JP2001264966A - Inorganic particle-containing photosensitive composition and sensitive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic particle-containing photosensitive composition capable of forming a high precision pattern and excellent in thermal decomposability of an organic component and a sensitive film obtained from the composition. SOLUTION: The inorganic particle-containing photosensitive composition contains a photopolymerization initiator having >=90% loss of weight at 400 deg.C.

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 forming dielectrics, electrodes, resistors, phosphors, partition walls, color filters, and black matrices that constitute each display cell of a plasma display panel, in order to form patterns with high thermal decomposition of organic components and high accuracy The present invention relates to an inorganic particle-containing photosensitive composition and a photosensitive film that can be suitably used.

[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,
In the photolithography method, although the positional accuracy of the pattern is excellent, there is a problem that the thermal decomposability of the photosensitive organic component in the firing 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 highly accurate pattern and is excellent in the thermal decomposability of an organic component. A second object of the present invention is to provide a photosensitive film having an inorganic particle-containing photosensitive resin layer that can form a highly accurate pattern and has excellent thermal decomposability of organic components. 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, (C) an ethylenically unsaturated group-containing compound and (D) 400 ° C. Wherein a photopolymerization initiator having a weight loss of 90% or more is contained. The photosensitive composition containing inorganic particles of the present invention preferably contains (D) two or more photopolymerization initiators whose weight loss at 400 ° C. is 95% or more. Further, the inorganic particle-containing photosensitive composition of the present invention preferably contains (D) a compound represented by the following formula (1) and a compound represented by the following formula (2) as a photopolymerization initiator. .

[0007]

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(In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms.)

[0009]

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(In the formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms.)

[0011] The photosensitive film of the present invention is characterized in that it contains an inorganic particle-containing photosensitive resin layer obtained from the inorganic particle-containing photosensitive composition of the present invention.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive material containing inorganic particles of the present invention will be described.
The details of the hydrophilic composition will be described.(A) Inorganic particles  The inorganic particles used in the inorganic particle-containing photosensitive composition have a shape
Depends on the type of material. Dielectric for PDP
And inorganic particles used in the partition wall forming material
Melting point glass frit and the like can be mentioned. This low melting glass
Sfrit has a softening point within the range of 400 to 600 ° C.
Is preferred. Softening point of glass frit is 40
When the temperature is lower than 0 ° C., the composition contains inorganic particles.
In the firing step of the photosensitive resin layer, an alkali-soluble resin
When organic substances such as fat are not completely decomposed and removed,
Since the frit melts, the
Some of the organic substances remain in the sintered body,
The light transmittance tends to decrease. Meanwhile, gala
If the softening point of the frit exceeds 600 ° C, 60
Because it is necessary to fire at a temperature higher than 0 ° C, a glass substrate
Is easily distorted.

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 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 a component other than the dielectric and the partition (for example, an electrode, a resistor, a phosphor, a color filter, and a black matrix). The content of the low-melting glass frit in this case varies depending on the application, but is usually 70 parts by mass or less, preferably 50 parts by mass or less, based on 100 parts by mass of the inorganic particles including the low-melting point glass frit. , More preferably 30 parts by mass or less.

The inorganic particles used in PDPs, LCDs, organic EL devices, printed circuit boards, multilayer circuit boards, multichip modules, and electrode forming materials such as LSIs include Ag, Au, Al, Ni, and Ag-Pd alloys. , 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. PDP, LCD, inorganic particles used in the color filter forming materials such as an organic EL element, such as Fe ₂ O ₃ as the red, such as Cr ₂ O ₃ as a green, CoO · Al ₂ O as a blue _{3 and the} like. Examples of inorganic particles used in black stripe (matrix) forming materials such as PDPs, LCDs, and organic EL devices include Co, Cr, Cu, Fe, Mn, and N.
Metals such as i, Ti, Zn, etc. and their oxides, composite oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, graphite, etc. can be used alone or in combination of two or more. Can be used. Among them, preferred inorganic particles include Co, C
Metal particles, metal oxide particles and composite oxide particles selected from the group consisting of r, Cu, Fe, Mn, Ni and Ti. Further, the average particle size is preferably 0.0
It is 1 to 10 μm, more preferably 0.05 to 5 μm, and particularly preferably 0.1 to 2 μm.

