JP2003313213A - Photopolymerizable unsaturated compound and process for manufacturing photosensitive resin composition, photosensitive element, and diffuse reflection plate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a photopolymerizable compound which gives a diffuse reflection substrate layer which is excellent, at a high temperature, in the shape retention of an uneven surface diffusing and reflecting light, is excellent in adhesion to a substrate at high temperature and humidity or in photolithography, and therefore enables a diffuse reflection plate for a reflective liquid crystal display to be produced in a high yield; and to provide a method for producing a photosensitive resin composition, a photosensitive element, and a reflective liquid crystal display using the compound. <P>SOLUTION: The photosensitive resin composition comprises (a) a silyl group- containing photopolymerizable unsaturated compound having at least two ethylenic unsaturated groups and at least one hydrolyzable group-containing silyl group, (b) a binder polymer, (c) a photopolymerizable unsaturated compound having at least one ethylenic unsaturated group, and (d) a photopolymerization initiator. The photosensitive element for a diffuse reflection substrate layer is formed on the uneven surface of a temporary support having the uneven surface. A process for manufacturing a diffuse reflection plate for a reflective liquid crystal display using them is provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable unsaturated compound used for a diffuse reflection plate for a reflection type liquid crystal display device, a photosensitive resin composition using the same, a photosensitive element and a reflection type liquid crystal display. The present invention relates to a method for manufacturing a diffuse reflector for a device.

[0002]

2. Description of the Related Art In recent years, liquid crystal display devices have been used for all kinds of applications such as notebook personal computers, electronic notebooks, portable information terminals, amusement devices, mobile phones, etc. Reflection-type liquid crystal display devices are being widely used from the viewpoint that power consumption is low because a backlight is not required, and that they can be made thin and lightweight. Generally, a reflection type liquid crystal display device uses reflection of external light as a light source. It is necessary to increase the intensity of light scattered in the direction perpendicular to the screen. As a useful method for achieving this, a transfer film in which a thin film layer is laminated on a temporary support on which an uneven surface capable of diffusing and reflecting light is formed is used. A method for forming a diffuse reflection plate by bonding the adhesive surface to the substrate surface, peeling off the temporary support, transferring the thin film layer to the substrate, and further applying a metal thin film on the thin film layer (JP 2000-47199A).
Issue).

However, when the diffuse reflection plate is manufactured by the conventional method, there is a problem that it is particularly difficult to select the material for the diffuse reflection underlayer and the production cannot be performed with a high yield. This was caused by the following two reasons. The first is a problem related to the heat resistance of the diffuse reflection underlayer material.
In the manufacture of a liquid crystal display device, a substrate provided with a diffuse reflection plate has a thickness of 200 to 25 due to the steps of forming a transparent electrode such as ITO, forming a color filter, and forming an overcoat layer.
It will be exposed to a high temperature of about 0 ° C several times. In the conventional diffuse reflection underlayer material and method, a metal thin film is laminated on the diffuse reflection underlayer by a sputtering method or the like to form a diffuse reflection plate. The surface shape, that is, the shape of the uneven surface capable of diffusely reflecting light is deformed, and desired reflection characteristics cannot be obtained, which causes a problem that manufacturing cannot be performed with high yield. The other is a problem related to the substrate adhesion of the diffuse reflection underlayer. Since it is expected that the liquid crystal display device will be used in all kinds of environments, it is necessary for reliability that the substrate adhesion of the diffuse reflection underlayer be good even at high temperature and high humidity. In the materials and methods, there is a problem that the adhesion to the substrate is significantly deteriorated in a high temperature and high humidity environment and reliability as a liquid crystal display device cannot be obtained due to the problem of moisture resistance. In addition, TF that can display at high speed with high image quality
In order to apply a diffuse reflection underlayer to a T-drive type liquid crystal display device, it is essential to form fine contact holes by photolithography, and the substrate adhesion of the diffuse reflection underlayer during photolithography exposure and development is also important. Although it is required to be good, the conventional diffuse reflection underlayer material has a problem that the substrate adhesion is significantly deteriorated and a fine contact hole cannot be stably formed.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an uneven surface which is capable of diffusively reflecting light in a diffuse reflection underlayer excellent in shape retention under high temperature, and which is diffused under high temperature and high humidity and photolithography. Provided is a silyl group-containing photopolymerizable unsaturated compound and a photosensitive resin composition using the same, which enables production of a diffuse reflector for a reflective liquid crystal display device with good yield by excellent adhesion of the reflective underlayer to the substrate. To do.

Another object of the present invention is to provide a photosensitive element for forming a diffuse reflection underlayer which is excellent in workability in addition to the above effects.

Another object of the present invention is to provide a method of manufacturing a diffuse reflection plate for a reflective liquid crystal display device, which can contribute to cost reduction in addition to the above effects.

[0007]

The present invention has (a) a silyl group-containing photopolymer having at least two ethylenically unsaturated groups in one molecule and at least one hydrolyzable group-containing silyl group. It relates to a polymerizable unsaturated compound. Further, the present invention is a compound having at least two ethylenically unsaturated groups in one molecule, and further having at least one hydrolyzable group-containing silyl group, which further has a urethane bond (a). It relates to a silyl group-containing photopolymerizable unsaturated compound. Further, the present invention relates to (A) a hydroxyl group of a photopolymerizable unsaturated compound having at least one hydroxyl group and at least two ethylenically unsaturated groups in one molecule,
The (a) silyl group-containing photopolymerizable unsaturated compound obtained by reacting an isocyanate group of an organosilicon compound having one isocyanate group in the molecule and further having at least one hydrolyzable group-containing silyl group Regarding

The present invention also provides (a) a silyl group-containing photopolymerizable unsaturated compound, (b) a binder polymer, (c) a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group, (d) A photosensitive resin composition containing a photopolymerization initiator. The present invention also relates to a photosensitive element for forming a diffuse reflection underlayer, which has a layer of the photosensitive resin composition on the uneven surface of the temporary support having the uneven surface. The present invention also includes (I) a step of laminating the photosensitive element for forming a diffuse reflection underlying layer on a substrate, (II) a step of imagewise irradiating the photosensitive resin composition layer with an actinic ray, (III ) A step of peeling and removing the temporary support having an uneven surface, (IV) a step of selectively removing the photosensitive resin composition layer by development to form a pattern,
By (V) a step of irradiating the patterned photosensitive resin composition layer with an actinic ray, and (VI) a step of heating the patterned photosensitive resin composition layer, a diffuse reflection having a desired uneven surface is obtained. The present invention relates to a method for manufacturing a diffuse reflection plate for a reflective liquid crystal display device, which comprises forming a base layer and further forming a reflection film on the diffuse reflection underlayer. Further, the present invention is obtained by reacting the hydroxyl group of the photopolymerizable unsaturated compound represented by the following general formula [1] with the isocyanate group of the organosilicon compound represented by the following general formula [2]. It relates to the silyl group-containing photopolymerizable unsaturated compound.

[Chemical 3] (In the general formula [1], R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ , R ⁵ and R ⁶ each independently represent an alkylene group having 1 to 8 carbon atoms or a carbon atom. When each of R ⁴ , R ⁵ and R ⁶ is a plurality of R ^{4 s} , R ^{5 s} and R ^{6 s} , the R ^{4 s} , R ^{5 s} and R ^{6 s} may be the same or different, and k, l and m is each independently an integer of 0 to 10)

[Chemical 4] (In the general formula [2], R ⁷ represents an alkylene group having 1 to 8 carbon atoms or an alkylene oxide group having 1 to 8 carbon atoms, R ⁷
When there are a plurality of R ⁷ , R ⁷ may be the same or different, R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 10. is there)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The (a) silyl group-containing photopolymerizable unsaturated compound of the present invention is
It has at least two ethylenically unsaturated groups in one molecule and at least one hydrolyzable group-containing silyl group. Further, the (a) silyl group-containing photopolymerizable unsaturated compound of the present invention is capable of improving heat resistance and further improving the substrate adhesion of the diffuse reflection underlayer under high temperature and high humidity and photolithography, It is preferable to have a urethane bond in the molecule.

The (a) silyl group-containing photopolymerizable unsaturated compound of the present invention comprises (A) at least 1 in one molecule.
With respect to the hydroxyl group of the photopolymerizable unsaturated compound having one hydroxyl group and at least two ethylenically unsaturated groups, (B)
It is obtained by reacting an isocyanate group of an organosilicon compound having one isocyanate group in one molecule and further having at least one silyl group containing a hydrolyzable group. At least 1 in one molecule of (A) in the present invention
As the photopolymerizable unsaturated compound having one hydroxyl group and at least two ethylenically unsaturated groups, if it has at least one hydroxyl group and at least two ethylenically unsaturated groups in one molecule, respectively. There is no particular limitation, and for example, epichlorohydrin-modified bisphenol A di (meth) acrylate, epichlorohydrin and alkylene oxide (the number of alkylene oxide groups having 2 to 8 carbon atoms is 1 to 20) modified bisphenol A di ( (Meth) acrylate, epichlorohydrin-modified polyalkylene glycol (the number of alkylene oxide groups having 2 to 8 carbon atoms is 1 to 2)
0) di (meth) acrylate, epichlorohydrin-modified alkyl (having 2 to 8 carbon atoms) di (meth) acrylate,
Hydroxyalkyl (C2-8) di (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, epoxy acrylate, glycerol di (meth) acrylate, diglycerol di (meth) acrylate, triglycerol di (Meth) acrylate, polyglycerol di (meth) acrylate, epichlorohydrin-modified glycerol tri (meth)
Acrylate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, alkylene oxide modified di (meth) acrylate having 2 to 20 alkylene oxide groups having 2 to 8 carbon atoms, epichlorohydr Phosphorus-modified phenoxydi (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate, epichlorohydrin-modified polyalkylene oxide (alkylene oxide group having 2 to 8 carbon atoms) Number of 1-2
0) Modified phthalic acid (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate and the like can be mentioned.

