JP2014026116A - Photosensitive resin composition for volume hologram recording, photosensitive substrate for volume hologram recording, and volume hologram recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition for volume hologram recording, having excellent heat resistance and capable of improving a refractive index difference without containing metal, a photosensitive substrate for volume hologram recording which has excellent heat resistance and can be made thin, and a volume hologram recording material having excellent heat resistance and suitably applicable to be used for an optical element.SOLUTION: The photosensitive composition for volume hologram recording comprises: an organic-inorganic hybrid polymer which has a main chain of an organic polymer and has a polysiloxane structure in at least either a side chain or a molecular end of the organic polymer and which contains a tri-functional siloxane unit by 10 mol% or more in the entire siloxane units; a photopolymerizable compound having a refractive index of 1.54 or more; and a photopolymerization initiator.

Description

  The present invention relates to a photosensitive resin composition for volume hologram recording, a photosensitive substrate for volume hologram recording, and a volume hologram recording body.

  In recent years, a volume hologram recording body is expected to be applied as an optical element and has been put into practical use. For example, Patent Document 1 discloses a projection-type image display device that uses a hologram recording medium to efficiently and sufficiently suppress speckle generation even when a coherent light source is used. . Here, the speckle is a speckled pattern that appears when a diffusing surface is irradiated with coherent light such as laser light. When speckle is generated on the screen, it is observed as speckled luminance unevenness, which is physiological to the observer. It becomes a factor that has a bad influence. According to the technique of Patent Document 1, compared to the conventional technique of vibrating or rotating the scattering plate, it is possible to reduce the size of the apparatus, save power, and efficiently suppress speckle generation. it can.

  Volume type hologram recording bodies used for optical element applications are required to have higher heat resistance and light resistance than before. For example, the hologram recording is required to be stably held even when irradiated with high-power laser light or when used for a long time. In addition, weather resistance becomes important when it can be used for outdoor and in-vehicle applications such as a head-mounted display and a head-up display. Thus, the volume hologram recording body used for optical element applications is required to have durability such as heat resistance, light resistance, and weather resistance.

  Patent Documents 2 and 3 disclose a hologram recording composition having a fluorine-containing polymer as a binder component. Improvement of heat resistance and refractive index is expected by using a fluorine-containing polymer. However, when a fluorine-containing polymer is used, the problem that adhesiveness with a base material falls arises. For this reason, when it is used in an aspect that requires adhesion to the substrate, the introduction rate of fluorine cannot be increased, and heat resistance may not be sufficiently exhibited.

  Patent Document 4 discloses a material system in which an inorganic substance network and a photopolymerizable monomer are used in combination. When an inorganic material that can form a network is used as a binder, this material has the advantages of being excellent in heat resistance, environmental resistance and mechanical strength, and having a large difference in refractive index from a photopolymerizable organic monomer. The hologram recording film formed by the system is rather fragile, and it is inferior in flexibility, processability and coating suitability, and the compatibility between the inorganic binder and the organic monomer is not good, so a uniform coating material is prepared. There was a problem that it was difficult to do.

  Patent Document 4 also discloses that an organic group is introduced into an inorganic substance network to impart flexibility to the inorganic binder and improve the brittleness of the hologram recording film. However, Patent Document 4 introduces an organic group into an inorganic network by hydrolysis and polycondensation of an organometallic compound having an organic moiety in the side chain or an organometallic compound having a functional group polymerizable with an organic monomer. Is only disclosed. That is, according to the disclosure of Patent Document 4, the network structure of the inorganic network itself is composed of chains in which inorganic compounds are connected to each other, and the organic group is only introduced into the network structure of the inorganic network as pendant side chains. It did not essentially change the rigid structure of the inorganic network.

  Patent Document 5 describes a photosensitive composition for volume hologram recording, which contains a specific organic-inorganic hybrid polymer, specific organometallic fine particles, and a photopolymerization initiator. When fine particles containing a metal element are used as in Patent Document 5, since the specific gravity of the metal fine particles is high, it is difficult to uniformly disperse the metal fine particles, such as sedimentation. It was also a factor that hindered monomer movement. In addition, if fine particles containing a metal element are included, the dielectric constant of the hologram recording layer may change when the obtained volume hologram recording body is irradiated with high-energy light such as laser light, requiring accuracy. However, it has been difficult to apply to optical element applications.

  Patent Document 6 describes a volume hologram recording photosensitive composition containing an organic-inorganic hybrid polymer using an organometallic compound, a photopolymerizable compound, and a photopolymerization initiator. Specifically, Patent Document 6 describes that an organic-inorganic hybrid polymer containing a high refractive index metal element such as zirconium is combined with a low refractive index photopolymerizable compound to increase the refractive index difference. ing. Even when an organic-inorganic hybrid polymer containing a metal element having a high refractive index such as zirconium is used as described above, when the obtained volume hologram recording body is irradiated with high energy light such as laser light, a hologram recording layer is obtained. The dielectric constant of the optical fiber may change, and it has been difficult to apply it to optical element applications that require accuracy.

  Patent Document 7 describes a photosensitive composition for hologram recording comprising a polymer compound having a polysiloxane compound part in the side chain, a compound having a polymerizable ethylenically unsaturated bond, and a photopolymerization initiator system. Yes. The polymer compound containing a polysiloxane compound part in the side chain in Patent Document 7 is a copolymer of a polysiloxane compound having a reactive functional group at one end and a monomer capable of reacting with the functional group, or Since it is synthesized as a graft copolymer of a polysiloxane compound having a reactive functional group at one end and a linear polymer having a reactive functional group capable of reacting with the functional group on the main chain. As the polysiloxane compound, a polysiloxane compound containing only a bifunctional siloxane unit is used. When such a polymer compound containing a polysiloxane compound is used, the hardness may be insufficient and the durability may be insufficient. In other words, polysiloxanes composed of bifunctional siloxane units are generally oily and have a post-recording performance compared to the case where resinous trifunctional siloxane units or glassy tetrafunctional siloxane units are used. The hologram tends to fluctuate due to heat and impact. Further, the technique described in Patent Document 7 is insufficient because the refractive index modulation amount is as small as 0.011 at the maximum.

Japanese Patent No. 4688980 Japanese Patent No. 2625028 Japanese Patent No. 3370762 Japanese Patent No. 2953200 Japanese Patent No. 4536276 Japanese Patent No. 4536275 JP-A-9-106241

  The present invention has been made under such circumstances, and does not contain a metal, has excellent heat resistance, and can improve the refractive index difference. A photosensitive composition for volume hologram recording, excellent in heat resistance, and thin layer It is an object of the present invention to provide a volume hologram recording photosensitive substrate that can be made into a large volume, and a volume hologram recording body that has excellent heat resistance and can be suitably applied to optical element applications.

As a result of intensive studies to achieve the above object, the present inventors have used a specific organic-inorganic hybrid polymer, a specific photopolymerizable compound, and a photopolymerization initiator in combination, thereby producing a metal. It has been found that heat resistance can be improved and the refractive index difference can be improved without containing elements.
The present invention has been completed based on such knowledge.

  The photosensitive composition for volume hologram recording according to the present invention has a main chain of an organic polymer, a polysiloxane structure in at least one of a side chain and a terminal of the organic polymer, and a trifunctional siloxane unit. It contains an organic-inorganic hybrid polymer containing 10 mol% or more with respect to all siloxane units, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator.

  The photosensitive substrate for volume hologram recording according to the present invention has an organic polymer as a main chain and a polysiloxane structure in at least one of a side chain and a terminal of the organic polymer, and contains all trifunctional siloxane units. A hologram recording layer for recording a hologram, comprising an organic-inorganic hybrid polymer containing 10 mol% or more based on a siloxane unit, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator. It was provided on the base material.

