JP2002365794A - Photosensitive dielectric forming composition, dielectric and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive dielectric forming composition capable of forming a dielectric layer that ensures a small heat loss, can be fired at low temperature and has a high dielectric constant with good dimensional accuracy and to provide a dielectric formed from the composition and electric parts. SOLUTION: The photosensitive dielectric forming composition contains (A) composite particles for the dielectric obtained by sticking an electrically conductive metal, its compound, an electrically conductive organic compound or an electrically conductive inorganic material to part of the surfaces of inorganic particles having a dielectric constant of >=30, (B) an alkali-soluble resin, (C) an ethylenically unsaturated group-containing compound and (D) a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a photosensitive dielectric which can be suitably used for forming a pattern with high dimensional accuracy, and a composition formed from the composition for forming a photosensitive dielectric. Related to dielectrics and electronic components.

[0002]

2. Description of the Related Art In recent years, a technique has been known in which a layer having a high dielectric constant is provided on a multilayer printed wiring board or the like, and this layer is used for a capacitor or the like. This high dielectric constant layer can be, for example,
An organic solvent made of a thermosetting resin to which an inorganic powder having a high dielectric constant is added is impregnated into a fiber reinforcing material such as glass fiber to compensate for the brittleness of the thermosetting resin, and the solvent is scattered by firing or the like. It is prepared by a method such as curing. However, in the conventional method, usually, for example, 3
It was difficult to obtain a layer having a high dielectric constant such as 0 or more or 50 or more.

Attempts have also been made to obtain a dielectric layer having a high dielectric constant by using various inorganic powders. For example, when Fe ₃ O ₄ or ZnO + carbon is added as an inorganic powder to polystyrene, a dielectric layer having a high dielectric constant is obtained. It is known that a body layer can be obtained. But in such a system,
Even if the dielectric constant can be increased, the dielectric loss tangent of the obtained dielectric layer is increased, so that the heat generated in the dielectric layer in an AC electric field is increased, such as in a multilayer printed wiring board provided with a dielectric film. There is a problem that deterioration and thermal stress cause defects such as breakage of a joint portion, and the reliability and durability of the semiconductor substrate are easily reduced.

On the other hand, to obtain a high dielectric constant, usually,
A method of forming a dielectric layer by heating and baking an inorganic powder having a high dielectric constant at a high temperature is known. However, this method
For example, since it is necessary to bake at a high temperature of about 1000 ° C., it cannot be applied to a case where a dielectric layer is provided in a state where an electronic component is mounted on a wiring board, and is generally used for various semiconductor substrate manufacturing processes. There was a problem that it could not be applied.

Furthermore, a screen printing method or the like is known as a method for forming a dielectric layer. However, as the size of a substrate is increased and the definition thereof is increased, the requirements for the positional accuracy of the pattern become very strict. There was a problem that it could not be handled. For this reason, the appearance of a photosensitive dielectric forming composition capable of forming a pattern having high dimensional accuracy while providing a dielectric layer having a high dielectric constant and a small heat loss by low-temperature baking has been desired.

Accordingly, the present inventors have conducted intensive studies to solve the above-mentioned problems, and have found that a photosensitive dielectric material containing particles having a conductive metal or organic compound attached to a part of the surface of specific inorganic particles. By using the body-forming composition, 50
The present inventors have found that firing at a low temperature of 0 ° C. or less is possible, and that a dielectric having a pattern having a high dielectric constant, a low dielectric loss tangent, and a high dimensional accuracy can be formed, and the present invention has been completed.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art described above, and it is possible to form a high-dielectric-constant dielectric layer which has a small heat loss and can be fired at a low temperature with high dimensional accuracy. An object of the present invention is to provide such a composition for forming a photosensitive dielectric, and a dielectric and an electronic component formed from the composition.

[0008]

SUMMARY OF THE INVENTION The composition for forming a photosensitive dielectric according to the present invention comprises (A) a conductive metal or a compound thereof or a conductive organic compound on a part of the surface of inorganic particles having a dielectric constant of 30 or more. It is characterized by containing a composite particle for a dielectric to which a compound or a conductive inorganic substance is attached, (B) an alkali-soluble resin, (C) a compound containing an ethylenically unsaturated group, and (D) a photopolymerization initiator. .

According to the composition for forming a photosensitive dielectric according to the present invention, a dielectric having a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less can be formed by heating at 500 ° C. or less. . The inorganic particles constituting the composite particles for dielectric material (A) are preferably a titanium-based metal oxide,
A conductive metal or a compound thereof, or a conductive organic compound or a conductive inorganic substance can be attached by an electroless plating method.

The alkali-soluble resin (B) is preferably any one of a (meth) acrylic resin, a hydroxystyrene resin, a novolak resin and a polyester resin. The ethylenically unsaturated group-containing compound (C)
In general, a (meth) acrylate compound can be used, and the compound having an ethylenically unsaturated group (C) is in a range of 20 to 500 parts by mass based on 100 parts by mass of the alkali-soluble resin (B). Is preferably included.

