JP6442268B2 - Transparent incombustible sheet and manufacturing method thereof - Google Patents

Description

  The present invention relates to a transparent incombustible sheet that can be suitably used as, for example, a smoke-proof hanging wall and a method for producing the same, and more specifically, to a base sheet in which a glass fiber fabric and a thermosetting resin cured product are combined and integrated. The present invention relates to a transparent non-combustible sheet which is obtained by adhering a plastic resin film with a second curable resin and has excellent visibility and toughness as well as non-combustibility and transparency and a method for producing the same. Furthermore, this invention relates to the smoke-proof hanging wall which consists of the said transparent incombustible sheet.

  Buildings such as commercial buildings are obliged to install smoke barriers on the ceiling to prevent the flow and diffusion of smoke and toxic gases in the event of a fire. Conventionally, a plastic plate or plate glass is usually used for the smoke-proof hanging wall so that a good visual field can be secured and the aesthetic appearance is not impaired.

  Plastic plates are lightweight and some are not easily damaged by impact, but they are not sufficient for nonflammability. Therefore, if a large amount of inorganic material is blended in the plastic plate to enhance nonflammability, the transparency will be poor.

  On the other hand, smoke-proof wall made of flat glass is certainly excellent in transparency and incombustibility, but has the disadvantage of being heavy, and measures are taken to prevent falling from the ceiling, For example, when a large earthquake occurs, it may fall and cause an unexpected accident or damage itself.

  Therefore, several transparent non-combustible sheets in which a resin cured product is integrated with a glass fiber fabric have been recently proposed (see Patent Document 1), but the refractive index of the resin cured product must be close to that of the glass fiber. Therefore, there are restrictions on the resins that can be used.

  In addition, a cured product of a thermosetting resin is integrated with a glass fiber fabric to form a base sheet, and then a glass fiber network and a flame retardant resin film are bonded to the base sheet with an adhesive to reinforce. A transparent noncombustible sheet having a layer has also been proposed (see Patent Document 2).

  Furthermore, a transparent noncombustible sheet is also proposed in which a glass fiber fabric surface-treated with a silane coupling agent is integrated with a cured product of a thermosetting resin mixture comprising diallyl phthalate and an unsaturated polyester resin (Patent Document). 3). However, none of them is necessarily satisfactory in terms of performance.

JP 2005-319746 A JP 2011-213093 A JP2013-119601A

  In view of the above-mentioned present situation in a transparent noncombustible sheet that can be used as a smoke-proof hanging wall, the present invention has been intensively studied to obtain a high-performance transparent noncombustible sheet. A thermoplastic resin film is bonded to the base sheet obtained by combining and integrating the cured product of the first thermosetting resin with the second curable resin, so that not only nonflammability and transparency but also visibility Further, it is an object of the present invention to provide a transparent non-combustible sheet that has excellent toughness and can impart various functionalities, and a method for producing the same.

  The transparent non-combustible sheet according to the present invention was impregnated into a glass fiber fabric composed of glass fibers surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule, and cured. A base sheet composed of a transparent cured product of the first thermosetting resin, and a cured product of the first thermosetting resin with the second curable resin on both surfaces of the base sheet. A transparent non-combustible sheet made of a bonded transparent thermoplastic resin film, wherein the difference between the refractive index of the first thermosetting resin and the refractive index of the glass fibers constituting the glass fiber fabric is 0.03 or less. It is what is.

  In addition, the method for producing a transparent non-combustible sheet according to the present invention provides a first thermosetting property to a glass fiber fabric comprising glass fibers surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule. It is impregnated with a resin and dried to obtain a prepreg containing the first thermosetting resin. Separately, a second curable resin is applied to the surface of the thermoplastic resin film, partially cured, and semi-cured. The semi-cured material layer on the thermoplastic resin film is overlaid on both surfaces of the prepreg and heated under pressure to form the first thermosetting resin contained in the prepreg in the second curing. A method for producing a transparent non-combustible sheet, comprising: curing a thermoplastic resin film integrally with a semi-cured resin layer, and adhering the thermoplastic resin film to a first thermosetting resin layer on the surface of the prepreg. Te, wherein the refractive index of the first thermosetting resin is of the difference between the refractive index of the glass fibers constituting the glass fiber fabric is 0.03 or less.