Further, the component (A) in the present invention is a compound represented by the above general formula [1] from the viewpoint that the adhesiveness in the photolithography step in the case of a photosensitive resin composition described later can be improved. Is preferred. In the general formula [1], R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group. In the general formula [1], R ⁴ , R ⁵ and R ⁶ each independently have 1 to 1 carbon atoms.
8 is an alkylene group or an alkylene oxide group having 2 to 8 carbon atoms, and when each of R ⁴ , R ⁵ and R ⁶ is plural,
R ⁴ , R ⁵ and R ⁶ may be the same or different,
It may have a block structure or a random structure. Further, in the general formula [1], k, l and m are each independently an integer of 0 to 10, but the irregularities formed on the surface of the patterned photosensitive resin composition layer formed by the steps described below. From the viewpoint of improving the characteristic of maintaining the shape under high temperature, k = 1 / m
Particularly preferred is pentaerythritol tri (meth) acrylate with = 0. Further, these (A) photopolymerizable unsaturated compounds having at least one hydroxyl group and at least two ethylenically unsaturated groups in one molecule are epoxy ester 3002A, epoxy ester 80MFA (manufactured by Kyoeisha Chemical Co., Ltd., Product name), Denacol DA-81
1, Denacol DM-811, Denacol DM-851,
Denacol DA-314, Denacol DA-321, Denacol DA-911 (manufactured by Nagase Kasei Co., Ltd., product name), SR-399 (manufactured by SARTOMER Company, product name), NK ester 701-A, NK ester 701,
NK ester A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), Aronix M-305, Aronix M-233 (manufactured by Toagosei Chemical Industry Co., Ltd., product name),
It is commercially available as KAYARAD PET-30, Kayamer PM-2 (manufactured by Nippon Kayaku Co., Ltd., product name) and the like. These may be used alone or in combination of two or more.

As the organosilicon compound (B) having one isocyanate group in one molecule and at least one hydrolyzable group-containing silyl group in the present invention,
There is no particular limitation as long as it has at least one isocyanate group in one molecule and at least one hydrolyzable group-containing silyl group in one molecule. For example, the compound represented by the general formula [2] Is preferred. In the general formula [2], R ⁷ represents an alkylene group having 1 to 8 carbon atoms or an alkylene oxide group having 1 to 8 carbon atoms, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group. , Hexylene group, methylene oxide group, ethylene oxide group, propylene oxide group, isopropylene oxide group, butylene oxide group, pentylene oxide group, hexylene oxide group and the like, and ethylene group and propylene group are preferable. If this R ⁷ is a plurality, R ⁷ is may be the same or different, may be a random structure in block structure. In the general formula [2], R ⁸ , R ⁹ and R ¹⁰ each independently have 1 to 8 carbon atoms.
Of the alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group or an ethyl group is preferable. In the general formula [2], n is 1 to 10,
From the viewpoint of reactivity with the component (A), n is preferably 1 to 3.

Examples of the compound represented by the general formula [2] include isocyanate methyltrimethoxysilane, isocyanate methyldimethoxysilane, isocyanate methylmonomethoxysilane, isocyanate methyltriethoxysilane, isocyanate methyldiethoxysilane, and isocyanatemethyl. Monoethoxysilane,
Isocyanate methyl tripropoxy silane, isocyanate methyl dipropoxy silane, isocyanate methyl monopropoxy silane, isocyanate methyl tributoxy silane, isocyanate methyl dibutoxy silane, isocyanate methyl monobutoxy silane, isocyanate ethyl trimethoxy silane, isocyanate ethyl dimethoxy silane, isocyanate ethyl mono Methoxysilane, Isocyanatoethyltriethoxysilane, Isocyanatoethyldiethoxysilane, Isocyanatoethylmonoethoxysilane, Isocyanatoethyltripropoxysilane, Isocyanatoethyldipropoxysilane, Isocyanatoethylmonopropoxysilane, Isocyanatoethyltributoxysilane, Isocyanatoethyldibu Xysilane, isocyanate ethyl monobutoxy silane, isocyanate propyl trimethoxy silane, isocyanate propyl dimethoxy silane, isocyanate propyl monomethoxy silane, isocyanate propyl triethoxy silane, isocyanate propyl diethoxy silane, isocyanate propyl monoethoxy silane, isocyanate propyl tripropoxy silane, isocyanate Propyldipropoxysilane, Isocyanatopropylmonopropoxysilane, Isocyanatopropyltributoxysilane, Isocyanatopropyldibutoxysilane, Isocyanatopropylmonobutoxysilane, Isocyanatobutyltrimethoxysilane, Isocyanatobutyldimethoxysilane, Isocyanatobutylmonomethoxy Orchid, isocyanate butyl triethoxy silane, isocyanate butyl diethoxy silane, isocyanate butyl monoethoxy silane, isocyanate butyl tripropoxy silane, isocyanate butyl dipropoxy silane, isocyanate butyl monopropoxy silane, isocyanate butyl tributoxy silane, isocyanate butyl dibutoxy silane, Isocyanate butyl monobutoxysilane, isocyanate pentyl trimethoxysilane, isocyanate pentyl dimethoxysilane, isocyanate pentyl monomethoxysilane, isocyanate pentyl triethoxysilane, isocyanate pentyl diethoxysilane, isocyanate pentyl monoethoxysilane, isocyanate pentyl tripropoxysilane, isocyanate Nate pentyl dipropoxy silane, isocyanate pentyl monopropoxy silane, isocyanate pentyl tributoxy silane, isocyanate pentyl dibutoxy silane, isocyanate pentyl monobutoxy silane, isocyanate hexyl trimethoxy silane,
Isocyanate hexyl dimethoxysilane, isocyanate hexyl monomethoxy silane, isocyanate hexyl triethoxy silane, isocyanate hexyl diethoxy silane, isocyanate hexyl monoethoxy silane, isocyanate hexyl tripropoxy silane,
Isocyanate hexyl dipropoxy silane, isocyanate hexyl monopropoxy silane, isocyanate hexyl tributoxy silane, isocyanate hexyl dibutoxy silane, isocyanate hexyl monobutoxy silane, ethylene oxide modified isocyanate trimethoxy silane, ethylene oxide modified isocyanate dimethoxy silane, ethylene oxide modified isocyanate monomethoxy silane, Ethylene oxide modified isocyanate triethoxysilane, ethylene oxide modified isocyanate diethoxysilane, ethylene oxide modified isocyanate monoethoxysilane, ethylene oxide modified isocyanate tripropoxysilane, ethylene oxide modified isocyanate dipropoxysilane, ethylene oxide modified isocyanate Sulfonate mono propoxysilane, ethylene oxide-modified isocyanate tributoxysilane silane,
Ethylene oxide modified isocyanate dibutoxysilane, ethylene oxide modified isocyanate monobutoxysilane, propylene oxide modified isocyanate trimethoxysilane, propylene oxide modified isocyanate dimethoxysilane, propylene oxide modified isocyanate monomethoxysilane, propylene oxide modified isocyanate triethoxysilane, propylene oxide modified isocyanate di Ethoxysilane, propylene oxide-modified isocyanate monoethoxysilane, propylene oxide-modified isocyanate tripropoxysilane, propylene oxide-modified isocyanate dipropoxysilane, propylene oxide-modified isocyanate monopropoxysilane, propylene oxide-modified isocyanate tributoxysilane, B propylene oxide-modified isocyanate dibutoxy silane, propylene oxide-modified isocyanate monobutoxy silane and the like, which may be used alone or in combination of two or more. Among these compounds, isocyanatopropyltrimethoxysilane or isocyanatopropyltriethoxysilane is particularly preferred from the viewpoint of improving the adhesiveness in the photolithography step when the photosensitive resin composition described below is used. Such a compound is Y-518
7, A-1310 (manufactured by Nippon Unicar Co., Ltd., product name)
Is commercially available as.

The photosensitive resin composition of the present invention comprises: (a) a silyl group-containing photopolymerizable unsaturated compound, (b) a binder polymer, and (c) a photopolymerizable compound having at least one ethylenically unsaturated group. It has an unsaturated compound and (d) a photopolymerization initiator.

