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WO2017022299A1 - Polymère de (méth)acrylate durcissable, composition durcissable, filtre coloré et dispositif d'affichage d'image - Google Patents

Polymère de (méth)acrylate durcissable, composition durcissable, filtre coloré et dispositif d'affichage d'image Download PDF

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Publication number
WO2017022299A1
WO2017022299A1 PCT/JP2016/065146 JP2016065146W WO2017022299A1 WO 2017022299 A1 WO2017022299 A1 WO 2017022299A1 JP 2016065146 W JP2016065146 W JP 2016065146W WO 2017022299 A1 WO2017022299 A1 WO 2017022299A1
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Prior art keywords
meth
curable
acrylate
group
acrylate polymer
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English (en)
Japanese (ja)
Inventor
正義 柳
恭章 川口
健宏 木下
坂本　淳
拓樹 倉本
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Resonac Holdings Corp
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Showa Denko KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention relates to a curable (meth) acrylate polymer, a curable composition containing the polymer, and use of the polymer in a color filter.
  • photosensitive polymer compositions curable with active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, and adhesives from the viewpoint of resource saving and energy saving. Yes. Also in the field of electronic materials such as printed wiring boards, photosensitive polymer compositions that can be cured by active energy rays are widely used for solder resists, color filter resists, 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, and a black matrix formed at the boundary of the pixels. And a protective film formed on the pixel and the black matrix.
  • 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.
  • the pixel and the black matrix are referred to as “colored pattern”.
  • the pigment / dye dispersion method described later gives a colored pattern that is excellent in durability such as light resistance and heat resistance and has few defects such as pinholes.
  • This pigment / dye dispersion method is a method for producing a color filter by a photolithography method using a photosensitive polymer composition as a resist and repeating the steps of coating, exposing, developing and baking. For this reason, the pigment / dye dispersion method has become the current mainstream.
  • the photosensitive polymer composition used for the photolithographic method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, and a solvent.
  • alkali-soluble resins Various types of polymers have been developed as alkali-soluble resins.
  • Patent Document 1 discloses a photosensitive material for a color filter using a modified polymer.
  • an alicyclic monomer such as tricyclodecanyl methacrylate or norbornene
  • an alkylene represented by ethoxylated o-phenylphenol (meth) acrylate that is, 2-phenylphenoxyethyl (meth) acrylate
  • An acid group and a polymerizable unsaturated bond are introduced into a copolymer of an oxide-derived structure and a (meth) acrylate having an aryl residue.
  • Patent Document 2 the following method is exemplified as a method for introducing an acid group and a polymerizable unsaturated bond, and equivalent performance can be obtained by any of the following methods (1) and (2). (See Example 3 and other examples of Patent Document 2).
  • (1) A method in which an unsaturated monobasic acid is copolymerized in advance, and a part of acid groups in the copolymer molecule is reacted with an unsaturated monomer having an epoxy group.
  • the present invention is an invention that has been studied and developed for further improved improvements under the background art as described above.
  • the object of the present invention is to improve sensitivity, developability, heat-resistant yellowing of cured products, solvent resistance, adhesion to a substrate, and dispersibility of a colorant when used as a material for a photosensitive polymer composition. It is to provide an excellent curable (meth) acrylate polymer and a production method thereof.
  • Another object of the present invention is to provide a curable composition capable of forming a coating film, which is excellent in sensitivity, developability, heat-resistant yellowing of a cured product, solvent resistance, adhesion to a substrate, and dispersibility of a dye. Is to provide things.
  • Still 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 cured pattern excellent in solvent resistance, adhesion to a substrate, and dispersibility of a colorant.
  • a curable (meth) acrylate polymer containing a repeating unit having a structure in which at least two carboxy groups are directly bonded to an alicyclic skeleton has been improved in sensitivity and development.
  • the present invention has been completed by finding that it is excellent in heat resistance, yellowing resistance as a cured product, solvent resistance, adhesion to the substrate, and dispersibility of the colorant.
  • the first aspect of the present invention is the following curable (meth) acrylate polymer.