  According to the present invention, a glass fiber fabric is impregnated with a first thermosetting resin to form a prepreg containing the first thermosetting resin, and separately, the thermoplastic resin film is coated with a half of the second curable resin. A cured product layer is provided, and the semi-cured product layer on the thermoplastic resin film is overlaid on both surfaces of the prepreg, respectively, and heated under pressure, and the first thermosetting resin contained in the prepreg is added to the first curable prepreg. 2 is cured integrally with the semi-cured product layer of the curable resin, and the thermoplastic resin film is adhered to the first thermosetting resin layer on the surface of the prepreg, and is composite-integrated. As a transparent noncombustible sheet.

  Therefore, the transparent non-combustible sheet according to the present invention is excellent in non-combustibility and transparency, and since the surface has high smoothness, it is excellent in visibility, and in addition, it is excellent in toughness, and even by bending and impact. In addition to being hard to break, it has excellent adhesion between the base sheet and the thermoplastic resin film, and furthermore, it can have various functions such as antistatic properties and printability by using the thermoplastic resin film. Therefore, the transparent noncombustible sheet according to the present invention can be suitably used as a smoke proof wall.

  The transparent non-combustible sheet according to the present invention was impregnated into a glass fiber fabric composed of glass fibers surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule, and cured. A base sheet composed of a transparent cured product of the first thermosetting resin, and a cured product of the first thermosetting resin with the second curable resin on both surfaces of the base sheet. A transparent non-combustible sheet made of a bonded transparent thermoplastic resin film, wherein the difference between the refractive index of the first thermosetting resin and the refractive index of the glass fibers constituting the glass fiber fabric is 0.03 or less. It is what is.

  In addition, according to the present invention, such a transparent non-combustible sheet is a first thermoset on a glass fiber fabric made of glass fiber surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule. A prepreg containing the first thermosetting resin, impregnated with a curable resin, and separately applied a second curable resin on the surface of the thermoplastic resin film, partially cured, The semi-cured material layer on the thermoplastic resin film is overlaid on both surfaces of the prepreg, respectively, and heated under pressure to form the first thermosetting resin contained in the prepreg as the second cured material layer. A method for producing a transparent incombustible sheet comprising: curing a semi-cured product layer of a curable resin integrally; and bonding the thermoplastic resin film to a first thermosetting resin layer on the surface of the prepreg. There, it is possible to obtain by using a refractive index of the first thermosetting resin is of the difference between the refractive index of the glass fibers constituting the glass fiber fabric is 0.03 or less.

  First, the manufacturing method of the transparent incombustible sheet by this invention is demonstrated.

  In the present invention, the glass fiber constituting the glass fiber fabric is a general-purpose non-alkali glass fiber (E glass), acid-resistant alkali-containing glass fiber (C glass), high-strength and high-modulus glass fiber (S glass, T glass or the like) or alkali resistant glass fiber (AR glass) may be used, and is not particularly limited, but among them, alkali-free glass fiber having high versatility is preferably used.

  According to the present invention, such a glass fiber preferably has a filament diameter in the range of 1 to 20 μm, particularly preferably in the range of 3 to 12 μm. Furthermore, according to the present invention, the glass fiber woven fabric composed of such glass fibers may be any of plain weave, satin weave, twill weave, oblique weave, silk weave, etc., among these, Plain weave, oblique weave and silk weave are preferred.

Moreover, according to this invention, it is preferable that the basic weight of a glass fiber fabric exists in the range of 40-220 g / m < ² >. Moreover, it is preferable that the thickness of a glass fiber fabric exists in the range of 0.03-0.20 mm.

  Furthermore, according to the present invention, the gap between adjacent warps in the glass fiber fabric is 0.5 mm or less so that the flame does not easily pass through the glass fiber fabric even if the glass fiber fabric contacts the flame. It is preferable that a gap between adjacent wefts in the fiber fabric is 0.5 mm or less, and it is particularly preferable that any gap is 0.2 mm or less.

  According to the present invention, the glass fiber fabric is previously prepared with a silane coupling agent so that the base sheet obtained by integrating the cured product of the first thermosetting resin with the glass fabric has excellent transparency. It is necessary to be surface-treated, and here, the silane coupling agent has an amino group or a quaternary ammonium structure in the molecule. When the glass fiber fabric is not surface-treated with the above silane coupling agent, the wettability between the cured resin and the glass fiber fabric is poor at the time of heat and pressure molding, voids are generated at the interface, and the transparency Is damaged. Moreover, when the obtained base material sheet is bent, peeling or cracking occurs between the glass fiber fabric and the cured resin, and the part becomes white and the transparency is impaired.

