JP2000190437A - Laminated sheet and interior finishing material for automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a balance between rigidity and lightweight properties by forming a laminated sheet adapted to an interior finishing material for an automobile such as a ceiling material, a trunk mat material or the like of a specific foamed sheet made of a polypropylene resin and a nonwoven fabric. SOLUTION: The laminated sheet is formed of a foamed sheet made of a polypropylene resin and having an expansion ratio χ of 2 to 10 times, a foam size of 300 μm or below and a thickness(h) of a formula of (100/E(1-(1-1/χ)2/3)1/3<=h<=2, and a nonwoven fabric, wherein E is a bending elastic modulus of an unfoamed resin for constituting the foamed sheet. The used polypropylene resin contains a crystalline polymer component obtained by polymerizing a sole propylene, a propylene, ethylene and/or 4-14C α-olefin and having a limiting viscosity of 5 dl/g or above and a crystalline polymer component obtained by polymerizing a sole propylene, a propylene, ethylene and/or 4-14C α-olefin and having a limiting viscosity of less than 3 dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminated sheet. More specifically, the present invention relates to a laminated sheet comprising a specific foamed sheet made of a polypropylene resin and a nonwoven fabric, and having an excellent balance between rigidity and lightness.

[0002]

2. Description of the Related Art JP-A-56-104054 discloses that
A laminated sheet formed by welding a polyolefin resin foamed sheet (base material) having high rigidity, a thickness of 1.0 to 10.0 mm, an apparent density of 0.25 g / cc or more, and a nonwoven fabric is described. It is described that the main raw material of the base material is a homopolymer or copolymer of propylene, high-density polyethylene or a mixture thereof.

[0003]

However, although the laminated sheet described in the above publication has good rigidity, it does not have a good balance between rigidity and lightness, so that it is used as an interior material for automobiles, for example. Not satisfactory. An object of the present invention is to provide a laminated sheet excellent in balance between rigidity and lightness, particularly suitable for an automobile interior material, and an automobile interior material comprising the same.

[0004]

Means for Solving the Problems The present inventors have intensively studied a laminated sheet excellent in balance between rigidity and lightness, which is particularly suitable for interior materials for automobiles. As a result, the present inventors have found that a laminated sheet composed of a specific polypropylene resin, a foamed sheet having a high expansion ratio and having fine cells and a nonwoven fabric, provides a laminated sheet having an excellent balance between rigidity and lightness. Was completed. That is, the present invention provides a laminate comprising a foamed sheet made of a polypropylene resin, having an expansion ratio (χ) of 2 to 10 times, a cell diameter of 300 μm or less, and a thickness h (cm) satisfying the following formula (1); The present invention relates to a sheet and an interior material for automobiles comprising the laminated sheet. (100 / E (1− (1-1 / χ) ^2/3 )) ^1/3 ≦ h ≦ 2 (1) (In the formula (1), E is the flexural modulus of the unfoamed resin constituting the foamed sheet. (Kgf / cm ² )) The present invention will be described in more detail below.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION "Polypropylene resin" used in the present invention means a resin having a polypropylene crystal structure, preferably a thermoplastic crystalline homopolymer resin of propylene, or propylene and ethylene and / or carbon A thermoplastic crystalline copolymer resin with an α-olefin having 4 to 12 atoms, wherein the content of a repeating unit derived from ethylene in the copolymer resin is 10% by weight.
Or less, wherein the content of the repeating unit derived from an α-olefin is 30% by weight or less. Here, ethylene, 1-butene, 4-methylpentene-1, 1-
When the content of the repeating unit derived from an α-olefin exemplified by octene and 1-hexene does not satisfy the above range, the resulting crystalline copolymer resin may have insufficient crystallinity.

The melt index of the preferred polypropylene resin used in the present invention (hereinafter referred to as MI)
Is 2 to 20 g / 10 min, the die swell ratio (hereinafter, referred to as SR) is 1.7 or more, and preferable polypropylene resins are (i) long-chain branched PP, (ii) PP containing a high intrinsic viscosity component, and (Iii) A mixture of the above (i) and (ii) can be exemplified.

[0007] The term "long-chain branched PP" means a polypropylene resin having a long-chain branch. As a long-chain branched PP,
Examples thereof include polypropylene resins described in JP-A-62-121704. As a commercially available long-chain branched PP, a high melt strength polypropylene resin manufactured and sold by Montell Corporation (High Melt Strength
Polypropylene (HMS-PP for short) homopolymer of propylene (grade name: PF814, MI = 3)
g / 10 min, SR = 2.36) or a copolymer of propylene and ethylene (grade name: SD632, MI = 3)
g / 10 minutes, SR = 2.16).

[0008] The "high intrinsic viscosity component-containing PP" refers to a crystal having an intrinsic viscosity of 5 dl / g or more obtained by polymerizing propylene alone or propylene with ethylene and / or an α-olefin having 4 to 12 carbon atoms. Crystalline polymer component (A) and propylene alone or a crystalline polymer component having an intrinsic viscosity of less than 3 dl / g obtained by polymerizing propylene with ethylene and / or an α-olefin having 4 to 12 carbon atoms ( B), having an intrinsic viscosity of 3 dl / g
Less than weight average molecular weight (Mw) and number average molecular weight (Mn)
(Mw / Mn) is less than 10, and the content of the polymer component (A) is 0.05% by weight or more and less than 35% by weight. Here, a monomer composition constituting the crystalline polymer component (A) (hereinafter, simply referred to as “polymer component (A)”) and a crystalline polymer component (B) (hereinafter, simply referred to as “polymer component (B)”) ))) May be the same or different.

Polymer component (A) and polymer component (B)
Are each independently a homopolymer of propylene; the content of the repeating unit derived from ethylene is 10% by weight.
The following is a random copolymer of ethylene and propylene; the following is a random copolymer of propylene and 1-butene whose content of a repeating unit derived from 1-butene is 30% by weight or less; or A random copolymer of ethylene, propylene and 1-butene, wherein the content of the repeating unit is 10% by weight or less and the content of the repeating unit derived from 1-butene is 30% by weight or less. Is preferred.

