阅读说明：本技术 柔版印刷版与使用其的液晶显示元件的制造方法 (Flexographic printing plate and method for manufacturing liquid crystal display element using same ) 是由 田所信彦 中下武文 高桥俊行 山本胜志 于 2019-08-21 设计创作，主要内容包括：本发明提供一种柔版印刷版及液晶显示元件的制造方法,所述柔版印刷版可高精度且并无厚度不均或针孔等、并且不会大幅变更印刷条件地形成厚度比现状大且为适合于液晶显示元件用途的厚度的液晶取向膜等,所述液晶显示元件的制造方法包括使用所述柔版印刷版并利用柔版印刷法来形成液晶取向膜的工序。柔版印刷版(1)是将用于担持油墨的版表面(3)设为比表面积RS为4.3以上且6.0以下、单位空间容积SV为12μm3/μm2以上且29μm3/μm2以下的粗糙面。液晶显示元件的制造方法包括使用所述柔版印刷版并利用柔版印刷法来形成液晶取向膜的工序。(The present invention provides a flexographic printing plate capable of forming a liquid crystal alignment film having a thickness larger than the current state and suitable for use in a liquid crystal display element with high accuracy and without thickness unevenness, pinholes, and the like, and without greatly changing printing conditions, and a method for manufacturing a liquid crystal display element including a step of forming a liquid crystal alignment film by a flexographic printing method using the flexographic printing plate. The flexographic printing plate (1) has a plate surface (3) for supporting ink as a rough surface having a specific surface area RS of 4.3 to 6.0 inclusive and a unit space volume SV of 12 [ mu ] m 3/[ mu ] m2 to 29 [ mu ] m 3/[ mu ] m2 inclusive. The method for manufacturing a liquid crystal display element includes a step of forming a liquid crystal alignment film by a flexographic printing method using the flexographic printing plate.)

1. A flexographic printing plate comprising a plate surface for holding ink, and the plate surface has a specific surface area R_SIs 4.3 to 6.0 inclusive and has a unit space volume S_VIs 12 μm³/μm²Above and 29 μm³/μm²The following rough surface.

2. The flexographic printing plate of claim 1, wherein the plate surface has a specific surface area R_SIs 5.0 to 5.3 inclusive.

3. The flexographic printing plate of claim 1 or 2, wherein the volume per space S of the plate surface_VIs 16 μm³/μm²Above and 22 μm³/μm²The following.

4. A method for manufacturing a liquid crystal display element, comprising a step of forming a liquid crystal alignment film by a flexographic printing method using the flexographic printing plate according to any one of claims 1 to 3.

Technical Field

The present invention relates to a flexographic printing plate and a method for manufacturing a liquid crystal display element using the same.

Background

For example, in a wide range of printing fields such as printing of packaging materials, a flexographic printing method is commonly used.

The following flexographic printing plates were used in the flexographic printing process: the ink-jet printing sheet includes a flexible resin sheet or the like, and the surface of the sheet is formed into a plate surface, that is, a surface that contacts a surface to be printed while holding ink and transfers the ink to the surface to be printed.

It is known that the flexographic printing method has good printing characteristics, and is also used for printing a liquid crystal alignment film of a liquid crystal display device, for example, as a special application other than the general application in which the flexographic printing method is effectively used.

In printing of a liquid crystal alignment film, the following requirements are required: reducing the thickness of a liquid crystal alignment film formed by transferring ink from the plate surface to a printed surface of a flexographic printing plate; or even if the thickness is reduced, the thickness precision of the liquid crystal orientation film is high, and uneven thickness, pinholes and the like are not generated.

As the ink for forming the liquid crystal alignment film with high accuracy and without thickness unevenness, pin holes, and the like, an ink which has low wettability to a resin or the like forming a flexographic printing plate and is easily released from the plate surface is suitably used.

Further, even when the ink has low wettability, a flexographic printing plate is used which has a plate surface having a rough surface with a constant specific surface area so as to support the plate surface while maintaining a uniform thickness without causing thickness unevenness or pinholes due to repulsion or the like (see patent document 1, patent document 2, and the like).

The flexographic printing plate is manufactured through the following steps: the surface of the layer of the photosensitive resin composition is brought into contact with the mold surface of a roughened sheet having a mold surface of a roughened surface corresponding to the roughened surface formed as the plate surface, and the photosensitive resin composition is cured by exposure to actinic rays such as ultraviolet rays in the above state.

When the roughened surface sheet is peeled off after curing, the three-dimensional shape of the mold surface of the roughened surface sheet is transferred to the surface of the layer of the cured photosensitive resin composition, and the surface is made into a roughened plate surface having a three-dimensional shape corresponding to the three-dimensional shape of the mold surface.

Hereinafter, the method for producing the flexographic printing plate may be simply referred to as "exposure transfer method".

The roughened sheet is produced by roughening one surface of a sheet to be a base thereof into a predetermined three-dimensional shape by press sheet molding using an emboss roller having an outer peripheral surface roughened by, for example, etching or molding by etching.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2013-119179

[ patent document 2] Japanese patent laid-open No. 2014-133335

Disclosure of Invention

[ problems to be solved by the invention ]

However, when the conventional flexographic printing plates described in patent documents 1 and 2 are used, there is a tendency that: the liquid crystal alignment film formed on the surface to be printed by the flexographic printing method has a thickness that is insufficient.

In addition, in the conventional technique, in order to increase the thickness of the liquid crystal alignment film, it is necessary to change various printing conditions.

