KR101645072B1 - Method for producing fiber composite resin layer-containing multilayered sheet, and optical device - Google Patents

Abstract

According to the present invention, there is provided a method for producing a multilayer sheet comprising a transparent fiber composite resin layer excellent in gas barrier property by forming a dense inorganic film on a transparent fiber-reinforced composite resin sheet. In the method for producing a multilayer sheet containing a transparent fiber composite resin layer according to the present invention, a multilayer original sheet containing a transparent fiber composite resin sheet or a transparent fiber composite resin layer is heated to form a transparent multi- A transparent inorganic film is formed on at least one surface. The heating is preferably carried out such that the temperature of the multi-layer original sheet containing the transparent fiber composite resin sheet or the transparent fiber composite resin layer is not lower than 150 ° C and not higher than the "deterioration temperature of the resin component".

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing a multilayer sheet containing a fiber composite resin layer,

The present invention relates to a method of producing a multilayer sheet containing a fiber composite resin layer and an optical device using the multilayer sheet containing a fiber composite resin layer obtained by the same manufacturing method as a substrate.

The present application claims priority based on Japanese Patent Application No. 2011-126055 filed on June 6, 2011, the contents of which are incorporated herein by reference.

A method of producing a highly transparent gas barrier film excellent in transmittance, vapor barrier property and oxygen barrier property by forming a metal oxide layer on a polymer film by a sputtering method " has been proposed in the past (see, for example, Patent Publication No. 2000-192237). The high transparency gas barrier film obtained by the above-described method is used not only in the field of packaging, but also in the fields of electronics such as liquid crystal display devices, solar cells, electromagnetic wave shields, touch panels, organic EL, And is also used as a film or a substrate.

Japanese Patent Application Laid-Open No. 2000-192237 Japanese Laid-Open Patent Publication No. 2010-043199 Japanese Patent Application Laid-Open No. 2007-224270

[0003] Recently, as a transparent resin sheet for the above-described electronic products, transparent resin is reinforced with a fiber sheet typified by a glass fabric or a glass fabric such as a glass nonwoven fabric (hereinafter, Fiber composite resin sheet ") is widely known (see, for example, JP-A-2010-043199 and JP-A-2007-224270). It is an object of the present invention to provide a method for producing a multilayer sheet comprising a transparent fiber composite resin layer which is superior in gas barrier property by forming a dense inorganic film on a sheet of such a transparent fiber-reinforced resin sheet.

(1) In the method for producing a multilayer sheet containing a transparent fiber composite resin layer according to the present invention, a multilayer original sheet containing a transparent fiber composite resin sheet or a transparent fiber composite resin layer is heated to form a transparent multi- A transparent inorganic film is formed on at least one side of the original sheet. Here, the " transparent fiber composite resin sheet " means a sheet composed of only a transparent fiber composite resin layer. Further, the " multilayer original sheet containing a transparent fiber composite resin layer " means a transparent multi-layer original sheet containing a transparent fiber composite resin layer. In the method for producing a multilayer sheet containing a transparent fiber composite resin layer, it is preferable that the temperature of the multilayer original sheet containing a transparent fiber-reinforced resin sheet or the transparent fiber composite resin layer is 150 ° C or higher "the deterioration temperature (decomposition temperature, softening temperature , Glass transition temperature, etc.) " or less. This is because a dense transparent inorganic film can be formed without deteriorating the resin. From the viewpoint of being advantageous for further densifying the transparent inorganic film, the heating temperature is more preferably 180 ° C or higher, and further preferably 200 ° C or higher.

For this reason, in the method for producing a multilayer sheet containing a transparent fiber composite resin layer, a dense inorganic film is formed on at least one side of a transparent fiber-reinforced composite resin sheet or a multilayer original sheet containing a transparent fiber composite resin layer. Therefore, the transparent-fiber composite resin layer-containing multilayer sheet obtained by the multilayer sheet production method containing the transparent fiber composite resin layer can exhibit higher gas barrier properties than the conventional transparent multilayer composite resin layer-containing multilayer sheet. In addition, the multilayer original sheet containing the transparent fiber composite resin sheet or the transparent fiber composite resin layer has a sufficiently low coefficient of linear expansion (CTE) as compared with a single resin film. Therefore, in this method for producing a multilayer sheet containing a transparent fiber composite resin layer, cracks generated in the transparent inorganic film can be reduced.

