JP2006199834A - Photosetting heat-decomposable composition and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the heat-decomposition problems of conventional photosetting heat-decomposable compositions containing cellulose esters such as the generation of heat in heat decomposition and the residue of carbon and provide a photosetting heat-decomposable composition having improved heat-decomposability and usable as a substitute for conventional photosetting heat-decomposable compositions containing a cellulose ester as a binder resin. <P>SOLUTION: The photosetting heat-decomposable resin composition contains a polyurethane resin composed of a repeating unit (a) expressed by formula (1) and a repeating unit (b) expressed by formula (2) and having a molar ratio of the repeating unit (a) of 0.35-0.99 and a molar ratio of the repeating unit (b) of 0.01-0.65, and further contains a photosetting monomer and a solvent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photocurable thermally decomposable composition that can be used for a photoresist or the like, and more specifically to the production of an inorganic powder paste using the composition, such as PDP (plasma display panel) and FED (field effect display). The present invention relates to a photocurable thermally decomposable inorganic powder paste suitable as a conductive paste, dielectric paste, partition material paste, phosphor paste, black matrix paste, sealing material paste, and a sheet using the same.

  PDP (plasma display panel) is regarded as the most promising next-generation large-screen TV display. Non-Patent Document 1 describes in detail the manufacturing process of PDP and the main materials used in each process. In a general PDP structure, a plasma discharge bus electrode and a black mask are formed on a front glass substrate, and a dielectric layer is formed thereon. Further, after the address electrode is formed on the rear glass substrate, a dielectric layer, a partition wall (barrier rib), and a phosphor layer are formed. Conventionally, each of these portions has been formed by applying various non-photocurable pastes by screen printing or the like. However, as PDP becomes more fine, patterning methods using photolithography are becoming increasingly common. It has become a target. For example, in the formation of barrier ribs (barrier ribs), a barrier rib material paste is applied and dried to form a barrier rib material layer, and a photoresist or dry film resist is placed thereon, and the resist layer is patterned by UV light irradiation and development. A method of patterning the partition wall material layer by sandblasting (scraping off the uncured portion of the resist with an abrasive) has already become common.

  Patent Document 1 discloses a photocurable composition mainly composed of a binder resin, a photocurable monomer, and water. This can be used, for example, as a photoresist when molding PDP partition walls (barrier ribs), and cellulose ethers are used as binder resins. The use of photolithography in parts other than the photoresist for patterning the partition walls and the dry film resist was somewhat delayed. For example, Patent Document 2 discloses a dielectric sheet made of an inorganic powder, a binder resin, and a photocurable monomer. As disclosed, cellulose ethers and the like are used as binder resins. Patent Document 3 discloses a photocurable paste capable of forming a partition, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix, and a photocurable sheet formed from the paste. These photocurable pastes are mainly composed of a binder resin, a photocurable monomer, a solvent, and an inorganic powder, and cellulose ethers are used as the binder resin. Further, Patent Document 4 discloses a photocurable glass paste comprising a low melting glass powder, a binder resin, and a photocurable monomer. Partition walls, electrodes, resistors, dielectrics, color filters, black matrices, and the like can be formed using this low melting glass paste, and cellulose ethers are used as binder resins. In these methods, the paste and the sheet itself are photocurable. The advantage that the paste and the sheet itself are photo-curing is, for example, in the case of the formation of a partition, for example, the photo-curing paste and the photo-curing sheet are cured by UV exposure through a photomask, then washed with water or a solvent and uncured. Since patterning can be performed by removing the portion, finer and more precise processing can be easily performed than the patterning of the partition wall by the conventional sandblast method.

In these patent documents, cellulose ethers are used as binder resins. These binder resins must be almost completely removed by a baking process after exposure and development. Cellulose ethers, however, are rapidly heated in this baking process, and partition walls, electrodes, resistors, dielectrics, phosphors, color filters, black matrices. However, there is still a point to be improved, such as being easily deteriorated by heat, or being carbonized during firing and easily degrading the performance of partition walls, electrodes, resistors, dielectrics, phosphors, color filters, black matrices, and the like.
On the other hand, the present inventors have disclosed in Patent Document 5 that the polyurethane resin used in the present invention can be used as a ceramic binder resin. However, the present invention discloses a photocurable resin composition, a photocurable paste, and a photocurable sheet. The invention was not reached.
JP-A-11-202486 JP 2003-197112 A JP 2002-328467 A JP 2000-29210 A JP-A-12-355618 Katsuya Yasuo “Technology Trends in PDP Materials” Hitachi Chemical Technical Report No. 33 (7), 9-16, 1999

