any one of claims 1 to 4. Laminated foam sheet. 〇 2020/174792 42 卩 (：171?2019/046369

[Claim 6] The thickness of the first non-foamed layer is 0. 05 to 0. 5 111 111.

The laminated foam sheet according to any one of 1 to 5.

[Claim 7] The laminated foam sheet according to any one of Claims 1 to 6, which has a density of 100 to 200 001 <9/013.

[Claim 8] A molded product obtained by molding the laminated foam sheet according to any one of claims 1 to 7.

[Claim 9] The molded product according to claim 8, which is a floor mat of a vehicle.

A [Claim ^'10' under cover of a vehicle, the molded body according to claim 8.

[Claim 11] The molded product according to claim 8, which is a luggage tray of a vehicle.

[Claim 12] The method for producing a laminated foam sheet according to any one of claims 1 to 7,

A laminated foam sheet, comprising a first laminating step of fusing the resin constituting the first non-foamed layer at 200 to 240° to one surface of the foamed sheet constituting the foamed layer. Manufacturing method.