JP2001264967A - Inorganic particle-containing photosensitive composition and sensitive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic particle-containing photosensitive composition having high sensitivity and capable of forming a pattern having high dimensional accuracy and a sensitive film obtained from the composition. SOLUTION: The inorganic particle-containing sensitive composition contains a compound having at least four (meth)acryloyl groups in one molecule as an ethylenically unsaturated group-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive composition containing inorganic particles and a photosensitive film.
In the formation of dielectrics, electrodes, resistors, phosphors, partition walls, color filters, and black matrices constituting each display cell of a plasma display panel, it is preferably used to form a pattern with high sensitivity and high dimensional accuracy. And a photosensitive film containing inorganic particles.

[0002]

2. Description of the Related Art In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 shows an AC type plasma display panel (hereinafter also referred to as “PDP”).
It is a schematic diagram which shows the cross-sectional shape of. In FIG. 1, reference numerals 1 and 2 denote glass substrates arranged opposite to each other, and reference numeral 3 denotes a partition. A cell is defined by the glass substrate 1, the glass substrate 2, and the partition 3. 4 is a transparent electrode fixed on the glass substrate 1, 5 is a bus electrode formed on the transparent electrode for the purpose of reducing the resistance of the transparent electrode, 6 is an address electrode fixed on the glass substrate 2, and 7 is a cell electrode. The retained phosphor, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is formed on the surface of the glass substrate 2 so as to cover the address electrode 6. Dielectric layer,
Reference numeral 10 denotes a protective film made of, for example, magnesium oxide.
In a direct current type PDP, a resistor is usually provided between an electrode terminal (anode terminal) and an electrode lead (anode lead). Further, in order to improve the contrast of the PDP, a color filter of red, green, and blue, or a black matrix having a stripe shape or a lattice shape is provided between the glass substrate 1 and the dielectric layer 8 or the dielectric material. It may be provided between the layer 8 and the protective film 10.

[0003] As a method of forming such various members of the PDP, (1) a screen printing method in which a non-photosensitive paste containing inorganic particles is screen-printed on a substrate to obtain a pattern and bake it, (2) Photolithography in which a film of a photosensitive inorganic particle-containing composition is formed on a substrate, and the film is irradiated with ultraviolet rays through a photomask and then developed to leave a pattern on the substrate, which is then baked. The law is known.

[0004]

However, in the screen printing method, the demand for the positional accuracy of the pattern becomes very severe with the increase in the size and definition of the panel.
There is a problem that normal printing cannot cope. Also,
The photolithography method has a problem that although the pattern position accuracy is excellent, the sensitivity in the depth direction of the inorganic particle-containing resin layer in the exposure step is low.

The present invention has been made based on the above circumstances. A first object of the present invention is to provide a photosensitive composition containing inorganic particles, which can form a pattern with high sensitivity and high dimensional accuracy. A second object of the present invention is to provide a photosensitive film having an inorganic particle-containing photosensitive resin layer capable of forming a pattern with high sensitivity and high dimensional accuracy. The inorganic particle-containing photosensitive composition and the photosensitive film of the present invention can be suitably used for forming members constituting each display cell of a plasma display panel.

[0006]

The photosensitive composition containing inorganic particles of the present invention comprises (A) inorganic particles, (B) an alkali-soluble resin, and (C) at least four (meth) acryloyl groups in one molecule. (Hereinafter, also referred to as a “specific (meth) acrylate compound”) and (D) a photopolymerization initiator. Further, in the photosensitive composition containing inorganic particles of the present invention, it is preferable to use a compound having a dipentaerythritol skeleton as the specific (meth) acrylate compound (C). The photosensitive film of the present invention contains an inorganic particle-containing photosensitive resin layer obtained from the inorganic particle-containing photosensitive composition of the present invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive composition containing inorganic particles of the present invention will be described in detail. (A) Inorganic particles The inorganic particles used in the inorganic particle-containing photosensitive composition vary depending on the type of the forming material. As the inorganic particles used for the dielectric and the partition wall forming material constituting the PDP, a low melting point glass frit and the like can be mentioned. The softening point of the low melting point glass frit is preferably in the range of 400 to 600 ° C. Softening point of glass frit is 40
When the temperature is lower than 0 ° C., in the step of baking the inorganic particle-containing photosensitive resin layer with the composition, the glass frit is melted at a stage where organic substances such as alkali-soluble resins are not completely decomposed and removed, so that formation is performed. Some of the organic substances remain in the sintered body to be formed, and as a result, the sintered body tends to be colored and its light transmittance tends to decrease. On the other hand, if the softening point of the glass frit exceeds 600 ° C.,
Since it is necessary to fire at a temperature higher than 0 ° C., distortion or the like is likely to occur in the glass substrate.

Specifically, lead oxide, boron oxide, silicon oxide (PbO—B ₂ O ₃ —SiO ₂ ), lead oxide, boron oxide, silicon oxide, aluminum oxide (P
_{bO-B 2 O 3 -SiO 2} -Al 2 O 3 system), zinc oxide,
Boron oxide, silicon oxide _{(ZnO-B 2 O 3 -SiO} 2
System), zinc oxide, boron oxide, silicon oxide, aluminum oxide-based _{(ZnO-B 2 O 3 -SiO} 2 -Al 2 O
₃ system), lead oxide, zinc oxide, boron oxide, silicon oxide _{(PbO-ZnO-B 2 O} 3 -SiO 2 system), lead oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide-based (PbO-ZnO —B ₂ O ₃ —SiO ₂ —Al ₂ O ₃
System), bismuth oxide, boron oxide, silicon oxide _{(Bi 2 O 3 -B 2 O} 3 -SiO 2 system), bismuth oxide,
Boron oxide, silicon oxide, aluminum oxide (Bi ₂
O ₃ —B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ ), bismuth oxide, zinc oxide, boron oxide, silicon oxide (Bi ₂ O ₃ −)
ZnO-B ₂ O ₃ -SiO ₂ system), bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide-based _{(Bi 2 O 3 -ZnO-B} 2 O 3 -SiO 2 -Al 2 O 3 system)
And other glass frit. The shape of the low melting glass frit is not particularly limited, and the average particle size is preferably 0.1 to 10 μm,
More preferably, it is 0.5 to 5 μm. The low melting point glass frit can be used alone or in combination of two or more kinds of low melting point glass frit having different glass frit compositions, different softening points, different shapes, and different average particle diameters.

These low-melting glass frit may be contained in a composition for forming components other than the dielectric and the partition (for example, electrodes, resistors, phosphors, color filters, black matrices). . The content of the low-melting glass frit in this case depends on the application, but the total amount of the inorganic particles including the low-melting glass frit is 100%.
It is usually at most 70 parts by mass, preferably at most 50 parts by mass, more preferably at most 30 parts by mass, relative to parts by mass.

As inorganic particles used for electrode forming materials such as PDPs, LCDs, organic EL devices, printed circuit boards, multilayer circuit boards, multi-chip modules and LSIs, Ag, Au, Al, Ni, Ag-Pd alloy , C
u, Cr and the like. Among these,
It is preferable to use relatively inexpensive Ag, which does not cause a decrease in conductivity due to oxidation even when fired in the air. The shape of the inorganic particles used in the electrode forming material is not particularly limited, such as a granular shape, a spherical shape, and a flake shape. The inorganic particles may be used alone or as a mixture of two or more types of inorganic particles. In addition, the average particle size is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm
It is also possible to use a mixture of inorganic particles having different average particle sizes.

Inorganic particles used for a transparent electrode forming material such as PDP, LCD, and organic EL device include indium oxide, tin oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), and fluorine-doped oxide. Indium (FIO), fluorinated tin oxide (FTO), fluorinated zinc oxide (FZO), and Al, Co, F
Examples include zinc oxide fine particles containing one or more metals selected from e, In, Sn and Ti. Examples of the inorganic particles used for the PDP resistor forming material include particles made of RuO ₂ or the like.

The inorganic particles used for the phosphor forming material of PDP are Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO for red.
^{_{5: Eu 3+, Y 3 Al}} 5 O 12: Eu 3+, YVO 4: Eu
³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ )
₂ : Mn, Zn ₂ SiO ₄ : Mn for green color,
BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, L
aPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅
O _12: Tb, etc., as the blue Y ₂ SiO _5: Ce,
BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : E
u ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : E
u ²⁺ , (Zn, Cd) S: Ag, and the like.

Inorganic particles used in color filter forming materials such as PDPs, LCDs, and organic EL devices include Fe ₂ O ₃ for red, Cr ₂ O ₃ for green, and CoO. Al ₂ O _{3 and the} like can be mentioned. Examples of the inorganic particles used for a black stripe (matrix) forming material such as PDP, LCD, and organic EL device include Co, Cr, Cu, Fe, and the like.
Metals such as Mn, Ni, Ti, Zn and oxides thereof,
Examples thereof include complex oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, and graphite. These can be used alone or in combination of two or more. Among these, preferred inorganic particles include C
o, Cr, Cu, Fe, Mn, Ni, and metal particles, metal oxide particles, and composite oxide particles selected from the group of Ti. In addition, the average particle size is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm
And particularly preferably 0.1 to 2 μm.

(B) Alkali-Soluble Resin As the alkali-soluble resin used in the photosensitive composition containing inorganic particles, various resins can be used. Here, “alkali-soluble” refers to a property of being dissolved by an alkaline developer and having such a solubility as to achieve the intended development processing. Specific examples of such alkali-soluble resins include, for example, (meth) acrylic resins, hydroxystyrene resins, novolak resins, polyester resins, and the like. Among such alkali-soluble resins, particularly preferred are copolymers of the following monomers (a) and (c), copolymers of monomers (a), (b) and (c) And acrylic resins.

Monomer (a): Carboxyl group-containing monomers Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) Acryloyloxyethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Monomer (b): OH-containing monomers Hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate;
o-hydroxystyrene, m-hydroxystyrene, p
-Phenolic hydroxyl group-containing monomers such as hydroxystyrene. Monomer (c): Other copolymerizable monomers Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-lauryl (meth) acrylate, (meth) acrylic acid Benzyl, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and other monomers (a) other than (a)
Acrylic esters; aromatic vinyl monomers such as styrene and α-methylstyrene; conjugated dienes such as butadiene and isoprene; polystyrene and poly (meth)
Macromonomers having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as methyl acrylate, poly (meth) acrylate, and poly (benzyl meth) acrylate:

The copolymer of the monomer (a) and the monomer (c), or the copolymer of the monomer (a), the monomer (b) and the monomer (c) may be a monomer (a) and / or a monomer (b) Due to the presence of the copolymer component derived from the phenolic hydroxyl group-containing monomer of (1), the compound has alkali solubility. Above all, a copolymer of the monomer (a), the monomer (b) and the monomer (c) is particularly preferable from the viewpoint of the dispersion stability of the inorganic particles (A) and the solubility in an alkali developer described later. The content of the copolymer component derived from the monomer (A) in this copolymer is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass, and the content of the copolymer component derived from the monomer (B) is The content rate is
It is preferably from 1 to 50% by mass, particularly preferably from 5 to 30% by mass. Further, as the monomer (b) component, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy (meth) acrylate
Hydroxyl-containing monomers such as hydroxypropyl are preferred.

[0017] The molecular weight of the alkali-soluble resin constituting the photosensitive composition containing inorganic particles is from 5,000 to 5,000-weight average molecular weight in terms of polystyrene by GPC (hereinafter, also simply referred to as "weight average molecular weight (Mw)"). 5,0
Preferably, it is 0.00000, more preferably 10,000 to 300,000. The content of the alkali-soluble resin in the inorganic particle-containing photosensitive composition is usually 1 to 50 parts by mass with respect to 100 parts by mass of the inorganic particles.
0 parts by mass, preferably 10 to 200 parts by mass. The inorganic particle-containing photosensitive composition may contain a resin other than the alkali-soluble resin.

(C) Specific (meth) acrylate compound The specific (meth) acrylate compound constituting the photosensitive composition containing inorganic particles of the present invention is a compound having at least four (meth) acryloyl groups in one molecule. . By containing the compound, an inorganic particle-containing photosensitive composition capable of forming a pattern with high sensitivity and high dimensional accuracy can be provided. Specific examples of such specific (meth) acrylate compounds include poly (meth) acrylates of polyhydric alcohols having a valency of 4 or more such as tetramethylolalkane, pentaerythritol and dipentaerythritol; polyalkylenes of a polyhydric alcohol having a valency of 4 or more Poly (meth) acrylates of glycol adducts; polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, spirane resin (meth) acrylate, etc. Oligo (meth) acrylates and the like.

Among these ethylenically unsaturated group-containing compounds, polymethacrylates of polyhydric alcohols having a valency of 4 or more such as tetramethylolalkane, pentaerythritol and dipentaerythritol; polyalkylene glycols of a polyhydric alcohol having a valency of 4 or more Polymethacrylates as adducts are preferred, and ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate is more preferred, and dipentaerythritol is preferred. Compounds having a dipentaerythritol skeleton, such as penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, are particularly preferred. These specific (meth) acrylate compounds can be used alone or in combination of two or more.

The photosensitive composition containing inorganic particles of the present invention comprises:
Other ethylenically unsaturated group-containing compounds can be used in combination with the specific (meth) acrylate compound. The other ethylenically unsaturated group-containing compound is not particularly limited as long as it is a compound capable of undergoing a radical polymerization reaction with a photopolymerization initiator described later. For example, di (meth) ene of an alkylene glycol such as ethylene glycol or propylene glycol may be used. ) Acrylates; di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; di (meth) acrylates of hydroxyl-terminated polymers such as hydroxy-terminated polybutadiene, hydroxy-terminated polyisoprene and hydroxy-terminated polycaprolactone ) Acrylates;
Di (meth) acrylates of cyclic diols such as 1,4-cyclohexanediol and 1,4-benzenediols; tri (meth) acrylates of trihydric alcohols such as glycerin, 1,2,4-butanetriol and trimethylolalkane A) acrylates; tri (meth) acrylates of polyalkylene glycol adducts of trihydric alcohols; and the monomers (a), (b) and (c) constituting the above-mentioned binder resin. Can be.

The molecular weight of these specific (meth) acrylate compounds and other ethylenically unsaturated group-containing compounds is not particularly limited.
00 or less. The amount of the specific (meth) acrylate compound to be used is generally 20 to 500 parts by mass, more preferably 40 to 100 parts by mass of the alkali-soluble resin.
２５０250 parts by mass. The amount of the other ethylenically unsaturated compound used may be an alkali-soluble resin
It is usually 100 parts by mass or less based on parts by mass.

(D) Photopolymerization Initiator As the photopolymerization initiator constituting the photosensitive composition containing inorganic particles, a radical is generated in the exposure step described below, and the polymerization of the aforementioned ethylenically unsaturated group-containing compound is carried out. There is no particular limitation as long as the compound initiates the reaction. Specific examples of such a photopolymerization initiator include benzyl,
Benzoin, benzophenone, Michler's ketone, 4,
4′-bisdiethylaminobenzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [ 4 '-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4-diethylthioxanthone, isopropyl Carbonyl compounds such as thioxanthone; bis (2,6-dimethoxybenzoyl) -2,
Phosphine oxide compounds such as 4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; mercaptan disulfide Organic sulfur compounds such as benzoyl peroxide, di-tert-butyl peroxide, te
organic peroxides such as rt-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 2,4-bis (trichloromethyl)-
6- (2'-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6
Trihalomethanes such as -bis (trichloromethyl) -1,3,5-triazine; 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl 1,2'-bi Examples thereof include imidazole dimers such as imidazole, and these can be used alone or in combination of two or more. Also, sensitizers,
A sensitizing aid, a hydrogen donor, and a chain transfer agent may be used in combination.
The content ratio of the photopolymerization initiator is usually 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, based on 100 parts by mass of the alkali-soluble resin and the ethylenically unsaturated group-containing compound in total. Department.

(E) Solvent The photosensitive composition containing inorganic particles usually contains a solvent. As the solvent, (A) the affinity with the inorganic particles and the solubility of other organic components are good, and it can impart an appropriate viscosity to the inorganic particle-containing photosensitive composition, and is dried. Preferably, it can be easily removed by evaporation. Specific examples of such a solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone; n-pentanol,
Alcohols such as methyl-2-pentanol, cyclohexanol and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether;
Ether alcohols such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; saturated aliphatic monocarboxylic acid alkyl esters such as n-butyl acetate and amyl acetate; lactate esters such as ethyl lactate and n-butyl lactate Methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl-
Ether esters such as 3-ethoxypropionate can be exemplified, and these can be used alone or in combination of two or more. As the content ratio of the solvent in the inorganic particle-containing photosensitive composition,
It can be appropriately selected within a range in which a good inorganic particle-containing photosensitive resin layer forming performance (fluidity or plasticity) can be obtained, and usually, 1 to 10,000 based on 100 parts by mass of (A) inorganic particles. Parts by mass, preferably 10 to 10 parts by mass.
It is 1,000 parts by mass.

(F) Various additives In addition to the components (A) to (E), the photosensitive composition containing inorganic particles contains a plasticizer, an adhesion aid, a dispersant, a storage stabilizer, and a defoamer. Various additives such as antioxidants, ultraviolet absorbers, leveling agents, and development accelerators may be contained as optional components. Plasticizer A plasticizer is added to the inorganic particle-containing photosensitive resin layer to be formed to exhibit good flexibility and flammability. Specifically, a compound represented by the following formula (1) or (2) is preferably used because it is easily decomposed and removed by heat and does not adversely affect the performance of various members obtained.

[0025]

Embedded image

(Wherein, R ¹ and R ⁴ each represent the same or different alkyl groups having 1 to 30 carbon atoms;
² and R ³ each represent the same or different methylene group or alkylene group having 2 to 30 carbon atoms;
And t is a number from 1 to 10. )

[0027]

Embedded image

(In the formula, R ⁵ represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms.)

In the above formula (1), the alkyl group represented by R ¹ or R ⁴ and the alkylene group represented by R ² or R ³ may be linear or branched. May be a saturated group or an unsaturated group.
The carbon number of the alkyl group represented by R ¹ or R ⁴ is 1 to
30, preferably 2 to 20, more preferably 4
To 10. If the alkyl group has more than 30 carbon atoms, the solubility of the plasticizer in the solvent may decrease, and good flexibility of the film may not be obtained.

Specific examples of the compound represented by the above formula (1) include dibutyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, dibutyl diglycol adipate and the like. Can be Preferably, n is a compound represented by 2 to 6.

In the above formula (2), the alkyl group and alkenyl group represented by R ⁵ may be linear or branched, and may be a saturated group or an unsaturated group. You may. The alkyl group or alkenyl group represented by R ⁵ has 1 to 30 carbon atoms, preferably 2 to 2 carbon atoms.
0, more preferably 10 to 18. Specific examples of the compound represented by the above formula (2) include propylene glycol monolaurate and propylene glycol monooleate.

The content ratio of the plasticizer in the inorganic particle-containing photosensitive composition is based on 100 parts by weight of the inorganic particles.
It is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

Adhesion Aid As the adhesion aid, a silane coupling agent [saturated alkyl group-containing (alkyl) alkoxysilane] such as a compound represented by the following formula (3) is preferably used.

[0034]

Embedded image

(Where p is an integer of 3 to 20, m is 1 to 3)
, N is an integer of 1 to 3, and a is an integer of 1 to 3. )

In the above formula (3), p indicating the number of carbon atoms of the saturated alkyl group is an integer of 3 to 20, preferably 4
整数 16.

Specific examples of the silane coupling agent represented by the above formula (3) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, and n-hexadecyldimethylmethoxysilane. , Saturated alkyldimethylmethoxysilanes such as n-icosanedimethylmethoxysilane (a =
1, m = 1, n = 1); saturation of n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, etc. Alkyldiethylmethoxysilanes (a =
1, m = 1, n = 2); saturated alkyldipropylmethoxy such as n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane Silanes (a = 1, m = 1, n = 3); n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n
Saturated alkyldimethylethoxysilanes (a = 1, m = 2, n = 1) such as hexadecyldimethylethoxysilane and n-icosanedimethylethoxysilane; n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-
Saturated alkyl diethyl ethoxy silanes (a = 1, m = 2, n = 2) such as hexadecyl diethyl ethoxy silane and n-icosane diethyl ethoxy silane; n-butyl dipropyl ethoxy silane, n-decyl dipropyl ethoxy silane , N-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane and other saturated alkyldipropylethoxysilanes (a = 1, m =
2, n = 3); saturated alkyldimethylpropoxysilanes such as n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethylpropoxysilane, and n-icosanedimethylpropoxysilane (A = 1, m = 3, n = 1); n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxy Saturated alkyldiethylpropoxysilanes such as silane (a = 1, m = 3, n = 2); n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n- Ikosan Saturated alkyl dipropyl propoxysilane such as propyl propoxysilane (a =
1, m = 3, n = 3);

N-propylmethyldimethoxysilane, n
Saturated alkylmethyldimethoxysilanes such as -butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane (a = 2, m = 1,
n = 1); n-propylethyldimethoxysilane, n-
Saturated alkylethyldimethoxysilanes such as butylethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, and n-icosaneethyldimethoxysilane (a = 2, m = 1, n
= 2); saturated alkylpropyldimethoxysilanes such as n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane (a = 2, m = 1, n = 3) Saturated alkylmethyl such as n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldiethoxysilane, n-icosanemethyldiethoxysilane Diethoxysilanes (a = 2, m = 2, n = 1); n
Saturated alkylethyldiethoxysilanes such as -propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane and n-icosaneethyldiethoxysilane ( a = 2, m = 2, n = 2); n
Saturated alkylpropyldiethoxysilanes such as -butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanopropyldiethoxysilane (a =
2, m = 2, n = 3); n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-
Saturated alkylmethyldipropoxysilanes such as decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane (a = 2, m = 3, n = 1); n-propylethyl Saturated alkylethyldipropoxysilanes such as dipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, and n-icosaneethyldipropoxysilane (a = 2 , M = 3, n = 2); n-
Saturated alkyl propyl dipropoxy silanes such as butyl propyl dipropoxy silane, n-decyl propyl dipropoxy silane, n-hexadecyl propyl dipropoxy silane, n-icosane propyl dipropoxy silane (a = 2, m = 3, n = 3);

Saturated alkyltrimethoxysilanes such as n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane and n-icosanetrimethoxysilane (a = 3 , M = 1); saturated alkyltriethoxysilanes such as n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane ( a = 3, m = 2); saturated alkyl tripropoxy such as n-propyl tripropoxy silane, n-butyl tripropoxy silane, n-decyl tripropoxy silane, n-hexadecyl tripropoxy silane, and n-icosane tripropoxy silane Silanes (a = 3, m = ) And the like can be illustrated, these may be used alone or in combination of two or more.

Among them, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-butyltrimethoxysilane
Butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-butyltripropoxysilane, n
-Decyltripropoxysilane, n-hexadecyltripropoxysilane and the like are particularly preferred.

The content of the adhesion aid in the photosensitive composition containing inorganic particles is preferably from 0.001 to 10 parts by weight, more preferably from 0.001 to 5 parts by weight, per 100 parts by weight of the inorganic particles. Parts by weight.

Dispersant Fatty acids are preferably used as the dispersant for the inorganic particles. In particular, fatty acids having 8 to 30 carbon atoms are preferred. Preferred specific examples of the above fatty acids include saturated fatty acids such as octanoic acid, undecylic acid, lauric acid, myristic acid, palmitic acid, pentadecanoic acid, stearic acid, and arachidic acid; elaidic acid, oleic acid, linoleic acid, linolenic acid, and arachidone. Examples thereof include unsaturated fatty acids such as acids, which can be used alone or in combination of two or more.

Dispersant in photosensitive composition containing inorganic particles
As the content ratio, based on 100 parts by weight of the inorganic particles,
It is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 20 parts by weight.
More preferably, it is 0.1 to 10 parts by weight. The inorganic particles of the present invention
The (A) inorganic particles, (B) the alkali particles
Resoluble resin, (C) specific (meth) acrylate compound
Product, (D) photopolymerization initiator, (E) solvent and
(F) Add various additives to a roll kneader, mixer,
Use a kneader such as a momixer, ball mill, bead mill, etc.
And can be prepared by kneading. above
The inorganic particle-containing photosensitive composition thus prepared is
A paste-like composition having fluidity suitable for cloth,
Its viscosity is usually 10 to 100,000 mPa · s^-1When
And preferably 50 to 10,000 mPa · s^-1, Yo
More preferably 100 to 5,000 mPa · s^-1And
You. The composition of the present invention is a photosensitive composition of the present invention described in detail below.
It can be used particularly preferably for producing films.
Wear.  <Photosensitive film> The photosensitive film of the present invention is usually
Support film and photosensitive material containing inorganic particles formed thereon
And a photosensitive resin containing the inorganic particles.
A protective film may be provided on the surface of the layer.

The support film constituting the photosensitive film of the present invention is preferably a resin film having heat resistance and solvent resistance and having flexibility. Since the support film has flexibility, the inorganic particle-containing photosensitive resin layer can be formed by applying the paste-like composition by a roll coater or the like, and the photosensitive film is wound in a roll shape. Can be stored and supplied. As the resin forming the support film, for example, polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide,
Examples include fluorine-containing resins such as polyvinyl alcohol and polyfluoroethylene, nylon, and cellulose. The thickness of the support film is, for example, 20 to 10
0 μm. The surface of the support film may be subjected to a release treatment. This makes it possible to easily perform the operation of peeling the support film in the pattern forming step described later. In addition, about a protective film, the same thing as a support film can be used. Further, the surface of the protective film is preferably subjected to a release treatment, and the peel strength between the protective film and the inorganic resin layer containing inorganic particles is smaller than the peel strength between the support film and the photosensitive resin layer containing inorganic particles. is necessary. The photosensitive film of the present invention is obtained by coating the inorganic particle-containing photosensitive composition of the present invention on a support film, drying the coating film and removing a part or all of the solvent to form an inorganic particle-containing photosensitive resin layer. It can be usually manufactured by forming (press bonding) a protective film on the inorganic particle-containing photosensitive resin layer.

As a method for coating the photosensitive composition containing inorganic particles on a support film to obtain a photosensitive resin layer containing inorganic particles, a method for forming a photosensitive resin layer containing inorganic particles having a uniform thickness and a large thickness (for example, 1 μm) is preferred.
m or more) It is preferable that the coating film can be formed efficiently. Specifically, a coating method using a roll coater, a coating method using a blade coater, a coating method using a slit coater, a coating method using a curtain coater, a wire Preferred examples include a coating method using a coater. The drying conditions of the coating film are set at 50 to 150 ° C. for about 0.5 to 30 minutes, and the residual ratio of the solvent after drying (content in the inorganic particle-containing photosensitive resin layer) is usually 2% by mass. It is as follows. The thickness of the inorganic particle-containing photosensitive resin layer formed on the support film as described above can be appropriately selected depending on the content of the inorganic particles, the type and size of the member, and the like.

<Method of Forming Member> The photosensitive composition containing inorganic particles and the photosensitive film of the present invention can be used as a dielectric, an electrode, a resistor, a phosphor, a partition, and a color filter constituting each display cell of a plasma display panel. In the formation of a black matrix, it can be suitably used for forming a pattern with high sensitivity and high dimensional accuracy.
In the method of forming a member using the photosensitive film of the present invention, at least (1) a step of transferring an inorganic particle-containing photosensitive resin layer, (2) an exposure step of an inorganic particle-containing photosensitive resin layer,
[3] each step of a developing step of the inorganic particle-containing photosensitive resin layer and [4] a baking step of the inorganic particle-containing photosensitive resin layer pattern. [1] Step of transferring inorganic particle-containing photosensitive resin layer In the transfer step, the photosensitive film of the present invention is used, and the inorganic particle-containing photosensitive resin layer constituting the photosensitive film is transferred onto a substrate. As the substrate material, for example, glass,
A plate member made of silicone, alumina, or the like is used, and a glass substrate is used for PDP. It is also possible to use a plate-shaped member having a desired pattern formed on the surface in advance. For the substrate surface, if necessary
An appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like; a plasma treatment; a thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum evaporation method, or the like may be performed. An example of the transfer step is as follows. After peeling off the protective film of the photosensitive film provided as needed, the photosensitive film is overlaid on the substrate so that the surface of the inorganic particle-containing photosensitive resin layer is in contact with the substrate, and the photosensitive film is heated. Thermocompression bonding using a roller. As a result, the photosensitive resin layer containing the inorganic particles is transferred onto the substrate and brought into close contact therewith.
Here, as the transfer conditions, for example, the surface temperature of the heating roller is 20 to 140 ° C., and the roll pressure by the heating roller is 1
５5 kg / cm ² , the moving speed of the heating roller is 0.1０．１1
0.0 m / min. The substrate may be preheated, and the preheating temperature is, for example, 40 to 100.
° C. Further, a photosensitive resin layer (resist layer) containing no inorganic particles may be further provided on the inorganic particle-containing photosensitive resin layer formed from the photosensitive film of the present invention. This photosensitive resin layer usually disappears from the pattern in a developing step and a baking step described later. Further, an inorganic particle-containing resin layer other than the resin layer obtained from the inorganic particle-containing photosensitive resin composition of the present invention may be provided. The inorganic particle-containing resin layer may be photosensitive or non-photosensitive.

[2] Exposure Step of Inorganic Particle-Containing Photosensitive Resin Layer In the exposure step, the surface of the inorganic particle-containing photosensitive resin layer is selectively irradiated (exposed) with radiation through an exposure mask. A latent image having a pattern of the inorganic particle-containing photosensitive resin layer is formed. Incidentally, the support film on the inorganic particle-containing photosensitive resin layer may be peeled off before the exposure step,
After the exposure step, it may be peeled and removed before a development step described later. From the viewpoint of increasing the sensitivity, the support film on the inorganic particle-containing photosensitive resin layer is preferably peeled and removed after the exposure step and before the development step described later. When the above-described resist layer is provided, the surface of the resist layer is irradiated with radiation through an exposure mask. The radiation to be selectively irradiated (exposed) with radiation in the exposure step includes visible light, ultraviolet light, far ultraviolet light, an electron beam or X-ray, and preferably visible light, ultraviolet light, and far ultraviolet light, More preferably, ultraviolet light is used. Although the exposure pattern of the exposure mask varies depending on the purpose, for example, a stripe having a width of 10 to 500 μm is used.
The radiation irradiating device is not particularly limited, such as an ultraviolet irradiating device used in the photolithography method, an exposure device used in manufacturing a semiconductor and a liquid crystal display device.

[3] Step of Developing Inorganic Particle-Containing Photosensitive Resin Layer In the developing step, the exposed inorganic particle-containing photosensitive resin layer is developed to form a pattern (latent image) of the inorganic particle-containing photosensitive resin layer. ) Is revealed. As the developer used in the step of developing the inorganic particle-containing photosensitive resin layer,
Alkaline developers can be used. This allows
The alkali-soluble resin contained in the inorganic particle-containing photosensitive resin layer can be easily dissolved and removed. Incidentally, the inorganic particles contained in the inorganic particle-containing photosensitive resin layer is uniformly dispersed in the alkali-soluble resin, by dissolving the alkali-soluble resin as a binder, by washing, the inorganic particles are also removed at the same time. You. Examples of the effective component of the alkali developer include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and ammonium dihydrogen phosphate. Inorganic, such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compound; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine,
Organic alkaline compounds such as trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine can be exemplified. Alkaline developer used in the developing step of the inorganic particle-containing photosensitive resin layer,
It can be prepared by dissolving one or more of the alkaline compounds in water or the like. here,
The concentration of the alkaline compound in the alkaline developer is
Usually, it is 0.001 to 10% by mass, preferably 0.0
1 to 5% by mass. The alkali developer may contain additives such as a nonionic surfactant and an organic solvent. After the development processing with an alkali developing solution, a washing treatment is usually performed. Further, if necessary, a step of scraping unnecessary portions remaining on the side surfaces of the photosensitive resin layer pattern containing inorganic particles and the exposed portion of the substrate after the development treatment may be included. Here, as the development processing conditions, the type, composition, and concentration of the developer, the development time, the development temperature, the development method (for example, the immersion method, the oscillating method, the shower method, the spray method, and the paddle method), the developing device, etc. You can choose. By this development step, the inorganic resin containing photosensitive resin layer remaining portion,
An inorganic particle-containing photosensitive resin layer pattern (a pattern corresponding to an exposure mask) composed of the inorganic particle-containing photosensitive resin layer removed portion is formed.

[4] Step of Firing Inorganic Particle-Containing Photosensitive Resin Pattern In this step, the inorganic particle-containing photosensitive resin layer pattern is fired to form a member. Thereby, the organic substance in the inorganic particle-containing photosensitive resin layer remaining portion is burned off,
A member can be obtained on the surface of the substrate. Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the residual portion of the resin layer is burned off.
0-600 ° C. The firing time is usually 10 to
90 minutes.

[0050]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, “parts” indicates “parts by mass”. The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) (trade name: HPC manufactured by Tosoh Corporation).
LC-802A) is the average molecular weight in terms of polystyrene measured by LC-802A).

<Examples> (1) Preparation of photosensitive composition containing inorganic particles: (A) Cr-C having an average particle size of 0.5 μm as inorganic particles
u composite oxide particles (granular) 70 parts, P having an average particle size of 1 μm
bO-B ₂ O ₃ -SiO ₂ based low melting glass frit (amorphous, softening point 500 ° C.) 30 parts, (B) as an alkali-soluble resin, methacrylic acid n- butyl / methacrylate 3
-Hydroxypropyl / methacrylic acid = 60/20/2
0 (% by mass) copolymer (Mw = 100,000) 40
Part, (C) a mixture of dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate (25/75) as an ethylenically unsaturated group-containing compound 4
0 parts, (D) as a photopolymerization initiator, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
After kneading 5 parts of butan-1-one, 150 parts of propylene glycol monomethyl ether acetate as a solvent (E) and 1 part of oleic acid as a dispersant (F) in a bead mill, a stainless steel mesh (500 mesh,
(25 μm diameter) to prepare a photosensitive composition containing inorganic particles.

(2) Preparation of photosensitive film: The inorganic particle-containing film of the present invention in which a support film, an inorganic particle-containing photosensitive resin layer, and a protective film are sequentially laminated by the following operations (a) and (b). Was prepared. (A) A photosensitive film containing inorganic particles is coated with a PET film as a supporting film (width 200 mm, length 30 m, thickness 3).
8 μm) using a blade coater, dried the coating at 100 ° C. for 5 minutes to completely remove the solvent, and formed an inorganic particle-containing photosensitive resin layer having an average thickness of 15 μm on the support film. (B) A protective film made of a PET film previously subjected to a release treatment is thermocompression-bonded to the inorganic particle-containing photosensitive resin layer formed in (a) above, and the support film, the inorganic particle-containing photosensitive resin layer, and the protective film are sequentially formed. A laminated photosensitive film was produced.

(3) Formation of member Transfer step of photosensitive resin layer containing inorganic particles: After peeling off and removing the protective film from the photosensitive film, the photosensitive resin layer containing inorganic particles is formed on the surface of a glass substrate for a 6-inch panel. The photosensitive films were overlapped so that the surfaces of the photosensitive films were in contact with each other, and the photosensitive films were thermocompression-bonded with a heating roller. Here, as the pressure bonding condition, the surface temperature of the heating roller is set to 120
C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the photosensitive resin layer containing the inorganic particles was transferred to and adhered to the surface of the glass substrate.

Exposure step and development step of inorganic particle-containing photosensitive resin layer: The inorganic particle-containing photosensitive resin layer was exposed to an i-line (U-line) through an exposure mask (a stripe pattern having a width of 50 μm) using an ultra-high pressure mercury lamp. (Ultraviolet light having a wavelength of 365 nm). Here, the irradiation amount was 100 mJ / cm ² .

After completion of the exposure step, the support film was peeled off from the inorganic particle-containing photosensitive resin layer, and then a 0.4% by mass aqueous sodium carbonate solution ( (30 ° C.) as a developing solution was carried out for one minute by a shower method. Next, a washing treatment with ultrapure water is performed, whereby the uncured inorganic particle-containing photosensitive resin layer not irradiated with ultraviolet rays is removed,
An inorganic particle-containing photosensitive resin layer pattern was formed.

Firing step of photosensitive resin layer pattern containing inorganic particles: The glass substrate on which the photosensitive resin layer pattern containing inorganic particles is formed is heated in a firing furnace at a temperature of 580 ° C. for 30 minutes.
The baking treatment was performed for minutes. As a result, a panel material having a black matrix pattern formed on the surface of the glass substrate was obtained. With respect to the black matrix pattern in the obtained panel material, the line width of the black matrix pattern was measured using a scanning electron microscope, and was found to be in the range of 50 μm ± 2 μm, showing excellent dimensional accuracy. . No pattern defect was observed.

<Comparative Example> A photosensitive composition containing inorganic particles was prepared in the same manner as in Example 1, except that 40 parts of trimethylolpropane triacrylate was used as the (C) ethylenically unsaturated group-containing compound. . A photosensitive film was produced in the same manner as in Example 1 except that the photosensitive composition containing inorganic particles was used. Example 1 except that the photosensitive film was used.
In the same manner as in the above, a panel material having a black matrix pattern formed on the surface of the glass substrate was obtained. The line width of the black matrix pattern in the obtained panel material was measured using a scanning electron microscope, and was found to be in the range of 50 μm ± 2 μm, which was excellent in dimensional accuracy. . However, a large number of pattern defects were observed.

[0058]

According to the photosensitive composition containing inorganic particles and the photosensitive film of the present invention, a pattern having high sensitivity and high dimensional accuracy can be formed. The inorganic particle-containing photosensitive composition and the photosensitive film of the present invention are suitable for forming a dielectric, an electrode, a resistor, a phosphor, a partition, a color filter and a black matrix constituting each display cell of a plasma display panel. Can be used.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel.

[Description of Signs] 1 Glass substrate (front substrate) 2 Glass substrate (rear substrate) 3 Partition wall 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Phosphor 8 Dielectric layer (front substrate) 9 Dielectric layer (rear substrate) 10 Protective film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 291/06 C08F 291/06 5C027 C08J 5/18 CEY C08J 5/18 CEY C08K 3/00 C08K 3/00 C08L 101/12 C08L 101/12 G03F 7/027 502 G03F 7/027 502 H01J 9/02 H01J 9/02 F F term (reference) 2H025 AA01 AA03 AB11 AB17 AC01 AD01 BC14 BC34 BC43 CC08 FA17 4F071 AA32 AA33 AB18 AB26 AB27 AC07 AE06 AE17 AF05 AH12 BA02 BB02 BC02 4J002 BG011 BG041 BG051 BG072 DE096 DE106 DE146 DJ016 EE037 EU117 EU187 EV307 EW147 FD016 FD142 FD157 4J011 AA05 AC04 PA07 PA13 PA14 PA15 PA69 PB22 QB24 QB02 QB23 PC02 SA76 SA78 SA80 SA84 UA01 VA01 WA01 4J026 AA16 AA45 AA47 AA48 AB01 AB07 BA28 DB06 DB36 GA07 5C027 AA01 AA05 AA09

Claims (3)

[Claims] 1. An inorganic particle, (B) an alkali-soluble resin, (C) a compound having at least four (meth) acryloyl groups in one molecule as a compound containing an ethylenically unsaturated group, and (D) photopolymerization. A photosensitive composition containing inorganic particles, comprising an initiator. 2. The photosensitive composition according to claim 1, wherein a compound having a dipentaerythritol skeleton is used as the component (C). 3. A photosensitive film comprising an inorganic particle-containing photosensitive resin layer obtained from the inorganic particle-containing photosensitive composition according to claim 1 or 2.