The binder polymer (b) in the present invention is not particularly limited, and examples thereof include vinyl copolymers. Examples of the vinyl monomer used in the vinyl copolymer include acrylic acid and methacrylic acid. , Maleic acid,
Fumaric acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate,
N-Butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylic Acid pentyl, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, Hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, methacryl Cycloheptyl acid, benzyl acrylate, benzyl methacrylate, phenyl acrylate, methacrylic acid Methyl, methoxyethyl acrylate, methoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, acrylic acid 2-chloroethyl, methacrylic acid 2
-Chloroethyl, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-
Examples thereof include methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like. These are used alone or in combination of two or more.

As the binder polymer (b) in the present invention, for example, at least one ethylene is added to a vinyl copolymer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, an oxirane ring and an acid anhydride. Radically polymerizable copolymer having an ethylenically unsaturated group in the side chain obtained by addition reaction of a compound having one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group and a carboxyl group Can also be used.

The above-mentioned carboxyl group, hydroxyl group, amino group,
The oxirane ring, as an essential vinyl monomer used for producing a vinyl copolymer having a functional group such as an acid anhydride,
For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, ethyl methacrylate isocyanate, glycidyl acrylate, glycidyl methacrylate. , Vinyl monomers having a functional group such as a carboxyl group such as maleic anhydride, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride. These are used alone or in combination of two or more.

In the production of a radical-polymerizable copolymer having an ethylenically unsaturated group in its side chain, a vinyl monomer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an oxirane ring, or an acid anhydride, if necessary. The vinyl monomers other than the body can be copolymerized, and these can be used alone or in combination of two or more kinds.

Radica having an ethylenically unsaturated group in the side chain
The concentration of ethylenically unsaturated group in the polymerizable copolymer is 1.0
X10^-Four~ 6.0 x 10^-3Mol / g is preferred
2.0X10^-Four~ 5.0 x 10^-3Mol / g
And more preferably 3X10 ^-Four~ 4.0X10^-3Mol /
It is particularly preferable to set g. This ethylenically unsaturated group
Concentration is 1.0 x 10^-FourAt less than mol / g, sufficient curability
Is inferior in heat resistance, moisture resistance, etc.
When used as a diffuse reflector, the effect of improving the efficiency of using external light is reduced.
6.0X10^-3If it exceeds mol / g,
Radical Polymerizable Copolymer Having Ethylenically Unsaturated Group in Side Chain
There is a tendency to cause gelation during the production of coalescence.

The weight average molecular weight (value measured by gel permeation chromatography and converted into standard polystyrene) of the (b) binder polymer in the present invention is such as heat resistance, moisture resistance, coating property and solubility in solvent. From the point,
It is preferably 1,000 to 300,000,
It is more preferably 5,000 to 150,000.

The binder polymer (b) in the present invention is
In the step of forming a pattern by selectively removing the photosensitive resin composition layer by (IV) development, which will be described later, the acid value can be regulated so that it can be developed by various known developing solutions. For example, sodium carbonate, potassium carbonate,
When developing with an alkaline aqueous solution such as tetramethylammonium hydroxide, the acid value is 50 to 260 mg KO.
It is preferably H / g. This acid value is 50mgK
If it is less than OH / g, it tends to be difficult to develop,
When it exceeds 0 mgKOH / g, the developer resistance (the property that the portion which is not removed by development and becomes the remaining pattern is not attacked by the developer) tends to be deteriorated. In the case of development using an alkaline aqueous solution containing water or an alkaline aqueous solution and one or more kinds of surfactants, the acid value is 16
It is preferable to set it to -260 mgKOH / g. If the acid value is less than 16 mgKOH / g, development tends to be difficult, and if it exceeds 260 mgKOH / g, the developing solution resistance tends to decrease.

The photopolymerizable unsaturated compound having at least one ethylenically unsaturated group (c) in the present invention is, for example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. , 2,2-bis (4-
(Di (meth) acryloxypolyethoxy) phenyl) propane, a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a urethane monomer, nonylphenyldioxylene (meth) acrylate, γ-chloro -Β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-
Hydroxyethyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'
Examples thereof include-(meth) acryloyloxyethyl-o-phthalate and (meth) acrylic acid alkyl ester.

Examples of the compound obtained by reacting the above polyhydric alcohol with α, β-unsaturated carboxylic acid include:
Polyethylene glycol di (meth) acrylate having 2-14 ethylene groups, 2-1 propylene groups
4, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate (pentaerythritol tri (meth) acrylate) ,
Tetramethylolmethane tetra (meth) acrylate,
Examples thereof include polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Examples of the α, β-unsaturated carboxylic acid include (meth)
Acrylic acid etc. can be fisted.

As the above 2,2-bis (4- (di (meth) acryloxypolyethoxy) phenyl) propane,
For example, 2,2-bis (4- (di (meth) acryloxydiethoxy) phenyl) propane, 2,2-bis (4-
(Di (meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4- (di (meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4- (di (meth) acryl) Roxydecaethoxy) phenyl) and the like.

Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy).
Phenyl etc. can be fisted.

As the urethane monomer, for example,
(Meth) acrylic monomer having OH group at β-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-
Addition reaction product with hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, ethylene oxide modified urethane di (meth) acrylate,
Examples thereof include ethylene oxide and propylene oxide-modified urethane di (meth) acrylate. Examples of the (meth) acrylic acid alkyl ester include (meth)
Examples thereof include acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester and the like. These may be used alone or in combination of two or more.

Examples of the (d) photopolymerization initiator in the present invention include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4 '. -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone-1 (Irgacure-369, manufactured by Ciba Specialty Chemicals, trade name), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and the like. Aromatic ketone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone,
Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone,
Quinones such as 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone, benzoin methyl ether, Benzoin ether compounds such as benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethylketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer , 2- (o-chlorophenyl)-
4,5-di (methoxyphenyl) imidazole dimer,
2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-
2,4,5-triarylimidazole dimers such as 4,5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1, 7-bis (9,9 '
-Acridinyl) heptane and other acridine derivatives, N-
Examples thereof include phenylglycine, N-phenylglycine derivative, and coumarin-based compound. In the 2,4,5-triarylimidazole dimer, two 2,
Substituents substituted on 4,5-triarylimidazole may be the same or different. Also, a thioxanthone compound and a tertiary amine compound may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. From the viewpoint of adhesion and sensitivity in the photolithography process, 2,4,5-triarylimidazole dimer is more preferable. These may be used alone or in combination of two or more.

The amount of the (a) silyl group-containing photopolymerizable unsaturated compound used in the present invention is 0.1 to 80 parts by weight per 100 parts by weight of the total amount of the components (a), (b) and (c). Parts, preferably 1 to 70 parts by weight, more preferably 5 to 65 parts by weight, and more preferably 10 parts by weight.
It is extremely preferable that the amount is -60 parts by weight. If the amount used is less than 0.1 part by weight, the effect of improving the adhesion in the photolithography process may not be sufficiently exhibited, and if it exceeds 80 parts by weight, the storage stability of the photosensitive resin composition will be poor. Tends to decline.

The amount of the binder polymer (b) used in the present invention is preferably 10 to 80 parts by weight based on 100 parts by weight of the total amount of the components (a), (b) and (c).
It is more preferably from 0 to 75 parts by weight, and more preferably from 25 to 73.
Particularly preferably, the amount is 30 to 70 parts by weight. If the amount used is less than 10 parts by weight, the coating property or film property tends to deteriorate, and if it exceeds 80 parts by weight, the photocurability or heat resistance tends to decrease.

The amount of the (c) photopolymerizable unsaturated compound having at least one ethylenically unsaturated group used in the present invention is 100 parts by weight based on the total amount of the components (a), (b) and (c). 10 to 80 parts by weight, and preferably 20 to 20 parts by weight
The amount is more preferably 75 parts by weight, particularly preferably 25 to 73 parts by weight, and most preferably 30 to 70 parts by weight. If the amount used is less than 10 parts by weight, photocurability or heat resistance tends to decrease, and
If it exceeds 0 parts by weight, the coating property or film property tends to deteriorate.

The amount of the (d) photopolymerization initiator used in the present invention is 0.05 to 20 parts by weight based on 100 parts by weight of the total amount of the components (a), (b) and (c). Preferably
More preferably 0.1 to 15 parts by weight, 0.1
It is particularly preferable that the amount is 5 to 10 parts by weight. If this amount is less than 0.05 parts by weight, photocuring tends to be insufficient, and if it exceeds 20 parts by weight, the absorption of active light on the surface irradiated with active light of the photosensitive resin composition layer described below increases. do it,
Internal photocuring tends to be inadequate. Further, the photosensitive resin composition of the present invention, if necessary, an adhesion imparting agent such as a silane coupling agent, a leveling agent, a plasticizer,
Fillers, defoamers, flame retardants, stabilizers, antioxidants, fragrances,
Colorants, thermal crosslinking agents, polymerization inhibitors, etc. (a), (b) and
0.01 to 2 for each 100 parts by weight of component (c)
About 0 parts by weight can be contained. These are used alone or in combination of two or more.