  Conventional photocurable thermally decomposable compositions containing cellulose ethers have problems to be improved in thermal decomposability, such as heat generation during thermal decomposition and residual carbon. An object of the present invention is to provide a photocurable heat-decomposable composition superior in thermal decomposability, which replaces a conventional photocurable heat-decomposable composition using cellulose ether as a binder resin. Another object of the present invention is to provide a photocurable thermally decomposable inorganic powder paste with improved carbon residue upon firing, and a sheet using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a photocurable thermodegradable composition containing a polyurethane resin containing a specific comb-shaped diol and polyoxyalkylene glycol as a diol component is heated. The present invention was completed by finding that it was excellent in degradability.
In addition, the photocurable thermodecomposable composition in the present application is irradiated with photopolymerizable light after the composition is dried (desolvent), and the photocurable monomer is photopolymerized and cured to become insoluble in the solvent. It is a composition that is thermally decomposed by heating the cured product at about 350 ° C. to 600 ° C.
That is, the photocurable thermally decomposable composition of the present invention is
(Z) The following formula (1)

(In the formula, A is a dealcohol residue (divalent group) of polyoxyalkylene glycol (compound A) HO-A-OH having hydroxyl groups at both ends, and B is diisocinaate (compound B) OCN-B). A repeating unit (a) represented by a de-NCO residue (divalent group) of -NCO),
The following formula (2)

(In the formula, D is a dealcohol residue (divalent group) of comb diol HO-D-OH having at least two hydrocarbon groups having 4 to 21 carbon atoms (monovalent group) in the molecule; B is a repeating unit (b) represented by diisocinaate (compound B) OCN-B-NCO de-NCO residue (divalent group)), and the molar ratio of the repeating unit (a) is 0. A polyurethane resin having a repeating unit (b) molar ratio of 0.01 to 0.65,
It is characterized by containing (Y) a photocurable monomer and (Z) a solvent.
As the comb diol HO-D-OH, the following formula (3)

(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group, R ² and R ³ are hydrocarbon groups having 4 to 21 carbon atoms, R ¹ , Part or all of hydrogen in R ² and R ³ may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different.
Y and Y ′ are hydrogen, a methyl group or a CH ₂ Cl group, and Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂ group, and Z and Z ′ may be the same or different. n is an integer of 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group. N ′ is an integer of 0 to 15 when Z ′ is oxygen, and 0 when Z ′ is sulfur or a CH ₂ group, and n and n ′ may be the same or different. Or a comb-shaped diol (compound D) represented by the following formula (4)

(In the formula, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ are hydrocarbon groups having 4 to 21 carbon atoms, and in R ⁵ , R ² and R ³ , Some or all of the hydrogen atoms may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different.
Y, Y ′ and Y ″ are hydrogen, methyl group or CH ₂ Cl group, Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂ group, Z and Z ′ may be the same or different, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and k is an integer of 0 to 15. n is when Z is oxygen. Is an integer from 0 to 15 and is 0 when Z is sulfur or CH ₂ , and n ′ is an integer from 0 to 15 when Z ′ is oxygen and Z ′ is sulfur or CH 2. _In the case of _two groups, it is 0, and n and n ′ may be the same or different.) A comb-shaped diol (compound D ′) represented by:
Moreover, it is a photocurable thermally decomposable inorganic powder paste further containing an inorganic powder in the photocurable thermally decomposable composition.
Moreover, it is a photocurable thermally decomposable inorganic powder sheet obtained by forming the photocurable thermally decomposable inorganic powder paste into a film and then drying the solvent.

  The photocurable thermodegradable composition of the present invention has an advantage that it does not cause problems such as deterioration due to heat generation during carbonization and carbon residue.

  Hereinafter, the paste composition of the present invention will be described in detail.

(X) Polyurethane resin (X) Polyurethane resin used in the present invention has the formula (1)

(In the formula, A is a dealcohol residue (divalent group) of polyoxyalkylene glycol (compound A) HO-A-OH having hydroxyl groups at both ends, and B is diisocinaate (compound B) OCN-B). A repeating unit (a) represented by a de-NCO residue (divalent group) of -NCO),
The following formula (2)

(In the formula, D is a dealcohol residue (divalent group) of comb diol HO-D-OH having at least two hydrocarbon groups having 4 to 21 carbon atoms (monovalent group) in the molecule; B consists of a repeating unit (b) represented by a de-NCO residue (which is a divalent group) of diisocininaate (compound B) OCN-B-NCO, and the molar ratio of the repeating unit (a) is 0.00. 35 to 0.99, and the molar ratio of the repeating unit (b) is 0.01 to 0.65 (provided that the sum of both is 1).

