JP6012755B2 - Photosensitive transfer material, substrate having photosensitive low refractive index transfer layer, method for producing photosensitive low refractive index transfer layer, method for forming permanent film, method for producing optical device - Google Patents

Description

  The present invention relates to a photosensitive transfer material, a substrate having a photosensitive low refractive index transfer layer, a method for producing a photosensitive low refractive index transfer layer, a method for forming a permanent film, an optical device, and a method for producing the same.

Low refractive index film is anti-reflection film, reflection film, semi-transmission semi-reflection film, visible light reflection infrared transmission film, infrared reflection visible light transmission film, blue reflection film, green reflection or red reflection film, bright line cut filter, color correction An optical functional film included in the film is formed on the optical member.
Not only optical members with a flat surface shape, but also optical function members such as brightness enhancement lens films and diffusion films for liquid crystal backlights, Fresnel lenses, lenticular lenses, and microlenses used for video projection television screens are all made of resin. The desired geometrical optical performance is obtained because the material has a fine structure, but an optical functional film including a low refractive index film is also required on the surface of the fine structure.
As conventional photosensitive resin compositions, the photosensitive resin compositions described in Patent Documents 1 and 2 are known. As a conventional photosensitive transfer material, a photosensitive transfer material described in Patent Document 3 is known.

JP 2012-32673 A JP 2012-13962 A JP 2006-349867 A

In particular, the backlight member for smartphone liquid crystal in recent years is merely a superposition, and an air layer or an adhesive layer is sandwiched between the members. For this reason, there has been a problem that the light transmission efficiency is lowered from the backlight in this overlapping portion.
An object of the present invention is to provide a photosensitive transfer material that has a low refractive index, a high light transmission efficiency, and an excellent in-plane film thickness uniformity after transfer.

The above-described problems of the present invention have been solved by means described in the following <1> or <10> to <13 > . It is described below together with <2> to <9>, <14> and <15> which are preferred embodiments.
<1> At least a photosensitive low refractive index material layer on a support, wherein the photosensitive low refractive index material layer comprises (Component A) hollow or porous particles, (Component B) a photopolymerization initiator, (Component C) a polymer having a polymerizable functional group and (Component D) a monomer , Component C contains a (meth) acrylic resin having an ethylenically unsaturated group, and Component D contains a fluorine atom. A photosensitive transfer material comprising an ethylenically unsaturated compound having
<2> The photosensitive transfer material according to <1>, wherein component A is hollow silica particles or porous silica particles,
<3> The ethylenically unsaturated group in the (meth) acrylic resin having the ethylenically unsaturated group is a (meth) acryloyl group, a (meth) acrylamide group, a thio (meth) acryloyl group, an allyl group or a vinyl group. <1> or the photosensitive transfer material according to <2>,
<Four> ethylenically unsaturated compound having the fluorine atom is a having a fluorine atom (meth) acrylate compounds, photosensitive transfer material according to any one of <1> to <3>,
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the ethylenically unsaturated compound having a fluorine atom is a polyfunctional (meth) acrylate compound having a fluorine atom.
<6> ethylenically unsaturated groups in (meth) acrylic resin having an ethylenically unsaturated group and acid group, an allyl group, <1> to photosensitive transfer according to any one of <5> material,
<7> The photosensitive transfer material according to any one of <1> to <6>, wherein the acid group in the (meth) acrylic resin having an ethylenically unsaturated group and an acid group is a carboxyl group,
<8> The photosensitive transfer material according to any one of <1> to <7>, wherein component A is hollow silica particles,
<9> The photosensitive property according to any one of <1> to <8>, wherein the content of the component A is 20 to 90% by mass with respect to the total mass of the photosensitive low refractive index material layer. Transfer material,
<10> a substrate having a photosensitive low refractive index transfer layer obtained by transferring the photosensitive low refractive index material layer from the photosensitive transfer material according to any one of <1> to <9>,
<11> The step of preparing the photosensitive transfer material according to any one of <1> to <9>, the photosensitive transfer material so that the member to be transferred and the photosensitive low refractive index material layer are in contact with each other. A method for producing a photosensitive low refractive index transfer layer, comprising: a step of laminating a film on a member to be transferred; and a step of peeling a support of the photosensitive transfer material.
<12> The step of preparing the photosensitive transfer material according to any one of <1> to <9>, the photosensitive transfer material so that the member to be transferred and the photosensitive low refractive index material layer are in contact with each other. A method of forming a permanent film, including a step of laminating a film on the member to be transferred, a step of peeling a support of the photosensitive transfer material, and a step of exposing the transferred photosensitive low refractive index material layer,
<13> The step of preparing the photosensitive transfer material according to any one of <1> to <9>, the photosensitive low refraction as at least one layer between the backlight module substrate and the color filter substrate. An optical device including a step of laminating the photosensitive transfer material so that a refractive index material layer and the backlight module substrate or the color filter substrate are in contact with each other, and a step of peeling the support of the photosensitive transfer material Method,
<14> The method for producing an optical device according to <13>, further comprising exposing the transferred photosensitive low refractive index material layer,
<15> The method for producing an optical device according to <13> or <14>, wherein the optical device is a backlight unit .

  According to the present invention, it is possible to provide a photosensitive transfer material capable of obtaining a layer having a low refractive index, high light transmission efficiency, and excellent in-plane film thickness uniformity after transfer.

It is a schematic cross section of an example of the photosensitive transfer material of the present invention. It is a schematic diagram which shows an example of the formation method of the permanent film of this invention. It is sectional drawing which shows an example of the backlight unit manufactured by the manufacturing method of the optical device of this invention. It is a schematic diagram which shows the prism sheet board | substrate used in the Example. It is a schematic diagram of the aa cross section in the prism sheet board | substrate of FIG. It is a cross-sectional schematic diagram of the transmittance | permeability measurement sample in an Example.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “(component A) hollow or porous particles” or the like is also simply referred to as “component A” or the like.
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. . In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of two or more preferred embodiments is more preferred.

(Photosensitive transfer material)
The photosensitive transfer material of the present invention has at least a photosensitive low refractive index material layer on a support, and the photosensitive low refractive index material layer comprises (Component A) hollow or porous particles, and (Component B). It contains a photopolymerization initiator, (Component C) a polymer having a polymerizable functional group, and (Component D) a monomer.

The photosensitive low refractive index material layer is a negative resist layer and is preferably a layer having a property of being cured by irradiation with actinic rays.
The photosensitive transfer material of the present invention is preferably a photosensitive transfer material for forming an optical device, more preferably a photosensitive transfer material for forming a display device, and a photosensitive transfer material for forming a backlight unit. More preferably, it is particularly preferably a photosensitive transfer material for forming a backlight unit of a touch panel member.
The low refractive index film (layer obtained by transferring and curing the photosensitive low refractive index material layer) obtained from the photosensitive transfer material of the present invention has a low refractive index. It can be suitably used for liquid crystal display elements such as televisions, mobile phones, and projectors.
The low refractive index film (layer obtained by transferring and curing the photosensitive low refractive index material layer) obtained from the photosensitive transfer material of the present invention exhibits excellent low refractive index properties. Specifically, the refractive index (wavelength 589 nm, measurement temperature 25 ° C.) of the low refractive index film is preferably 1.35 or less, more preferably 1.10 to 1.34, and 1. It is particularly preferably 23 to 1.33.
The refractive index is preferably a value measured at a wavelength of 589 nm and 25 ° C. using an ellipsometer (VASE) manufactured by JA Woollam Japan.
The thickness of the photosensitive low refractive index material layer is preferably 0.01 to 2.0 μm, more preferably 0.1 to 1.5 μm, and still more preferably 0.2 to 1.0 μm.
The thickness of the low refractive index film is preferably 0.01 to 2.0 μm, more preferably 0.1 to 1.5 μm, and still more preferably 0.2 to 1.0 μm.

<Photosensitive low refractive index material layer>
Hereinafter, each component of the photosensitive low refractive index material layer will be described in detail.

(Component A) Hollow or porous particles The photosensitive low refractive index material layer contains (Component A) hollow or porous particles.
The hollow particle is a structure having a cavity inside and refers to a particle having a cavity surrounded by an outer shell, and the porous particle refers to a particle having a large number of cavities on the surface and inside.
The porosity of such particles is preferably 10-80%, more preferably 20-60%, and most preferably 30-60%. The porosity of the hollow or porous particles is preferably in the above range from the viewpoint of reducing the refractive index and maintaining the durability of the particles.
The hollow or porous particles are more preferably hollow particles from the viewpoint of easily reducing the refractive index. For example, when the hollow particles are made of silica, the hollow silica particles have air with a low refractive index (refractive index = 1.0), and therefore the refractive index is normal silica (refractive index = Compared with 1.46), it is significantly lower.

  Examples of the method for producing hollow particles include the method described in JP-A-2001-233611. Examples of the method for producing porous particles include methods described in JP-A Nos. 2003-327424, 2003-335515, 2003-226516, 2003-238140, and the like.

The hollow or porous particles preferably have an average primary particle size of 1 to 200 nm, more preferably 10 to 100 nm.
The average primary particle diameter of the hollow or porous particles can be obtained from a photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom to obtain the average particle size (usually, 300 or more particles are measured in order to obtain the average particle size).

The refractive index of the hollow or porous particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and particularly preferably 1.15 to 1.30.
The refractive index here represents the refractive index of the entire particle. When the particle is a hollow particle, the refractive index of the hollow particle is an apparent refractive index, and is a value of the refractive index in a form including a medium. Say. The refractive index can be measured by a conventional ellipsometer. When the particles are porous particles, the refractive index of the porous particles can also be measured using an Abbe refractometer (manufactured by Atago Co., Ltd.).

The hollow or porous particles may be inorganic particles or organic particles such as resin particles, but hollow or porous inorganic particles are preferable from the viewpoint of lowering the refractive index. Examples of the inorganic low refractive index particles include magnesium fluoride and silica particles, and silica particles are more preferable from the viewpoint of low refractive index properties, dispersion stability, and cost.
The average primary particle diameter of these inorganic particles is preferably 1 to 100 nm, and more preferably 1 to 60 nm.
The inorganic particles may be crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical shape, but may be a bead shape, a shape having a ratio of the major axis to the minor axis of 1 or more, or an indefinite shape. Further, the ratio of the major axis to the minor axis is preferably 100 or less.

The specific surface area of the inorganic particles is preferably 10~2,000m ² / g, more preferably 20~1,800m ² / g, further preferably 50~1,500m ² / g .