(2) In the method for producing a multilayer sheet containing a transparent fiber composite resin layer described in (1) above, the transparent inorganic film is preferably formed by sputtering, chemical vapor deposition (CVD), or ion plating.

(3) In the method for producing a multilayer sheet containing a transparent fiber composite resin layer described in the above (1) or (2), the transparent inorganic film may be at least one selected from the group consisting of aluminum (Al) Of atoms.

(4) In the method for producing a multilayer sheet containing a transparent fiber composite resin layer as described in the above items (1) to (3), the transparent inorganic film is at least one selected from the group consisting of aluminum (Al) Of oxides, nitrides or oxynitrides containing atoms of silicon atoms.

(5) In the method for producing a multilayer sheet containing a transparent fiber composite resin layer described in the above (1) to (4), the fiber sheet in the multilayer original sheet containing a transparent fiber- desirable. It is more preferable that the glass woven fabric includes a plurality of first glass fibers and a plurality of second glass fibers. Here, the term "in the glass fiber" is, for example, a glass yarn, and the first glass fiber is oriented in the first direction. The second glass fiber bundle is woven into the first glass fiber along a direction (hereinafter referred to as a "second direction") that is substantially perpendicular to the first direction as seen in plan view. In this glass woven fabric, the ratio of the cross-sectional area of the glass component in the first glass fiber bundle per unit width to the cross-sectional area of the glass component in the second glass fiber bundle per unit width is more preferably 1.04 or more and 1.40 or less. Here, the cross-sectional area of the glass component refers to the sum of the cross-sectional areas of the glass filaments constituting the glass fiber (glass yarn).

(6) In the method for producing a multilayer sheet containing a transparent fiber composite resin layer described in (5), the cross-sectional area of the glass component in the first glass fiber is substantially equal to the cross-sectional area of each glass component in the second glass fiber desirable. In this case, the ratio of the number of the first glass fibers per unit width to the number of the second glass fibers per unit width is more preferably 1.02 or more and 1.18 or less.

In the optical device according to the present invention, the multilayer sheet containing a transparent fiber composite resin layer obtained by the multilayer sheet production method comprising a transparent fiber composite resin layer according to any one of the above-mentioned (1) to (6) is used as a substrate. The "optical device" referred to here is, for example, a display device such as a liquid crystal display or an organic EL display, or a display illumination device such as an organic EL light.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a simplified block diagram of an apparatus for producing a multilayer sheet containing a transparent fiber composite resin layer according to an embodiment of the present invention. FIG.
2 is a cross-sectional view of a multilayer sheet containing a transparent fiber composite resin layer according to an embodiment of the present invention.
3 is a cross-sectional view of a multilayer sheet containing a transparent fiber composite resin layer according to Modification (A).
4 is a simplified block diagram of an apparatus for producing a multilayer sheet containing a transparent fiber composite resin layer according to Modification (B).
5 is a simplified block diagram of an apparatus for producing a multilayer sheet containing a transparent fiber composite resin layer according to Modification (C).

In the method for producing a multilayer sheet containing a transparent fiber composite resin layer according to the embodiment of the present invention, in the state that the multilayer original sheet (Sb) containing a transparent fiber composite resin layer is directly heated, A transparent inorganic film 153 is formed on the sheet Sb to produce a multilayer sheet Sa containing a transparent fiber composite resin layer (see Fig. 2). Hereinafter, a concrete apparatus for realizing such a method for producing a multilayer sheet containing a transparent fiber composite resin layer will be described.

<Multilayer Sheet Production Apparatus Containing Transparent Fiber Composite Resin Layer>

As shown in Fig. 1, an apparatus 100 for producing a multilayer sheet having a transparent fiber composite resin layer mainly comprises a vacuum chamber 110 and a multilayer sheet production section 120 including a transparent fiber composite resin layer. Hereinafter, the vacuum chamber 110 and the multilayer sheet production section 120 including a transparent fiber composite resin layer will be described in detail.

