KR20100102534A - Polarization diffraction element - Google Patents

Abstract

PURPOSE: A polarization diffraction element is provided to improve in-plane regularity of an optical characteristic. CONSTITUTION: A pattern unit(5) continuously forms a concave part(9) and a convex part(7) on a base made of a transparent resin. A filling unit is comprised by filling the corresponding concave part. One sides of the convex part and the filling unit are made of optically isotropic materials. The other sides of the convex part and the filling unit are made of optically anisotropic materials.

Description

Polarizing diffraction element {POLARIZATION DIFFRACTION ELEMENT}

The present invention relates to a polarizing diffraction element that can be used in an optical system such as an optical pickup device capable of recording or reproducing information on an optical recording medium such as an optical disc.

BACKGROUND OF THE INVENTION An optical disc apparatus is an optical information recording and reproducing apparatus which has been greatly expanded in recent years because of noncontact, abundance of information amount per unit volume, high speed accessibility, low cost, and the like, and various recording media have been developed utilizing these characteristics. For example, information can be written only once by a laser such as a compact disc (CD), a laser disc (LD), a CD-ROM, a DVD-ROM, and the like, which reproduces previously recorded information as a sound, an image, or a computer program. And optical pickup apparatuses capable of repeating recording and reproducing of information, such as CD-R, DVD-R, etc. capable of reproducing related information, and DVD-RAM, DVD-RW, and the like. have.

In the optical system of such an optical pickup device, various optical components are mounted and used for the purpose of miniaturization and high performance of the device. For example, laser, a diffraction grating, a wave plate, a half mirror, a polarization diffraction element, an objective lens, etc. which are light sources are examples of typical components.

Among these components, the polarization diffraction element is an optical component for blocking so-called regression light, which transmits a laser light of linearly polarized light in a path and does not transmit in a path.

As a polarizing diffraction element, the diffraction grating is conventionally produced using a glass substrate or a plastic substrate (refer patent document 1, 2), or the organic birefringence film formed on the optically isotropic substrate (patent document 3, 4) is known.

In these polarizing diffraction elements, the refractive index difference which is a difference between the refractive index of the isotropic material of a diffraction grating and the normal light refractive index of an anisotropic material is almost zero. In the polarization diffraction element, when this refractive index difference is 0, there is an advantage that the transmittance can be maximized and the wave front aberration can be minimized.

On the other hand, in manufacture of a polarization diffraction element, in-plane nonuniformity of an optical characteristic may become large. In general, a polarizing diffraction element is manufactured by fabricating a size having an area of several square centimeters or more and cutting it (chip cut product) to a size of several square millimeters. If the optical properties in the plane of transmittance or wavefront aberration are large in the state of being made in an area of several square centimeters or more, there is a problem that the final shape of the chip cut product includes a decrease in optical properties. Inspection is necessary. Here, if the nonuniformity of the in-plane optical characteristic of a polarizing diffraction element is small, and the optical characteristic of the whole surface is homogeneous, since the inferior optical characteristic will not be mixed in the obtained chip cut product, the necessity of a whole article inspection will be eliminated, It is expected that the productivity will be greatly improved. For this reason, the polarization diffraction element which has small in-plane nonuniformity and homogeneous optical characteristic of the whole surface is calculated | required.

In addition, all the said conventional polarizing diffraction elements are manufactured through a photolithography process or an etching process.

However, when manufactured through a photolithography process or an etching process, only a single wafer can be used as a board | substrate because of the constraint of an apparatus. Therefore, since it can only manufacture by what is called a batch process, it is the situation that continuous productivity is lacking. The photolithography process and the etching process are based on the premise that there are materials removed by the photoresist or etching, and the complicated manufacturing process of the polarization diffraction element is also complicated. There was.

Japanese Laid-Open Patent Publication No. 11-64615 Japanese Patent Laid-Open No. 11-125710 Japanese Laid-Open Patent Publication 2003-43254 Japanese Laid-open Patent Publication 2003-50312

An object of the present invention is to provide a polarization diffraction element having high light utilization efficiency, high industrial productivity, and high in-plane uniformity of optical properties.

As a result of earnestly researching in view of the above-mentioned prior art, the inventors of the present invention have found that optical characteristics (by controlling the optical characteristic ( It has been found that the in-plane unevenness of the transmittance and the wave front aberration can be suppressed to increase the in-plane uniformity, thereby completing the present invention.

That is, the polarizing diffraction element of the present invention has a diffraction grating layer formed of at least one surface of a transparent base material by an optically isotropic material and an optically anisotropic material to satisfy the following formulas (iii) and (ii): It is characterized by.

(Ⅰ) 0.008≤ | Nu (λ ₁ ) -No (λ ₁ ) | ≤0.012

(Ii) 0.004≤ | Nu (λ ₂ ) -No (λ ₂ ) | ≤0.009

[In formula (i), (ii),

λ ₁ : linearly polarized light having a wavelength of 660 nm,

λ ₂ : linearly polarized light having a wavelength of 785 nm,

Nu (λ ₁ ): refractive index of the optically isotropic material at wavelength λ ₁ ,

No (λ ₁ ): normal light refractive index of the optically anisotropic material at wavelength λ ₁ ,

Nu (λ ₂ ): the refractive index of the optically isotropic material at wavelength λ ₂ ,

No (λ ₂ ): normal light refractive index of the optically anisotropic material at wavelength λ ₂

(However, the refractive index and the normal light refractive index are measured at 25 ° C). Here, the normal light refractive index means a refractive index corresponding to normal light propagating in a direction perpendicular to the optical axis of the anisotropic material.]

In the polarizing diffraction element of the present invention, the diffraction grating layer has a pattern portion in which recesses and protrusions are formed continuously, and a filling portion formed by filling the recesses, and the pattern portion in which the recesses and protrusions are continuously formed and the It is preferable that either of the charging sections is made of an optically isotropic material and the other is made of an optically anisotropic material. In the polarizing diffraction element of the present invention, the pattern portion in which the concave portion and the convex portion are continuously formed is made of an optically anisotropic material, and the filling portion is made of the optical isotropic material, or the pattern portion in which the concave portion and the convex portion is formed continuously is optically isotropic. It is also preferable that the filling part may be made of a material, and the filling part may be made of an optically anisotropic material, and the pattern part in which the concave part and the convex part are continuously formed is formed by transfer.

It is preferable that the said transparent base material consists of resin in the polarization diffraction element of this invention.

It is preferable that the said transparent resin consists of cyclic olefin resin in the polarizing diffraction element of this invention.

It is preferable that the layer which has molecular orientation capability is formed in the surface which forms the said diffraction grating layer of the base material which consists of transparent resin for the polarizing diffraction element of this invention.

In the polarizing diffraction element of the present invention, the optically anisotropic material preferably includes an ultraviolet curable liquid crystal.

It is preferable that the optically isotropic material of the polarizing diffraction element of this invention contains an ultraviolet curable (meth) acrylic resin.

It is preferable that the polarizing diffraction element of this invention has an antireflection layer at least on single side | surface, and it is preferable to further satisfy following formula (i)-(v) or (v)-(v).

(V) To (λ ₁ ) ≥95%

(V) To (λ ₂ ) ≥95%

(v) Te (λ ₁ ) ≤ 5%

(Iii) Te (λ ₂ ) ≤ 15%

(V) To (λ ₁ ) ≥95%

(V) To (λ ₂ ) ≥95%

(Iii) Te (λ ₁ ) ≤15%

(Iii) Te (λ ₂ ) ≤ 5%

In formulas (i) to (iii),

λ ₁ : linearly polarized light having a wavelength of 660 nm,

λ ₂ : linearly polarized light having a wavelength of 785 nm,

To (λ ₁ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₁ ,

To (λ ₂ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₂ ,

Te (λ ₁ ): the ideal light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₁ ,

Te (λ ₂ ): the extraordinary light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₂

Indicates.]

       The polarizing diffraction element of the present invention is preferably laminated with a wave plate and / or a diffraction grating.

ADVANTAGE OF THE INVENTION According to this invention, a polarizing diffraction element satisfy | fills said Formula (i) and (ii), and can provide the polarization diffraction element which has high light utilization efficiency, high industrial productivity, and is excellent in in-plane uniformity of an optical characteristic. have. Since the polarization diffraction element of the present invention is excellent in in-plane uniformity of optical properties (transmittance and wave front aberration), the defective products having poor optical properties are not mixed in the chip cut products manufactured using the same, and thus inspection of the whole article of the chip cut products is performed. Since it can omit, a production efficiency can be improved significantly.

1 shows the substrate (b-3) of Example 3 of the present invention.
2 shows a polarizing diffraction element of Example 3 of the present invention.
3 shows the substrate (b-1) of Example 1 of the present invention.
4 shows a polarizing diffraction element of Example 1 of the present invention.
5 shows a method for manufacturing the polarizing diffraction element of Example 5 of the present invention.
6 shows the polarizing diffraction element of Example 5 of the present invention.

(Form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

The polarizing diffraction element of the present invention has a diffraction grating layer formed of an optically isotropic material and an optically anisotropic material on at least one side of the transparent substrate. The diffraction grating layer may be a layer in which a portion made of an optically anisotropic material acts as a diffraction grating, but is not particularly limited. Preferably, the diffraction grating layer is formed by filling a concave portion and a pattern portion continuously formed with convex portions and the concave portion. It has a filling part, The pattern part in which the said recessed part and the convex part were formed continuously, One of the said filling parts consists of an optically isotropic material, and the other consists of an optically anisotropic material.

materials

The base material used by this invention should just be transparent, glass, resin, a composite material of glass and resin, etc. can be used, It is preferable that it is plate shape-film shape. The base material may be formed only by one layer, and may be formed in multiple layers. Moreover, it is also preferable that a base material has a layer which has molecular orientation capability.

It is preferable that the transparent base material used by this invention is made of resin.

As transparent resin which comprises a base material, if it is transparent in the laser wavelength at the time of using the polarizing diffraction element of this invention, it can be used without a restriction | limiting, However, It is preferable that it is 85% or more by the light transmittance by wavelength in a laser wavelength, More preferably, it is 87% or more, Most preferably, it is 89% or more.

As such transparent resin, thermoplastic resins, such as triacetyl cellulose (TAC), PMMA, PS, PC, PES, PSU, cyclic olefin resin, ultraviolet curable resin, etc. can be used, for example.

Although thermoplastic resin is normally used as transparent resin, the ultraviolet curable resin which prepared the structure suitably can also be used. As ultraviolet curable resin, the ultraviolet curable (meth) acrylic resin mentioned later can be used, for example.

Especially, as transparent resin, cyclic olefin resin is preferable from a heat resistance, durability, and a workability viewpoint. As cyclic olefin resin, glass transition temperature (Tg) used as the index of heat distortion temperature is 90-200 degreeC normally, Preferably it is 100-190 degreeC, More preferably, it is 110-180 degreeC. When Tg is 90 degreeC or more, since the obtained polarizing diffraction element has the outstanding heat resistance, it is preferable. When Tg is less than 90 degreeC, since heat distortion temperature becomes low, there exists a possibility that a problem may arise in heat resistance, and the problem that the change of the optical characteristic by temperature increases in the film obtained may arise. On the other hand, when Tg exceeds 200 degreeC, since processing temperature becomes high too much, when processing into a film form, the coloring by oxidative deterioration may arise and the problem that an optical characteristic may fall may arise.

Here, glass transition temperature (Tg) is the maximum peak temperature (A point) and the maximum of the differential differential scanning calorie curve obtained when measured in a temperature increase rate of 20 degree-C / min and nitrogen atmosphere using a differential scanning calorimeter (DSC). The temperature (point B), which is -20 ° C from the peak temperature, is plotted on the differential scanning calorimetry curve, and is obtained as the intersection of the tangent on the baseline starting from the B point and the tangent starting from the A point.

The base material which consists of said transparent resin may be a form of sheet | leaf, and may have a form long in the longitudinal direction. A so-called roll shape having a long shape in the longitudinal direction is more preferable from the viewpoint of continuous productivity, but it is also preferable to cut in the form of a sheet after forming into a roll shape. Moreover, since the base material which concerns on this invention consists of transparent resin, compared with a glass substrate and a crystalline substrate, since it can be rolled smoothly and easily, it is preferable, and it is easy to process, such as punching to a desired shape. It is preferable because of that. As a method of processing into such a roll shape, shaping | molding methods, such as extrusion molding and the solution casting method, can be used for transparent resin. Although the width | variety of a base material does not have a restriction | limiting in particular when making a roll shape, In consideration of industrial handleability, Preferably it is 150-2200 mm, More preferably, it is good to set it as 300-1500 mm. When the width is narrower than 150 mm, it is not preferable from the viewpoint of economical productivity. When the width is wider than 2200 mm, the width of the width is larger than the size of 2200 mm. The thickness of the base material is not particularly limited as long as it can maintain the shape as an optical component. However, the thickness of the base material is preferably 30 to 500 m, more preferably 50 to 300 m, most preferably 80. It is -200 micrometers. If the thickness is less than 30 µm, the rigidity as the base material is weak, which is not preferable. In addition, if the thickness exceeds 500 µm, it is difficult to form a roll. In addition, since the winding length when the roll is shortened, the continuous productivity decreases. Not desirable In addition, when the thickness exceeds 500 µm, it is not preferable from the viewpoint that burrs or cracks are easily generated when the punching or the like is processed. In the case of forming a sheet, in consideration of industrial handleability, the width and length are preferably 3 to 100 cm, more preferably 5 to 80 cm. In addition, width and length do not need to correspond, and what is necessary is just to set it to the magnitude | size which is easy to process suitably. For example, when it is A4 size and it is a form of sheet | leaf, it becomes the size of 21 cm x 30 cm. In the case of single sheets, the width and length of less than 3 cm are not preferable because industrially the productivity is lowered. In the case of width and length of more than 100 cm, the size of the apparatus becomes large and the workability is lowered. Because it is not desirable.

