WO2019004406A1 - Élément optique de diffraction, son procédé de fabrication, composition de résine acrylique pour former un élément optique de diffraction, et dispositif d'éclairage - Google Patents

Élément optique de diffraction, son procédé de fabrication, composition de résine acrylique pour former un élément optique de diffraction, et dispositif d'éclairage Download PDF

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Publication number
WO2019004406A1
WO2019004406A1 PCT/JP2018/024734 JP2018024734W WO2019004406A1 WO 2019004406 A1 WO2019004406 A1 WO 2019004406A1 JP 2018024734 W JP2018024734 W JP 2018024734W WO 2019004406 A1 WO2019004406 A1 WO 2019004406A1
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Prior art keywords
resin composition
refractive index
acrylic resin
optical element
meth
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PCT/JP2018/024734
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English (en)
Japanese (ja)
Inventor
英範 吉岡
由紀子 伴
ノリ子 永松
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大日本印刷株式会社
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Publication of WO2019004406A1 publication Critical patent/WO2019004406A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings

Definitions

  • the present disclosure relates to a diffractive optical element having sticking resistance under wet heat conditions and having a small amount of pattern burrs, a method of manufacturing the same, an acrylic resin composition for forming the diffractive optical element, and a lighting apparatus.
  • the need for sensor systems has increased in recent years, such as the need for personal identification to avoid security risks through the spread of networks, the flow of automated driving of cars, and the spread of the so-called "Internet of Things".
  • sensors There are various types of sensors, and the information to be detected is various.
  • One of the means is that the light source emits light to the object and information is obtained from the reflected light.
  • a pattern authentication sensor or an infrared radar is an example.
  • the light source of these sensors is used with wavelength distribution, brightness and spread according to the application.
  • the wavelength of light visible light wavelengths to infrared light wavelengths are often used.
  • infrared light is hard to be affected by external light, is invisible, and it is possible to observe the inside of the surface vicinity of an object. It is widely used.
  • an LED light source, a laser light source, and the like are often used.
  • a laser light source with less spread of light is preferably used to detect a distant place, and an LED light source is preferably used to detect a relatively close place or to illuminate an area having a certain extent of spread.
  • the size and shape of the illuminated area on the object do not necessarily match the spread (profile) of the light from the light source, in which case it is necessary to shape the light with a diffuser, lens, shield, etc. is there.
  • a diffuser called Light Shaping Diffuser (LSD) has been developed that can shape the shape of light to some extent.
  • a diffractive optical element DOE
  • the DOE is basically designed for light of a single wavelength, it is theoretically possible to shape the light into almost any shape.
  • the light intensity in the irradiation area is a Gaussian distribution
  • the DOE it is possible to control the uniformity of the light distribution in the irradiation area.
  • Such characteristics of DOE are advantageous in terms of high efficiency by suppressing irradiation to unnecessary regions, downsizing of the apparatus by reduction of the number of light sources, and the like.
  • the DOE is applicable to both parallel light sources such as lasers and diffused light sources such as LEDs, and is applicable to a wide range of wavelengths from ultraviolet light to visible light and infrared light.
  • DOE requires microfabrication in nano order, and in particular, in order to diffract light of long wavelength, it has been necessary to form a fine shape with a high aspect ratio. Therefore, electron beam lithography technology using an electron beam is conventionally used to manufacture the DOE. For example, after forming a hard mask or a resist on a quartz plate transparent in the ultraviolet to near infrared regions, a predetermined shape is drawn on the resist using an electron beam, resist development, dry etching of the hard mask, dry of quartz After etching is sequentially performed to form a pattern on the surface of the quartz plate, the hard mask can be removed to obtain a desired DOE.
  • a form called a grating cell array As a form of a diffractive optical element, a form called a grating cell array (grating cell array) is conventionally used.
  • the grating cell array type diffractive optical element for example, square fine unit regions (cells) are arranged in a matrix. Then, in one unit area of the grating cell array type diffractive optical element, a diffraction grating whose rotation direction in the plane is directed in a fixed direction at a fixed pitch is arranged. Further, in the grating cell array type diffractive optical element, the pitches and rotational directions of the diffraction gratings arranged are different for each unit region, and one diffractive optical element is configured as an aggregate thereof.
  • a diffractive optical element based on this grating cell array is manufactured by patterning glass.
  • the patterning of the glass generally includes a direct writing method such as a laser or an electron beam.
  • This direct writing method is not suitable for mass production because it takes time to produce a diffractive optical element having a fine pattern of several ⁇ m or less because it draws one by one and is not widely used.
  • the nanoimprinting method is a method in which a master plate pattern is contact-transferred onto a replica plate, and a product of the same type as the master plate can be produced at high speed.
  • the side to be transferred is not glass but resin material. That is, the replica plate to be a product is not patterned by glass but patterned by resin.
  • an acrylic UV curable resin is generally known (see Patent Documents 2-3).
  • the above-mentioned acrylic UV curable resin has low heat resistance, and it is known that material deterioration occurs under high temperature conditions or high humidity conditions.
  • wet heat conditions under wet and high temperature conditions (hereinafter, such conditions are referred to as wet heat conditions), a phenomenon in which adjacent patterns are attached or separated by the meniscus force generated when water is released from between the fine patterns (Sticking) may be confirmed.
  • An object of the present invention is to provide a manufacturing method, an acrylic resin composition for forming a diffractive optical element, and a lighting device.
  • the diffractive optical element of the present disclosure is a diffractive optical element that shapes light from a light source, and includes at least one surface side of a transparent substrate, one or more high refractive index convex portions protruding from the surface of the transparent substrate,
  • the high-refractive-index convex portion is formed of a cured product of an acrylic resin composition, and the high-refractive-index convex portion is formed at 60 ° C. and relative to the cured product.
  • the storage elastic modulus (E ′) at a humidity of 95% is characterized by being 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less.
  • a diffraction grating portion in which one or more high refractive index convex portions protruding from the surface of the transparent base and one or more low refractive index portions are disposed on at least one surface side of the transparent base
  • a method of manufacturing a diffractive optical element that shapes light from a light source Preparing a mold having a cavity shape for forming the high refractive index convex portion and the low refractive index portion; A cured product sample obtained by irradiating an acrylic resin composition to a cavity of the mold, and curing the acrylic resin composition with ultraviolet light so that the integrated light amount is 1,000 mJ / cm 2 .
  • an acrylic resin composition having a storage elastic modulus (E ′) at 60 ° C. and a relative humidity of 95% of 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less A step of curing the acrylic resin composition by bringing the transparent substrate and the acrylic resin composition into contact with each other on the side of the cavity opening of the mold and irradiating active energy rays; Forming a diffraction grating portion having a high refractive index convex portion formed of a cured product of an acrylic resin composition on a transparent substrate by pulling the mold away from the substrate; It is characterized by having.
  • one or more high refractive index convex portions protruding from the surface of the transparent substrate and one or more low refractive index portions are disposed on at least one side of the transparent substrate.
  • the storage elastic modulus (E ') at 60 ° C. and 95% relative humidity of a cured product sample obtained by curing by irradiation with ultraviolet light so as to be 1 cm 2 / cm 2 is 0.90 ⁇ 10 9 Pa or more 2.6 ⁇ 10 It is characterized by being 9 Pa or less.
  • the storage elastic modulus (E ′) at 30 ° C. and a relative humidity of 30% of the cured product of the acrylic resin composition may be 1 ⁇ 10 8 Pa or more and 5 ⁇ 10 9 Pa or less.
  • the acrylic resin composition contains a urethane bond from the viewpoint of excellent sticking resistance under wet heat conditions and less pattern burrs.
  • the acrylic resin composition is an active energy ray curable resin composition containing a tetrafunctional or higher functional (meth) acrylate and a bifunctional (meth) acrylate, which is resistant to sticking under moist heat conditions. It is preferable from the point that it is excellent in quality and less in pattern pattern.
  • the active energy ray-curable resin composition contains 40% by mass or more and 80% by mass or less of the (meth) acrylate having four or more functional groups with respect to all the curable components, and the bifunctional (meth) It is preferable to contain 10% by mass or more and 60% by mass or less of acrylate from the viewpoint of excellent sticking resistance under wet heat conditions and less pattern burrs.
  • the tetrafunctional or higher functional (meth) acrylate contains a tetrafunctional or higher functional urethane (meth) acrylate from the viewpoint of excellent sticking resistance under wet heat conditions and less pattern unevenness.
  • the tetrafunctional or higher urethane (meth) acrylate is formed of the isocyanate group of the polyvalent isocyanate compound and the hydroxyl group of a compound having one hydroxyl group and two or more (meth) acrylic groups in the molecule. It is preferable that the compound is a urethane-bonded compound from the viewpoint of excellent sticking resistance under wet heat conditions and less pattern mottle.
  • the bifunctional (meth) acrylate has a molecular weight (Mw) of 100 or more and 5,000 or less from the viewpoint of excellent sticking resistance under wet heat conditions and less pattern burrs. .
  • a cured product of the acrylic resin composition as measured by a Vickers hardness test performed according to JIS Z 2 244 (2003) and under a measurement condition of maximum load 0.2 mN and holding time 10 seconds. It is preferable from the point which is further excellent in the sticking resistance under moist heat conditions that the restoration ratio of is 60% or more.
  • the high refractive index convex portion have a portion having a height of 400 nm or more from the viewpoint of being able to diffract light having a relatively long wavelength.
  • the top of the high refractive index convex portion is defined as the upper end, and the position of the valley bottom between the high refractive index convex portion and another high refractive index convex portion adjacent thereto, or the high refractive index convex portion Among the positions of the flat part closest to the top of the high-refractive-index convex part, the lower end of the high-refractive-index convex part is defined as the lower end of the high-refractive-index convex part.
  • the ratio of the height of the high refractive index convex portion to the width of the high refractive index convex portion at a position corresponding to half the height is defined as the aspect ratio of the high refractive index convex portion
  • the high refractive index convex portion The aspect ratio of the high refractive index con
  • An illumination device includes a frame having a conductive portion capable of supplying power from the outside and an opening serving as a light emitting surface, a light source, and the above-described diffractive optical element, and the light source is fixed in the inner space of the frame. And the diffractive optical element is disposed in the opening.
  • the light source may be a light source emitting an infrared ray having a wavelength of 780 nm or more.
  • the storage elastic modulus (E ′) under moist heat conditions for the cured product of the acrylic resin composition forming the high refractive index convex portion is within the specific range, so sticking under the moist heat conditions is It can be prevented and the pattern can be reduced.
  • FIG. 1 is a plan view schematically showing an embodiment of a diffractive optical element.
  • FIG. 1 is a schematic perspective view of an embodiment of a diffractive optical element. It is a figure which shows one Embodiment of a diffractive optical element, and is sectional drawing which shows typically an example of the A-A 'cut surface of FIG.
  • FIG. 5 is a cross-sectional view schematically showing another embodiment of the diffractive optical element in which a base 3 is present between the transparent base 1 and the diffraction grating portion 2.
  • FIG. 7 is a cross-sectional view schematically showing another embodiment of the diffractive optical element, in which the covering layer 5 is provided on the opposite side of the transparent base 1 with the diffraction grating portion 2 interposed therebetween.
  • FIG. 1 is a plan view schematically showing an embodiment of a diffractive optical element.
  • FIG. 1 is a schematic perspective view of an embodiment of a diffractive optical element. It is a figure which shows one Embodi
  • FIG. 7 is a cross-sectional view schematically showing another embodiment of the diffractive optical element, in which the covering layer 5 is provided on the opposite side of the transparent base 1 with the diffraction grating portion 2 interposed therebetween.