That is, it is necessary to change an anilox roll for supporting ink on the plate surface, change the composition of ink, change nip pressure (nip pressure), change the printing speed, and the like.

However, there are problems as follows: a great deal of effort and cost are required to change these printing conditions.

The purpose of the present invention is to provide a flexographic printing plate which can form a liquid crystal alignment film or the like having a thickness larger than the current state and suitable for use in liquid crystal display elements with high accuracy and without thickness unevenness or pinholes or the like, and without significantly changing printing conditions.

Another object of the present invention is to provide a method for manufacturing a liquid crystal display element, the method including a step of forming a liquid crystal alignment film by a flexographic printing method using the flexographic printing plate.

[ means for solving problems ]

The invention relates to a flexographic printing plate, which comprises a plate surface for supporting ink, wherein the plate surface has a specific surface area R_SIs 4.3 to 6.0 inclusive and has a unit space volume S_VIs 12 μm³/μm²Above and 29 μm³/μm²The following rough surface.

The present invention is also a method for manufacturing a liquid crystal display element, including a step of forming a liquid crystal alignment film by a flexographic printing method using the flexographic printing plate.

[ Effect of the invention ]

According to the present invention, it is possible to provide a flexographic printing plate which can form a liquid crystal alignment film or the like having a thickness larger than the current state and suitable for use in a liquid crystal display element with high accuracy and without thickness unevenness or pinholes or the like, and without greatly changing printing conditions.

Further, according to the present invention, there can be provided a method for manufacturing a liquid crystal display element, the method including a step of forming a liquid crystal alignment film by a flexographic printing method using the flexographic printing plate.

Drawings

Fig. 1 is a perspective view showing an example of an embodiment of a flexographic printing plate of the present invention.

Fig. 2 is a perspective view illustrating a method of determining a specific surface area and a unit space volume of a plate surface of a flexographic printing plate.

Fig. 3 is a cross-sectional view showing an example of a three-dimensional shape of a plate surface of a flexographic printing plate.

Fig. 4 is a sectional view showing a layer structure of an example of a roughened sheet used for manufacturing a flexographic printing plate.

Fig. 5(a) to 5(c) are cross-sectional views showing an example of a process for producing the flexographic printing plate of the example of fig. 1.

Fig. 6(a) to 6(c) are cross-sectional views showing an example of the subsequent steps of fig. 5(a) to 5 (c).

FIG. 7 is a photomicrograph of the plate surface of an embodiment of the present invention.

Fig. 8 is a photomicrograph of the plate surface of the comparative example.

[ description of symbols ]

1: flexographic printing plate

2: resin layer

3: plate surface

4: reinforced sheet

5: gripping part

6: trough part

7: chuck hole

8: hollow depression

9: printing ink

10: roughened sheet

11: reinforced membrane

12: surface layer

13: adhesive resin

14: fine particles

15: die surface

16: supporting substrate

17: opposite side

18: surface of

19: photosensitive resin composition

20: layer(s)

21: opposite substrate

22: facing surface

23: laminated body

24: work bench

25: resin original plate for printing

A: measurement area

H: height of space

P_H: highest point

P_L: lowest point

R_S: specific surface area

S_V: volume per unit space

V: convex volume

W₁: longitudinal direction

W₂: horizontal bar

Detailed Description

Flexographic printing plate

Fig. 1 is a perspective view showing an example of an embodiment of a flexographic printing plate 1 of the present invention.

Referring to fig. 1, a flexographic printing plate 1 of the present example includes a flexible resin layer (resin layer) 2, and a reinforcing sheet 4 is laminated on one surface (upper surface in the figure) of the resin layer 2 as a plate surface 3 and on the opposite surface (lower surface in the figure), and is formed in a rectangular flat plate shape as a whole.

A grip portion 5 having a constant width is provided outside the plate surface 3 in the vicinity of 2 sides of the rectangular shape of the flexographic printing plate 1 parallel to each other across the entire width of each side, and the grip portion 5 is gripped and gripped by a not-shown gripper (vise) when each flexographic printing plate 1 is set in the flexographic printing machine.

Further, a groove portion 6 having a constant width is provided between the grip portion 5 and the plate surface 3 in parallel with the grip portion 5.

Further, chuck holes 7 for inserting fixing pins (not shown) into the grip portion 5 gripped by the clamp are formed at equal intervals at a plurality of positions (5 positions in the drawing) in the longitudinal direction of the grip portion 5, respectively.

< specific surface area R_SAnd unit space volume S_V＞

The plate surface 3 of the flexographic printing plate 1 is required to have a specific surface area R as described above_SIs 4.3 to 6.0 inclusive and has a unit space volume S_VIs 12 μm³/μm²Above and 29 μm³/μm²The following rough surface.

The reason for this is as follows.

I.e. the specific surface area R_SA relatively smooth plate surface 3 of less than 4.3 cannot support the ink in a uniform thickness because the wettability of the ink is too low.

In addition, the specific surface area R_SThe plate surface 3 having large unevenness exceeding 6.0 still cannot support ink in a uniform thickness due to the influence of the unevenness.

Therefore, in any of the above cases, the accuracy of the thickness of the liquid crystal alignment film formed by transferring the carried ink to the surface to be printed is lowered, and unevenness in thickness, pinholes, and the like are likely to occur in all of them.