Although the base material which consists of transparent resin which can be used by this invention may be formed only by the said transparent resin, On the transparent resin base material, For example, the primer layer and a molecule for improving the adhesiveness of a base material and a diffraction grating layer It is also preferable that the layer (henceforth an orientation layer) which has an orientation capability is formed. Although the layer which has molecular orientation capability may be formed in the single side | surface of the transparent resin base material, and may be formed in both surfaces, it is preferable that it is formed in the surface which forms the pattern part which consists of an optically anisotropic material mentioned later.

molecule Orientation ability  Having layer Alignment layer )

The layer having molecular orientation capability is usually a composition (B) containing at least one selected from a (meth) acrylic compound, polyimide, polyvinyl alcohol and polyurethane, or a polymer having a structure represented by the following formula (1): It is formed by the composition (B ') containing.

(Formula 1)

-R ¹ -CH = CH-Z ¹ -Ar ¹

In Formula 1, R ¹ is 1,4-phenylene having a group selected from —C (O) O—, —CONH—, —CO—E—, an unsubstituted or halogen atom, a cyano group and a nitro group, or Pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thiophendiyl, 2,5-furanylene, 1,4-naphthylene, or 2,6-naphthylene,

E is 1,4-phenylene, or pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thiophenediyl having a group selected from unsubstituted or halogen atoms, cyano groups and nitro groups , 2,5-furanylene, 1,4-naphthylene, or 2,6-naphthylene,

Z ¹ is 1,4-phenylene, or pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5 having a group selected from a single bond, an unsubstituted or halogen atom, a cyano group and a nitro group -Thiophendiyl, 2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl or 1,4-piperidyl,

Ar ¹ represents a monovalent group having an aromatic ring.]

As a composition for layer formation (B) which has the molecular orientation capability containing the said (meth) acrylic-type compound, the (meth) acrylic resin obtained using the same thing as the (meth) acrylic-type compound which can be used as an optically isotropic material mentioned later is included. It may be used, and the composition containing a (meth) acrylic compound and a photoinitiator may be sufficient. Moreover, as a photoinitiator, the thing similar to what can be used at the time of hardening of the same optically isotropic material can be used. Although a (meth) acrylic-type compound is used as an optically isotropic material mentioned later, the film | membrane obtained with the composition containing this compound can be used also as a layer which has molecular orientation capability by a rubbing process, an extending | stretching process, etc. As a layer which has molecular orientation capability, when the base material which consists of transparent resin is cyclic olefin resin, it is preferable to include the monofunctional monomer and polyfunctional monomer which contain an alicyclic structure especially from a viewpoint of adhesiveness with a base material.

As a monofunctional monomer containing the said alicyclic structure, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, carbonyl (meth) acrylate, isobonyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and the like. In addition, examples of the polyfunctional monomer containing an alicyclic structure include tricyclodecanediyldimethyldi (meth) acrylate and the like.

Examples of the layer-forming composition (B) having a molecular orientation capability containing the polyimide include those obtained by dehydrating a polyamic acid obtained by reacting tetracarboxylic dianhydride with diamine, and the like as polyvinyl alcohol. The modified polyvinyl alcohol which substituted the hydroxyl group of vinyl alcohol with an organic group, etc. are mentioned, As a polyurethane, the polymer etc. which make polyether polyol and polyisocyanate react are mentioned.

As the composition (B) for forming a layer having a molecular orientation function, including the polyvinyl alcohol, 0.2mol% of the hydroxyl groups of polyvinyl alcohol with a substituent _{-OCOPhO (CH 2) 4 OCOCH =} CH 2, the substituent -OCOCH ₃ 5 mass parts of the modified polyvinyl alcohol powder of saponification degree 88 mol% and polymerization degree 300 which have a structure substituted by 11.8 mol% was mixed with respect to 100 mass parts of distilled water, 35 mass parts of methanol was added, and it melt | dissolved. Etc. can be mentioned.

Polyether polyurethane etc. are mentioned as a composition for layer formation (B) which has the said molecular orientation ability containing the said polyurethane. As a commercial item of such a polyurethane resin, the hydrane WLS-201 (made by DIC Corporation) which is a polyether polyurethane material is mentioned.

As a layer which has the said molecular orientation ability, it is preferable to form from the composition containing a (meth) acrylic-type compound from a viewpoint of adhesiveness with a base material.

Moreover, as another component contained in the composition containing at least 1 sort (s) chosen from a (meth) acrylic-type compound, a polyimide, polyvinyl alcohol, and a polyurethane, it adheres to the surface of a base material in the range which does not impair the target physical property. From the viewpoint of further improving the properties, a functional silane-containing compound, an epoxy compound, or the like may be contained.

Although there is no limitation in particular as a polymer which has a structure represented by the said General formula (1), For example, as a polymer which has the said General formula (1) in a side chain, For example, see Unexamined-Japanese-Patent No. 2003-307736 and Unexamined-Japanese-Patent No. 6-287453. The polyimide polymer described above or the acrylic polymer may be mentioned. Moreover, as another component contained in the composition (B ') containing the polymer which has a structure represented by General formula (1), from the viewpoint of improving adhesiveness to the surface of the above-mentioned base material within the range which does not impair the target physical property. It may contain a functional silane containing compound, an epoxy compound, etc.

When the base material has a layer having molecular alignment capability, the thickness of the layer having molecular orientation capability is preferably 1 to 5000 nm, more preferably 5 to 500 nm, most preferably 10 to 200 nm.

<Method of providing molecular orientation ability>

Application | coating formed by composition (B), when the layer which has the said molecular orientation capability consists of a composition (B) containing at least 1 sort (s) chosen from a (meth) acrylic-type compound, a polyimide, polyvinyl alcohol, and a polyurethane It is preferable that molecular orientation capability is provided to film (B) by the method of any one of a rubbing process and an extending | stretching process.

(1) Method by rubbing treatment

Although rubbing processing can be performed by a well-known method, For example, the composition (B) containing at least 1 sort (s) chosen from a (meth) acrylic-type compound, a polyimide, polyvinyl alcohol, and a polyurethane is apply | coated to a base material, The process which forms a coating film (B) on a base material, touches the surface of the said coating film, and gives molecular orientation capability, winding a rubbing cloth, such as a surface and a rayon, on the surface of a metal roll, and rotating the said roll Can be mentioned. Although it does not specifically limit as processing conditions of a rubbing process, 100-2000 rpm of roll rotation speed is preferable, More preferably, it is 200-1500 rpm, Most preferably, it is 300-900 rpm. As for the conveyance speed of the base material which provided the coating film, 1-50 m / min is preferable, More preferably, it is 3-30 m / min. The roll indentation amount is preferably 0.1 to 0.5 mm, more preferably 0.2 to 0.4 mm.

When the treatment conditions are performed, a uniform rubbing treatment can be performed over the entire surface of the coating film (B), so that a layer having molecular alignment ability can be suitably formed. Although the rubbing direction is determined by the angle formed between the rotation axis direction of the rubbing roll and the longitudinal direction of the film (the base material on which the coating film B is formed), the rubbing direction is not particularly limited as long as the rubbing roll can cover the entire film width. . Since the rubbing direction determines the orientation direction of the liquid crystal molecules, the rubbing direction may be set in a desired direction to perform a rubbing treatment.

In addition, the rubbing treatment may be accompanied by foreign matter generation. This is because the fiber of a rubbing cloth fell off, the material of the film surface provided for rubbing was scraped off, and the foreign material of a surrounding environment adheres by the static electricity which generate | occur | produces. Therefore, it is necessary to remove these foreign substances, and it is preferable to blow off the foreign substances and to suck or wash them. Among them, washing with water is preferably used. In particular, the coating film (B) formed by applying the composition (B) containing a polyimide is derived from a polyimide structure, has high resistance to water, and will be described later without impairing the rubbing effect even after washing with water. It is preferable because the optically anisotropic material can be oriented. Moreover, the coating film (B) formed by apply | coating the composition (B) containing at least 1 sort (s) chosen from a polyvinyl alcohol and a polyurethane has low resistance to water when polyvinyl alcohol and a polyurethane are water-washed. Therefore, since the optically anisotropic material mentioned later cannot be orientated, water washing is not preferable. In addition, in the case of using a modified polyvinyl alcohol having a crosslinked structure as the polyvinyl alcohol or a modified polyurethane such as a polymer obtained by reacting a polyether polyol having a crosslinked structure with a polyisocyanate as a polyurethane, Since resistance to water is expressed by this, the coating film (B) formed by applying the composition (B) containing polyvinyl alcohol and a polyurethane is mentioned later without damaging the rubbing effect even if water washing is performed. The optically anisotropic material can be oriented.

When the layer having the molecular orientation ability is made of a composition (B ′) containing a polymer having the structure represented by the formula (1), the molecular orientation capability is preferably provided by irradiation of radiation such as ultraviolet rays or visible light. Do.

(2) method by stretching treatment

Molecular orientation ability can also be provided by extending | stretching the base material which consists of transparent resin which has the coating film (B) formed with the composition for layer formation (B) which has the said molecular orientation ability.

The coating film formed by the layer forming composition (B) which has molecular orientation capability by extending | stretching the base material which consists of transparent resin which has the coating film (B) formed by the layer forming composition (B) which has molecular orientation capability ( Molecular orientation ability can be provided to B), and the optically anisotropic material formed on this layer can be oriented.

The said extending | stretching process is normally performed by extending | stretching the coating film (B) formed with the base material which consists of transparent resin, and the layer forming composition (B) which has molecular orientation capability. Heat stretching is preferable because the generation of foreign matters and the like is less compared with the rubbing treatment, and the yield can be produced with good yield.

As said extending | stretching process, the method of uniaxially extending | stretching the coating film (B) formed with the base material which consists of transparent resin, and the layer forming composition (B) which has molecular orientation ability under heating (stretching processing method (1) ) And a method of uniaxially stretching the coating film (B) formed by the substrate and the layer-forming composition (B) having molecular orientation capability in the width direction under heating (stretching treatment method (2)) is preferable.

When extending | stretching the coating film (B) formed with the base material which consists of transparent resin, and the layer formation composition (B) which has molecular orientation capability, the heating temperature at the time of extending | stretching is a layer which has a base material which consists of transparent resin, and molecular orientation capability It is preferable to be controlled precisely in the whole extending | stretching site | part of the coating film (B) formed with the composition (B) for formation. For example, the uniaxial stretching in the longitudinal direction in the stretching processing method (1), that is, the longitudinal monoaxial stretching, has a temperature distribution within a set temperature of ± 0.6 ° C, preferably within a set temperature of ± 0.4 ° C, more preferably. Preferably it is done in an oven controlled to within the set temperature ± 0.2 ° C.

Here, the set temperature may be an equivalent temperature in the entire region in the oven, or may be a temperature in which a distribution is formed stepwise or gradient. In the case where the set temperature is the temperature at which the distribution is formed, it is preferable that the actual temperature distribution in the oven and the set temperature distribution are within ± 0.6 ° C, preferably within ± 0.4 ° C, and more preferably within ± 0.2 ° C. .

The setting temperature of the extending | stretching processing method (1) uses the base material which consists of a transparent resin, and the coating film (B) formed by the layer forming composition (B) which has molecular orientation capability, and the kind of raw material, draw ratio and draw rate, a base material, It can also be set according to the thickness of the layer which has molecular orientation capability, the desired phase difference of the optically anisotropic material after extending | stretching, etc., It is not specifically limited, For example, it references the glass transition temperature (Tg) of the transparent resin of the base material which consists of transparent resins, for example. It is a range of (Tg + 0) ° C to (Tg + 30) ° C. In such a temperature range, it does not generate | occur | produce thermal deterioration of the coating film (B) formed by the base material which consists of a transparent resin, and the composition for layer formation (B) which has molecular orientation capability, and does not break | rupture. It is preferable because it can.

In the said extending | stretching processing method (1), the draw ratio of longitudinal uniaxial stretching is 1.1-2.5 times, Preferably it is 1.1-2.0 times, Especially preferably, it is the range of 1.2-1.5 times. If the draw ratio is less than 1.1 times, it is not preferable because the orientation of the optically anisotropic material is not uniformly expressed properly, and if the draw ratio exceeds 2.5 times, it is not preferable because problems such as breakage of the substrate occur during processing. not.

Moreover, the extending | stretching speed of the longitudinal uniaxial stretching in the said extending | stretching processing method (1) is 2-100 m / min, for example, Preferably it is the range of 5-50 m / min.

The uniaxial stretching in the width direction of the stretching treatment method (2), that is, the uniaxial stretching in the width direction is performed under temperature control more precisely than the uniaxial stretching in the longitudinal direction, whereby a homogeneous polarizing diffraction element can be suitably obtained on the entire surface. Can be. For example, the uniaxial stretching in the width direction is preferably performed in an oven in which the temperature distribution is controlled to within the set temperature ± 0.5 ° C, preferably within the set temperature ± 0.3 ° C, and more preferably within the set temperature ± 0.2 ° C.

The setting temperature of the said extending | stretching processing method (2) may be the same temperature in all the area | regions in an oven similarly to the case of longitudinal uniaxial stretching, and may be the temperature which formed distribution in steps or gradient. In the case where the set temperature is the temperature at which the distribution is formed, it is preferable that the actual temperature distribution in the oven and the set temperature distribution are within ± 0.5 ° C, preferably within ± 0.3 ° C, more preferably within ± 0.2 ° C. . The set temperature of the width direction uniaxial stretching may be the same as or different from the set temperature in the process of the longitudinal direction uniaxial stretching.