  • FIG. 6 is a cross-sectional view schematically showing another embodiment of the diffractive optical element in which the low refractive index resin 3 is filled in the low refractive index portion 3;
  • FIG. 6 is a cross-sectional view schematically showing another embodiment of the diffractive optical element in which the low refractive index resin 3 is filled in the low refractive index portion 3;
  • FIG. 10 is a cross-sectional view schematically showing an embodiment including the anti-reflection layer 9 which is another embodiment of the diffractive optical element.
  • FIG. 10 is a cross-sectional view schematically showing an embodiment including the anti-reflection layer 9 which is another embodiment of the diffractive optical element. It is a figure which is provided for explanation of an aspect ratio, and is a fragmentary sectional view of a diffraction grating part containing a high refractive index convex part of binary shape.
  • FIG. 6 is a view provided for describing an aspect ratio, and is a schematic partial cross-sectional view of a diffraction grating portion including multi-step (4-level) high refractive index convex portions.
  • FIG. 7 is a cross-sectional view schematically showing an embodiment in which the thickness of the high refractive index convex portion 2 a is intermittently increased from the tip to the root, which is another embodiment of the cross-sectional shape of the diffraction grating portion.
  • FIG. 10 is a cross-sectional view schematically showing an embodiment in which the thickness of the high refractive index convex portion 2 a is continuously increased from the tip to the root, which is another embodiment of the cross-sectional shape of the diffraction grating portion.
  • FIG. 10 is a cross-sectional view schematically showing an embodiment in which the thickness of the high refractive index convex portion 2 a is continuously increased from the tip to the root, which is another embodiment of the cross-sectional shape of the diffraction grating portion.
  • FIG. 10 is a cross-sectional view schematically showing an embodiment in which the high refractive index convex portions 2a have a multistage shape (4-level), which is another embodiment of the cross-sectional shape of the diffraction grating portion.
  • FIG. 7 is a cross-sectional view schematically showing another embodiment of the cross-sectional shape of the diffraction grating portion, in which the high refractive index convex portion 2a has a multi-stage shape (8-level).
  • FIG. 5 is a schematic perspective view showing that the irradiation light 21 is diffracted by the diffractive optical element 10 and a square image 24 is formed at the center of the screen 22.
  • FIG. 5 is a schematic perspective view showing that the irradiation light 21 is diffracted by the diffractive optical element 10 and a square image 24 is formed on the top of the screen 22.
  • FIG. 10A is a front view of screen 22 shown to FIG. 10A.
  • FIG. 10B is a schematic diagram of an example of the metal mold
  • FIG. 7 is a schematic cross-sectional view showing an example of the acrylic resin composition filling step in the manufacturing method of the present disclosure, and showing a state in which the acrylic resin composition 32 is placed on the surface of the mold 31.
  • FIG. 7 is a schematic cross-sectional view showing an example of the acrylic resin composition filling step in the manufacturing method of the present disclosure, and showing a state in which the acrylic resin composition 32 is placed on the surface of the mold 31.
  • FIG. 7 is a schematic cross-sectional view showing an example of the acrylic resin composition filling step in the manufacturing method of the present disclosure, and showing a state of applying the acrylic resin composition 32 to the surface of the mold 31. It is a schematic diagram of an example of the acrylic resin composition hardening process in the manufacturing method of this indication. It is a schematic diagram of an example of the mold release process in the manufacturing method of this indication. It is a sectional view showing typically one embodiment of a lighting installation. It is a perspective view showing a case where light which becomes circular [irradiation area 23] is projected directly to screen 22 of plane shape.
  • FIG. 6 is a schematic perspective view of the diffractive optical element 50 in which sticking has occurred.
  • the diffractive optical element of the present disclosure and a method of manufacturing the same, an acrylic resin composition for forming the diffractive optical element, and a lighting apparatus will be described in detail in order, the present disclosure is limited to the following embodiments. Instead, various modifications may be made within the scope of the present invention.
  • the shapes and geometrical conditions as well as the degree of them are specified. For example, terms such as “parallel” and values of length and angle etc. It shall be interpreted including the extent to which the function can be expected.
  • the term “plan view” in this specification means that the image is viewed from the direction perpendicular to the top surface of the diffractive optical element.
  • plan view corresponds to visual recognition from the direction perpendicular to the surface of the diffractive optical element having the diffraction grating portion (corresponding to the direction of the plan view as shown in FIG. 1).
  • the active energy ray is not only visible light and electromagnetic waves of wavelengths in the invisible region such as ultraviolet light and X-rays, but also curing of acrylic resin compositions that collectively refers to particle rays such as electron rays and alpha rays. It contains radiation with energy quanta that is sufficient to As active energy rays, ultraviolet rays are preferred.
  • (meth) acrylic represents each of acrylic or methacrylic
  • (meth) acrylate represents each of acrylate or methacrylate
  • (meth) acryloyl represents each of acryloyl or methacryloyl.
  • shapeing the light means that the shape (irradiation area) of the light projected onto the target object or the target area is made to be an arbitrary shape by controlling the traveling direction of the light. . For example, by transmitting light (FIG. 14) in which the irradiation area 23 is circular when projected directly onto the flat screen 22 (FIG. 14A), the irradiation area is square (24 in FIG. 10A).
  • the diffractive optical element and emitted as it is without being diffracted as zero-order light (25 in FIG. 10A), and diffracted light generated by the diffractive optical element is referred to as first-order light (26a to 26d in FIG. 10A).
  • first-order light 26a to 26d in FIG. 10A
  • the cross-sectional shape of the diffraction grating portion is defined as that in which the diffractive optical element is placed on a horizontal surface. In the example of FIG.
  • the X axis is taken in the repetition direction of the periodic structure, orthogonal to the X axis, the Y axis taken so that XY forms a horizontal plane, and the Z axis taken in the direction perpendicular to the XY horizontal plane.
  • a valley bottom (minimum point of Z) between convex portions is a reference of height 0, and a portion of height 0 is a concave portion.
  • a portion having a height H (H> 0) is a convex portion.
  • the depth to the valley bottom between the protrusions may be referred to as the maximum height of the protrusions, but in the present disclosure, the height and the depth have a relationship between front and back, and the protrusions In the case of focusing on the height, the case of focusing on the recess, and the depth, it is substantially the same.
  • it is a binary (2-level) shape that the cross-sectional shape of the diffraction grating portion is a repetitive structure of a concave portion with a height of 0 and a convex portion with a height H as shown in the example of FIG. It is said that.
  • a convex portion having two or more flat portions may be referred to as a multistage shape, and the multistage convex portion and the concave portion are combined to n If there are two flats, it may be called n-level shape.
  • “transparent” refers to one that transmits light of at least a target wavelength. For example, even if it does not transmit visible light, if it transmits infrared rays, it shall be treated as transparent when used for infrared applications.
  • the diffractive optical element according to the present disclosure is a diffractive optical element that shapes light from a light source, and includes at least one high refractive index convex projecting from the surface of the transparent base on at least one surface side of the transparent base Portion and one or more low refractive index portions are provided, and the high refractive index convex portion is formed of a cured product of an acrylic resin composition, and the cured product of the cured product
  • the storage elastic modulus (E ') at 0 ° C and a relative humidity of 95% is characterized by being 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less.
  • the high refractive index convex portion in the diffractive optical element of the present disclosure is an acrylic resin having a specific storage elastic modulus (E ′) under the conditions of 60 ° C. and 95% relative humidity. It is formed of a cured product of the composition.
  • E ′ specific storage elastic modulus
  • E ' storage elastic modulus
  • FIG. 2 is a schematic perspective view of an embodiment of a diffractive optical element.
  • high-refractive-index convex portions 2 a connected in a long and thin manner are arranged on one surface side of the transparent base material 1 at a constant interval.
  • DOE and GCA usually have such a so-called line & space structure.
  • FIG. 15 is a schematic perspective view of a diffractive optical element in which sticking has occurred.
  • hatched portions indicate portions where sticking has occurred.
  • all or part of adjacent high refractive index convex portions 2 a are sticking and are in contact with each other.
  • the long and thin convex portions are arranged in a fine size, the sticking that has once occurred is easily propagated as a whole compared to the dot-like moth-eye structure and the like.
  • GCA is usually smaller in size than DOE, sticking is more likely to occur.
  • FIG. 16A is a schematic cross-sectional view showing a state in which water has infiltrated between fine patterns of the diffractive optical element.
  • FIG. 16B is a schematic cross-sectional view of the diffractive optical element in which the sticking has occurred, corresponding to a part of the BB ′ cut surface in FIG.
  • the diffractive optical element 10 provided with the diffraction grating portion 2 on the transparent substrate 1 is depicted.
  • the diffraction grating portion 2 includes a high refractive index convex portion 2a and a low refractive index portion 2b, and in the example of FIG. 16A, the low refractive index portion 2b is air. However, as shown in FIG. 16A, the moisture 51 infiltrates into one of the low refractive index portions 2b. In this case, the stress ⁇ acting on the high refractive index convex portion 2a in contact with the moisture 51 is expressed by the following formula (1).
  • the stress ⁇ disappears, so the sticking is canceled and the high refractive index convex portion 2a in contact may be separated, but the high refractive index convex portion 2a is fused together particularly under wet heat conditions In some cases, sticking may not be eliminated. In order to prevent sticking, it is required that the material forming the high refractive index convex portion be so hard that it can withstand stress ⁇ .
  • the high refractive index convex portion has a portion extending in a ridge line shape (a portion extending narrowly in the surface direction and linearly extending), and extends in a ridge line shape of the high refractive index convex portion Stucking is particularly likely to occur when at least a portion of the portions are separated by low refractive index portions having a width narrower than the height of the high refractive index convex portions and adjacent in parallel or substantially in parallel.
  • assembly may be performed under wet heat conditions.
  • pattern peeling occurs at the time of mold release.
  • pattern wrinkling means that a part of the entire or a part of the high refractive index convex portions forming the fine pattern in the diffraction grating portion is broken or taken off from the root. means.
  • FIG. 17 is a schematic cross-sectional view showing a state in which pattern peeling has occurred at the time of mold release of the diffractive optical element. Such a pattern is found, for example, in the case of replicating a diffractive optical element by imprinting with a resin using a mold prepared by electron beam lithography.
  • the cured resin 102 When pulling the convex cured resin 102 on the substrate 101 away from the mold 103, if the cured resin 102 is too hard, the cured resin 102 may break in the mold 103. It is necessary for the cured resin 102 to be deformed to a certain extent at the time of mold release, but when the resin cured product 102 is too hard, free deformation can not be expected, and as a result, the load required for mold release increases. It is considered that breakage occurs in a portion where particular load concentrates. When the cured resin material 102 is broken, high refractive index convex portions having a desired height can not be obtained as illustrated. Such a problem of pattern peeling is not limited to the cured resin on the molded diffractive optical element.
  • the desired fine pattern can not be obtained when the high refractive index convex portions are too hard or too soft.
  • high refractive index convex portions are formed of a cured product of an acrylic resin composition, and the storage elastic modulus (E ′) of the cured product at 60 ° C. and 95% relative humidity is 0. It became clear that sticking could be prevented under moist heat conditions and that the pattern could be suppressed from mold release at the time of mold release when it is not less than 90 ⁇ 10 9 Pa and not more than 2.6 ⁇ 10 9 Pa.
  • the storage elastic modulus (E ') at 60 ° C.
  • the cured product has a relative humidity of 60 ° C. and a relative humidity of 95 because it can prevent sticking under moist heat conditions, suppress breakage and breakage of the cured product, and is excellent in releasability and deformation during release.
