JP2019044309A - Resin adhesion glass fiber fabric, printed matter by gravure printing on the resin adhesion glass fiber fabric, and building interior material containing the printed matter - Google Patents

Abstract

To provide a novel resin adhesion glass fiber fabric capable of achieving clear pattern or the like without laminating a film or the like as an ink reception layer or arranging a thick resin layer, and making hard to make color or pattern of a laminated wall or the like being peered through.SOLUTION: There is provided a resin adhesion glass fiber fabric containing a glass fiber fabric constituted by a glass yarn, and a resin adhered to at least a part of a glass fiber surface constituting the glass yarn, in which yarn count of the glass yarn is 20 to 70 tex, thickness of the resin adhesion glass fiber fabric is 0.08 mm or more, apparent density of the resin adhesion glass fiber fabric calculated by thickness (mm) of the resin adhesion glass fiber fabric and mass (g/m2) is 1.05 to 1.50 (g/cm3) and ignition loss of the resin adhesion glass fiber fabric is 0.8 to 10 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin-attached glass fiber woven fabric, and in particular, a resin-attached glass fiber woven fabric having good printability such as gravure printing, a printed matter obtained by applying gravure printing to the resin-attached glass fiber fabric, and an architecture including the printed matter. For interior materials.

  To improve the design of building exteriors such as exterior walls of buildings, entrance doors of houses, exteriors and interiors of automobiles, exteriors and interiors of vehicles and ships, etc. is there. And when nonflammability is calculated | required, the decorative sheet which used the glass fiber fabric as the base material may be used.

  As a decorative glass fiber sheet, a decorative glass fiber sheet is known which is colored by spraying or brushing paints or letters for advertising or decoration on the surface of a glass fiber fabric (for example, patents). Reference 1). However, the decorative glass fiber sheet is inferior in productivity and reproducibility because it is necessary to spray or brush the paint every time.

  On the surface of the substrate having a layer made of glass woven fabric as a surface layer, the surface of the glass woven fabric side has a printed layer formed by gravure printing via a first smoothing layer, and the first smoothing layer is A decorative sheet that is a resin film is known (for example, see Patent Document 2). It is disclosed that the decorative sheet is thin and lightweight, and can have extremely excellent non-flammability performance without being bonded to a non-combustible substrate or the like, and is excellent in flexibility and flexibility. . It is also disclosed that the high designability of the pattern by gravure printing can be maintained.

  In addition, a glass cloth for printing is known in which an acrylic resin or / and a PVA resin added with a pigment is applied to the printing surface (see, for example, Patent Document 3). This document discloses that a sealing treatment is preferably performed, and a blend of an acrylic resin and a urethane resin is preferable as the sealing agent.

JP 59-93347 A JP 2014-117850 A JP 2002-326842 A

  However, the decorative sheet disclosed in Patent Document 2 requires a step of bonding a resin film to a glass woven fabric in order to provide a smoothing layer that receives ink.

  The glass cloth for printing disclosed in Patent Document 3 does not include a resin film like the decorative sheet disclosed in Patent Document 2 above, but on the other hand, when printed by gravure printing, a clear pattern or the like may appear. There is a problem that it may not be possible. In addition, since the ink receiving layer obtained by adding a pigment to an acrylic resin or / and a PVA resin and a layer made of a sealing agent are provided, the number of steps and the amount of resin are increased, and the cost is also high. There is a problem that sometimes. In addition, depending on the type of glass fiber fabric, when the printed glass fiber fabric is affixed to a wall or the like, the glass fiber fabric may show the color or pattern of the wall or the like and affect the visibility of the printed pattern. .

  The present invention solves the above-mentioned problems, can display a clear pattern even when printed by gravure printing, for example, without attaching a film or the like as an ink receiving layer or providing a thick resin layer, and , A new resin-attached glass fiber woven fabric that can make the color and pattern of the attached wall and the like difficult to see through (reducing the show-through), and a printed matter in which the resin-attached glass fiber fabric is subjected to gravure printing It is another object of the present invention to provide a building interior material including the printed matter.

  In order to solve the above problem, the present inventor first omitted the ink receiving layer in which a pigment is added to an acrylic resin and / or PVA resin from the glass cloth for printing disclosed in Patent Document 3, and the document It was considered that only the sealing agent disclosed in (1) was adhered. However, if the ink-receiving layer is omitted from the printing glass cloth, the cost is improved, but a clear pattern cannot be produced when printing is performed by, for example, gravure printing.

  The inventor has intensively studied the reason why the above-mentioned clear design cannot be revealed, and has found out that there is a cause in the configuration of the glass fiber woven fabric as the base material. And in order to make printability favorable, it turned out that it is effective to make thickness and an apparent density into a specific range, improving the smoothness of a resin adhesion glass fiber fabric.

  Specifically, for example, when the glass yarn is too thick (the count is too large), the inventor has a large unevenness of the resin-attached glass fiber fabric, and the ink accumulated in the concave portion of the gravure printing cylinder is sufficiently transferred. It was learned that it was impossible to show clear symbols. That is, in the glass fiber fabric, when the warp and the weft are repeatedly floated and settled, the ink is more easily transferred to the part where one of the warp or the weft floats with respect to the other, and the glass fiber sunk when the glass thread is too thick It has been found that not only the degree increases but also the area per sinking area increases, so that the contact with the roll of the gravure printing machine becomes insufficient, and it becomes impossible to express a clear pattern or the like. If the thickness and apparent density of the resin-attached glass fiber fabric are too small, the color and pattern of the object on the side opposite to the ink receiving side of the resin-attached glass fiber fabric will be seen through, and the resin receiving glass fiber fabric will be seen from the ink receiving layer side. It has been found that there is a case where the visibility of the pattern or the like imparted to the resin-attached glass fiber fabric may be affected. Further, when the apparent density of the resin-attached glass fiber fabric is too low, not only the smoothness may be inferior, but also the resin-attached glass fiber fabric is thickened by repeated contact with the concave portions and non-recess portions of the plate cylinder during printing. It has been found that it moves slightly in the direction of the head and the like, and as a result, a clear pattern or the like cannot be displayed.

  Then, the inventor attaches a minimum amount of resin to the surface of the glass fiber and sets the count and apparent density of the glass yarn to a specific range, thereby improving the smoothness and preventing the concave portion and the concave portion of the plate cylinder from being printed. Reduces the movement of the resin-attached glass fiber fabric in the thickness direction even if contact is repeated, and further sets the thickness and apparent density to a specific range, so that the color and pattern of the object on the side opposite to the ink receiving side can be changed. I recalled not to see through. The present invention has been completed by further studies based on this finding.