In the stretching treatment method (2), the draw ratio of the uniaxial stretching in the width direction may be determined in accordance with the desired characteristics of the polarizing diffraction element to be produced, for example, 1.5 to 5 times, preferably 1.7 to 4 times, Especially preferably, it is 2 to 3.5 times of range. If the draw ratio is less than 1.5 times, it is not preferable because the orientation of the optically anisotropic material is not uniformly expressed properly. If the draw ratio exceeds 5 times, it is preferable because problems such as breakage of the substrate occur during processing. Not.

The extending | stretching speed of the said width direction uniaxial stretching is 2-100 m / min, for example, Preferably it is the range of 5-50 m / min.

diffraction Lattice layer

The polarizing diffraction element of the present invention is optically isotropic to at least one side of a substrate made of the above-mentioned transparent resin (that is, a substrate formed of a transparent resin or a substrate having a layer having molecular orientation capability on a substrate made of a transparent resin). It has a diffraction grating layer formed of a material and an optically anisotropic material.

This diffraction grating layer consists of a pattern part and a filling part, and the pattern part and the part which consists of an optically anisotropic material, and the part which consists of an optically anisotropic material may exist alternately by a predetermined pattern, Preferably, the concave formed on the base material The pattern portion in which the portion and the convex portion are formed continuously, and the filling portion filling the concave portion, are formed of one of optical isotropic material and the other of optical anisotropic material, so that the convex portion and the charging portion having different optical characteristics are alternately formed. It is preferable that this becomes a diffraction grating layer.

Pattern part

The pattern portion in which the concave portion and the convex portion are continuously formed may be formed of an optically isotropic material or may be formed of an optically anisotropic material.

Optical isotropic material (D)

The optically isotropic material is not particularly limited as long as it is an optically isotropic resin. However, the optically isotropic material is preferably formed of an optically isotropic material-forming composition containing an ultraviolet curable resin because it is easy to continuously produce a polarizing diffraction element economically. It is more preferable to contain an ultraviolet curable (meth) acrylic resin from the point which is easy to acquire transparency and optical isotropy.

As said ultraviolet curing type (meth) acrylic resin, it is preferable to use resin obtained by superposing | polymerizing the (meth) acrylate compound shown below. The (meth) acrylate compound is not particularly limited as long as it has at least one (meth) acryloyl group in the molecule. For example, as a (meth) acrylate compound, a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound are mentioned.

Although the ultraviolet curable (meth) acrylic resin which can be used for this invention hardens | cures with an ultraviolet-ray, as an example of the light source which produces an ultraviolet-ray, a metal halide lamp and a high pressure mercury lamp are mentioned. In addition, ultraviolet irradiation can be performed from the surface side which forms the pattern of a base material, and can also be performed from the surface side which does not form the pattern of a base material. Moreover, when forming a pattern continuously, it is preferable to irradiate an ultraviolet-ray from the opposite side of the said mold, ie, the surface side which does not form the pattern of a base material, and when a mold contacts the composition containing an ultraviolet curable (meth) acrylic resin, In a state, irradiation can also be performed from the surface side which does not have a pattern.

In addition, in this invention, a (meth) acrylate compound represents at least 1 sort (s) of compound chosen from the group which consists of an acrylate compound and a methacrylate compound, and a (meth) acryloyl group is acryloyl group and methacryl At least 1 group chosen from the group which consists of a royl group is shown.

As a specific example of a monofunctional (meth) acrylate compound, methyl (meth) acrylate, ethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acryl Rate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl ( Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate Isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. Alkyl (meta ) Acrylates;

Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate;

Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;

Alkoxyalkyl (meth), such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and methoxybutyl (meth) acrylate ) Acrylates;

Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, etc. Polyethylene glycol (meth) acrylates;

Polypropylene glycol (meth), such as a polypropylene glycol mono (meth) acrylate, a methoxy polypropylene glycol (meth) acrylate, an ethoxy polypropylene glycol (meth) acrylate, and a nonylphenoxy polypropylene glycol (meth) acrylate ) Acrylates;

Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cycloalkyl, such as cyclopentenyloxyethyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, carbonyl (meth) acrylate, isobonyl (meth) acrylate, and tricyclodecanyl (meth) acrylate (Meth) acrylates;

Benzyl (meth) acrylate; Tetrahydrofurfuryl (meth) acrylate etc. are mentioned. These monofunctional (meth) acrylate compounds can be used individually by 1 type or in mixture of 2 or more types.

Among these monofunctional (meth) acrylate compounds, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentadienyl ( Since meta) acrylate is excellent in adhesiveness with the base material which consists of transparent resin, it is especially preferable.

Moreover, as a specific example of a polyfunctional (meth) acrylate compound, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethyleneglycol di (meth) acryl Alkylene glycol di (meth) acrylates such as late, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and neopentylglycol di (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, trimethylolpropane trihydroxyethyl tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Poly (meth) acrylates of polyhydric alcohols such as acrylate, dipentaerythritol hexa (meth) acrylate and hydroxypivalate neopentylglycol di (meth) acrylate;

Isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate Poly (meth) acrylates of isocyanurate;

Poly (meth) acrylates of cycloalkanes such as tricyclodecanediyldimethyl di (meth) acrylate;

Di (meth) acrylate of ethylene oxide adduct of bisphenol A, Di (meth) acrylate of propylene oxide adduct of bisphenol A, Di (meth) acrylate of alkylene oxide adduct of bisphenol A, Hydrogenation ) Di (meth) acrylate of ethylene oxide adduct of bisphenol A, di (meth) acrylate of propylene oxide adduct of hydrogenated bisphenol A, di (meth) acrylate of alkylene oxide adduct of hydrogenated bisphenol A, bisphenol (Meth) acrylate derivatives of bisphenol A, such as (meth) acrylate obtained from A diglycidyl ether and (meth) acrylic acid;

3,3,4,4,5,5,6,6-octafluorooctane di (meth) acrylate, 3- (2-perfluorohexyl) ethoxy-1,2-di (meth) acrylo Fluorine-containing (meth) acrylates such as ylpropane and N-n-propyl-N-2,3-di (meth) acryloylpropyl perfluorooctylsulfonamide;

The urethane (meth) acrylates obtained by making the polyol (a) which has the following bisphenol structure, organic polyisocyanate (b), and hydroxyl-containing (meth) acrylate (c) react are mentioned.

Moreover, as (a) the polyol which has a bisphenol structure, the alkylene oxide addition diol of bisphenol A, the alkylene oxide addition diol of bisphenol F, the alkylene oxide addition diol of hydrogenated bisphenol A, the alkylene oxide addition diol of hydrogenated bisphenol F, etc. Can be mentioned. Of these, alkylene oxide addition diols of bisphenol A are preferred. As these commercial items, Nichi Oil Co., Ltd. DA-400, DB-400, etc. are mentioned, for example.

(b) As organic polyisocyanate, diisocyanate is preferable, For example, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, 1, 3- xylylene diisocyanate, 1, 4- xylyl Ethylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'- diphenylmethane diisocyanate, 4,4'-di Phenylmethane diisocyanate, 3,3'- dimethylphenylene diisocyanate, 4,4'- biphenylene diisocyanate, etc. are mentioned. Among these, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, 1, 3- xylylene diisocyanate, and 1, 4- xylylene diisocyanate are preferable.

(c) As hydroxyl-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy- 3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, Dipentaerythritol penta (meth) acrylate and the like. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. are preferable.

These polyfunctional (meth) acrylate compounds can be used individually by 1 type or in mixture of 2 or more types.

Among these polyfunctional (meth) acrylate compounds, many of the acryloyl groups contained in 1 molecule, such as dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate, The polyfunctional (meth) acrylate compound which can aim at the improvement of a crosslinking density and gives the outstanding film hardness is especially preferable.

Photopolymerization initiator (photoradical generator)

In the case of using an ultraviolet curable (meth) acrylic resin as the optical isotropic material, the (meth) acrylate compound is polymerized (cured), but a photopolymerization initiator (photoradical generator) is preferably used during the polymerization.

As a specific example of a photoinitiator (photo radical generator), 1-hydroxycyclohexyl phenyl ketone, 2, 2- dimethoxy- 2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'- dimethoxy benzophenone, 4,4'- diamino benzophenone, Michler's ketone, benzoylpropyl ether, benzoin ethyl ether , Benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone , Diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1- [4- (2-hydroxy) Ethoxy) phenyl] -2-hydroxy-2-methyl-propan-1-one. These photoinitiators (photoradical generators) can be used individually by 1 type or in combination of 2 or more type.

Among these photoinitiators (photoradical generators), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine Oxides and 1-hydroxycyclohexylphenyl ketones are preferred.

Moreover, a commercial item can be used for such a photoinitiator (photo radical generator). For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one is Irgacure 907 (manufactured by Chiba Specialty Chemicals Co., Ltd.). In addition, 1-hydroxycyclohexyl phenyl ketone can be obtained as Irgacure 184 (made by Chiba Specialty Chemicals).

The amount of the photopolymerization initiator (photoradical generator) added is not particularly limited as long as the curing reaction proceeds sufficiently, but is usually 0.1 to 20 parts by mass, preferably 0.5 to 10, based on 100 parts by mass of the (meth) acrylate compound. It is preferable that it is a mass part. When the addition amount of a photoinitiator (photoradical generator) becomes less than the said minimum, hardening reaction of the said (meth) acrylate compound does not fully advance and a sufficient hardness may not be obtained. Moreover, when the addition amount of a photoinitiator (photoradical generator) exceeds the said upper limit, the storage stability of an ultraviolet curable type (meth) acrylic resin may fall.

When the pattern part in which the concave part and the convex part were formed continuously was formed on the base material which consists of transparent resin using the composition containing the optically isotropic material as mentioned above, the part derived from the convex part of a polarization diffraction element is optical It is isotropic.

Optically anisotropic materials

As the optically anisotropic material, any material having optically anisotropy can be used without particular limitation, but a liquid crystal material is preferably used. Among the liquid crystal materials, an ultraviolet curable liquid crystal is preferably used from the viewpoint of continuously and economically producing a polarizing diffraction element.

It does not specifically limit as an ultraviolet curable liquid crystal, The thing which introduce | transduced one or more acrylate group and / or methacrylate group into the nematic liquid crystal and smectic liquid crystal can be used.

As an example of such an ultraviolet curable liquid crystal, a cyan clock liquid crystal, a cyano biphenyl type liquid crystal, a Schiff type liquid crystal, a cyano phenyl ester type liquid crystal, a cyano phenyl cyclohexane type liquid crystal, a benzoic acid phenyl ester type liquid crystal, a cyclohexane carboxylic acid phenyl ester type liquid crystal The ultraviolet curable liquid crystal which introduce | transduced one or more acrylate group and / or methacrylate group into low molecular liquid crystals, such as a phenylpyrimidine type liquid crystal and a phenyl dioxane type liquid crystal. In addition, these ultraviolet curable liquid crystals may be used independently, and may mix and use 2 or more types.

When forming a pattern part using an ultraviolet curable liquid crystal as an optically anisotropic material, when an ultraviolet curable liquid crystal itself has fluidity, it may be used only by an ultraviolet curable liquid crystal, may be used by the mixture containing an ultraviolet curable liquid crystal, and an ultraviolet curable liquid crystal In order to improve the applicability | paintability of the solvent, the solution which added the solvent can also be used as a composition. At this time, as a solvent used, when forming a pattern part on the layer which has molecular orientation ability, the thing which does not impair the molecular orientation capability is selected suitably.

Specifically, the volatilization rate affects the molecular orientation ability of the optically anisotropic material, and when the volatilization rate is relatively low, the volatilization rate can be uniformly volatilized in the applied surface, which is preferable because of the uniform molecular orientation.

That is, the molecular orientation ability of an optically anisotropic material can be controlled by the difference of the boiling point of the solvent to be used. For example, in a solvent having a boiling point of about 40 ° C. such as acetone, the volatilization rate at the time of drying is fast, so that the molecular orientation ability can be controlled relatively low, and in a solvent having a boiling point of about 80 ° C. such as methyl ethyl ketone, the volatilization rate is high. Since is relatively slow, the fall of molecular orientation ability by latent heat of evaporation can be suppressed, and high molecular orientation ability can be controlled. In addition, it is preferable to volatilize a solvent after apply | coating this composition on a base material, and to volatilize a solvent by heating etc., and it is preferable to carry out before carrying out an ultraviolet curing. At this time, the addition amount of a solvent becomes like this. Preferably it is 1-500 mass parts, More preferably, it is 10-400 mass parts, Especially preferably, it is 20-300 mass parts with respect to 100 mass parts of ultraviolet curable liquid crystals.

Moreover, in order to obtain the pattern part in which the concave part and convex part which consisted of the composition containing an ultraviolet curable liquid crystal were continuously formed, ultraviolet-ray is irradiated to the coating film formed by the composition containing an ultraviolet curable liquid crystal, and ultraviolet curing of the said ultraviolet curable liquid crystal is carried out. It is preferable to obtain the hardened | cured material (polymer) of the said ultraviolet curable liquid crystal.

