JPS6213182B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fibrous molded article having a three-dimensional uneven surface. More specifically, it has a heat-compression molded uneven surface and is highly functional and aesthetically pleasing.
This invention relates to fibrous molded products suitable for use as soundproofing materials, heat insulating materials, cushioning materials, etc. Conventionally, a fibrous material consisting of an aggregate of many fibers (hereinafter sometimes referred to as fibers) is opened and mixed with a thermosetting or thermoplastic resin adhesive to obtain a fleece, that is, a nonwoven web, which is heated. It is known that fibrous molded products obtained by compression molding can be used as soundproofing materials, heat insulating materials, cushioning materials, etc. for buildings, vehicles, factory equipment, furniture, etc. However, such fibrous molded products consisting only of hot compression molded products of nonwoven webs have drawbacks such as poor aesthetics, fuzzing, and poor functionality such as abrasion resistance, waterproofness, and flame retardancy. There is. Therefore, conventionally, on the surface of fibrous molded products,
It is well known to improve the aesthetics and/or functionality of fibrous molded articles by attaching sheet materials such as paper, plastic films, woven fabrics, non-woven fabrics, etc. These sheet-like materials are usually attached to the surface of the fibrous molded product using an adhesive, but such pasting work is troublesome, especially when the molded product has an uneven surface. Even more complicated, if the sheet-like material does not have sufficient deformability, it will not be able to fully conform to the uneven surface of the fibrous molded material, and the surface of the sheet-like material and the fibrous molded material will Unfavorable results may occur in terms of appearance, such as gaps or wrinkles appearing between the parts. Recently, several methods have been proposed in which a nonwoven web as described above is laminated with a sheet-like material as described above, and compression molded under heating to produce a fibrous molded product with a surface protection in one step. ing. For example, JP-A-51-30271, JP-A-51-112889.
Please refer to the publication number, etc. In these known methods, the sheet material for surface protection is a vinyl chloride resin sheet (PVC leather), a rubber sheet, a polyester film,
It has been proposed to use a dense sheet-like material such as polyamide film, or a porous sheet-like material such as thermosetting synthetic resin-impregnated paper cloth having openings, but the former dense sheet-like material When applied to a fibrous molded product with a large deformation rate, that is, a highly uneven surface, it does not fit well to the uneven surface, causing wrinkles or web damage. There are disadvantages such as a gap between the surface and the sheet-like material and unevenness in the sheet-like material itself.Another drawback is that the sheet-like material has poor sound absorption effect due to poor air permeability. There is also. On the other hand, the conventionally used paper cloth impregnated with the above-mentioned thermosetting synthetic resin has better properties than the above-mentioned dense sheet-like material, but it also has a small thermal deformability and a surface-protected fibrous material that is preferable in terms of appearance. Do not give molded objects. The object of the present invention is to provide an improved fibrous molding which does not have the disadvantages mentioned above. Another object of the present invention is to provide a fibrous molded product with a beautiful appearance and excellent aesthetics. Another object of the present invention is to provide a fibrous molded article with improved functionality such as surface abrasion resistance, waterproofness, flame retardancy, surface smoothness, and/or weather resistance. Other objects and advantages of the invention will become apparent from the following description. According to the present invention, a laminate of a nonwoven fibrous web A that can be heat-compressed and a non-woven fibrous sheet B laminated on at least one side of the web A is integrally heat-compressed using a mold. A fibrous molded article having an uneven surface formed by molding; (a) The nonwoven fibrous web A has a compressive stress of at least 0.5 g/cm ² at 10% compression at a hot compression molding temperature; , has a thickness of 5 to 60 mm, and contains at least 5% thermosetting resin adhesive based on the weight of the web; (b) the nonwoven fibrous sheet B is heated An assembly of thermoplastic polymer fibers having an initial modulus of less than 5 g/denier and an elongation of at least 20% at compression molding temperatures, and each fiber is interconnected with spaced adjacent fibers. Consisting of a continuous, integral mesh sheet structure, the plastic deformation rate at 30% elongation at the hot compression molding temperature is at least 50%, and the elongation stress at 30% elongation at the hot compression molding temperature is 0.15 kg. /cm or less; (c) And the web A and the sheet B are:
The following relational expression is satisfied, S≦0.03T [wherein, T represents the compressive stress (g/cm 2 ) of the above web A at 10% compression at the heating compression molding temperature, and S represents the compressive stress (g/cm ² ) of the above web A at the heating compression molding temperature. Represents the elongation stress (Kg/cm) at 30% elongation at the heating compression molding temperature. (iv) Furthermore, there is provided a fibrous molded product having an uneven surface, characterized in that the fibrous molded product has a density of 0.02 to 0.5. Note that various terms used in this specification will be collectively defined later. Hereinafter, the fibrous molded product of the present invention will be specifically explained with reference to the accompanying drawings as appropriate. FIG. 1 is a cross-sectional view of a laminate according to the present invention before hot compression molding; FIG. 2 is a perspective view of one embodiment of a fibrous molded product having an uneven surface according to the present invention. As shown in FIG.
and a nonwoven fibrous sheet B laminated on at least one surface of the web A [in FIG.
The case in which the sheet (B) is laminated on only one side of the sheet (B) is shown)] is manufactured by heating and compression molding the laminate D. FIG. 2 shows an example of the state of the uneven surface of the fibrous molded product of the present invention formed in this way, for ease of understanding. It will be easily understood that various changes can be made depending on the purpose of use. A feature of the present invention is that in providing a fibrous molded product useful as a soundproofing material, a heat insulating material, and a cushion material by an integral heating compression molding method, a nonwoven fibrous web A serving as a substrate and a surface material What kind of materials are carried as the non-woven fibrous sheet B and how they are used in combination, and in particular, the most significant feature lies in the material of the non-woven fibrous sheet B which is the surface material. be. The web A and sheet B will be explained in detail below. Non-woven fibrous web A The fibrous web A is a relatively loose aggregate of long fibers and/or short fibers that retains its shape semi-permanently by heating and compression molding. A non-woven fibrous material in the form of a sheet or mat is used. The type of fiber constituting the fibrous material is not particularly limited, and natural, recycled, or synthetic inorganic or organic fibers may be used alone or in combination of two or more. Specific examples of such fibers include cotton,
Natural organic fibers such as linen and wool; Natural or synthetic inorganic fibers such as glass fiber, stainless steel fiber, asbestos fiber, and rock wool; Renewable fibers such as rayon and acetate; Synthetic fibers such as polyester, polyamide, acrylic resin, and polycarbonate The fiber diameter is usually in the range of 1 to 100μ, preferably 5 to 30μ. Furthermore, these fibers must not substantially melt under the heat compression molding conditions described below, and generally have a melting temperature of at least 200°C, preferably at least 220°C. These fibers are formed into a nonwoven web in the form of short or long fibers, or a mixture of both.
Forming into a non-woven web is performed by a method known per se, for example, Japanese Patent Publication No. 53-30827, Guide to Non-woven.
This can be carried out by the method described in literature such as Fabrics (INDA), 19 (1978). If the fibrous material constituting the nonwoven web has thermoformability itself and has the property of retaining its shape semi-permanently after heating and compression molding, Although no resin adhesive is required, in many cases fibrous materials do not have such properties, or even if they do, they are insufficient, so a resin adhesive is impregnated in the fibrous web A.
It is necessary to enable heat compression molding. Such a resin adhesive can be mixed into the fibrous web A in the form of a powder, solution or dispersion, and the amount applied depends on the type of resin adhesive, but is generally based on the weight of A. , at least 5% by weight, preferably from about 10 to about 40%, more preferably from about 15 to about 30%. Examples of suitable resin adhesives include thermosetting resins such as phenolic resins, epoxy resins, urethane resins, melamine resins, and urea resins. The form of the web A mixed with such a resin adhesive is not limited and can be varied widely depending on the intended use of the final product, but the thickness is generally about 5 mm.
to about 60 mm, preferably about 10 to about 40 mm, and the apparent density is generally about 0.005 to about 0.15
Advantageously, it ranges ^{from about 0.01 to about 0.1 g/cm 3 .} The most important requirement that the web A used in the present invention should have is at least 0.5 g/cm ² , preferably at least 1.0 g/cm ² , more preferably at least
It must have a compressive stress of 2.0 g/cm ² at 10% compression. The compressive stress at 10% compression at the heating compression molding temperature of web A is 0.5
If it is less than g/cm ² , shape retention after heat compression molding is poor. As the web A used in the present invention having the properties as described above, known webs can be used,
For example, Taka #812″ and Taka #810″ manufactured by Nippon Tokushu Toyo Co., Ltd.; a web consisting of 80 to 70 parts by weight of recycled wool and 20 to 30 parts by weight of uncured phenol resin powder (curing temperature: 150°C); 40 to 60 parts by weight, 40 to 20 parts by weight of fallen cotton, and uncured phenolic resin powder (melting point: 185°C,
Web consisting of 20-30 parts by weight of curing temperature: 210℃; synthetic resin fiber waste (melting point: 200℃ or higher) 40-60
Web consisting of 40 to 20 parts by weight of loose cotton and 20 to 30 parts by weight of uncured melamine resin powder (curing temperature: 170°C); 80 parts by weight of glass fiber with a diameter of 8μ and uncured phenolic resin powder (curing temperature: Web consisting of 20 parts by weight of glass fiber with a diameter of 12μ and uncured melamine resin powder (curing temperature:
There are webs made of 15 parts by weight of asbestos short fibers (170°C) and 30 parts of uncured phenolic resin powder (curing temperature: 190°C). Non-woven fibrous sheet B The non-woven fibrous sheet B is integrally bonded to the above-described web A after heat compression molding to protect the surface of the formed web A, and in the present invention, As a sheet material for such surface protection,
A large assembly of thermoplastic polymer fibers having an initial modulus of 5 g/denier or less and an elongation of at least 20% at the hot compression molding temperature described below, and each fiber is interconnected with an adjacent fiber at intervals. It consists of a continuous, integral reticulated sheet structure E that is joined, and has a plastic deformation rate of at least 50% at 30% elongation at the hot compression molding temperature described below, preferably at least
60%, more preferably 70 to 100%, and the elongation stress at 30% elongation at the heating compression molding temperature is 0.15 Kg/cm or less, preferably 0.1 Kg/cm or less,
The most important feature lies in the use of the nonwoven fibrous sheet B, which preferably has a weight of 0.03 to 0.08 kg/cm. In the present invention, by using the nonwoven fibrous sheet B having such a structure and physical properties, the sheet B closely and closely conforms to the deformation of the web A during the heating compression molding of the web A, and the To provide a fibrous molded product that is extremely aesthetically pleasing in appearance, without creating any voids between the sheet B, wrinkles in the sheet B, or uneven thickness or thinness in the sheet B. It has been discovered that it can be done. The mesh sheet structure E constituting the sheet B that provides such an excellent fibrous molded product is:
As mentioned above, at the heating compression molding temperature,
an initial modulus of less than or equal to 5 g/denier, preferably less than or equal to 3 g/denier, more preferably less than or equal to 2 g/denier, and at least 20%, preferably at least 25%, more preferably at least 30
It is important that the fibers are comprised of substantially unstretched thermoplastic polymer fibers having an elongation of %. As long as each fiber constituting the structure satisfies the above-mentioned tensile strength and elongation requirements, the reticulated sheet structure E used in the present invention can be
Any known type can be used; for example, a mesh (or nonwoven) sheet structure manufactured by the method described below can be used. (A) A method in which a molten thermoplastic polymer is continuously discharged from a spinneret, the discharged continuous filaments are immediately collected on a flat surface by the action of air or static electricity, and then pressed to form a sheet. “Spunbond Method” (U.S. Patent No.
3338992); (B) A molten thermoplastic polymer containing a blowing agent is discharged through an elongated slit having a width gap, and a draft is applied while cooling the extrudate almost simultaneously with the discharge. A method of fiberizing an extrudate (see U.S. Pat. No. 3,954,928); (C) discharging a molten thermoplastic polymer from a spinneret and using the resulting tow as long fibers or as appropriate After crimping, the weave is opened into a flat shape, two or more sheets of tow so opened are overlapped, and after being further stretched, the tow is pressed to form a sheet (for example, Japanese Patent Publication No. 1983-6795); (D) A method in which a molten thermoplastic polymer is discharged from a spinneret, and the resulting tow is made into a web by a dry or wet method (for example, Text, World, 121 , 78,
1972-6; Inter, Text, Bull.Spinning, 4 ,
303, 1969). Among these methods, the reticulated sheet structure produced by the methods described in (B) and (C), especially the method described in (B), is particularly preferred. Therefore, the above method (B) and the most preferred reticulated sheet structure of the present invention obtained by this method will now be explained in more detail. That is, the reticulated sheet structure, each fiber of which has the specified tensile strength and elongation described above, advantageously comprises an expandable melt of a thermoplastic polymer.
The extrudate is extruded and foamed through a long and narrow slit having a narrow gap not exceeding 500 microns, and the extrudate is drafted at the maximum draft rate under the conditions or 1/3 of the draft rate while cooling near the exit of the slit. A method consisting of fibrillating the obtained thin fibrous sheet F as it is or suitably fibrillating it and developing it in a direction approximately perpendicular to the axis of the resulting fibers, and stacking and pressing at least two sheets to form a sheet ( This method can be easily molded using the "BF method" (hereinafter referred to as the "BF method"). The above BF method is a unique method developed by the applicant, and the details of this unique method are as follows.
U.S. Patent No. 3954928, issued May 4, 1976
It should be understood that the disclosure of the above-mentioned US patent is hereby incorporated by reference as part of the disclosure of the present invention. The thin fibrous sheet F produced by this BF method is composed of thermoplastic weights having tensile strength and elongation within the above-mentioned ranges, which are arranged substantially two-dimensionally, that is, in a substantially constant direction in a plane. A large collection of coalesced fibers, each fiber interconnected with randomly spaced adjacent fibers to form a continuous, unitary network. The thin fibrous sheet F made by the above BF method is
At first glance, in the unstretched state, it looks like a collection of extremely thin fibers aligned in the direction of the fiber axis (vertical axis) of the fibers. When deployed, the fibers are randomly and irregularly spaced and interlock to form a continuous, substantially unitary network structure in which each network is non-uniform in size and shape. The large number of fibers constituting the thin fibrous sheet F produced by this method has a cross section of each fiber when cut at any point in the aggregate in a direction perpendicular to it (direction perpendicular to the axis of the fibers). The fibers have irregular, asymmetrical concave and convex shapes with different shapes and sizes, and each fiber also has a cross section with an irregularly different shape and size along its fiber axis. The cross-sectional area (S _f ) of each fiber is measured for the cross-sections of irregularly different shapes and sizes seen when the above aggregate is cut at any point in the direction perpendicular to it, and the average of each fiber is The diameter (z) is calculated using the following formula:
(1) [Here, S _f is the cross-sectional area of the fiber, and π is the circumference. ], and this average diameter (z) is determined by measuring micrographs of arbitrary 100 fiber cross sections and determining whether at least 80%, especially at least 90% of the fiber cross sections are distributed in the range from 0.05μ to 60μ. is suitable. In addition, the above 100 of the average diameter (z) of each fiber
The average value (Z ₁₀₀ ) of the cross sections is calculated using the following formula (2). _Expressed as
It is preferable that the value falls within the range of μ to 35μ. Furthermore, it has already been explained that the thin fibrous sheet F forms a network structure when it is expanded in a direction perpendicular to the fiber axis; Each fiber branches in a Y-shape to form an irregular network of different shapes and sizes. Two or more thin fibrous sheets F produced by the BF method are stacked on top of each other and formed into a mesh sheet structure E. Two or more thin fibrous sheets F stacked on top of each other
It is desirable that the respective layers of F are bonded relatively gently, and usually, a stack of multiple thin fibrous sheets F is bonded together without the aid of a resin adhesive.
At a temperature between above the softening temperature of the constituent fibers and below the melting temperature of the constituent fibers, preferably about 50°C or more below the melting temperature,
Preferably, those laminated by compression under a pressure of 1 to 10 kg/cm ² are suitable. The fibers constituting the mesh sheet structure E used in the present invention can be made of a thermoplastic polymer that does not substantially melt at the temperature during heat compression molding, which will be described later. Sheet B also desirably has a melting temperature higher than the temperature during the hot compression molding, preferably 200°C or higher. Specific examples of such thermoplastic polymers include aromatic polyesters such as polybutylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate, nylon 6, and nylon-6.
66, polyamides such as nylon-610; bisphenol A polycarbonates; polymers with a melting temperature of 200°C or higher such as vinyl fluoride polymers, or polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymers, ethylene- 200℃ for acrylic acid metal salt copolymers, polyacetals, aliphatic petroleum resins, aromatic petroleum resins, etc.
Polymers having the following melting temperatures are included, and these can be used alone or in a blend of two or more. The above examples include those which themselves have a melting temperature lower than the hot compression molding temperature, but even such low melting temperature polymers may be blended with polymers having a high melting temperature. This allows mixed polymers to have a melting temperature higher than the hot compression molding temperature, and such mixed polymers can also be used as thermoplastic polymers. Additionally, the thermoplastic polymers may contain conventional resin additives, such as lead-containing heat stabilizers such as dibasic lead stearate, dibasic lead phosphite, tribasic lead sulfate, lead stearate; barium (Ba ), cadmium (Cd), zinc (Zn), calcium (Ca) or lead (Pb) stearate or laurate; di-n-butyltin malate, di-n-octyltin Organotin heat stabilizers such as malate; antioxidants such as various organic sulfides, various organic phosphites, various phenols, and various amines; benzophenone-based such as UV-9 and UV-24, Tinuvin P, Tinuvin 326 Benzotriazole series such as Uvinul N-539,
Acrylate-based UV absorbers such as Uvinul N-35 or salicylate-based UV absorbers such as Zalol and TBS; Inorganic pigments such as carbon black, graphite, molybdenum disulfide, titanium dioxide, and iron oxide; Anthraquinone-based or diazo-based UV absorbers Organic pigments such as; lubricants such as talc and kaolin;
Metal powders such as aluminum powder and zinc powder; high viscosity mixing aids such as paraffin, silicone oil, and polyethylene glycol may also be included in small amounts that are commonly used. The average spacing between the bonding points of each fiber, which defines the mesh size of the mesh sheet structure E, is not strictly limited, but is generally 1 to 50.
mm, preferably within the range of 5 to 30 mm, and the diameter of each fiber is generally 1 to 100 mm.
μ, preferably within the range of 10 to 50 μ. Nonwoven fibrous sheet B generally has a thickness of about 0.06 to about 0.2
mm, preferably from about 0.08 to about 0.15 mm, and generally, but not exclusively, 15