  • [1] including a repeating unit having a structure in which at least two carboxy groups are directly bonded to an alicyclic skeleton,
  • a curable (meth) acrylate polymer characterized in that The curable (meth) acrylate polymer preferably has the following characteristics.
  • [2] The curing according to [1], wherein the alicyclic skeleton is at least one selected from a cycloalkane skeleton having 5 to 8 carbon atoms and a bridged ring skeleton having 7 to 11 carbon atoms. (Meth) acrylate polymer.
  • the repeating unit having a hydroxy group in the (meth) acrylate polymer is The curable (meth) acrylate polymer according to [4], which is a repeating unit in which a compound having an epoxy group is added to a repeating unit having a carboxy group in a side chain.
  • the repeating unit having a hydroxy group in the side chain of the (meth) acrylate polymer is a repeating unit in which a compound having a carboxy group is added to a repeating unit having an epoxy group in a side chain.
  • R 9 and R 10 each represent a hydrogen atom or a methyl group, or a saturated or unsaturated ring connected to each other. * Represents a bond linked to a (meth) acryloyloxy group).
  • Norbornene monomer represented by the following formula (4) (X and Y in the formula (4) each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, wherein R 1 and R 2 are each Independently represents a hydrogen atom, a carboxy group or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may have a cyclic structure connecting R 1 and R 2 ).
  • the second aspect of the present invention is the following curable composition.
  • a curable composition comprising the curable (meth) acrylate polymer according to any one of [1] to [10] and at least one of a solvent, a reactive diluent, a photopolymerization initiator, and a colorant.
  • the curable composition according to [11] wherein the colorant is at least one of a dye and a pigment.
  • the third aspect of the present invention is the following color filter.
  • the fourth aspect of the present invention is the following image display element. [14] An image display device comprising the color filter according to [13].
  • step (i) includes the following steps: (I-1) preparing a (meth) acrylate polymer having a carboxy group in the side chain or a (meth) acrylate polymer having an epoxy group in the side chain; and (i-2) adding an epoxy compound to the carboxy group. Or Adding a compound having a carboxy group to the epoxy group to form a (meth) acrylate polymer having a hydroxy group in the side chain;
  • the curable composition [11] is preferably a photosensitive polymer composition.
  • the present invention when used as a photosensitive material, heat resistance yellowing, sensitivity, developability, solvent resistance as a cured product, adhesion to a substrate, and dispersibility of a colorant are excellent in curability.
  • a (meth) acrylate polymer can be provided.
  • the cured coating film formed from the photosensitive polymer composition of the present invention is excellent in sensitivity, developability, solvent resistance, adhesion to the substrate, and dispersibility of the colorant. From these facts, the polymer and composition of the present invention have extremely high utility value in various resist fields. Among them, particularly when used as a photosensitive material for a color filter, it is possible to obtain a color filter having a coloring pattern that is very excellent in solvent resistance, adhesion to a substrate, and dye dispersibility.
  • the present invention relates to a curable (meth) acrylate polymer, a curable composition comprising the polymer, and uses of the polymer. More specifically, the present invention relates to a curable (meth) acrylate polymer suitable as a photosensitive material for a color filter, a method for producing the curable (meth) acrylate polymer, and a curable composition containing the curable (meth) acrylate polymer.
  • the first aspect of the present invention is a curable (meth) acrylate polymer.
  • This polymer is characterized by including a repeating unit having a structure in which at least two carboxy groups are directly bonded to an alicyclic skeleton.
  • the repeating unit having a structure in which at least two carboxy groups are directly bonded to the alicyclic skeleton is any repeating unit as long as all of the at least two carboxy groups are directly bonded to the alicyclic skeleton. May be.
  • the carboxy group is directly bonded to the alicyclic skeleton, particularly excellent effects can be obtained in the availability of raw materials and the yellowing resistance of the cured product.
  • bonded with the alicyclic skeleton For example, a number can be selected from 2, 3, 4, 5, 6, etc.
