JPH06348013A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a high sensitivity photosensitive resin compsn. capable of satisfactory photosetting even when the amt. of a filler added is increased by using specified substd. benzoyldiphenylphosphine oxide as a photopolymn. initiator. CONSTITUTION:Substd. benzoyldiphenylphosphine oxide represented by the formula is used as a photopolymn. initiator in this photosensitive resin compsn. In the formula, R<1> is 1-5C lower alkyl, the number (l) of the substituent it 1-3, each of R<2> and R<3> is H, 1-5C lower alkyl or alkoxy and each of the numbers (m), (n) of the substituents is 1-3 and R2 may be different from R3 each other. Since the substd. benzoyldiphenylphosphine oxide represented by the formula is used as a photopolymn. initiator, this photosensitive resin compsn. can be satisfactorily photoset even when the amt. of a filler added is increased.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating layer provided in an electronic display device such as a fluorescent display and a plasma display panel.
The present invention relates to a photosensitive resin composition for forming a conductor pattern, a fluorescent display element, etc.

[0002]

2. Description of the Related Art Conventionally, in order to form a fine fluorescent display element or the like provided in an electronic display device, for example, Japanese Unexamined Patent Application Publication No. Hei 4 (1999) -1998
As described in JP-A-116558, an organic polymer binder, a photopolymerizable monomer, a photopolymerization initiator, a phosphor powder and an organic solvent are kneaded to prepare a paste composition, and this composition is used as a substrate. It was patterned by the lithographic method after it was applied to.

Further, by using 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one as the photopolymerization initiator, the sensitivity of the photosensitive resin can be increased and the phosphor It compensated for the decrease in ultraviolet transmittance caused by the mixture of powder.

[0004]

However, in the above-mentioned photopolymerization initiator, if the addition amount of the phosphor powder or the like as a filler is excessively increased, the ultraviolet ray transmission amount is lowered and the photosensitive resin causes curing failure. For example, it has been impossible to add a large amount of red phosphor powder to increase the emission brightness of the display element and display bright red.

The present invention has been made to solve the above problems, and an object thereof is to provide a highly sensitive photosensitive resin composition which can be sufficiently photocured even if the amount of filler added is increased. is there.

[0006]

In order to solve the above problems, in the present invention, the following general formula 2 is used as a photopolymerization initiator.
(Wherein, R ¹ is the number _l of this substituent a lower alkyl group of 1 to 5 carbon atoms is 1 to 3. Also, R ² and R ³
May be different from each other and represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms or an alkoxy group, and the numbers _m and _n of the substituents are 1 to 3. Substituted benzoyldiphenylphosphine oxide shown in (1) is used.

[Chemical 2]

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, a remarkable effect can be obtained only when a photopolymerization initiator of the compound group represented by the general formula 2 is used. The present invention has been completed and the present invention has been completed.

Among the photopolymerization initiators represented by the above general formula 2, particularly preferable one is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, for example BA.
It is sold by SF under the product name "Lucirin TPO".

In addition to the photopolymerization initiator based on the present invention, other known photopolymerization initiators may be used in combination. As such a photopolymerization initiator, a decomposition type, a hydrogen transfer type and the like can be used. Specific examples include anthraquinones such as ethylanthraquinone, benzanthraquinone, diaminoanthraquinone and 1-chloroanthraquinone, benzophenone, N, N-dimethylaminobenzophenone, 3,3-
Benzophenones such as dimethyl-4-methoxy-benzophenone, 1,1-dichloroacetophenone, 2,2-
Acetophenones such as dimethoxy-2-phenylacetophenone, benzoins, benzoin methyl ether, benzoin ethyl ether, isobutyl benzoin ether, benzoins such as isopropyl benzoin ether, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, 1-chlorothioxanthone, 2-chloro Thioxanthones such as thioxanthone and 2-methylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1
-One, Michler's ketone, 2,4,6- (trihalomethyl) triazine, 2- (o-chlorophenyl) -4,
5-diphenylimidazolyl dimer, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane,
1,5-bis (9-acridinyl) pentane, 1,3-
Examples thereof include bis (9-acridinyl) propane, and a mixture thereof.

Since the photopolymerization initiator represented by the general formula 2 of the present invention represented by 2,4,6-trimethylbenzoyldiphenylphosphine oxide has a high crosslinking efficiency, it is described in the prior art, for example, JP-A-4-116558. In comparison with 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, the exposure time during curing of the photosensitive resin composition was 1/2 when the same amount was used. From 1
It can be shortened to / 3. Further, when the exposure time is the same, the addition amount can be reduced, so that the filler amount is increased to increase the packing density, and in the case of a fluorescent display element, the emission luminance is increased to show a vivid color, and the insulating layer The insulating effect can be further enhanced, and the conductive pattern can further enhance the conductivity.