The dielectric of the present invention can be formed by heating and curing the composition for forming a photosensitive dielectric at 500 ° C. or lower, and has a dielectric constant of 30 or more and a dielectric loss tangent of 0.
It is preferably 1 or less. An electronic component according to the present invention is characterized in that it is formed using the composition for forming a photosensitive dielectric.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the composition for forming a photosensitive dielectric of the present invention will be described in detail. [Composition for forming a photosensitive dielectric] The composition for forming a photosensitive dielectric according to the present invention comprises (A) a conductive metal or a compound thereof or a conductive metal on a part of the surface of inorganic particles having a dielectric constant of 30 or more. A composite particle for a dielectric to which a conductive organic compound or a conductive inorganic substance is attached, (B) an alkali-soluble resin,
(C) an ethylenically unsaturated group-containing compound, (D) a photopolymerization initiator and, if necessary, (E) a solvent, and (F) various additives, by using 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 composition for forming a photosensitive dielectric prepared as described above is a paste-like composition having fluidity suitable for coating, and its viscosity is usually 100 to 100,
000 mPa · s, preferably 500 to 10,000
00 mPa · s. Hereinafter, each component constituting the photosensitive dielectric composition will be described. (A) Composite particles for dielectric material <Inorganic particles> The inorganic particles used in the present invention have a dielectric constant of 30 or more, preferably 50 or more, more preferably 70 or more. There is no problem with the high dielectric constant,
The upper limit is not particularly limited, but may be, for example, about 30,000.

As such inorganic particles, those composed of metal oxides are preferably used, and titanium-based metal oxides are particularly preferred. Here, “titanium-based metal oxide” refers to a compound containing a titanium element and an oxygen element as essential elements. As such a titanium-based metal oxide, a titanium-based single metal oxide containing titanium as a single metal element constituting a crystal structure, and a titanium-based double oxide containing titanium and other metal elements as a metal element Are preferably used.

The titanium-based single metal oxide includes, for example, a titanium dioxide-based metal oxide. Examples of such a titanium dioxide-based metal oxide include titanium dioxide-based metal oxides having an anatase structure or a rutile structure. Examples of the titanium-based double oxide include:
Metal oxides such as barium titanate, lead titanate, strontium titanate, bismuth titanate, magnesium titanate, neodymium titanate, and calcium titanate can be used.

The above "titanium dioxide-based metal oxide"
The term refers to a system containing only titanium dioxide or a system containing a small amount of other additives to titanium dioxide, which retains the crystal structure of the main component, titanium dioxide, and a metal of another system. The same applies to oxides. In addition, the “titanium-based composite oxide” is an oxide formed by combining a titanium-based single metal oxide and a metal oxide composed of at least one other metal element. Oxic acid ion does not exist.

In the present invention, the titanium-based metal oxide constituting such inorganic particles is preferably a titanium dioxide-based metal oxide having a rutile structure among titanium-based single metal oxides. Among the oxides, barium titanate-based metal oxides can be preferably used. Among these, a barium titanate-based metal oxide can be particularly preferably used.

Further, in order to improve the dispersibility in an aqueous medium, particles obtained by modifying the surface of the inorganic particles with silica, alumina or the like can be suitably used. The average particle diameter of such inorganic particles is preferably 0.1 to 5.0 μm, more preferably 0.1 to 3.0 μm, more preferably 0.1 to 2.0 μm, and particularly preferably 0.2 to 2.0 μm. 1.0μ
m is desirable. If the average particle size exceeds 5 μm, the composition of the dielectric layer may be likely to be non-uniform when the film thickness is reduced. When the average particle diameter is smaller than 0.1 μm, the cohesive force between the powders becomes so strong that coarse particles may be generated.

The shape of the inorganic particles of the present invention is not particularly limited, but examples include spherical, granular, plate-like, flake-like, whisker-like, rod-like, and filament-like shapes. Among these shapes, it is preferable that the shape is spherical, granular, flaky, or scaly. These inorganic particles can be used alone or in combination of two or more. <Dielectric Composite Particles> In the dielectric composite particles used in the present invention, a part of the surface of the inorganic particles is coated with a conductive substance. Examples of such a conductive substance include a conductive metal or a compound thereof, or a conductive organic compound or a conductive inorganic substance. These conductive substances may be adhered to a part of the surface of the inorganic particles, alone or in combination of plural kinds.

As the conductive metal, for example,
Gold, silver, copper, tin, platinum, palladium, ruthenium, Fe,
At least one metal selected from Ni, Co, Ge, Si, Zn, Ti, Mg, Al and the like can be used. These alloys can also be used as the metal. As the conductive metal compound, a nitride of the conductive metal can be used.

As the conductive organic compound, TCN is used.
At least one compound selected from Q (7,7,8,8-tetracyanoquinodimethane), polypyrrole, polyaniline, polythiophene and the like can be used. As the conductive inorganic substance, at least one kind selected from carbon, graphite and the like other than the above metals or metal compounds can be used.

The ratio of the inorganic particles contained in the composite particles for dielectric used in the present invention is preferably 60 to 99% by weight, more preferably 65 to 95% by weight, based on the total weight of the composite particles for dielectric. %, Particularly preferably 70 to 90% by weight. Further, the ratio of the conductive metal or a compound thereof or the conductive organic compound or the conductive inorganic substance, that is, the amount of the conductive substance adhered, preferably 1 to the total weight of the dielectric composite particles. It is desirable that it be contained in an amount of 40% by weight, more preferably 5 to 35% by weight, particularly preferably 10 to 30% by weight.

