JPH1158640A - Laminated sheet and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a sheet, the lightweight properties, strength and appearance of which are improved, by a method wherein a propylene-based resin is integrally laminated onto both sides of a crosslinked foamed sheet and further a colored organic fiber-containing surface layer is integrally laminated onto the propylene- based resin layer. SOLUTION: A propylene-based resin layer is integrally laminated onto one side of a crosslinked foamed sheet through extrusion lamination. Further, onto the other side of the crosslinked foamed sheet, a propylene-based resin composed of the propylene-based resin layer and a colored organic fiber-containing resin composed of a surface layer are coextruded. Furthermore, a resultant sheet-like melted resin obtained by integrally laminating the polypropylene-based resin layer and the surface layer onto each other is integrally laminated to the polypropylene-based resin layer under the condition that the polypropylene-based resin layer faces to the crosslinked foamed sheet side. The obtained laminated sheet is excellent in lightweight properties and mechanical strength. In addition, the surface of the sheet presents the excellent appearance like a non-woven fabric and is excellent in appearance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sheet used for interior materials for automobiles and the like and a method for producing the same.

[0002]

2. Description of the Related Art Interior materials for automobiles, particularly ceiling materials for automobiles, are required to have properties such as lightness, moldability, heat resistance, and deflection resistance. As a device satisfying the required performance, Japanese Patent Publication No. 9137/1992 discloses a laminated sheet in which a non-foamed propylene polymer sheet is laminated on both sides of a cross-linked foamed sheet composed of an ethylene polymer and a propylene polymer. And Japanese Patent Publication No. 6-24767 discloses a non-foamed skin made of a propylene polymer on one surface of two crosslinked foamed sheets made of a propylene polymer and an ethylene polymer. There is disclosed a method for manufacturing an interior material for an automobile in which layers are laminated, and the crosslinked foamed sheets of the obtained laminate are melted and pressure-bonded to be integrated.

[0003] However, in the above-mentioned laminated sheet and interior material for automobiles, the surface is merely laminated with a surface layer made of a propylene-based resin, and the appearance is not always satisfactory. It could not meet the demands of consumers.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated sheet which is excellent in lightness and strength and has a nonwoven fabric appearance on its surface, and a method for producing the same.

[0005]

Means for Solving the Problems The laminated sheet of the present invention comprises:
A propylene-based resin layer is laminated and integrated on both sides of a cross-linked foamed sheet made of a propylene-based resin and an ethylene-based resin, and at least one of the propylene-based resin layers further contains a colored organic fiber. The surface layer is laminated and integrated.

The propylene resin constituting the crosslinked foamed sheet (hereinafter referred to as “propylene resin (A)”)
Is a copolymer with another monomer containing propylene as a main component, and examples thereof include a propylene-α-olefin copolymer, and a propylene-α-olefin copolymer is a block copolymer or a random copolymer. Any of a polymer and a random block copolymer may be used, and these may be used alone or in combination.

[0007] Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like. If the content of the α-olefin in the α-olefin copolymer is large, the surface properties of the crosslinked foamed sheet may be reduced, and if the content is small,
Since the flexibility and elongation of the crosslinked foamed sheet may be reduced and the moldability may be reduced, the content is preferably 1 to 8% by weight,
5% by weight is more preferred.

Further, when the melt index (hereinafter referred to as “MI”) of the propylene resin (A) is large,
The heat resistance of the crosslinked foamed sheet may be reduced, and if the heat resistance is reduced, the moldability of the crosslinked foamed sheet may be reduced and the surface property of the obtained molded product may be reduced. 10 minutes is preferred. In the present invention, MI refers to that measured in accordance with JIS K7210.

Further, the propylene resin (A)
If the amount eluted at 94 ° C or higher by
As the moldability of the foamed sheet decreases, the resulting molding
The surface properties of the product may be reduced,
The heat resistance of the foamed sheet is reduced, and air bubbles are broken during molding.
50 to 95% by weight is preferable,
0 to 90% by weight is more preferred. And the cross fractionation method
The weight average molecular weight of the eluate at 94 ° C or higher by
In this case, the moldability of the crosslinked foamed sheet decreases and
The surface properties of the resulting molded product may also be
In this case, the heat resistance of the crosslinked foamed sheet decreases,
2 × 10 ^Five -10 × 10
^Five Is preferred.

