JPS5938049A - Aromatic polyamide fiber laminated layer sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides aromatic 4? This invention relates to a Lyamide fiber laminated sheet.

Conventionally, synthetic #J1! Fibros, for example? A laminated sheet, such as a waterproof sheet, in which one or both sides of a base fabric made of polyester fiber yarn or vinylon fiber Kenhigashi is coated with synthetic resin, such as Girihanka vinyl, or synthetic rubber, such as polyurethane, etc. Forces such as X are known. Such synthetic MImfllli layer sheets are widely used for berths, truck canopies, tents, etc.

In this case, a woven fabric made of synthetic mackerel fiber filament yarn is generally used as the base fabric. However, when the base fabric is thin (@t), the tensile strength of the resulting laminated sheet becomes unsatisfactory.In order to prevent this drawback, the texture of the base fabric is made dense. The tear strength of the laminated sheet was unsatisfactory, leading to problems such as cracking and cracking. Furthermore, when the base fabric is thick, there are problems in that the weight of the resulting 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 -mva synthetic resin or synthetic rubber must be used, which increases the manufacturing cost. In addition to the drawbacks, the weight of the resulting laminated sheet becomes larger and its tear strength becomes lower.

In view of the above-mentioned current situation, it was considered almost impossible to simultaneously satisfy the 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 was one of the important issues.

As one way to respond to the above requests,
The use of aromatic polyamide fibers is considered. Aromatic polyamide fiber (e.g. Keoler manufactured by DE:Lbon), 2
It has a tensile strength of 0 to 25 Ii/d and an elongation at break of 3 to 5%. A laminated sheet whose base fabric is a woven fabric made of yarns containing high-strength aromatic polyamide fibers as a main component has an outstanding tensile strength. Even if it is made thinner, it is possible to obtain a sand layer sheet that has a tensile strength that is practically satisfactory. However, it has been found that such a laminated sheet KFi has a drawback in that it is susceptible to key tearing. It is known that the resistance of a laminated sheet to tearing corresponds approximately to its tear strength. Therefore, in order to increase the resistance of the aromatic polyamide fiber laminate sheet to tearing, it is necessary to improve its tear strength.

In order to improve the above tear strength, the present inventors have already
Aromatic series? We have proposed a laminated sheet whose base fabric is a fabric composed of lyamide fiber threads and different types of fiber threads.

However, the heat resistance of the different fiber yarns is inferior to that of the aromatic polyamide fiber yarns, so the heat resistance of the resulting laminated sheet depends on the low heat resistance of the different fiber yarns.

For this reason, in a laminated sheet containing different types of fiber threads, there is a problem in that the processing conditions and selection of processing materials are restricted by the low heat resistance of the different types of fiber threads.

An object of the present invention is to provide an aromatic polyamide fiber laminate sheet that not only has excellent tear strength but also excellent heat resistance.

The above objects are achieved by the present invention. The aromatic polyamide fiber laminate sheet of the present invention has a mixing ratio of 60 to 99.
tensile strength of 15 to 40 g/d and 1 to 8
Aromatic preamide fiber yarn (1
) and an aromatic l-aryamide fiber yarn (U) having a mixing ratio of 40 to 1% by weight and having a tensile strength of 10.9/d or less and a breaking elongation of 101 or more. It comprises a base fabric and a covering layer formed on at least one surface of the base fabric and made of synthetic resin or synthetic rubber.

In the laminated sheet of the present invention, the low-strength aromatic polyamide fiber yarn (...) mixed with the high-strength aromatic polyamide fiber yarn (1) has a tensile strength higher than that of the yarn (1). Even if it is quite small, for example, 1/2 or less, if the elongation at break is 10 inches or more, for example, 2.5 times or more the elongation at break of the yarn (1), it is considered serious. Fortunately, the resulting laminated sheet exhibits extremely high tear strength.

And low-potency aromatics? The laminated sheet obtained by controlling the mixing ratio of Liamide fiber yarn ([1) to 1 to 40%, e.g., 1 to 8 fibers per 2.54 cnL, maintains a practically satisfactory tensile strength. I can do it.