If the proportion of the inorganic particle component exceeds 99% by weight, a high dielectric constant may not be obtained when the dielectric material is used. When the proportion of the inorganic particle component is less than 60% by weight, the insulation of the dielectric may be deteriorated. The average particle size of the composite particles for a dielectric used in the present invention is preferably 0.1 to 5.0 μm, more preferably 0.1 to 5.0 μm.
It is desirable that the thickness be 3.0 μm, more preferably 0.1 to 2.0 μm, and particularly preferably 0.2 to 1.0 μm.
If the average particle size exceeds 5 μm, the composition of the dielectric layer may be likely to be non-uniform when the film thickness is reduced.
The average particle diameter of the dielectric composite particles is particularly preferably 2 μm or less in order to make the composition of the dielectric layer uniform even when the film thickness is reduced.

The specific surface area of the dielectric composite particles used in the present invention is preferably 1 to 20 m ² / g, more preferably 1.2 to 15 m ² / g, and more preferably 1.5 to 1 m ² / g.
0 m ² / g, it is desirable particularly preferably 1.5~8m ² / g. When the specific surface area is within the above range, a dielectric having a high dielectric constant and a low dielectric loss tangent can be obtained. Such composite particles for a dielectric used in the present invention can be prepared by a known method, and the production method is not limited.

For example, when a conductive metal is coated on the surface of inorganic particles by plating or the like, it can be performed by an electroless plating (chemical plating) method or the like. In addition, as a method for obtaining the composite particles for a dielectric having the above average particle diameter, specifically, it is composed of inorganic particles to which a metal component (for example, copper) of 1 to 40% by weight is attached by electroless plating or the like. From the composite particles for a dielectric, a powder having an average particle size of 0.1 to 10 μm is collected by a classifier, and the powder is ultrasonically dispersed in pure water to sufficiently disperse the powder. In a sulfuric acid bath, only the Cu content on the surface is eluted, whereby dielectric composite particles having such an average particle diameter can be obtained. (B) Alkali-soluble resin Various resins can be used as the alkali-soluble resin used in the photosensitive dielectric composition. Here, “alkali-soluble” refers to the property of being dissolved by an alkaline developer, and more specifically, it is only necessary to have solubility to the extent that the intended development processing is performed.

Specific examples of such alkali-soluble resins include, for example, (meth) acrylic resins, hydroxystyrene resins, novolak resins, polyester resins and the like. Among these alkali-soluble resins, (meth) acrylic resins are preferred, and particularly preferred are, for example, carboxyl group-containing monomers (a) (hereinafter also referred to as “monomer (a)”) and other copolymerizable polymers. Copolymer of monomer (c) (hereinafter also referred to as “monomer (c)”), or monomer (a) and OH group-containing monomer (b) (hereinafter also referred to as “monomer (b)”) and monomer A (meth) acrylic resin such as a copolymer with (c) can be used.

The above-mentioned monomer (a) (monomer containing carboxyl group) includes, for example, 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.

Examples of the monomers (b) (OH group-containing monomers) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. Hydroxyl-containing monomers of the formula: o-hydroxystyrene, m
Phenolic hydroxyl group-containing monomers such as -hydroxystyrene and p-hydroxystyrene; and the like.

The above-mentioned monomers (c) which are other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. Acid n-lauryl,
When a monomer (a) such as benzyl (meth) acrylate, glycidyl (meth) acrylate, or dicyclopentanyl (meth) acrylate (including a monomer (b), a monomer (b) other than the monomers (a) and (b)) ) Acrylic esters; aromatic vinyl monomers such as styrene and α-methylstyrene; conjugated dienes such as butadiene and isoprene; polystyrene, poly (methyl (meth) acrylate), poly (ethyl (meth) acrylate, and poly ( Meta)
Macromonomers having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as benzyl acrylate; and the like.

The copolymer of the monomer (a) and the monomer (c) and the copolymer of the monomer (a), the monomer (b), and the monomer (c) may be a monomer (a) and / or a monomer (c). Due to the presence of the copolymerization component derived from the carboxyl group-containing or phenolic hydroxyl group-containing monomer b), the monomer becomes alkali-soluble. Among them, a copolymer of the monomer (a), the monomer (b), and the monomer (c) is particularly preferable from the viewpoint of dispersion stability of the dielectric composite particles (A) and solubility in an alkali developer described later. The content of the copolymer component unit derived from the monomer (a) in this copolymer is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass, and the copolymer component derived from the monomer (b) The content of the unit 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 (C) is preferably 1 to 98% by mass, particularly preferably Preferably it is 40-90 mass%. Further, as the monomer (b) component, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylic acid 2
Hydroxyl-containing monomers such as -hydroxypropyl and 3-hydroxypropyl (meth) acrylate are preferred.
The molecular weight of the alkali-soluble resin (B) constituting the composition for forming a photosensitive dielectric is determined by the weight average molecular weight in terms of polystyrene by GPC (hereinafter simply referred to as “weight average molecular weight (M
w))), preferably from 5,000 to 5,000
0000, more preferably 10,000 to 300,
000 is desirable.