[0018](B) Alkali-soluble resin  Alkali solubility used for photosensitive composition containing inorganic particles
Various resins can be used as the resin. here
In addition, “alkali-soluble” refers to an alkaline developer.
To the extent that the desired development process is performed.
Refers to a property having resolvability. Of such alkali-soluble resin
Specific examples include (meth) acrylic resin,
Roxystyrene resin, novolak resin, polyester tree
And the like. Such alkali soluble
Among the conductive resins, particularly preferred are the following
Copolymer of monomer (a) and monomer (c), monomer
(A), copolymerization of monomer (b) and monomer (c)
An acrylic resin such as a body can be used.

Monomers (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.

The molecular weight of the alkali-soluble resin constituting the inorganic particle-containing photosensitive composition is from 5,000 to 5,000-weight average molecular weight in terms of polystyrene by GPC (hereinafter, 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.

[0022](C) Ethylenically unsaturated group-containing compound  Ethylenic unsaturation constituting the photosensitive composition containing inorganic particles
The group-containing compound contains an ethylenically unsaturated group,
A radical polymerization reaction can be caused by a photopolymerization initiator described below.
The compound is not particularly limited as long as it is a compound.
(T) An acrylate compound is used. Take (meta)
Specific examples of the acrylate compound include ethylene glycol
Glycol, alkylene glycol such as propylene glycol
Di (meth) acrylates; polyethylene glycol
And polyalkylene glycols such as polypropylene glycol
Recol di (meth) acrylates; hydroxy at both ends
Cypolybutadiene, both ends hydroxy polyisoprene,
Both ends hydration such as hydroxy polycaprolactone at both ends
Di (meth) acrylates of roxylated polymers; glyce
Phosphorus, 1,2,4-butanetriol, trimethylol
Alkanes, tetramethylolalkanes, pentaerythri
Trivalent or higher polyvalent such as toll or dipentaerythritol
Poly (meth) acrylates of alcohol; trivalent or higher
Polyalkylene glycol adduct of polyhydric alcohol
Li (meth) acrylates; 1,4-cyclohexanedi
Cyclic polio such as all and 1,4-benzenediols
Poly (meth) acrylates; polyester (me
T) acrylate, epoxy (meth) acrylate, c
Rethane (meth) acrylate, alkyd resin (meth) a
Acrylate, silicone resin (meth) acrylate,
Oligo (meth) a such as pyran resin (meth) acrylate
Crylates and the like can be mentioned. Note that
Monomers constituting the alkali-soluble resin (a),
The compounds shown in (b) and (c) may be used.
No. Of these, contain two or more ethylenically unsaturated groups
Are preferably used. These ethylenic
The molecular weight of the unsaturated group-containing compound is not particularly limited.
However, the molecular weight is usually 5,000 or less. these
(Meth) acrylate compounds may be used alone or in combination of two or more.
Can be used in combination.
20 to 500 mass per 100 mass parts of potassium soluble resin
Parts, more preferably 40 to 250 parts by weight
You.

[0023](D) Photopolymerization initiator  Photopolymerization constituting the photosensitive composition containing inorganic particles of the present invention
The initiator has a weight loss at 400 ° C. of 90% or more.
It is characterized by the following. That is, several types of photopolymerization initiators are used.
When used, at 400 ° C. of the total amount of the photopolymerization initiator
It is sufficient that the weight loss is 90% or more. The photopolymerization initiator
To form a highly accurate pattern,
Provide photosensitive composition containing inorganic particles with excellent thermal decomposability
can do. Here, “weight loss at 400 ° C.
“Small” means that the photopolymerization initiator is heated at a rate of 10 ° C./min.
｛1- (weight at 400 ° C./weight at 50 ° C.)
Amount)｝ × 100 (%) As this photopolymerization initiator
Generates radicals in the exposure step described below,
To initiate polymerization of the ethylenically unsaturated group-containing compound
The compound is not particularly limited as long as it is a compound to be
Can be used in combination of two or more.
More preferably, the weight loss at 400 ° C. is 95% or more.
A mixture of two or more compounds is used.

