JPH10306101A - Modified cellulose compound and photopolymerizable resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified cellulose compound improved in photocurability, adhesion to substrates, flexibility, the easiness of peel upon treatment with a peeling solution and decomposability in baking by substituting part of the hydroxyl groups of a cellulose (derivative) by urethane (meth)acrylate groups, SOLUTION: Either of the isocyanate groups of a diisocyanate compound and a hydroxy (meth)acrylate compound are subjected to an urethane formation reaction at 60-90 deg.C for 2-24 hr in the presence of an organometallic catalyst, an amine catalyst or the like. The remaining isocyanate group of the obtained reaction product is reacted with the hydroxyl groups of a cellulose (derivative) at 60-90 deg.C for 2-24 hr to obtain a modified cellulose compound having a degree of substitution of hydroxyl groups with urethane (meth)acrylate groups of 1-50% and having a weight-average molecular weight of 8,000-500,000. 100 pts.wt., in total, 100 pts.wt modified cellulose compound, 0.1-25 pts.wt. polymerization initiator and 150 pts.wt. or below ethylenic compound is mixed with 50-95 pts.wt. inorganic and/or metallic powders to obtain the title composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified cellulose compound and a photopolymerizable resin composition containing the same, and in particular, has photocurability, excellent adhesion to a substrate, high flexibility, and a release liquid. The present invention relates to a modified cellulose compound which has good releasability from, and easily decomposes and volatilizes even when fired, and a photopolymerizable resin composition containing the same. The modified cellulose compound of the present invention can be used for forming a UV curable paint, a photosensitive screen printing plate, a resist for lift-off, a priming rib of a plasma display panel (PDP), a resistance pattern, a conductive pattern, and the like. It is applicable to resin compositions.

[0002]

2. Description of the Related Art Conventionally, cellulose derivatives represented by methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, etc. are emulsion paints, paper coating agents, various adhesives, ultraviolet curable paints, It is widely used in photosensitive screen printing resists, lift-off resists, and paste compositions.
This has some open issues.

For example, emulsion paints, paper coating agents,
When a cellulose derivative is used for various adhesives, UV-curable paints, photosensitive screen printing resists, lift-off resists, paste compositions, and the like, the coatings obtained by coating and drying are poor in water resistance. In these applications, adhesion to a substrate is poor, and peeling or chipping may occur after a film is formed.

[0004] As a means for solving these problems, a hydrogen atom of a residual hydroxyl group of a cellulose derivative having an average degree of substitution per unit glucose ring of a predetermined substituent is specified by an N-methyleneacrylamide group. A substituted compound is known (Japanese Patent Application Laid-Open No. 2-298501). However, a material having further improved adhesiveness and flexibility with a substrate, releasability to a release solution, decomposition when burned, volatilization, and the like, is disclosed. Was desired.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide excellent adhesion to a substrate, high flexibility, good releasability to a release solution, and sintering. Easy to decompose and volatilize even when used, and used for UV curable paints, photosensitive screen printing plates, resists for lift-off, priming ribs for plasma display panels, resistance patterns, conductive patterns, etc. An object of the present invention is to provide a modified cellulose compound applicable to the photopolymerizable resin composition to be used and a photopolymerizable resin composition containing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the hydroxyl groups of cellulose or cellulose derivatives were converted to urethane (meth) acrylate groups at a specific reaction rate. The present inventors have found that the above problems can be solved by using a substituted modified cellulose compound in a photopolymerizable resin composition, and have completed the present invention.

That is, the present invention relates to a modified cellulose compound in which 1 to 50% of the hydroxyl groups of cellulose or a cellulose derivative are substituted by urethane (meth) acrylate groups.

[0008] The present invention also relates to a photopolymerizable resin composition comprising (a) the above modified cellulose compound and (b) a photopolymerization initiator.

The photopolymerizable resin composition further comprises (c)
It preferably contains an ethylenic compound.

The photopolymerizable resin composition further comprises (d)
It preferably contains inorganic and / or metal powder.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.

In the modified cellulose compound as the component (a) used in the present invention, 1 to 50% of the hydroxyl groups of the cellulose or the cellulose derivative are substituted by urethane (meth) acrylate groups. Such substitution is performed, for example, by bonding 1 to 50% of the hydroxyl groups of cellulose or a cellulose derivative to a (meth) acrylate compound having a hydroxyl group via a diisocyanate compound.

Preferred specific embodiments of the substitution of the urethane (meth) acrylate group for the hydroxyl group include:
(I) reacting a diisocyanate compound with a (meth) acrylate compound having a hydroxyl group so that only one isocyanate group is urethanized;
And (II) converting the other isocyanate group of the diisocyanate compound to the hydroxyl group in cellulose or a cellulose derivative by a reaction rate of the hydroxyl group of 1 to 50.
% Of the reaction. In the above, after the step (I), the step (II)
The step may be performed, or the step (I) may be performed after the step (II).

More specifically, after reacting a diisocyanate compound with a (meth) acrylate compound having a hydroxyl group so that only one isocyanate group is urethanized, the other remaining isocyanate group of the reaction product is reacted. And a hydroxyl group in cellulose or a cellulose derivative by reacting the hydroxyl group in a reaction rate of 1 to 50%.

As a method for reacting one isocyanate group of the diisocyanate compound with a (meth) acrylate compound having a hydroxy group to form a urethane,
A diisocyanate compound and a (meth) acrylate compound having a hydroxyl group are placed in a reaction vessel in the presence of a catalyst such as an organometallic catalyst (for example, an organotin compound) or an organic amine catalyst, and the reaction is carried out at a temperature of 60 to 90 ° C. For example, a method performed in a time of 2 to 24 hours is exemplified.

As a method of reacting the remaining isocyanate group of the urethanized reactant with the hydroxyl group of the above-mentioned cellulose or cellulose derivative, an organometallic catalyst (for example, an organotin compound, etc.) ), A method of putting the urethanized reactant and cellulose or a cellulose derivative in a reaction vessel in the presence of a catalyst such as an organic amine catalyst, and synthesizing the mixture at a temperature of 60 to 90 ° C. for a reaction time of 2 to 24 hours. Is mentioned.

Here, (meth) having a hydroxyl group
Examples of the acrylate compound include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,
-(2-hydroxyethoxy) ethyl methacrylate,
2- (2-hydroxyethoxy) ethyl acrylate,
2-hydroxycyclohexyl methacrylate, 2-hydroxycyclohexyl acrylate, (1-hydroxycyclohexyl) methyl methacrylate, (1-hydroxycyclohexyl) methyl acrylate, 2- (2
-Hydroxy-1,1-dimethylethoxy) -1,1-
Dimethylethyl methacrylate, 2- (2-hydroxy-1,1-dimethylethoxy) -1,1-dimethylethyl acrylate, 2-hydroxy-2-phenylethyl methacrylate, 2-hydroxy-2-phenylethyl acrylate, 2-hydroxy -3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, 2
-Hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxy-3- (2-propenyloxy) propyl methacrylate, 2-hydroxy-3-
(2-propenyloxy) propyl acrylate, 2-
Hydroxy-3-propoxypropyl methacrylate,
2-hydroxy-3-propoxypropyl acrylate, 2-hydroxy-2-methylpropyl methacrylate, 2-hydroxy-2-methylpropyl acrylate, 2-hydroxy-2-methoxypropyl methacrylate, 2-hydroxy-2-methoxypropyl acrylate, 3-hydroxy-2- (methoxymethyl) -4-
Pentenyl methacrylate, 3-hydroxy-2- (methoxymethyl) -4-pentenyl acrylate and the like can be mentioned. Among them, 2-hydroxyethyl methacrylate and the like are preferably used.

As the diisocyanate compound, an aromatic diisocyanate compound, a cycloaliphatic diisocyanate compound, or the like can be arbitrarily used as long as it has two isocyanate groups (-NCO). Specifically, for example, cyclohexane-1,2-diisocyanate, cyclohexane-1,3-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-ethylcyclohexane-2,4-diisocyanate, 4,5-dimethylcyclohexane -1,3-diisocyanate, 1,
2-dimethylcyclohexane-ω, ω'-isophorone diisocyanate, dicyclohexylmethane-4,4'-
Diisocyanate, 2,2'-dimethyldicyclohexylmethane-4,4'-diisocyanate, 3,3'-dimethyldicyclohexylmethane-4,4'-diisocyanate, 3,3'-5,5'tetramethyldicyclohexylmethane-4, 4′-diisocyanate, 2- (γ-
Isocyanatopropyl) cyclohexyl isocyanate, 5-dimethyl-1,3-cyclohexylene diisocyanate, 1,3-diphenylpropane-1,3-diisocyanate, 1,4-dimethylnaphthalene-ω, ω ′
-Diisocyanate, 1,5-dimethylnaphthalene-
ω, ω'-diisocyanate, diphenyl ether-
4,4'-bismethyl isocyanate, 4,4'-n-
Propylbiphenyl-ω, ω'-diisocyanate, bis (2-isocyanateethyl) terephthalate, bis (2-isocyanateethyl) isophthalate, 4-phenylisocyanate-methylisocyanate, 4-phenylisocyanate-β-ethylisocyanate,
-Phenyl isocyanate-α-ethyl isocyanate, 4-phenyl isocyanate-γ-propyl isocyanate, 3-phenyl isocyanate-γ-propyl isocyanate, 4-phenyl isocyanate-γ-butyl isocyanate, tetrahydronaphthylene-1,5
-Diisocyanate, hexahydrobenzidine-4,
4'-diisocyanate, 1,3-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2 1,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,6-phenylene diisocyanate, 1,3-xylylene diisocyanate , M-phenylenebis (isopropyl isocyanate) and the like. In particular, those having isocyanate groups having different reactivities from each other are preferable because it is easy to selectively react only one of the isocyanate groups with a (meth) acrylate compound having a hydroxyl group to form a urethane.

In the present invention, the conversion of the hydroxyl group in the cellulose or cellulose derivative is in the range of 1 to 50%, preferably 5 to 40%. If the reaction rate of the hydroxyl group is less than 1%, the adhesion to the object to be treated is reduced,
On the other hand, if it exceeds 50%, the releasability decreases, which is not preferable.

The above hydroxyl group also includes a modified hydroxyl group. That is, for example, the case where the hydroxyl group of cellulose is etherified in the cellulose derivative is also included.

As described above, by having a cellulose skeleton in the main chain and introducing a specific urethane (meth) acrylate group into the side chain at a predetermined ratio, the elasticity and flexibility can be increased, and Good adhesion to the body, even when fired, has the property of easily decomposing and volatilizing,
Because of its excellent releasability, the modified cellulose compound of the present invention can be used for forming a UV curable coating, a photosensitive screen printing plate, a resist for lift-off, a priming rib of PDP, a resistance pattern, a conductive pattern, and the like. It is suitably used for a polymerizable resin composition.

Examples of the cellulose or cellulose derivative as a precursor of the modified cellulose compound include cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose, cellulose acetate phthalate and the like. Can be. One or more of these are used.

The weight average molecular weight of the modified cellulose compound is preferably from 8,000 to 500,000, more preferably from 10,000 to 150,000. Molecular weight 8,
If it is less than 000, the coating properties may decrease, while 5
If it exceeds 000, the viscosity increases, which is not preferable.

The photopolymerization initiator as the component (b) is not particularly restricted but includes, for example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1 -One, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecy Phenyl) -2-hydroxy -
2-methylpropan-1-one, 4-benzoyl-4 '
-Methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethyl Aminobenzoic acid-2-isoamyl,
2,2-diethoxyacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal,
1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone,
4,4'-bisdiethylaminobenzophenone, 4,
4'-dichlorobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-
n-butyl ether, benzoin isobutyl ether,
Benzoin butyl ether, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone,
Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-
Dichloro-4-phenoxyacetophenone, pentyl-
4-dimethylaminobenzoate and the like. One or more of these are used. Among them, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4-diethylthioxanthone and the like are preferably used.

The photopolymerization initiator is modified cellulose compound 1
It is preferable to mix in an amount of 0.1 to 25 parts by weight with respect to 00 parts by weight. Less than 0.1 part by weight may cause poor exposure and curing, while more than 25 parts by weight may reduce the coating properties and the abrasion resistance and chemical resistance of the coating after exposure and curing, and are preferably Absent.

In the present invention, in order to improve the sensitivity and chemical resistance of the photopolymerizable resin composition, an ethylenic compound is further added as the component (c) in addition to the components (a) and (b). Can be. This ethylenic compound is a compound containing at least one ethylenically unsaturated double bond capable of addition polymerization. When the photopolymerizable resin composition is irradiated with an energy ray, the photopolymerization initiator acts. Works to cure by addition polymerization.

Examples of the ethylenic compound include unsaturated carboxylic acids, esters of aliphatic (poly) hydroxy compounds with unsaturated carboxylic acids; esters of aromatic (poly) hydroxy compounds with unsaturated carboxylic acids; Esters obtained by esterification of carboxylic acids and polyvalent carboxylic acids with the above-mentioned aliphatic (poly) hydroxy compounds and polyvalent hydroxy compounds such as aromatic (poly) hydroxy compounds; unsaturated carboxylic acid amides; unsaturated Carboxylic acid nitrile and the like can be mentioned.

Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, Ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate,
Monofunctional monomers such as benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate,
Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate ,
Trimethylolpropane trimethacrylate, tetramethylolpropane tetramethacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate,
Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxydi In addition to polyfunctional monomers such as acrylate and cardepoxy dimethacrylate, these compounds were replaced with `` ~ acrylate '' and `` ~ methacrylate '' with `` ~ fumarate '', `` ~ maleate '', `` ~ crotonate '', `` ~ itaconate '' , Fumaric acid ester, maleic acid ester, crotonic acid ester, itaconic acid ester, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, italic acid Acid, hydroquinone monoacrylate, hydroquinone monomethacrylate, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol diacrylate, pyrogallol triacrylate, condensates of acrylic acid with phthalic acid and diethylene glycol, acrylic acid Condensates of maleic acid and diethylene glycol, condensates of methacrylic acid with terephthalic acid and pentaerythritol, condensates of acrylic acid with adipic acid and butanediol with glycerin, ethylenebisacrylamide, ethylenebismethacrylamide, diallyl phthalate Allyl ester, divinyl phthalate and the like are exemplified.

Further, a polymer having a functional group having a reactive activity such as a hydroxyl group or a halogenated alkyl group in a side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin and the like, acrylic acid, methacryl A polymer obtained by a polymer reaction with an unsaturated carboxylic acid such as an acid, fumaric acid, maleic acid, crotonic acid, and itaconic acid is also preferably used. One or more of these are used.

Among the above ethylenic compounds, monomers having an ethylenically unsaturated double bond, particularly monomers of acrylate or methacrylate are preferably used. Here, the “monomer” includes not only a monomer in a narrow sense but also a dimer, a trimer, and an oligomer.

It is preferable that the ethylenic compound is added in a range of up to 150 parts by weight based on 100 parts by weight of the modified cellulose compound. If the amount exceeds 150 parts by weight, the coating properties may be reduced.

In the present invention, in addition to the components (a) and (b) or the components (a) to (c), (d) an inorganic and / or metal powder can be appropriately blended. Such inorganic and / or metal powders include:
Specifically, PbO—SiO ₂ system, PbO—B ₂ O ₃ —S
iO ₂ system, ZnO-SiO ₂ system, ZnO-B ₂ O ₃ -SiO
₂ system, BiO-SiO _{2 -based, BiO-B 2 O 3 -SiO} 2 system borosilicate lead glass, borosilicate zinc glass, and glass powders such as borosilicate bismuth glass, cobalt oxide, iron oxide, chromium oxide, Nickel, copper oxide, manganese oxide, neodymium oxide, vanadium oxide, cerium chippek yellow, cadmium oxide, alumina, silica,
Na, K, Mg, Ca, B such as macnesia and spinel
a, each oxide such as Ti, Zr, and Al, ZnO: Zn, Z
n ₃ (PO ₄ ) ₂ : Mn, Y ₂ SiO ₅ : Ce, CaWO ₄ :
Pb, BaMgAl ₁₄ O ₂₃ : Eu, ZnS: (Ag, C
d), Y ₂ O ₃ : Eu, Y ₂ SiO ₅ : Eu, Y ₃ Al
₅ O ₁₂ : Eu, YBO ₃ : Eu, (Y, Gd) BO ₃ : E
u, GdBO ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ :
Eu, Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, S
rAl ₁₃ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn, YB
O ₃ : Tb, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : T
b, GdBO ₃ : Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ O
₃ Cl ₄ : Eu, ZnS: (Cu, Al), ZnS: A
g, Y ₂ O ₂ S: Eu, ZnS: Zn, (Y, Cd) BO
₃ : In addition to phosphor powders such as Eu and BaMgAl ₁₂ O ₂₃ : Eu, conductive particles such as iron, nickel, copper, aluminum, silver, and gold may be added to form a conductive pattern. it can. One or more of these are used.

The inorganic and / or metal powder as the component (d) is contained in a total of 100 parts by weight of the photopolymerizable resin composition.
It is preferable to mix in the range of 0 to 95 parts by weight. If the amount is less than 50 parts by weight, problems such as applicability and shrinkage after firing may occur. On the other hand, if the amount is more than 95 parts by weight, photocurability may decrease.

In the present invention, in addition to the above components, a polymer binder usually contained in the photosensitive resin composition may be appropriately blended as long as the effects of the present invention are not impaired. Examples of such a polymer binder include acrylic acid, methacrylic acid, crotonic acid, maleic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and N-butyl. Acrylate, N-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc. Polyesters obtained by polycondensation of unsaturated divalent carboxylic acids such as itaconic acid, propylidene succinic acid and ethylidene malonic acid with dihydroxy compounds, itaconic acid, propylidene succinic acid, ethylidene In addition to polyamide obtained by the polycondensation reaction of an unsaturated divalent carboxylic acid such as malonic acid and a diamine, phenol novolak type epoxy acrylate, phenol novolak Type epoxy methacrylate, cresol novolak epoxy acrylate, cresol novolak epoxy methacrylate, bisphenol A
Type epoxy acrylate, bisphenol S type epoxy acrylate, urethane acrylate oligomer, urethane methacrylate oligomer and the like. Also,
A product obtained by further reacting a polybasic acid anhydride with the epoxy (meth) acrylate may be blended. Examples of such polybasic acid anhydrides include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, -Ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride,
Examples thereof include 4-ethyltetrahydrophthalic anhydride and maleic anhydride, and among them, hexahydrophthalic anhydride and tetrahydrophthalic anhydride are preferably used.

Further, a solvent may be added to the photopolymerizable resin composition of the present invention to improve coating properties. Such solvents include ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether,
Propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol Monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethyl Glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, -Methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-
Methyl-3-methoxybutyl acetate, 3-ethyl-
3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl Acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate,
4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, 2-hydroxypropion Methyl acid, 2
-Ethyl hydroxypropionate, 2-hydroxy-2
-Methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl- 3-methoxypropionate, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, amyl lactate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl acetate, ethyl acetate, acetic acid Propyl, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate,
Ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, Benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol,
Examples thereof include diethylene glycol and glycerin.

The solvent is a total of 10 parts of the photopolymerizable resin composition.
2000 parts by weight or less, preferably 100 parts by weight with respect to 0 parts by weight
It can be contained in a range of 0 parts by weight or less.

In the present invention, in addition to the above components, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a surfactant, an antifoaming agent, and other additives can be further added as required.

As the sensitizer, specifically, eosin B
(CI No. 45400), Eosin J (CI.
No. 45380), alcohol-soluble eosin (C.
I. No. 45386), cyanosine (C.I. No.
45410), bengal rose, erythrosine (C.
I. No. 45430), 2,3,7-trihydroxy-9-phenylxanthen-6-one, and xanthene dyes such as rhodamine 6G; thionine (C.I.
52000), Azure A (CI No. 5200)
5) and thiazine dyes such as Azure C (CI No. 52002); pyronin B (CI No. 4500)
5), and pyronin GY (CI No. 4500)
5) etc., 3-acetylcoumarin, 3
Coumarin compounds such as -acetyl 7-diethylaminocoumarin.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, p-methoxyphenol, pyrogallol, catechol, and 2,6-di-tert.
-Butyl-p-cresol, β-naphthol and the like.

As the plasticizer, dioctyl phthalate,
Didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like can be mentioned.

Examples of the surfactant include various anionic, cationic and nonionic surfactants.

Examples of the defoaming agent include various defoaming agents such as silicone type and fluorine type.

The modified cellulose compound of the present invention and the photopolymerizable resin composition containing the same can be suitably used for an ultraviolet curable paint, a photopolymerizable screen printing plate, and a lift-off resist. Further, the photopolymerizable resin composition containing the inorganic and / or metal powder is applied to a substrate by a screen printing method or the like, dried, and then exposed by contacting a negative mask, followed by development, drying, and baking to obtain a paste. A pattern is formed. By sequentially forming a conductive paste pattern and an insulating paste pattern on the insulating paste pattern, a multilayer wiring pattern can be manufactured.

Hereinafter, a pattern forming method using the photopolymerizable resin composition of the present invention will be described with reference to FIG.

FIG. 1 shows an example of a pattern forming method using the photopolymerizable resin composition of the present invention. First, a solution obtained by dissolving the photopolymerizable resin composition of the present invention in a solvent is applied on a substrate 1 using a spinner or the like, and dried to form a photoresist layer 2 (FIG. 1A). As the substrate 1, for example, in the production of a liquid crystal panel, a polarizing plate and, if necessary, a black matrix layer and a color filter layer are provided,
Further, a glass substrate provided with a transparent conductive circuit layer may be used.

Next, the photoresist layer 2 is selectively exposed through a predetermined negative mask pattern 3 (FIG. 1).
(B)). Exposure is performed by using a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, an excimer laser generator, or the like, and irradiating a sufficient amount of light to form a negative image. In the present invention, at the time of exposure, a photopolymerization reaction occurs in a portion irradiated with the actinic ray, photocuring occurs, and becomes insoluble in an alkaline aqueous solution. Then, when this is immersed in a developing solution, the unexposed portion is selectively dissolved and removed, and a photoresist pattern 4 faithful to the mask pattern 3 can be obtained (FIG. 1C).

Examples of the developer include hydroxides, carbonates, bicarbonates, phosphates and pyrophosphates of alkali metals such as lithium, sodium and potassium; primary amines such as benzylamine and butylamine; dimethylamine Tertiary amines such as trimethylamine, triethylamine and triethanolamine; cyclic amines such as morpholine, piperazine and pyridine; polyamines such as ethylenediamine and hexamethylenediamine; tetraethylammonium hydroxide , Ammonium hydroxides such as trimethylbenzylammonium hydroxide and trimethylphenylbenzylammonium hydroxide; trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, Sulfonium hydroxide such as chill benzyl sulfonium hydroxide; other choline, 1-10 wt% aqueous solution are used.

If desired, for example, in forming a priming rib of a PDP, the temperature may be 350-700 ° C.
It is preferable to bake for about 0.5 to 8 hours. The photopolymerizable composition of the present invention has a property that the modified cellulose compound is easily decomposed and volatilized even after firing, has excellent releasability, and can form a pattern faithful to a mask pattern.

Further, a multi-layer wiring pattern can be manufactured by sequentially forming a conductive paste pattern and an insulating paste pattern on the photoresist pattern thus formed.

[0050]

EXAMPLES Cellulose urethane (meth) acrylate compounds (modified cellulose compounds) were synthesized by the methods of Synthesis Examples 1 to 8 below.

(Synthesis Example 1) 3.9 parts by weight of 2-hydroxyethyl methacrylate, diphenyltin diacetate 0.1 part by weight.
03 parts by weight and 3 parts by weight of methyl ethyl ketone were put into a reactor, and 6.67 parts by weight of isophorone diisocyanate was sequentially dropped while heating to a temperature of 80 ° C., and further reacted at 75 ° C. for 5 hours to obtain a urethane methacrylate compound. .

Next, hydroxypropyl cellulose (weight average molecular weight: about 50,000, hydroxypropyl etherification degree: 55% (-OCH (C
H ₃ ) Assuming that the degree of repetition of the CH ₂ -segment is 1,
Hydroxypropylcellulose 55% is etherified)) 12 parts by weight, 4 parts by weight of methyl ethyl ketone, and 0.01 part by weight of diphenyltin diacetate. The urethane methacrylate compound reaction liquid was sequentially dropped, and the reaction was further performed at 80 ° C. for 7 hours.

After the reaction product was cooled, it was filtered, and the obtained crude product was poured into hot water at 90 ° C., washed and dried to obtain a purified product. In the modified cellulose compound (A-1) obtained, 15% of the hydroxyl groups had reacted with the isocyanate compound.

(Comparative Synthesis Example 1) In the synthesis example 1, when the urethane methacrylate compound was reacted with hydroxypropyl cellulose, hydroxypropyl cellulose 24
The reaction was carried out in the same manner as in Synthesis Example 1 except that 0 parts by weight and methyl ethyl ketone were 40 parts by weight, followed by filtration. The obtained crude product was poured into hot water at 90 ° C., washed and dried to obtain a purified product. Was. In the resulting modified cellulose compound (B-1), 0.7% of the hydroxyl groups had reacted with the isocyanate compound.

(Synthesis Example 2) A reaction was carried out in the same manner as in Synthesis Example 1, except that the reaction between the urethane methacrylate compound and hydroxypropyl cellulose was 36 parts by weight of hydroxypropyl cellulose and 12 parts by weight of methyl ethyl ketone. Then, the mixture was filtered, and the obtained crude product was added to 9
It was poured into hot water of 0 ° C., washed and dried to obtain a purified product. In the resulting modified cellulose compound (A-2), 4.95% of the hydroxyl groups had reacted with the isocyanate compound.

(Synthesis Example 3) A reaction was carried out in the same manner as in Synthesis Example 1 except that the reaction between the urethane methacrylate compound and hydroxypropyl cellulose was changed to 5 parts by weight of hydroxypropyl cellulose and 1 part by weight of methyl ethyl ketone. Thereafter, the mixture was filtered, and the obtained crude product was 90
It was poured into hot water at ℃, washed and dried to obtain a purified product. In the obtained modified cellulose compound (A-3), 36.3% of the hydroxyl groups had reacted with the isocyanate compound.

(Comparative Synthesis Example 2) In the same manner as in Synthesis Example 1, except that in the reaction of the urethane methacrylate compound with hydroxypropyl cellulose, 3 parts by weight of hydroxypropyl cellulose and 1 part by weight of methyl ethyl ketone were used. After the reaction, the mixture was filtered.
It was poured into hot water of 0 ° C., washed and dried to obtain a purified product. In the resulting modified cellulose compound (B-2), 55.8% of the hydroxyl groups had reacted with the isocyanate compound.

(Synthesis Example 4) 4.32 parts by weight of 2-hydroxypropyl methacrylate, 0.01 part by weight of diphenyltin diacetate, and 1 part by weight of methyl ethyl ketone were put into a reactor, and cyclohexane was heated to a temperature of 80 ° C. 4.92 parts by weight of -1,3-diisocyanate was sequentially added dropwise, and the mixture was further reacted at 75 ° C. for 5 hours to obtain a urethane methacrylate compound.

Then, hydroxyethyl cellulose (weight average molecular weight of about 350,000, hydroxyethyl etherification degree of 60% (-OCH ₂ C bound in cellulose)
Assuming that the degree of repetition of the H ₂ -segment is 1, 60% of the hydroxyl groups in the cellulose are etherified)) 12 parts by weight, methyl ethyl ketone 4
Parts by weight and 0.01 parts by weight of diphenyltin diacetate were placed in a reactor, and the above-mentioned urethane methacrylate compound reaction solution was sequentially dropped while heating to a temperature of 80 ° C., and further reacted at 80 ° C. for 7 hours.

After cooling the reaction product, it was filtered, and the obtained crude product was poured into hot water of 90 ° C., washed and dried to obtain a purified product. In the obtained modified cellulose compound (A-4), 14.7% of the hydroxyl groups had reacted with the isocyanate compound.

(Synthesis Example 5) 6.54 parts by weight of triethylene glycol monomethacrylate, 0.01 part by weight of diphenyltin diacetate, and 1 part by weight of methyl ethyl ketone were placed in a reactor, and heated at a temperature of 80 ° C. , 4
5.23 parts by weight of tolylene diisocyanate were sequentially added dropwise, and the mixture was further reacted at 75 ° C. for 5 hours to obtain a urethane methacrylate compound.

Next, methyl cellulose (weight average molecular weight: about 10,000, methyl etherification degree: 20% (when the repetition degree of —OCH ₂ CH ₂ —segment bonded to cellulose is 1; % Is etherified)) 12 parts by weight, 4 parts by weight of methyl ethyl ketone and 0.01 part by weight of diphenyltin diacetate
The reaction solution of the urethane methacrylate compound was sequentially dropped while heating to ℃, and the reaction was further carried out at 80 ℃ for 7 hours.

The reaction product was cooled, filtered, and the obtained crude product was poured into hot water of 90 ° C., washed and dried to obtain a purified product. In the obtained modified cellulose compound (A-5), 26.7% of the hydroxyl groups had reacted with the isocyanate compound.

Example 1 The following compounds (1) to (5) were well stirred and kneaded to prepare a photopolymerizable resin composition. (1) 20 parts by weight of the modified cellulose compound (A-1) synthesized in Synthesis Example 1 (2) 1 part by weight of 2,4-diethylthioxanthone (3) 3 parts by weight of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide (4) PbO-ZnO-B 2 O 3 based glass powder (average particle size 10 [mu] m) 100 parts by weight (5) dimethylbenzyl ketal (polymerization inhibitor) 0.3 part by weight then, the photopolymerizable resin composition 125 Using a mesh / inch screen, a dried film thickness of 2 was formed on a PDP glass substrate on which a wiring pattern was previously formed.
The entire surface was coated so as to have a thickness of 5 μm, and dried at 80 ° C. for 1 hour. After drying, 150mJ / c through the required negative mask
Exposure with an active energy dose of m ² ,
Spray developed for 0 seconds. At this time, the coating property of the photopolymerizable composition, and the chipping and peeling of the pattern after exposure and development were observed. Table 1 shows the results.

Next, the obtained plasma display (P
The glass substrate for DP) is heated in an electric furnace at a temperature of 540 to 56.
By firing at 0 ° C. for 5 hours, a priming rib of PDP was formed. Chipping, peeling, discoloration,
And display unevenness of pixels of a PDP manufactured using the same. Table 1 shows the results.

Comparative Example 1 In Example 1, the modified cellulose synthesized in Comparative Example 1 was replaced with 20 parts by weight of the modified cellulose compound (A-1) synthesized in Synthesis Example 1 as the component (1). The test and evaluation were performed in the same manner as in Example 1 except that 20 parts by weight of the cellulose compound (B-1) was used. Table 1 shows the results.

Example 2 In Example 1, the modified cellulose synthesized in Synthesis Example 2 was replaced with 20 parts by weight of the modified cellulose compound (A-1) synthesized in Synthesis Example 1 as the component (1). The test and evaluation were performed in the same manner as in Example 1 except that 20 parts by weight of the compound (A-2) was used. Table 1 shows the results.

Example 3 In Example 1, the modified cellulose synthesized in Synthesis Example 2 was replaced with 20 parts by weight of the modified cellulose compound (A-1) synthesized in Synthesis Example 1 as the component (1). The test and evaluation were performed in the same manner as in Example 1 except that 20 parts by weight of the compound (A-3) was used. Table 1 shows the results.

(Comparative Example 2) In Example 1, the modified cellulose synthesized in Comparative Synthesis Example 2 was replaced with 20 parts by weight of the modified cellulose compound (A-1) synthesized in Synthesis Example 1 as the component (1). The test and evaluation were performed in the same manner as in Example 1 except that 20 parts by weight of the cellulose compound (B-2) was used. Table 1 shows the results.

Example 4 The following compounds (1) to (6) were well stirred and kneaded to prepare a photopolymerizable resin composition. (1) 20 parts by weight of the modified cellulose compound (A-4) synthesized in Synthesis Example 4 (2) 1 part by weight of 2,4-diethylthioxanthone (3) 3 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (4) PbO-ZnO-B 2 O 3 based glass powder (average particle size 10 [mu] m) 5 parts by weight (5) silver powder (average particle size 10 [mu] m) 100 parts by weight (6) dimethylbenzyl ketal (polymerization inhibitor) 0. 3 parts by weight Next, this photopolymerizable resin composition was dried on a glass substrate for PDP on which a wiring pattern had been formed in advance using a 125-mesh / inch screen to a thickness of 2 after drying.
The entire surface was coated so as to have a thickness of 5 μm, and dried at 80 ° C. for 1 hour. After drying, 400mJ / c through the required negative mask
Exposure with an active energy dose of m ² ,
Spray developed for 0 seconds. At this time, the coating property of the photopolymerizable composition, and the chipping and peeling of the pattern after exposure and development were observed. Table 1 shows the results.

Next, the obtained glass substrate for PDP is baked in an electric furnace at a temperature of 540 to 560 ° C. for 5 hours.
Was formed. The priming rib after formation was examined for chipping, peeling, discoloration, and display unevenness of pixels of a plasma display panel manufactured using the same. Table 1 shows the results.

[0072]

[Table 1]

Example 5 The compounds (1) to (4) shown below were mixed for 1 hour with a mixer, followed by filtration through a 70 μm glass filter to prepare a resin composition. (1) 20 parts by weight of the modified cellulose compound (A-5) synthesized in Synthesis Example 5 (2) 100% by weight of a 10% aqueous solution of butyralized PVA (manufactured by Sekisui Chemical Co., Ltd .: Esrec KW-10, degree of butyralization: 8%) Part (3) 25 parts by weight of an acrylic polymer emulsion (manufactured by Taisei Kayaku Co., Ltd .: AC-120T1) (solid content: 30%) (4) 0.05 part by weight of an ultraviolet absorber (manufactured by Shonan Chemical Co., Ltd .: ASL-24S) 100 parts by weight of the above resin composition, as a diazo compound, 3
-Methoxy-4-diazodiphenylamine sulfate and 4,
4 parts by weight of a 10% aqueous solution of a condensate of 4'-methoxydiphenyl ether in a phosphoric acid bath (condensation ratio: 2: 1) was added, stirred, and then defoamed to obtain a photopolymerizable resin composition. The photopolymerizable resin composition was applied once on a 120-mesh screen frame in the order of a printing surface and a squeegee surface.
Dry at 0 ° C. for 20 minutes. The same process was repeated once more to prepare a photosensitive screen having a thickness of 5 μm.

The screen was irradiated with ultraviolet light having an energy amount of 300 mJ / cm ² through a negative mask capable of reproducing a thread pattern having a ratio of image portion to opening portion of 9: 1, immersed in water for 2 minutes, and spray pressure applied thereto. Spray development was carried out with 40 kg / cm ² of water. After performing this developing operation twice,
After drying at 40 ° C. for 20 minutes, post-exposure was performed with ultraviolet rays of 1000 mJ / cm ² . Pinholes in the image and opening,
No scum or the like was observed. A 1: 1 mixture of a 4% glutaraldehyde aqueous solution and a 2% hydrochloric acid aqueous solution was applied to the image area with a sponge, and air blown for 2 minutes.
After drying at 0 ° C. for 20 minutes, a screen printing plate was completed. When the obtained screen printing plate was printed using a printing press for printing paste, 10,000 sheets could be printed.

[0075]

As described in detail above, according to the present invention,
It has the property of being easily decomposed and volatilized even when baked, has excellent releasability, can enhance elasticity and flexibility, and has good adhesion to the substrate, so it can be used as a UV-curable resin paint or screen. A photopolymerizable resin composition suitable for use in forming a printing plate, a resist for lift-off, a priming rib of a PDP, a resistance pattern, a conductive pattern, and the like can be provided.

[Brief description of the drawings]

FIG. 1 is a conceptual explanatory view showing a process of forming a pattern using a photopolymerizable resin composition of the present invention.

[Explanation of symbols]

 Reference Signs List 1 substrate 2 photoresist layer 3 mask pattern 4 resist pattern

Claims (7)

[Claims] 1. A modified cellulose compound in which 1 to 50% of hydroxyl groups of cellulose or a cellulose derivative are substituted by urethane (meth) acrylate groups. 2. The substitution of a hydroxyl group by the urethane (meth) acrylate group is carried out by reacting (I) a diisocyanate compound with a (meth) acrylate compound having a hydroxyl group so that only one isocyanate group is urethanized. And (II) reacting the other isocyanate group of the diisocyanate compound with a hydroxyl group in cellulose or a cellulose derivative in a reaction rate of the hydroxyl group of 1 to 50%. The modified cellulose compound according to the above. 3. A weight average molecular weight of 8,000 to 500,
The modified cellulose compound according to claim 1, which has a molecular weight of 000. 4. A weight average molecular weight of 10,000 to 15.
3. The modified cellulose compound according to claim 1, which has a molecular weight of 000. 5. A photopolymerizable resin composition comprising (a) the modified cellulose compound according to any one of claims 1 to 4 and (b) a photopolymerization initiator. 6. A photopolymerizable resin composition comprising the photopolymerizable resin composition according to claim 1 and further comprising (c) an ethylenic compound. 7. A photopolymerizable resin composition comprising the photopolymerizable resin composition according to claim 1, further comprising (d) an inorganic and / or metal powder.