JP2020082366A - Transparent flexible sheet - Google Patents

Abstract

To provide a transparent flexible sheet for industrial material sheet, in which presence of a fiber substrate (coarse lattice structure) does not largely blocks views even the fiber substrate (coarse lattice structure) is compounded for dimensional stability and strength maintenance, having weather resistance (color fastness) and antifouling property with enhanced visibility of whole sheet.SOLUTION: In a laminate having a specific fluorine-based resin layer formed on one side surface or more of a composite by laminating a transparent resin sheet on whole areas of a front surface and a back surface of a coarse lattice structure respectively, in which the coarse lattice structure constituted by a resin processed multifilament yarn strip 1 is a substrate, the resin processed multifilament yarn strip contains a vinyl chloride resin composition containing an aromatic phosphoric acid ester compound, further having transparent coated layers 1-4, difference of refraction indexes between a multifilament 1-1 and the vinyl chloride resin composition is within 0.05, and difference of refraction indexes between the transparent coated layer and the vinyl chloride resin composition is within 0.05.SELECTED DRAWING: Figure 1

Description

The present invention relates to a transparent flexible sheet having excellent visibility by seeing through even if a coarse lattice-like structure for maintaining dimensional stability and strength is combined as a support, and for example, a membrane structure building (pavilion exterior, museum). Objects, museum objects), body materials for outdoor applications such as sheet houses, horticultural houses, and parts materials such as lighting windows, and partitions, curtains, and equipment used for indoor applications such as electronic and electrical equipment factories, hospitals and research facilities. In general industrial material sheets used for covers, bags and other miscellaneous goods such as leisure sheets, even if a coarse grid structure is compounded, it does not greatly obstruct the view and the visibility of the entire sheet is improved. The present invention relates to a transparent flexible sheet having improved antifouling property and weather resistance (discoloration resistance).

Part of the exterior and interior of the pavilion and museums is designed as a three-dimensional frame structure, and the film and sheet are stretched and covered along the shape of the three-dimensional frame.In the design, a transparent and strong film with excellent weather resistance and stain resistance is used. Sheets are used. However, when these films and sheets are used alone, they have a problem that the film is slackened or deformed due to factors such as wind pressure, snow, temperature rise, etc., and particularly in a stretched film, there is a drawback that the film easily tears due to contact with a sharp object. Therefore, a fiber base material is required as a reinforcing material for maintaining the dimensional stability and obtaining the destruction prevention effect. An example of such reinforcement is a polyester fiber plain weave woven cloth (yarn density warp 1 /2 cm x weft 1 /2 cm: void ratio 90%) with a non-colored olefin resin film laminated on both sides. There are 95% of film materials (Patent Document 1: Example 1 and the like), but these are conspicuous because the polyester fiber plain weave coarse woven cloth is conspicuous as it is visible, and obstructs the visibility depending on the application. It was

Therefore, the applicant of the present invention contains a partition sheet material having high visibility, an aromatic phosphate ester compound on the entire surface of a base material made of glass fiber as a fiber composite sheet for a light ceiling material that does not reduce the luminous intensity of the light source. A glass fiber base material obtained by forming a resin-impregnated coating layer of a soft vinyl chloride resin composition and obtaining a difference in refractive index (JIS K7142) between glass fiber and the soft vinyl chloride resin composition of 0.03 or less. A transparent composite sheet (Patent Document 2), which is inconspicuous in shape, was examined. After that, the applicant of the present invention is a transparent glass cloth sheet used for non-combustible building materials such as smoke-proof hanging walls, which does not damage the appearance due to whitening scratches inside the sheet due to bending or folding of the sheet, handling and light resistance. A transparent composite sheet having excellent fastness was examined. This is a glass cloth treated with a silane coupling agent, an adhesive impregnated and coated glass cloth obtained by impregnating and curing an adhesive component containing a specific non-aromatic triisocyanate compound and a binder resin, and its both surfaces. A transparent noncombustible sheet (Patent Document 3) in which a soft vinyl chloride resin transparent layer having an aromatic phosphate compound and having a refractive index (JIS K7142) of 1.52 to 1.58 is provided.

Both of the transparent composite sheet of Patent Document 2 and the transparent noncombustible sheet of Patent Document 3 make the glass fiber base material (glass cloth) translucent, thereby providing sufficient visibility by fluoroscopy. Depending on the viewing angle, interference fringes are generated in the field of view through the glass fiber base material (glass cloth), or a large amount of aromatic phosphate compound is included, which causes the field of view through the sheet to become yellowish. It has the drawback. Therefore, even if the technique of Patent Document 2 or Patent Document 3 is applied to the sheet of Patent Document 1, the problem of yellowing the field of view through the sheet cannot be solved. In addition, Patent Document 2 is a light ceiling material, and Patent Document 3 is a non-combustible building material such as a smoke-proof hanging wall, both of which are used for indoor purposes, and thus are fatal for the heavy use of aromatic phosphate compounds that are slightly inferior in ultraviolet resistance. Although there is no problem, the frequent use of an aromatic phosphate compound in a film structure for outdoor use may lead to yellowing and coloring problems. On the other hand, in the field of liquid crystal display devices, a lightweight and unbreakable transparent resin substrate containing glass cloth as a core material as a substitute material for a glass plate has been studied, and a prepreg made of a composite of glass cloth and epoxy resin has been used. ing. By approximating the refractive indices of these to each other, the presence of glass cloth disappears optically to give an unrecognizable appearance, but by using a cured epoxy resin, the texture is extremely hard and a thick sheet Since the shape is plate-like, it is essentially unsuitable for application to industrial materials that require flexibility. Therefore, it is a transparent flexible sheet that includes a fiber base material for maintaining dimensional stability and strength and can be used outdoors, and even if the fiber base material is compounded, it does not greatly hinder the visibility and the visibility of the entire sheet is improved. A transparent flexible sheet having improved antifouling property and weather resistance (discoloration resistance) is desired.

JP, 2002-046237, A JP, 2010-052370, A JP, 2014-075653, A JP, 2005-225104, A

The present invention has been made in view of the above conventional circumstances, and its problem is a main material and a lighting window for outdoor use such as a film structure building (pavilion exterior, museum object, museum object), sheet house, garden house, and the like. For parts materials such as, and for industrial materials sheets used for partitions used for indoor applications such as electronic and electrical equipment factories, hospitals and research facilities, curtains, equipment covers, and miscellaneous goods such as bags and leisure sheets. Even if a fiber base material (coarse lattice structure) for maintaining dimensional stability and strength is compounded, the presence of the fiber base material (coarse lattice structure) does not greatly hinder the visibility and the sheet. An object of the present invention is to provide an antifouling and weather-resistant (discoloration-resistant) transparent flexible sheet with improved overall visibility.

As a result of repeated studies to solve the above-mentioned problems, a rough lattice-shaped structure composed of resin-processed multifilament yarns is used as a substrate, and a transparent resin sheet is provided on each of the entire front and back surfaces of the rough lattice-shaped structure. A laminated body in which a fluororesin layer is formed on one or more surfaces of a laminated composite, wherein the fluororesin layer comprises a fluororesin layer/aminoethylated acrylic resin epoxy cured product layer. , Fluorine-based resin layer/acrylic-based resin layer double-layered body, Fluorine-based resin layer/acrylic-based resin layer/aminoethylated acrylic resin epoxy cured material layer-based double-layered body, and fluorine-based resin layer/acrylic-based resin Layer/vinyl chloride resin layer, which is any one kind selected from multi-layered bodies, wherein the resin-processed multifilament yarn is 1) a vinyl chloride resin composition containing an aromatic phosphate ester compound. By covering the filament yarns and filling the entire voids between the filaments constituting the multifilament yarns, 2) the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0. Within 5 and 3) further having a transparent coating layer of at least one selected from an epoxy resin, a styrene resin, and an acrylic resin on the entire surface of the yarn of 1). Since the difference in the refractive index (JIS K7142) from the vinyl chloride resin composition is within 0.05, the visibility of the entire sheet is improved without the presence of the coarse grid structure hindering the visibility. The inventors have found that an industrial material sheet can be obtained, and have completed the invention of a transparent flexible sheet excellent in visibility, antifouling property and weather resistance. This is because the difference in the refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is within 0.05, or the same, so that the presence of the multifilament can be optically translucent to transparent. In addition, a transparent coating layer of at least one selected from an epoxy resin, a styrene resin, and an acrylic resin is provided on the entire surface of the (semi)transparent 1) yarn, and the transparent coating is provided. By keeping the difference in refractive index (JIS K7142) between the layer and the vinyl chloride resin composition within 0.05, the transparency of the (semi)transparent 1) yarn is maintained and a transparent coating layer is provided. However, it does not cause a defect that greatly impairs flexibility. Further, this transparent coating layer is a barrier layer for keeping the aromatic phosphate ester compound contained in the vinyl chloride resin composition in the resin-processed multifilament yarn and preventing the aromatic phosphate ester compound from migrating and diffusing to the transparent resin sheet side. This makes it possible to stably maintain the transparent effect of the resin-processed multifilament yarn (coarse grid-like structure) and stably maintain the weather resistance (discoloration resistance) of the sheet.

In the transparent flexible sheet of the present invention, the cross-sectional shape of the resin-processed multifilament yarn is elliptical or substantially rectangular with arcuate ends, and the ratio of height to width in this cross-sectional shape is 2:3 to 1:5. Preferably. As a result, a large number of filaments are thinly overlapped and aligned with each other, and even if they are present flatly, the multifilament and the vinyl chloride resin composition are refracted while maintaining sufficient strength and dimensional stability as a multifilament yarn. When the difference (JIS K7142) difference is within 0.05 or the same, the presence of the multifilament can be made optically transparent and difficult to see.

In the transparent flexible sheet of the present invention, the multifilament forming the resin-processed multifilament yarn is one or more selected from glass fiber, polyester fiber, polyamide fiber, polypropylene fiber, vinylon fiber, and vinyl chloride fiber. Preferably. Particularly, a resin-processed multifilament yarn made of glass fiber (particularly E glass: refractive index of 1.55 to 1.56) is preferable.

In the transparent flexible sheet of the present invention, the coarse grid structure is 1) a woven fabric composed of warp/multifilament yarn groups and weft/multifilament yarn groups, or 2) warp/multifilament yarn groups. , And a triaxial woven fabric composed of 40° to 65° bias/multifilament yarn groups, or 3) warp/multifilament yarn groups, weft/multifilament yarn groups, and 40° to 65° bias/multi A tetraaxial woven fabric composed of filament yarn groups is used as a base material, coated with and filled with the vinyl chloride resin composition, and further the epoxy resin, styrene resin, and acrylic resin. one that is transparent coated with one or more selected from the system resin, wherein in a range area of 25mm ² ~111mm ² of coarse grid 1 per the coarse grid-like structure, all coarse containing these It is preferred that the areas of the gratings be approximately equal.