More preferably, the photopolymerization initiator is a compound represented by the above formula (1) (hereinafter also referred to as "photopolymerization initiator (1)") and a compound represented by the above formula (2) (Hereinafter, also referred to as “photopolymerization initiator (2)”). R ¹ and R in the above formula (1)
^{As 2} , an alkyl group having 1 to 4 carbon atoms, specifically,
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group,
A t-butyl group is preferred, and a methyl group is particularly preferred. As R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (2), an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-
A butyl group, an i-butyl group, a sec-butyl group and a t-butyl group are preferred, and an ethyl group is particularly preferred.

The photosensitive composition containing inorganic particles of the present invention includes:
It is particularly preferable that both the photopolymerization initiator (1) and the photopolymerization initiator (2) are contained. When both the photopolymerization initiator (1) and the photopolymerization initiator (2) are contained, the sensitivity at the time of exposure is increased as compared with the case where each is contained alone, and a good pattern shape can be obtained. . The content ratio of the photopolymerization initiator (1) and the photopolymerization initiator (2) is such that the photopolymerization initiator (2) is contained in a range not exceeding the photopolymerization initiator (1) in terms of mass. It is preferable that the content ratio of photopolymerization initiator (1): photopolymerization initiator (2) is 50:50 to 95: 5.

Other photopolymerization initiators include 2,4-
And thioxanthone-based photopolymerization initiators such as diethylthioxanthone. Further, the photosensitive composition containing inorganic particles of the present invention may contain a sensitizer, a sensitization aid, a hydrogen donor, a chain transfer agent, and the like. 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.

[0027](E) Solvent  The inorganic particle-containing photosensitive composition usually contains a solvent.
You. Examples of the solvent include (A) affinity with inorganic particles, and
Good solubility of organic and other organic components, containing inorganic particles
Appropriate viscosity can be imparted to the photosensitive composition, and drying
That can be easily removed by evaporation.
Is preferred. A specific example of such a solvent is diethyl.
Ketone, methyl butyl ketone, dipropyl ketone, shik
Ketones such as rohexanone; n-pentanol, 4-
Methyl-2-pentanol, cyclohexanol, dia
Alcohols such as seton alcohol; ethylene glyco
Monomethyl ether, ethylene glycol monoethyl
Ether, ethylene glycol monobutyl ether,
Propylene glycol monomethyl ether, propylene
Ether alcohols such as glycol monoethyl ether
And saturated fats such as n-butyl acetate and amyl acetate
Aromatic monocarboxylic acid alkyl esters; ethyl lactate, milk
Lactic acid esters such as n-butyl acid; methyl cellosol
Buacetate, ethyl cellosolve acetate, propyle
Glycol monomethyl ether acetate, ethyl-
Ether esters such as 3-ethoxypropionate
And the like, which can be used alone or
Two or more can be used in combination. Inorganic particles
As the content ratio of the solvent in the child-containing photosensitive composition,
Good performance of forming photosensitive resin layer containing inorganic particles (fluidity and
Is selected within the range where plasticity is obtained.
Can be formed, but usually (A) relative to 100 parts by mass of the inorganic particles.
And 1 to 10,000 parts by mass, preferably 10 to 10 parts by mass.
It is 1,000 parts by mass.

[0028](F) Various additives  Inorganic particle-containing photosensitive compositions include the above (A) to (E)
In addition to ingredients, plasticizer, adhesion aid, dispersant, storage stability
Agents, defoamers, antioxidants, UV absorbers, leveling
Various additives such as developer and development accelerator are included as optional components
It may be. Plasticizer Plasticizer is good for the formed inorganic particle-containing photosensitive resin layer.
It is added in order to exhibit high flexibility and flammability. Ingredient
Physically, a compound represented by the following formula (3) or (4)
Is easily decomposed and removed by heat,
It is preferably used because it does not adversely affect the performance.

[0029]

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(Wherein, R ⁷ and R ¹⁰ each represent the same or different alkyl groups having 1 to 30 carbon atoms;
⁸ and R ⁹ each represent the same or different methylene group or alkylene group having 2 to 30 carbon atoms, and s represents 0
And t is a number from 1 to 10. )

[0031]

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(In the formula, R ¹¹ represents an alkyl group or alkenyl group having 1 to 30 carbon atoms.)