The propylene resin (A) has an MI of 0.2 to 10 g / 10 min, an elution amount at 94 ° C. or higher of 50 to 95% by weight by a cross separation method, and a weight average of the elution amount. Most preferred is a propylene-α-olefin copolymer having a molecular weight of 2 × 10 ⁵ to 10 × 10 ⁵ .

The elution amount by the cross fractionation method and the weight-average molecular weight of the elution amount referred to in the present invention are those measured by the following methods. That is, first, after the resin is dissolved in o-dichlorobenzene at 140 ° C. or a temperature at which the resin is completely dissolved, the resin is cooled at a constant temperature, and the surface of the inert carrier prepared in advance has high crystallinity. It is formed as a thin polymer layer in order. Next, the temperature is raised continuously or stepwise, the temperature of the eluted components is sequentially detected, and the composition distribution (crystallinity distribution) is measured. This is referred to as temperature rise elution fractionation. At the same time, the eluted components are analyzed by high-temperature GPC to measure the molecular weight and the molecular weight distribution. This allows
The amount eluted at each temperature and the weight average molecular weight of the eluted portion are calculated. In the present invention, a cross-separation chromatograph (trade name "C manufactured by Mitsubishi Chemical Corporation") having both the above-mentioned temperature-eluting elution fractionation part and the high-temperature GPC part as a system is provided.
FC-T150A type ").

The ethylene resin (hereinafter referred to as "ethylene resin (A)") constituting the crosslinked foamed sheet is a copolymer with another monomer containing ethylene as a main component. -Olefin copolymers, which may be used alone or in combination.

The above α-olefin includes, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,
Octene, etc., and the ethylene content in the ethylene-α-olefin copolymer is low. If the content is small, the heat resistance of the crosslinked foamed sheet may be reduced. Therefore, the content is preferably 60% by weight or more, and more preferably 80% by weight or more. Is more preferred.

The MI of the ethylene resin (A) is as follows:
If it is large, the heat resistance of the crosslinked foamed sheet may decrease, and the surface properties of the obtained molded article may also decrease.
Also, when the size is reduced, the flowability of the resin component may be reduced and the productivity of the crosslinked foamed sheet may be reduced.
10 g / 10 min is preferable, 0.7 to 4 g / 10 min is more preferable, and 0.9 to 3 g / 10 min is particularly preferable.

Furthermore, if the amount of the ethylene resin (A) eluted at 94 ° C. or higher by the cross fractionation method is large, the recovery of the crosslinked foamed sheet from the compressive strain may be reduced. Since the heat resistance of the crosslinked foamed sheet may be reduced and the surface properties of the obtained molded article may be reduced, the content is preferably 5 to 20% by weight, more preferably 6 to 10% by weight. If the weight average molecular weight of the elution at 94 ° C. or higher by the cross fractionation method is large, the recovery of the crosslinked foamed sheet from the compressive strain may be reduced,
Further, when the particle size is small, the heat resistance of the crosslinked foamed sheet is reduced, and the surface property of the obtained molded product is sometimes reduced. Therefore, 1.5 × 10 ⁵ to 10 × 10 ⁵ is preferable, and 2 × 1
0 ^{5 to} 5 × 10 ⁵ is more preferable.

The ethylene-based resin (A) has an MI of 0.5 to 10 g / 10 min, an elution amount at 94 ° C. or higher of 5 to 20% by weight by a cross separation method, and a weight average of the elution amount. Most preferred is an ethylene-α-olefin copolymer having a molecular weight of 1.5 × 10 ⁵ to 10 × 10 ⁵ .

The crosslinked foamed sheet comprises the propylene-based resin (A) and the ethylene-based resin (A). If the content of the propylene-based resin (A) is large, the flexibility and compression strain of the crosslinked foamed sheet are increased. In some cases, the recovery of the crosslinked foamed sheet is reduced, and when the content is small, the heat resistance of the crosslinked foamed sheet is reduced. The ethylene resin (A)
Is preferably 50 to 10% by weight, and more preferably 45 to 15% by weight.
% Is more preferred.

The combination of the propylene resin (A) and the ethylene resin (A) may be a propylene resin (A) having an MI of 0.2 to 10 g / 10 min. Elution amount of 50-95% by weight
And the weight average molecular weight of the eluted portion is 2 × 10 ⁵ to 10 × 1.
With 0 ⁵ a is propylene -α- olefin copolymer, as the ethylene-based resin (A), MI is 0.5 to 10
g / 10 min, the amount of elution at 94 ° C. or higher by the cross fractionation method is 5 to 20% by weight, and the weight average molecular weight of the eluted portion is 1.5%.
It is preferable to use an ethylene-α-olefin copolymer having a size of × 10 ⁵ to 10 × 10 ⁵ .

