JP4582548B2 - Radiation curable branched polyurethane and radiation curable composition containing the same - Google Patents

Description

  The present invention relates to a branched polyurethane cured by radiation and an ink composition cured by radiation containing the branched polyurethane.

  In general, one of the most important components in a liquid crystal display is a color filter of a thin film transistor liquid crystal display (TFT LCD). Its main function is to convert the white backlight into the three primary colors such as red (R), green (G), blue (B), etc., so that the display can be fully colored. Today, this color filter is produced by a spin coating method, and a photoresist is applied to a glass substrate, pre-baked, exposed using a photomask, and then developed. The above process is repeated three times, and the three primary colors of RGB are sequentially etched on the glass substrate. However, such a manufacturing process is not only complicated, but nearly 90% of the photoresist solution is applied during spin coating and development. Lost and high manufacturing costs. Therefore, an ink jet method has been researched and developed instead of the traditional spin coating. In this ink jet system, red (R), green (G), and blue (B) pigment inks are spray-applied on a substrate and then cured by heating or ultraviolet irradiation. To complete. Such inkjet coating method does not require photoresist coating, pre-baking, exposure by photomask, development, etc., as in spin coating method, and significantly reduces equipment costs compared to traditional methods. The process can be simplified, waste liquid can be generated, and the use efficiency of the color ink material can be improved.

  As a method for producing a color filter, although the inkjet method simplifies the production process, is good for environmental protection, and has many features such as saving of materials, there are many problems in its research and development. For example, in a production process using a traditional color photoresist, a polymer photosensitive resin is usually used to satisfy physical properties such as heat resistance and adhesion of the product. In the case of production of a filter, it is difficult to use such a traditional color photoresist as a jet cross-linking ink used in an ink jet method after improvement.

  In past research on this, Canon Inc. has announced its production process. For example, in US Pat. No. 6,162,150, an epoxy resin having an aqueous photosensitive group is used as an ink, and a color filter is produced by an inkjet method. The method is public. Also, in the published patent publication 2004-11026 of the Republic of China (Taiwan), there is disclosed a method for improving adhesiveness using a cross-linked ultraviolet photosensitive resin as a water-based ink material.

  The inks listed in the above patents are used in the ink jet system, but in order not to clog the jet head, it is necessary to lower the viscosity of the ink. Therefore, the main component resin contained in the ink The content (that is, the solid component) cannot be increased. Therefore, when a filter having a specific thickness is produced, a necessary thickness is obtained only by performing jet coating repeatedly several times, which is a problem.

In view of the disadvantages of the above-mentioned know-how, the present inventors have extensively researched on photosensitive resins and have completed the present invention.
US patent US61625110 Published patent publication 2004-11026 of Taiwan (Taiwan)

  The present invention relates to a branched polyurethane cured by radiation and a composition cured by radiation containing the same.

  More specifically, the present invention relates to a branched polyurethane having a core structure, and each branch structure has three terminal acryloyl groups.

The branched polyurethane having a branched structure of the present invention is represented by the following general formula (I) .
In the above, R represents a divalent aromatic group or an aliphatic group, R ′ represents a tetravalent aliphatic group, R ″ represents an aliphatic group, and R ′ ″ represents a hydrogen atom or a methyl group. And n ≧ 3, preferably in the range of 3 to 128, more preferably in the range of 3 to 64.

As a method for producing a branched polyurethane having a branched structure according to the present invention, first, three terminal acryloyl groups, an acrylic acid-based compound having a hydroxy group functional group, and a diisocyanate are reacted, and then three terminal acryloyls are reacted. A urethane having a group and a terminal isocyanate group is synthesized, and then the terminal isocyanate group and a simple substance containing at least three hydroxy groups are subjected to a condensation reaction.
The reaction process is shown below:
In the above, R represents a divalent aromatic group or aliphatic group, R ′ represents a divalent aliphatic group, R ″ represents an aliphatic group, and R ′ ″ represents a hydrogen atom or a methyl group. And n ≧ 3, preferably a value in the range of 3 to 128, more preferably a value in the range of 3 to 64.