  A in the repeating unit (a) represented by the formula (1) is polyoxyalkylene glycol. In particular, polyoxyalkylene glycols having 2 to 6 carbon atoms in the alkylene group are preferably used. More specifically, polyethylene glycol (PEG), propylene glycol (PPG), a copolymer of polyethylene oxide and polypropylene oxide, polytetramethylene ether glycol (PTMEG), polyhexamethylene ether glycol and the like can be mentioned.

  The molecular weight of the compound A is preferably 400 to 100,000, more preferably 40000 to 20,000, and still more preferably 900 to 9,000 in terms of number average molecular weight (Mn). A resin having a number average molecular weight of 400 or more and sufficient characteristics as a binder can be obtained. If the number average molecular weight is 100,000 or less, a sufficient polymerization reaction can be performed.

 As the polyoxyalkylene glycol (compound A), two or more kinds of polyoxyalkylene glycols may be used in combination. For example, polyethylene glycol and polypropylene glycol or polytetramethylene ether glycol can be used in combination. Also, up to 20% by weight of glycols, low molecular weight glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tetramethylene glycol and hexamethylene glycol may be used in combination with other polyoxyalkylene glycols. .

  The comb-shaped diol HO-D-OH in the repeating unit (b) represented by the formula (2) is a diol having at least two monovalent hydrocarbon groups having 4 to 21 carbon atoms in the molecule. A plurality of monovalent hydrocarbon groups are grafted as side chains on the skeleton of the diol molecule, and this shape is called comb-shaped diol. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group.

The monovalent hydrocarbon group of the comb diol is bonded to the skeleton via a methylene group, an ether group, a thioether group, a polyether group, or the like. The skeleton of the comb-shaped diol may consist of only hydrocarbons, but diols having a polar group such as an ether group (—O—), a polyether group or a tertiary amino group (—N (R) —) in the skeleton may also be used. Preferably used. For example, an ether group (—O—) or a polyether group (—O—CH ₂ CH ₂ —O— etc.) as disclosed in JP-A-10-298261 and US-4426485 is used as a skeleton. Or a diol having a tertiary amino group as described in the formulas (3) and (4).

  The hydrocarbon group of the comb diol has low polarity, and in a polar solvent, the interaction between the hydrocarbon groups causes a hydrophobic interaction between the polymer chains of the polyurethane. Therefore, even polyurethane with a relatively low molecular weight can be printed. It is considered that the viscosity necessary for the production can be obtained. The comb-shaped diol is also considered to have an effect as a plasticizer (internal plasticizer) fixed in the polymer skeleton of the polyurethane. The effect of such a comb-shaped diol is particularly remarkable in a diol having a tertiary amino group in the skeleton as described in the formulas (3) and (4). The method for producing the comb diol is described in detail in JP-A-11-343328 and JP-A-12-297133.

  The diisocyanate compound (compound B) is a diisocyanate compound selected from the group consisting of chain aliphatic diisocyanates, cycloaliphatic diisocyanates and aromatic diisocyanates. As the diisocyanate, diisocyanates having 3 to 18 carbon atoms in total (including the carbon atoms of the NCO group) are more preferably used.

  The chain aliphatic diisocyanates are polyisocyanate compounds having a structure in which NCO groups are connected by linear or branched alkylene groups. Specific examples thereof include methylene diisocyanate and ethylene diisocyanate. , Trimethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate (commonly abbreviated as HMDI) , Heptamethylene diisocyanate, 2,2'-dimethylpentane-1,5-diisocyanate, lysine diisocyanate methyl ester (commonly abbreviated as LDI), octamethylene diisocyanate, 2,5-dimethylhexane-1 , 6-Diisocyanate, 2,2,4-Trimethylpentane-1,5-diisocyanate, Nonamechi Diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate, dodecamethylene diisocyanate, tridecamethylene diisocyanate, tetradecamethylene diisocyanate Examples thereof include diisocyanates such as narate, pentadecamethylene diisocyanate, hexadecamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

  Cycloaliphatic diisocyanates are polyisocyanate compounds in which an alkylene group connected between NCO groups has a cyclic structure. Specific examples thereof include cyclohexane-1,2-diisocyanate, cyclohexane-1,3- Diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1-ethylcyclohexane-2,4-di Isocyanate, 4,5-dimethylcyclohexane-1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω'-diisocyanate, 1,4-dimethylcyclohexane-ω, ω'-diisocyanate, Isophorone diisocyanate (commonly abbreviated as IPDI), dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethylmethane-4,4'-diisocyanate, dicyclohexyldimethyl Lumethane-4,4'-diisocyanate, 2,2'-dimethyldicyclohexylmethane-4,4'-diisocyanate, 3,3'-dimethyldicyclohexylmethane-4,4'-diisocyanate, 4,4 '-Methylene-bis (isocyanatocyclohexane), isopropylidenebis (4-cyclohexylisocyanate) (commonly abbreviated as IPCI), 1,3-bis (isocyanatomethyl) cyclohexane, hydrogenated tolylene diisocyanate (commonly known as H- Abbreviated as TDI), hydrogenated 4,4'-diphenylmethane diisocyanate (commonly abbreviated as H-MDI), hydrogenated xylylene diisocyanate (commonly abbreviated as H-XDI), norbornane diisocyanate methyl (commonly abbreviated as NBDI). ) And the like.