Next, a method for producing a crosslinked foamed sheet will be described. As a method for producing a crosslinked foamed sheet, any known method for producing a foam can be used, and an example thereof will be described below.

That is, first, a crosslinking aid is added to a resin component comprising a propylene resin (A) and an ethylene resin (A).
In addition to the pyrolytic foaming agent, if necessary, an antioxidant, a metal harm inhibitor, a heat stabilizer, a pigment, etc. are added, and these are added to a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer. , Melt-kneaded at a temperature lower than the decomposition temperature of the pyrolytic foaming agent in a kneading device such as a roll, extruded into a sheet shape, irradiated the resulting sheet with ionizing radiation, crosslinked the sheet, A method of producing a crosslinked foamed sheet by heating the foaming agent to a temperature equal to or higher than the decomposition temperature of the foaming agent to foam the sheet.

As the crosslinking aid, generally used polyfunctional monomers and monofunctional monomers are used. For example, divinylbenzene, trimethylolpropane trimethacrylate, 1,9-nonanediol dimethacrylate, 1,1 10-decanediol dimethacrylate, triallylic acid triallyl ester, triallyl isocyanurate, ethylvinylbenzene, neopentyl glycol dimethacrylate, 1,2,4-benzenetricarboxylic acid triallyl ester, 1,6-hexanediol dimethacrylate , Lauryl methacrylate, stearyl methacrylate and the like, which may be used alone or in combination.

When the amount of the crosslinking aid is small, the crosslinking density is insufficient and a uniform crosslinked foamed sheet may not be obtained. On the other hand, when the amount is large, the crosslinking density is increased and the moldability of the crosslinked foamed sheet is increased. May be reduced, so the amount is preferably 0.5 to 10 parts by weight, and more preferably 0.8 to 10 parts by weight based on 100 parts by weight of the total amount of the propylene resin (A) and the ethylene resin (A).
-6 parts by weight is more preferred.

The pyrolytic foaming agent is not particularly limited as long as it has been conventionally used in the production of foams. Examples thereof include azodicarbonamide, hydradodicarbonamide, barium azodicarboxylate, Nitrosoguanidine, p, p'-oxybisbenzenesulfonyl semicarbazide, benzenesulfonyl hydrazide, N,
N'-dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide, 4,4-oxybis (benzenesulfonyl hydrazide), azobisisobutyronitrile, and the like, among which the decomposition temperature is 180 to 270
C. is preferred.

The amount of the pyrolytic foaming agent to be added is appropriately adjusted according to the desired expansion ratio of the crosslinked foamed sheet. If the amount is large, the foam may be broken. Therefore, with respect to 100 parts by weight of the total amount of the propylene-based resin (A) and the ethylene-based resin (A), 3 to
It is preferably 40 parts by weight, more preferably 4 to 25 parts by weight.

The degree of crosslinking by ionizing radiation is as follows:
The gel fraction is adjusted as a guide, as the gel fraction,
If it is large, the moldability of the crosslinked foamed sheet may be reduced, and if it is small, the flexural strength of the crosslinked foamed sheet may be reduced, so that it is preferably 30 to 70% by weight, more preferably 40 to 65% by weight. %, And the ionizing radiation dose is usually 1 to 20 Mrad. The ionizing radiation is not particularly limited as long as it is conventionally used for crosslinking a foam, and examples thereof include α-rays, β-rays, γ-rays, and electron beams.

In the present invention, the gel fraction means a value measured by the following method. First, a predetermined amount of a crosslinked foamed sheet is weighed, immersed in 25 ml of xylene at 120 ° C. for 24 hours, filtered through a 200-mesh stainless steel wire mesh, and the insoluble matter on the wire mesh is vacuum-dried. next,
The weight of the vacuum-dried insoluble matter is weighed, and the gel fraction is calculated by the following formula. [Gel fraction (%)] = (weight of insoluble matter / weight of weighed crosslinked foam sheet) × 100

The antioxidant is not particularly limited as long as it is conventionally added to the crosslinked foamed sheet. For example, a phenolic antioxidant such as 2,6-di-t-butyl-p-cresol is used. Oxidizing agents, sulfur-based antioxidants such as dilaurylthiopropionate, phosphorus-based antioxidants, amine-based antioxidants and the like can be mentioned.