  • the storage elastic modulus (E ') in% is preferably 1.0 ⁇ 10 9 Pa or more and 2.5 ⁇ 10 9 Pa or less, and more preferably 1.1 ⁇ 10 9 Pa or more and 2.3 ⁇ 10 9 Pa or more. It is 9 Pa or less, and more preferably 1.2 ⁇ 10 9 Pa or more and 2.0 ⁇ 10 9 Pa or less.
  • the storage elastic modulus (E ′) is a physical property that does not depend on the shape or size of the object to be measured. In the present disclosure, it is measured with a test piece cut out from a diffractive optical element, or with a test piece obtained by separately polymerizing an acrylic resin composition. In the present disclosure, the storage elastic modulus (E ′) is measured by the following method in accordance with JIS K7244. First, a test piece for measurement is prepared. The test piece is obtained by cutting out the appropriate dimension from the diffraction grating portion of the diffractive optical element.
  • the acrylic resin composition is sufficiently cured by irradiating ultraviolet light so that the integrated light amount is 1,000 mJ / cm 2 , thereby obtaining a single film of an appropriate size, which is used as a test piece. It can also be done.
  • the storage elastic modulus at 60 ° C. and 95% relative humidity is measured by measuring the dynamic viscoelasticity based on the conditions of the measurement temperature 60 ° C. and the relative humidity 95% and the measurement conditions shown in Table A in the examples. (E ') is required.
  • the storage elastic modulus at 30 ° C. and 30% relative humidity is measured by measuring the dynamic viscoelasticity based on the conditions of measurement temperature 30 ° C. and relative humidity 30% and the measurement conditions shown in Table A in the examples.
  • E ' is required.
  • a measurement device for example, Rheogel E4000 manufactured by UBM can be used.
  • an indenter can be pressed into the surface of the test piece to determine the storage elastic modulus (E ′) of the surface of the test piece.
  • an AFM (Atomic Force Microscope) nano indenter such as TI950 TRIBOINDENTER manufactured by Hysitron can be used. Measurement with an AFM nanoindenter has the advantage that the surface mechanical strength of the diffractive optical element surface can be measured directly. However, in this measurement, in order to prevent variations in measured values, it is preferable to measure by pressing an indenter in the vicinity of the center of the high refractive index convex portion.
  • a recess on the surface of a diffractive optical element is selected as a measurement location, the width of a Berkovich indenter usually used in an AFM nanoindenter often can not penetrate to the bottom of the recess, so the bottom of the recess is selected.
  • Surface mechanical strength is difficult to measure.
  • the high refractive index convex portion is expected to be bent by the pressing of the indenter, so that it is difficult to obtain an accurate measurement value of the surface mechanical strength.
  • the outline of the measurement in the case of using the AFM nanoindenter is as follows. First, the measurement sample is set on the stage, and the measurement position is confirmed by the CCD camera. Next, after performing calibration as appropriate, the sample is moved under a Berkovich indenter to obtain an AFM image of the surface of the diffractive optical element in a dynamic force mode (DFM mode).
  • DFM mode dynamic force mode
  • the high refractive index convex portion is specified from the obtained AFM image, and several places around the center of the high refractive index convex portion are selected to be the measurement place. At this measurement site, measurement is performed by the contact mode of AFM. Examples of measurement conditions are shown below.
  • the indentation hardness H IT can be determined based on the relationship between the displacement and the load obtained at the load unloading time. This indentation hardness H IT, storage modulus of interest (E ') is obtained.
  • requiring storage elastic modulus (E ') using the test piece of acrylic resin composition single film is realistic.
  • the storage elastic modulus of the base adjacent to the high refractive index convex portion on the diffractive optical element is approximately the same value as the storage elastic modulus of the test piece obtained by curing the acrylic resin composition.
  • the storage modulus (E ′) of the test piece obtained by curing the composition is the same as the storage modulus (E ′) of the high refractive index convex portion on the diffractive optical element.
  • the storage elastic modulus (E ′) at 30 ° C. and 30% relative humidity of the cured product of the acrylic resin composition may be 1 ⁇ 10 8 Pa or more and 5 ⁇ 10 9 Pa or less.
  • a cured product having the above storage elastic modulus (1 ⁇ 10 8 Pa or more and 5 ⁇ 10 9 Pa or less) under normal temperature and normal humidity conditions the physical properties necessary for the diffractive optical element can be satisfied under the conditions.
  • the moist heat condition A diffractive optical element having anti-sticking resistance in the lower part and with less pattern blurring can be obtained.
  • the storage elastic modulus (E ′) under high humidity conditions of 95% relative humidity.
  • the high humidity condition is considered to be a factor of sticking because it causes excessive moisture in the diffraction grating portion of the diffractive optical element (the above-mentioned FIG. 16A and FIG. 16B).
  • the high temperature condition of 60 ° C. is considered to be a factor for promoting sticking, since it promotes the supply of water to the diffraction grating portion. Therefore, storage elastic modulus (E ') under moist heat conditions of 60 ° C. and 95% relative humidity is important in examining the sticking resistance.
  • the composition of the acrylic resin composition is adjusted so that the storage elastic modulus (E ′) at 60 ° C. and 95% relative humidity is 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less.
  • the storage elastic modulus (E ′) at 60 ° C. and 95% relative humidity is 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less.
  • the contact angle of water on the surface of the diffraction grating portion is preferably 90 degrees or more, more preferably 100 degrees or more, and even more preferably 110 degrees or more.
  • the measuring method of the contact angle of water is as follows. A droplet of 2.0 ⁇ L is dropped with the surface of the diffraction grating portion of the diffractive optical element up, and the contact angle after 0.5 seconds of deposition is measured.
  • a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. can be used as a measuring apparatus.
  • the contact angle of water is determined using the cured product of the acrylic resin composition having the composition. It may be measured.
  • the acrylic resin composition is coated on a transparent substrate, and the acrylic resin composition is cured by irradiation with ultraviolet light so that the integrated light amount becomes 1,000 mJ / cm 2 , and the coating is performed. Form a film. With the coated film side as the upper surface, it is horizontally attached to a black acrylic plate with an adhesive layer. Next, a 2.0 ⁇ L water droplet is dropped onto the coating, and the contact angle after 0.5 seconds of deposition is measured.
  • the measuring device is the same as above.
  • Glass transition temperature (Tg) measurement of acrylic resin composition” of the Example mentioned later Temperature Tg (degreeC) is mentioned.
  • the glass transition temperature Tg may be 45 ° C. or more and 80 ° C. or less, and may be 48 ° C. or more and 79 ° C. or less.
  • the glass transition temperature Tg is a secondary index.
  • the storage elastic modulus (E ′) at 60 ° C. and 95% relative humidity is the most important parameter for exhibiting the effect of the anti-sticking effect and the effect of preventing the pattern cracking.
  • the acrylic resin composition preferably contains a urethane bond, because it is easy to obtain a diffractive optical element having sticking resistance under wet heat conditions and having few patterns.
  • the said acrylic resin composition is an active energy ray curable resin composition containing the (meth) acrylate more than tetrafunctional and the bifunctional (meth) acrylate from the same reason.
  • tetrafunctional or higher urethane (meth) acrylates tend to increase the storage elastic modulus (E ′) of the resulting cured product under moist heat conditions
  • the bifunctional urethane (meth) acrylate is a obtainable cured product.
  • the acrylic resin composition is more preferably an active energy ray curable resin composition containing a tetrafunctional or higher functional urethane (meth) acrylate and a bifunctional urethane (meth) acrylate.
  • the active energy ray-curable resin composition does not contain as much as possible a material that is susceptible to moisture or a material that absorbs water and tends to swell. This is because the sticking resistance of the resulting diffractive optical element may be reduced if the material contains a large amount of such materials.
  • the material susceptible to moisture include known materials that decompose by reacting with water.
  • a material which absorbs water and tends to swell for example, a material having high hydrophilicity can be mentioned, and more specifically, vinyl pyrrolidone, ammonium acrylate, carboxyethyl acrylate and the like can be mentioned.
  • the total content of the material sensitive to moisture and the material which easily absorbs water and swells is preferably 10% by mass or less, based on 100% by mass of the whole active energy ray-curable resin composition. Is 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0% by mass.
  • the tetrafunctional or higher (meth) acrylate means a polyfunctional acrylate having four or more (meth) acryloyl groups in one molecule.
  • the tetrafunctional or higher (meth) acrylates include both monomers and polymers.
  • Examples of tetrafunctional or higher (meth) acrylates include pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane hexa (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetratetra
  • examples thereof include (meth) acrylates, oligoester tetra (meth) acrylates, and dipentaerythritol polyacrylates; ethylene oxide-modified compounds thereof, propylene oxide-modified compounds, and ⁇ -caprolactone-modified compounds.
  • the modified number n ⁇ 6 is preferable. This is because in the case of the modification number n> 6, the cured product of the active energy ray curable resin composition tends to be too soft and sticking may easily occur.
  • These tetrafunctional or higher functional (meth) acrylates can be used alone or in combination of two or more.
  • the content of the tetrafunctional or higher (meth) acrylate is preferably 40% by mass or more and 80% by mass or less, and more preferably 55% by mass or more and 65% by mass with respect to all the curable components of the active energy ray curable resin composition. It is more preferable that the content is less than%.
  • the tetrafunctional or higher functional (meth) acrylate is a tetrafunctional or higher functional urethane from the viewpoint of enhancing the shape retention and heat resistance of the obtained diffractive optical element by increasing the crosslink density by chemical bonding and densifying the network structure. It is preferred to contain meta) acrylate. There are no particular limitations on the position and number of urethane bonds in this case, and whether or not the (meth) acryloyl group is at the end of the molecule. Particularly preferred are compounds having 6 or more (meth) acryloyl groups in the molecule, and more preferred are compounds having 10 or more.
  • the upper limit of the number of (meth) acryloyl groups in the molecule is not particularly limited, but is preferably 15 or less.
  • the curability of the resulting cured product may be reduced, and the storage modulus may be reduced.
  • the number of (meth) acryloyl groups in the urethane (meth) acrylate molecule is too small, the curability of the resulting cured product may be reduced, and the storage modulus may be reduced.
  • the number of (meth) acryloyl groups in the urethane (meth) acrylate molecule is too large, the consumption rate of carbon-to-carbon double bonds of the (meth) acryloyl group by polymerization, that is, the reaction rate may not be sufficiently increased.
  • the structure of the tetrafunctional or higher urethane (meth) acrylate is not particularly limited, but from the viewpoint of excellent sticking resistance under wet heat conditions and less pattern mottle, the isocyanate group of the polyvalent isocyanate compound (a), It is preferable that it is a compound in which one hydroxyl group and a hydroxyl group of the compound (b) having two or more (meth) acrylic groups in the molecule are urethane-bonded.
  • it is preferable that substantially all of the isocyanate groups in the polyvalent isocyanate compound (a) form a urethane bond with the hydroxyl group in the compound (b).
  • polyvalent isocyanate compound (a) there is no particular limitation on the polyvalent isocyanate compound (a) in this case, and a compound having two or more isocyanate groups in the molecule can be mentioned.
  • compounds having two isocyanate groups in the molecule include 1,5-naphthyl diisocyanate, 4,4′-diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate , Tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate , Isophorone diisocyanate, lysine diisocyan
  • a nurate body etc. are mentioned.
  • isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like are particularly preferable in the present disclosure.
  • the compound (b) having one hydroxyl group and two or more (meth) acrylic groups in the molecule is not particularly limited, but a compound having three or more (p) hydroxyl groups in the molecule Examples of the compound in which (meth) acrylic acid is reacted (p-1) with the hydroxyl group of b-1); and compounds in which glycidyl (meth) acrylate and (meth) acrylic acid undergo ring opening reaction.