In addition, the specific surface area R_SThe relatively smooth plate surface 3 of less than 4.3 may not support a sufficient amount of ink, and thus the thickness of the liquid crystal alignment film formed by transferring the supported ink to the surface to be printed is insufficient.

In addition, the unit space volume S_VThe volume of the plate surface 3 per unit area is an index indicating a space for supporting ink, which is formed by the unevenness, particularly the recess, formed on the plate surface 3, on the plate surface 3.

If the unit space volume S_VLess than 12 μm³/μm²The amount of ink that can be carried by the plate surface 3 is still insufficient, and the thickness of the liquid crystal alignment film formed by transferring the carried ink to the surface to be printed is insufficient.

On the other hand, the unit space volume S_VOver 29 μm³/μm²The plate surface 3 having a large unevenness of (a) cannot support ink in a state of a uniform thickness due to the influence of the unevenness.

Therefore, the accuracy of the thickness of the liquid crystal alignment film formed by transferring the ink carried by the liquid crystal alignment film to the surface to be printed is lowered, and unevenness in thickness, pinholes, and the like are likely to occur.

In contrast, the specific surface area R of the plate surface 3 of the flexographic printing plate 1 is determined by_SAnd unit space volume S_VAll of them are within the above range, and even if the ink has low wettability, the ink can be supported on the plate surface while maintaining a uniform thickness3。

In addition, the amount of ink that can be carried on the plate surface 3 at one printing can be increased more than it is.

And, only by adjusting the unit space volume S within the range_VThe amount of ink that can be carried on the plate surface 3 can also be adjusted without significantly changing the printing conditions.

Therefore, a liquid crystal alignment film having a thickness larger than the current state and suitable for use in a liquid crystal display element, for example, can be formed with high accuracy without thickness unevenness, pinholes, and the like, and without greatly changing printing conditions.

Further, in order to further improve these effects, the specific surface area R of the plate surface 3 of the flexographic printing plate 1 is set to be larger than the specific surface area R of the plate surface 3_SWithin the range, it is preferably 5.0 or more, and preferably 5.3 or less.

In addition, the unit space volume S_VIn said range, preferably 16 μm³/μm²Above, and preferably 22 μm³/μm²The following.

(measurement method)

Specific surface area R_SAnd unit space volume S_VFor example, the three-dimensional data can be obtained from three-dimensional data of the plate surface 3 measured using a shape analysis laser microscope (VK-X160 manufactured by keyence corporation).

FIG. 2 is a view illustrating the determination of the specific surface area R by using the shape analysis laser microscope_SAnd unit space volume S_VPerspective view of the method of (1).

First, on the plate surface 3, a vertical W is set₁[μm]W transverse₂[μm]Reference area S₀＝W₁×W₂[μm²]The rectangular measurement area a of (2) is scanned with laser light using a shape analysis laser microscope to obtain three-dimensional data of the plate surface 3 in the measurement area a.

Then, the actual surface area S [ mu ] m of the plate surface 3 in the measurement region A is determined by three-dimensional analysis from the obtained three-dimensional data²]From said actual surface area S [ mu ] m²]And the reference area S₀[μm²]And by the formula (1):

R_S＝S/S₀(1)

determination of specific surface area R_S。

Further, the lowest point P of the plate surface 3 in the measurement region A is determined based on the obtained three-dimensional data_LWith the highest point P_HCalculating the difference P between the two_H-P_LSpatial height H [ μm ] of]And the height H [ mu ] m of the space in the measurement region A is determined]A convex volume V [ mu ] m of the resin layer 2 including the plate surface 3 in the range of³]。

Then, these results are compared with the reference area S of the measurement region A₀[μm²]And by the formula (2):

S_V＝H×S₀-V (2)

determining each of the reference areas S₀[μm²]Is the unit space volume S_V[μm³/μm²]。

Stereoscopic shape of plate surface 3

In order to set the plate surface 3 of the flexographic printing plate 1 to satisfy the specific surface area R simultaneously_SAnd unit space volume S_VThe rough surface in the range of (1) may be formed by adjusting the three-dimensional shape of the rough surface.

That is, the conventional rough surface formed by etching or the like is generally a three-dimensional shape in which a convex portion and a valley portion having a substantially triangular wave-shaped cross section are continuous, as shown in fig. 2, for example.

However, according to the study of the inventors, the conventional rough surface having the three-dimensional shape may be as follows: even the specific surface area R_SSatisfies the above-mentioned range of 4.3 to 6.0, and has a unit space volume S_VAlso fails to satisfy 12 μm³/μm²The above range.

Fig. 3 is a cross-sectional view showing an example of a three-dimensional shape of the plate surface 3 of the flexographic printing plate 1.

In order to simultaneously control the specific surface area R of the plate surface 3_SMaintaining the unit space volume S in the range_VLarger than the current situation, for example, as shown in FIG. 3, it is preferable thatThe plate surface 3 has a three-dimensional shape in which hemispherical depressions 8 having a substantially constant diameter are randomly and densely arranged.

Thereby, the unit space volume S_VSet to 12 μm³/μm²As described above, by increasing the amount of the ink 9 carried on the plate surface 3 at the time of one printing as compared with the current state, it is possible to form a liquid crystal alignment film or the like having a thickness larger than the current state and suitable for the application of a liquid crystal display element.

In order to manufacture the flexographic printing plate 1 including the plate surface 3 having the three-dimensional shape, any manufacturing method may be employed.