  Examples of the silane coupling agent having an amino group in the molecule include 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl) -3. -Aminopropyltrimethoxysilane and the like can be mentioned. However, in the present invention, the silane coupling agent having an amino group in the molecule is not limited to these examples.

  Examples of the silane coupling agent having a quaternary ammonium structure in the molecule include trimethoxysilylpropyloctadecyldimethylammonium chloride, trimethoxysilylpropyldecylmethylammonium chloride, triethoxysilylpropyloctadecyldimethylammonium chloride, 1-trimethyl. Examples thereof include methoxysilylpropyl-1-methylmorpholinium iodide, but in the present invention, the silane coupling agent having a quaternary ammonium structure in the molecule is limited to the above examples. It is not something.

  According to the present invention, if necessary, a silane coupling agent having an amino group in the molecule and a silane coupling agent having a quaternary ammonium structure may be used in combination.

  According to the present invention, the first thermosetting resin is impregnated with the first thermosetting resin in the glass fiber fabric made of the glass fiber surface-treated with the silane coupling agent in advance and dried. Is semi-cured to obtain a prepreg. Separately, a second curable resin is applied on a thermoplastic resin film, heated, or irradiated with ionizing radiation such as ultraviolet rays or electron beams, and the second curable resin is applied. A part of the curable resin is polymerized and semi-cured, and then the semi-cured layer of the second curable resin on the thermoplastic resin film is overlaid on both surfaces of the prepreg, respectively, and heated and pressed. The first thermosetting resin of the prepreg and the semi-cured product layer of the second curable resin are integrally cured to thereby integrate the first thermosetting resin integrated with the glass fiber fabric. Base material consisting of a transparent cured product And a thermoplastic resin film integrated with the base material layer by a cured product of the second thermosetting resin, and has a high smoothness on the surface and a composite sheet with excellent visibility The transparent incombustible sheet according to the present invention can be obtained.

  According to the present invention, as the first thermosetting resin, the resin component is diallyl phthalate and / or unsaturated polyester so that the obtained composite sheet is excellent in transparency, visibility, and strength, particularly toughness. What consists of resin, ie, what consists of 0 to 100 weight% of diallyl phthalate, and 100 to 0 weight% of unsaturated polyester resin, is used preferably.

  Furthermore, in the present invention, from the viewpoint of ease of molding, when the second thermosetting resin layer of the second curable resin is layered on the first thermosetting resin of the prepreg and heated under pressure, In order to prevent the thermosetting resin 1 from flowing too much, a resin comprising 10 to 90% by weight of diallyl phthalate and 90 to 10% by weight of an unsaturated polyester resin is preferably used, particularly 50 to 90% by weight of diallyl phthalate. What consists of 50 to 10 weight% of saturated polyester resins is used preferably.

  When the first thermosetting resin flows too much when the second thermosetting resin layer on the thermoplastic resin film is overlaid on the first thermosetting resin of the prepreg and heated under pressure. Is that the cured product of the first curable resin becomes too thin, and in some cases, the glass fiber fabric is exposed without being coated with the cured product of the first thermosetting resin, and as a result, This is because the transparency of the resulting composite sheet may be significantly impaired.

  The refractive index of the glass fiber is usually in the range of 1.54 to 1.58, the refractive index of diallyl phthalate is 1.57, and the refractive index of the unsaturated polyester resin is usually 1.48 to 1. The range is 57. In the present invention, the refractive index of diallyl phthalate resin, the refractive index of unsaturated polyester resin, and the refractive index of thermosetting resin composed of diallyl phthalate and unsaturated polyester resin are the refraction of the cured product of each thermosetting resin. Say rate.

  In general, the transparency of a composite obtained by integrally curing a glass fiber fabric is determined by the refractive index of the glass fiber and the refractive index of the thermosetting resin. Therefore, in the present invention, in order to obtain a base sheet having excellent transparency, and thus a composite sheet having excellent transparency, the refractive index of the first thermosetting resin integrated with the glass fiber fabric to be used. And the difference between the refractive indexes of the glass fibers constituting the glass fiber fabric is preferably 0.03 or less.

  As described above, since the unsaturated polyester resin usually has a refractive index in the range of 1.48 to 1.57, when the first thermosetting resin is composed of diallyl phthalate and unsaturated polyester resin, The kind and ratio of the unsaturated polyester resin to be used are determined so that the difference between the refractive index and the refractive index of the glass fiber constituting the glass fiber fabric to be used is 0.03 or less.