As a method for producing a PP containing a high intrinsic viscosity component, in the first step, propylene alone or propylene is polymerized with ethylene and / or an α-olefin having 4 to 12 carbon atoms to have an intrinsic viscosity of 5 dl / g. The above polymer component (A) is produced, and subsequently, in the second step, propylene alone or propylene and ethylene and / or α-C 4 -C 12 in the presence of the polymer component (A). A production method of polymerizing an olefin to produce a polymer component (B) having an intrinsic viscosity of less than 3 dl / g (hereinafter, referred to as “continuous polymerization method”) can be exemplified.

[0011] The continuous polymerization method may be a batch production method or a continuous production method. Examples of the batch production method include a method of producing the polymer component (A) and the polymer component (B) in, for example, the same polymerization tank. Further, as a continuous production method, a polymer component (A) is continuously produced in a first polymerization vessel of two polymerization vessels arranged in series, and is continuously transferred to a second polymerization vessel. And a method for continuously producing the polymer component (B) in the second polymerization tank. The number of polymerization tanks in the continuous production method may be three or more.

As another method for producing a PP containing a high intrinsic viscosity component, there is a method of mixing a polymer component (A) and a polymer component (B) which are separately produced (hereinafter, referred to as a “mixing method”). It can also be illustrated. From the viewpoint of obtaining a high intrinsic viscosity component-containing PP having a high melt strength, the continuous polymerization method is preferred.

The intrinsic viscosity of the polymer component (A) is preferably 6 dl / g or more, and more preferably 7 dl / g, from the viewpoint that a better foamed sheet can be obtained by using a high intrinsic viscosity component-containing PP having a high melt strength. g or more is more preferable. Further, the content of the polymer component (A) in the high intrinsic viscosity component-containing PP is preferably such that the use of the high intrinsic viscosity component-containing PP having high melt strength can provide a better foamed sheet.
0.3% by weight or more is preferable, and PP containing a high intrinsic viscosity component
From the viewpoint of the elongation characteristics of the rubber, it is preferably at most 20% by weight. The content of the polymer component (A) in the case of producing a high intrinsic viscosity component-containing PP by a continuous polymerization method can be controlled by appropriately setting the production conditions of the polymer component (A).

The intrinsic viscosity [η] _A (d) of the polymer component (A)
l / g) and the content W _A (% by weight) of the polymer component (A).
From the viewpoint of obtaining a high intrinsic viscosity component-containing PP having high melt strength, it is preferable to satisfy the following expression (2). W _A ≧ 400 × EXP (−0.6 × [η] _A ) (2)

From the viewpoint of the flowability and processability of the PP containing the high intrinsic viscosity component, the intrinsic viscosity of the polymer component (B) is 3 dl /
g and the intrinsic viscosity of the high intrinsic viscosity component-containing PP is 3
less than dl / g, Mw /
Mn is less than 10 from the viewpoint of the appearance of the foam sheet. The intrinsic viscosity of the polymer component (B) when producing a high intrinsic viscosity component-containing PP by a continuous polymerization method is as follows:
Can be controlled by appropriately setting the production conditions. The intrinsic viscosity of the polymer component (B) is, as described later, the intrinsic viscosity of the high intrinsic viscosity component-containing PP, the intrinsic viscosity and the content of the polymer component (A), and the content of the polymer component (B). From this, it can be obtained by calculation.

The high intrinsic viscosity component-containing PP can be produced, for example, by using an olefin polymerization catalyst containing titanium (Ti), magnesium (Mg) and halogen as essential components. Kaiping 0
The catalyst described in JP-A-7-216017 can be exemplified.

As a specific polymerization catalyst for producing a PP containing a high intrinsic viscosity component, the following (a) a solid catalyst component:
Examples of the catalyst include (b) an organoaluminum compound and (c) an electron-donating compound.

(A) Solid Catalyst Component As a solid catalyst component, an alkoxysilane compound represented by the formula Si (OR ₁ ) _m (R ₂ ) _4-m (wherein R ₁ and R _{2 each} have 1 carbon atom) And an organosilicon compound having a Si—O bond, wherein
In the presence of an ester compound, the compound of formula Ti (OR ₃ ) _a X _4-a
(Wherein, R ₃ is a hydrocarbon group having 1 to 20 carbon atoms, X
Is a halogen atom, a is 0 <a ≦ 4, preferably 2
≦ a ≦ 4, particularly preferably a = 4) is reduced with an organomagnesium compound to obtain a solid product, and the solid product is treated with an ester compound. A trivalent titanium compound-containing solid catalyst component obtained by treating the treated product with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound is preferred.

Here, as the alkoxysilane compound, m
= 4 tetraalkoxysilane compounds are particularly preferred;
Examples of the ester compound include mono- and polyvalent carboxylate esters, and among them, unsaturated aliphatic carboxylate esters such as methacrylate esters and maleate esters, and aromatic phthalate esters. Carboxylic acid esters are preferred, and diesters of phthalic acid are particularly preferred; Grignard compounds, dialkylmagnesium compounds and diarylmagnesium compounds are particularly preferred as organomagnesium compounds; dialkylethers, especially dibutylether and diisoamylether, are preferred as ether compounds.

(B) Organoaluminum Compound Preferred examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, and tetraethyldialumoxane.

(C) Electron-donating compound As a preferred electron-donating compound, tert-butyl-
Examples thereof include n-propyldimethoxysilane, tert-butylethyldimethoxysilane, and dicyclopentyldimethoxysilane.

With respect to the general use amounts of the components (a) to (c), the Al atom in the component (b) and the T in the component (a)
The molar ratio (Al / Ti) to the i atom is 1 to 2000, preferably 5 to 1500, and the molar ratio of the component (c) to the Al atom in the component (b) (electron donating compound / Al atom).
Is from 0.02 to 500, preferably from 0.05 to 50.

As the production method (polymerization method) of the polymer components (A) and (B), hexane, heptane, octane,
Solvent polymerization using a hydrocarbon typically represented by decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene as an inert solvent; bulk polymerization using a liquid monomer as a solvent; polymerization in a gaseous monomer A gas phase polymerization method; or a polymerization method comprising a combination thereof can be exemplified. From the viewpoint of high polymerization activity and ease of post-polymerization treatment, a bulk polymerization method, a gas phase polymerization method, or a polymerization method comprising a combination thereof is preferred.