The content of the alkali-soluble resin (B) in the composition for forming a photosensitive dielectric is usually from 1 to 500 parts by mass per 100 parts by mass of the composite particles for dielectric (A).
Preferably from 10 to 500 parts by mass, more preferably from 10 to 500 parts by mass.
Desirably, it is 200 parts by mass. The photosensitive dielectric composition may contain a resin other than an alkali-soluble resin such as a polyimide resin, a bismaleimide resin, and an epoxy resin. (C) Ethylenically unsaturated group-containing compound The ethylenically unsaturated group-containing compound (C) constituting the composition for forming a photosensitive dielectric contains an ethylenically unsaturated group,
The photopolymerization initiator (D) described below is not particularly limited as long as it is a compound capable of undergoing a radical polymerization reaction.
(Meth) acrylate compounds are used.

Specific examples of such (meth) acrylate compounds include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol; Di (meth) acrylates of hydroxyl-terminated polymers such as hydroxyl-terminated polyhydroxybutadiene, hydroxyl-terminated polyisoprene and hydroxyl-terminated hydroxypolycaprolactone; glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane Poly (meth) of trihydric or higher polyhydric alcohols such as pentaerythritol and dipentaerythritol
Acrylates; poly (meth) acrylates of polyalkylene glycol adduct of trihydric or higher polyhydric alcohol; poly (meth) acrylates of cyclic polyol such as 1,4-cyclohexanediol, 1,4-benzenediol Oligo (meth) acrylates such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate. be able to. As the (meth) acrylate compound, in addition to the above-mentioned compounds, the compounds shown in the above-mentioned monomers (a), (b) and (c) constituting the alkali-soluble resin (B) may be used. .

These ethylenically unsaturated group-containing compounds (C) containing (meth) acrylate compounds can be used alone or in combination of two or more.
It is used in an amount of 20 to 500 parts by mass, preferably 20 to 480 parts by mass, more preferably 40 to 250 parts by mass based on 100 parts by mass of the alkali-soluble resin (B). (D) Photopolymerization Initiator As the photopolymerization initiator (D) constituting the photosensitive dielectric forming composition, a radical is generated in an exposure step described later, and the above-mentioned ethylenically unsaturated group-containing compound (C)
There is no particular limitation as long as it is a compound that initiates the polymerization reaction of

Specific examples of such a photopolymerization initiator include benzyl, benzoin, benzophenone, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. , 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone,
Carbonyl compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4-diethylthioxanthone and isopropylthioxanthone; bis (2,6-dimethoxybenzoyl) -2 , 4,4-Trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl)-
Phosphine oxide compounds such as phenylphosphine oxide; azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde;
Organic sulfur compounds such as mercaptan disulfide; organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 2,4-bis (trichloromethyl ) -6- (2'-Chlorophenyl) -1,3,5-
Triazine, 2- [2- (2-furanyl) ethylenyl]
Trihalomethanes such as -4,6-bis (trichloromethyl) -1,3,5-triazine; 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl 1, Examples thereof include imidazole dimers such as 2'-biimidazole, and these can be used alone or in combination of two or more. Also,
A sensitizer, a sensitization aid, a hydrogen donor, a chain transfer agent, and the like may be used in combination with the photopolymerization initiator (D).

The content ratio of the photopolymerization initiator (D) is as follows.
With respect to 100 parts by mass of the total amount of the alkali-soluble resin (B) and the ethylenically unsaturated group-containing compound (C),
It is desirably 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass. (E) Solvent The composition for forming a photosensitive dielectric contains a solvent (E) as necessary. As the solvent (E), the affinity with the composite particles (A) for the dielectric, the alkali-soluble resin (B), the compound containing an ethylenically unsaturated group (C), the photopolymerization initiator (D), and It has good solubility with various additives (F) to be described later, and can impart a suitable viscosity to the composition for forming a photosensitive dielectric, and can be easily evaporated and removed by drying. It is preferred that

Specific examples of such a solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone; and n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol. Alcohols; ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; saturated aliphatic monocarbonates such as n-butyl acetate and amyl acetate Carboxylic acid alkyl esters; lactate esters such as ethyl lactate and n-butyl lactate; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomer Ether acetate, ethyl-3
Ether esters such as -ethoxypropionate;
More than one species can be used in combination.

The content of the solvent (E) in the composition for forming a photosensitive dielectric can be appropriately selected within a range in which good fluidity can be obtained, and usually, the composite particles (A) for a dielectric are generally used. 1 to 10, for 100 parts by mass
000 parts by mass, preferably 10 to 1,000 parts by mass. (F) Various additives In addition to the components (A) to (E), the composition for forming a photosensitive dielectric includes a plasticizer, an adhesion aid, a dispersant, a filler, a storage stabilizer, and an antifoaming agent. Various additives such as antioxidants, ultraviolet absorbers, leveling agents, and development accelerators may be contained as optional components. 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 (1) is preferably used.