That is, this invention provides the resin-attached glass fiber fabric of the aspect hung up below, the printed matter by which the gravure printing was given to this resin-attached glass fiber fabric, and the building interior material containing this printed matter.
Item 1. A resin-attached glass fiber fabric comprising a glass fiber fabric composed of glass yarn and a resin adhering to at least a part of the glass fiber surface constituting the glass yarn, wherein the glass yarn count is 20 to 20 70 tex, the thickness of the resin-attached glass fiber fabric is 0.08 mm or more, and the resin-attached glass fiber calculated from the thickness (mm) and mass (g / m ² ) of the resin-attached glass fiber fabric The apparent density of the woven fabric is 1.05 to 1.50 (g / cm ³ ), and the loss on ignition of the resin-attached glass fiber woven fabric measured according to JIS R 3420: 2013 7.3 is 0.8 to 10 Resin-attached glass fiber woven fabric in mass%.
Item 2. Item 2. The resin-attached glass fiber fabric according to Item 1, wherein the weft density of the warp and weft of the resin-attached glass fiber fabric is 15 to 120 yarns / 25 mm.
Item 3. Item 3. The resin-attached glass fiber fabric according to Item 1 or 2, wherein the mass is 70 to 450 / m ² .
Item 4. Item 4. The resin-attached glass fiber fabric according to any one of Items 1 to ^{3, wherein the} air permeability is from 0.1 to 50 cm ³ / cm ² / sec.
Item 5. Item 5. The resin-attached glass fiber fabric according to any one of Items 1 to 4, wherein the resin comprises an acrylic acid-styrene copolymer and an ethylene-vinyl acetate copolymer.
Item 6. Ratio of mass of nonvolatile component of acrylic acid-styrene copolymer to mass of nonvolatile component of ethylene-vinyl acetate copolymer (mass of ethylene-vinyl acetate copolymer (g / m ² ) / acrylic acid-styrene) Item 6. The resin-attached glass fiber fabric according to Item 5, wherein the copolymer has a mass (g / m ² ) of 1.0 to 3.0.
Item 7. 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 in which the surface of the sheet is irradiated with radiant heat of 50 kW / m ² , the maximum heat generation rate does not exceed 200 kW / m ² for 20 minutes after the start of heating and does not exceed 200 kW / m ² for 20 minutes after the start of heating. Item 7. The resin-attached glass fiber fabric according to any one of Items 1 to 6, wherein the amount is 8 MJ / m ² or less.
Item 8. Item 8. The resin-attached glass fiber fabric according to any one of Items 1 to 7, which is used as a gravure printing substrate.
Item 9. Item 10. A printed material obtained by applying gravure printing to the resin-attached glass fiber fabric according to any one of items 1 to 8.
Item 10. An architectural interior material including the printed matter according to Item 9.

  According to the present invention, without attaching a film or the like as an ink-receiving layer or providing a thick resin layer, it is possible to show a clear pattern or the like when printed by, for example, gravure printing, Resin-attached glass fiber woven fabric capable of making it difficult to see the color and pattern of the resin, a printed matter obtained by applying gravure printing to the resin-attached glass fiber woven fabric, and a building interior material including the printed matter can be provided. .

The resin-attached glass fiber fabric of the present invention is a resin-attached glass fiber fabric comprising a glass fiber fabric composed of glass yarn and a resin that adheres to at least a part of the surface of the glass fiber constituting the glass yarn. The glass yarn count is 20 to 70 tex, the thickness of the resin-attached glass fiber fabric is 0.08 mm or more, and the thickness (mm) and mass (g / m ² ) of the resin-attached glass fiber fabric. The apparent density of the resin-attached glass fiber woven fabric calculated from the above is 1.05-1.50 (g / cm ³ ), and the resin-attached glass fiber woven fabric is measured according to JIS R 3420: 2013 7.3. The loss on ignition is 0.8 to 10% by mass. Hereinafter, the resin-attached glass fiber fabric of the present invention will be described in detail.

  The resin-attached glass fiber fabric of the present invention includes a glass fiber fabric composed of glass yarn. Thereby, it can be made easy to be excellent in nonflammability.

  About the glass material of the glass fiber which comprises a glass thread, 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 fiber constituting the glass yarn 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.

  In this invention, the count of the glass yarn which comprises the resin adhesion glass fiber fabric is 20-70 tex. By setting it to 20 tex or more, the thickness of the resin-attached glass fiber fabric can be easily set to 0.08 mm, and the color and pattern of an object on the side opposite to the ink receiving side of the resin-attached glass fiber fabric described later are hardly transmitted. It becomes possible. Moreover, by setting it as 70 tex or less, the smoothness of the resin-attached glass fiber woven fabric obtained is improved, the ink accumulated in the concave portion of the gravure printing cylinder is sufficiently transferred, and a clear pattern or the like can be exhibited. It becomes possible. From the viewpoint of making the improvement in smoothness and making the color and pattern of the object on the side opposite to the ink receiving side of the resin-attached glass fiber fabric, which will be described later, more transparent, the above-mentioned count is 10 -30 tex is preferable, 20-30 tex is more preferable, and 20-25 tex is particularly preferable. The count is measured and calculated in accordance with JIS R 3420: 2013 7.1.

  Although the diameter of the glass fiber (single fiber) constituting the glass yarn is not particularly limited, for example, 3 to 10 μm may be mentioned, and 3 to 8 μm from the viewpoint of further improving the smoothness and easily increasing the apparent density described later. Is preferred. From the viewpoints described above and from the viewpoint of making it difficult to see the color and pattern of the object on the side opposite to the ink receiving side of the resin-attached glass fiber fabric, 6 to 8 μm is more preferable, and 6.5 to 7.5 μm is particularly preferable. . The single fiber diameter is measured and calculated according to JIS R 3420: 2013 7.6 A method. The number of single fibers in the glass yarn is not particularly limited, and examples thereof include 30 to 1000. Improve smoothness, make it easier to increase the apparent density, and make the color and pattern of objects on the opposite side of the resin-attached glass fiber fabric opposite to the ink receiving side more transparent. From the viewpoint, the number of the single fibers is preferably 100 to 400, and more preferably 150 to 250.

  In the resin-attached glass fiber woven fabric of the present invention, the woven structure is not particularly limited, and examples thereof include plain weave, satin weave, twill weave, oblique weave, and woven weave. Among these, a plain weave is preferable from the viewpoint of excellent uniformity. Although plain weave is excellent in uniformity, it has a large number of warp and weft structure points and is difficult to achieve a relatively high apparent density described later. In this case, the apparent density described later can be achieved by adopting a preferable manufacturing method described later.

  The resin-attached glass fiber fabric of the present invention has a thickness of 0.08 mm or more. This makes it difficult to see the color and pattern of the object on the side opposite to the ink receiving side of the resin-attached glass fiber fabric, and the visibility of the pattern and the like imparted to the resin-attached glass fiber fabric when viewed from the ink receiving side. Will be excellent. The thickness is 0.08 to 0.3 mm from the viewpoint of further improving the smoothness while making it difficult to see the color and pattern of the object on the side opposite to the ink receiving side of the resin-attached glass fiber fabric. Preferably, 0.08 to 0.20 mm is more preferable, and 0.08 to 0.10 mm is particularly preferable. The thickness of the resin-attached glass fiber woven fabric was measured up to an order of 0.01 mm (10 μm) using a micrometer according to JIS R 3420 2013 7.10.1A method, and this was performed at five locations. The average value of the five locations is rounded according to JIS Z 8401 rule B, and calculated to the order of 0.01 mm (10 μm).

