JP2005172896A - Coating liquid for antireflection film formation and antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide coating liquid for antireflection film and an antireflection film which has a visual low reflection factor while maintaining a low refractive index, and has high film strength and antifouling property. <P>SOLUTION: The coating liquid for antireflection film formation is characterized in that it contains hydrolysate liquid obtained by hydrolyzing and condensing compound particles consisting of porous particles and coating layers provided on porous particle surfaces or hollow particle having hollows inside and an alkoxy silicon compound of ≥0.1 in the ratio (A1/A2) of Raman scatter peak intensity (A2) measured within 20 minutes after the hydrolysis starts to Raman scatter peak intensity (A1) appearing between 660 and 645 cm<SP>-1</SP>, 300 to 10,000 in weight average molecular weight, and ≥1.8 in ration (W1/W2) of a half-value width (W2) at a peak 1/5 time as high as a maximum value of an absorption peak restored to Si-O tensile vibration in IR measurement to a half-value width at a peak which is 1/2. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antireflection film-forming coating liquid and an antireflection film, and more particularly to an antireflection film-forming coating liquid and an antireflection film having low luminous reflectance and high film strength and antifouling properties.

  For an antireflection film used on the outermost surface of a display device such as a liquid crystal, a technique has been proposed in which an antireflection layer of an optical interference system is provided to reduce the reflectance.

  As a technique for lowering the reflectance, it is known to lower the reflectance by lowering the refractive index of the low refractive index layer on the outermost surface. There are many low refractive index materials and methods that lower the refractive index by increasing the gap. However, the film strength is a weak point in any technique.

  A recently proposed technique using hollow silica-based fine particles having an outer shell layer and having a porous or hollow inside (for example, see Patent Documents 1 to 3) maintains a decrease in refractive index due to voids. This is a technique to increase the film strength. However, the film strength is insufficient, and there is a problem that when hollow fine particles are added in an amount of 20% by mass with respect to the binder component, the film strength falls below the practical film strength.

  In addition, a method of forming a metal oxide film by applying a metal alkoxide typified by titanium alkoxide or silane alkoxide on the surface of a support, drying, and heating has been performed. However, this method requires a high heating temperature of 300 ° C. or higher and damages the support, and the heating temperature as described in JP-A-8-75904 has a relatively low heating temperature of 100 ° C. A long time was required for the production, and both had problems.

  On the other hand, as a method of forming a metal oxide film, for example, a method of forming a silica-based film as a base film of a functional film by a so-called sol-gel method (see Patent Document 4), A method of forming by a sol-gel method (see Patent Document 5) is known. However, this method was also insufficient in scratch resistance.

In addition, the technique using a fluorine-based resin as a binder component (see, for example, Patent Documents 6 to 8) also has a problem that the film strength is weak although the refractive index is lowered. That is, there is a trade-off relationship between lowering the refractive index and film strength, and there is a need for improvement.
Japanese Patent Laid-Open No. 2001-167637 JP 2001-233611 A JP 2002-79616 A JP-A-11-269657 JP 2000-910 A JP 2003-236970 A JP 2003-240906 A JP 2003-255103 A

  An object of the present invention is to provide an antireflection film-forming coating solution and an antireflection film having low luminous reflectance, high film strength and antifouling properties while maintaining a low refractive index.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
In the coating liquid for forming an antireflection film containing inorganic fine particles and a matrix precursor, the inorganic fine particles are (1) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (2) A hollow particle having a void inside and filled with a solvent, a gas or a porous substance, and the matrix precursor is a hydrolyzed solution obtained by hydrolyzing and condensing an alkoxysilicon compound. The ratio (A1 / A2) between the Raman scattering peak intensity (A1) appearing at 660 to 645 cm ⁻¹ in Raman spectroscopy and the Raman scattering peak intensity (A2) measured within 20 minutes from the start of hydrolysis is 0.2 or less. There, the weight average molecular weight of 300 to 10,000, has an absorption attributed to Si-O stretching vibration between 1075～1055Cm ^-1 in IR measurement, 1172-11 Observed shoulder peak between 3 cm ^-1, and one-fifth of the height of the peak half width (W1) of the maximum value in the absorption peak attributable to Si-O stretching vibration between 1075～1055Cm ^-1 A coating liquid for forming an antireflection film, wherein the ratio of half width of peak half width (W2) (W1 / W2) is 1.8 or more.
(Claim 2)
The coating liquid for forming an antireflection film according to claim 1, wherein acetic acid or nitric acid is used as a hydrolysis catalyst in the hydrolysis of the alkoxysilicon compound.
(Claim 3)
The coating solution for forming an antireflection film according to claim 1 or 2, further comprising sodium acetate.
(Claim 4)
The coating liquid for forming an antireflection film according to any one of claims 1 to 3, wherein the inorganic fine particles are mixed when the alkoxysilicon compound is hydrolyzed.
(Claim 5)
An antireflection film comprising a low refractive index layer obtained by coating the coating liquid for forming an antireflection film according to claim 1.

  According to the present invention, it is possible to provide an antireflection film-forming coating solution and an antireflection film having low luminous reflectance, high film strength and antifouling properties while maintaining a low refractive index.

  As a result of diligent research, the present inventor has used hollow inorganic fine particles and a hydrolyzed liquid of an alkoxy silicon compound in which the degree of hydrolysis, the subsequent increase in molecular weight due to condensation, and the progress of oligomer or polymer formation are adjusted. The inventors have found that a coating solution for forming an antireflection film having a low luminous reflectance and a high film strength and antifouling property can be obtained while maintaining a low refractive index.

  Hereinafter, the present invention will be described in detail.

[Coating solution for forming low refractive index layer]
The coating solution for forming a low refractive index layer used in the present invention comprises the following inorganic fine particles, matrix precursor, solvent and the like. You may add a silane coupling agent, a hardening | curing agent, etc. as needed. As the matrix precursor, a hydrolyzed liquid of an alkoxysilicon compound is generally used.

[Inorganic fine particles]
The composite particles having the porous particles used in the present invention and the coating layer provided on the surface of the porous particles, or the hollow particles filled with a solvent, gas, or porous substance inside will be described.

  The inorganic fine particles are (1) composite particles composed of porous particles and a coating layer provided on the surface of the porous particles, or (2) a cavity inside, and the content is a solvent, gas or porous substance It is a hollow particle filled with. The antireflection film-forming coating solution only needs to contain either (1) composite particles or (2) hollow particles, or may contain both.

  Note that the cavity particles are particles having a cavity inside, and the cavity is surrounded by a particle wall. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such inorganic fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The inorganic fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and may be in the range of 2/3 to 1/10 of the film thickness of the formed transparent film such as a low refractive index layer. desirable. These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. In some cases, the composite particles enter the inside of the composite particles and the internal porosity is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. .

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. The coating layer of the composite particle or the particle wall of the hollow particle may contain a component other than silica, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO _2. CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain porous particles having a molar ratio MOX / SiO ₂ of less than 0.0001, and even if obtained, those having a lower refractive index are not obtained. On the other hand, if the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the silica ratio decreases, so that particles having a small pore volume and a low refractive index may not be obtained.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such inorganic fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the inorganic compound particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the above-described alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when seed particles are used, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, a silicic acid solution obtained by removing the alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step. Alternatively, it is preferable to form a silica protective film by adding a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

  The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organosilicon compound used for forming the silica protective film includes a general formula RnSi (OR ′) 4-n [R, R ′: hydrocarbon such as alkyl group, aryl group, vinyl group, acrylic group, etc. An alkoxysilane represented by the group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third Step: Formation of Silica Coating Layer In the third step, a hydrolyzable organosilicon compound or silicic acid solution is added to the porous particle dispersion prepared in the second step (in the case of hollow particles, a hollow particle precursor dispersion). Etc. is added to coat the surface of the particles with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

  Examples of the hydrolyzable organosilicon compound used for forming the silica coating layer include the general formula RnSi (OR ′) 4-n [R, R ′: alkyl group, aryl group, vinyl group, acrylic group as described above. Etc., and alkoxysilanes represented by n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.44. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