  Aromatic diisocyanates are polyisocyanate compounds in which NCO groups are connected by aromatic groups such as phenylene groups, alkyl-substituted phenylene groups, and aralkylene groups, or hydrocarbon groups containing aromatic groups. 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), 1-methyl-2,6-phenylene diisocyanate ( 2,6-TDI), 1-methyl-2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl- 2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-pheny Range isocyanate, m-xylene diisocyanate, die Rubenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene-2,4-diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3 , 5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methylnaphthalene-1,5-diisocyanate, naphthalene-2 , 6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'- Diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI) ), Diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4 And diisocyanates such as' -diisocyanate and xylylene diisocyanate (XDI).

  The polyurethane resin can be suitably produced by referring to the production methods described in detail in JP-A-11-343328 and JP-A-12-297133. The polyurethane resin preferably has a weight average molecular weight of 10,000 to 1,000,000, more preferably 50,000 to 500,000. If the weight average molecular weight is in this range, the viscosity of the composition is suitable, and stringing during processing such as coating and screen printing hardly occurs.

(Y) Photocurable monomer
The kind of (Y) photocurable monomer used for this invention is not specifically limited. Low molecular compounds and oligomers (prepolymers) having two or more curable functional groups in the molecule can be used. For example, polyether (meth) acrylate monomers, urethane (meth) acrylate monomers, polyester (meth) acrylate monomers, epoxy (meth) acrylate monomers, and the like can be used.
Among these, epoxy (meth) acrylate monomers (such as ethylene glycol diglycidyl ether dimethacrylate) and urethane (meth) acrylate monomers (such as a reaction product of pentaerythritol triacrylate and sophorone diisocyanate) are particularly suitable. is there.

(Z) Solvent The type of (Z) solvent used in the present invention is not particularly limited. Any solvent that can dissolve the binder resin and the photocurable monomer can be used. For example, alcohols such as methanol, ethanol, isopropanol, butanol, 2- (2-methoxyethoxy) ethanol, terpineol, aromatics such as benzene, toluene, xylene, benzyl alcohol, 2-phenoxyethanol, ethyl acetate, butyl acetate, etc. Esters, ethers such as tetrahydrofuran and dioxane, N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, propylene carbonate, water, and mixed solvents thereof can be used.
Moreover, you may use a monofunctional photopolymerizable monomer as a solvent. Although this monomer is monofunctional and cannot be sufficiently photocured by itself, it can be photocured by copolymerizing with a photocurable monomer. Since it has a relatively low viscosity, it can be used as a solvent to reduce the viscosity of the composition to such an extent that it can be applied. Examples include (meth) acrylic acid, various monoacrylates, N-substituted acrylamides, and styrene.

Photocurable Thermally Decomposable Composition The photocurable thermally decomposable composition of the present invention has 1 to 40% by weight of (X) polyurethane resin and 1 to 50 of (Y) photocurable monomer in 100% by weight. % By weight and (Z) 10 to 98% by weight of solvent. A polyurethane resin content of 1% by weight or more is sufficient as a binder resin. If the polyurethane resin is 40% by weight or less, the composition can be sufficiently applied. As other components, a small amount of known additives such as a photopolymerization initiator, a sensitizer, a polymerization inhibitor, a plasticizer, an antifoaming agent, and a silane coupling agent may be blended. In addition, cellulose ethers, acrylic polymers, polyvinyl alcohol, and the like, which are conventional binder resins, can be used in combination with the polyurethane resin of the present invention.

  This photocurable thermodegradable composition can also be used as a dry film resist by forming it into a film and drying the solvent. Moreover, various inorganic powders can be mixed with this photocurable thermodegradable composition and used as a photocurable thermodegradable inorganic powder paste. Further, the inorganic powder paste can be formed into a sheet shape, and the solvent can be dried to be used as a photocurable thermally decomposable inorganic powder sheet. All have the common characteristics of being cured by light and having good thermal decomposability.

