JP2000169751A - Photosensitive paste composition for baking, and structural member and substrate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive paste composition for baking applicable to a substrate having a low thermal expansion coefficient such an alkali-free glass for liquid crystal and a structural member fabricated using the composition. SOLUTION: A photosensitive paste composition for baking comprises at least (A) an inorganic powder, (B) a photopolymerization initiator, (C) a photosensitive monomer containing a bifunctional or more acryloyl group, and (D) a photosensitive monomer comprising as a main component a photosensitive monomer containing a monofunctional or more acrloyl group and containing a 4C or more chain, saturated hydrocarbon structure, wherein the inorganic powder (A) includes a glass frit having a thermal expansion coefficient in the temperature range to 50 deg.C-300 deg.C in a range of 50×10-7-100×10-7/ deg.C and a low expansion inorganic powder having a thermal expansion coefficient of not greater than 50×10-7/ deg.C. A structural member is fabricated by a printing method, a transfer method or the like with the use of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive paste composition for forming an inorganic structure by firing. More specifically, circuit boards for electronic devices,
In the manufacture of various displays and the like, it is used to form inorganic structures such as insulators, dielectrics, and conductors utilizing thick film formation technology.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an inorganic thick film such as an insulator or a dielectric, there are a printing coating technique such as screen printing and a transfer technique. A pattern is formed on a substrate by printing and transferring a paste composed of an inorganic substance as a final forming material and an organic substance imparting pattern moldability, and the pattern is fired to obtain an inorganic fired pattern.

As such a firing paste, there are a solvent-type non-photosensitive firing paste and a solvent-type photosensitive firing paste. In these methods, after the pattern is formed, the pattern is cured by heat drying to form the pattern. Heat drying,
Tact time is greatly increased because cooling is required.

[0004] In order to solve such a problem, a solventless photosensitive firing paste is disclosed in Example 1 of JP-A-54-13591. However, since the solvent is not used in the non-solvent type photosensitive fired paste, an organic substance is contained in a larger amount than the solvent type in order to enhance the moldability of the structure. For this reason, there was a problem that cracking and peeling occurred during firing. Japanese Patent Application Laid-Open No. 10-22594 discloses a solventless photosensitive firing paste that can prevent the cracking and peeling and can cope with the formation of a fine pattern. In addition, even if the photosensitive paste composition for solvent-type baking, by minimizing the amount of solvent, without performing the above-mentioned heat drying and cooling steps, molding by radiation curing including photocuring. It is possible.

Further, as a substrate for forming a pattern,
In general, an inorganic substrate that is resistant to firing is used, and a glass substrate, an alumina substrate, or a substrate made of a mixed material thereof is used depending on the application. In manufacturing an inorganic structure by firing, reduction of the tact time at the time of temperature reduction is an issue. In the case of a substrate having a small thermal shock coefficient and a large thermal expansion coefficient, there is a problem that the substrate is cracked when the cooling rate is increased. For this reason, a substrate having a small thermal expansion coefficient has recently been used, and a typical example is a non-alkali substrate for liquid crystal used as a display substrate (thermal expansion coefficient α = 40 to 50 × 10 ⁻⁷ / ° C.). There is. Specifically, in a plasma addressed liquid crystal display, the alkali-free glass for liquid crystal is used as a substrate. However, the conventional paste composition is for soda-lime glass, and none of them can be used for a low expansion substrate.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in order to solve such a problem, and an object of the present invention is to apply the method to a substrate having a small coefficient of thermal expansion and to perform a heat drying and cooling process. It is an object of the present invention to provide a photosensitive paste composition for firing that does not use any of the above, and a structure formed using the same.

[0007]

In order to solve the above-mentioned problems, the present invention firstly claims that at least (A) an inorganic powder (B) a photopolymerization initiator (C) containing at least a bifunctional or more acryloyl group. Then, in the photosensitive paste composition for firing mainly containing a photosensitive monomer having a chain type saturated monovalent hydrogen structure having 4 or more carbon atoms, (A) the inorganic powder is heated from 50 ° C to 3 ° C.
The coefficient of thermal expansion at 00 ° C. is 50 to 100 × 10 ⁻⁷ /
Glass frit in the range of ℃ and thermal expansion coefficient of 50 × 10 ^-7
A photosensitive paste composition for baking, characterized by containing a low-expansion inorganic powder of at most / ° C.