[Matrix precursor]
In the present invention, the matrix precursor is a reaction such as hydrolysis and subsequent condensation of an alkoxysilicon compound such as tetraethoxysilane, and after a predetermined time has elapsed, the SiO2 of the alkoxysilicon compound in the Raman spectroscopy of the hydrolyzed solution. _{4 The} Raman scattering peak intensity (A2) appearing at 660 to 645 cm ⁻¹ attributed to the total symmetry stretching vibration is 20% or less compared to the Raman scattering peak intensity (A1) measured within 20 minutes from the start of hydrolysis. An alkoxy silicon compound hydrolyzed solution is used. The matrix precursor and the inorganic fine particles are diluted with a solvent to prepare a low refractive index coating liquid (adding additives as necessary), and the polystyrene-reduced molecular weight using GPC in the prepared low refractive index coating liquid. The weight average molecular weight by measurement is in the range of 300 to 10,000, and Si—O by formation of a siloxane bond (—Si—O—Si—) between 1075 and 1055 cm ⁻¹ in IR measurement of the low refractive index coating liquid. The strongest absorption attributed to stretching vibrations appeared, and a shoulder peak between 1172 and 1153 cm ⁻¹ (the shoulder peak was not accurately assigned, but alkoxysilicon was condensed to form a lattice. It is estimated that it is derived from a silicon-oxygen bond), and a low refractive index coating solution is applied onto the film substrate at a predetermined level. Low-reflection layer obtained by cloth, was found to be required for stably obtain a low reflective layer excellent in the physical properties.

The degree to which a shoulder peak is recognized between 1172 and 1153 cm ⁻¹ in IR measurement of the low refractive index coating solution appears between 1075 and 1055 cm ⁻¹ because the shoulder peak does not become a peak having a clear maximum value. It is defined by the ratio of the half width of the strong absorption peak attributed to the Si—O stretching vibration. That is, the peak half-value width at the height of one fifth of the maximum value in the strong absorption peak attributed to the Si—O stretching vibration appearing between 1075 to 1055 cm ⁻¹ is W1, and the height is ½. When the peak half width is W2, the shoulder is recognized so that W1 / W2 is 1.8 or more.

  Hereinafter, the Raman spectroscopic measurement of the alkoxysilicon hydrolyzed liquid, the molecular weight measurement by GPC of the low refractive index layer coating liquid, and the IR measurement will be described.

<Raman spectroscopy measurement>
The peak intensity in Raman spectroscopy varies depending on the output of the irradiation laser, the exposure time to the sample, the laser irradiation position on the sample, the solid angle of the objective lens, the brightness of the spectrometer, the sensitivity of the detector, etc., but the same measurement The degree of hydrolysis can be determined quantitatively by measuring the measurement conditions with the apparatus completely aligned, by specifying the relative value and the relative residual ratio.

  That is, it is defined as a relative residual rate after the predetermined hydrolysis time has elapsed, assuming that the peak intensity at the time of unreacted (or measured within 20 minutes immediately after mixing) is 100%.

In the Raman spectroscopy measurement, for example, a basic probe condition is measured as follows using a holoprobe 532 manufactured by Kaiser Optical Systems. The coating solution is put in a glass sample tube (length: 4.8 mm, inner diameter: 6 mm, diameter: 8 mm cylindrical shape) as it is, and measurement is performed over 20 minutes under conditions of room temperature of 25 ° C. and humidity of 50%. (The spectrum immediately after preparation starts measurement immediately after preparation.)
Laser wavelength: 532 nm
Output: 50mW
Exposure time: 100 sec
Total number of times: 6 times Total measurement time: about 20 minutes (background (100 sec × 6 times = 600 sec), sample (100 sec × 6 times = 600 sec), total 20 minutes)
Data point: 0.5cm ^-1
Detector: Electro-cooled CCD detector Microscope: Olympus BX60, x20 is used as the objective lens during measurement.
Note that the spectrum is smoothed as necessary.

  FIG. 1 shows an example of a Raman scattering spectrum of a hydrolyzed composition of an alkoxysilicon compound based on the Raman spectroscopy measurement. A calculation method for obtaining (A2 / A1) using this will be described.

The peak attributed to the SiO ₄ total symmetry stretching vibration of the alkoxysilicon compound is specified as follows. That is, in the Raman scattering spectrum obtained by changing the hydrolysis time (Fig. 1), and at the 739cm ^-1 in wave number, also a line connecting the at the 568cm ^-1 in wave number as a baseline, 660～645Cm ^{For the} maximum peak (654 cm ⁻¹ ) attributed to SiO ₄ symmetrical stretching vibration appearing between ⁻¹ , the Raman scattering intensity at the time of unreacted (or within 20 minutes after mixing with the acid) is measured (referred to as A1), Subsequently, the Raman scattering intensity is measured by the same procedure from the Raman spectrum measured under the same conditions after a predetermined time has elapsed (referred to as A2). From the obtained data, the relative residual rate is calculated using the following formula.
(Raman scattering intensity after a predetermined time (A2) / Raman scattering intensity (A1) when not reacted (or within 20 minutes after mixing with acid)) × 100
In FIG. 1, (a) is a Raman scattering spectrum of a tetraethoxysilane (TEOS) -containing liquid before acid addition (when not reacted) measured under the above-described measurement conditions, and (b) and (c) are respectively acetic acid additions. It is a Raman scattering spectrum after 2 hours and after 20 hours. The Raman scattering peak (654 cm ⁻¹ ) attributed to the SiO ₄ total symmetry stretching vibration derived from the tetraethoxysilane (TEOS) becomes smaller as time elapses after the start of the hydrolysis treatment, as shown in FIG. In tetraethoxysilane (TEOS) when not reacted, the peak intensity (A1) = 12986, but it is 9740 after 2 hours from the addition of acetic acid, and 2078 after 20 hours. When the ratio of the peak intensity A2 when a predetermined time has elapsed with respect to the peak intensity A1 at the time of unreacted is expressed in%, in (b), A2 / A1 × 100 = 75 (%), 20 hours have elapsed after the acid addition In (c), A2 / A1 × 100 = 16 (%), so that a decrease in unreacted tetraethoxysilane (TEOS) can be quantitatively monitored.

  In this way, it is necessary to measure the relative residual rate of the alkoxysilicon compound and use a hydrolyzate having at least 20% or less.

  Further, in the present invention, it is necessary that not only hydrolysis but also condensation reaction accompanying hydrolysis reaction proceeds to some extent and molecular weight must be increased. GPC was used after preparing the low refractive index layer coating solution. It is necessary to measure the weight average molecular weight, and a coating solution having a weight average molecular weight of 300 to 10,000, preferably 500 to 5,000 is used. A coating solution in which a long time has passed after the addition of the hydrolysis catalyst and crosslinking due to condensation has become excessively deteriorated in the uniformity of the coating film, such as uneven application of the coating locally due to increased viscosity or gelation.

<GPC analysis conditions>
The weight average molecular weight measurement method by GPC is diluted with THF so that the sample solid content concentration becomes 0.8%, and the measurement is performed at a column temperature of 25 ° C. under the following conditions.
Column: Tosoh Corporation TSKgelG5000HXL-TSKgelG2000H XL
Eluent: THF
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Detection: RI Model 504 (manufactured by GL Sciences)
Sample concentration: 0.8%
Standard sample / calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples are used.

<Measurement of FT-IR-ATR>
In addition to molecular weight measurement, in the present invention, infrared absorption measurement is performed when the low refractive index coating solution is used, and a shoulder peak is observed at a certain degree between 1172 and 1153 cm ^−1. It is also necessary to use from the same. Although the shoulder peak is not assigned correctly, it is presumed to be due to silicon-oxygen bonds formed in a lattice form by condensation of alkoxysilicon and its hydrolyzate. A state in which a certain degree of crosslinking is formed is preferable for use as a coating solution. Therefore, in the present invention, not only the molecular weight but also the FT-IR-ATR measurement is performed after preparing the low refractive index coating solution.

  The apparatus and measurement of FT-IR-ATR can be performed under the following conditions. The device is a Magne 860 manufactured by Nicolet, and the single-reflection ATR device manufactured by Harrick is used for the ATR attachment.

The prism is a semi-cylindrical germanium prism, and the incident angle is 45 degrees. The resolution at the time of measurement is set to 4 cm ⁻¹ and the number of integrations is set to 64 times. Data interpolation is 0.5 cm ^−1, and measurement is performed by dropping the coating solution onto the germanium prism and drying at room temperature for 10 to 30 minutes to form a coating film, and then measuring at room temperature of 23 ° C. and humidity of 50%. Do.