The resin-attached glass fiber woven fabric of the present invention has a thickness (mm) of the resin-attached glass fiber woven fabric and the mass (g / m) of the resin-attached glass fiber woven fabric measured and calculated according to JIS R 3420: 2013 7.2. ² ) and the apparent density (g / cm ³ ) calculated from 1.05 to 1.50 (g / cm ³ ). For example, the glass cloth of H170 described in Patent Document 3 as Example 1 has a thickness of 0.21 mm and a mass of 170 (g / m ² ), and the apparent density calculated from the thickness and the mass is 0.8 (g / cm ³ ). Therefore, the glass cloth moves slightly in the thickness direction and the like due to repeated contact with the concave portion and the non-recessed portion of the plate cylinder during printing, so that a clear pattern or the like can be exhibited. It was something that disappeared. On the other hand, according to the resin-attached glass fiber woven fabric of the present invention, since it has the above-mentioned apparent density, even when contact with the non-recessed portion of the plate cylinder is repeated during printing while improving the smoothness of the resin-attached glass fiber woven fabric. It is possible to reduce the movement of the resin-attached glass fiber fabric in the thickness direction. The apparent density is preferably from ^{1.10~1.30g / cm 3, 1.15~1.25g / cm} 3 is more preferable. In addition, the apparent density of the resin-attached glass fiber fabric is calculated by the following formula (A).
Apparent density (g / cm ³ ) = mass of resin-attached glass fiber fabric (g / m ² ) / (thickness of resin-attached glass fiber fabric (mm) × 1000) Formula (A)

  Although the woven density of the resin-attached glass fiber fabric of the present invention is not particularly limited, for example, the warp density is 15 to 120 yarns / 25 mm, more preferably 20 to 70 yarns / 25 mm, and 40 to 70 yarns / 25 mm. 25 mm is more preferable, and 50 to 70 is particularly preferable. The weft density is 15 to 90/25 mm, more preferably 15 to 70/25 mm, more preferably 40 to 70, and particularly preferably 50 to 70. Further, from the viewpoint of making the apparent density easier to increase, the warp density can be larger than the weft density. Specifically, the ratio between the warp density and the weft density (= warp density / weft density). Is, for example, 1.01 to 1.40, preferably 1.05 to 1.40, and more preferably 1.05 to 1.10. In addition, the weave density of the resin-attached glass fiber fabric is measured and calculated according to JIS R 3420 2013 7.9.

The mass of resin adhesion glass fiber fabric of the present invention (g / ^{m 2)} is not particularly limited, for example, 70~450g / ^{m 2} can be mentioned, 80~250g / ^{m 2} are preferably exemplified, 90～120G / M ² is more preferable. The mass is measured and calculated according to JIS R 3420: 2013 7.2.

  The resin-attached glass fiber fabric of the present invention contains a resin that adheres to at least a part of the glass fiber surface. As a result, it is possible to reduce the movement of the resin-attached glass fiber fabric in the thickness direction even when contact with the recesses and non-recesses of the plate cylinder is repeated during printing while improving the smoothness of the resin-attached glass fiber fabric. Become.

In the resin-attached glass fiber fabric of the present invention, the loss on ignition measured according to JIS R 3420: 2013 7.3 is 0.8 to 10% by mass. As described above, the resin-attached glass fiber woven fabric of the present invention is composed of glass yarn, the count of the glass yarn is 20 to 70 tex, the thickness is 0.08 mm or more, and the thickness (mm) and mass Since the apparent density calculated from (g / m ² ) is 1.05-1.50 g / cm ^3, it is minimal without attaching a film or the like as the ink receiving layer or providing a thick resin layer. By attaching the resin, it becomes possible to show a clear pattern or the like when printed by gravure printing. And the ignition loss measured according to JISR3420 is prescribed | regulated as 0.8-10 mass% as said minimum resin amount. In addition, when the ignition loss is too large, tackiness tends to become strong. When the tackiness is too strong, for example, when a resin-attached glass fiber woven fabric is used as a roll product and the product is rewound, the glass fiber constituting the resin-attached glass fiber woven fabric is damaged and fluff is generated. There is a risk that the eyes will be rough. If the occurrence of fluff or rough eyes increases too much, a clear pattern or the like may not be displayed when printing is performed. Accordingly, the ignition loss is preferably 1.0 to 8.0% by mass, more preferably 1.0%, from the viewpoint that the tackiness is also good and it is possible to express a clear pattern or the like. -5.0 mass%, More preferably, 2.0-5.0 mass% is mentioned.

  In the resin-attached glass fiber fabric of the present invention, the resin species attached to at least a part of the glass fiber surface is not particularly limited. For example, polyvinyl chloride resin, polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer, polyamide resin, polyarylate resin, acrylic acid-styrene copolymer, etc. Is mentioned. Among them, it is preferable to include an ethylene-vinyl acetate copolymer and / or an acrylic acid-styrene copolymer from the viewpoint of showing a clearer pattern when printed by gravure printing using a solvent-based ink, for example. More preferably, an ethylene-vinyl acetate copolymer and an acrylic acid-styrene copolymer are included.

  According to the study of the present inventor, for example, when a solvent-based ink is used as a printing ink, if the resin species contained on the glass fiber surface is an ethylene-vinyl acetate copolymer, the ink fixing property is further improved. I found it. On the other hand, the present inventor, for example, when solvent-based ink is used, the resin adhering to at least a part of the glass fiber surface may be affected by the solvent. It has been found that there is a case where the effect is lowered and the sharpness of the printed pattern is affected by the swelling of the resin. And in order to be excellent in solvent resistance and to make the eyes of the resin-attached glass fiber fabric more difficult to shift, it is particularly preferable that the resin species contained in at least a part of the glass fiber surface is an acrylic acid-styrene copolymer. We also found it effective. Therefore, the present inventors further examined, from the viewpoint of making the ink fixing property and the sharpness of the printed pattern more parallel, as a resin species contained in the glass fiber surface, an ethylene-vinyl acetate copolymer and It has been found that it is preferable to include an acrylic acid-styrene copolymer.

  Preferred examples of the ethylene-vinyl acetate copolymer include those represented by the following chemical formula (1). Examples of the acrylic acid-styrene copolymer include 2-ethylhexyl acrylate / styrene copolymer, methyl acrylate / styrene copolymer, ethyl acrylate / styrene copolymer, butyl acrylate / styrene copolymer, 1 selected from the group consisting of styrene / α-methylstyrene / acrylic acid copolymer, acrylic acid / butyl acrylate / styrene copolymer, one represented by the following chemical formula (2), and one represented by the following chemical formula (3) More than species are preferred. When an ethylene-vinyl acetate copolymer and an acrylic acid-styrene copolymer are included, a resin composition obtained by mixing the compounds of the following chemical formulas (1), (2) and (3) is more preferable. Can be mentioned.