(1) Vacuum chamber

The vacuum chamber 110 is a highly airtight chamber and includes a multilayer sheet production section 120 having a transparent fiber composite resin layer inside. In addition, the vacuum chamber 110 is once in a sufficiently vacuum state. Thereafter, after a necessary amount of inert gas (such as argon or nitrogen) is introduced into the vacuum chamber 110 (for example, after an inert gas is introduced until a predetermined pressure is reached) The manufacture of the multilayer sheet Sa (see Fig. 2) is disclosed.

(2) Multilayer sheet production unit containing a transparent fiber composite resin layer

1, the multilayer sheet production section 120 having a transparent fiber composite resin layer mainly comprises a feed roll 121, a main roll 129, a first sub roll 122, a second sub roll 123 ), A take-up roll 124 and a target 125. [

The feeding roll 121 feeds the multilayer original sheet Sb (see Fig. 2) containing a transparent fiber composite resin layer toward the first sub-roll 122. [ In the present embodiment, the multi-layered original sheet Sb containing a transparent fiber composite resin layer is composed of a transparent fiber composite resin layer 151 and a planarization resin layer 152 as shown in Fig. The transparent fiber composite resin layer 151 is formed of a transparent resin composition 151b having a glass cloth 151a and a refractive index substantially equal to the refractive index of the glass cloth 151a.

The first sub-roll 122 guides the multi-layered original sheet Sb containing the transparent fiber composite resin layer fed from the feed roll 121 to the main roll 129.

The main roll 129 has a heating source (not shown) therein and sends the multi-layer original sheet Sb containing the transparent fiber composite resin layer to the opposite position of the target 125 while heating. The transparent inorganic film 153 (see FIG. 2) is formed on the multi-layered original sheet Sb containing the transparent fiber composite resin layer sputtered near the target 125, and the intended transparent resin multi- Sa). The multilayer sheet Sa containing the transparent fiber composite resin layer is sent by the main roll 129 until reaching the second sub-roll 123.

As a method of heating the multi-layered original sheet Sb containing a transparent fiber composite resin layer, a method of forming a heat source in the vicinity of the surface of the main roll 129 in place of the method of forming a heating source in the main roll 129 described above A method of disposing an external heater or the like.

The second sub-roll 123 guides the multilayer sheet Sa containing the transparent fiber composite resin layer fed from the main roll 129 to the take-up roll 124.

The winding roll 124 winds the multilayer sheet Sa containing a transparent fiber composite resin layer.

The target 125 is a piece of oxide, nitride, or nitride oxide such as aluminum (Al), silicon (Si), or the like. When an inert gas ionized by a high voltage impinges on the target 125, atoms on the surface of the target 125 are splashed and attached on the multi-layered original sheet Sb containing a transparent fiber composite resin layer, The intended transparent inorganic film 153 is formed on the multilayer disc sheet Sb having the layer.

The formation of the transparent inorganic film 153 is not limited to the sputtering method described above, and for example, a reactive sputtering method, an ion plating method, a chemical vapor deposition method (CVD), or the like may be used.

<Details of Multilayer Sheet Containing Transparent Fiber Composite Resin Layer>

Next, as shown in Fig. 2, the multilayer sheet Sa having a transparent fiber composite resin layer is composed of a transparent fiber composite resin layer 151, a planarization resin layer 152 and a transparent inorganic film 153. [ Hereinafter, the transparent fiber composite resin layer 151, the flattening resin layer 152 and the transparent inorganic film 153 will be described in detail.

(1) Transparent fiber composite resin layer

The transparent fiber composite resin layer 151 is formed of the resin composition 151b having the refractive index substantially equal to the refractive index of the glass cloth 151a and the glass cloth 151a as described above. Hereinafter, the glass cloth 151a and the resin composition 151b will be described in detail.

(A) Glass fabric

Examples of the glass fabric 151a include glass woven fabric and glass nonwoven fabric. When the glass fabric 151a is a glass fabric, the fabric structure of the glass fabric includes plain fabric, mat fabric, jute fabric, and twill fabric. Examples of the material of the glass fiber constituting the glass fabric include E glass, C glass, A glass, S glass, D glass, T glass, NE glass, quartz glass, low induction ratio glass and intrinsic viscosity glass.