It is advantageous to have a basis weight of ~150 g/m ² , preferably 20-50 g/m ² . In addition, since the nonwoven fibrous sheet B plays the role of a surface protection material, it is desirable that it has mechanical properties of at least a certain level, and at least 0.1 Kg/cm ² at the temperature during heat compression molding described below. , preferably at least 0.15 Kg/cm, more preferably 0.2 to 0.6 Kg/cm, and at least 5%, preferably at least 10%, more preferably 20% at the hot compression molding temperature. It is desirable to have an elongation of ~80%. Furthermore, the nonwoven fibrous sheet B has a thickness of about 0.2 to about 0.6
It can have an apparent density of from about 0.3 to about 0.5 g/cm ³ , preferably from about 0.3 to about 0.5 g/cm ³ . The nonwoven fibrous sheet B may be made flame retardant by flame retardant treatment, if necessary, depending on the use of the fibrous molded product of the present invention. The flame retardant treatment method includes immersing the nonwoven fibrous sheet B in a solution or dispersion containing a flame retardant; coating the surface of the nonwoven fibrous sheet B with a solution or dispersion containing a flame retardant. Method: At least one of the above thin fibrous sheets F produced by the BF method before stacking
Examples include a method in which sheets are subjected to flame retardant treatment in advance as described above and then laminated, or a method in which a flame retardant is dispersed and mixed into a molten polymer. Examples of flame retardants that can be used in this flame retardant treatment include decabromodiphenyl ether, tetrabromo bisphenol A
and its carbonate oligomers, solid flame retardants such as hexabromobenzene, tetrabromophthalic anhydride, perchlorpentacyclodecane; bromotrichloromethane, tetrabromoethane, 1 and 2
-dibromo-1,1,2,2-tetrachloroethane, tribromopropane, tris-(2,3-dibromopropyl)phophate, among others, decabromodiphenyl ether, tetrabromophthalic anhydride, hexabromobenzene is preferred. In addition, if the nonwoven fibrous sheet B adheres to the mold surface during hot compression molding, which will be described later, it will reduce productivity, so the adhesion force to metal at the hot compression molding temperature is generally 7 g/cm ² The following is preferably 4 g/cm ² or less, and if the sheet B has an adhesion force greater than the above metal adhesion force, at least the surface of the sheet B in contact with the mold A mold release agent can be added to the mold. Examples of such mold release agents include polydimethylsiloxane, Teflon particles, liquid paraffin, graphite, molybdenum disulfide particles, and the like. Furthermore, the sheet B may be reinforced by incorporating reinforcing fiber material. As such reinforcing fiber materials, individually separated spun yarns or nonwoven fibers made from such spun yarns are used. The reinforcing fiber material generally has at least 0.1
It is desirable to have a tensile strength of Kg/cm, preferably at least 0.2 Kg/cm, and the blending ratio in the sheet B is generally based on the weight of the sheet B.
30% by weight or less is sufficient. Among the reinforcing nonwoven fibers, it is preferable to use a type made by the method described in Japanese Patent Publication No. 51-6795, in which a large number of parallel fibers are adhesively bonded at intervals. . Laminate D The nonwoven fibrous sheet B described above is according to the present invention,
It is superimposed on one or both sides of the nonwoven fibrous web A, and then heated and compression molded. What is important in overlapping web A and sheet B is that the temperature of web A is 10%
The compressive stress during compression (unit: g/cm ² , hereinafter indicated by the symbol "T") and the elongation stress (unit: Kg/cm, hereinafter indicated by the symbol "S") at 30% elongation at the heating compression molding temperature of sheet B ) is to select and combine web A and sheet B so that the following formula (3) S≦0.03T (3) is satisfied. If the compressive stress T and tensile stress S of web A and sheet B that are overlapped satisfy the relationship shown in equation (3) above, when the laminate of web A and sheet B is heated and compression molded, unevenness will be reduced. There are no wrinkles near the interface, no space is created between the web A and the sheet B at the bottom of the concave surface, or the sheet B is lifted, and even at a very large deformation rate (i.e. concave, convex). It has been discovered that even when hot compression molding (extremely aggressive) is carried out, a fibrous molded product with an extremely beautiful appearance and a sharply contoured uneven surface can be obtained. In particular, web A and sheet B are expressed by the following formula (3-
1) S≦0.025T (3-1) In particular, it is advantageous to combine so that the following formula (3-2) S≦0.02T (3-2) is satisfied. Some specific examples of such combinations are as follows. Example 1 (i) Nonwoven fibrous sheet B: Fibrous sheet F made of a blend of 70% by weight polyethylene terephthalate/30% by weight isotactic polypropylene produced by the method described in B above is laminated and spread. , 140℃,
A mesh sheet structure with a basis weight of 37 g/m ² pressed at 10 Kg/cm ² (during heat compression molding at 180°C)
Elongation stress (S) at 30% elongation (S) 0.06 Kg/cm, plastic deformation rate at 30% elongation 72%) (ii) Nonwoven fibrous web A: “Taka #812” manufactured by Nippon Tokushu Toyo Co., Ltd. (at 180°C) Ten
Example ² (i) Nonwoven fibrous sheet B; Nylon produced by the method described in B above.
Fibrous sheet F consisting of a blend of 680% by weight/10% by weight of isotactic polypropylene/10% by weight of high-density polyethylene was laminated, rolled out, and pressed at 150°C and 5 kg/cm ² to give a fabric weight of 30.
g/cm ² mesh sheet structure (elongation stress (S) at 30% elongation during heat compression molding at 165℃)
(0.07Kg/cm, plastic deformation rate 75% at 30% elongation) (ii) Nonwoven fibrous web A: Apparent consisting of 80% by weight of long fiber glass fibers with a diameter of 7μ and 20% by weight of water-soluble uncured phenolic resin. Glass matte with a density of 0.012 g/ ^cm3 (10
Compressive stress at % compression (T) 0.9 to 1.5 g/cm ² ) Example 3 (i) Nonwoven fibrous sheet B; 100% by weight polybutylene terephthalate was spun at a spinning speed of 500 m/min (8 denier) and bundled. A fibrous sheet is obtained by applying 3.5% by weight of polyacrylic acid ester by rolling it out in the horizontal direction, and then stacking the sheets, rolling out the sheets, and then rolling out 3.5% by weight of polyacrylic ester.
Adhering weight% polyacrylic ester 180
A mesh sheet structure with a basis weight of 40 g/m ² obtained by pressing at 10 Kg/cm ² at 185° C.
cm, plastic deformation rate 70% at 30% elongation) (ii) Nonwoven fibrous web A; Mat made of asbestos with an apparent density of 0.06 g/ ^cm3 (compressive stress (T) at 10% compression at 185°C) 1.3 ~2.0
g/ ^cm2 ) Depending on the material of web A and/or sheet B, web A and sheet B may be able to be integrally joined without using any adhesive, but if necessary, Preferably, between the web A and the sheet B, as an adhesive for bonding them together, a polymer sheet material C that melts at the heating compression molding temperature is preferably used.
It is advantageous to intervene. The adhesive polymer sheet C preferably has a melting temperature lower than the temperature at which the laminate D is heated and compression molded, preferably about 5° C. or more lower than the temperature at which the laminate D is heated and compression molded. ,about
Those with melting temperatures within the range of 100 to about 180°C are preferred. In addition, the shape includes a film shape, a perforated film shape, a nonwoven fabric shape, a knitted woven fabric shape, and the like. In particular, using a thermoplastic polymer having a low melting temperature and using a reticulated sheet structure produced by the method described in US Pat. No. 3,954,928 (BF method) as the adhesive polymer sheet C, Most preferably, this is superimposed on the sheet B in advance and then superimposed on the web A to form a laminate D. Examples of the material of the polymer sheet C include polypropylene, polyethylene, and ethylene-
Hot melt film or nonwoven fabric made of vinyl acetate copolymer, ethylene-acrylic acid metal salt copolymer, etc.; Film or nonwoven fabric made of polyamide hot melt polymer; Film or nonwoven fabric made of polyester hot melt polymer; Uncured phenol A nonwoven fabric made of threads made of resin, uncured melamine resin, uncured epoxy resin, etc. is suitable, and the sheet-like material C generally has a
It can have a basis weight of about 100 g/m ² , preferably within the range of about 1 to about 30 g/m ² . Alternatively, a thermoplastic resin or thermoset powder having a melting temperature below the hot compression molding temperature, preferably within the range of about 100 to about 200°C, is used as the adhesive to bond the web. The resin powder may be spread in an amount of about 5 to about 100 g/m ² on the surface of sheet A to be overlapped with sheet B, and then heated and compression molded. Heat Compression Molding The heat compression molding of the laminate D can be carried out using a mold according to a method known per se. The temperature during this heating compression molding is not limited and can be varied widely depending on the types of web A and sheet B used, but it must be at least above the temperature at which web A and sheet B are thermally deformed. Of course, the temperature is usually between about 120°C and 10°C lower than the lower of the respective melting temperatures of Web A and Sheet B, especially from about 150°C to Web A and Sheet B. 20 from the lower melting temperature of each of B.
Temperatures of up to 50°C are preferred. On the other hand, the compression pressure during the heating compression molding depends on the physical properties required for the final fibrous molded product.
Pressures vary widely depending on the type of material, etc., and cannot be specified unconditionally, but usually, a pressure of 0.01 to 50 Kg/cm ² , preferably 0.02 to 20 Kg/cm ² is advantageously used.
When the web A is composed of inorganic fibers, the weight is preferably 0.01 to 20 Kg/cm ² , more preferably 0.02 to 20 Kg/cm 2 .
A pressure of 3 Kg/cm ² , in particular 0.05 to 50 Kg/cm ² , especially if web A is composed of organic fibers.
A pressure of 0.1 to 20 Kg/ ^cm2 is suitable. In addition, the degree of compression, that is, the ratio of the average thickness of the laminate D to the average thickness of the fibrous molded product before hot compression molding is generally (1.1 to 15):1, preferably (1.5 to