The metal damage inhibitor is not particularly limited as long as it has been conventionally added to a crosslinked foamed sheet, and examples thereof include methylbenzotriazole.

If the expansion ratio of the above-mentioned crosslinked foamed sheet is large, the mechanical strength of the crosslinked foamed sheet may be reduced, and if it is small, the lightness of the crosslinked foamed sheet may be reduced. 50 times is preferred, and 15 to 40
Double is more preferred. Incidentally, the expansion ratio in the present invention,
It refers to the volume of the crosslinked foamed sheet divided by its weight.

Next, a propylene-based resin layer is laminated and integrated on both sides of the crosslinked foamed sheet, and at least one of the skin layers further comprises a surface layer containing colored organic fibers. Are laminated and integrated.

The propylene resin constituting the propylene resin layer (hereinafter referred to as “propylene resin (B)”)
In addition to the homopropylene resin, those similar to the propylene-based resin (A) used in the crosslinked foamed sheet are used, and these may be used alone or in combination. And among these propylene-based resins (B),
From the viewpoint of excellent physical strength such as bending strength of the obtained laminated sheet, when used alone, homopropylene resin and block propylene resin, when used in combination, homopropylene resin and block propylene resin Combinations are preferred. And the propylene-based resin (B)
If the melting point of the high, the moldability of the resulting laminated sheet is reduced, whitening may occur on the surface during molding, and if it is low, the grain retention of the laminated sheet may decrease, 160-170 ° C is preferred. In addition,
In the present invention, the melting point refers to a peak temperature of a differential thermal analysis curve at a heating rate of 10 ° C./min.

As the homopropylene resin, an isotactic propylene resin having excellent mechanical strength, heat resistance and friction resistance is preferable. Examples of the block propylene resin include a propylene-α-olefin block copolymer containing propylene as a main component.
Examples of the olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like, with ethylene being preferred.

If the MI of the propylene-based resin (B) is large, the melt viscosity is reduced, making it difficult to form a sheet.
On the other hand, if it is small, molding distortion tends to remain when the laminated sheet is molded, and molding stability is reduced.
5 g / 10 min is preferred.

If necessary, a polyethylene resin (hereinafter referred to as "polyethylene resin (B)") or a low-melting propylene resin may be added to the propylene resin layer. Examples thereof include polyethylene such as low-density polyethylene, medium-density polyethylene, and high-density polyethylene, and the ethylene-α-olefin copolymer used in the polyethylene resin (A), and the ethylene content is 70% by weight. The above ethylene-α-olefin copolymer is preferred.

The low-melting-point propylene-based resin is not particularly limited as long as it has a melting point lower than that of the propylene-based resin (B). For example, a propylene-α-olefin random copolymer, propylene -Ethylene-butene terpolymer and the like;
Examples of the olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like, with ethylene being preferred.

When the content of the α-olefin of the low melting point propylene resin is large, the heat resistance of the propylene resin layer is lowered and the grain retention is lowered. When the content is small, the laminated sheet is formed. In this case, the surface may be whitened, so that the content is preferably 2 to 10% by weight.

If the melting point of the low melting point propylene resin is high, whitening may occur on the surface of the laminated sheet when the laminated sheet is formed, and if the melting point is low, the heat resistance of the laminated sheet is reduced and the molding stability is lowered. May decrease, so that 125 to 1
50 ° C. is preferred.

The MI of the low-melting-point propylene-based resin is set to 0. 1 for the same reason as in the case of the propylene-based resin (B).
3-15 g / 10 min is preferred.

When the content of the low-melting-point propylene-based resin in the propylene-based resin layer is large, the heat resistance of the propylene-based resin layer is reduced, and the grain retention of the laminated sheet may be reduced. And, the stress relaxation property of the obtained laminated sheet is reduced, or the sheet is deformed at a high temperature during molding, or, when highly stretched during secondary processing, the surface of the obtained molded article is whitened, Since the surface properties may decrease,
1 to 5 with respect to 100 parts by weight of the propylene-based resin (B)
0 parts by weight is preferred.

Further, an inorganic filler may be added to the propylene-based resin layer in order to improve the strength of the obtained laminated sheet, and the form may be any of powder, balun, and fiber. The inorganic filler is not particularly limited.Examples of the powdery inorganic filler include, for example, calcium carbonate, talc, kaolin clay, mica, and titanium oxide.Examples of the balun-like inorganic filler include, for example, white balun, glass balun, and fly ash. Examples of the fibrous inorganic filler include glass fibers and whiskers. Among these inorganic fillers, calcium carbonate, talc, and mica are preferred, and talc and mica are more preferred, from the viewpoint that the effect of improving rigidity with respect to the resin is large and the obtained laminated sheet has excellent molding stability.

