KR101855239B1 - Blocked isocyanato group-containing polymer, composition containing polymer, and applications thereof - Google Patents

Abstract

An acid group, a polymerizable unsaturated group and a curable polymer having a block isocyanato group and a weight average molecular weight of 1,000 to 50,000 in terms of polystyrene, preferably an acid value of 20 to 300 KOH mg / g, an unsaturated group equivalent of 100 to 4,000 g / ㏖ and a block having a socyanate equivalent of 400 to 6,000 g / mol. The curable polymer and the solvent are mixed, a reactive diluent, a photopolymerization initiator, and a colorant are further compounded to prepare a photosensitive material for a color filter. After forming a pattern by using it, baking is preferably performed at a temperature of 210 캜 or less, A filter is obtained.

Description

BLOCKED ISOCYANATO GROUP-CONTAINING POLYMER, COMPOSITION CONTAINING POLYMER, AND APPLICATIONS THEREOF BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a novel curable polymer containing a cyanine group and a use thereof, and more particularly to a curable polymer suitable as a photosensitive material for a color filter, a polymer composition comprising the curable polymer, An initiator, a color filter formed of the photosensitive polymer composition, a method of producing the color filter, and an image display device comprising the color filter.

In recent years, photosensitive polymer compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in various fields of coatings, printing, paints, and adhesives from the viewpoints of resource saving and energy saving. Also, in the field of electronic materials such as printed wiring boards, photosensitive polymer compositions that can be cured by active energy rays are used for solder resists, resists for color filters, and the like.

The color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundary between the pixels, As shown in FIG. A color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. As a method of forming a pixel and a black matrix (hereinafter, a pixel and a black matrix will be referred to as a "colored pattern"), various manufacturing methods have been proposed. Among them, the pigment / dye dispersion method, which is produced by a photolithography method in which a photosensitive polymer composition is used as a resist and is repeatedly applied, exposed, developed and baked, is excellent in durability such as light resistance and heat resistance, It is the present mainstream because it gives a pattern.

Generally, the photosensitive polymer composition used in the photolithography process contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. On the other hand, the pigment / dye dispersion method has the above-mentioned merits, while the alkali-soluble resin that becomes the binder of the coating film is required to have high heat-resistant decomposition resistance and heat-resistant yellowing resistance in that the black matrix, R, G and B patterns are repeatedly formed . As a new material according to this demand, the present inventors have previously proposed a structure derived from an alkylene oxide represented by an alicyclic monomer and ethoxylated o-phenylphenol (meth) acrylate (i.e., 2-phenylphenoxyethyl (Meth) acrylate having an aryl moiety is used (Patent Document 1).

When this copolymer is used, it is possible to obtain a photosensitive polymer composition having excellent heat decomposition resistance and heat resistance yellowing resistance as compared with resins conventionally known and having a monomer containing maleimide as a copolymerization component. The copolymer preferably contains a carboxyl group in the molecule and preferably has an acid value of 20 to 300 KOH mg / g (see claim 2 of patent document 1) and more preferably has an unsaturated group in the molecule 1). However, in the photosensitive polymer composition prepared using this copolymer, a pattern showing excellent performance can be obtained by baking the coated film after alkali development at a high temperature such as 230 DEG C. However, if the baking temperature is lower than 200 DEG C, And the reliability of the resulting color filter is not sufficient. In general, when a dye is used as a coloring material, it is expected that a coloring pattern having a higher luminance is obtained as compared with the case of using a pigment. However, when the copolymer is used as a dye dispersion method, The expected performance of the material for use could not be obtained.

Further, when a copolymer of para-cumylphenol with ethylene oxide (EO) modified or propylene oxide (PO) modified (meth) acrylate with (meth) acrylic acid and / or (meth) acrylate is used, It is also known that an excellent photosensitive coloring composition can be obtained and the sensitivity of the photosensitive coloring composition can be improved by introducing an ethylenic double bond into the side chain of the copolymer (Patent Document 2). However, as described in Patent Document 1, the heat resistance of this material is not sufficient, and the solvent resistance of the pattern obtained when curing at a baking temperature of relatively low temperature below 200 DEG C after alkali development is not necessarily sufficient .

On the other hand, a photosensitive polymer composition containing a polymer (a) having a block-derived constituent unit derived from a isocyanato compound, a photopolymerizable monomer (b) and a photopolymerization initiator (c) (Patent Document 3). It is described that the polymer (a) preferably contains an acid group in the molecule and can thereby have good developing properties (see paragraph 0024). However, this material is superior in terms of adhesion of the resin pattern to the substrate, but there is a problem in that development is difficult when the amount of exposure is small.

WO 2012/141000 Japanese Patent Application Laid-Open No. 2004-101728 Japanese Patent Application Laid-Open No. 2010-197567

The main object of the present invention is to provide a photosensitive composition which is excellent in sensitivity and developability when used as a material for a photosensitive polymer composition and exhibits sufficient solvent resistance even when the baking temperature at the time of pattern formation is lowered And a curable polymer. Another object of the present invention is to provide a polymer composition capable of forming a coating film excellent in solvent resistance. Another object of the present invention is to provide a photosensitive polymer composition suitable as a material for a color filter capable of forming a pattern excellent in sensitivity and developing property and excellent in solvent resistance even at a low baking temperature, And a method of manufacturing the same, and an image display device having the color filter.

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the inventors of the present invention have found that when an acid value and a polymerizable unsaturated group described in Patent Documents 1 and 2 and a curable polymer containing a socyanato group in a block described in Patent Document 3 It has been found that when used as a material for a photosensitive polymer composition, not only excellent developability and sensitivity at the time of alkali development but also excellent solvent resistance of the obtained pattern are obtained even when the baking temperature at the time of pattern formation is lowered, .

As described above, according to the present invention, as the first invention, there is provided a curable polymer characterized by having an acid group, a polymerizable unsaturated group and a block containing a socyanato group in the molecule and having a weight average molecular weight in terms of polystyrene of 1,000 to 50,000. As a second invention, there is provided a polymer composition containing the curable polymer (A), the solvent (B) and the optionally added reactive diluent (C), and as the third invention, the curable polymer (A), the solvent ), A reactive diluent (C), a photopolymerization initiator (D) and optionally a coloring material (E). As a fourth aspect of the invention, there is provided a color filter formed using the photosensitive polymer composition, wherein as the fifth invention, the photosensitive material including a coloring material is applied to a substrate, exposed through a mask, A method of manufacturing a color filter that bakes at a temperature of 210 DEG C or less is provided, and as an image display device having the color filter as a sixth invention, there is provided.

(Effects of the Invention)

According to the present invention, a photosensitive polymer composition comprising the curable polymer capable of forming a cured coating film having sufficient solvent resistance even when the baking temperature at the time of forming a pattern is low, as well as sensitivity and developability are good and a curable polymer composition containing the curable polymer is obtained . Further, the cured coating film formed from the photosensitive polymer composition of the present invention is excellent in sensitivity and developability, and also has excellent solvent resistance, and thus has a very high value in use in various types of resists. In particular, it is used as a photosensitive material for color filters A color filter having a coloring pattern excellent in solvent resistance can be obtained. Further, even if the baking temperature is lowered, since the crosslinking reaction proceeds sufficiently, a coloring material having a difficulty in heat resistance can be used, and energy consumption can also be reduced.

The curable polymer of the present invention contains an acid group, a polymerizable unsaturated group and a block in a molecule and has a weight average molecular weight in terms of polystyrene of 1,000 to 50,000. Incidentally, in the present specification, this polymer is referred to as a " curable polymer " in that the polymerizable unsaturated group present in the polymer molecule contributes to the crosslinking reaction between the polymers.

The structure of the curable polymer is not particularly limited as long as it contains an acid group, a polymerizable unsaturated group and a block isocyanato group in the molecule, but usually the following (a) block has a polymerization unit of a monomer containing a isocyanato group, Is shown in the following (I) or (II).

(I) an unsaturated monomer containing a functional group reactive with an acid group is reacted with a copolymer of (a) a block-containing isocyanato group-containing monomer, (b) an unsaturated acid monomer and (d) A modified polymer into which a polymerizable unsaturated bond is introduced.

(C) a copolymer of unsaturated monomers having functional groups reactive with an acid group and (d) other monomers optionally used; (e) unsaturated monobasic acids and (d) f) a modified polymer obtained by reacting a dibasic acid or its anhydride monomer to introduce an acid group and a polymerizable unsaturated bond into the side chain.

≪ Preparation of Curable Polymer (I) >

The curable polymer represented by the above formula (I) is prepared by copolymerizing the block-containing monomer with a cyanato group, (b) an unsaturated acid monomer and (d) other monomer used according to a desired method according to a conventional method to prepare a precursor of a curable polymer (B) reacting an unsaturated monomer having a functional group reactive with the acid group with an acid group derived from an unsaturated acid monomer, and introducing a polymerizable unsaturated bond into the side chain.

≪ Monomer used for preparing precursor of curable polymer &

Blocks used in the production of copolymers The isocyanate group-containing monomer is a block-blocked isocyanate group in an isocyanate compound having a reactive ethylenically unsaturated group such as a vinyl group or a (meth) acryloyloxy group in the molecule. The preferable isocyanate compound is a compound represented by the following formula (1).

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is -CO-, -COOR ³ - (R ³ is an alkylene group having 2 to 6 carbon atoms), or -COO-R ⁴ O- CONH-R ⁵ wherein R ⁴ is an alkylene group having 2 to 6 carbon atoms and R ⁵ is an alkylene group or an arylene group having 2 to 12 carbon atoms which may have a substituent. R ² is preferably -COOR ³ -, and particularly preferably R ³ is an alkylene group having 1 to 4 carbon atoms.

Specific examples of the isocyanate compound represented by the above formula (1) include 2-isocyanate ethyl (meth) acrylate, 2-isocyanate propyl (meth) acrylate, 3-isocyanate propyl (meth) Methyl (meth) acrylate, 2-isocyanate-1,1-dimethylethyl (meth) acrylate, 4-isocyanate cyclohexyl (meth) acrylate and methacryloyl isocyanate. Also, a 1: 1 reaction product of 2-hydroxyalkyl (meth) acrylate (preferably an ethyl group or an n-propyl group as the alkyl group, and particularly preferably an ethyl group) and a diisocyanate compound can be used. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI) (Isocyanatomethyl) cyclohexane, lysine diisocyanate, and the like can be used in the present invention. Examples of the diisocyanate include trimethyl-3-isocyanate methylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, . (Meth) acrylate, particularly 2-isocyanate ethyl (meth) acrylate and 2-isocyanate (meth) acrylate, in which R ^{3 in} the formula (1) is an alkylene group having 1 to 4 carbon atoms, Propyl (meth) acrylate is preferable.

In the present specification, the term (meth) acrylate means that either acrylate or methacrylate may be used, and the notation of (meth) acrylic acid may be any of acrylic acid and methacrylic acid It means.

Examples of the blocking agent include lactam-based compounds such as? -Caprolactam,? -Valerolactam,? -Butyrolactam and? -Propiolactam; Alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol and cyclohexanol; Butylphenol such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol and p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, Phenol compounds such as thymol, p-naphthol, p-nitrophenol and p-chlorophenol; Active methylenes such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone; Mercaptan systems such as butyl mercaptan, thiophenol and tert-dodecyl mercaptan; Amines such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Acid amides such as acetanilide, acetanisidide, acetic acid amide and benzamide; Acid imide systems such as succinic acid imide and maleic acid imide; Imidazole compounds such as imidazole, 2-methylimidazole and 2-ethylimidazole; Urea, thiourea, urea; Carbamates such as phenyl N-phenylcarbamate and 2-oxazolidone; Ethylene imine, polyethylene imine and the like; Oxime compounds such as formaldehyde, formaldehyde, acetaldehyde, acetoxime, methylethylketooxime, methylisobutylketooxime and cyclohexanone oxime; Sodium sulfate, sodium bisulfite, and potassium bisulfate.

These block agents may be used alone or in combination of two or more. Among them, lactam-based and alcohol-based blocking agents are preferable, and? -Caprolactam and 1-methoxy-2-propanol (that is, propylene glycol monomethyl ether) are particularly preferable.

The blocking group protects the highly reactive isocyanate group, but the blocking group is eliminated by heating, and an isocyanate group appears. In the present invention, the isocyanate group reacts with a reactive functional group contained in the curable polymer or the reactive diluent (that is, a hydroxyl group or an amino group included in an acid group or a desired state) to form a cured product having a high crosslinking density.

A preferred block isocyanate compound has a dissociation temperature of 100 to 200 캜, more preferably 140 to 190 캜, particularly 150 to 180 캜. As specific examples of such a compound, methacryloyloxyethyl (meth) acrylate represented by the following formula (Reaction product of methacryloyloxyethyl isocyanate and propylene glycol monomethyl ether represented by the following formula (3) (the reaction product of isocyanate, i.e., 2-isocyanate ethyl methacrylate and? -Caprolactam Karenz MOI-BM (a reaction product of methacryloyloxyethyl isocyanate and methyl ethyl ketoxime, SHOWA DENKO KK, dissociation temperature of 130 占 폚), Karenz MOI-BP (methacryloyloxyethyl isocyanate And 3,5-dimethylpyrazole, SHOWA DENKO KK, dissociation temperature 110 DEG C), acrylates corresponding to these, and the like.

The dissociation temperature of the block isocyanate compound was adjusted by adjusting an n-octanol solution having a compound concentration of 20% by mass, and adding thereto 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine ) Was added, and the reduction ratio of the compound after heating at a predetermined temperature for 30 minutes was measured by HPLC analysis. The temperature at which the reduction ratio became 80% or more was defined as the dissociation temperature.

If the dissociation temperature of the block isocyanate compound is excessively lowered, the storage stability of the resulting polymer is lowered and a crosslinking reaction which is not intended at the time of the modification reaction which will be described later is likely to occur. On the other hand, It is difficult to improve the solvent resistance of the cured coating film.

The reaction of the isocyanate compound with the blocking agent can be carried out regardless of the presence or absence of the solvent. When a solvent is used, it is necessary to use a solvent which is inert to the isocyanate group. In the blocking reaction, organic metal salts such as tin, zinc and lead, tertiary amines and the like may be used as catalysts. The reaction can be carried out generally at -20 to 150 ° C, but preferably at 0 to 100 ° C.

The unsaturated acid monomer (b) used in the production of the copolymer is not particularly limited as long as it has a polymerizable unsaturated bond and an acid group, and examples thereof include unsaturated carboxylic acid or its anhydride, unsaturated sulfonic acid and unsaturated phosphonic acid. Specific examples of preferred unsaturated acid monomers include (meth) acrylic acid,? -Bromo (meth) acrylic acid,? -Furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid,? -Cyanosinic acid, Unsaturated carboxylic acids or their anhydrides such as acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride; Unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butyl acrylamide sulfonic acid and p-styrenesulfonic acid; And unsaturated phosphonic acids such as vinyl phosphonic acid and the like. Among these, (meth) acrylic acid is preferable. These monomers may be used alone or in combination of two or more. the alkali developability when the curable polymer obtained by using (b) an unsaturated acid monomer as a copolymer component is used as a photosensitive material is greatly improved.

In the present invention, (a) a block containing a cyanocitric group-containing monomer, (b) an unsaturated acid monomer and (d) other monomer copolymerizable therewith can be used in combination. (d) Specific examples of other monomers include styrene,? -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, , aromatic vinyl compounds such as m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene and p-acetylaminostyrene;

(Biscyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] Cyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca- Cyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] deca-8-ene, tricyclo [5.2.1.0 ^{2, 6} ] deca-3-ene, tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene, tricyclo [6.2.1.0 ^1,8 ] undeca-9-ene, tricyclo [6.2.1.0 ^{1 8} ] undeca-4-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,12] dodeca-3-ene, 8-ethylidene tetracyclo [4.4 .0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, penta-cyclo [6.5.1.13.6.0 ^9,13 .0 ^2,7] deca-penta-4-ene, bicyclo cyclopenta [ 7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] ^pentadec -3-ene. Cyclic olefins;

Dienes such as butadiene, isoprene and chloroprene;

Propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (Meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (Meth) acrylate, norbornyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (Meth) acrylate, 5-ethyl norbornyl (meth) acrylate (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl acrylate isobornyl (meth) acrylate, adamantyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, perfluoro (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (Meth) acrylate, cumyl (meth) acrylate, 4-phenoxy (meth) acrylate, (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, biphenyloxyethyl (Meth) acrylate (Meth) acrylic acid ester of a byte, anthracene (meth) acrylate and the like;

(Meth) acrylic acid amide, N, N-dimethyl amide, N, N-diethyl amide, N, N-dipropyl amide, (Meth) acrylamides such as isopropyl amide and anthracenyl amide (meth) acrylate;

Vinyl compounds such as (meth) acrylate anilide, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinylidene fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate and vinyltoluene;

Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate;

And monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide. These may be used alone or in combination of two or more.

Of these, aromatic vinyl compounds and cyclic olefins are preferably used. When the aromatic vinyl compound is copolymerized, heat resistance and pigment dispersibility are improved, and when the cyclic olefin is copolymerized, heat resistance, vulcanization resistance and pigment dispersibility are improved.

The proportion of the (a) block-containing isocyanato group-containing monomer, (b) the unsaturated acid monomer and (d) other monomer used in the production of the precursor is usually from 1 to 50 mol% , Preferably 3 to 40 mol%, more preferably 5 to 20 mol%, and (b) 20 to 90 mol%, preferably 30 to 70 mol%, and more preferably 40 to 60 mol% of the unsaturated acid monomer (D) 0 to 79 mol%, preferably 5 to 67 mol%, and more preferably 20 to 55 mol% of other monomers.

If the monomer (a) contains too little socyanate group-containing monomer, the solvent resistance of the cured coating film is not sufficiently improved. On the other hand, if the monomer is excessively large, the storage stability of the precursor polymer is deteriorated and the physical properties of the coating film tend to be difficult . On the other hand, when the unsaturated acid monomer (b) is excessively small in the amount of the unsaturated acid monomer (a), the rate of alkali development becomes slow when it is used as a photosensitive polymer, and conversely, when it is excessively large, it becomes difficult to form a precise and dense pattern. In the production of the precursor, (d) other monomers are not necessarily essential, but by using the monomers of (d) in combination, the heat resistance, pigment dispersibility, and film properties can be suitably improved. In particular, when aromatic vinyl compounds or cyclic olefins are used as the monomer (d), heat resistance, vulcanization resistance and pigment dispersibility are improved as described above, and therefore, it is preferable to use an appropriate amount of these monomers.

The copolymerization reaction of (a) the block-containing isocyanate group-containing monomer, (b) the unsaturated acid monomer and (d) the other monomer used as desired is carried out in the presence or absence of a polymerization solvent according to the radical polymerization method well- It can be done in the absence. For example, these monomers may be dissolved in a solvent as desired, the polymerization initiator may be added to the solution, and the polymerization reaction may be carried out at 50 to 130 ° C for 1 to 20 hours. At this time, when the polymerization is carried out at a temperature at which the block is decomposed, the isocyanate group generated by decomposition reacts with the acid group to form a gel. Therefore, the temperature at which the block is below the dissociation temperature of the sausage and the earthenware, It is preferable to carry out the polymerization at a temperature lower than about 50 캜.

Examples of the solvent that can be used in the copolymerization reaction include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as ethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Methyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylacetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, Propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propyl acetate, n-butyl acetate, Esters such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

And carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among them, a (poly) alkylene glycol monoalkyl ether solvent such as propylene glycol monomethyl ether and a (poly) alkylene glycol monoalkyl ether acetate solvent such as propylene glycol monomethyl ether acetate, that is, a glycol ether solvent is preferable .

The amount of the polymerization solvent to be used is not particularly limited, but it is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass when the total amount of monomer injected is 100 parts by mass. Particularly, when the amount of the solvent to be used is 1,000 parts by mass or less, the decrease in the molecular weight of the copolymer due to the chain transfer action can be suppressed, and the viscosity of the copolymer can be controlled within an appropriate range. In addition, by making the amount of the solvent to be 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and the coloring and gelation of the copolymer can be prevented.

The polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisobalonitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. . These may be used alone or in combination of two or more. The amount of the polymerization initiator to be used is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers to be injected.

≪ Preparation of Curable Polymer (I) >

In the present invention, the addition copolymer thus prepared is used as a precursor of the curable polymer (I). This precursor contains an acid group derived from an unsaturated acid monomer (b), and an unsaturated monomer having a functional group reactive with the acid group (c) is reacted with the acid group to introduce a polymerizable unsaturated bond into the side chain, A curable polymer (I) having a polymerizable unsaturated group and a blocked isocyanato group in the molecule and having a weight average molecular weight in terms of polystyrene of 1,000 to 50,000 can be obtained. The presence of polymerizable unsaturated bonds in the molecule greatly improves sensitivity and developability when the curable polymer is used as a photosensitive material for a color filter.

Preferable examples of the unsaturated monomer having a functional group reactive with the acid group (c) to be provided in this reaction are unsaturated compounds having functional groups such as an epoxy group, a hydroxyl group, an amino group and a vinyl ether group, and specific examples thereof include glycidyl (meth) 3,4-epoxycyclohexylmethyl (meth) acrylate having alicyclic epoxy and its lactone adduct (for example, CYCLOMER A200, M100 manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), 3,4-epoxycyclohexyl A mono (meth) acrylic acid ester of methyl-3 ', 4'-epoxycyclohexanecarboxylate, an epoxide of dicyclopentenyl (meth) acrylate, an epoxide of dicyclopentenyloxyethyl (meth) A radically polymerizable monomer having an epoxy group; (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl Radopolymerizable monomers having a hydroxy group such as hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate and allyl alcohol; Radical-polymerizable monomers having an amino group such as 4-aminostyrene; And radically polymerizable monomers having a vinyl ether group such as 2-vinyloxyethoxyethyl (meth) (meth) acrylate. Among them, when a radically polymerizable monomer having an epoxy group is used, a hydroxy group is simultaneously generated when an unsaturated bond is introduced by reaction with an acid group, and the acid group can be easily introduced by using this hydroxy group.

The reaction between the precursor and (c) the unsaturated monomer having a functional group reactive with an acid group can be carried out according to a conventional method. For example, both components are added to a reaction solvent, and a polymerization inhibitor and a catalyst are further added to the reaction mixture to remove the block in the precursor at a temperature at which the socyanate group is not decomposed, for example, 50 to 150 ° C, Lt; 0 > C. In this denaturation reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included, so that the denaturation reaction can be performed without removing the solvent after completion of the copolymerization reaction.

When the denaturation reaction is carried out, a polymerization inhibitor is added to prevent gelation, if necessary. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether and the like. Examples of the catalyst include, but are not limited to, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. .

Thus, a curable polymer (I) having a weight average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000 in terms of polystyrene can be obtained. If the molecular weight is less than 1,000, defects in the coloring pattern tend to occur after alkali development when used as a photosensitive polymer composition. On the other hand, when the molecular weight exceeds 50,000, development time becomes too long and practicality is lost.

The acid value of the curable polymer (JIS K6901 5.3) can be appropriately selected, but is generally in the range of 20 to 300 KOH mg / g, preferably 30 to 200 KOH mg / g when used as a photosensitive polymer. If the acid value is less than 20 KOH mg / g, the alkali developability as a photosensitive polymer may be deteriorated. On the other hand, if the acid value exceeds 300 KOH mg / g, the exposed portion (photocured portion) tends to dissolve in the alkaline developer and the pattern shape may become insufficient.

The unsaturated group equivalent of the curable polymer (I) is not particularly limited, but is usually in the range of 100 to 4,000 g / mol, preferably 300 to 2,000 g / mol. The equivalent of an unsaturated group of 100 g / mol or more is effective in enhancing physical properties and alkali developability of the coating film, and conversely, an unsaturated group equivalent of less than 4,000 g / mol is effective to further increase the sensitivity. The unsaturated bond equivalent is the mass of the polymer per mol of the unsaturated bond of the polymer, which can be obtained by dividing the mass of the polymer by the amount of unsaturated bonds in the polymer (g / mol). In the present invention, the unsaturated bond equivalent is a theoretical value calculated from the amount of the raw material used for introducing the unsaturated bond.

In the curable polymer (I) of the present invention, the block contains a socyanato group in the molecule. The content of the socyanate group in the block may be suitably selected, but is usually selected in the range of the block and socianeto-group equivalent of 400 to 6,000, preferably 1,000 to 5,000. Socianeto group equivalent of the block is obtained by dividing the mass of the polymer by the number of moles of the isocyanato group in the block contained in the polymer, wherein the block contained in the polymer is the mass of the polymer per 1 mole of the socioanthochie (g / mol) . In the present invention, the equivalent amount of the block-like isocyanate group is a theoretical value calculated from the amount of the block-containing monomer containing the isocyanate group.

≪ Preparation of Precursor of Curable Polymer (II) >

The curable polymer represented by the above formula (II) is obtained by copolymerizing (c) a monomer having a functional group reactive with an acid group and (d) other monomers which are used as desired, (E) an unsaturated monobasic acid and (f) a polybasic acid or an anhydride thereof to a precursor of the curable polymer (II), and introducing an acid group and a polymerizable unsaturated bond into the side chain.

≪ Monomer used for producing a precursor of the curable polymer (II) >

The (a) block-containing isocyanato group-containing monomer and the (d) other monomer used for producing this precursor are the same as those used for the production of the curable polymer (I). In the case of the curable polymer (I), an unsaturated monomer (b) is used as an essential component, but in the case of the curable polymer (II), an unsaturated monomer having a functional group reactive with an acid group (c) Is used. Specific examples of the component (c) are the same as those used in the production of the curable polymer (I), and unsaturated monomers having an epoxy group, in particular glycidyl (meth) acrylate, are preferably used.

The precursor is produced in the same manner as in the case of the curable polymer (I). By reacting the obtained precursor with (e) an unsaturated monobasic acid and (f) a polybasic acid or an anhydride thereof, an acid group and a polymerizable unsaturated bond are formed. The unsaturated monobasic acid used herein may be exemplified as the unsaturated acid monomer (b) used in the production of the curable polymer (I), and (f) the polybasic acid or its anhydride may be any of those exemplified as unsaturated acid monomers (b) Unsaturated polybasic acids and their anhydrides as well as unsaturated polybasic acids and their anhydrides which do not have polymerizability, saturated polybasic acids and their anhydrides. Specific examples of such compounds include malonic acid, succinic acid, glutaric acid, adipic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, Dibasic acid such as norbornene-2,3-dicarboxylic acid and phthalic acid, tribasic acid such as trimellitic acid and the like, pyromellitic acid and the like, and anhydrides thereof. Of these, dicarboxylic acid anhydrides are preferably used.

When the precursor is a copolymer of an unsaturated monomer having an epoxy group, (e) reacting the unsaturated monobasic acid causes cleavage of the epoxy group in the molecule to introduce an unsaturated bond into the side chain and at the same time to generate a hydroxy group. The acid group is introduced by reacting (f) with a polybasic acid or its anhydride using this hydroxy group. When the precursor is a copolymer of an unsaturated monomer having a hydroxyl group, the unsaturated monobasic acid (e) and the polybasic acid or its anhydride are reacted to introduce an unsaturated bond into the side chain, and an acid group can be introduced have.

These modifying reactions may be carried out according to a conventional method. For example, both components may be added to a reaction solvent, and a polymerization inhibitor and a catalyst may be further added to the reaction mixture to form a block in the precursor under a temperature at which the isocyanato group is not decomposed, The reaction may be carried out at 150 ° C, preferably 80 to 130 ° C. Thus, a curable polymer (II) having an intended acid group, polymerizable unsaturated group and block-containing isocyanato group in the molecule and having a weight average molecular weight in terms of polystyrene of 1,000 to 50,000 can be obtained. The range of the weight average molecular weight, acid value and unsaturated bond equivalent of this curable polymer (II) is the same as in the case of the curable polymer (I).

The curable polymer in the present invention is represented by the modified polymers of the above (I) and (II), but is not limited by the production method as far as the acid group, the polymerizable unsaturated group and the block contain a socyanato group. For example, the objective curable polymer can also be obtained by the following method.

(1) synthesizing a precursor by using an unsaturated monomer containing a monomer having an isocyanate group and an epoxy group in the block, reacting the polybasic acid anhydride to introduce an acid group, and then reacting the 2- (meth) acryloyloxyethyl isocyanate, And an isocyanate compound containing an unsaturated bond such as 2- (meth) acryloylethyl isocyanate is reacted with a hydroxy group formed by cleavage of an epoxy group.

(2) synthesizing a precursor using a monomer having a block isocyanate group and an unsaturated monomer containing a hydroxyl group, and then reacting the hydroxyl group in the molecule with an isocyanate compound containing a polybasic acid anhydride and an unsaturated bond to introduce an acid group and an unsaturated bond Way.

(3) a precursor containing a functional group (for example, a hydroxyl group or an amino group) reactive with an acid group and an isocyanate group is prepared without using a monomer containing a socioanthoruber group, and then the unsaturated bond is removed by any one of the methods described above And then introducing a block isocyanato group into the polymer by reacting a functional group reactive with isocyanate group in the molecule and a diisocyanate compound blocked at one end.

≪ Polymer composition >

In the present invention, in addition to the curable polymer (A), a polymer composition comprising a solvent (B) and optionally a reactive diluent (C) is provided. The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the curable polymer (A), and can be of the same category as the solvent used in producing the curable polymer (A). Specific examples thereof are as described above, and preferably (poly) alkylene glycol monoalkyl ether solvents such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate Based solvent, that is, a glycol ether-based solvent, is used.

The polymer composition of the present invention can be prepared by appropriately mixing a desired solvent (B) with the curable polymer (A) isolated from the polymerization system. However, it is not always necessary to isolate the curable polymer (A) from the polymerization system, The solvent contained at the time of completion can be used as it is, and at that time, a desired solvent can be further added as needed. In addition, a solvent contained in other components used in preparing the polymer composition may be used as a component of the solvent (B).

The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and among these, it is preferable to have a plurality of polymerizable functional groups. Although such a reactive diluent is not necessarily an essential component of the polymerizable composition, it is possible to improve the strength of the cured product formed by using the reactive diluent in combination with the curable polymer (A) and the adhesion to the substrate.

Examples of the monofunctional monomer used as a reactive diluent include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (Meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl , 2,2,3,3-tetrafluoropropyl (meth) acrylate (Meta) acrylates such as half (meth) acrylate of phthalic acid derivatives; Aromatic vinyl compounds such as styrene,? -Methylstyrene,? -Chloromethylstyrene and vinyltoluene; And carboxylic acid esters such as vinyl acetate and vinyl propionate. These may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, diethylene glycol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acryloyloxypropyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2- Acrylate, (Meth) acrylate, glycerin tri (meth) acrylate, glycerin tri (meth) acrylate, glycerin tri (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di A reaction product of 2-hydroxyethyl (meth) acrylate such as trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, a reaction product of tris (meth) acrylate, urethane (meth) acrylate (Meth) acrylates such as tri (meth) acrylate of hydroxyethyl) isocyanurate; Aromatic vinyl compounds such as divinylbenzene, diallyl phthalate and diallylbenzenephosphonate; Dicarboxylic acid esters such as adipic acid divinyl; (Meth) acrylamide, (meth) acrylamide methylene ether, condensates of polyhydric alcohols with N-methylol (meth) acrylamide, and the like. These may be used alone or in combination of two or more.

The blending amount of the curable polymer (A), the solvent (B) and the reactive diluent (C) in the polymer composition may be suitably selected according to the purpose of use. Usually, 100 parts by mass of the total of the components (A) (B) and 30 to 1,000 parts by mass of the curable polymer (A), 0 to 90 parts by mass of the reactive diluent (C), and preferably 20 to 80 parts by mass of the curable polymer (A) (B) is from 50 to 800 parts by mass, the reactive diluent (C) is from 20 to 80 parts by mass, more preferably from 30 to 75 parts by mass of the curable polymer (A) And the reactive diluent (C) is 25 to 70 parts by mass. When the amount is within this range, a polymer composition having an appropriate viscosity can be obtained. In addition to being usable for preparing a photosensitive polymer composition described later, it can be used as a binder for various coatings, adhesives, and printing inks.

≪ Photosensitive polymer composition >

Also provided in the present invention is a photosensitive polymer composition comprising a curable polymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D) and optionally a colorant (E). The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin butyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy- 1- (4-methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; Acylphosphine oxides, and the like. These may be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator (D) in the photosensitive polymer composition is generally 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, per 100 parts by mass of the total amount of the components (A) and (C) in the photosensitive polymer composition , And more preferably 1 to 15 parts by mass. When the amount is in this range, a photosensitive polymer composition having appropriate photocurability is obtained.

The colorant (E) is not particularly limited as long as it is soluble or dispersible in the solvent (B), and examples thereof include a dye and a pigment. As the dye, an acidic dye having an acidic group such as a carboxylic acid or a sulfonic acid, a salt of a nitrogen compound of an acidic dye, a salt of an acidic dye, or the like, from the viewpoints of solubility in a solvent (B) or an alkali developer, interaction with other components in the photosensitive polymer composition, It is preferable to use a sulfonamide form of an acidic dye or the like.

Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257 , 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof. Among them, preferred are azo dyes, xanthan dyes, anthraquinone dyes or phthalocyanine dyes. These can be used alone or in combination of two or more kinds depending on the color of the target pixel.

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, , 138, 139, 147, 148, 150, 153, 154, 166, 173, 194 and 214; Orange pigments such as C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, Pigments; Blue pigments such as C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C. I. violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; Green pigments such as C.I. Pigment Green 7, 36, 58; Brown pigments such as C.I. Pigment Brown 23, 25; C. I. pigment black 1, black pigment such as carbon black, titanium black and iron oxide, and the like.

These can be used alone or in combination of two or more kinds depending on the color of the target pixel. The dyes and pigments may be used in combination according to the color of the target pixel. The blending amount of the colorant (E) is generally 5 to 80 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 70 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the total amount of the components (A) 60 parts by mass.

When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive polymer composition from the viewpoint of improving the dispersibility of the pigment. As the dispersing agent, it is preferable to use a polymer dispersing agent having excellent dispersion stability over time. Examples of the polymer dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified ester-based dispersant. As such polymer dispersing agents, even those which are commercially available under the trade names EFKA (manufactured by EFKA Chemicals bv (EFKA), DISPERBYK (BYK-Chemie GmbH), DISPARLON (manufactured by Kusumoto Chemicals, Ltd.), SOLSPERSE (manufactured by AstraZeneca KK) good. The blending amount of the dispersing agent may be appropriately set depending on the kind of pigment to be used.

When the photosensitive polymer composition contains the colorant (E), the blending amount of the curable polymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D) and the colorant (E) 10 to 90 parts by mass of the curable polymer (A), 30 to 1,000 parts by mass of the solvent (B), 10 to 90 parts by mass of the reactive diluent (C), and 10 to 90 parts by mass of the reactive diluent (C) (A) is contained in an amount of 20 to 80 parts by mass, the solvent (B) is contained in an amount of 50 to 800 parts by mass, the amount of the curing polymer (B) is 50 to 800 parts by mass, The reactive diluent (C) is 20 to 80 parts by mass, the photopolymerization initiator (D) is 0.5 to 20 parts by mass and the colorant (E) is 5 to 70 parts by mass, more preferably the curable polymer (A) (D) and 10 to 60 parts by mass of the colorant (E), the reactive diluent (C), the photopolymerization initiator (D) and the colorant (E) are 100 to 700 parts by mass, 25 to 70 parts by mass, Also, even when the photosensitive polymer composition does not contain the colorant (E), the above-mentioned numerical range can be applied to the blending amount of the curable polymer (A), the solvent (B), the reactive diluent (C) and the photopolymerization initiator (D).

The polymer composition and the photosensitive polymer composition of the present invention may be blended with known additives such as known coupling agents, leveling agents and heat polymerization inhibitors in order to impart predetermined characteristics to the above components. The amount of these additives to be added is not particularly limited as long as the effect of the present invention is not impaired.

The photosensitive polymer composition of the present invention can be produced by using a known mixing apparatus and mixing the above components. A polymer composition containing the curable polymer (A) and the solvent (B) is prepared in advance and then mixed with a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E) It is also possible.

The photosensitive polymer composition obtained as described above is suitable as a resist since it has alkali developability. In the curing of the photosensitive polymer composition, the baking temperature may be appropriately selected within the range of 250 占 폚 or less. However, since the curable polymer of the present invention has excellent curing property at low temperatures, the baking temperature can be lowered compared with the conventional materials. For example, when the photosensitive polymer composition is used in the pigment / dye dispersion method, the baking temperature can be suppressed to 210 占 폚 or less. The lower the baking temperature, the more favorable the energy consumption is, and in the case of the dye dispersion method, the original characteristics of the dye become easier to obtain. From such a viewpoint, the baking temperature is preferably 210 DEG C or lower, preferably 200 DEG C or lower, more preferably 190 DEG C or lower. The lower limit of the baking temperature is not necessarily the same as the block contained in the curable polymer depending on the type of the socio-organic group, but it is required that the block has a dissociation temperature of not less than 100 ° C, preferably not less than 150 ° C , More preferably not lower than 160 캜. When the baking temperature is excessively lowered, it is difficult to sufficiently improve the solvent resistance of the coating film. The time required for baking can be appropriately selected, but is usually from 10 minutes to 4 hours, preferably from 20 minutes to 2 hours.

The photosensitive polymer composition of the present invention is suitable as a resist used for producing a color filter mounted on various types of resists, particularly organic EL display liquid crystal display devices, solid-state image pickup devices such as CCD and CMOS, and the like. Further, since the photosensitive polymer composition of the present invention gives a cured film excellent in solvent resistance and curing property at low temperature, it can be used for various coatings, adhesives, binders for printing inks and the like.

<Color filter>

Next, the color filter prepared using the photosensitive polymer composition of the present invention will be described. The color filter of the present invention has a coloring pattern formed using the photosensitive polymer composition. A color filter is usually composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundary between each pixel, and a protective film formed on the black matrix. In this configuration, other known structures can be employed for the other structures, except that the pixel and the black matrix (colored pattern) are formed using the photosensitive polymer composition.

Next, one embodiment of a method for manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. More specifically, a black matrix and RGB pixels are sequentially formed on a substrate. The material of the base material is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, .

The coloring pattern can be formed by photolithography. Specifically, the photosensitive polymer composition is coated on a substrate to form a coating film, and then the coating film is exposed through a photomask of a predetermined pattern to photo-cure the exposed portion. Then, the unexposed portions are developed with an aqueous alkaline solution and then baked to form a predetermined pattern.

The method of applying the photosensitive polymer composition is not particularly limited, but a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like can be used. After the application of the photosensitive polymer composition, the solvent (B) may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate, if necessary. The heating conditions are not particularly limited and may be appropriately set depending on the kind of the photosensitive polymer composition to be used. Generally, it is preferable to heat at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.

Subsequently, the formed coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser beams through a negative type mask. The energy dose to be irradiated may be appropriately selected depending on the composition of the photosensitive polymer composition, and is preferably 30 to 2000 mJ / cm 2, for example. The light source used for exposure is not particularly limited, but a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.

The alkali aqueous solution to be used for development is not particularly limited, and examples thereof include aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; An aqueous solution of an amine compound such as ethylamine, diethylamine or dimethylethanolamine; Amino-N-ethyl-N -? - hydroxyethylaniline, 3-methyl-4-amino-N Methyl-4-amino-N-ethyl-N -? - methoxyethylaniline and their sulfate, hydrochloride or p-toluenesulfonate salts, An aqueous solution of a lanediamine compound or the like can be used. A defoaming agent or a surfactant may be added to these aqueous solutions as necessary. Further, after development with the above-mentioned alkali aqueous solution, it is preferable to wash with water and dry.

The baking condition is not particularly limited, and the heat treatment may be carried out depending on the kind of the photosensitive polymer composition to be used. Conventionally, the known photosensitive polymer composition lacks solvent resistance when the baking temperature is 200 DEG C or less, but the photosensitive polymer composition of the present invention can provide a coating film showing sufficient solvent resistance even when baking at a temperature of 200 DEG C or less ( See Examples 6 and 8). Therefore, the baking temperature can be lowered, and in the case of baking at a high temperature, the treatment time can be shortened, which is a great advantage in manufacturing. From this point of view, heating is usually carried out at a temperature of 210 DEG C or less, preferably 200 DEG C or less, particularly preferably 190 DEG C or less, for 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

A desired coloring pattern can be formed by repeating the above-described application, exposure, development and baking in sequence using a photosensitive polymer composition for a black matrix and a photosensitive polymer composition for a red, green and blue color. In the above description, a method of forming a colored pattern by photo-curing has been described. However, when a photosensitive polymer composition containing a curing accelerator and a known epoxy resin is used in place of the photo-polymerization initiator (D) A desired coloring pattern may be formed. Then, a protective film is formed on the coloring pattern (RGB pixels and black matrix). The protective film is not particularly limited and may be formed using a known film.

The color filter manufactured in this way is excellent in sensitivity and developability and is manufactured using a photosensitive polymer composition that gives a colored pattern excellent in solvent resistance, so that the color change is small and an excellent coloring pattern is obtained.

<Image Display Device>

The image display element of the present invention is a display element having the color filter, and specific examples thereof include a liquid crystal display element, an organic EL display element, and a solid-state image pickup element such as a CCD element or a CMOS element. Such an image display device may be produced by a conventional method other than the use of the color filter. For example, when a liquid crystal display device is manufactured, the color filter is formed on a substrate, and electrodes, spacers, and the like are sequentially formed. Then, an electrode or the like may be formed on another substrate, and a predetermined amount of liquid crystal may be injected and sealed by attaching them to each other.

Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In this embodiment, parts and percentages are based on mass unless otherwise specified. The acid value, the unsaturated group equivalent, and the weight average molecular weight are measured as follows.

(1) Acid value: The acid value of the curable polymer (A) measured according to JIS K6901 5.3 means the number of mg of potassium hydroxide required for neutralizing the acidic component contained in 1 g of the curable polymer (A).

(2) The unsaturated group equivalent is a molecular weight per mol of the polymerizable unsaturated bond, and is a calculated value based on the amount of the monomer used.

(3) The equivalent of the socioanthophore of the block is the calculated value based on the amount of the monomer used, which is the molar equivalent molecular weight of the socioantho-group of the block.

(4) The weight average molecular weight (Mw) means the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) under the following conditions.

Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by SHOWA DENKO K.K.)

Column temperature: 40 ° C

Samples: 0.2% tetrahydrofuran solution of copolymer

Developing solvent: tetrahydrofuran

Detector: Differential refractometer (Shodex RI-71S) (manufactured by SHOWA DENKO K.K.)

Flow rate: 1 mL / min

Example 1

162.2 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introducing tube, stirred while replacing nitrogen, and heated to 120 캜.

Subsequently, a solution obtained by dissolving 4.7 g (0.05 mol) of norbornene, 53.0 g (0.45 mol) of vinyltoluene, 32.4 g (0.45 mol) of acrylic acid, and 50 g of methacryloyloxyethyl isocyanate and propylene glycol monomethyl ether 10.3 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, NOF CORPORATION agent, perbutyl O) was added to a monomer mixture comprising 12.25 g (0.05 mol) of a reaction product (dissociation temperature 160 ° C) Was dropwise added to the flask from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120 DEG C for 2 hours to carry out a copolymerization reaction to produce an addition copolymer (precursor of a curable polymer). Subsequently, the inside of the flask was replaced with air. Then, 22.5 g (0.16 mol) of glycidyl methacrylate, 0.4 g of triphenylphosphine (catalyst) and 0.4 g of methylhydroquinone were charged into the addition copolymer solution, The reaction was continued for 10 hours, and a polymerizable unsaturated bond was introduced into the side chain of the polymer by reacting the carboxyl group derived from acrylic acid with the epoxy group of glycidyl methacrylate to obtain a curable polymer (A). The polymer had an acid value of 131.5 mgKOH / g, an unsaturated group equivalent of 851 g / mol, a block-like isocyanato group equivalent of 2,700 g / mol and a weight average molecular weight of 10,500.

Then, 82.0 g of propylene glycol monomethyl ether was added to the reaction solution to prepare an aggregate solution having a polymer component concentration of 34% of the curable polymer (A). This is referred to as sample 1.

Example 2

232.8 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introducing tube, stirred while replacing nitrogen, and heated to 120 캜. Subsequently, 6.09 g (0.06 mol) of norbornene, 68.33 g (0.58 mol) of vinyltoluene, 82.0 g (0.58 mol) of glycidyl methacrylate, and 50 g of a mixture of methacryloyloxyethyl isocyanate and propylene Butyl peroxy-2-ethylhexanoate (polymerization initiator, NOF CORPORATION agent, perbutyl O (manufactured by Nippon Aerosil Co., Ltd.)) was added to a monomer mixture comprising 15.88 g (0.06 mol) of a reaction product of glycol monomethyl ether ) Was added dropwise to the flask over 2 hours from the dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 120 DEG C for 2 hours to carry out a copolymerization reaction to produce an addition copolymer. Thereafter, 42.0 g (0.58 mol) of acrylic acid, 0.5 g of triphenylphosphine (catalyst) and 0.5 g of methylhydroquinone were charged into the addition copolymer solution while replacing air in the flask with air, and the reaction was carried out at 110 DEG C for 10 hours , 48.0 g (0.29 mol) of tetrahydrophthalic anhydride was further added and the polymerizable unsaturated bond was introduced into the side chain of the polymer by the reaction between the epoxy group derived from glycidyl methacrylate and the carboxyl group of acrylic acid, The reaction was continued for 3 hours to react the hydroxyl group generated by the cleavage of the epoxy group and the anhydride group of the tetrahydrophthalic anhydride. The polymerizable polymer (B) thus obtained had an acid value of 92.5 mgKOH / g, an unsaturated group equivalent of 392 g / mol, a blocked isocyanato group equivalent of 4,100 g / mol and a weight average molecular weight of 12,000.

Then, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare an aggregate solution having a polymer concentration of 44.5% of the polymerizable polymer (B). This is referred to as sample 2.

Example 3

Except that 12.25 g (0.05 mol) of the reaction product of methacryloyloxyethyl isocyanate and propylene glycol monomethyl ether represented by the above formula (3) was replaced by 2-isocyanate ethyl methacrylate represented by the formula (2) A polymerizable polymer (C) was obtained in the same manner as in Example 1 except that 13.4 g (0.05 mol) of the reaction product of caprolactam (dissociation temperature 160 캜) was used. The polymer had an acid value of 130.2 mgKOH / g, an unsaturated group equivalent of 859 g / mol, a block-like isocyanato group equivalent of 2,700 g / mol and a weight average molecular weight of 15,900.

Then, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare an aggregate solution having a polymer concentration of 34% of the polymerizable polymer (C). This is referred to as Sample 3.

Example 4

Instead of 15.88 g (0.06 mol) of the reaction product of methacryloyloxyethyl isocyanate and propylene glycol monomethyl ether represented by the above formula (3), 2-isocyanate ethyl methacrylate represented by the formula (2) A polymerizable polymer (D) was obtained in the same manner as in Example 2 except that 17.37 g (0.06 mol) of the reaction product of caprolactam was used. The polymer had an acid value of 92.5 mgKOH / g, an unsaturated group equivalent of 392 g / mol, a blocked isocyanato group equivalent of 4,100 g / mol and a weight average molecular weight of 18,000.

Then, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare an aggregate solution having a polymer concentration of 44.5% of the polymerizable polymer (D). This is designated Sample 4.

Comparative Example 1

Except that 15.88 g (0.06 mol) of the reaction product of methacryloyloxyethyl isocyanate and propylene glycol monomethyl ether represented by the above formula (3) was not used and that the amount of vinyl toluene used was 76.48 g (0.65 mol) A polymerizable polymer (E) was obtained in the same manner as in Example 2. The polymer had an acid value of 138.5 mgKOH / g, an unsaturated group equivalent of 800 g / mol and a weight average molecular weight of 9,000.

Subsequently, 103.3 g of propylene glycol monomethyl ether was added to the reaction solution to prepare an aggregate solution having a polymer concentration of 35% of the polymerizable polymer (E). This is referred to as sample 5.

Comparative Example 2

Except that 13.4 g (0.05 mol) of the reaction product of 2-isocyanate ethyl methacrylate and? -Caprolactam represented by the above formula (2) was not used and 59.0 g (0.5 mol) of vinyl toluene was used A polymerizable polymer (F) was obtained in the same manner as in Example 3. The polymer had a polymer dispersion weight of 142.2 mgKOH / g, an unsaturated group equivalent of 800 g / mol and a weight average molecular weight of 10,000.

Then, 106.53 g of propylene glycol monomethyl ether was added to the reaction solution to prepare an aggregate solution having a polymer concentration of 44.5% of the polymerizable polymer (F). This is referred to as Sample 6.

Example 5 and Comparative Example 3

&Lt; Preparation of Photosensitive Polymer Composition (Pigment Type) >

10 parts of C. I. Pigment Green 36, 33.75 parts of propylene glycol monomethyl ether acetate, and 6.25 parts of a dispersant (DISPERBYK-161 manufactured by BYK Japan KK) were charged into a stainless steel vessel filled with 180 parts of zirconia beads having a diameter of 0.5 mm , And the mixture was dispersed by mixing with a paint shaker for 3 hours to prepare a green pigment dispersion.

These green pigment dispersions were mixed with the other mixing components shown in Table 1 (i.e., curable polymer, reactive diluent, photopolymerization initiator, and solvent) to prepare photosensitive polymer compositions (composition Nos. 1 to 6) shown in Table 2. The mixing ratios of the respective components are as shown in Table 1. In addition, the amount of the curable polymer in Table 1 does not include a solvent, and the amount of the solvent used for preparing the aggregate solution is added in the solvent as the blending component.

Example 6 and Comparative Example 4

&Lt; Evaluation of color resist (pigment type) >

The performance when the photosensitive polymer composition obtained in Example 5 was used as a color resist (pigment type) was evaluated as follows.

(1) Pattern formation by color resist

The prepared color resist (pigment type) was spin-coated on a 5 cm x 5 cm glass substrate (non-alkali glass substrate) so that the thickness after exposure was 2.5 m, and then heated at 90 deg. C for 3 minutes to volatilize the solvent. Subsequently, a photomask having a predetermined pattern was disposed at a distance of 100 mu m from the coated film, and the coated film was exposed through the photomask (exposure amount: 150 mJ / cm2), and the exposed portion was photocured. Subsequently, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 캜 and a pressure of 0.3 MPa to dissolve and develop the unexposed portions, followed by baking at 230 캜 for 30 minutes to form a predetermined pattern.

(2) Evaluation of pattern formed from color resist

The pattern formed as described above was evaluated for alkali developability and sensitivity as follows.

(2-1) Alkali developing property

The alkali developability was confirmed by the residue after the alkali development and the development form. The residue after the alkali development was confirmed by observing the pattern after the alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The criteria for this evaluation are as follows.

○: No residue

X: Residual

(2-2) Sensitivity

The alkaline development using the spray was performed for 30 seconds, and the amount of decrease in the pattern thickness before and after the alkali development was measured to determine the sensitivity of the sensitivity. Since the pattern thickness can be said to be good as the reduction amount is smaller, the criterion of this evaluation is as follows.

?: Less than 0.20 占 퐉

×: 0.20 μm or more

(3) Evaluation of solvent resistance

On a 5 cm x 5 cm glass substrate (non-alkali glass substrate), a polymer composition of the type obtained by removing the pigment from the color resist was spin-coated to a thickness of 2.5 mu m after the exposure, and then heated at 90 DEG C for 3 minutes to volatilize the solvent. Subsequently, the coated film was exposed to light having a wavelength of 365 nm, and the exposed portion was photo-cured. Then, the coated film was allowed to stand in a dryer at baking temperatures of 180 캜, 200 캜, and 230 캜 for one hour to prepare a cured coating film. 200 mL of n-methyl-2-pyrrolidone was placed in a glass bottle having a capacity of 500 mL, and the test piece having the cured coating film was immersed therein. The color change after 1 hour at 23 캜 was measured with a spectrophotometer UV -1650PC (manufactured by Shimadzu Corporation), and the solvent resistance was evaluated based on the results. The criteria for this evaluation are as follows.

?:? E ^* ab is less than 0.3

×: ΔE ^* ab is 0.3 or more

The evaluation results of the alkali developability, sensitivity and solvent resistance are shown in Table 2.

As can be seen from the results in Table 2, the color resists (Experiments Nos. 5-1 to 5-4) using the photosensitive polymer compositions of Examples 1 to 4 exhibited good alkali developability and sensitivity and excellent solvent resistance (Experiments Nos. 5-5 to 5-6) using the photosensitive polymer compositions of Comparative Examples 1 and 2 were evaluated for alkali developing properties or sensitivity, and when the baking temperature was as low as 180 占 폚 and 200 占 폚 There was a lack of solvent resistance.

Example 7 and Comparative Example 5

&Lt; Preparation of photosensitive polymer composition (dye type) >

A photosensitive polymer composition (dye type) containing a dye (acid green 3) was prepared according to the blending components and compounding ratios shown in Table 3. The amount of the curable polymer in Table 3 does not include a solvent, and the amount of the solvent used for preparing the aggregate solution is added in the solvent as a blending component.

Example 8 and Comparative Example 6

&Lt; Evaluation of color resist (dye type) >

The performance when the photosensitive polymer composition obtained in Example 7 was used as a color resist (dye type) was evaluated by the same method as in Example 8. [ The results are shown in Table 4.

As can be seen from the results of Table 4, the color resists (Experiments Nos. 7-1 to 7-4) using the photosensitive polymer compositions of Examples 1 to 4 were excellent in alkali developability and sensitivity and excellent in solvent resistance The color resists (Experiments Nos. 7-5 to 7-6) using the photosensitive polymer compositions of Comparative Examples 1 and 2 were found to have poor alkaline developability or sensitivity and, when the baking temperature was a little low, such as 180 占 폚 and 200 占 폚, My castle is falling behind.

Comparative Example 7

A polymerizable polymer (G) was obtained in the same manner as in Example 1 except that the modification reaction with glycidyl methacrylate was not performed. The polymer had an acid value of 324.0 mgKOH / g, a block isocyanate group equivalent of 2,300 g / mol and a weight average molecular weight of 9,000. Subsequently, 52.2 g of propylene glycol monomethyl ether was added to the reaction solution to prepare an aggregate solution having a polymer concentration of 35.0% of the polymerizable polymer (G). A photosensitive polymer composition (dye type) was prepared in the same manner as in Example 7 except that this aggregate solution was used, and the performance as a color resist was evaluated. As a result, it was found to be insufficient in sensitivity and solvent resistance as compared with the present invention.

As can be seen from the above results, according to the present invention, sensitivity and developability are good when used as a photosensitive material, and curing property capable of forming a cured coating film having sufficient solvent resistance even at a low baking temperature at the time of pattern formation Polymer can be provided. By using the curable polymer, a photosensitive polymer composition excellent in sensitivity developability and solvent resistance and suitable as a color filter resist can be obtained. Further, by using the above photosensitive polymer composition, a color filter having excellent solvent resistance and high reliability can be obtained.

Claims (23)

An acid group, a polymerizable unsaturated group, and a block isocyanato group in the molecule and having a weight average molecular weight in terms of polystyrene of 1,000 to 50,000,
The curable polymer is characterized in that the block having an ethylenically unsaturated bond is any one of the following (I) and (II) having a polymerized unit of a cyanato group-containing monomer in its main chain and a polymerizable unsaturated group in its side chain Curable polymer.
(I) a copolymer of (a) a block copolymer having an isocyanato group, (b) an unsaturated acid monomer and (d) other monomer used as desired, (c) an unsaturated monomer having a functional group reactive with an acid group And then introducing a polymerizable unsaturated bond into the side chain.
(C) a copolymer of unsaturated monomers having a functional group reactive with an acid group and, optionally, (d) other monomers, wherein the block (a) (f) a modified polymer obtained by reacting a polybasic acid or its anhydride to introduce a polymerizable unsaturated bond and an acid group into a side chain.
(C) a monomer having a cisocyanate group in the above (a) block (a) is a block material formed from a block agent with an isocyanate group-containing (meth) acrylate, Is at least one member selected from an aromatic vinyl compound and a cyclic olefin) The method according to claim 1,
Wherein the acid value is 20 to 300 KOH mg / g, the unsaturated group equivalent is 100 to 4,000 g / mol, and the block isocyanato group equivalent is 400 to 6,000 g / mol. delete 3. The method according to claim 1 or 2,
Wherein the acid group is a carboxyl group or an acid anhydride group. delete 3. The method according to claim 1 or 2,
Wherein the block has a dissociation temperature of 100 to 200 占 폚. delete The method according to claim 1,
Wherein the blocking agent is a lactam-based compound or an alcohol-based compound. delete A polymer composition comprising the curable polymer (A) and the solvent (B) according to claim 1 or 2. 11. The method of claim 10,
And a reactive diluent (C). 12. The method of claim 11,
And a photopolymerization initiator (D). 13. The method of claim 12,
And further contains a colorant (E). 14. The method of claim 13,
And the colorant (E) is a dye. A photosensitive material for a color filter, which comprises the polymer composition according to claim 13. A color filter formed by using the photosensitive material for a color filter according to claim 15. A process for producing a color filter, characterized in that the photosensitive material for a color filter according to claim 15 is applied to a substrate, exposed through a mask, developed with alkali to form a pattern, and then baked at a temperature of 210 캜 or less. 18. The method of claim 17,
Wherein the colorant (E) is a dye. An image display device comprising the color filter according to claim 16. 3. The method according to claim 1 or 2,
Wherein the block-containing isocyanate group-containing monomer is at least one selected from 2-isocyanate ethyl (meth) acrylate and 2-isocyanate propyl (meth) acrylate and a block formed by a block agent. 3. The method according to claim 1 or 2,
The aromatic vinyl compound may be at least one selected from the group consisting of styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, -Methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene and p-acetylaminostyrene. 3. The method according to claim 1 or 2,
Wherein the cyclic olefin is a cyclic olefin having a norbornene structure. 23. The method of claim 22,
The cyclic olefin having the norbornene structure is preferably a norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept- 1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] 4-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] deca- Ene, tricyclo [5.2.1.0 ^2,6 ] dec-3-ene, tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene, tricyclo [6.2.1.0 ^1,8 ] undeca- Ene, tricyclo [6.2.1.0 ^1,8 ] undeca-4-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca- Cyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,12 ] ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, penta-cyclo [6.5.1.13.6.0 ^2,7 .0 ^9,13] Pentadec-4-ene and pentacyclo [7.4.0.1 ^2,5 .1 ^{9 , 12.08,13} ] ^pentadec -3-ene. &^Lt; / RTI &gt;