8): It is preferable to perform compression molding so that the ratio is 1. The hot compression molding can be carried out using an ordinary mold. This thickness ratio may vary depending on the location of the same fibrous molded product. By partially changing the thickness ratio in this way, it is expected that the frequency dependence of the sound absorption coefficient will be improved and other characteristics will be improved. Fibrous Molded Product The fibrous molded product provided by the present invention has at least one surface covered with sheet B having an uneven shape, that is, as shown in FIG. The surface of the fibrous molded product 1 on the side covered with the sheet B has a surface structure that is a combination of a raised convex portion 2 and a recessed portion 3 that is lower than the level of the convex portion. It is characterized by the fact that it is not a flat surface. The other surface of the fibrous molded product may have a uniform planar shape or may have an uneven shape. The shape of the unevenness on the surface of the fibrous molded product is not limited to a specific shape, and can be freely and widely varied depending on the use of the molded product. However, in view of the physical properties of web A, it is generally difficult to mold a fibrous molded product with a recessed part when the depth of the recessed part is extremely deep compared to the frontage area of the recessed part. is difficult to obtain. Therefore, the total surface area of each recess on the surface of the fibrous molded product provided by the present invention is typically determined by the frontage area of the recess [this frontage area is equal to the amount of the laminated layers necessary to form the recess]. Equal to the surface area of sheet B side of object D before forming]
It can be at most 40 times or less, preferably at most 2.5 times or less. Regarding the average unevenness ratio of the entire surface of the fibrous molded product, let S ₀ be the total surface area of the sheet B side that is deformed in the laminate before molding, and make the unevenness of the fibrous molded product after molding. When the total surface area of the sheet B side (that is, the same side) is S, S/
The ratio of S ₀ is generally between 1.01 and 2.0, preferably between 1.03 and
Ideally it should be between 1.7. In the fibrous molded product provided by the present invention, the web A serving as the substrate and the sheet B serving as the surface material are completely integrated in close contact with each other, and the surface of the sheet B has no wrinkles, no unevenness, and no irregularities. The outline of the boundary is clear and the appearance is extremely beautiful. Furthermore, the fibrous molded product of the present invention has excellent physical properties as described below. The thickness and density of the fibrous molded product are also not limited and can vary widely depending on the use of the molded product, but the thickness is generally 1 to 60 mm, preferably
It is advantageous to have a thickness of between 1.5 and 50 mm, with a density generally between about 0.02 and about 0.5, preferably between about 0.05 and about
It is appropriate that it be in the range of 0.3. Further, other typical physical properties desired for the fibrous molded product are as follows. (a) Air permeability: >2ml・cm ^-2・sec ^-1 , preferably >10ml・cm ^-2・sec ^-1 (b) Sound absorption coefficient: 100-500Hz...>3%, preferably >5% 500 ~2000Hz...>3%, preferably >5% >2000Hz...>30%, preferably >70% (c) Flexural strength: >0.03Kg/cm ^-1 , preferably >
0.05Kg/cm ^-1 (d) Elastic modulus: >0.04Kg/cm ^-2 , preferably >0.08
Kg/cm ^-2 Application of fibrous moldings As mentioned above, the fibrous moldings of the present invention have excellent aesthetics and functionality, and can be used, for example, as sound absorbing materials for buildings and vehicles, especially for automobiles. It can be widely used as sound-absorbing boards in engine rooms, vibration-proofing materials for machinery and vehicles, and heat-insulating walls in buildings. Definition of terms (1) Compressive stress at 10% compression The "compressive stress at 10% compression" used for web A means the same thickness of web A when an initial load of 0.05 g/cm ² is applied. In this case, the load required to make the thickness of A the same by 0.9 (unit: g/
^cm2 ). This load can be easily measured by attaching an instrument for measuring compressive stress to an Instron type tensile tester. That is, a disk with a diameter of 10 cm was cut out from web A as a sample for measurement, and this was attached to the above Instron type tensile tester, and at a compressive deformation speed of 1 cm/min, the thickness of web A was 0.9%. Measure the required load. If the thickness of web A is less than 2 cm, overlap them until the total thickness exceeds 2 cm and use them as samples for measurement. "Compressive stress at 10% compression at hot compression molding temperature" is the load measured after raising the temperature of the sample attached to an Instron type tensile tester to the temperature during hot compression molding of laminate D. , Heating is performed using an air heating box. The temperature of the sample is measured using a thermocouple with a diameter of 1 mm or less embedded almost in the center of the sample, and when the sample temperature reaches a temperature that is 20°C lower than the heating compression molding temperature, the sample is Installed on testing machine, initial load 0.05g/cm ²
The temperature is raised at a rate of 1 to 5° C./min, and when the desired heating compression molding temperature is reached, it is left as it is for 1 minute, and then measurements are taken. In addition, if the sample is significantly thermally denatured at a temperature lower than the heating compression molding temperature and the measured value changes greatly depending on the heating rate, the compressive stress when the heating rate becomes infinite is The compressive stress at 10% compression is determined by extrapolation. The average of the five measured values is defined as the "compressive stress at 10% compression" in this specification. (2) Plastic deformation rate at 30% elongation and elongation stress at 30% elongation Measured using an Instron type tensile tester. In other words, a sample with a length of 10 cm and a width of 5 cm is stretched by approximately 3 cm at a tensile speed of 10 cm/min.
Hold for 1 minute. 1 required for this retention
Tensile force per cm width (unit: Kg/cm) is 30%
elongation stress during elongation. The testing machine is then returned to its original position at a speed of 10 cm/min. If the gap between the chucks of the sample is measured when the tensile force is reduced to 0.002 Kg/cm, and this is defined as bcm, the "plastic deformation rate at 30% elongation" can be expressed by the following formula. b-10/10×100 (%) The plastic deformation rate and elongation stress at 30% elongation at the hot compression molding temperature are the same as when the laminate D is hot compression molded using a sample attached to an Instron type tensile tester. It can be determined by heating to a temperature equal to the temperature and then measuring using the method described above. Heating of the sample is usually done using an air heating box. For measurement, when the temperature at the center of the sample reaches just 20℃ lower than the heating compression molding temperature, attach the sample to the testing machine and apply the initial load.
Apply 0.01Kg (tensile force of 0.002Kg/ ^cm2 ) and
The temperature is increased at a rate of 5° C./min, and when the desired temperature is reached, measurement is started as described above. If the sample undergoes significant thermal denaturation at temperatures lower than the heating compression molding temperature and the measured values vary considerably depending on the heating rate, exclude the plastic deformation rate and elongation stress when the heating rate is infinite. The plastic deformation rate and elongation stress at 30% elongation are determined by In addition, if the measured value differs depending on the cutting direction of the sample, the plastic deformation rate at 30% elongation is the measured value in the direction that gives the minimum measured value for the plastic deformation rate, and the maximum measured value for the elongation stress. 30% with the measured value in the direction giving the value
This is the elongation stress during elongation. Here, the average values of the five measured values are respectively defined as "plastic deformation rate at 30% elongation" and "elongation stress at 30% elongation." (3) Tensile strength, tensile strength, and elongation In the case of nonwoven fibrous sheet B: Take a sample to a width of 5 cm, attach it to an Instron type tensile tester at an initial length of 10 cm, and test the sample at a tensile speed of 10 cm/min. Pull until it breaks. The maximum breaking strength is defined as "strong", and the elongation at that time is defined as "elongation". Measure 5 times and take the numerical average. In the case of fiber: The fiber used in nonwoven fibrous sheet B is attached to an Instron type tensile tester equipped with an air heating box and measured. The initial length is 0.5 cm and the pulling speed is 0.5 cm/min. The method of heating the fiber to the molding temperature and measuring it is the same as the method of measuring the plastic deformation rate at 30% elongation and elongation stress. The initial modulus is expressed by the slope of the tangent to the rising curve of the obtained stress/strain curve. The unit is g/denier. Elongation is the elongation rate (%) of the fiber when it is cut. Measure 5 times and take the numerical average. (4) Heat compression molding temperature The heat compression molding temperature refers to the temperature of nonwoven fibrous sheet B.
is the maximum temperature raised during hot compression molding, and is usually equal to the surface temperature of the mold in contact with the nonwoven fibrous sheet B. The temperature is preferably 150°C
The above is 20℃ higher than the melting temperature of nonwoven fibrous sheet B.
Lower temperature, more preferably 170℃
The above temperature is 30°C lower than the melting temperature of Sheet B. On the other hand, the surface temperature of the mold in contact with the nonwoven fibrous web A is preferably higher than the temperature at which the web A hardens or is thermally fused and lower than the melting temperature of the web A. Usually this temperature range is 180°C to 250°C, more preferably 190°C to 240°C. (5) Melting temperature The sample is placed on a heating plate and heated at a heating rate of 10℃/min.The melting temperature is determined by the temperature at which the sample melts and loses its original shape. It is called. (6) Apparent density The apparent density of web A and sheet B or fibrous molded product D is determined by cutting a square sample of 10 cm in length and width from web A or sheet B and using the following formula. Apparent density (g/cm ³ )=w/100×d [where w is the weight of the sample (g) and d is the thickness of the sample (cm). ] In the case of web A, thickness d refers to the thickness when a load of 0.05 g/cm ² is applied to web A as described above, and in the case of sheet B and fibrous molded product D, it refers to the thickness of the dial thickness gauge. It refers to the thickness when measured at 5 different points, and is the average value when measured at 5 different points. (7) Average spacing between bonding points and fiber diameter Obtained by observing the mesh sheet structure with a magnifying glass or microscope. A mesh sheet structure is one in which the fibers themselves are bonded two-dimensionally or three-dimensionally. The distance between these joining points can be measured by taking a magnifying glass photograph with different magnifications. Since the connection point has a finite size,
