JP2017209943A - Transparent sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent sheet which is easy to be excellent in peeling strength even when a fluororesin is laminated without using an adhesive and hardly causes deterioration in transparency by bleeding of a plasticizer.SOLUTION: A transparent sheet contains a glass fiber fabric and a resin layer contained in the glass fiber fabric in a state of impregnated therein, where the resin layer contains a styrenic elastomer. The styrenic elastomer preferably contains at least one or more compounds selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butadiene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, and a modified product thereof.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent sheet.

  The Building Standards Law and the Building Standards Law Enforcement Ordinance stipulate that smoke-exhaust facilities should be installed so that smoke, toxic gases, etc. generated in the event of a building fire can be prevented and evacuation and fire fighting activities can be carried out smoothly. Yes. Therefore, in buildings such as office buildings and commercial facilities, smoke barriers are often installed as smoke exhausting equipment and smoke shielding equipment. In addition, for example, a sheet shutter that moves up and down during use may be installed at an entrance / exit of a factory, a warehouse, or the like. Such a sheet shutter may be composed of a transparent resin sheet and a framework so that the other side can be seen even when the sheet shutter is lowered (see, for example, Patent Document 1). By imparting smoke resistance to such a sheet shutter, it can be expected to suppress the flow of smoke and the like in the event of a fire. Therefore, it is conceivable to use a sheet shutter as disclosed in Patent Document 1 as a smoke-proof shutter.

  In addition, smoke barriers are usually used for the purpose of temporarily blocking the flow of smoke and toxic gases from the fire to the corridors and upper floors to ensure the time required for evacuation. It is attached to the ceiling of the object. For this reason, transparent plate glass, a transparent resin composite of glass fiber and resin, or the like is used as the smoke proof wall so that the visual field is not hindered by the smoke proof wall and the aesthetic appearance is not impaired. The transparent resin composite of glass fiber and resin has the advantage that it is less likely to break compared to transparent plate glass.

  For example, Patent Document 2 discloses a transparent sheet including a glass fiber fabric and a cured resin layer. In Patent Document 3, a glass fiber fabric is embedded in a cured resin layer, and a thermoplastic resin layer is laminated on at least one surface of the cured resin layer, and whitening occurs due to a bending test of JIS P 8115. However, the lighting non-combustible sheet of 30 times or more is disclosed. Patent Document 4 discloses a transparent composite sheet having a base material made of glass fiber and a resin-impregnated coating layer containing a soft vinyl chloride resin impregnated and applied to the entire front and back surfaces.

Japanese Patent Laid-Open No. 06-173557 JP 2005-319746 A JP 2014-201007 A JP 2010-52370 A

  For example, since the sheet shutter disclosed in Patent Document 1 is made of transparent vinyl chloride, it can exhibit excellent transparency, but it is not only inferior incombustibility but also has a very high mechanical strength. Has the problem of low. On the other hand, in the transparent sheet as disclosed in Patent Documents 2 and 3, a glass fiber fabric is sandwiched between a pair of cured resin layers. Moreover, in the transparent composite sheet disclosed in Patent Document 4, the entire front and back surfaces of the glass fiber substrate are covered with a soft vinyl chloride resin. For this reason, the transparent composite sheet disclosed in Patent Documents 2 to 4 has an advantage that it is superior in mechanical strength as compared with the sheet shutter disclosed in Patent Document 1.

  However, as a result of studies by the present inventors, the transparent composite sheet disclosed in Patent Documents 2 and 3 is a cured resin layer in which the resin layer contained in a state impregnated with glass fiber is, for example, the above-mentioned It has been found that when a cover layer made of a fluororesin or a polyolefin resin is further laminated on the cured resin layer in order to improve antifouling properties, it cannot be directly laminated without an adhesive. And when the present inventors laminate the cover layer via an adhesive on the cured resin layer, there is a problem that the transparency of the obtained sheet may be impaired depending on the type of adhesive. I knew it.

  Further, the transparent composite sheet disclosed in Patent Document 4 is formed by impregnating and applying a soft vinyl chloride resin composition to the entire front and back surfaces of a substrate made of glass fiber, and the refractive index adjuster is applied to the soft vinyl chloride resin composition. As mentioned above, 40 mass% or more of an aromatic phosphate ester compound which is a kind of plasticizer is included. For this reason, in the said transparent composite sheet, the stickiness of the surface becomes large, and there exists a problem that dust etc. are adsorb | sucked to the said surface and it is easy to get dirty. Further, when a cover layer made of a fluororesin or a polyolefin resin is laminated on the soft vinyl chloride resin, the resulting composite sheet is excellent in transparency immediately after production, but in the soft vinyl chloride resin composition as time passes. It has been clarified that the clearing agent of this causes bleed, which moves to the cover layer side. When the plasticizer used as a clearing agent shifts, the refractive index of the transparent composite sheet changes with time, and the difference between the refractive index of the glass fiber and the refractive index of the soft vinyl chloride resin composition increases. As a result, there is a problem that the transparency of the transparent composite sheet is deteriorated at an early stage.

  Under such circumstances, the present invention, for example, when the fluororesin layer is laminated without using an adhesive, is easily excellent in peel strength, and is less likely to cause a decrease in transparency due to plasticizer bleeding, The main purpose is to provide transparent sheets.