In the above formula (3), the alkyl group represented by R ⁷ or R ¹⁰ and the alkylene group represented by R ⁸ or R ⁹ may be linear or branched. May be a saturated group or an unsaturated group.
The carbon number of the alkyl group represented by R ⁷ or R ¹⁰ 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 (3) 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 (4), the alkyl group and alkenyl group represented by R ¹¹ 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 ¹¹ 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 (4) 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 (5) is preferably used.

[0038]

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(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 (5), 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 (5) 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.

Of these, 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 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, based on 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.

The content ratio of the dispersant in the inorganic particle-containing photosensitive composition is based on 100 parts by weight of the inorganic particles.
It is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. The photosensitive composition containing inorganic particles of the present invention generally comprises (A) inorganic particles, (B)
An alkali-soluble resin, (C) a specific methacrylate compound, (D) a photopolymerization initiator, (E) a solvent and, if necessary, various additives, are added to a roll kneader, a mixer, a homomixer, a ball mill, a bead mill, or the like. It can be prepared by kneading using a kneader. The inorganic particle-containing photosensitive composition prepared as described above is a paste-like composition having fluidity suitable for application, and has a viscosity of usually 10 to 100,000 mPa · s ⁻¹ , preferably 50~10,000mPa · s ^-1, more preferably a 100~5,000mPa · s ^-1.
The composition of the present invention can be particularly preferably used for producing the photosensitive film of the present invention described in detail below.

<Photosensitive Film> The photosensitive film of the present invention generally comprises a support film and a photosensitive resin layer containing inorganic particles formed on the support film. A protective film may be provided on the surface of the resin 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. Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, and polyfluoroethylene, nylon, and cellulose. The thickness of the support film is, for example, 20 to 100.
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 film of the present invention is formed 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. Usually, a protective film is provided (press-bonded) on the inorganic particle-containing photosensitive resin layer.
It can be manufactured by the following.

As a method of applying the inorganic particle-containing photosensitive composition onto a support film to obtain an inorganic particle-containing photosensitive resin layer, a film having a uniform thickness and a large thickness (for example, 1 μm) can be used.
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 for forming each display cell of a plasma display panel. In addition, in forming a black matrix, the organic component is excellent in thermal decomposability and can be suitably used for forming a highly accurate pattern. In the method for 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, and [3] The method includes the steps of developing an inorganic particle-containing photosensitive resin layer and [4] baking an 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.

[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] Developing Step of Inorganic Particle-Containing Photosensitive Resin Layer In the developing step, the exposed inorganic-particle-containing photosensitive resin layer is subjected to a developing treatment to thereby form a pattern (latent image) ) 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 baking the photosensitive resin layer pattern containing inorganic particles In this step, the photosensitive resin layer pattern containing inorganic particles is subjected to a baking treatment 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. In addition, it is preferable that the firing process of the inorganic particle-containing photosensitive resin layer pattern is performed simultaneously with the firing process of the other members from the viewpoint of improving the manufacturing efficiency, unless the performance of the target member is significantly impaired.

[0056]

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).

<Example 1> (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) 60 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.) 40 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
Parts, (C) 40 parts of trimethylolpropane triacrylate as an ethylenically unsaturated group-containing compound, and (D) 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1 as a photopolymerization initiator. -5 parts of propanone (97% weight loss at 400 ° C), 4,4'-
5 parts of bisdiethylaminobenzophenone (96% weight loss at 400 ° C.) 5 parts of (E) 150 parts of propylene glycol monomethyl ether acetate as a solvent and (F) 1 part of oleic acid as a dispersant were kneaded with a bead mill, and then kneaded with a stainless steel mesh ( 500 mesh, 2
By filtering with a 5 μm diameter, a photosensitive composition containing inorganic particles was prepared. The weight loss at 400 ° C. of the total amount of the photopolymerization initiator (D) in the inorganic particle-containing photosensitive composition was 97%.

(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 the protective film from the photosensitive film, a 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 the inorganic particle-containing photosensitive resin layer: The inorganic particle-containing photosensitive resin layer is exposed to an exposure mask (400 μm width stripe pattern) through the exposure mask.
I-ray (ultraviolet light with a wavelength of 365 nm) by an ultra-high pressure mercury lamp
Was irradiated. Here, the irradiation amount was 400 mJ / cm ² . After the exposure step, the support film is peeled off from the inorganic particle-containing photosensitive resin layer, and then, with respect to the exposed inorganic particle-containing photosensitive resin layer, a 0.4% by mass aqueous sodium carbonate solution (30 ° C.) Was used for a developing solution by a shower method over 1 minute. Next, a washing treatment with ultrapure water was performed, whereby the uncured inorganic particle-containing photosensitive resin layer that was not irradiated with ultraviolet rays was removed to form an inorganic particle-containing photosensitive resin layer pattern.