  • the curable (meth) acrylate polymer of the present invention having such a repeating unit include an alicyclic acid anhydride in the hydroxy group of the (meth) acrylate polymer as a raw material containing a monomer unit having a hydroxy group.
  • skeleton and a carboxy group can be mentioned.
  • (meth) acrylate means one or both of acrylate (acrylic acid ester) and methacrylate (methacrylic acid ester).
  • precursor the raw material (meth) acrylate polymer (hereinafter sometimes referred to as “precursor”) containing the monomer unit having a hydroxy group will be described below.
  • the (meth) acrylate polymer (precursor) as a raw material used for the synthesis of the (meth) acrylate polymer of the present invention includes a monomer unit having a hydroxy group. Examples of a method for obtaining a precursor containing such a monomer unit include the following three methods.
  • a (meth) acrylate monomer (a) having a hydroxy group is optionally converted into an ethylenic carbon that does not contain other “structure in which at least two carboxy groups are directly bonded to an alicyclic skeleton”.
  • -Radical polymerizable monomer having carbon double bond (d) hereinafter sometimes simply referred to as "other radical polymerizable monomer (d)"
  • radical (co) This is a polymerization method.
  • Specific examples of the (meth) acrylate monomer (a) having a hydroxyl group are not particularly limited.
  • Examples thereof include hydroxyethyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • hydroxyethyl (meth) acrylate is preferably used from the viewpoint of availability and reactivity.
  • These monomers (a) may be used independently and may be used in combination of 2 or more type.
  • radical polymerizable monomers (d) that can be used in combination as required include radical polymerization having an ethylenic carbon-carbon double bond that does not include a structure in which at least two carboxy groups are directly bonded to the alicyclic skeleton.
  • radical polymerization having an ethylenic carbon-carbon double bond that does not include a structure in which at least two carboxy groups are directly bonded to the alicyclic skeleton.
  • the monomer (d-1) having no aromatic ring is used as the monomer (d)
  • a curable polymer excellent in dye dispersibility can be obtained.
  • the monomer (d-2) having an aromatic ring is used, a curable polymer having excellent pigment dispersibility can be obtained.
  • These monomers may be used alone or in combination.
  • a photosensitive material that exhibits good performance in the pigment dispersion method when applied to the dye dispersion method, does not always exhibit sufficient performance, or the reverse pattern often occurs.
  • a monomer (d-1) having no aromatic ring and a monomer (d-2) having an aromatic ring are used in combination as necessary, so that any of the above-mentioned dispersion methods can be used.
  • a curable polymer exhibiting performance can be obtained.
  • the use ratio of the monomer (d-1) and the monomer (d-2) can be selected as necessary, but the molar ratio of (d-1) / (d-2) is 1/10 to 5/1. It is generally 1/5, preferably 1/5 to 2/1, and more preferably 1/3 to 1/1.
  • Other radical polymerizable monomers (d) will be described later.
  • the second method is to prepare a (meth) acrylate polymer having a monomer unit having an epoxy group in the side chain, and to add an addition reaction of a compound having a carboxyl group, preferably (meth) acrylic acid, to the polymer.
  • This is a method of opening an epoxy group.
  • (meth) acrylic acid means one or both of acrylic acid and methacrylic acid.
  • side chain means that the ethylenic carbon-carbon double bond of a monomer is polymerized.
  • the (meth) acrylate polymer having a monomer unit having an epoxy group in the side chain has an epoxy group
  • the (meth) acrylate monomer (b) can be obtained by a method in which other radical polymerizable monomer (d) is used in combination, if necessary, and radical (co) polymerization is performed according to a conventional method.
  • the (meth) acrylate monomer (b) having the epoxy group can be arbitrarily selected.
  • glycidyl (meth) acrylate 2-glycidyloxyethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy, and lactone adducts thereof (for example, Daicel Chemical Industries).
  • glycidyl (meth) acrylate is preferably used from the viewpoint of availability and reactivity.
  • These monomers (b) may be used independently and may be used in combination of 2 or more type.