  Furthermore, this invention relates to the resin composition hardened | cured by a radiation, (A) Branched-chain polyurethane of the branched structure of this invention, (B) Acrylic acid simple substance, and (C) Photoinitiator.

  In the composition of the present invention, the weight ratio of the branched polyurethane (A) having the branch structure of the present invention to the acrylic acid alone (B) is 95 to 70: 5 to 30, and the photoinitiator The content of (C) is 1 to 50% by weight based on the total weight of component (A) and component (B).

  In the composition of the present invention, if necessary, the composition may further contain one or more of an adhesion promoter (D), a colorant (E), a dispersant (F) and a solvent (G). The amount of these components used can be varied within a wide range as long as the object of the present invention is not affected.

  In the present invention, as the diisocyanate used in the production of the branched polyurethane, diisocyanate having an isocyanate function having two different reactivities is used. Specifically, for example, 2,4-toluene Examples thereof include diisocyanate ester (2,4-TDI) or trimethylcyclohexanone diisocyanate ester (ISOPHORONE DIISOCYANATE, IPDI).

  In the present invention, acrylic acid compounds having three terminal acryloyl groups and hydroxyl group functional groups used in the synthesis of branched polyurethanes include, for example, triacrylic acid pentaerythrate ester (trade name of Shinriki Tech Company). : AgiSyn2884).

In the present invention, the simple substance having at least three hydroxyl groups used for the synthesis of the branched polyurethane includes many polyols such as trimethylolpropane (TMP), glycerin, pentaerythritol, dipentaerythritol. Sorbitol and other simple substances having a branched polyhydroxyl group. These simple substances can be adjusted in shape and molecular weight by further extending and modifying the carbon chain with ethylene oxide, propylene oxide, caprolactone or the like. Moreover, the compound containing four hydroxyl group functional groups formed by adding and reacting ethylenediamine and ethylene oxide or propylene oxide simple substance can also be used.

  The branched polyurethane having a branched structure of the present invention has a higher molecular weight and more acrylic acid groups, so that it can be cured and cross-linked by radiation to improve its physical properties, adhesion and heat resistance. Furthermore, since it has lower viscosity and fluidity even under high solid component conditions, there is no concern that the jet head will be blocked due to viscosity problems even when printing is performed using this. In addition, since it has a high solid component, the required thickness can be obtained with a small number of jet prints. In addition, the branched polyurethane of the present invention has a hydrogen-bonded amine ester group structure and is inexpensive, so that its physical properties and heat resistance can be further improved.

  Examples of the acrylic acid simple substance (B) used in the composition of the present invention include a monofunctional group simple substance, a difunctional group simple substance, a trifunctional group simple substance, and a polyfunctional group simple substance. Examples of the monofunctional group include, for example, acrylic acid 2-phenoxyethyl ester, acrylic acid tethydrofuranyl ester, acrylic acid isobornyl ester, methacrylic acid isobornyl ester, acrylic acid 2- (2-ethoxyethoxy) Examples thereof include ethyl ester, acrylic acid isodecyl ester, acrylic acid lauryl ester and methacrylic acid lauryl ester. Examples of the simple bifunctional group include dipropylene glycol diacrylate, 1,6-hexadiol diacrylate, 1,6-hexadiol dimethacrylate, dipropylene glycol diacrylate, diethylene glycol dimethacrylate, and dimethacrylic acid. Examples include ethylene glycol ester, diacrylic acid triethylene glycol ester, dimethacrylic acid triethylene glycol ester, and dimethacrylic acid tetraethylene glycol ester. Examples of the trifunctional group or polyfunctional group alone include, for example, triacrylic acid trimethylolpropyl ester, trimethacrylic acid trimethylolpropyl ester, tetraacrylic acid di (trimethylolpropyl ester), pentaacrylic acid dipentaerythritol ester Examples include hexaacrylic acid dipentaerythritol ester. These acrylic acid groups alone may be used alone or in combination of two or more.

  The photoinitiator (C) used in the composition of the present invention is cleaved in its molecular structure by irradiation with visible rays, ultraviolet rays, far ultraviolet rays, electron beams and X-rays, for example, free radicals, An active site such as a cation or an anion is formed, and a polymerization reaction can be performed between the branched polyurethane (A) having a branched structure and the acrylic acid alone (B).