In the transparent flexible sheet of the present invention, the coarse grid structure is 4) biaxial in which warp/resin-processed multifilament yarn groups and weft/resin-processed multifilament yarn groups are fixed at warp/weft intersections. Net or 5) warp/resin processed multifilament yarn group and 40° to 65° bias/resin processed multifilament yarn group fixed at warp/bias intersection, or 6) warp/resin Processed multifilament yarn group, weft/resin processed multifilament yarn group, and 40°-65° bias/resin processed multifilament yarn group are selected from four-axis nets fixed at warp/weft/bias intersections. In any one of the above, the resin-processed multifilament yarn is coated and filled with a vinyl chloride resin composition, and further selected from the epoxy resin, styrene resin, and acrylic resin. was clear coating the above species, area per coarse grating is within the range of 100mm ² ~2600mm ^2, it is preferred that approximately equal area of all coarse grid including these.

In the transparent flexible sheet of the present invention, the aromatic phosphate compound is one selected from tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate. As described above, it is preferably 50 to 200 mass% with respect to the mass of the vinyl chloride resin in the vinyl chloride resin composition. This is particularly the case where a resin-processed multifilament yarn made of glass fiber (for example, E glass: refractive index of 1.55 to 1.56) is used in combination with these aromatic phosphoric acid ester compounds, and the difference in refractive index between them is 0. By setting it to be within 05, it is possible to make the existence of the coarse grid-like structure inconspicuous.

In the transparent flexible sheet of the present invention, the vinyl chloride resin composition further comprises epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid butyl, epoxidized fatty acid 2-ethylhexyl, epoxy hexahydrophthalate 2-ethylhexyl, and epoxy. It is preferable that one or more epoxy compounds selected from diepoxystearyl hexahydrophthalate are contained in an amount of 1 to 25 mass% with respect to the total amount of the aromatic phosphate compound. By containing these epoxy compounds, the weather resistance (discoloration resistance) of the aromatic phosphate ester compound contained as an essential component in the vinyl chloride resin composition can be improved.

In the transparent flexible sheet of the present invention, the transparent resin sheet is composed of a soft vinyl chloride resin composition mainly containing a vinyl chloride resin and a plasticizer, and the plasticizer is a dialkyl phthalate ester, a dialkyl isophthalate ester, or terephthalate. It is preferable that one or more kinds selected from acid dialkyl ester, cyclohexanedicarboxylic acid dialkyl ester, and cyclohexene dicarboxylic acid dialkyl ester be used, and the blending amount is 35 to 100% by mass relative to the mass of the vinyl chloride resin. By mainly using these plasticizers, the weather resistance (discoloration resistance) of the transparent resin sheet can be stably maintained.

In the transparent flexible sheet of the present invention, nanoparticles made of an inorganic colloidal substance having a primary particle diameter of 3 nm to 150 nm are used as a binder component containing a hydrolyzed condensate of a silane coupling agent on the surface of the fluororesin layer. An antistatic antifouling layer that is supported is provided, and the inorganic colloidal substance is a photocatalytic titanium oxide sol, a photocatalytic zinc oxide sol, a photocatalytic tin oxide sol, a titanium oxide sol, a zinc oxide sol, a tin oxide sol, At least one metal oxide selected from silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and complex oxide (zinc oxide-antimony pentoxide complex or tin oxide-antimony pentoxide complex) sol. preferable. Without impairing the visibility of the transparent flexible sheet of the present invention due to the addition of this antistatic stain-proof layer, it suppresses the attachment and accumulation of soot dust due to electrification, and even if soot dust adheres, it can be easily wiped off and removed, and even rainfall. The appearance of the self-cleaning effect at the time makes it possible to keep the appearance beautiful.

The transparent flexible sheet obtained by the present invention has a rough lattice-shaped structure composed of a resin-processed multifilament yarn as a base, and a transparent resin sheet is laminated on each of the entire front and back surfaces of the rough lattice-shaped structure. A laminated body in which a fluororesin layer is formed on one or more surfaces of the composite body, wherein the fluororesin layer comprises a fluororesin layer/aminoethylated acrylic resin epoxy cured product layer, and a fluororesin layer. Multilayer of resin layer/acrylic resin layer, fluororesin layer/acrylic resin layer/aminoethylated acrylic resin epoxy cured product layer, and fluororesin layer/acrylic resin layer/chlorination The resin-processed multifilament yarn is any one selected from a multi-layered body composed of a vinyl-based resin layer, wherein the resin-processed multifilament yarn is 1) a vinyl chloride resin composition containing an aromatic phosphate ester compound. By covering and filling the entire voids between the filaments constituting the multifilament yarn, and 2) making the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition within 0.05, The presence of the resin-processed multifilament yarn is optically assimilated to the soft vinyl chloride resin composition, and as a result, the presence of the coarse lattice structure is optically eliminated, and the yarn of 3) and 1) is further produced. The entire surface of the strip has a transparent coating layer of at least one selected from epoxy resin, styrene resin, and acrylic resin, and the refractive index of this transparent coating layer and vinyl chloride resin composition (JIS K7142) By setting the difference to be within 0.05, the transparency of the yarn of 1) is maintained, and even if the transparent coating layer is provided, there is no drawback that the flexibility is greatly impaired. Further, this transparent coating layer acts as a barrier layer for preventing the aromatic phosphate ester compound from migrating and diffusing to the transparent resin sheet side, so that the aromatic phosphate ester compound is stably contained in the resin-processed multifilament yarn. The presence of the coarse grid-like structure does not cause cloudiness and exposure that hinders the visibility over time, and excellent stain resistance and stain removability maintain good visibility of the entire sheet. Since it is possible to obtain a transparent flexible sheet that is excellent in weather resistance (discoloration resistance) for a long period of time, for example, a film structure building (pavilion exterior, museum object, museum object), sheet house, garden house, etc. Main body materials for outdoor applications and parts materials such as lighting windows, and partitions used for indoor applications such as electronic and electrical equipment factories, hospitals and research facilities, curtains, equipment covers, and other miscellaneous goods such as bags and leisure sheets. It can be widely used for industrial materials such as.

Sectional view of a resin-processed multifilament yarn constituting a coarse lattice-like structure which is a base material of the transparent flexible sheet of the present invention The figure which shows an example of the coarse grid-like structure which is a base material of the transparent flexible sheet of this invention. The figure which shows an example of the transparent flexible sheet of this invention. The figure which shows the cross section of the transparent flexible sheet of this invention.

The transparent flexible sheet of the present invention is a composite obtained by laminating a transparent resin sheet on the entire surface of each of the front surface and the back surface of the coarse lattice-like structure, which is a base of the coarse lattice-like structure made of resin-processed multifilament yarn. A laminated body in which a fluororesin layer is formed on at least one side of the body, wherein the fluororesin layer comprises a fluororesin layer/aminoethylated acrylic resin epoxy cured product layer, a fluororesin layer/ Multi-layered body composed of acrylic resin layer, multi-layered body composed of fluorocarbon resin layer/acrylic resin layer/aminoethylated acrylic resin epoxy cured material layer, and fluorocarbon resin layer/acrylic resin layer/vinyl chloride resin The resin-processed multifilament yarn is any one selected from a multi-layered body consisting of layers, and 1) the multifilament yarn is coated with a vinyl chloride resin composition containing an aromatic phosphate ester compound, And filling the entire voids between the filaments constituting the multifilament yarn, 2) the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is within 0.05, and 3) further 1 ) Has a transparent coating layer of at least one selected from epoxy resin, styrene resin, and acrylic resin on the entire surface of the yarn, and the refractive index of the transparent coating layer and the vinyl chloride resin composition ( The difference of JIS K7142) is within 0.05.

The coarse lattice-like structure used for the transparent flexible sheet of the present invention is 1) a woven fabric composed of warp/multifilament yarn groups and weft/multifilament yarn groups, or 2) warp/multifilament yarn groups, 40° to 65°, preferably 55° to 65°, particularly preferably 60° left rising bias/multifilament yarn group, and 40° to 65° preferably 55° to 65° particularly preferably 60° right rising bias /Triaxial woven fabric composed of multifilament yarn groups, or 3) warp/multifilament yarn groups, weft/multifilament yarn groups, 40° to 65°, preferably 40° to 50°, particularly preferably 45° Left-biasing bias/multifilament yarn group, and 40° to 65°, preferably 40° to 50°, and particularly preferably 45° right-raising bias/multifilament yarn group. Using any one of the above as a base material, the entire base material is coated and filled with a vinyl chloride resin composition, and further transparent with one or more kinds selected from an epoxy resin, a styrene resin, and an acrylic resin. A fabric provided with a coating layer, or 4) a woven fabric using warp/resin-processed multifilament yarn groups and weft/resin-processed multifilament yarn groups, or 5) warp/resin-processed multifilament yarns Group, 40° to 65°, preferably 55° to 65°, particularly preferably 60° left-up bias/resin-processed multifilament yarn group, and 40° to 65°, preferably 55° to 65°, particularly preferably 60° Rightward bias/triaxial woven fabric using resin-processed multifilament yarn group, or 6) warp/resin-processed multifilament yarn group, weft/resin-processed multifilament yarn group, 40° to 65° Preferably 40° to 50°, particularly preferably 45° leftward bias/resin processed multifilament yarn group, and 40° to 65°, preferably 40° to 50° particularly preferably 45° rightward bias/resin processed It is a four-axis woven fabric woven using a multifilament yarn group. Examples of the woven fabric include plain woven fabric, basket woven fabric, simulated woven fabric, woven fabric having a porosity of 40 to 90%, particularly 50 to 85%, triaxial woven fabric, or tetraaxial woven fabric. Within area of 25mm ² ~111mm ² of coarse grid 1 per the coarse grid-like structure, it is preferable that all of the coarse grid area approximately equal. If the area per coarse grid is less than 25 mm ² , the ratio of the coarse grid structure to the entire sheet may be increased, and the discoloration of the resin-processed multifilament yarn may be noticeable. Further, if the area per coarse grid exceeds 111 mm ² , it becomes difficult to form a plain weave with a small unevenness in the woven structure. In particular, in the case of the woven fabrics of 1) and 4), as a result, in the case of the triaxial woven fabric of which the driving density of the resin-processed multifilament yarn group of each warp/weft is 2 to 4 threads/inch, 2) and 5), As a result, in the case of a four-axis woven fabric in which the warp/bias resin-processed multifilament yarn groups have a driving density of 2 to 4 threads/inch, 3) and 6), as a result, each warp/weft/bias resin The shot density of the processed multifilament yarn group is 2 to 4 threads/inch.