In the laminated sheet of the present invention, the base fabric, knitted fabric, or woven fabric may be used. In the case of a woven fabric, the warp and/or weft of the aromatic polyamide P## fiber thread (1) may be used.
The main component is

This aromatic polyamide fiber yarn (1) Fi, 15-40
It has a tensile strength of H' and a breaking elongation of 1 to 8%, and its fineness is generally 1 to 8%, although there are no particular restrictions on its fineness.
It is preferable to have a fineness of 00 to 1500 deniers. Further, this yarn (1) may be any of Snowyan yarn, monofilament yarn, multifilament yarn, and chive yarn, but generally it is a filament with a single fiber fineness of 1 to 15 denier, more preferably 1.5 to 57 J neel. Preferably, it is a multifilament yarn consisting of.

Aromatic/17 amide fiber yarn (1) and/or (H
) is composed of at least 70 moles of the following formula (1) and (10: +A r , -〇〇NH'+ (1) and +Ar, -CONH-Ar2-NHCO→ (It)
[However, Ar1 and Ar2 represent divalent aromatic groups, and these may be the same or different. ] It is preferable that the main repeating group is at least one type selected from the repeating groups of □. At this time, the above formula (
1) and (II), a divalent aromatic group represented by Ar1 and Ar2, [However, A is 10-, -8-, -8O-, -8O2-,
-CO-.

-CH2- or -c (CH3)2-] is preferably selected from the group of aromatic residues represented by -CH2- or -c (CH3)2-. These aromatic residues may contain inert substituents such as Ir, 1, halogeno, alkyl groups, and nitro groups.

Generally, the aromatic tetraamide constituting the yarn (1) is preferably one in which M has the following repeating unit as a main component. Oh, in general,
The aromatic polyamide constituting the yarn (II) is preferably one having the following repeating single 6L as a main component.

The base fabric used in the laminated sheet of the present invention is preferably made of a fabric containing aromatic polyamide fiber yarn (1) as a main component in the warp and/or weft.

Although there are no particular limitations on the basis weight and texture of this fabric, it generally has a basis weight of 30 to 20,017 m2, a warp density of 5 to 150 lines/2.54 crrt, and a weft density of 5 to 150 lines/2.54 cIn. A woven fabric, especially a plain woven fabric, having the following is preferred.

The aromatic polyamide fiber yarn (II) has a tensile strength of 10 g/d or less, preferably 3 to 10 Il/d, and a tensile strength of 1 (
1 or more, preferably 10 to 50 inches, and the breaking elongation is at least 2.5 times the breaking elongation of the aromatic polyamide fiber yarn (1). It is particularly preferable. If the elongation at break of the yarn (II) is less than 10%, or if the tensile strength is 101//d or more, the tear strength of the resulting laminated sheet will be unsatisfactory.

The shape of the yarn (n) may be snow yarn, yarn, monofilament yarn, multifilament yarn, or chishan yarn, but generally the total fineness is made of filaments having a single wire #a fineness of 1 to 15 deniers. It is preferable that it is a multifilament of 100 to 1509 deniers, and the thickness of the yarn (n),
It is preferable that the threads (1) mixed therein have approximately the same thickness, thereby making it possible to obtain a laminated sheet with a flat surface.

In the base fabric made of woven fabric, the threads (1) are inserted between the threads (1) one by one or in groups of 2 to 5 threads arranged in parallel at intervals. Ru. At this time, the thread (
The mixing ratio of II) is 1 to 40 inches, preferably 5 to 20 inches, particularly preferably 1 to 8 pieces per 2.54 cm, and more preferably 1 to 5 pieces per 2.54 cm. Yarn (It)
) is less than 1%, the tear strength of the resulting laminated sheet will be unsatisfactory. In addition, when the blending rate of yarn (10) exceeds 40%, the tensile strength of the resulting laminated sheet may become unsatisfactory.Especially,
1) Small total fineness (e.g. 100~2505″)
If the yarn (U) has a large total fineness (
For example, when the fiber has a yarn (denier of 500 to 1500), it is preferable that the mixing ratio of yarn (10) is 50% or more.