  FIG. 2 shows an example of an absorption spectrum by FT-IR-ATR measurement of a low refractive index layer coating solution prepared from a hydrolyzed solution obtained by hydrolyzing the tetraethoxysilane for a predetermined time. It is a FT-IR-ATR measurement result of the coating film which dripped the low refractive index layer coating liquid on the germanium prism, and dried for 30 minutes at room temperature. In order to quantitatively evaluate the presence of a shoulder peak with a certain size, it is defined as follows.

As shown in FIG. 2, between 1172 and 1153 cm ⁻¹ recognized as the strongest absorption shoulder attributed to Si—O stretching vibration appearing between 1075 and 1055 cm ⁻¹ in the FT-IR-ATR measurement result. to quantitatively evaluate the magnitude of the peak, and the minimum value between 1284～1250Cm ^-1, as a baseline a line connecting a local minimum between the 1007～985Cm ^-1, between 1095～1060Cm ^-1 The peak height is measured for the maximum peak attributed to the Si—O stretching vibration appearing in (L). Next, a horizontal line is drawn from the baseline of the peak height at a height of ½ of the peak height, and the peak width (W2) of the portion where the line and the absorption peak intersect is measured. Similarly, a line is drawn horizontally at the height of 1/5 of the peak height from the base line, and the peak width (W1) of the portion where this line and the absorption peak intersect is measured. The ratio of these two peak widths is calculated.

W1 (1/5 height peak width) / W2 (1/2 height peak width)
When the shoulder peak size exceeds a predetermined level, this ratio increases.

  In the present invention, when this ratio is 1.8 or more, the lattice-like silicon-oxygen bond is appropriately formed, and by applying the low refractive index layer coating liquid in this state, A coating layer having excellent physical properties (hard surface hardness and hardly cracks) and good scratch resistance and alkali resistance can be obtained.

  FIG. 2 (a) is a coating solution hydrolyzed with acetic acid, and the peak width ratio at 24 hours after addition of acetic acid is about 2.10 when evaluated by the above method, while FIG. 2 (b) The peak width ratio after 6 hours of the coating solution hydrolyzed with hydrochloric acid is about 1.366.

  As described above, the state of the alkoxysilicon hydrolyzed solution prepared by allowing the hydrolysis reaction to occur for a predetermined time is monitored using Raman spectroscopic measurement, and other additives necessary for this are mixed and diluted. Even after preparing a low refractive index layer coating liquid (composition), the molecular weight is measured by GPC, and infrared spectroscopic measurement is performed to monitor the degree of cross-linking, and this is applied to a substrate such as a film. By drying, a low refractive index layer having excellent physical properties can be formed on the substrate. According to the present invention, by monitoring the above items, the adhesion and physical properties of the obtained low refractive index layer, that is, the surface hardness, the difficulty of entering cracks, scratch resistance, etc. are improved, and the low physical properties are stably reduced. The problem that the refractive index layer coating film cannot be obtained is solved. Moreover, it is excellent in the physical properties under high temperature and high humidity conditions.

  These low refractive index layer coating solutions according to the present invention are coated on a high refractive index layer formed on a film substrate, and by forming the low refractive index layer, the surface is hardly damaged, and there are few cracks or alkali. A highly resistant antireflection film (low reflection laminate) can be obtained.

(Alkoxy silicon compound)
In the present invention, the alkoxysilicon compound (hereinafter also referred to as alkoxysilane) used for the preparation of the coating solution for the low refractive index layer is preferably represented by the following general formula.

General formula R _4-n Si (OR ′) _n
Here, R and R ′ represent a hydrogen atom or a monovalent substituent, and n is 3 or 4.

  In the general formula, R ′ represents an alkyl group, R represents a hydrogen atom or a monovalent substituent, and n represents 3 or 4.

  Examples of the alkyl group represented by R ′ include groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, which may have a substituent, and the substituent exhibits properties as an alkoxysilane. If it is, there is no restriction | limiting in particular, For example, although it may be substituted by the halogen atom, the alkoxy group, etc., More preferably, it is an unsubstituted alkyl group, and especially a methyl group and an ethyl group are preferable.

  The monovalent substituent represented by R may be a compound exhibiting properties as an alkoxysilane, and specifically includes an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aromatic heterocyclic group, a silyl group. Group and the like. Of these, an alkyl group, a cycloalkyl group, and an alkenyl group are preferable. These may be further substituted. Examples of the substituent of R include various substituents that do not impair the properties of alkoxysilane, such as halogen atoms such as fluorine atom and chlorine atom, amino group, epoxy group, mercapto group, hydroxyl group, and acetoxy group.

Specific preferred examples of the alkoxysilane represented by the general formula include tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetra t- Butoxysilane, tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane,
Further, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, n-hexyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Mercaptopropyltrimethoxysilane, acetoxytriethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, (3, 3, - trifluoropropyl) trimethoxysilane, pentafluorophenyl phenylpropyl trimethoxysilane, further vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane and the like.

  Alternatively, quantified silicon compounds such as silicate 40, silicate 45, silicate 48, and M silicate 51 manufactured by Tama Chemical, in which these compounds are partially condensed may be used.

  Since the alkoxysilane has a silicon alkoxide group that can be hydrolyzed and polycondensed, these alkoxysilanes are crosslinked by hydrolysis and condensation to form a network structure of the polymer compound. A layer containing uniform silicon oxide is formed on the base material by applying it on the base material and drying it as a refractive index layer coating solution.

The hydrolysis reaction can be performed by a known method. In order to easily mix the hydrophobic alkoxysilane with water, a predetermined amount of water and a hydrophilic organic solvent such as methanol, ethanol, and acetonitrile coexist and dissolve. -After mixing, a hydrolysis catalyst is added to hydrolyze and condense the alkoxysilane. Usually, by carrying out hydrolysis and condensation reaction at 10 to 100 ° C., a liquid silicate oligomer having two or more hydroxyl groups is generated, and a hydrolyzed solution is formed. The degree of hydrolysis can be appropriately adjusted depending on the amount of water used. Here, the degree of hydrolysis and subsequent condensation appears between 660 and 645 cm ⁻¹ belonging to the total symmetry stretching vibration of SiO ₄ in the Raman spectroscopic measurement after hydrolysis and condensation for a predetermined time. The Raman scattering peak intensity (A2) is set to an intensity ratio of 20% or less compared to the Raman scattering peak intensity (A1) measured within 20 minutes from the start of hydrolysis.

  In this way, a hydrolyzed solution is prepared, diluted with a solvent, and if necessary, an additive is added and mixed with components necessary to form a low refractive index layer coating solution. A coating solution is used.

  In the present invention, it is preferable to use one or two kinds of methanol and ethanol as a solvent to be added to alkoxysilane together with water because it is inexpensive and has excellent properties and excellent hardness. . Although isopropanol, n-butanol, isobutanol, octanol, and the like can be used, the hardness of the obtained film tends to be low. The amount of the solvent is 50 to 400 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the tetraalkoxysilane before hydrolysis.

(Hydrolysis catalyst)
Examples of the hydrolysis catalyst include acids, alkalis, organic metals, metal alkoxides, etc. In the present invention, inorganic acids or organic acids such as sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, and boric acid are preferable, In particular, carboxylic acids such as nitric acid and acetic acid, polyacrylic acid, benzenesulfonic acid, paratoluenesulfonic acid, methylsulfonic acid, and the like are preferable, and among these, nitric acid, acetic acid, citric acid, tartaric acid, and the like are preferably used. In addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvic acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D- Gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are also preferably used.

  Of these, those which volatilize the acid during drying and do not remain in the film are preferred, and those having a low boiling point are preferred. Therefore, acetic acid and nitric acid are particularly preferable.

  The added amount is 0.001 to 10 parts by mass, preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the alkoxysilicon compound (for example, tetraalkoxysilane) to be used. In addition, the amount of water added may be equal to or greater than the amount that the partial hydrolyzate can theoretically hydrolyze to 100%, and an amount equivalent to 100 to 300%, preferably an amount equivalent to 100 to 200% is added.