Printing step of dielectric paste: A dielectric paste (YPT030 manufactured by Asahi Glass Co., Ltd.) was screen-printed on a glass substrate on which a photosensitive resin pattern containing inorganic particles was formed, and then dried at 100 ° C. for 5 minutes. Then, a dielectric paste film having an average film thickness of 30 μm was formed.

Baking step of the inorganic particle-containing photosensitive resin layer pattern and the dielectric paste film: The glass substrate having the dielectric paste film formed on the inorganic particle-containing photosensitive resin layer pattern is heated at 580 ° C. in a baking furnace. The baking treatment was performed for 30 minutes under. As a result, a panel material having the black matrix pattern and the dielectric layer formed on the surface of the glass substrate was obtained. When the dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope, bubbles, pinholes, and the like having a diameter of 20 μm or more were not observed in the dielectric layer.

Example 2 (A) As inorganic particles, 95 parts of Ag particles (granular), average
Bi with a particle size of 3 μm_Two O _Three -ZnO-B_Two O_Three -SiO_Two 
-Al_Two O_Three Low melting point glass frit (irregular shape, softening point
(520 ° C.) 5 parts, (D) 2-meth
Ru- [4 '-(methylthio) phenyl] -2-morpho
Reno-1-propanone (weight loss 97 at 400 ° C.)
%) 7 parts, 4,4'-bisdiethylaminobenzopheno
3 parts (96% weight loss at 400 ° C)
In the same manner as in Example 1 except that
A composition was prepared. In addition, the photosensitive composition containing the inorganic particles
Of the total weight of the photopolymerization initiator (D) at 400 ° C.
The number was 97%. The photosensitive composition containing the inorganic particles
A photosensitive film was prepared in the same manner as in Example 1 except that the photosensitive film was used.
Was made. Other than using the photosensitive film
In the same manner as in Example 1, the transfer of the inorganic particle-containing photosensitive resin layer was performed.
Copying process and exposure process of photosensitive resin layer containing inorganic particles
Performs the imaging process to form a photosensitive resin layer pattern containing inorganic particles.
Done. Next, the same as in the first embodiment,
Printing process and photosensitive resin layer pattern containing inorganic particles
Firing process for the dielectric paste and dielectric paste film.
Electrode pattern and dielectric layer on the surface of the glass substrate.
The formed panel material was obtained. Panel obtained
For the dielectric layer on the electrode pattern in the material, optical
Microscopic observation showed that the dielectric layer had a diameter of 20 μm or less.
Above bubbles, pinholes, etc. were not observed.

Example 3 (D) 5 parts of 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone (97% weight loss at 400 ° C.) as a photopolymerization initiator, 2,4
-A photosensitive composition containing inorganic particles was prepared in the same manner as in Example 1 except that 5 parts of diethylthioxanthone (weight loss at 400 ° C: 93%) was used. The weight loss at 400 ° C. of the total amount of the photopolymerization initiator (D) in the inorganic particle-containing photosensitive composition was 95%. A photosensitive film was produced in the same manner as in Example 1 except that the photosensitive composition containing inorganic particles was used. Except for using the photosensitive film, in the same manner as in Example 1, the step of transferring the inorganic particle-containing photosensitive resin layer and the step of exposing and developing the inorganic particle-containing photosensitive resin layer were performed. A resin layer pattern was formed. Then, a printing process of the dielectric paste and a firing process of the inorganic particle-containing photosensitive resin layer pattern and the dielectric paste film were performed in the same manner as in Example 1, whereby the black matrix pattern and the dielectric material were formed on the surface of the glass substrate. A panel material having the layers formed was obtained. The dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope.
Although a few bubbles of 0 μm or more were observed, the pattern accuracy was at a level that was not problematic for use.