For example, the flexographic printing plate 1 can be manufactured by directly forming the hemispherical depressions 8 in a large amount on the plate surface 3 by ultra-short pulse laser processing or the like.

Among them, the flexographic printing plate 1 is preferably produced by the exposure transfer method using a roughened surface sheet having a large number of hemispherical protrusions corresponding to the depressions 8 on the mold surface.

Specifically, the resin layer 2, one side of which is made into the roughened plate surface 3 in the flexographic printing plate 1, is formed by curing the photosensitive resin composition by an exposure transfer method using the roughened sheet.

Further, a reinforcing sheet 4 is laminated on the opposite surface of the resin layer 2 by the curing, thereby manufacturing the flexographic printing plate 1 having the layer structure shown in fig. 1.

Roughened sheet

Fig. 4 is a cross-sectional view showing a layer structure of an example of the roughened surface sheet 10 used in the exposure transfer method.

Referring to fig. 4, the matte sheet 10 of the present example includes: a reinforcing film 11, and a surface layer 12 laminated on one surface (upper surface in the figure) of the reinforcing film 11.

The surface layer 12 includes a binder resin 13 and a plurality of spherical fine particles 14 dispersed in the binder resin 13, and at least a part of the fine particles 14 protrudes from the surface of the surface layer 12 as hemispherical protrusions, thereby forming a roughened mold surface 15 corresponding to the three-dimensional shape of fig. 3.

In the example shown in the figure, the surface of the protruding fine particles 14 is coated with an extremely thin film containing the binder resin 13.

However, the surface of the fine particles 14 may be exposed without being coated with a film, or a coated portion and an exposed portion may be mixed.

The surface layer 12 is formed by, for example, applying a coating agent including a binder resin 13 and fine particles 14 to one surface of the reinforcing film 11, drying the coating agent, and curing the coating agent when the binder resin 13 has a curing property.

The roughened sheet 10 is produced, for example, as follows: while continuously feeding the long reinforcing film 11, a coating agent is continuously applied to one surface thereof to continuously form the surface layer 12.

The produced roughened surface sheet 10 can be cut into a predetermined length, a predetermined width, or the like as needed and used for manufacturing the flexographic printing plate 1 by the exposure transfer method.

As the binder resin 13 forming the surface layer 12, for example, various resins having transparency to actinic rays such as ultraviolet rays, which are exposed when the photosensitive resin composition is cured to form the resin layer 2, can be used.

Examples of the binder resin 13 include: one or more of acrylic resin, polycarbonate, polyvinyl chloride, polystyrene, polyester, polyurethane, and the like.

Particularly preferred are thermoplastic, two-pack curable, actinic ray curable, or thermosetting acrylic resins, and among them, acrylic polyurethane two-pack curable acrylic resins are preferred.

Examples of the acrylic urethane two-pack curable acrylic resin include a resin obtained by combining a main agent containing an acrylic polyol and a curing agent containing isocyanate.

In short, since the acrylic resin has high affinity or wettability with the photosensitive resin composition which forms the base of the resin layer 2, the three-dimensional shape of the mold surface 15 can be transferred to the plate surface 3 well.

As the fine particles 14, one or more kinds of particles of a resin, particles of an inorganic material, or the like can be used.

Examples of the resin particles include particles of acrylic resin, silicone resin, polystyrene, polycarbonate, and the like.

Examples of the particles of the inorganic material include: particles of glass, titanium oxide, barium sulfate, talc, clay, alumina, calcium carbonate, silica, and the like.

Among them, the fine particles 14 are preferably fine particles 14 containing a material that is transparent to actinic rays such as ultraviolet rays, which are exposed when the photosensitive resin composition is cured to form the resin layer 2.

The coating agent is prepared, for example, by blending a base agent and a curing agent, which are bases of the coating agent, with the fine particles 14 at a predetermined ratio and, if necessary, adding a solvent, when an acrylic resin of an acrylic urethane two-pack curing type is used as the binder resin 13.

The reinforcing film 11 has a function of literally reinforcing the entire rough-surfaced sheet 10, such as increasing the tensile strength thereof, and also functions to correct: the roughened sheet 10 warps due to shrinkage or the like at the time of curing the actinic ray-curable binder resin 13.

As the reinforcing film 11, a polyethylene terephthalate (PET) film having excellent functions of the reinforcing film 11 is preferably used.

In particular, the PET film is preferably a PET film that is transparent to actinic rays such as ultraviolet rays that are exposed when the flexographic printing plate 1 is manufactured by the exposure transfer method.

Among them, as the reinforcing film 11, for example, a film of polyvinyl alcohol (PVA), polyamide, Polyimide (PI), polycarbonate, cellulose acetate, or the like can be used.

If necessary, primer treatment may be performed on one surface (upper surface in the figure) of the laminated surface layer 12 of the reinforcing film 11 to improve the adhesion of the surface layer 12.

Examples of the primer treatment include one or more of corona discharge treatment, flame treatment, ozone treatment, ultraviolet irradiation treatment, blast treatment, solvent treatment, and the like.

For example, a primer layer including various materials having excellent affinity and adhesion with the PET forming the reinforcing film 11 or the binder resin 13 forming the surface layer 12 may be formed.

The minimum value of the particle size distribution (particle size distribution) of the fine particles 14 forming the surface layer 12 is preferably 4 μm or more, and particularly preferably 4.5 μm or more, and the maximum value of the particle size distribution is preferably 30 μm or less, and particularly preferably 25 μm or less.