In the method for producing the polymer components (A) and (B), the production efficiency of these polymer components and the reduction of coloring and heat resistance which are considered to be caused by the catalyst remaining in these polymer components are considered. From the viewpoint of suppression, the polymerization rate (catalytic activity) is preferably higher. As a polymerization catalyst for producing the polymer component (A), for example, 1 g of a solid catalyst component,
The amount of the polymer component (A) produced per one hour of the polymerization time is 2
It is preferable to select a polymerization catalyst having a weight of 000 g or more. As the polymerization catalyst for producing the polymer component (B), a solid catalyst is preferred from the viewpoint of production efficiency and easy production of a PP containing a high intrinsic viscosity component. The amount of the polymer component (B) produced per 1 g of the catalyst component and one hour of the polymerization time is preferably twice or more (4000 g or more) that of the polymer component (A), more preferably three times or more. preferable.

The temperature (polymerization temperature) for producing the polymer component (A) and the temperature (polymerization temperature) for producing the polymer component (B) may be the same or different. The temperature usually ranges from about 20 to about 150C, preferably from about 35 to about 95C.

The resulting PP with a high intrinsic viscosity component may be subjected to post-treatments such as deactivation of a catalyst, desolvation, demonomerization, drying and granulation, if necessary.

When a mixture of long-chain branched PP and high intrinsic viscosity component-containing PP is used as the polypropylene resin used in the present invention, the MI of the mixture is 2 to 20 g / 10
Therefore, it is preferable that SR is 1.7 or more.

The polypropylene resin used in the present invention may be any other resin, a primary antioxidant, a secondary antioxidant, an ultraviolet absorber, or the like, as long as the effects of the present invention are not impaired.
It may be used as a composition obtained by combining with various additives exemplified by an antistatic agent, a pigment, and a filler.

The other resin has a density of 0.93 g.
/ Cm ² or less low density polyethylene (density is 0.91 g
/ Cm ² or less ultra low density polyethylene (ULDPE), medium density polyethylene, density 0.94g / cm
Examples thereof include ^two or more high-density polyethylenes, copolymers of ethylene and α-olefin, and copolymers of ethylene and vinyl acetate, with low-density polyethylene being preferred.

When a composition in which a polypropylene resin is combined with another resin or an additive is used, the polypropylene resin constituting the composition is preferably a main component,
The mixing ratio of the polypropylene resin is usually 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, from the viewpoint of the rigidity and heat resistance of the obtained foamed sheet.

The expansion ratio (χ) of the foam sheet used in the present invention is 2 to 10 times. If the expansion ratio is less than 2 times, it is not preferable from the viewpoint of the lightness of the laminated sheet of the present invention, and from the viewpoint of obtaining a laminated sheet having excellent lightness,
The expansion ratio is preferably 4 times or more, more preferably 6 times or more. When the expansion ratio is more than 10 times, there is often no advantage justified by increasing the expansion ratio. Therefore, the expansion ratio is usually 10 times or less. The expansion ratio can be controlled by adjusting the amount of a foaming agent or a foaming gas to be injected, which will be described later. Here, the “expansion ratio” is a ratio of the density of an unfoamed body (resin that has not been foamed) to the density of a foamed body (resin that has been foamed).
It is obtained by measurement according to the underwater displacement method (Method A) in accordance with IS K 7112.

The bubble diameter of the foam sheet used in the present invention is 300 μm or less, preferably 250 μm or less. A foam sheet having a bubble diameter larger than 300 μm makes it easier for dust, dirt, moisture, etc. to enter the end face of the foam sheet constituting the laminated sheet, or a ruled line processed product obtained by applying a ruled line processing described later to the laminated sheet. It is not preferable because the hinge property of the ruled line portion is inferior, and a thermoformed product obtained by subjecting the laminated sheet to thermoforming such as vacuum forming may have poor appearance such as blemishes.
The lower limit of the bubble diameter is not particularly limited, and the finer the bubble diameter, the better.

The thickness h of the foam sheet used in the present invention
(Cm) satisfies the expression (1) from the viewpoint of the balance between the lightness and rigidity of the laminated sheet. E in the formula (1) is a flexural modulus of the resin (unfoamed resin) constituting the foamed sheet, and the flexural modulus is usually 10,000 to 20,000.
kgf / cm ² .

The foamed sheet and nonwoven fabric used in the present invention
The lightness of such a sheet-like object depends on the unit area of the sheet-like object.
The weight of the set, that is, the basis weight (g / m^Two)
The smaller the basis weight, the lighter the sheet
Indicates that Weight of foam sheet used in the present invention
Is 2000g / m^TwoThe following is preferable, and 1000 g / m ^Two
Below is more preferred.

The rigidity of the sheet can be evaluated by the bending elastic gradient. Here, the bending elastic gradient is JIS K
It is measured according to the bending test of No. 7203, and represents a load when a sheet-like material having a width of 1 cm causes a deflection of 1 cm. The greater the bending elastic gradient, the higher the rigidity of the sheet. The bending elastic gradient of the foamed sheet used in the present invention is preferably 0.4 kgf / cm · 1 cm width or more, more preferably 1.0 kgf / cm · 1 cm width or more, and even more preferably 1.5 kgf / cm · 1 cm width. .

If the thickness of the foamed sheet is out of the range of the formula (1), it is difficult to obtain a laminated sheet excellent in balance between lightness and rigidity. That is, the laminated sheet is light in weight but inferior in rigidity, and conversely, the laminated sheet is excellent in rigidity but inferior in light weight. From the viewpoint of lightness, a more preferable thickness is 1 cm or less.

For a foamed sheet satisfying the thickness h (cm) of the formula (1), the elastic modulus of the resin for producing the foamed sheet is measured in advance, the amount of the foaming agent or the foaming gas is adjusted, and described later. It can be obtained by adjusting the lip gap at the die tip of the extruder.