  As a result of intensive studies by the present inventors, it has been found that the above problems can be solved at once by including a styrene-based elastomer as the resin layer impregnated in the glass fiber fabric. That is, the refractive index of the styrene-based elastomer can be easily adjusted by adjusting the styrene content. For example, a glass fiber fabric can be used without adding a refractive index adjusting agent that easily bleeds as in Patent Document 4. It was found that it was easy to approximate the refractive index of the resin, and it was difficult for the transparency to decrease due to bleeding of the plasticizer. In addition, if a styrene elastomer is used, it is possible to directly laminate the fluororesin layer with excellent peel strength without using an adhesive, and it is possible to prevent a decrease in transparency due to the use of an adhesive. I found it. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. A transparent sheet comprising a glass fiber fabric and a resin layer contained in an impregnated state of the glass fiber fabric, wherein the resin layer contains a styrene-based elastomer.
Item 2 The styrene elastomer is a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butadiene-styrene block copolymer, or a styrene-ethylene-propylene-styrene block copolymer. Item 2. The transparent sheet according to Item 1, comprising at least one compound selected from the group consisting of a coalescence and a modified product thereof.
Item 3. The transparent sheet according to Item 1 or 2, wherein the styrene-based elastomer has a styrene content of 15 to 45% by mass.
Item 4. The transparent sheet according to any one of Items 1 to 3, wherein a difference in refractive index between the glass fiber fabric and a resin layer impregnated in the glass fiber fabric is 0.05 or less.
Item 5. The transparent sheet according to any one of Items 1 to 4, wherein a mass ratio of the styrene-based elastomer in the resin layer is 40% by mass or more.
Item 6 Any one of Items 1 to 5, wherein in the transparent sheet, a total ratio of the mass of the glass fiber fabric in a total amount of the mass of the glass fiber fabric and the mass of the resin layer is 20 to 55 mass%. The transparent sheet of crab.
Item 7. The transparent sheet according to any one of Items 1 to 6, further comprising a cover layer on the resin layer.
Item 8. The transparent sheet according to Item 7, further comprising a network layer composed of a glass fiber network between the resin layer and the cover layer.
Item 9 The transparent sheet according to Item 7 or 8, wherein the cover layer contains a fluororesin, an olefin resin, or a vinyl chloride resin.
Item 10 The transparent sheet according to any one of Items 1 to 9, wherein the thickness is 40 to 400 μm.
Item 11. The transparent sheet according to any one of Items 1 to 10, wherein the total light transmittance is 80% or more.
Item 12. The transparent sheet according to any one of Items 1 to 11, wherein the haze is 65% or less.
Item 13. Radiation electricity measured according to 4.10.2 exothermic test / evaluation method in the "Fireproof and Fireproof Performance Test / Evaluation Procedure Method" (modified on March 1, 2014) of the Building Materials Testing Center in exothermic tests for irradiating radiant heat of 50 kW / m @ 2 from the heater to the surface of the sheet, not exceed 200 kW / ^{m 2} maximum heat release rate after the start of heating is continued more than 10 seconds, the total calorific value 8 MJ / ^{m 2} or less The transparent sheet according to any one of Items 1 to 12, which is
Item 14. A smoke-proof hanging wall, a lighting cover, a partition wall, a smoke-proof curtain, a touch panel, a solar panel, or a roofing material, comprising the transparent sheet according to any one of Items 1 to 13.

  According to the transparent sheet of the present invention, for example, when the fluororesin layer is laminated without using an adhesive, the peel strength is easily excellent, and the effect that the transparency is not easily lowered due to plasticizer bleed or the like. Can play.

It is a schematic sectional drawing of the transparent sheet of this invention. It is a schematic sectional drawing of the transparent sheet of this invention. It is a schematic sectional drawing of the transparent sheet of this invention. It is a schematic sectional drawing of the transparent sheet of this invention.

  The transparent sheet of the present invention is a transparent sheet comprising a glass fiber fabric and a resin layer impregnated in the glass fiber fabric, wherein the resin layer contains a styrene-based elastomer.

  For example, as shown in FIG. 1, the sheet 1 of the present invention has a laminated structure including a glass fiber fabric 2 and a resin layer 3 impregnated in the glass fiber fabric 2. In the sheet 1, the glass fiber fabric 2 only needs to include at least one layer, and may include a plurality of layers. For example, as shown in FIG. 4, in the transparent sheet 1 of the present invention, the two glass fiber fabrics 2 may be arranged so as to be positioned on both surface sides of the resin layer 3, respectively.

  As shown in FIGS. 1 to 4, in the sheet 1 of the present invention, the resin layer 3 fills the gap between the glass fibers constituting the glass fiber fabric 2, and one surface side portion 31 of the resin layer 3. And the other surface side part 32 is connected through the said clearance gap part.

  Moreover, in the sheet | seat 1 of this invention, although the glass fiber fabric 2 should just be contained in the state which impregnated the resin layer 3, as shown in FIGS. 1-4 from a viewpoint of improving transparency further. It is preferable that the resin layer 3 portion where the glass fiber fabric 2 does not exist is formed on both surfaces of the glass fiber fabric 2.

  In the sheet 1 of the present invention, on the resin layer 3, for example, as shown in FIGS. 2 and 3, the nonflammability of the sheet 1 is increased or the mechanical strength (hardness) is increased. The cover layer 4 may be laminated as necessary. Further, as shown in FIG. 3, between the resin layer 3 and the cover layer 4, for the purpose of increasing the mechanical strength (hardness) of the sheet 1, etc., it is made of glass fiber as necessary. The network layer 5 may be laminated. The cover layer 4 and the net body layer 5 may be laminated on one side of the layer of the glass fiber fabric 2, respectively, or may be laminated on both sides as shown in FIGS.

Detail the composition of each layer constituting the sheet 1 of each layer of the composition present invention.

[Glass fiber fabric 2]
The glass fiber fabric 2 is composed of a plurality of glass fibers. In the glass fiber fabric 2, the plurality of glass fibers are entangled with each other to form a single fabric. Examples of the glass fiber fabric 2 include a glass fiber fabric (glass cloth) composed of a plurality of warps and a plurality of wefts. The woven structure of the glass fiber woven fabric is not particularly limited, and examples thereof include plain weave, satin weave, twill weave, oblique weave, and woven weave. The woven density of the glass fiber fabric is not particularly limited, but when the resin contained in the sheet 1 is burned, a large through-hole is less likely to be formed in the glass fiber fabric 2 and a more excellent nonflammability performance is maintained. From the viewpoint that the warp and the latitude are 40/25 mm or more, 50/25 mm or more is more preferable.