Although heating is performed in order to orientate a liquid crystal, when a solvent is added as a composition containing an ultraviolet curable liquid crystal, it is also performed in order to volatilize a solvent. As heating temperature, although it depends also on the kind of liquid crystal to be used, it is preferable to raise to temperature higher than liquid crystal transition temperature normally, and when it considers the heat resistance of the base material which consists of transparent resin, and the layer which has molecular orientation ability, it shall be 40-150 degreeC. Preferably, it is 50-140 degreeC more preferably. In the case of forming the pattern portion on the layer having molecular alignment ability, if the heating temperature exceeds 150 ° C., the layer having molecular alignment capability may be deformed, which is not preferable. Conversely, if the heating temperature is less than 40 ° C., the desired orientation is desired. It is not preferable because it cannot be obtained, and it is not preferable because the solvent does not volatilize and remains when the solvent is added. In addition, if it is the said temperature range, heating temperature may be raised in steps.

Moreover, it is preferable that the photopolymerization initiator (photo radical generator) is added to the composition containing an ultraviolet curable liquid crystal. As a photoinitiator, the thing similar to the photoinitiator (photo radical generator) which can be used when superposing | polymerizing (curing) optically isotropic materials, such as the above-mentioned (meth) acrylate compound, can be used.

As addition amount of a photoinitiator (photoradical generator), Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it is 3 mass parts or less with respect to 100 mass parts of ultraviolet curable liquid crystals. When the addition amount exceeds 10 parts by mass, the unreacted photopolymerization initiator is not preferable because the influence of the influence on the physical properties of the polarizing diffraction element such as the liquid crystal transition temperature cannot be ignored. Moreover, as a composition containing a commercially available ultraviolet curable liquid crystal, Licrivue (registered trademark) RMM727 etc. by Merck Co., Ltd. are mentioned, for example.

As an example of the light source at the time of performing ultraviolet curing, a metal halide lamp and a high pressure mercury lamp are mentioned. In addition, although ultraviolet irradiation may be performed from the surface side which has a pattern, and may be performed from the surface side which does not have a pattern, when forming a pattern continuously, in the state which the mold contacted the composition containing an ultraviolet curable liquid crystal, Irradiation may be performed from the surface side which does not have.

When the pattern part in which the recessed part and the convex part were formed continuously was formed on the base material which consists of transparent resin using the composition containing the ultraviolet-curable liquid crystal as mentioned above, the part derived from the convex part of the polarizing diffraction element obtained will Optical anisotropy.

The pattern portion in which the concave portion and the convex portion according to the present invention are continuously formed is formed of any one of the above-described optically isotropic material or optically anisotropic material. The formation method of a pattern part is not specifically limited, It may be formed by photolithography and etching using a photoresist, and may also be formed by transfer. As a method of forming the pattern part in which the recessed part and the convex part were formed continuously by photolithography and etching, a conventionally well-known method can be employ | adopted suitably.

In this invention, it is preferable that the pattern part in which the recessed part and the convex part were formed continuously was formed by transfer.

In pattern part formation by transfer, after apply | coating the composition containing the optically anisotropic material or optically anisotropic material mentioned above on a base material by transfer, a dry coating film is obtained by processes, such as a heating.

As a specific coating method, for example, spin coating method, lip coating method, comma coating method, roll coating method, die coating method, blade coating method, dip coating method, bar coating method, flexible film formation method, gravure coating method, printing Law and the like. Especially, the comma coating method, the gravure coating method, etc. are used preferably from a viewpoint of thickness precision and mass productivity.

Although there is no restriction | limiting in particular as thickness of the coating film containing the apply | coated optically anisotropic material or an optically anisotropic material, if the desired pattern part can be provided, Preferably it is 1-30 micrometers, More preferably, 1 20 micrometers, Most preferably, it is 1-15 micrometers. As the depth of the recessed part of the pattern, the design varies depending on the wavelength of the laser to be used and the type of material to be used, but is generally in the range of 1 to 10 µm. Therefore, by controlling the thickness of the material applied in the above-mentioned range, it is preferable because the design can be excellent in economic efficiency without using unnecessary materials while ensuring thickness accuracy. In addition, when the width | variety of the convex part and the recessed part of a pattern shows the width of the convex part as L, and the width | variety of the recessed part is represented by S, it is preferable that the value of L / S is 0.4 <{L / (L + S)} <0.6. More preferably, it is 0.45≤ {L / (L + S)} ≤0.55. Especially, when L = S, ie, when the width | variety of a convex part and the width | variety of a concave part match, it is especially preferable.

Moreover, it is preferable that the width | variety L of a convex part is 1 micrometer <= L <= 10micrometer, More preferably, it is 1 micrometer <= L <= 5micrometer, Most preferably, 1 micrometer <= L <= 3micrometer. The width S of the recess is also preferably 1 µm ≤ S ≤ 10 µm, more preferably 1 µm ≤ S ≤ 5 µm, and most preferably 1 µm ≤ S ≤ 3 µm. When the width | variety L of such a convex part and the width S of a concave part are selected, since the desired polarization diffraction capability can be obtained, it is preferable.

As a method of providing the pattern part in which the recessed part and the convex part were formed continuously in the coating film formed by the composition containing the optically anisotropic material or the optically anisotropic material mentioned above, the mold in which the recessed part and the convex part was formed continuously is used preferably. The material of the mold in which the concave portion and the convex portion are continuously formed is not particularly limited as long as a desired pattern can be produced. However, a metal such as nickel, a silicon, or a transparent such as synthetic quartz is preferably used. Moreover, in order to improve the mold release after closely contacting with a coating film in order to give a shape, it is also preferable to perform a mold release process, such as coating a fluorine-type or silicone type mold release agent to the mold surface in which the recessed part and the convex part were formed continuously. The shape of the mold in which the concave portion and the convex portion are continuously formed is not particularly limited as long as a desired pattern such as a flat plate shape or a roll shape can be produced. In the case of a form, it is good to use a roll-shaped mold.

In order to obtain the pattern part in which the recessed part and convex part which consisted of an optically anisotropic material or an optically anisotropic material were formed continuously, the ultraviolet-ray was formed in the coating film in which the pattern was formed by the composition containing an optically anisotropic material or an optically anisotropic material, and a photoinitiator as mentioned above. It is preferable to irradiate and harden radiation, such as.

Charging part

The polarization diffraction element of the present invention preferably has a charging portion filled with a recess of the pattern portion. The filling portion is formed of an optically anisotropic material when the pattern portion is made of an optically isotropic material, and is formed of an optically isotropic material when the pattern portion is made of an optically anisotropic material. As an optically anisotropic material or optically isotropic material which can form a charging part, what was used for formation of a pattern part can use suitably the above-mentioned thing.

It is preferable to form the filling part which concerns on this invention using the composition for filling part formation containing an optically anisotropic material or an optically isotropic material and the photoinitiator (optical radical generating agent) mentioned above as what can be used for formation of a pattern part.

A filling part can be suitably formed by apply | coating the composition for filling part formation to the surface which has a pattern part of the said base material 1, filling the said recessed part, and hardening by ultraviolet irradiation etc. as needed. In addition, in FIG. 2 which shows the schematic diagram of the form of this invention, although the charging part 11 is provided only in the said recessed part 9, in reality, the charging part is also provided in the upper part of the convex part 7 simultaneously with the filling to the recessed part. The composition for formation is apply | coated and the coating film which consists of this composition may exist in the upper part of the convex part 7, and this form may be sufficient as the polarizing diffraction element of this invention.

Although it does not specifically limit as such the polarizing diffraction element of this invention, It is preferable that the convex part 7 consists of an optically anisotropic material, and the charging part 11 consists of an optically isotropic material.

Moreover, in this invention, in the transparent resin which comprises a board | substrate, the layer which has the molecular orientation capability formed on a board | substrate as needed, the pattern part in which the recessed part and the convex part were formed continuously, and the composition used as a material which forms a filling part, If necessary, known additives such as antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, antifoaming agents, and surfactants (release agents) can be added within a range in which the effects of the invention are not impaired.

Antireflection layer

The polarizing diffraction element of the present invention usually further has an antireflection layer in order to increase the use efficiency of light passing through the element.

It is preferable that the polarization diffraction element of this invention has an antireflection layer. The antireflection layer may be formed by coating the thermosetting resin composition or the photocurable resin composition with a known coating method such as gravure coating, die coating, slot coating, drying as necessary, and then curing and forming. It may also be formed by sputtering or vapor deposition. These layers may be formed on one side of a base material, or may be formed on both surfaces.

The antireflection layer is usually made of a low refractive index layer, and may have a laminated structure of a low refractive index layer and a high refractive index layer in order to further improve antireflection performance, and in order to further secure scratch resistance, a hard coat layer You may have The lamination order is preferably laminated in the order of a hard coat layer / high refractive index layer / low refractive index layer from the outermost layer side of the polarizing element. If necessary, the medium refractive index layer may be provided between the low refractive index layer and the high refractive index layer or between the hard coat layer and the high refractive index layer.

As a composition for forming a low refractive index layer and a high refractive index layer, the well-known curable composition which consists of binder resin, a photoinitiator, high hardness particle, etc. is mentioned. For example, the binder resin contains at least one epoxy resin, phenol resin, melamine resin, alkyd resin, cyanate resin, acrylic resin, polyester resin, urethane resin, siloxane resin and the like. Further, the composition for forming the low refractive index layer contains a fluorine-containing compound, and the composition for forming the high refractive index layer includes inorganic particles having high refractive index, such as silica, alumina, titania, zirconia, ceria, scandia, magnesium fluoride, and the like. Contains oxide particles.

Although the refractive index and thickness of the low refractive index layer and the high refractive index layer are used in a well-known range, in order to enhance the antireflection effect in the wavelength to be used, the refractive index of the low refractive index layer (average refractive index at 25 ° C. and a wavelength of 589 nm) is , 1.45 or less, and the thickness of the low refractive index layer is preferably 50 to 300 nm. Moreover, it is preferable that the refractive index (25 degreeC, average refractive index in wavelength 589nm) of a high refractive index layer is refractive index 0.05 or more larger than the refractive index of a low refractive index layer, and it is preferable that thickness is 50-10,000 nm.

Polarization diffraction  device

In the polarizing diffraction element of the present invention, a diffraction grating layer comprising a diffraction grating layer, preferably a pattern portion in which concave portions and convex portions are continuously formed, and a filling portion formed by filling the concave portions, is formed on one surface of a substrate made of a transparent resin. It may be formed, or may be formed on both sides, preferably formed only on one side. The polarizing diffraction element of the present invention has a diffraction grating layer in which the diffraction grating layer is alternately formed of an optically isotropic material and an optically anisotropic material, and the diffraction grating layer comprises a pattern portion in which concave portions and convex portions are continuously formed, In the case of the filling portion formed by filling, either the pattern portion forming the convex portion or the filling portion is made of an optically isotropic material, and the other is made of an optically anisotropic material.

It is also preferable that the uneven | corrugated part formed in the single side | surface is encapsulated with the base material, and the polarizing diffraction element of this invention apply | coats the optical isotropic material or the optically anisotropic material of a charging part, and adheres to it by UV-hardening with an sealing base material, adhesiveness becomes favorable.

Although the thickness of the polarizing diffraction element of this invention does not specifically limit, For example, thickness can be made into the film shape of 60-500 micrometers, More preferably, about 100-300 micrometers. Since the thickness can be made thin in this manner, the optical component can be reduced in size and weight. Moreover, since the polarizing diffraction element of this invention is made of resin further in addition to such thickness, since it is easy to process, such as punching to a desired shape and producing a chip cut article, it is preferable.

The polarizing diffraction element of the present invention, when the linearly polarized light having a wavelength of 660 nm is λ ₁ and the linearly polarized light having a wavelength of 785 nm is λ ₂ ,

Nu (λ ₁ ): refractive index of the optically isotropic material at wavelength λ ₁ ,

No (λ ₁ ): normal light refractive index of the optically anisotropic material at wavelength λ ₁ ,

Nu (λ ₂ ): refractive index of the optically isotropic material at wavelength λ ₂ ,

No (λ ₂ ): normal light refractive index of the optically anisotropic material at wavelength λ ₂

This satisfies the following formulas (iii) and (ii).

(Ⅰ) 0.008≤ | Nu (λ ₁ ) -No (λ ₁ ) | ≤0.012

(Ii) 0.004≤ | Nu (λ ₂ ) -No (λ ₂ ) | ≤0.009

Also, the following formulas (i ') and (ii') are preferably satisfied.

(Ⅰ ') 0.008≤ | Nu (λ ₁ ) -No (λ ₁ ) | ≤0.010

(Ii ') 0.004≤ | Nu (λ ₂ ) -No (λ ₂ ) | ≤0.007

In addition, in this invention, refractive index and normal light refractive index mean the measured value in 25 degreeC. Here, since the optically anisotropic material has no anisotropy, the refractive index has one value, while for the optically anisotropic material, there are two refractive indices in the normal plane for light incident perpendicularly to the material. The light propagating in the direction perpendicular to the optical axis is called the normal light and the light propagating in the parallel direction is called the abnormal light, and the refractive index corresponding to the normal light is referred to as the normal light refractive index and the refractive index corresponding to the abnormal light, respectively. It is called.

Thus, in the polarization diffraction element of the present invention, the wavelength 660㎚ top of the optically anisotropic material of the refractive index (Nu (λ ₁₎₎ and wavelength 660㎚ (λ ₁₎ of the optical anisotropic material of the (λ ₁₎ refractive index (No (λ ₁₎₎ and a wavelength of the refractive index of the optical isotropic material in the _{785㎚ (λ 2) (Nu (} λ 2)) and wavelength 785㎚ ordinary ray of the optical anisotropic material of the (λ ₂₎ Refractive index No ((lambda) ₂ ) has the significant difference of the said specific range, respectively.