  Further, the volume hologram recording material according to the present invention has a main chain of an organic polymer, a polysiloxane structure at least one of a side chain and a terminal of the organic polymer, and a trifunctional siloxane unit having all siloxane units. A hologram recording layer for recording a hologram, comprising an organic-inorganic hybrid polymer containing 10 mol% or more with respect to a unit, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator, A hologram layer having a hologram recorded thereon is provided on a substrate.

  In the photosensitive composition for volume hologram recording, the photosensitive substrate for volume hologram recording, and the volume hologram recording body according to the present invention, the organic-inorganic hybrid polymer has at least the following general formula as a main chain component. Hydrolysis of a copolymer obtained by copolymerizing an organosilicon compound represented by (1) and an organic monomer having an ethylenically unsaturated double bond, and an organosilicon compound represented by the following general formula (2) An organic-inorganic hybrid polymer containing a decomposition polycondensate and containing 10 mol% or more of trifunctional siloxane units based on the total siloxane units is preferable from the viewpoint of excellent heat resistance.

RmSi (OR ′) n General formula (1)
(In the general formula (1), R may be the same or different, and may be an ethylenic double bond-containing group having 1 to 10 carbon atoms, R ′ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, m + n = 4, m ≧ 1, and n ≧ 1.)

R ″ m′Si (OR ′ ″) n ′ General formula (2)
(In general formula (2), R ″ may be the same or different, and an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, vinyl group, acryloyl group, methacryloyl group, epoxy group, amide group, sulfonyl group, hydroxyl group. Alternatively, a hydrocarbon group having 1 to 10 carbon atoms having a carboxyl group, R ′ ″ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, m ′ + n ′ = 4, m ′ ≧ 0, n '≧ 1.)

  In the photosensitive composition for volume hologram recording according to the present invention, the photosensitive substrate for volume hologram recording according to the present invention, and the hologram recording layer in the volume hologram recording body according to the present invention, It is preferable that a thermoplastic resin is contained from the viewpoint of promoting the diffusion movement of the monomer during the reaction and improving the refractive index difference of the obtained hologram.

  In the photosensitive composition for volume hologram recording according to the present invention, the photosensitive substrate for volume hologram recording according to the present invention, and the hologram recording layer in the volume hologram recording body according to the present invention, The content of the photopolymerizable compound having a refractive index of 1.54 or more is 20% by mass or more based on the total amount of the photopolymerizable compound, and the refractive index having one photopolymerizable group in the molecule is 1.48 or more. The total content of the photopolymerizable compound and the photopolymerizable compound having a refractive index of 1.48 or more having two or more photopolymerizable groups in the molecule is 80% by mass or more based on the total amount of the photopolymerizable compound. The content of the photopolymerizable compound having one photopolymerizable group in the molecule and a refractive index of 1.48 or more and the refractive index having two or more photopolymerizable groups in the molecule are 1.48. The ratio to the content of the above photopolymerizable compound is 1 10 to 10: it is a 1, is excellent in heat resistance, can improve refractive index difference, the surface shape becomes favorable, and, from the viewpoint of dispersion of the diffraction efficiency in the plane is further reduced.

  According to the present invention, a photosensitive composition for volume hologram recording that does not contain a metal, has excellent heat resistance and can improve the difference in refractive index, and has excellent heat resistance and can be thinned. And a volume hologram recording body that is excellent in heat resistance and can be suitably applied to optical element applications.

FIG. 1 is a schematic view showing an example of a photosensitive substrate for volume hologram recording of the present invention. FIG. 2 is a schematic view showing an example of the volume hologram recording body of the present invention.

Hereinafter, the photosensitive composition for volume hologram recording according to the present invention, the photosensitive substrate for volume hologram recording according to the present invention, and the volume hologram recording body according to the present invention will be described in order.
In the present invention, (meth) acrylate represents methacrylate and / or acrylate, and (meth) acryloyl represents methacryloyl and / or acryloyl.
In the present invention, the trifunctional siloxane unit refers to a unit in which a silicon atom is bonded to three oxygen atoms in a polysiloxane structure.
In the polysiloxane structure, a monofunctional siloxane unit in which a silicon atom is bonded to one oxygen atom, a bifunctional siloxane unit in which a silicon atom is bonded to two oxygen atoms, and 4 silicon atoms Those bonded to two oxygen atoms are referred to as tetrafunctional siloxane units, respectively.
In the present invention, the refractive index of the photopolymerizable compound can be measured using an Abbe refractometer. If the refractive index is 1.54 or more in the range of 20 ° C. to 25 ° C., it can be used as a photopolymerizable compound having a refractive index of 1.54 or more.

[Photosensitive composition for volume hologram recording]
The photosensitive composition for volume hologram recording according to the present invention has a main chain of an organic polymer, a polysiloxane structure in at least one of a side chain and a terminal of the organic polymer, and a trifunctional siloxane unit. It contains an organic-inorganic hybrid polymer containing 10 mol% or more with respect to all siloxane units, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator.

In the present invention, by using a combination of the specific organic-inorganic hybrid polymer, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator, heat resistance can be obtained even without containing a metal element. Excellent in refractive index and can improve the refractive index difference.
In the case where the volume hologram recording body does not contain a metal element, the problem of change in dielectric constant due to light does not occur, so that the volume hologram recording body can be suitably used particularly for an optical element.
Further, by improving the refractive index difference, it is possible to make the volume hologram into a thin film, which can be suitably used for optical element applications.

By the above specific combination, it is estimated as follows as an effect | action which exhibits the above effects.
The Si—O bond energy is 444 kJ / mol, which is more stable than the C—C bond energy (356 kJ / mol) and the C—O bond energy (339 kJ / mol), and the Si—O bond is about 50 % Is energetically stable because it has ionic bonding. Therefore, when it has a polysiloxane structure, heat resistance and weather resistance are improved. In addition, since the polysiloxane structure is included in the system, the C═O bond and the C—C bond, which are relatively weak against heat as compared with the siloxane bond, are surrounded by the polysiloxane structure, and yellowing to blackening due to heating is changed. It is estimated that it can be suppressed.
The polysiloxane structure of the organic-inorganic hybrid polymer used in the present invention includes, among other things, a specific amount of trifunctional siloxane units. Therefore, when the polysiloxane forms a three-dimensional network structure, heat resistance, light resistance, Weather resistance and hardness are improved. Therefore, the hologram after recording becomes difficult to fluctuate due to heat and impact, and the durability of the hologram increases.
Further, since the main chain is an organic polymer, the hologram recording layer has flexibility as compared with the case where only the inorganic binder is used, and the brittleness problem is solved. The organic-inorganic hybrid polymer is a graft or block-like polymer having a main chain of an organic polymer and a polysiloxane structure at the side chain or terminal. Each of the structures can form a domain to some extent. Therefore, compared with a polymer in which organic-inorganic polymer is randomly polymerized, the functions of the organic polymer and the polysiloxane structure can be expressed. The flexibility of the organic polymer and the trifunctional siloxane unit are It becomes possible to have both the heat resistance and hardness of the polysiloxane structure contained in a specific amount.
In the present invention, a photopolymerizable compound having a refractive index of 1.54 or more is used in combination with the specific organic-inorganic hybrid polymer. Since the specific organic-inorganic hybrid polymer has a low refractive index when it contains a silicon atom, the refractive index difference can be increased by using a high refractive index photopolymerizable compound having a refractive index of 1.54 or more. .

The photosensitive composition for volume hologram recording of the present invention contains at least an organic-inorganic hybrid polymer, a photopolymerizable compound, and a photopolymerization initiator, as long as the effects of the present invention are not impaired. If necessary, other components may be contained.
Hereinafter, each component of the photosensitive composition for volume hologram recording of the present invention will be described in detail in order.