Inorganic particles are used in a dispersion or coating solution to stabilize the dispersion, or to increase the affinity and binding properties with the binder component, such as a physical surface such as plasma discharge treatment or corona discharge treatment. Although chemical surface treatment with a treatment, a surfactant, a coupling agent, or the like may be performed, particles that are chemically surface treated with a coupling agent are particularly preferable. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
That is, when the inorganic particles are silica particles and the coupling agent is a silane compound, organosilyl groups (monoorganosilyl, diorganosilyl, triorganosilyl groups) are converted into silica particles by the reaction between the silane compound and the silanol group. It binds to the surface. Examples of the organic group that the surface-treated silica particles have on the surface include saturated or unsaturated hydrocarbon groups having 1 to 18 carbon atoms and halogenated hydrocarbon groups having 1 to 18 carbon atoms.
The above-mentioned coupling agent may be used as a surface treatment agent for inorganic particles in order to perform surface treatment in advance before the preparation of the coating solution for low refractive index film, or may be further added as an additive during the preparation of the coating solution.
The inorganic particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

As a silica particle, what is marketed can be used preferably.
For example, Julia Catalytic Chemical's Thruria series (isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK, methylisobutylketone) dispersion, etc.), OSCAL series, Nissan Chemical's Snowtex series ( IPA dispersion, ethylene glycol dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene-n-butanol dispersion, Toluene dispersion, etc.), Silex manufactured by Nippon Steel Mining Co., Ltd., PL series produced by Fuso Chemical Industry Co., Ltd. (IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone content) Etc.), EVONIK Co. Aerosil series (propylene glycol acetate dispersion, ethylene glycol dispersion, MIBK dispersion, etc.), it is possible to use silica particles, such as EVONIK Co. AERODISP series. From the viewpoint of low refractive index, Julia Catalytic Chemical's through rear series is preferred.

  When the silica particles are added to the photosensitive composition as a dispersion containing silica particles and a dispersant (details of the dispersant will be described later), the content of the silica particles in the silica dispersion is 10 to 10. 50 mass% is preferable, 15-40 mass% is more preferable, 15-30 mass% is still more preferable.

The hollow or porous particles may be used alone or in combination of two or more. When using 2 or more types together, you may use a hollow particle and a porous particle together, for example.
The content of the hollow or porous particles with respect to the total mass of the photosensitive low refractive index material layer is preferably 5 to 95 mass%, more preferably 10 to 90 mass%, and more preferably 20 to 90 mass%. More preferably.

When the film is formed using the photosensitive resin composition, the coating amount of the hollow or porous particles is preferably 1 to 100 mg / m ^2, more preferably ^{5~80mg / m 2, 10~60mg / m} 2 Is more preferable. When it is 1 mg / m ² or more, the effect of lowering the refractive index and the effect of improving scratch resistance can be reliably obtained, and when it is 100 mg / m ² or less, fine irregularities are formed on the surface of the film. It is possible to suppress deterioration of the integrated reflectance.

(Component B) Photopolymerization initiator The photosensitive low refractive index material layer contains a photopolymerization initiator.
The photosensitive transfer material of the present invention having a photosensitive low refractive index material layer imparted with photosensitivity by containing a photopolymerization initiator in the photosensitive low refractive index material layer is a photoresist, a color resist, or an optical material. It can be suitably used for a coating material or the like.

The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferred and photoexcited. It may be an activator that produces some action with a sensitizer and generates active radicals, or an initiator that initiates cationic polymerization according to the type of monomer.
Further, the photopolymerization initiator contains at least one component having a molecular extinction coefficient of 50 L / (mol · cm) or more within a wavelength range of about 200 to 800 nm (more preferably 300 to 450 nm). It is more preferable to contain at least one component having a molecular extinction coefficient of 50 to 10 ⁶ L / (mol · cm) within a wavelength range of about 200 to 800 nm (more preferably 300 to 450 nm). preferable.

  Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.

-Photo radical polymerization initiator-
Examples of the radical photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazole compounds, lophine dimers, benzoins, ketals. 2,3-dialkyldione compounds, organic peroxides, thio compounds, disulfide compounds, azo compounds, borates, inorganic complexes, coumarins, ketone compounds (benzophenones, thioxanthones, thiochromanones, anthraquinones) Oximation of aromatic onium salts, fluoroamine compounds, ketoxime ethers, acetophenones (aminoacetophenone compounds, hydroxyacetophenone compounds), acylphosphine compounds such as acylphosphine oxides, and oxime derivatives Things and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. , 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether.

  Examples of borates include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and “Rad Tech'98. Proceeding April” by Kunz, Martin et al., Pages 19-22 (1998, Chicago). ) And the like described in the organic borate. Moreover, the compound of Paragraph 0022-0027 of the said Unexamined-Japanese-Patent No. 2002-116539 is mentioned. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

In addition, as radical polymerization initiators other than the above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-cal Nilbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phenylphosphine oxide, Lucirin TPO, etc.), metallocenes (e.g., bis (eta ^{5-2,4-cyclopentadiene-1-yl)} Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, η ⁵ -cyclopentadienyl-η ⁶ -cumenyl iron (1+) hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A Nos. 53-133428, 57-1819, 57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzo Down propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, such as N- butyl-chloro-acridone and the like.

  The radical polymerization initiator is more preferably a compound selected from the group consisting of aminoacetophenone compounds, hydroxyacetophenone compounds, acylphosphine compounds, and oxime compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, an oxime initiator, and an oxime initiator. As the agent, compounds described in JP-A No. 2001-233842 can also be used.

  As an aminoacetophenone compound, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Japan Ltd.) that are commercially available products can be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE 819 and DAROCUR TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.

  The hydroxyacetophenone compound is preferably a compound represented by the following formula (V).

In formula (V), R ¹ is a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms), or a divalent organic compound. Represents a group. When R ¹ is a divalent organic group, two photoactive hydroxyacetophenone structures (that is, a structure in which the substituent R ¹ is excluded from the compound represented by the formula (V)) are linked via R ¹ It represents a dimer. R ² and R ³ each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). R ² and R ³ may combine to form a ring (preferably a ring having 4 to 8 carbon atoms).
Alkyl and alkoxy group in the R ^1, the alkyl group in R ² and R ^3, as well, the ring R ² and R ³ are formed by bonding, may further have a substituent.

Examples of the hydroxyacetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173), 2-hydroxy-2-methyl-1-phenylbutan-1-one, and 1- (4 -Methylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2-hydroxy-2-methyl-1- (4-octylphenyl) propan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- (4-methoxyphenyl) -2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methylpropan-1-one, 1- (4-Chlorophenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-bromophenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- (4- Hydroxyphenyl) -2-methylpropan-1-one, 1- (4-dimethylaminophenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-carboethoxyphenyl) -2-hydroxy- 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one ( IRGACURE 2959).
In addition, as commercially available α-hydroxyacetophenone compounds, Irgacure 184 (IRGACURE 184), Darocur 1173 (DAROCURE 1173), Irgacure 127 (IRGACURE 127), Irgacure 2959 (IRGACURE 2959), IR Gacure AC 1800 (IRGACURE 1800) from Ciba Specialty Chemicals. 1800), Irgacure 1870 (IRGACURE 1870) and Darocur 4265 (DAROCUR 4265) are also available.

  As the acylphosphine compound, commercially available products IRGACURE 819, IRGACURE 819DW, DAROCUR TPO (trade names: all manufactured by BASF Japan Ltd.) can be used. A phosphine initiator described in JP-A-2009-134098 can also be applied.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE OXE01 (manufactured by BASF Japan), IRGACURE OXE02 (manufactured by BASF Japan), CGI-124 (manufactured by BASF Japan), CGI-242 (manufactured by BASF Japan) are also preferably used as commercial products. It is done.
Furthermore, the cyclic oxime compounds described in JP 2007-231000 A and JP 2007-322744 A can also be suitably used.
Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime compound is preferably a compound represented by the following formula (I). The NO bond of the oxime bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. Good.

（式（Ｉ）中、Ｒ及びＢはそれぞれ独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。）

(In formula (I), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  Preferred examples of the monovalent substituent represented by B in the above formula (I) include an aryl group, a heterocyclic group, an arylcarbonyl group, and a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (II) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A in the above formula (I) include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group having 6 to 12 carbon atoms, and an alkynylene group having 2 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (I), the structure of “SAr” formed by Ar and adjacent S is preferably the following structure from the viewpoint of sensitivity. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (II).

（式（ＩＩ）中、Ｒ及びＸはそれぞれ独立に一価の置換基を表し、Ａ及びＹはそれぞれ独立に二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）

(In formula (II), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)

R, A, and Ar in formula (II) have the same meanings as R, A, and Ar in formula (I), and preferred examples are also the same.
Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (II) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the above formula (II).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (III).

（式（ＩＩＩ）中、Ｒ及びＸはそれぞれ独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）

(In formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)

R, X, A, Ar, and n in the formula (III) are respectively synonymous with R, X, A, Ar, and n in the formula (II), and preferred examples are also the same.
Specific examples (B-1) to (B-10) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and more preferably has a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm.

From the viewpoint of sensitivity, the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 3,000 to 300,000, more preferably 5,000 to 300,000, and 10,000 to 200. Is particularly preferred.
For the measurement of the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, an ethyl acetate solvent is used in an ultraviolet-visible spectrophotometer (Vary, Inc., Carry-5 spectrphotometer). It is preferable to measure at a concentration of 0.01 g / L.

-Photocationic polymerization initiator-
The cationic photopolymerization initiator may be any compound that generates a substance that initiates cationic photopolymerization by receiving energy rays such as ultraviolet rays, preferably an onium salt, more preferably an aromatic onium salt, and an arylsulfonium. Further preferred are salts and aryliodonium salts.

Specific examples of the onium salt include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl- 4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) phenyl] sulfide, η ⁵ -2,4- (Cyclopentadienyl) [(1,2,3,4,5,6-η)-(methylethyl) benzene] iron (1+) and the like. Specific examples of the anion include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl). ₆ ^-), perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion (CF ₃ SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene Examples include sulfonate anions.

  In particular, specific examples of the aromatic onium salt include aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, JP Group VIA aromatic onium salts described in JP-A-52-30899, JP-A-56-55420, JP-A-55-125105, etc., Group VA-aromatics described in JP-A-50-158698, etc. Onium salts, oxosulfoxonium salts described in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., described in JP-A-49-17040, etc. Aromatic diazonium salts, thiobililium salts, iron / allene complexes, aluminum complexes / photolytic silicon compound systems described in US Pat. No. 4,139,655 Initiator, halides that photogenerate a hydrogen halide, o- nitrobenzyl ester compounds, imide sulfonate compound, bissulfonyldiazomethane compounds, mention may be made of an oxime sulfonate compound.

  As the photocationic polymerization initiator that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization can be widely used (edited by Organic Electronics Materials Research Group, “Organization for Imaging”). Materials, "Bunshin Publishing (1993), pages 187-192). These compounds are described in THE CHEMICAL SOCIETY OF JAPAN Voi. 71 no. It can be easily synthesized by a known method as in the case of the photocationic polymerization initiator described in 11, 1998, Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993).