  When the alkoxysilane is hydrolyzed, the inorganic fine particles are preferably mixed.

  The hydrolyzed solution is allowed to stand for a predetermined time after the start of hydrolysis, and is used after the so-called aging step, after the progress of hydrolysis reaches a predetermined level by the Raman spectroscopic measurement.

  The standing time is a time during which the above-described crosslinking by hydrolysis and condensation proceeds sufficiently to obtain desired film characteristics. Specifically, depending on the type of acid catalyst used, for example, acetic acid requires 15 hours or more at room temperature. The aging temperature affects the aging time. Generally, the aging proceeds quickly at high temperatures, but when heated to 100 ° C. or higher, gelation occurs, so heating at 20 to 60 ° C. and keeping the temperature are appropriate.

  The inorganic fine particles and additives are added to the silicate oligomer solution thus formed by hydrolysis and condensation, and necessary dilution is performed to prepare a low refractive index layer coating solution. The weight average molecular weight by GPC as described above and the measurement by FT-IR-ATR were performed, and the increase in molecular weight and the degree of crosslinking due to the formation of silicate oligomer or polymer by condensation were observed. By applying and drying, a layer containing an excellent silicon oxide film as a low refractive index layer can be formed.

  In the present invention, in addition to the above alkoxysilane, for example, a modified product modified with a silane compound (monomer, oligomer, polymer) having a functional group such as an epoxy group, an amino group, an isocyanate group, or a carboxyl group. It may be used alone or in combination.

Thus, the SiO ₂ content in the hydrolyzed liquid obtained from the alkoxysilicon compound is 1 to 100%, preferably 10 to 99%.

(Additive)
The coating solution for forming a low refractive index layer of the present invention may contain additives such as a silane coupling agent and a curing agent as necessary. The silane coupling agent is a compound represented by the following formula (2): It is.

Formula (2): RmSi (OR ′) n
In the formula, R is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), or a reaction such as a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group, a carboxyl group, or an alkoxyl group. R ′ represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), and m + n is 4.

  Specific examples include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 3- (2-aminoethylaminopropyl) trimethoxysilane.

  Examples of the curing agent include organic acid metal salts such as sodium acetate and lithium acetate, and sodium acetate is particularly preferable. The amount of addition to the silicon alkoxysilane hydrolysis solution is preferably in the range of about 0.1 to 1 part by mass with respect to 100 parts by mass of the solid content present in the hydrolysis solution.

  Moreover, it is preferable to add various surface leveling agents, surfactants, low surface tension substances such as silicone oil to the coating solution for each layer of the present invention. Specific silicon oils include the compounds in Table 1.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. When these components are added in an excessive amount, they cause repelling during coating. Therefore, it is preferable to add them in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

(solvent)
Solvents used in the coating solution for coating the low refractive index layer according to the present invention are alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellsolve, butylcellsolve, ethylcarbitol, butylcarbitol, diethylcellsolve, diethylcarbitol And glycol ethers such as propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, water, and the like. These may be used alone or in combination of two or more.

  An antireflection film (low reflection laminate) provided with a low refractive index layer formed by using the low refractive index layer coating solution according to the present invention will be described.

(Layer structure)
The antireflection film (low reflection laminate) in which the low refractive index layer according to the present invention is laminated as an optical interference layer is a high refractive index layer from the support side on at least one surface of the support, and the low refractive index according to the present invention. This is a laminated body of optical interference layers in which refractive index layers are laminated in order (other layers may be added as described later), and the optical film thicknesses of the high refractive index layer and the low refractive index layer with respect to light of wavelength λ. Is set to λ / 4 to produce an antireflection laminate. The optical film thickness is an amount defined by the product of the refractive index n and the film thickness d of the layer. The level of the refractive index is substantially determined by the metal or compound contained therein. For example, the high refractive index layer is formed of a Ti compound, and the low refractive index layer is formed of a compound containing Si or F. The refractive index and the film thickness can be calculated and calculated by measuring the spectral reflectance.

  As the antireflection film (low reflection laminate), a film composed of a multilayer optical interference layer, for example, a film obtained by coating a clear hard coat layer with a low reflection layer can be considered. The low-reflection laminate has a hard coat layer, which will be described later, on a transparent substrate as necessary, and a refractive index, a film thickness, the number of layers, and a layer so that the reflectance is reduced by optical interference on the layer. Some are laminated in consideration of order, others are coated with a single layer. The antireflection layer is usually composed of a combination of a high refractive index layer having a higher refractive index than that of the substrate and a low refractive index layer having a lower refractive index than that of the substrate. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer). , A layer having a lower refractive index than the high refractive index layer) / a high refractive index layer / a low refractive index layer, and the like. Among them, from the viewpoint of durability, optical properties, productivity, etc., a medium refractive index layer / a high refractive index layer / a low refractive index layer laminated in this order on a substrate having a hard coat layer, a medium refractive index layer / What laminated | stacked the low-refractive-index layer is preferable.

  The example of the preferable layer structure of the antireflection film (low reflection laminated body) concerning this invention is shown below.

Base film / hard coat layer / low refractive index layer Base film / hard coat layer / medium refractive index layer / low refractive index layer Base film / hard coat layer / high refractive index layer / low refractive index layer Base film / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Base film / Anti-glare layer / High refractive index layer / Low refractive index layer Base film / Anti-glare layer / Medium refractive index layer / High refractive index Index layer / Low refractive index layer Base film / Antistatic layer / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Antistatic layer / Base film / Hard coat layer / Medium refractive index layer / High refractive index layer / low refractive index layer Base film / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer Antistatic layer / base film / antiglare layer / medium refractive index Layer / high refractive index layer / low refractive index layer antistatic layer / base film / antiglare layer / high refractive index layer / low refractive index layer / high refractive Index layer / low refractive index layer As long as the reflectance can be reduced by optical interference, it is not particularly limited to these layer configurations. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO, etc.), and can be provided by coating or atmospheric pressure plasma treatment.

(Medium refractive index layer, coating liquid for forming a high refractive index layer)
The medium refractive index layer and the high refractive index layer are not particularly limited as long as a predetermined refractive index layer is obtained, but are preferably composed of metal oxide fine particles having a high refractive index, a binder, a solvent, and the like. In addition, you may contain an additive. The refractive index of the middle refractive index layer is preferably 1.55 to 1.75, and the refractive index of the high refractive index layer is preferably 1.75 to 1.95.

(Metal oxide fine particles)
Although metal oxide fine particles are not particularly limited, for example, titanium dioxide, aluminum oxide (alumina), zirconium oxide (zirconia), zinc oxide, antimony-doped tin oxide (ATO), antimony pentoxide, indium-tin oxide (ITO), Iron oxide or the like can be used as a main component. A mixture of these may also be used. When titanium dioxide is used, photocatalytic activity can be achieved by using metal oxide particles having a core / shell structure in which titanium dioxide is the core and the shell is coated with alumina, silica, zirconia, ATO, ITO, antimony pentoxide, or the like. It is preferable in terms of suppression. When a conductive material such as ATO, ITO, or antimony pentoxide is used for the metal oxide fine particles, conductivity can be imparted.

  The refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, more preferably 1.90 to 2.50. The average particle size of the primary particles of the metal oxide fine particles is 5 to 200 nm, more preferably 10 to 150 nm. If the particle size is too small, the metal oxide fine particles tend to aggregate and the dispersibility deteriorates. If the particle size is too large, the haze increases, which is not preferable. The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

  The metal oxide fine particles may be surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are most preferred. Two or more kinds of surface treatments may be combined.

  By appropriately selecting the kind and addition ratio of the metal oxide, a high refractive index layer and a medium refractive index layer having a desired refractive index can be obtained.

(Binder)
The binder is added to improve the film formability and physical properties of the coating film. As the binder, for example, ionizing radiation curable resin, acrylic resin, methacrylic resin, or the like can be used.

(Ionizing radiation curable resin)
As the ionizing radiation curable resin, a monomer or oligomer having two or more functional groups that cause polymerization reaction directly by irradiation of ionizing radiation such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator is used. Can be used. Examples of the functional group include a group having an unsaturated double bond such as a (meth) acryloyloxy group, an epoxy group, and a silanol group. Among these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. Examples of such compounds include polyfunctional acrylate compounds. Here, the polyfunctional acrylate compound is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient. The ionizing radiation curable resin preferably has a hydroxyl group in the molecule.

