JPH1138605A - Production of relief pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form uniform relief patterns to a large area with high accuracy by forming a photosensitive resin layer on a substrate having a surface region where surface roughness is within a specific range and exposing and developing this layer. SOLUTION: A photosensitive film having a base film and the photosensitive resin layer of 100 to 300 μm is thickness is honded onto a substrate having the surface region of 3 to 50 μm in Rz (ten point average roughness) by directing the photosensitive resin layer surface toward the substrate surface and is then exposed and developed, by which the relief patterns are formed on the substrate. The substrate having the surface region of 3 to 50 μm in Rz is a substrate for a rear surface plate of a plasma. display panel provided with electrodes of 3 to 50 μm height on a flat glass plate. The photosensitive film is obtd. by applying a soln. of a photosensitive resin compsn. on the base film (polyethylene terephthalate film) of 3 to 100 μm thickness and drying the coating, thereby forming the photosensitive resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a relief pattern.

[0002]

2. Description of the Related Art Conventionally, in the precision processing industry, for example, in the manufacture of printed wiring boards, a transparent support such as a polyethylene terephthalate film is used for forming a resist such as plating and etching, and for forming a permanent mask such as an electroless plating mask and a solder mask. It is known to use a photosensitive film in which a photosensitive resin layer is formed on a film, and a protective film such as a polyethylene film is bonded thereon. The lithographic pattern formation method using this photosensitive film has the advantage of being able to form fine wires with a uniform thickness and a large area with high precision compared to the screen printing method. For color TV, VTR
The formation of components for various industrial electronic devices, such as components for electronic devices and audio devices, has been widely studied for application to the formation of components for consumer electronic devices. Accordingly, it has become necessary to form a photosensitive pattern with high precision and uniformity on a substrate having irregularities of 3 to 30 μm in height, such as conductive patterns of various metals on the surface.

[0003] The thickness of a photosensitive resin layer of a conventional photosensitive film is mainly 25 to 50 µm. However, when these photosensitive films are bonded together, the unevenness of the substrate cannot be sufficiently covered. It is very difficult to form a photosensitive resin layer without involving air bubbles on it.
In the formation of a solder mask for a printed wiring board,
When forming a photosensitive resin layer on a substrate on which a copper pattern having a height of 10 to 20 μm is formed, in order to sufficiently cover the copper pattern with the photosensitive resin, bonding is performed under vacuum. There are problems that the process is complicated and that high equipment investment is required. In addition, in forming a barrier on a back plate of a plasma display panel by an additive method (photo embedding method), a photosensitive resin layer is formed on a glass plate having a striped silver electrode having a height of about 10 μm,
A relief pattern is formed by a known photo-patterning method. In this case, if the thickness of the photosensitive resin layer is 50 μm or less, depending on the bonding direction, if the bonding is performed in a cross direction with the electrode line, bubbles are trapped. There is an inevitable problem. If there is a gap such as air bubbles between the photosensitive resin layer and the substrate, the photosensitive resin pattern obtained upon exposure and development will have problems such as floating, chipping, disconnection, and the like, which is not practical.

[0004]

According to the first aspect of the present invention, there is provided a substrate having a surface area having a surface roughness Rz (ten-point average roughness) of 3 to 50 μm (for example, a metal pattern such as a conductive pattern of various metals). A substrate having a convex portion of about 50 μm on the surface), forming a photosensitive resin layer without involving air bubbles, exposing and developing the photosensitive resin layer to form a uniform relief pattern with high precision over a large area. It provides a manufacturing method. The invention according to claim 2 provides a method of manufacturing a relief pattern which can manufacture a plasma display panel rear plate substrate provided with a relief pattern, which is suitable for a large-area high-quality plasma display panel.

[0005]

According to the present invention, a photosensitive film having a support film and a photosensitive resin layer having a thickness of 100 to 300 μm has an _Rz (ten-point average roughness) of 3 to 5 mm.
A method of manufacturing a relief pattern, comprising: bonding a photosensitive resin layer surface to a substrate surface having a surface area of 0 μm with the photosensitive resin layer surface facing the substrate surface, and then exposing and developing to form a relief pattern on the substrate. About. Also,
According to the present invention, a substrate having a surface region having an _Rz (ten-point average roughness) of 3 to 50 μm is formed on a flat glass plate with a height of 3 to 50 μm.
The present invention relates to a method for manufacturing a relief pattern which is a substrate for a back plate of a plasma display panel provided with a μm electrode.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive film used in the present invention is a support film (for example, having a thickness of 3 to 100 μm).
A photosensitive resin composition solution is applied on a polyethylene terephthalate film) and dried to form a photosensitive resin layer. This photosensitive resin layer is uncured,
Since it is flexible and somewhat sticky, a protective film such as polyethylene with a thickness of 3 to 100 μm may be stuck on the photosensitive resin layer as necessary to prevent external damage and adhesion of foreign matter. Can be.