  Commercially available photocationic polymerization initiators include UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide), Adekaoptomer SP-150, SP-151. , SP-170, SP-171, SP-172 (above, manufactured by ADEKA Corporation), Irgacure 261, IRGACURE OXE01, IRGACURE CGI-1397, CGI-1325, CGI-1380, CGI-1311, CGI-263, CGI -268, CGI-1397, CGI-1325, CGI-1380, CGI-1311 (above, manufactured by Ciba Specialty Chemicals), CI-2481, CI-2624, CI-2638, CI-2039 (above, Nippon Soda) CD-1) 10, CD-1011, CD-1012 (manufactured by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (and above) , Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (Nippon Kayaku Co., Ltd.), PHOTOINITIATOR 2074 (Rhodia Co., Ltd.), UR-1104, UR- 1105, UR-1106, UR-1107, UR-1113, UR-1114, UR-1115, UR-1118, UR-1200, UR-1201, UR-1202, UR-1203, UR-1204, UR-1205, UR-1207, UR-1401, UR-1402, UR-1403, UR M1010, UR-M1011, UR-M10112, UR-SAIT01, UR-SAIT02, UR-SAIT03, UR-SAIT04, UR-SAIT05, UR-SAIT06, UR-SAIT07, UR-SAIT08, UR-SAIT09, UR-SAIT10, UR-SAIT11, UR-SAIT12, UR-SAIT13, UR-SAIT14, UR-SAIT15, UR-SAIT16, UR-SAIT22, UR-SAIT30 (above, manufactured by URAY). Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-171, SP-172, CD-1012 and MPI-103 have higher photocuring sensitivity due to the composition containing them. Can be expressed. Said photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  A radical photopolymerization initiator or a cationic photopolymerization initiator may be used alone, or two or more kinds may be freely combined.

  The content of the photopolymerization initiator in the photosensitive low refractive index material layer is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and 1 to 5% by mass. More preferably.

(Component C) Polymer having polymerizable functional group The photosensitive low refractive index material layer contains (Component C) a polymer having a polymerizable functional group.
The polymer structure of component C is not particularly limited, and examples thereof include (meth) acrylic resins, urethane resins, styrene resins, and vinyl resins, and (meth) acrylic resins are preferable.
Component C may be a homopolymer or a copolymer, but is preferably a homopolymer or copolymer of a (meth) acrylate compound, and a copolymer of a (meth) acrylate compound It is more preferable that
Component C preferably has a polar group (hereinafter also referred to as “alkali-soluble group”) in order to easily perform water development or alkali development.
In Component C, the polymerizable functional group or polar group may be present in the main chain of the polymer or in the side chain, but is preferably present in the side chain.

-Polymerizable functional group-
The polymerizable functional group in the present invention is not particularly limited, but is preferably a radical, a cation, or a group having a bond that undergoes a polymerization reaction by heating, an unsaturated group (such as a carbon-carbon unsaturated double bond), an epoxy group, or oxetanyl. Group etc. can be mentioned, It is more preferable that they are an ethylenically unsaturated group or an acetylenic unsaturated group.

  Examples of the ethylenically unsaturated group include (meth) acryloyl group, (meth) acrylamide group, thio (meth) acryloyl group or (meth) acryloyl group, (meth) acrylamide group and ethylenic groups other than thio (meth) acryloyl group An unsaturated group is mentioned.

As the ethylenically unsaturated group or acetylenically unsaturated group other than the above (meth) acryloyl group, (meth) acrylamide group and thio (meth) acryloyl group, a radical polymerizable group, a cationic polymerizable group or a bond that reacts by heating A group having Examples of such ethylenically unsaturated groups or acetylenically unsaturated groups include vinyl groups, allyl groups, propargyl groups, cyclopentenyl groups, cyclohexenyl groups, styryl groups, vinyl ether groups, vinyl ester groups, allyl ether groups, allyl esters. Group, propargyl ether group, propargyl ester group and dicyclopentenyl group are preferable, vinyl group, allyl group, allyl ester group, propargyl ester group and dicyclopentenyl group are particularly preferable, and allyl group is most preferable.
The polymerizable functional group is preferably a (meth) acryloyl group, a (meth) acrylamide group, a thio (meth) acryloyl group, an allyl group or a vinyl group, and a (meth) acryloyl group, a (meth) acrylamide group, an allyl group or vinyl. Group is more preferable, and an allyl group is particularly preferable.

-Polar group (alkali-soluble group)-
Examples of the polar group include an acid group, an alcoholic hydroxyl group, a pyrrolidone group, and an alkylene oxide group. A group that generates a salt by reaction with an alkali developer is preferable, and an acid group is more preferable. Examples thereof include a carboxyl group, an active methylene group, a phosphoric acid group, and a sulfonic acid group.
The polar group is more preferably a carboxyl group or an active methylene group, particularly preferably a carboxyl group, from the viewpoint of low refractive index. As the active methylene group is preferably a group represented by _{-NH-C (O) -CH 2} -C (O) -R M, R M represents an alkyl group or an alkoxy group, these groups May have a substituent such as a fluorine atom. R _M is preferably an alkyl group or alkoxy group having 1 to 6 carbon atoms, and more preferably a methyl group, a trifluoromethyl group, or a methoxy group.
Among these, Component C is preferably a polymer having an allyl group and a carboxyl group, and more preferably a (meth) acrylic resin having an allyl group and a carboxyl group.

In order to introduce a polymerizable functional group into the binder resin, for example, by using a monomer using two types of polymerizable functional groups having different reactivity, a method of polymerizing only one polymerizable functional group having high reactivity, The polymer can be polymerized using a monomer capable of imparting a polymerizable functional group after the polymerization, and a method for performing a treatment for imparting the polymerizable functional group after the polymerization can be performed.
Examples of the combination of two kinds of polymerizable functional groups having different reactivities include a combination of a (meth) acryloxy group and an epoxy group, oxetanyl group, allyl group, vinyl group or propargyl group.
Monomers using two polymerizable functional groups having different reactivities include glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenyl vinyl acrylate, 1-propenyl acrylate, allyl acrylate, and propargyl acrylate. Glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, propargyl methacrylate and the like.

  Examples of the polymer having a polymerizable functional group include, for example, carboxyl group-containing resins, glycidyl group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxy acrylate, and 2-hydroxy methacrylate. Resin in which unsaturated alcohol is reacted, carboxyl group-containing resin having hydroxyl group, free isocyanate group-containing unsaturated compound, resin in which unsaturated acid anhydride is reacted, addition reaction product of epoxy resin and unsaturated carboxylic acid In addition, a resin obtained by reacting a polybasic acid anhydride, a resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride, and a base treatment can be eliminated. A resin having a specific functional group that is generated and gives an unsaturated group is synthesized, and the resin is subjected to basic treatment. Such as ethylene resin to produce a unsaturated group can be cited as typical resin be subjected.

  Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate or allyl glycidyl ether, or a resin obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester compound ( ) Resin obtained by reacting (meth) acrylic acid ester having a free isocyanate group such as acrylic acid-2-isocyanatoethyl, resin having structural units represented by formulas (21) to (23) described later, and base treatment A resin having a specific functional group that causes an elimination reaction to give an ethylenically unsaturated group was synthesized, and the resin was subjected to a base treatment to generate an ethylenically unsaturated group while maintaining an alkali-soluble group. A resin or the like is more preferable.

  The alkali-soluble binder resin having a polymerizable functional group preferably contains at least one selected from structural units represented by any of the following formulas (21) to (23).

In the above formulas (21) to (23), A ¹ , A ² and A ³ each independently represents an oxygen atom, a sulfur atom or —N (R ²¹ ) —, and R ²¹ may have a substituent. Represents a good alkyl group. G ¹ and G ² each independently represent a divalent linking group. G ³ represents a single bond or a divalent linking group. X represents an oxygen atom, a sulfur atom or —N (R ²² ) —, and R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents an alkyl group which may have a substituent. Z represents a single bond, an oxygen atom, a sulfur atom or —N (R ²² ) —. R ^{1 to} R ²⁰ each independently represents a hydrogen atom or a monovalent substituent.

In the above formula (21), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. ¹ and R ² are preferably a hydrogen atom, and R ³ is preferably a hydrogen atom or a methyl group.
R ^{4 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and examples of R ⁴ include a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom, A methyl group and an ethyl group are preferred. R ⁵ and R ⁶ may each independently have a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. A good aryl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ¹ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and X represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Here, examples of R ²¹ and R ²² include an alkyl group which may have a substituent.
G ¹ represents a divalent linking group, but an alkylene group that may have a substituent is more preferable. More preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be present may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, or cyclo that may have a substituent having 3 to 10 carbon atoms. An alkylene group and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferable in terms of performance such as strength and developability.

Here, the substituent in G ¹ is preferably a group in which a hydrogen atom is bonded to a heteroatom, excluding a hydroxyl group, for example, a group not containing an amino group, a thiol group, or a carboxyl group.

In the formula (22), R ^{7 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. ⁷ and R ⁸ are preferably hydrogen atoms, and R ⁹ is preferably a hydrogen atom or a methyl group.
R ^{10 to} R ¹² each independently represents a hydrogen atom or a monovalent substituent. Specific examples of R ^{10 to} R ¹² include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, and a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group may be mentioned. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.
Here, examples of the substituent that can be introduced include those exemplified in the formula (21).

A ² represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and examples of R ²¹ include a hydrogen atom and an alkyl group which may have a substituent.
G ² represents a divalent linking group, but an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ² is preferably a group in which a hydrogen atom is bonded to a heteroatom, excluding a hydroxyl group, for example, a group not containing an amino group, a thiol group, or a carboxyl group.
Y represents an oxygen atom, a sulfur atom, -N (R ²³⁾ - represents a or phenylene group which may have a substituent. Here, examples of R ²³ include a hydrogen atom and an alkyl group which may have a substituent.

In the above formula (23), R ^{13 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. ¹³ and R ¹⁴ are preferably hydrogen atoms, and R ¹⁵ is preferably a hydrogen atom or a methyl group.
R ^{16 to} R ²⁰ each independently represents a hydrogen atom or a monovalent substituent. R ^{16 to} R ²⁰ are, for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, or a nitro group. , A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, substituted An alkylsulfonyl group which may have a group, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, a substituent The aryl group which may have is preferable. Examples of the substituent that can be introduced include those listed in Formula (21).
A ³ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and Z represents a single bond, an oxygen atom, a sulfur atom, or —N (R ²² ) —. Examples of R ²¹ and R ²² are the same as those in formula (21). Z is preferably a single bond.