(a) When a glass fabric is used as the glass fabric 151a, it is preferable that the glass fabric comprises a plurality of first glass fibers and a plurality of second glass fibers. The term &quot; in the glass fiber &quot; is glass yarn. The first glass fiber bundle is oriented in the first direction. The second glass fiber bundle is woven into the first glass fiber along a direction (hereinafter referred to as a "second direction") that is substantially perpendicular to the first direction as seen in plan view. In this glass woven fabric, the ratio of the cross-sectional area of the glass component in the first glass fiber bundle per unit width to the cross-sectional area of the glass component in the second glass fiber bundle per unit width is more preferably 1.04 or more and 1.40 or less. Here, the cross-sectional area of the glass component refers to the sum of the cross-sectional areas of the glass filaments constituting the glass fiber (glass yarn).

In this glass woven fabric, the ratio of the cross-sectional area of the glass component in the first glass fiber bundle per unit width to the cross-sectional area of the glass component in the second glass fiber bundle per unit width is preferably 1.04 or more and 1.40 or less. Therefore, when the glass woven fabric is processed into a multilayer sheet containing a transparent fiber composite resin layer, the difference in linear expansion coefficient between the longitudinal direction and the transverse direction can be sufficiently reduced.

Therefore, when the glass woven fabric is processed into a multilayer sheet containing a transparent fiber composite resin layer, it is possible to reduce the haze value of the multilayer sheet containing a transparent fiber composite resin layer, The difference in the coefficient of linear expansion in the direction and the transverse direction can be sufficiently reduced. By reducing the difference in the coefficient of linear expansion, it is possible to reduce the deformation difference when the barrier is laminated, thereby reducing the optical anisotropy due to the deformation difference. Therefore, this glass woven fabric can impart "additional transparency", "uniformity of linear expansion coefficient in the longitudinal and transverse directions" and "reduction of optical anisotropy derived from deformation difference" to the multilayered sheet containing a transparent fiber composite resin layer have.

(b) It is preferable that, in the glass woven fabric according to (a), the cross-sectional area of each glass component in the first glass fiber is substantially equal to the cross-sectional area of each glass component in the second glass fiber. In this case, the ratio of the number of the first glass fibers per unit width to the number of the second glass fibers per unit width is preferably 1.02 or more and 1.18 or less.

According to the above, the glass woven fabric can obtain the same effect as the glass woven fabric related to the aforementioned (a) with only the glass fibers of the same thickness. Therefore, the manufacturing cost of the glass woven fabric, that is, the transparent glass fiber composite resin sheet can be kept low.

In order to obtain a transparent glass fiber composite resin sheet as described above, the cross-sectional area ratio or number ratio of the glass fibers or glass fibers described above may be set in a range of 80% or more of the entire glass cloth.

(B) Resin composition

Examples of the resin composition 151b include an epoxy resin, an acrylic resin, a phenol resin, a cyanate resin, and a blend resin thereof. As the epoxy resin, for example, an alicyclic epoxy resin can be mentioned. Examples of the acrylic resin include thermosetting or photo-curable acrylic resins.

When an epoxy resin is used as the resin composition 151b, it is preferable to use an alicyclic epoxy resin represented by the following general formula (A) having an alicyclic structure from the viewpoint of achieving both transparency and heat resistance.

[Chemical Formula 1]

(In the formula, -X- is, -O-, -S-, -SO-, -SO 2 -, -CH 2 -, -CH (CH 3) -, -C (CH 3) 2 - or a single It is a combination.)

(2) The planarization resin layer

The planarization resin layer 152 is a layer for planarizing the surface of the transparent fiber composite resin layer 151 and is made of a transparent resin. The transparent resin constituting the flattening resin layer 152 may be formed of the same transparent resin composition as that of the above-mentioned transparent resin composition 151b, or may be formed of another transparent resin composition.

When the smoothing resin layer 152 is formed on the surface of the transparent fiber composite resin layer 151, the surface can be smoothened, and the effect of reducing the defects of the transparent inorganic film, which will be described later, Can be ensured.

(3) Transparent inorganic film

The transparent inorganic film 153 is formed of an oxide such as aluminum (Al) or silicon (Si), a nitride, or a nitride oxide.