  That is, when using the thing which consists of diallyl phthalate and unsaturated polyester resin as a 1st thermosetting resin, the refractive index of this 1st thermosetting resin is the refractive index of the glass fiber which comprises a glass fiber fabric. The unsaturated polyester resin preferably has a refractive index in the range of 1.53 to 1.57, and the ratio thereof is determined so as to be close to 1.54 to 1.58.

  In the present invention, the prepolymer is preferably used as diallyl phthalate. The diallyl phthalate prepolymer is an organic peroxide or azo polymerization initiator added to diallyl phthalate (monomer), bulk polymerization is performed, the polymerization is stopped at the stage of production of the linear polymer, and precipitated in a poor solvent. A white powder obtained by filtration and drying.

  On the other hand, an unsaturated polyester resin is typically an unsaturated polyester resin obtained by condensing an unsaturated acid such as maleic anhydride and a saturated polybasic acid such as phthalic anhydride together with a dihydric alcohol. A liquid resin in which a saturated polyester is dissolved in a polymerizable monomer such as a styrene monomer or an appropriate organic solvent.

  The first thermosetting resin comprising a diallyl phthalate prepolymer and / or an unsaturated polyester resin usually contains a polymerization initiator, and further contains a polymerization inhibitor, an internal mold release agent and the like as necessary. As the polymerization initiator, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, and the like are usually used, but are not limited to these examples.

  When the glass fiber fabric is impregnated with such a mixture containing the first thermosetting resin, the mixture has a viscosity capable of sufficiently penetrating so as not to leave voids between the glass fibers of the glass fiber fabric. As described above, it is diluted with an appropriate organic solvent to obtain a liquid resin composition having an appropriate solid content concentration, impregnated into a glass fiber fabric, and, for example, a squeeze roll or the like is used to obtain a predetermined amount of resin. Then, for example, a prepreg containing the first thermosetting resin semi-cured is obtained by drying using a hot air dryer. As the organic solvent, a combination of a low-boiling solvent and a high-boiling solvent, for example, a combination of acetone and propyl acetate is preferably used so that voids are not generated in the resin during the drying.

  In the glass fiber fabric prepreg thus obtained, the first thermosetting resin fills the voids inside the glass fiber fabric and covers both the front and back surfaces of the glass fiber fabric.

  According to the present invention, when the second curable resin is applied to the thermoplastic resin film in order to improve the wettability and adhesiveness of the thermoplastic resin film, an appropriate adhesion treatment is performed on the surface of the thermoplastic resin film in advance. It is preferable to apply.

  As the above-mentioned adhesion treatment, as well known, there are various treatments such as adhesive application, mechanical treatment, chemical treatment, physical treatment, etc., any of which is any two or more types. However, in the present invention, for example, corona treatment is preferably adopted in adhesive application and physical treatment, and among others, the surface of the thermoplastic resin film is appropriately subjected to corona treatment. An adhesive treatment in which an adhesive is applied is preferable. As the adhesive, for example, a urethane resin adhesive or an acrylic resin adhesive is preferably used.

  In the present invention, the thermoplastic resin film is not particularly limited as long as it is transparent and excellent in smoothness. Accordingly, examples of such a thermoplastic resin film include a polyester film and an acrylic resin film. In the present invention, the thermoplastic film has high smoothness, excellent heat resistance, and low cost. Therefore, a polyethylene terephthalate film is particularly preferably used.

In the present invention, when a polyethylene terephthalate film is used as the thermoplastic resin film, the thicker the film, the higher the repulsive compression force of the obtained composite sheet, and the higher the smoothness of the surface of the obtained composite sheet. Visibility is improved because the diffused reflection is reduced, but when it is too thin, there is no problem with nonflammability, but the rebound compression force and visibility are not improved. From such a viewpoint, according to the present invention, a polyethylene terephthalate film having a thickness in the range of 38 μm (basis weight 50 g / m ² ) to 75 μm (basis weight 98 g / m ² ) is preferably used.

  In order to form the semi-cured layer of the second curable resin on the thermoplastic resin film, as described above, the thermoplastic resin film is preferably subjected to an adhesion treatment, and then the second surface is formed on the surface of the thermoplastic resin film. When the above curable resin is applied, and then heated or irradiated with ionizing radiation such as ultraviolet rays or an electron beam, the resin has no tackiness, and is overlapped with the above-described prepreg and heated under pressure. The first thermosetting resin does not mix with each other, but at the interface, it is dried and partially polymerized to the extent that it is copolymerized (co-crosslinked), that is, bonded to each other, Semi-cured.

  When forming the semi-cured layer of the second curable resin on the thermoplastic resin film, the second curable resin is applied, partially polymerized, and semi-cured twice or more as necessary. May be repeated.