The larger the size of the inorganic filler, the lower the low-temperature impact strength of the laminated sheet, so that the particle size or fiber diameter is preferably 20 μm or less.

When the content of the inorganic filler in the propylene-based resin layer is large, the lightness of the obtained laminated sheet is reduced, and when the content is small, the rigidity of the laminated sheet is reduced.
1 to 5 with respect to 100 parts by weight of the propylene-based resin (B)
0 parts by weight is preferred.

In the laminated sheet of the present invention, a surface layer containing colored organic fibers is further laminated and integrated on at least one of the propylene resin layers, and this surface layer is laminated and integrated. As a result, the surface of the obtained laminated sheet has a nonwoven fabric appearance.

As the resin constituting the surface layer containing the colored organic fiber, the same resin as the propylene-based resin (B) is used. As the colored organic fiber contained in the surface layer, the propylene-based resin is used. It is not particularly limited as long as it has a softening point higher than the softening point of the resin (A) or the propylene resin (B), and natural fibers such as cotton, silk, wool, and cannabis, polyester, polyamide, polyvinyl alcohol, Regenerated fibers such as polyacetal, polyurethane, acrylic, aramid-based synthetic fibers, rayon, cupra, polynosic, etc. may be mentioned. These organic fibers need to be colored in order to obtain a nonwoven fabric feeling on the obtained laminated sheet surface. It is. Then, the degree of coloring of the organic fibers, that is, the color tone, may be any as long as the nonwoven fabric feeling can be expressed, and it is preferable to make the color tone conspicuous to the color tone of the surface layer containing the colored organic fibers, A plurality of fibers having different colors may be used in combination.

If the fineness of the organic fiber is large, the extrudability of the resin may be reduced during the production of a laminated sheet.
If it is small, the resulting laminated sheet surface may not be able to exhibit a nonwoven fabric appearance,
Denier is preferred.

If the fiber length of the organic fiber is long, the extrudability of the resin may be reduced during the production of the laminated sheet.
If the length is too short, the resulting laminated sheet surface may not be able to exhibit a nonwoven fabric appearance.
m is preferred.

If the content of the organic fiber in the resin layer is large, the extrudability of the resin may be reduced. If the content is small, a nonwoven fabric appearance cannot be exhibited on the surface of the obtained laminated sheet. 0.1 to 4% by weight
Is preferred.

Next, a method for manufacturing a laminated sheet will be described. The method for manufacturing a laminated sheet in which the surface layer is laminated and integrated only on one of the propylene-based resin layers laminated and integrated on both sides of the crosslinked foamed sheet includes, for example, (1) one surface of the crosslinked foamed sheet. While the propylene-based resin layer is laminated and integrated by extrusion lamination, a propylene-based resin constituting the propylene-based resin layer and a resin containing colored organic fibers constituting the surface layer are co-extruded on the other surface of the crosslinked foamed sheet. A method of laminating a sheet-like molten resin obtained by laminating and integrating the obtained propylene-based resin layer and the surface layer such that the propylene-based resin layer is on the crosslinked foamed sheet side; The propylene resin constituting the propylene resin layer is laminated by extrusion lamination on one side of a crosslinked foamed sheet made of a resin and an ethylene resin. A propylene-based resin layer and a surface layer obtained by co-extruding a propylene-based resin constituting a propylene-based resin layer and a resin containing colored organic fibers constituting a surface layer while forming a two-layer laminate by integration. A three-layer laminate is formed by laminating a sheet-like molten resin obtained by laminating and integrating a sheet on one surface of a crosslinked foamed sheet made of a propylene-based resin and an ethylene-based resin so that the propylene-based resin layer is on the crosslinked foamed sheet side. And a method in which the crosslinked foamed sheets of the obtained two-layer laminate and three-layer laminate are heat-fused with each other to integrate the two-layer laminate and the three-layer laminate.