The method for producing the foamed sheet used in the present invention is not particularly limited. For example, a known extrusion foaming method, that is, a mixture of a resin for producing a foamed sheet and a pyrolytic foaming agent is used as a raw material inlet. (Hopper), causing the resin to melt in the extruder and generating gas due to the decomposition of the foaming agent. The molten resin and gas are sufficiently kneaded and homogenized, and the homogenized mixture is foamed. After cooling to a suitable temperature, the mixture can be extruded from a die, foamed, cooled by a take-off machine and formed into a foamed sheet. As a gas for foaming, an inert gas such as nitrogen gas or carbon dioxide gas may be used instead of the thermal decomposition type foaming agent (the inert gas is directly injected into the extruder). You may use together with an inert gas.

From the viewpoint that a foam sheet having a fine cell diameter can be obtained, it is preferable to use a mixed gas of nitrogen gas and carbon dioxide gas as the foaming gas. In this case, for example, a mixed gas of nitrogen gas and carbon dioxide gas is used. Examples of the method include directly injecting a gas into an extruder, and a method using a pyrolytic blowing agent that mainly generates nitrogen gas by decomposition and a pyrolytic blowing agent that mainly generates carbon dioxide gas by decomposition. . When two or more thermal decomposition type foaming agents are used in combination, these foaming agents may be used separately, or a foaming agent (composite foaming agent) obtained by mixing these foaming agents in advance may be used. As the composite foaming agent, a composite foaming agent comprising a pyrolytic foaming agent that mainly generates nitrogen gas and a pyrolytic foaming agent that mainly generates carbon dioxide gas is preferable.

As thermal decomposition type foaming agents which mainly generate nitrogen gas, azodicarbonamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, p-
Examples include toluenesulfonyl hydrazide and p, p'-oxy-bis (benzenesulfonyl hydrazide), and azodicarbonamide is preferred. These foaming agents may be used in combination.

Examples of the pyrolytic foaming agent that mainly generates carbon dioxide gas include sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate, with sodium bicarbonate being preferred. These foaming agents may be used in combination.

The foaming agent usually has a decomposition temperature of 140 to
Those having a temperature of around 180 ° C. are preferred, but the decomposition temperature is 180 ° C.
When a foaming agent exceeding the above is used, a foaming agent and a foaming aid may be used in combination. As foaming aids, zinc oxide, zinc nitrate, basic zinc carbonate, zinc stearate, lead phthalate,
Examples include lead carbonate, urea, and glycerin. It is also preferable to use a powder of calcium carbonate, talc, silica or the like as a foam nucleating agent in combination.

When a thermally decomposable organic foaming agent that mainly generates nitrogen gas and a pyrolyzable inorganic foaming agent that mainly generates carbon dioxide gas are used in combination, the weight ratio of the former foaming agent to the latter foaming agent is as follows: 1/99 to 30/70, preferably 1/9, from the viewpoint that the foamed sheet obtained has a fine and uniform cell diameter and the obtained foamed sheet has good surface smoothness (beautiful appearance).
9-20 / 80, more preferably 1 / 99-10 / 90
It is.

When a mixed gas of nitrogen gas and carbon dioxide gas is used as the foaming agent, the volume ratio of nitrogen gas to carbon dioxide gas is 1/99 to 30/70, preferably 1/99 to 20/8.
0, more preferably 1/99 to 10/90. In this case, it is preferable to use a powder of calcium carbonate, talc, silica or the like as a foam nucleating agent.

There is no particular limitation on the extruder used for the production of the foamed sheet. At least an extruder capable of sufficiently kneading and homogenizing the resin and the foaming gas, and cooling and adjusting the temperature to a temperature suitable for foaming. Often, examples of such an extruder include a single-screw extruder and a multi-screw extruder. As a multi-screw extruder, a twin-screw extruder is generally used,
The directions of rotation of the screws may be the same or different. Regarding the type of the twin-screw extruder, a parallel twin-screw extruder in which the diameter of the screw is constant or an oblique twin-screw extruder in which the tip of the screw has a small diameter may be used. In the case of a twin-screw extruder, a sealing segment is preferably provided on the screw because the foaming gas easily escapes from the hopper. The single-screw extruder is preferably used from the viewpoint that the foaming gas hardly comes out of the hopper and the cost is low. Also,
It is also possible to use a tandem extruder combining a single screw extruder and a multi-screw extruder. As the die of the extruder, a flat die or a circular die can be used, and the thickness of the foam sheet can be controlled by adjusting the lip gap at the tip of the die.

The nonwoven fabric used in the present invention is mainly used to impart flexibility and a beautiful appearance to the laminated sheet of the present invention, and the nonwoven fabric is laminated on at least one surface of the foamed sheet. Examples of the nonwoven fabric include a needle punched nonwoven fabric and a spunbonded nonwoven fabric. Needle punched nonwoven fabrics produced by needling and entanglement of the web with special needles are particularly preferred.

As a resin spinning system constituting the nonwoven fabric,
A single spinning system such as nylon, polyester, and polypropylene, and a mixed spinning system thereof can be exemplified. A nonwoven fabric made of a resin of the same type as the resin for producing a foamed sheet is particularly preferred from the viewpoint of ease of recycling the laminated sheet, that is, from the viewpoint that there is no need to separate the foamed sheet and the nonwoven fabric.

The basis weight of the nonwoven fabric used in the present invention is not particularly limited, and a nonwoven fabric having a basis weight may be selected according to the use, and the basis weight is usually 200 g / m ² or less. When using a non-woven fabric with a low basis weight, when the laminated sheet is viewed from the side of the non-woven fabric, the foamed sheet may be seen through, or the non-woven fabric may lack the touch and cushioning properties. Preferably, a sheet is used. When the laminated sheet is used in an arrangement where the nonwoven fabric can be seen, it is preferable to use a nonwoven fabric having a basis weight of about 80 to 200 g / m ² . Generally, when the foamed sheet and the nonwoven fabric are of the same color (for example, black), the laminated sheet has a preferable appearance.