[0008] Claim 2 contains at least (A) an inorganic powder, (B) a photopolymerization initiator, (C) a photosensitive monomer having a bifunctional or higher acryloyl group, and (D) a monofunctional or higher functional acryloyl group. In a photosensitive paste composition for firing mainly containing a photosensitive monomer having a chain type saturated monovalent hydrogen structure having 4 or more carbon atoms, (A) the inorganic powder contains 5
Coefficient of thermal expansion from 0 ° C to 300 ° C is 50 to 100
Glass frit in the range of × 10 ^-7 / ° C and thermal expansion coefficient of 5
A photosensitive paste composition for baking, characterized by containing a low expansion inorganic powder of 0 × 10 ⁻⁷ / ° C. or less.

A third aspect of the present invention is a photosensitive paste composition for baking, wherein a black pigment is added to the photosensitive paste composition for baking according to the first or second aspect.

According to a fourth aspect of the present invention, there is provided a structure formed by patterning the photosensitive paste composition for firing according to any one of the first to third aspects, followed by exposure and curing, and firing the cured product. It is.

A fifth aspect is a structure formed by transferring the photosensitive paste composition for firing according to any one of the first to third aspects onto an object to be transferred.

[0012] Further, claim 6 has a thermal expansion coefficient of 50 × 1.
A lead titanate compound of 0 ^-7 / ° C or less, or a lead titanate solid solution in which part of the lead is substituted by an alkali metal or an alkaline earth metal, mullite, willemite, cordierite, β-eucryptite, The structure according to claim 4, wherein β-spodumene, aluminum titanate, zirconia, or two or more thereof are included.

According to a seventh aspect of the present invention, there is provided a substrate wherein the structure according to any one of the fourth to sixth aspects is formed on a non-alkali substrate for liquid crystal.

[0014]

Embodiments of the present invention will be described below.

The inorganic powder in the present invention is composed of a glass frit and an aggregate (filler), and a conductor is made of a conductive metal or a nonmetal. Glass frit is made of PbO-B2O3-S, which has a low melting point due to the lower firing temperature.
iO2, PbO-ZnO-B2O3, PbO-Zn
It is preferable to use O-B2O3-SiO2 or the like. However, the coefficient of thermal expansion of these low-melting-point lead glass frit becomes larger than the target low-expansion substrate. For the purpose of complementing it, a filler having a lower coefficient of thermal expansion is added. As a filler,
A lead titanate-based compound having a low coefficient of thermal expansion is preferable, and a lead titanate solid solution in which part of lead is substituted with an alkali metal or an alkaline earth metal is particularly preferably used. In addition, Mullite, Willemite, Cordierite, β
-Eucryptite, β-spodumene, aluminum titanate, zirconia and the like can be used. These glass frit and aggregate are suitably mixed and used as an inorganic powder. Examples of the conductive metal include gold, silver, nickel, palladium, platinum, tungsten, and molybdenum, and examples of the nonmetal include graphite and ITO.
These conductive materials can be used alone or as a mixture of two or more to obtain appropriate conductivity.

As the photopolymerization initiator, acetophenone,
2,2′-dioxyacetophenone, benzyldimethyl ketal, benzophenone, methyl o-benzoylbenzoate, benzoin-n-butyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-propiophenone, 2-methylthioxanthone, -Chlorothioxanthone or the like can be used. These can be used alone or in combination of two or more.

Specifically, as the substance having a chain type saturated hydrocarbon structure having 4 or more carbon atoms, t-butyl (meth)
Acrylate, isosterial (meth) acrylate,
1 such as isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc.
A photosensitive monomer containing a functional acryloyl group,
1,4-butadiol di (meth) acrylate, 1,3
-Butadiol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,10-decambudiol di (meth) ) There is a photosensitive monomer containing a bifunctional acryloyl group such as acrylate. These can be used alone or in combination of two or more.

The photosensitive monomer having a bifunctional or higher acryloyl group used in the present invention includes epoxy acrylate, urethane acrylate, polyester acrylate, ethylene glycol di (meth) acrylate, propylene (meth) acrylate, and bisphenol (meth). There are acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol (meth) acrylate, and the like. These can be used alone or in combination of two or more.

For the purpose of adjusting the viscosity and the state of photocuring, a monofunctional photosensitive monomer as described below may be added. These are monomers other than the above-mentioned monofunctional photosensitive monomer containing a chain saturated hydrocarbon structure having 4 or more carbon atoms. Specifically, methoxypolyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, phenoxyethyl (meth)
Ethers such as acrylates, hydroxys such as 2-hydroxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypolypropyl (meth) acrylate, and (meth) acrylates such as amines, halogens and silicones in the grave Kind. These can be used alone or in combination of two or more.