&Lt; Characteristics of Multilayer Sheet Production Method Containing Transparent Fiber Composite Resin Layer >

In the method for producing a multilayer sheet containing a transparent fiber composite resin layer according to the embodiment of the present invention, a multi-layer original sheet (Sb) containing a transparent fiber composite resin layer is heated by a main roll 129, A transparent inorganic film 153 is formed on the sheet Sb. Here, the multilayer sheet containing a transparent fiber composite resin layer according to the present invention is superior in heat resistance to a sheet of several sheets because a glass fabric is used. Therefore, since a transparent inorganic film can be formed at a higher temperature than when a transparent resin sheet is produced without using a glass fabric, a dense inorganic layer can be formed. In addition, since the glass cloth itself is inorganic, it can be expected that the adhesion at the time of forming the inorganic layer is good. Therefore, in this method for producing a multilayer sheet containing a transparent fiber composite resin layer, a transparent inorganic film 153 that is more dense than the conventional transparent inorganic film is formed on the multilayer original sheet Sb containing a transparent fiber composite resin layer. Therefore, the multilayer sheet (Sa) containing a transparent fiber composite resin layer obtained by the method for producing a multilayer sheet containing a transparent fiber composite resin layer can be obtained by using a sheet made of a resin alone or a transparent fiber composite resin layer containing no transparent heat- It is possible to exhibit higher gas barrier properties than multilayer sheets.

<Modifications>

(A) In the foregoing embodiment, a sheet having the flattening resin layer 152 is used as the multilayer original sheet Sb having a transparent fiber composite resin layer. However, only the transparent fiber composite resin layer 151 is used as the original sheet Sb ' (See Fig. 3) may be used. In this case, the multilayer sheet Sa 'containing the transparent fiber composite resin layer is composed of the transparent fiber composite resin layer 151 and the transparent inorganic film 153, as shown in Fig.

(B) In the above embodiment, the multilayer sheet Sa having a transparent fiber composite resin layer is produced by the multilayer sheet production apparatus 100 having a transparent fiber composite resin layer shown in Fig. 1, (Sa) can also be produced by the multilayer sheet production apparatus 100A having a transparent fiber composite resin layer shown in Fig. The multilayer sheet production apparatus 100A having a transparent fiber composite resin layer is not limited to the structure in which the partition wall 126, the preliminary heating device 127 and the cryo pump 128 are provided, Layered sheet production apparatus 100 for producing a composite resin layer. Therefore, the same constituent elements as those of the apparatus for producing a multilayer sheet with transparent fiber composite resin layer 100 are denoted by the same reference numerals, and a description thereof will be omitted.

The partition wall 126 isolates the target 125 and a portion of the main roll 129 facing the target 125 from the other space SP2. In other words, the partition wall 126 may isolate the sputtering area SP1 from the other space SP2.

By isolating the sputtering area SP1 from the other space SP2 by the partition wall 126, it is possible to prevent atoms / molecules emitted from the target 125 from diffusing from SP1 and to prevent contamination of other spaces .

The preliminary heating device 127 is disposed between the feed roll 121 and the first sub roll 122 and heats the multilayer original sheet Sb containing the transparent fiber composite resin layer fed out from the feed roll 121 , And moisture is discharged from the multilayer original sheet (Sb) containing a transparent fiber composite resin layer.

By discharging moisture from the multilayer original sheet (Sb) containing a transparent fiber composite resin layer, the transparent inorganic film to be laminated thereafter is not affected by moisture, so that a transparent inorganic film having a high gas barrier property and a high quality is formed It becomes possible.

The cryo pump 128 is a storage vacuum pump, and condenses moisture captured from the multilayer original sheet Sb containing a transparent fiber composite resin layer by a preliminary heating device 127 to be condensed. 4, the cryopump 128 mainly includes a heat exchanger 128a, a chiller unit 128b, a refrigerant supply pipe 128c, and a refrigerant return pipe 128d. In addition, the above-described moisture is condensed and captured by the heat exchanger 128a.

(C) In the method for producing a multilayer sheet containing a transparent fiber composite resin layer according to the foregoing embodiment, a sputtering method is used for forming the transparent inorganic film 153. However, for forming the transparent inorganic film 153, A CVD method or the like may be used.