The photosensitive element for forming a diffuse reflection underlayer of the present invention comprises a layer of the above-mentioned photosensitive resin composition on the uneven surface of a temporary support having an uneven surface. The temporary support having an uneven surface in the present invention is not particularly limited, and known ones can be used, but the point at which the photosensitive element for forming the diffuse reflection underlayer is stuck on the substrate and the diffuse reflection under A film made of polypropylene, polyethylene terephthalate, polyester, etc. is used as a base film because it is particularly suitable in that it is peeled off after a photosensitive element for forming a ground layer is adhered, photocured, and then sandblasted. Etc. to form a temporary support by directly providing an uneven surface, or by laminating a photocurable resin and / or a thermosetting resin on the base film and providing the uneven surface by imagewise exposure or thermoforming. It is particularly preferable that the temporary support is combined with the base film. Further, the uneven surface at this time may have a structure capable of increasing the intensity of light scattered in the vertical direction in order to more efficiently utilize outside light and obtain a bright display. Therefore, there is no particular limitation.

As a method for forming the photosensitive resin composition layer on the uneven surface of the temporary support in the present invention, a known coating method can be used, for example, a doctor blade coating method, a wire bar coating method, Examples thereof include roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating method and the like. The thickness of the photosensitive resin composition layer in the present invention is preferably 0.1 to 20 μm, and preferably 0.3 to 15 μm, in consideration of electrical characteristics in the case of a reflective liquid crystal display device. Is more preferable and 0.5 to 10 μm is particularly preferable. In addition, the viscosity of the photosensitive resin composition layer in the present invention is such that when the roll-shaped photosensitive element described later is used, exudation of the photosensitive resin composition from the end surface of the photosensitive element for one month or more is prevented. And from the standpoint of preventing defective exposure and undeveloped residue caused by the debris of the photosensitive resin composition adhering to the substrate when the photosensitive element is cut, 3
At 0 ° C., it is preferably 15 to 100 MPa · s, more preferably 20 to 90 MPa · s, and particularly preferably 25 to 80 MPa · s.
The viscosity is 1.96 × at 30 ° C. and 80 ° C. in the thickness direction of a photosensitive resin composition sample having a diameter of 7 mm and a thickness of 2 mm.
The rate of change in thickness was measured by ^applying a load of 10 ^-2 N, and the value was converted to viscosity on the assumption of Newtonian fluid from this rate of change.

In the photosensitive element for forming the diffuse reflection underlayer of the present invention, a cover film may be further laminated on the photosensitive resin composition layer.

As the cover film, polyethylene,
A film having a thickness of about 5 to 100 μm made of polypropylene, polyethylene terephthalate, polycarbonate or the like can be used.

The thus-obtained photosensitive element for forming a diffuse reflection underlayer can be wound in a roll and stored or used.

An example of the method of manufacturing the diffuse reflection plate for the reflective liquid crystal display device of the present invention will be described below. [(I) on the substrate,
Step of laminating a photosensitive element for forming a diffuse reflection underlying layer formed by laminating a layer of a photosensitive resin composition on the irregular surface of a temporary support having an irregular surface] The substrate used in the present invention, There is no limitation, and examples thereof include a ceramic plate, a plastic plate, and a glass plate. An insulating layer, an electrode, a TFT and the like may be provided on this substrate.

In the present invention, as a method for laminating the photosensitive element for forming the diffuse reflection underlayer on the substrate, when the cover film is present in contact with the photosensitive resin composition layer, the cover film is present. After the removal, the pressure-sensitive adhesive roll may be pressure-bonded so that the photosensitive resin composition layer contacts the substrate.

The pressure-bonding roll may be equipped with a heating means so that it can be heat-pressure bonded, and the heating temperature in the heat-pressure bonding is preferably 10 to 180 ° C.
It is more preferable that the temperature is 0 to 160 ° C., and 30 to 150
It is particularly preferable to set the temperature to ° C. This heating temperature is 10 ℃
When it is less than 180 ° C., the adhesiveness between the photosensitive resin composition layer and the substrate tends to decrease, and when it exceeds 180 ° C., the constituent components of the photosensitive resin composition layer tend to be thermoset or thermally decomposed.

The crimping pressure during heating and crimping is 5 in linear pressure.
It is preferably from 0 to 1 × 10 ⁵ N / m, and 2.5 × 1
It is more preferable that it is from 0 ^{2 to 5} × 10 ⁴ N / m, and 5 × 1
It is particularly preferable that it is from 0 ^{2 to 4} × 10 ⁴ N / m. When the pressure bonding pressure is less than 50 N / m, the adhesiveness between the photosensitive resin composition layer and the substrate tends to decrease, and the pressure is 1 × 10 ⁵ N / m.
If it exceeds m, the substrate tends to be broken.

If the photosensitive element for forming the diffuse reflection underlayer is heated as described above, it is not necessary to preheat the substrate, but the point of further improving the adhesion between the photosensitive resin composition layer and the substrate. Therefore, it is preferable to preheat the substrate. The preheating temperature at this time is preferably 30 to 180 ° C. In this way, the photosensitive resin composition layer of the photosensitive element for forming the diffuse reflection underlayer of the present invention can be laminated on the substrate.

Further, in the present invention, as another method for laminating a photosensitive resin composition layer as a diffuse reflection underlayer on a substrate, (I ′) a photosensitive resin composition layer may be formed on the substrate. After forming the layer, a step of laminating a temporary support having an uneven surface so that the uneven surface is in contact with the layer of the photosensitive resin composition may be mentioned. As a method of forming a layer of the photosensitive resin composition on a substrate, in the photosensitive element for forming a diffuse reflection underlayer, a known coating method on the uneven surface of the temporary support having an uneven surface After forming a layer of the photosensitive resin composition on the base film using the same method or a known coating method to form a layer of the photosensitive resin composition using Examples include a method of pressure-bonding the resin composition layer using the pressure roll so that the resin composition layer is in contact with the resin composition layer. Further, as a method for laminating a temporary support having an uneven surface so that the uneven surface is in contact with the layer of the photosensitive resin composition, a method of laminating the photosensitive element for forming the diffuse reflection underlayer on a substrate In the same manner as above, a method of pressure bonding using the pressure bonding roll and the like can be mentioned.

[(II) Step of imagewise irradiating the photosensitive resin composition layer with an actinic ray] In the present invention, the method of imagewise irradiating the photosensitive resin composition layer with an actinic ray is as follows. A known method is to irradiate the laminated photosensitive resin composition layers with a known actinic ray through a photomask. At this time, when a temporary support having the above-mentioned uneven surface is present on the photosensitive resin composition layer, the actinic rays are irradiated also through this temporary support. Further, as the actinic ray in the present invention, a known actinic light source can be used, and examples thereof include a carbon arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, and the like, and it is particularly limited as long as it effectively radiates ultraviolet rays. Not done.

[(III) Step of peeling and removing the temporary support having an uneven surface] In the present invention, the temporary support having an uneven surface in contact with the photosensitive resin composition layer is peeled and removed. Examples of the method include a method of adhering an adhesive tape to the temporary support or a method of physically peeling the temporary support by using a hook type jig or the like. In addition, for the purpose of improving workability, we use power such as static electricity and suction power,
A method in which the temporary support is physically peeled off may also be used.

[(IV) Step of Forming Pattern by Selectively Removing Photosensitive Resin Composition Layer by Development] The developing method in the present invention includes an alkaline aqueous solution, an aqueous developing solution,
Using a known developing solution such as an organic solvent, a known method such as spraying, rocking dipping, brushing, scraping, and the like is used to perform development, and a method for removing unnecessary portions is mentioned. From the viewpoint, an alkaline aqueous solution is preferable.

Examples of the base of the aqueous alkali solution include alkali hydroxide (lithium, sodium or potassium hydroxide, etc.), alkali carbonate (lithium, sodium or potassium carbonate or bicarbonate, etc.), alkali metal phosphate ( Potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc., among which tetramethylammonium hydroxide, etc. are preferred. It is mentioned as a thing. The development temperature and time can be adjusted according to the developability of the photosensitive resin composition layer in the present invention. Further, a surfactant, a defoaming agent, a small amount of an organic solvent for accelerating the development and the like can be mixed in the alkaline aqueous solution. In addition, after development, the base of the aqueous alkali solution remaining in the photosensitive resin composition layer after photocuring, an organic acid, an inorganic acid or an aqueous solution of these acids is used, spraying, rocking dipping,
The acid treatment (neutralization treatment) can be performed by a known method such as brushing or scraping. Furthermore, a step of washing with water can be performed after the acid treatment (neutralization treatment).