The ionizing radiation used in the present invention can be used without limitation as long as it is an energy source that activates the compound by ultraviolet rays, electron beams, γ rays, etc., but ultraviolet rays and electron beams are preferable, especially easy handling and high energy are easy. Ultraviolet rays are preferable in that they are obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 40 to 2000 mJ / m ^2, more preferably 100 to 1500 mJ / cm ² . If the amount of irradiation light is small, curing is insufficient, and if the amount of irradiation is too large, base deformation or the like due to heat generation occurs. The ultraviolet rays may be irradiated to the multilayer antireflection layer one by one or after lamination.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 KeV emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type, preferably 100 to 100 An electron beam having an energy of 300 KeV can be mentioned.

  In order to accelerate the curing of the ionizing radiation curable resin, the photopolymerization initiator is preferably contained in an amount of 5 to 30% by mass with respect to the ionizing radiation curable resin. The photopolymerization initiator is not particularly limited, and various known ones can be used. As a photoinitiator, photoinitiators, such as Irgacure 184, Irgacure 651 (made by Ciba Specialty Chemicals), Darocur-1173 (made by Merck), etc., can be used, for example. Furthermore, you may use together photosensitizers, such as a benzophenone, a benzoyl methyl benzoate, p-dimethylbenzoic acid ester, and thiochitosan.

(Acrylic resin or methacrylic resin)
As the acrylic or methacrylic resin, an alcohol-soluble acrylic resin or methacrylic resin having a molecular weight of 100,000 to 500,000 can be preferably used. Specifically, an alkyl (meth) acrylate polymer or an alkyl (meth) acrylate copolymer, for example, a copolymer such as n-butyl methacrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, is preferably used. The copolymer component is not limited to these. Commercially available products include Dianal BR-50, BR-51, BR-52, BR-60, BR-64, BR-65, BR-70, BR-73, BR-75, BR-76, BR-77. , BR-79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-89, BR-90, BR-93, BR-95, BR-96, BR -100, BR-101, BR-102, BR-105, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118 (above, Mitsubishi Rayon Co., Ltd.) can be used.

The acrylic resin or methacrylic resin preferably has a Tg (glass transition point) of 30 ° C. or lower. Tg is measured using a SOLIDS ANALYZER-RSAII manufactured by Rheometrics with a frequency of 100 rad / sec and a strain of 8.0 × 10 ⁻⁴ , and the temperature at which the peak value of tan δ reaches the glass transition. It can be obtained as a point (Tg).

(Metal compounds, silane coupling agents)
As other additives, a metal compound, a silane coupling agent, and the like may be added. Metal compounds and silane coupling agents can also be used as binders.

  As the metal compound, a compound represented by the following formula (1) or a chelate compound thereof can be used.

Formula (1): A _n MB _xn
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the above formula (1) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxides, zirconium alkoxides, silicon alkoxides or chelate compounds thereof from the viewpoints of the reinforcing effect of refractive index and coating film strength, ease of handling, material cost, and the like. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Silicon alkoxide has a slow reaction rate and a low refractive index, but is easy to handle and has excellent light resistance. Since the silane coupling agent can react with both the inorganic fine particles and the organic polymer, a tough coating film can be formed. Moreover, since titanium alkoxide has the effect of promoting the reaction between the ultraviolet curable resin and the metal alkoxide, the physical properties of the coating film can be improved even by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  The silicon alkoxide and the silane coupling agent are compounds represented by the following formula (2).

Equation _{(2): R m Si (} OR ') n
In the formula, R is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), or a reaction such as a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group, a carboxyl group, or an alkoxyl group. R ′ represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), and m + n is 4.

  Specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapenta Ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane , Γ-glycidoxypropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane and the like.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against water mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably less than 5% by mass in terms of metal oxide in the medium refractive index composition, and less than 20% by mass in terms of metal oxide in the high refractive index composition. Is preferred.

(Hard coat layer)
The low reflection laminate of the present invention can be provided with a hard coat layer. In particular, it is preferable to provide an active energy ray-curable resin layer as a hard coat layer on a substrate and provide the optical interference layer thereon.

  It is preferable to provide a hard coat layer between the optical interference layer including the low refractive index layer and the high refractive index layer according to the present invention and the substrate. The hard coat layer used in the present invention may be formed directly on the substrate or may be formed on another layer such as an antistatic layer or an undercoat layer.

  The hard coat layer used in the present invention preferably contains an active energy ray-curable resin that is cured by irradiation with active energy rays such as ultraviolet rays. The same active energy ray curable resin as that described above can be used as the active energy ray curable resin. The light source of active energy rays, the irradiation amount, the photoinitiator and the photosensitizer, the amount of use thereof, and the like are the same as described above.

  The hard coat layer used in the present invention preferably has a refractive index in the range of 1.45 to 1.70 from the viewpoint of optical design for obtaining an antireflection film. Moreover, the film thickness of a hard-coat layer can be made into the range of 0.5-15 micrometers. This is because if the film thickness is less than 0.5 μm, sufficient durability and impact resistance cannot be obtained, and if the film thickness exceeds 15 μm, there is a problem in flexibility or economy. More preferably, it is 0.5-7 micrometers.

  In order to increase the heat resistance of the cured layer, an antioxidant that does not inhibit the photocuring reaction can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-t-3-methylphenol), 4,4′-butylidenebis (6-t-butyl-3-methylphenol), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-t-butylbenzyl phosphate.

  Examples of the ultraviolet curable resin include Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) ), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101 FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 )), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UC Corporation), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102 RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.), Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sun Rad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (Grace (Available from Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), or other commercially available products.

  The coating composition of the active energy ray-curable resin layer preferably has a solid content concentration of 10 to 95% by mass, and an appropriate concentration is selected depending on the coating method.

As the light source for forming the cured coating layer by photocuring reaction of the active energy ray curable resin, any light source that generates ultraviolet rays can be used. Specifically, the light source described in the item of the active energy ray can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~1200mJ / cm ^2, preferably from 50~1000mJ / cm ^2. From the near ultraviolet region to the visible light region, it can be used by using a sensitizer having an absorption maximum in that region.

  The active energy ray-curable resin composition is applied and dried, and then irradiated with ultraviolet rays. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 minutes from the curing efficiency and work efficiency of the ultraviolet curable resin. Is more preferable.

  In order to impart antiglare properties to the surface of the liquid crystal display panel, to prevent adhesion to other substances, and to improve scratch resistance, etc., an inorganic or organic coating composition for the cured coating layer is used. Fine particles can also be added.

  Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, antimony oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate.

  The organic fine particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin. Examples thereof include powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluoroethylene resin powder. These can be used in addition to the ultraviolet curable resin composition. The average particle size of these fine particle powders is 0.01 to 10 μm, and the amount used is desirably 0.1 to 20 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin composition. . In order to impart an antiglare effect, it is preferable to use 1 to 15 parts by mass of fine particles having an average particle diameter of 0.1 to 1 μm with respect to 100 parts by mass of the ultraviolet curable resin composition.

  By adding such fine particles to the ultraviolet curable resin, it is possible to form an antiglare layer having preferable irregularities having a center line average surface roughness Ra of 0.1 to 0.5 μm. Further, when such fine particles are not added to the ultraviolet curable resin composition, the hard surface having a good smooth surface with a center line average surface roughness Ra of less than 0.05 μm, more preferably less than 0.002 to 0.04 μm. A coat layer can be formed. A high refractive index layer (preferably a refractive index of 1.6 to 2.3), a low refractive index layer (preferably a refractive index of 1.35 to 1.5), and the like are further formed on these hard coat layers and the like. An antireflection layer can also be formed. Alternatively, it is preferable to provide a medium refractive index layer.

  In addition, as an element that performs the blocking prevention function, 0.1 to 5 parts by mass of ultrafine particles having a volume average particle size of 0.005 to 0.1 μm with the same components as described above with respect to 100 parts by mass of the resin composition Can also be used.

In the active energy ray-curable resin-containing layer used in the present invention, a binder such as a known thermoplastic resin, thermosetting resin, or hydrophilic resin such as gelatin can be mixed with the active energy ray-curable resin. . These resins preferably have polar groups in the molecule. Examples of the polar _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali A metal or an ammonium group, X represents an acid forming an amine salt, R represents a hydrogen atom or an alkyl group).