<Organic-inorganic hybrid polymer>
The organic-inorganic hybrid polymer used in the present invention has a main chain of an organic polymer, a polysiloxane structure in at least one of a side chain and a terminal of the organic polymer, and trifunctional siloxane units as all siloxane units. It is an organic-inorganic hybrid polymer containing 10 mol% or more based on the above.
The organic-inorganic hybrid polymer is excellent in heat resistance, light resistance, weather resistance, and mechanical strength by containing 10 mol% or more of trifunctional siloxane units with respect to all siloxane units in the polysiloxane structure.
Also, in the polysiloxane structure, the hydrophilic part is bonded to the base material, and the hydrophobic part tends to be distributed near the surface of the hologram recording layer, so that the releasability from the peelable protective film tends to be improved. is there. By appropriately adjusting the ratio between the organic polymer and the polysiloxane structure, it is possible to perform soft adhesion in a peelable manner without using a release treatment.
Furthermore, by using an organic-inorganic hybrid polymer, there is no compatibility problem, and the uniformity of the photosensitive composition for volume hologram recording is excellent.

(Organic polymer)
The main chain of the organic-inorganic hybrid polymer is an organic polymer. The said organic polymer can be obtained by superposing | polymerizing combining a conventionally well-known monomer suitably in the range which does not impair the effect of this invention. As the main chain portion of the organic polymer, an addition polymer obtained by addition polymerization of an ethylenically unsaturated double bond is preferably used. In the present invention, it is preferable to use a combination of an organic monomer having an ethylenically unsaturated bond and an organosilicon compound having an ethylenically unsaturated bond. By using an organosilicon compound having an ethylenically unsaturated bond, a polysiloxane structure described later can be introduced into the side chain or terminal of the organic polymer. Alternatively, a reactive functional group capable of reacting with an organic silicon compound such as a hydroxyl group is introduced into the side chain or terminal of the organic polymer, and the reactive functional group and the organic silicon compound are reacted to form an organic silicon compound. You may introduce | transduce into a polymer. With the organosilicon compound, a polysiloxane structure can be introduced at a desired location.

Examples of the organic monomer having an ethylenically unsaturated double bond include organic monomers having an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and the like.
Specific examples of the monomer having an ethylenically unsaturated double bond include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl metallate, benzyl (meth) acrylate, and phenyl (meth) acrylate. , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α-methylstyrene, vinylcyclohexane and the like, but are not limited thereto.
The monomer which has an ethylenically unsaturated double bond can be used individually by 1 type or in combination of 2 or more types.

  The organosilicon compound having an ethylenically unsaturated bond is preferably an organosilicon compound represented by the following general formula (1).

RmSi (OR ′) n General formula (1)
(In the general formula (1), R may be the same or different, and may be an ethylenic double bond-containing group having 1 to 10 carbon atoms, R ′ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, m + n = 4, m ≧ 1, and n ≧ 1.)

As said ethylenically unsaturated bond containing group, an acryloyl group, a methacryloyl group, a vinyl group, an allyl group etc. are mentioned, for example.
Specific examples of the organosilicon compound represented by the general formula (1) include various vinyl alkoxysilanes such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, vinyltriallyloxysilane, and vinyltetraethoxy. Examples include, but are not limited to, silane, vinyltetramethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.
An organosilicon compound can be used individually by 1 type or in combination of 2 or more types.

  A copolymer obtained by copolymerizing an organic monomer having an ethylenically unsaturated bond and an organosilicon compound having an ethylenically unsaturated bond may be a random copolymer or a block copolymer. May be.

  In addition, the content ratio of the organic monomer to the organosilicon compound in the copolymer obtained by copolymerizing an organic monomer having an ethylenically unsaturated bond and an organosilicon compound having an ethylenically unsaturated bond is introduced. What is necessary is just to select suitably according to the quantity of the polysiloxane structure to want.

(Polysiloxane structure)
The polysiloxane structure in the organic-inorganic hybrid polymer of the present invention contains at least 10 mol% of trifunctional siloxane units based on the total siloxane units. The ratio of trifunctional siloxane units to total siloxane units in the organic-inorganic hybrid polymer can be measured by ²⁹ Si-NMR.
When the polysiloxane structure contains only an oily bifunctional siloxane unit, the system tends to flow, and the diffraction efficiency peak shifts to the lower wavelength side by heating. This is particularly noticeable under a high temperature test of 200 ° C. or higher. On the other hand, when a trifunctional siloxane unit is included in the polysiloxane structure, the three-dimensional network structure is more rigid than the oil-like structure having a high degree of freedom, so that the system is difficult to move. It is believed that the more trifunctional siloxane units, the greater the rigidity, and as a result, the wavelength shift of the diffraction efficiency peak is suppressed. The effect of improving heat resistance due to the inclusion of trifunctional siloxane units can be confirmed from the case of containing about 10 mol% with respect to all siloxane units, and at 50% mol or more, durability that can withstand a high temperature test of 250 ° C. or more is obtained. To do.

The amount of the trifunctional siloxane unit contained in the polysiloxane structure is sufficient when the trialkoxysilane is used as the organosilicon compound having an ethylenically unsaturated bond at the time of polymerization of the organic polymer. In some cases, it is preferably contained in the side chain or terminal polysiloxane.
The polysiloxane structure may contain a monofunctional siloxane unit, a bifunctional siloxane unit, and a tetrafunctional siloxane unit in addition to the trifunctional siloxane unit.

From the viewpoint of improving heat resistance, the polysiloxane structure contains 10% by mole or more of trifunctional siloxane units with respect to all siloxane units, more preferably 30% by mole or more with respect to all siloxane units. % Or more is even more preferable. On the other hand, the polysiloxane structure contains 90 mol% or less of trifunctional siloxane units with respect to the total siloxane units from the viewpoint of the mobility of the photopolymerizable compound in the photosensitive resin composition for volume hologram recording. Is preferred.
The polysiloxane structure may contain 10 mol% or more of bifunctional siloxane units based on the total siloxane units from the viewpoint of the mobility of the photopolymerizable compound in the photosensitive resin composition for volume hologram recording. Preferably, from the viewpoint of improving heat resistance, the bifunctional siloxane unit is preferably 90 mol% or less, more preferably 70 mol% or less, and more preferably 50 mol% based on the total siloxane units. % Or less is even more preferable.
On the other hand, since the monofunctional siloxane unit can form the terminal of the polysiloxane structure, the average molecular weight of the polysiloxane structure can be controlled by appropriately adjusting the content of the monoalkoxysilane.

The polysiloxane structure is preferably a hydrolysis polycondensation product of an organosilicon compound portion of the above-described organic polymer and an organosilicon compound such as various alkoxysilanes. An organosilicon compound can be used individually by 1 type or in combination of 2 or more types.
As a preferable organosilicon compound capable of performing hydrolytic polycondensation, a compound represented by the following general formula (2) can be given.
R ″ m′Si (OR ′ ″) n ′ General formula (2)
(In general formula (2), R ″ may be the same or different, and an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, vinyl group, acryloyl group, methacryloyl group, epoxy group, amide group, sulfonyl group, hydroxyl group. Alternatively, a hydrocarbon group having 1 to 10 carbon atoms having a carboxyl group, R ′ ″ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, m ′ + n ′ = 4, m ′ ≧ 0, n '≧ 1.)

  For example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, Tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, dimethylpropoxysilane, dimethyl Toxisilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3- (2-aminoethylamino) Propyl) trimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ Chloropropyltrimethoxysilane, and the like, but not limited thereto.