[0038]

Embedded image

(Where p is an integer of 3 to 20, m is 1 to 3)
, N is an integer of 1 to 3, and a is an integer of 1 to 3. In the formula (1), p indicating the number of carbon atoms of the saturated alkyl group is an integer of 3 to 20, and preferably an integer of 4 to 16. Specific examples of the silane coupling agent represented by the above formula (1) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n- Saturated alkyldimethylmethoxysilanes such as icosanedimethylmethoxysilane (a = 1,
m = 1, n = 1); saturated alkyl diethyl such as n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane Methoxysilanes (a = 1, m
= 1, n = 2); saturated alkyldipropylmethoxysilanes such as n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane ( a = 1, m = 1, n = 3); n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethylethoxysilane, n-icosanedimethylethoxysilane, etc. Saturated alkyldimethylethoxysilanes (a = 1, m = 2, n = 1); n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-Icosane diethylethoxysilane Saturated alkyl diethyl ethoxy silanes (a = 1, m = 2, n = 2); n- butyl dipropyl silane, n- decyl dipropyl silane, n- hexadecyl dipropyl silane,
saturated alkyldipropylethoxysilanes such as n-icosanedipropylethoxysilane (a = 1, m = 2, n
= 3); n-propyldimethylpropoxysilane, n-
Saturated alkyldimethylpropoxysilanes (a = 1, such as butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethylpropoxysilane, and n-icosanedimethylpropoxysilane)
m = 3, n = 1); saturated alkyl diethyl such as n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane Propoxysilanes (a = 1, m = 3, n = 2); n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n
Saturated alkyldipropylpropoxysilanes such as icosanedipropylpropoxysilane (a = 1, m = 3,
n = 3); n-propylmethyldimethoxysilane, n-
Saturated alkylmethyldimethoxysilanes such as butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, and n-icosanemethyldimethoxysilane (a = 2, m = 1, n
= 1); saturated alkylethyldimethoxysilanes such as n-propylethyldimethoxysilane, n-butylethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, and n-icosaneethyldimethoxysilane (a) = 2, m = 1, n
= 2); saturated alkylpropyldimethoxysilanes such as n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, and n-icosanepropyldimethoxysilane (a = 2, m = 1, n = 3) n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n
Saturated alkylmethyldiethoxysilanes (a = 2, m = 2, n = 1) such as decylmethyldiethoxysilane, n-hexadecylmethyldiethoxysilane and n-icosanemethyldiethoxysilane; n-propyl Ethyldiethoxysilane, n-butylethyldiethoxysilane, n
Saturated alkyl ethyl diethoxy silanes (a = 2, m = 2, n = 2) such as decyl ethyl diethoxy silane, n-hexadecyl ethyl diethoxy silane, n-icosane ethyl diethoxy silane; n-butyl Propyldiethoxysilane, n-decylpropyldiethoxysilane,
saturated alkylpropyldiethoxysilanes such as n-hexadecylpropyldiethoxysilane and n-icosanepropyldiethoxysilane (a = 2, m = 2, n = 3);
Saturated alkylmethyldipropoxysilanes such as n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, and n-icosanemethyldipropoxysilane (A = 2, m =
3, n = 1); n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane, etc. Saturated alkylethyldipropoxysilanes
(A = 2, m = 3, n = 2); n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n
Saturated alkylpropyldipropoxysilanes such as icosanepropyldipropoxysilane (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 alkyltriethoxysilane such as n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, and n-icosanetriethoxysilane (A = 3, m = 2); saturated alkyl such as n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane Tripropoxysilanes (a = 3, m = 3 And the like can be illustrated, these may be used alone or in combination of two or more.

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

The content ratio of the adhesion auxiliary agent in the composition for forming a photosensitive dielectric is determined as follows.
The amount is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight with respect to parts by weight. Dispersant As the dispersant for the dielectric composite particles (A), fatty acids are preferably used, and in particular, fatty acids having 3 to 30 carbon atoms, preferably 4 to 30 carbon atoms, and more preferably 4 to 20 carbon atoms are preferable. Preferred specific examples of the fatty acid include malonic acid, octanoic acid, undecylic acid, lauric acid, myristic acid, palmitic acid, pentadecanoic acid, stearic acid,
Saturated fatty acids such as arachiic acid; fumaric acid, itaconic acid, citraconic acid, elaidic acid, oleic acid, linoleic acid,
Unsaturated fatty acids such as linolenic acid and arachidonic acid; aromatic fatty acids such as phthalic acid; and the like, and these can be used alone or in combination of two or more.

The content ratio of the dispersant in the composition for forming a photosensitive dielectric is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the composite particles (A) for a dielectric. Desirably, parts by weight are used. Filler The composition for forming a photosensitive dielectric of the present invention comprises the above (A) to
In addition to the component (E), a filler may be further contained. Examples of such fillers include additives that improve the dielectric constant, such as carbon fine powder (eg, acetylene black, Ketjen black, etc.), conductive fine particles such as graphite fine powder, and semiconductor fine particles such as silicon carbide fine powder. No. When these fillers for improving the dielectric constant are added, the filler is preferably 0 to 10% by weight, more preferably 0.5 to 10% by weight, particularly preferably 1 to 10% by weight, based on the composite particles (A) for a dielectric. It is desirable to use it in an amount of up to 5% by weight.