  About the glass material of the glass fiber which comprises the glass fiber fabric 2, it does not restrict | limit in particular, A well-known glass material can be used. Specific examples of the glass material include alkali-free glass (E glass), acid-resistant alkali-containing glass (C glass), high-strength / high-modulus glass (S glass, T glass, etc.), alkali-resistant glass (AR). Glass) and the like. Among these glass materials, alkali-free glass (E glass) having high versatility is preferable. The glass fibers constituting the glass fiber fabric 2 may be made of one kind of glass material, or may be a combination of two or more kinds of glass fibers made of different glass materials.

  The count of the glass fiber constituting the glass fiber fabric 2 is not particularly limited as long as the glass fiber fabric 2 can be formed. The count of the glass fiber is preferably 20 tex or less from the viewpoint of further improving the transparency of the sheet 1. The glass fiber fabric 2 may be formed of one type of glass fiber, or may be formed of two or more types of glass fiber. The tex count of glass fiber corresponds to the number of grams per 1000 m.

  The glass fiber constituting the glass fiber fabric 2 is preferably a glass yarn in which a plurality of single fibers, which are long glass fibers, are twisted together. The number of single fibers in the glass yarn is preferably about 30 to 500 from the viewpoint of further improving the transparency of the sheet 1. From the viewpoint of further improving the transparency of the sheet 1, the diameter of the single fiber in the glass yarn is preferably about 3.0 to 10.0 μm. The count of the glass yarn is preferably 3 to 80 tex from the viewpoint of further improving the transparency of the sheet 1.

  For example, when the sheet 1 of the present invention is used for a daylighting tent and the visibility through the sheet 1 is emphasized and the haze value is smaller, the number of single fibers in the glass yarn is 30 to 30 About 120 are more preferable. From the same viewpoint, the diameter of the single fiber in the glass yarn is more preferably about 3.0 to 6.0 μm, and further preferably about 3.0 to 5.0 μm. Further, from the same viewpoint, the count of the glass yarn is more preferably 3 to 12 tex, and further preferably 3 to 5 tex. Although the diameter of the single fiber in the glass yarn constituting the glass fiber fabric 2 and the count of the glass yarn are within the above ranges, the details of the mechanism by which the transparency of the sheet 1 can be further improved are not clear. By satisfying such conditions, the glass fiber fabric 2 is smoothed, and light scattering at the interface with the resin layer 3 is effectively suppressed. As a result, the transparency of the sheet 1 can be further improved. It is considered to be.

  In addition, for example, when the sheet 1 of the present invention is used for a lighting cover, when light diffusibility is important and the haze value is larger, the number of single fibers in the glass yarn is 180 to 500. The degree is more preferable. From the same viewpoint, the diameter of the single fiber in the glass yarn is more preferably about 7.0 to 10.0 μm, and further preferably about 8.0 to 10.0 μm. From the same viewpoint, the count of the glass yarn is more preferably 20 to 80 tex, further preferably 50 to 80 tex.

  From the viewpoint of further improving the adhesion between the glass fiber fabric 2 and the resin layer 3 and further improving the transparency of the sheet 1 of the present invention, the surface of the glass fiber constituting the glass fiber fabric 2 is a silane cup. It is preferable that the surface is treated with a ring agent.

In the sheet 1, the ratio (mass%) of the glass fiber fabric 2 is such that the glass fiber fabric 2 and the resin layer 3 to be described later are provided from the viewpoint of providing excellent incombustibility while further improving the transparency of the sheet 1. 10-70 mass% is preferable with respect to the total amount of, 20-55 mass% is more preferable, 20-50 mass% is especially preferable. Also, one of the mass of the glass fiber fabric ² (g / ^m 2) is preferably 10~1000 (g / ^{m 2),} more preferably ^{20~800 (g / m 2),} 20~700 (g / m ² ) is more preferred.

As described above, at least one glass fiber fabric 2 may be included in the resin layer 3, but a plurality of glass fiber fabrics 2 may be included. Here, when the glass fiber fabric 2 includes a plurality of layers, for example, as shown in FIG. 4, the central portion N in the thickness direction of the glass fiber fabric 2 is more surface than the central portion M in the thickness direction of the resin layer 3. It is preferable that the glass fiber fabrics 2 are respectively disposed on both surface sides (31 side and 32 side in FIG. 4) of the resin layer 3 so as to be located on the side. Thus, the two glass fiber fabrics 2 are arranged so as to be located on both surface sides (31 side and 32 side in FIG. 4) of the resin layer 3, respectively, so that only the central portion of the resin layer 3 is present. Compared to the sheet on which the glass fiber fabric 2 is disposed, the mechanical strength (hardness) can be further increased, and warping due to heat can be more effectively suppressed. More specifically, the shortest distance L1 from the surface of the resin layer 3 to the central portion N of the glass fiber fabric 2 and the thickness L0 of the resin layer 3 may satisfy the relationship of the following formula (I). preferable.
0% <L1 / L0 × 100 <30% (I)

Moreover, it is more preferable that one glass fiber fabric 2 is included on each of both surface sides of the resin layer 3 so as to satisfy the relationship of the formula (I). Furthermore, it is preferable that L1 and L0 satisfy the relationship of the following formula (II).
10 (%) <L1 / L0 × 100 <20 (%) (II)

Further, the glass fiber fabric 2 is disposed on both surface sides of the resin layer 3 such that the central portion N in the thickness direction of the glass fiber fabric 2 is located on the surface side of the central portion M in the thickness direction of the resin layer 3. 2 is disposed, and the ratio of the glass fiber fabric 2 in the sheet 1 is 10 to 70 (mass%), and the mass of one glass fiber fabric 2 is 20 to 50 (g / m ^2). ), The transparency of the sheet 1 and the mechanical strength (hardness) can be made particularly compatible.