  When an ethylene-vinyl acetate copolymer and an acrylic acid-styrene copolymer are included, the mass ratio of both nonvolatile components (the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer / the nonvolatile component of the acrylic acid-styrene copolymer) Is preferably 1.0 to 3.0, and more preferably 2.0 to 3.0, from the viewpoint of making the ink fixability, solvent resistance, and misalignment prevention properties more parallel. More preferably. In addition, the non-volatile component in this invention means the absolute dry component when a solvent etc. are removed by heat-processing at 105 degreeC under a normal pressure, and constant weight is reached.

  The resin composition made of the resin may contain other components. For example, crosslinkable ethylene / vinyl acetate / acrylate copolymer, monomer components (vinyl acetate monomer, phosphate ester monomer, (meth) acrylic acid monomer, (meth) acrylic acid ester monomer, styrene Monomers, etc.) and various additives (UV absorbers, antioxidants, antiseptics, antifungal agents, antialgae agents, antibacterial agents, flame retardants, insecticides, chemical adsorbents, hygroscopic substances, fragrances, pigments , Colorant, catalyst, photocatalyst, phosphorescent agent, fluorescent agent, glitter pigment, surfactant, etc.).

The resin-attached glass fiber fabric of the present invention is a resin-attached glass fiber fabric comprising a glass fiber fabric composed of glass yarn and a resin that adheres to at least a part of the surface of the glass fiber constituting the glass yarn. The glass yarn count is 20 to 70 tex, the thickness of the resin-attached glass fiber fabric is 0.08 mm or more, and the thickness (mm) and mass (g / m ² ) of the resin-attached glass fiber fabric. The apparent density of the resin-attached glass fiber woven fabric calculated from the above is 1.05-1.50 (g / cm ³ ), and the resin-attached glass fiber woven fabric is measured according to JIS R 3420: 2013 7.3. Since the ignition loss is 0.8 to 10% by mass, it is possible not to laminate the resin film as the ink receiving layer.

In the resin adhering glass fiber fabric of the present invention, the mass of the resin is not particularly limited, for example, 1 to 30 g / ^{m 2} can be mentioned, 1 to 10 g / ^{m 2} may be preferably mentioned. In addition, the mass of the resin is calculated by the following formula (B).
Resin mass (g / m ² ) = (mass of resin-attached glass fiber fabric measured according to JIS R 3420: 2013 7.2 (g / m ² )) × (ignition of resin-attached glass fiber fabric described above) Weight loss (mass%) ÷ 100 ... Formula (B)

As the air permeability of the resin-attached glass fiber fabric of the present invention, the viewpoint of making it easier to increase the apparent density, and making it difficult to see the color and pattern of the object on the side opposite to the ink receiving side of the resin-attached glass fiber fabric. From this viewpoint, 0.1 to 100 cm ³ / cm ² / second is preferable, 0.1 to 50 cm ³ / cm ² / second is more preferable, and 5 to ³⁰ cm ³ / cm ² / second is particularly preferable. The air permeability is measured and calculated according to JIS R 3420: 2013 7.13.

  It does not specifically limit as a manufacturing method of the resin adhesion glass fiber fabric of this invention. Preferable examples include, for example, (1) a step of weaving glass fiber fabric, (2) a heat cleaning step of subjecting the woven glass fiber fabric to a heat cleaning treatment as necessary, and (3) necessary for a heat-cleaned glass fiber fabric. A surface treatment step for applying a silane coupling agent or the like according to the method, a fiber opening treatment step for subjecting the glass fiber fabric obtained in (4), (1), (2) or (3) to a fiber opening treatment as necessary. (5) A resin impregnation step for impregnating the glass fiber fabric obtained in any one of the steps (1) to (4) into the resin solution, (6) (5) The resin solution was included immediately after the resin impregnation step. A manufacturing process including a pressing step of pressing a glass fiber fabric at a press pressure of 0.05 to 0.5 MPa, and (7) a drying step of drying a resin solution contained in the pressed glass fiber fabric immediately after the pressing step. Law, and the like.

  Among them, (1) a step of weaving a glass fiber fabric, (2) a resin impregnation step of impregnating the glass fiber fabric obtained in the steps of (1) into a resin solution without performing heat cleaning, (3) (2) Immediately after the resin impregnation step, a pressing step of pressing the glass fiber fabric containing the resin solution at a press pressure of 0.05 to 0.5 MPa, (4) drying the resin solution contained in the pressed glass fiber fabric immediately after the pressing step A production method including a drying step is more preferable. That is, when the heat cleaning treatment is not performed (that is, when a sizing agent component such as starch adheres to the glass fiber fabric), the glass fiber fabric is superior in flexibility compared to the one subjected to the treatment. It is easy to become a thing. And it becomes easy to raise an apparent density further by impregnating a resin solution in the state excellent in the softness | flexibility, pressing, and drying immediately after that.

(Characteristics of resin-attached glass fiber fabric)

(Non Flammable)
The resin-attached glass fiber woven fabric of the present invention is composed of glass yarns and has an ignition loss of 0.8 to 10% by mass, and thus has excellent nonflammability. From the viewpoint of further improving the nonflammability of the resin-attached glass fiber fabric of the present invention, the resin-attached glass fiber fabric of the present invention preferably satisfies the following requirements.
<Requirements>
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 in which the surface of the sheet is irradiated with radiant heat of 50 kW / m ² , the maximum heat generation rate does not exceed 200 kW / m ² for 20 minutes after the start of heating and does not exceed 200 kW / m ² for 20 minutes after the start of heating. The amount is 8 MJ / m ² or less.

  Examples of the method for satisfying the above requirements for the resin-attached glass fiber woven fabric of the present invention include adjustment of the amount of resin, selection of the type, and a resin composition containing a flame retardant. .

In addition, the film material of the present invention is a 4.10.2 exothermic test / evaluation method in the “Fireproof Performance Test / Evaluation Business Method” (modified on March 1, 2014) of the Building Materials Testing Center. In the exothermic test in which the surface of the sheet is irradiated with radiant heat of 50 kW / m ² from the radiant electric heater as measured in accordance with the above, it is more preferable that there is no 0.5 mm square or more through hole for 20 minutes after the start of heating. . As a method for easily satisfying this requirement, for example, the weaving density, the warp configuration, and the weft configuration are set so that the gap interval between the warp yarns and the gap interval between the weft yarns constituting the resin-attached glass fiber fabric are 0.5 mm or less. Adjustment, selection, etc. are mentioned.

(Tensile strength)
Although it does not restrict | limit especially as tensile strength of the resin adhesion glass fiber fabric of this invention, For example, the warp direction is 200-1200 N / 25mm, 500-1200 N / 25mm is mentioned preferably. Further, the weft direction is 100 to 1000 N / 25 mm, and preferably 300 to 1000 N / 25 mm. The tensile strength is in accordance with JIS R 3420: 2013 7.4.2, using a constant speed extension type tensile tester (manufactured by Intesco Corporation), the test piece length is 250 mm, and the test piece width (from both ends). The width before unwinding the thread) is 40 mm, the gripping interval is 100 mm, the width of the test piece (the width after unwinding the thread from both ends) is 25 mm, and the constant speed tensile speed is 50 mm / min. The warp direction (warp direction) and the weft direction (weft direction) are each measured five times, and the average value is taken as the tensile strength (N / 25 mm) in each of the warp direction and the weft direction.