Comparative Example 1 (D) As a photopolymerization initiator, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl1,2′-biimidazole (400 Inorganic particle-containing photosensitive composition in the same manner as in Example 1 except that 5 parts by weight at 22 ° C.) and 5 parts of 4,4′-bisdiethylaminobenzophenone (96% by weight at 400 ° C.) were used. Was prepared. The weight loss at 400 ° C. of the total amount of the photopolymerization initiator (D) in the inorganic particle-containing photosensitive composition was 59%. A photosensitive film was produced in the same manner as in Example 1 except that the photosensitive composition containing inorganic particles was used. Except for using the photosensitive film, in the same manner as in Example 1, the step of transferring the inorganic particle-containing photosensitive resin layer and the step of exposing and developing the inorganic particle-containing photosensitive resin layer were performed. A resin layer pattern was formed. Then, a printing process of the dielectric paste and a firing process of the inorganic particle-containing photosensitive resin layer pattern and the dielectric paste film were performed in the same manner as in Example 1, whereby the black matrix pattern and the dielectric material were formed on the surface of the glass substrate. A panel material having the layers formed was obtained. When the dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope, many pinholes having a diameter of 50 μm or more were observed in the dielectric layer.

<Comparative Example 2> (D) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (85% weight loss at 400 ° C.) as a photopolymerization initiator A photosensitive composition containing inorganic particles was prepared in the same manner as in Example 1 except that 10 parts were used. A photosensitive film was produced in the same manner as in Example 1 except that the photosensitive composition containing inorganic particles was used. Except for using the photosensitive film, in the same manner as in Example 1, the step of transferring the inorganic particle-containing photosensitive resin layer and the step of exposing and developing the inorganic particle-containing photosensitive resin layer were performed. A resin layer pattern was formed. Then, a printing process of the dielectric paste and a firing process of the inorganic particle-containing photosensitive resin layer pattern and the dielectric paste film were performed in the same manner as in Example 1, whereby the black matrix pattern and the dielectric material were formed on the surface of the glass substrate. A panel material having the layers formed was obtained. When the dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope, many bubbles having a diameter of 20 μm or more were observed in the dielectric layer.

[0067]

According to the photosensitive composition and the photosensitive film containing inorganic particles of the present invention, a pattern having high thermal decomposability of organic components and high 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.

[Description of the drawings]

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

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 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 symbol FI Theme coat ゛ (Reference) C08F 291/06 C08F 291/06 5C040 C08J 5/18 CEY C08J 5/18 CEY C08K 3/00 C08K 3/00 C08L 101/12 C08L 101/12 G03F 7/027 501 G03F 7/027 501 7/031 7/031 H01J 11/02 H01J 11/02 EF term (reference) 2H025 AA02 AA03 AB11 AB13 AB17 AC01 AD01 BC14 BC33 BC43 CA02 CA03 CB51 CC08 CC20 FA28 FA29 4F071 AA32 AA33 AB18 AB26 AB27 AC07 AE06 AE17 AF05 AH12 BA02 BB02 BC02 4J002 BG011 BG041 BG051 BG072 DE096 DE106 DE146 DJ0 6 QA24 QB14 QB16 QB24 QB25 SA01 SA05 SA25 SA78 SA83 UA01 VA01 WA01 4J026 AA16 AA45 AA47 AA48 AB 01 AB07 BA28 DB06 DB36 GA07 5C040 GC18 GC19 GD07 GD09 GF18 GF19 GG07 GG09 GH03 GH07 JA09 JA15 JA19 KA16 KB03 KB11 KB14 KB17 KB19 MA23 MA24

Claims (4)

[Claims] 1. An inorganic particle (A), an alkali-soluble resin (B), a compound containing an ethylenically unsaturated group (C), and (D)
A photosensitive composition containing inorganic particles, which comprises a photopolymerization initiator whose weight loss at 400 ° C. is 90% or more. (D) The weight loss at 400 ° C. is 95
%. The photosensitive composition containing inorganic particles according to claim 1, wherein the photosensitive composition contains two or more photopolymerization initiators in an amount of at least 2%. 3. The inorganic material according to claim 1, wherein (D) a photopolymerization initiator contains a compound represented by the following formula (1) and a compound represented by the following formula (2). Particle-containing photosensitive composition. Embedded image (In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms.) (In the formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms.) 4. A photosensitive film comprising an inorganic particle-containing photosensitive resin layer obtained from the inorganic particle-containing photosensitive composition according to claim 1.