[Dielectric] By using the photosensitive dielectric composition of the present invention, a dielectric having a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less can be formed by heating at 500 ° C. or less. Can be. Hereinafter, the method for forming the dielectric and the physical properties of the dielectric according to the present invention will be described in detail. <Method of Forming Dielectric Layer Pattern> The method of forming a dielectric layer pattern using the photosensitive dielectric forming composition of the present invention comprises:
[1] a step of applying a composition for forming a photosensitive dielectric, [2] a step of exposing a dielectric layer, [3] a step of developing a dielectric layer, [4]
The method includes the steps of curing the dielectric layer pattern. [1] Step of Applying Photosensitive Dielectric Forming Composition In the applying step, the photosensitive dielectric forming composition of the present invention is applied on a substrate using, for example, an applicator to form a dielectric layer. . Here, preferable coating machines include a screen printing machine, a gravure coater, a roll coater, and a bar coater. Examples of the substrate material include, but are not particularly limited to, a printed board, a plate-like member made of glass, silicone, alumina, and the like.

Specifically, for example, the composition for forming a photosensitive dielectric of the present invention is printed on a printed wiring board or the like by a screen printer or the like, and the composition for forming a photosensitive dielectric is formed using an oven or the like. The material is dried to form a dielectric layer. [2] Exposure Step of Dielectric Layer In the exposure step, the surface of the dielectric layer formed as described above is selectively irradiated (exposed) with radiation through an exposure mask, and the dielectric layer is exposed to radiation. Form a latent image of the pattern.

In the exposure step, the radiation to be selectively irradiated (exposed) includes, for example, visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray, and preferably visible light, ultraviolet light and far ultraviolet light. Preferably, ultraviolet light is used. Although the exposure pattern of the exposure mask varies depending on the purpose, for example, a dot pattern of 10 to 1000 μm square is used.

Examples of the radiation irradiating device include an ultraviolet irradiating device used in photolithography and an exposing device used in manufacturing semiconductors and liquid crystal display devices, but are not particularly limited thereto. Not something. [3] Developing Step of Dielectric Layer In the developing step, a pattern (latent image) of the dielectric layer is revealed by developing the exposed dielectric layer.

As a developer used in the step of developing the dielectric layer, an alkali developer can be used. Thereby, the alkali-soluble resin contained in the dielectric layer can be easily dissolved and removed. Since the dielectric composite particles contained in the dielectric layer are uniformly dispersed in the alkali-soluble resin, by dissolving the alkali-soluble resin as a binder and washing it, the dielectric composite particles are simultaneously dispersed. Removed.

The effective components of the alkali developer include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate,
Ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate , Inorganic alkaline compounds such as ammonia; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
Organic alkaline compounds such as ethanolamine can be exemplified.

The alkaline developer used in the step of developing the dielectric layer can be prepared by dissolving one or more of the above alkaline compounds in a solvent such as water. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by mass,
Preferably it is 0.01-5 mass%. The alkali developer may contain additives such as a nonionic surfactant or an organic solvent.

It should be noted that, 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 surface of the photosensitive transfer layer pattern and the exposed portion of the substrate after the development processing may be included. The development processing conditions include the type, composition, and concentration of the developer, the development time, the development temperature, the development method (for example, the immersion method, the swing method, the shower method, the spray method, and the paddle method), and the development device according to the purpose. It can be selected as appropriate.

By this developing step, the remaining portion of the dielectric layer is
A dielectric layer pattern (a pattern corresponding to an exposure mask) composed of the dielectric layer removed portion is formed. [4] Step of curing dielectric layer pattern In the curing step, the dielectric layer pattern is thermally cured to form a pattern. Such heating temperature is 50
It can be carried out at 0 ° C. or lower, preferably 100 to 100 ° C.
It is desirable to carry out at 500 ° C, more preferably at 150 to 300 ° C. The heating time is preferably in the range of 1 minute to 24 hours, more preferably 10 minutes to 12 hours.

The heating method for heating and curing the composition for forming a photosensitive dielectric includes, for example, an oven,
A method of heating with an infrared lamp, a hot plate or the like can be used. <Physical Properties of Dielectric> The dielectric obtained from the composition for forming a photosensitive dielectric of the present invention has a dielectric constant of 30 or more, preferably 100 or more, more preferably 150 or more, and particularly preferably 200 or more. Desirably. The upper limit of the dielectric constant is not particularly limited, but may be, for example, about 30,000. The dielectric obtained from the composition for forming a photosensitive dielectric of the present invention preferably has a dielectric loss tangent of 0.1 or less, preferably 0.08 or less, and more preferably 0.06 or less. The lower limit of the dielectric loss tangent is not particularly limited, but may be, for example, about 0.001.

In this specification, the dielectric constant and the dielectric loss tangent are values measured by the method described in JIS K6481 (frequency 1 MHz). Further, the volume resistivity of such a dielectric is preferably 10 ¹¹ Ω · cm or more, more preferably 10 ¹² Ω · cm or more.

The thickness of the dielectric is preferably 1
It is desirable that the thickness be not more than 00 μm, more preferably not more than 30 μm. The lower limit of the film thickness is not particularly limited, but is usually 1 μm or more. [Electronic Components] The dielectric of the present invention can be obtained by heating and firing at a low temperature of 500 ° C. or less, has a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less, is a thin film and has a large capacitance. A capacitor or the like can be formed. Further, electronic components such as a printed circuit board, a semiconductor package, a capacitor, and a high-frequency antenna provided with the dielectric can be small and have a high density.