The minimum value and the maximum value of the particle size distribution mean the minimum value and the maximum value of the particle size in the measurement result of the particle size distribution obtained for the fine particles 14 to be measured.

When the minimum value of the particle size distribution of the fine particles 14 is less than 4 μm, the fine particles 14 include: the plate surface 3 of the flexographic printing plate 1 is set to satisfy the specific surface area R simultaneously_SAnd unit space volume S_VThe coarse surface of the three-dimensional shape in the range of (1) is too small.

On the other hand, in the case where the maximum value of the particle size distribution of the fine particles 14 exceeds 30 μm, the fine particles 14 include the following particles: for setting the plate surface 3 to satisfy the specific surface area R at the same time_SAnd unit space volume S_VThe range of (3) is too large for the three-dimensional rough surface.

Therefore, there are cases where: although depending on the coating thickness of the coating agent, the blending ratio of the fine particles 14, etc., in any case, the plate surface 3 of the flexographic printing plate 1 cannot be made to satisfy the specific surface area R at the same time_SAnd unit space volume S_VA three-dimensional rough surface in the range of (1).

Further, the liquid crystal alignment film formed by the flexographic printing method may have insufficient thickness or may have low thickness accuracy, which may cause thickness unevenness or pinholes.

In contrast, by setting the minimum value and the maximum value of the particle size distribution of the fine particles 14 to the above ranges, the particles having an excessively small particle size or the particles having an excessively large particle size can be excluded.

Therefore, the plate surface 3 of the flexographic printing plate 1 can be set to satisfy the specific surface area R at the same time_SAnd unit space volume S_VA three-dimensional rough surface in the range of (1).

The fine particles 14 are preferably formed by combining the standard deviation σ of the particle size distribution and the average particle size according to formula (3):

coefficient of variation Cv ═ standard deviation σ)/(average particle diameter) (3)

The coefficient of variation Cv obtained and indicating the variation in particle size distribution is 0.35 or less.

When the coefficient of variation Cv exceeds 0.35, the deviation of the particle size distribution becomes large, and the fine particles 14 include a large amount of the particles having an excessively small particle size or particles having an excessively large particle size.

Therefore, there are cases where: although it still depends on the coating thickness of the coating agent, the blending ratio of the fine particles 14, and the like, the plate surface 3 of the flexographic printing plate 1 cannot be made to satisfy the specific surface area R at the same time_SAnd unit space volume S_VA three-dimensional rough surface in the range of (1).

In contrast, by setting the coefficient of variation Cv to the above range, particles having an excessively small particle size and particles having an excessively large particle size can be excluded.

Therefore, the plate surface 3 of the flexographic printing plate 1 can be set to satisfy the specific surface area R at the same time_SAnd unit space volume S_VA three-dimensional rough surface in the range of (1).

In order to further enhance the above effect, the coefficient of variation Cv is preferably 0.25 or less within the above range.

However, when the coefficient of variation Cv is too small, the pitches of the irregularities formed on the mold surface 15 of the roughened surface sheet 10 and the plate surface 3 of the flexographic printing plate 1 are nearly uniform because the particle diameters are nearly monodisperse.

In this case, the range of pitches itself is a single pitch although it is different, and moire (moire) fringes may occur in the liquid crystal alignment film formed on the electrode-formed surface due to interaction with the electrode-formed surface including the portion formed with the irregularities, for example, the substrate constituting the liquid crystal display element.

Therefore, in consideration of suppressing the occurrence of moire, the coefficient of variation Cv is preferably 0.10 or more, and particularly preferably 0.18 or more within the above range.

In addition, even in this case, for the reasons described above, the minimum value of the particle size distribution of the fine particles 14 is preferably 4 μm or more, and particularly preferably 4.5 μm or more, and the maximum value of the particle size distribution is preferably 30 μm or less, and particularly preferably 25 μm or less.

In order to suppress the occurrence of moire, a mixed particle of two types of fine particles having different particle size distributions may be used as the fine particle 14.

When the mixed particles of two types of fine particles having different particle size distributions are used in combination, the pitch of the irregularities formed on the mold surface 15 of the roughened surface sheet 10 and the plate surface 3 of the flexographic printing plate 1 can be suppressed from becoming close to unity.

Therefore, for example, by interaction with the electrode formation surface of the substrate constituting the liquid crystal display element, moire can be suppressed from occurring in the liquid crystal alignment film formed on the electrode formation surface.

In addition, even in this case, for the reason described above, the coefficient of variation Cv of the entire mixed particle is preferably 0.35 or less, particularly preferably 0.25 or less, and preferably 0.10 or more, particularly preferably 0.18 or more.

Further, it is preferable that the respective variation coefficients Cv of the two types of fine particles constituting the mixed particle are within the above ranges.

The range of the particle size distribution of the two types of fine particles constituting the mixed particle can be arbitrarily set.

The ranges of the particle size distributions of the two types of fine particles may be different from each other, or may be repeated in a part.

Among these, for the reasons described above, the minimum values of the particle size distributions of both types of fine particles are preferably 4 μm or more, particularly preferably 4.5 μm or more, and the maximum values of the particle size distributions are preferably 30 μm or less, particularly preferably 25 μm or less.

The blending ratio of the two types of fine particles may be set to any range depending on the range or variation coefficient Cv of the particle size distribution of each fine particle, the variation coefficient Cv of the whole mixed particle, or the like.