Further, each of the yarns (1) and (1) may be a single yarn, or may be a twisted yarn of two or more single yarns, or may be a drawn yarn. Furthermore, each single yarn may be a non-twisted yarn or a twisted yarn.

The thread * (II) may be twisted together with the thread (1),
Alternatively, they may be aligned.

The woven structure of the base fabric used in the present invention is not particularly limited, but generally includes plain weave, square weave, xford weave, leno weave,
Alternatively, other fabrics containing leno yarn are used.

The insertion of yarn (n) between yarns (1) is performed by inserting one yarn (
II) or 2 to 5 yarns (1
1) It is preferable that the groups are arranged so as to separate one yarn (1) from each other or a group of 2 to 150 yarns (1) that are adjacently arranged in parallel.

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 - of the coating layer can be arbitrarily determined depending on the purpose of coating and the type of coating material, but generally it is 20 to 5001.
Preferably, the weight is 50 to 30,017 m.
More preferably, it is m2.

The synthetic resin and synthetic rubber that form the coating layer can be arbitrarily selected depending on the purpose of the coating, but are generally used for waterproofing, such as polyvinyl chloride, ethylene-yellow vinyl copolymer, etc. polyester, polyamide (nylon 12, etc.), polyolefin (polyethylene, polyzolopyrene), polyimide, polyamideimide, polyether, polyketone,
One or more polymers selected from thermoplastic polymers such as polysulfone, silicone resins, 4-lyphosphazenes, and synthetic polymers such as polyurethanes and fluorine-containing resins can be used. The synthetic resin or synthetic resin forming the coating layer is generally elastic and flexible, but thermosetting resins such as phenolic resin, epoxy 41
It may be made of one or more of 1-fat, non-abrasive polyester resin, polyimide resin, triazine resin, melamine resin, bisdiene-rimer resin, etc., or it may be a mixture of these and a thermoplastic resin. .

At this time, the synthetic resins used include heat-resistant l11i silicone resin, Iliimide resin, polyamideimide resin, poly7
When osphite resin or fluorine-containing resin is used, a laminated sheet with extremely high heat resistance as a whole can be obtained together with a highly heat-resistant aromatic polyamide fiber base fabric.

To form the coating layer on the base fabric, use a conventional impregnation method, adhesion method, or coating method to apply a solution or emulsion of the desired resin, sometimes a dispersion, or a coating layer to the base fabric as desired. It can be applied to the surface of

Next, the present invention will be further explained by examples.

Example aromatic polyamide fiber yarn (1): 400d/26
7f Kepler 29 fiber yarn (cut-1 strength crab 22.9/
d, elongation at break: 4%), and as yarn (11) 40
Using 0d/48f Nomex rutted fiber (Dupont) yarn (cutting strength: 5.51/d, breaking elongation: 20%) and varying the mixing ratio, 680 plain woven fabrics having the following structure were woven.

400d/I
dl, and its mixing rate was as shown in the tlL1 table.

The obtained plain woven fabric was used as a base fabric, and after scouring and drying it by a conventional method, a pace coat processing agent was applied to the surface of the fabric, and PTV silicone rubber (Toshiba Silicone Corporation) 10
A mixture of 1 part by weight crosslinking agent and 1 part by weight was applied using a knife coater to a coating amount of 90 p/ln.Next, this was applied to a heating cylinder heated to 140°C and a linear pressure applied to this. 10 kg/
Pass it through a heating calendar consisting of a pressure roll that is pressed at a pressure of ca.
did. Further, on the obtained pace coat layer, approximately i
The coating was applied to a coating amount of 7 m'', the surface condition was adjusted, and heat treated at 180°C.

Table 1 shows the tensile strength and tear strength of the obtained laminated sheet.

