JPS6153948B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved composite sheet-like structure having excellent properties, in particular, a high degree of flexibility, excellent pilling resistance, good air permeability, excellent strength, good heat sealability, and light weight. This invention relates to an improved composite sheet-like structure that has various properties such as. More specifically, the present invention comprises (A) a nonwoven sheet-like web made of continuous filaments of synthetic resin (a); and (B) a mixture of at least two resins having integrated network intersection points and having different melting points. (A) and (B) of a net-like sheet web made of continuous thermoplastic synthetic resin net strands (b) are a composite sheet-like structure that is bonded by heating; (ii) The web (B) has a basis weight of about 1 to about 10 g/m ² , and the average diameter of the net strands (b) is about 1 to about 100 g/m ² .
μ, the network average length is at most 5 mm, and the net strand (b) is made of a mixture of at least two resins with melting points different by about 20°C or more, and the melting point of the resin having the lowest melting point among these resins is: about 20° C. or more lower than that of the filament (a) and in an amount of about 5 to about 95% by weight based on the mixture; (iii) the web (A) and the web in the composite sheet-like structure; (iv) the composite sheet-like structure has a basis weight of about 10 to about 200% by weight, based on the total weight of (B);
g/m ² , and (v) the filament (a) is
(b) is partially conjugated throughout the composite sheet-like structure. The present invention relates to a composite sheet-like structure characterized by the following. Conventionally, a large number of techniques have been known regarding nonwoven sheet-like webs made of continuous filaments of synthetic resin in which individual filaments are randomly arranged, and their manufacturing methods, such as spunbond methods, spread methods, and various other methods. A method has been proposed. Numerous techniques are also known for bonding means for imparting practical filament-to-filament bonding to such nonwoven sheet-like webs. For example, a bonding method using a binder, a bonding method using physical entanglement such as needling using a needle or a fluid, a bonding method using heat pressure bonding using the melt adhesive property of the filament itself, and a combination thereof. Coupling means, etc. are known. However, for example, high flexibility and good fuzz resistance, high flexibility and good strength,
There are properties that are difficult to reconcile, such as good air permeability and good fuzz resistance or good strength, and these properties, such as a high degree of flexibility, good fuzz resistance, good air permeability and The reality is that it is practically impossible to combine excellent strength in a well-balanced manner. Conventionally, in order to provide a nonwoven composite sheet-like structure that has a fibrous texture, air permeability, and practical strength, (A) a nonwoven composite made of continuous filaments of synthetic thermoplastic resin (a) has been developed. A net-like sheet web consisting of a woven sheet-like web and (B) a net strand of a thermoplastic synthetic resin made of at least two resins having integrated mesh crossing points and having different melting points; It has already been proposed that (A) and the web (B) are joined by heating (Japanese Patent Laid-open No. 52
-Refer to Publication No. 49284). In this proposal, polyethylene (melting point:
100-135℃) and polypropylene (melting point: 160-175
A foaming agent is added to a mixture of at least two types of resins having different melting points, such as resins having different melting points (e.g. , a reinforcing member (for example, a polyethylene net having fused reticular intersection points) made of a resin having a melting point that is the same as or close to that of the resin having a low melting point among the resins is layered, and the reinforcing member is fused with the foamed and defibrated reticulated sheet web. Heat and pressure fusion is carried out under conditions such that the material will adhere. However, as shown later in Comparative Example 6, in the composite sheet-like structure of this proposal, webs (A) and webs (B) can be fused together to maintain sufficient strength; It was found that the flexibility of the sheet-like structure was significantly lost, and that it was not possible to obtain a sheet-like structure that had both of these mutually incompatible properties. It was also found that the product was inferior in terms of breathability. The present inventors ensured a uniform and random dispersion arrangement of the filaments, and balanced various properties that could not be achieved conventionally, such as a high degree of flexibility, excellent fuzz resistance, good air permeability, and excellent strength. Research has been carried out to provide a significantly improved composite structure with improved properties. As a result, unlike the above proposal, the melting point was approximately 20℃.
It is composed of a mixture of at least two different resins, and the melting point of the resin having the lowest melting point among these resins is the same as that of the synthetic resin continuous filament constituting the web (A).
(B) consisting of a net strand (b) having a melting point of about 20° C. or more below the melting point of (a) and having an amount of from about 5 to about 95% by weight, based on the weight of the mixture; By using a reticulated sheet web with
It is possible to provide a composite sheet-like structure having
This sheet-like structure satisfies the above-mentioned requirements (i) to (v), and has high flexibility, excellent fuzz resistance, good air permeability, and We discovered that it is possible to create a composite sheet-like structure that has various properties such as high strength, good heat sealability, and light weight. Furthermore, this composite sheet-like structure has a well-balanced combination of the above-mentioned improved properties, and is suitable for industrial use, agriculture, horticulture, other wide industrial fields, packaging, clothing,
For interior use and other wide range of consumer materials, etc.