On the other hand, the coarse lattice-like structure used for the transparent flexible sheet of the present invention is 7) in which warp/resin-processed multifilament yarn groups and weft/resin-processed multifilament yarn groups are fixed at warp/weft intersections. A shaft net (non-woven fabric) having a transparent coating layer of at least one selected from an epoxy resin, a styrene resin, and an acrylic resin as an outermost layer can be used. The yarn arrangement at the warp/weft intersections in these biaxial nets (non-woven fabric) is as follows: a) Place all warp yarn groups at equal intervals on all weft yarns in which weft yarn groups are evenly spaced. Arranged biaxial nets (including front and back sides reversed), b) Weft yarn groups are arranged at equal intervals (for example, n intervals), and part of the warp yarn groups is equally spaced (for example, 2n intervals). A biaxial net (front and back) in which the remaining warp yarn groups are laid on the weft yarn group at equal intervals (for example, 2n intervals) and the warp yarn groups are evenly spaced (for example, n intervals). C) the warp yarn groups are arranged at equal intervals (for example, n intervals), and a part of the weft yarn groups are arranged at equal intervals (for example, 2n intervals) on the warp yarn groups, and A biaxial net in which the remaining weft yarn groups are laid on the warp yarn group at equal intervals (for example, 2n intervals) and the weft yarn groups are arranged at equal intervals (for example, n intervals) (including a mode in which the front and back are reversed). Is mentioned. Here, the relationship between "some yarn groups" and "remaining yarn groups" is that when some yarn groups are arranged in odd-numbered positions, the remaining yarn groups are arranged in even-numbered positions. It is the relationship of yarns (odd numbers are arbitrary such as 1, 3, 5, 7, 9... Or 1, 5, 9, 13..., and even numbers are the same). Further, when the arrangement order of some yarn groups is a pair of “1, 2”, “5, 6”, “9, 10”,..., The arrangement order of the remaining yarn groups is “3, 4”, “ 7, 8", "11, 12"... Pairs and 3 or more pairs have the same rule sequence arrangement. In particular, some yarn groups may be random, and the remaining yarn groups may be random.

Or 8) warp/resin-processed multifilament yarn group, 40° to 65°, preferably 55° to 65°, and particularly preferably 60° leftward rising bias resin processed multifilament yarn group, and 40° to 65°, preferably 55° to 65°, particularly preferably 60° to the right, the bias resin-processed multifilament yarn group is a triaxial net (non-woven fabric) fixed at the warp/bias intersection, and It is possible to use those which are coated and filled with a vinyl chloride resin composition and further provided with a transparent coating layer of at least one selected from an epoxy resin, a styrene resin, and an acrylic resin. The yarn arrangement at the warp/bias intersections in these triaxial nets (non-woven fabrics) is as follows: d) All 40 warp yarns on all warp/resin-processed multifilament yarn groups arranged at equal intervals. ° to 65° Leftward bias/resin-processed multifilament yarn groups are placed at equal intervals, and 40° to 65° rightward bias/resin-processed multifilament yarn groups are placed at equal intervals. Triaxial non-woven nets placed on top of each other (including the case where the front and back are reversed), e) Warp/resin-processed multifilament yarn groups are arranged at equal intervals, and all of them are placed on these warp yarn groups. 40° to 65° left (right) rising bias/resin processed multifilament yarn groups are placed at equal intervals, and all 40° to 65° right (left) rising bias/resin processed multifilament yarn groups A triaxial non-woven net (including an aspect in which the front and back are reversed) arranged so as to be laid on all warp yarn groups at equal intervals, f) warp/resin processed multifilament yarn groups are equally spaced (for example, n intervals) 40° to 65° rightward bias/a part of the resin-processed multifilament yarn group is placed on all of these warp yarn groups arranged at the same intervals (for example, 2n intervals), and the remaining yarn groups are arranged. The groups are arranged so as to be laid on all the warp yarn groups at equal intervals (for example, 2n intervals), and further, 40° to 65° leftward bias/a part of the resin-processed multifilament yarn group on the warp yarn group. Are arranged at equal intervals (for example, 2n intervals), and the remaining yarn groups are arranged at equal intervals (for example, 2n intervals) so as to be laid on all warp yarn groups. Are equidistant (for example, n intervals), and the yarns of the right bias yarn groups are equidistant (for example, n intervals), triaxial net (including an aspect in which the front and back are reversed), g) 40° to 65° right The rising bias/resin-processed multifilament yarn group and the right rising bias/resin-processed multifilament yarn group are arranged at equal intervals (for example, n intervals), and the warp is placed on the left and right bias yarn groups. / Part of the resin-processed multifilament yarn group is placed at equal intervals (for example, 2n intervals), and the remaining yarn groups are laid at equal intervals (for example, 2n intervals) on all left and right bias yarn groups. , And the warp/resin-processed multifilament yarn groups are equidistantly spaced (for example, n intervals) on a triaxial net (including a mode in which the front and back are reversed), h) The left and right bias in the mode of g) above. A triaxial net in which yarn groups are alternately arranged above and below the other yarn ( (Including an embodiment in which the front and back are reversed) can be used. For the relationship between "partial yarn group" and "remaining yarn group", refer to the end of paragraph [0020].

Or 9) warp/resin-processed multifilament yarn group, weft/resin-processed multifilament yarn group, 40° to 65°, preferably 40° to 50°, and upward rising bias resin processed multifilament yarn group of 45°. Group, and 40° to 65°, preferably 40° to 50°, and most preferably 45° upward rising bias resin-processed multifilament yarn group fixed at warp/weft/bias intersections (non-woven) Then, the resin-processed multifilament yarn group was coated and filled with a vinyl chloride resin composition, and further provided with a transparent coating layer of at least one selected from an epoxy resin, a styrene resin, and an acrylic resin. Things can be used. The yarn arrangement at the warp/weft/left-right bias intersection points in these four-axis nets is determined by combining the biaxial net embodiment described in paragraph [0020] and the triaxial net embodiment group described in paragraph [0021]. It is either.

7) coarse grid-like structures to 9) (within the area per coarse grid in the net) of 100mm ² ~2600mm ^2, it is preferred that all of the coarse grid area approximately equal. If the area per coarse grid is less than 100 mm ² , the ratio of the coarse grid structure to the entire sheet may be increased, and discoloration of the resin-processed multifilament yarn may be noticeable. Further, if the area per coarse grid exceeds 2600 mm ² , the ratio of the coarse grid structure occupying the entire sheet may be reduced, and the strength and dimensional stability of the transparent flexible sheet may be impaired. In particular, in the case of 7) biaxial net, the warp/weft resin-processed multifilament yarns have a driving density of 0.5 to 2.5 yarns/inch, and in the case of 8) triaxial net, warp/bias respectively. In the case of the resin-processed multifilament yarn of 0.5 to 2.5 yarns/inch, 9) four-axis net, the warp/weft/bias of each resin-processed multifilament yarn has It is 0.5 to 2.5 lines/inch.

In the coarse latticed structures 1) to 9) used for the transparent flexible sheet of the present invention, the resin-processed multifilament yarn is selected from glass fiber, polyester fiber, polyamide fiber, polypropylene fiber, vinylon fiber, and vinyl chloride fiber. It is possible to use one or more kinds of multifilaments (100 to 500 single filaments having a diameter of 1 to 20 μm are converged), and it is particularly preferable to use glass fibers. The multifilament yarn made of glass fiber is preferably a multifilament yarn having a fineness of 138 to 1111 dtex (decitex), particularly 277 to 833 dtex and a refractive index of 1.55 to 1.56. The diameter is 1 μm to 15 μm, especially 5 μm to 12 μm, and a yarn formed by bundling 50 to 500, especially 200 to 400, of these filament single yarns is preferable. In particular, examples of the glassy material forming the filament include known glass compositions such as E (non-alkali) glass, C (alkali-containing) glass, M glass, A glass, S glass, and D glass, but especially for industrial material sheets Then, E glass (JIS K7142: refractive index 1.55 to 1.56) is preferable, and thereby, it is optically integrated by approximating the refractive index of the vinyl chloride resin composition, and (semi)transparency is measured. It is possible to make the presence of the coarse-grained lattice-like structure inconspicuous in the transparent appearance of the sheet obtained in (1) and not to obstruct the visual field. Particularly when glass fibers are used, it is also possible to use glass fibers whose surface has been modified in refractive index with a known silane coupling agent for the purpose of adjusting the refractive index.

The cross-sectional shape of the multi-filament thread used for the resin-processed multi-filament thread is an ellipse or a substantially rectangular shape with arcuate ends, and the ratio of height to width in this cross-sectional shape is 2:3 to 1:5, particularly 1:. By setting the ratio to 2 to 1:5, it is possible to further improve the transparency in the observation from the front of the sheet when the (semi)transparency is measured by the approximation with the refractive index of the vinyl chloride resin composition. These multifilament yarns are preferably yarns twisted at a pitch of 0 to 1 time/25 mm in the spinning process. In the present invention, it is most preferable to use a non-twisted yarn having a twist number of 0, but a weakly twisted yarn that has been twisted 0.5 to 0.7 times is particularly preferable for the convenience of preventing fray of the yarn and handling. These multifilament yarns that have been treated with a sizing agent, an oil agent, a sizing agent, etc. can also be used. Therefore, in the coarse grid-like structures 1) to 6) used for the transparent flexible sheet of the present invention, the cross-sectional shape of the resin-processed multifilament yarn is an ellipse or a substantially rectangular shape in which both ends are arcuate, and the height and width in this cross-sectional shape. By setting the ratio of 2 to 3 to 1:5, particularly 1:2 to 1:5, from the front of the sheet when measuring (semi)transparency by approximation with the refractive index of the vinyl chloride resin composition. It is possible to further improve the transparency in observation.

The resin-processed multifilament yarn is a base material of a vinyl chloride resin composition containing an aromatic phosphoric acid ester compound, using 1) a woven fabric, a triaxial woven fabric, or a tetraaxial woven fabric as a base material. Coarse grid-like structure obtained by coating the outermost layer of the base material, which is filled with the gaps between the multifilaments, with an epoxy resin or a styrene resin/acrylic resin blend to form a transparent coating layer. Is a component of. 2) In addition, the outermost layer of the multifilament yarn in which the vinyl chloride resin composition containing an aromatic phosphate ester compound is coated on the multifilament yarn and the gap between the multifilaments is filled with epoxy It is a yarn in which a transparent coating layer is provided by resin coating with at least one selected from a series resin, a styrene resin, and an acrylic resin. By fixing the pile of the resin-processed multifilament yarns, a non-woven coarse grid structure is formed. 3) Further, with respect to the multifilament yarn, a yarn in which the vinyl chloride resin composition containing an aromatic phosphate ester compound is coated with the multifilament yarn and the gaps between the multifilaments are filled is used. A non-woven coarse structure is formed by stacking and fixing the above, and the outermost layer of the coarse structure is resin-coated with at least one selected from an epoxy resin, a styrene resin, and an acrylic resin to be transparent. It is a constituent element of a coarse lattice structure obtained by providing a different coating layer.