  The difference in refractive index between the glass fiber fabric 2 and the resin layer 3 described later is preferably 0.05 or less. Thus, when the difference in refractive index between the glass fiber fabric 2 and the resin layer 3 is 0.05 or less, light scattering on the glass fiber surface can be further reduced, and the resulting sheet has better transparency. It becomes possible. From the viewpoint of more effectively improving the transparency, the difference in refractive index between the glass fiber fabric 2 and the resin layer 3 is more preferably 0.04 or less, further preferably 0.03 or less, and particularly preferably 0.8. 02 or less.

  In addition, the refractive index of the glass fiber fabric 2 is measured according to the method B of JIS K7142: 2008. Specifically, first, the glass fiber constituting the glass fiber fabric is pulverized to such an extent that a Becke line can be observed when the glass fiber is observed with an optical microscope at a magnification of 400 times. Then, using a halogen lamp provided with a D-line interference filter as a light source, using an optical microscope, observed and measured under conditions of a magnification of 400 times and a temperature of 23 ° C., and refracted the average value of three tests. The value of rate. Moreover, the measurement of the refractive index of the resin layer 3 is performed according to B method of JISK7142: 2008. Specifically, the resin layer 3 is pulverized to such an extent that a Becke line can be observed when it is observed with an optical microscope at a magnification of 400 times. Then, using a halogen lamp provided with a D-line interference filter as a light source, using an optical microscope, observed and measured under conditions of a magnification of 400 times and a temperature of 23 ° C., and refracted the average value of three tests. The value of rate.

  Although it does not restrict | limit especially as thickness per glass fiber fabric 2, For example, about 10-1000 micrometers is mentioned. From the viewpoint of further improving the transparency of the sheet 1, the thickness per sheet of the glass fiber fabric 2 is preferably 20 to 800 μm, more preferably about 30 to 700 μm. In addition, for example, when the sheet 1 of the present invention is used for a daylighting tent, when the visibility through the sheet 1 is emphasized and the haze value is smaller, the per-glass fiber fabric 2 per sheet As thickness, 20-50 micrometers is especially preferable. Further, by setting the thickness per glass fiber fabric 2 to 20 to 50 μm, the flexibility of the cover layer 4 and the glass fiber fabric 2 is further approximated, and the cover layer 4 is impregnated into the glass fiber fabric 2. It becomes easy to follow by the resin layer 3 made, and it can further suppress that whitening arises even if the bending stress mentioned later is repeatedly added, and it becomes easier to maintain the outstanding transparency. In addition, for example, when the sheet 1 of the present invention is used for a lighting cover, when the light diffusibility is important and the haze value is larger, the thickness per piece of the glass fiber fabric 2 is as follows. 50 to 800 μm is particularly preferable.

[Resin layer 3]
In the sheet 1 of the present invention, the resin layer 3 is included in a state of being impregnated in the glass fiber fabric 2 described above, and the resin layer 3 includes a styrene-based elastomer.

  In the present invention, the styrenic elastomer contained in the resin layer 3 is a copolymer of at least three blocks composed of styrene and a specific diene, and two blocks at both ends contain polystyrene, and an internal block (one One or more soft blocks) are those containing polydienes or hydrogenated dienes. By including a styrene-based elastomer as a resin layer that is impregnated with glass fibers, it is easy to excel in peel strength when a fluororesin layer is laminated without using an adhesive, and a plasticizer bleed, etc. It is possible to achieve an effect that the transparency is not easily lowered. The styrene elastomer contains a hard segment and a soft segment (for example, an ethylene-butadiene portion in a styrene-ethylene-butadiene-styrene block copolymer) of a styrene portion. And since it can have rubber elasticity by having the soft segment, a cover layer made of, for example, a fluororesin or a polyolefin resin is laminated and bent on a resin layer impregnated in a glass fiber cloth and containing a styrene-based elastomer. Even when stress is repeatedly applied, the resin layer impregnated in the glass fiber fabric can easily follow the deformation of the cover layer such as the outer fluororesin or polyolefin resin, and can further suppress the occurrence of whitening. Can also be played.

  Examples of the styrene elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS) obtained by hydrogenating the double bond portion of butadiene, and styrene- Isoprene-styrene block copolymer (SIS), styrene-ethylene-propylene-styrene block copolymer (SEPS) in which the isoprene double bond portion is hydrogenated, styrene-isoprene-butadiene-styrene block copolymer (SIBS) Styrene-ethylene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene-butadiene-styrene block copolymer (SBBS), wherein the double bond portion of butadiene or isoprene is hydrogenated, Styrene - styrene - ethylene - butadiene - styrene block copolymer (SSEBS), butadiene - that styrene random copolymer hydrogenated product (HSBR) and their denatured, and the like. Above all, from the viewpoint of further suppressing the occurrence of whitening when a resin layer impregnated in a glass fiber fabric is laminated with a cover layer such as a fluororesin or a polyolefin resin and bending stress is repeatedly applied, styrene-ethylene. -Butylene-styrene block copolymer (SEBS) and styrene-ethylene-propylene-styrene block copolymer (SEPS) are preferable, and styrene-ethylene-butylene-styrene block copolymer (SEBS) is particularly preferable.

  As described above, the difference in refractive index of the resin layer 3 from the refractive index of the glass fiber fabric 2 is preferably 0.05 or less, more preferably 0.04 or less, still more preferably 0.03 or less, particularly Preferably 0.02 or less is mentioned. And in order to approximate the refractive index of the resin layer 3 to the refractive index of the glass material which comprises the glass fiber fabric 2 to be used, it is possible by adjusting the styrene content of a styrene-type elastomer. That is, for example, as disclosed in Japanese Patent No. 5646793, it is known that the refractive index of a styrene elastomer increases proportionally when the styrene content is increased. Therefore, the difference in refractive index with the glass fiber fabric 2 can be approximated by selecting and adjusting the type of styrene elastomer and the styrene content so as to approximate the refractive index of the glass material to be used. Moreover, the resin layer 3 can also contain 2 or more types of styrene-type elastomers from which a refractive index differs from a viewpoint of refractive index adjustment.