  In the present invention, since a predetermined amount or more of trifunctional siloxane units are contained in the polysiloxane structure, it is preferable to use an organosilicon compound capable of deriving trifunctional siloxane units such as trialkoxysilane. As an organosilicon compound capable of deriving a trifunctional siloxane unit such as trialkoxysilane, it can be appropriately selected from conventionally known compounds. Among them, those having a structure in which n = 3 (m = 1) in the general formula (2) are preferable because they are excellent in heat resistance and durability and can improve the refractive index difference.

The organic-inorganic hybrid polymer used in the present invention is, for example, an organic polymer by first copolymerizing the organic monomer having the ethylenically unsaturated double bond and the organosilicon compound having the ethylenically unsaturated bond. It can be obtained by forming a coalescence, mixing the organic polymer and the organosilicon compound, and hydrolytic polycondensation.
Among them, the organic-inorganic hybrid polymer used in the present invention is a copolymer of at least an organosilicon compound represented by the following general formula (1) as a main chain component and an organic monomer having an ethylenically unsaturated double bond. An organic-containing polycondensation product of a copolymer of the above and an organosilicon compound represented by the following general formula (2) and containing 10 mol% or more of trifunctional siloxane units based on the total siloxane units An inorganic hybrid polymer is preferable from the viewpoint of excellent heat resistance.
RmSi (OR ′) n General formula (1)
(In the general formula (1), R may be the same or different, and may be an ethylenic double bond-containing group having 1 to 10 carbon atoms, R ′ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, m + n = 4, m ≧ 1, and n ≧ 1.)
R ″ m′Si (OR ′ ″) n ′ General formula (2)
(In general formula (2), R ″ may be the same or different, and an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, vinyl group, acryloyl group, methacryloyl group, epoxy group, amide group, sulfonyl group, hydroxyl group. Alternatively, a hydrocarbon group having 1 to 10 carbon atoms having a carboxyl group, R ′ ″ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, m ′ + n ′ = 4, m ′ ≧ 0, n '≧ 1.)

The mass average molecular weight of the organic-inorganic hybrid polymer used in the present invention is preferably 10,000 or more, and more preferably 20,000 or more.
The mass average molecular weight here is a polystyrene conversion value by GPC (gel permeation chromatography).

The silicon atom content relative to the whole organic-inorganic hybrid polymer is preferably 5 to 40% by mass, and more preferably 10 to 37% by mass. When the silicon atom content is at least the above lower limit, the heat resistance, light resistance and weather resistance are sufficiently exhibited, and the refractive index of the hybrid polymer is sufficiently low. On the other hand, if it is less than the said upper limit, the problem of the adhesive fall to the base material mentioned later does not arise.
Here, the silicon atom content can be measured by ICP (inductively coupled radio frequency plasma) mass spectrometry, TG-DTA (differential thermal-thermogravimetric measurement), or DSC (differential scanning calorimetry).

  The refractive index of the organic-inorganic hybrid polymer is at least lower than 1.54, and is preferably 1.50 or less, and more preferably 1.47 or less. The organic-inorganic hybrid polymer generally has a refractive index of less than 1.54 for both the organic polymer and the siloxane structure. By increasing the content of the siloxane structure having a lower refractive index, the refractive index can be further reduced. Further, the refractive index can be controlled by the structure of the monomer used. By increasing the difference in refractive index from the photopolymerizable compound described later, the desired diffraction efficiency can be obtained in a thinner state. A thin film has the advantage that the amount of dye in the entire hologram recording layer can be reduced accordingly. The sensitizing dye remaining in the hologram absorbs light of a specific wavelength and may have adverse effects such as side reactions and heat generation. However, if the film is made thinner, this phenomenon can be avoided and the cost can be simply reduced. . The volume hologram recording layer can be made thin.

  The organic-inorganic hybrid polymer is preferably 5 to 89.5% by mass, more preferably 10 to 60% by mass, based on the total solid content of the photosensitive composition for volume hologram recording.

<Photopolymerizable compound>
The photosensitive resin composition for volume hologram recording of the present invention contains a photopolymerizable compound having a refractive index of 1.54 or more as an essential component.

What is necessary is just to select a well-known thing suitably for the photopolymerizable group in a photopolymerizable compound. Among these, a group having an ethylenically unsaturated double bond is preferable, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group. The photopolymerizable compound having a refractive index of 1.54 or more may have one photopolymerizable group in the molecule, or may have two or more.
The photopolymerizable compound is a so-called monomer, and its molecular weight is usually 2000 or less.

Examples of the photopolymerizable compound having a refractive index of 1.54 or more include an ethylenically unsaturated double bond, a halogen atom other than fluorine (a chlorine atom, a bromine atom, an iodine atom, etc.), a sulfur atom, and It can be selected from compounds having one or more selected from the group consisting of aromatic rings.
Among them, it is represented by the following general formula (4) or the following general formula (5), which has an ethylenically unsaturated double bond and two or more aromatic rings are directly bonded to one carbon atom or nitrogen atom. A compound having a high refractive index and high stability is preferable. In other words, in the case of a compound containing a halogen atom, there is a risk of causing a side reaction such as regenerating a double bond by causing a dehydrohalogenation reaction with a peripheral alkyl group during heating. However, in the case of a compound represented by the following general formula (4) or the following general formula (5), there is a risk of accelerating the deterioration of the mold or coloring due to light deterioration. High stability without fear of reaction or deterioration.

（一般式（４）及び一般式（５）中、Ａｒ^１、Ａｒ^２、Ａｒ^３、及びＡｒ^４は、芳香族基を表し、Ｒ^１、Ｒ^２、及びＲ^３は、ヘテロ原子を有していてもよい炭化水素基を表す。Ａｒ^１とＡｒ^２、Ａｒ^３とＡｒ^４が炭素鎖を介して互いに結合していてもよい。上記芳香族基及び上記炭化水素基は、置換基を有していてもよい。）

(In General Formula (4) and General Formula (5), Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ represent an aromatic group, and R ¹ , R ² , and R ³ have a hetero atom. Ar ¹ and Ar ² , Ar ³ and Ar ⁴ may be bonded to each other via a carbon chain, and the aromatic group and the hydrocarbon group have a substituent. You may do it.)

The aromatic group in Ar ^{1 to} Ar ⁴ may be an aromatic hydrocarbon group other than an aromatic hydrocarbon group composed of a carbocyclic ring. Examples of the aromatic hydrocarbon in the aromatic hydrocarbon group include condensed polycyclic aromatic hydrocarbons such as naphthalene ring, indene ring, anthracene ring and phenanthrene ring, biphenyl bonded by a single bond, in addition to the benzene ring. It is done. The heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, and pyrazine. And condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.
Examples of the substituent that the aromatic group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and the like, and a group having an ethylenically unsaturated double bond.

Ar ¹ and Ar ² , Ar ³ and Ar ⁴ may be bonded to each other via a carbon chain. For example, a fluorene ring or a carbazole ring may be formed.

The hydrocarbon group in R ^{1 to} R ³ is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. It may have a saturated double bond. Further, the hydrocarbon group may further have a substituent.

Since it is a photopolymerizable compound, it always contains a photopolymerizable group. In the general formulas (4) and (5), the aromatic groups Ar ¹ and Ar ² and Ar ³ and Ar ⁴ are photopolymerized. The hydrocarbon group in R < ¹ > -R < ³ > may have a photopolymerizable group.

Examples of the photopolymerizable compound having a refractive index of 1.54 or more include pentabromophenyl acrylate and pentabromophenyl methacrylate as long as they contain halogen. Those not containing halogen are preferably selected from bisphenol A derivatives, bisphenol F derivatives, fluorene derivatives, and carbazole derivatives. Specific examples include N-vinylcarbazole, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, ethoxylated phenylphenol acrylate, ethoxylated (3) bisphenol A diacrylate, and the like. .
As the photopolymerizable compound having a refractive index of 1.54 or more, it is preferable to use a photopolymerizable compound having a refractive index of 1.60 or more.
Further, the content of the photopolymerizable compound having a refractive index of 1.54 or more is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the photopolymerizable compound.
The total amount of photopolymerizable compound is the total amount of photopolymerizable compound.