(Application method)
Low refractive index layer middle refractive index layer, high refractive index layer, hard coat layer Application method of dipping, spin coat, knife coat, bar coat, air doctor coat, blade coat, squeeze coat, reverse roll coat, A known coating method such as gravure roll coating, curtain coating, spray coating, die coating or the like can be used, and a coating method capable of continuous coating or thin film coating is preferably used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm in terms of wet film thickness. The coating speed is preferably 10 to 60 m / min.

  When the composition of the present invention is applied to a substrate, the thickness of the layer, coating uniformity, and the like can be controlled by adjusting the solid content concentration and the coating amount in the coating solution. Moreover, in order to improve the applicability | paintability of a composition, you may add a trace amount surfactant etc. in a coating liquid.

(Base film)
As a base film used for the antireflection film (low reflection laminate) of the present invention, it is easy to produce, a hard coat layer or an antireflection layer is easily adhered, and is optically isotropic. In particular, it is preferably optically transparent. Any of these may be used, for example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate. Polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin Film, polymethylpentene film, polyetherketone film, Polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, cycloolefin polymer films, there may be mentioned polymethyl methacrylate film or an acrylic film or the like, but are not limited to. Of these, cellulose triacetate films (for example, KC8UX2MW, KC4UX2MW, KC4UNY, KC5UN (manufactured by Konica Minolta Opto)), polycarbonate films, and polysulfones (including polyethersulfone) are preferable. In the present invention, cellulose triacetate is particularly preferable. A film or a cellulose acetate propionate film is preferable from the viewpoint of production, cost, transparency, isotropy, adhesiveness and the like.

(Cellulose ester film)
The cellulose ester used in the present invention is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 8-231761 , Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  If the molecular weight of the cellulose ester is too small, the tear strength decreases. However, if the molecular weight is excessively increased, the viscosity of the cellulose ester solution becomes too high, resulting in a decrease in productivity. The molecular weight of the cellulose ester is preferably 70,000 to 200,000, more preferably 100,000 to 200,000 in terms of number average molecular weight (Mn).

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Of these, cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group is usually present as a hydroxyl group. These can be synthesized by known methods.

  As the cellulose ester, a cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from cotton linter (hereinafter sometimes referred to simply as linter) alone or in combination.

  The cellulose ester film used in the present invention is preferably stretched at least in the width direction, and is 1.01-1 in the width direction particularly when the residual amount of peeling is 3 to 40% by mass in the solution casting step. It is preferable that the film is stretched 5 times. More preferably, it is biaxially stretched in the width direction and the longitudinal direction, and when the amount of residual dissolution is 3 to 40% by mass, it is 1.01 to 1.5 times in the width direction and the longitudinal direction, respectively. It is desirable to be stretched. By carrying out like this, the antireflection film excellent in visibility can be obtained. Furthermore, by performing biaxial stretching and knurling, it is possible to remarkably improve the deterioration of the winding shape during storage of the long low-reflection film in a roll form.

  The draw ratio at this time is preferably 1.01 to 1.5 times, and more preferably 1.03 to 1.45 times.

  The cellulose ester film according to the present invention is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film support according to the present invention preferably has a thickness of 10 to 100 μm, and the moisture permeability is preferably 200 g / m ² · 24 hours or less at 25 ° C. and 90 ± 2% RH. More preferably, it is 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less.

  In particular, it is preferable that the film thickness is 10 to 60 μm and the moisture permeability is within the above range.

  Here, the moisture permeability of the support was measured according to the method described in JIS Z 0208.

(Plasticizer)
When a cellulose ester film is used for the support used in the present invention, the following plasticizer is preferably contained. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethylglycolate, butylphthalylbutylglycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid, and the like can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl- Examples include 1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable. There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof. Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. And aromatic monocarboxylic acids possessed by them, or derivatives thereof. Particularly preferred is benzoic acid. The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used in the polyhydric alcohol ester of the present invention may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are.

  These plasticizers are preferably used alone or in combination.

  The amount of these plasticizers used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film performance, processability and the like.

(UV absorber)
The ultraviolet absorber according to the support used in the present invention will be described. For the support of the low reflection laminate, an ultraviolet absorber is preferably used.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. It is not limited to these.

  As the benzotriazole ultraviolet absorber, a compound represented by the following general formula (7) is preferably used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber used for this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (8) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone-based compound represented by the general formula (8) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the above-mentioned ultraviolet absorbers preferably used in the present invention, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers that are highly transparent and excellent in preventing deterioration of polarizing plates and liquid crystals are preferable, and unnecessary coloring A benzotriazole-based ultraviolet absorber with a lower content is particularly preferably used.

  In addition, an ultraviolet absorber having a distribution coefficient of 9.2 or more described in Japanese Patent Application No. 11-295209 is excellent in surface quality of the support and excellent in coating properties when used in the support. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorber (or ultraviolet ray) described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039. Absorbable polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

(Back side)
In the present invention, the back surface of the antireflection film (low reflection laminate) provided with the optical interference layer including the low refractive index layer according to the present invention has 1 to 500 protrusions having a height of 0.1 to 10 μm. It is preferable to have 0.01 mm ² . Preferably from 10 to 400 pieces /0.01mm ^2, more preferably from 15 to 300 pieces /0.01mm ^2. This not only prevents the occurrence of blocking even if it is wound into a roll once during the application of each optical interference layer, but can also significantly reduce coating unevenness when the next optical interference layer is applied. . Although the cause of coating unevenness is not completely clarified, it is presumed that as one of the causes, peeling electrification at the time of feeding a film wound up in a roll shape to the coating process is related. By adding fine particles into the base film, it is possible to have 1 to 500 protrusions / 0.01 mm ² with a height of 0.1 to 10 μm on the back surface. At this time, the base film can be formed into a multilayer structure, and fine particles can be included only in the surface layer.

  The fine particles to be added may be organic compounds or inorganic compounds, such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate. It is preferable to contain inorganic fine particles such as magnesium silicate and calcium phosphate and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film. The average particle size of the secondary particles of the fine particles is 0.1 to 10 μm, and the content is preferably 0.04 to 0.3% by mass with respect to the cellulose ester of the base material. In many cases, fine particles such as silicon dioxide are surface-treated with an organic substance, which is preferable because the haze of the film can be reduced. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the mat effect, and on the contrary, the smaller the average particle size is, the better the transparency. It is. As the fine particles of silicon dioxide, AEROSIL (Aerosil) 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Aerosil Co., Ltd. can be mentioned, preferably AEROSIL (Aerosil) 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

  In the present invention, the fine particles may be dispersed together with cellulose ester, other additives and an organic solvent at the time of preparing the dope. However, the dope may be dispersed in a sufficiently dispersed state like a fine particle dispersion separately from the cellulose ester solution. Is preferably prepared. In order to disperse the fine particles, it is preferably preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force. After that, it is preferable to disperse in a larger amount of organic solvent, merge with the cellulose ester solution, and mix with an in-line mixer to obtain a dope. In this case, an ultraviolet absorbent may be added to the fine particle dispersion to form an ultraviolet absorbent liquid.

Moreover, by providing a layer containing fine particles on the back surface side of the optical interference layer, a low reflective laminate having 1 to 500 protrusions with a height of 0.1 to 10 μm / 0.01 mm ² on the back surface is provided. Can do.

(Deflection plate)
When the antireflection film according to the present invention is used as the protective film for a polarizing plate on the outermost surface of the liquid crystal display device, at least one surface of the polarizing film is bonded to the antireflection film of the present invention to produce a polarizing plate.

  Here, the polarizing film refers to an element that passes only light having a plane of polarization in a certain direction, and there are one in which the polyvinyl film according to the present invention is dyed with iodine and one in which the dichroic dye is dyed. These are formed by forming a polyvinyl alcohol aqueous solution into a film and uniaxially stretching it to dye it. However, after dyeing and uniaxially stretching, those subjected to a durability treatment with a boron compound are preferably used. The antireflection film of the present invention is bonded as a protective film for a polarizing plate on both surfaces of the polarizing film thus produced to form a polarizing plate. When using as a polarizing plate protective film to produce a polarizing plate by using a 5% aqueous solution of completely saponified polyvinyl alcohol as an adhesive to produce a polarizing plate, the antireflective film according to the present invention is subjected to a treatment such as alkali saponification. Alkali resistance is required.