Photocurable thermodecomposable inorganic powder paste The photocurable thermodegradable inorganic powder paste of the present invention is generally composed of 10 to 90 wt% of the photocurable thermodegradable composition in 100 wt% of the inorganic powder. 10 to 90% by weight. When the photocurable thermally decomposable composition is within this range, it is possible to form a sufficient inorganic powder film after calcination, particularly after firing.

Other components may contain a small amount of known additives such as plasticizers, antifoaming agents, and dispersing agents. The type of inorganic powder varies depending on the type of paste such as conductive paste, dielectric paste, barrier rib material paste, and phosphor paste, and includes low melting point glass powder, conductive metal powder, ceramic powder, phosphor powder, and the like. The particle size of the inorganic powder is generally preferably 100 μm or less.
Here, the low melting point glass means glass that can be fused at a temperature at which the plate glass is not thermally deformed, or glass that can be fused at a temperature lower than the heat resistance temperature of the plate glass. The low melting point glass has a Tg of 600 ° C. or lower, preferably 400 ° C. or lower, more preferably 350 ° C. or lower and 250 ° C. or higher. Such low-melting glass is generally used as sealing glass, sealing glass, solder glass, dielectric glass, partition wall glass, and the like. It is also used as glass for conductive paste. The particle size of the glass powder is more preferably 100 μm or less, and further preferably 1 to 50 μm. If the particle diameter is 100 μm or less, a sufficiently dense film can be formed after firing.
The method for preparing the paste is not particularly limited. For example, the photocurable thermally decomposable composition and the inorganic powder can be kneaded with a three-roll mill or the like to obtain a photocurable thermally decomposable inorganic powder paste. The main photocurable thermally decomposable inorganic powder paste is described below, but the present invention is of course not limited to the following paste.

Conductive paste When the present invention is used as a conductive paste, 10 to 90% by weight of the photocurable thermally decomposable composition, 10 to 90% by weight of conductive metal powder, low melting point in 100% by weight of the paste. Contains 0-50% by weight of glass powder. The conductive paste can be produced without using low-melting glass, but it is usually preferable to add in an amount of 50% by weight or less in order to increase the strength of the conductive film. As the conductive metal powder, metal powder such as gold, silver, nickel, copper, and aluminum can be used.
The low melting point glass powder is not particularly limited. A low melting glass powder for conductive paste used for PDP or the like can be suitably used. For example, P ₂ O ₅ —SnO glass, P ₂ O ₅ —SnO—B ₂ O ₃ glass, PbO—B ₂ O ₃ glass, V ₂ O ₅ —BaO—ZnO—B ₂ O ₃ glass, V ₂ O ₅ —BaO—ZnO—TeO ₂ glass or the like is preferably used.

Dielectric Paste When the present invention is used as a dielectric paste, 10 to 90% by weight of the photocurable pyrolyzable composition, 10 to 90% by weight of dielectric glass powder in 100% by weight of the paste, Inorganic fillers (alumina, quartz, etc.) other than dielectric glass are included in an amount of 0 to 10% by weight.
If the dielectric glass powder is 10% by weight or more, sufficient insulation and transparency can be obtained. If the dielectric glass powder is 90% by weight or less, the paste can be applied uniformly.
More preferable composition is 40 to 70% by weight of dielectric glass powder in 100% by weight of paste, 0 to 5% by weight of inorganic filler (alumina, quartz, etc.) other than dielectric glass, and photocurable thermodegradable composition. Is 30 to 60% by weight.
The glass powder used for the paste is not particularly limited. The dielectric glass powder used for PDP can be used suitably. This dielectric glass is glass used for forming a dielectric layer of PDP, and has a high withstand voltage without defects at the firing temperature of the dielectric layer (usually 400-600 ° C, preferably 530-580 ° C). It is glass which can form the film shown. The Tg of the dielectric glass is usually 600 ° C. or lower and 300 ° C. or higher, preferably 500 ° C. or lower and 390 ° C. or higher. For example, PbO—B ₂ O ₃ —SiO ₂ —ZnO—CaO glass, PbO—B ₂ O ₃ —SiO ₂ —ZnO—BaO—CaO—Bi ₂ O ₃ glass, ZnO—Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ —CaO—SrO—BaO-based glass or the like is preferably used.
An inorganic filler may be omitted, but an appropriate amount can be added in order to adjust the fluidity and thermal expansion coefficient of the paste. The kind of filler is not particularly limited, and a dielectric filler used for PDP can be preferably used. For example, alumina, α-quartz, titania, zirconia and the like.

Partition wall material paste When the present invention is used as a partition wall material paste, 10 to 90% by weight of the dielectric glass powder in 100% by weight of the paste, and the inorganic filler other than the dielectric glass (alumina, quartz Etc.) and 10 to 90% by weight of the photocurable thermodegradable composition.