  • the monomer unit having an epoxy group in the side chain in the (meth) acrylate polymer is derived from the (meth) acrylate monomer (b) having these epoxy groups.
  • the other radical polymerizable monomer (d) that can be used together as desired includes an ethylenic carbon that does not include a structure in which at least two carboxy groups are directly bonded to the alicyclic skeleton described in the first method. -The same radically polymerizable monomer having a carbon double bond can be used. Details will be described later.
  • the amount of the compound having a carboxyl group can be appropriately selected according to the target value in the hydroxyl group equivalent of the (meth) acrylate polymer (precursor) as a raw material. Generally, it is 0.90 to 1 mol, preferably 0.95 to 1 mol, per mol of the epoxy group contained in the polymer having a (meth) acrylate monomer unit having an epoxy group. It is preferable that the amount used is in the above-mentioned range because no side reaction occurs in the subsequent reaction.
  • the conditions for the above reaction can be selected as necessary, and can be carried out according to a conventional method.
  • both of the above components may be added to the reaction solvent, and a catalyst may be further added.
  • the reaction may be performed at 50 to 150 ° C., preferably 80 to 130 ° C. for 3 to 12 hours. In this reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included. For this reason, it is also possible to carry out the modification reaction without removing the solvent after the completion of the copolymerization reaction.
  • a polymerization inhibitor as necessary to prevent gelation.
  • the kind of polymerization inhibitor is not specifically limited, It selects as needed. Examples include hydroquinone, methyl hydroquinone, and hydroquinone monomethyl ether.
  • the type of the catalyst is not particularly limited and is selected as necessary. Examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium.
  • the third method is a method in which a (meth) acrylate polymer having a monomer unit having a carboxy group in the side chain is prepared, and an epoxy group is ring-opened by addition reaction of a compound having an epoxy group.
  • the (meth) acrylate polymer having a monomer unit having a carboxy group in the side chain can be arbitrarily selected.
  • a (meth) acrylate monomer (c) having a carboxy group can be selected from other radical polymerizable monomers (d ) In combination and radical (co) polymerization according to a conventional method.
  • the (meth) acrylate monomer (c) having a carboxy group can be arbitrarily selected. Specific examples thereof include (meth) acrylic acid, ⁇ -bromo (meth) acrylic acid, ⁇ -furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, ⁇ -cyanocinnamic acid, monomethyl maleate, And unsaturated carboxylic acids such as monoethyl maleate, monoisopropyl maleate, monomethyl fumarate and monoethyl itaconate. Among these, (meth) acrylic acid is most preferably used. These monomers (c) may be used independently and may be used in combination of 2 or more type.
  • the monomer unit having a carboxy group in the side chain in the (meth) acrylate polymer is derived from the (meth) acrylate monomer (c) having these carboxy groups.
  • the compound having an epoxy group can be arbitrarily selected. Specific examples thereof include glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy, and lactone adducts thereof (for example, Daicel Chemical Industries).
  • glycidyl (meth) acrylate is preferably used from the viewpoint of availability and reactivity. These compounds may be used alone or in combination of two or more.
  • the other radical polymerizable monomer (d) that can be used in combination as needed does not include an ethylenic structure that does not include a structure in which at least two carboxy groups are directly bonded to the alicyclic skeleton described in the first method. This is equivalent to a radically polymerizable monomer having a carbon-carbon double bond, which will be described later.
  • the addition amount of the compound having an epoxy group can be appropriately selected according to the target value in the hydroxyl group equivalent of the (meth) acrylate polymer (precursor) as a raw material. Generally, it is 0.05 to 0.8 mol, preferably 0.1 to 0.7 mol, per mol of carboxy group contained in the polymer having a (meth) acrylate monomer unit having a carboxy group. .
  • the amount of the compound having an epoxy group is 0.05 mol or more, the unsaturated group equivalent is not excessively increased, and as a result, sensitivity and solvent resistance are not deteriorated.