However, in order to further enhance the above-described effect of using the mixed particles, the proportion of fine particles having a small particle size distribution in the total amount of the mixed particles is preferably 10% by mass or more, and preferably 90% by mass or less.

In the present invention, the particle size distribution of the fine particles 14 or each fine particle constituting the mixed particle is represented by a volume distribution measured by a laser diffraction/scattering method based on Mie scattering theory.

The standard deviation σ that forms the basis of the coefficient of variation Cv is obtained from the result of conversion on a number basis assuming that the shape of the particle is spherical.

The average particle diameter is an arithmetic average diameter based on the number, which is obtained by integrating the shape of the particles assumed to be spherical and converted to the number and dividing the result by the number of the particles.

In the examples, the volume distribution of the fine particles was measured by using a laser diffraction/scattering particle size distribution measuring apparatus LA-950V2 manufactured by horiba, Ltd, but the measuring apparatus is not limited thereto.

The mixing ratio of the binder resin 13 and the fine particles 14 may be such that the plate surface 3 of the flexographic printing plate 1 satisfies the specific surface area R_SAnd unit space volume S_VThe range of (3) is adjusted within an arbitrary range of the three-dimensional rough surface.

However, if the amount of the binder resin 13 is too small, a continuous and strong surface layer 12 may not be formed.

On the other hand, when the binder resin 13 is too much, the unevenness formed on the die surface 15 as the surface of the surface layer 12 becomes too small, and there are cases where: the plate surface of the flexographic printing plate 1 cannot be made3 is made while satisfying the specific surface area R_SAnd unit space volume S_VA three-dimensional rough surface in the range of (1).

In consideration of the size of the irregularities, etc., the surface layer 12 is preferably formed in the following state: the fine particles are embedded in the binder resin 13 at a ratio of 1/2 to 1/8 on a volume basis.

Therefore, the blending ratio of the binder resin 13 and the fine particles 14 is preferably set to 30 vol% or more and 80 vol% or less, as represented by the volume ratio of the binder resin 13 (the solid content of the resin excluding the volatile component) to the total amount of the binder resin 13 and the fine particles 14.

The thickness of the surface layer 12, that is, the thickness from one surface of the reinforcing film 11 to the tip of the convex portion of the unevenness of the die surface 15 formed by the fine particles 14 can be arbitrarily set based on the particle diameter of the fine particles 14.

For example, when the particle diameter of the fine particles 14 is in the range of 4 μm to 30 μm, the thickness of the surface layer 12 is not limited thereto, but is, for example, preferably 0.010mm (10.0 μm) or more and preferably 0.025mm (25.0 μm) or less.

The thickness of the reinforcing film 11 is 0.050mm or more, preferably 0.075mm or more, and 0.300mm or less, preferably 0.250mm or less.

When the thickness is less than the above range, the roughened surface sheet 10 is likely to be broken when, for example, the long roughened surface sheet 10 before cutting is wound into a roll, the cut roughened surface sheet 10 is used for manufacturing a flexographic printing plate, or the cut roughened surface sheet 10 is wound for storage or the like.

When the roughened surface sheet 10 is broken, a break defect may occur in the mold surface 15 or the plate surface 3 of the flexographic printing plate 1, and for example, the following problems may occur: it is impossible to form a liquid crystal alignment film or the like having a uniform and continuous thickness.

On the other hand, when the thickness of the reinforcing film 11 exceeds the above range, the weight of the rough-surfaced sheet 10 increases, and it becomes difficult to bend or roll up the rough-surfaced sheet 10, so that the handling property at the time of the above-mentioned handling or the like may be lowered.

Further, as the thickness of the reinforcing film 11 increases, the thickness variation of the reinforcing film 11 also increases, and thus the coating thickness of the coating agent is likely to vary.

In addition, in a portion where the thickness of the reinforcing film 11 is small, the thickness of the binder resin 13 becomes large, and the fine particles 14 are buried in the binder resin 13, and a region where the surface is not sufficiently roughened compared to the surrounding area may be generated.

That is, unevenness may be easily generated in the distribution of the unevenness of the surface layer 12, that is, the mold surface 15, or in the three-dimensional shape of the rough surface.

On the other hand, by setting the thickness of the reinforcing film 11 in the above range, the handling property of the roughened surface sheet 10 and the like can be improved while suppressing the occurrence of breakage and the like as much as possible, and the unevenness of the distribution of irregularities can be eliminated to make the three-dimensional shape of the die surface 15 uniform.

In view of further uniformizing the three-dimensional shape of the die surface 15, it is preferable that the thickness of the reinforcing film 11 is smaller in the above range.

That is, as the thickness of the reinforcing film 11 is reduced, the thickness unevenness of the reinforcing film 11 can be reduced, and the coating thickness of the coating agent which forms the base of the surface layer 12 can be made uniform, and the three-dimensional shape of the rough surface can be made uniform.

Particularly, in the case of combining with the fine particles 14 having the particle size range of 4 μm or more and 30 μm or less, the thickness of the reinforcing film 11 is preferably 0.200mm or less within the above range.

This further improves the effect of making the three-dimensional shape of the rough surface uniform.

Among them, if the prevention of the break defect and the like is also considered, the thickness of the reinforcing film 11 is preferably 0.100mm or more, and particularly preferably 0.150mm or more.

When a primer layer is formed on one surface of the reinforcing film 11 as a primer treatment, the thickness of the reinforcing film 11 is the total thickness of the reinforcing film 11 and the primer layer.