  • a compound in which (meth) acrylic acid is reacted (p-1) times with a compound (b-1) having p (p is an integer of 3 or more) hydroxyl groups in the molecule there are no particular limitations on the “compound (b-1) having three or more hydroxyl groups in the molecule”, and examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tetramethylolethane, diglycerin and ditriol.
  • Methylol ethane ditrimethylol propane, dipentaerythritol, ditetramethylol ethane; ethylene oxide-modified compounds thereof; propylene oxide-modified compounds thereof; ethylene oxide-modified compounds of isocyanuric acid, propylene oxide-modified compounds, ⁇ -caprolactone-modified compounds; Ester etc. .
  • the number of hydroxyl groups in the compound (b-1) is particularly preferably 4 or more, and more preferably 6 or more, in that the number of functional groups in the resulting urethane (meth) acrylate can be increased.
  • diglycerin, ditrimethylolethane, ditrimethylolpropane, dipentaerythritol, ditetramethylolethane and the like are particularly preferable.
  • (meth) acrylic acid is reacted with three hydroxyl groups of four hydroxyl groups of diglycerin to give one hydroxyl group and two or more hydroxyl groups (in this case)
  • a compound (b) having three (meth) acrylic groups is synthesized.
  • polyvalent isocyanate compound (a) is isophorone diisocyanate
  • Two (b) react with each other to synthesize “a tetrafunctional or higher urethane (meth) acrylate”.
  • the bifunctional (meth) acrylate means a polyfunctional acrylate having two (meth) acryloyl groups in one molecule.
  • Specific examples of the difunctional (meth) acrylate include, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate Etc.
  • difunctional (meth) acrylates can be used alone or in combination of two or more.
  • the content of the bifunctional (meth) acrylate is preferably 10% by mass or more and 60% by mass or less, and 30% by mass or more and 45% by mass or less based on all the curable components of the active energy ray curable resin composition. It is more preferable that
  • the molecular weight (Mw) of the bifunctional (meth) acrylate is preferably 100 or more and 5,000 or less, from the viewpoint that the cured product of the active energy ray curable resin composition has an appropriate hardness, and is more preferable. 100 or more and 4,000 or less, more preferably 100 or more and 2,000 or less.
  • the molecular weight (Mw) of the bifunctional (meth) acrylate is 100 or more, as a result of the cured product having appropriate flexibility, the sticking resistance of the resulting diffractive optical element becomes better.
  • the molecular weight (Mw) of the bifunctional (meth) acrylate is 5,000 or less, as a result of the cured product being able to maintain an appropriate hardness, it is difficult to form a pattern in the obtained diffractive optical element.
  • the difunctional (meth) acrylate may contain a difunctional urethane (meth) acrylate.
  • the content of the bifunctional urethane (meth) acrylate is preferably 30% by mass or less, and more preferably 20% by mass or less, based on all the curable components of the active energy ray curable resin composition. The content is more preferably 10% by mass or less, and particularly preferably 0% by mass.
  • the difunctional (meth) acrylate may contain a difunctional (meth) acrylate other than the difunctional urethane (meth) acrylate.
  • the content of the bifunctional (meth) acrylate other than the bifunctional urethane (meth) acrylate is 10% by mass or more and 50% by mass or less with respect to the entire curable component of the active energy ray curable resin composition Is preferable, and 20 to 45% by mass is more preferable.
  • the bifunctional urethane (meth) acrylate is preferably a bifunctional urethane (meth) acrylate having one (meth) acrylic group at each end of the molecule.
  • the weight average molecular weight is preferably 1,000 to 30,000, and 2,000 to 5,000. Is particularly preferred. If the molecular weight is too low, the flexibility may decrease, and if the molecular weight is too high, it may lead to a decrease in storage modulus.
  • the bifunctional urethane (meth) acrylate is not particularly limited, but the following are particularly preferable. That is, the diisocyanate compound (d) is reacted with both ends of the polymer or oligomer (c) such as hydroxyl group and amino group at both ends, and the obtained “polymer or oligomer having isocyanate group at both ends” is further added It is particularly preferable to react the compound (e) having a hydroxyl group and a (meth) acrylic group in the molecule at its both terminals.
  • the polymer or oligomer (c) having hydroxyl groups at both ends is not particularly limited, and examples thereof include ester oligomers, ester polymers, urethane oligomers, urethane polymers, polyethylene glycol, polypropylene glycol and the like. Among these, particularly preferred are ester oligomers and ester polymers.
  • the molecular weight of such an oligomer or polymer is not particularly limited, but a weight average molecular weight of 1,000 to 5,000 is preferable in view of curability, and 2,000 to 3,000 is particularly preferable.
  • the diol component of the above-mentioned ester is not particularly limited, but ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2,2'-thiodiethanol Etc. Particularly preferred are 1,4-butanediol, 1,6-hexanediol and the like.
  • the dicarboxylic acid component of the ester is not particularly limited, and examples thereof include alkylene dicarboxylic acids such as oxalic acid, succinic acid, maleic acid and adipic acid; and aromatic dicarboxylic acids such as terephthalic acid and phthalic acid. Particularly preferred are adipic acid and terephthalic acid.
  • diisocyanate compound (d) to be reacted at both ends of the polymer or oligomer, and the same diisocyanate compounds as those described in the item of the polyvalent isocyanate compound (a) above can be used.
  • Particularly preferred is isophorone diisocyanate and the like.
  • the “compound (e) having a hydroxyl group and a (meth) acrylic group in the molecule, which is reacted at both ends of the polymer or oligomer having an isocyanate group at both ends obtained above is not particularly limited, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate and the like can be mentioned.
  • the active energy ray-curable resin composition contains monofunctional (meth) acrylate and / or trifunctional (meth) acrylate besides tetrafunctional (meth) acrylate and bifunctional (meth) acrylate. It may be.
  • the monofunctional (meth) acrylate means an acrylate having one (meth) acryloyl group in one molecule.
  • the trifunctional (meth) acrylate means a polyfunctional acrylate having three (meth) acryloyl groups in one molecule. However, the lower the content of monofunctional (meth) acrylate and trifunctional (meth) acrylate, the better.
  • the total content of monofunctional (meth) acrylate and trifunctional (meth) acrylate is 10% by mass or less with respect to the total curable component of the active energy ray curable resin composition. Is preferable, 5% by mass or less is more preferable, and 0% by mass is more preferable.
  • monofunctional (meth) acrylates include phenoxyethyl acrylate, trimethylcyclohexanol acrylate, isobornyl acrylate, phenylphenol acrylate, nonylphenol acrylate and the like.
  • trifunctional (meth) acrylates include glycerin PO-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, trimethylolpropane PO-modified tri (meth) Acrylate, EO modified triisocyanurate (meth) acrylate, EO modified isocyanurate E-caprolactone modified tri (meth) acrylate, 1,3,5-triacryloylhexahydro-s-triazine, pentaerythritol tri (meth) acrylate, di- Pentaerythritol tri (meth) acrylate tripropionate and the like can be mentioned.
  • the crosslinking density depending on the magnitude of the molecular weight may contribute to the determination of the storage elastic modulus under wet heat conditions.
  • the acrylic resin composition may contain one or more photopolymerization initiators, if necessary.
  • the content of the photopolymerization initiator is usually 0.2 to 15% by mass, preferably 0.3 to 13% by mass, based on the total solid content of the acrylic resin composition. It is more preferable that the content be 10% by mass.
  • the photopolymerization initiator is not particularly limited, but known ones conventionally used for radical polymerization, such as acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyl Aryl ketone photopolymerization initiators such as dimethyl acetals, benzoyl benzoates, ⁇ -acyloxime esters; sulfur-containing photo polymerization initiators such as sulfides and thioxanthones; acyl phosphine oxides such as acyl diaryl phosphine oxides; Anthraquinones etc. are mentioned. Moreover, a photosensitizer can also be used together.
  • the acrylic resin composition preferably contains a release agent (material having releasability).
  • the mold release agent can suppress the pattern of the cured product by improving the release property of the cured product of the acrylic resin composition.
  • the storage elastic modulus (E ') at 60 ° C. and 95% relative humidity of the cured product is 0.90 ⁇ 10 9 Pa or more 2.6 ⁇ 10 9 by appropriately selecting the type of the release agent. It can be adjusted to the range of Pa or less, and the cured product can also be provided with sticking resistance. That is, the release agent brings about a better effect in both of the suppression of the pattern scum and the sticking prevention in the cured product.
  • the addition of the release agent can prevent the reduction of the mold life due to the resin clogging at the time of release.
  • the release agent is not particularly limited as long as it is usually used for producing a diffractive optical element.
  • the mold release agent can be appropriately selected from known mold release agents such as silicone type, fluorine type, and phosphoric acid type as needed, and used. Further, as these releasing agents, those fixed to the cross-linked structure of the acrylic resin composition and those existing in a free state can be selected according to the application. Among them, as the release agent, non-reactive silicone, reactive silicone, and phosphoric acid-based release agent are preferably used, and among these, non-reactive silicone is more preferable.
  • the acrylic resin composition only needs to contain at least the above-mentioned active energy ray curable component, and may further contain other components as necessary.
  • a plurality of antistatic agents, ultraviolet light absorbers, infrared light absorbers, light stabilizers, antioxidants and the like can be added.
  • Antistatic agents are effective in preventing dust deposition during processing and use, and ultraviolet absorbers, infrared absorbers, light stabilizers and antioxidants are effective in improving durability.
  • compounding with an inorganic material such as silsesquioxane is also effective.
  • the acrylic resin composition does not substantially contain a solvent in consideration of the environment, it contains a solvent in consideration of adhesion to a substrate, adjustment of viscosity, improvement of surface quality, etc. It is also good.
  • the resin is applied to the substrate or the mold, and the solvent is dried and then shaped.
  • the acrylic resin composition may contain a resin other than the acrylic resin.
  • the acrylic resin composition is, for example, a compound having an ethylenically unsaturated double bond other than an acrylic resin, specifically, vinyl such as triethylene glycol divinyl ether, 2- (2-vinyloxyethoxy) ethyl acrylate, etc. You may contain a system compound etc.
  • the diffractive optical element of the present disclosure preferably has excellent reflow resistance.
  • excellent reflow resistance means that the mass change rate before and after heating (for example, 260 ° C. for 1.5 minutes) is 2% or less, and the transmittance fluctuation before and after the heating is 1% or less. means.
  • Method of manufacturing diffractive optical element” described later in the case of manufacturing an illumination device using the diffractive optical element, a temporary assembly including the diffractive optical element is used. The process (reflow process) put into a reflow oven and heated on high temperature conditions may be implemented.
  • the light source and the frame surrounding the same can be electrically connected to the mounting substrate by, for example, solder or the like, and the lighting device can be efficiently manufactured.
  • the material since a high temperature of 200 ° C. or higher is instantaneously applied to the material constituting the lighting device, the material may be dissolved or sublimated.
  • the diffractive optical element of the present disclosure preferably has excellent reflow resistance.
  • the diffractive optical element having excellent reflow resistance can be said to be excellent in formability because the shape of the high refractive index convex portion is not easily damaged in the reflow step.
  • a diffractive optical element having excellent reflow resistance for example, a diffractive optical element in which a cured product of an acrylic resin composition containing a tetrafunctional or higher functional (meth) acrylate is used to form a high refractive index convex portion is It can be mentioned.