In order to ensure the necessary fluidity of the paste,
A binder solution may be added. The binder solution is generally a solution in which a binder resin is dissolved in a solvent. For example, the binder resin may be a cellulosic polymer such as nitrocellulose, acetylcellulose, ethylcellulose, carboxymethylcellulose, or methylcellulose, or a natural polymer such as natural rubber, polybutadiene rubber, chloroprene rubber, acrylic rubber, isoprene-based synthetic rubber, or cyclized rubber. Synthetic polymers such as polyethylene, polypropylene, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyester, polycarbonate, polyacrylonitrile, polyvinyl chloride, polyamide, and polyurethane. These resins are used alone, as a mixture or as a copolymer.

Examples of the solvent include hydrocarbon solvents such as toluene and xylenetetralin, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ethylene glycol solvents and diethylene glycol solvents. Etc. can be used.

Other additives include dispersants such as isobitane fatty acid ester and benzenesulfonic acid, plasticizers such as butyl cetearate, butyl benzyl phthalate, dibutyl phthalate and diisodecyl phthalate, wetting agents, dispersants, and polymerization inhibitors. Etc. may be added as needed.

A roll mill, a bead mill,
A paste is prepared using a mixing device such as an automatic mortar.

Patterning is performed using the prepared paste. The composition of the present invention does not have developability.
Therefore, it is necessary to form a pattern utilizing the property of curing by radiation such as ultraviolet rays. Therefore,
Examples of the pattern forming method include a screen printing method, a transfer method using an intaglio plate and a release film, and the like, but any method may be used. After the pattern is formed, it is cured by radiation such as ultraviolet rays, and then fired at a high temperature of 400 ° C. or more after the pattern is formed, whereby an inorganic structure having a desired shape can be produced. The structure that can be manufactured using this composition is a fine structure with a width of 100 μm or less, a complex structure, and a three-dimensional structure with an aspect ratio of about 3.

[0025]

The present invention will be described below with reference to examples.

Example 1 First, the composition of a photosensitive paste composition for firing that functions as a dielectric layer under a high voltage after firing is shown below. Inorganic powder Glass frit 68 parts by weight PbO 57% by weight SiO2 40% by weight B2O3 3% by weight Filler 9 parts by weight Ca 10% substituted PbTIO3 Organic trimethylolpropane trimethacrylate 12 parts by weight Stearyl acrylate 4 parts by weight Benzophenone 2 parts by weight 5% ethyl cellulose / diethylene glycol Monomethyl ether acetate solution 5 parts by weight The above composition was sufficiently kneaded with a roll mill to obtain a paste.

The paste was applied to the entire surface of a 10 cm square non-alkali glass for liquid crystal by screen printing to a thickness of 10 μm, and then irradiated with ultraviolet rays at 2000 mJ / cm 2. Next, baking was performed at 600 ° C. After firing, no cracks or peeling occurred.

Example 2 First, the composition of the photosensitive paste composition for firing is shown below. Inorganic powder Nickel powder (average particle size 10 μm) 75 parts by weight Glass frit 4 parts by weight PbO 57% by weight SiO2 40% ZnO 2% by weight B2O3 1% by weight Filler 1 part by weight Ca 10% substituted PbTIO3 Organic 1,9-nonanediol methacrylate 10 Parts by weight 2-methoxyethyl acrylate acrylate 3 parts by weight Benzophenone 1 part by weight Diphenyl phthalate 1 part by weight 5% ethyl cellulose / diethylene glycol monomethyl ether acetate solution 3 parts by weight The above composition was sufficiently kneaded by a roll mill to obtain a paste.

The conductive pattern paste thus obtained was screen-printed on a PET film to form a linear pattern having a width of 50 μm and a thickness of 5 μm, and then irradiated with ultraviolet rays at 2000 mJ / cm 2. Next, a 5 μm thick non-alkali glass for liquid crystal coated with an acrylic resin-based adhesive and a patterned PET film were applied for 1k.
gf / cm2 and press after the adhesive has solidified.
The ET film was peeled off. Next, the formed pattern is
Baking was performed at 00 ° C. to form a conductive pattern. The fired pattern was free from cracks, peeling, and the like, and no short circuit occurred.