As the distance between bonding points, the distance from the center of the bonding points to the center is measured. The value obtained by measuring between 100 bonding points and averaging them is defined as the "average distance between bonding points" of the mesh sheet structure. The "fiber diameter" can be determined by taking a microscopic photograph of the fiber cross section, measuring the area S _f (average value of 100 pieces) of the fiber cross section, and using the following formula. (8) Adhesive force to metal The bottom plate of the press has a diameter of 5.0 cm and a weight of 5.0 cm.
Place 137 g on iron disk A with a 150-mesh matte hard chrome plating finish. On the other hand, a 150-mesh iron flat plate B with a matte finish and hard chrome plating is fixed to the top plate of the press. However, the iron flat plate B should be wider than the iron disk A. The temperature of the surfaces of disk A and flat plate B (i.e., the hard chrome plated parts) is maintained at the temperature to be measured, and a disk-shaped sample to be measured with a diameter of 6.0 cm is placed so as to cover the entire disk A. The press machine is operated, and the sample is pressed at 10 kg/cm ² for 1 minute by the disk A and the flat plate B to deweight the sample. The above procedure was repeated 5 times, and the sample did not break during degravering all 5 times, and the disc A was replaced by the flat plate B.
When the metal is separated from the metal, it is defined that the metal adhesion strength is 7 g/cm ² or less. (9) Air permeability Measure according to the method shown in JIS P8117. Using a Type B Gallley densometer, the cross-sectional area of the sample is 5.0 x 5.0 cm, and the air permeability (p) is expressed by the following formula, where the time taken for 100 ml of air to pass through the sample is t (sec). p=100/5.0×5.0×t=25/t(mlcm
^-2 sec ^-1 ) (10) Sound absorption coefficient Measure using the standing wave method (normal incidence method). diameter 10
Put the sample to be measured into one side of the cm tube and introduce a sound wave with a constant frequency from the other side to create a standing wave. Measure the maximum and minimum sound pressure with a microphone, and calculate the ratio (R) of the maximum and minimum amplitude of the standing wave. measure,
Find the sound absorption coefficient (α) according to the following formula. Sound absorption coefficient (α) = 4S ² / (S ² +1) ² × 100 (%
) [The larger the α value, the better the sound absorption. S is the ratio of maximum to minimum sound pressure. ] (11) Bending strength and elastic modulus Measured using an Instron type compressive stress measuring machine. Take sample pieces of 5.0 x 15 cm and space them 10 cm apart.
Place it on a support head with a radius of curvature of 0.5 cm and a width of 7.0 cm, and place it on a support head with a radius of curvature of 0.5 cm and a width of 7.0 cm.
) was bent at a compression speed of 5.0 cm min ^-1 from a support head with a radius of curvature of 0.5 cm and a width of 7.0 cm attached to a stress gauge for measuring compressive stress, and the load-deflection curve was plotted. The bending strength (f) and elastic modulus (e) are calculated using the following formula. Bending strength (f) = F/5 (Kgcm ^-1 ) [F indicates the load (Kg) at the time of breaking of the sample. ] Elastic modulus (e) = E/5 [E represents the load (Kg) when the initial slope straight line of the load-deflection curve is extended to a deflection of 1 cm. ] (12) Thermoformability "Thermoformability" used in the Examples below is evaluated as follows. i.e. height 1.5
cm, the upper surface diameter is 2.8 cm, the lower surface diameter is 5.0 cm, and a female and male mold with a radius of 7.5 cm and a truncated cone with a green curvature radius of 5 mm protrudes from the center are placed on the lower plate and upper plate of the press, respectively. Attach to.
(Fix the male mold to the upper plate.) After bringing the surface of the mold to the measurement temperature, place the laminate D of web A and sheet B on the female mold (unless otherwise specified, resheet B has an inner diameter of 20 cm). (scissors, fix and place on the ring), press and evaluate. At this time, the load of the ring should not be applied to the web A. After releasing the mold, the fibrous molded product is removed and visually inspected. If thermoforming is not performed properly, the following phenomena will occur. Web A and sheet B are separated at the circumferential portion of the upper and lower surfaces of the truncated cone (this is called "floating"); sheet B is becoming thinner due to deformation (this is called "fraying"); B sticks to the mold and breaks; Sheet B wrinkles in the direction perpendicular to the circumference of the truncated cone. Evaluate 5 times and record phenomena that occur 3 or more times. Perform the test five times and process and record the data as follows. ◎...When the above-mentioned phenomena did not occur in all five times and a molded plate that adhered well to the mold was obtained. 〇...If the above symptoms are slightly observed. The ratio is 1/20 or less of the circumference of the upper or lower circumference that occurs (average of 5 times)
In the case of ;, the extent to which one or more samples are torn at a portion of 5 mm ² or less (record the reason after the circle). Other...If any of the above phenomena occurs to a degree exceeding ○, record the phenomenon. (13) Elongation rate during thermoforming When laminate D is heat compression molded, sheet B stretches or shrinks in a certain direction. The ratio (%) of the elongation or shrinkage of the sheet B to the original length is called the elongation rate. This elongation rate is determined by marking a line segment of a certain length on the surface of the sheet B, measuring the length of the line segment again after hot compression molding, and calculating the ratio. (14) Measurement of initial modulus and elongation of fiber The fiber forming nonwoven fibrous sheet B is attached to an Instron type tensile tester equipped with an air heating box and measured. Measurement is initial length 0.5
cm, and the pulling speed is 0.5 cm/min. The fiber to be measured is heated to the hot compression molding temperature and measured in the same manner as in the measurement of "plastic deformation rate at 30% elongation and elongation stress at 30% elongation" in (2) above. The initial modulus is expressed by the slope of the tangent to the rising curve of the measured stress-strain curve. The unit is g/de (denier). Further, elongation is expressed as a ratio (%) of the length of the fiber at the time of cutting to the initial length of the fiber. The present invention will be explained in more detail with reference to Examples below, but the scope of the present invention is not limited only to these Examples. In the examples, unless otherwise specified, % means % by weight. The amount (%) of the resin adhesive means the ratio (%) to the weight of the web A. In addition, the abbreviations used in the examples have the following meanings: PET...Polyethylene terephthalate Ny-6...Nylon 6 Ny-6,6...Nylon 6,6 PP...Isotactic polypropylene [η]...Intrinsic viscosity Example 1 69.5% polyethylene terephthalate (PET) chips with [η] = 0.73, 29.2% polypropylene (PP) chips with [η] = 2.0, 0.3% carbon black
and 1.0% talc are blended and put into a hopper. After drying the chips by blowing hot air at 140℃ into the hopper for 2 hours, the chips are fed to a screw whose melting zone is maintained at a temperature higher than the melting point of PET, and the blend is melted by being caught in the screw and conveyed by wheel. Then, nitrogen was blown in from the vent part at a pressure of 60 kg/cm ² , and then the molten polymer and nitrogen were sufficiently kneaded in the metering zone.
Pass it through a spiral mandrel, diameter 16
cm, 60g/ from a ring die with a slit width of 0.25mm
A reticular fiber sheet (PF) with countless cracks in the winding direction was obtained by discharging at a discharge rate of 50 mg/min and winding at a speed of 50 mg/min, which is 0.8 times the maximum draft while cooling with cooling air. This sheet was expanded twice in the transverse direction and the average distance between bonding points and fiber diameter were determined to be 12 mm and 52 μm, respectively. Also, the fiber of this sheet (PF) is 190℃
The initial modulus and elongation are each 0.6
g/de was 60%. Next, the (PF) was laminated in 32 layers, overfeeded at a rate of 1.9 times, and stretched 10 times in the transverse direction, and the temperature
Pressed at 130℃ and pressure 10Kg/ ^cm2 , weight 40g/
^m2 , thickness 110μ, strength and elongation in machine direction 0.3
Kg/cm and 50%, lateral strength and elongation 0.2
A nonwoven fabric B having an apparent density of 0.36 g/cm ³ and 15% was obtained. The plastic deformation rate and elongation stress at 30% elongation at 190°C of the nonwoven fabric B are 113% and 0.065, respectively.
It was Kg/cm. The nonwoven fabric B has a basis weight of 1200 g/m ² and a thickness of 2.5 cm.
Uncured phenolic resin particles (curing start temperature 185
°C) 20%, 40% lost cotton, and 40% recycled wool, was placed on one side of a nonwoven fibrous web A made of 40% lost cotton, and 40% recycled fibers, and was applied using the method described in the text (i.e., the overall unevenness ratio was 1.05, and the unevenness ratio of the truncated conical part (deformed part) was 1.48. thermoformability was evaluated. The male mold was heated to 190°C and the female mold to 230°C, and the nonwoven fabric was placed on the male mold side and pressed for 1 minute with a spacer placed between them so that the thickness of the fibrous molded product was 4 mm. Thermoformability was very good. The maximum thermal deformation occurred at the side of the truncated cone, where the thermoforming elongation deformation was 35%. In addition, the temperature of nonwoven fibrous web A at 190°C is 10
The compressive stress at % compression was 6.3 g/cm ² . In addition, PP nonwoven fabric C with a basis weight of 3 g/m ² is added to the nonwoven fabric B.
PP nonwoven fabric C side is layered with nonwoven fibrous web A
The fibrous molded product D obtained by molding the nonwoven fabric B side at 195°C and the web A side at 230°C for 1 minute into an uneven shape with an overall unevenness ratio of 1.2 is different from the nonwoven fabric A. The web B was firmly bonded.
The apparent specific gravity of the fibrous molded product D is 0.3, the bending strength of the general surface is 0.054 Kg/cm, and the bending elastic modulus is
It was mechanically excellent at 0.12Kg/cm ² , and the aesthetics of the nonwoven fabric B side were also excellent. Also, the sound absorption coefficient measured with a 5cm space behind the general surface was 3000.
It was 73% in Hz. Examples 2 to 6 and Comparative Examples 1 to 4 In these Examples and Comparative Examples, the initial modulus and elongation of the fiber at the forming temperature; 30% of the sheet.
Nonwoven fibrous sheet B made of various materials with various values of plastic deformation rate at elongation and stress at 30% elongation and PP nonwoven fabric with a basis weight of 3 g/m ² (acts as an adhesive)
and 1 of the nonwoven fibrous web A used in Example 1.
The sheets were assembled one by one, and the thermoformability was evaluated as described in the text (ie, overall unevenness 1.05, truncated cone (deformed part) unevenness 1.48). Molding conditions: The nonwoven fibrous sheet B is placed on the male mold side, and the nonwoven fibrous web A is placed on the female mold side. Molding thickness = 4mm (using a 4mm spacer) Molding temperature is shown in the table.