In the present invention, the photopolymerizable compound may be used singly or in combination of two or more.
The photopolymerizable compound used in combination also preferably has a high refractive index, preferably 1.48 or more, and more preferably 1.50 or more.
For example, when a photopolymerizable compound having one photopolymerizable group in the molecule is used, flexibility can be imparted to the entire film as a diluent, and the effect of improving the mobility of the photopolymerizable compound in the coating film can be obtained. It is preferable from a certain point. Among them, it is preferable to use a photopolymerizable compound having one photopolymerizable group in the molecule and a refractive index of 1.48 or more.
On the other hand, if the film is too flexible, the coating film cannot be solidified on the substrate, or the in-plane film thickness variation may become large because the coating film is not stable, which may cause variations in diffraction efficiency. There is. On the other hand, it is preferable to use a photopolymerizable compound having two or more photopolymerizable groups in the molecule because it functions as a thickener or a crosslinking component and the flexibility of the entire film can be made appropriate. Among these, it is preferable to use a photopolymerizable compound having a refractive index of 1.48 or more and having two or more photopolymerizable groups in the molecule.

  In particular, a photopolymerizable compound having one photopolymerizable group in the molecule and a refractive index of 1.48 or more, and a photopolymerizability having a refractive index of two or more photopolymerizable groups in the molecule and 1.48 or more. Use in combination with a compound is preferable from the viewpoint of improving diffraction efficiency and improving in-plane uniformity of diffraction efficiency.

A photopolymerizable compound having a refractive index of 1.48 or more having one photopolymerizable group in the molecule, and a photopolymerizable compound having a refractive index of 1.48 or more having two or more photopolymerizable groups in the molecule. These may be appropriately selected from those listed above for the photopolymerizable compound having a refractive index of 1.54 or more.
Alternatively, as the photopolymerizable compound having a refractive index of 1.48 or more, a photopolymerizable compound having a refractive index of 1.48 or more and less than 1.54 can also be used.
Therefore, as a photopolymerizable compound having a refractive index of 1.48 or more and having one photopolymerizable group in the molecule, for example, alkoxylated 2-phenoxyethyl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, phenoxy polyethylene glycol Acrylate or the like can also be used.
Examples of the photopolymerizable compound having two or more photopolymerizable groups in the molecule and a refractive index of 1.48 or more include ethoxylated (3) bisphenol A di (meth) acrylate and ethoxylated (4) bisphenol. A di (meth) acrylate, ethoxylated (10) bisphenol A di (meth) acrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tricyclodecane dimethanol dimethacrylate, and the like can also be used.
In addition, for example, ethoxylation (4) in ethoxylated (4) bisphenol A di (meth) acrylate means that-(CH ₂ CH ₂ O) ₂ -is bonded to _two acryloyloxy groups to form an ethoxy group. It represents that it is contained in 4 molecules.

When the photopolymerizable compound is used in combination, the content of the photopolymerizable compound having a refractive index of 1.54 or more is 20% by mass or more based on the total amount of the photopolymerizable compound, and the photopolymerizable group is added. The content of the photopolymerizable compound having a refractive index of 1.48 or more having one in the molecule and the content of the photopolymerizable compound having a refractive index of 1.48 or more having two or more photopolymerizable groups in the molecule. The content of the photopolymerizable group and the content of the photopolymerizable group having a total refractive index of 80% by mass or more based on the total amount of the photopolymerizable compound and having one photopolymerizable group in the molecule and a refractive index of 1.48 or more. Are combined so that the ratio of the refractive index of the photopolymerizable compound having a refractive index of 1.48 or more in the molecule is from 1:10 to 10: 1. The surface shape is good, and the in-plane diffraction efficiency varies. From the viewpoint of being reduced.
Among them, the content of the photopolymerizable compound having a refractive index of 1.54 or more is 30% by mass or more based on the total amount of the photopolymerizable compound, and the refractive index having one photopolymerizable group in the molecule is 1. The sum of the content of the photopolymerizable compound of 48 or more and the content of the photopolymerizable compound having a refractive index of 1.48 or more having two or more photopolymerizable groups in the molecule is 90% of the total amount of the photopolymerizable compound. The content of the photopolymerizable compound having a refractive index of not less than 1.48% and having one photopolymerizable group in the molecule and a refractive index having two or more photopolymerizable groups in the molecule. It is further preferable to combine them so that the ratio to the content of the photopolymerizable compound of 1.48 or more is 1: 4 to 10: 1.

  The total amount of the photopolymerizable compound is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, based on the total solid content of the photosensitive composition for volume hologram recording.

<Photopolymerization initiator>
In the present invention, as the photopolymerization initiator, a conventionally known photoradical polymerization initiator can be appropriately selected and used. The photopolymerization initiator is not limited to a compound that functions as a photopolymerization initiator alone, but may be a combination of a sensitizer, an active radical generating compound, and / or an acid generating compound.

Examples of the photo radical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5-isoxazolone 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651, manufactured by BASF), 1-hydroxy- Cyclohexyl-phenyl-ketone (trade name Irga Interview A 184, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butan-1-one (trade name Irgacure 369, manufactured by BASF), bis (eta ^5-2,4 -Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) (trade name Irgacure 784, manufactured by BASF), 2,2′-bis ( o-Chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole and the like, but are not limited thereto.

The photopolymerization initiator is preferably decomposed after hologram recording from the viewpoint of the stability of the recorded hologram.
Content of a photoinitiator is 0.1-20 mass parts normally with respect to 100 mass parts of said photopolymerizable compound whole quantity, and it is preferable to set it as 5-15 mass parts.

  In the present invention, a sensitizer may be used in combination with a photopolymerization initiator. The sensitizer plays a role of increasing the sensitivity to the recording term of the photopolymerization initiator. Specifically, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salts System dyes, cyclopentanone dyes, cyclohexanone dyes, and the like. Specific examples of cyanine dyes and merocyanine dyes include, for example, 3,3′-dicarboxyethyl-2,2′-thiocyanine bromide, 1-carboxymethyl-1′-carboxyethyl-2,2′-quino Cyanine bromide, 1,3′-diethyl-2,2′-quinothiacyanine iodide, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolidelidene) ethylidene] -2-thioxo-4 -Oxazolidine, 3-ethyl-9-methyl-3 '-(3-sulfatobutyl) thiacarboxyanine betaine and the like, and specific examples of coumarin dyes and ketocoumarin dyes include 3- (2'-benzo Imidazole) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7′-dimethoxycoumarin), 3,3′-carbonylbis 7-acetoxycoumarin), and the like but not limited thereto.

The sensitizer is preferably one that is decomposed and becomes colorless by heating after hologram recording, ultraviolet irradiation, or the like, particularly when high transparency such as an optical element is required.
The content of the sensitizer is usually 0.01 to 20 parts by mass and preferably 0.1 to 10 parts by mass with respect to the total amount of the photopolymerizable compound.

<Other ingredients>
The photosensitive resin composition for volume hologram recording of the present invention is a polymerization inhibitor, a silane coupling agent, a plasticizer, a colorant, fine particles, a thermoplastic resin, if necessary, as long as the effects of the present invention are not impaired. A surfactant or the like may be used in combination.
Among them, in the present invention, it is preferable that a thermoplastic resin is included because the hologram recording layer can be given flexibility, the mobility of the photopolymerizable compound can be improved, and hologram formation can be promoted.
It is also preferable to promote the formation of hologram fringes using a chain transfer agent. Specific examples of the chain transfer agent include 4-methyl-4H-1,2,4-triazole-3-thiol, tetrachloromethane, 2-mercaptobenzoxazole and the like.