G ³ represents a single bond or a divalent linking group, preferably a single bond or an alkylene group which may have a substituent, more preferably a single bond, and both G ³ and Z are a single bond. Particularly preferred. The divalent linking group is preferably an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or 6 to 6 carbon atoms. Examples thereof include an aromatic group which may have 20 substituents, among which a linear or branched alkylene group having 1 to 10 carbon atoms and a substituent having 3 to 10 carbon atoms which may have a substituent. From the viewpoints of performance such as strength and developability, a cycloalkylene group which may have an aromatic group and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferable.
Here, the substituent in G ³ is preferably a group in which a hydrogen atom is bonded to a heteroatom, excluding a hydroxyl group, for example, a group not containing an amino group, a thiol group, or a carboxyl group.

  The structural unit represented by the above formulas (21) to (23) is preferably a compound contained in one molecule in a range of 20 mol% or more and less than 95 mol% from the viewpoint of improving curability and reducing development residue. The compound contained in the range of more than mol% and less than 90 mol% is more preferable, and the compound contained in the range of more than 30 mol% and less than 85 mol% is still more preferable.

  The synthesis | combination of the polymer which has a structural unit represented by the said Formula (21)-(23) can be performed based on the synthesis method of Paragraph 0027-0057 of Unexamined-Japanese-Patent No. 2003-262958. Among these, it is preferable to use the synthesis method 1) in the publication.

  In order to introduce an epoxy group into a polymer, for example, a monomer having an epoxy group (hereinafter sometimes referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types. When the monomer component for obtaining the polymer also includes the monomer for introducing the epoxy group, the content ratio is not particularly limited, but is 5 to 70% by mass in the total monomer component, preferably It is good that it is 10-60 mass%.

In order to introduce a polar group into a polymer, for example, a monomer having a polar group and / or a monomer capable of imparting a polar group after polymerization (hereinafter also referred to as “monomer for introducing a polar group”). May be polymerized as a monomer component. In addition, when introduce | transducing a polar group by using the monomer which can provide an acid group after superposition | polymerization as a monomer component, the process for providing a polar group as mentioned later after superposition | polymerization is needed.
Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, and carboxylic acids such as maleic anhydride and itaconic anhydride. Although the monomer etc. which have an acid anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of monomers that can impart an acid group after polymerization include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meth). And monomers having an isocyanate group such as acrylate.
In the case of using a monomer capable of imparting an acid group after polymerization, the treatment for imparting the acid group after polymerization includes a treatment of modifying a part of the polar group of the polymer side chain by a polymer reaction.
Examples of the monomer having an alcoholic hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-hydroxy. Examples thereof include propyl methacrylate and 4-hydroxybutyl methacrylate.
Examples of the monomer capable of imparting an alcoholic hydroxyl group after polymerization include monomers having an epoxy group such as glycidyl (meth) acrylate.
Examples of the monomer having an epoxy group include glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like.
Examples of the monomer capable of imparting an epoxy group after polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate, and the like. It is done.
Only one type of monomer for introducing these polar groups may be used, or two or more types may be used.

  Examples of the monomer copolymerizable with a monomer having a polymerizable functional group or a monomer having a polar group that can be suitably used for synthesizing Component C include the following compounds (1) to (11).

(1) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl and 2-allyloxyethyl acrylate;

(2) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, methacryl Alkyl methacrylates such as hexyl acid, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 2-allyloxyethyl methacrylate;

(3) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.

(4) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(5) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(6) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

(7) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(8) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(9) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.

(10) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.

(11) Methacrylic acid monomers having a hetero atom bonded to the α-position, for example, compounds described in JP-A No. 2002-309057, JP-A No. 2002-311569 and the like can be mentioned.

  Component C includes (meth) acrylic resins having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and side chains described in JP-A Nos. 2000-187322 and 2002-62698. And an alkali-soluble resin having a double bond.

  Component C may be any of a random polymer, block polymer, graft polymer and the like.

Component C can be synthesized by a conventionally known method.
Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, 2-methoxyethyl acetate, Diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water, etc. Is mentioned.
These solvents are used alone or in combination of two or more.

The radical polymerization initiator used in the synthesis of component C includes benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, and t-butyl peroxide. Examples thereof include organic peroxides such as oxybenzoate and azo compounds such as 2,2′-azobisisobutyronitrile.
These radical polymerization initiators are preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the monomer.

  Specific examples of Component C include (E-1) to (E-7) below, but are not particularly limited thereto. The numerical value shown in each unit represents the mole fraction of each unit in the resin molecule.

  Among these, the component C is preferably a copolymer obtained by copolymerizing at least allyl (meth) acrylate, and is a copolymer obtained by copolymerizing allyl (meth) acrylate and (meth) acrylic acid. Is more preferable, and a copolymer obtained by copolymerizing allyl methacrylate and methacrylic acid is particularly preferable. In the above embodiment, sufficient curability can be ensured even if the component A is contained in a large amount, and a layer having a lower refractive index and excellent in-plane film thickness uniformity after transfer is obtained. Can do.

  The polystyrene equivalent number average molecular weight (Mn) of component C by gel permeation chromatography (GPC) method is preferably 400 to 50,000, more preferably 600 to 40,000, and most preferably 800 to 30,000. . The polystyrene-converted weight average molecular weight (Mw) of Component C by gel permeation chromatography (GPC) method is preferably 1,500 to 200,000, more preferably 2,400 to 150,000, and 3,000 to 120,000 is most preferred. If the weight average molecular weight and the number average molecular weight are within the above ranges, Component C has good solubility and can be cured without being dissipated during heating. More specifically, if the number average molecular weight is 400 or more, good coatability and curability can be obtained, and if the number average molecular weight is 50,000 or less, good developability is obtained.

When Component C has an acid group, the acid value of Component C is preferably 30 to 300 mgKOH / g, more preferably 50 to 200 mgKOH / g, and particularly preferably 70 to 160 mgKOH / g. When the acid value is within this range, the development residue is less likely to remain during pattern formation, and the coating uniformity is further improved.
When the polymerizable functional group of component C is an ethylenically unsaturated group, from the viewpoint of improving photosensitivity, the unsaturated value of component C is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more. 1.0 mmol / g or more is most preferable. The unsaturated value of component C is preferably 10 mmol / g or less. Here, the unsaturated value means the number of millimole of the unsaturated bond per 1 g of the binder polymer.
By making the unsaturated equivalent of component C 0.1 mmol / g or more, that is, by increasing the number of ethylenically unsaturated bonds in this resin, photopolymerizability and sensitivity are improved. The improvement improves the adhesion to the solid surface such as the support and the fixing property of the contained hollow or porous particles, and as a result, there are few defects in the hollow or porous particles in the pattern film in the development, and the tapered shape. A pattern having a rectangular cross-sectional shape tends to be obtained, which is preferable.

Component C may be used alone or in combination of two or more.
The content of component C in the photosensitive low refractive index material layer is blended at a ratio of 0.01 to 25% by mass with respect to the total mass of the photosensitive low refractive index material layer. It is preferable from a viewpoint of property, and adding in 3-20 mass% is still more preferable. When the content of Component C is in the range of 3 to 20% by mass, the film can be given hardness while taking advantage of the low refractive index property of the hollow or porous particles.

(Component D) Monomer The photosensitive low refractive index material layer in the photosensitive transfer material of the present invention contains (Component D) a monomer (also referred to as “polymerizable compound”).
However, Component D is a compound other than (Component C) a polymer having a polymerizable functional group, a compound having a molecular weight of less than 1,500, preferably a compound having a molecular weight of less than 1,000, and having a molecular weight of less than 800. More preferably, it is a compound. Component D is preferably a compound having a molecular weight of 50 or more.
Hereinafter, the monomer will be described.

Specifically, the monomer is a compound having at least one ethylenically unsaturated bond, and preferably a compound having two or more ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or a mixture thereof and a (co) polymer thereof. The monomer in this invention may be used individually by 1 type, and may use 2 or more types together.
The monomer is preferably a compound having an ethylenically unsaturated bond at the molecular end.

Preferred examples of the monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. More preferred are esters with aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group or mercapto group, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogeno group A substituted reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as thiol or tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in JP-A-2009-288705, paragraphs 0095 to 0108 can also be suitably used in the present invention.

  As the monomer, a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure (1 atm) having at least one addition-polymerizable ethylenically unsaturated group is also preferable. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Polyfunctional alcohols such as nurate, glycerin and trimethylolethane added with ethylene oxide or propylene oxide and then (meth) acrylated, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates described in JP-B-48-64183, JP-B-49-43191, JP-B-52-30490, epoxy Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of a resin and (meth) acrylic acid, and mixtures thereof.

Further, as the compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. It is.
Moreover, as a monomer, the ethylenically unsaturated compound which can be used for manufacture of the component C mentioned above can also be used suitably.

  In addition to the above, monomers represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In formula (MO-1)-(MO-5), n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
As specific examples of the monomers represented by the formulas (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of JP-A-2007-2699779 are also preferably used in the present invention. Can do.

Component D preferably includes a monomer having a fluorine atom, and more preferably includes a polyfunctional monomer having a fluorine atom. In the above embodiment, a photosensitive low refractive index material layer having a lower refractive index can be obtained.
Moreover, as a monomer which has a fluorine atom, the (meth) acrylate compound which has a fluorine atom is preferable, and the polyfunctional (meth) acrylate compound which has a fluorine atom is more preferable.
As the polyfunctional monomer having a fluorine atom, a compound represented by the following formula (Df) is preferable.

（式（Ｄｆ）中、Ｒ¹は、酸素原子を含んでいてもよいｎ価のフッ化アルキル基又は４級炭素を表し、Ｒ²はそれぞれ独立に、酸素原子を含んでもよい一価のフッ化アルキル基又はフッ素原子を表し、ｍはそれぞれ独立に、０又は１を表し、ｎは２以上の整数を表し、Ｇはそれぞれ独立に、エチレン性不飽和結合を有する基を表す。）

(In the formula (Df), R ¹ represents an n-valent fluorinated alkyl group or a quaternary carbon which may contain an oxygen atom, and each R ² independently represents a monovalent fluorine which may contain an oxygen atom. An alkyl group or a fluorine atom, m independently represents 0 or 1, n represents an integer of 2 or more, and G independently represents a group having an ethylenically unsaturated bond.)

In the formula (Df), the n-valent fluorinated alkyl group in R ^{1 and} the n-valent fluorinated alkyl group in R ¹ may be linear, branched or cyclic fluorinated alkyl groups, As carbon number, it is preferable that it is 1-20, it is more preferable that it is 1-10, and it is still more preferable that it is 1-5.
R ¹ in formula (Df) is preferably an n-valent perfluoroalkyl group or a quaternary carbon, and more preferably a quaternary carbon.
R ² in Formula (Df) is preferably an n-valent perfluoroalkyl group or a fluorine atom, and more preferably a fluorine atom.
M in the formula (Df) is preferably 1.
N in the formula (Df) is preferably an integer of 3 to 20, more preferably an integer of 3 to 10, still more preferably an integer of 3 to 6, and particularly preferably 4. .
G in the formula (Df) is preferably a (meth) acryl group, a vinyl group or an allyl group, and more preferably a (meth) acryl group.