  The antireflection film of the present invention is a liquid crystal display member, for example, a polarizing plate, a protective film for a polarizing plate, a retardation plate, a reflecting plate, a viewing angle improving film, an antiglare film, an antireflection film, an antistatic film, etc. Applicable to.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
An antireflection film 1 was produced according to the following method.

  A cellulose acetate film (Konica Minolta Opto KC8UX, thickness 80 μm) was used as a transparent substrate. The following hard coat layer composition 1 was applied to one surface of this cellulose acetate film, dried at 80 ° C. for 30 seconds, and then cured by irradiation with a 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds to obtain a hard coat layer. 1 was provided. The thickness of the hard coat layer 1 was 6.0 μm.

<< Preparation of hard coat layer >>
<Hard coat layer composition 1>
Dipentaerythritol hexaacrylate monomer 600g
Dipentaerythritol hexaacrylate dimer 200g
Dipentaerythritol hexaacrylate trimer 200g
Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) 20g
10g of silicone surfactant
Methyl ethyl ketone 500g
Ethyl acetate 500g
Isopropyl alcohol 500g
Next, an antireflection film 1 was prepared by coating an antireflection layer in the order of a medium refractive index layer, a high refractive index layer, and a low refractive index layer.

<< Preparation of antireflection layer: medium refractive index layer >>
On the hard coat layer, the following medium refractive index layer composition 1 was applied by an extrusion coater, dried at 100 ° C. for 30 seconds, and then irradiated with an 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds. A refractive index layer 1 was provided. The thickness of the medium refractive index layer 1 was 95 nm.

<Medium refractive index layer composition 1>
LCOM V-2504 (manufactured by Catalyst Kasei Kogyo Co., Ltd., ITO sol, solid content 20%)
100g
Dipentaerythritol hexaacrylate 6.4g
Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) 1.6g
Tetrabutoxy titanium 4.0g
10% FZ-2207 (Nihon Unicar Co., Ltd., propylene glycol monomethyl ether solution) 3.0 g
Isopropyl alcohol 530g
90g of methyl ethyl ketone
265 g of propylene glycol monomethyl ether
<Preparation of antireflection layer: high refractive index layer>
On the medium refractive index layer, the following high refractive index layer composition 1 was applied with an extrusion coater, dried at 100 ° C. for 30 seconds, and then irradiated with an 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds, A high refractive index layer 1 was provided. The thickness of the high refractive index layer 1 was 50 nm.

<High refractive index layer composition 1>
RTSPNB (Cai Kasei Kogyo Co., Ltd., titanium oxide fine particle dispersion, solid content 15%)
60g
γ-methacryloxypropyl trimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.)
2g
Tetrabutoxy titanium 5g
10% FZ-2207 (Nihon Unicar Co., Ltd., propylene glycol monomethyl ether solution) 3 g
Isopropyl alcohol 560g
90g of methyl ethyl ketone
280 g of propylene glycol monomethyl ether
<< Preparation of antireflection layer: low refractive index layer >>
On the high refractive index layer, the following low refractive index layer composition 1 was applied with an extrusion coater, dried at 100 ° C. for 30 seconds, and then irradiated with an 80 W / cm high-pressure mercury lamp from a distance of 12 cm for 4 seconds, A low refractive index layer 1 was provided. The thickness of the low refractive index layer 1 was 100 nm.

<Preparation of hydrolyzate A>
172 g of tetraethoxysilane and 700 g of ethanol were mixed, and 129 g of 0.4% nitric acid aqueous solution was added thereto to prepare a hydrolyzate A.

  Furthermore, the hydrolysis reaction proceeds by stirring the hydrolyzed liquid A at room temperature (25 ° C.) for 5 hours, and the measurement results of Raman spectroscopy, GPC analysis, and FT-IR-ATR fall within the target ranges. It was prepared as follows. Raman spectroscopy, GPC analysis, and FT-IR-ATR were measured according to the following methods. The measurement results are shown in Table 2.

<Measurement of Raman spectroscopy>
The measuring device is a holoprobe 532 manufactured by Kaiser Optical Systems. The hydrolyzed solution is directly put into a glass sample tube (length 4.8 mm, inner diameter 6 mm, diameter 8 mm cylindrical shape) and measured at 25 ° C. and humidity 50%. did. The basic measurement conditions are as follows.

Laser wavelength: 532 nm
Output: 50mW
Exposure time: 100 sec
Total number of times: 6 Total measurement time: Approximately 20 minutes (10 minutes for each background and sample)
Data point: 0.5cm ^-1
Detector: Electro-cooled CCD detector Microscope: Olympus BX60, x20 was used as the objective lens during measurement.
The spectrum was smoothed as necessary.

Calculation of measurement results by Raman spectroscopy was performed as follows. With the line connecting the average value of 758 to 720 cm ^{-1 and} the average value of 590 to 547 cm ^-1 as the baseline, it is attributed to SiR _n (OR) _4-n symmetrical stretching vibration that appears between 660 to 645 cm ^-1 The Raman scattering intensity of the silicon compound within 20 minutes from the start of hydrolysis was measured for the maximum peak, and then the Raman scattering intensity was measured from the Raman spectrum measured under the same conditions 20 hours after the start of hydrolysis. From the obtained data, the relative residual ratio was calculated using the following formula.

Relative residual ratio = Raman scattering intensity after 20 hours (A1) / Raman scattering intensity within 15 minutes from start of hydrolysis (A2) × 100 (%)
<GPC measurement conditions>
The sample was diluted with THF so that the solid content concentration was 0.8%, and the measurement was performed at a column temperature of 25 ° C.

Column: Tosoh Corporation TSKgelG5000HXL-TSKgelG2000HXL
Eluent: THF
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Detection: RI Model 504 (manufactured by GL Sciences)
Sample concentration: 0.8%
Standard sample and calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000 to 500 standard calibration curves with 13 standard samples were used. It is preferable to obtain 13 standard samples at approximately equal intervals.

<Measurement of FT-IR-ATR>
The apparatus and measurement of FT-IR-ATR were performed under the following conditions. The device used was a Nicolet Corp., Magna 860, and the ATR attachment was a Harrick Inc. single reflection ATR device. The prism was a semi-cylinder and a refractive index of 4.00 germanium prism was used. The resolution at the time of measurement was set to 4 cm ⁻¹ and the number of integrations was set to 64 times. Data interpolation was 0.5 cm ⁻¹ . The measurement was carried out under conditions of 23 ° C. and 50% humidity after dropping the coating solution onto a germanium prism and drying at room temperature for 10 to 30 minutes.

The calculation method by IR was performed as follows.
The line connecting the minimum value between the minimum value and 1007～985Cm ^-1 between 1284～1250Cm ^-1 as the baseline, peak attributed to Si-O stretching vibration appearing between 1095～1060Cm ^-1 Measure the peak height for the peak. Next, a horizontal line is drawn from the baseline of the peak height at a half height of the peak height, and the half width (peak width, W2) of the portion where the line and the absorption peak intersect is measured. . Similarly, a line is drawn horizontally at a height of one-fifth of the peak height from the base line, and the half width (peak width, W1) of the portion where the line and the absorption peak intersect is measured. The ratio of the two peak widths (W1 / W2) is calculated.

(Low refractive index layer composition 1)
The following low refractive index layer composition 1 was prepared using the produced hydrolyzed liquid A.

Propylene glycol monomethyl ether 366 parts by mass Isopropyl alcohol 366 parts by mass Hydrolyzed liquid A (hydrolysis time 5 hours) 232 parts by mass ELCOM P special product 4 (manufactured by Catalytic Chemical Industry, hollow silica dispersion, solid content 20%)
29 parts by mass γ-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.)
2.1 parts by mass 10% FZ-2207 (manufactured by Nippon Unicar Co., Ltd., propylene glycol monomethyl ether solution) 1.9 parts by mass Reflecting in the same manner as the antireflection film 1 except that the following hydrolysates B to I were used Prevention films 2 to 21 were produced. However, the reaction time of the hydrolyzed solution and the addition amount of the ELCOM P special product 4 were changed as shown in Table 2. Moreover, about the antireflection films 19 and 20, sodium acetate was added so that it might become the quantity of Table 2. In addition, the addition amount of Table 2 is the mass% with respect to solid content in a coating liquid.