That is, in the polarization diffraction element of the present invention, Nu (λ ₁ ), No (λ ₁ ), and Nu (λ ₂ ) and No (λ ₂ ) each have a difference in the above specific range, and at any wavelength, The refractive index of the optically isotropic material and the normal light refractive index of the optically anisotropic material are not the same, and have a difference controlled to a specific range. Accordingly, although the absolute value of the transmittance is slightly lower than that of the difference of these refractive indices is 0, the vibration width of the refractive index derived from the material can be absorbed by the refractive index width of the design, and as a result, the optical characteristics ( Transparency) can be made almost homogeneous throughout the plane.

As Nu (λ ₁ ), usually 1.600 to 1.400, preferably 1.550 to 1.450, and No (λ ₁ ) is usually 1.600 to 1.400, preferably 1.550 to 1.450, and as Nu (λ ₂ ), usually 1.600 to 1.400. Preferably, it is 1.550-1.450 and said No ((lambda) ₂ ) is 1.600-1.400 normally, Preferably it is 1.550-1.450. When each Nu and No are in the said range, since the optically anisotropic material and optically isotropic material used for the polarizing diffraction element obtained can be in the range of a general liquid crystal or acrylic resin, it is also preferable from a viewpoint of material supply stability.

In addition, in the present invention, by performing the above refractive index control, the curvature of the transmission wavefront of the normal light in λ ₁ and λ ₂ can be made almost homogeneous to a low value in the entire surface of the polarizing diffraction element.

In addition, the bending rate of a transmission wave front is called transmission wave front aberration, and 25 m (lambda) or less is preferable in a polarization diffraction element, More preferably, it is 20 m (lam) or less, More preferably, it is 15 m (lam) or less. If the wave front aberration is larger than 25 mλ, the laser beam passing through the polarization diffraction element is distorted, which is not preferable because it causes a poor reading of the disc when mounted on the optical pickup device.

The difference between the refractive index of the optically isotropic material and the normal light refractive index of the optically anisotropic material can be controlled to a desired range by appropriately selecting the kind of the optically isotropic material and the optically anisotropic material forming the convex portion and the filling portion.

When the polarizing diffraction element of the present invention has the antireflection layer, when the linearly polarized light having a wavelength of 660 nm is λ ₁ and the linearly polarized light having a wavelength of 785 nm is λ ₂ ,

To (λ ₁ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₁ ,

To (λ ₂ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₂ ,

Te (λ ₁ ): the extraordinary light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₁ , and

Te (λ ₂ ): the extraordinary light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₂

Preferably, in the range which satisfies the following formulas (i) to (i) or (i) to (i), most preferably (i ') to (i') or (i ') to (i'). Can be controlled to a range that satisfies

(V) To (λ ₁ ) ≥95%

(V) To (λ ₂ ) ≥95%

(v) Te (λ ₁ ) ≤ 5%

(Iii) Te (λ ₂ ) ≤ 15%

(V) To (λ ₁ ) ≥95%

(V) To (λ ₂ ) ≥95%

(Iii) Te (λ ₁ ) ≤15%

(Iii) Te (λ ₂ ) ≤ 5%

(^ ') To (λ ₁ ) ≥98%

(^ ') To (λ ₂ ) ≥98%

(v ') Te (λ ₁ ) ≤ 3%

(Ⅵ ′) Te (λ ₂ ) ≤ 10%

(^ ') To (λ ₁ ) ≥98%

(^ ') To (λ ₂ ) ≥98%

(Ⅸ ′) Te (λ ₁ ) ≤ 10%

(Ⅹ ′) Te (λ ₂ ) ≤ 3%

The polarization diffraction element of the present invention can be set to any Te (λ) if the Nu (λ) and Ne (λ) are set to satisfy the following formula (i).

(Iii) Te (λ) = cos ² [[d (Ne (λ) —Nu (λ)) / λ] / p] × 100

 In the above formula, d represents the depth of the grooves of the uneven portions, and p represents the repetition length (pitch) of the uneven portions.

In addition, by setting Nu (λ) and No (λ) to satisfy the following formula (Xii) and having the above-described antireflection film, To (λ)? 98%.

(Xii) | Nu (λ) -No (λ) | ≤0.012

In the polarization diffraction element of the present invention, each average value of To (λ ₁ ), To (λ ₂ ), Te (λ ₁ ), and Te (λ ₂ ) measured at a plurality of measurement points is preferably the formula (ⅲ) Although it is good to exist in the range which satisfy | fills (a)-(v) or (v)-(v), Most preferably, it is in the range which meets (v ')-(v') or (v ')-(v'), 95% or more, more preferably 97% or more of the values of To (λ ₁ ), To (λ ₂ ), Te (λ ₁ ) and Te (λ ₂ ) of each measuring point measured at a plurality of measuring points, In the range satisfying the formulas (i) to (v) or (v) to (v), most preferably in the range to satisfy (v ') to (v') or (v ') to (v'). It is desirable to have.

In the polarization diffraction element of the present invention, the average value of the transmission wavefront aberration at the wavelength? ₁ measured at the plurality of measurement points is preferably 25 mλ or less, more preferably 20 mλ or less, still more preferably 15 mλ or less.

The polarizing diffraction element of the present invention can have high in-plane uniformity, and for example, in-plane uniformity of optical characteristics by the evaluation method described in Examples described later is 95% or more, preferably 97% or more. More preferably, it can be 99% or more.

(Example)

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In addition, each property was measured and evaluated as follows.

(1) normal light transmittance, Lee Sang-gwang  Transmittance and In-Plane Uniformity

Using the RETS-1200VA manufactured by Otsuka Denshi Co., Ltd., the top of the vertical incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material of the optically anisotropic material under the condition of a diameter of 2 mmφ. The optical transmittance To (λ) and the optical transmittance Te (λ) of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary refractive index of the optically anisotropic material are each within a 10 cm square area. 2500 points | pieces were measured by 2 mm space | interval, and average value a _o ((lambda)) and a _e ((lambda)) were calculated | required. From the results of these 2500 measurement points, the in-plane uniformity of the normal light transmittance and the abnormal light transmittance was determined by the following formula (xiii).

 X / 2500 x 100 (%). (xiii)

[Equation (xiii), X is normal light transmittance To (λ ₁ ) ≧ 95%, To (λ ₂ ) ≧ 95%, abnormal light transmittance Te (λ ₁ ) ≦ 5%, and Te (λ ₂₎ A measurement point that satisfies? ≦ 15%, or a normal light transmittance To (λ ₁ ) ≧ 95%, a To (λ ₂ ) ≧ 95%, an ideal light transmittance Te (λ ₁ ) ≦ 15%, and Te (λ ₂ ) a number of ≤ 5%]

(2) wavefront aberration

Using a laser interferometer R-10 manufactured by FUJINON Co., Ltd., using a laser beam having a wavelength of 656 nm and a diameter of 2 mm phi, the front RMS (λrms) is 10 cm square, respectively, as a wavefront aberration of the polarization diffraction element. in the area of the 100-point measured by 10㎜ interval, an average value was determined λrms _{a ve.} From the results of these 100 measurement points, the points at which the measured values were 15 mλ or less were counted, and the score was defined as in-plane uniformity (%).

(3) reflectance

The surface on the opposite side of the surface on which the antireflection layer is formed is coated with black spray, and a spectroscopic reflectance measuring device (spectral photometer U-3410, manufactured by Hitachi Seisakusho Co., Ltd., equipped with a large sample chamber integrating sphere accessory 150-09090) is manufactured. By measuring, the reflectance in wavelength 660nm and 785nm of a polarization diffraction element was measured and evaluated from the reflection prevention layer side. Specifically, the reflectance was measured at 660 nm and 785 nm with the reflectance in the vapor deposition film of aluminum as a reference | standard (100%).

(4) glass transition temperature ( Tg )

The temperature rising rate was measured under 20 degreeC and nitrogen stream every minute using the DSC6200 made by Seiko Instruments. Tg of the resin plots the maximum peak temperature (point A) of the differential differential scanning calorimetry and the temperature (point B) which is -20 ° C from the maximum peak temperature on the differential scanning calorimetry curve, and on the base line starting from the point B It calculated | required as the intersection of the tangent line and the tangent line starting from A point. Tg of the ultraviolet curable acrylic resin measured the glass transition temperature as a cured film using the dynamic-viscoelasticity measuring apparatus of a forced resonance oscillation type | mold. Specifically, the loss tangent was measured at a temperature increase rate of 3 ° C./min while applying a vibration of frequency 10 Hz to the cured film. The temperature whose loss tangent showed the maximum value was made into glass transition temperature (Tg).

(5) All rays  Transmittance, Haze

The total light transmittance of the film was measured using the haze meter (HGM-2DP type) by the Sugashi Kenki Corporation.

(6) refractive index

Using a prism coupler (PC2010 type) manufactured by Metricon, the refractive indices at 408 nm, 632.8 nm and 830 nm were measured, and fitting was performed by Cauchy's dispersion equation in the wavelength range of 410 nm to 800 nm. The refractive index in 25 degreeC of was calculated | required.

Synthesis Example 1 (Synthesis of Resin (A-1) (cyclic olefin resin))

225 parts by mass of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (DNM) and bicyclo [2.2.1] hept-2-ene (Norbornene) 25 mass parts is used as a monomer, and it puts into the reaction container which carried out the nitrogen substitution with 27 mass parts of 1-hexene (molecular weight regulator) and 750 mass parts of toluene (solvent for ring-opening polymerization reaction), Heated to ° C. Next, tungsten hexachloride (tert-butanol: methanol: tungsten = 0.35) modified with 0.62 parts by mass of a toluene solution of triethylaluminum (1.5 mol / liter) and tert-butanol and methanol in the solution in the reaction vessel as a polymerization catalyst. 3.7 parts by mass of a toluene solution (concentration 0.05 mol / liter) of mol: 0.3 mol: 1 mol) was added, and the solution was subjected to ring-opening polymerization reaction by heating and stirring at 80 ° C for 3 hours to obtain a ring-opening polymer solution. The polymerization conversion ratio in this polymerization reaction was 97%.

The hydrogenated polymer (henceforth "resin (A-1)") was obtained by carrying out the hydrogenation reaction of the ring-opened polymer obtained in this way.

Thus, Tg of resin (A-1) obtained was 130 degreeC.

Synthesis Example 2 (Synthesis of Resin (A-2) (cyclic olefin resin))

Molecular weight using 71 parts by mass of DNM, 15 parts by mass of dicyclopentadiene (tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene) (DCP) and 1 part by mass of norbornene (NB) as monomers It was put into the reaction container which carried out the nitrogen substitution with 18 mass parts of 1-hexene which is a regulator, and 200 mass parts of toluene, and it heated at 100 degreeC.

0.005 parts by mass of triethylaluminum and 0.005 parts by mass of methanol-modified WCl ₆ (anhydrous methanol: PhPOCl ₂ : WCl ₆ = 103: 630: 427 mass ratio) were added and reacted for 1 minute. Then, 10 parts by mass of DCP and 3 parts by mass of NB were added thereto. The mixture was further added to 5 minutes and reacted for 45 minutes to obtain a copolymer having a structural unit of 69.77 / 26.01 / 4.23 (mass%) derived from a structural unit / NB derived from a structural unit / DCP derived from DNM.

Next, the hydrogenated copolymer was obtained by carrying out the hydrogenation reaction of the obtained copolymer (henceforth "resin (A-2)").

Thus, Tg of resin (A-2) obtained was 131 degreeC.

Synthesis Example 3 (Synthesis of Resin (A-3) (cyclic olefin resin))

53 parts by mass of tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene 46 Toluene is used as a solvent for the ring-opening polymerization reaction by using a mass part and 66 parts by mass of tricyclo [4.3.0.1 ^2,5 ] -deca-3,7-diene, and adding an amount of 1-hexene (molecular weight regulator) to 22 parts by mass. A hydrogenated polymer (hereinafter referred to as "resin (A-3)") was obtained in the same manner as in Synthesis example 1 except that cyclohexane was used instead.

The glass transition temperature (Tg) of obtained resin (A-3) was 125 degreeC.

Synthesis Example 4 (Synthesis of Polyimide)

As tetracarboxylic acid dianhydride, 22.4 g (0.1 mol) of 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride and 19.8 g (0.1 mol) of 4,4'- diamino diphenylmethane as a diamine compound are N- It dissolved in 800 g of methyl-2-pyrrolidone, and made it react at 60 degreeC for 4 hours. The reaction solution was then poured into excess methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 390 g of polyamic acid having a logarithmic viscosity of 0.32 dl / g. 25 g of the obtained polyamic acid was dissolved in 475 g of N-methyl-2-pyrrolidone, 39.5 g of pyridine and 30.6 g of acetic anhydride were added and dehydrated and closed for 4 hours at 110 ° C. It carried out and obtained logarithmic viscosity 0.64 dl / g and 19.5 g of polyimides of 92% of imidation ratios.

Synthesis Example 5 (Synthesis of Polyamic Acid Ester)

0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 0.1 mol (10.8 g) of p-phenylenediamine were dissolved in 300 g of N-methyl-2-pyrrolidone and 6 at 60 ° C. The reaction was time. The reaction mixture was then poured into excess methanol to precipitate the reaction product. Thereafter, the mixture was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 27.4 g of polyamic acid. 350 g of N-methyl-2-pyrrolidone, 38.7 g of 1-bromo-6- (4-carbonyloxy) hexane, and 13.8 g of potassium carbonate were added to 16.6 g of the obtained polyamic acid, and the mixture was reacted at 120 ° C for 4 hours. . The reaction mixture was then poured into water to precipitate the reaction product. The obtained precipitate was wash | cleaned with water, and it dried under reduced pressure for 15 hours, and obtained 35.4 g of polyamic acid esters.