The photosensitive resin layer has properties (solubility in a solvent or the like, tackiness, viscosity,
Fluidity, elastic modulus, elongation, viscoelasticity such as strength, surface tension, etc.).
Any known materials can be used without particular limitation, and examples thereof include a negative photosensitive resin composition and a positive photosensitive resin composition. As the positive photosensitive resin composition, known ones can be used without particular limitation, for example, a soluble-based photogenerating composition using a 1,2-naphthoquinonediazide compound, an o-nitrobenzyl compound, or the like, Photoacid generation / acid decomposition type compositions using onium salts and the like are included.
The negative photosensitive resin composition is not particularly limited and known ones can be used. For example, (a) an ethylenically unsaturated compound,
(B) a film-forming property-imparting polymer and (c) a photopolymerization initiator as essential components, and (d) a dye or pigment, (e) other additives, and (f) an organic solvent as optional components.

Examples of the (a) ethylenically unsaturated compound include butyl acrylate, tetraethylene glycol diacrylate, γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate, tetrapropylene glycol diacrylate. Acrylate,
2,2-bis [(4-methacryloxypentaethoxy)
[Phenyl] propane, trimethylolpropane triacrylate, acrylates such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, and methacrylates corresponding thereto.

(B) Examples of the film-forming polymer include acrylic acid, methacrylic acid, an alkyl ester of acrylic acid having 1 to 22 carbon atoms, an alkyl ester of methacrylic acid having 1 to 22 carbon atoms, and 2-hydroxyethyl. Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, acrylonitrile, N-
Vinyl copolymers, polyesters and polyamides obtained by copolymerizing vinyl monomers such as methylol acrylamide, N-methyl methacrylamide, styrene and vinyl toluene with monomers copolymerizable with these vinyl monomers Acids and the like. It is preferable that the polymer (b) having a film-forming property is a polymer having a carboxyl group from the viewpoint that development can be performed with an alkaline developer having excellent environmental properties.

(C) Examples of the photopolymerization initiator include benzophenone, 4,4'-diethylaminobenzophenone, 2-ethylthioxanthone, 1,7-bis (9-acridinyl) heptane, benzoin methyl ether, benzyldimethyl ketal and the like. Is mentioned. (D) Examples of the dye or pigment include malachite green and phthalocyanine green. (E) Other additives include, for example, a plasticizer such as diethylene glycol, an adhesion improver such as benzotriazole and tetrazole, a silicon-based surfactant having a leveling effect and an antifoaming effect, leuco crystal violet,
Coloring agents such as tribromomethylphenylsulfone; (F) As the organic solvent, for example, acetone, methyl ethyl ketone, toluene, ethyl acetate, butyl acetate, 2-
Butoxyethanol, 2-ethoxyethanol, 2-ethoxyethyl acetate, methanol, N-methyl-2-pyrrolidone and the like.

Here, the amount of the component (a) is determined from the viewpoints of film formability, low edge fusion, light sensitivity and the like.
The amount is preferably 20 to 80 parts by weight based on 100 parts by weight of the total of the components (a) and (b). (B)
The amount of the component is preferably 20 to 80 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b) from the viewpoints of photosensitivity, low edge fusion properties, film forming properties, and the like. The amount of the component (c) is preferably 1 to 10 parts by weight based on 100 parts by weight of the total of the components (a) and (b) from the viewpoint of light sensitivity and the like. Also,
The amount of the component (d) is 0.1 to 1 based on 100 parts by weight of the total amount of the components (a) and (b) from the viewpoint of workability and the like.
It is preferably 0 parts by weight. The amount of the component (e) is 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b) from the viewpoint of sufficiently exhibiting the effect.
It is preferable to use parts by weight. The amount of the component (f) is preferably 50 to 300 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b) from the viewpoints of coatability, productivity and the like.