(Use of resin-attached glass fiber fabric)
The resin-attached glass fiber woven fabric of the present invention has characteristics suitable for printing characters, symbols, designs and the like by gravure printing, and can be used as a gravure printing substrate. Especially, it can utilize more suitably as the to-be-printed object of the gravure printing using the resin-type ink which melt | dissolved resin in the solvent and disperse | distributed the pigment. A suitable resin-based ink is not particularly limited, and examples thereof include vinyl chloride ink, acrylic ink, and urethane ink. The resin-attached glass fiber fabric of the present invention is not limited to gravure printing, but can also be suitably used as a printing material such as other printing methods such as solvent inkjet printing and flexographic printing.

  Moreover, since the printed matter on which the gravure printing of the resin-attached glass fiber woven fabric of the present invention is excellent in nonflammability, it is suitable for building interior materials including the printed matter.

  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.

Example 1
As the warp and weft, ECE225 1/0 1Z (number 22.5 tex, single fiber diameter 7 μm, number of single fibers 200) manufactured by Unitika Glass Fiber Co., Ltd., warp density 60/25 mm, weft density 57 / Weaving was performed with a plain weave structure so as to be 25 mm to obtain a green glass cloth.

The raw glass cloth obtained was impregnated with the resin solution of the following formulation as it was without heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to conditions of a temperature of 180 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 60/25 mm, a weft density of 57/25 mm, a thickness of 0.09 mm, and a mass of 108 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.20 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 3.8% by mass. The ratio of the mass of the nonvolatile component of the acrylic acid-styrene copolymer and the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer in the obtained resin-attached glass fiber fabric was 2.4. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 25 cm ³ / cm ² / sec.
(Prescription 1)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 174 parts by mass Acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer represented by chemical formula (3) Mixture of polymer emulsion (non-volatile component 40%): 100 parts by mass Pure water: 726 parts by mass

(Example 2)
As the warp and weft, ECE225 1/0 1Z (number 22.5 tex, single fiber diameter 7 μm, number of single fibers 200) manufactured by Unitika Glass Fiber Co., Ltd., warp density 60/25 mm, weft density 57 / Weaving was performed with a plain weave structure so as to be 25 mm to obtain a green glass cloth.

The raw glass cloth obtained was impregnated with the resin solution of the following formulation as it was without heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to conditions of a temperature of 180 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 60/25 mm, a weft density of 57/25 mm, a thickness of 0.10 mm, and a mass of 109 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.09 g / cm ³ . Moreover, the ignition loss of the obtained resin adhesion glass fiber fabric was 4.5 mass%. The ratio of the mass of the nonvolatile component of the acrylic acid-styrene copolymer to the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer was 1.2. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 22 cm ³ / cm ² / sec.
(Prescription 1)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 174 parts by mass Acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer represented by chemical formula (3) Mixture of polymer emulsion (nonvolatile component 40%): 200 parts by mass Pure water: 626 parts by mass

(Example 3)
As the warp and weft, ECE225 1/0 1Z (number 22.5 tex, single fiber diameter 7 μm, number of single fibers 200) manufactured by Unitika Glass Fiber Co., Ltd., warp density 60/25 mm, weft density 57 / Weaving was performed with a plain weave structure so as to be 25 mm to obtain a green glass cloth.

The raw glass cloth obtained was impregnated with the resin solution of the following formulation as it was without heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to conditions of a temperature of 180 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 60/25 mm, a weft density of 57/25 mm, a thickness of 0.10 mm, and a mass of 110 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.10 g / cm ³ . Moreover, the loss on ignition of the obtained resin-attached glass fiber fabric was 5.6% by mass. The ratio of the mass of the nonvolatile component of the acrylic acid-styrene copolymer to the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer was 2.4. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 14 cm ³ / cm ² / sec.
(Prescription 1)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 296 parts by mass of acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer represented by chemical formula (3) Mixture of polymer emulsion (non-volatile component 40%): 170 parts by mass Pure water: 534 parts by mass

Example 4
As warps and wefts, ECG75 1/0 0.7Z (number 67.5 tex, single fiber diameter 9 μm, number of single fibers 400) manufactured by Unitika Glass Fiber Co., Ltd., warp density 44/25 mm, weft density 32 Weaving was carried out with a plain weave structure so as to have a length of 25 mm / 25 mm to obtain a green glass cloth.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 44/25 mm, a weft density of 32/25 mm, a thickness of 0.18 mm, and a mass of 213 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.18 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 3.6% by mass. The ratio of the mass of the nonvolatile component of the acrylic acid-styrene copolymer to the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer was 1.2. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 3 cm ³ / cm ² / sec.
(Prescription 1)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 217 parts by mass of acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer represented by chemical formula (3) Mixture of polymer emulsion (non-volatile component 40%): 250 parts by mass Pure water: 533 parts by mass

(Example 5)
As the warp and weft, ECE225 1/0 1Z (number 22.5 tex, single fiber diameter 7 μm, number of single fibers 200) manufactured by Unitika Glass Fiber Co., Ltd., warp density 60/25 mm, weft density 57 / Weaving was performed with a plain weave structure so as to be 25 mm to obtain a green glass cloth.

The raw glass cloth obtained was impregnated with the resin solution of the following formulation as it was without heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to conditions of a temperature of 180 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 60/25 mm, a weft density of 57/25 mm, a thickness of 0.09 mm, and a mass of 108 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.20 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 3.4 mass%. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 25 cm ³ / cm ² / sec.
(Prescription 1)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 174 parts by mass Pure water: 826 parts by mass

(Example 6)
As warps and wefts, ECG75 1/0 0.7Z (number 67.5 tex, single fiber diameter 9 μm, number of single fibers 400) manufactured by Unitika Glass Fiber Co., Ltd., warp density 44/25 mm, weft density 32 Weaving was carried out with a plain weave structure so as to have a length of 25 mm / 25 mm to obtain a green glass cloth.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber fabric has a warp density of 44/25 mm, a weft density of 32/25 mm, a thickness of 0.18 mm, and a mass of 211 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.17 g / cm ³ . Moreover, the ignition loss of the obtained resin adhesion glass fiber fabric was 2.5 mass%. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 7 cm ³ / cm ² / sec.
(Prescription 1)
Mixture of acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer emulsion represented by chemical formula (3) (non-volatile component 40%): 100 parts by mass Pure water: 900 parts by mass

(Example 7)
As warps and wefts, ECG75 1/0 0.7Z (number 67.5 tex, single fiber diameter 9 μm, number of single fibers 400) manufactured by Unitika Glass Fiber Co., Ltd., warp density 44/25 mm, weft density 32 Weaving was carried out with a plain weave structure so as to have a length of 25 mm / 25 mm to obtain a green glass cloth.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 44/25 mm, a weft density of 32/25 mm, a thickness of 0.18 mm, and a mass of 213 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.18 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 3.2 mass%. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 5 cm ³ / cm ² / sec.
(Prescription 1)
Mixture of acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer emulsion represented by chemical formula (3) (non-volatile component 40%): 200 parts by mass Pure water: 800 parts by mass

(Example 8)
As the warp and weft, ECE225 1/0 1Z (number 22.5 tex, single fiber diameter 7 μm, number of single fibers 200) manufactured by Unitika Glass Fiber Co., Ltd., warp density 60/25 mm, weft density 57 / Weaving was performed with a plain weave structure so as to be 25 mm to obtain a green glass cloth.