The method for laminating the foamed sheet and the nonwoven fabric is not particularly limited, and the following methods can be exemplified, and from the viewpoint of cost, or the above method is preferable. A method of laminating by laminating a foam sheet and a nonwoven fabric using an adhesive. A method in which a molten thermoplastic resin film is extruded and sandwich-laminated between a foamed sheet and a nonwoven fabric. A method in which the surface of a foamed sheet is heated and melted by a heater or a flame, and then laminated with a non-woven fabric by pressure bonding. A method in which a foamed sheet whose surface immediately after extrusion foaming is still in a molten state and a nonwoven fabric are overlapped and pressure-bonded to be laminated. A method in which the back surface of a nonwoven fabric is heated and melted by a heater or a flame, and the foamed sheet whose surface is preheated or melted is laminated by pressure bonding. In this method, when a nonwoven fabric of a two-layer structure backed by a resin film or another nonwoven fabric having a melting point lower than the melting point of any resin constituting the nonwoven fabric or the foamed sheet, It can be easily laminated with a nonwoven fabric. A method in which a powder made of a thermoplastic resin is sprayed on the surface of a foamed sheet, the powder is heated and melted, and the powder is laminated with a nonwoven fabric by pressure bonding. A method of laminating by superimposing a foamed sheet and a nonwoven fabric with a special needle, so that the yarns constituting the nonwoven fabric are buried in the foamed sheet and entangled with each other.

The laminated sheet of the present invention can be punched and processed into a desired shape by a known press machine or the like, or can be subjected to ruled line processing at a desired position. The method of applying the ruled line is not particularly limited, and the following application methods can be exemplified. From the viewpoint that the durability of the ruled line product is excellent (the number of reciprocal bending is large), the method of or the method is particularly preferable. preferable. A method of locally compressing mechanically. A method of compressing locally by applying heat. A method of making a slit to a predetermined depth using a cutter or the like.

The laminated sheet of the present invention is further processed into a desired shape by thermoforming such as vacuum forming, and then the peripheral portion thereof is punched out with a press or the like to obtain a molded article having a beautiful end face and appearance. Can also. The thermoforming method is not particularly limited. For example, after a laminated sheet is uniformly heated by a heater at a temperature in the range of about 130 to 200 ° C., it is adjusted to a desired shape by a temperature-controlled male and female mold. The method of shaping and cooling can be exemplified as a preferred method.

[0052]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The analytical values in the examples were obtained by the following methods.

1. Melt index (MI) In accordance with JIS K7210, a resin having a repeating unit derived from propylene as a main component has a temperature of 2
The measurement was carried out at 30 ° C. and a load of 2.16 kgf, and the resin having a repeating unit derived from ethylene as a main component was measured at a temperature of 190 ° C. and a load of 2.16 kgf.

2. Die swell ratio Using a capillary with a length of 20 mm, a diameter of 1 mm, and a flat inflow angle, and a temperature of 18 according to JIS K7199.
The measurement was performed at 5 ° C. and a shear rate of 121 sec ⁻¹ .

3. The content of the content of the polymer component of the high intrinsic viscosity component-containing PP produced in the composition analysis continuous polymerization method _(A) (W A (% by weight)) and component _(B) (W B (wt%)) Was determined from the material balance at the time of producing the PP containing the high intrinsic viscosity component.

4. Intrinsic Viscosity The intrinsic viscosity [η] _A of the polymer component (A) in the high intrinsic viscosity component-containing PP produced by the continuous polymerization method was determined by measuring the product obtained in the first step. [Η] _A and the intrinsic viscosity [η] of the high intrinsic viscosity component-containing PP were measured in tetralin at 135 ° C. using an Ubbelohde viscometer. The intrinsic viscosity [η] _B of the polymer component (B) was determined from the following equation. [Η] _A × W _A / 100 + [η] _B × W _B / 100 = [η]

5. Mw / Mn value P. C. (Gel permeation chromatography) was measured under the following conditions. Model: 150CV type (Millipore Waters) Column: Shodex M / S 80 Measurement temperature: 145 ° C. Solvent: orthodichlorobenzene Sample concentration: 5 mg / 8 mL The calibration curve is standard polystyrene (NBS706: Mw / Mn)
= 2.0). Mw / Mn of the standard polystyrene measured under the above conditions was 1.9 to 2.0.

6. Flexural modulus Using a test piece having a size of 10 mm (width) x 150 mm (length), and using a test piece of 10 mm / width in accordance with JIS K7203.
And the span was measured at a bending speed of 100 mm.

7. Bending elasticity gradient Using a test piece having a size of 50 mm (width) x 150 mm (length), and using a test piece of 10 mm / mm in accordance with JIS K7203.
The load-strain curve was determined by measuring the bending rate at a span of 100 mm, and the slope of the tangent at the rising portion of the curve was divided by the width (50 mm) of the test piece to determine the bending elastic gradient per 1 cm width. .

8. Cell diameter According to JIS K6402, the value obtained by dividing the thickness of the foamed sheet by the number of cells existing on a straight line in the thickness direction was defined as the cell diameter.

9. The number of times the ruled part can be bent was measured in accordance with JIS P8115 using a test piece having a size of 15 mm (width) x 110 mm (length).

Example 1 85 parts by weight of a propylene homopolymer having MI of 6 g / 10 min and SR of 1.9 (corresponding to "polypropylene resin"), MI of 1 g / 10 min, and a density of 0.87 / Cm ³ ,
When the content of the repeating unit derived from propylene is 22
Wt% ethylene-propylene copolymer ("other resin")
After mixing with 15 parts by weight in a tumbler,
The mixture was extruded at a cylinder temperature of 220 ° C. and a die temperature of 220 mm using an extruder having a diameter of 90 mm and a strand die.
C., melt kneading under the conditions of a screw rotation speed of 40 rpm,
Flexural modulus 15600 kgf / cm ² , density 0.9 g /
cm ³ of a thermoplastic resin composition was obtained.