Synthesis Example 6 (Synthesis of Urethane Acrylate)

In a reaction vessel equipped with a stirrer, 49.96 parts by mass of 2-phenoxyethyl acrylate, 0.01 parts by mass of 2,6-di-t-butyl-p-cresol, 0.04 parts by mass of di-di-n-butyl tin, 17.74 mass parts was added to tolylene diisocyanate and it cooled to 5-15 degreeC. When temperature became 10 degrees C or less, it stirred dropwise, stirring 11.84 mass parts of 2-hydroxyethyl acrylate, and stirred for 1 hour, controlling liquid temperature to 20-35 degreeC. Thereafter, 20.40 parts by mass of alkylene oxide added diol (DA-400 manufactured by Nichi Oil Co., Ltd.) of bisphenol A was added thereto, and the reaction was continued at 55 to 65 ° C for 3 hours, when the residual isocyanate became 0.1% by mass or less. The reaction was completed and urethane acrylate was obtained.

PREPARATION EXAMPLE 1 (Preparation of the composition for orientation layer formation (B-1))

88% by weight of modified polyvinyl alcohol having a degree of substitution of 0.2 mol% of a hydroxyl group of polyvinyl alcohol by substituent-OCOPhO (CH ₂ ) ₄ OCOCH = CH ₂ and 11.8 mol% by substituent -OCOCH ₃ , 5 mass parts of powders were mixed with respect to 100 mass parts of distilled water, 35 mass parts of methanol was added, and it melt | dissolved. This solution was filtered using the filter of 1 micrometer of pore diameters, and the composition for orientation layer formation (B-1) was prepared.

PREPARATION EXAMPLE 2 (Preparation of the composition for orientation layer formation (B-2))

The polyimide obtained by the synthesis example 4 was melt | dissolved in (gamma) -butyrolactone, 0.75 mass part of N-ethoxycarbonyl 3-aminopropyl triethoxysilanes are melt | dissolved with respect to 100 mass parts of polymers, and solid content concentration 4 mass It was set as the solution of%. This solution was filtered using the filter of 1 micrometer of pore diameters, and the composition for orientation layer formation (B-2) was prepared.

PREPARATION EXAMPLE 3 (Preparation of the composition for orientation layer formation (B-3))

The polyamic acid ester obtained in the synthesis example 5 was melt | dissolved in (gamma) -butyrolactone, 0.75 mass part of N-ethoxycarbonyl 3-aminopropyl triethoxysilanes are melt | dissolved with respect to 100 mass parts of polymers, and solid content concentration 4 It was set as the mass% solution. This solution was filtered using the filter of 1 micrometer of pore diameters, and the composition for orientation layer formation (B-3) was prepared.

PREPARATION EXAMPLE 4 (Preparation of the composition for orientation layer formation (B-4))

Each component was put into the reaction container provided with the stirrer at the compounding ratio (mass part) shown below, and it stirred and mixed at room temperature for 1 hour, and obtained the liquid composition. Specific compounding ratios are 90.1 mass parts of dicyclopentanyloxyethyl acrylates, 7.2 mass parts of isocyanurate triacrylates, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholino propane-1 -It was set as 2.7 mass parts of temperature and 100.0 mass parts or more in total. The viscosity of the ultraviolet curable acrylic material as an obtained liquid composition was 24 mPa * s at the value in 25 degreeC using a rotational viscometer according to JIS K7117, and obtained the composition for orientation layer formation (B-4) by irradiating an ultraviolet-ray. .

Preparation Example 5 (Preparation of Composition (D-1) for Optically Isotropic Material Formation)

Each component was put into the reaction container provided with the stirrer at the compounding ratio (mass part) shown below, and it stirred and mixed at 50 degreeC for 1 hour, and obtained the composition (D-1). Specifically, the compounding ratio was 7.8 parts by mass of urethane acrylate obtained in Synthesis Example 6, 11.7 parts by mass of trimethylolpropane triacrylate, 31.4 parts by mass of tris (2-hydroxyethyl) isocyanuric acid acrylate, polyoxyalkylene bisphenol A 32.3 parts by mass of diacrylate, 4.9 parts by mass of a mixture of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate, 9.8 parts by mass of N-vinyl-2-pyrrolidone, and 1.5 parts by mass of 1-hydroxycyclohexylphenyl ketone , 0.3 parts by mass of thiodiethylene bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 0.1 parts by mass of diethylamine, and 0.3 parts by mass of polyoxyalkylene alkyl ether phosphate ester In addition, the total amount was 100.1 parts by mass. The viscosity of the obtained composition (D-1) is 540 mPa * s at the value in 25 degreeC using the rotational viscometer according to JIS K7117, Tg of resin after ultraviolet curing is 120 degreeC, and refractive index (Nu) is 660 nm. It was 1.530 in and 1.530 in 785 nm.

Preparation Example 6 (Preparation of Composition (D-2) for Optically Isotropic Material Formation)

Each component was put into the reaction container provided with the stirrer at the compounding ratio (mass part) shown below, and it stirred and mixed at room temperature for 1 hour, and obtained the composition (D-2). Specific compounding ratios were 12.1 mass parts of 1, 6- hexanediol diacrylates, 5.0 mass parts of 2-phenoxyethyl acrylates, 79.9 mass parts of dicyclopentenyl oxyethyl acrylates, and 3.0 mass of 1-hydroxycyclohexyl phenyl ketones. In addition, the total amount was 100.0 parts by mass. The viscosity of the obtained composition (D-2) is 21 mPa * s at the value in 25 degreeC using the rotational viscometer according to JIS K7117, and the refractive index (Nu) of resin after ultraviolet curing is 1.530,785 at 660 nm. It was 1.528 in nm.

PREPARATION EXAMPLE 7 (Preparation of the composition for optically isotropic material formation (D-3))

Each component was put into the reaction container provided with the stirrer at the compounding ratio (mass part) shown below, and it stirred and mixed at room temperature for 1 hour, and obtained the composition (D-3). Specific compounding ratios are 51.2 parts by mass of 1,6-hexanediol diacrylate, 26.2 parts by mass of 2-phenoxyethyl acrylate, 19.7 parts by mass of isocyanurate triacrylate, and 2.9 parts by mass of 1-hydroxycyclohexylphenyl ketone. The total amount was 100.0 parts by mass or more. The viscosity of the obtained composition (D-3) is 17 mPa * s at the value in 25 degreeC using a rotational viscometer according to JIS K7117, and the refractive index (Nu) of resin after ultraviolet curing is 1.520,785 at 660 nm. It was 1.517 in nm.

Preparation Example 8 (Preparation of Ultraviolet Curable Acrylic Resin)

Each component was put into the reaction container provided with the stirrer at the compounding ratio (mass part) shown below, and it stirred and mixed at 50 degreeC for 1 hour, and obtained the liquid composition. The specific compounding ratio was 9.8 mass parts of urethane acrylate obtained in the synthesis example 6, 13.7 mass parts of trimethylol propane triacrylates, 29.4 mass parts of tris (2-hydroxyethyl) isocyanuric-acid acrylic acid ester, and polyoxyalkylene bisphenol A 32.3 parts by mass of diacrylate, 4.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, 7.8 parts by mass of N-vinyl-2-pyrrolidone, and 1.5 parts by mass of 1-hydroxycyclohexylphenyl ketone , 0.3 parts by mass of thiodiethylene bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 0.1 parts by mass of diethylamine, and 0.3 parts by mass of polyoxyalkylene alkyl ether phosphate ester In addition, the total amount was 100.1 parts by mass. The viscosity of the ultraviolet curable acrylic material as the obtained liquid composition is 540 mPa · s at a value at 25 ° C. using a rotational viscometer in accordance with JIS K7117, and the Tg of the resin after ultraviolet curing is 120 ° C. and the refractive index (Nu) is 660. It was 1.534 in nm, and 1.530 in 785 nm.

Production Example 1 (Manufacture of Substrate (a-1))

As a resin (A-1) and the antioxidant obtained in Synthesis Example 1, a pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was used as a twin screw extruder ( Extruded using TEM-48 manufactured by Toshiba Kikai Co., Ltd., and the resin strand flowing out of the strand die is cooled in a cooling bath, sent to a strand cutter, cut into fine particles, and granulated. I) Resin (transparent resin (A-1)) was obtained. The antioxidant addition amount was 0.1 mass part with respect to 100 mass parts of resin.

This granulated resin was obtained using the single screw extruder (90 mmΦ), and the resin film of 130 micrometers in thickness was obtained (henceforth "base material (a-1)"). The amount of residual solvent of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 130 degreeC.

Production Example 2 (Manufacture of Substrate (a-2))

In Production Example 1, a resin film having a thickness of 130 μm was obtained in the same manner as in Production Example 1 except that the resin (A-2) obtained in Synthesis Example 2 was used instead of the resin (A-1) (hereinafter. , "Substrate (a-2)". The amount of residual solvent of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 131 degreeC.

Production Example 3 (Manufacture of Substrate (a-5))

In Production Example 1, a resin film having a thickness of 100 μm was obtained in the same manner as in Production Example 1, except that Resin (A-3) obtained in Synthesis Example 3 was used instead of Resin (A-1) ( Hereinafter, it is called "substrate (a-5)". The amount of residual solvent of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 124 degreeC.

Example 1

On the one side of the base material (a-1) obtained in Production Example 1, a roll speed was 600 rpm, a film conveyance speed was 3 m / min, and a roll press-in amount was 0.3 mm, using a rubbing machine manufactured by Inuma Co., Ltd. The rubbing process was performed so that a rubbing direction might become parallel to a film longitudinal direction, and the base material (a'-1) was obtained. Subsequently, methyl ethyl ketone as a solvent was added to 100 parts by mass of RMM727, a UV curable liquid crystal material manufactured by Merck Co., Ltd., using a small diameter gravure roll of 200 mesh with an INVEX lab coater manufactured by Inoue Kinzoku Co., Ltd. The added portion was subjected to the rubbing treatment of the substrate (a'-1) under 50 ° C conditions, applied to the surface to which the molecular alignment ability was imparted, dried, and oriented to form an optically anisotropic layer having a thickness of 4 µm. As a result of measuring the refractive index of the optically anisotropic layer on the substrate (a'-1), in the light of the linearly polarizable wavelength of 660 nm, the abnormal light refractive index Ne was 1.678 and the normal light refractive index No was 1.542 and 785 nm. The abnormal light refractive index Ne was 1.665, and the normal light refractive index No was 1.535.

Next, using the transfer roll prepared so that the pattern part in which the recessed part and the convex part were formed continuously was transferred, the pattern part in which the recessed part and the convex part was continuously formed was transferred to the coating surface. Moreover, the recessed part and convex part of the transfer roll surface were prepared so that the groove | channel of the unevenness | corrugation may be formed along the circumferential direction of a roll.

At the same time as the transfer, ultraviolet rays were irradiated with an energy amount of 500 mJ / cm 2 from the surface side not having the pattern of the substrate (a'-1) using a high-pressure mercury lamp to form a pattern in which concave portions and convex portions were formed continuously. -1) was obtained. The width of the convex portion was 2.5 μm, the width of the concave portion was 2.5 μm, and the depth of the concave portion was 2.6 μm. Next, the optically isotropic material formation composition (D-1) obtained by the preparation example 5 was apply | coated to the formed recessed part using the 300-mesh small-gravure gravure roll by the INNOV KINKO CORPORATION INVEX lab coater. The ultraviolet-ray was irradiated and hardened | cured by the amount of energy of 500mJ / cm <2> from the side which does not have a pattern using a high pressure mercury lamp, and the filling part which consists of an optically isotropic material was formed and the base material (c-1) was obtained. The thickness of the optically isotropic material was 4 µm from the bottom of the recess to the outermost layer.

The antireflection process was performed on both surfaces of the base material (c-1), and the polarizing diffraction element 1 was obtained. The average value (ao (λ)) of the normal light transmittance of the 2500 point measurement of the obtained polarizing diffraction element 1 is ao (λ ₁ ) = 98.8% in light having a wavelength of 660 nm of linearly polarizing light, and a wavelength of 785 nm. ao (λ ₂ ) = 99.5%, and the average value of the ideal light transmittance was ae (λ ₁ ) = 2.5% at a wavelength of 660 nm, and ae (λ ₂ ) = 7.7% at a wavelength of 785 nm. In addition, in-plane uniformity was 100%. The reflectance is 0.1% at 660 nm and 0.1% at a wavelength of 785 nm from the side of the side (pattern side) having the pattern and the filling portion, and is 660 nm from the side of the substrate (a'-1) side (base side). It was 0.2% and 0.2% in wavelength 785 nm. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 10m (lambda), in-plane uniformity is 100% and the flat surface was made.

The thickness of the polarizing diffraction element was 139 µm. Table 1 shows the evaluation results of the obtained polarizing diffraction element.

[Example 2]

The base material (a-2) obtained in the manufacture example 2 was tenter-laterally stretched by extending | stretching speed 5.0m / min and draw ratio 3.5x in the reaction tank of the temperature of 155 degreeC in a drawer furnace, and roll of 37 micrometers in thickness The shaped stretched film (base material (a'-2)) was obtained. Except having used the base material (a'-2), it carried out similarly to Example 1, and formed the optically anisotropic layer. As a result of measuring the refractive index of the optically anisotropic layer on the base material (a'-2), in the light of the linearly polarizable wavelength of 660 nm, the abnormal light refractive index Ne was 1.678 and the normal light refractive index No was 1.542 and 785 nm. The abnormal light refractive index Ne was 1.663 and the normal light refractive index No was 1.534.