The raw glass cloth obtained was impregnated with the resin solution of the following formulation as it was without heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to conditions of a temperature of 180 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 60/25 mm, a weft density of 57/25 mm, a thickness of 0.10 mm, and a mass of 110 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.10 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 4.0% by mass. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 20 cm ³ / cm ² / sec.
(Prescription 1)
Mixture of acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer emulsion represented by chemical formula (3) (non-volatile component 40%): 377 parts by mass Pure water: 623 parts by mass

Example 9
As warps and wefts, ECG75 1/0 0.7Z (number 67.5 tex, single fiber diameter 9 μm, number of single fibers 400) manufactured by Unitika Glass Fiber Co., Ltd., warp density 32/25 mm, weft density 25 Weaving was carried out with a plain weave structure so as to have a length of 25 mm / 25 mm to obtain a green glass cloth.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.2 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber fabric has a warp density of 32/25 mm, a weft density of 25/25 mm, a thickness of 0.15 mm, and a mass of 160 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.07 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 3.5% by mass. The ratio of the mass of the nonvolatile component of the acrylic acid-styrene copolymer to the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer was 1.2. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 70 cm ³ / cm ² / sec.
(Prescription)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 174 parts by mass Acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer represented by chemical formula (3) Mixture of polymer emulsion (nonvolatile component 40%): 200 parts by mass Pure water: 626 parts by mass

(Example 10)
As warps and wefts, ECG75 1/0 0.7Z (number 67.5 tex, single fiber diameter 9 μm, number of single fibers 400) manufactured by Unitika Glass Fiber Co., Ltd., warp density 31/25 mm, weft density 25 Weaving was carried out with a plain weave structure so as to have a length of 25 mm / 25 mm to obtain a green glass cloth.

The obtained green machine glass cloth was impregnated with the resin solution of the following formulation as it was without performing heat cleaning treatment, and then pressed twice with a nip roll at a pressure of 0.2 MPa. It was made to dry on conditions for 5 minutes, and the resin adhesion glass fiber fabric of this invention was obtained. The obtained resin-attached glass fiber fabric has a warp density of 31 yarns / 25 mm, a weft density of 25 yarns / 25 mm, a thickness of 0.11 mm, and a mass of 155 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.41 g / cm ³ . Moreover, the loss on ignition of the obtained resin-attached glass fiber fabric was 2.8% by mass. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 95 cm ³ / cm ² / sec.
(Prescription)
Mixture of acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer emulsion represented by chemical formula (3) (non-volatile component 40%): 416 parts by mass Pure water: 584 parts by mass

(Example 11)
As warps and wefts, ECG75 1/0 0.7Z (number 67.5 tex, single fiber diameter 9 μm, number of single fibers 400) manufactured by Unitika Glass Fiber Co., Ltd., warp density 44/25 mm, weft density 32 Weaving was carried out with a plain weave structure so as to have a length of 25 mm / 25 mm to obtain a green glass cloth.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber fabric has a warp density of 44/25 mm, a weft density of 32/25 mm, a thickness of 0.19 mm, and a mass of 225 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.18 g / cm ³ . Moreover, the ignition loss of the obtained resin adhesion glass fiber fabric was 10.0 mass%. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 2 cm ³ / cm ² / sec.
(Prescription)
Acrylic acid-styrene copolymer emulsion (acrylic acid-butyl acrylate-styrene copolymer emulsion, non-volatile component 50%): 850 parts by mass Pure water: 150 parts by mass

(Comparative Example 1)
Unita Glass Fiber Co., Ltd. ECG150 1/0 1Z (number 33.7 tex, single fiber diameter 9 μm, number of single fibers 200) was used as the weft, and Unita Glass Fiber Co., Ltd. ECG75 1/0 0.7Z. Weaving with a plain weave structure so that the warp density is 30/25 mm and the weft density is 20/25 mm using a count (67.5 tex, single fiber diameter 9 μm, number of single fibers 400) to obtain a raw glass cloth It was.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 30/25 mm, a weft density of 20/25 mm, a thickness of 0.11 mm, and a mass of 98 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 0.89 g / cm ³ . Moreover, the ignition loss of the obtained resin adhesion glass fiber fabric was 4.5 mass%. The ratio of the mass of the nonvolatile component of the acrylic acid-styrene copolymer to the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer was 1.2. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 170 cm ³ / cm ² / sec.
(Prescription 1)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 174 parts by mass Acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer represented by chemical formula (3) Mixture of polymer emulsion (non-volatile component 40%): 304 parts by mass Pure water: 522 parts by mass

(Comparative Example 2)
As warps and wefts, ECG150 1/0 1Z (number 33.7 tex, single fiber diameter 9 μm, number of single fibers 200) manufactured by Unitika Glass Fiber Co., Ltd., warp density 39/25 mm, weft density 32 / Weaving was performed with a plain weave structure so as to be 25 mm to obtain a green glass cloth.

The raw glass cloth obtained was impregnated with the resin solution of the following formulation as it was without heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to conditions of a temperature of 180 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber woven fabric has a warp density of 39/25 mm, a weft density of 32/25 mm, a thickness of 0.11 mm, and a mass of 100 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 0.91 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 4.0% by mass. The ratio of the mass of the nonvolatile component of the acrylic acid-styrene copolymer to the mass of the nonvolatile component of the ethylene-vinyl acetate copolymer was 1.2. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 130 cm ³ / cm ² / sec.
(Prescription 1)
Ethylene-vinyl acetate copolymer emulsion represented by chemical formula (1) (non-volatile component 56%): 174 parts by mass Acrylic acid-styrene copolymer emulsion represented by chemical formula (2) and acrylic acid-styrene copolymer represented by chemical formula (3) Mixture of polymer emulsion (nonvolatile component 40%): 200 parts by mass Pure water: 626 parts by mass

(Comparative Example 3)
As warps and wefts, ECD450 1/0 1Z (number 11.2 tex, single fiber diameter 5 μm, number of single fibers 200) manufactured by Unitika Glass Fiber Co., Ltd., warp density 60/25 mm, weft density 47 / Weaving was performed with a plain weave structure so as to be 25 mm to obtain a green glass cloth. The obtained glass cloth had a thickness of 0.06 mm and a mass of 49 g / m ² , and an apparent density calculated from the thickness and the mass was 0.82 g / cm ³ .