Specific examples of the thermoplastic resin include polyvinyl acetate, polyvinyl butyrate, polyvinyl formal, polyvinyl carbazole, polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polybutyl acrylate, poly Methacrylonitrile, polyethyl methacrylate, polybutyl methacrylate, polyacrylonitrile, poly-1,2-dichloroethylene, ethylene-vinyl acetate copolymer, syndiotactic polymethyl methacrylate, poly-α-vinyl naphthalate, polycarbonate, cellulose Acetate, cellulose triacetate, cellulose acetate butyrate, polystyrene, poly-α-methylstyrene, poly-o-methylstyrene, poly- p-methylstyrene, poly-p-phenylstyrene, poly-2,5-dichlorostyrene, poly-p-chlorostyrene, poly-2,5-dichlorostyrene, polyarylate, polysulfone, polyethersulfone, styrene- Acrylonitrile copolymer, styrene-divinylbenzene copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, ABS resin, polyethylene, polyvinyl chloride, polypropylene, polyethylene terephthalate, polyvinyl pyrrolidone, polyvinylidene chloride, Examples thereof include hydrogenated styrene-butadiene-styrene copolymer, transparent polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of (meth) acrylic acid cycloaliphatic ester and methyl (meth) acrylate, and the like.
A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  When using a thermoplastic resin, it is preferable to set it as 80 mass% or less with respect to the total solid of the volume type hologram recording photosensitive composition.

  The photosensitive composition for volume hologram recording is usually dissolved in a solvent and used as a coating solution. The solvent may be appropriately selected from those that do not react with the above components and that can dissolve or uniformly disperse the above components. Examples of such solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4- Examples include dioxane, 1,2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol and the like. A solvent can be used individually by 1 type or in combination of 2 or more types.

[Photosensitive substrate for volume hologram recording]
The photosensitive substrate for volume hologram recording according to the present invention has an organic polymer as a main chain and a polysiloxane structure in at least one of a side chain and a terminal of the organic polymer, and contains all trifunctional siloxane units. A hologram recording layer for recording a hologram, comprising an organic-inorganic hybrid polymer containing 10 mol% or more based on a siloxane unit, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator. And provided on a base material.

  FIG. 1 is a schematic view showing an example of a photosensitive substrate for volume hologram recording of the present invention. As illustrated in FIG. 1, the volume type hologram recording photosensitive substrate 10 according to the present invention has a hologram recording layer 2 provided on a base material 1.

The photosensitive substrate for volume hologram recording of the present invention has at least a hologram recording layer and a base material, and further has other layers as necessary unless the effects of the present invention are impaired. It may be.
Hereinafter, each layer which comprises the photosensitive substrate for volume type hologram recording is demonstrated in order.

[Base material]
In the photosensitive substrate for volume hologram recording according to the present invention, as the base material, a conventionally known base material can be appropriately selected and used according to the application.
When the volume hologram recording photosensitive substrate is used for an optical element, a transparent resin substrate or a glass substrate is usually used as the substrate.

  In the present invention, “transparent” means that the transmittance in the visible light region is 80% or more, and preferably 90% or more. Here, the transmittance | permeability of a transparent resin base material can be measured by JISK7361-1 (The test method of the total light transmittance of a plastic-transparent material).

As the transparent resin substrate, a known transparent resin substrate can be appropriately selected and used. Examples of transparent resin base materials include polyethylene film, polypropylene film, polyvinyl fluoride film, polyvinylidene fluoride film, polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol film, polyvinyl alcohol film, polymethyl methacrylate film. Polyester sulfone film, polyether ether ketone film, polyamide film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film, polyester film such as polyethylene terephthalate film, and polyimide film.
The transparent substrate may be a glass substrate, or a roll-shaped thin film may be used.

  In the present invention, the thickness of the substrate may be appropriately set according to the required strength, but is usually preferably 2 to 200 μm, more preferably 10 to 150 μm.

[Hologram recording layer]
The hologram recording layer used in the present invention has an organic polymer as a main chain, a polysiloxane structure at least one of a side chain and a terminal of the organic polymer, and trifunctional siloxane units with respect to all siloxane units. The organic-inorganic hybrid polymer containing 10 mol% or more, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator.

  The hologram recording layer is formed by, for example, dissolving or dispersing the volume-type hologram recording photosensitive resin composition according to the present invention in a solvent, coating the substrate as a coating liquid, and removing the solvent by drying. Can be formed.

  About each component which forms the said hologram recording layer, since it can be made to be the same as that of what was demonstrated in the said photosensitive resin composition for volume type hologram recording, description here is abbreviate | omitted.

  What is necessary is just to select the coating method of the said composition for hologram recording layers from a conventionally well-known method suitably. Specifically, for example, methods such as a spin coater, a gravure coater, a comma coater, and a bar coater can be used.

  The film thickness of the hologram recording layer may be appropriately set within a range in which a desired hologram can be recorded. For example, it may be appropriately set within a range of 1 to 100 μm, preferably 5 to 40 μm.

<Peelable protective layer>
In the photosensitive substrate for volume hologram recording according to the present invention, when the hologram recording layer after drying is sticky, it is used as a peelable protective layer such as a polyester film or a polyethylene film, usually as a base film, for example. Such films can be laminated.

[Volume type hologram recording body]
The volume hologram recording material according to the present invention has a main chain of an organic polymer, a polysiloxane structure in at least one of a side chain and a terminal of the organic polymer, and trifunctional siloxane units as all siloxane units. On the other hand, the hologram is contained in a hologram recording layer for recording a hologram, comprising an organic-inorganic hybrid polymer containing 10 mol% or more, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator. The recorded hologram layer is provided on a substrate.

  FIG. 2 is a schematic view showing an example of the volume hologram recording body of the present invention. As illustrated in FIG. 2, the volume hologram recording body 20 according to the present invention includes a hologram layer 3 on which a hologram is recorded on a hologram recording layer on a base material 1.

  The substrate and the specific hologram recording layer in the volume hologram recording body according to the present invention can have the same configuration as the volume hologram recording photosensitive substrate according to the present invention. The description in is omitted. The volume hologram recording body according to the present invention may be one in which a hologram is recorded on the hologram recording layer of the photosensitive substrate for volume hologram recording according to the present invention.

A hologram recording method for recording a hologram on the hologram recording layer to form a hologram layer is not particularly limited, and a known method may be appropriately selected and used. For example, in the hologram recording layer, the photopolymerizable compound is polymerized by an ordinary holographic exposure apparatus using laser light or light having excellent coherence (for example, light having a wavelength of 300 to 1200 nm), and interference fringes are recorded therein. .
Further, in order to promote the amount of refractive index modulation by interference exposure and complete the polymerization reaction, it is possible to appropriately perform a process such as full exposure with ultraviolet rays or heating after the interference exposure.
Note that the diffraction efficiency, the peak wavelength of diffracted light, the half-value width, and the like can be changed by treating the recording layer with heat or infrared rays.

  The volume hologram recording body of the present invention can be applied to conventionally known applications and can be suitably used particularly for optical element applications. Examples of optical element applications include lenses, diffraction gratings, interference filters, head-up display devices, three-dimensional displays, head-mounted displays, laser displays, scanners, illumination devices, and optical pickup applications.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

Example 1
(1) Production of photosensitive composition for volume hologram recording Photosensitive composition 1 for volume hologram recording having the following composition was produced.
<Composition of photosensitive composition 1 for volume hologram recording>
Organic-inorganic hybrid polymer (trifunctional siloxane unit is 65 mol% with respect to the total siloxane unit, silicon atom content in organic-inorganic hybrid polymer is 27% by mass: JSR, Glasca HPC7506): 8.660 parts by mass Photopolymerizable compound (N-vinylcarbazole, manufactured by Tokyo Chemical Industry, refractive index (25 ° C.) 1.68): 2.100 parts by massPhotopolymerizable compound (alkoxylated 2-phenoxyethyl acrylate, manufactured by Sartomer, CD9087, Refractive index (25 ° C.) 1.504): 2.410 parts by mass / photopolymerizable compound (ethoxylated (4) bisphenol A diacrylate, manufactured by Sartomer, SR601, refractive index (25 ° C.) 1.534): 0. 542 parts by mass-photopolymerization initiator (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl 1,2'-biimidazole (manufactured by Kurokin Kasei): 0.586 parts by mass-sensitizing dye (3-ethyl-9-methyl-3 '-(3-sulfatobutyl) thiacarbocyanine betaine, Inc. Hayashibara): 0.023 parts by mass. Reaction accelerator (4-methyl-4H-1,2,4-triazole-3-thiol, manufactured by Tokyo Chemical Industry): 0.367 parts by mass. Methyl ethyl ketone: 50 parts by mass. Methanol. : 10 parts by mass

(2) Production of photosensitive substrate for volume hologram recording The photosensitive composition 1 for volume hologram recording obtained in (1) is placed on a 60 μm polyethylene terephthalate (PET) film (Toray Lumirror T-60). Using an applicator, coating and drying were carried out so that the film thickness after drying was 8 μm to obtain a hologram recording layer, whereby a volume type hologram recording photosensitive substrate 1 of Example 1 was obtained.

(3) Manufacture of volume hologram recording body The hologram recording layer side of the volume hologram recording photosensitive substrate of Example 1 obtained in (2) is laminated on a mirror, and PET of the volume hologram recording photosensitive substrate is obtained. A 532 nm laser beam was incident at 1 J / cm ² from the side, interference exposure was performed, and a volume hologram was recorded. At that time, the incident angle of the light beam was set to an angle of 45 degrees from the normal direction of the substrate surface of the hologram recording photosensitive substrate.
Next, ultraviolet irradiation is performed on the entire surface, and then the reaction is promoted by heating at 100 ° C. for 30 minutes to fix the hologram recording layer. Obtained.
The hologram recording layer on which the interference fringes were recorded was able to form a uniform hologram within the plane in all the light-irradiated portions without peeling from the substrate. In addition, no cloudiness was observed, and no irregularities such as repelling that caused phase separation in the plane were observed.

(Example 2)
(1) Production of photosensitive composition for volume hologram recording A photosensitive composition 2 for volume hologram recording having the following composition was produced.
<Composition of photosensitive composition 2 for volume hologram recording>
Organic-inorganic hybrid polymer (manufactured by JSR, Glasca HPC 7506): 6.495
Thermoplastic resin (polyvinyl acetate, polystyrene-converted mass average molecular weight: 100,000): 2.165 parts by mass Photopolymerizable compound (N-vinylcarbazole, manufactured by Tokyo Chemical Industry, refractive index (25 ° C.) 1.68): 2.100 parts by mass / photopolymerizable compound (alkoxylated 2-phenoxyethyl acrylate, manufactured by Sartomer, CD9087, refractive index (25 ° C.) 1.504): 2.410 parts by mass / photopolymerizable compound (ethoxylated (4 ) Bisphenol A diacrylate, manufactured by Sartomer, SR601, refractive index (25 ° C.) 1.534): 0.542 parts by mass / photopolymerization initiator (2,2′-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, manufactured by Kurokin Kasei): 0.586 parts by mass-sensitizing dye (3-ethyl-9-methyl-3'-(3-sulfatobuty ) Thiacarbocyanine betaine, Hayashibara Institute of Biological Sciences): 0.023 parts by mass. Reaction accelerator (4-methyl-4H-1,2,4-triazole-3-thiol, manufactured by Tokyo Chemical Industry): 0.367 masses Parts / methyl ethyl ketone: 50 parts by mass / methanol: 10 parts by mass

(2) Production of photosensitive substrate for volume hologram recording The photosensitive composition 2 for volume hologram recording obtained in (1) was used in place of the photosensitive composition 1 for volume hologram recording of Example 1. The volume type hologram recording photosensitive substrate 2 was manufactured in the same manner as in Example 1 except that the hologram recording layer was formed.

(3) Production of Volume Type Hologram Recorder Instead of the volume type hologram recording photosensitive substrate 1 of Example 1, the volume type hologram recording photosensitive substrate 2 obtained in (2) was used to produce a volume type hologram. The volume hologram recording body 2 was manufactured in the same manner as in Example 1 except that.
The hologram recording layer on which the interference fringes were recorded was able to form a uniform hologram within the plane in all the light-irradiated portions without peeling from the substrate. In addition, no cloudiness was observed, and no irregularities such as repelling that caused phase separation in the plane were observed.

(Example 3)
(1) Production of photosensitive composition for volume hologram recording A photosensitive composition 3 for volume hologram recording having the following composition was produced.
<Composition of photosensitive composition 3 for volume hologram recording>
Organic-inorganic hybrid polymer (manufactured by JSR, Glasca HPC7506): 4.330
Thermoplastic resin (polyvinyl acetate, polystyrene-equivalent mass average molecular weight: 100,000): 4.330 parts by mass Photopolymerizable compound (N-vinylcarbazole, manufactured by Tokyo Chemical Industry, refractive index (25 ° C.) 1.68): 2.100 parts by mass / photopolymerizable compound (alkoxylated (3) 2-phenoxyethyl acrylate, manufactured by Sartomer, CD9087, refractive index (25 ° C.) 1.504): 2.410 parts by mass / photopolymerizable compound (ethoxy (4) Bisphenol A diacrylate, manufactured by Sartomer, SR601, refractive index (25 ° C.) 1.534): 0.542 parts by mass / photopolymerization initiator (2,2′-bis (o-chlorophenyl) -4, 5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, manufactured by Kurokin Kasei): 0.586 parts by mass / sensitizing dye (3-ethyl-9-methyl-3 ′-(3-sulfa) (Butyl) thiacarbocyanine betaine, Hayashibara Institute of Biological Sciences): 0.023 parts by mass. Reaction accelerator (4-methyl-4H-1,2,4-triazole-3-thiol, manufactured by Tokyo Chemical Industry): 0.367 Parts by mass, methyl ethyl ketone: 50 parts by mass, methanol: 10 parts by mass

(2) Production of photosensitive substrate for volume hologram recording The photosensitive composition 3 for volume hologram recording obtained in (1) was used in place of the photosensitive composition 1 for volume hologram recording of Example 1. The volume type hologram recording photosensitive substrate 3 was manufactured in the same manner as in Example 1 except that the hologram recording layer was formed.

(3) Production of Volume Type Hologram Recording Body Instead of the volume type hologram recording photosensitive substrate 1 of Example 1, the volume type hologram recording photosensitive substrate 3 obtained in (2) was used to produce a volume type hologram. The volume hologram recording body 3 was manufactured in the same manner as in Example 1 except that was recorded.
The hologram recording layer on which the interference fringes were recorded was able to form a uniform hologram within the plane in all the light-irradiated portions without peeling from the substrate. In addition, no cloudiness was observed, and no irregularities such as repelling that caused phase separation in the plane were observed.