  Specific examples of the photoinitiator (C) include, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2 '-Diimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2-Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetrakis ( 4-Etoki Sicarbonylphenyl) -1,2-diimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′- Diimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-diimidazole, 2,2 '' -Bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2 , 4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2-bromophenyl-4, 4 ', 5, '-Tetrakis (4-methoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-diimidazole, 2 , 2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2, 4-dibromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2,4-dibromophenyl) -4, 4 ', , 5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-Methoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonyl) Phenyl) -1,2-diimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2 '-Diimidazole, 2,2'-bis (2-cyanophenyl) -4,4', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-imidazole, 2,2'-bis (2-Cyanofe Nyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5 5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) ) -1,2′-diimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2-ethyl) Phenyl) -4, ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2-ethylphenyl) -4,4', 5,5'-tetrakis (4 -Ethoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2' -Diimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2-Phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ', 5 5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Diimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4,6) -Trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-diimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2 ′ -Bis (2,4,6-tribromophenyl) -4,4 ', 5 , 5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2 , 2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4,6-tricyano Phenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-diimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetramethyl-1,2' Diimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4-diethylphenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′- Tetraphenyl-1,2'-diimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, 2,2'- Bis (2,4-diphenylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4,6-triphenylphenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-diimidazole, etc. Imidazoles such as derivatives. Among them, preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2-diimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole and 2,2′-bis (2 , 4,6-tribromophenyl) -4,4 ', 5,5 - tetraphenyl-1,2'-diimidazole. Examples of benzoin photoinitiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoyl benzoate, and derivatives thereof. Examples of those having an acetophenone structure include 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylprop-1-one, and 1- (4-isopropylphenyl)- 2-hydroxy-2-methylprop-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone-, 2,2-diethoxyacetophenone, 2 -Methyl- (4-mercaptophenyl) -2-morpholinyl-1-prop-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) but-1-one, 1-hydroxy Cyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenyleth-1-one, 4-azidoacetofu Enone, 4-azidobenzylideneacetophenone, and derivatives thereof. Examples of benzophenones include benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, and derivatives thereof. Can be mentioned. Examples of the photoinitiator having an α-diketone structure include diacetyl formate, dibenzoyl formate, methyl benzoyl formate and derivatives thereof. Examples of the photoinitiator having a polyquinone structure include anthraquinone, 2-ethylanthoquinone, 2-tert-butylanthraquinone, 1,4-naphthaquinone, and derivatives thereof. Examples of the photoinitiator having a xanthone structure include xanthone, thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and derivatives thereof. Examples of the photoinitiator having a diao structure include 4-diazodiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-azido-3-methoxydiphenylamine, and derivatives thereof. Examples of photoinitiators having a triazine structure include 2- (2′-furanylethylidene) -4,6-di (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxy). Styrene) -4,6-di (trichloromethyl) -s-triazine, 2- (4′-methoxynaphthyl) -4,6-di (trichloromethyl) -s-triazine, 2- (2′-bromo-4) '-Methylphenyl) -4,6-di (trichloromethyl) -s-triazine, 2- (2'-Chenylethylidene) -4,6-di (trichloromethyl) -s-triazine, and derivatives thereof It is done.

  In addition to the photoinitiators listed above, for example, 4-diazobenzaldehyde, azidopyrene, di (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphooxide, N-phenylthioacridone, triphenyl Examples include pyrenium perchlorate and its derivatives. These photoinitiators can be used alone or in combination of two or more.

  Examples of the adhesive (D) used in the composition of the present invention include vinyl functional silanes such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane; for example, 2- (3,4- Epoxycyclohexyl) -ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane and other silanes having an epoxy functional group; Metaacrylates such as methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, and 3-methacryloyloxypropyltriethoxysilane Silanes having a liloyloxy group; for example, silanes having an acryloyloxy group such as 3-acryloyloxypropyltrimethoxysilane; for example, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Amine functionality such as silanyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylphenmethyl) -2-aminopropyltrimethoxysilane hydrochloride Silanes having a group; for example, 3-ure Silanes having a ureido functional group such as dopropyltriethoxysilane; for example, silanes having a chloropropyl functional group such as 3-chloropropyltrimethoxysilane; for example, 3-mercaptopropylmethyldimethoxylane, 3-mercaptopropyltri Silanes having mercapto functional groups such as methoxysilane; for example, silanes having sulfoether functional groups such as di (triethoxysilanepropyl) tetrasulfoether; for example, isocyanate functionalities such as 3-isocyanatopropyltriethoxysilane And silanes having a group. The amount of these used is about 0 to 3% by weight based on the total weight of the ink composition.

  Examples of the colorant (E) used in the composition of the present invention include C.I. I. Yellow pigment 83, C.I. I. Yellow pigment 110, C.I. I. Yellow pigment 138, C.I. I. Yellow pigment 150 and C.I. I. Yellow pigment 155; C.I. I. Orange pigment 71, C.I. I. Purple pigment 19 and C.I. I. Purple pigment 23; C.I. I. Red pigment 48: 1, C.I. I. Red pigment 48: 2, C.I. I. Red pigment 48: 3, C.I. I. Red pigment 48: 4, C.I. I. Red pigment 122, C.I. I. Red pigment 177, C.I. I. Red pigment 202, C.I. I. Red pigment 206, C.I. I. Red pigment 207, C.I. I. Red pigment 209, C.I. I. Red pigment 224 and C.I. I. Red pigment 254; C.I. I. Blue pigment 15: 3, C.I. I. Blue pigment 15: 4 and C.I. I. Blue pigment 15: 6; C.I. I. Green pigment 7 and C.I. I. Green pigment 36; C.I. I. Brown pigment 23 and C.I. I. Brown pigment 25; C.I. I. Black pigment 1 and C.I. I. Organic pigments having heat resistance such as black pigment 7 can be raised (in the above, CI is established and published by The Society of Dyers and Colorists Co.). These colorants may be used alone or in combination of two or more, and the amount used is about 5 to 40% based on the total weight of the ink composition.

  The dispersant (F) used in the composition of the present invention includes S32000 manufactured by Avecia, which reacts a cationic poly (alkylimine) with a hydroxy stearate having a free acid group. Acid amide synthesized. After the addition, further dispersion is promoted to promote stable dispersion of the colorant. The amount of these used is 30% by weight of the colorant (E).

  The solvent (G) used in the composition of the present invention is used for maintaining a liquid state and adjusting the viscosity of the composition to an appropriate viscosity when jetting. Therefore, the solvent used may be any solvent that dissolves or disperses the components contained in the composition, does not participate in the reaction, and has appropriate volatility.

  Examples of these solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether , (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether For example, (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; and others such as diethylene glycol dimethyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol Ethers such as coal diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactates such as 2-hydroxypropionic acid methyl ester and 2-hydroxypropionic acid ethyl ester For example, 2-hydroxy-2-methylpropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethoxyacetic acid Ethyl ester, hydroxyacetic acid ethyl ester, 2-hydroxy-3-methylbutyric acid methyl ester, acetic acid 3-methyl-3-methoxyphtyl ester, propionic acid 3-methyl- 3-methoxybutyl ester, acetic acid ethyl ester, acetic acid n-butyl ester, acetic acid isobutyl ester, formic acid isovaleryl ester, acetic acid isovaleryl ester, propionic acid n-butyl ester, butyric acid isopropyl ester, butyric acid ethyl ester, butyric acid n-butyl ester , Acetone acid methyl ester, acetone acid ethyl ester, acetone acid n-propyl ester, acetyl acetic acid methyl ester, acetyl acetic acid ethyl ester and 2-oxobutyric acid ethyl ester; for example, aromatic hydrocarbons such as toluene and xylene For example, acid amides such as N-methylpyrrolidone (NMP), N, N-dimethylformamide and N, N-dimethylacetamide are used.

  The above-mentioned solvents may be used alone or in combination of two or more, and the addition amount is not particularly limited as long as the required viscosity can be obtained. Usually, about 5 to 60% by weight is based on the total weight of the composition. used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Formulation Examples, but the present invention is not limited to these Examples and Formulation Examples.