  • the calculation method of mass change rate and transmittance fluctuation is as follows. (Calculation method of mass change rate of diffractive optical element) The mass of the diffractive optical element before and after the reflow is measured, and the mass change rate a is calculated from the following formula I.
  • Formula I a ⁇ (M 0 -M 1 ) / M 0 ⁇ ⁇ 100
  • a a mass change rate (%)
  • M 0 a mass of the diffractive optical element before reflow (mg)
  • M 1 a mass of the diffractive optical element after reflow (mg).
  • the transmittance (%) of the diffractive optical element before and after reflow is measured.
  • the transmittance is measured using an ultraviolet visible near infrared (UV-Vis-NIR) spectrophotometer (for example, UV-3150 manufactured by Shimadzu Corporation).
  • UV-Vis-NIR ultraviolet visible near infrared
  • the transmittance of the transparent base and the diffraction grating portion of the diffractive optical element having a wavelength of 850 nm is measured by this device.
  • the absolute value of the difference between the transmittance of the diffractive optical element before reflow and the transmittance of the diffractive optical element after reflow is taken as the transmittance fluctuation (%) of the diffractive optical element.
  • the refractive index of the cured product of the acrylic resin composition constituting the high refractive index convex portion is not particularly limited, but is preferably 1.4 to 2.0 and 1.45 to 1.8. More preferable. According to the present disclosure, a shape having an aspect ratio of 2 or more can be stably formed, and a favorable diffractive optical element can be obtained even with a resin having a lower refractive index than silicon oxide and the like. Further, in the present disclosure, the transmittance of the cured product of the resin composition constituting the high refractive index convex portion is not particularly limited, but the infrared transmittance (wavelength 850 nm) is preferably 90% or more, 92% or more It is more preferable that
  • the diffractive optical element has excellent sticking resistance under wet heat conditions because the cured product exhibits the property as an elastic body more strongly.
  • the loss modulus (E ′ ′) at 60 ° C. and 95% relative humidity of the cured product of the acrylic resin composition can be measured by the same method as the storage modulus (E ′).
  • cured material of an acrylic resin composition is 60% or more. It is because a cured product having such a recovery rate has better resistance to sticking.
  • the acrylic resin in the acrylic resin composition preferably contains a urethane bond, and more preferably contains a tetrafunctional or higher functional urethane (meth) acrylate, from the viewpoint that the recovery rate is 60% or more.
  • the measurement conditions of the recovery rate are as follows.
  • a test piece cut out from a diffractive optical element may be used, or a test piece obtained by separately polymerizing the acrylic resin composition is used. It is also good.
  • the method of preparing these test pieces is as described above. Based on JIS Z 2244 (2003), the Vickers hardness test is carried out under the following measurement conditions. Specifically, an indenter is pressed into the surface of the test piece under the following measurement conditions, and the recovery rate (%) of the surface of the test piece is measured.
  • a measuring device for example, PICODENTER HM-500 manufactured by Fisher Instruments can be used.
  • FIG. 1 is a plan view schematically showing an embodiment of the diffractive optical element of the present disclosure.
  • FIG. 2 is a perspective view schematically showing an embodiment of the diffractive optical element of FIG.
  • FIG. 3 is a cross-sectional view schematically showing an example of a cross section taken along line AA ′ of FIG.
  • the diffractive optical element 10 of the present disclosure includes the diffraction grating portion 2 on one surface side of the transparent substrate 1.
  • the diffraction grating portion 2 includes one or more high refractive index convex portions 2 a protruding from the surface of the transparent substrate 1 and one or more low refractive index portions 2 b.
  • FIG. 1 is a plan view schematically showing an embodiment of the diffractive optical element of the present disclosure.
  • FIG. 2 is a perspective view schematically showing an embodiment of the diffractive optical element of FIG.
  • FIG. 3 is a cross-sectional view schematically showing an example of a cross section taken along line AA ′ of FIG
  • the diffractive optical element of the present disclosure generally has a plurality of regions (for example, 2A to 2D regions in FIG. 1) having different periodic structures.
  • the partial periodic structure 2A to 2D is a binary (2-level) of concavities and convexities (for example, the diffraction grating portion 2 of FIG. 3), but the shape of the region is required to shape the light as desired. The depth must be designed appropriately.
  • FIG. 4 shows an embodiment in which a base 3 is present between the transparent substrate 1 and the diffraction grating portion 2.
  • the high refractive index convex portions 2 a may be isolated from each other (FIG. 3), or the high refractive index convex portions 2 a may be separated by the base 3. It may be connected (FIG. 4).
  • the diffractive optical element 10 may include such a base 3.
  • FIGS. 5A and 5B show an embodiment in which the covering layer 5 is provided on the opposite side of the transparent substrate 1 with the diffraction grating portion 2 interposed therebetween.
  • the covering layer 5 may be in direct contact with the diffraction grating portion 2 or may be provided on the diffraction grating portion 2 via an adhesive layer (adhesive layer).
  • adding the covering layer 5 to the embodiment shown in FIG. 3 corresponds to the embodiment shown in FIG. 5A
  • adding the covering layer 5 to the embodiment shown in FIG. 4 corresponds to the embodiment shown in FIG. 5B.
  • Do. 6A and 6B show an embodiment in which the low refractive index portion 3 is filled with the low refractive index resin 7.
  • the low refractive index portion is preferably air.
  • the low refractive index portion 3 is preferably made of the low refractive index resin 7 from the viewpoint that a diffractive optical element excellent in mechanical strength can be obtained.
  • the low refractive index resin 7 added to the embodiment shown in FIG. 3 corresponds to the embodiment shown in FIG. 6A, and the low refractive index resin 7 added to the embodiment shown in FIG. 4 is shown in FIG. 6B. It corresponds to the embodiment.
  • FIG. 7A and 7B show an embodiment in which the anti-reflection layer 9 is provided on the opposite side of the diffraction grating portion 2 with the transparent substrate 1 interposed therebetween.
  • the antireflective layer 9 may be provided in direct contact with the transparent substrate 1, or another member (such as a glass layer or an adhesive layer) may be interposed between the antireflective layer 9 and the transparent substrate 1. May be
  • FIG. 3 with the addition of the antireflection layer 9 corresponds to the embodiment shown in FIG. 7A
  • FIG. 4 with the addition of the antireflection layer 9 shown in FIG. 7B. It corresponds to the embodiment.
  • the high refractive index convex portion have a portion having an aspect ratio of 2 or more, which is conceptualized as “the ratio of height to width” or “the length of the protrusion”.
  • a diffractive optical element including a high refractive index convex portion having an aspect ratio of 2 or more can obtain diffracted light of a desired shape even if it is an infrared ray (for example, an infrared ray of 780 nm or more) having a longer wavelength than conventional It is possible to suppress zero-order light in diffracted light.
  • the diffractive optical element having a relatively large aspect ratio as described above is a transmissive diffractive optical element.
  • the high refractive index convex portion may have a binary shape or a multistage shape.
  • FIG. 8A is a schematic cross-sectional view of a binary high-refractive-index convex part
  • FIG. 8B is a schematic cross-sectional view of a multi-level (4-level) high-refractive-index convex.
  • the root 41 of the high refractive index convex portion 2a may be a transparent base material or a base. Therefore, the aspect ratio of the high refractive index convex portion in the present disclosure is defined as follows. First, as shown in FIG.
  • the aspect ratio when the high refractive index convex portion has a binary shape is as follows: (height H of high refractive index convex portion) / (half of height of high refractive index convex portion) It is defined as the width W) of the high refractive index convex portion at the position of the height (H / 2).
  • the height H of the high refractive index convex portion means the height difference from the top of the high refractive index convex portion to the concave portion (the position of the valley bottom between the adjacent high refractive index convex portions) . Further, as shown in FIG.
  • the aspect ratio when the high refractive index convex portion has a multi-stage shape is as follows: (height H of high refractive index convex portion) / (minimum processing width W min of high refractive index convex portion) It is defined as Here, the minimum processing width W min of the high refractive index convex portion in the present disclosure is a portion corresponding to the height h in the figure as shown in FIG. 8B, that is, the middle belly of the high refractive index convex portion having a multistage shape.
  • the width is defined as the width.
  • the uppermost flat portion (height: H) of the high refractive index convex portion is the upper end, and the flat portion of the second stage from the top of the high refractive index convex portion
  • the width at half height (h / 2) from the lower end with the height: H ⁇ h) as the lower end is the minimum processing width W min of the high refractive index convex portion.
  • the “aspect ratio of the high refractive index convex portion” in a broad sense which includes both the high refractive index convex portion having the binary shape and the high refractive index convex portion having the multistage shape
  • the top of the high refractive index convex portion is defined as the upper end, and the position of the valley bottom between the high refractive index convex portion and another high refractive index convex portion adjacent thereto, or the closest from the top of the high refractive index convex portion
  • the height from the lower end to the upper end of the high refractive index convex portion corresponds to half the height difference between the upper end and the lower end It is defined as the ratio of the height of the high refractive index convex portion to the width of the high refractive index convex portion.
  • the aspect ratio in this manner, it is possible to design the diffraction grating portion precisely in an optical manner, and to correlate the correlation between the ease of removal of the high refractive index convex portion from the mold and the aspect ratio of the high refractive index convex portion. It can be raised.
  • the height H, the width W, and the minimum processing width W min of the high refractive index convex portion can be calculated from, for example, an SEM image of the cross-sectional shape of the diffraction grating portion.
  • the shape of the diffraction grating is determined by the wavelength of light, the refractive index (difference) of the material through which light is transmitted, and the required diffraction angle.
  • the groove depth of the diffraction grating is optimum as the wavelength of light becomes longer. It becomes deeper, and a 850 nm depth is required for infrared rays of wavelength 850 nm.
  • the high refractive index convex portion preferably includes a portion having a height of 850 nm or more, and curing shrinkage (eg, 10%) by active energy rays It is more preferable that the height is 944 nm or more in consideration of the above, and it is preferable that the height be about 994 nm in consideration of the manufacturing error (for example, 5%).
  • the aspect ratio of the high refractive index convex portion is about 1.1, and for diffracting in the direction of 70 °, the aspect ratio of about 2.1 is sufficient. .
  • this is a case where light is diffracted in only one direction, and when actually used as a light source of a sensor, it is necessary to spread diffracted light uniformly over a predetermined area. For this purpose, it is necessary to combine regions having various diffraction angles and diffraction directions in a complicated manner, but as a result, a region in which the pitch is narrowed to ⁇ / 4 is included.
  • the aspect ratio may be 2.1 or more, sometimes exceeding 4, when the pitch is narrow.
  • the material is quartz, and when designing a rectangular diffusion shape extending at long sides ⁇ 50 ° ⁇ short side ⁇ 3.3 ° at 2-level, the original of the diffraction grating is optimum.
  • the maximum aspect ratio exceeds 4 when the depth is 994 nm and the pitch of the narrowest feature is 212 nm.
  • the high refractive index convex portion have a portion having an aspect ratio of 2 or more from the viewpoint that infrared rays with a wavelength of 780 nm or more can be shaped into a desired shape.
  • the cross-sectional shape of the diffraction grating portion may be rectangular as shown in FIGS. 3 to 7B, or may be another shape.
  • 9A to 9D are schematic cross-sectional views showing other embodiments of the cross-sectional shape of the diffraction grating portion.
  • the root 41 of the high refractive index convex portion 2a may be a transparent base material or a base.
  • the cross-sectional shape of the high refractive index convex portion is tapered, and therefore, the releasability from the mold at the time of manufacture is excellent.
  • the thickness of the high refractive index convex portion 2a may increase intermittently from the tip to the root (FIG.