  The styrene content is preferably 10 to 45% by mass, more preferably 15 to 45% by mass, from the viewpoint of further improving the transparency when the glass fiber is a general-purpose E glass. -40 mass% is further more preferable, and 20-30 mass% is especially preferable.

  In the present invention, the styrene content of the styrene elastomer is measured by nuclear magnetic resonance spectrum analysis (NMR). Specifically, it measures using brand name JNM-ECA500 (made by JEOL Ltd.) as a measuring instrument. First, a styrene elastomer is dissolved in deuterated chloroform so as to be 30 mg / ml. Then, 1 mg of 1,4-bis (trimethylsilylbenzene) -d4 was added and dissolved to prepare a sample. As a measurement condition, an observation frequency was set to 500 MHz, deuterated chloroform, a pulse delay of 24.8126 seconds, Measurement is performed at 32 scans, a pulse width of 45 °, and a measurement temperature of 20 ° C. The obtained spectrum is assigned and the styrene content of the styrene elastomer is calculated based on the peak intensity of 1,4-bis (trimethylsilylbenzene) -d4.

  The ratio of the styrene-based elastomer contained in the resin layer 3 is not particularly limited, and is preferably, for example, 40% by mass or more. For example, a cover layer such as a fluororesin or a polyolefin resin is laminated on the resin layer 3, and bending stress is applied. From the viewpoint of further suppressing the occurrence of whitening when repeatedly added, 40 to 80% by mass is more preferable, and 50 to 70% by mass is particularly preferable.

  The resin layer 3 may further contain additives such as a flame retardant, an ultraviolet absorber, a filler, an antistatic agent, and a light diffusing agent in addition to the styrene elastomer. Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, trichloroethyl phosphate, triallyl phosphate, ammonium polyphosphate, and phosphate ester. Examples of the ultraviolet absorber include benzotriazole. Examples of the filler include calcium carbonate, silica, and talc. Examples of the antistatic agent include a surfactant. Examples of the light diffusing agent include colloidal silica and transparent microspheres such as glass beads and acrylic beads. These additives may be used individually by 1 type, and may be used in combination of 2 or more types.

In the present invention, the thickness of the resin layer 3 is not particularly limited, and examples thereof include 10 to 1000 μm, preferably 10 to 800 μm, and more preferably 20 to 700 μm. Moreover, the mass in particular of the resin layer 3 is not restrict | limited, For example, 10-1000 g / m < ² >, Preferably it is 10-800 g / m < ² >, More preferably, 20-700 g / m < ² > is mentioned.

[Cover layer 4]
The transparent sheet of the present invention may further have a cover layer 4 on the cured resin composition layer 3 as necessary for the purpose of increasing nonflammability or increasing mechanical strength. The resin constituting the cover layer 4 is not particularly limited, and examples thereof include a fluororesin, a polyvinyl chloride resin, a polyolefin resin such as polyethylene and polypropylene, a polyester resin, and a polyamide resin. Of these, fluororesin and polyolefin resin are preferable.

  For example, a polyolefin resin, particularly a polypropylene resin, is inferior in adhesion to a glass fiber cloth, and it is difficult to impregnate the glass fiber cloth with the polyolefin resin to form a sheet. On the other hand, when the cover layer 4 made of polyolefin resin is laminated on the resin layer 3 in the sheet 1 of the present invention, the adhesiveness between the resin layer 3 and the cover layer 4 made of polyolefin resin becomes good, and bending stress is repeatedly applied. In combination with the effect of further suppressing the occurrence of whitening.

  Also, for example, the refractive index of fluororesin is about 1.3 to 1.4, the refractive index of glass fiber fabric is about 1.5 to 1.7, and the difference in refractive index between the two is large. In a sheet in which a glass fiber fabric is impregnated with a fluororesin, a large amount of light is scattered at the interface between the glass fiber and the fluororesin, and this makes it difficult to obtain excellent transparency. On the other hand, when the cover layer 4 made of a fluororesin is laminated on the resin layer 3 in the sheet 1 of the present invention, the glass fiber fabric 2 and the resin layer impregnated therein are adjusted by adjusting the styrene content as described above. 3 can be reduced, and the scattering of light on the surface of the glass fiber can be reduced. Therefore, the obtained sheet has good transparency, and is whitened even when bending stress is repeatedly applied. Combined with the effect of further suppressing the occurrence, it is preferable.

  In the present invention, the fluororesin is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer, such as polyvinylidene fluoride (PVDF), polyfluoride. Vinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoroalkyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, fluorine Vinyl chloride Den / pentafluoropropylene copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / pentafluoropropylene / tetrafluoroethylene copolymer, vinylidene fluoride / perfluoroalkyl vinyl ether / Tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), and vinylidene fluoride / chlorotrifluoroethylene copolymer. These fluororesins may be used individually by 1 type, and may be used in combination of 2 or more type. Among these fluororesins, when directly laminating the resin layer 3 and the cover layer 4, PVDF, ETFE, or ECTFE is more easily suppressed from causing whitening even when bending stress is repeatedly applied. Are more preferable, and PVDF and ETFE are particularly preferable.

  When the sheet | seat 1 of this invention has the cover layer 4, the thickness in particular of the cover layer 4 is not restrict | limited, For example, about 50-200 micrometers, Preferably about 80-150 micrometers is mentioned.