(Comparative Example 4)
As warps and wefts, ECG37 1/0 0.7Z (count 135tex, single fiber diameter 9 μm, number of single fibers 800) manufactured by Unitika Glass Fiber Co., Ltd., warp density 33/25 mm, weft density 30 / Weaving with a satin weave structure to a thickness of 25 mm gave a green glass cloth.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber fabric has a warp density of 33/25 mm, a weft density of 30/25 mm, a thickness of 0.30 mm, and a mass of 370 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.23 g / cm ³ . Moreover, the ignition loss of the obtained resin-attached glass fiber fabric was 8.0% by mass. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 5 cm ³ / cm ² / sec.
(Prescription)
Acrylic acid-styrene copolymer emulsion (acrylic acid-butyl acrylate-styrene copolymer emulsion, non-volatile component 50%): 850 parts by mass Pure water: 150 parts by mass

(Comparative Example 5)
Unita Glass Fiber Co., Ltd. ECG37 1/0 0.7Z (number 135 tex, single fiber diameter 9 μm, number of single fibers 800) was used as the weft, and Unita Glass Fiber Co., Ltd. ECG75 1/0 0.7Z. (67.5 tex, single fiber diameter 9 μm, number of single fibers 400), weaving in a plain weave structure so that the warp density is 50/25 mm and the weft density is 40/25 mm, to obtain a raw glass cloth It was.

The obtained raw glass cloth was impregnated with the resin solution having the following formulation as it was without performing heat cleaning treatment, and then pressed with a nip roll at a pressure of 0.1 MPa, and the pressed glass cloth was subjected to a temperature of 200 ° C. for 5 minutes. The resin-attached glass fiber fabric of the present invention was obtained. The obtained resin-attached glass fiber fabric has a warp density of 50/25 mm, a weft density of 40/25 mm, a thickness of 0.36 mm, and a mass of 415 g / m ^2, which is calculated from the thickness and the mass. The apparent density was 1.15 g / cm ³ . Moreover, the loss on ignition of the obtained resin-attached glass fiber fabric was 8.5% by mass. Moreover, the air permeability of the obtained resin-attached glass fiber fabric was 6 cm ³ / cm ² / sec.
(Prescription)
Acrylic acid-styrene copolymer emulsion (acrylic acid-butyl acrylate-styrene copolymer emulsion, non-volatile component 50%): 850 parts by mass Pure water: 150 parts by mass

(Evaluation method)
1. Loss on ignition (mass%)
About the resin adhesion glass fiber fabric obtained by each Example and the comparative example, it measured and computed according to JISR3420: 20137.3.

2. Nonflammability Regarding the resin-attached glass fiber woven fabric obtained in each of the Examples and Comparative Examples, 4 in the “Fireproof and Fireproof Performance Test and Evaluation Business Method” (modified on March 1, 2014) of the Building Materials Testing Center .10.2 In the exothermic test where the surface of the sheet is irradiated with 50 kW / m ² of radiant heat measured according to the exothermic test / evaluation method, (1) the maximum exothermic rate is 20 minutes after the start of heating. Continued for 10 seconds or more and did not exceed 200 kW / m ² , (2) The total calorific value for 20 minutes after the start of heating was 8 MJ / m ² or less, (3) 20 minutes after the start of heating, 0.5 mm square or more The case where there was no through-hole was evaluated as ◯, and the case where any one of the three requirements (1) to (3) was not satisfied was evaluated as x.

3. Breathability (cm ³ / cm ² / sec)
The resin-attached glass fiber woven fabric obtained in each example and comparative example was measured and calculated according to JIS R 3420: 2013 7.13.

4). Tensile strength (N / 25mm)
According to JIS R 3420: 2013 7.4.2, using a constant speed extension type tensile tester (manufactured by Intesco Corporation), the length of the test piece is 250 mm, the width of the test piece (the width before loosening the yarn from both ends) Was 40 mm, the grip interval was 100 mm, the width of the test piece (the width after loosening the yarn from both ends) was 25 mm, and the constant speed tensile speed was 50 mm / min. The resin-attached glass fiber fabric was measured five times for the warp direction (warp direction) and the weft direction (weft direction), and the average value was taken as the tensile strength (N / 25 mm) in the warp direction and the weft direction.

5. Printability Using the obtained resin-attached glass fiber fabric as a printing material, using a printing bureau type gravure printing tester (manufactured by Kumagai Riki Co., Ltd.), using a solvent-based polyurethane resin ink manufactured by Toyo Color Co., Ltd. Monochrome printing was performed on the test piece using a printing plate, and the following (1) to (3) were visually evaluated and evaluated by five panelists.
(1) Sharpness of printing The printed matter was evaluated according to the following criteria in a state where the printed matter was separated by 50 cm. Three or more points were accepted.
5 points: The outline of the printed part was very clear, the color of the image was as designed, and the sharpness was particularly excellent.
4 points: Although the outline of the printed part is slightly blurred, the color of the image is almost as designed and excellent in sharpness.
3 points: There is a portion where the outline of the printing portion is blurred, and although it is recognized that the color of the image is slightly thinner than the design, the sharpness is at a level that does not cause any problem in practice.
2 points: It was recognized that the outline of the printed part was blurred and the color of the image was thinner than the design, and the sharpness was at a somewhat problematic level in practical use.
1 point: The outline of the printed part is blurred, the color of the image is considerably thinner than the design, and the sharpness is at a level that is problematic in practice.
(2) Degree of show-through
Place a thousand yen bill on the desk, place the resin-attached glass fiber fabric printed above about 50 cm above the thousand yen bill, and place the resin-attached glass fiber from 10 cm above the resin-attached glass fiber fabric. You can see the thousand-yen bill through the fabric and see the existence of the thousand-yen bill. Was evaluated based on whether or not it could be read clearly. The evaluation criteria are as follows. From the viewpoint of practicality, in the present invention, three or more points were accepted.
5 points: The existence of a thousand yen bill was not seen, and there was no show-through.
4 points: The existence of a thousand yen bill could be confirmed thinly, but the characters of “thousand yen”, “Bank of Japan” and serial numbers could not be confirmed, and the show-through was sufficiently prevented.
3 points: The existence of a thousand yen bill can be confirmed, and although the characters “thousand yen” can be seen thinly, the “Bank of Japan note” and serial number characters cannot be confirmed, and the degree of show-through is visible There was no problem with sex.
2 points: The existence of a thousand yen bill could be confirmed, the characters “1000 yen” and “Bank of Japan Banknote” were confirmed to be thin, and the degree of show-through was at a slightly problematic level in the visibility of the printed surface.
1 point: The existence of a thousand yen bill can be confirmed, the characters of “thousand yen”, “Banknotes”, and serial numbers are confirmed to be thin, and the degree of show-through is at a level that is problematic for the visibility of the printed surface. It was.
(3) Ink fixing property After printing, the printed surface of the resin-attached glass fiber fabric dried at 70 ° C. for 30 seconds was rubbed with the printed image of the resin-attached glass fiber fabric before and after being lightly rubbed with a white non-woven fabric. The nonwoven fabric was evaluated according to the following criteria. Three or more points were accepted.
5: The blue color of the ink adhering to the resin-adhered glass fiber fabric was not reflected on the nonwoven fabric, and no change was observed in the printed image of the resin-adhered glass fiber fabric.
Four points: Although the blue color of the ink adhering to the resin-adhered glass fiber woven fabric was slightly visible on the nonwoven fabric, no change was observed in the printed image of the resin-adhered glass fiber woven fabric.
3 points ... Although the blue color of the ink adhering to the resin-attached glass fiber fabric is slightly reflected on the non-woven fabric, the printed image of the resin-attached glass fiber fabric is slightly discolored at the portion where the non-woven fabric is rubbed. The level was practically acceptable.
2 points: The blue color of the ink adhering to the resin-attached glass fiber fabric is reflected on the non-woven fabric, and the printed image of the resin-attached glass fiber fabric is slightly discolored at the level where the non-woven fabric is rubbed. there were.
1 point: The blue color of the ink adhering to the resin-adhered glass fiber fabric appears on the non-woven fabric, and the printed image of the resin-adhered glass fiber fabric slightly discolors the part where the non-woven fabric is rubbed. Met.