  • This reaction can be carried out under the same conditions as the reaction described in the second method. For example, it is preferable that both components are added to the reaction solvent and a catalyst is further added, and the reaction is carried out at 50 to 150 ° C., preferably 80 to 130 ° C., for example. In this reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included. For this reason, it is possible to carry out the modification reaction without removing the solvent after the completion of the copolymerization reaction.
  • an ethylenic group other than the repeating unit containing a structure in which at least two carboxy groups are directly bonded to another alicyclic skeleton that can be used in combination in addition to the essential monomer component, if necessary, an ethylenic group other than the repeating unit containing a structure in which at least two carboxy groups are directly bonded to another alicyclic skeleton that can be used in combination.
  • the radically polymerizable monomer (d) having a carbon-carbon double bond literally has a radically polymerizable property having an ethylenic carbon-carbon double bond that does not include a structure in which at least two carboxy groups are directly bonded to an alicyclic skeleton. If it is a monomer, there will be no restriction
  • Preferable specific examples include polymerizable monomers having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms.
  • the bridged cyclic hydrocarbon means one having a structure represented by the following formula (1) or (2) represented by adamantane, norbornane and the like.
  • the bridged cyclic hydrocarbon group refers to a group corresponding to the remaining part excluding some hydrogen atoms in these structures.
  • a 1 and B 1 each represent a linear or branched alkylene group (which may include a ring), and R 4 represents a hydrogen atom or a methyl group.
  • a 1 and B 1 is the same, They may be different, and the branches of A 1 and B 1 may be connected to form a ring.
  • a 2 , B 2 , and L each represent a linear or branched alkylene group (which may include a ring), and R 5 represents a hydrogen atom or a methyl group.
  • a 2 , B 2 and L may be the same or different, and the branches of A 2 , B 2 and L may be connected to form a ring.
  • (meth) acrylate having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms is preferable.
  • adamantyl (meth) acrylate or (meth) acrylate having a structure represented by the following formula (3) is more preferable.
  • R 6 to R 8 each represent a hydrogen atom or a methyl group.
  • R 9 and R 10 are each a hydrogen atom or a methyl group, or are linked together to form a saturated or unsaturated ring.
  • the ring is preferably a 5-membered ring or a 6-membered ring, wherein * represents a bond connected to a (meth) acryloyloxy group.
  • Examples of the polymerizable monomer include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.
  • dicyclopentanyl methacrylate is more preferable from the viewpoint of heat decomposition resistance and heat discoloration.
  • These monomers can be used alone or in combination of two or more.
  • norbornene monomers represented by the following formula (4) are also examples of preferable monomers (d).
  • X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms
  • R 1 and R 2 each independently represent hydrogen.
  • a hydrocarbon group having 1 to 20 carbon atoms which may have an atom, a carboxy group or a substituent.
  • R 1 and R 2 may form a linked cyclic structure.
  • X and Y are linear or branched hydrocarbon groups having 1 to 4 carbon atoms, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples include isobutyl group and t-butyl group.
  • examples of R 1 and R 2 are methyl group, ethyl group, n- propyl group, Linear or branched alkyl groups such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group; aryl groups such as phenyl group; cyclohexyl And alicyclic groups such as t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group and 2-methyl-2-adamantyl group.
  • substituent include an alkoxy group such as a methoxy group and an ethoxy group, and an aryl group such as a phenyl
  • norbornene monomer examples include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2. .1] Hept-2-ene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 .
  • radical polymerizable monomers (d) that can be used in combination include styrene, ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chloro.
  • Aromatic vinyl compounds such as styrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene; Diene compounds such as butadiene, isoprene, chloroprene;
  • (Meth) acrylic acid amide (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic amides such as N-di-isopropylamide, (meth) acrylic acid anthracenyl amide; Vinyl compounds such as (meth) acrylic acid anilide, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene; Unsaturated dicarboxylic acid diester compounds such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate; Monomaleimide compounds such as N-phenylmaleimide, N-cyclohex
  • those containing no nitrogen atom in the molecule are preferably used from the viewpoint of yellowing resistance.
  • the polymerizable monomer having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms in a proportion of 15 to 70 mol% in the polymer because the heat decomposition resistance and the color change resistance are improved.