If the dielectric glass powder is 10% by weight or more, sufficient insulation and transparency can be obtained. If the dielectric glass powder is 90% by weight or less, the paste can be applied uniformly.
More preferably, the dielectric glass powder is 40 to 80% by weight in 100% by weight of the paste composition, the inorganic filler (alumina, quartz, etc.) other than the dielectric glass is 0 to 5% by weight, and the photocurable pyrolysis The active composition is 20 to 60% by weight.
The glass powder is not particularly limited as long as it is a low-melting glass, and a partition wall glass powder used for PDP can be suitably used (hereinafter, the glass powder used for the partition wall material paste composition is referred to as “partition wall material”). Also called “glass”.) Examples of the partition wall glass include PbO—B ₂ O ₃ —SiO ₂ glass, BaO—ZnO—B ₂ O ₃ —SiO ₂ glass, and ZnO—Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ glass. Glass or the like is preferably used.
The inorganic filler other than glass is not particularly limited. The filler for a partition material used for PDP can be preferably used. For example, alumina, α-quartz, titania, zirconia, or the like can be used.

Phosphor paste When the present invention is used as a phosphor paste, the phosphor powder contains 10 to 90 wt% and the photocurable thermodecomposable composition contains 10 to 90 wt% in 100 wt% thereof. . If the phosphor powder is 10% by weight or more, sufficient emission intensity can be obtained. If the phosphor powder is 90% by weight or less, the paste can be applied uniformly. More preferably, the phosphor powder is 30 to 70% by weight and the photocurable thermodegradable composition is 30 to 70% by weight in 100% by weight of the paste composition.
The phosphor powder is not particularly limited, and a phosphor powder used for PDP can be suitably used. Examples of the phosphor powder include, for example, BaMgAl ₁₄ O ₂₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, SrMg (SiO ₄ ) ₂ : Eu and the like for blue phosphors, and (Y, Gd) for red phosphors. ) BO ₃ : Eu, Y ₂ O ₃ : Eu, Y (P, V) O ₄ : Eu, (Y, Gd) ₂ O ₃ : Eu, etc. are green phosphors, Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, YBO ₃ : Tb, etc. are preferably used.
These various pastes are coated on the target substrate at the desired thickness, dried, exposed to light using a photomask, photocured, and washed with water or an organic solvent to cure the inorganic powder with the desired pattern. You can get things. The coating method is not particularly limited, and a known method such as a roll coater, a bar coater, or screen printing can be used. The exposure method is not particularly limited, and a normal UV curing device or the like can be used. By subjecting this cured product to thermal decomposition at 350 ° C. or higher, preferably 400 to 600 ° C., the desired molded body (conductor, dielectric, partition, phosphor, etc.) can be obtained. The atmosphere during firing may be air or an inert gas such as nitrogen, but is usually fired in air.

Photocurable thermodegradable inorganic powder sheet The photocurable inorganic powder sheet of the present invention is obtained by applying the photocurable inorganic powder paste onto a base resin such as a PET film, forming the film, and then drying the solvent. It is the formed sheet-like photocurable composition. The thickness of the sheet is 1 to 100 μm, more preferably 5 to 50 μm. After the sheet is affixed on the target substrate, the base resin is peeled off to form a photocurable film on the substrate.

The photocurable inorganic powder paste is a sheet obtained by applying a paste on a substrate and then drying the solvent to form a photocurable film, whereas the photocurable inorganic powder sheet is obtained by previously drying the solvent. A photocurable film is formed by sticking a photocurable composition in the form of a substrate onto a substrate. Although the characteristics as a film are the same, there is an advantage that the solvent drying step can be omitted.
This sheet is attached on a target substrate, exposed and photocured using a photomask or the like, and washed with water or an organic solvent to obtain a cured product of an inorganic powder having a target pattern. By subjecting this cured product to thermal decomposition at 350 ° C. or higher, preferably 400 to 600 ° C., the desired molded body (conductor, dielectric, partition, phosphor, etc.) can be obtained. The atmosphere during firing may be air or an inert gas such as nitrogen, but is usually fired in air.
The main photocurable inorganic powder sheets will be described below, but the present invention is of course not limited to the following sheets.

A photocurable dielectric paste is applied over the entire surface of the photocurable thermodegradable dielectric sheet PET resin film using a roll coater, applicator, bar coater, etc., and the solvent is dried. A thickness of 2 to 500 μm is appropriate. Next, the solvent is dried at 80 to 150 ° C. with a hot air dryer or the like to form a dielectric layer having a thickness of about 1 to 100 μm.
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is of course not limited to the following examples.