In the ion plating method, an apparatus 100B as shown in Fig. 5 is usually used. 5, the apparatus 100B mainly comprises a vaporizing material 131, a high-frequency coil 132, and a holder 133. [

The evaporation material 131 is, for example, an oxide, a nitride, or a nitride of oxide such as aluminum (Al) and silicon (Si).

In the holder 133, a multi-layer original sheet Sb containing a transparent fiber composite resin layer is held.

The high frequency coil 132 evaporates the evaporation material 131 by heating.

(D) Although not specifically mentioned in the previous embodiment, a layer other than the planarization resin layer 152 may be additionally formed in the multilayer original sheet Sb containing a transparent fiber composite resin layer. In place of the planarization resin layer 152, another layer may be formed on the multilayer original sheet Sb containing a transparent fiber composite resin layer.

Example

<Examples>

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The present invention is not limited to these examples.

(Example 1)

1. Fabrication of Multilayer Sheet Containing Transparent Fiber Composite Resin Layer

(1) Fabrication of multilayer original sheet containing transparent fiber composite resin layer

90 parts by weight of an alicyclic epoxy resin E-DOA (hereinafter abbreviated as "E-DOA", having a refractive index of 1.513 after curing (crosslinking), manufactured by Daicel Chemical Industries, (Hereinafter referred to as &quot; SI-100L &quot;), a mixture of 10 parts by weight of a silsesquioxane (hereinafter abbreviated as OX-SQH, TOA Synthetic Co., Ltd., refractive index 1.47 after curing 1 part by weight, manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed to prepare a resin composition.

(2)

Subsequently, the above-mentioned resin composition was impregnated with NE glass-based glass cloth (thickness: 95 mu m) to prepare a resin-impregnated glass cloth, and then the resin-impregnated glass cloth was defoamed. In this glass cloth, when the first direction is the MD direction (flow direction) and the second direction is the TD direction (vertical direction), the number of the longitudinal direction glass yarns per 1 inch width in the MD direction is 58, The number of transverse direction glass yarns per 1 inch width in the TD direction is 50 pieces. That is, when the number of the transverse direction glass yarns per inch width in the TD direction is 1, the ratio of the number of transverse direction glass yarns per inch width in the MD direction is 1.16.

The ratio of the cross-sectional area of the glass component in the glass yarn per 1 inch width in the MD direction is 1.35 when the cross-sectional area of the glass component in the glass yarn per 1 inch width in the TD direction is 1. Then, the resin-impregnated glass cloth was sandwiched between the two glass plates subjected to the releasing treatment, heated at 80 ° C for 2 hours, and further heated at 250 ° C for 2 hours to obtain a transparent fiber- Thereby obtaining a transparent fiber-reinforced composite resin sheet.

(2) The film of the smoothing layer

100 parts by mass of an alicyclic epoxy resin (E-DOA) and 1 part by mass of a cationic photopolymerization initiator (manufactured by ADEKA Corporation, SP-170) were mixed to prepare a coating material. Subsequently, the resultant was applied on both sides of the transparent fiber composite resin layer with a bar coater, and then irradiated with ultraviolet rays of 1100 mJ / cm 2 using a high-pressure mercury lamp. Further, a smooth layer (planarization resin layer) having an average thickness of 5 탆 was formed by heating at 250 ° C for 2 hours to obtain a multilayer original sheet containing a transparent fiber composite resin layer.

(3) Deposition of the gas barrier layer

Subsequently, the multi-layer original sheet containing a transparent fiber composite resin layer was placed in a chamber of an RF sputtering apparatus. Then, after reducing the pressure in the chamber, Ar gas was introduced at 0.5 Pa and O ₂ gas was introduced at a partial pressure of 0.005 Pa. Subsequently, RF power of 0.3 kW was applied between the Si ₃ N ₄ target placed in the chamber and the transparent fiber composite resin layer to discharge. On the other hand, the multi-layer original sheet containing a transparent fiber composite resin layer was heated to 200 ° C to open a shutter formed between the target and the transparent fiber composite resin layer when discharge was stable, and a gas barrier layer composed of SiO _x N _y . Thereafter, when the average thickness of the gas barrier layer reached 100 nm, the shutter was closed to complete the film formation. Then, the chamber was opened to the atmosphere to obtain a multilayer sheet containing a transparent fiber composite resin layer.