  • the ratio of the monomer (d) can be selected as necessary.
  • the ratio of the (meth) acrylate monomer (a) having a hydroxy group to the total amount of the monomers is 10 to 50 mol%, more preferably 15 to 40 mol%, still more preferably 20 to 35 mol%. %.
  • the ratio of the (meth) acrylate monomer (b) or (c) used in the second method and the third method and the other radical polymerizable monomer (d) can be selected as necessary.
  • each (meth) acrylate monomer (b) or (c) is 30 to 90 mol%, more preferably 35 to 80 mol%, still more preferably 40 to 75 mol%.
  • the ratio of the other radical polymerizable monomer (d) can be arbitrarily selected, and is, for example, 10 to 70 mol%, preferably 20 to 65 mol%, and more preferably 25 to 60 mol%.
  • the (meth) acrylate monomer (a) having a hydroxy group is 10 mol% or more, at least two carboxy groups are directly bonded to a desired amount of the alicyclic skeleton on the side chain of the polymer. It is easy and preferable to introduce a new structure. Moreover, when it is 50 mol% or less, the solvent resistance is sufficient, which is preferable.
  • the (meth) acrylate monomer (b) or (c) when the (meth) acrylate monomer (b) or (c) is 30 mol% or more, it becomes easy to introduce a desired amount of hydroxy groups into the side chain of the polymer.
  • the (meth) acrylate monomer (b-1) when used, it is preferable because a structure in which at least two carboxy groups are directly bonded to a desired amount of the alicyclic skeleton can be easily introduced.
  • adhesion and dispersibility with dyes and pigments are sufficient, which is preferable.
  • the other radical polymerizable monomer (d) is not essential.
  • the heat resistance and the pigment dispersibility can be appropriately improved by using the monomer (d) in combination as necessary.
  • other radical polymerizable monomer (d) is used in combination with a polymerizable monomer having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms, heat resistance and yellowing resistance are improved. Therefore, it is preferable to use an appropriate amount of these monomers.
  • the conditions for the copolymerization reaction for the polymerizable monomer (d) can be arbitrarily selected.
  • the reaction can be carried out in the presence or absence of a polymerization solvent according to radical polymerization methods known in these technical fields.
  • these monomers can be dissolved in a solvent selected as necessary, and then a polymerization initiator can be added to the solution, and the polymerization reaction can be carried out at 50 to 130 ° C. for 1 to 20 hours.
  • the (meth) acrylate monomer (a) having the hydroxy group the (meth) acrylate monomer (b) having an epoxy group, the (meth) acrylate monomer (c) having a carboxy group, and used as necessary.
  • the other radical polymerizable monomer (d) may be used in combination as necessary, as long as any of the monomers (a) to (c) is contained.
  • the monomer (a) and the monomer (b) may be manufactured in combination, the monomer (a) and the monomer (c) may be combined, or the monomers (a) to (c) may be combined. May be used.
  • the ratio can be selected arbitrarily.
  • the solvent that can be used for the copolymerization reaction is not particularly limited and can be selected as necessary.
  • chromatography monoethyl ether poly alkylene glycol monoalkyl ether compound
  • Poly alkylene glycol monoalkyl ether compound
  • ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl a
  • (poly) alkylene glycol monoalkyl ether solvents such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetate solvents such as propylene glycol monomethyl ether acetate, that is, glycol ether solvents are preferable.
  • the amount of the solvent used for polymerization is not particularly limited and can be selected as necessary.
  • the total amount of monomers charged is 100 parts by mass, it is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass.
  • the amount of the solvent used is 1,000 parts by mass or less, the molecular weight of the copolymer due to chain transfer action can be effectively suppressed, and the viscosity of the copolymer can be controlled within an appropriate range. it can.
  • the compounding quantity of a solvent is 30 mass parts or more, it can prevent that abnormality arises in a polymerization reaction, and a polymerization reaction can be performed stably. Moreover, coloring and gelation of a copolymer can also be prevented.