[0055]

As described above, when the composition for forming a photosensitive dielectric according to the present invention is used, the heating temperature is as low as 500 ° C. or less, and the dielectric loss tangent is as low as 0.1 or less.
A dielectric having a high dielectric constant as described above can be formed. Since the dielectric of the present invention is thin and has a high dielectric constant, it is suitably used in electronic parts such as printed circuit boards, semiconductor packages, capacitors, high frequency antennas and the like.

Since the electronic component of the present invention includes the above-mentioned dielectric, it can be reduced in size and thickness.

[0057]

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).

[0058]

Example 1 (1) Production of dielectric composite particles Barium titanate particles (trade name “HPBT-1”, manufactured by Fuji Titanium Co., Ltd., average particle diameter 0.6 μm, dielectric constant 20)
00) was coated with silver by electroless silver plating to obtain composite particles (a) for a dielectric.

Observation of the obtained powder by SEM (scanning electron microscope) confirmed that silver fine particles were partially adhered to the particle surface. Further, it was confirmed by SIMS (secondary ion mass spectrometry) that 10% of silver was attached to the surface of barium titanate in terms of weight ratio. On the other hand, the specific surface area of the powder was 3.8 m ² / g. (2) Preparation of a composition for forming a photosensitive dielectric (A) 100 parts of the composite particles for a dielectric (A) as composite particles for a dielectric, and (B) n-butyl methacrylate / methacryl as an alkali-soluble resin 3-hydroxypropyl acid / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 50,000) 10 parts, (C) triethylolpropane triacrylate 5 parts as an ethylenically unsaturated group-containing compound , (D) as a photopolymerization initiator, 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (1 part), (E) propylene glycol monomethyl ether 100 as a solvent
Part and (F) oleic acid as a dispersant, 1 part of oleic acid and 0.5 part of acetylene black as a filler are kneaded with a bead mill, and then filtered with a stainless mesh (500 mesh) to form a photosensitive dielectric composition. Was prepared. (3) Step of Applying Photosensitive Dielectric Forming Composition The photosensitive dielectric forming composition is applied on a printed wiring board using a blade coater, and the coating is dried at 100 ° C. for 5 minutes to completely remove the solvent. To form a photosensitive dielectric layer having a thickness of 20 μm. (4) Exposure Step / Development Step of Dielectric Layer The photosensitive dielectric layer was exposed through an exposure mask (a dot pattern of 500 μm square) with an ultra-high pressure mercury lamp.
Irradiation (ultraviolet light with a wavelength of 365 nm). Here, the irradiation amount was 400 mJ / cm ² .

After the exposing step, the exposed photosensitive dielectric layer is subjected to a developing process by a shower method using a 0.5% by mass aqueous solution of sodium carbonate (30 ° C.) for 1 minute. went. Next, a washing treatment with ultrapure water was performed, whereby the uncured photosensitive dielectric layer not irradiated with the ultraviolet rays was removed to form a pattern. (5) Curing Step of Dielectric Layer Pattern The printed wiring board on which the photosensitive dielectric layer pattern was formed was cured in an oven at a temperature of 200 ° C. for 30 minutes. As a result, a dielectric pattern was obtained on the surface of the printed wiring board.

The patterning characteristics and dielectric characteristics of the obtained dielectric pattern were evaluated by the methods described below. Table 1 shows the results.

[0062]

Example 2 (B) 20 parts of n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (% by mass) copolymer (Mw = 100,000) as an alkali-soluble resin (C) A photosensitive dielectric forming composition was prepared in the same manner as in Example 1 except that 10 parts of trimethylolpropane triacrylate was used as the ethylenically unsaturated group-containing compound. Example 1 except that the composition for forming a photosensitive dielectric was used.
After a photosensitive dielectric layer having a thickness of 20 μm was formed in the same manner as described above, exposure, development, and curing steps were performed to produce a dielectric pattern, which was evaluated. Table 1 shows the results.

[0063]

Example 3 Barium titanate particles (trade name "BT-0")
2 ", manufactured by Sakai Chemical Co., Ltd., average particle diameter 0.2 μm, dielectric constant 2000), and the surface was coated with silver by an electroless silver plating method to obtain dielectric composite particles (b). From the SEM observation of the obtained powder, it was confirmed that silver fine particles were partially adhered to the particle surface. Further, it was confirmed by SIMS that 20% of silver was adhered to the barium titanate surface in terms of weight ratio. On the other hand, the specific surface area of the powder was 4.0 m ^2.
/ G.

A composition for forming a photosensitive dielectric was prepared in the same manner as in Example 1 except that (A) 100 parts of the composite particles for dielectric (b) were used as the composite particles for dielectric. Except that the composition for forming a photosensitive dielectric was used, a photosensitive dielectric layer having a thickness of 20 μm was formed, followed by exposure, development, and curing steps to form a dielectric pattern in the same manner as in Example 1. And evaluated. Table 1 shows the results.