  The means for applying the second curable resin onto the thermoplastic resin film is not limited at all, and may be a normal application means such as a gravure roll or a knife coater.

  According to the present invention, unless the transparency is hindered, the thermoplastic resin film is subjected to treatment for imparting various functions such as printability, antistatic properties, weather resistance, flame retardancy, and the like. Can do. For example, to add flame retardant by blending an additive into polyethylene terephthalate, for example, as a flame retardant, for example, aluminum hydroxide, magnesium hydroxide, trichloroethyl phosphate, triallyl phosphate, ammonium polyphosphate, phosphorus An acid ester etc. can be mentioned. Moreover, as an antistatic agent, surfactant can be mentioned, for example.

  In the present invention, as the second curable resin, various resins can be used regardless of the refractive index as long as a transparent cured product layer can be formed. That is, according to the present invention, the second curable resin on the thermoplastic resin film is semi-cured, and even if it is overlapped with the glass fiber fabric prepreg containing the first thermosetting resin, Since it does not mix, the second curable resin can be used regardless of its refractive index as long as the cured product is transparent.

  Therefore, as such a curable resin, for example, diallyl phthalate, unsaturated polyester resin, urethane resin, epoxy resin, melamine resin and the like can be cited as preferable resins. Of these, unsaturated polyester resins, diallyl phthalates, and further mixtures thereof are preferably used.

  That is, in the present invention, the second curable resin is a semi-cured product of the second curable resin so that the resulting composite sheet is excellent in transparency, visibility and strength, in particular, toughness. The resin component is composed of diallyl phthalate and / or unsaturated polyester resin so as to easily achieve strong adhesion with the semi-cured product of the first thermosetting resin, that is, 0 to 100% by weight of diallyl phthalate What consists of 100 to 0 weight% of unsaturated polyester resins is used preferably.

  In particular, in the present invention, the second curable resin does not flow too much when the semi-cured layer of the second curable resin is layered on the first thermosetting resin of the prepreg and heated under pressure. Thus, those comprising 10 to 90% by weight of diallyl phthalate and 90 to 10% by weight of unsaturated polyester resin are preferably used, and particularly from 50 to 90% by weight of diallyl phthalate and 50 to 10% by weight of unsaturated polyester resin. Is preferably used.

  In the present invention, the second curable resin applied to the thermoplastic resin film is polymerized (cured) by irradiation with ionizing radiation when partially polymerized and semi-cured as described above. ) Are easy to handle and can be easily polymerized, for example, those having UV curable properties are preferred. On the other hand, in the final production process, a thermoplastic resin film is laminated on a prepreg, Since it is advantageous to mold, the second curable resin preferably has thermosetting properties. That is, in the present invention, the second curable resin is preferably ionizing radiation curable, particularly ultraviolet curable, and thermosetting.

  As the ultraviolet rays, those containing ultraviolet rays having a wavelength of 200 to 380 nm are suitable, and as the ultraviolet ray source, for example, a metal halide, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp or the like is preferably used.

  In the present invention, the second curable resin in the obtained composite sheet is smoothed by filling the unevenness of the surface of the prepreg, and the thermoplastic resin film is bonded to the prepreg by the second curable resin. However, this adhesive film also increases the smoothness of the surface of the resulting composite film, and thus the transparent non-combustible sheet obtained as a composite sheet according to the present invention has excellent visibility.

Therefore, in the present invention, the greater the amount of the second curable resin applied, that is, the amount applied to the thermoplastic resin film, the better the visibility of the resulting composite sheet. It adversely affects the non-flammability of the composite sheet and makes it difficult to apply it uniformly to the film. However, when the amount is too small, the visibility is not improved. Therefore, the amount of the second curable resin applied to the thermoplastic resin film, that is, usually in the range of 10 to 50 g / m ² per one surface of the prepreg is preferable.

And according to this invention, the quantity (solid content) of the 1st thermosetting resin which a prepreg contains first, so that the composite sheet obtained may be excellent in transparency and visibility, the glass fiber fabric 100 is sufficient. It is preferably 27 parts by weight or more with respect to parts by weight. Further, secondly, the total amount of the first thermosetting resin (solid content), the second curable resin (solid content) and the thermoplastic resin film so that the resulting composite sheet has nonflammability, It is preferably 400 g or less per 1 m ^{2 of} glass fiber fabric.