  • the cross-sectional shape of the diffraction grating portion may be changed from a usual binary (2-level: FIGS. 3 to 7B) to a multistage (4-level (FIG. 9C), 8- It is effective to increase the level (FIG. 9D)).
  • a usual binary (2-level: FIGS. 3 to 7B
  • a multistage (4-level (FIG. 9C)
  • 8- It is effective to increase the level (FIG. 9D)).
  • the groove depth becomes deeper.
  • the refractive index of the cured product of the acrylic resin composition is 1.5
  • the groove depth at 4-level is 1.5 times the target wavelength
  • the groove depth at 8-level Is 1.75 times the target wavelength.
  • the longer the target wavelength the deeper the required groove depth, and the more difficult the processing.
  • the minimum machined groove width set at the time of design is usually about 1 ⁇ 4 of the target wavelength. In order to increase the efficiency, the minimum machined groove width may be made finer. However, if the minimum machined groove width is too narrow, machining is difficult and time-consuming, so the minimum machined groove width is preferably about 80 to 100 nm.
  • the line & space ratio (L / S) is not particularly limited when the high refractive index convex portion is a line (L) and the low refractive index portion is a space (S).
  • the line and space ratio (L / S) is determined by the following equation (A).
  • (L / S) l / (l + s)
  • (L / S) represents a line & space ratio
  • l represents a line width (nm)
  • s represents a space width (nm).
  • the line and space ratio (L / S) may be appropriately set so as to obtain desired diffracted light, but can be appropriately set, for example, in the range of 0.1 to 0.9. The range of 0.4 to 0.6 is preferable from the point of efficiency.
  • the diffractive optical element of the present disclosure it is preferable that the diffractive optical element have a multistage shape having two or more flat portions in terms of easily increasing the diffraction angle.
  • the diffractive optical element of the present disclosure can weaken 0th-order light when the aspect ratio is 2 or more, but when the diffraction angle is increased, the 0th-order light from the projection region of the diffracted light can be obtained. It is also possible to obtain diffracted light of a desired shape while removing. This will be described with reference to the drawings.
  • FIG. 10A and FIG. 10B are drawings for explaining the diffractive optical element.
  • 11A is a front view of the screen 22 shown in FIG. 10A, and FIG.
  • FIG. 11B is a front view of the screen 22 shown in FIG. 10B.
  • FIG. 10A is a schematic perspective view showing how the irradiation light 21 is diffracted by the diffractive optical element 10 and a square image 24 is formed at the center of the screen 22.
  • FIG. 11A since the square image 24 includes the zero-order light irradiation position 27, the zero-order light is included in the image 24.
  • the aspect ratio is 2 or more, the zeroth-order light is suppressed, and therefore, even when the zeroth-order light is included in the image 24, good diffracted light can be obtained.
  • the diffraction grating portion preferably has a multistage shape having two or more flat portions, and further preferably has an aspect ratio of 3.5 or more.
  • the transparent substrate used in the present disclosure can be appropriately selected and used according to the application from among known transparent substrates.
  • the material used for the transparent substrate include, for example, acetyl cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene and polymethylpentene, and acrylic resins Transparent resin such as resin, polyurethane resin, polyether sulfone and polycarbonate, polysulfone, polyimide, polyether, polyether ketone, acronitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, soda glass, potash glass, Glass such as lead glass, ceramics such as PLZT, quartz, transparent inorganic materials such as fluorite, etc.
  • the birefringence of the transparent substrate does not affect the effect itself of the diffractive optical element, it has an appropriate birefringence when the phase difference of the light incident on the diffractive optical element and the diffused light is an issue.
  • the base material may be selected.
  • transparent refers to a state in which the other side can be seen through visually, but if light of the target wavelength designed by the diffractive optical element can be transmitted, it is practically problematic even if it is colored visually There is no.
  • the thing which cuts an active energy ray to irradiate as much as possible of a transparent base material is preferable.
  • the thickness of the transparent substrate can be appropriately set according to the application of the present disclosure, and is not particularly limited, but is usually 5 to 5,000 ⁇ m, and the transparent substrate is supplied in the form of a roll However, it may be one that does not bend enough to be wound, but that bends under load or does not bend completely.
  • the configuration of the transparent substrate used in the present disclosure is not limited to the configuration composed of a single layer, and may have a configuration in which a plurality of layers are laminated. When a plurality of layers are stacked, layers of the same composition may be stacked, or a plurality of layers having different compositions may be stacked. Moreover, you may perform surface treatment for improving adhesiveness with an acrylic resin composition, and a primer layer formation to a transparent base material.
  • the primer layer preferably has adhesiveness to both the transparent substrate and the resin composition, and transmits light of the target wavelength.
  • the primer layer preferably has adhesiveness to both the transparent substrate and the resin composition, and transmits light of the target wavelength.
  • the diffractive optical element of the present disclosure has the above-mentioned diffraction grating part on a transparent base material from the viewpoint of preventing damage and the like of the diffraction grating part and having excellent mechanical strength. It may be the composition which has a covering layer in this order (Drawing 5A and Drawing 5B). Although it does not specifically limit as a coating layer, It is preferable to use the thing similar to the said transparent base material. Moreover, when providing a coating layer on a diffraction grating part, you may provide an adhesive (adhesive agent) layer between a diffraction grating part and a coating layer.
  • the pressure-sensitive adhesive or adhesive for the pressure-sensitive adhesive layer may be appropriately selected from conventionally known ones, such as a pressure-sensitive adhesive (pressure-sensitive adhesive), a two-component curable adhesive, an ultraviolet curable adhesive, A thermosetting adhesive, a heat melting adhesive, etc. can be suitably used in any bonding form, but when the low refractive index portion is air, an adhesive or adhesive having low flowability should be used. Is preferred. In the case where a part of the low refractive index portion is filled with the adhesive or the adhesive, the diffraction grating portion may be designed in consideration of the amount.
  • the covering layer by providing such a covering layer, the secondary effect that it is possible to prevent the reverse engineering which used the unevenness
  • an anti-reflection layer may be further provided on the surface of the transparent base material or the surface of the covering layer opposite to the diffraction grating portion (FIGS. 7A and 7B).
  • the antireflection layer may be appropriately selected from conventionally known ones.
  • it may be a refractive index layer consisting of a low refractive index layer or a single layer of a high refractive index layer, and the low refractive index layer and high refractive index It may be a multilayer film in which layers with a rate layer are sequentially laminated, or it may be an antireflection layer in which a fine concavo-convex shape is formed.
  • the said transparent base material, the said coating layer, the said adhesion layer (adhesion layer) may contain the conventionally well-known additive in the range which does not impair the effect of this indication.
  • additives include ultraviolet light absorbers, infrared light absorbers, light stabilizers, and antioxidants.
  • the diffractive optical element of the present disclosure may be a transmissive diffractive optical element or a reflective diffractive optical element. Among these, the diffractive optical element of the present disclosure is preferably a transmissive diffractive optical element.
  • the aspect ratio of the high refractive index convex portion in the diffraction grating portion needs to be set larger than that of the reflection type diffractive optical element, and as a result, the problem of sticking tends to occur easily. Therefore, a transmissive diffractive optical element having a high refractive index convex portion satisfying the storage elastic modulus (E ′) under the moist heat conditions described above has a higher refractive index convex portion than a reflective diffractive optical element having a similar high refractive index convex portion. Highly effective in preventing sticking.
  • Method of Manufacturing Diffractive Optical Element at least one surface side of a transparent substrate, one or more high refractive index convex portions protruding from the surface of the transparent substrate, and one or more low refractive index portions
  • a manufacturing method of a diffractive optical element provided with the diffraction grating part which arranges, and shapes light from a light source, Preparing a mold having a cavity shape for forming the high refractive index convex portion and the low refractive index portion (hereinafter referred to as a mold preparing step);
  • a cured product sample obtained by irradiating an acrylic resin composition to a cavity of the mold, and curing the acrylic resin composition with ultraviolet light so that the integrated light amount is 1,000 mJ / cm 2 .
  • a step of filling an acrylic resin composition having a storage elastic modulus (E ′) at 60 ° C. and a relative humidity of 95% of 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less (hereinafter, acrylic resin Composition filling process)
  • a process of forming a mold (hereinafter referred to as a mold release process), It is characterized by having.
  • FIGS. 12A to 12E are process diagrams schematically showing an example of a method of manufacturing a diffractive optical element.
  • a mold 31 having a cavity shape corresponding to the surface structure of a target diffraction grating portion is prepared (mold preparation step).
  • the acrylic resin composition 32 is filled in the cavity 31a of the mold (acrylic resin composition filling step).
  • the acrylic resin composition 32 is the same composition as the acrylic resin composition described in the above “1. Diffractive optical element”.
  • the filling method is not particularly limited, and a conventionally known method may be appropriately selected. For example, as shown in FIGS.
  • the acrylic resin composition 32 may be filled in the cavity 31a by applying the acrylic resin composition 32 to the surface of the mold 31.
  • the acrylic resin composition 32 is placed on the surface of the mold 31 (FIG. 12B), and the transparent substrate 33 is placed thereon.
  • the acrylic resin composition 32 is uniformly spread on the surface of the mold 31 over the transparent base material 33 by the pressure roller 34 (FIG. 12C), and the acrylic resin composition 32 is placed in the cavity 31a.
  • a part of the acrylic resin composition 32 may protrude from the cavity 31a of the mold.
  • the protruding portion of the acrylic resin composition 32 becomes a base after curing.
  • the acrylic resin composition 32 may be filled in the mold cavity 31a.
  • the coating film of the acrylic resin composition 32 is irradiated with active energy rays from the side of the cavity opening of the mold (35) to cure the acrylic resin composition 32.
  • the contact between the transparent substrate and the acrylic resin composition may be performed at the same time as the filling of the acrylic resin composition, or may be performed later than the filling of the acrylic resin composition.
  • the obtained cured product 36 is released from the mold 31 to obtain a diffractive optical element (releasing step).
  • releasing step the detail of each process of the said manufacturing method is demonstrated. The description similar to that of the diffractive optical element of the present disclosure will be omitted.
  • a mold for manufacturing a diffractive optical element can be processed by techniques such as laser lithography, electron beam lithography, FIB (Focused Ion Beam), etc., but electron beam lithography is usually suitably used. .
  • the material may be any material that can be processed at a high aspect ratio, but usually quartz or Si is used.
  • the mold surface can be subjected to a release treatment, if necessary.
  • a fluorine-based or silicon-based mold release agent, diamond like carbon, Ni plating, etc. can be applied.
  • the processing method can be appropriately selected from vapor phase processing such as vapor deposition or sputtering, ALD (Atomic Layer Deposition) or the like, and liquid phase processing such as coating or dipping or plating. Since the shape required for the diffractive optical element is usually as small as several mm square to several cm square, the efficiency of replication can be increased by arranging and processing the shapes of a plurality of diffraction grating parts in one mold. When emphasis is placed on throughput, the above-mentioned molds or copy molds may be arranged side by side and replicated to be used as a multi-faced mold.
  • the opening on the opening side may be wider than the back of the fine structure of the mold (FIGS. 9A to 9D).
  • the surface of the diffraction grating portion of the obtained diffractive optical element becomes thin.
  • the diffractive optical element of the present disclosure generally includes a plurality of grooves having different pitches (openings) with respect to one diffractive optical element, since there are a plurality of regions with different periodic structures.
  • Acrylic resin composition filling step "A cured product sample obtained by irradiating and curing ultraviolet light so that the integrated light amount is 1,000 mJ / cm 2 to the acrylic resin composition” means the diffraction obtained It simulates the cured product of the acrylic resin composition that will actually be contained in the diffraction grating portion of the optical element.