As the filler according to the present invention, various fillers can be used depending on the use of the photosensitive resin composition of the present invention. For example, in order to form a display element of a fluorescent display, ZnS, CdS, AgCl, (Zn, Cd) S: Ag, Zn
O: Zn, ZnS: Cu, Al, ZnS: Ag, Y ₂ O ₂ S: E
u, ZnS: Zn, (Y , Cd) BO 3: Eu, Zn 2 SiO 4:
Phosphor powders such as Mn, BaMgAl ₁₂ O ₂₃ : Eu can be used.

Hard glass powder, ceramic powder, etc. can be used to form an insulating layer of an electronic display device, and a heat resistant pigment is used to form a black insulating layer having a light shielding property. For example, Fe ₂ O ₃ , Cr ₂ O ₃ , CuO, Mn
A mixture of O _{2 and the} like may be used.

Further, in order to form a conductor pattern of an electronic display device, for example, Ag, Au, Cu, W having conductivity is formed.
And the like can be used. In addition, the adhesiveness of the fine powder can be enhanced by using a glass having a low-melting point of about 0.1 to 10% by weight, which does not reduce the conductivity of these fillers.

As the above-mentioned low melting point glass, known ones can be used, and examples thereof include the following compositions. SiO ₂ ...... 52 to 67 wt% RO ...... 13.3 to 23.3 〃 R ₂ O ₃ …… 7.7 to 12.7 〃 R ₂ O …… 11 to 13 〃 However, the above RO is PbO, Represents CaO, etc., and R ₂ O ₃ is B
₂ O ₃ , Al ₂ O _{3 and the} like, and R ₂ O represents Na ₂ O and the like.

The organic polymer compound according to the present invention includes
What is used for the conventional photosensitive resin can be used, for example, as the water-developable polymer compound, cellulose such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethylpropyl cellulose, acryloylmorpholine, acrylamide. , Homopolymers of monomers such as dimethylacrylamide, copolymers of these monomers with acrylic acid, methacrylic acid, and the like, specifically polyacryloylmorpholine, acryloylmorpholine and β-
A copolymer of hydroxyethyl acrylate, a copolymer of acryloylmorpholine and β-hydroxypropyl acrylate, an acrylic polymer such as a copolymer of polyacrylamide, polydimethylacrylamide, methylacrylamide and acrylic acid, and a polymer compound thereof. A mixture may be mentioned.

The photopolymerizable monomer according to the present invention is photopolymerized by an active light source in the presence of a photopolymerization initiator and becomes insoluble in a developing solution. Examples thereof include acrylic acid and methacrylic acid. Acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, diethylene glycol diacrylate, diethylene glycol di Methacrylate, triethylene glycol diacrylate,
Triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 2,2'-dimethylpropane diacrylate, 2,2'-dimethylpropane dimethacrylate,
Examples thereof include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, cardoepoxy diacrylate, and mixtures thereof.

Further, in the photosensitive resin composition of the present invention, conventionally known compounds such as a polymerization inhibitor, a plasticizer and a dye can be appropriately used as other components, if necessary.

In the photosensitive resin composition of the present invention, it is preferable to adjust the viscosity of the composition to form a paste and use an organic solvent in order to improve the coating performance. Examples of such organic solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol,
Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 1,1,1
-Trichloroethane, trichloroethylene, 3-methyl-3-methoxybutanol, methoxybutylacetate, terpineol, and mixtures thereof can be mentioned.

The preferred blending ratio of each component of the photosensitive resin composition of the present invention will be described below. However, since this blending ratio varies depending on the type of each component, the purpose of use of the composition, etc., it is only a guide and is within the scope of the present invention. Is not limited.

The amount of the photopolymerizable monomer added is 30 to 200 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight of the organic polymer compound. Further, the amount of the photopolymerization initiator added cannot be determined unconditionally because it depends on the amount of the colored filler added.
The amount is 0.01 to 25 parts by weight, and more preferably 0.1 to 15 parts by weight. In the photopolymerization initiator, the substituted benzoyldiphenylphosphine oxide represented by the general formula 2 preferably accounts for at least 50% by weight. The amount of the filler added is 10 to 300 parts by weight based on 100 parts by weight of the total composition except the organic solvent.
It is more preferably 20 to 200 parts by weight.