When an adhesive is applied to the thermoplastic resin film as an adhesive treatment, the first thermosetting resin (solid content) and the second curable resin (solid content) are used so that the resulting composite sheet has nonflammability. ), The thermoplastic resin film, and the adhesive (solid content) is preferably 400 g or less per 1 m ^{2 of} glass fiber fabric.

  In addition, although the said 1st and 2nd curable resin contains a polymerization initiator and a mold release agent, since content in the curable resin of these polymerization initiators or a mold release agent is small when seen from the amount of resin. Can usually be ignored.

  Thus, according to the present invention, the semi-cured product layer of the second curable resin on the thermoplastic resin film is overlaid on the prepreg containing the semi-cured first thermosetting resin described above, By molding, the intended transparent noncombustible sheet can be obtained.

  More specifically, for example, a thermoplastic resin film having a semi-cured material layer of a prepreg and a second curable resin is sandwiched between aluminum plates to form a laminate, and further, the laminate is sandwiched between cushions, After heating and pressing between a pair of heating plates at a temperature of 120 to 150 ° C. and a pressure of 1.0 to 7.0 MPa for 10 minutes to 1 hour, the release film is peeled off, and then the first and A transparent incombustible sheet obtained by integrating the cured product of the second thermosetting resin and the thermoplastic resin film can be obtained.

  As described above, according to the present invention, the semi-cured product layer of the second curable resin on the thermoplastic resin film is superimposed on the semi-cured product layer of the first thermosetting resin that the prepreg has on the surface. In this case, the first thermosetting resin and the second curable resin are not mixed with each other at the interface, but are copolymerized (co-cured) at the interface. The first thermosetting resin is integrally cured with the glass fiber fabric, and the thermoplastic resin adhesive film is made of the base sheet by the second curable resin that is integrally cured with the first thermosetting resin. The transparent noncombustible sheet according to the present invention can be obtained by being integrally bonded to the substrate.

  Therefore, in the transparent non-combustible sheet according to the present invention, the cured product of the first thermosetting resin fills the voids inside the glass fiber fabric and flattens both the front and back surfaces of the glass fiber fabric. In addition to being integrated with the glass fiber fabric, the cured product layer of the second curable resin is also integrated with the cured product of the first thermosetting resin. A thermoplastic resin film is adhered to the cured layer of the thermosetting resin, and the front and back surfaces of the glass fiber fabric are coated together with the cured layer of the second thermosetting resin to smooth the surface. It is useful for.

  Thus, the transparent non-combustible sheet according to the present invention is excellent in non-combustibility, transparency and visibility, and also has excellent toughness and bending properties, and is difficult to break even under impact. Can be suitably used.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the visibility, nonflammability, total light transmittance, and refractive index of the obtained sheets were evaluated or measured as follows.

(Visibility)
Visibility refers to the property that an object can be clearly identified through a sheet. Through the obtained sheet, it is tested how many “new” characters on paper 2 m away can be clearly identified, and “new” characters can be clearly identified The number of points was obtained as an indicator of visibility. It can be said that the smaller the number of points, the better the visibility.

(Non Flammable)
It evaluated by the heat_generation | fever test based on the corn calorimeter method prescribed | regulated to ISO 5660-1. That is, according to the present invention, the heating test of irradiating radiant heat 50 KW / m ² on the surface of the sample sheet by radiation electric heater, (1) the total amount of heat generated by the heating start after 20 minutes 8 MJ / m ² or less (ISO According to 5660-1, it is 7.2 MJ / m ² or less.) (2) 20 minutes after the start of heating, the maximum heat generation rate continues for 10 seconds or more, and does not exceed 200 KW / m ^2. (3) Even after the exothermic test, when all the conditions that the distance between the warps and the distance between the wefts in the glass fiber fabric are both 0.5 mm or less are set as “pass”, the above (1) A case where at least one of the conditions (3) to (3) was not satisfied was defined as “fail”.

(Total light transmittance)
According to JIS K-7105.
(Refractive index)
The measurement was performed using an Abbe refractometer (manufactured by Atago Optical Instruments Co., Ltd.). In the following, the refractive index of the curable resin is the refractive index of the cured product.
(Rebound compression rate)
The obtained composite sheet was cut into a strip shape having a width of 25 mm and a length of 50 mm, and this was wound in the longitudinal direction to produce an annular body. The circumferential surface of the annular body was brought into contact with a horizontal plane, The repulsive force of the annular body when the uppermost part was pushed down by 5 mm was measured as the repulsive compression force. A universal tensile testing machine (TCM-10KNB manufactured by Minebea Co., Ltd.) was used for the measurement.