[Table] Symbol explanation of nonwoven fibrous sheet B (S) PET-PF28/PET-DF1: Stretched-crimped tow of PET with 28 layers of (PF) obtained in Example 1 and 2 denier single yarn ( Stretching ratio 3.5
One layer of parallel sheets (DF) with a fabric weight of 27 g/m ² with 4% polyacrylic acid ester applied by opening the fibers (16 crimps/inch) and laminating the (DF) in the center. (The ratio of DF was 17%), a sheet obtained by spreading and pressing under the same conditions as in Example 1. (Weight
42g/m ² , thickness 105μ) (S) (Ny-6)-PF24: Nylon-6 (Ny-6) chip with [η] = 1.3
79% polypropylene (PP) chips, 19.5% polypropylene (PP) chips, 0.3% carbon black, and 1.2% talc, melted in the same manner as in Example 1, kneaded by blowing nitrogen, and discharged from the same slit in an amount of 55 g/
24 layers of cracked reticular sheets with an average distance of 5 mm between bonding points obtained by discharging at 54 m/min (77% of maximum draft) and overfeeding 1.9 times are supplied in the lateral direction. Expanded 6.0 times, then 154
Sheet obtained by pressing at 15Kg/cm ² at ℃. (Weight: 28 g/m ² , thickness: 95 μ) (S) PET-UF2: Undrawn PET yarn with a single yarn of 6.5 de is opened, 4% polyacrylic acid ester is attached, and the average between bonding points is Obtain parallel sheets (UF) with a distance of 4 mm and a basis weight of 170 g/m ² . Example 1 by stacking two of these sheets
A sheet obtained by spreading under the same conditions as in Example 1, attaching an additional 5% polyacrylic acid ester, and pressing under the same conditions as in Example 1. (Weight: 75 g/m ² , thickness: 130 μ) (S) (Ny-6)-UF2: Undrawn Ny-6 yarn with a single yarn of 7.0 de is opened and 4% polyacrylic acid ester is attached. A parallel sheet (UF) with an average distance between bonding points of 5 mm and a basis weight of 190 g/m ² is obtained. Example 1 by stacking two of these sheets
A sheet obtained by spreading under the same conditions as above, adhering 5% polyacrylic acid ester, and pressing at 155°C and 15Kg/cm ² . (Weight: 81 g/m ² , thickness: 138 μ) (US) PET-PF2: A sheet obtained by stacking two parallel crack sheets (PF) obtained in Example 1 without stretching and pressing at 130°C. . (Weight: 36g/m ² , thickness: 105μ) PET-SF: A drawn-crimped tow of PET with a single yarn of 2de (stretching ratio: 3.5x, number of crimps: 12/inch) was cut into a length of 5cm, A sheet obtained by forming a web using a dry method, applying 20% polyacrylic ester, and pressing at 200℃. (Average distance between bonding points = 0.1
mm, basis weight 53g/m ² , thickness 130μ) (S)PET-DF6: Parallel sheet (DF) with an average distance between bonding points of 2mm used in (S)PET-PF28/PET-DF1
6 layers were stacked, overfed and spread in the same manner as in Example 1, and polyacrylic acid ester was applied so that the final adhesion amount was 20%, dried, and
Sheet obtained by pressing at ℃. (Weight: 29g/m ² , thickness: 100μ) PET-film: Thickness: 12μ obtained by stretching 3 times in the vertical and horizontal directions.
A film made of PET. (Ny-6)-SB: Ny-6 is discharged from a nozzle and stretched by an air flow to make the single thread de 1.8, and then accumulated on a wire mesh by an air flow to form a 0.5 mm wide, 1 x 1 mm square mesh. Sheet obtained by embossing. (Weight 27g/m ² , thickness 130μ)