If the amount of the photopolymerizable monomer is less than 30 parts by weight, the photocuring may be insufficient and the image area may be eluted during development, and an image may not be formed. Further, in the case of a fluorescent display, the light emitting property may be deteriorated. There is. On the other hand, if it exceeds 200 parts by weight, the resolution of a fine image is deteriorated and sticking easily occurs, which is not preferable.

The amount of the photopolymerization initiator added is 0.0
If the amount is less than 1 part by weight, the photocuring at a normal exposure amount becomes insufficient, so that the image part may be eluted during development and an image may not be formed. Since the amount decreases, the performance of the insulating layer, the conductor pattern, the fluorescent display element, and the like formed may deteriorate. Further, the general formula 2 contained in the photopolymerization initiator
Substituted benzoyldiphenylphosphine oxide of 50
Even if it is less than wt%, the photocuring may be insufficient.

If the amount of the filler added is less than 10 parts by weight, the performance of the formed insulating layer, conductor pattern, fluorescent display element, etc. may deteriorate. The larger the amount of the filler added, the more preferable. However, if it exceeds 300 parts by weight, the transmittance of the ultraviolet light for exposure is extremely reduced, which may result in poor curing.

The organic solvent has a viscosity at 25 ° C. of preferably 5 to 400 Pa · S, more preferably 200 to 200 Pa · S in order to make the photosensitive resin composition of the present invention into a paste form. Can be added appropriately.

Next, an example of using the photosensitive resin composition of the present invention to form a fluorescent display device will be described. First, the photosensitive resin composition of the present invention containing a phosphor powder as a filler is formed into a paste having an appropriate viscosity by adjusting the viscosity with an organic solvent, and the paste has a film thickness after drying of 10 to 10.
It is applied to the entire surface of the glass substrate by a screen printing method so as to have a thickness of 60 μm, and is applied in an atmosphere of 75-80 ° C. for 15-
Dry for 20 minutes. Then, the glass substrate is selectively irradiated with an actinic ray such as an ultraviolet ray through a mask having a desired pattern. This irradiation amount is preferably 5 to 200 mJ / cm ² for an ultra-high pressure mercury lamp, for example. Next, it is developed with an aqueous or oily developing solution by a spray method, a dipping method or the like to remove the uncured portion, dried by a dryer or the like, and then baked in a baking furnace. The firing temperature at this time varies depending on the type of phosphor powder used, but an approximate maximum temperature is about 500 to 550 ° C. The film thickness of the fluorescent display device obtained by firing is about 10 to 40 μm.

Also when the photosensitive resin composition of the present invention is used for forming an insulating layer of an electronic display device, a photosensitive resin composition containing a combination of a black pigment, ceramic powder, etc. and a low melting point glass as a filler component. It is the same as in the case of the above-mentioned fluorescent display device except that the thing is used. Further, when used for forming a conductor pattern, in the case of the above fluorescent display device except that a photosensitive resin composition containing a combination of fine conductor powder such as metal powder and low melting point glass is used as a filler component. The firing temperature is up to about 1000 ° C, and the film thickness after firing is 1 to
The coating amount is adjusted to be 10 μm.

[0027]

The present invention provides a phosphor powder that prevents the transmission of ultraviolet rays and the like.
A photosensitive resin, which is difficult to be photocured because it contains ceramic powder, conductor powder, etc., can be cured by blending a photopolymerization initiator with high sensitivity.

[0028]

EXAMPLES Examples according to the present invention will be described below. Example 1 A photosensitive resin composition having the following composition was kneaded with a three-roll mill to prepare a phosphor paste. Photosensitive resin composition human hydroxypropyl cellulose (average molecular weight of about 60,000) 100 parts by weight pentaerythritol triacrylate 100 〃2,4,6-trimethylbenzyldiphenyl phosphine oxydide 5〃methyl human quinoquinone 0.5〃 (Zn, Cd) S: Ag, Cl (phosphor powder) 510〃 3-methyl-3-methoxybutanol 300〃

The viscosity of this paste is 90 at 25 ° C.
It was Pa.S (measured by a B-type rotational viscometer).
Next, this paste was applied over the entire surface of a glass substrate for a fluorescent display tube through a 150-mesh screen, allowed to stand for 10 minutes, dried at 80 ° C. for 20 minutes, and allowed to stand at room temperature. Then 3K through a mask with a predetermined pattern
Selectively irradiate ultraviolet rays of 100 mJ / cm ² using a W ultra-high pressure mercury lamp, develop with water for 1 minute, and then heat this at 530 ° C.
By baking for 10 minutes, a phosphor layer having a film thickness of 20 μm having a dot pattern of 80 μm square was formed. When the light-emitting characteristics of the phosphor layer thus obtained were examined using a fluorescent display tube, bright red light emission with high brightness was obtained.