  Table 1 shows the physical properties and the like of the resin-attached glass fiber fabrics of Examples 1 to 11 and Comparative Examples 1 to 5.

The resin-attached glass fiber woven fabrics of Examples 1 to 11 are glass fiber woven fabrics composed of glass yarns, and the glass yarn counts are 20 to 70 tex, and the thickness of the glass fiber woven fabrics is 0.08 mm or more. The apparent density calculated from the thickness (mm) and mass (g / m ² ) of the glass fiber fabric is 1.05 to 1.50 (g / cm ³ ), and constitutes the glass yarn Since the loss on ignition of the glass fiber woven fabric, which includes a resin on the glass fiber surface and is measured according to JIS R 3420, is 0.8 to 10% by mass, a clear pattern or the like appears when printed by gravure printing. It was possible to make it difficult to see the color and pattern of the attached wall and the like.

  When Example 1 is compared with Example 5 or Example 8, Example 1 is that the resin contained in the glass fiber surface contains an acrylic acid-styrene copolymer and an ethylene-vinyl acetate copolymer. Therefore, while being excellent in ink fixability and excellent in solvent resistance, the resin-adhered glass fiber fabric is less likely to be misaligned, and is excellent in sharpness of a printed image. Among Examples 1 to 4 and 9, in which the resin contained on the glass fiber surface includes an acrylic acid-styrene copolymer and an ethylene-vinyl acetate copolymer, Examples 1 and 3 are ethylene-vinyl acetate copolymer. The mass ratio of the non-volatile component of the polymer and the acrylic acid-styrene copolymer (the mass of the non-volatile component of the ethylene-vinyl acetate copolymer / the mass of the non-volatile component of the acrylic acid-styrene copolymer) is 2.0 to 3.0. Therefore, the ink fixing property was further improved while being further improved in sharpness. Moreover, when Example 4, 6 or 7 and Example 10 are compared, since Example 4, 6 or 7 had an ignition loss of 1.0 to 5.0% by mass, tackiness was also improved. It was good and made it possible to express a clearer pattern or the like.

On the other hand, in Comparative Examples 1 and 2, since the apparent density of the resin-attached glass fiber fabric is less than 1.05 (g / cm ³ ), the contact with the concave portion and the non-recessed portion of the plate cylinder during printing is repeated. The resin-attached glass fiber fabric slightly moved in the thickness direction and the like, and as a result, it was impossible to display a clear pattern or the like.

In Comparative Example 3, since the apparent density of the glass fiber fabric is less than 1.05 (g / cm ³ ), the thickness of the glass fiber fabric is increased by repeated contact with the recesses and non-recesses of the plate cylinder during printing. It moved slightly in the direction, etc., and as a result, it was impossible to show a clear pattern or the like. In addition, since Comparative Example 3 includes a glass yarn count of less than 20 tex, and the thickness of the glass fiber fabric is less than 0.08 mm, the glass fiber fabric is on the side opposite to the ink receiving side. It was difficult to see through the color and pattern, and there was a problem in the visibility of the pattern and the like applied to the glass fiber fabric when viewed from the ink receiving side.

  In Comparative Examples 4 and 5, since the glass yarn count exceeds 70 tex, the resulting resin-attached glass fiber fabric is inferior in smoothness, and the ink accumulated in the recesses of the gravure printing cylinder is sufficiently transferred. It was not possible to show clear symbols.

Claims (10)

A glass fiber fabric composed of glass yarn,
A resin-attached glass fiber fabric comprising a resin attached to at least a part of the glass fiber surface constituting the glass yarn,
The glass yarn count is 20 to 70 tex,
The thickness of the resin-attached glass fiber fabric is 0.08 mm or more,
The apparent density of the resin-attached glass fiber fabric calculated from the thickness (mm) and mass (g / m ² ) of the resin-attached glass fiber fabric is 1.05-1.50 (g / cm ³ ),
Resin-attached glass fiber woven fabric, in which the loss on ignition of the resin-attached glass fiber fabric measured in accordance with JIS R 3420: 2013 7.3 is 0.8 to 10% by mass.   The resin-attached glass fiber woven fabric according to claim 1, wherein the weft density of the warp and weft of the resin-attached glass fiber woven fabric is 15 to 120 pieces / 25 mm. Mass of 70 to 450 / ^{m 2,} resin adhesion glass fiber fabric according to claim 1 or 2. The resin-attached glass fiber woven fabric according to any one of claims 1 to 3, wherein the air permeability is 0.1 to 50 cm ³ / cm ² / sec.   The resin-attached glass fiber fabric according to any one of claims 1 to 4, wherein the resin includes an acrylic acid-styrene copolymer and an ethylene-vinyl acetate copolymer. Ratio of mass of nonvolatile component of acrylic acid-styrene copolymer to mass of nonvolatile component of ethylene-vinyl acetate copolymer (mass of ethylene-vinyl acetate copolymer (g / m ² ) / acrylic acid-styrene) The resin-attached glass fiber woven fabric according to claim 5, wherein the copolymer has a mass (g / m ² ) of 1.0 to 3.0. 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 in which the surface of the sheet is irradiated with radiant heat of 50 kW / m ² , the maximum heat generation rate does not exceed 200 kW / m ² for 20 minutes after the start of heating and does not exceed 200 kW / m ² for 20 minutes after the start of heating. The resin-attached glass fiber fabric according to any one of claims 1 to 6, wherein the amount is 8 MJ / m ² or less.   The resin-attached glass fiber woven fabric according to any one of claims 1 to 7, which is used as a substrate for gravure printing.   The printed matter by which the gravure printing was given to the resin adhesion glass fiber fabric of any one of Claims 1-8.   A building interior material including the printed matter according to claim 9.