[Reticulated body layer 5]
The sheet 1 of the present invention is a network layer composed of a glass fiber network between the resin layer 3 and the cover layer 4 as necessary for the purpose of increasing nonflammability or increasing mechanical strength. 5 may be further included. The glass fiber network constituting the network layer 5 is not particularly limited, and examples thereof include the same glass fiber network as the glass fiber exemplified in the glass fiber fabric 2. The shape and structure of the glass fiber network are not particularly limited, and examples of the glass fiber network include a glass fiber orthogonal laminated net in which a weft is sandwiched between two warps and fixed with a resin. In the network layer 5, by setting the opening width between the glass fibers to preferably 3 to 20 mm, high transparency of the transparent incombustible sheet 1 can be secured, and further, through the opening between the glass fibers. Can be well lit and the strength of the entire transparent sheet 1 can be increased. The transparent incombustible sheet 1 of the present invention preferably has a net layer 5 on both sides from the viewpoint of enhancing incombustibility and increasing mechanical strength.

  When the transparent sheet 1 of the present invention has the network layer 5, the thickness of the network layer 5 is not particularly limited, and may be about 50 to 300 μm, preferably about 100 to 200 μm, for example.

  When the transparent sheet 1 of the present invention includes the cover layer 4 or the cover layer 4 and the network layer 5, the thickness of the sheet 1 is not particularly limited, and is, for example, 100 to 2000 μm, preferably 150 to 1500 μm, More preferably, 200-1000 micrometers is mentioned. The thickness of the sheet 1 of the present invention is preferably 40 to 400 μm from the viewpoint of further achieving both incombustibility and transparency.

[Transparency and nonflammability characteristics]
The sheet 1 of the present invention preferably has high transparency. From the viewpoint of ensuring high transparency, the total light transmittance of the sheet 1 of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more. By satisfying such a total light transmittance, for example, when used as a roofing material of a building, a tent warehouse material or the like, it is possible to increase the amount of light collected from outside to inside. In order to increase the total light transmittance, the difference between the refractive index of the glass fiber fabric 2 and the refractive index of the resin layer 3 is set to 0.05 or less, for example, the fiber of the glass fiber constituting the glass fiber fabric 2 The glass fiber fabric has a small diameter, count, glass fiber fabric thickness, etc., to increase the smoothness of the glass fiber fabric, to have a low woven density, or to the total amount of the glass fiber fabric and the resin layer 3. It becomes possible by adjusting the ratio of 2.

  In addition, the haze of the sheet 1 of the present invention is preferably 60% or less, more preferably 50% or less, and more preferably 40% when the visibility through the sheet is important, for example, when used in a lighting tent. The following is more preferable. For example, when the light diffusibility is important, such as when used for a lighting cover, the haze of the sheet 1 of the present invention is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. . In order to increase the haze, techniques such as increasing the fiber diameter of the glass fibers constituting the glass fiber fabric 2 and increasing the weave density can be used. It is also possible to increase haze by dispersing glass beads in the resin layer 3. In the present invention, the total light transmittance and haze of the sheet 1 are values obtained by measurement according to JIS K7375 2008 “Plastics—How to obtain total light transmittance and total light reflectance”, respectively.

Since the sheet 1 of the present invention includes the glass fiber fabric 2, the sheet 1 can be provided with a property that does not easily burn (nonflammability). In addition, as the nonflammability of the sheet 1 of the present invention, 4.10.2 exothermic property in the “Fireproofing Performance Test / Evaluation Business Method Manual” (modified on March 1, 2014) of the Building Materials Testing Center, Japan is measured according to the test and evaluation methods, the heating test of irradiating radiant heat of 50 kW / m @ 2 from the radiant electric heater on the surface of the sheet, exceed 200 kW / m ² maximum heat release rate after the start of heating is continued more than 10 seconds The total calorific value is preferably 8 MJ / m ² or less. In order to further improve the incombustibility, for example, in the resin layer 3, addition of a flame retardant, reduction of the amount of organic substances, or the like may be performed.

  Moreover, since the resin layer contained in the state impregnated in the glass fiber fabric contains a styrene-based elastomer, the sheet 1 of the present invention is easily excellent in peeling strength when the fluororesin layer is laminated without using an adhesive. Become. The peel strength of the fluororesin layer is preferably 10 N / 30 mm or more, more preferably 20 N / 30 mm or more, and particularly preferably 20 to 30 N / 30 mm. In the present invention, the peel strength of the fluororesin layer is measured and calculated according to JIS K 6854-2: 1999 “Peel adhesion strength test method (180 degree peel)”.

[Usage]
The sheet 1 of the present invention can be suitably used as a film material used for smoke-proof hanging walls, smoke-proof sheets, partition walls, smoke-proof curtains, touch panels, solar panels, roofing materials, daylighting tents, and the like. .

[Production method]
The method for producing the transparent sheet 1 of the present invention is not particularly limited, and examples thereof include the following production methods. For example, a sheet containing one glass fiber fabric 2 can be produced by impregnating the glass fiber fabric 2 with the above resin composition for forming the resin layer 3 and heating or drying to solidify.

  When the transparent sheet 1 of this invention shall have the cover layer 4, it does not restrict | limit especially as a manufacturing method of this sheet 1, For example, the following manufacturing methods are mentioned. For example, after the resin film constituting the cover layer 4 is disposed on the resin layer 3 obtained above, the cover layer 4 is formed on the resin layer 3 by heating and pressing using a press machine or the like. can do. Moreover, when it has further the network body layer 6 which consists of a glass fiber network between the resin layer 3 and the cover layer 4, for example, the adhesive agent which consists of urethane type resin etc. on the resin layer 3, for example After the coating, the above glass fiber network constituting the network layer 6 is arranged from above, and the above resin film constituting the cover layer 4 is further arranged on the glass fiber network, followed by a press machine, etc. The network layer 5 and the cover layer 4 can be formed on the resin layer 3 by heating and pressurizing using.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

In Examples and Comparative Examples, as a glass fiber fabric, a commercially available glass fiber fabric shown in Table 1 (glass material: E glass, specific gravity 2.54 g / cm ³ ) was cut into 200 mm × 200 mm and used. In Table 1, E03R SK is a trade name of E glass fiber fabric manufactured by Unitika Ltd. The E glass fiber fabric is subjected to a heat treatment for removing organic substances and a surface treatment with a silane coupling agent. The glass material used in the examples had the above glass volume ratio of 39.4%.