Example 2 In place of 5 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide which is the photopolymerization initiator in Example 1, 3.5 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was used. And a phosphor layer was formed in the same manner as in Example 1 except that 1.5 parts by weight of 2,4-diethylthioxanthone was combined. Similar to Example 1, this phosphor layer also emitted bright red light with high brightness.

Comparative Example 1 In place of 5 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide of Example 1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- An attempt was made to form a phosphor layer in the same manner as in Example 1 except that the same amount of ON (5 parts by weight) was used. However, it was not possible to obtain a phosphor layer having an accurate pattern dimension due to severe film loss due to poor curing due to insufficient sensitivity.

Example 3 A photosensitive resin composition having the following composition was kneaded with a three-roll mill to prepare an insulating layer paste. Photosensitive resin composition Human doxypropyl cellulose (average molecular weight of about 60,000) 100 parts by weight Pentaerythritol triacrylate 100 〃 2,4,6-trimethylbenzyldiphenyl phosphine oxydose 5 〃 Methyl human quinone 0.5 〃 Defoamer 0.2 〃 Low melting point glass (PbO ・ B ₂ O ₃・ SiO ₂ ) 675 〃 Black pigment (Black pigment # 560 manufactured by Iwaki Glass Co., Ltd.) 75 〃 3-Methyl-3-methoxybutanol 300 〃

The viscosity of this paste is 95 at 25 ° C.
It was Pa.S (measured by a B-type rotational viscometer).
Next, this paste was applied to the entire surface of the glass substrate through a 150-mesh stainless screen so that the film thickness was 40 μm, dried in a warm air dryer at 80 ° C. for 20 minutes, and then allowed to reach room temperature. I left it. Next, ultraviolet rays of 100 mJ / cm ² were irradiated with an ultra-high pressure mercury lamp having an illuminance of 10 mW / cm ² through a mask having a predetermined pattern, and spray development was carried out with water for 30 seconds. The thickness of the remaining part is 40 μm
Met. This was baked for 1 hour at a maximum temperature of 550 ° C. to obtain a glass insulating thin layer having a 100 μm line pattern and a thickness of 20 μm.

Example 4 A photosensitive resin composition having the following composition was kneaded with a three-roll mill to prepare a conductor pattern paste. Photosensitive resin composition Human doxypropyl cellulose (average molecular weight: about 60,000) 100 parts by weight Pentaerythritol triacrylate 100 〃 2,4,6-Trimethylbenzyldiphenyl phosphine oxydose 40 〃 Methyl human quinone 0.5 〃 Defoamer 0.2 〃 Low melting point glass (PbO ・ B ₂ O ₃・ SiO ₂ ) 5〃 fine silver powder (average particle size 1 μm) 400〃 3-methyl-3-methoxybutanol 300〃

The viscosity of this paste is 65 at 25 ° C.
It was Pa · s. Next, this paste was applied to the entire surface of a glass substrate through a 250-mesh stainless screen so that the film thickness was 10 μm, dried in a warm air dryer at 80 ° C. for 20 minutes, and then allowed to reach room temperature. I left it. Next, an illuminance of 1 through a mask with a predetermined pattern
Ultraviolet light of 500 mJ / cm ² was irradiated with an ultra-high pressure mercury lamp of 0 mW / cm ² , and spray development was performed with water for 30 seconds. The film thickness of the remaining portion was 8 μm. This was baked for 1 hour at a maximum temperature of 580 ° C. to obtain a silver wiring with a thickness of 3 μm having a 150 μm line pattern.

[0036]

As described above, the photosensitive resin composition of the present invention is highly sensitive because it uses the substituted benzoyldiphenylphosphine oxide represented by the general formula 2 as a photopolymerization initiator. Even if the addition amount of is increased, it can be sufficiently photocured. Therefore, it is possible to form an insulating layer, a conductor pattern, a fluorescent display element, and the like provided in a good electronic display device.

Claims (1)

[Claims] 1. A photosensitive resin composition containing an organic polymer compound, a photopolymerizable monomer, a photopolymerization initiator and a filler, wherein the composition has the following general formula 1 ( However, R ¹ is a lower alkyl group having 1 to 5 carbon atoms, and the number _{l of} this substituent is 1 to 3. R ²
R ³ and R ³ may be different from each other and represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms or an alkoxy group, and the numbers _m and _n of the substituents are 1 to 3. The photosensitive resin composition characterized by using the substituted benzoyl diphenyl phosphine oxide shown to these. [Chemical 1]