A method for producing a laminated sheet in which the surface layer is laminated and integrated on both of the propylene-based resin layers laminated and integrated on both sides of the crosslinked foamed sheet is as follows.
For example, a propylene-based resin constituting the propylene-based resin layer and a resin containing colored organic fibers constituting the surface layer are co-extruded, and the obtained propylene-based resin layer and the surface layer are laminated and integrated to form a sheet. The molten resin is laminated and integrated on one surface of a crosslinked foamed sheet made of a propylene-based resin and an ethylene-based resin by lamination such that the propylene-based resin layer is on the crosslinked foamed sheet side, and the one side of the crosslinked foamed sheet is A propylene-based resin layer and a surface layer are laminated and integrated in this order to form two three-layer laminates, and the crosslinked foamed sheets of the obtained three-layer laminate are thermally fused to each other to form a three-layer laminate. A method of integrating the laminates and the like can be given.

The thickness of the laminated sheet is preferably from 1 to 10 mm, because if it is thick, lightness may be reduced, and if it is thin, mechanical strength such as bending strength may be reduced. The thickness of the propylene-based resin layer laminated on both sides of the cross-linked foam sheet, for the same reason as the laminate,
0.1-1 mm is preferred. The thickness of the surface layer containing the colored organic fibers is preferably 0.01 to 1 mm.

The ratio of the thickness of the propylene-based resin layer laminated on the crosslinked foamed sheet to the thickness of the surface layer containing the colored organic fibers is such that if the thickness ratio of the surface layer is high, they can be co-extruded and integrated. The uniformity of the sheet-like molten resin thickness obtained by reducing the spreadability of the molten resin is impaired, and, if low,
Since the nonwoven fabric appearance may not be exhibited on the surface of the obtained laminated sheet, the thickness ratio of the surface layer is 50% of the total thickness of the propylene-based resin layer and the surface layer containing the colored organic fiber.
% Or less is preferable.

Finally, the surface layer containing the colored organic fibers may be subjected to graining. In this way, when the surface layer surface is subjected to graining, a more excellent nonwoven fabric appearance can be obtained due to a synergistic effect of the colored organic fiber and the graining.

[0053]

EXAMPLES In Examples 1 to 7 and Comparative Examples 1 and 2,
The compounds shown below were used. However, the elution amount is the amount eluted at 94 ° C. or higher by the cross fractionation method, and the elution amount is the resin component eluted at 94 ° C. or higher by the cross separation method.

Propylene resin (A) PE copolymer 1; MI = 2 g / 10 min, elution amount = 75
Propylene-ethylene random copolymer whose weight-average molecular weight is 3.4 × 10 ⁵ , molecular weight distribution is 4.5, and ethylene content is 3.2% by weight.

PE copolymer 2: MI = 0.5 g / 10
Min, elution amount = 75% by weight, weight-average molecular weight of elution portion =
Propylene-ethylene random copolymer having 4.5 × 10 ⁵ , molecular weight distribution = 4.6, ethylene content = 3.2% by weight

PE copolymer 3: MI = 1.8 g / 10
Min, elution amount = 45% by weight, weight-average molecular weight of elution portion =
Propylene-ethylene random copolymer having 3.6 × 10 ⁵ , molecular weight distribution = 4.5 and ethylene content = 3.8% by weight

Ethylene resin (A) LLDPE1; density = 0.917 g / cm ³ , MI =
2.5 g / 10 min, elution amount = 6.8% by weight, weight average molecular weight of eluted portion = 2.3 × 10 ⁵ , ethylene content = 85
% By weight of ethylene-1-octene copolymer

LLDPE2; density = 0.920 g / cm
³ , MI = 2 g / 10 min, elution amount = 7% by weight, weight average molecular weight of eluted portion = 2.5 × 10 ⁵ , ethylene content = 8
5% by weight of ethylene-1-octene copolymer

LLDPE3; density = 0.920 g / cm
³ , MI = 2 g / 10 min, elution amount = 7% by weight, weight average molecular weight of eluted portion = 2.3 × 10 ⁵ , ethylene content = 8
5% by weight of ethylene-1-octene copolymer

LLDPE4; density = 0.916 g / cm
³ , an ethylene-1-octene copolymer having MI = 10 g / 10 min, elution amount = 5.5% by weight, weight average molecular weight of the elution portion = 1.3 × 10 ⁵ = ethylene content = 85% by weight

Propylene resin (B) PE copolymer 4; MI = 4 g / 10 min, melting point = 16
Propylene-ethylene block copolymer at 6.7 ° C

Fiber Masterbatch PE copolymer 4 85% by weight and brown and blue colored rayon fibers (denier 15 denier, fiber length 0.5 mm,
1: 1) 15% by weight of blue fiber and brown fiber
Fiber master batch consisting of

Pigment masterbatch Light gray pigment masterbatch based on low density polyethylene

(Examples 1 to 6) A predetermined amount of P shown in Table 1
-E copolymers 1-3, LLDPE 1-4, trimethylolpropane trimethacrylate, azodicarbonamide, 2,6-di-t-butyl-p-cresol, dilaurylthiopropionate and methylbenzotriazole, After melt-kneading at 190 ° C. with a screw extruder, a foamable resin sheet having a thickness of 1.0 mm was continuously extruded.