In paragraphs [0026] 1 to 3), a means for coating a yarn (or a base material) with a vinyl chloride resin composition containing an aromatic phosphoric acid ester compound and filling a gap between multifilaments is aromatic. Dip the yarn (or base material) in a liquid bath of a vinyl chloride resin paste sol that contains a phosphate ester compound (liquid) and whose viscosity is adjusted, and use the capillary phenomenon due to the gap between the multifilaments, or Under reduced pressure, the vinyl chloride resin paste sol is infiltrated into the gaps between the multifilaments and completely replaced with the air present in the gaps between the multifilaments, and then the yarn (or base material) is pulled up, By pressing with a rubber roll, it is possible to cover the yarn (or base material) with a thickness of 0.005 to 0.1 mm and to fill the gaps between the multifilaments, and then at 150 to 200° C. for 15 to 120 seconds. This is achieved by gelling (solidifying) the vinyl chloride resin paste sol by heating. Alternatively, a vinyl chloride resin paste sol containing an aromatic phosphoric acid ester compound (liquid) and having a viscosity adjusted, extrusion coating, knife coating, gravure coating, etc., on the yarn (or substrate), Using the capillary phenomenon due to the gap or under reduced pressure, the vinyl chloride resin paste sol is permeated into the gap between the multifilaments and completely replaced with the air present in the gap between the multifilaments, and then at 150 to 200°C. By coating the yarn (or base material) with a thickness of 0.005 to 0.1 mm by gelling (solidifying) the vinyl chloride resin paste sol by heating for 15 to 120 seconds and filling the gap between the multifilaments. Is achieved.

The vinyl chloride resin composition described in paragraphs [0026] 1) to 3) and paragraph [0027] is a vinyl chloride resin (refractive index 1.54), an aromatic phosphate ester compound (JIS K7142: refractive index 1. 508 to 1.563 liquid), which is a transparent (gel) transparent resin composition of JIS K7142 having a refractive index of 1.52 to 1.56, and other known plasticizers for vinyl chloride resin, It is preferable to adjust the blending of known stabilizers (for example, epoxy compounds) for vinyl chloride resin within the range of the refractive index of the vinyl chloride resin composition of 1.52 to 1.56. If necessary, known additives such as an ultraviolet absorber, a light resistance stabilizer, an antioxidant and a fungicide can be used, and the refractive index of the vinyl chloride resin composition has the same restrictions as above. The vinyl chloride resin is most preferably a homopolymer of vinyl chloride monomer (emulsion polymer powder), but a vinyl chloride copolymer resin of vinyl chloride monomer and other vinyl monomer can also be used. The compounding amount of the aromatic phosphate ester compound is 50 to 200 parts by mass, preferably 750 to 150 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Aromatic phosphate ester compounds include tricresyl phosphate (refractive index 1.557), triphenyl phosphate (refractive index 1.552 to 1.563), trixylenyl phosphate (refractive index 1.554), cresyl phosphate. One or more selected from diphenyl (refractive index 1.560) and 2-ethylhexyl diphenyl phosphate (refractive index 1.508 to 1.511) can be used. Refractive index is according to JIS K 7142.

The vinyl chloride resin composition according to paragraphs [0026] to [0028], and the vinyl chloride resin composition in which a plasticizer and/or an epoxy compound are used in combination have a JIS K7142 refractive index of 1.52 to 1.56. Is preferred. By setting the difference in the refractive index (JIS K7142) between the vinyl chloride resin composition and the multifilament yarn to be within 0.05, the presence of the resin-processed multifilament yarn is considered to be an optically soft vinyl chloride resin composition. Assimilation, and as a result, the presence of the coarse grid structure is optically eliminated, thereby improving the transparency and visibility of the sheet. The refractive index (JIS K7142) of such a multifilament yarn is 1.47 to 1.61. The plasticizer that can be additionally included in the vinyl chloride resin composition described in paragraphs [0026] to [0028] includes phthalic acid dialkyl ester, isophthalic acid dialkyl ester, terephthalic acid dialkyl ester, cyclohexanedicarboxylic acid dialkyl ester, and The amount of one or more selected from cyclohexene dicarboxylic acid dialkyl ester is preferably 1 to 35% by mass based on the mass of the aromatic phosphate compound used. If the blending amount of these plasticizers exceeds 35% by mass, the difference in refractive index exceeds 0.05, the presence of the multifilament yarn is not (semi)transparent, and the presence of the coarse lattice structure is conspicuous. May reduce the visibility of. Further, the epoxy compound that can be contained in the vinyl chloride resin composition described in paragraph [0027] acts as a heat/weather resistance stabilizer for the vinyl chloride resin, and these are epoxidized soybean oil, epoxidized linseed oil, and epoxy. At least one selected from butyl ester of epoxidized fatty acid, 2-ethylhexyl of epoxidized fatty acid, 2-ethylhexyl of epoxyhexahydrophthalate, and diepoxystearyl of epoxyhexahydrophthalate. On the other hand, a compounding amount of 1 to 25 mass% is preferable. When the compounding amount of these epoxy compounds exceeds 25% by mass, the difference in refractive index exceeds 0.05, the presence of the multifilament yarn is not (semi)transparent, and the presence of the coarse lattice structure is conspicuous. The visibility of the seat may be deteriorated.

The resin-processed multifilament yarn according to paragraphs 1) to 3) of paragraph [0026] is an epoxy resin, a styrene resin, and an acrylic resin on the entire surface of the yarn (or substrate) manufactured in paragraph [0027]. A transparent coating layer having a refractive index (JIS K7142) of 1.47 to 1.61, preferably 1.52 to 1.56, is provided in a thickness range of 0.001 to 0.1 mm. It is a thing. This transparent coating layer acts as a barrier layer for preventing the aromatic phosphate ester compound from migrating and diffusing to the transparent resin sheet side, and the aromatic phosphate ester compound stays stably in the resin-processed multifilament yarn. Thus, the transparent effect of the coarse lattice structure is stably maintained, there is no exposure that obstructs the visual field with time, and the visibility of the entire sheet can be favorably maintained. By setting the difference in refractive index (JIS K7142) between this transparent coating layer and the vinyl chloride resin composition (resin-processed multifilament yarn) to be within 0.05, the transparency of the (semi)transparent yarn is improved. It is possible to maintain the weather resistance (discoloration resistance) of the sheet stably without sacrificing flexibility even if the transparent coating layer is provided. The transparent coating layer is 1) a solvent-based paint containing one or more selected from an epoxy resin, a styrene resin, and an acrylic resin dissolved therein, or 2) an epoxy resin emulsion, a styrene resin emulsion, an acrylic resin. It can be formed by immersing the yarn (or base material) produced in paragraph [0027] in a liquid bath of an aqueous paint containing at least one selected from emulsions, pulling it up and drying it. In the method, the above-mentioned solvent-based paint or water-based paint can be used to form a thread (or substrate) by extrusion coating, knife coating, gravure coating, or the like.

The epoxy resin is a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a trifunctional epoxy resin having a bisphenol A skeleton. (Trifunctional epoxy resin containing bisphenol A skeleton), stilbene type epoxy resin, fluorene skeleton containing epoxy resin, triphenolmethane type epoxy resin, triphenolmethane skeleton containing novolac type epoxy resin, tetraphenolethane type epoxy resin, alkyl modified triphenol One or more having a JIS K7142 refractive index of 1.56 to 1.70 selected from methane type epoxy resin, biphenyl type epoxy resin, glyoxal type epoxy compound, aryl alkylene type epoxy resin, and aliphatic type epoxy compound. Is mentioned. The curing agent used in combination with these is preferably an acid anhydride curing agent or a cationic catalyst. Acid anhydride curing agents include phthalic anhydride, maleic anhydride, (hydrogenated) nadic acid anhydride, methyl hydrogenated nadic acid anhydride, glutaric acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, and tetrahydrophthalic acid anhydride. , Methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, dichlorosuccinic anhydride, benzophenonetetracarboxylic acid anhydride, chlorendic acid anhydride, cyclohexanetricarboxylic acid One or more selected from acid anhydrides and the like can be mentioned, and the epoxy resin has a refractive index of 1.50 to 1.60 according to JIS K7142 as a composition containing 20 to 50 mass% of a reaction product of these curing agents. Those are preferable. In particular, methylhexahydrophthalic anhydride and methyl hydrogenated nadic anhydride are preferable because of their excellent transparency. In particular, in order to accelerate the curing reaction, a peroxide-based compound, an amine-based compound, a phenol-based compound, a quaternary ammonium-based compound, a quaternary phosphonium-based compound, an aromatic sulfonium salt, or the like is added in an amount of 0.1 to 0.5% by mass. It is preferable to use.

As the styrene resin, polystyrene, styrene-methylstyrene copolymer, styrene-1,3-dimethylstyrene copolymer, styrene-4-propylstyrene copolymer, styrene-4-cyclohexylstyrene copolymer, styrene- Examples thereof include styrene resins such as 4-dodecylstyrene copolymer and styrene-2-ethyl-4-benzylstyrene copolymer, and copolymer resins of styrene monomers and other copolymerizable monomers. Is, for example, a styrene-acrylonitrile copolymer having a refractive index of 1.50 to 1.60 of JIS K7142, a styrene-methyl methacrylate copolymer, a styrene-methyl methacrylate-(meth)acrylic acid ester copolymer, styrene. -Methyl methacrylate-(meth)acrylic acid copolymer, styrene-maleic anhydride copolymer and the like. Examples of other styrene-based copolymers and styrene-based copolymers that can be used in combination with the styrene-based copolymers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-vinylisoprene. -Styrene block copolymer, styrene-ethylene-butene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-ethylene -Butene block copolymers, styrene-ethylene-butene block copolymers having a refractive index of 1.50 to 1.60 according to JIS K7142 can be used. Examples of the styrene monomer of these styrene-based copolymers include styrene, methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 1-vinyl. Examples include anthracene.