Example 1
70 parts by weight of diallyl phthalate prepolymer powder as a resin component (Daiso Co., Ltd., Daiso Dup, refractive index 1.57, hereinafter the same) and liquid unsaturated polyester resin (D-Materials Co., Ltd. Sandoma DH-2200) , Refractive index 1.54) 30 parts by weight (solid content) benzoyl peroxide 3.5 parts by weight (solid content), mold release agent (Chukyo Yushi Co., Ltd. phosphoric acid alkyl ester, Separ 325, the same below) 0.5 parts by weight, 65 parts by weight of acetone and 10 parts by weight of propyl acetate were uniformly mixed to prepare a liquid first thermosetting resin. The refractive index of this first thermosetting resin was 1.56.

A plain weave glass fiber woven fabric having a basis weight of 110 g / m ² made of glass fiber (refractive index of 1.56) which has been surface-treated with a cationic silane coupling agent having a quaternary ammonium salt structure in advance is the first thermosetting. After impregnating the resin and adjusting it using a squeeze roll so as to obtain a predetermined resin amount, the resin is dried using a hot air dryer, and the first thermosetting resin amount (solid) per 1 m ^{2 of} glass fiber fabric. Minute) A prepreg containing 33 g (30 parts by weight of resin based on 100 parts by weight of glass fiber fabric) was obtained.

  70 parts by weight of diallyl phthalate prepolymer powder and 30 parts by weight (solid content) of liquid unsaturated polyester resin (trade name Sandoma DH-2200, refractive index 1.54, manufactured by DH Material Co., Ltd.) Co., Ltd. Irgacure 184) 3.5 parts by weight (solid content, hereinafter the same), 0.5 parts by weight of mold release agent, 65 parts by weight of acetone and 10 parts by weight of propyl acetate were mixed uniformly, 2 curable resin (refractive index 1.56) was prepared.

After corona treatment was applied to the surface of a polyethylene terephthalate film having a thickness of 50 μm (basis weight 65 g / m ² ), a urethane resin adhesive was applied with a gravure coater and dried using a hot air dryer. Next, the second curable resin is applied thereon with a gravure coater, dried using a hot air drier, and then irradiated with ultraviolet rays to form a resin having a resin amount (solid content) of 39 g / m ² . A semi-cured product layer of 2 curable resin was formed.

  For each of the polyethylene terephthalate films, the semi-cured product layer of the second curable resin was immersed in acetone, and the elution amount of the second curable resin was measured. It was confirmed that the curable resin No. 2 formed a semi-cured product.

  The prepreg is sandwiched and stacked between a pair of polyethylene terephthalate films so that the semi-cured layer of the second curable resin on the polyethylene terephthalate film faces the prepreg. The transparent non-combustible sheet according to the present invention is sandwiched between aluminum plates, further sandwiched between cushions, and then heated and pressed between a pair of heating plates at a temperature of 130 ° C., a pressure of 5.0 MPa, and a time of 30 minutes. Was obtained as a composite sheet.

Comparative Example 1
A prepreg was produced in the same manner as in Example 1.

After corona treatment is applied to the surface of a polyethylene terephthalate film having a thickness of 50 μm (basis weight 65 g / m ² ), a urethane resin adhesive is applied and dried using a hot air dryer in the same manner as in Example 1. It was. The prepreg was sandwiched between a pair of polyethylene terephthalate films so that the urethane-based adhesive layer on the polyethylene terephthalate film faced the prepreg, thereby forming a laminate.

  The laminate was sandwiched between a pair of aluminum plates, and further sandwiched between cushions, and then heated and pressed between a pair of heating plates under conditions of a temperature of 130 ° C., a pressure of 5.0 MPa, and a time of 30 minutes. A transparent noncombustible sheet as a composite sheet was obtained.

Comparative Example 2
A prepreg was produced in the same manner as in Example 1, and a liquid second curable resin was prepared in the same manner as in Example 1.

A polyethylene terephthalate film is used as a release film, a release agent is applied thereto, the second curable resin is applied using a gravure coater, dried using a hot air dryer, and then irradiated with ultraviolet rays. Then, a semi-cured product layer of a second curable resin having a resin amount (solid content) of 39 g / m ² was formed on the release film. In order to confirm the degree of cure of the semi-cured product layer of the second curable resin, the amount of the second curable resin was measured by immersing in acetone and measuring about 2%. It was confirmed to be a semi-cured product layer.