[(V) Step of Irradiating Actinic Ray on Photosensitive Resin Composition Layer Having Pattern] In the present invention, the uneven shape formed on the surface of the photosensitive resin composition layer having a pattern is formed under high temperature. Performing a step of irradiating the patterned photosensitive resin composition layer with actinic rays for the purpose of maintaining, improving substrate adhesion under high temperature and high humidity, and improving chemical resistance. You can In the present invention, as a method of irradiating the patterned photosensitive resin composition layer with actinic rays, a known method of effectively irradiating the patterned photosensitive resin composition layer on the substrate with actinic rays is used. If there is no particular limitation. In addition, the actinic ray in the present invention includes a known actinic light source that can be used in the step (II), and is not particularly limited as long as it can effectively radiate ultraviolet rays and the like. At this time, the irradiation amount of the actinic ray is usually 1 × 10 ^{2 to} 1 × 10 ⁵ J / m ² , and heating can be accompanied during the irradiation. If the actinic ray irradiation amount is less than 1 × 10 ² J / m ² , the effect tends to be insufficient, and if it exceeds 1 × 10 ⁵ J / m ² , the photosensitive resin composition layer tends to be discolored.

[(VI) Step of Heating Patterned Photosensitive Resin Composition Layer] In the present invention, as a method of heating the patterned photosensitive resin composition layer, hot air radiation, infrared irradiation heating, etc. may be used. There is no particular limitation as long as it is a method of effectively heating the photosensitive resin composition layer having a pattern formed on the substrate. The temperature during heating is preferably 140 to 300 ° C., and 15
It is more preferable that the temperature is 0 to 290 ° C., and 160 to 28
Particularly preferably, the temperature is 0 ° C. This heating temperature is 14
Below 0 ° C, the effect tends to be insufficient,
When the temperature exceeds ° C, the constituent components of the photosensitive resin composition layer tend to be thermally decomposed.

The diffuse reflection underlayer having a desired uneven surface can be formed by the method described above. The diffuse reflection plate for a reflective liquid crystal display device according to the present invention can be obtained by forming a reflection film on the diffuse reflection underlayer. As a method for forming the reflective film on the diffuse reflection base layer, a known method can be used, and examples thereof include a method for forming a metal film of Ag, Al or the like by a sputtering method, a vapor deposition method or the like. The photosensitive resin composition of the present invention is not limited to the use of a diffuse reflection plate for a reflection type liquid crystal display device, for example, a resist for forming a conductor circuit such as a printed wiring board, for forming various members in a plasma display panel. It can also be suitably used for applications such as resists. At this time, the photosensitive resin composition of the present invention can also be used as a photosensitive element formed on a support such as a polyethylene terephthalate film.

[0050]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

Production Example 1 [Preparation of Binder Polymer Solution (b-1)] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer was charged with (1) shown in Table 1 and charged with nitrogen. The temperature was raised to 80 ° C. in a gas atmosphere, and (2) shown in Table 1 was uniformly added dropwise over 4 hours while maintaining the reaction temperature at 80 ° C. ± 2 ° C.

After the dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution having a weight average molecular weight of about 30,000 (solid content: 40.6% by weight) (b-1). Obtained.

[0053]

[Table 1]

Production Example 2 [Preparation of Binder Polymer Solution (b-2)] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer was charged with (1) shown in Table 2 and charged with nitrogen. The temperature was raised to 80 ° C. in a gas atmosphere, and (2) shown in Table 2 was uniformly added dropwise over 4 hours while maintaining the reaction temperature at 80 ° C. ± 2 ° C.
After the dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and then (3) shown in Table 2 was added. After adding (3), the reaction system was heated to 100 ° C., and (4) shown in Table 2 was added dropwise over 0.5 hour. After the dropwise addition of (4), the mixture was continuously stirred at 100 ° C. for 20 hours and then cooled to room temperature (25 ° C.) to give a film-forming polymer solution having a weight average molecular weight of about 30,000 (solid content: 36.0% by weight). And an ethylenically unsaturated group concentration of 6.3 × 10 ⁻⁴ mol / g) (b-2) was obtained.

[0055]

[Table 2]

Example 1 [Production of silyl group-containing photopolymerizable unsaturated compound (a-1)] Table 3 shows a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer ( (1) was charged, and (2) shown in Table 3 was uniformly added dropwise over 2 hours under a dry nitrogen gas atmosphere while maintaining the reaction temperature at 30 ° C ± 2 ° C.

After the addition of (2), stirring was continued at 30 ° C. ± 2 ° C. for 2 hours, and then (3) shown in Table 3 was added dropwise to 30 ° C.
The mixture was stirred at ± 2 ° C for 0.5 hour to obtain a silyl group-containing photopolymerizable unsaturated compound (a-1).

[0058]

[Table 3]

[Preparation of Photosensitive Resin Composition Solution (V-1)]
The materials shown in Table 4 were mixed with a stirrer for 15 minutes to prepare a photosensitive resin composition solution (V-1).

[Table 4]

[Preparation of Photosensitive Element (i) for Forming Diffuse Reflecting Underlayer] A sandblasted polyethylene terephthalate film was used as a temporary support having an uneven surface, and the obtained photosensitive resin composition solution ( V-
1) is uniformly applied on the surface of the temporary support having an uneven shape using a comma coater, and dried for 3 minutes with a hot air convection dryer at 100 ° C. to remove the solvent, and a photosensitive resin composition layer is formed. Formed. The thickness of the obtained photosensitive resin composition layer is 5 μm.
Met. Next, a polyethylene film having a thickness of 25 μm was laminated on the obtained photosensitive resin composition layer as a cover film to prepare a photosensitive element (i) for forming a diffuse reflection underlayer.

[Production of Diffuse Reflection Underlayer-Forming Substrate] The photosensitive resin composition layer was formed on a glass substrate having a thickness of 1 mm while peeling off the polyethylene film of the obtained photosensitive element (i) for forming a diffuse reflection underlayer. Laminator (made by Hitachi Chemical Co., Ltd., trade name HLM-1500
Mold) and a roll temperature of 120 ° C. and a substrate feed rate of 0.
5m / min, crimping pressure (cylinder pressure) 4X10 ⁵ Pa
(Using a substrate with a thickness of 1 mm, a length of 10 cm and a width of 10 cm,
The linear pressure at this time was laminated under the condition of 9.8 × 10 ³ N / m) to prepare a substrate in which the photosensitive resin composition layer and the temporary support were laminated on the glass substrate. Next, diameter 5μ
m using a photomask having an actinic ray opaque portion,
Reduction projection exposure machine (Canon Co., FPA-300
0i) was used to imagewise expose actinic radiation with an exposure dose of 6 × 10 ² J / m ² .

Then, after removing the temporary support by peeling it off, 0.5% by weight containing 0.5% by weight of a surfactant.
25 with an aqueous solution of tetramethylammonium hydroxide
A hole pattern was formed by spray-developing at 50 ° C. for 50 seconds to selectively remove the photosensitive resin composition layer. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed.

After development, it is dried at 80 ° C. for 10 minutes and 3 × 10 is obtained by using a Toshiba ultraviolet irradiation device manufactured by Toshiba Denshi Co., Ltd.
Ultraviolet irradiation of ⁴ J / m ² was performed. Then, it was heated for 30 minutes in a hot air convection dryer at 250 ° C. to obtain a substrate on which a diffuse reflection underlayer was formed. When the surface of the obtained diffused reflection underlayer was observed, it was confirmed that the uneven shape was almost the same as the transferred shape of the sandblasted unevenness. The substrate for forming a diffuse reflection underlayer obtained in the above step is heated at a temperature of 60.
After putting it in a constant temperature bath kept at ℃ and humidity of 90% for 24 hours,
When a cross-cut test (JIS-K5400, 1 mm square grid method) was carried out, the diffuse reflection underlayer did not peel off at all, and the substrate adhesion was good.

<Production of Diffuse Reflecting Plate for Reflective Liquid Crystal Display> An Al film (as a reflecting film) was formed on the substrate for forming the diffuse reflection underlayer heated at 250 ° C. for 30 minutes by a hot air convection dryer by a sputtering method. 0.2 μm of the layers were stacked to prepare a diffuse reflection plate for a reflective liquid crystal display device. The obtained diffuse reflection plate for a reflective liquid crystal display device maintained the uneven surface having excellent diffuse reflection characteristics, and the diffuse reflection characteristics as designed were obtained. Further, when the interface between the diffuse reflection underlayer and the Al film was observed, no peeling of the Al film from the surface of the diffuse reflection underlayer occurred, and the form as a good diffuse reflection plate was maintained.

<Evaluation of Adhesion during Development of Photosensitive Resin Composition Layer> The photosensitive element (i) for forming the diffuse reflection underlayer described above.
Was laminated on a glass substrate in the same manner as described above to prepare a substrate on which a photosensitive resin composition layer and a temporary support were laminated, and then reduced projection using a line pattern photomask with a line / space of 5 μm / 5 μm. Using an exposure machine (Canon, FPA-3000i), the exposure amount is 6X
The actinic radiation was imagewise irradiated at 10 ² J / m ² . Then, after removing the temporary support by peeling it off, 0.5% by weight
Using a 0.5 wt% aqueous solution of tetramethylammonium hydroxide containing a surfactant, the mixture was spray-developed at 25 ° C. for 50 seconds to selectively remove the photosensitive resin composition layer to form a line pattern. .. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate and the line / space was 5 μm / 5.
A line pattern of μm was formed, and the substrate adhesion was good.