  Specific examples of the polyfunctional monomer having a fluorine atom include the following, but the present invention is not limited thereto.

  Although there is no restriction | limiting in particular as a synthesis method of the monomer which has the above fluorine atoms, The method as described in Unexamined-Japanese-Patent No. 2008-280294 can be mentioned suitably.

Component D may be contained singly or in combination of two or more.
The content of Component D in the photosensitive low refractive index material layer is preferably from 0.1 to 30% by mass, more preferably from 0.2 to 20% by mass, based on the total mass of the photosensitive low refractive index material layer. 0.3 to 15% by mass is particularly preferable.

<Other ingredients>
The photosensitive low refractive index material layer may further contain optional components described in detail below, if necessary, as long as the effects of the present invention are not impaired.
Hereinafter, optional components that can be contained in the photosensitive low refractive index material layer will be described.

(Component E) Surfactant The photosensitive low refractive index material layer preferably contains a surfactant.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

  In particular, since the photosensitive resin composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved. That is, in the case of forming a film using a coating liquid to which a photosensitive composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Japan Rouble) Zole Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. It is.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by BYK Chemie.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive low refractive index material layer is preferably 10 parts by mass or less with respect to 100 parts by mass of the total mass of the photosensitive low refractive index material layer. It is more preferable that it is a mass part, and it is still more preferable that it is 0.01-3 mass parts.

(Component F) Dispersant The photosensitive low refractive index material layer preferably further contains (Component F) a dispersant from the viewpoint of improving the dispersibility of the hollow or porous particles.
Dispersants include polyamidoamine and its salts, polycarboxylic acid and its salts, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid A dispersion resin such as a formalin condensate and a compound such as a polyoxyethylene alkyl phosphate ester, a polyoxyethylene alkyl amine, and an alkanol amine can be exemplified, but a resin is preferable (hereinafter referred to as “dispersion resin”). Also called.) In addition, the component F shall not have a polymeric group.
Dispersing resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

  The dispersion resin is adsorbed on the surface of the particles and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.

The weight average molecular weight of the dispersing resin (measured in terms of polystyrene by GPC method) is preferably 1,000~2 × 10 ^5, more preferably in a 2,000~1 × 10 ^{5, 5,} 000 to 5 × 10 ⁴ is particularly preferable.

  The dispersion resin is also available as a commercial product. As such a specific example, “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group) manufactured by BYK Chemie. ), 111, 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA Corporation “EFKA 4047, 4050-4010-4165 (polyurethane)”, EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (Fatty acid polyester), 6745 (phthalosy Nin derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703, manufactured by Enomoto Kasei Co., Ltd. 50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation, “Homogenol L-18 (polymeric polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxy) Tylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (end part) manufactured by Lubrizol Corporation 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene mono) manufactured by Nikko Chemicals Co., Ltd. " Stearate), manufactured by Morishita Sangyo Co., Ltd. “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450”, Sun Examples thereof include dispersion resins such as “Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100” manufactured by Nopco Corporation.

The dispersion resin may have at least one selected from the group consisting of structural units represented by any of the formulas (21) to (23) in the component C described above.
Further, the dispersion resin may be a resin obtained by using the compound represented by the formula (E-1) in Component C described above as a copolymerization monomer.

These dispersants may be used alone or in combination of two or more.
The content of the dispersant in the photosensitive low refractive index material layer is preferably 1 to 100% by mass, more preferably 5 to 80% by mass with respect to the content of the hollow or porous particles. More preferably, it is 60 mass%.
Specifically, when the dispersant is a dispersion resin, the amount used is preferably 5 to 100% by mass, and 10 to 80% by mass with respect to the content of the hollow or porous particles. Is more preferable.

(Component G) Sensitizer The photosensitive low refractive index material layer may contain a sensitizer for the purpose of improving radical generation efficiency such as a photopolymerization initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, those that sensitize the above-described photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer used in the photosensitive low refractive index material layer include compounds described in paragraphs 0101 to 0154 of JP-A-2008-32803.
In the case of containing a sensitizer, the content of the sensitizer in the photosensitive low refractive index material layer is the total of the photosensitive low refractive index material layer from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency. It is preferable that it is 0.1-20 mass% with respect to mass, and 0.5-15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

(Component H) Polymerization inhibitor In the photosensitive low refractive index material layer, in order to prevent unnecessary thermal polymerization of the monomer during the production of the photosensitive low refractive index material layer or during storage of the photosensitive transfer material. A small amount of a polymerization inhibitor may be added.
As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned.

When the polymerization inhibitor is contained, the addition amount of the polymerization inhibitor is preferably 0.0005 to 5% by mass with respect to the total mass of the photosensitive low refractive index material layer.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and unevenly distributed on the surface of the coating film during the drying process after coating. Good. When the photosensitive low refractive index material layer contains a higher fatty acid derivative, the addition amount of the higher fatty acid derivative may be 0.5 to 10% by mass with respect to the total mass of the photosensitive low refractive index material layer. preferable.

(Component I) Adhesion promoter The photosensitive low refractive index material layer may contain any adhesion promoter as long as the object of the present invention is not impaired.
Examples of the adhesion promoter include 3-glycidyloxypropyltrimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- Examples include aminopropyltrimethoxysilane. In addition, the compounds described in paragraph 0048 of JP2008-243945A can be used.
When the adhesion promoter is contained, the preferred amount of the adhesion promoter is not particularly limited, but is preferably 10% by mass or less, based on the total mass of the photosensitive low refractive index material layer, 0.005 More preferably, it is -5 mass%.

-Other additives-
Further, the photosensitive low refractive index material layer may contain known additives such as inorganic fillers and plasticizers in order to improve the physical properties of the cured film.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. When a plasticizer is used, it is preferable to add 10% by mass or less based on the total mass of Component C and Component D.

The photosensitive composition used for forming the photosensitive low refractive index material layer generally contains an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the applicability of the photosensitive composition are satisfied, and in particular, the organic solvent should be selected in consideration of the solubility, applicability and safety of the binder. Is preferred. Examples of the organic solvent include various solvents described in paragraph 0187 of JP-A-2008-32803.

  Specific examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and methyl lactate. , Ethyl lactate, alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc. And 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate) , Methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, And methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropion Acid methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, aceto Ethyl, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether. (PGME: alias 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA: alias 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-described components and the solubility of the above-described components and improvement of the coated surface. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, methyl ethyl ketone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

  As content in the photosensitive composition of an organic solvent, it is preferable to set it as the quantity from which a total solid content concentration in a composition will be 5-80 mass% from a viewpoint of applicability | painting, and will be 5-60 mass%. The amount is more preferable, and the amount that becomes 10 to 50% by mass is particularly preferable.

<Method for forming photosensitive low refractive index material layer>
The method for forming the photosensitive low refractive index material layer is not particularly limited. For example, a photosensitive resin composition containing at least component A to component D and an organic solvent is spin coated, roller coated, dip coated, scanned. After applying to the support by any method such as spraying, spraying, bar coating, ink jet, etc., the organic solvent is removed by heat treatment as necessary to form a coating film (photosensitive low refractive index material layer) It can form by forming and performing a prebaking process.

  As a method of applying to the support, a spin coating method, a scanning method, and an ink jet method are preferable. Particularly preferred is a spin coating method. A commercially available apparatus can be used for the spin coating method. For example, a clean truck series (manufactured by Tokyo Electron Co., Ltd.), D-spin series (manufactured by Dainippon Screen Mfg. Co., Ltd.), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used.

  The spin coating conditions may be any rotational speed. In the method for discharging the photosensitive resin composition, either dynamic discharge for discharging the photosensitive resin composition onto a rotating support or static discharge for discharging the photosensitive resin composition onto a stationary support. However, dynamic discharge is preferable from the viewpoint of in-plane uniformity of the film. In addition, from the viewpoint of suppressing the consumption of the composition, a method of preliminarily discharging only the main solvent of the composition onto the support to form a liquid film and then discharging the composition from the top is used. You can also. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the support, it is also preferable to perform a treatment (edge rinse, back rinse) so as not to leave the film on the edge of the support.

  Note that the photosensitive resin composition can be easily cleaned and removed using a known cleaning liquid even when it adheres to, for example, the nozzle of the coating apparatus discharge section, the piping section of the coating apparatus, or the inside of the coating apparatus. In this case, in order to perform more efficient cleaning and removal, it is preferable to use the organic solvent listed above as the organic solvent contained in the photosensitive composition as the cleaning liquid.

JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can also be suitably used as a cleaning liquid for cleaning and removing the photosensitive resin composition.
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and still more preferably 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the photosensitive resin composition, the surfactant described above as a surfactant that can be contained in the photosensitive resin composition may be added to the cleaning liquid.

  The pre-bake treatment method is not particularly limited, and generally used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. are applied. be able to. A heating method using hot plate heating or furnace is preferable. A commercially available device can be preferably used as the hot plate, and the Clean Track Series (manufactured by Tokyo Electron), D-Spin Series (manufactured by Dainippon Screen Mfg. Co., Ltd.), SS Series or CS Series (Tokyo Ohka Kogyo Co., Ltd.) )) And the like can be preferably used. As the furnace, Cx series (manufactured by Tokyo Electron Ltd.) and the like can be preferably used. Examples of the prebaking condition include a condition of heating at 60 ° C. to 150 ° C. (preferably 60 ° C. to 120 ° C.) for 0.5 to 15 minutes using a hot plate or an oven.

<Layer structure of photosensitive transfer material>
The photosensitive transfer material of the present invention is obtained by providing at least the above-mentioned photosensitive low refractive index material layer on a support, and if necessary, a thermoplastic resin layer, an intermediate layer, and / or a protective layer. Can be provided.
The photosensitive low refractive index material layer may be provided at least on the support, may be in direct contact with the support, or may be provided via another layer. It may be provided on the entire upper surface or a part thereof.
The film thickness of the photosensitive low refractive index material layer is preferably in the range of 0.01 to 2.0 μm, more preferably in the range of 0.1 to 1.5 μm, and still more preferably in the range of 0.2 to 1.0 μm. .

FIG. 1 is a schematic cross-sectional view of an example of a preferred embodiment of the photosensitive transfer material of the present invention.
In the photosensitive transfer material 10 shown in FIG. 1, a thermoplastic resin layer 14, an intermediate layer 16, a photosensitive low refractive index material layer 18, and a protective layer 20 are provided on a support 12 in this order. An antistatic layer 22 is provided on the opposite surface of 12.
When transferring using the photosensitive transfer material 10, the protective layer 20 is removed in advance.
The thermoplastic resin layer 14 and the intermediate layer 16 are preferably actinic ray transmissive layers so that the photosensitive low refractive index material layer 18 can be easily exposed.