Example 3 First, the composition of the photosensitive paste composition for firing is shown below. This system differs from Example 2 in that a black pigment is added to an inorganic powder. Inorganic powder 67 parts by weight Glass frit 67 parts by weight PbO 57 parts by weight SiO2 40 parts by weight B2O3 3 parts by weight Black pigment Fe-Cu-Cr system 2 parts by weight Filler 8 parts by weight Ca 10% substituted PbTIO3 organic substance Ethylene oxide added trimethylol propane triacrylate (n = 10) 11 parts by weight Methoxy polyethylene glycol methacrylate (n = 10) 6 parts by weight Lauryl acrylate 4 parts by weight Benzophenone 3 parts by weight Diphenyl phthalate 2 parts by weight The above composition was kneaded by a roll mill to obtain a paste.

The paste for an insulator pattern obtained in this manner is applied to a grid-shaped concave mold (width 50 μm, height 12 μm).
(0 μm, pitch 180 μm) and embedded using a doctor. Ultraviolet rays of 2000 mJ / cm2 were irradiated from the surface coated with the paste. Next, a thickness of 5 μm
The mold in which the paste was embedded with alkali-free glass for liquid crystal coated with an acrylic resin-based adhesive and a paste was pressed at a pressure of 1 kgf / cm2, and the mold was peeled off after the adhesive was solidified.
Next, the formed pattern was fired at 600 ° C. to form an insulator pattern. The fired pattern cracks,
No peeling occurred. .

Comparative Example 1 A paste was prepared from the inorganic powder described in Example 1 without adding an aggregate. This paste was subjected to pattern formation in the same manner as in Example 1 and
Firing was performed at ℃. As a result, cracking and peeling occurred on the entire surface.

[0033]

According to the fired photosensitive paste composition of the present invention,
Then, in the method of forming the structure by printing or transfer method
Has a coefficient of thermal expansion of 5 as represented by an alkali-free substrate for liquid crystal.
0x10 ^-7/ Compact, three-dimensional
Use thermal drying and cooling processes for dielectrics and insulators.
It can be formed without any problem.

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Claims (7)

[Claims] (1) At least (A) an inorganic powder, (B) a photopolymerization initiator, (C) a bifunctional or more acryloyl group, and having 4 carbon atoms.
In the photosensitive paste composition for firing mainly containing a photosensitive monomer having the above-mentioned chain type saturated monovalent hydrogen structure,
(A) The inorganic powder includes a glass frit having a coefficient of thermal expansion in the range of 50 to 100 × 10 ⁻⁷ / ° C. at 50 ° C. to 300 ° C. and a low-expansion inorganic powder having a coefficient of thermal expansion of 50 × 10 ⁻⁷ / ° C. or less. A photosensitive paste composition for firing, characterized by being included. 2. A photosensitive monomer having at least (A) an inorganic powder, (B) a photopolymerization initiator, (C) a difunctional or higher functional acryloyl group, and (D) a monofunctional or higher functional acryloyl group-containing carbon atom. In a photosensitive paste composition for firing mainly containing a photosensitive monomer having a chain-type saturated monovalent hydrogen structure of 4 or more,
(A) The inorganic powder comprises a glass frit having a thermal expansion coefficient in the range of 50 to 100 × 10 ⁻⁷ / ° C. at 50 ° C. to 300 ° C. and a low expansion inorganic powder having a thermal expansion coefficient of 50 × 10 ⁻⁷ / ° C. or less. A photosensitive paste composition for firing, characterized by being included. 3. A photosensitive paste composition for firing according to claim 1, wherein an inorganic black pigment is added to the photosensitive paste composition for firing according to claim 1. 4. A structure formed by patterning the photosensitive paste composition for firing according to any one of claims 1 to 3, curing by exposure, and firing the cured product. 5. A structure formed by transferring the photosensitive paste composition for firing according to any one of claims 1 to 3 onto an object to be transferred. 6. A lead titanate compound having a coefficient of thermal expansion of 50.times.10.sup.- ⁷ / .degree. C. or less, or a solid solution of lead titanate in which a part of the lead is replaced by an alkali metal or an alkaline earth metal, mullite, willemite , Cordierite, β-
The structure according to claim 4, wherein the structure comprises eucryptite, β-spodumene, aluminum titanate, zirconia, or two or more thereof. 7. A substrate, wherein the structure according to claim 4 is formed on a non-alkali substrate for liquid crystal.