  • Polymerization initiator It does not specifically limit as a polymerization initiator which can be used for this copolymerization reaction, It can select as needed. Examples include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. These polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator used can be arbitrarily selected. For example, when the total amount of monomers charged is 100 parts by mass, it is generally 0.5 to 20 parts by mass, preferably 0.7 to 15 parts by mass, more preferably 1 to 10 parts by mass. Part by mass.
  • a compound having an alicyclic acid anhydride skeleton and a carboxy group is added to a (meth) acrylate polymer (precursor) as a raw material containing a monomer unit having a hydroxy group prepared as described above.
  • the curable (meth) acrylate polymer of the present invention having a monoester of a compound having an acid anhydride skeleton and a carboxy group as a monomer unit can be prepared.
  • the use of a compound having an alicyclic acid anhydride skeleton tends to be excellent in transparency.
  • the compound having an alicyclic acid anhydride skeleton and a carboxy group can be selected as necessary.
  • the alicyclic skeleton is preferably either a cycloalkane skeleton having 5 to 8 carbon atoms or a bridged ring skeleton having 7 to 11 carbon atoms.
  • those having a carboxy group bonded thereto are more preferable, and those in which the alicyclic skeleton is any one of a cyclohexane skeleton, a cycloheptane skeleton and a bicyclo [3,2,0] heptane skeleton are further preferable.
  • 1,2,4-cyclohexanetricarboxylic acid anhydride represented by the following formula (5) 1,2,4-cyclopentanetricarboxylic acid anhydride represented by the following formula (6), and 3-oxa And bicyclo [3,2,0] heptane-6-carboxylic acid, 7,7-dimethyl-2,4-dioxo (CAS: 1378785-58-0)).
  • 1,2,4-cyclohexanetricarboxylic acid anhydride is preferable from the viewpoint of reactivity and availability.
  • An example of a compound having an alicyclic acid anhydride skeleton and a carboxy group is shown as an example of a carboxy group, but the number of carboxy groups is not particularly limited and may be one or more.
  • the number of carboxy groups in the compound may be 2, 3, 4, 5, or the like.
  • a curable (meth) acrylate polymer Incorporates a structure represented by the following formula.
  • 1,2,4-cyclopentanetricarboxylic acid anhydride is used, a structure in which the hexane skeleton of the following formula is a heptane skeleton is incorporated.
  • the weight average molecular weight obtained by gel permeation chromatography in terms of polystyrene is preferably 800 to 48,000, more preferably 2000 to 38,000. Depending on the required effects and conditions, the preferred range is preferably 2000 to 30,000, 2000 to 20,000, and the like. When the weight average molecular weight is 800 or more, it is preferable that a colored pattern is not lost after alkali development when used as a photosensitive polymer composition.
  • the (meth) acrylate polymer used in the present invention is preferably a linear polymer, but may have a chain, branched, or crosslinked structure as necessary, and has a network structure. May be. Any polymer may be used as long as it is within the scope of the present invention, and a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer may be used.
  • the (meth) acrylate polymer as a raw material may be produced by combining the first to third methods as necessary.
  • the reaction between the (meth) acrylate polymer (precursor) as a raw material containing a monomer unit having a hydroxy group and the compound having an alicyclic acid anhydride skeleton and a carboxy group can be arbitrarily selected. It can be carried out according to the law. For example, the above reaction can be carried out by adding both components to the reaction solvent, adding a polymerization inhibitor and a catalyst, and reacting at 50 to 150 ° C., preferably 80 to 130 ° C. for 1 to 10 hours. Can do.
  • the amount of the compound having an alicyclic acid anhydride skeleton and a carboxy group used in the reaction can be appropriately selected according to the value of the hydroxyl equivalent of the target curable (meth) acrylate polymer.
  • the amount used is 0.1 to 0.8 mole per mole of hydroxy group contained in the raw material (meth) acrylate polymer (precursor) containing monomer units having a hydroxy group, preferably 0.2 to 0.7 mol.
  • the amount used is excessively large, a side reaction may occur, so that an appropriate amount is preferably used.