【table】

【table】

【table】

[Table] Examples 7 to 9 and Comparative Examples 5 to 7 Here, the finishing conditions of the same material were changed to obtain sheets with different plastic deformation rates at 30% elongation and elongation stress at 30% elongation, and thermoforming was performed. Show the results of the test. In the same process as in Example 3, except for the press temperature conditions, the raw material of Example 3 was used to obtain an initial modulus of 1.5 to 0.42 g/de and an elongation of 55 to 55 at 160 to 180°C.
A sheet consisting of 70% fiber is obtained. The roll press temperature at which each sheet was manufactured and 30%
Plastic deformation rate at elongation, elongation stress at 30% elongation and 5℃
Table 3 shows the results of the thermoforming test described in the text, which was performed by varying the temperature. For the thermoforming test, the same web A as in Example 1 was used, and the adhesive was a 3 g/m ² PP nonwoven fabric. It is clear from Table 3 that the plastic deformation rate at 30% elongation and 30
It can be seen that both values of elongation stress at % elongation are not within the claimed range, and a satisfactory thermoformed plate cannot be obtained.

【table】

[Table] In Comparative Examples 5, 6, and 7, the temperature of the male mold was further raised to 185°C, but the nonwoven fabric adhered to the mold. The thickness of the thermoformed plate is 4 mm, and the 10% compressive stress of the Taka used is 6.5 to 4.0 g/in the temperature range of the male mold mentioned above.
It was warm in ^cm2 . Examples 10-12 and Comparative Examples 8-10 Nonwoven fiber sheet PET-PF28/PET of Example 2
- Using DF1, the thermoforming temperature was changed every 10°C, and the initial modulus of the constituent fibers, elongation, plastic deformation rate at 30% elongation of the sheet, changes in stress at 30% elongation, and thermoforming as described in the text. Table 4 shows the results of measuring changes in sex. A polyethylene nonwoven fabric with a basis weight of 3 g/m ² was used as the adhesive. The nonwoven fiber web A used was the same as in Example 1. The thickness of the molded product after molding was set to 6 mm.

【table】

[Table] As is clear from Table 4, even if other items are within the claimed range, if the stress at 30% elongation is outside the range, thermoformability is poor. (Mainly floating occurs.) Examples 13 to 14 and Comparative Examples 11 to 12 Nonwoven fabric of Example 2, PET-PF28/PET-DF1
The thermoforming test described in the text was conducted by changing the 10% compressive stress at the thermoforming temperature of the pine (that is, by changing the apparent density), and the occurrence of "wrinkles" was observed. Table 5 shows the results. Obviously S/
When T<0.03, wrinkles are less likely to occur.

[Table] Examples 15 to 16 and Comparative Examples 13 to 14 The composition was 50% wool, 30% cotton, and 20% uncured phenolic resin powder. Compressive stress at 10% compression at 180°C was 3.7 g/cm ² Fabric weight with a certain apparent density of 0.025
750 g/m ² of pine and PET-PF28/ of Example 2
The thermoforming test described in the text was conducted using nonwoven fabrics similar to PET-DF1 with a basis weight of 25, 50, 75, and 100 g/ ^m2 obtained by varying the number of laminated PET-PF sheets. We investigated the occurrence of As shown in Table 6, when S/T<0.03, the occurrence of wrinkles was clearly reduced.