Example 2 [Preparation of silyl group-containing photopolymerizable unsaturated compound (a-2)] Table 5 shows a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer ( (1) was charged, and (2) shown in Table 5 was uniformly added dropwise over 2 hours under a dry nitrogen gas atmosphere while maintaining the reaction temperature at 30 ° C ± 2 ° C.

After the dropping of (2), stirring was continued at 30 ° C. ± 2 ° C. for 2 hours, and then (3) shown in Table 5 was added dropwise to 30 ° C.
The mixture was stirred at ± 2 ° C for 0.5 hour to obtain a 50 mol% silyl group-containing photopolymerizable unsaturated compound (a-2).

[0068]

[Table 5]

[Preparation of Photosensitive Resin Composition Solution (V-2)]
The materials shown in Table 6 were mixed for 15 minutes using a stirrer to prepare a photosensitive resin composition solution (V-2).

[Table 6]

[Preparation of Diffuse Reflecting Underlayer-Forming Photosensitive Element (ii)] In the preparation of the diffuse reflecting underlayer-forming photosensitive element of Example 1, the photosensitive resin composition solution (V
-1) is the photosensitive resin composition solution (V-
A photosensitive element (ii) for forming a diffused reflection underlayer was obtained in the same manner as in Example 1 except that the substituting step 2) was performed.

[Production of Diffuse Reflection Underlayer-Forming Substrate] In the production of the diffuse reflection underlayer-forming substrate of Example 1, the diffuse reflection underlayer-forming photosensitive element (i) was used as the diffuse reflection underlayer-forming substrate obtained here. The procedure was performed in the same manner as in Example 1 except that the forming photosensitive element (ii) was used, and after a substrate in which the photosensitive resin composition layer and the temporary support were laminated was prepared on the glass substrate, the photosensitive resin was formed. The composition layer was selectively removed to form a hole pattern. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed. Then, in the same manner as in Example 1, a substrate on which a diffuse reflection underlayer was formed was obtained. When the surface of the obtained diffused reflection underlayer was observed, it was confirmed that the uneven shape was almost the same as the transferred shape of the sandblasted unevenness. A cross-cut test was performed on the obtained diffused reflection underlayer-formed substrate in the same manner as in Example 1. As a result, the diffused reflection underlayer did not peel off at all and had good substrate adhesion.

<Production of Diffuse Reflecting Plate for Reflective Liquid Crystal Display Device> An Al film was laminated on the obtained substrate for forming a diffuse reflective underlayer in the same manner as in Example 1, and diffuse reflection for a reflective liquid crystal display device was performed. A plate was made. The obtained diffuse reflection plate for a reflective liquid crystal display device maintained the uneven surface having excellent diffuse reflection characteristics, and the diffuse reflection characteristics as designed were obtained. Also, when observing the interface between the diffuse reflection underlayer and the Al film, no peeling of the Al film from the surface of the diffuse reflection underlayer occurs,
It retained its form as a good diffuse reflector.

<Evaluation of Adhesion during Development of Photosensitive Resin Composition Layer> In the evaluation of adhesion during development of the photosensitive resin composition layer of Example 1, the photosensitive element (i) for forming a diffuse reflection underlayer is used.
Was performed in the same manner as in Example 1 except that the photosensitive element (ii) for forming a diffuse reflection underlayer obtained in this step was replaced with a line pattern was formed. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate and the line / space was 5 μm / 5 μ.
A line pattern of m was formed, and the substrate adhesion was good.

Example 3 [Production of silyl group-containing photopolymerizable unsaturated compound (a-3)] Table 7 shows a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer ( (1) was charged, and (2) shown in Table 7 was uniformly added dropwise over 2 hours under a dry nitrogen gas atmosphere while maintaining the reaction temperature at 30 ° C ± 2 ° C.

After the dropping of (2), stirring was continued at 30 ° C. ± 2 ° C. for 2 hours, and then (3) shown in Table 7 was added dropwise to obtain 30 ° C.
The mixture was stirred at ± 2 ° C for 0.5 hour to obtain a silyl group-containing photopolymerizable unsaturated compound (a-3).

[0076]

[Table 7]

[Preparation of Photosensitive Resin Composition Solution (V-3)]
The materials shown in Table 8 were mixed with a stirrer for 15 minutes to prepare a photosensitive resin composition solution (V-3).

[Table 8]

[Preparation of Diffuse Reflecting Underlayer Forming Photosensitive Element (iii)] In the preparation of the diffuse reflecting underlayer forming photosensitive element of Example 1, the photosensitive resin composition solution (V-1) was used here. The resulting photosensitive resin composition solution (V-
The procedure of Example 1 was repeated except that 3) was changed to obtain a photosensitive element (iii) for forming a diffuse reflection underlayer.

[Production of Diffuse Reflection Underlayer-Forming Substrate] In the production of the diffuse reflection underlayer-forming substrate of Example 1, the diffuse reflection underlayer-forming photosensitive element (i) was used as the diffuse reflection underlayer-forming substrate obtained here. Example 1 was repeated except that the forming photosensitive element (iii) was used instead of the forming photosensitive element (iii).
After preparing a substrate in which the photosensitive resin composition layer and the temporary support were laminated, the photosensitive resin composition layer was selectively removed to form a hole pattern. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed. Then, in the same manner as in Example 1, a substrate on which a diffuse reflection underlayer was formed was obtained. When the surface of the obtained diffused reflection underlayer was observed, it was confirmed that the uneven shape was almost the same as the transferred shape of the sandblasted unevenness. A cross-cut test was performed on the obtained diffused reflection underlayer-formed substrate in the same manner as in Example 1. As a result, the diffused reflection underlayer did not peel off at all and had good substrate adhesion.

<Manufacture of Diffuse Reflecting Plate for Reflective Liquid Crystal Display Device> An Al film was laminated on the obtained substrate for forming a diffuse reflective underlayer, in the same manner as in Example 1, and diffuse reflection for a reflective liquid crystal display device was performed. A plate was made. The obtained diffuse reflection plate for a reflective liquid crystal display device maintained the uneven surface having excellent diffuse reflection characteristics, and the diffuse reflection characteristics as designed were obtained. Also, when observing the interface between the diffuse reflection underlayer and the Al film, no peeling of the Al film from the surface of the diffuse reflection underlayer occurs,
It retained its form as a good diffuse reflector.

<Evaluation of Adhesion during Development of Photosensitive Resin Composition Layer> In the evaluation of adhesion during development of the photosensitive resin composition layer of Example 1, the photosensitive element (i) for forming a diffuse reflection underlayer was used.
Was carried out in the same manner as in Example 1 except that the photosensitive element (iii) for forming a diffuse reflection underlayer obtained here was replaced by
A line pattern was formed. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate and the line / space was 5 μm / 5.
A line pattern of μm was formed, and the substrate adhesion was good.

Example 4 [Production of silyl group-containing photopolymerizable unsaturated compound (a-4)] Table 9 shows a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer ( (1) was charged, and (2) shown in Table 9 was uniformly added dropwise over 2 hours while maintaining the reaction temperature at 30 ° C. ± 2 ° C. in a dry nitrogen gas atmosphere.

After the dropping of (2), stirring was continued at 30 ° C. ± 2 ° C. for 2 hours, and then (3) shown in Table 9 was added dropwise to 30 ° C.
The mixture was stirred at ± 2 ° C for 0.5 hour to obtain a silyl group-containing photopolymerizable unsaturated compound (a-4).

[0084]

[Table 9]

[Preparation of Photosensitive Resin Composition Solution (V-4)]
The materials shown in Table 10 were mixed with a stirrer for 15 minutes,
A photosensitive resin composition solution (V-4) was prepared.

[Table 10]

[Preparation of Photosensitive Element (iv) for Forming Diffuse Reflecting Underlayer] In preparation of the photosensitive element for forming diffuse reflecting underlayer in Example 1, the photosensitive resin composition solution (V
-1) is the photosensitive resin composition solution (V-
The same procedure as in Example 1 was carried out except that 4) was changed to obtain a photosensitive element (iv) for forming a diffuse reflection underlayer.

[Production of Diffuse Reflection Underlayer-Forming Substrate] In the production of the diffuse reflection underlayer-forming substrate of Example 1, the diffuse reflection underlayer-forming photosensitive element (i) was used as the diffuse reflection underlayer-forming substrate obtained here. The procedure is performed in the same manner as in Example 1 except that the forming photosensitive element (iv) is used, and after a substrate in which the photosensitive resin composition layer and the temporary support are laminated is produced on the glass substrate, the photosensitive resin is formed. The composition layer was selectively removed to form a hole pattern. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed. Then, in the same manner as in Example 1, a substrate on which a diffuse reflection underlayer was formed was obtained. When the surface of the obtained diffused reflection underlayer was observed, it was confirmed that the uneven shape was almost the same as the transferred shape of the sandblasted unevenness. A cross-cut test was performed on the obtained diffused reflection underlayer-formed substrate in the same manner as in Example 1. As a result, the diffused reflection underlayer did not peel off at all and had good substrate adhesion.