<Support (temporary support)>
There is no restriction | limiting in particular as a support body in the photosensitive transfer material of this invention, Well-known support bodies, such as polyester and a polystyrene, can be used.
The support in the photosensitive transfer material of the present invention is unnecessary after the photosensitive low refractive index material layer is transferred to a desired transfer target such as a substrate, and is also referred to as a “temporary support”. The support is preferably removed simultaneously with or after the transfer of the photosensitive low refractive index material layer.
Among these, as the support, a polyethylene terephthalate film is preferable from the viewpoints of cost, heat resistance, and dimensional stability.
The thickness of the support is preferably 15 to 200 μm, more preferably 30 to 150 μm. When the thickness of the support is within the above range, it is possible to effectively suppress the occurrence of the wrinkle of the tin plate due to heat during the lamination process, which is advantageous in terms of cost.

<Thermoplastic resin layer>
Further, it is preferable to provide a thermoplastic resin layer between the support and the photosensitive low refractive index material layer or between the support and the intermediate layer. The thermoplastic resin layer is preferably removed at the same time as or after the transfer of the photosensitive low refractive index material layer. Moreover, it is preferable that the said thermoplastic resin layer is alkali-soluble.
The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness on the base surface (including unevenness due to an already formed image, etc.). It is preferable to have a property that can be deformed.

Examples of the alkali-soluble resin contained in the thermoplastic resin layer include saponified products of ethylene and acrylic acid ester copolymers, saponified products of styrene and (meth) acrylic acid ester copolymers, vinyltoluene and (meth). Saponified product such as saponified product with acrylic ester copolymer, poly (meth) acrylic acid ester, and (meth) acrylic acid ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. It is preferable that there is at least one. In addition, use organic polymers soluble in alkaline aqueous solutions from the "Plastic Performance Handbook" (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968). You can also.
Of these thermoplastic resins, those having a softening point of 80 ° C. or less are preferable. Moreover, it is preferable that a softening point is 30 degreeC or more.

Among the resins contained in the thermoplastic resin layer, it is preferable to select and use a weight average molecular weight in the range of 3,000 to 500,000 (Tg = 0 to 170 ° C.), and further a weight average molecular weight of 4,000 to 200,000. A range of (Tg = 30 to 140 ° C.) is more preferable.
Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-44615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP 60-159743, JP 60-247638, JP 60-208748, JP 60-214354, JP 60-230135, JP 60-258539, JP JP 61-1669829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP 64- No. 5551, JP-A 64-55550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-5-241340 Examples thereof include resins that are soluble in an alkaline aqueous solution.

  Of these, methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159, JP-B-55-38961, Examples thereof include styrene / (meth) acrylic acid copolymers described in each publication of No. 5-241340.

The thermoplastic resin layer has various plasticizers, various polymers, supercooling substances, adhesion improvers, surfactants or mold release agents, etc. in order to adjust the adhesive force between the thermoplastic resin layer and the support. Can be added.
Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono ( Addition reaction product with (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of rate, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate.
The amount of the plasticizer in the thermoplastic resin layer is preferably 200% by mass or less, and more preferably 20 to 100% by mass with respect to the total mass of the thermoplastic resin.

The thickness of the thermoplastic resin layer is preferably 1 μm or more. If the thickness of the thermoplastic resin layer is 1 μm or more, irregularities on the base surface can be completely absorbed.
The upper limit is preferably 100 μm or less and more preferably 50 μm or less from the viewpoint of developability and production suitability.

In the present invention, the solvent of the coating solution used when forming the thermoplastic resin layer can be used without particular limitation as long as it dissolves the resin constituting this layer.
Examples of the solvent include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.

<Intermediate layer>
In the photosensitive transfer material of the present invention, an intermediate layer may be provided between the support and the photosensitive low refractive index material layer. The intermediate layer is preferably removed at the same time as or after the transfer of the photosensitive low refractive index material layer.
The resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble.
Examples of the resin constituting the intermediate layer include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Can be mentioned.
A resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is not usually alkali-soluble, such as a polyester resin, can also be preferably used.
Of these, polyvinyl alcohol is preferred.
The polyvinyl alcohol preferably has a saponification degree of 80% or more, more preferably 83 to 98%.

The resin constituting the intermediate layer may be used singly or in combination of two or more, but preferably used in combination of two or more, polyvinyl alcohol and polyvinyl pyrrolidone, It is particularly preferable to use a mixture of these. The mass ratio between the two is preferably polyvinyl pyrrolidone / polyvinyl alcohol = 1/99 to 75/25, more preferably 10/90 to 50/50. When the mass ratio is in the above range, the surface shape of the intermediate layer is good, the adhesiveness with the photosensitive light-shielding layer coated thereon is good, and further, the oxygen barrier property is lowered and the sensitivity is lowered. Can be prevented.
Note that an additive such as a surfactant can be added to the intermediate layer as necessary.

The intermediate layer preferably has a thickness of 0.1 to 5 μm, and more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, it is possible to prevent an increase in the intermediate layer removal time during development without reducing the oxygen barrier property.
The coating solvent for the intermediate layer is not particularly limited as long as the above resin dissolves, but water is particularly preferable, and a mixed solvent obtained by mixing water with the above-described water-miscible organic solvent is also preferable.
Specific examples of preferable coating solvents include, for example, water, water / methanol = 90/10, water / methanol = 70/30, water / methanol = 55/45, water / ethanol = 70/30, water / 1-propanol. = 70/30, water / acetone = 90/10, water / methyl ethyl ketone = 95/5 (where the ratio represents a mass ratio) and the like.

<Other layers>
The photosensitive transfer material of the present invention may have an antistatic layer as necessary. The antistatic layer is preferably provided on the surface of the support opposite to the surface on which the photosensitive low refractive index material layer is provided.
As an antistatic layer, the electroconductive layer described in Unexamined-Japanese-Patent No. 11-149008 is mentioned, for example.
Further, the photosensitive transfer material of the present invention may have a protective layer as necessary in order to prevent adhesion of dirt or the like to the photosensitive low refractive index material layer. The protective layer is preferably provided on the photosensitive low refractive index material layer.
The protective layer may be a layer made of a known material, but a resin film is preferable. More preferable examples of the material for the resin film include polypropylene, polyvinyl alcohol, and polyvinyl pyrrolidone.
Further, the photosensitive transfer material of the present invention may have a known layer other than those described above, if necessary.

<Production of photosensitive transfer material>
As a method for producing the photosensitive transfer material of the present invention, for example, a photosensitive resin composition containing at least component A to component D is used on a support, for example, a spinner, a wheeler, a roller coater, a curtain coater, or a knife coater. A method of forming by applying and drying using a coating machine such as a wire bar coater or an extruder is preferred.
In the case of providing an alkali-soluble thermoplastic resin layer, it can be formed in the same manner.
The photosensitive resin composition preferably contains an organic solvent. A coating film having a thin film and high film thickness uniformity can be produced with the above embodiment.

(Substrate having a photosensitive low refractive index transfer layer)
The substrate having the photosensitive low refractive index transfer layer of the present invention is a substrate having a photosensitive low refractive index transfer layer obtained by transferring the photosensitive low refractive index material layer from the photosensitive transfer material of the present invention.
A method for producing the substrate having the photosensitive low refractive index transfer layer is not particularly limited, but the photosensitive transfer material of the present invention is applied to the photosensitive transfer material on a substrate, preferably a light-transmitting substrate. The low-refractive-index material layer is placed so as to be in contact with each other, and then the support is peeled off from the laminate of the photosensitive transfer material and the substrate. A method of developing and forming a substrate having a photosensitive low refractive index transfer layer is preferred.
This method for producing a substrate having a photosensitive low refractive index transfer layer does not require complicated steps and is low in cost.

(Method for producing photosensitive low refractive index transfer layer)
The method for producing the photosensitive low refractive index transfer layer of the present invention is not particularly limited as long as it is a method using the photosensitive transfer material of the present invention. (Also referred to as “preparation step”), and a step of laminating the photosensitive transfer material on the member to be transferred such that the member to be transferred and the photosensitive low refractive index material layer are in contact (hereinafter also referred to as “lamination step”). And a step of peeling the support of the photosensitive transfer material (hereinafter also referred to as “peeling step”).
In the preparation step, the photosensitive transfer material of the present invention may be produced by the method described above.
As a member to be transferred in the laminating step, on a reflector, a light guide plate, a glass substrate, a substrate on which various metal layers are formed, a substrate on which a plastic film is formed, a diffusion sheet, a prism sheet, An optical sheet such as a microlens unit can be used. Among them, optical sheets such as a diffusion sheet, a prism sheet, and a microlens unit are preferable, and it is more preferable to manufacture a backlight module by laminating the transfer material of the present invention between optical sheets.
There is no restriction | limiting in particular as the peeling method of the support body in the said peeling process, What is necessary is just to peel by a well-known method.
Moreover, the manufacturing method of the photosensitive low refractive index transfer layer of the present invention may include other known steps.

(Permanent film formation method)
The method for forming a permanent film of the present invention is not particularly limited as long as it is a method using the photosensitive transfer material of the present invention, but is also a step of preparing the photosensitive transfer material of the present invention (also referred to as “preparation step”). ), A step of laminating the photosensitive transfer material on the member to be transferred such that the member to be transferred and the photosensitive low refractive index material layer are in contact with each other (also referred to as “lamination step”), and supporting the photosensitive transfer material. A step of peeling the body (also referred to as “peeling step”) and a step of exposing the transferred photosensitive low refractive index material layer (photosensitive low refractive index transfer layer) (also referred to as “exposure step”). It is preferable to contain.
Preferred embodiments of the preparation step, the lamination step, and the peeling step in the method for forming a permanent film of the present invention are the preferred embodiments of the preparation step, the lamination step, and the separation step in the method for producing the photosensitive low refractive index transfer layer of the present invention described above. It is the same.

The exposure in the exposure step is performed through a mask as necessary.
Examples of the actinic ray or radiation for exposure in the exposure step include infrared light, g-rays, h-rays, i-rays, KrF light, ArF light, X-rays, and electron beams. From the viewpoint of exposure amount, sensitivity, and resolution, i-line, KrF light, ArF light, and electron beam are preferable, and from the viewpoint of versatility, i-line and KrF light are most preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} . When using KrF light, it is preferable to irradiate with an exposure dose of 30 mJ / cm ^{2 to} 300 mJ / cm ² .
Moreover, you may heat-process the exposed layer using a hotplate and oven as needed. The heating conditions are not particularly limited, but are preferably 70 ° C. to 180 ° C. and 0.5 to 15 minutes, for example.
In the exposure process, the photopolymerization initiator is decomposed to generate polymerization initiation species. The polymerizable functional group of component C, component D and the like are polymerized by the generated polymerization initiating species, and the exposed portion is cured to obtain a permanent film.
As the exposure light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.