100 parts by weight of the resin composition, 8% by weight of azodicarbonamide and 92% by weight of sodium bicarbonate
1.4 parts by weight of a composite foaming agent having the following composition, 1.4 parts by weight of zinc oxide (foaming aid), and 1.5 parts by weight of a black pigment masterbatch were mixed using a tumbler.
Extrusion foaming is performed by an extruder having a diameter of 120 mm equipped with a flat die having a width of mm (cylinder-temperature: 170-200 ° C. in a screw supply section, 190-200 ° C. in a compression section, 160-170 ° C. in a measuring section, die temperature: 170 ° C.). , Screw rotation speed: 40 rpm, discharge rate: 200 kg / h
r) Take-off molding with a polishing roll controlled at a temperature of 60 to 90 ° C. to obtain a foamed sheet.

The obtained foam sheet has a thickness of 0.5 cm.
Density 0.3 g / cm ³ , bubble diameter 150 μm, basis weight 151
7 g / m ² , bending elastic gradient 1.85 kgf / cm · 1c
m width. The expansion ratio is defined as the density of the resin composition being 0.1.
Since the ratio is 9 g / cm ³ and the density of the foamed sheet is 0.3 g / cm ³ , 0.9 / 0.3 = 3.
It was asked to double. E = 15600 kg on the left side of equation (1)
Substituting f / cm ² and ３ = 3 times, the value on the left side is 0.3c
m, and the thickness of the obtained foamed sheet of 0.5 cm satisfied expression (1).

Both sides of the foamed sheet are polished
With an infrared heater installed immediately after the
Melted by heat and the basis weight is 60 g / m^TwoAnd 100g
/ M ^TwoRoll with two types of polypropylene non-woven fabric
Compression bonding, laminated sheet with non-woven fabric stuck on both sides of foam sheet
I got it. Punch the obtained laminated sheet with a press
At the same time, a ruled line is applied to make the interior material for automobiles shown in FIG.
We made all the trunk mat materials. This trunk mat
Since the material has no burrs on the end surface and the bubbles are fine,
Since the appearance was beautiful, no end face treatment was required. Ruled line
Is the shape shown in FIG. 2 formed by local mechanical compression
And the number of times the ruled line can be folded is 1000
The hinge property was excellent at 0 or more times.

Separately, the laminate was uniformly heated to 160 ° C. by a heater, and vacuum-molded using male and female molds controlled at 50 ° C., and then the periphery of the obtained molded product was punched out. 3
And trays having the shapes shown in FIGS. This tray is installed under the trunk mat material as shown in FIG.
This is for storing articles such as spare tires and tools. This tray has a beautiful end face because the bubbles of the foam sheet are fine, and no swelling during vacuum forming is seen.
The appearance was good.

Example 2 A propylene homopolymer having an MI of 3 g / 10 min and an SR of 2.36 (a long-chain branched P
P) 85 parts by weight, MI of 1 g / 10 min, density of 0.8
Performed in the same manner as in Example 1 using 7 g / cm ³ and 15 parts by weight of an ethylene-propylene copolymer (corresponding to “other resin”) having a content of a repeating unit derived from propylene of 22% by weight. , Flexural modulus 12,500 kgf / cm
^{2. A} thermoplastic resin composition having a density of 0.9 g / cm ³ was obtained. The foamed sheet obtained in the same manner as in Example 1 using the resin composition had a thickness of 0.5 cm and a density of 0.3 g / cm.
³ , bubble diameter 250μm, expansion ratio 3 times, weight 1517g
/ M ² , a bending elastic gradient of 1.48 kgf / cm · 1 cm width, and a thickness of 0.5 cm satisfied Expression (1).

In the same manner as in Example 1, the foamed sheet and the nonwoven fabric were laminated to obtain a laminated sheet, and a trunk mat member and a tray were prepared from the laminated sheet. The end surface of the obtained trunk mat material was good, and the hinge property was as good as 10,000 times or more. With respect to the tray, the swelling during molding was slightly observed, and the appearance was good.

Example 3 The same procedure as in Example 2 was carried out except that the addition amount of the composite foaming agent was 3.5 parts by weight, the thickness was 0.6 cm, and the density was 0.15.
g / cm ³ , bubble diameter 300 μm, expansion ratio 6 times, basis weight 9
10 g / m ² , bending elastic gradient 1.24 kgf / cm · 1
A cm wide foam sheet was obtained. Thickness of the foam sheet 0.6
cm satisfied the expression (1). The foamed sheet and the nonwoven fabric were bonded together in the same manner as in Example 2 to obtain a laminated sheet, and a trunk mat member and a tray were prepared from the laminated sheet.
The end surface of the obtained trunk mat material was good, and the hinge property was as good as 10,000 times or more. Regarding the tray, the swelling during molding was only slightly observed,
The appearance was good.

Example 4 85 parts by weight of a high intrinsic viscosity component-containing PP obtained by a continuous polymerization method, an MI of 1 g / 10 min, and a density of 0.87 g / c
m ^3, the content of the repeating units derived from propylene 22 wt% ethylene - (corresponding to "other resin") propylene copolymer obtained in the same manner as in Example 1 by using the 15 parts by weight, the bending A thermoplastic resin composition having an elastic modulus of 17000 kgf / cm ² and a density of 0.9 g / cm ³ was obtained. The high intrinsic viscosity component-containing PP has an intrinsic viscosity [η] of 1.8 d.
1 / g, Mw / Mn is 6.2, MI is 9 g / 10 min, S
R is 2.5, 8 wt% of the polymer component (A) having an intrinsic viscosity [η] _A of 8 dl / g, and an intrinsic viscosity [η] _B of 1.2
6 dl / g of polymer component (B) 92% by weight.

The foam sheet obtained in the same manner as in Example 1 had a thickness of 0.5 cm, a density of 0.3 g / cm ³ , and a cell diameter of 1
The foaming ratio was 50 μm, the expansion ratio was 3 times, the basis weight was 1517 g / m ² , the bending elasticity gradient was 2.01 kgf / cm · 1 cm, and the thickness was 0.5 cm. The laminated sheet was obtained by laminating the foam sheet and the nonwoven fabric in the same manner as in Example 1.
A trunk mat material and a tray were prepared from the laminated sheet. The end surface of the obtained trunk mat material is beautiful,
The hinge property was as good as 10,000 times or more. Regarding the tray, no swelling was observed at the time of molding, and the appearance was good.