Subsequently, similarly to Example 1, the pattern part in which the recessed part and the convex part were formed continuously was formed in the optically anisotropic layer surface, and the base material (b-2) was obtained. Next, it carried out similarly to Example 1, and formed the charging part using the composition for optically isotropic material formation (D-1), and obtained the base material (c-2). The thickness of the optically isotropic material was 4 µm from the bottom of the recess to the outermost layer.

The antireflection process was performed on both surfaces of the base material (c-2), and the polarizing diffraction element 2 was obtained. The average value of the transmittance | permeability of the 2500-point measurement of the obtained polarizing diffraction element 2 is ao ((lambda) ₁ ) = 98.8%, ao ((lambda) ₂ ) = 99.8%, ae ((lambda) ₁ ) = 2.4% and ae ((lambda) ₂₎ ) = 7.2%. In addition, in-plane uniformity was 100%. The reflectance is 0.2% at 660 nm and 0.1% at a wavelength of 785 nm on the side of the side (pattern side) having the pattern and the charging portion, and at 660 nm on the side of the substrate (a'-2) side (base side). It was 0.2% in 0.2% and wavelength 785 nm. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 9m (lambda), in-plane uniformity is 100%, and the flat surface was made. Table 1 shows the evaluation results of the obtained polarizing diffraction element.

Example 3

On a triacetyl cellulose film (base material (a-3)) having a thickness of 80 µm, an orientation layer obtained in Preparation Example 1 using an INVEX lab coater manufactured by Inoue Kinzoku Co., Ltd., using a small diameter gravure roll of 200 mesh. The composition for formation (B-1) was coated. When coating, it filtered with the 0.2 micrometer PTFE filter, and after passing through the dryer, volatilizing and drying a solvent, the coating layer was formed. After drying for 30 second at 100 degreeC, it carried out at 120 degreeC for 30 second on conditional stages. Then, the rubbing process was carried out with a roll speed of 800 rpm, a film conveying speed of 3 m / min, and a roll indenting amount of 0.3 mm, using a rubbing machine manufactured by Inuma Co., Ltd. It carried out so that it might become parallel to this film longitudinal direction, and obtained the base material (a'-3) provided with the molecular orientation capability. Next, similarly to Example 1, the optically anisotropic layer was formed. As a result of measuring the refractive index of the optically anisotropic layer on the substrate (a'-3), the abnormal light refractive index (Ne) = 1.674 and the normal light refractive index (No) = 1.543, 785 nm in the linearly polarized wavelength 660 nm. The refractive index Ne was 1.661 and the normal light refractive index No was 1.536.

Subsequently, similarly to Example 1, the pattern part in which the recessed part and the convex part were formed continuously was formed in the optically anisotropic layer surface, and the base material (b-3) was obtained. The width of the convex portion was 2.5 μm, the width of the concave portion was 2.5 μm, and the depth of the concave portion was 2.6 μm. Next, it carried out similarly to Example 1, and formed the charging part using the composition for optically isotropic material formation (D-1), and obtained the base material (c-3). The thickness of the optically isotropic material was 4 µm from the bottom of the recess to the outermost layer.

The antireflection process was performed on both surfaces of the base material (c-3), and the polarizing diffraction element 3 was obtained. The average value of the transmittance | permeability of the 2500-point measurement of the obtained polarizing diffraction element 3 is ao ((lambda) ₁ ) = 98.5%, ao ((lambda) ₂ ) = 99.6%, ae ((lambda) ₁ ) = 2.4%, ae ((lambda) ₂₎ ) = 8.3%. In addition, in-plane uniformity was 100%. The reflectance is 0.2% at 660 nm and 0.3% at a wavelength of 785 nm on the side of the side (pattern side) having the pattern and the charging portion, and 0.3 at 660 nm on the side of the substrate (a-3) side (base side). % And 0.2% in wavelength 785nm. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 9m (lambda), in-plane uniformity is 100%, and the flat surface was made. Table 1 shows the evaluation results of the obtained polarizing diffraction element.

Example 4

A coating layer was formed like Example 3 except having used the 90-micrometer-thick polycarbonate film (base material (a-4)), and the composition for orientation layer formation (B-2) obtained in the preparation example 2, The rubbing process was performed, and the base material (a'-4) was obtained. Next, similarly to Example 1, the optically anisotropic layer was formed. As a result of measuring the refractive index of the optically anisotropic layer on the base material (a'-4), the ideal light refractive index = 1.676, the normal light refractive index (No) = 1.544, and 785 nm in the linearly polarizable wavelength 660 nm, and the abnormal light transmittance = 1.663, Normal light refractive index (No) was 1.537.

Subsequently, the pattern part formed continuously was formed similarly to Example 1, and the base material (b-4) was obtained. The width of the convex portion was 2.5 μm, the width of the concave portion was 2.5 μm, and the depth of the concave portion was 2.6 μm. Next, it carried out similarly to Example 1, and formed the charging part using the composition for optically isotropic material formation (D-1), and obtained the base material (c-4). The thickness of the optically isotropic material was 4 µm from the bottom of the recess to the outermost layer.

The antireflection process was performed on both surfaces of the base material (c-4), and the polarizing diffraction element 4 was obtained. The average value of the transmittance | permeability of the 2500-point measurement of the obtained polarizing diffraction element 4 is ao ((lambda) ₁ ) = 98.1%, ao ((lambda) ₂ ) = 99.7%, ae ((lambda) ₁ ) = 2.7% and ae ((lambda) ₂₎ ) = 8.2%. In addition, the in-plane uniformity was 99%. The reflectance is 0.3% at 660 nm and 0.3% at a wavelength of 785 nm on the side of the side (pattern side) having the pattern and the charging portion, and at 660 nm on the side of the substrate (a-4) side (base side). It was 0.3% in 0.4% and the wavelength of 785 nm. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 10m (lambda), in-plane uniformity is 99%, and the flat surface was made. The thickness of the polarizing diffraction element was 110 µm.

Table 1 shows the evaluation results of the obtained polarizing diffraction element.

Example 5

The coating layer was formed like Example 3 except having used the base material (a-5) obtained by the manufacture example 3, and the composition for orientation layer formation (B-3) obtained in the preparation example 3. The coating layer was dried at 100 ° C. for 30 seconds and then subjected to stepwise conditions at 120 ° C. for 30 seconds. Subsequently, using the Hg-Xe lamp, the surface of the formed coating layer makes the wavelength of 365 nm main through Pyrex (trademark) glass polarizing plate SPF-50C-32 (made by Sigma Co., Ltd.). The ultraviolet-ray 0.5J / cm <2> linearly polarized was irradiated and the base material (a'-5) was obtained. The polarization plane direction of linearly polarized light was performed so that it might become parallel to a film longitudinal direction. Next, similarly to Example 1, the optically anisotropic layer was formed. As a result of measuring the refractive index of the optically anisotropic layer on the base material (a'-5), the abnormal light refractive index (Ne) = 1.678 and the normal light refractive index (No) = 1.542, 785 nm in the linearly polarizable wavelength 660 nm. The refractive index Ne was 1.665 and the normal light refractive index No was 1.535.

Next, it carried out similarly to Example 1, and formed the pattern part continuously formed and obtained the base material (b-5). The width of the convex portion was 2.5 μm, the width of the concave portion was 2.5 μm, and the depth of the concave portion was 2.6 μm.

Next, the composition for optically isotropic material formation obtained by the preparation example 5 using the 300-mesh small-gravure gravure roll by the INVEX lab coater by Inoue Kinzoku Co., Ltd. on the base material (a-1) obtained by the manufacture example 1. (D-1) was applied, and the air cylinder pressure was 0.1 MPa and the feed rate was 1 / min using the unevenness forming side of the base material (b-5) and the VA-700 manufactured by Taisei Laminator. The uneven | corrugated formation side of the base material (b-5) is laminated, and ultraviolet-ray is irradiated and hardened | cured by the amount of energy of 500 mJ / cm <^2> from the base material (a-1) side using a high pressure mercury lamp, and a base material (b-5) ) The optically isotropic filling part was formed in the recessed part, and the base material (c-5) was obtained. The thickness of the ultraviolet curing acrylic material was 5 µm from the bottom of the recess to the substrate (a-1).

The antireflection process was performed on both surfaces of the base material (c-5), and the polarizing diffraction element 5 was obtained. The average value of the transmittance | permeability of the 2500-point measurement of the obtained polarizing diffraction element 5 is ao ((lambda) ₁ ) = 98.6%, ao ((lambda) ₂ ) = 99.4%, ae ((lambda) ₁ ) = 2.5% and ae ((lambda) ₂₎ ) = 7.9%. In addition, in-plane uniformity was 100%. The reflectance is 0.2% at 660 nm and 0.2% at a wavelength of 785 nm from the surface on the substrate (a-1) side, 0.3% at 660 nm and at a wavelength of 785 nm from the surface on the substrate (a-5) side. 0.2%. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 5m (lambda), in-plane uniformity is 100% and the flat surface was made. The thickness of the polarizing diffraction element was 279 mu m. Table 1 shows the evaluation results of the obtained polarizing diffraction element.

Example 6

The base material (a-1) obtained by the manufacture example 1, and the dilution | diluted thing of Hylan WLS-201 (made by DIC Corporation) which are polyether polyurethane materials to 3% with methanol were manufactured by Inoue Kinzoku Kogyo Co., Ltd. It apply | coated using 200-meter small diameter gravure roll with the INVEX lab coater of and heat-dried at 80 degreeC for 5 minutes, and the base material which has a polyurethane layer was obtained. A rubbing machine manufactured by Inuma Maage Seisakusho Co., Ltd. performs rubbing treatment with a roll rotation speed of 600 rpm, a film conveying speed of 3 m / min, and a roll press amount of 0.3 mm so that the rubbing direction is parallel to the film length direction. The base material (a'-6) to which alignment capability was provided was obtained. Next, similarly to Example 1, the optically anisotropic layer was formed. As a result of measuring the refractive index of the optically anisotropic layer on the substrate (a'-6), the abnormal light refractive index (Ne) = 1.676 and the normal light refractive index (No) = 1.542, 785 nm in the linearly polarized wavelength 660 nm. The refractive index Ne was 1.663 and the normal light refractive index No was 1.534.

Next, it carried out similarly to Example 1, and formed the charging part using the composition for optically isotropic material formation (D-1), and obtained the base material (c-6). The thickness of the optically isotropic material was 4 µm from the bottom of the recess to the outermost layer.

The antireflection process was performed on both surfaces of the base material (c-6), and the polarizing diffraction element 6 was obtained. The average value of the transmittance | permeability of the 2500-point measurement of the obtained polarizing diffraction element 6 is ao ((lambda) ₁ ) = 98.4%, ao ((lambda) ₂ ) = 99.3%, ae ((lambda) ₁ ) = 2.5% and ae ((lambda) ₂₎ ) = 7.8%. In addition, in-plane uniformity was 100%. The reflectance is 0.1% at 660 nm and 0.1% at a wavelength of 785 nm on the side of the side (pattern side) having the pattern and the charging portion, and at 660 nm on the side of the substrate (a-1) side (base side). It was 0.2% in 0.2% and wavelength 785 nm. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 12m (lambda), in-plane uniformity is 98%, and the flat surface was made. The thickness of the polarizing diffraction element was 140 µm. Table 1 shows the evaluation results of the obtained polarizing diffraction element.

Example 7

On one side of the substrate (a-1) obtained in Production Example 1, an optically isotropic material-forming composition obtained in Preparation Example 5 using an INVEX lab coater manufactured by Inoue Kinzo Kogyo Co., Ltd. with a small diameter gravure roll of 300 mesh (D -1) was apply | coated and the pattern part in which the recessed part and the convex part were continuously formed was transferred to the application surface using the transfer roll prepared so that the pattern part which formed the recessed part and the convex part continuously was transferred. Moreover, the recessed part and convex part of the transfer roll surface were prepared so that the groove | channel of the unevenness | corrugation may be formed along the circumferential direction of a roll.

At the same time as the transfer, a high-pressure mercury lamp was used to irradiate ultraviolet rays with an energy amount of 500 mJ / cm 2 from the surface side not having the pattern of the substrate (a-1) to form a pattern portion in which concave portions and convex portions were formed in succession. -7) was obtained. The width of the convex portion was 2.5 μm, the width of the concave portion was 2.5 μm, and the depth of the concave portion was 2.6 μm.

Subsequently, on the single side | surface of the base material (a-1) obtained by the manufacture example 1, 600 rpm of roll rotation speeds, 3 m / min of film conveyance speeds, and 0.3 mm of roll press-in amounts are carried out with the rubbing machine manufactured by Inuma Co., Ltd. The rubbing process was performed so that a rubbing direction might become parallel to a film longitudinal direction, and the base material (a "-7) was obtained. Next, a 200-mesh small-gravure gravure roll was used with the INVEX lab coater by Inoue Kinzoku Co., Ltd. Then, 30 parts by mass of acetone, which is a solvent, was added to 100 parts by mass of RMM727 which is a UV curable liquid crystal material manufactured by Merck Co., Ltd. It was set to micrometer. As a result of measuring the refractive index of the alignment layer on the base material (a "-7), the abnormal light refractive index (Ne) = 1.678 and the normal light refractive index (No) = 1.542, 785 nm in the linearly polarized wavelength 660 nm. (Ne) = 1.665 and normal light refractive index (No) = 1.535.