It was found that it can be used as an excellent material free from the limitations of conventional products. Accordingly, an object of the present invention is to provide a heat-bonded composite sheet structure having excellent properties. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The composite sheet-like structure of the present invention comprises (A) a non-woven sheet-like web made of a synthetic resin continuous filament (a), and (B) at least two types of non-woven sheet-like webs having integrated mesh intersection points and having different melting points. A net-like sheet web (A) and (B) consisting of continuous thermoplastic synthetic resin net-strands (b) made of a mixture of resins are bonded together by heating to form a composite sheet-like structure. The layers of the web (A) and the web (B) can be of any suitable number of layers adjacent to each other and superimposed in the form of a multilayer structure of two or more. The individual filaments (a) constituting the nonwoven sheet-like web (A) are either partially bonded to each other or not bonded to each other. Even when the web is bonded, the bond is partially bonded by means such as binder treatment, physical entanglement treatment, bonding treatment using the adhesive force of the filament (a) itself, and the web (A) is preferably a web with a loose structure as a whole. That is, in the present invention, the web (A) is a nonwoven sheet-like web that can be easily deformed against external stress, and the individual filaments (a) constituting the web are bonded together. Preferably, the web is of a loose structure, either uncoupled or loosely connected in parts. In order to specify the above-mentioned loose structure, a web (A) having a looseness defined below of about 0.05 to 5.0 (g/5 cm/g/m ² ) is particularly preferable. Method for measuring looseness of web (A); Measured by the tensile strength measuring method described in JIS L-1085. The sample size is 5 cm x 20 cm, the chuck grip interval is 10 cm, and the tensile speed is 30 cm per minute. Looseness can be expressed as the stress at 30% elongation (g/5cm) with respect to the original length of the sample, but this value can be divided by the weight per unit area of the web (A) (g/m ² ). It is appropriate to express it as a value (g/5cm/g/m ² ). However, the average value of n = 20 for each vertical and horizontal random portion from the 1m square web (A). In the present invention, the filament (a) having a crimp is suitable as the filament (a) for providing the nonwoven sheet-like web (A) having a loose structure as described above. It is preferable that such a crimped filament (a) has a number of crimps (number of crimps) of about 10 to about 40 per inch of filament (a).
The preferred fineness of the filament (a) is approximately
A fineness of 0.1 to about 15 denier can be exemplified. In the present invention, the above-mentioned (A) nonwoven sheet-like web made of the synthetic resin continuous filament (a) has the following requirements: (i) the web (A) has a basis weight of about 2 to about 30 g/m ² , preferably about 3;
It is necessary to satisfy the condition of ~20 g/m ² as a bonding parameter with other requirements. web
If the basis weight of (A) is too large beyond the above range, the bonding properties with the net strands that satisfy requirement (ii) constituting the web (B) will be poor, causing problems such as delamination. If it is too small, it will be difficult to maintain a satisfactory strength of the composite sheet-like structure of the present invention, so it is required that the above requirement (i) be satisfied. It is preferable that the filaments (a) are distributed uniformly in the web (A). Also, the web (A)
In addition to continuous filaments of thermoplastic synthetic resin (a), for example, recycled fibers such as rayon, semi-synthetic fibers such as acetate, inorganic fibers such as carbon fiber, etc.
Other filaments such as natural fibers such as silk may also be included. Such other filaments are preferably utilized in amounts such as, for example, from about 1% to about 30% by weight in web (A). (A) Continuous filament of synthetic resin used in the present invention
There are no particular restrictions on the manufacturing method of the nonwoven sheet-like web made of (a), and any manufacturing method that can form a preferable web with a loose structure as described above can be adopted. Hereinafter, several aspects thereof will be illustrated. One example is shown in Japanese Patent Publication No. 42-27599. This process consists of extruding a high polymer material in the molten or solution state through a number of adjacent holes into a continuous filament, which is sprayed from a spinneret substantially parallel to each side of the filament band in an undisturbed manner. The continuous filament is drawn out using a stream of gas or steam, stretched and solidified, and the entire filament band is passed through a flat air conduit with both ends open and slightly wider than the filament band so that the filaments are combined into a thread. The material is transported in the form of a wide band as it exits the spinneret without formation, and after exiting the conduit, it is collected on a collection mold that moves at a speed less than the spinning speed, thereby entangling, crossing, and forming layers. ``A method for producing a fibrous molded article comprising a continuous filament.'' Another example is the method described in Japanese Patent Publication No. 37-4993, in which "a multifilament yarn of continuously synthesized organic filaments is run and electrostatically charged to separate the filaments in the charged portions of the yarn. A method for producing a filamentous structure, characterized in that the filaments are collected while remaining separated. Still another example is the method disclosed in Japanese Patent Publication No. 51-6795, in which "a crimped tow is opened so that the fibers are substantially aligned in one direction, and then the fibers are bonded together with a small amount of adhesive. The fiber sheets are temporarily bonded together to form a fiber sheet, and one or more of the sheets are appropriately overlapped and stretched in the width direction, and then treated with an adhesive, or the fibers themselves are heat-sealed. A method for producing a nonwoven fabric, which is characterized by fixing a network structure. Among these manufacturing methods, preferred is the method disclosed in Japanese Patent Publication No. 51-6595, in which a crimped tow is opened and a pre-bonded fiber sheet is stretched in the width direction to form a web. Furthermore, as a method of opening crimped tow,
No. 46-6114 discloses that ``Continuous multi-filament long fibers are fed to a pair of gear-like rollers that rotate in mesh at a speed slower than the surface speed of the rollers to bend them, and then the fibers are once relaxed. A process for the production of sheet-like materials, characterized in that the mutual position of the single fibers is fixed, especially after they have been deposited in sheet form. In the present invention, (B) is another web that forms a composite sheet-like structure together with the above-mentioned web (A).