  In Examples and Comparative Examples, the resin compositions impregnated in the above glass fiber fabrics have the compositions shown in Table 1. Styrene elastomer (trade name “PPET1501” manufactured by Toagosei Co., Ltd., refractive index 1.55), “PPET1505” manufactured by Toagosei Co., Ltd., refractive index 1.53) and polyester resin (“Plus Coat Z687”) Co., Ltd., refractive index 1.56), vinyl ester resin ("# 8114" manufactured by Nippon Iupika Co., Ltd.), styrene monomer (manufactured by Nippon Iupika Co., Ltd.), bifunctional (meth) acrylate and photopolymerization initiator mixture (Refractive index 1.56) was used. In addition, as bifunctional (meth) acrylate which is a hardening | curing agent, NPGDA (Neopentylglycol diacrylate, molecular weight 212, (made by Nippon Iupika Co., Ltd.) shown in Table 1 was used. 2 parts by mass with respect to a total of 100 parts by mass of vinyl ester resin, styrene monomer, and bifunctional (meth) acrylate, and polyester resin ("Eritel UE-3400" manufactured by Unitika Ltd.) as toluene as the adhesive layer / MEK mixed solvent (ratio 8/2) was used by dissolving to a solid content of 30%.

  As a sheet for forming the cover layer 4, an ETFE sheet (trade name “Neofuron”, manufactured by Daikin Industries, Ltd., thickness 0.1 mm) was used.

<Example 1>
First, 100 g / m ² of PPET1501 manufactured by Toagosei Co., Ltd. was applied on the above ETFE sheet. Next, the glass fiber cloth described in Table 1 was placed on the coated styrene-based elastomer, and the resin was impregnated in the gap between the glass fiber cloths for 1 minute. Next, in order to volatilize the solvent of the applied styrene-based elastomer, heat treatment is performed in two stages of 70 ° C. for 8 minutes and 150 ° C. for 8 minutes to form a film on the styrene-based elastomer impregnated in the glass fiber fabric. did. Next, one ETFE sheet is placed on the coated styrene elastomer, and pressure is applied from above the ETFE sheet with a roller to remove air bubbles between the ETFE sheet and the coated styrene elastomer resin. The glass fiber fabric is pressed with a heating press machine at a temperature of 160 ° C., a press pressure of 30 kgf / cm ² , and the time is 30 minutes, and the styrene elastomer layer impregnated into the glass fiber fabric is bonded to the ETFE sheet. A sheet of the present invention having a laminated structure in which a resin layer 3 (styrene elastomer) impregnated in a glass fiber fabric and a cover layer 4 (fluororesin) are directly laminated on both surfaces of the resin layer 3 was obtained.

In the obtained sheet, the mass of the resin layer 3 (styrene elastomer) was 30 g / m ² and the thickness was 30 μm. Moreover, the mass of the obtained sheet | seat was 400 g / m < ² >, and thickness was 260 micrometers.

<Example 2>
A sheet of the present invention was obtained under the same conditions as in Example 1 except that PPET 1505 was used instead of PPET 1501 as the styrene elastomer. In the obtained sheet, the mass of the resin layer 3 (styrene elastomer) was 30 g / m ² and the thickness was 30 μm. Moreover, the mass of the obtained sheet | seat was 400 g / m < ² >, and thickness was 260 micrometers.

<Comparative Example 1>
A sheet was obtained under the same conditions as in Example 1 except that polyester resin plus coat Z687 was used instead of styrene elastomer PPET1501. In the obtained sheet, the mass of the resin layer 3 (polyester resin) was 30 g / m ² and the thickness was 30 μm. Moreover, the mass of the obtained sheet | seat was 400 g / m < ² >, and thickness was 260 micrometers.

<Comparative example 2>
First, a resin composition blended as shown in Table 1 was applied to a PET film having a thickness of 0.05 mm at 30 g / m ² . Next, the glass fiber fabric described in Table 1 was placed on the resin composition and allowed to stand for 1 minute to impregnate the above resin composition in the gaps of the glass fiber fabric. Next, a PET film having a thickness of 0.05 mm was placed from above, and pressure was applied from above with a roller. Thereafter, the resin composition is cured by irradiating the resin composition with the above PET film (light irradiation condition: integrated light quantity 200 mJ / cm ² ) to form a resin layer 3 (containing a vinyl ester resin and a styrene monomer). And the intermediate sheet which consists of glass fiber fabric and the resin layer 3 (hardened | cured material, such as vinyl ester resin) impregnated to the glass fiber fabric of the previous term was obtained.

Next, in order to form an adhesive layer on the ETFE sheet, 15 g of a solution obtained by dissolving a polyester resin (Unitika Elitel UE-3400) in a toluene / MEK mixed solvent so as to have a solid content of 30% is obtained. / m applied at ^2, on the applied polyester resin solution was placed the intermediate sheet. Furthermore, in order to form an adhesive amount on the upper surface side of the intermediate sheet, 15 g / m ^{2 of} the above-mentioned Eritel UE-3400 solution was applied. Subsequently, in order to volatilize the solvent in the applied polyester resin solution, heat treatment was performed in two stages of 70 ° C. for 8 minutes and 120 ° C. for 8 minutes in a dryer to form a polyester resin film. One of the above ETFE sheets is placed on the polyester resin filmed on the upper side of the intermediate sheet, and is pressed with a roller from above the ETFE sheet, and is between the ETFE sheet and the filmed polyester resin. Air bubbles were removed, and the sheet was pressed with a hot press machine at 160 ° C. under a pressure of 30 kgf / cm ² for 30 minutes to obtain a sheet in which the ETFE sheet and the intermediate sheet were bonded via a polyester resin.