In view of suppressing the occurrence of breakage as much as possible, the total thickness of the rough-surfaced sheet 10, which is the sum of the thickness of the reinforcing film 11 and the thickness of the top sheet 12, is preferably 0.150mm or more, and particularly preferably 0.180mm or more.

In view of improvement in handling properties of the roughened sheet 10, the overall thickness is preferably 0.240mm or less, and more preferably 0.220mm or less.

Method for manufacturing flexographic printing plate

Fig. 5(a) to 5(c) are sectional views showing an example of a process for producing the flexographic printing plate 1 by an exposure transfer method using the roughened surface forming sheet 10 of the example of fig. 4.

Fig. 6(a) to 6(c) are cross-sectional views showing an example of the subsequent steps of fig. 5(a) to 5 (c).

Referring to fig. 5(a), in the manufacturing method of this example, a support substrate 16 is prepared, and the support substrate 16 is made of a material that is hard and transparent to actinic rays such as ultraviolet rays, for example, glass, or a hard resin such as an acrylic resin, a polycarbonate resin, or a polyester resin.

In addition, as the rough-surfaced sheet 10, for example, a material that is transparent to actinic rays is used for the reinforcing film 11, the binder resin 13 forming the surface layer 12, and the fine particles 14.

The roughened surface sheet 10 is superimposed on the upper surface 18 of the support substrate 16 in the drawing so that the mold surface 15, which is the surface of the top sheet 12, is located above and the opposite surface 17, which is the exposed surface of the reinforcing film 11, is located below.

Specifically, for example, while one end of the opposite surface 17 of the roughened surface sheet 10 is brought into contact with the surface 18 of the support substrate 16, the roughened surface sheet 10 is sequentially superimposed from one end of the surface 18 toward the other end as indicated by the arrow of the dashed line in the figure.

The roughened surface sheet 10 overlapping the support substrate 16 is required to be resistant to positional displacement with respect to the support substrate 16 due to a shearing force when the spread liquid photosensitive resin composition is applied thereto, or a contraction force when the photosensitive resin composition is cured, and to be easily replaced after use.

Therefore, it is preferable that the roughened surface sheet 10 stacked on the support substrate 16 be detachably fixed to the surface 18 of the support substrate 16 by any one of the following methods (i) to (iii), for example.

(i) The roughened surface forming sheet 10 is detachably fixed to the surface 18 of the support substrate 16 by adhesion via a weakly adhesive layer containing a material that is transparent to actinic rays.

(ii) A suction groove is formed in the surface 18 of the support substrate 16, and vacuum suction is performed through the suction groove, whereby the roughened sheet 10 is suction-fixed to the surface 18 of the support substrate 16 so as to be attachable/detachable.

(iii) The roughened surface sheet 10 is press-fixed to the surface 18 of the support substrate 16 in a state of being spread between a pair of chuck jigs spaced apart from each other in the dimension in the surface direction of the support substrate 16.

As the weakly adhesive layer used for the adhesive fixation in (i), any of the following layers can be used: a layer having weak adhesion to both the support substrate 16 and the PET film as the reinforcing film 11, and containing various adhesives having transparency to actinic rays.

The weakly adhesive layer is formed by applying an adhesive to at least one of the surface 18 of the support substrate 16 and the opposite surface 17 of the roughened surface sheet 10 by various application methods such as spray application.

After the weakly adhesive layer is formed, as shown by the arrow of the chain line in fig. 5(a), the roughened surface sheet 10 is sequentially stacked with the back surface 17 facing downward from one end toward the other end of the surface 18 of the supporting substrate 16, with care being taken so that air does not enter therebetween.

In this case, the roughened surface sheet 10 is fixed to the surface 18 by the adhesive force of the weakly adhesive layer.

When the fixed roughened surface sheet 10 is removed from the surface 18, for example, the roughened surface sheet 10 may be sequentially peeled off from the other end of the support substrate 16 toward one end against the adhesive force of the weakly adhesive layer, contrary to the arrow in fig. 5 (a).

For the adsorption and fixation in (ii), the surface 18 of the support substrate 16 is smoothly finished, and a suction groove is formed substantially over the entire surface of the surface 18 and connected to a vacuum system including a vacuum pump and the like.

In the roughened surface sheet 10, the vacuum system is operated with the back surface 17 facing downward and being superposed on the front surface 18 of the support substrate 16, or the vacuum system operated first is connected to a suction tank.

In this manner, the overlapped roughened surface sheet 10 is vacuum-sucked through the suction grooves and fixed to the surface 18.

When the fixed matte sheet 10 is removed from the surface 18, the vacuum system may be stopped or the connection between the vacuum system and the suction groove may be interrupted.

Next, referring to fig. 5(b), in the manufacturing method of this example, a predetermined amount of liquid photosensitive resin composition 19 that forms the base of the resin layer 2 of the flexographic printing plate 1 is supplied onto the mold surface 15 of the roughened surface sheet 10 fixed to the surface 18 of the support substrate 16.

The supplied photosensitive resin composition 19 is sandwiched between the roughened surface sheet 10 and the reinforcing sheet 4 constituting the flexographic printing plate 1 together with the resin layer 2.

Further, as shown by the arrow of the dashed line in fig. 5(b), the photosensitive resin composition 19 is spread on the die surface 15 of the roughened surface sheet 10 in order from one end of the surface 18 of the support substrate 16 toward the other end, with care being taken so that air does not enter therebetween.