A reticulated sheet web consisting of a continuous net strand (b) of a thermoplastic synthetic resin made of a mixture of at least two resins having an integrated network crossing point and different melting points shall satisfy the following requirement (ii). is required as a coupling parameter with other requirements. (ii) The web (B) has a basis weight of about 1 to about 10 g/m ² , and the average diameter of the net strand (b) is about 1 to about 100 g/m 2 .
μ, the network average length is at most 5 mm, and the net strand (b) is made of a mixture of at least two resins with melting points different by about 20°C or more, and the melting point of the resin having the lowest melting point among these resins is: The temperature is about 20 DEG C. or more lower than that of filament (a), and the amount is about 5 to about 95 percent by weight, based on the mixture. This requirement (ii), together with requirements (i), (iii), and (iv), is an important factor for satisfying the structural feature of requirement (v) of the present invention. Net strands (b) constituting the reticulated sheet web (B) as specified in requirement (ii) above;
have melting points of about 20°C or higher, e.g. about 20°C to about 200°C.
It consists of a mixture of at least two species having different degrees of temperature. Further, the melting point of the resin having the lowest melting point among these resins is about 20°C or more, for example, about 20°C to about 200°C lower than the melting point of the resin of the filament (a) constituting the web (A). Moreover, the amount of the lowest melting point resin is from about 5 to about 95 weight percent, preferably from about 10 to about 90 weight percent, based on the weight of the mixture. In the present invention, the above-mentioned at least two having different melting points
Using a single resin instead of a seed mixture
When bonding (A) and web (B) by heating, it is practically impossible to control the heat treatment conditions to a satisfactory degree, and slight variations in the heat treatment conditions,
Even if there is a slight variation that cannot be avoided during normal operation, problems such as insufficient bonding between webs (A) and webs (B), resulting in fuzzing, may be unavoidable, and/or problems may occur when webs (A) and webs (B) delamination may occur, or conversely, instead of obtaining satisfactory results in these respects, the entire composite sheet-like structure approaches a film-like structure and the desired flexibility is lost. Trouble cannot be avoided. In addition, by satisfying both the melting point requirement and the usage amount requirement of the resin with the lowest melting point, the web (A) can easily withstand stress from the outside under conditions of bonding with other requirements. A composite sheet obtained by heat-treating filaments (a) constituting the heat-treated web (A) with said net strands (b) without the risk of substantially losing its deformable loose structure. It is possible to ensure the formation of a structure that satisfies requirement (v), which will be described in detail later, of conjugation partially and at multiple locations throughout the shaped structure. The difference in melting point of at least two resins constituting the mixture is too small by less than about 20°C, and/or the amount of the resin having the lowest melting point among the resins is too large or too small outside the above range. If the above requirement (v)
It is practically impossible to form a structure that satisfies the following, and it is not possible to provide the composite sheet-like structure of the present invention that has the above-mentioned mutually incompatible properties. Further, in the present invention, the web (B) has a basis weight of about 1 to about 10 g/m ² , preferably about 2 to about 8 g/m ² ,
The average diameter of the net strands (b) is about 1 to about 100
A web (B) is used having a .mu., preferably from about 2 to about 80 .mu., and an average mesh length of at most about 5 mm, preferably from about 0.1 to about 4 mm. If the basis weight exceeds the above range and is too large, the preferable flexibility of the resulting composite sheet-like structure will deteriorate, and if it is too small, it will be difficult to avoid the problem of fluffing, so the above range should be adopted. or,
If the average diameter is too large beyond the above range, the flexibility will deteriorate, and if it is too small, problems such as poor air permeability will occur. Furthermore, the average mesh length is approximately 5
The use of a reticulated sheet web that is too large, exceeding mm, should be avoided because it causes disadvantages such as deterioration in fluffing resistance and poor heat sealability. A web (B) that satisfies the basis weight, average diameter, and average mesh length specified in requirement (ii) above is such that a straight line connecting any two points on any part of the surface of the web (B) is
Expressed in terms of how many net strands (b) are crossed, if the above straight line is drawn at 2 mm intervals, the number of strands (b) that cross this straight line is approximately 3.
~100, particularly about 6 to about 30, are preferred. There are no particular restrictions on the manufacturing method itself of the reticulated sheet web (B) that satisfies the above requirement (ii) used in the present invention, and any manufacturing method that can form a reticulated sheet web that satisfies the above requirement (ii) may be used. be able to.