[Table] Example 17 Example 3 During the production of (Ny-6)-PF24, silicone oil was applied to the surface layer on one side at a concentration of 3% based on the total weight of the nonwoven fabric, spread and pressed. The nonwoven fabric thus obtained had a metal adhesion strength of 7 g/cm ² at 190°C, and the results of the same thermoforming test as in Example 3 were ◎ up to 190°C. On the other hand, non-woven fabrics without silicone oil can only reach temperatures of 183℃◎
However, the metal adhesion strength exceeded 7 g/cm ² at 185°C. Example 18 The metal adhesion strength of the nonwoven fabrics of Examples 2, 3, 4, and 6 at the thermoforming temperature was all 7 g/cm ² or less. Example 19 Nonwoven fabric in Example 2, PET-PF28/PET
- When manufacturing DF1, a flame retardant suspension of 50% decabromodiphenyl ether/45% liquid paraffin/5% graphite is added to the intermediate layer by 60% of the weight of the nonwoven fabric.
The sheet B obtained by adhering, spreading, and pressing was bonded to a sheet with a fabric weight of 1000 containing 20% uncured phenol resin powder, using a 6 g/m ² PP nonwoven fabric as an adhesive.
g/m ² , a thickness of 3 cm, and a fiber diameter of 7 μm, it was attached to one side of a glass mat while being thermoformed into irregularities.
(Mold temperature on the non-woven fabric side = 185°C, mold temperature on the glass mat side = 220°C, molding thickness (general surface) = 2cm, molding time = 2 minutes) The average apparent density of this aesthetically molded plate is 0.07g. /cm ³ , overall unevenness ratio is 1.1, bending strength is 0.08Kg/cm , bending elastic modulus is 0.08Kg/cm ² ,
The sound absorption coefficient at 3000Hz is 75%, and it was installed on the engine hood of a car and was suitably used as a soundproof mat. Further, when the general surface was cut into a rectangle of 1.0 cm x 30 cm and the sheet B was placed on the bottom surface, evaluation was made according to FMVSS 302, and it was found to be "self-extinguishing". Example 20 79.5% of polybutylene terephthalate chips with [η] = 1.1, 19.2% of PP chips with [η] = 2.0, 0.3% of carbon black and 1.0% of talc were blended and dried in the same manner as in Example 1. Feed it through a screw, melt it, blow in nitrogen and knead it, then pass it through a mandrel with a slit width of 0.25 mm.
It was discharged at a rate of 57 g/min from a ring die with a diameter of 16 cm, and wound at a speed of 50 m/min while being cooled by cooling air, with an average distance of 10 mm between joint points with numerous cracks in the winding direction. A reticular fiber sheet (PF) with a fiber diameter of 43μ was obtained. The (PF) was laminated in 34 layers, overfeeded at a rate of 1.9 times, stretched 10 times in the transverse direction, and heated at a temperature of 150
℃ and a pressure of 12 kg/cm ² to obtain a nonwoven fibrous sheet B having a basis weight of 41 g/m ² and a thickness of 105 μm. The initial modulus of the fiber of the nonwoven fabric B at 185°C is 1.2 g/de, and the fiber of the nonwoven fabric B has an initial modulus of 185
The plastic deformation rate and elongation stress at 30% elongation at °C were 74% and 0.073 Kg/cm, respectively. The same flame retardant suspension as in Example 19 was applied to the non-woven fabric B so that the amount was 35% of the non-woven fabric, and 5% of silicone oil was further applied to increase the water repellency.
m ² of PP nonwoven fabric was used as an adhesive, and the overall unevenness was adjusted to Taka #12 (a nonwoven fiber web made of organic fibers containing thermosetting resin with a basis weight of 1200 g/m ² ) manufactured by Nippon Tokushu Toyo Co., Ltd. It was thermoformed to a size of 1.25 and attached at the same time. (Mold temperature on the nonwoven fabric side = 185℃, Taka
#812 side mold temperature = 235℃, molding thickness (general surface) =
4.5mm, molding time 1 minute) The average apparent density of the resulting aesthetic fibrous molded product is 0.21g/cm ³ , bending strength is 0.06Kg/cm , bending modulus is 0.12Kg/cm ³ , 3000Hz The sound absorption coefficient is 73% (5cm
(creates an air layer), making it suitable as a soundproof mat for automobile engine hoods. Further, the general side was cut into a rectangle of 10 cm x 30 cm, and the flame retardance was evaluated according to JIS D1201 with the sheet B as the bottom surface, and it was found to be "self-extinguishing".

[Brief explanation of the drawing]

Attached FIG. 1 shows an example of a cross-sectional view of the laminate before hot compression molding in the present invention, and FIG.
The figure is a perspective view showing an example of a fibrous molded product having an uneven surface according to the present invention.

Claims (1)

[Claims] 1. A nonwoven fibrous web A that can be heat compression molded;
A fibrous molded product having an uneven surface obtained by integrally heating and compression molding a laminate of the web A and a nonwoven fibrous sheet B laminated on at least one side using a mold, (a) The above-mentioned nonwoven fibrous web A has a compressive stress of at least 10% compression at the heating compression molding temperature.
0.5 g/cm ² and a thickness of 5 to 60 mm, and at least 5% based on the weight of the web A.
(b) The nonwoven fibrous sheet B is a thermoplastic polymer having an initial modulus of 5 g/denier or less and an elongation of at least 20% at a hot compression molding temperature. It is an aggregate of fibers and consists of a continuous, unitary reticulated sheet structure in which each fiber is mutually bonded to its adjacent fibers at intervals, and is plastically deformed at 30% elongation at a hot compression molding temperature. of at least 50%, and the elongation stress at 30% elongation at the hot compression molding temperature is 0.15Kg/
cm or less, (c) Moreover, the nonwoven fibrous web A and the nonwoven fibrous sheet B satisfy the following relational expression, S≦0.03T [where T is the nonwoven fiber Compressive stress (g/
cm ² ), and S represents the elongation stress (Kg/cm) at 30% elongation of the nonwoven fibrous sheet B at the heating compression molding temperature. ] (d) A fibrous molded article having an uneven surface, further characterized in that the fibrous molded article has a density of 0.02 to 0.5. 2 Nonwoven fibrous web A has a weight of 0.005 to 0.15 g/cm ²
The molded article according to claim 1, having an apparent density of . 3. The molded article according to claim 1, wherein the nonwoven fibrous sheet B has a basis weight of 15 to 150 g/ ^m2 . 4. The nonwoven fibrous sheet B has a weight of at least 0.1 kg/
The molded article according to claim 1, having a tensile strength of cm. 5. The molded article according to claim 1, wherein the nonwoven fibrous sheet B has an elongation of at least 5%. 6 The average distance between the bonding points of each fiber of the mesh sheet structure constituting the nonwoven fibrous sheet B is 1 to 50 mm.
A molded article according to claim 1. 7. The mesh sheet structure constituting the nonwoven fibrous sheet B is an aggregate of a large number of thermoplastic polymer fibers arranged substantially two-dimensionally in a substantially constant direction, and each fiber is randomly spaced. A thin fibrous sheet and/or a thin fibrous sheet interconnected with adjacent fibers at a distance.
Or, the molded article according to claim 1, which is obtained by stacking at least two fibrous sheets developed in a direction substantially perpendicular to the axis of the fibers. 8. The molded product according to claim 1, wherein the nonwoven fibrous sheet B has a plastic deformation rate at 30% elongation at a hot compression molding temperature of at least 60%. 9. The molded product according to claim 1, wherein the nonwoven fibrous sheet B has an elongation stress at 30% elongation at a hot compression molding temperature of 0.1 Kg/cm or less. 10 Nonwoven fibrous web A and nonwoven fibrous sheet B
Claim 1, in which a polymer sheet-like material C that melts at the heating compression molding temperature is interposed between the
Molded products described in Section 1. 11. The molded product according to claim 1, wherein the total surface area of the linear molded product on the side covered with sheet B is 0.01 to 2.0 times the total surface area of the same side of the laminate before molding.