In this case, the layer 20 of the photosensitive resin composition 19 is formed, and the reinforcing sheet 4 is laminated thereon.

Next, referring to fig. 5(c), the facing surface 22 of the facing substrate 21 is brought into contact with the reinforcing sheet 4.

While the facing surface 22 of the facing substrate 21 is maintained in parallel with the surface 18 of the supporting substrate 16 with a constant gap therebetween, the facing substrate 21 is pressed in the direction of the supporting substrate 16 as indicated by black arrows in fig. 5(c), and the layer 20 is pressure-bonded to the die surface 15 of the roughened sheet 10.

In this state, the layer 20 is exposed to actinic rays through the support substrate 16 and the roughening sheet 10 as indicated by solid arrows in fig. 5(c), thereby curing the photosensitive resin composition 19 forming the layer 20.

At this time, the interval between the surface 18 of the support substrate 16 and the facing surface 22 of the facing substrate 21 is set as follows: the dimension obtained by adding the thickness of the roughened surface sheet 10 to the thickness of the flexographic printing plate 1 to be produced (i.e., the thickness of the resin layer 2 + the thickness of the reinforcing sheet 4) is maintained.

The opposing substrate 21 may be made of any material such as metal, glass, or hard resin.

Here, the counter substrate 21 may be formed of the same material as the supporting substrate 16, which is transparent to actinic rays, and the reinforcing sheet 4 may be formed of the same material as the roughened sheet 10, which is transparent to actinic rays.

In this case, for example, the photosensitive resin composition 19 may be cured by exposing the layer 20 to actinic rays not only from the supporting substrate 16 side but also from the counter substrate 21 side.

In this case, since the photosensitive resin composition 19 may be cured by exposing the layer 20 to actinic rays only from the side of the counter substrate 21, the roughened surface sheet 10 may be formed of a material that is not transparent to actinic rays, for example.

Next, referring to fig. 6(a) and 6(b), the laminate 23 of the reinforcing sheet 4 and the resin layer 2 and the roughened sheet 10 formed by curing the photosensitive resin composition 19 is taken out from between the supporting substrate 16 and the opposing substrate 21, and the reinforcing sheet 4 is placed on the work table 24 with the reinforcing sheet 4 facing downward.

Then, as shown by the arrow of the dashed line in fig. 6(b), the roughened surface sheet 10 is peeled off in order from one end of the laminate 23 toward the other end.

In this way, the roughened surface shape of the mold surface 15 of the roughened surface sheet 10 is transferred to the upper surface side in the drawing of the resin layer 2 to form a roughened plate surface 3, and a printing resin original plate 25 shown in fig. 6(c) is produced.

Thereafter, although not shown, 4 sides of the printing resin original plate 25 are cut to trim the entire planar shape into a rectangular shape.

Next, as shown in fig. 1, the resin layer 2 near the 2 parallel sides is thermally cut by, for example, laser processing, to form the grip portion 5, the groove portion 6, and the chuck hole 7.

If a predetermined print pattern is further formed on the plate surface 3 as necessary, the flexographic printing plate 1 is completed.

As the photosensitive resin composition 19, various resin compositions satisfying the following conditions can be used.

Can be hardened by exposure to actinic rays such as ultraviolet rays.

After hardening, it has a suitable flexibility or rubber elasticity for use in flexographic printing.

A cured product having excellent resistance (solvent resistance) to a solvent contained in ink used for printing or used for cleaning a printing plate can be formed.

The photosensitive resin composition satisfying these conditions is not limited to this, but examples thereof include a composition containing a prepolymer having a 1, 2-butadiene structure and an ethylenic double bond at the terminal, an ethylenically unsaturated monomer, and a photopolymerization initiator.

As the photopolymerization initiator, benzoin alkyl ether is preferable.

As the reinforcing sheet 4, for example, a sheet containing various thermoplastic resins such as Polyethylene (PE), polypropylene (PP), PET, tetrafluoroethylene hexafluoropropylene copolymer (FEP), and the like can be used.

As described above, the reinforcing sheet 4 preferably has transparency to actinic rays.

Method for manufacturing liquid crystal display element

The present invention is a method for manufacturing a liquid crystal display element, including a step of forming a liquid crystal alignment film by a flexographic printing method using the flexographic printing plate of the present invention.

Other steps of the method for manufacturing a liquid crystal display element can be performed in the same manner as before.

That is, a transparent electrode layer corresponding to a predetermined matrix pattern or the like is formed on the surface of a transparent substrate such as a glass substrate, a liquid crystal alignment film is formed through the above-described steps, and the surface of the liquid crystal alignment film is subjected to alignment treatment by rubbing or the like as necessary to produce a substrate.

Then, 2 substrates were prepared, and a liquid crystal material was sandwiched between the substrates and fixed to each other with the transparent electrode layers aligned, thereby forming a laminate, and polarizing plates were further disposed on both outer sides of the laminate as needed, thereby manufacturing a liquid crystal display element.

The configuration of the present invention is not limited to the example in the drawings described above.

For example, in the flexographic printing plate 1, the reinforcing sheet 4 may also be omitted.

In the method for manufacturing the flexographic printing plate 1, the layer 20 of the photosensitive resin composition is not pressed toward the support substrate 16 by the counter substrate 21, but is coated and spread to have a constant thickness by forming the roughened surface sheet 10 into a roll or the like, and the surface thereof is roughened.

In addition, various modifications can be made without departing from the scope of the present invention.