<Manufacture of Diffuse Reflecting Plate for Reflective Liquid Crystal Display Device> An Al film was laminated on the obtained substrate for forming a diffuse reflective underlayer in the same manner as in Example 1, and diffuse reflection for a reflective liquid crystal display device was performed. A plate was made. The obtained diffuse reflection plate for a reflective liquid crystal display device maintained the uneven surface having excellent diffuse reflection characteristics, and the diffuse reflection characteristics as designed were obtained. Also, when observing the interface between the diffuse reflection underlayer and the Al film, no peeling of the Al film from the surface of the diffuse reflection underlayer occurs,
It retained its form as a good diffuse reflector.

<Evaluation of Adhesion during Development of Photosensitive Resin Composition Layer> In the evaluation of adhesion during development of the photosensitive resin composition layer of Example 1, the photosensitive element (i) for forming a diffuse reflection underlayer was used.
Was performed in the same manner as in Example 1 except that the photosensitive element (iv) for forming a diffuse reflection underlayer obtained here was replaced with a line pattern was formed. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate and the line / space was 5 μm / 5 μ.
A line pattern of m was formed, and the substrate adhesion was good.

Example 5 [Preparation of Photosensitive Resin Composition Solution (V-5)] The materials shown in Table 11 were mixed with a stirrer for 15 minutes to prepare a photosensitive resin composition solution (V-5). did.

[Table 11]

[Preparation of Photosensitive Element (v) for Forming Diffuse Reflecting Underlayer] In the preparation of the photosensitive element for forming diffuse reflecting underlayer in Example 1, the photosensitive resin composition solution (V
-1) is the photosensitive resin composition solution (V-
A photosensitive element (v) for forming a diffused reflection underlayer was obtained in the same manner as in Example 1 except that 5) was replaced.

[Production of Diffuse Reflection Underlayer-Forming Substrate] In the production of the diffuse reflection underlayer-forming substrate of Example 1, the diffuse reflection underlayer-forming photosensitive element (i) was used as the diffuse reflection underlayer-forming substrate obtained here. After performing the same procedure as in Example 1 except that the forming photosensitive element (v) was used, a substrate in which the photosensitive resin composition layer and the temporary support were laminated on the glass substrate was prepared, and then the photosensitive resin was formed. The composition layer was selectively removed to form a hole pattern. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed. Then, in the same manner as in Example 1, a substrate on which a diffuse reflection underlayer was formed was obtained. When the surface of the obtained diffused reflection underlayer was observed, it was confirmed that the uneven shape was almost the same as the transferred shape of the sandblasted unevenness. A cross-cut test was performed on the obtained diffused reflection underlayer-formed substrate in the same manner as in Example 1. As a result, the diffused reflection underlayer did not peel off at all and had good substrate adhesion.

<Manufacture of Diffuse Reflecting Plate for Reflective Liquid Crystal Display Device> An Al film was laminated on the obtained substrate for forming a diffuse reflective underlayer, and the diffuse reflection for a reflective liquid crystal display device was performed in the same manner as in Example 1. A plate was made. The obtained diffuse reflection plate for a reflective liquid crystal display device maintained the uneven surface having excellent diffuse reflection characteristics, and the diffuse reflection characteristics as designed were obtained. Also, when observing the interface between the diffuse reflection underlayer and the Al film, no peeling of the Al film from the surface of the diffuse reflection underlayer occurs,
It retained its form as a good diffuse reflector.

<Evaluation of Adhesion during Development of Photosensitive Resin Composition Layer> In the evaluation of the adhesion during development of the photosensitive resin composition layer of Example 1, the photosensitive element (i) for forming a diffuse reflection underlayer was used.
A line pattern was formed in the same manner as in Example 1 except that the photosensitive element (v) for forming a diffuse reflection underlayer obtained in this step was replaced with. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate and the line / space was 5 μm / 5 μ.
A line pattern of m was formed, and the substrate adhesion was good.

Example 6 [Production of Diffuse Reflecting Underlayer-Forming Substrate] The photosensitive resin composition solution (V-1) of Example 1 was uniformly applied onto a glass substrate having a thickness of 1 mm by using a comma coater. , 100
Dry with a hot air convection dryer at ℃ for 3 minutes to remove the solvent,
A photosensitive resin composition layer was formed. The thickness of the obtained photosensitive resin composition layer was 5 μm. Then, using a polyethylene terephthalate film subjected to sandblasting as a temporary support having an uneven surface, a laminator (so that the uneven surface of the temporary support is in contact with the photosensitive resin composition layer formed on the substrate ( Manufactured by Hitachi Chemical Co., Ltd.
Roll name 12 using the product name HLM-1500)
0 ° C., substrate feed rate 0.5 m / min, pressure bonding (cylinder pressure) 4 × 10 ⁵ Pa (thickness 1 mm, length 10 cm × width 10 cm is used, and the linear pressure at this time is 9.8 × 10 ³
N / m) was laminated to prepare a substrate in which the photosensitive resin composition layer and the temporary support were laminated on the glass substrate. Then, using a photomask having an actinic ray opaque portion having a diameter of 5 μm, a reduction projection exposure machine (Canon Co., Ltd., FPA-3000i) was used and the exposure amount was 6 × 1.
The image was irradiated with actinic radiation at 0 ² J / m ² .

Then, after removing the temporary support by peeling it off, 0.5% by weight containing 0.5% by weight of a surfactant.
25 with an aqueous solution of tetramethylammonium hydroxide
A hole pattern was formed by spray-developing at 50 ° C. for 50 seconds to selectively remove the photosensitive resin composition layer. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed.

After development, it is dried at 80 ° C. for 10 minutes and 3 × 10 3
Ultraviolet irradiation of ⁴ J / m ² was performed. Then, it was heated for 30 minutes in a hot air convection dryer at 250 ° C. to obtain a substrate on which a diffuse reflection underlayer was formed. When the surface of the obtained diffused reflection underlayer was observed, it was confirmed that the uneven shape was almost the same as the transferred shape of the sandblasted unevenness. A cross-cut test was performed on the diffused reflection underlayer-formed substrate obtained in the above step in the same manner as in Example 1. As a result, the diffused reflection underlayer did not peel off at all and had good substrate adhesion.

<Manufacture of Diffuse Reflecting Plate for Reflective Liquid Crystal Display Device> An Al film was laminated on the obtained substrate for forming a diffuse reflective underlayer in the same manner as in Example 1, and diffuse reflection for a reflective liquid crystal display device was performed. A plate was made. The obtained diffuse reflection plate for a reflective liquid crystal display device maintained the uneven surface having excellent diffuse reflection characteristics, and the diffuse reflection characteristics as designed were obtained. Also, when observing the interface between the diffuse reflection underlayer and the Al film, no peeling of the Al film from the surface of the diffuse reflection underlayer occurs,
It retained its form as a good diffuse reflector.

<Evaluation of Adhesion during Development of Photosensitive Resin Composition Layer> Photosensitive resin composition solution (V-1) was prepared in the same manner as described above.
After forming a photosensitive resin composition layer having a thickness of 5 μm on a glass substrate, a temporary support having an uneven surface is laminated on the photosensitive resin composition layer to form a photosensitive resin on the glass substrate. A substrate in which the composition layer and the temporary support were laminated was produced. Then, a line pattern having a line / space of 5 μm / 5 μm was formed by the same method as in the evaluation of the adhesiveness during development of the photosensitive resin composition layer in Example 1. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate, and a line pattern with a line / space of 5 μm / 5 μm was formed, indicating good substrate adhesion. .

Comparative Example 1 [Preparation of Photosensitive Resin Composition Solution (V-6)] The materials shown in Table 12 were mixed with a stirrer for 15 minutes to prepare a photosensitive resin composition solution (V-6). did.

[Table 12]

[Production of Diffuse Reflecting Underlayer Forming Photosensitive Element (vi)] In the production of the diffuse reflecting underlayer forming photosensitive element of Example 1, the photosensitive resin composition solution (V
-1) is the photosensitive resin composition solution (V-
A photosensitive element (vi) for forming a diffused reflection underlayer was obtained in the same manner as in Example 1 except that 6) was used.

[Production of Diffuse Reflection Underlayer-Forming Substrate] In the production of the diffuse reflection underlayer-forming substrate of Example 1, the diffuse reflection underlayer-forming photosensitive element (i) was used as the diffuse reflection underlayer-forming substrate obtained here. The procedure was performed in the same manner as in Example 1 except that the forming photosensitive element (vi) was used, and a substrate in which the photosensitive resin composition layer and the temporary support were laminated on the glass substrate was prepared, and then the photosensitive resin was prepared. The composition layer was selectively removed to form a hole pattern. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed. Then, in the same manner as in Example 1, a substrate on which a diffuse reflection underlayer was formed was obtained. When the surface of the obtained diffused reflection underlayer was observed, the shape to which the sandblasted irregularities were transferred was slightly deformed and flattened. Further, a cross-cut test was performed on the obtained diffuse reflection underlayer-forming substrate in the same manner as in Example 1. However, peeling of the diffuse reflection underlayer was partially generated, and the substrate adhesion was slightly poor. It was

<Manufacture of Diffuse Reflecting Plate for Reflective Liquid Crystal Display Device> An Al film was laminated on the obtained substrate for forming a diffuse reflective underlayer in the same manner as in Example 1, and the diffuse reflection for a reflective liquid crystal display device was performed. A plate was made. When the interface between the diffuse reflection underlayer and the Al film of the obtained diffuse reflection plate for the reflective liquid crystal display device was observed, no peeling of the Al film from the surface of the diffuse reflection underlayer occurred, but the diffuse reflection plate The surface is slightly flattened,
The diffuse reflection property was deteriorated.

<Evaluation of Adhesion during Development of Photosensitive Resin Composition Layer> In the evaluation of adhesion during development of the photosensitive resin composition layer of Example 1, the photosensitive element (i) for forming a diffuse reflection underlayer was used.
Was performed in the same manner as in Example 1 except that the photosensitive element (vi) for forming a diffuse reflection underlayer obtained in this step was replaced with a line pattern. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate and the line / space was 5 μm / 5 μ.
The line pattern of m is peeled from the glass substrate,
The substrate adhesion was poor.

Comparative Example 2 [Preparation of Photosensitive Resin Composition Solution (V-7)] The materials shown in Table 13 were mixed with a stirrer for 15 minutes to prepare a photosensitive resin composition solution (V-7). did.

[Table 13]

[Production of Diffuse Reflecting Underlayer Forming Photosensitive Element (vii)] In the production of the diffuse reflecting underlayer forming photosensitive element of Example 1, the photosensitive resin composition solution (V-1) was used here. The resulting photosensitive resin composition solution (V-
A photosensitive element (vii) for forming a diffuse reflection underlayer was obtained in the same manner as in Example 1 except that the step (7) was replaced.

[Production of Diffuse Reflection Underlayer-Forming Substrate] In the production of the diffuse reflection underlayer-forming substrate of Example 1, the diffuse reflection underlayer-forming photosensitive element (i) was used as the diffuse reflection underlayer-forming substrate obtained here. Example 1 was repeated except that the forming photosensitive element (vii) was used instead of the forming photosensitive element (vii).
After preparing a substrate in which the photosensitive resin composition layer and the temporary support were laminated, the photosensitive resin composition layer was selectively removed to form a hole pattern. Observation of the obtained hole pattern showed that the photocured photosensitive resin composition layer was not peeled from the substrate, and a hole pattern having a diameter of 5 μm was well formed. Then, in the same manner as in Example 1, a substrate on which a diffuse reflection underlayer was formed was obtained. When the surface of the obtained diffuse reflection underlayer was observed, it was found that the uneven shape substantially the same as the transferred shape of the sandblasted unevenness was maintained. Further, in the same manner as in Example 1,
A cross-cut test was performed on the obtained diffused reflection underlayer-formed substrate, but peeling of the diffused reflection underlayer partially occurred, and the substrate adhesion was slightly inferior.

<Manufacture of Diffuse Reflecting Plate for Reflective Liquid Crystal Display Device> An Al film was laminated on the obtained substrate for forming a diffuse reflective underlayer in the same manner as in Example 1 to perform diffuse reflection for a reflective liquid crystal display device. A plate was made. Observation of the interface between the diffuse reflection underlayer and the Al film of the obtained diffuse reflection plate for a reflective liquid crystal display device revealed that no peeling of the Al film from the surface of the diffuse reflection underlayer was observed, indicating good diffuse reflection. It retained its form as a plate. <Evaluation of Adhesion at Development of Photosensitive Resin Composition Layer> In the evaluation of adhesion at development of the photosensitive resin composition layer of Example 1, the photosensitive element (i) for forming a diffuse reflection underlayer was obtained here. Photosensitive element for forming diffuse reflection underlayer (vii)
A line pattern was formed in the same manner as in Example 1 except that the above procedure was used. Observation of the obtained line pattern revealed that the photocured photosensitive resin composition layer did not peel off from the substrate, and the line pattern with a line / space of 5 μm / 5 μm was peeled off from the glass substrate. It was inferior.

[0109]

The silyl group-containing photopolymerizable unsaturated compound according to claims 1 to 3 and the photosensitive resin composition according to claim 4 are an uneven surface capable of diffusely reflecting light in a diffuse reflection underlayer. The excellent shape retention property under high temperature and the excellent substrate adhesion of the diffuse reflection underlayer under high temperature and high humidity and photolithography makes it possible to manufacture the diffuse reflection plate for the reflective liquid crystal display device with high yield. . The photosensitive element for forming a diffuse reflection underlayer according to claim 5 can manufacture a diffuse reflection plate and a reflection type liquid crystal display device with excellent workability in addition to the above effects. In addition to the above effects, the method of manufacturing a diffuse reflection plate for a reflection type liquid crystal display device according to claim 6 can contribute to further cost reduction in the manufacture of the diffusion reflection plate and the reflection type liquid crystal display device. .

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/02 G02B 5/02 C 4J011 5/08 5/08 A 4J026 C 4J100 G02F 1/1335 520 G02F 1 / 1335 520 G03F 7/027 502 G03F 7/027 502 513 513 7/075 501 7/075 501 501 7/09 7/09 F term (reference) 2H025 AB11 AB14 AC01 AD01 BC13 BC42 BC50 BC66 BC83 DA20 2H042 BA04 BA15 BA20 DA02 DA11 DB00 DC02 DC08 DE00 2H091 FA14Z FB02 LA30 4H006 AA01 AB46 AB92 4H049 VN01 VQ44 VR21 VR43 VU20 VU29 4J011 AA05 AC04 BA04 CC04 CC10 PA65 PA66 PA68 PA69 PA74 PA76 PB38 PB39 QA14 QA25 QA43 SA05 SA22 SA25 SA26 SA32 SA34 SA54 SA62 SA63 SA78 UA01 VA01 WA01 4J026 AA17 AA25 AA38 AA43 AA44 AA45 AA49 AA50 AA61 AA68 AC23 AC24 BA28 BA39 BA43 BB01 BB02 DB06 DB 36 FA05 GA06 4J100 AL66P BA38P BA77P CA01 CA03 JA38

Claims (7)

[Claims] 1. A (a) silyl group-containing photopolymerizable unsaturated compound having at least two ethylenically unsaturated groups in one molecule and further having at least one hydrolyzable group-containing silyl group. 2. A compound having at least two ethylenically unsaturated groups in one molecule and at least one hydrolyzable group-containing silyl group, which further has a urethane bond. (A) A photopolymerizable unsaturated compound containing a silyl group. 3. To (A) a hydroxyl group of a photopolymerizable unsaturated compound having at least one hydroxyl group and at least two ethylenically unsaturated groups in one molecule, (B) one in one molecule The (a) silyl group-containing photopolymerizable unsaturated compound according to claim 1, which is obtained by reacting the isocyanate group of an organosilicon compound having at least one hydrolyzable group-containing silyl group . 4. The (a) silyl group-containing photopolymerizable unsaturated compound according to any one of claims 1 to 3, (b) a binder polymer, and (c) at least one ethylenically unsaturated group. A photosensitive resin composition comprising: a photopolymerizable unsaturated compound having (d) a photopolymerization initiator. 5. A photosensitive element for forming a diffuse reflection underlayer having a layer of the photosensitive resin composition according to claim 4 on the uneven surface of a temporary support having an uneven surface. 6. (I) a step of laminating the photosensitive element for forming a diffuse reflection underlayer according to claim 5 on a substrate,
(II) a step of imagewise irradiating the photosensitive resin composition layer with an actinic ray, (III) a step of peeling and removing a temporary support having an uneven surface, (IV) a photosensitive resin composition layer by development To selectively remove the light to form a pattern, (V) to irradiate the patterned photosensitive resin composition layer with actinic rays, and (VI) to heat the patterned photosensitive resin composition layer. A method of manufacturing a diffuse reflection plate for a reflective liquid crystal display device, comprising forming a diffuse reflection underlayer having a desired uneven surface by a step, and further forming a reflection film on the diffuse reflection underlayer. 7. The component (A) is a photopolymerizable unsaturated compound represented by the following general formula [1], and the component (B) is an organosilicon compound represented by the following general formula [2]. Item (a) The silyl group-containing photopolymerizable unsaturated compound according to Item 3. [Chemical 1] (In the general formula [1], R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ , R ⁵ and R ⁶ each independently represent an alkylene group having 1 to 8 carbon atoms or a carbon atom. When each of R ⁴ , R ⁵ and R ⁶ is a plurality of R ^{4 s} , R ^{5 s} and R ^{6 s} , the R ^{4 s} , R ^{5 s} and R ^{6 s} may be the same or different, and k, l and m is independently an integer of 0 to 10) (In the general formula [2], R ⁷ represents an alkylene group having 1 to 8 carbon atoms or an alkylene oxide group having 1 to 8 carbon atoms, R ⁷
When there are a plurality of R ⁷ , R ⁷ may be the same or different, R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 10. is there)