As is clear from Table 1 below, the i-layer sheet (Sample 6) using a base fabric made only of yarn (II) and the yarn (
Both the tensile strength and tear strength of the laminated sheet (sample 5) using a base fabric containing II) at a mixing ratio of 5 (l) were lower than that of the yarn (
The laminated sheet (sample 1) using a base fabric composed only of 1) is clearly inferior to that of the laminated sheet (sample 1). % (Samples 2, 3゜4), the resulting fjt# sheets surprisingly showed an improved and increased tear strength over Samples 1゜5 and 6; It was also practically satisfactory.

In addition, the obtained laminated sheet of Sample 2.3.4 according to the present invention has a base fabric with excellent heat resistance and a silicone resin coating.
Since it is composed of H, it exhibits excellent heat resistance as a whole, and because it is thin, it is practically excellent as a double-fold welding material with excellent workability as well as heat resistance.

Procedural amendment (voluntary) October 2, 1980 Director-General of the Patent Office Kazuo Wakasugi 1, Indication of the case 1982 Patent Application No. 147703 2, Name of the invention Aromatic polyamide fiber laminate sheet 3, Person making the amendment Case Relationship with Patent applicant name Hiraoka Orisen Co., Ltd. 4, Agent 5, “Detailed description of the invention J, Column 6 of the specification subject to amendment, Contents of amendment - Hosho 1, page 14, line 2, "50%" r 5.0
Correct to %J.

(2) rRT l'-PTVJ on page 17, line io
Correct to VJ.

Claims (1)

[Claims] 1. Mixed with an aromatic polyamide fiber yarn (1) having a mixing ratio of 60 to 99% by weight, a tensile strength of 15 to jO≠, and a breaking elongation of 1 to 8 inches. With a ratio of 40 to 1% by weight, 1
0 IVd or less tensile strength and 10. □A base fabric made of a knitted fabric made of an aromatic polyamide fiber thread (II) having a breaking elongation of 1 or more, and a synthetic resin or synthetic An aromatic polyamide fiber laminate sheet comprising a coating layer made of rubber. 2. The base fabric is made of kneaded material having the yarn (1) as the main component in the warp and/or weft, and the warp and/or weft including the yarn (1) as the main component is 2.54 crILm91~
The laminated sheet according to item 1, comprising eight of the threads (n). □3,
Between the yarns (1), one yarn (II) or a group of 2 to 5 yarns (n) arranged adjacent to each other are inserted at intervals. A laminated sheet according to claim 2'. 4: The elongation at break of the yarn (II) is the same as that of the yarn (1).
Claim 1, which is 2.5 times or more the elongation at break of
Laminated sheet as described in section. □ 5, 'The aromatic lyamide constituting the yarn □ (I) and/or the yarn (II) has at least 70 moles of the following formulas (I) and (n): +Ar, -CONH+ ( 1)
' □ + A'r, -Co)JH-Ar 2-NHCO+
(II) [Ar1 and Ar2 represent divalent aromatic groups, and □ these may be the same or different. ] The laminate sheet according to claim 1, which has at least one type selected from repeating groups. 6. In the formulas (I) and (10), the right divalent aromatic group represented by Ar1 [However, A is -g-, -8-, -8O-, -8O2-
The laminate sheet according to claim 5, wherein the laminate sheet is selected from the group of aromatic residues represented by the following: t-C0-, -CH2-1 or -C(CI,)2-. 7. In the above formulas (1) and (n), the divalent aromatic group represented by Ar2 is
-CO-. Claim 5 selected from the group of aromatic residues represented by -CH2- or -0(CH,)2- f
rAM sheet described in section. 8. The yarn (1) has a tensile strength of 15 to 30 Vd;
The laminated sheet according to claim 1, having a breaking elongation of 1 to 8%. 9, the yarns (1) and (II) are each 1()
The laminated sheet according to claim 1, having a fineness of 0 to 1500 deniers. ]0. Claim 1, wherein the yarns (1) and (II) are each a spun yarn, a monofilament yarn, a multifilament yarn or a tape yarn.
Laminated sheet as described in section. 11. The one yarn (It), or a group of 2 to 5 yarns (II) in adjacent i, vt rows, mutually carry one yarn (1), or 1-sheet according to claim 1, wherein groups of 2 to 150 yarns (1) are arranged in parallel and adjacent to each other.