Several aspects will be described below. (i) A method in which countless irregular cracks are created in a thin film and then widened. (ii) A two-layer ring die having a large number of thin nozzles arranged in an annular shape is rotated and a fibrous material is extruded from the nozzles to form a mesh. There are methods of forming sheets continuously, but the method disclosed in Japanese Patent Publication No. 49-3458 is particularly preferred. This method involves extruding and pulling a molten thermoplastic polymer containing an expandable material through a die to produce a sheet-like structure having numerous discontinuous cracks along one direction, with the cracks aligned in the same direction. The laminate is fed in a relaxed state from the entrance roller at a speed ratio of pushing roller supply speed: entrance roller supply speed = 1.1 to 3.0:1,
A method for producing a spread web, which comprises opening the fibers at a spreading angle of 10 to 60 degrees and a spreading magnification of 3 to 15 times. ”. In the present invention, the web (B) as described above has integral mesh crossing points and is composed of continuous net strands. In particular, the above-mentioned Special Public Service 1977-
A reticular sheet web of the type manufactured by the method described with reference to Publication No. 3458 is a continuous multifilament aggregate structure, with each net strand being randomly and irregularly spaced from each other. The connections form a large number of meshes that vary randomly and irregularly in shape and size. Then, the above continuous points are
They form integrated mesh crossing points as branching points of the strands. Furthermore, the composite sheet-like structure of the present invention
Based on the total weight of (A) and web (B), the amount of web (A) is from about 30 to about 90%, preferably from about 40 to about 80% by weight.
It is about % by weight. This requirement (iii) is also essential for the composite sheet-like structure of the present invention as a bonding parameter with other requirements. That is, in the composite sheet-like structure of the present invention, the weight occupied by each of web (A) and web (B) per unit area is expressed by their weight ratio: web (A)/web (B). = approx. 30 to approx. 90/approx.
70 to about 10, preferably about 40 to about 80/about 60 to about 20
It is. In the composite sheet-like structure of the present invention, if the amount of web (A) exceeds the above range, the fluffing resistance and heat sealability of the composite sheet-like structure will deteriorate, and the amount of web (A) will decrease. If it is too high, it will cause disadvantages such as deterioration of flexibility and breathability, so the above requirement (iii)
is required to satisfy the following requirements. Generally, within the above range, as the amount of web (A) increases, flexibility and breathability tend to increase, and as the amount of web (B) increases, fluffing resistance increases. Tend. The proportions of web (A) and web (B) can be appropriately selected according to the above guideline depending on the desired balance of the above-mentioned properties. In the composite sheet-like structure of the present invention, as a combination parameter with other requirements, further requirement (iv) is that the basis weight of the composite sheet-like structure is about 10 to about 200 g/m ² ,
Preferably, it is necessary to satisfy the condition of about 12 to about 150 g/m ² . If the basis weight exceeds the above conditions and is too large, properties such as flexibility and air permeability will deteriorate, and if it is too small, the strength will decrease and practicality will be lost. Therefore, it is desirable to satisfy requirement (iv) above. Furthermore, the composite sheet-like structure of the present invention has a unique characteristic three-dimensional structure in the relative structure in the thickness direction of the sheet-like structure and the sheet plane direction (vertical and horizontal). That is, the composite sheet-like structure of the present invention has requirements (i), (ii), (iii), and (iv) as well as requirement (v) that the filament (a) is the net strand (b). ), the composite sheet-like structure has a partially joined structure at multiple points throughout the composite sheet-like structure. This conjugated structure constitutes an overall loose structure of the web (A), i.e. an unbonded or loosely bonded non-woven sheet-like web (A) that is easily deformable in response to external stresses. This is a structure in which the web (A) and the web (B) are integrated to an extent that allows the filaments (a) to be relatively easily displaced from each other. This conjugation structure is such that the resin having the lowest melting point in the resin mixture constituting the net strand (b) of the web (B) is partially bonded to the filament (a) of the web (A). A structure in which the filament (a) is completely or incompletely fused at a number of points;
The resin with the lowest melting point in the filament (b) forms a web with or without the above-mentioned sucking structure.
A structure in which (A) is interposed between the web and the adjacent multiple layers of web (B) to completely or incompletely bridge them in the thickness direction of the composite sheet-like structure; A filament (a) in which a resin with a melting point is located closer to the web (B) is interposed between the web (A) and a filament located further away from the web (B).
A structure that completely or incompletely bridges between (a) and web (B) in the thickness direction of the composite sheet structure; the above bridging structure may be diagonal in the thickness direction, etc. Contains structure. Due to such a conjugated structure, the nonwoven filaments (a) in the web (A) can be attached to the net strands of the web (B) without losing the ease of displacement between them.
(b) is partially conjugated throughout the composite sheet-like structure, and the web (B) has integrated mesh intersection points and is a reticulated sheet web consisting of continuous net strands. Coupled with this, the composite sheet-like structure of the present invention that satisfies the above-mentioned requirements (i) to (v) is a unique composite structure that combines various mutually incompatible improved properties that were previously desired but could not be realized. It becomes a sheet-like structure. Next, an example of the composite sheet-like structure of the present invention will be explained using the accompanying drawings. The attached drawings are web (B) - web (A) - web (B) -
5-layer web (B) and 4-layer web (B) which are stacked in the order of web (A) - web (B) - web (A) - web (B) - web (A) - web (B) and bonded by heat treatment. These are enlarged optical micrographs of an example of the composite sheet-like structure of the present invention made of web (A), magnified 300 times in the case of a cross section and 100 times in the case of the surface. FIG. 1 is a plan view of the above structure, and FIG.