2. Measurement of various physical properties

(1) Measurement of haze

The haze was measured using NDH2000 manufactured by Nippon Seimei Kogyo Co., Ltd. in accordance with JIS K7136. As a result, the haze of the multilayer sheet containing a transparent fiber composite resin layer according to Example 1 was 1.8%.

(2) Measurement of coefficient of linear expansion

A test piece was cut out from the multilayer sheet containing a transparent fiber composite resin layer, and the test piece was set in a thermal stress deformation measuring apparatus (TMA / SS120C type manufactured by Seiko Electronics Co., Ltd.). Thereafter, in a nitrogen atmosphere, the test piece of no-load was raised from the ambient temperature of 30 ° C to 150 ° C at a heating rate of 5 ° C / min, and then cooled to 0 ° C. Further, while the test piece was pulled with a load of 5 g, the temperature of the atmosphere was elevated from 30 ° C to 150 ° C at a heating rate of 5 ° C / min, and the coefficient of linear expansion in the MD and TD directions was measured. As a result, the coefficient of linear expansion in the MD direction was 12.1 ppm / K and the coefficient of linear expansion in the TD direction was 12.8 ppm / K in the multilayer sheet containing a transparent fiber composite resin layer according to Example 1.

(3) Evaluation of gas barrier property

The water vapor permeability was measured in accordance with JIS K 7129 B (see Table 1). As a result, the water vapor permeability in the MD direction of the multilayer sheet containing a transparent fiber composite resin layer according to Example 1 was equal to or less than the measurement limit value (0.01).

(4) Evaluation of optical anisotropy

The multilayer sheet containing the transparent fiber composite resin layer was observed with a polarizing microscope with Cross-Nicol. Then, the optical axis of the polarization microscope was fixed, and the multilayer sheet containing the transparent fiber composite resin layer was rotated with the intensity of the light source kept constant so that a part or all of the substrate was set at an angle at which it became the brightest. Then, an observation portion of 2.4 mm x 1.8 mm was made into an image (the number of pixels 640 x 480) and taken into a personal computer, and the taken image was converted into a monochrome image in which each pixel had a grayscale of 0 to 255. The gradation of each pixel in the obtained monochrome image was summed up, and this was used as an evaluation value of the optical anisotropy. As a result, the optical anisotropy of the multilayer sheet containing a transparent fiber composite resin layer according to Example 1 was 3.3.

3. Overall rating

From the above, it can be seen that the multilayer sheet containing a transparent fiber composite resin layer according to the present embodiment has a low haze value, a low linear expansion coefficient anisotropy, a low water vapor transmission rate and a low optical anisotropy, Layer-containing multilayer sheet.

(Comparative Example 1)

Except that the multi-layer original sheet containing a transparent fiber composite resin layer was heated at 200 ° C, and the multi-layer original sheet containing a transparent fiber composite resin layer was held at 30 ° C in place of the multilayer original sheet having a transparent fiber composite resin layer heated at 200 ° C A multilayer sheet containing a transparent fiber composite resin layer was prepared, and physical properties were measured in the same manner as in Example 1.

As shown in Table 1, the haze was 1.9%, the coefficient of linear expansion in the MD direction was 12.2 ppm / K, the coefficient of linear expansion in the TD direction was 12.8 ppm / K, the water vapor The transmittance was 0.02 g / m 2 / day / 40 ° C, 90% RH, and the optical anisotropy was 3.5. That is, the multilayer sheet containing a transparent fiber composite resin layer according to Comparative Example 1 has a low haze value, a low coefficient of linear expansion, low optical anisotropy, and a high water vapor permeability, It was not.

(Comparative Example 2)

Glass cloths were changed to "NE glass glass cloths having 60 longitudinal glass yarns per 1 inch width in the MD direction and 50 lateral glass yarns per 1 inch width in the TD direction" Except that the multi-layer original sheet containing a transparent fiber composite resin layer was maintained at a temperature of 30 degrees C, instead of heating the multi-layer original sheet containing a transparent fiber composite resin layer at 200 degrees C, A multilayer sheet containing a transparent fiber composite resin layer was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1.