Example 5 85 parts by weight of a high intrinsic viscosity component-containing PP obtained by a continuous polymerization method, MI of 1 g / 10 min, and density of 0.87 g / c
m ^3, the content of the repeating units derived from propylene 22 wt% ethylene - (corresponding to "other resin") propylene copolymer obtained in the same manner as in Example 1 by using the 15 parts by weight, the bending A thermoplastic resin composition having an elastic modulus of 17000 kgf / cm ² and a density of 0.9 g / cm ³ was obtained. The PP having a high intrinsic viscosity component has an intrinsic viscosity [η] of 2.29.
dl / g, Mw / Mn is 6.7, MI is 4.4 g / 10
Min, SR is 3.26, intrinsic viscosity [η] _A is 7.5
dl / g of polymer component (A) 14.4% by weight, and intrinsic viscosity [η] _B of polymer component (B) 8 having 1.41 dl / g.
5.56% by weight.

The procedure of Example 1 was repeated except that the amount of the composite foaming agent was changed to 3.5 parts by weight.
Density 0.15 g / cm ³ , cell diameter 200 μm, expansion ratio 6 times, basis weight 910 g / m ² , bending elastic gradient 1.73 kg
A foam sheet having a width of f / cm · 1 cm was obtained. The thickness of 0.6 cm of the foam sheet satisfied Expression (1). Example 1
The laminated sheet was obtained by laminating the foamed sheet and the nonwoven fabric in the same manner as described above, and a trunk mat material and a tray were prepared from the laminated sheet. The end surface of the obtained trunk mat material was beautiful, and the hinge property was as good as 10,000 times or more. Regarding the tray, no swelling was observed at the time of molding, and the appearance was good.

Example 6 The same procedure as in Example 5 was carried out except that the extrusion foaming conditions were changed (the degree of opening of the lip gap was increased), and the thickness was 0.8
cm, density 0.15 g / cm ³ , cell diameter 200 μm, expansion ratio 6 times, basis weight 1213 g / m ² , flexural elasticity gradient 4.
A foam sheet having a width of 1 kgf / cm · 1 cm was obtained. The thickness of the foamed sheet of 0.8 cm satisfied Expression (1). The foam sheet and the nonwoven fabric were bonded together in the same manner as in Example 1 to obtain a laminated sheet, and a trunk mat member and a tray were prepared from the laminated sheet. The end surface of the obtained trunk mat material was beautiful, and the hinge property was as good as 10,000 times or more. As for the tray, no swelling during molding was observed.
The appearance was good.

Example 7 The procedure of Example 5 was repeated except that the amount of the foaming agent added was 5.1 parts by weight, and the thickness was 0.8 cm and the density was 0.11 g /
cm ³ , bubble diameter 250 μm, foaming ratio 8.2 times, basis weight 8
90 g / m ² , bending elastic gradient 2.98 kgf / cm · 1
A cm wide foam sheet was obtained. 0.8 thickness of the foam sheet
cm satisfied the expression (1). The foam sheet and the nonwoven fabric were bonded together in the same manner as in Example 1 to obtain a laminated sheet, and a trunk mat member and a tray were prepared from the laminated sheet.
The end surface of the obtained trunk mat material was good, and the hinge property was as good as 10,000 times or more. As for the tray, it was only a small amount of bubbling observed during molding.
The appearance was good.

Comparative Example 1 85 parts by weight of a propylene homopolymer having an MI of 6 g / 10 minutes and an SR of 1.6, an MI of 1 g / 10 minutes, and a density of 0.
The same operation as in Example 1 was carried out using 87 g / cm ³ and 15 parts by weight of an ethylene-propylene copolymer having a content of a repeating unit derived from propylene of 22% by weight, and the flexural modulus was 15,600 kgf / cm ² . Density is 0.9g / c
m ³ of a thermoplastic resin composition was obtained. The foamed sheet obtained by using this thermoplastic resin composition in the same manner as in Example 1 had a thickness of 0.2 cm, a density of 0.8 g / cm ³ , an expansion ratio of 1.1, and a cell diameter of The sheet had a low foaming ratio of 800 μm, which had a large outgassing and poor appearance, and was not worthy of evaluation.

Comparative Example 2 The procedure of Example 1 was repeated, except that 1.47 parts by weight of sodium bicarbonate was used instead of the composite blowing agent as the blowing agent. The thickness was 0.5 cm and the density was 0.3 g / cm ^3. , Expansion ratio 3 times, basis weight 1517 g / m ² , bending elastic gradient 1.85 k
A foam sheet having a gf / cm · 1 cm width was obtained. The bubble diameter is 1
It was as coarse as 500 μm. The foam sheet and the nonwoven fabric were bonded together in the same manner as in Example 1 to obtain a laminated sheet, and a trunk mat member and a tray were prepared from the laminated sheet. The appearance of the end face of the obtained trunk mat material was poor enough to require the end face treatment because the foam of the foam sheet was coarse, and the hinge property was poor at 6000 times. With respect to the tray, many burrs were observed during molding, and the appearance was poor.

Comparative Example 3 A foamed sheet was obtained in the same manner as in Example 4 except that a circular die having a diameter of 100 mm was used and the amount of the foaming agent was changed to 3.5 parts by weight. The foam sheet has a thickness of 0.2
cm, density 0.15 g / cm ³ , cell diameter 200 μm, expansion ratio 6 times, basis weight 303 g / m ² , flexural elasticity gradient 0.0
The width was 6 kgf / cm · 1 cm, and the flexural rigidity was considerably low. The thickness of 0.2 cm did not satisfy the formula (1), and was not worthy of being bonded to a nonwoven fabric for evaluation.

[0079]

The laminated sheet of the present invention is a laminated sheet comprising a foamed sheet having a high expansion ratio and having fine cells and a nonwoven fabric, and having an excellent balance between lightness and rigidity. This laminated sheet is a laminated sheet that can be subjected to thermoforming such as ruled line processing and vacuum forming and has excellent recyclability.
Since the air bubbles are fine, there is no appearance defect such as blemishes (bubbled air bubbles) etc. in thermoforming, and the punched end surface is beautiful, and dust, dirt, water, etc. hardly enter from the end surface. Also, no end face treatment is required, and a molded article with a beautiful appearance can be obtained. The creased line product made of the laminated sheet of the present invention has excellent durability (the number of times of reciprocating bending is large), and is particularly suitable as an interior material for automobiles such as a trunk mat material and a ceiling material.