<Preparation of hydrolyzate B>
289 g of tetraethoxysilane and 553 g of ethanol were mixed, and 157 g of 1.6% acetic acid aqueous solution was added thereto to prepare a hydrolyzate B.

<Preparation of hydrolyzate C>
A hydrolyzate C was prepared by mixing 295 g of tetraethoxysilane and 563 g of ethanol and adding 142 g of a 0.6% hydrochloric acid aqueous solution thereto.

<Preparation of hydrolyzate D>
289 g of tetraethoxysilane and 553 g of ethanol were mixed, and 157 g of 1.6% aqueous citric acid solution was added thereto to prepare a hydrolyzate D.

<Preparation of hydrolyzate E, F, G, H>
Hydrolysates E, F, G, H in the same manner as hydrolyzate A, except that the concentration of the nitric acid aqueous solution was 0.04%, 0.2%, 2.0%, 4.0%, respectively. Were prepared respectively.

<Preparation of hydrolyzate I>
A hydrolyzate I was prepared by mixing 120 g of tetraethoxysilane, 475 g of ELCOM P special product 4 and 680 g of ethanol, and adding 125 g of 0.4% nitric acid aqueous solution thereto.

  The antireflective films 22 and 23 were produced in the same manner as the antireflective film 1 except that the medium refractive index layer and the high refractive index layer were not applied and the amount of the ELCOM P special product 4 was as shown in Table 2. .

  Antireflection films 24 and 26 were produced in the same manner as the antireflection film 23 except that the hard coat layer 1 was changed to the following hard coat layer compositions 2 and 4 to provide the hard coat layers 2 and 4. Further, except that the hard coat layer 1 is changed to a two-layer coating solution as in the following hard coat layer compositions 3-1 (upper layer) and 3-2 (lower layer) and the hard coat layer 3 is provided, Similarly, an antireflection film 25 was produced.

<Hard coat layer composition 2>
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoreaction initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Ethyl acetate 150 parts by mass Propylene glycol monomethyl ether 150 parts by mass Silicon compound (anti-glare particles, BYK-307 (manufactured by Big Chemie Japan))
0.4 parts by mass <Hardcoat layer composition 3-1>
Acrylic monomer (KAYARAD DPHA, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 323 parts by mass Photoinitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals)
36 parts by mass Leveling agent (FZ2207, manufactured by Nippon Unicar, 10% propylene glycol monomethyl ether solution) 7 parts by mass Propylene glycol monomethyl ether 317 parts by mass Ethyl acetate 317 parts by mass <Hardcoat layer composition 3-2>
Acrylic monomer (KAYARAD DPHA, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Photoinitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals)
25 parts by mass of conductive fine particles (ELCOM V2504, ITO sol, solid content 20%, manufactured by Catalyst Chemical)
540 parts by mass Leveling agent (FZ2207, manufactured by Nippon Unicar, 10% propylene glycol monomethyl ether solution) 7 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass <Hardcoat layer composition 4>
Dipentaerythritol hexaacrylate 70 parts by mass Dipentaerythritol pentaacrylate 30 parts by mass Photoinitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) 5 parts by mass Ethyl acetate 120 parts by mass Propylene glycol monomethyl ether 120 parts by mass Conductive fine particles (ELCOM V2504) , ITO sol, solid content 20%, made by catalytic conversion)
540 parts by mass

<Evaluation>
The produced antireflection film was evaluated by the following method. The evaluation results are shown in Table 3.

(Luminous reflectance)
The reflectance of the antireflection film was measured using a micro-reflection spectral film thickness meter (FE-3000 manufactured by Otsuka Electronics Co., Ltd.), and the average reflectance in the wavelength range of 400 to 700 nm was measured as the luminous reflectance. If the luminous reflectance is 1.0% or less, there is no practical problem, but it is preferably 0.5% or less, and more preferably 0.3% or less.

(Scratch resistance immediately)
A load of 200 g / cm ² was applied to # 0000 steel wool (SW) in an environment of 23 ° C. and 55% RH on the antireflection film, and the number of scratches per 1 cm width was measured after 10 reciprocations. In addition, the number of scratches is measured at a place where the number of scratches is the largest among the portions where the load is applied. If it is 10 / cm or less, there is no practical problem, but 5 / cm or less is preferable, and 3 / cm or less is more preferable.

(Scratch resistance and wet heat resistance)
The antireflection film was put in a thermostat of 60 ° C. and 90% RH for 500 hours and subjected to wet heat treatment, and then measured by the same method as the above scratch resistance / immediate. Evaluation criteria are the same as scratch resistance and immediate.

(Dust adhesion)
The anti-reflection film and copy paper cut to 5 mm × 5 mm are conditioned for 24 hours at 23 ° C. and 20% RH. The antireflection film is placed on an insulating rubber sheet, and the surface of the antireflection film is rubbed 10 times with a roller made of neoprene rubber and charged. The charged film is brought close to a copy paper cut into 5 mm × 5 mm gradually from a distance of 30 cm, and the distance when the paper sticks to the film due to static electricity is measured. If it is 5 cm or less, there is no practical problem, but it is preferably 1 cm or less, and more preferably 0 cm (not sticking at all).

  As described above, it can be seen that the antireflection film produced using the coating solution for forming an antireflection film of the present invention has high luminous reflectance, good scratch resistance, and excellent dust adhesion. It can be seen that it is excellent in scratch resistance even at high temperature and high humidity.

It is a figure which shows the example of a Raman scattering spectrum of the hydrolysis composition of an alkoxy silicon compound. It is a figure which shows the example of an absorption spectrum by FT-IR-ATR measurement of the low refractive index layer coating liquid prepared from the hydrolyzed liquid which hydrolyzed tetraethoxysilane for the predetermined time.

Explanation of symbols

A1 Raman scattering intensity when alkoxysilicon compound is not hydrolyzed (or within 20 minutes after mixing with acid) A2 Raman scattering intensity after a predetermined time of hydrolysis of alkoxysilicon compound L Appears between 1095 and 1060 cm ⁻¹ -O Maximum peak height attributed to stretching vibration W1 A part where a line is drawn horizontally from the base line of the maximum peak height L at a height of 1/5 of the maximum peak height L and this line and the absorption peak intersect Peak width W2 A horizontal line is drawn from the baseline of the maximum peak height L at a height of 1/2 of the maximum peak height L, and the peak width of the part where this line and the absorption peak intersect

Claims (5)

In the coating liquid for forming an antireflection film containing inorganic fine particles and a matrix precursor, the inorganic fine particles are (1) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (2) A hollow particle having a void inside and filled with a solvent, a gas or a porous substance, and the matrix precursor is a hydrolyzed liquid obtained by hydrolyzing and condensing an alkoxysilicon compound. The ratio (A1 / A2) of Raman scattering peak intensity (A1) appearing at 660 to 645 cm ⁻¹ in Raman spectroscopic measurement and Raman scattering peak intensity (A2) measured within 20 minutes from the start of hydrolysis is 0.2 or less. There, the weight average molecular weight of 300 to 10,000, has an absorption attributed to Si-O stretching vibration between 1075～1055Cm ^-1 in IR measurement, 1172-11 Observed shoulder peak between 3 cm ^-1, and one-fifth of the height of the peak half width (W1) of the maximum value in the absorption peak attributable to Si-O stretching vibration between 1075～1055Cm ^-1 A coating solution for forming an antireflection film, wherein the ratio of half width of peak half width (W2) (W1 / W2) is 1.8 or more. 2. The coating solution for forming an antireflection film according to claim 1, wherein acetic acid or nitric acid is used as a hydrolysis catalyst in the hydrolysis of the alkoxysilicon compound. The coating liquid for forming an antireflection film according to claim 1 or 2, wherein the coating liquid contains sodium acetate. The coating liquid for forming an antireflection film according to any one of claims 1 to 3, wherein the inorganic fine particles are mixed when the alkoxysilicon compound is hydrolyzed. An antireflection film comprising a low refractive index layer obtained by applying the antireflection film-forming coating solution according to claim 1.

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