  The prepreg is sandwiched and stacked between a pair of polyethylene terephthalate films so that the semi-cured layer of the second curable resin on the release film faces the prepreg. After being sandwiched between the aluminum plates, and further sandwiched between the cushions, they were heated and pressed between a pair of hot plates under the conditions of a temperature of 130 ° C., a pressure of 5.0 MPa, and a time of 30 minutes. The obtained laminate is allowed to cool to room temperature to obtain a laminate in which the cured product of the second curable resin is integrally laminated on the base sheet, and the release film is peeled from the laminate, A transparent incombustible sheet as a comparative example was obtained as a composite sheet.

  With respect to the transparent noncombustible sheet obtained as a composite sheet in Example 1 and Comparative Examples 1 and 2, the total light transmittance, visibility, noncombustibility, and rebound compression ratio were measured. The results are shown in Table 1. In Table 1, DAP means diallyl phthalate resin and UPE means unsaturated polyester resin.

  As is clear from the results shown in Table 1, the transparent non-combustible sheet according to Example 1 is not only excellent in non-combustibility, but also has high total light transmittance, excellent transparency, and visibility. It has excellent rebound compression force and excellent toughness.

  However, since the transparent non-combustible sheet according to Comparative Example 1 is formed by adhering a polyethylene terephthalate film to a base sheet only with a urethane resin adhesive, regardless of the second curable resin, Both the visibility and the rebound compression force are inferior to the transparent noncombustible sheet according to Example 1.

The transparent non-combustible sheet according to Comparative Example 2 is obtained by bonding a cured product layer of a second curable resin directly to the surface of a base sheet, and polyethylene on the cured product layer of the second curable resin. Since the terephthalate film is not bonded, the rebound compression force is remarkably small, the toughness is inferior, and the visibility is also inferior.

Claims (11)

  Transparent glass fiber fabric made of glass fiber surface-treated with a silane coupling agent having an amino group or quaternary ammonium structure in the molecule, and the first thermosetting resin impregnated and cured in this glass fiber fabric And a transparent thermoplastic resin film bonded to the cured product of the first thermosetting resin with a second curable resin on both surfaces of the substrate sheet. A transparent non-combustible sheet, wherein the difference between the refractive index of the first thermosetting resin and the refractive index of the glass fibers constituting the glass fiber fabric is 0.03 or less. Transparent incombustible sheet.   The transparent noncombustible sheet according to claim 1, wherein the first thermosetting resin comprises 0 to 100% by weight of diallyl phthalate and 100 to 0% by weight of an unsaturated polyester resin.   The transparent noncombustible sheet according to claim 1, wherein the first thermosetting resin comprises 50 to 90% by weight of diallyl phthalate and 50 to 10% by weight of unsaturated polyester resin. The transparent incombustible sheet according to claim 1, wherein the thermoplastic resin film is a polyester film or an acrylic resin film.   A glass fiber fabric made of glass fibers surface-treated with a silane coupling agent having an amino group or a quaternary ammonium structure in the molecule is impregnated with a first thermosetting resin, dried, and the first heat Separately, a second curable resin is applied to the surface of the thermoplastic resin film and partially cured to form a semi-cured product layer, and the thermoplastic is applied to both surfaces of the prepreg. The semi-cured product layers on the resin film are respectively stacked, heated under pressure, and the first thermosetting resin included in the prepreg is integrally cured with the semi-cured product layer of the second curable resin. A method for producing a transparent incombustible sheet comprising adhering the thermoplastic resin film to a first thermosetting resin layer on the surface of the prepreg, wherein the refractive index of the first thermosetting resin is Above glass Wherein the difference between the refractive index of the glass fibers constituting the 維織 product is not less than 0.03. The method according to claim 5 , wherein the first thermosetting resin comprises 0 to 100% by weight of diallyl phthalate and 100 to 0% by weight of unsaturated polyester resin. The method according to claim 5 , wherein the first thermosetting resin comprises 50 to 90% by weight of diallyl phthalate and 50 to 10% by weight of unsaturated polyester resin. The method according to claim 5 , wherein after the adhesive treatment is applied to the thermoplastic resin film, a second curable resin is applied. The method according to claim 5 , wherein the resin component of the second curable resin comprises 0 to 100% by weight of diallyl phthalate and 100 to 0% by weight of unsaturated polyester resin. The method according to claim 5 , wherein the resin component of the second curable resin comprises 50 to 90% by weight of diallyl phthalate and 50 to 10% by weight of unsaturated polyester resin. A smoke barrier wall comprising the transparent incombustible sheet according to any one of claims 1 to 4 .