As shown in Table 1, the haze was 2.1%, the coefficient of linear expansion in the MD direction was 9.5 ppm / K, the coefficient of linear expansion in the TD direction was 12.6 ppm / K, the water vapor The transmittance was 0.02 g / m 2 / day / 40 ° C, 90% RH, and the optical anisotropy was 4.9. In other words, although the haze value is low, it is not preferable for an optical device because the anisotropy of the linear expansion coefficient, the water vapor transmission rate, and the optical anisotropy are high.

(Comparative Example 3)

Glass cloths were changed to "NE glass glass cloths having 50 longitudinal glass yarns per 1 inch width in the MD direction and 50 lateral glass yarns per 1 inch width in the TD direction" Except that the multilayer original sheet containing a transparent fiber composite resin layer was maintained at a temperature of 30 degrees C instead of heating the multilayer original sheet with a transparent fiber composite resin layer at 200 degrees C , A multilayer sheet containing a transparent fiber composite resin layer was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner as in Example 1. [

As shown in Table 1, the haze was 4.1%, the coefficient of linear expansion in the MD direction was 12.3 ppm / K, the coefficient of linear expansion in the TD direction was 13.1 ppm / K, the water vapor The transmittance was 0.02 g / m 2 / day / 40 ° C, 90% RH, and the optical anisotropy was 3.6. That is, although the anisotropy of the coefficient of linear expansion is small and the optical anisotropy is low, the haze value and the water vapor transmission rate are high, which is not preferable for optical devices.

Industrial availability

The method for producing a multilayer sheet containing a transparent fiber composite resin layer according to the present invention is characterized by being capable of producing a multilayer sheet comprising a transparent fiber composite resin layer exhibiting higher gas barrier properties than a conventional multilayer sheet comprising a transparent fiber composite resin layer For example, a transparent resin substrate usable in a liquid crystal display device, a solar cell, an electromagnetic wave shield, a touch panel, an organic EL substrate, a color filter and the like.

151: Transparent fiber composite resin layer (transparent fiber composite resin sheet)
153: Transparent inorganic film
Sa, Sa ': multilayer sheet containing a transparent fiber composite resin layer
Sb: multi-layer original sheet containing a transparent fiber composite resin layer
Sb ': original sheet (transparent fiber composite resin sheet)
[Table 1]

Claims (11)

A transparent inorganic fiber film is formed on at least one side of the transparent fiber composite resin sheet or the multilayer original sheet containing the transparent fiber composite resin layer while heating the multilayer original sheet containing the transparent fiber composite resin sheet or the transparent fiber composite resin layer at 180 캜 or higher,
The fiber sheet in the transparent fiber-reinforced composite resin sheet or the multilayer original sheet containing the transparent fiber composite resin layer is a glass woven fabric,
The glass woven fabric includes a plurality of first glass fibers oriented in a first direction and a plurality of second glass fibers woven in the first glass fibers along a direction orthogonal to the first direction when viewed in plan view Respectively,
Wherein the ratio of the cross-sectional area of the glass component in the first glass fiber bundle per unit width to the cross-sectional area of the glass component in the second glass fiber bundle per unit width is 1.04 or more and 1.40 or less. . The method according to claim 1,
Wherein the transparent inorganic film is formed by sputtering. The method according to claim 1,
Wherein the transparent inorganic film is formed by chemical vapor deposition (CVD) or ion plating. 4. The method according to any one of claims 1 to 3,
Wherein the transparent inorganic film contains at least one kind of atom selected from the group consisting of aluminum (Al) atoms and silicon (Si) atoms. 5. The method of claim 4,
Wherein the transparent inorganic film is formed of an oxide, a nitride, or an oxynitride containing at least one atom selected from the group consisting of aluminum (Al) atoms and silicon (Si) atoms. delete delete The method according to claim 1,
Sectional area of each of the glass components in the first glass fiber is equal to the cross-sectional area of each glass component in the second glass fiber,
Wherein the ratio of the number of the first glass fibers per unit width to the number of the second glass fibers per unit width is 1.02 or more and 1.18 or less. A multilayer sheet comprising a transparent fiber composite resin layer obtained by the method for producing a multilayer sheet containing a transparent fiber composite resin layer according to any one of claims 1 to 3 is used as a substrate. delete delete

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