Air cylinder pressure 0.1MPa, conveying speed 1 / using the uneven | corrugated formation side of the obtained base material (b-7) and the RMM727 application side of the base material (a "-7) using VA-700 made by Taisei Laminator. The base material (c-7) was obtained by laminating at min, and irradiating and hardening an ultraviolet-ray by the amount of energy of 500mJ / cm <2> using a high pressure mercury lamp.

The antireflection process was performed on both surfaces of the base material (c-7), and the polarizing diffraction element 7 was obtained. The average value of the normal light transmittance of the 2500-point measurement of the obtained polarizing diffraction element 7 is ao ((lambda) ₁ ) = 98.7% in the wavelength of 660nm of linearly polarization, and ao ((lambda) ₂ ) = 99.4% in the wavelength of 785nm. The ideal light transmittance was ae (λ ₁ ) = 1.8% at a wavelength of 660 nm, and ae (λ ₂ ) = 8.1% at a wavelength of 785 nm. In addition, in-plane uniformity was 100%. The reflectance is 0.1% at 660 nm and 0.1% at a wavelength of 785 nm from the surface on the substrate (b-7) side, 0.2% at 660 nm and a wavelength of 785 nm at the surface on the substrate (a ″ -7) side. In addition, when the wave front aberration was measured, it turned out that (lambda) rms _ave = 4m (lambda) and in-plane uniformity were 100% and the flat surface was made. The thickness of the polarization diffraction element was 280 micrometers. Table 1 shows the evaluation results of the optical diffraction element.

Example 8

The composition for orientation layer formation obtained in the preparation example 4 using the small diameter gravure roll of 300 mesh with the INVEX lab coater by Inoue Kinzoku Co., Ltd. on the single side | surface of the base material (a-1) obtained by the manufacture example 1 (B-4). ), And the ultraviolet-ray was irradiated with the energy amount of 500mJ / cm <2> from the application surface side using the high pressure mercury lamp immediately after application | coating, and the base material (a "-1) was obtained.

Subsequently, the base material (a "-1) is longitudinally stretched at a drawing speed of 5.0 m / min and a draw ratio of 1.5 times in a reaction tank at a temperature of 145 ° C in the drawing machine, and a roll-shaped stretched film having a thickness of 106 µm (base material) (a "-2)) was obtained. Subsequently, an optically anisotropic layer was formed in the same manner as in Example 1 on the coated surface side of the composition for forming an alignment layer (B-4) of the stretched film (base material (a ″ -2)). As a result of measuring the refractive index of the optically anisotropic layer of the phase, the abnormal light refractive index (Ne) = 1.670, the normal light refractive index (No) = 1.540, and the 785 nm abnormal light refractive index (Ne) = 1.665 and normal light refractive index (No) = 1.535.

Subsequently, similarly to Example 1, the pattern part in which the recessed part and the convex part were formed continuously was formed, and the base material (b-8) was obtained. The width of the convex portion was 2.5 μm, the width of the concave portion was 2.5 μm, and the depth of the concave portion was 2.6 μm. Next, the optically isotropic material formation composition (D-2) obtained by the preparation example 6 was apply | coated to the formed recessed part using the 300 mesh small gravure roll by the INVEX lab coater by Inoue Kinzoku Kogyo Co., Ltd. , The coated surface and the base material (a-1) were laminated using a VA-700 manufactured by Taisei Laminator Co., Ltd. at an air cylinder pressure of 0.1 MPa and a feed rate of 1 / min. , The base material (c-8) was obtained by irradiating and hardening with the energy amount of 500mJ / cm <2>.

The antireflection process was performed on both surfaces of the base material (c-8), and the polarizing diffraction element 8 was obtained. The average value of the normal light transmittance of the 2500-point measurement of the obtained polarizing diffraction element 8 is ao ((lambda) ₁ ) = 99.1% in wavelength 660nm of linearly polarizable light, and ao ((lambda) ₂ ) = 99.3% in wavelength 785nm. The ideal light transmittance was ae (λ ₁ ) = 2.9% at a wavelength of 660 nm and ae (λ ₂ ) = 2.1% at a wavelength of 785 nm. In addition, in-plane uniformity was 100%. The reflectance is 0.1% at 660 nm and 0.1% at a wavelength of 785 nm from the surface of the substrate (b-8) side, 0.2% at 660 nm and a wavelength of 785 nm from the surface of the substrate (a-1) side. In the case of 0.2%. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 5m (lambda), in-plane uniformity is 100% and the flat surface was made. The thickness of the polarization diffraction element 8 was 270 micrometers. Table 1 shows the evaluation results of the obtained polarizing diffraction element 8.

Example 9

In Example 8, the substrate (a "was similarly prepared except that the longitudinal draw ratio was 1.2 times and the ultraviolet curable acrylic material (D-2) was changed to the optically isotropic material-forming composition (D-3) obtained in Preparation Example 7. -3) and the polarization diffraction element 9. As a result of measuring the refractive index of the RMM727 layer on the base material (a "-3), the abnormal light refractive index Ne = 1.678 and normal light in wavelength 660nm of linearly polarization. At refractive index (No) = 1.530, 785 nm, the abnormal light refractive index (Ne) = 1.670, and the normal light refractive index (No) = 1.523. The average value of the transmittance at the 2500 point measurement of the polarization diffraction element 9 is ao (λ ₁ ) = 99.2%, ao (λ ₂ ) = 99.4%, ae (λ ₁ ) = 2.7%, ae (λ ₂ ) = It was 11.4%. In addition, in-plane uniformity was 100%. The reflectance is 0.1% at 660 nm and 0.1% at a wavelength of 785 nm on the side of the side (pattern side) having the pattern and the charging portion, and at 660 nm on the side of the substrate (a-1) side (base side). It was 0.2% in 0.2% and wavelength 785 nm. Moreover, as a result of measuring wave front aberration, it turned out that (lambda) rms _ave = 5m (lambda), in-plane uniformity is 100% and the flat surface was made. The thickness of the polarizing diffraction element was 270 µm. Table 1 shows the evaluation results of the obtained polarizing diffraction element.

Comparative Example 1

In Example 1, the base material (a'-7) and the polarizing diffraction element 10 were obtained similarly except having made the roll indentation amount of a rubbing machine into 0.4 mm. As a result of measuring the refractive index of the RMM727 layer on the substrate (a'-7), the abnormal light refractive index Ne was 1.681, the normal light refractive index No was 1.538, and 785 nm at a wavelength of 660 nm of linearly polarized light. (Ne) = 1.667 and normal light refractive index (No) = 1.531. The average value of the transmission factor of the 2500-point measurement of the polarization diffraction element 10, ao and _{(λ 1) = 97.4%,} ao (λ 2) = 99.1%, ae (λ 1) = 5.1%, ae (λ 2) = 12.4%. In addition, in-plane uniformity was 80%. The reflectance is 0.1% at 660 nm and 0.1% at a wavelength of 785 nm on the side of the side (pattern side) having the pattern and the charging portion, and 0.2 at 660 nm on the side of the substrate (a-1) side (base side). % And 0.2% in wavelength 785nm. Moreover, as a result of measuring wave front aberration, (lambda) rms _ave = 14m (lambda) and in-plane uniformity were 90%. The thickness of the polarization diffraction element 10 was 139 micrometers. Table 1 shows the evaluation results of the obtained polarizing diffraction element 10.

Comparative Example 2

In Example 3, the roll indentation amount of the rubbing machine was set to 0.2 mm, and was changed to methyl ethyl ketone with respect to RMM727, which is an ultraviolet curable liquid crystal material, and acetone was additionally added. The optical diffraction element 11 was obtained. As a result of measuring the refractive index of the RMM727 layer on the substrate (a'-8), the abnormal light refractive index (Ne) = 1.669 and the normal light refractive index (No) = 1.551, 785 nm at a wavelength of 660 nm of linearly polarized light. (Ne) = 1.656 and normal light refractive index (No) = 1.544. The average value of the transmittance | permeability of the 2500-point measurement of the polarization diffraction element 11 is ao ((lambda) ₁ ) = 96.5%, ao ((lambda) ₂ ) = 97.9%, ae ((lambda) ₁ ) = 6.7% and ae ((lambda) ₂ ) = 15.7%. In addition, in-plane uniformity was 48%. The reflectance is 0.1% at 660 nm and 0.1% at a wavelength of 785 nm on the side of the side (pattern side) having the pattern and the charging portion, and 0.2 at 660 nm on the side of the substrate (a-1) side (base side). % And 0.2% in wavelength 785nm. Moreover, as a result of measuring wave front aberration, (lambda) rms _ave = 16m (lambda) and in-plane uniformity were 61%. The thickness of the polarization diffraction element 11 was 141 micrometers. Table 1 shows the evaluation results of the obtained polarizing diffraction element 11.

<Industrial availability>

The polarizing diffraction element of the present invention can be usefully used in an optical system such as an optical pickup device capable of recording or reproducing information on an optical recording medium such as CD, DVD, MO, or the like.

1: description
3: layer having molecular orientation capability
5: pattern portion (optical anisotropic material)
7: convex
9: recess
11: live part (optical isotropic material)
13: description
15: Pattern part in which the concave part and the convex part which consist of optically anisotropic materials were formed continuously
17: description
19: Coating surface formed of the composition containing an optically isotropic material
21: optically isotropic material

Claims (14)

At least one surface of a transparent base material has the diffraction grating layer formed with the optically anisotropic material and the optically anisotropic material,
The polarizing diffraction element which satisfy | fills following formula (iii) and (ii).
(Ⅰ) 0.008≤ | Nu (λ ₁ ) -No (λ ₁ ) | ≤0.012
(Ii) 0.004≤ | Nu (λ ₂ ) -No (λ ₂ ) | ≤0.009
[In formula (i), (ii),
λ ₁ : linearly polarized light having a wavelength of 660 nm,
λ ₂ : linearly polarized light having a wavelength of 785 nm,
Nu (λ ₁ ): refractive index of the optically isotropic material at wavelength λ ₁ ,
No (λ ₁ ): normal light refractive index of the optically anisotropic material at wavelength λ ₁ ,
Nu (λ ₂ ): the refractive index of the optically isotropic material at wavelength λ ₂ ,
No (λ ₂ ): normal light refractive index of the optically anisotropic material at wavelength λ ₂
(However, the refractive index and the normal light refractive index are measured at 25 ° C.) The method of claim 1,
The diffraction grating layer has a pattern portion in which concave portions and convex portions are continuously formed, and a filling portion formed by filling the concave portions, and either one of the pattern portion in which the concave portion and convex portions are continuously formed and the filling portion is formed of an optically isotropic material. A polarizing diffraction element, wherein the other side is made of an optically anisotropic material. The method of claim 2,
A patterned portion in which concave portions and convex portions are continuously formed is made of an optically anisotropic material, and a filling portion is made of an optically isotropic material. The method of claim 2,
A patterned portion in which concave portions and convex portions are formed continuously is made of an optically isotropic material, and a filling portion is made of an optically anisotropic material. The method of claim 2,
And a pattern portion in which the concave portion and the convex portion are formed in succession are formed by transfer. The method according to any one of claims 1 to 5,
The said transparent base material is resin, The polarizing diffraction element characterized by the above-mentioned. The method of claim 6,
The said transparent resin consists of cyclic olefin resin, The polarizing diffraction element characterized by the above-mentioned. The method according to any one of claims 1 to 5,
A layer having a molecular orientation capability is formed on a surface of the substrate made of a transparent resin to form the diffraction grating layer. The method according to any one of claims 1 to 5,
An optically anisotropic material contains an ultraviolet curable liquid crystal, The polarizing diffraction element characterized by the above-mentioned. The method according to any one of claims 1 to 5,
The optically isotropic material contains an ultraviolet curable (meth) acrylic resin, The polarizing diffraction element characterized by the above-mentioned. The method according to any one of claims 1 to 5,
A polarizing diffraction element comprising at least one surface an antireflection layer. The method of claim 11,
The following formula (i)-(i) are further satisfied, The polarizing diffraction element characterized by the above-mentioned.
(V) To (λ ₁ ) ≥95%
(V) To (λ ₂ ) ≥95%
(v) Te (λ ₁ ) ≤ 5%
(Iii) Te (λ ₂ ) ≤ 15%
In formulas (i) to (iii),
λ ₁ : linearly polarized light having a wavelength of 660 nm,
λ ₂ : linearly polarized light having a wavelength of 785 nm,
To (λ ₁ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₁ ,
To (λ ₂ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₂ ,
Te (λ ₁ ): the ideal light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₁ ,
Te (λ ₂ ): the extraordinary light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₂
Indicates.] The method of claim 11,
The following formula (i)-(i) satisfy | fill the polarizing diffraction element characterized by the above-mentioned.
(V) To (λ ₁ ) ≥95%
(V) To (λ ₂ ) ≥95%
(Iii) Te (λ ₁ ) ≤15%
(Iii) Te (λ ₂ ) ≤ 5%
In formulas (i) to (iii),
λ ₁ : linearly polarized light having a wavelength of 660 nm,
λ ₂ : linearly polarized light having a wavelength of 785 nm,
To (λ ₁ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₁ ,
To (λ ₂ ): normal light transmittance of normal incident light having a polarization plane in a direction parallel to the normal light refractive index direction of the optically anisotropic material at wavelength λ ₂ ,
Te (λ ₁ ): the ideal light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₁ ,
Te (λ ₂ ): the extraordinary light transmittance of vertically incident light having a polarization plane in a direction parallel to the direction of the extraordinary light refractive index of the optically anisotropic material at the wavelength λ ₂
Indicates.] The method according to any one of claims 1 to 5,
A polarizing diffraction element, which is laminated with one or both of a wave plate and a diffraction grating.

Images