Next, one side of the obtained foamable resin sheet was irradiated with 3 Mrad of electron beam having an accelerating voltage of 800 kV to crosslink, and then foamed into a vertical foaming furnace maintained at 250 ° C. by hot air and an infrared heater. The expandable resin sheet was continuously supplied to expand the expandable resin sheet to obtain a crosslinked foam sheet. In addition, the thickness of the obtained crosslinked foamed sheet is 2 m.
m, the expansion ratio was 20 times, and the gel fraction was as shown in Table 1.

Next, the P-
E copolymer 4 and PE copolymer 4 constituting the surface layer
A resin consisting of 86% by weight, 10% by weight of a fiber masterbatch and 4% by weight of a pigment masterbatch is coextruded, and the obtained propylene-based resin layer and the surface layer are laminated and integrated into a sheet-like molten resin. A propylene-based resin layer made of a 0.2 mm thick PE copolymer 4 is laminated on one surface of the crosslinked foamed sheet by laminating the propylene-based resin layer on one surface of the crosslinked foamed sheet so as to be on the crosslinked foamed sheet side. And a surface layer containing a colored organic fiber having a thickness of 0.1 mm in this order to obtain a three-layer laminate (hereinafter, referred to as “laminate A”). When laminating the sheet-like molten resin on one surface of the crosslinked foamed sheet, the surface layer surface was subjected to texturing using a paper roll.

On the other hand, on one surface of the separately prepared crosslinked foamed sheet, a PE copolymer 4 constituting a propylene resin layer melt-kneaded at a resin temperature of 210 ° C. by a twin screw extruder was 0.3 mm thick. Extrusion lamination to form a two-layer laminate (hereinafter referred to as “laminate B”) having a thickness of 2.3 mm in which a propylene-based resin layer having a thickness of 0.3 mm is laminated on one surface of a crosslinked foamed sheet. Obtained.

The crosslinked foamed sheets of the laminates A and B obtained as described above were heated to 130 ° C., and then the crosslinked foamed sheets of the laminates A and B were pressed and thermally fused. Then, the laminate A and the laminate B are integrated to have a thickness of 4.6.
mm laminated sheet was obtained.

The appearance and bending strength of the obtained laminated sheet were measured by the following methods, and the results are shown in Table 2.

(Appearance) When the surface of the surface layer containing the colored organic fibers laminated on one surface of the laminated sheet was visually observed, in any of Examples 1 to 6, the feeling of nonwoven fabric appeared on the surface. It was excellent in appearance.

(Bending strength) The bending strength of the obtained laminated sheet was measured in accordance with JIS K7171. However, the size of the sample piece was 50 × 150 mm, the load speed was 50 mm / min, and the measurement temperature was 80 ° C.

(Example 7) A laminated sheet was obtained in the same manner as in Example 1 except that the irradiation amount of the electron beam to the foamable resin sheet was 1.5 Mrad. The appearance and bending strength of the obtained laminated sheet were measured in the same manner as in Example 1, and the results are shown in Table 2.

(Comparative Example 1) A resin comprising 96% by weight of a PE copolymer and 4% by weight of a pigment masterbatch was extrusion-laminated on one surface of the crosslinked foamed sheet obtained in Example 1, whereby A two-layer laminate (hereinafter, referred to as “laminate C”) was obtained in which a resin layer having a thickness of 0.3 mm was laminated and integrated on one surface of the crosslinked foamed sheet.

The crosslinked foamed sheets of the obtained laminate C and the laminate B obtained in Example 1 were heated to 130 ° C.
The crosslinked foamed sheets of the laminate C and the laminate B were pressure-bonded to each other and thermally fused to integrate the laminate C and the laminate B to obtain a laminate sheet having a thickness of 4.6 mm. The appearance and bending strength of the obtained laminated sheet were measured in the same manner as in Example 1, and the results are shown in Table 2. In addition, the appearance of the laminated sheet was inferior to the appearance, in which the nonwoven fabric feeling was not expressed on the surface.