[Brief description of the drawings]

FIG. 1 is a plan view showing a trunk mat member made using the laminated sheet of the present invention.

FIG. 2 is a sectional view showing a shape of a ruled line of the trunk mat material of FIG. 1;

FIG. 3 is a plan view showing a tray created by using the laminated sheet of the present invention.

FIG. 4 is a sectional view showing the tray of FIG. 3;

5 is a plan view showing a state in which the tray of FIG. 3 is installed below the trunk mat member of FIG. 1;

[Explanation of symbols]

 1: trunk mat material 2: ruled line 3: foam sheet 4: non-woven fabric 5: tray 6: article storage space 7: article

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 23:10

Claims (15)

[Claims] 1. A polypropylene resin having an expansion ratio (χ) of 2 to 10 times, a cell diameter of 300 μm or less, and a thickness h
A laminated sheet comprising a foamed sheet (cm) satisfying the following expression (1) and a nonwoven fabric. (100 / E (1− (1-1 / χ) ^2/3 )) ^1/3 ≦ h ≦ 2 (1) (In the formula (1), E is the flexural modulus of the unfoamed resin constituting the foamed sheet. (Kgf / cm ² ) 2. The laminated sheet according to claim 1, wherein the polypropylene resin has a melt index of 2 to 20 g / 10 minutes and a die swell ratio of 1.7 or more. 3. The laminated sheet according to claim 1, wherein the polypropylene resin is a polypropyne resin having a long chain branch. 4. A crystalline polymer component having an intrinsic viscosity of 5 dl / g or more obtained by polymerizing propylene alone or propylene with ethylene and / or an α-olefin having 4 to 12 carbon atoms. A) and a crystalline polymer component (B) having a limiting viscosity of less than 3 dl / g obtained by polymerizing propylene alone or propylene with ethylene and / or an α-olefin having 4 to 12 carbon atoms. Having a limiting viscosity of less than 3 dl / g and a ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
/ Mn) is less than 10, and the content of the crystalline polymer component (A) is 0.05% by weight or more and less than 35% by weight of a polypropylene resin.
The laminated sheet according to the above. 5. A crystalline resin having a limiting viscosity of 5 dl / g or more in a first step by polymerizing propylene alone or propylene with ethylene and / or an α-olefin having 4 to 12 carbon atoms. The combined component (A) is produced, and subsequently, in the second step, propylene alone or propylene is mixed with ethylene and / or an α-olefin having 4 to 12 carbon atoms in the presence of the polymer component (A). The ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), obtained by polymerizing to produce a crystalline polymer component (B) having an intrinsic viscosity of less than 3 dl / g and having an intrinsic viscosity of less than 3 dl / g. 2. A polypropylene resin having a (Mw / Mn) of less than 10 and a crystalline polymer component (A) content of 0.05% by weight or more and less than 35% by weight.
Or the laminated sheet according to 2. 6. An intrinsic viscosity [η] of the crystalline polymer component (A).
_A (dl / g) and the content W of the crystalline polymer component (A)
The laminated sheet according to claim 4 or 5, wherein _A (% by weight) satisfies the relationship of the following expression (2). W _A ≧ 400 × EXP (−0.6 × [η] _A ) (2) 7. The crystalline polymer component (A) and the crystalline polymer component (B) are each independently a homopolymer of propylene; the content of a repeating unit derived from ethylene is 10% by weight or less. A random copolymer of ethylene and propylene; a random copolymer of propylene and 1-butene having a content of a repeating unit derived from 1-butene of 30% by weight or less; or derived from ethylene. A repeating unit content of 10% by weight or less,
A random copolymer of ethylene, propylene and 1-butene having a content of repeating units derived from -butene of 30% by weight or less, wherein
7. The laminated sheet according to any one of 6. 8. The crystalline polymer component (A) has an intrinsic viscosity of 7
The laminated sheet according to any one of claims 4 to 7, wherein the thickness is not less than dl / g. 9. The crystalline polymer component (A) in the first stage
Of the catalyst containing titanium, magnesium and halogen as essential components and 20 g / hour of polymerization time.
The polymerization rate of the crystalline polymer component (B) in the second stage is 4000 g or more per 1 g of the catalyst and 1 hour of the polymerization time.
The laminated sheet according to the above. 10. The laminated sheet according to claim 1, wherein the polypropylene resin is a polypropylene resin comprising a mixture of the following resins (i) and (ii). (I) Polypropyne resin having a long chain branch (ii) In the first step, propylene alone or propylene is polymerized with ethylene and / or an α-olefin having 4 to 12 carbon atoms to have an intrinsic viscosity of 5 dl / g or more. And then in a second step, in the presence of the polymer component (A), in the presence of propylene alone or propylene and ethylene and / or ethylene having 4 to 12 carbon atoms.
Is obtained by producing a crystalline polymer component (B) having an intrinsic viscosity of less than 3 dl / g by polymerizing an α-olefin of the formula (I) with an intrinsic viscosity of less than 3 dl / g and a weight average molecular weight (Mw) and a number average molecular weight. The ratio (Mw / Mn) to (Mn) is less than 10, and the content of the crystalline polymer component (A) is 0.05% by weight.
More than 35% by weight of resin 11. The laminated sheet according to claim 1, wherein the expansion ratio 、 ４ is 4 to 10 times. 12. The laminated sheet according to claim 1, wherein the foamed sheet is a foamed sheet formed by using a mixed gas of nitrogen gas and carbon dioxide gas as a foaming gas. . 13. The laminated sheet according to claim 1, wherein the nonwoven fabric is a nonwoven fabric made of a polypropylene resin. 14. An interior material for an automobile, comprising the laminated sheet according to any one of claims 1 to 13. 15. The interior material for an automobile according to claim 14, wherein the interior material for an automobile is a ceiling material or a trunk mat material.