Example 1
[Synthesis of Comb Diol 1]
A magnetic stirrer, a thermometer, and a dropping funnel were installed in a 500 ml round bottom flask, charged with 64.6 g of 2-ethylhexylamine (Kanto Chemical), and the inside of the flask was replaced with nitrogen. The flask was heated to 60 ° C. in an oil bath, and 220.0 g of 2-ethylhexyl glycidyl ether (Asahi Denka, Adeka Glycilol ED518, Epoxy value 220) was added dropwise over 40 minutes while stirring. After completion of dropping, the temperature of the oil bath was raised to 80 ° C., and the flask was heated for 10 hours. Subsequently, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted substances were distilled off under reduced pressure using a vacuum pump at a degree of vacuum of 3 mmHg. Comb-shaped diol 1 (average molecular weight 532 from OH value) in which 2-ethylhexyl glycidyl ether was added at a ratio of 2 mol to 1 mol of 2-ethylhexylamine was obtained in a yield of 90%.

[Synthesis of polyurethane resin 1]
A 1000 ml SUS separable flask was charged with 200 g of commercially available PEG # 6000 (Sanyo Kasei, number average molecular weight 8,630) and melted at 150 ° C. under a nitrogen seal. This was stirred for 3 hours under reduced pressure (3 mmHg) with stirring. Residual moisture was 200 ppm. The temperature was lowered to 70 ° C., and the flask was filled with 1 atm of nitrogen. 300 ppm of BHT (di-ter-butylhydroxytoluene) was added as an antioxidant. While stirring the flask, 1.90 g of comb diol 1 and 4.36 g of hexamethylene diisocyanate (Tokyo Kasei) were charged (NCO / OH = 0.97 mol / mol). When 0.05 g of DBTDL was added as a catalyst, the viscosity increased rapidly in about 10 minutes. Stirring was stopped and the reaction was carried out at 70 ° C. for 2 hours. The temperature was raised to 120 ° C. and kept at a constant temperature for 30 minutes, after which the product was removed from the flask. The weight average molecular weight of the product was 200,000.
The product taken out was cut into small pieces and allowed to cool. This was cooled with liquid nitrogen and pulverized with a small impact electric mill. The pulverized product was sieved to obtain a powder having a particle size of 600 μm or less as polyurethane resin 1. The average particle size of the powder was 400 μm.

[Production of Photocurable Pyrolytic Composition 1]
The following raw materials were charged into a 200 ml glass separable flask and dissolved by stirring for 1 hour while heating to 60 ° C. to obtain a photocurable thermodegradable composition 1.
10g of polyurethane resin 1
Polyethylene glycol diglycidyl ether dimethacrylate (manufactured by Nagase ChemteX DM-811, photocurable monomer)
20g
N-methylpyrrolidone (solvent) 80g
IRUGACURE-369 (photopolymerization initiator) manufactured by Ciba Geigy
1g
[Production of Dielectric Paste 1]
35 g of the above-mentioned photocurable thermodegradable composition 1 and 65 g of dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass) were kneaded to obtain dielectric paste 1.

[Formation of dielectric layer]
The dielectric paste 1 was applied on the entire surface of the soda glass substrate by screen printing. The solvent was dried at 80 ° C. in a vacuum dryer. A photomask is placed on this substrate and cured by irradiating 100mW / cm ² of UV light from a high pressure mercury lamp with a UV curing device manufactured by USHIO ELECTRIC CO., LTD. And the desired pattern was obtained.
This substrate was baked in air at 550 ° C. for 30 minutes to form a dielectric layer having a thickness of 40 μm.
When the surface roughness Ra was measured using a stylus type surface roughness meter, it was a flat surface of 0.15 μm. The membrane was clear and not turbid.

Example 2
[Production of Photocurable Pyrolytic Composition 2]
The following raw materials were charged into a 200 ml glass separable flask and dissolved by stirring for 1 hour while heating to 60 ° C. to obtain a photocurable thermodegradable composition 2.
10g of polyurethane resin 1
Reaction product of pentaerythritol triacrylate and isophorone diisocyanate (UA-306I, Kyoeisha Chemical Co., Ltd., photocurable monomer)
20g
Methanol (solvent) 80g
Ciba Geigy DAROCUR-1173 (photopolymerization initiator)
1g
[Production of Dielectric Paste 2]
35 g of the above-described photocurable thermodegradable composition 2 and 65 g of dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass) were kneaded to obtain dielectric paste 2.

[Formation of dielectric layer]
The dielectric paste 2 was applied on the entire surface of the soda glass substrate by screen printing. The solvent was dried at 80 ° C. in a vacuum dryer. A photomask is placed on this substrate and cured by irradiating 100 mW / cm ² of UV light from a high pressure mercury lamp with a UV curing device manufactured by USHIO ELECTRIC CO., LTD. The desired pattern was obtained.
This substrate was baked in air at 550 ° C. for 30 minutes to form a dielectric layer having a thickness of 40 μm.
When the surface roughness Ra was measured using a stylus type surface roughness meter, it was a flat surface of 0.25 μm. The membrane was clear and not turbid.