Sheet performance evaluation (total light transmittance and haze)
After the sheets of Examples and Comparative Examples were stored in a room at a temperature of 20 ° C. and a humidity of 40% for one week after production, the total light transmittance and haze of the sheets were measured according to JIS K7361-1 1997 “Plastic-Transparent Material”. The total light transmittance was measured in accordance with “Test method of Part 1—Single beam method”. The haze was measured according to JIS K7136 2000 “Plastics—How to determine haze of transparent material”.

(Evaluation of nonflammability)
Cone calorimeter tester according to fire prevention test method and performance evaluation standard based on Building Standard Act Article 9 No. 9 and Building Standard Act Enforcement Order Article 108-2 using each sheet obtained in Examples 1-10 The maximum heat generation rate after the start of heating continued for 10 seconds or more and did not exceed 200 kW / m ² and the total heat generation amount was 8 MJ / m ² or less.

(Ease of whitening when bending stress is repeatedly applied to the sheet)
A test was conducted in accordance with JIS R 3420: 2013 7.14 “Folding strength of cloth”, and the presence or absence of white lines due to bending was visually observed in the bent portion of the sheet test piece, and the white line was confirmed to be bent. It was evaluated by the number of times. Moreover, n number of the test piece was set to 3, and it evaluated by the average value.

(Peeling strength of cover layer)
The peel strength of the resin layer 3 and the cover layer 4 was measured in accordance with JIS K 6854-2: 1999 “Peel adhesion strength test method (180 degree peel)”.

  The results are shown in Table 1.

  In the sheets obtained in Examples 1 and 2, since the resin layer 3 contained in a state impregnated in the glass fiber fabric contained a styrene-based elastomer, the fluororesin layer was used without using an adhesive. When laminated, the peel strength was easily excellent, and the transparency was not easily lowered due to plasticizer bleeding or the like. In addition, the sheets obtained in Examples 1 and 2 are such that the styrenic elastomer impregnated into the glass fiber fabric is formed from the outer fluororesin even when a cover layer made of fluororesin is laminated and bending stress is repeatedly applied. It becomes easy to follow the deformation of the cover layer, and it is easier to suppress the occurrence of whitening. In particular, the sheets obtained in Examples 1 and 2 were more excellent in that the total light transmittance was 90% or more because the difference in refractive index between the glass fiber fabric 2 and the resin layer 3 was 0.04 or less. In particular, in Example 1, since the refractive index difference was 0.02 or less, the haze could be 40% or less.

  In contrast, Comparative Example 1 using a polyester resin for the resin layer 3 has a high total light transmittance, but the peel strength of the cover layer is 1 N / 30 mm, which is inferior in adhesive strength. It was. Further, when a cover layer made of a fluororesin is laminated and bending stress is repeatedly applied, whitening is likely to occur.

  Moreover, in the comparative example 2 which laminated | stacked the cover layer through the polyester adhesive agent on the cured resin, the said adhesive agent affected, and the total light transmittance was as low as 79%, and it was inferior to transparency.

DESCRIPTION OF SYMBOLS 1 ... Transparent sheet 2 ... Glass fiber fabric 3 ... Resin layer 31, 32 ... Surface of resin layer 4 ... Cover layer 5 ... Network layer

Claims (14)

A transparent sheet comprising a glass fiber fabric and a resin layer contained in a state impregnated in the glass fiber fabric,
The resin layer includes a styrene-based elastomer,
A transparent sheet characterized by that.   The styrene elastomer is a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butadiene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, The transparent sheet according to claim 1, comprising at least one compound selected from the group consisting of and modified products thereof.   The transparent sheet according to claim 1 or 2, wherein the styrene elastomer has a styrene content of 15 to 45 mass%.   The transparent sheet according to any one of claims 1 to 3, wherein a difference in refractive index between the glass fiber fabric and a resin layer impregnated in the glass fiber fabric is 0.05 or less.   The transparent sheet in any one of Claims 1-4 whose mass ratio of the said styrene-type elastomer in the said resin layer is 40 mass% or more.   The said transparent sheet WHEREIN: The total ratio of the mass of the said glass fiber fabric in the total amount of the mass of the said glass fiber fabric and the mass of the said resin layer is 20-55 mass%, Any one of Claims 1-5. The transparent sheet as described in 1.   The transparent sheet according to claim 1, further comprising a cover layer on the resin layer.   The transparent sheet according to claim 7, further comprising a network layer made of a glass fiber network between the resin layer and the cover layer.   The transparent sheet according to claim 7 or 8, wherein the cover layer contains a fluororesin, an olefin resin, or a vinyl chloride resin.   The transparent sheet in any one of Claims 1-9 whose thickness is 40-400 micrometers.   The transparent sheet in any one of Claims 1-10 whose total light transmittance is 80% or more.   The transparent sheet in any one of Claims 1-11 whose haze is 65% or less. From radiant electric heaters measured according to 4.10.2 exothermic test and evaluation method in “Fireproof and Fireproof Performance Test and Evaluation Method of Operation” of the Building Materials Testing Center (modified version on March 1, 2014) In the exothermic test where the surface of the sheet is irradiated with radiant heat of 50 kW / m ² , the maximum heat generation rate after the start of heating continues for 10 seconds or more and does not exceed 200 kW / m ² , and the total calorific value is 8 MJ / m ² or less. The transparent sheet in any one of Claims 1-12 which exists. A smoke-proof hanging wall, a lighting cover, a partition wall, a smoke-proof curtain, a touch panel, a solar panel, or a roofing material comprising the transparent sheet according to claim 1.