In the present invention, the thickness of the photosensitive resin layer is 75
~ 300 μm, the thicker, the more effective at covering irregularities,
The thickness is preferably 100 μm or more, more preferably 160 μm or more, and particularly preferably 200 μm or more. If the thickness is less than 75 μm, the effect of covering the unevenness is low, and if it exceeds 300 μm, the sensitivity is low. 100μ
The photosensitive resin layer having a thickness of at least m can be obtained by applying the photosensitive resin composition to a predetermined thickness on a support film and drying at 80 to 130 ° C. for 5 to 10 minutes. Alternatively, a photosensitive film may be used in which a photosensitive resin layer having a thickness of about 20 to 90 μm is formed in advance, and this is laminated to form a photosensitive resin layer having a thickness of 100 μm or more. The fluidity of the photosensitive resin layer is 100 to 30 from the viewpoint of followability to an adherend such as a substrate, low deformability, low edge fusion, and the like.
It is preferably 0 μm, and more preferably 100 to 250 μm. The fluidity can be controlled within the above range by adjusting the types and amounts of the components (a) to (f). The fluidity herein refers to a photosensitive resin layer having a diameter of 20 mm and a thickness of 2 mm as a sample, which is placed on a flat substrate, and a diameter of 50 mm is placed thereon.
When a 5 kg static load of a 5 mm cylindrical shape is applied and the thickness (T ₁ μm) of the photosensitive resin layer deforming after 10 seconds and the thickness (T ₂ μm) after 900 seconds are measured, T ₁ − T ₂ (μm).

In the present invention, R _z (ten-point average roughness) is 3
Substrates having a surface area of ５０50 μm include various plastic plates, various plastic films, glass epoxy plates, ceramic plates, FRP plates, glass plates, and sheets obtained by laminating those plates and films with various metal foils. _Rz (ten-point average roughness) of 3 to 5 with uneven surface
One having a thickness of 0 μm is exemplified. Further, the above-mentioned plate, film or sheet having a flat surface and a conductive pattern of various metals formed on the flat surface, and the like, specifically, as such, on a flat glass plate There is a substrate for a back plate of a plasma display panel provided with electrodes having a height of 3 to 50 μm, and when this substrate is used, the effects of the present invention are well exhibited. R _z (ten point average roughness) is 3
If it is less than μm or more than 50 μm, the effects of the present invention will not be sufficiently exhibited. R _z (ten-point average roughness) is 3 to 50 μm
May cover the entire substrate, may cover substantially the entire substrate, or may be present on a portion of the substrate.

In the present invention, the surface region having an _Rz (ten-point average roughness) of 3 to 50 μm further complies with JIS B060.
The effect of the present invention is remarkable when R _max (maximum height) defined by 1 is 8 μm or more, and more remarkable when it is 10 μm or more. In the present invention, R _z (ten-point average roughness) is defined by JIS B0601,
In the present invention, an arithmetic average of at least five R _z randomly extracted from a predetermined surface region of the substrate is adopted as R _z .

When the photosensitive resin layer is bonded to the substrate, a laminator roll having a surface temperature of 25 to 160.degree.
By applying a pressure of about 7 kgf / cm ^{2, the} photosensitive resin layer can be bonded without entrapping air bubbles. In particular, on the back plate of a plasma display panel having a stripe-shaped silver electrode or the like on a glass plate, lamination can be performed in any of a direction parallel to the electrode and a direction perpendicular to the electrode without involving bubbles.

After a photosensitive resin layer having a predetermined thickness is formed on the substrate, it is exposed in a pattern by irradiating active light through a negative mask having a predetermined pattern. Is heated at 60 to 120 ° C. for 1 to 30 minutes to improve the temperature. At this time, as an active ray to be used, a ray that effectively emits ultraviolet rays such as a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp is used. After exposure in a pattern form and, if necessary, heat treatment, the support film is peeled off and developed to form a photosensitive resin pattern.

The developer used herein is not particularly limited as long as it can dissolve, swell, and peel off the unexposed or exposed portions. For example, a weakly alkaline diluted aqueous solution such as sodium carbonate and potassium carbonate is preferable. Development method is dip method,
It can be performed by a spray method or the like. Thereby, a relief pattern can be formed on the substrate with high accuracy and uniformity.

[0018]

Next, the present invention will be described with reference to examples. Examples 1-5 and Comparative Examples 1-3 Methyl methacrylate / ethyl acrylate / methacrylic acid copolymer (53/30/17 (weight ratio), weight average molecular weight 100,000) 41% by weight of methyl cellosolve / toluene ( 8
/ 2 (weight ratio)) 137 g of solution (solid content 55 g), 2,2
-Bis [(4-methacryloxypentaethoxy) phenyl] propane 34 g, γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate 11 g, 2,2′-methylenebis (4-ethyl-6
-T-butylphenol) 0.1 g, tribromomethylphenylsulfone 1.2 g, 1,7-bis (9-acridinyl) heptane 0.2 g, benzyldimethylketal 3 g, leuco crystal violet 1.0 g, malachite green 0.05 g , Toluene 7 g, methyl ethyl ketone 13 g and methanol 3 g to obtain a photosensitive resin composition solution.