(Comparative Example 1)
(1) Production of photosensitive composition for comparative volume hologram recording Photosensitive composition 1 for comparative volume hologram recording having the following composition was produced.
<Composition of photosensitive composition 1 for comparative volume hologram recording>
Organic-inorganic hybrid polymer (polydimethylsiloxane graft polyacrylate: Aldrich, trade name poly (dimethylsiloxane) -graft-polyacrylate, trifunctional siloxane unit is 0 mol% with respect to all siloxane units, organic-inorganic hybrid (Silicon atom content in polymer: 33% by mass): 5.770
Thermoplastic resin (polyvinyl acetate, polystyrene equivalent weight average molecular weight: 100,000): 5.770 parts by weight Photopolymerizable compound (2-phenoxyethyl acrylate, manufactured by Sartomer, SR339A, refractive index (25 ° C.) 1.516 ): 3.960 parts by mass-photopolymerization initiator (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, manufactured by Kurogane Kasei) ): 0.586 parts by mass-sensitizing dye (3-ethyl-9-methyl-3 '-(3-sulfatobutyl) thiacarbocyanine betaine, Hayashibara Institute of Bioscience): 0.023 parts by mass Agent (4-methyl-4H-1,2,4-triazole-3-thiol, manufactured by Tokyo Chemical Industry): 0.367 parts by mass-Methyl ethyl ketone: 50 parts by mass-Methanol: 10 parts by mass

(2) Production of photosensitive substrate for comparative volume hologram recording Photosensitive composition 1 for comparative volume hologram recording obtained in (1) instead of the photosensitive composition 1 for volume hologram recording of Example 1 A comparative volume hologram recording photosensitive substrate 1 was produced in the same manner as in Example 1 except that a hologram recording layer was formed using

(3) Manufacture of Comparative Volume Type Hologram Recording Body Instead of the volume type hologram recording photosensitive substrate 1 of Example 1, the comparative volume type hologram recording photosensitive substrate 1 obtained in (2) was used. A comparative volume hologram recording body 1 was manufactured in the same manner as in Example 1 except that the type hologram was recorded.

[Evaluation of heat resistance]
Glass was adhered to both surfaces of the volume hologram recording body 3 obtained in Example 3 using an adhesive (Aronix LCR0628A (manufactured by Toagosei Co., Ltd.)), and a UV curing agent (Aronix LCR0628A (manufactured by Toagosei Co., Ltd.) was also formed around it. )) To produce an element. In addition, a comparative element was similarly produced using the comparative volume hologram recording body 1 obtained in Comparative Example 1.
The obtained element was heated at the following temperature for 180 minutes, and spectral data of the hologram before and after the heating were measured. Even after heating at 270 ° C., each element maintained its hologram shape. However, the peak of diffraction efficiency shifted to the lower wavelength side as shown in Table 1. Compared with Comparative Example 1 in which the amount of wavelength shift after heating is composed only of bifunctional siloxane units, Example 3 is less and it has been clarified that the alteration of the hologram due to heat is further suppressed.

[Evaluation of refractive index modulation (Δn)]
For the volume hologram recording bodies of Examples 1 to 3, the refractive index modulation amount (Δn) was determined as follows. The results are shown in Table 2. The refractive index modulation amount (Δn) of Comparative Example 1 was 0.011.

<Calculation method of Δn>
About each volume type hologram recording body of Examples 1-3, the transmittance | permeability was measured using the spectrophotometer (Shimadzu Corporation make, UV-2450), and the spectral transmittance curve was obtained. In the obtained spectral transmittance curve, the peak transmittance Tp and the base transmittance Tb were obtained, and the diffraction efficiency η was obtained by the following formula (1).
Diffraction efficiency η = (Tb−Tp) / Tb (%) Formula (1)
Next, Δn was calculated by the Kogelnik theoretical formula (the following formula (2)) using the value of the diffraction efficiency η obtained by the formula (1).
η = tanh ² (π (Δn) d / λcos θ ₀ ) Equation (2)
(In formula (2), d is the film thickness (μm) of the hologram recording layer, λ is the recording laser wavelength (nm), and θ ₀ is the incident angle of the recording laser light to the hologram recording layer.)

[Evaluation of in-plane uniformity of refractive index]
The volume hologram recording body (5 cm × 5 cm) thus obtained was divided into 9 sections, and the refractive index was measured in each of the 9 divided areas, and the variation in the measured values of the 9 refractive indexes was evaluated.
Table 2 shows the standard deviation and the maximum and minimum values.

It was clarified that the volume hologram recording material of the example has high heat resistance, and the alteration of the hologram due to heat is further suppressed.
In addition, the volume hologram recording body of the example had a high refractive index modulation amount and good in-plane uniformity of the refractive index.

DESCRIPTION OF SYMBOLS 1 Base material 2 Hologram recording layer 3 Hologram layer in which hologram was recorded 10 Photosensitive substrate for volume type hologram recording 20 Volume type hologram recording body

Claims (6)

  Organic-inorganic hybrid whose main chain is an organic polymer, has a polysiloxane structure in at least one of the side chain and the terminal of the organic polymer, and contains 10 mol% or more of trifunctional siloxane units with respect to the total siloxane units A photosensitive composition for volume hologram recording, comprising a polymer, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator. A copolymer obtained by copolymerizing the organic-inorganic hybrid polymer with at least an organosilicon compound represented by the following general formula (1) as a main chain component and an organic monomer having an ethylenically unsaturated double bond: An organic-inorganic hybrid polymer containing a hydrolytic polycondensate with an organosilicon compound represented by the following general formula (2) and containing 10 mol% or more of trifunctional siloxane units based on the total siloxane units. The photosensitive composition for volume type hologram recording according to claim 1.

RmSi (OR ′) n General formula (1)
(In the general formula (1), R may be the same or different, and may be an ethylenic double bond-containing group having 1 to 10 carbon atoms, R ′ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, m + n = 4, m ≧ 1, and n ≧ 1.)

R ″ m′Si (OR ′ ″) n ′ General formula (2)
(In general formula (2), R ″ may be the same or different, and an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group, vinyl group, acryloyl group, methacryloyl group, epoxy group, amide group, sulfonyl group, hydroxyl group. Alternatively, a hydrocarbon group having 1 to 10 carbon atoms having a carboxyl group, R ′ ″ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, m ′ + n ′ = 4, m ′ ≧ 0, n '≧ 1.)   Furthermore, the photosensitive composition for volume type hologram recording of Claim 1 or 2 containing a thermoplastic resin.   The content of the photopolymerizable compound having a refractive index of 1.54 or more is 20% by mass or more based on the total amount of the photopolymerizable compound, and the refractive index having one photopolymerizable group in the molecule is 1.48 or more. The total content of the photopolymerizable compound and the content of the photopolymerizable compound having two or more photopolymerizable groups in the molecule and a refractive index of 1.48 or more is 80% by mass with respect to the total amount of the photopolymerizable compound. In addition, the content of the photopolymerizable compound having one photopolymerizable group in the molecule and a refractive index of 1.48 or more and the refractive index having two or more photopolymerizable groups in the molecule are 1. The volume hologram recording photosensitive composition according to any one of claims 1 to 3, wherein a ratio of the photopolymerizable compound content of 48 or more is 1:10 to 10: 1.   Organic-inorganic hybrid whose main chain is an organic polymer, has a polysiloxane structure in at least one of the side chain and the terminal of the organic polymer, and contains 10 mol% or more of trifunctional siloxane units with respect to the total siloxane units Photosensitive for volume hologram recording, comprising a hologram, a hologram recording layer for recording a hologram, comprising a polymer, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator. substrate.   Organic-inorganic hybrid whose main chain is an organic polymer, has a polysiloxane structure in at least one of the side chain and the terminal of the organic polymer, and contains 10 mol% or more of trifunctional siloxane units with respect to the total siloxane units A hologram recording layer for recording a hologram containing a polymer, a photopolymerizable compound having a refractive index of 1.54 or more, and a photopolymerization initiator, A volume hologram recording body provided.

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