Comparative Example 2 A resin comprising 486% by weight of a PE copolymer, 10% by weight of a fiber masterbatch and 4% by weight of a pigment masterbatch was coated on one surface of the crosslinked foamed sheet obtained in Example 1. By extrusion lamination, a two-layer laminate (hereinafter, referred to as “laminate D”) was obtained in which a 0.3 mm-thick resin layer containing colored organic fibers was laminated and integrated on one surface of the crosslinked foamed sheet. .

The crosslinked foamed sheets of the obtained laminate D and the laminate B obtained in Example 1 were heated to 130 ° C.
The crosslinked foamed sheets of the laminate D and the laminate B were pressure-bonded to each other and thermally fused to integrate the laminate D and the laminate B to obtain a laminate sheet having a thickness of 4.6 mm. The appearance and bending strength of the obtained laminated sheet were measured in the same manner as in Example 1, and the results are shown in Table 2. In addition, the appearance of the laminated sheet was inferior to the appearance of the crosslinked foamed sheet because a part of the surface layer was transparent, although a feeling of nonwoven fabric was expressed on the surface. .

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

As described above, the laminated sheet of the present invention is excellent in light weight since the center portion is made of a crosslinked foamed sheet, and at least a propylene resin layer is integrally laminated on both sides of the crosslinked foamed sheet. Also, its mechanical strength is excellent.

Further, since a surface layer containing colored organic fibers is laminated on at least one of the propylene-based resin layers, the surface exhibits an excellent nonwoven fabric appearance, It is also excellent.

Claims (4)

[Claims] 1. A propylene resin layer is integrally laminated on both sides of a cross-linked foamed sheet made of a propylene resin and an ethylene resin, and at least one of the propylene resin layers further has a color. A laminated sheet, wherein a surface layer containing organic fibers is laminated and integrated. 2. The crosslinked foamed sheet has a melt index of 0.2 to 10 g / 10 min.
50-90% by weight of a propylene-α-olefin copolymer having a weight-average molecular weight of 2 × 10 ⁵ to 10 × 10 ⁵ at 50 ° C. or more and a melt index of 0.5 to 95% by weight. Ethylene-α-olefin copolymer having an eluted amount of 5 to 20% by weight at 94 ° C. or higher and a weight-average molecular weight of 1.5 × 10 ⁵ to 10 × 10 ⁵ at 10 g / 10 min. What is obtained by crosslinking and foaming a foamable resin sheet composed of 100 parts by weight of a resin component consisting of 50 to 10% by weight, 0.5 to 10 parts by weight of a crosslinking aid, and 3 to 40 parts by weight of a pyrolytic foaming agent. The laminated sheet according to claim 1, wherein: 3. A cross-linked foamed sheet made of a propylene-based resin and an ethylene-based resin, a propylene-based resin constituting a propylene-based resin layer is laminated and integrated by extrusion lamination on one surface of the cross-linked foamed sheet, and a propylene-based resin layer is formed on one surface of the cross-linked foamed sheet. To form a two-layer laminate in which the propylene resin constituting the propylene resin layer and the resin containing the colored organic fibers constituting the surface layer are co-extruded to obtain a propylene resin. A sheet-like molten resin in which a layer and a surface layer are laminated and integrated, on one surface of a crosslinked foamed sheet made of a propylene-based resin and an ethylene-based resin,
A three-layer laminate in which the propylene-based resin layer is laminated and integrated so that the propylene-based resin layer is on the crosslinked foamed sheet side, and the propylene-based resin layer and the surface layer are laminated and integrated in this order on one surface of the crosslinked foamed sheet. Forming a body, heat-fusing the crosslinked foamed sheets of the obtained two-layer laminate and three-layer laminate, and integrating the two-layer laminate and the three-layer laminate. The method for producing a laminated sheet according to claim 1. 4. A propylene-based resin constituting a propylene-based resin layer and a resin containing colored organic fibers constituting a surface layer are coextruded, and the obtained propylene-based resin layer and the surface layer are laminated and integrated. The sheet-like molten resin is laminated and integrated with one surface of a crosslinked foamed sheet made of a propylene-based resin and an ethylene-based resin by lamination such that the propylene-based resin layer is on the crosslinked foamed sheet side. A three-layer laminate in which the propylene-based resin layer and the surface layer are laminated and integrated in this order on one surface is 2
3. The laminate according to claim 1, wherein the crosslinked foamed sheets of the obtained three-layer laminate are heat-sealed with each other to integrate the three-layer laminate with each other. 4. Sheet manufacturing method.