As the acrylic resin, as the acrylic resin, a homopolymer of one kind of monomer selected from monofunctional (meth)acrylic acid esters, a copolymer of two or more kinds of monomers, and a polyfunctional ( Homopolymers of one type of monomer selected from (meth)acrylic acid esters, or copolymers of two or more types of monomers, one or more types selected from these monomers and modified (meth)acrylic acid esters (for example, A (co)polymer having a refractive index of 1.50 to 1.60 of JIS K7142, such as a copolymer with a monomer such as epoxy-modified, polyester-modified, or urethane-modified) is preferable. Here, “(meth)acrylic acid ester” is a notation that represents two types of “acrylic acid ester” and “methacrylic acid ester” at the same time. Alkyl esters having 1 to 18, particularly 1 to 8 carbon atoms in these ester moieties are preferred. Further, the acrylic resin may be a copolymer with a monomer other than acrylic, and the monomer other than acrylic may include maleic acid, itaconic anhydride, ethylenically unsaturated carboxylic acids such as succinic anhydride, acrylamide, and meta. Amide compounds such as acrylamide, N-methyl acrylamide and N-methylol acrylamide, hydroxyl group-containing (meth)acrylic acids such as hydroxyethyl acrylate and hydroxyethyl methacrylate, styrenes, α-olefins, vinyl ethers, alkenyls , Vinyl esters and aromatic vinyl compounds can also be used.

The transparent resin sheet laminated on each of the front surface and the back surface of the coarse grid structure is composed of a soft vinyl chloride resin composition mainly containing a vinyl chloride resin and a plasticizer, and the plasticizer is a dialkyl phthalate ester. , An isophthalic acid dialkyl ester, a terephthalic acid dialkyl ester, a cyclohexanedicarboxylic acid dialkyl ester, and a cyclohexene dicarboxylic acid dialkyl ester, in an amount of 35 to 100 parts by mass based on the mass of the vinyl chloride resin. is there. The plasticizer of the transparent resin sheet includes adipic acid ester, sebacic acid ester, trimellitic acid ester, pyromellitic acid ester, adipic acid polyester, adipic acid polyester, citric acid ester, benzoic acid ester, ethylene/carbon monoxide/acetic acid. A vinyl ester terpolymer, ethylene/carbon monoxide/acrylic acid ester terpolymer, etc. can be used in combination. As the transparent resin sheet, a transparent film having a thickness of 0.1 mm to 0.5 mm processed by calender molding or T-die extrusion molding of soft vinyl chloride resin can be used, and in order to impart weather resistance and UV resistance. , Known benzotriazole compounds, benzophenone compounds, cyanoacrylate compounds and other known UV absorbers, hindered amine compounds (HALS) known light stabilizers, phenolic compounds, hindered phenolic compounds and other known antioxidants It is preferable to add 0.01 to 3 parts by mass of each of the agents and the like to the mass of the vinyl chloride resin. The transparent flexible sheet of the present invention is obtained by using a rough grid structure as a substrate, and laminating a transparent resin sheet on each of the front surface and the back surface of the rough grid structure by thermocompression lamination or by using an adhesive. The sheet of the composite has a thickness of 0.2 mm to 2.0 mm, and particularly preferably 0.4 mm to 0.8 mm.

In the transparent flexible sheet of the present invention, the fluororesin layer is formed on at least one surface of the composite body obtained by laminating the transparent resin sheet on the coarse grid structure. This fluororesin layer is a multi-layered product consisting of a fluororesin layer/aminoethylated acrylic resin epoxy cured product layer, a multi-layered product consisting of a fluororesin layer/acrylic resin layer, a fluororesin layer/acrylic resin Layer/aminoethylated acrylic resin/epoxy cured material layer, and a fluororesin layer/acrylic resin layer/vinyl chloride resin layer. Fluorine-based resins include monomers such as vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene (TrEE), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), and hexafluoropropylene (HFP). Homopolymers such as polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), polytrifluoroethylene (PTrEE), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), Examples thereof include polyhexafluoropropylene (PHFP), but in the present invention, polyvinyl fluoride (PVF) and polyvinylidene fluoride (PVdF) are preferable. The fluororesin is a VdF-TFE copolymer resin, a VdF-CTFE copolymer resin, a VdF-HFP copolymer resin, a TFE-, which is obtained by copolymerizing two or more kinds selected from the above monomers. CTFE copolymer resin, TFE-HFP copolymer resin, CTFE-HFP copolymer resin, VdF-TFE-CTFE copolymer resin, VdF-TFE-HFP copolymer resin, TFE-CTFE-HFP copolymer resin It may be a resin, a VdF-CTFE-HFP copolymer resin, a VdF-TFE-CTFE-HFP copolymer resin, or the like.

Among the fluororesin layers, 1) a multi-layered body composed of a fluororesin layer/aminoethylated acrylic resin epoxy cured product layer has a thickness of at least one selected from the fluororesins described in paragraph [0035]. 20 μm to 200 μm, in particular 50 μm to 100 μm, of a corona-treated film layer (preferably PVF or PVdF may be biaxially stretched), and a thickness of 1 μm to 50 μm of an aminoethylated acrylic resin epoxy cured product. It is a multi-layered body with layers. Among these, the aminoethylated acrylic resin epoxy cured material layer is a liquid material in which an aminoethylated acrylic resin is used in combination with one or more selected from the epoxy resins described in paragraph [0031], on the fluorine resin film side, and/or Alternatively, a coating layer formed by coating on the composite side and reacting it with epoxy to form an aminoethylated acrylic resin epoxy cured product layer on the composite side first, and then laminating and bonding a fluororesin film layer thereon Aspects are also included. In the process of forming the fluororesin layer on the composite obtained by laminating the transparent resin sheet on the coarse grid structure, the aminoethylated acrylic resin epoxy cured product layer is in the process of being cured, and the fluororesin layer is Formation is completed when the reaction of the aminoethylated acrylic resin epoxy cured product is completed over time. Such aminoethylated acrylic resin is one or more acrylic resins selected from the acrylic resins described in paragraph [0033], for example, methacrylic acid alkyl ester/methacrylic acid copolymer, or methacrylic acid alkyl ester. in primary amino group-containing acrylic resin polyethyleneimine grafted to a carboxyl group such as acrylic acid alkyl ester-methacrylic acid copolymer, an amine side chain, represented by the chemical formula _{-COO (CH 2 CH 2 NH)} n H Those having a valency (the number of mmol of amine contained in 1 g of solid content) of 0.6 to 1.3 mmol/g are preferable. 2) Next, the multilayer body composed of a fluororesin layer/acrylic resin layer is a layer (preferably PVF or 100 μm) having a thickness of 10 μm to 100 μm and made of one or more selected from the fluororesins described in paragraph [0035]. PVdF) and a layer of acrylic resin having a thickness of 10 μm to 100 μm are integrated by interfacial integration, and particularly, a PVdF layer (5 to 10 μm)/acrylic resin layer (50 to 100 μm). preferable. The acrylic resin may be one or more selected from the acrylic resins described in paragraph [0033], and the two-layer film may be produced by a known co-extrusion method, and may be biaxially stretched. .. This two-layer film can be laminated on the composite by a known thermal laminating method. 3) Next, the multi-layered body composed of the fluorine-based resin layer/acrylic resin layer/aminoethylated acrylic resin epoxy cured product layer is the acrylic resin side of the two-layer film specification of the above 2) and/or the composite side. In addition, the aminoethylated acrylic resin epoxy cured product layer of the above 1) is used together, and the aminoethylated acrylic resin epoxy cured product layer is first provided on the composite side, and the fluororesin film layer is laminated and adhered thereon. Aspects are also included. 4) A multi-layered body composed of a fluororesin layer/acrylic resin layer/vinyl chloride resin layer has a known structure in which a vinyl chloride resin layer having a thickness of 10 μm to 100 μm is added to the two-layer film specification of 2) above. It may be produced by a co-extrusion method, and may be biaxially stretched with a three-layer film specification in which the interfaces are fused and integrated. Particularly preferred is a PVdF layer (5 to 10 μm)/acrylic resin layer (10 to 50 μm)/soft vinyl chloride resin layer (10 to 100 μm). This three-layer film is a vinyl chloride resin by a known thermal lamination method. It can be directly laminated on the specified composite (transparent resin sheet is vinyl chloride resin). When forming the fluororesin composite multilayer body of the above aspects 1 to 4) on the composite, a coating film (3 to 30 μm) of an acrylic resin solvent-based paint is preliminarily formed as an adhesive layer on both surfaces of the composite. By doing so, it is possible to further improve the adhesiveness with the fluorine-containing resin multilayer body, and further to improve the strength of lap joining between the transparent flexible sheets of the present invention by heating or high frequency induction heating.

In the transparent flexible sheet of the present invention, on the surface of the fluororesin layer, nanoparticles made of an inorganic colloidal substance having a primary particle diameter of 3 nm to 150 nm are used as a binder component containing a hydrolyzed condensate of a silane coupling agent. An antistatic antifouling layer which is carried can be provided. Examples of the inorganic colloidal substance include photocatalytic titanium oxide sol, photocatalytic zinc oxide sol, photocatalytic tin oxide sol, titanium oxide sol, zinc oxide sol, tin oxide sol, silica sol, aluminum oxide sol, zirconium oxide sol, cerium oxide sol, and complex oxides. One or more metal oxides selected from the sol (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol are preferable. The antistatic antifouling layer is transparent to a liquid composition containing 1 to 25% by mass of an inorganic colloidal substance and 1 to 10% by mass of a silane coupling agent based on the mass of nanoparticles made of the inorganic colloidal material. On the surface of the flexible sheet (transparent resin sheet), gravure coating method, microgravure coating method, comma coating method, roll coating method, reverse roll coating method, bar coating method, kiss coating method, flow coating method, spray method, etc. It is a sol-gel thin film having a thickness of 0.1 μm to 10 μm obtained by drying and solidifying with hot air or a heater after coating. The surface resistance value (measurement method: JIS K6911: 1995: measurement condition: humidity 30% RH−temperature 23° C.) of the obtained transparent flexible sheet can be made to be an antistatic property of less than 1.0E+12Ω. The silane coupling agent is used in combination in the form of a hydrolyzed condensate of the silane coupling agent to improve the wear resistance of the antistatic antifouling layer, and the silane coupling agent has the general formula: XR-Si(Y) ₃ A compound having two or more different reactive groups in the molecule represented by, for example, X=amino group, vinyl group, epoxy group, chloro group, mercapto group (R=alkyl chain), Y=methoxy group , An ethoxy group, and the like. The antistatic antifouling layer is preferably a transparent flexible sheet (transparent resin sheet) formed over the entire surface, but may be formed in a lattice network.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples of the present invention are shown below.
(1) Visibility (good or bad visibility)
A test piece sheet (height 60 cm x width 100 cm) within one month of manufacture is applied to the height of the eyes of the transparent window glass (inside the room) on the third floor of the company building, and the four corners of the test sheet are fixed to the window glass with transparent tape. However, 10 panelists rated the visual field when the outdoor scenery was observed at a standing position of 1 m from the window glass on a three-point scale. The observation evaluation was carried out for 30 minutes from 1:00 pm on a sunny day in September, and the observation was performed on a window surface with a scenic view.
Evaluation "A": Presence of coarse grid-like structure is not conspicuous and visibility is good (wide field of view).
Evaluation "B": Presence of coarse grid-like structure is a little conspicuous and visibility is a little poor (visual field is a little narrow)
Evaluation “C”: Presence of coarse grid structure is conspicuous and visibility is poor (narrow field of view)
(2) Visibility of the seat after 6 months of use (good or bad visibility)
The test sheet was left standing for 6 months from April to September, and the same evaluation as in (1) was performed.
(3) Seat visibility after accelerated heating (good or bad visibility)
A test sheet (height 60 cm×width 100 cm), which was left standing in an air circulation type oven at 65° C. for 480 hours, was fixed in the same manner as in (1) and evaluated in the same manner as in (1).
(4) Discoloration by accelerated light resistance test Accelerated light resistance test (JIS-K5600) by xenon arc lamp is performed for 1000 hours, and the degree of discoloration and fading of the surface after the test is based on the test sheet before acceleration and the color difference ΔE (JIS -Z8729) and the discolorability was evaluated.