<< Comparative Example 1 >>
A photocurable thermally decomposable composition 3 was obtained in the same manner as in Example 1 except that ethylcellulose was used in place of the polyurethane resin.
35 g of the above-mentioned photocurable thermodegradable composition 3 and 65 g of dielectric glass powder (PbO—B ₂ O ₃ —SiO ₂ —CaO glass) were kneaded to obtain dielectric paste 3.
The solvent was dried at 80 ° C. in a vacuum dryer. A photomask was placed on the substrate, cured by UV light irradiation of 100 mW / cm ² using a UV curing device manufactured by USHIO, and washed with isopropanol to remove uncured portions, thereby obtaining a target pattern.
This substrate was baked at 550 ° C. for 30 minutes to form a dielectric layer having a thickness of 40 μm.
When the surface roughness Ra was measured using a stylus type surface roughness meter, it was a surface with many irregularities of 1.0 μm. There was a crack on the surface, and a decrease in pressure resistance was expected. Moreover, transparency was impaired due to unevenness and residual carbon. This unevenness is thought to be due to the rapid combustion heat of cellulose ether. Thus, although the paste using ethyl cellulose has an opaque and uneven surface, a transparent and flat surface was obtained when the polyurethane resin of the present invention was used.

It can be used to form partition walls, electrodes, resistors, dielectrics, phosphors, color filters, black matrices and the like of PDP (plasma display). It can also be used to form FED phosphors and electrodes for electronic components. Moreover, it can use for a photoresist.

Claims (5)

(X) The following formula (1)

(In the formula, A is a dealcohol residue (divalent group) of polyoxyalkylene glycol (compound A) HO-A-OH having hydroxyl groups at both ends, and B is diisocinaate (compound B) OCN-B). A repeating unit (a) represented by a de-NCO residue (divalent group) of -NCO),
The following formula (2)

(In the formula, D is a dealcohol residue (divalent group) of comb diol HO-D-OH having at least two hydrocarbon groups having 4 to 21 carbon atoms (monovalent group) in the molecule; B is a repeating unit (b) represented by diisocinaate (compound B) OCN-B-NCO de-NCO residue (divalent group)), and the molar ratio of the repeating unit (a) is 0. A polyurethane resin having a repeating unit (b) molar ratio of 0.01 to 0.65,
A photocurable thermodegradable composition comprising (Y) a photocurable monomer and (Z) a solvent. The comb diol HO-D-OH is represented by the following formula (3)

(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group, R ² and R ³ are hydrocarbon groups having 4 to 21 carbon atoms, R ¹ , Part or all of hydrogen in R ² and R ³ may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different.
Y and Y ′ are hydrogen, a methyl group or a CH ₂ Cl group, and Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂ group, and Z and Z ′ may be the same or different. n is an integer of 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group. N ′ is an integer of 0 to 15 when Z ′ is oxygen, and 0 when Z ′ is sulfur or a CH ₂ group, and n and n ′ may be the same or different. Or a comb-shaped diol (compound D) represented by the following formula (4)

(In the formula, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ are hydrocarbon groups having 4 to 21 carbon atoms, and in R ⁵ , R ² and R ³ , Some or all of the hydrogen atoms may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different.
Y, Y ′ and Y ″ are hydrogen, methyl group or CH ₂ Cl group, Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂ group, Z and Z ′ may be the same or different, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and k is an integer of 0 to 15. n is when Z is oxygen. Is an integer from 0 to 15 and is 0 when Z is sulfur or CH ₂ , and n ′ is an integer from 0 to 15 when Z ′ is oxygen and Z ′ is sulfur or CH 2. _The photocurable heat according to claim 1, wherein the photocurable heat is a comb-shaped diol (compound D ′) represented by the following formula: 0 in the case of ₂ groups, and n and n ′ may be the same or different. Degradable composition. Claims containing (X) 1 to 40% by weight of polyurethane resin, (Y) 1 to 50% by weight of photocurable monomer, and (Z) 10 to 98% by weight of solvent in 100% by weight of the photocurable thermally decomposable composition. Item 3. The photocurable thermally decomposable composition according to Item 1 or 2. A photocurable thermally decomposable inorganic powder paste further comprising an inorganic powder in the photocurable thermally decomposable composition according to claim 1. A photocurable thermally decomposable inorganic powder sheet obtained by forming the photocurable inorganic powder paste into a film and then drying the solvent.