The method for forming a permanent film of the present invention may further include a step of developing the exposed photosensitive low refractive index material layer (also referred to as “development step”).
In the development step, unexposed portions that have not been cured are removed with a developer and developed to form a negative image (permanent film).
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include a 0.4% by mass aqueous solution, a 0.5% by mass aqueous solution, a 0.7% by mass aqueous solution, or a 2.38% by mass aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After the development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.

In addition, the method for forming a permanent film of the present invention includes a step of heating and / or exposing the developed photosensitive low refractive index material layer as necessary after the development step (“post-heating and / or post-exposure step”). May also be included. Thereby, light resistance, climate resistance, and film strength can be improved, and low refractive index properties can also be improved.
As the post-heating and / or post-exposure step, it is preferable to perform heat treatment (firing). For example, a polymerization reaction during post-heating such as the polymerizable functional group of component C remaining in the resin or the ethylenically unsaturated group of component D can be used. The conditions for the post-heat treatment are preferably 100 to 600 ° C., more preferably 200 to 500 ° C., particularly preferably 200 ° C. to 450 ° C., preferably 1 minute to 3 hours, more preferably 1 minute to 2 hours, Especially preferably, it is the range of 1 minute-1 hour. The post-heating treatment may be performed in several times. The post-heating step can be performed by heating the developed photosensitive low refractive index material layer with a heating device such as a hot plate or an oven.
In this post-heating step, the heating temperature is preferably 120 to 250 ° C, more preferably 160 to 230 ° C. Moreover, although heating time changes with heating means, when heating on a hotplate, 5 to 30 minutes are preferable, and when heating in an oven, 30 to 90 minutes are preferable.
In the post-heating process, a step baking method in which heating is performed twice or more can be employed.

Further, after the development step, the polymerizable functional groups and components of the component C still remaining in the polymer by irradiating with high energy rays such as light irradiation and radiation irradiation instead of heat treatment, if necessary. The film may be hardened by causing a polymerization reaction between the ethylenically unsaturated groups of D. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited thereto.
The energy when an electron beam is used as the high energy beam is preferably 0.1 to 50 keV, more preferably 0.2 to 30 keV, and particularly preferably 0.5 to 20 keV. The total dose of the electron beam, preferably 0.01~5μC / cm ^2, more preferably ^{0.01~2μC / cm 2, 0.01~1μC / cm} 2 is particularly preferred. The substrate temperature when irradiating the electron beam is preferably 0 to 500 ° C, more preferably 20 to 450 ° C, and particularly preferably 20 to 400 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa.
From the viewpoint of preventing oxidation of the polymer, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.

Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when using ultraviolet rays is preferably 160 to 400 nm, and the output is preferably 0.1 to 2,000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C, more preferably 250 to 400 ° C, and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the polymer, it is preferable to use an inert atmosphere such as Ar, He, or nitrogen as the atmosphere around the substrate. Further, the pressure at that time is preferably 0 to 133 kPa.

  The film may be hardened by performing heat treatment and high energy ray treatment irradiation such as light irradiation and radiation irradiation simultaneously or sequentially.

  The method for forming a permanent film of the present invention may include other known steps.

FIG. 2 is a schematic view showing an example of the method for forming a permanent film of the present invention.
First, as shown in FIG. 2A, the photosensitive transfer material 100 is provided with a thermoplastic resin layer 104, an intermediate layer 106, and a photosensitive low refractive index material layer 108 in this order on a support 102. The two rollers 112 are bonded so that the photosensitive low refractive index material layer 108 and the transferred member 110 are in direct contact with each other.
Subsequently, the support 102 is peeled off (not shown), and as shown in FIG. 2B, the active light beam 114 is irradiated from the thermoplastic resin layer 104 side to expose the photosensitive low refractive index material layer 108.
As shown in FIGS. 2C to 2D, unexposed portions of the thermoplastic resin layer 104, the intermediate layer 106, and the photosensitive low refractive index material layer 108 are removed with a developer and developed. The removal of the unexposed portions of the thermoplastic resin layer 104, the intermediate layer 106, and the photosensitive low refractive index material layer 108 may be sequentially performed or two or more layers may be simultaneously performed.
Subsequently, as shown in FIG. 2E, the developed photosensitive low refractive index material layer 108 may be rubbed with a brush 116 to remove the development residue.

(Optical device manufacturing method)
The optical device manufacturing method of the present invention includes the step of preparing the photosensitive transfer material of the present invention, the photosensitive low refractive index material layer and the back as at least one layer between the backlight module substrate and the color filter substrate. A step of laminating the photosensitive transfer material so as to contact the light module substrate or the color filter substrate, and a step of peeling the support of the photosensitive transfer material.
The preferred embodiment of each step in the method for producing an optical device of the present invention is not particularly limited as long as it is a method using the photosensitive transfer material of the present invention. Except for laminating the photosensitive transfer material so that the photosensitive low refractive index material layer and the backlight module substrate or the color filter substrate are in contact with each other as at least one layer between the color filter substrate and the color filter substrate. It is the same as that of the preferable aspect of each process in the manufacturing method of the photosensitive low refractive index transfer layer of this invention.
As said optical device, a liquid crystal display etc. are mentioned, for example, Especially the backlight unit provided with the backlight module board | substrate and the color filter board | substrate is mentioned suitably.

In addition, the method for producing an optical device of the present invention further includes a step of exposing the transferred photosensitive low refractive index material layer (photosensitive low refractive index transfer layer) (also referred to as “exposure step”). preferable.
The preferable aspect of the exposure process in the manufacturing method of the optical device of this invention is the same as the preferable aspect of the exposure process in the formation method of the permanent film of this invention mentioned above.
The method for producing an optical device of the present invention may further include a step of developing the exposed photosensitive low refractive index material layer (also referred to as “development step”).
A preferred embodiment of the developing step in the method for producing an optical device of the present invention is the same as the preferred embodiment of the developing step in the method for forming a permanent film of the present invention described above.
In the optical device manufacturing method of the present invention, after the development step, the developed photosensitive low refractive index material layer is heated and / or exposed as necessary (also referred to as “post-heating and / or post-exposure step”). May also be included.
The preferable aspect of the post-heating and / or post-exposure process in the method for producing an optical device of the present invention is the same as the preferable aspect of the post-heating and / or post-exposure process in the method for forming a permanent film of the present invention described above.
Moreover, the manufacturing method of the optical device of this invention may include the other well-known process.

A preferred example of the method for producing an optical device of the present invention will be described below with reference to the drawings.
FIG. 3 is a cross-sectional view showing an example of a backlight unit manufactured by the method for manufacturing an optical device of the present invention.
The light-sensitive transfer material of the present invention is superposed on the reflecting plate 202 and bonded together using a laminator (manufactured by Hitachi Industries (Lamic II type)), and then supported from the light-sensitive transfer material. The reflector (polyethylene terephthalate film) is peeled off, and then the thermoplastic resin layer is removed (not shown), whereby the reflector 202 having the photosensitive low refractive index material layer laminated thereon is obtained. A lamp unit 210 including a lamp 206 and a lamp reflection plate 208 as a light source is provided at the end of the light guide plate 204, and the reflection plate 202 in which the light guide plate 204 and the photosensitive low refractive index material layer are laminated is photosensitive low refractive. The refractive index material layer and the light guide plate 204 are bonded to each other, and the photosensitive low refractive index material layer is exposed and cured to obtain the light guide plate 204 including the lamp unit 210 and the reflection plate 202. Similarly, a photosensitive low-refractive index material layer is transferred and laminated on the diffusion sheet 212 and the prism sheet 214 from the photosensitive transfer material of the present invention, laminated and bonded to the light guide plate 204, and transferred from the photosensitive transfer material. The refractive index material layer is cured to form the low refractive index layer 216, and the backlight unit 200 is obtained.
The obtained backlight unit 200, which is an optical device, includes a reflector 202, a low refractive index layer 216, a light guide plate 204, a low refractive index layer 216, a diffusion sheet 212, a low refractive index layer 216, a prism from the bottom of FIG. A low refractive index layer 216 matching the shapes of the sheet 214 and the prism sheet 214 is laminated in this order, and a lamp unit 210 including a lamp 206 and a lamp reflecting plate 208 is provided on the edge of the light guide plate 204. It has been.
Further, the backlight unit manufactured by the optical device manufacturing method of the present invention is one in which at least one of the four low refractive index layers 216 in FIG. 3 is formed of the photosensitive transfer material of the present invention. That's fine. As shown in FIG. 3, the photosensitive transfer material of the present invention can be used in various layers in an optical device such as a backlight unit.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, unless otherwise specified, “part” represents “part by mass”, and “molecular weight” in the polymer compound represents “weight average molecular weight”.

(Examples 1 to 4 and Comparative Examples 3 and 4)
<Preparation of coating solution for photosensitive low refractive index material layer>
The following composition was mixed to prepare a coating solution for photosensitive low refractive index material layer. In addition, the unit of the numerical value showing the usage-amount of each component of Table 1 is a mass part.

Details of each component described in Table 1 are as follows.
PGMEA: propylene glycol monomethyl ether acetate Allyl / MAA = 80/20: copolymer (polymer shown below) having a molar ratio of allyl methacrylate to methacrylic acid of 80:20, molecular weight Mw = 30,000
BzMA / MAA = 80/20: copolymer of benzyl methacrylate and methacrylic acid having a molar ratio of 80:20 (polymer shown below), molecular weight Mw = 30,000
DPHA: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
FFA-1: 40 mass% PGMEA solution of monomer FFA-1 shown below IRGACURE OXE-01: Compound shown below F-554: 2 mass% PGMEA solution of perfluoroalkyl group-containing nonionic surfactant, DIC Corporation Manufactured through rear 4320: 20% by mass methyl isobutyl ketone (MIBK) dispersion of hollow silica particles, manufactured by JGC Catalysts & Chemicals Co., Ltd., average primary particle size 60 nm
SiO ₂ particles: 30% by mass MIBK dispersion of silica particles that are not hollow or porous, MIBK-ST manufactured by Nissan Chemical Industries, Ltd., particle size 10-20 nm

<Production of photosensitive transfer material>
Using a biaxially stretched 75 μm thick polyethylene terephthalate film support surface with a glass substrate coater (manufactured by FS Japan, trade name: MH-1600) having slit-like nozzles, as follows: The prepared coating solution for a thermoplastic resin layer was applied to a thickness of 15 μm and dried at 100 ° C. for 5 minutes to form a thermoplastic resin layer. Next, an intermediate layer coating solution was applied thereon so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 5 minutes to form an intermediate layer. Further thereon, a coating solution for photosensitive low refractive index material layer is applied to a dry film thickness of 2.0 μm and dried at 100 ° C. for 5 minutes to form a photosensitive low refractive index material layer. A transfer material was prepared.