  • the acrylic resin composition whose storage elastic modulus (E ') at 60 ° C. and 95% relative humidity in the cured product sample is 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less
  • Diffractive optical element Although the above-mentioned example was what forms the coating film of an acrylic resin composition in the metal mold
  • a suitable coating method can be selected from conventionally known coating methods such as die coating, bar coating, gravure coating, and spin coating.
  • the transparent substrate those described in the above "1. Diffractive optical element” can be used.
  • the transparent substrate may be a sheet-like one, or a long one may be used to sequentially perform the coating step, the acrylic resin composition curing step, and the release step by a roll-to-roll method.
  • the mold is a hard material that is hard to bend, it is preferable that the transparent substrate be flexible so as to resist bubbles. Conversely, when using a hard transparent substrate, it is preferable to use a soft mold as the mold.
  • the irradiation of ultraviolet light or electron beam may be performed at one time or divided into multiple times, and when divided into multiple times, additional irradiation may be performed after curing to some extent and releasing.
  • the frame 11 provided with the conduction part 11a and the internal space 11c is prepared.
  • the frame 11 may be a combination of two or more members (for example, a combination of a flat substrate and a hollow cylinder).
  • the light source 12 is placed in the internal space 11c of the frame 11, and the light source 12 and the conducting part 11a are electrically connected using the lead 13 and the like.
  • the diffractive optical element 10 is mounted on the frame 11.
  • a temporary assembly By mounting the structure obtained in this manner on the mounting substrate 14, a temporary assembly can be obtained. At this time, alignment is performed such that the position of the solder ball placed on the mounting substrate 14 overlaps the position of the conductive portion 11 a of the frame 11.
  • the temporary assembly is placed in a reflow furnace and heated at a temperature of 260 to 280 ° C. for 0.5 to 1.5 minutes to solder the mounting substrate 14 and the frame 11 to obtain the lighting device 20.
  • the acrylic resin composition of the present disclosure comprises, on at least one side of a transparent substrate, one or more high refractive index protrusions projecting from the surface of the transparent substrate, and one or more low refractive indexes
  • An acrylic resin composition for forming a high refractive index convex portion of a diffractive optical element having a diffraction grating portion in which the light from the light source is shaped, wherein the integration is performed with respect to the acrylic resin composition The storage elastic modulus (E ') at 60 ° C.
  • the acrylic resin composition preferably contains an active energy ray curable component, and the above physical properties can be obtained after curing. Moreover, if light of the designed target wavelength can be transmitted, there is no practical problem even if it is visually colored after curing.
  • the details of the acrylic resin composition of the present disclosure are as described in “(1) Cured product of acrylic resin composition” in “1. Diffractive optical element” described above. Further, the method of forming the high refractive index convex portion using the acrylic resin composition of the present disclosure is as described in the above-mentioned “2. Method of manufacturing a diffractive optical element”.
  • an acrylic resin is preferable such that the viscosity at 25 ° C. of the acrylic resin composition is about several tens of mPas to several thousands of mPas. Since viscosity changes also with temperature, when forming a high refractive index convex part using the acrylic resin composition of this indication, it is preferable to perform suitable temperature control suitably.
  • Lighting Device (1) Configuration of Lighting Device
  • a lighting device includes a frame having a conductive portion capable of supplying power from the outside and an opening serving as a light exit surface, a light source, and the above-described diffractive optical element
  • the light source is fixed in an internal space of the body and connected to the conductive portion, and the diffractive optical element is disposed in the opening. According to the illumination device of the present disclosure, light shaped into a desired shape can be emitted.
  • FIG. 13 is a cross-sectional view schematically showing an embodiment of a light irradiation apparatus according to the present disclosure.
  • the illumination device 20 shown in the example of FIG. 13 includes a frame 11, a light source 12, and the above-described diffractive optical element 10.
  • the frame 11 has a conducting portion 11 a which can be supplied with power from the outside, and an opening 11 b which is a light emitting surface.
  • the frame 11 further includes an internal space 11 c, and the light source 12 is fixed to the internal space 11 c. Furthermore, the light source 12 is connected to the conducting part 11a.
  • the light source 12 may be connected in direct contact with the conducting portion 11a, or may be connected to the conducting portion 11a via the conducting wire 13 as shown in FIG. Then, the diffractive optical element 10 is disposed in the opening 11 b.
  • the frame 11 may be a combination of two or more members.
  • the frame 11 may be a combination of a flat substrate (base portion) for light source control and a hollow cylinder placed thereon.
  • the light source is not particularly limited, and a known light source can be used. Since the diffractive optical element according to the present disclosure is designed for the purpose of diffraction of a specific wavelength, it is preferable to use a laser light source having a high intensity of the specific wavelength, an LED (light emitting diode) light source or the like as a light source. In the present disclosure, any light source such as a directional laser light source or a diffusive LED (light emitting diode) light source can be suitably used. In the present disclosure, it is preferable that the light source be appropriately selected from among reproducible light sources to be simulated in designing the diffractive optical element according to the present disclosure.
  • a diffractive optical element that diffracts an infrared ray having a wavelength of 780 nm or more
  • the illumination device of the present disclosure may include at least one diffraction grating according to the present disclosure, and may further include other optical elements as needed.
  • Other optical elements include, for example, a polarizing plate, a lens, a prism, and a pass filter that transmits a target wavelength of a specific wavelength, particularly a diffractive optical element. When using it combining a several optical element, it is preferable to bond optical elements together from the point which suppresses interface reflection.
  • the lighting device according to the present disclosure can emit light shaped into a desired shape, and is preferably used as a lighting device for a sensor from the viewpoint that infrared rays can be used.
  • infrared illumination for nighttime illumination for security sensor, illumination for human detection sensor, illumination for collision prevention sensor for unmanned aerial vehicles and automobiles, illumination for personal identification device, illumination for inspection device, from the point that light can be effectively shaped , Etc., and simplification, downsizing and power saving of the light source become possible.
  • quartz DOE Using a 6-inch square synthetic quartz plate, a designed shape of quartz DOE was produced by an electron beam lithography process using an electron beam drawing apparatus and a dry etching apparatus. In SEM observation, it could be confirmed that it had finished to a predetermined size, and when a laser of 980 nm was made incident and the diffracted light was projected on a screen and observed with an infrared camera, it could be confirmed that it had spread into a predetermined rectangular shape. .
  • the acrylic resin composition 1 to 13 is prepared by blending the (meth) acrylate compound (tetra- or higher functional (meth) acrylate, bifunctional (meth) acrylate) shown in Table 1 below and the photopolymerization initiator in the amounts shown in Table 1 Was prepared.
  • the numerical value regarding these compounds in Table 1 shows a mass part, and the total amount of a (meth) acrylate compound will be 100 mass parts.
  • Resin molding of the diffraction grating portion was performed as follows. First, using the above-mentioned quartz DOE as a mold, any one of acrylic resin compositions 1 to 11 and 13 was dropped on the diffractive surface. Next, a PET film (Toyobo Co., Ltd., A4300, 100 ⁇ m thick) as a transparent substrate was laminated from above with a roller, and the acrylic resin composition was spread uniformly. Furthermore, after irradiating an ultraviolet-ray from the transparent base material side so that an accumulated light quantity may be 1,000 mJ / cm ⁇ 2 > in that state, and hardening the said acrylic resin composition, a transparent base material and a shaping layer are mold-formed.
  • a PET film Toyobo Co., Ltd., A4300, 100 ⁇ m thick
  • the diffraction grating portion of the obtained diffractive optical element has the following periodic structure 1.
  • the periodic structure 1 has about 20 high refractive index convex portions. Each high refractive index convex portion has a linear shape in a plan view, a rectangular cross section, and a constant height (H).
  • widths (W) of the respective high refractive index convex portions are formed to be different from one another within the following range.
  • a lighting device was produced using the diffractive optical elements of Example 6 and Comparative Example 2 described above. The following description is based on the reference numerals shown in FIG.
  • the light source 12 was placed in the internal space 11 c of the frame 11, and the light source 12 and the conductive portion 11 a were electrically connected using the conducting wire 13.
  • the diffractive optical element of Example 6 or Comparative Example 2 was placed on the frame 11.
  • a temporary assembly was obtained.
  • alignment was performed so that the position of the solder ball placed on the mounting substrate 14 overlapped with the position of the conductive portion 11 a of the frame 11.
  • the temporary assembly was placed in a reflow furnace, heated under a temperature condition of 260 ° C. for 1.5 minutes, and the mounting substrate 14 and the frame 11 were soldered to manufacture the lighting device of Example 6 or Comparative Example 2. .
  • variation before and behind reflow were investigated by the following method, respectively.
  • the mass of the diffractive optical element before and after the reflow was measured, and the mass change rate a was calculated from the following formula I.
  • Formula I a ⁇ (M 0 -M 1 ) / M 0 ⁇ ⁇ 100
  • a a mass change rate (%)
  • M 0 a mass of the diffractive optical element before reflow (mg)
  • M 1 a mass of the diffractive optical element after reflow (mg).
  • the allowable range of mass change rate is 2.0% or less.
  • the transmittance of the transparent substrate and the diffraction grating portion of the diffractive optical element having a wavelength of 850 nm was measured from this device.
  • the absolute value of the difference between the transmittance of the diffractive optical element before reflow and the transmittance of the diffractive optical element after reflow was taken as the transmittance fluctuation (%) of the diffractive optical element.
  • the allowable range of the transmittance fluctuation is 1.0% or less.
  • the mass change rate before and after reflow for the reflow at 260 ° C. for 1.5 minutes is 3.8%, and the transmittance fluctuation before and after the reflow is 0.0% It is. Therefore, this result is beyond the allowable range of the mass change rate.
  • the compound used for the diffractive optical element of Comparative Example 2 is a bifunctional acrylic resin, this bifunctional acrylic resin is instantaneously exposed to a high temperature environment of 260 ° C. As a result of sublimation, it is conceivable that the fine structure of the diffraction grating portion changes.
  • the mass change rate before and after reflow for the reflow at 260 ° C. for 1.5 minutes is 1.5%
  • the transmittance change before and after the reflow is It is 0.1%. All these results are within the acceptable range.
  • the acrylic resin composition used for the diffractive optical element of Example 6 is exposed to a high temperature environment of 260 ° C. instantaneously because it contains a large amount of highly heat resistant tetrafunctional or higher urethane acrylate. Even in this case, mass fluctuation hardly occurs, and as a result, it is considered that the change in the fine structure of the diffraction grating portion can be minimized.
  • the measurement apparatus used Rheogel E4000 made from UBM.
  • the storage modulus E ′ (60 ° C., 95%) and tan ⁇ (60 ° C., 95%) are shown in Table 1. Furthermore, by measuring the dynamic viscoelasticity based on the conditions of a measurement temperature of 30 ° C. and a relative humidity of 30% and the measurement conditions shown in Table A below, using the same test single film, in accordance with JIS K7244.
  • the storage elastic modulus E ′ was determined at 30 ° C. and 30% relative humidity. Each value of storage elastic modulus E ′ (30 ° C., 30%) is shown in Table 1.
  • Tg Glass Transition Temperature
  • acrylic resin compositions 1 to 13 ultraviolet rays are irradiated and cured so that the integrated light amount is 1,000 mJ / cm 2 , and the substrate and the unevenness are obtained.
  • Test single films each having a thickness of 0.1 mm, a width of 5 mm, and a length of 20 mm were obtained without any shape.
  • DMS6100 dynamic viscoelasticity tester manufactured by Seiko Instruments Inc.
  • Apply a periodic external force at a frequency of 10 Hz in the length direction of each test piece and measure in the range of -20 ° C to 200 ° C.
  • the width of the high refractive index convex portion is taken as the minimum width W 1 min (nm) in the sticking evaluation, and the value obtained by dividing the height H (500 nm) by the minimum width W 1 min in the sticking evaluation
  • the maximum aspect ratio was used. As the minimum width W 1 min is smaller and the maximum aspect ratio is larger, it can be said that the cured product forming the high refractive index convex portion has an appropriate hardness, so that sticking is less likely to occur.
  • Pattern haze evaluation was performed as follows. First, for the periodic structure 1, among the high refractive index convex portions in which no pattern burrs were generated, the high refractive index convex portion having the smallest width was specified.
  • the width of the high refractive index convex portion, and a minimum width W 2 min (nm) in the pattern Moge evaluation was calculated in the same manner as the above-mentioned sticking evaluation.
  • the minimum width W 2 min is smaller and the maximum aspect ratio is larger, it can be said that the cured product forming the high refractive index convex portion has appropriate flexibility, so that the pattern is less likely to occur.
  • Table 1 summarizes the compositions, physical property values, and evaluation results of the acrylic resin compositions used in Examples 1 to 9 and Comparative Examples 1 to 4.
  • “> 500” for the maximum width of the sticking evaluation means that sticking occurred for all of the high refractive index convex portions having the width (W) within the range of 50 nm to 500 nm. Do. Therefore, in this case, the aspect ratio is not calculated.
  • Comparative Example 3 no diffractive optical element was obtained as described above, so there is no description of the sticking evaluation result and the pattern evaluation result.
  • compound (1) is a hexafunctional urethane acrylate (Mw: 1,400) represented by PETA-IPDI-PETA.
  • PETA indicates pentaerythritol triacrylate
  • IPDI indicates isophorone diisocyanate
  • - indicates a urethane bond.
  • the compound (2) is a 9-functional urethane acrylate (Mw: 11,000) represented by the following formula (i).
  • PETA represents pentaerythritol triacrylate
  • HDI represents hexamethylene diisocyanate
  • - represents a urethane bond, respectively.
  • compound (3) is a 10-functional urethane acrylate (Mw: 2,000) represented by DPPA-IPDI-DPPA.
  • DPPA indicates dipentaerythritol pentaacrylate
  • IPDI indicates isophorone diisocyanate
  • - indicates a urethane bond.
  • the compound (4) is a 15-functional urethane acrylate (Mw: 2,300) represented by the following formula (ii).
  • DPPA dipentaerythritol pentaacrylate
  • HDI hexamethylene diisocyanate
  • - indicates a urethane bond, respectively.
  • the compound (5) is a bifunctional urethane acrylate (Mw: 2,000) represented by caprolactone modified HEA-hydrogenated MDI-caprolactone modified HEA.
  • HEA indicates hydroxyethyl acrylate
  • MDI indicates diphenylmethane diisocyanate
  • - indicates a urethane bond.
  • the compound (6) is 1,9-nonanediol diacrylate (CAS No. 107481-28-7, Mw: 268).
  • compound (7) is polyethylene glycol # 600 diacrylate (Mw: 700).
  • Comparative Example 1 will be examined.
  • an acrylic resin composition 10 having a storage elastic modulus (E ′) at 60 ° C. and a relative humidity of 95% of 0.42 ⁇ 10 9 Pa is used in Comparative Example 1.
  • the minimum width W 2 min of the high refractive index convex portion in which no pattern burrs are generated is 90 nm, and the maximum aspect ratio is 5.6. Therefore, there is no problem in the flexibility of the high refractive index convex portion.
  • sticking occurs even if the width W of the high refractive index convex portion is 500 nm. This is considered to be because the storage elastic modulus (E ′) under wet heat conditions is smaller than 0.90 ⁇ 10 9 Pa and the high refractive index convex portion is too soft.
  • Comparative Example 2 The acrylic resin composition 11 whose storage elastic modulus (E ') at 60 ° C. and 95% relative humidity of the cured product is 0.06 ⁇ 10 9 Pa is used in Comparative Example 2.
  • the minimum width W 2 min of the high refractive index convex portion in which no pattern burrs are generated is 85 nm, and the maximum aspect ratio is 5.9. Therefore, there is no problem in the flexibility of the high refractive index convex portion.
  • the minimum width W 1 min of the high refractive index convex portion in which sticking does not occur is as large as 250 nm, and the maximum aspect ratio is as small as 2.0.
  • the diffractive optical element of Comparative Example 2 is susceptible to sticking. This is formed as a result that the acrylic resin composition 11 does not contain a tetrafunctional or higher functional (meth) acrylate while the storage elastic modulus (E ') under wet heat conditions is smaller than 0.90 ⁇ 10 9 Pa. It is considered that the high refractive index convex portion is too soft.
  • Comparative Example 3 an acrylic resin composition 12 whose storage elastic modulus (E ′) at 60 ° C. and 95% relative humidity of a cured product is 3.10 ⁇ 10 9 Pa is used.
  • the acrylic resin composition 12 has a high viscosity and the composition 12 can not be filled in the cavity of the mold, the cured product can not be shaped, and a diffractive optical element can not be obtained. It is considered that this is because, as a result of the storage elastic modulus (E ′) under wet heat conditions being greater than 2.6 ⁇ 10 9 Pa, the acrylic resin composition 12 lacks flexibility.
  • Comparative Example 4 an acrylic resin composition 13 whose storage elastic modulus (E ′) at 60 ° C. and 95% relative humidity of a cured product is 0.18 ⁇ 10 9 Pa is used.
  • the minimum width W 2 min of the high refractive index convex portion in which no pattern haze occurs is 90 nm, and the maximum aspect ratio is 5.6. Therefore, there is no problem in the flexibility of the high refractive index convex portion.
  • the storage elastic modulus (E ′) at 60 ° C. and 95% relative humidity after curing is 0.90 ⁇ 10 9 Pa or more and 2.6 ⁇ 10 9 Pa or less It has become clear that, by using the acrylic resin composition, sticking can be prevented under moist heat conditions, and pattern burrs can be reduced.
  • the storage elastic modulus (E ') at 60 ° C. after curing and at a relative humidity of 95% is 1.0 ⁇ 10 9 Pa or more and 2.0 ⁇ 10 9 Pa or less from Examples 1 to 9
  • the highest refractive index convex portion where sticking does not occur as compared with the other examples It can be seen that the small width W 1 min is as small as 120 nm or less, and the maximum aspect ratio is as large as 4.2 or more. This can be said to be due to the fact that sticking is difficult to occur due to having a suitable storage elastic modulus (E ′) under moist heat conditions and a high recovery rate.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Diffracting Gratings Or Hologram Optical Elements (AREA)

Abstract

La présente invention concerne un élément optique de diffraction qui présente une résistance à l'adhérence dans une condition de chaleur humide, et dans lequel un motif est rarement déchiré, son procédé de fabrication, une composition de résine acrylique pour former l'élément optique de diffraction, et un dispositif d'éclairage. Cet élément optique de diffraction forme une lumière provenant d'une source de lumière, et est pourvu, sur au moins un côté de surface d'un substrat transparent, d'une partie de réseau de diffraction dans laquelle une ou plusieurs sections saillantes à indice de réfraction élevé faisant saillie depuis la surface du substrat transparent, et une ou plusieurs sections à indice de réfraction faible sont disposées, la section saillante à indice de réfraction élevé étant formée d'un produit durci d'une composition de résine acrylique, et le module d'élasticité de conservation (E') du produit durci à 60 °C et une humidité relative de 95 % est de 0,90×109-2,6×109 Pa inclus.
PCT/JP2018/024734 2017-06-30 2018-06-28 Élément optique de diffraction, son procédé de fabrication, composition de résine acrylique pour former un élément optique de diffraction, et dispositif d'éclairage WO2019004406A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114384618A (zh) * 2022-03-23 2022-04-22 深圳珑璟光电科技有限公司 一种二维光栅及其形成方法、光波导及近眼显示设备
WO2023032804A1 (fr) * 2021-09-06 2023-03-09 デクセリアルズ株式会社 Procédé de fabrication de dispositif électronique, et verre de protection

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004004515A (ja) * 2002-03-29 2004-01-08 Dainippon Printing Co Ltd 微細凹凸パターン形成材料、微細凹凸パターン形成方法、転写箔、光学物品及びスタンパー
JP2005084561A (ja) * 2003-09-11 2005-03-31 Dainippon Printing Co Ltd 微細パターン形成体およびその製造方法
JP2007178724A (ja) * 2005-12-28 2007-07-12 Mitsubishi Rayon Co Ltd 表面に微細凹凸構造を有する成形体の製造方法および反射防止物品
JP2015087762A (ja) * 2013-09-25 2015-05-07 大日本印刷株式会社 反射部材
JP2016112869A (ja) * 2014-12-18 2016-06-23 三菱レイヨン株式会社 透明フィルムの製造方法
JP2017065173A (ja) * 2015-09-30 2017-04-06 旭化成株式会社 モールド、及び加工用積層体
WO2017119400A1 (fr) * 2016-01-08 2017-07-13 大日本印刷株式会社 Élément optique de diffraction et dispositif de rayonnement de lumière

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4644429B2 (ja) * 2004-02-02 2011-03-02 三菱瓦斯化学株式会社 フォトクロミックレンズおよびその製造方法
JP4380396B2 (ja) * 2004-04-09 2009-12-09 住友ベークライト株式会社 紫外線硬化型塗料および塗膜付き透明プラスチック製基材
JP2012131900A (ja) * 2010-12-21 2012-07-12 Sumitomo Bakelite Co Ltd 紫外線硬化性樹脂組成物の硬化物、樹脂積層体、および紫外線硬化性樹脂組成物
JP2014081413A (ja) * 2012-10-12 2014-05-08 Fujifilm Corp 偏光板及び液晶表示装置
CN105209940A (zh) * 2013-03-28 2015-12-30 三菱丽阳株式会社 光学膜、光学膜的制造方法和面发光体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004004515A (ja) * 2002-03-29 2004-01-08 Dainippon Printing Co Ltd 微細凹凸パターン形成材料、微細凹凸パターン形成方法、転写箔、光学物品及びスタンパー
JP2005084561A (ja) * 2003-09-11 2005-03-31 Dainippon Printing Co Ltd 微細パターン形成体およびその製造方法
JP2007178724A (ja) * 2005-12-28 2007-07-12 Mitsubishi Rayon Co Ltd 表面に微細凹凸構造を有する成形体の製造方法および反射防止物品
JP2015087762A (ja) * 2013-09-25 2015-05-07 大日本印刷株式会社 反射部材
JP2016112869A (ja) * 2014-12-18 2016-06-23 三菱レイヨン株式会社 透明フィルムの製造方法
JP2017065173A (ja) * 2015-09-30 2017-04-06 旭化成株式会社 モールド、及び加工用積層体
WO2017119400A1 (fr) * 2016-01-08 2017-07-13 大日本印刷株式会社 Élément optique de diffraction et dispositif de rayonnement de lumière

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023032804A1 (fr) * 2021-09-06 2023-03-09 デクセリアルズ株式会社 Procédé de fabrication de dispositif électronique, et verre de protection
CN114384618A (zh) * 2022-03-23 2022-04-22 深圳珑璟光电科技有限公司 一种二维光栅及其形成方法、光波导及近眼显示设备
CN114384618B (zh) * 2022-03-23 2022-06-10 深圳珑璟光电科技有限公司 一种二维光栅及其形成方法、光波导及近眼显示设备

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