1 and 2-2 are partial cross-sectional views showing the bonded structure of the composite sheet-like structure of the present invention after bonding by heat treatment. FIG. 1 clearly shows the reticulated sheet web (B) coated over the web (A). This figure is an example in Embodiment 1, and shows Fig. 2-1,
As shown in Figure 2-2, the filaments of the web (A) are formed into a composite sheet-like structure by the net strands (b) of the web (B) alternately laminated with the web (A). are bridged at multiple points and partially conjugated throughout the structure. The three-dimensional structure of the composite sheet-like structure of the present invention due to the conjugation structure of requirement (v) allows the web (A) and the web (B) to be bonded together without losing the loose structure of the web (A) as a whole. This is useful for imparting improved properties to the composite sheet-like structure of the present invention, including a high degree of flexibility, excellent fluffing resistance, good air permeability, and excellent strength. Web constituting the composite sheet-like structure of the present invention
Various combinations of materials for (A) and web (B) can be selected as long as the above requirement (ii) is satisfied. Examples of these resins include the following homopolymers and copolymers. (1) Homopolymers or copolymers of two or more starting materials such as ethylene, propylene, styrene, acrylic esters, vinyl acetate, acrylonitrile, vinyl chloride, etc.; (2) For example, phthalic acids (phthalic acid, isophthalic acid , terephthalic acid, their nuclear alkyl substituted products), aromatic dicarboxylic acids having 8 to 15 carbon atoms such as naphthalene dicarboxylic acid, and 6 carbon atoms
At least one dicarboxylic acid component selected from the group consisting of ~30 aliphatic dicarboxylic acids and alicyclic dicarboxylic acids (or its lower alkyl ester), and an aliphatic glycol or alicyclic glycol having 2 to 12 carbon atoms. and at least one glycol component selected from the group consisting of an aromatic dihydroxy compound having 6 to 15 carbon atoms, or a hydroxycarboxylic acid having 4 to 12 carbon atoms (or a lower alkyl ester thereof) (3) For example, a carbon number of 4 to 12
A polyamide formed from an aliphatic dicarboxylic acid and an aliphatic or aromatic diamine having 4 to 15 carbon atoms, a polyamide formed from an amino acid (or lactam), or a mutual copolymer thereof; (4) For example, bisphenol-based Examples include polycarbonate; (5) polyacetal; and (6) various polyurethanes. In the composite sheet-like structure of the present invention, the web (A)
The filament (a) constituting the structure is a base filament that maintains the strength of the entire structure, and is preferably a filament made of a resin with a relatively high melting point. Preferably polyethylene terephthalate, polybutylene terephthalate, polycapramide, poly-m-phenylene isophthalamide,
It is preferable to use a resin selected from the group consisting of polypropylene, polyacrylonitrile, or polymers (including copolymers) of two or more of these, and which has been stretched and oriented. Further, in the composite sheet-like structure of the present invention, the filament (b) constituting the web (B) is preferably selected from the following resins so as to satisfy the melting point condition of requirement (ii). Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyamides such as polycapramide and polyhexamethylene adipamide; Polyolefins such as polyethylene and polypropylene; Polyvinyl polymers such as polyvinyl alcohol, polyvinyl acetate, and polyacrylonitrile; Polyurethane or copolymers thereof Preferably, one selected from among the combinations. More preferably, it has a melting point of 100°C to 300°C. The composite sheet-like structure of the present invention satisfies the requirements (i) of the present invention.
The web (A) that satisfies the requirement (ii) of the present invention and the web (B) that satisfies the requirement (ii) of the present invention are each formed by alternately laminating and heat-treating at least one layer so as to form the conjugated structure. can. At this time, it is preferable that the outermost surface layer on at least one side of the laminated sheet-like structure is formed by the reticulated sheet web (B). The heat treatment thereby produces web (A) and web (B).
can be bonded to form the conjugated structure, for example, by heat treatment while passing the laminated sheet-like assembly between a pair or a plurality of pairs of hot press rollers. The roller surface of such a press roller is preferably a flat surface. Preferable conditions for this heat treatment include a web (B) consisting of a mixture of at least two resins having melting points different by at least 20°C.
The melting point (decomposition point if it does not have a melting point) (℃) of each resin in strand (b) is T ₁ , T ₂ , T ₃ ,...
...... Tn, and the respective weight percentages (weight percentages each resin occupies in the mixture) are W ₁ , W ₂ , W ₃ ,
......Wn, and the melting point (decomposition point if it does not have a melting point) (℃) of the resin of the filament (a) constituting the web (A) is expressed as T(a), and the following formula [] and Examples of temperature X (°C) conditions that satisfy [ ] can be given. Σ [(T ₁ ~ Tn) × (W ₁ ~ Wn / 100)] +30≧X≧Σ [(T ₁ ~ Tn) × (W ₁ ~ Wn / 100)] -30 ......Formula [] T (a)-30≧X ...Formula [] More preferably, the above formula [] is the following formula []'. Σ [(T ₁ ~ Tn) × (W ₁ ~ Wn) / 100] +25≧X≧Σ [(T ₁ ~ Tn) + (W ₁ ~ Wn / 100] -25 ......Formula []' Eventually In any case, the heat treatment is a mixture of at least two resins whose melting points are 30°C or more lower than the melting point of the filament (a) that makes up the web (B), and whose melting points differ by at least 20°C that make up the web (B). It is preferable to carry out the process at a temperature equal to or higher than the melting point of the resin having the lowest melting point minus 30°C.The composite sheet-like structure of the present invention is composed of a combination of a high melting point component and a low melting point component. Ori,
Bags with strong seals can be easily obtained by well-known methods such as heat sealing and high-frequency sealing, so they are useful as packaging materials that are soft, strong, and breathable with little fluff. It is. Furthermore, by choosing ingredients with good weather resistance,
It has little fuzz, is flexible, strong, and breathable, making it useful as an agricultural material. In addition, by taking advantage of the many features already mentioned, it can be used not only for general industrial materials, industrial materials, daily necessities, sanitary materials, etc., but also for clothing. The composite sheet-like structure of the present invention may be provided with a suitable substance in order to improve or impart coloring, electrical properties, chemical properties, physical properties, and other properties. Examples of such substances are:
Examples include pigments, antistatic agents, flame retardants, plasticizers, antioxidants, stabilizers, ultraviolet absorbers, lubricants, oils, perfumes, and the like. The composite sheet-like structure of the present invention can be a laminate in which two or more structures are further laminated. At this time, examples of the laminating means include adhesive means using a binder, physical joining means such as needle punching, sewing means using a sewing machine, and joining means using hot press. In the lamination, the entire surface of the composite sheet-like structure may be bonded together, or may be partially bonded. Furthermore, it may be laminated with other sheet materials. Examples of such other sheet materials include woven or knitted fabrics, nonwoven fabrics, paper, glass mats, films, foam sheets, corrugated boards, wire mesh, and the like. In addition, in the present invention, the net on the web (B)
The average diameter of the strands (b), the average mesh length, the fiber density of the web (B), and various properties of the composite sheet-like structure are as follows. (1) Average mesh length of web (B): Take continuous photographs of an arbitrary ^10cm2 area of the composite sheet-like structure using a microscope, and calculate the distance between adjacent mesh intersection points on the surface. Measure the distance li (100 measurement points) for each mesh using a caliper, and divide it by the measurement frequency (n) to obtain the value (l), which is the average mesh length (l) mm, as shown in the formula [] below. shall be. (2) Average diameter of the net strands (b) of the web (B): Draw a straight line at an arbitrary angle on the micrograph of (1) above, and calculate the diameter of the net strands (b) at the point where it intersects with the net strands (b). Measure the thickness (di) (100 measurement points), divide it by the measurement frequency (n), and use the value (d) as the average diameter (d)μ as shown in the following formula []. (3) Fiber density of web (B): Net strands that cross a straight line connecting any two points with a spacing of 2 mm in the micrograph of (1) above.
(b) and the number of net strands (b) that cross the straight line between these two points (n') by selecting any two points with an interval of 2 mm on a straight line perpendicular to the straight line.
and calculate the density (Fd) using the formula []. Fd=n+n'/2...Formula [] (4) Tensile strength of composite sheet structure The tensile strength is measured by the method described in JIS L-1085. The sample size is 5 cm x 20 cm, the chuck grip interval is 10 cm, and the pulling speed is 30 cm per minute.
It will be carried out. The strength of a nonwoven fabric is appropriately expressed as a value obtained by dividing the weight per unit area of the product (g/m ² ) by the tensile strength (g/5 cm). The composite sheet-like structure of the present invention has a strength of about
It is preferably about 100 to about 400 g/5 cm/g/m ² . However, from a 1 m square nonwoven fabric, n = 20 measurements were taken at random vertical and horizontal sections, and the average value was taken. (5) Flexibility of composite sheet-like structures: (5-1) Initial Young's modulus: This is one indicator of the degree of flexibility. A low initial Young's modulus indicates how easily the composite sheet-like structure deforms when external force is applied. This is JIS L-
It is calculated from the stretching curve obtained by conducting the tensile test described in JIS L-1074, using the formula described in Note 2 of Section 5-10 of JIS L-1074.
However, as for the specific gravity used in this formula, the apparent density (g/cm ² ) is used. Preferably, the composite sheet-like structure of the present invention has an initial Young's modulus of about 0.5 to about 40 Kg/mm ² .
(However, it is the average value of the vertical and horizontal values.) (5-2) Bending resistance: Furthermore, bending resistance is an index that indicates the degree of flexibility. This is measured by method A (45° cantilever method) in Section 5-7 of JIS L-1085, and a value in mm is obtained. This value (mm)
, the weight per unit area of the product (g/m ² )
The value divided by is the bending resistance (mm/g/m ² ). The composite sheet-like structure of the present invention has a bending resistance of approximately
Preferably it is from 0.5 to about 8 mm/g/m ² . However, from a 1 m square nonwoven fabric, n = 10 measurements were taken at random vertical and horizontal sections, and the average value was taken as the average value. (6) Air permeability of a composite sheet-like structure: Air permeability is expressed by passing air at a certain flow rate through a composite sheet-like structure with a certain area and measuring the pressure difference on both sides of the structure. I can do it. A composite sheet-like structure is sandwiched in the middle of a PVC cylinder with an inner diameter of 60 mm so as to cross the cylinder at right angles, and while air is flowing at a rate of 3 m/s from one end of the cylinder through a rectifying plate, the pressure difference on both sides of the structure is created. is measured with a manometer. This allows the surface of the structure with a cross-sectional area of 28.3 cm ² to be spread at 3 m/s.
The ventilation resistance (mmAq.) when air passes through is calculated. The value obtained by dividing this ventilation resistance (mmAq.) by the weight per unit area of the product (g/m ² ) is defined as the air permeability (mmAq./g/m ² ). The composite sheet-like structure of the present invention has an air permeability of about 0.1 to about 5 mmAq. /g/m ² is preferred. However, n=5 measured values are obtained from any part of a 1 m square nonwoven fabric, and the average value is taken as the value. (7) Fluffing resistance of composite sheet-like structure: Fluffing resistance is determined by rubbing the surface of the product under certain conditions and observing the state of fluffing. This uses a friction tester type described in Section 3 of JIS L-0823. However, white cotton cloth is used for the surface of the friction element, and the load is 1.5 kg. The end point of the test is reached at a different rate depending on the sample, but the end point is the formation of round fluff that occurs during the process of peeling off the fibers from the surface, and is expressed as the number of frictions. The nonwoven fabric of the present invention has a pilling resistance of about 25 times
Preferably about 200 times. However, from a 1 m square nonwoven fabric, n = 20 measurements were obtained for each of the vertical and horizontal directions, and the average value was taken as the average value. The following Examples and Comparative Examples are for illustrating the present invention, and are not intended to limit the present invention in any way. Example 1 Single 6de long polyethylene terephthalate fibers were drawn approximately parallel to each other to give a total of 1.3 million De, stretched 4 times and crimped at 18 ke/inch.
After heat setting at a temperature of 180℃ for 2 minutes, this is stretched once to form a sheet, which is then fed to a pair of gear-shaped rollers that rotate intermeshing at a speed slower than the surface speed of the rollers. The emulsion was made by opening the fibers and expanding them to a width of 1.5 m using an arcuate bar, and then emulsifying the copolymer of ethyl acrylate/butyl acrylate = 50% by weight/50% by weight with a small amount of emulsifier. The entire surface of the mold was impregnated with a mold adhesive in an amount of 4 wt%, and dried at a temperature of 100°C to obtain a long fiber parallel sheet with a basis weight of 30 g/m ² . Next, this sheet was stretched 13.5 times in the width direction using a pin tenter while being fed at an overfeed of 1.8 times to obtain a long fiber nonwoven web. was a random long thick nonwoven fabric web with a single yarn of 1.5 de and a basis weight of 4 g/m ² . Next, polypropylene 85wt%, nylon-
A mixture of 610wt% polyethylene and 5wt% polyethylene is melted in an extruder, mixed with _N2 gas, extruded through a slit die, rapidly cooled, and taken out with a draft to create countless discontinuous cracks in the longitudinal direction. A Hearst fiber sheet with a basis weight of 1.7 g/m ² was obtained. Eight sheets of this were stacked and fed at an overfeed of 1.8 times, and stretched to 14.4 times in the width direction to obtain a mesh-like continuous fiber sheet. The average single yarn diameter was 40μ, each fiber was continuously laid to form a mesh, and the fabric weight was 1.7g/m ² . The 7 and 8 sheets obtained in this way are
A laminate was obtained by laminating alternately so that ＋＋＋＋……＋＋. Here, the temperature X suitable for heat-treating this laminate
(℃) using the formula []' and formula [], the melting point of polyethylene terephthalate (PET) is
Since the temperature is 260℃, polypropylene (PP) is 160℃, natron-6 (Ny-6) is 225℃, and polyethylene (PE) is 110℃, 189≧X≧139. Therefore, this laminate was pressed with a pair of flat surface hot press rollers at a surface temperature of 160°C, and the area weight was 41.6 g/m ² and the / ratio was 67/33 wt%.
A long-length nonwoven fabric was obtained. When this was observed with an electron microscope, the average size of the mesh on the surface was 1.04 mm, and the average fiber density was
The average thickness of the 19 fibers was 40μ, and some of the fibers were observed to be conjugated to other fibers. When the properties of this nonwoven fabric were confirmed by the method described above, it was found to be a long, thick nonwoven fabric of excellent quality with little fuzz, flexibility, strength, and air permeability. Example 2 The same procedure as Example 1 was carried out except that the number of laminated sheets was 3 and 4, respectively. Layer the obtained two long-thickness nonwoven fabrics together at a temperature of 200.
When heat-sealed at ℃, an extremely strong bond was obtained. The components of Example 3 were 70% by weight of polyethylene terephthalate and 30% by weight of polypropylene, to which was added 0.5 part of an ultraviolet absorber Tinuvin 327 (manufactured by Ciba Geigy), and the spreading conditions were set to an overfeed of 1.5%. times, extension magnification 10
The method was the same as in Example 1 except that the temperature was doubled and the hot press temperature was 200°C. The obtained nonwoven fabric had little fuzz, was strong, and had air permeability, and could maintain its properties for a long period of time even when used outdoors as a protective sheet for agriculture. Example 4 Drawn long fibers of polyacrylonitrile with a single yarn of 1.7 de are aligned approximately parallel to each other to a total of 150,000 De, crimped at 20 crimps/inch, and opened continuously. Expanded and further polyurethane/polyacrylonitrile butadiene copolymer = 80/
20wt% butyl acetate/dimethylformamide =
4/1wt% solution (concentration 20%), effective deposition amount 8%
The sheet was impregnated and dried, and then spread at an overfeed of 2 times and a stretching ratio of 9 times to obtain a basis weight of 4.9 g/m ² . These 7 sheets and the 8 sheets of Example 1 are combined into ＋＋＋…………＋
After laminating the flats in such a way that
^A flexible, long-length nonwoven fabric with less fuzz was obtained. By adding beautiful pattern printing to this,
We were able to create a strong, flexible duvet cover with little fuzz. Example 5 Single yarns of 1.2 DE drawn and oriented nylon - 6-length fibers were drawn approximately parallel to each other to a total of 200,000 DE, crimped at 18 strands/inch, and this crimped tow was used as an example. Treated in the same manner as in 1 to obtain a basis weight of 11g/m ²
A long-length nonwoven web was obtained. Next, 80wt% polypropylene, nylon
A mixture of 610 wt% polyethylene and 5 wt% polyethylene was treated in the same manner as in Example 1 to obtain a continuous mesh sheet with a basis weight of 2.5 g/m ² . Nine such sheets and ten sheets were alternately laminated so that the two sheets were on the surface, and then pressed at a temperature of 165° C. to obtain a long thick nonwoven fabric with a basis weight of 124 g/m ² . When this was observed under a microscope, the average size of the mesh was 0.93mm, the density of fibers was 22 on average, and the thickness of fibers was 33μ on average, and some of the fibers were conjugated by other fibers. Some areas were observed. The properties of this nonwoven fabric were within the scope of the present invention. Comparative Example 1 Eight sheets of the material obtained in Example 1 were laminated, and the temperature was 200.
An emulsion-type adhesive made by adding a small amount of emulsifier to a copolymer of butyl acrylate/methyl methacrylate = 50/50 wt% is pressed with a pair of hot press rollers on a flat surface at ℃. The entire surface was impregnated to a coating amount of 20 wt% and dried to obtain an adhesive type long thick nonwoven fabric with a basis weight of 38.4 g/m ² . This was likely to cause fluff. Comparative Example 2 Six sheets of the material obtained in Example 1 were laminated, and on each of the front and back sides, a web with a fabric weight of 10 g/m 2 obtained by card forming a short polypropylene fiber with a cut length of 2 cm and a single yarn of ² de. They were further laminated, bonded together by needle punching, and then hot pressed under exactly the same conditions as in Example 1. When various properties of the obtained nonwoven fabric were measured by the method described in the specification, it was found that there were large variations and lacked uniformity. Comparative example 3 8 sheets and 7 sheets, +++…………
The procedure was the same as in Example 1 except that the layers were stacked alternately so as to have a positive polarity and the pressing temperature was 200°C. Since there was no surface layer, it fluffed up easily when rubbed. Comparative Example 4 In Example 1, by changing the cooling conditions after extrusion during production, the grain was thicker and
In addition, everything was the same except that the mesh was rougher. When this was observed using an electron microscope, the average size of the mesh on the surface was 11 mm, and the average thickness of the grain was 11 mm.
It was 160μ. This had a slightly harder texture than that of Example 1 and was easily fluffed. Comparative Example 5 A fabric weight of 2.1 g/m ² was obtained by the method shown in Example 1 using nylon-6. This was laminated in combination with that of Example 1, and pressed at a pressing temperature of 200°C. It was easily fluffy. Comparative Example 6 Drawn split yarns made of polyethylene were laminated vertically and horizontally, and the pressing temperature was
A split yarn sheet with a basis weight of 25.6 g/m ² was produced by pressing at 100°C. Apart from this, the ingredients of polyethylene 50wt
% and polypropylene was 50 wt%. This and +++++++++
Laminate them so that they are the same, heat press them at 120℃,
A long thick nonwoven fabric of 61.4 g/m ² was obtained. this is,
the component with the lowest melting point of (i.e. polyethylene)
Since they have the same melting point and are hot pressed at that temperature, the obtained nonwoven fabric was extremely filmy and lacked flexibility. Table 1 shows the characteristics of the examples and comparative examples described above.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 shows a plan view (enlarged photograph) of a composite sheet-like structure according to an example of the present invention, and FIG.
1 and 2 of FIG. 2 show enlarged photographs of the vertical cross section of the structure.

Claims (1)

[Scope of Claims] 1. (A) A nonwoven sheet-like web made of continuous filaments of synthetic resin (a), and (B) a mixture of at least two resins having integrated mesh crossing points and different melting points. (A) and (B) of a net-like sheet web made of continuous thermoplastic synthetic resin net strands (b) are bonded together by heating, and (i) the web (A) (ii) The web (B) has a basis weight of about 1 to about 10 g/m ² , and the average diameter of the net strand (b) is about 1 to about 100 g/m ² .
μ, the network average length is at most 5 mm, and the net strand (b) is made of a mixture of at least two resins having melting points different by about 20°C or more, and the melting point of the resin having the lowest melting point among these resins is: about 20° C. or more lower than that of the filament (a) and in an amount of about 5 to about 95% by weight based on the mixture; (iii) the web (A) and the web in the composite sheet-like structure; (iv) the composite sheet-like structure has a basis weight of about 10 to about 200% by weight, based on the total weight of (B);
g/m ² , and (v) the filament (a) is
(b) is partially conjugated throughout the composite sheet-like structure. A composite sheet-like structure characterized by: 2. The composite sheet-like structure of claim 1, wherein said filament (a) is a filament of about 0.1 to about 15 denier. 3. The composite sheet-like structure according to item 1, wherein the filament (a) has crimps.