[Example 1]
(1) Coarse lattice structure intermediate 1 (net)
Glass with a single yarn diameter of 9 μm (E glass: JIS K7142 refractive index 1.56) Filament x 400 filaments x 0.7 twists/25mm 68.7tex count multifilament yarn (with a substantially rectangular cross section) The ratio of height to width in the cross-sectional shape is 2:7) is used for the warp yarn group and the weft yarn group, the warp yarn groups are arranged at 2 cm intervals, and the odd yarns in the arrangement order of the weft yarn groups are arranged at 4 cm intervals. The warp yarns and the weft yarns are arranged on the weft yarn group, and even yarns in the order of arrangement of the weft yarn yarns are laid on the weft yarns at intervals of 4 cm so that the distance between the weft yarn groups is 2 cm. A non-woven biaxial net having a driving density of 1.27 filaments/inch and a porosity of 80% was used.
(2) Coarse grid structure intermediate 2 (resin-impregnated coated net)
A vinyl chloride resin paste sol composition of the following [formulation 1] is prepared to have an appropriate viscosity, and a biaxial net is immersed in a liquid bath filled with the paste sol composition of the [formulation 1] to prepare a multifilament yarn. Was completely impregnated with the [compound 1] paste sol composition, the biaxial net was pulled up, and at the same time, squeezed with a rubber roll and gelled with the [blend 1] paste sol composition for 3 minutes in a hot air oven at 180°C. A coarse grid-like structure intermediate body 2 having a biaxial net, which was completed and impregnated with and covered with the vinyl chloride resin composition of [formulation 1], was obtained. This gelled vinyl chloride resin composition had a refractive index of 1.548 according to JIS K7142.
[Formulation 1] Soft vinyl chloride resin paste sol composition Emulsion-polymerized polyvinyl chloride resin (polymerization degree 1700) 100 parts by mass Tricresyl phosphate (refractive index 1.557) 140 parts by mass Epoxidized soybean oil (stabilizer) 10 parts by mass Zinc stearate (stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass (3) Coarse grid structure Epoxy system of the following [formulation 2] A resin transparent composition was prepared to an appropriate viscosity with a MEK diluent, and the liquid composition of this [formulation 2] was gravure coated on both sides of the coarse grid structure intermediate body 2 with a 60 mesh gravure roll to form a coarse grid. [Compound 2] liquid composition is adhered to the entire outermost layer of the intermediate structure 2 and heated and dried in a hot air oven at 150° C. for 3 minutes to cure the transparent transparent epoxy resin composition [Compound 2]. A coarse grid structure (1) having a coating layer was obtained. According to JIS K7142, a transparent coating layer formed by a reaction between a trifunctional epoxy resin containing a bisphenol A skeleton (65 parts by mass) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (35 parts by mass). The refractive index was 1.568.
[Formulation 2] Epoxy resin transparent composition epoxy resin (bisfunctional A skeleton-containing trifunctional epoxy resin) 65 parts by mass
*Epoxy equivalent 260g/eq
Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride 35 parts by mass
* Carboxyl equivalent 100g/eq
Peroxide-based curing accelerator 0.25 parts by mass Methyl ethyl ketone (MEK diluent) 200 parts by mass (4) Transparent flexible sheet Coarse lattice structure (1) Both sides of the following [formulation 3] soft vinyl chloride resin transparent composition A transparent resin sheet having a thickness of 0.18 mm, which is calender-molded from a product under heat conditions of 165° C. to 180° C., is used as a front transparent resin sheet and a back transparent resin sheet, and the front and back sheets are based on the coarse grid structure (1). A transparent flexible sheet having a thickness of 0.36 mm and a mass of 457 g/m ² which is sandwiched by a laminator under a heat roll condition of 170° C. and is heat-softened to form a transparent resin sheet. (1) was obtained. In the obtained transparent flexible sheet (1), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition was 0.012 (within 0.05), and the transparent coating layer and the vinyl chloride resin composition The difference in the refractive index (JIS K7142) with is 0.02 (within 0.05), and the obtained sheet is semitransparent in the coarse lattice structure, and the transparency is the same as that of the laminated transparent resin sheet. The visibility was extremely good, and this effect was still good after 6 months of use and after promotion at 65° C. for 480 hours. Due to the presence of the transparent coating layer (epoxy resin), the aromatic phosphate ester compound contained in the vinyl chloride resin composition is retained in the resin-processed multifilament yarn, and the aromatic phosphate ester compound is placed on the transparent resin sheet side. It is due to the invention that it acts as a barrier layer to prevent migration and diffusion.
[Formulation 3] Soft vinyl chloride resin transparent composition Suspension polymerization polyvinyl chloride resin (polymerization degree 1300) 100 parts by mass Diisononyl phthalate (DINP) 65 parts by mass Epoxidized soybean oil (plasticizer) 5 parts by mass Zinc stearate (Stabilizer) 2 parts by mass Barium stearate (stabilizer) 2 parts by mass Benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass (5) Fluorine-based resin layer In the transparent flexible sheet (1) of (4) above. Gravure the acrylic resin paint of the following [Compound 4] on both sides with a gravure roll of 100 mesh and heat dry for 2 minutes in a hot air oven at 120°C to obtain the thickness of the acrylic resin coating layer on the front and back. A transparent flexible sheet (2) having a weight of 0.36 mm and a mass of 462 g/m ² was obtained.
[Formulation 4] Acrylic resin paint, methacrylic acid alkyl ester/acrylic acid alkyl ester copolymer
100 parts by mass Methyl ethyl ketone (MEK diluent) 250 parts by mass Toluene (diluent) 250 parts by mass Next, on one surface of this transparent flexible sheet (2), a solution of the following [formulation 5] aminoethylated acrylic resin epoxy composition is prepared. Gravure coating with a 100 messiu gravure roll, heat drying in a hot air oven at 120° C. for 2 minutes, and an acrylic resin coating layer attached to the surface side in a semi-cured state, thickness 0.36 mm, mass 465 g/ A transparent flexible sheet (3) of m ² was obtained.
[Formulation 5] Aminoethylated acrylic resin epoxy composition Polyethyleneimine is grafted onto the carboxyl group of a methacrylic acid alkyl ester/acrylic acid alkyl ester/methacrylic acid copolymer, and the side chain is —COO(CH ₂ CH ₂
NH) _n H amine value represented by the chemical formula (the number of mmol of amine contained in 1 g of solid content) 0.7 to
1.3 mmol/g of primary amino group-containing acrylic resin 100 parts by mass Epoxy resin (epoxy equivalent of 260 g/eq bisphenol A skeleton-containing trifunctional epoxy resin) 20 parts by mass Methyl ethyl ketone (MEK diluent) 150 parts by mass Toluene (diluted Agent) 150 parts by mass Next, the corona-treated surface side of a 25 μm-thick polyvinylidene fluoride (PVdF) film is opposed to the aminoethylated acrylic resin epoxy semi-cured material layer surface side of this transparent flexible sheet (3). At a temperature of 150° C. through a laminator under hot roll conditions and thermocompression bonding to form a fluororesin layer (1) composed of a fluororesin/aminoethylated acrylic resin epoxy cured product multi-layer body, and having a thickness of 0. A transparent flexible sheet (4) having a mass of 0.36 mm and a mass of 510 g/m ² was obtained. This fluororesin layer formation process is carried out by gravure-coating a solution of the aminoethylated acrylic resin epoxy composition of [formulation 5] on the corona-treated surface side of a polyvinylidene fluoride (PVdF) film with a 100-mesh gravure roll. The transparent flexible sheet (4) can also be produced by thermally laminating the film having the semi-cured material layer obtained by drying the transparent flexible sheet (2). The stain resistance of the two types of transparent flexible sheets before and after attaching this fluororesin layer (1) was drawn on a commercially available oil-based pen (red) and the DRY tissue paper wipe-removal property after drying at room temperature for 60 seconds ( As a result of evaluation by rubbing back and forth 10 times), it was found that the sheet having the fluorine-based resin layer (which also serves to prevent migration of the plasticizer to the surface of the sheet) was excellent in removing red ink characters. On the other hand, in the sheet not provided with the fluorine-based resin layer, the red ink characters penetrated into the sheet, and the ink stain was spread on the rubbed portion, which was unsightly. Also, these two types of transparent flexible sheets were exposed outdoors for 3 months from August to October, and evaluated by the WET tissue paper wipe-removability (scraping reciprocating 10 times). The sheet that has the function of preventing the migration of plasticizer) also has an excellent ability to remove adhering dust and recovers the initial appearance, whereas the sheet that does not have the fluororesin layer has a plasticizer on the surface of the sheet. However, the adhered dust adhered firmly and the initial appearance could not be recovered. Regardless of the presence or absence of the fluororesin layer (1), the difference in refractive index between the multifilament and the vinyl chloride resin composition and the difference in refractive index between the transparent coating layer and the vinyl chloride resin composition do not change.

[Example 2]
A fluororesin layer (1) was added in the same manner as in Example 1 except that the epoxy resin transparent composition of [Formulation 2] of Example 1 was changed to the styrene resin transparent composition of [Formulation 6] below. A transparent flexible sheet (5) having a thickness of 0.36 mm and a mass of 510 g/m ² was obtained. In the obtained transparent flexible sheet (5) regardless of the presence or absence of the fluororesin layer (1), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0.012 (within 0.05). ), the difference in refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.563) and the vinyl chloride resin composition is 0.015 (within 0.05), and the obtained transparent flexible sheet In (5), the coarse grid-like structure is semi-transparent and the transparency is assimilar to that of the laminated transparent resin sheet, so that the visibility is very good. This effect is obtained after 6 months of use and at 65° C. for 240 hours. It was still good after the promotion. Due to the presence of the transparent coating layer (styrene resin), the aromatic phosphate ester compound contained in the vinyl chloride resin composition is retained in the resin-processed multifilament yarn, and the aromatic phosphate ester compound is placed on the transparent resin sheet side. It is due to the invention that it acts as a barrier layer to prevent migration and diffusion.
[Formulation 6] Styrenic resin transparent composition Styrene-1,3-dimethylstyrene copolymer 50 parts by mass Styrene-butadiene-styrene block copolymer 50 parts by mass Methyl ethyl ketone (MEK diluent) 150 parts by mass Toluene (diluent) 150 parts by mass

[Example 3]
A fluororesin layer (1) was added in the same manner as in Example 1 except that the epoxy resin transparent composition of [Formulation 2] of Example 1 was changed to the acrylic resin transparent composition of [Formulation 7] below. A transparent flexible sheet (6) having a thickness of 0.36 mm and a mass of 510 g/m ² was obtained. In the obtained transparent flexible sheet (6), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0.012 (within 0.05) regardless of the presence or absence of the fluororesin layer (1). ), the difference in refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.566) and the vinyl chloride resin composition is 0.018 (within 0.05), and the obtained transparent flexible sheet In (6), the coarse grid structure is semi-transparent and the transparency is assimilar to that of the laminated transparent resin sheet, so that the visibility is very good. This effect is obtained after 6 months of use and at 65° C. for 240 hours. It was still good after the promotion. Due to the presence of the transparent coating layer (acrylic resin), the aromatic phosphate ester compound contained in the vinyl chloride resin composition is retained in the resin-processed multifilament yarn, and the aromatic phosphate ester compound is placed on the transparent resin sheet side. It is due to the invention that it acts as a barrier layer to prevent migration and diffusion.
[Formulation 7] Acrylic resin transparent composition Alkyl methacrylic acid/alkyl acrylate copolymer 50 parts by mass Styrene-methyl methacrylate-(meth)acrylic acid ester copolymer 50 parts by mass Methyl ethyl ketone (MEK diluent) 150 parts by mass Toluene (diluent) 150 parts by mass

[Example 4]
The same procedure as in Example 1 except that the biaxial net used in Example 1 was changed to the following triaxial net, and the transparent resin having the fluororesin layer (1) had a thickness of 0.36 mm and a mass of 540 g/m ² . A flexible sheet (7) was obtained. In the obtained transparent flexible sheet (7) regardless of the presence or absence of the fluororesin layer (1), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0.012 (within 0.05). ), and the difference in the refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.566) and the vinyl chloride resin composition was 0.02 (within 0.05).
Triaxial net single-fiber diameter 9 μm glass (E glass: JIS K7142 refractive index 1.56) filament x 400 filaments x 0.7 twists/25 mm multi-filament yarn of 68.7tex count (cross-sectional shape is The ratio of height to width in the cross-sectional shape is 2:7) is used for the warp yarn group, the 60° rightward-biased multifilament yarn group, and the 60° leftward-biased multifilament yarn group. On top of all the warp yarn groups arranged at 2 cm intervals, a part of the multi-filament yarn group with a bias of 60° to the right is placed at 4 cm intervals, and the remaining yarn groups are arranged at 4 cm intervals for all warp yarn groups. Arrange them so that they are laid in groups, and further, place a part of the bias multi-filament yarn group that rises 60° to the left on the warp yarn group at an interval of 4 cm, and place the remaining yarn groups at all at an interval of 4 cm. Arranged so as to be laid on the warp yarn group, the yarns between the right upward bias yarn groups are arranged at 2 cm intervals, and the yarns between the left upward bias yarn group are arranged at 2 cm intervals, and the driving density of the warp yarns and the bias yarn groups is set. Was 1.27 filaments/inch and a non-woven triaxial net having a porosity of 70% was used.

[Example 5]
Same as Example 1 except that the biaxial net used in Example 1 was changed to the following tetraaxial net, the fluororesin layer (1) was attached, and the thickness was 0.36 mm and the mass was 570 g/m ² . A flexible sheet (8) was obtained. In the obtained transparent flexible sheet (8) regardless of the presence or absence of the fluororesin layer (1), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0.012 (within 0.05). ), and the difference in the refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.566) and the vinyl chloride resin composition was 0.02 (within 0.05).
Tetraaxial net Single fiber diameter 9μm glass (E glass: JIS K7142 refractive index 1.56) Filament x 400 filaments x 0.7 times/25mm 68.7tex count multifilament yarn A substantially rectangular cross-sectional shape with a height-width ratio of 2:7) is used for warp yarn groups, weft yarn groups, 45° right upward bias multifilament yarn groups, and 45° left upward bias multifilament yarn groups. The warp yarn groups are arranged at 2 cm intervals, the odd yarns in the arrangement order of the weft yarn groups are arranged at 4 cm intervals on the warp yarn group, and the even yarns in the arrangement order of the weft yarn groups are arranged at 4 cm interval. It was laid on the weft yarns and arranged so that the distance between the weft yarn groups was 2 cm. Next, on each of these warp and weft yarn groups, a part of the 45° upward-sloping bias multifilament yarn group is placed at an interval of 4 cm, and the remaining yarn groups are arranged at an interval of 4 cm. The upper part of the multi-filament yarn group with a bias of 45° to the left is placed on the warp yarn group at an interval of 4 cm, and the rest of the yarn group is placed at a 4 cm interval. Arranged so as to be laid on the yarn group, the yarns between the right upward bias yarn groups are arranged at 2 cm intervals, and the yarns between the left upward bias yarn group are arranged at 2 cm intervals, and the warp weft yarn and the bias yarn are driven in. A non-woven tetraaxial net having a density of 1.27 filaments/inch and a porosity of 60% was used.

[Example 6]
On the fluororesin layer (1) of Example 1, an antistatic antifouling paint of the following [Formulation 8] was applied with a 120-mesh gravure roll, and heated and dried in a hot air oven at 120°C for 2 minutes, An antistatic antifouling layer obtained by sol-gel curing the antistatic antifouling paint of [Formulation 8] was additionally formed to obtain a transparent flexible sheet (9) having a thickness of 0.36 mm and a mass of 511 g/m ² . The antistatic antifouling layer is a sol-gel thin film in which an inorganic colloidal substance (a photocatalytic titanium oxide sol and a silica sol) is supported by a binder component formed by a hydrolytic condensation product of a silane coupling agent. Antistatic property The surface resistance value (measurement method: JIS K6911: 1995: measurement condition: humidity 30% RH-temperature 23°C) of the transparent flexible sheet (9) before and after the attachment of the antifouling layer is clearly antistatic property. The sheet with the antifouling layer exhibited an antistatic property of about 1.0E+11Ω, but the sheet without the antistatic antifouling layer remained at about 1.0E+14Ω. Therefore, by attaching the antistatic stainproof layer, it is possible to significantly reduce the attachment of dust due to static electricity. In the obtained transparent flexible sheet, the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition was 0.012 (regardless of the presence or absence of the fluororesin layer (1) and the antistatic stainproof layer. The difference in refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.566) and the vinyl chloride resin composition was 0.018 (within 0.05).
[Compound 8] Antistatic antifouling paint (for forming antistatic antifouling layer)
Photocatalytic titanium oxide sol (particle size 10 nm x solid content 8% by mass) 50 parts by mass Silica sol (particle size 12 nm x solid content 20% by mass) 50 parts by mass γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 2 parts by mass Part Water/ethanol (diluent consisting of 1:1 mass ratio) 50 parts by mass *Water/ethanol promotes the hydrolysis-condensation reaction of the silane coupling agent, and it is used together with inorganic colloidal substances (photocatalytic titanium oxide sol and silica sol). Form a sol-gel intermediate.

[Example 7]
The fluororesin layer (1) of Example 1 was a "multilayer composed of a PVdF layer of 25 µm/aminoethylated acrylic resin epoxy cured material layer", and a "multilayer of a PVdF film layer of 5 µm/acrylic resin layer of 35 µm". A transparent flexible sheet (10) having a thickness of 0.37 mm and a mass of 510 g/m ² was obtained in the same manner as in Example 1 except that the fluororesin layer (2) which was a “body” was used. In the obtained transparent flexible sheet (10) regardless of the presence or absence of the fluororesin layer (2), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0.012 (within 0.05). ), and the difference in the refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.566) and the vinyl chloride resin composition was 0.02 (within 0.05).

[Example 8]
The fluororesin layer (1) of Example 1 "a multi-layered body comprising a PVdF layer of 25 µm/aminoethylated acrylic resin epoxy cured material layer" was changed to "5 µm PVdF film layer/acrylic resin layer of 35 µm/aminoethylated". A transparent flexible sheet having a thickness of 0.38 mm and a mass of 514 g/m ² (same as in Example 1 except that the fluororesin layer (3), which is a “multi-layered body composed of an acrylic resin/epoxy cured material layer”, is used. 11) was obtained. In the obtained transparent flexible sheet (11) regardless of the presence or absence of the fluororesin layer (3), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0.012 (within 0.05). ), and the difference in the refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.566) and the vinyl chloride resin composition was 0.02 (within 0.05).

[Example 9]
The fluorine-based resin layer (1) of Example 1 was a “multilayered body composed of a PVdF layer of 25 μm/aminoethylated acrylic resin epoxy cured material layer”, and a “5 μm PVdF film layer/10 μm acrylic resin layer/25 μm soft layer”. A transparent flexible sheet (12) having a thickness of 0.38 mm and a mass of 520 g/m ^{2 in} the same manner as in Example 1 except that the fluororesin layer (4), which is a “multilayered body made of a vinyl chloride resin layer”, is used. Got In the obtained transparent flexible sheet (12) regardless of the presence or absence of the fluororesin layer (4), the difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is 0.012 (within 0.05). ), and the difference in the refractive index (JIS K7142) between the transparent coating layer (JIS K7142 refractive index 1.566) and the vinyl chloride resin composition was 0.02 (within 0.05).

[Comparative Example 1]
In the resin-processed multifilament yarn constituting the coarse lattice structure of the transparent flexible sheet of Example 1, the thickness was the same as in Example 1 except that the outermost transparent coating layer (epoxy resin) was omitted. A transparent flexible sheet (13) having a size of 0.36 mm and a mass of 510 g/m ² was obtained. The obtained sheet was translucent in the coarse lattice structure and had the same transparency as the laminated transparent resin sheet, and thus the visibility was equivalent to that of the transparent flexible sheet (4) of Example 1. However, this effect is lost after 6 months of use and after accelerated for 65 hours at 65° C., and the coarse grid-like structure becomes cloudy and exposed. As a result, the presence of the coarse grid-like structure obstructs the visibility. Became. This is because the transparent coating layer (epoxy resin), which is a barrier layer, is omitted, so that the tricresyl phosphate (aromatic phosphate compound) contained in the vinyl chloride resin composition is transparent resin sheet from inside the resin-processed multifilament yarn. Due to the fact that the refractive index of the vinyl chloride resin composition gradually decreases due to migration and diffusion to the side, and the difference in the refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition exceeds 0.05. It is a bug to do.

[Comparative Example 2]
In the resin-processed multifilament yarn that constitutes the coarse grid structure of the transparent flexible sheet of Example 1, formation of the outermost transparent coating layer (epoxy resin) was omitted, and the surface of the coarse grid structure and A thickness of 0.36 mm was obtained in the same manner as in Example 1 except that the formulation [formulation 3] of the transparent resin sheet laminated on the entire back surface was changed to the soft vinyl chloride resin transparent composition of the following [formulation 9]. A transparent flexible sheet (14) having a mass of 510 g/m ² was obtained.
[Formulation 9] Soft vinyl chloride resin transparent composition Suspension polymerization polyvinyl chloride resin (polymerization degree 1300) 100 parts by mass Tricresyl phosphate (refractive index 1.557) 65 parts by mass Epoxidized soybean oil (plasticizer) 5 parts by mass Parts zinc stearate (stabilizer) 2 parts by mass barium stearate (stabilizer) 2 parts by mass benzotriazole-based compound (ultraviolet absorber) 0.2 parts by mass In the obtained sheet, the coarse lattice structure is translucent. Since the transparency was assimilated to the laminated transparent resin sheet, the visibility was equivalent to that of the transparent flexible sheet (4) of Example 1. As in Comparative Example 1, by omitting the transparent coating layer (epoxy resin) which is a barrier layer, the tricresyl phosphate (aromatic phosphate ester compound) was easily transferred from the resin-processed multifilament yarn to the transparent resin sheet side. Nevertheless, since tricresyl phosphate was used as the plasticizer for the transparent resin sheet, the visibility was the same as that of the transparent flexible sheet (4) of Example 1 without the coarse lattice-like structure being exposed to cloudiness even after 6 months. It was the same as after 6 months. However, as a result of 1000 hours of accelerated light resistance test (JIS-K5600) using a xenon arc lamp, the presence of a large amount of tricresyl phosphate contained in the transparent resin sheet causes color yellowing (JIS-Z8729 color difference ΔE6.5), It became clear that it was unsuitable as a sheet material that was exposed to sunlight.

[Comparative Example 3]
In the resin-processed multifilament yarn that constitutes the coarse lattice structure of the transparent flexible sheet of Example 1, the formation of the outermost transparent coating layer (epoxy resin) according to [Blending 2] was carried out by the following blending [Blending 10]. A transparent flexible sheet (15) having a thickness of 0.36 mm and a mass of 510 g/m ² was obtained in the same manner as in Example 1 except that the transparent transparent urethane resin composition (refractive index 1.495) was used. In the obtained sheet, the transparent coating layer made of the urethane-based resin certainly exhibits the function as a barrier layer for preventing tricresyl phosphate (aromatic phosphate ester compound) migration, but the transparent coating layer and the vinyl chloride resin are used. By increasing the difference in refractive index (JIS K7142) from the composition to 0.053 (exceeding 0.05), the coarse grid structure becomes cloudy and exposed, resulting in the presence of the coarse grid structure. Became an obstacle to visibility.

The transparent flexible sheet obtained by the present invention has a rough lattice-shaped structure composed of a resin-processed multifilament yarn as a base, and a transparent resin sheet is laminated on each of the entire front and back surfaces of the rough lattice-shaped structure. A laminated body in which a specific fluorine-based resin layer is formed on one or more surfaces of a composite made of a multifilament forming a coarse lattice structure and a refractive index (JIS K7142) of a vinyl chloride resin composition. By setting the difference within 0.05 and simultaneously achieving the difference in the refractive index (JIS K7142) between the transparent coating layer of the resin-processed multifilament yarn and the vinyl chloride resin composition within 0.05, the rough grid Of the present invention, which makes it possible to optically (semi)transparent the existence of the granular structure, and since the transparent coating layer is also effective for preventing migration of the aromatic phosphate ester compound, The presence of the sheet does not become cloudy and becomes a factor that impairs the visibility, maintains good visibility of the entire sheet, and is excellent in long-term weather resistance (discoloration resistance) and stain resistance. For example, membrane structures (pavilion exteriors, museum objects, museum objects), body materials for outdoor applications such as sheet houses and garden houses, and parts materials such as lighting windows, electronic and electrical equipment factories, hospitals and research facilities, etc. It can be widely used for industrial materials such as partitions used for indoor use, curtains, equipment covers, as well as miscellaneous goods such as bags and leisure sheets.

(1) Resin-processed multifilament yarn (1-1) Filament (1-2) Multifilament yarn (1-3) Vinyl chloride resin composition (1-4) Transparent coating layer (2) Coarse lattice structure (3) Transparent resin sheet (4) Fluorine resin layer (5) Transparent flexible sheet

Claims (9)

Resin-processed multi-filament yarn is used as a base body, and a transparent resin sheet is laminated on the entire front and back surfaces of the coarse grid structure, and a fluororesin is formed on one or more surfaces of the composite. A laminated body in which layers are formed, wherein the fluororesin layer is a multi-layer body composed of a fluororesin layer/aminoethylated acrylic resin epoxy cured product layer, and a fluororesin layer/acrylic resin layer composite layer. From a layered body, a multilayered body composed of a fluorine resin layer/an acrylic resin layer/an aminoethylated acrylic resin epoxy cured product layer, and a multilayered body composed of a fluorine resin layer/an acrylic resin layer/a vinyl chloride resin layer The resin-processed multifilament yarn is any one selected, and the multifilament yarn is coated with a vinyl chloride resin composition containing 1) an aromatic phosphate ester compound, and the multifilament yarn is 2) The difference in refractive index (JIS K7142) between the multifilament and the vinyl chloride resin composition is within 0.05, and 3) the yarn of 1) above. The entire surface of the strip has a transparent coating layer of at least one selected from epoxy resin, styrene resin, and acrylic resin, and the refractive index of this transparent coating layer and the vinyl chloride resin composition (JIS K7142 ) A transparent flexible sheet having a difference of 0.05 or less. The transparent flexible according to claim 1, wherein the cross-sectional shape of the resin-processed multifilament yarn is elliptical or substantially rectangular with arcuate ends, and the ratio of height to width in this cross-sectional shape is 2:3 to 1:5. Sheet. The multifilament constituting the resin-processed multifilament yarn is one or more selected from glass fiber, polyester fiber, polyamide fiber, polypropylene fiber, vinylon fiber, and vinyl chloride fiber. Transparent flexible sheet. The coarse lattice structure is 1) a woven fabric composed of warp/multifilament yarn groups and weft/multifilament yarn groups, or 2) warp/multifilament yarn groups, and 40° to 65° bias Or a triaxial woven fabric composed of multifilament yarn groups, or 3) warp/multifilament yarn groups, weft/multifilament yarn groups, and 40° to 65° bias/multifilament yarn groups Tetraaxial woven fabric as a base material, which is coated and filled with the vinyl chloride resin composition, and further selected from the epoxy resin, the styrene resin, and the acrylic resin. one that is transparent coated by the above, a transparent flexible sheet according to the claim 1 area of coarse grid 1 per the coarse grid-like structure is in the range of 25mm ² ~111mm ² .. The coarse grid structure is 4) a biaxial net in which warp/resin processed multifilament yarn groups and weft/resin processed multifilament yarn groups are fixed at warp/weft intersections, or 5) warp/resin A processed multifilament yarn group and a 40° to 65° bias/resin processed multifilament yarn group are fixed at a warp/bias intersection, or 6) a warped/resin processed multifilament yarn group, weft /A resin-processed multifilament yarn group and a 40° to 65° bias/a resin-processed multifilament yarn group are selected from one of four-axis nets fixed at warp/weft/bias intersections. In each case, the resin-processed multifilament yarn was coated with and filled with a vinyl chloride resin composition, and further transparently coated with one or more selected from the epoxy resin, styrene resin, and acrylic resin, transparent flexible sheet according to any one of claims 1 to 3 area per coarse lattice is in the range of 100mm ² ~2600mm ^2. The aromatic phosphate compound is at least one selected from tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate, and the vinyl chloride resin composition The transparent flexible sheet according to any one of claims 1 to 5, which is 50 to 200 mass% with respect to the mass of vinyl chloride resin in the product. The vinyl chloride resin composition further comprises epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid butyl, epoxidized fatty acid 2-ethylhexyl, epoxyhexahydrophthalate 2-ethylhexyl, and epoxyhexahydrophthalate diepoxystearyl. The transparent flexible sheet according to any one of claims 1 to 6, which contains 1 to 25 mass% of one or more selected epoxy compounds with respect to the total amount of the aromatic phosphate ester compound. The transparent resin sheet is composed of a vinyl chloride resin and a soft vinyl chloride resin mainly containing a plasticizer, the plasticizer is a dialkyl phthalate ester, dialkyl isophthalate ester, dialkyl terephthalate ester, dialkyl ester cyclohexane dicarboxylic acid, And 1 or more kinds selected from cyclohexene dicarboxylic acid dialkyl ester, and a blending amount of 35 to 100 mass% with respect to the mass of the vinyl chloride resin, The transparent flexible according to any one of claims 1 to 7. Sheet. Antistatic property in which nanoparticles made of an inorganic colloidal substance having a primary particle diameter of 3 nm to 150 nm as a raw material are carried on a binder component containing a hydrolyzed condensate of a silane coupling agent on the surface of the fluororesin layer. An antifouling layer is provided, and the inorganic colloidal substance is a photocatalytic titanium oxide sol, a photocatalytic zinc oxide sol, a photocatalytic tin oxide sol, a titanium oxide sol, a zinc oxide sol, a tin oxide sol, a silica sol, an aluminum oxide sol, an oxide. 9. One or more metal oxides selected from zirconium sol, cerium oxide sol, and composite oxide (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol. The transparent flexible sheet according to the item.