[0065]

Example 4 Calcium titanate particles (average particle size 2
(μm, dielectric constant 140) was coated on the surface with nickel by an electroless phosphor-nickel plating method to obtain dielectric composite particles (c). From the SEM observation of the obtained powder, it was confirmed that nickel fine particles were partially adhered to the particle surface. Further, it was confirmed by SIMS that nickel adhered to the calcium titanate surface by 10% in terms of weight ratio. On the other hand, the specific surface area of the powder was 2.0 m ² / g.

(A) A composition for forming a photosensitive dielectric was prepared in the same manner as in Example 1, except that 100 parts of the composite particles for dielectric material (c) were used as the composite particles for dielectric material. Except that the composition for forming a photosensitive dielectric was used, a photosensitive dielectric layer having a thickness of 20 μm was formed, followed by exposure, development, and curing steps to form a dielectric pattern in the same manner as in Example 1. And evaluated. Table 1 shows the results.

[0067]

Reference Example 1 A photosensitive dielectric forming composition was prepared in the same manner as in Example 1, except that 1 part of trimethylolpropane triacrylate was used as the (C) ethylenically unsaturated group-containing compound. Except that the composition for forming a photosensitive dielectric was used, a thickness of 20 μm was obtained in the same manner as in Example 1.
After the photosensitive dielectric layer of m was formed, exposure, development and curing steps were performed to form a dielectric pattern, which was evaluated. Table 1 shows the results.

[0068]

Reference Example 2 A photosensitive dielectric forming composition was prepared in the same manner as in Example 1 except that 50 parts of trimethylolpropane triacrylate was used as the (C) ethylenically unsaturated group-containing compound. Except that the composition for forming a photosensitive dielectric was used, a thickness of 20
After forming a photosensitive dielectric layer having a thickness of μm, exposure, development and curing steps were performed to prepare a dielectric pattern, which was evaluated. Table 1 shows the results. [Patterning Characteristics] The width and height of the dielectric patterns obtained by Examples 1 to 4 and Reference Examples 1 and 2 were measured using a scanning electron microscope (SEM), and the width was measured. About 500μm ± 10
Those in the μm range were evaluated as ○, and the others were evaluated as ×. Observation was also made on the lack of a pattern, and evaluation was made as “○” when there was no omission and as “×” when there was omission. [Dielectric constant, dielectric loss tangent and volume resistivity] JIS K64
81.

The dielectric constant and the dielectric loss tangent are measured values at a frequency of 1 MHz. [Heat and moisture resistance (HAST test)]
A moist heat resistance test was performed for 72 hours under the conditions of 121 ° C., 100% humidity and 2 atm, and infrared spectroscopy was performed before and after the test, and the moist heat resistance was evaluated according to the following criteria according to the degree of change.

・ ・ ・: No change and resistance is observed X: change is large and resistance is not observed

[0071]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/028 G03F 7/028 7/032 7/032 (72) Inventor Nobuyuki Ito Tsukiji, Chuo-ku, Tokyo F-term (reference) No. 11-24, JSR Co., Ltd. QB24 QB25 SA01 SA21 SA31 SA41 SA64 SA73 SA76 SA79 SA80 SA82 SA83 SA84 UA01 UA03 UA04 UA06 WA01 4J026 AA17 AA20 AA43 AA45 AA48 AA53 AA68 AA69 AA76 AB01 AB07 AC00 AC09 BA28 BA50 DB02 DB36 GA07

Claims (9)

[Claims] 1. A composite for a dielectric, in which a conductive metal or a compound thereof, a conductive organic compound or a conductive inorganic substance is attached to a part of the surface of an inorganic particle having a dielectric constant of 30 or more. Particles, (B) an alkali-soluble resin,
A composition for forming a photosensitive dielectric, comprising: (C) an ethylenically unsaturated group-containing compound; and (D) a photopolymerization initiator. 2. The photosensitive dielectric according to claim 1, wherein a dielectric having a dielectric constant of 30 or more and a dielectric loss tangent of 0.1 or less can be formed by heating at 500 ° C. or less. Body-forming composition. 3. The photosensitive dielectric composition according to claim 1, wherein the inorganic particles constituting the dielectric composite particles (A) are titanium-based metal oxides. 4. In the composite particles for dielectric material (A),
The photosensitive dielectric material according to any one of claims 1 to 3, wherein a conductive metal or a compound thereof, a conductive organic compound or a conductive inorganic substance is attached by an electroless plating method. Composition. 5. The method according to claim 1, wherein the alkali-soluble resin (B) is any one of a (meth) acrylic resin, a hydroxystyrene resin, a novolak resin and a polyester resin. A composition for forming a photosensitive dielectric. 6. The composition for forming a photosensitive dielectric according to claim 1, wherein the ethylenically unsaturated group-containing compound (C) is a (meth) acrylate compound. 7. The method according to claim 1, wherein the ethylenically unsaturated group-containing compound (C) is contained in an amount of from 20 to 500 parts by mass based on 100 parts by mass of the alkali-soluble resin (B). 7. The composition for forming a photosensitive dielectric according to any one of items 1 to 6. 8. The composition for forming a photosensitive dielectric material according to claim 1, wherein the composition is cured by heating at 500 ° C. or less, and has a dielectric constant of 30 or more and a dielectric loss tangent of 0. .1 or less. 9. An electronic component formed by using the composition for forming a photosensitive dielectric according to claim 1. Description: