JPS6154590B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aromatic polyamide fiber laminate sheet with improved tear strength. Conventionally, one or both sides of a base fabric made of synthetic fiber threads, such as polyester fiber threads or vinylon fiber threads, are coated with synthetic resin, such as polyvinyl chloride, or synthetic rubber, such as polyurethane. Sheets, such as waterproof sheets, are known. Such synthetic fiber laminated sheets are widely used for truck canopies, tent fabrics, and the like. In this case, a woven fabric made of synthetic fiber filament yarn is generally used as the base fabric. However, if this base fabric becomes thin (lightweight), the tensile strength of the resulting laminated sheet becomes unsatisfactory, and if the texture of the base fabric is made dense to prevent this drawback, the resulting laminated sheet may tear. There were problems such as unsatisfactory strength and the tendency to tear the key. Furthermore, when the base fabric is thick, there are problems in that the weight of the resulting laminated sheet becomes excessively large, making it inconvenient to handle, and its tear strength is not very high. Furthermore, the surface of the thick base fabric has large irregularities, and in order to smooth it, a large amount of synthetic resin or synthetic rubber must be used for coating, which has the disadvantage of increasing manufacturing costs. apart from,
This results in disadvantages in that the weight of the resulting laminated sheet increases and its tear strength decreases. In view of the current situation as described above, it has been thought that it is almost impossible to simultaneously satisfy the three requirements of reducing the weight of a laminated sheet, improving its tensile strength, and improving its tear strength. However, in recent years, there has been a strong demand for laminated sheets such as waterproof sheets to be lighter and thinner while maintaining satisfactory tensile strength and tear strength. This has become one of the important issues. One possible way to meet the above demands is to use aromatic polyamide fibers. Aromatic polyamide fibers (e.g. Dupont Kevlar) have a tensile strength of 20-25 g/d and a
It has a breaking elongation of 5%. A laminated sheet whose base fabric is a woven fabric made of yarns mainly composed of high-strength aromatic polyamide fibers has excellent tensile strength, and therefore is practically satisfactory even if the base fabric is made lightweight and thin. A laminated sheet having the desired tensile strength can be obtained. However, it has been found that such a laminated sheet has the drawback of being susceptible to key tearing. It is known that the resistance of a laminate sheet to key tearing corresponds approximately to its tear strength. Therefore, in order to increase the resistance of an aromatic polyamide fiber laminate sheet to tearing, it is necessary to improve its tear strength. An object of the present invention is to provide an aromatic polyamide fiber laminate sheet having excellent tear strength. The above objects are achieved by the present invention. The aromatic polyamide fiber laminate sheet of the present invention comprises a base fabric made of a woven fabric whose warp and/or weft are mainly composed of yarns made of aromatic polyamide fibers;
and a coating layer formed on at least one surface of the base fabric and made of synthetic resin or synthetic rubber, the warp and/or weft of the base fabric containing the aromatic polyamide fiber yarn as a main component. contains a mixture ratio of 1 to 40%, or 1 to 8 different fiber threads per 2.54 cm, and the different fiber threads have a breaking elongation of 10% or more, or the aromatic polyamide fiber thread The elongation at break is 2.5 times or more than the elongation at break of the thread, and one dissimilar fiber thread or a group of two to five dissimilar fiber threads arranged in parallel are mutually It is characterized in that it is inserted between the aromatic polyamide fiber threads at intervals. In the laminated sheet of the present invention, even if the tensile strength of the different types of fiber threads inserted between the aromatic polyamide fiber threads is considerably smaller than that of the aromatic polyamide fiber threads, for example, 1/ Even if the elongation at break is 2 or less, the elongation at break is 10% or more, or
The elongation at break of the aromatic polyamide fiber yarn is 2.5
Surprisingly, the resulting laminated sheet exhibits extremely high tear strength. Then, the mixing ratio of different types of fiber threads is 1 to 40.
% or 1 to 8 fibers per 2.54 cm, the laminated sheet obtained can maintain a practically satisfactory tensile strength. In the laminated sheet of the present invention, the warp and/or weft of the base fabric is mainly composed of aromatic polyamide fiber threads. Although there is no particular limitation on the degree of weave of this aromatic polyamide fiber yarn, it is generally preferable to have a degree of weave of 100 to 1,500 deniers, and this yarn may be spun yarn, monofilament yarn,
It can be either multifilament yarn or tape yarn, but generally the single fiber fineness is 1.
Preferably, it is a multifilament yarn consisting of filaments of ~15 denier, more preferably 1.5 to 5 denier. The aromatic polyamide constituting the aromatic polyamide fiber has at least 70 mol% of the following formulas () and (): (−Ar ₁ −CONH)− () and (−Ar ₁ −CONH−Ar ₂ −NHCO)− () [However, Ar ₁ and Ar ₂ represent divalent aromatic groups, and these may be the same or have different formulas. ] Preferably, the main repeating group is at least one selected from the following repeating groups. At this time, in the above formulas () and (), the divalent aromatic groups represented by Ar ₁ and Ar ₂ are:

【formula】

【formula】

[expression] and

[Formula] [However, A is -O-, -S-, -SO-, -SO ₂
-, -CO-, _-CH2- , or -C( _CH3 ) _2- ] is preferably selected from the group of aromatic residues represented by the following. In addition, the aromatic polyamide has a content of 30 mol% or less,
The following formula:

【formula】

[Formula] and Beauty

One or more types selected from divalent aromatic residues having the formula [Formula] may be included as a subcomponent. These subcomponents may include inert substituents such as halogens, alkyl groups, nitro groups, and the like. The above-mentioned subcomponents are effective for improving the solubility of the polyamide polymer. The base fabric used in the laminated sheet of the present invention is a woven fabric containing aromatic polyamide fiber threads as a main component in the warp and/or weft. Although there are no particular limitations on the basis weight and structure of this fabric, it generally has a basis weight of 30 to 200 g/ ^m2 , a warp density of 5 to 150 pieces/2.54 cm, and a fabric of 5 to
A woven fabric having a weft density of 150 threads/2.54 cm, particularly a plain woven fabric, is preferred. The different types of fiber yarns, which are mixed in the warp and/or weft and are mainly composed of aromatic polyamide fiber yarns, are made of fibers different from the aromatic polyamide fibers, and
% or more, or 2.5 times or more the elongation at break of the aromatic polyamide fiber yarn. If the elongation at break of the dissimilar fiber yarn is less than 10% or less than 2.5 times the elongation at break of the aromatic fiber yarn mixed with it, the tear strength of the resulting laminated sheet may be unsatisfactory. Become something. The type of different fiber used in the present invention is not particularly limited as long as it satisfies the above conditions regarding elongation, but it is generally 10% or more, more preferably
Polyester (polyethylene terephthalate) fibers and polyamide (nylon 6, nylon 66) fibers having a breaking elongation of 12 to 25% are preferred. Also,
In order to maintain the heat resistance of the entire product at the level of aromatic polyamide fibers, it is necessary to use aromatic polyamide fibers (e.g. Nomex,
You may also use a yarn made of Conex). The different fiber yarns may be spun yarns, monofilament yarns, multifilament yarns, or tape yarns, but generally have a total fineness of 150 to 1500 deniers, consisting of filaments having a single fiber fineness of 1 to 15 deniers. It is preferable that the multifilament is a multifilament, and it is also preferable that the thickness of the different types of fiber threads and the thickness of the aromatic polyamide fiber threads mixed therein are approximately equal,
This makes it possible to obtain a laminated sheet with a flat surface. The different types of fiber yarns are inserted between the aromatic polyamide fiber yarns one by one or in groups of 2 to 5 adjacently arranged at intervals. At this time, the mixing rate is limited to 1 to 40%, preferably 5 to 20%, or 1 to 8 pieces per 2.54 cm, preferably 1 to 5 pieces. Mixing rate of fiber threads of different types of fibers is 1%
When the tear strength is less than 1 or less than 1 per 2.54 cm, the tear strength of the resulting laminated sheet becomes unsatisfactory. Furthermore, when the mixing ratio of different types of fiber threads exceeds 40% or exceeds 8 threads per 2.54 cm, the tensile strength of the resulting laminated sheet may become unsatisfactory. In particular, when the aromatic polyamide fiber yarn has a small total fineness (e.g. 100 to 250 deniers), the mixing ratio of different types of fiber yarns may be 1% or more, but if the aromatic polyamide fiber yarn has a large total fineness (e.g. 500 to 1500 deniers) When it has, it is preferable that the mixing ratio of different types of fiber threads is 5.0% or more. Further, the plied thread may be a single thread, or may be a plied and twisted thread of two or more single threads, or may be a drawn thread. Further, each single yarn may be a non-twisted yarn or a twisted yarn. The different types of fiber threads may be twisted together with the aromatic polyamide fiber threads, or may be aligned. The woven structure of the base fabric used in the present invention is not particularly limited, but plain weave, oxford weave, leno weave, or other fabrics having leno threads are generally used. The insertion of the different types of fiber threads between the aromatic polyamide fiber threads can be carried out by inserting one different type of fiber thread or a group of 2 to 5 different types of different fiber threads arranged in parallel.
It is preferable that one aromatic amide fiber thread or a group of 2 to 150 aromatic polyamide fiber threads arranged adjacent to each other be separated and arranged. In the laminated sheet of the present invention, a covering layer made of synthetic resin or synthetic rubber is formed on one side or both sides of the base fabric. The amount of the coating layer can be determined arbitrarily depending on the purpose of the coating and the type of coating material, but in general
Preferably, the weight is between 20 and 500 g/ ^m2 , and 50
More preferably, it is 300 g/m ² . The synthetic resin and synthetic rubber that form the coating layer can be arbitrarily selected depending on the purpose of the coating, but in general, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyester, polyamide (such as nylon 12) are used for waterproofing. ), polyolefin (polyethylene, polypropylene), polyimide, polyamideimide, polyether, polyketone, thermoplastic polymer such as polysulfone, silicone resin, polyphosphazene and polyurethane, synthetic rubber such as fluorine-containing resin, etc. are used. be able to. The synthetic resin or synthetic rubber forming the coating layer is generally highly elastic and flexible, but thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins,
It may be made of one or more of polyimide resins, triazine resins, melamine resins, bisdiene polymer resins, etc., or it may be a mixture of these and thermoplastic resins. To form the coating layer on the base fabric, a solution or emulsion, sometimes a dispersion, or a film of the desired resin is applied to the desired surface of the base fabric using a conventional impregnation method, adhesion method, or coating method. All you have to do is give it to . Next, the present invention will be further explained by examples. Examples: 400d/267f Kevlar 29 fiber yarn (cutting strength: 22g/d, breaking elongation: 4%) as aromatic polyamide fiber yarn, and 500d/48f as different fiber yarn
Polyethylene terephthalate yarn (cutting strength:
8.5 g/d, elongation at break: 15.5%), six types of plain weave fabrics having the following structures were woven by varying the mixing ratio. 400d/1 (500d/1) x 400d/1 (500d/1)/33/25.4mm x 33/25.4mm The different types of fiber threads are made of aromatic polyamide fiber threads at intervals. The mixing ratio was as shown in Table 1. The obtained plain woven fabric was used as a base fabric, and after scouring and drying it in a conventional manner, the following composition was applied to both sides: Mixed amount of ingredients (parts by weight): Polyvinyl chloride resin 80 Butyl benzyl phthalate 68 Epoxidized soybean oil 7 Calcium carbonate A resin treatment solution containing 20 Cd-Ba stabilizers, 3 pigments, 8 toluene (solvent), and 130 parts was applied. The laminated sheet coated with this resin treatment solution was dried at 90°C for 1 minute, and then heated to 180°C.
was heated for 2 minutes. The dry weight of the coating layer in the obtained laminated sheet was approximately 100% of the weight of the base fabric. Table 1 shows the tensile strength and tear strength of the obtained laminated sheet.

[Table] As is clear from Table 1, both the tensile strength and tear strength of the laminated sheet using the polyester fiber thread base fabric (Sample 6) and the tear strength of the laminated sheet using the aromatic polyamide fiber thread base fabric are lower. Although it is clearly weaker than that of the sheet (sample 1), polyester fiber threads are added to the aromatic polyamide fiber threads.
When mixed at a mixing rate of ~40% (Samples 2, 3,
4) Surprisingly, the resulting laminated sheet showed improved tear strength, and its tensile strength was also practically satisfactory.

Claims (1)

[Scope of Claims] 1. A base fabric made of a fabric whose warp and/or weft yarns are made of aromatic polyamide fibers as the main component;
and a coating layer formed on at least one surface of the base fabric and made of synthetic resin or synthetic rubber, the warp and/or weft of the base fabric containing the aromatic polyamide fiber yarn as a main component. , a mixture ratio of 1 to 40%, or 1 to 8 different fiber threads per 2.54 cm, and the different fiber threads have a breaking elongation of 10% or more, or the aromatic polyamide fiber threads have a breaking elongation of 10% or more. has an elongation at break of 2.5 times or more than the elongation at break, and
One of the different types of fiber threads or a group of 2 to 5 different types of fiber threads arranged in parallel are inserted between the aromatic polyamide fiber threads at intervals. Aromatic polyamide fiber laminated sheet with excellent tear strength. 2 The aromatic polyamide constituting the aromatic polyamide fiber has at least 70 mol% of the following formula ()
and (): (-Ar ₁ -CONH)- () and (-Ar ₁ -CONH-Ar ₂ -NHCO)- () [However, Ar ₁ and Ar ₂ represent divalent aromatic groups; may be the same or have different formulas. ] The laminate sheet according to claim 1, which also has at least one type of repeating group selected from the following. 3 In the above formulas () and (), the divalent aromatic group represented by Ar ₁ is [Formula] [Formula] [Formula] and [Formula] [However, A is -O-, -S-, -SO −，− _SO2
-, -CO-, _-CH2- , or -C( _CH3 ) _2- ] The laminate sheet according to claim 2, which is selected from the group of aromatic residues represented by -, -CO-, -CH2-, or -C(CH3)2-. 4 In the above formulas () and (), the divalent aromatic group represented by Ar ₂ is [Formula] [Formula] [Formula] and [Formula] [However, A is -O-, -S-, −SO−,− _SO2
-, -CO-, _-CH2- , or -C( _CH3 ) _2- ] The laminate sheet according to claim 2, which is selected from the group of aromatic residues represented by the following. 5 The aromatic polyamide fiber yarn is 15 to 30 g/
having a tensile strength of d and a breaking elongation of 1 to 8%,
A laminated sheet according to claim 1. 6 The aromatic polyamide fiber threads are 100 to 1500
The laminated sheet according to claim 1, having a fineness of denier. 7. The laminated sheet according to claim 1, wherein the different types of fiber threads are spun yarns, monofilament yarns, multifilament yarns, or tape yarns made of polyester fibers or polyamide fibers. 8 The single dissimilar fiber thread or the group of 2 to 5 dissimilar fiber threads arranged adjacently in parallel are mutually 1
The laminated sheet according to claim 1, wherein one aromatic polyamide fiber thread or a group of 2 to 150 aromatic polyamide fiber threads arranged adjacent to each other are arranged separately.