<Preparation of coating solution for thermoplastic resin layer>
The following composition was mixed to prepare a coating solution for a thermoplastic resin layer.
Copolymer of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid (55 / 11.7 / 4.5 / 28.8) (molecular weight 80,000): 58 parts Styrene / acrylic acid = 63 / Copolymer of 37 (molecular weight 7,000): 136 parts 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylate): 90 parts Fluorosurfactant (trade name: F780F, manufactured by Dainippon Ink & Chemicals, Inc.): 1 part • Methyl ethyl ketone: 541 parts • 1-methoxy-2-propanol: 63 parts • Methyl alcohol: 111 parts

<Adjustment of coating solution for intermediate layer>
The following composition was mixed to prepare an intermediate layer coating solution.
Polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550): 32.2 parts : 14.9 parts-Distilled water: 524 parts-Methanol: 429 parts

<Production of photosensitive material>
The prism sheet substrate with unevenness having a height of 1.0 μm shown in FIGS. 4 and 5 and the photosensitive transfer material obtained as described above are brought into contact with the prism sheet substrate having a photosensitive low refractive index material layer of 2 μm. And laminated together using a laminator (manufactured by Hitachi Industries (Lamic II type)). The lamination conditions were a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min. Thereafter, the support (polyethylene terephthalate film) was peeled from the photosensitive transfer material to produce a photosensitive material.

<Preparation of low refractive index material layer>
The resulting photosensitive material is exposed and cured with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount is 2,000 mJ / cm ² (illuminance: 20 mW / cm ² ). did. Subsequently, the following three development processes were performed to develop and remove the thermoplastic resin layer and the intermediate layer, and a low refractive index material layer was obtained on the 2 μm prism sheet shown in FIGS.

[Development processing]
First step: Development processing was performed using a developing solution (trade name: T-PD1, manufactured by FUJIFILM Corporation, alkaline developer) at a temperature of 30 ° C. for 40 seconds.
Second step: Development processing was performed using a developing solution (trade name: T-CD1, manufactured by Fuji Film Co., Ltd., alkaline developer) at a temperature of 33 ° C. for 20 seconds.
Third step: Development processing was performed using a developing solution (trade name: T-SD1, manufactured by FUJIFILM Corporation, alkaline developer) at a temperature of 33 ° C. for 20 seconds.
The photosensitive transfer materials of Examples 1 to 4 and Comparative Examples 3 and 4 were produced.

  In Examples 1 to 4 and Comparative Examples 3 and 4, the obtained coating liquid for photosensitive low refractive index material layer and photosensitive transfer material were used, and the following evaluations were performed. The evaluation results are summarized in Table 2.

<Evaluation of in-plane film thickness uniformity during transfer>
In the obtained photosensitive material, the film thickness was measured at intervals of 2 cm in the vertical direction and the horizontal direction in A4 size.
The evaluation criteria were A for any film thickness measurement results within 2.0 μm ± 0.1 μm, and B for those exceeding the measurement results.

<Measurement of refractive index of film>
The photosensitive low refractive index material layer coating solution obtained above was applied onto a silicon wafer, and then heated at 100 ° C. for 2 minutes on a hot plate to obtain a photosensitive low refractive index film.
Subsequently, the photosensitive low refractive index film thus obtained was exposed and cured under the following conditions using an ellipsometer MC-200 manufactured by JA Woollam to obtain a low refractive index film.
Low refractive index film production conditions: pre-bake: 80 ° C. for 120 minutes, exposure: ghi-mix, 200 mJ / cm ² , post-bake: 230 ° C. for 60 minutes Using the above ellipsometer, the wavelength of this low refractive index film is 589 nm, 25 ° C. The value measured in was used as the refractive index.

<Measurement of transmittance (light transmission efficiency evaluation)>
As shown in FIG. 6, the low refractive index layer 44 is applied and dried on a polyethylene terephthalate substrate 42 so as to have a thickness of 1.0 μm, and a polyethylene terephthalate film 46 is bonded with a thermal laminator, and a wavelength of 550 nm is measured with a spectrophotometer. The light transmittance of was measured. The higher the transmittance, the better the light transmission efficiency.
Using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), the substrate was heated at 140 ° C. and laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min. did.

<Pencil hardness evaluation>
A pencil hardness test was performed based on JIS K5600-4 for a film produced in the same manner as that used for measuring the refractive index of the film. Higher strength is preferred. The results are shown in Table 2.
Note that UNI (registered trademark) manufactured by Mitsubishi Pencil Co., Ltd. was used as the pencil.

(Comparative Example 1)
Using the coating solution for photosensitive low refractive index material layer obtained in Example 1, in the measurement of the in-plane film thickness uniformity during transfer, on a prism sheet having a height of 1.0 μm instead of transfer, The photosensitive low refractive index material layer coating solution was applied using a spin coater so that the dry film thickness was 2.00 μm, and dried at 100 ° C. for 5 minutes to form a photosensitive low refractive index material layer. Except for the above, evaluation was performed in the same manner as in Example 1.
In addition, the photosensitive low refractive index material layer coating solution obtained in Example 1 was used, and in the measurement of transmittance and pencil hardness evaluation, the photosensitive low refractive index material layer coating solution was applied using a spin coater. Except for the application, evaluation was performed in the same manner as in Example 1, but in all cases, bubbles were generated in the film, and the transmittance and strength of the film were clearly inferior, and evaluation was not possible.

(Comparative Example 2)
The transmittance was evaluated in the same manner as in Example 1 except that the low refractive index layer was not formed. That is, Comparative Example 2 was measured by simply superimposing films without a low refractive index layer. The evaluation results are summarized in Table 2.

(Example 5)
A backlight unit was produced by the following method.
FIG. 3 is a cross-sectional view of the backlight unit 200 manufactured in the fifth embodiment.
After superposing the photosensitive transfer material of Example 1 in contact with the reflector 202 and laminating both using a laminator (manufactured by Hitachi Industries (Lamic II type)), The support (polyethylene terephthalate film) was peeled off, and then the thermoplastic resin layer was removed. A lamp unit 210 including a lamp 206 and a lamp reflector 208 as a light source is prepared on the edge of the light guide plate 204. The refractive index material layer and the light guide plate 204 were bonded together so as to be in contact with each other. Subsequently, the obtained laminate was exposed by a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 2,000 mJ / cm ² (illuminance: 20 mW / cm ² ). It hardened | cured and the light guide plate 204 which comprises the lamp unit 210 and the reflecting plate 202 was obtained. Similarly, the photosensitive low refractive index material layer is transferred and laminated on the diffusion sheet 212 and the prism sheet 214 from the photosensitive transfer material of Example 1, and bonded to the light guide plate 204, and then the photosensitive transfer material of Example 1 is used. The transferred photosensitive low refractive index material layer was cured to form a low refractive index layer 216, and the backlight unit 200 of Example 5 was obtained. The obtained backlight unit 200 showed good luminance.

  10: photosensitive transfer material, 12: support, 14: thermoplastic resin layer, 16: intermediate layer, 18: photosensitive low refractive index material layer, 20: protective layer, 22: antistatic layer, 30: prism sheet substrate 32: polyethylene film, 34: prism member, 40: transmittance measurement sample, 42: polyethylene terephthalate substrate, 44: low refractive index layer, 46: polyethylene terephthalate film, 100: photosensitive transfer material, 102: support, 104 : Thermoplastic resin layer, 106: intermediate layer, 108: photosensitive low refractive index material layer, 110: transferred member, 112: roller, 114: actinic ray, 116: brush, 200: backlight unit, 202: reflector , 204: light guide plate, 206: lamp, 208: lamp reflector, 210: lamp unit, 212: diffusion sheet, 214: prism Sheet, 216: low refractive index layer

Claims (15)

Having at least a photosensitive low refractive index material layer on the support,
The photosensitive low refractive index material layer comprises (Component A) hollow or porous particles, (Component B) a photopolymerization initiator, (Component C) a polymer having a polymerizable functional group, and (Component D) a monomer. Containing ,
Component C includes a (meth) acrylic resin having an ethylenically unsaturated group and an acid group,
Component D contains an ethylenically unsaturated compound having a fluorine atom . A photosensitive transfer material.   The photosensitive transfer material according to claim 1, wherein component A is hollow silica particles or porous silica particles.   The ethylenically unsaturated group in the (meth) acrylic resin having an ethylenically unsaturated group and an acid group is a (meth) acryloyl group, a (meth) acrylamide group, a thio (meth) acryloyl group, an allyl group, or a vinyl group. The photosensitive transfer material according to claim 1 or 2. The ethylenically unsaturated compound having a fluorine atom, a having a fluorine atom (meth) acrylate compounds, photosensitive transfer material according to any one of claims 1 to 3.   The photosensitive transfer material according to claim 1, wherein the ethylenically unsaturated compound having a fluorine atom is a polyfunctional (meth) acrylate compound having a fluorine atom. The ethylenically unsaturated ethylenically unsaturated groups in (meth) acrylic resin having a group and acid group, an allyl group, a photosensitive transfer material according to any one of claims 1 to 5.   The photosensitive transfer material according to claim 1, wherein the acid group in the (meth) acrylic resin having an ethylenically unsaturated group and an acid group is a carboxyl group.   The photosensitive transfer material of any one of Claims 1-7 whose component A is a hollow silica particle.   The photosensitive transfer material of any one of Claims 1-8 whose content of the component A is 20-90 mass% with respect to the total mass of the said photosensitive low refractive index material layer.   A substrate having a photosensitive low refractive index transfer layer obtained by transferring the photosensitive low refractive index material layer from the photosensitive transfer material according to claim 1. A step of preparing the photosensitive transfer material according to claim 1;
Laminating the photosensitive transfer material on the transferred member so that the transferred member and the photosensitive low refractive index material layer are in contact with each other; and
A method for producing a photosensitive low refractive index transfer layer, comprising the step of peeling the support of the photosensitive transfer material. A step of preparing the photosensitive transfer material according to claim 1;
Laminating the photosensitive transfer material on the transferred member so that the transferred member and the photosensitive low refractive index material layer are in contact with each other;
Peeling the support of the photosensitive transfer material, and
Exposing the transferred photosensitive low refractive index material layer to a permanent film forming method. A step of preparing the photosensitive transfer material according to claim 1;
Laminating the photosensitive transfer material as at least one layer between the backlight module substrate and the color filter substrate so that the photosensitive low refractive index material layer and the backlight module substrate or the color filter substrate are in contact with each other. ,as well as,
A method for producing an optical device, comprising: peeling off a support of the photosensitive transfer material.   The method of manufacturing an optical device according to claim 13, further comprising exposing the transferred photosensitive low refractive index material layer.   The method for manufacturing an optical device according to claim 13 or 14, wherein the optical device is a backlight unit.

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