The TMP used in the following examples was purchased from Bayer, and there are three hydroxy groups. The pentaerythritol for EO modification uses polyol PP50, a product of Perstorp, and the number of hydroxy groups. No. 4 and sugar / glycerin as a mixture for reforming Initiator PO, using boranol 280 manufactured by Dow, its theoretical hydroxy group value is 7, Bolton P500 was purchased from Perstorp, and its molecular weight was 1500 g. / Mol, and the hydroxy value is about 560 to 630 mg.
KOH / g, the number of theoretical hydroxyl groups was 16. A product of Mitsui Chemicals Japan Ltd. was used for TDI, and AgiSyn 2884 of Shinriki Tech Co., Ltd. was used for pentaerythritol triacrylate. As a catalyst, T-12 manufactured by Air Products Co. was used.

In a reaction flask equipped with a condenser and a temperature sensor, 93.2 g of TDI is added, and 482.8 g of Agi Syn 2884 is gradually added dropwise. The temperature is raised to 60 ° C., maintained for 60 minutes, then further heated to 65 ° C. and held for 60 minutes. Next, 0.3 g of T-12 is added and the temperature is maintained at 65 ° C. and maintained for 60 minutes. Finally, 24 g of TMP is added, the temperature is raised to 70 ° C., and the temperature is maintained until the NCO% = 0% by titration. The branched polyurethane (1) having the branch structure of the present invention is thus obtained. Its structural formula is shown in Chemical Formula 4 below.

In a reaction flask equipped with a condenser and a temperature sensor, 90.0 g of TDI is added, and 464.0 g of AgiSyn2884 is gradually added dropwise. The temperature is warmed to 60 ° C., held as it is for 60 minutes, then warmed to 65 ° C. and held for another 60 minutes. Next, 0.3g of T-12 is added and kept at 65 ° C for 60 minutes. Finally, 46.0 g of PP50 is added, the temperature is raised to 70 ° C., and the temperature is maintained until NCO% = 0% in the titration test. The branched polyurethane (2) having the branched structure of the present invention is thus obtained.

  In a reaction flask equipped with a cooling tube and a temperature sensor, 82.0 g of TDI was added, and 424.0 g of AgiSyn2884 was gradually added dropwise. The temperature was raised to 60 ° C. and held for 60 minutes, and then further lowered to 65 ° C. And hold for 60 minutes. Thereafter, 0.3 g of T-12 is added, and the temperature is kept at 65 ° C. and held for 60 minutes. Finally, 94.0 g of boranol 280 is added, the temperature is raised to 70 ° C., and the temperature is maintained until NCO% = 0% by a titration test. As described above, a branched polyurethane (3) having a branched structure of the present invention is obtained.

  In a reaction flask equipped with a condenser and a temperature sensor, 89.5 g of TDI was added, 461.5 g of AgiSyn2884 was gradually added dropwise, the temperature was raised to 60 ° C. and held for 60 minutes, and then further heated to 65 ° C. Hold for 60 minutes. Next, 0.3 g of T-12 is added and the temperature is kept at 65 ° C. and held for 60 minutes. Finally, 49.0 g of P500 is added, the temperature is raised to 70 ° C., and the temperature is maintained until NCO% = 0% by a titration test. The branched polyurethane (4) having the branched structure of the present invention is thus obtained.

Formulation Example 1
The branched polyurethanes (1) to (4) having a branched structure synthesized according to Examples 1 to 4 using the components and amounts shown in Table 1 below are mixed thoroughly, and then are appropriately mixed by a polishing machine. Ink compositions (1) to (4) were prepared by measuring the dispersant so that the particle size was 200 nm or less.
註:
TPGDA: Tripropylene glycol diacrylate, a product of Shinriki Tech Company.
KBM503: 3-Methacryloyloxypropyltriethoxysilane, a product of Nippon Shin-Etsu.
Igacure 907: 2-methyl- (4-methylchenyl) -2-morpholine-1-prop-1-non, product of Shiba.
PMA: propylene glycol monomethyl ether acetate.
S32000: Dispersant, Avecia product.

Each of the ink compositions (1) to (4) obtained as described above was applied to a glass substrate, was baked at 70 to 100 ° C. for 100 to 300 seconds, and then exposed under 100 mJ / cm ² conditions. Bake at ˜250 ° C. for 20-30 minutes and immerse this coated glass substrate in various solvents (for example, 80 ° C. water, PM, NMP, TMAH 2.38%, etc.) for 5-15 minutes, or After exposure to each environment (for example, 170 ° C., 10 to 20 minutes), yellowing resistance (ΔEab) was measured, and the results are shown in Table 2 below.
Further, the pencil hardness of the coated glass substrate was measured, and the results are also shown in Table 2.
The ink composition prepared from the polyurethane (1) obtained from Example 1 from the above test has 9 acrylic acids in the structure of the polyurethane (1) itself, even though the ratio is only 10.0% by weight. Since it has a functional group, excellent heat resistance and oxidation resistance (ΔEab ≦ 3) can be provided. In addition, the fact that the entire system exhibits a single phase indicates that the composition of the present invention has a very high compatibility phase.

Since the branched polyurethane of the present invention is a highly crosslinked resin that is cured by radiation, when such a resin is used as a main component of a photoresist solution, the pigment is strongly fixed to the glass substrate and light resistance after film formation is achieved. , Resistance and heat resistance can be improved. In addition, by blending an appropriate dispersant, the surface tension and viscosity of the ink composition prepared using the dispersant can be adjusted. When the ink composition is jet-printed on a glass substrate, it diffuses rapidly and uniformly. In addition, non-uniform thickness of the film and light leakage can be avoided. Also, in a photoresist formulation, since the entire system exhibits a single oil phase, the entire system is very compatible and can be used as a jet print ink composition that cures with very good radiation. it can.

Claims (13)

A branched polyurethane having a branch structure represented by the general formula (I) ,
In the formula, R represents a divalent aromatic or aliphatic group, R ′ represents a tetravalent aliphatic group, R ″ represents an aliphatic group, and R ′ ″ represents a hydrogen atom or a methyl group. And n ≧ 3. The branched polyurethane according to claim 1, wherein n represents an integer in the range of 3 to 128. The branched polyurethane according to claim 1, wherein n represents an integer in the range of 3 to 64. An acrylic compound containing three terminal acryloyl groups and a hydroxy functional group and a diisocyanate ester are reacted first to obtain an amine ester having three terminal acryloyl groups and a terminal isocyanate ester, and then the terminal isocyanate. The branched polyurethane according to claim 1, wherein the acid ester and a simple substance containing at least three hydroxy groups are produced by a condensation reaction. The branched polyurethane according to claim 4, wherein the acrylic compound having three terminal acryloyl groups and a hydroxy functional group is pentaerythritol triacrylate. The branched polyurethane according to claim 4, wherein the diisocyanate has two different reactive isocyanate functions. The branched polyurethane according to claim 6, wherein the diisocyanate is 2,4-toluene diisocyanate or trimethylcyclohexanone diisocyanate. Claim 4 wherein the simple substance comprising at least three hydroxy groups is selected from the group of simple substances having trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, sorbitol and other branched polyhydroxy groups. The branched chain polyurethane described. The branched polyurethane according to claim 8, wherein the polyol is further modified by extending the carbon chain with ethylene oxide, propylene oxide, caprolactone or the like. The branched polyurethane according to claim 1, which is a polyurethane that is cured by radiation. (A) a branched polyurethane having a branched structure according to claim 1, (B) an acrylic acid alone, and (C) a photoinitiator, among which a branched structure has a branched structure The weight ratio of the chain polyurethane (A) and the acrylic acid simple substance (B) is 95 to 70: 5 to 30, and the content of the photoinitiator (C) is the total of the components (A) and (B). A resin composition curable by radiation, which is 1 to 50% by weight of the weight. The resin composition according to claim 11, further comprising one or more of adhesion promoter (D), colorant (E), dispersant (F), and solvent (G). The resin composition according to claim 11, further comprising a dispersion aid.