This photosensitive resin composition solution was uniformly coated on a polyethylene terephthalate film having a thickness of 20 μm, and dried with a hot air convection dryer at 80 to 120 ° C. for 5 to 10 minutes to form a photosensitive resin layer. . Adjust the coating thickness,
The thickness of the photosensitive resin layer after drying is 150 μm, 75 μm,
A 50 μm film was obtained. 150 μm obtained here
Thick photosensitive resin layer formed on film 1, 75μ
A film 2 having a thickness of 150 μm and a photosensitive resin layer having a thickness of 50 μm was formed as a film 2 and a film 3 having a thickness of 50 μm.

Next, a plate in which striped copper lines were formed on a glass epoxy plate measuring 30 cm (length) × 40 cm (width) (a glass epoxy plate having a thickness of 1.6 mm, a copper line thickness of 18 μm,
Line width 150 μm, line interval 150 μm, 18 μm
_{R z; L2.5mm: 18μmR max;} L2.5mm), vertical 30 cm × horizontal 40cm flat glass plate to form a stripe-shaped silver line on the plate (3mm thick flat glass plate surface of the surface of the silver Line thickness 10 μm, line width 100 μm,
Line spacing 120 μm, 10 μm R _z ; L2.5 mm: 1
Films 1 and 2 were bonded once and film 3 was bonded three times on 0 μm R _max ; L2.5 mm) to form a 150 μm thick photosensitive resin layer. In the case of Example 5, a plate in which stripe-shaped silver lines were formed on a flat glass plate having a length of 30 cm and a width of 40 cm and a dielectric film was further formed thereon (a flat glass plate having a flat surface) was formed. Thickness 3mm, silver line thickness 10μm, line width 100μm, line interval 12
0 μm, dielectric film thickness 10 μm, 9 μm R _z ; L2.5 mm:
9 μm R _max ; L2.5 mm) to form a 150 μm thick photosensitive resin layer. here,
R _z (ten point average roughness) and R _max (maximum height) are JIS
The measurement was carried out in accordance with B0601 (using a surf coder SE-30D (manufactured by Kosaka Laboratory Co., Ltd.) of a stylus-type surface roughness measuring device), and was perpendicular to the longitudinal direction of the striped line on each substrate. The stylus was moved to Lamination was performed at a laminating roll temperature of 130 ° C. and a roll pressure of 4.0.
The test was performed under the conditions of kgf / cm ² and a speed of 1.0 m / min.

Next, a negative mask was placed on polyethylene terephthalate, and a 3 kw high-pressure mercury lamp (HMW-590,
(Manufactured by Oak Manufacturing Co., Ltd.) at 60 mJ / cm ² . Then, it was heated at 80 ° C. for 10 minutes within 5 minutes after exposure. Next, after peeling off the polyethylene terephthalate film, spray development was carried out with a 1% by weight aqueous solution of sodium carbonate at 30 ° C., washed with water and dried at 80 ° C. for 5 minutes to form a relief pattern. In Examples 1 to 5 and Comparative Examples 1 to 3, the presence or absence of bubbles after bonding and the presence or absence of abnormalities in the photosensitive resin pattern after development were examined. The results are shown in Table 1.

[0022]

[Table 1]

As is clear from the results shown in Table 1, in the case of bonding using a photosensitive film having a thick photosensitive resin layer, even if the substrate has irregularities, the irregularities of the substrate can be sufficiently covered with the photosensitive resin layer. Since it can be covered, it can be bonded without entrapment of air bubbles between the photosensitive resin layer and the substrate, and by exposing and developing this, a good photosensitive resin pattern can be formed.

[0024]

The method for producing a relief pattern according to the first aspect of the present invention is directed to a method for manufacturing a substrate having a surface region having a surface area of _Rz (ten-point average roughness of 3 to 50 μm).
A photosensitive resin layer is formed on a substrate having a projection of 50 μm on the surface without entrapping air bubbles, and the photosensitive resin layer is exposed and developed to form a uniform relief pattern with high precision over a large area. The method for manufacturing a relief pattern according to the second aspect is capable of manufacturing a substrate for a rear plate of a plasma display panel provided with a relief pattern thereon, which is suitable for a large-area high-quality plasma display panel.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor: Hajime Kadomaru 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd. No. 1 Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (2)

[Claims] 1. A support film and a thickness of 100 to 30.
A photosensitive film having a photosensitive resin layer of
_z The surface of the photosensitive resin layer is bonded to a substrate having a surface area of 3 to 50 μm (ten-point average roughness), and then exposed and developed to form a relief pattern on the substrate. A method for producing a relief pattern. 2. A substrate having a surface area with a _Rz (ten-point average roughness) of 3 to 50 μm on a flat glass plate having a height of 3 to 50 μm.
The method for producing a relief pattern according to claim 1, which is a substrate for a back plate of a plasma display panel provided with an electrode of 50 µm.