  • the polymerization inhibitor and catalyst used in the reaction those mentioned in the preparation of the raw material (meth) acrylate polymer (precursor) containing the monomer unit having a hydroxy group can be used here as well.
  • the curable (meth) acrylate polymer of the present invention preferably has a weight average molecular weight obtained by gel permeation chromatography in terms of polystyrene of 1,000 to 50,000, more preferably 3,000 to 40,000. More preferably, it is 5,000 to 20,000, and particularly preferably 6,000 to 10,000.
  • the weight average molecular weight is 1,000 or more, it is preferable that a colored pattern is not lost after alkali development when used as a photosensitive polymer composition.
  • the molecular weight is 50,000 or less, the development time becomes an appropriate time, which is practical and preferable for use.
  • the acid value (JIS K6901 5.3) of the curable (meth) acrylate polymer of the present invention can be selected as appropriate.
  • a photosensitive polymer it is generally 10 to 300 KOH mg / g, preferably 20 to 250 KOH mg / g.
  • the acid value is 10 KOHmg / g or more, sufficient alkali developability as a photosensitive polymer is obtained, which is preferable.
  • the acid value is 300 KOHmg / g or less, the exposed portion (photocured portion) is not dissolved in the alkali developer, and as a result, an excellent pattern shape is obtained.
  • the hydroxyl value (JIS K0070) of the polymer can be selected as necessary. Generally, it is 70 to 300 KOH mg / g, and preferably in the range of 85 to 250 KOH mg / g. A hydroxyl value of 70 KOHmg / g or more is preferable because adhesion and developability are sufficient. On the other hand, when the hydroxyl value is 300 KOHmg / g or less, the solvent resistance is sufficient, which is preferable. *
  • the unsaturated group equivalent of the polymer is not particularly limited and can be arbitrarily selected. Generally, it is 100 to 4,000 g / mol, preferably 200 to 2,000 g / mol, and more preferably 300 to 500 g / mol. When the unsaturated group equivalent is 100 g / mol or more, it is effective and preferable in enhancing the physical properties of the coating film and the alkali developability. On the other hand, when the unsaturated group equivalent is 4,000 g / mol or less, it is effective in increasing the sensitivity.
  • the unsaturated bond equivalent is the mass of the polymer per 1 mol of unsaturated bonds in the polymer.
  • This value can be determined by dividing the mass of the polymer by the amount of unsaturated bonds in the polymer (g / mol).
  • the “unsaturated bond equivalent” is a theoretical value calculated from the amount of raw materials used for introducing an unsaturated bond.
  • the curable (meth) acrylate polymer of the present invention can have various monomer units derived from the monomers and compounds used. Some of these preferred examples are described below.
  • the curable composition of the present invention is a component arbitrarily selected, for example, , Solvent (component B, hereinafter sometimes referred to as B), reactive diluent (component C, hereinafter sometimes referred to as C), photopolymerization initiator (component D, hereinafter sometimes referred to as D), And it can be set as a curable composition by including at least 1 type of a coloring agent (E component, and may be hereafter called E).
  • the solvent (B) is an inert solvent that dissolves the curable polymer (A), has compatibility with the reactive diluent (C) described later, and does not react with the curable polymer (A). It is not limited and can be selected arbitrarily.
  • the same solvent as that which can be used when producing the curable (meth) acrylate polymer (A) can be used. Specific examples thereof include the above-described examples.
  • (poly) alkylene glycol monoalkyl ether solvents such as propylene glycol monomethyl ether
  • (poly) alkylene glycol monoalkyl ether acetate solvents such as propylene glycol monomethyl ether acetate, that is, glycol ether solvents are used.
  • the curable composition of the present invention is prepared by isolating the desired curable (meth) acrylate polymer (A) from the mixed liquid after polymerization, and appropriately mixing the desired solvent (B) therein. You can also. However, in order to obtain the curable composition of the present invention, it is not always necessary to isolate the curable (meth) acrylate polymer (A) from the polymerization system. The solvent contained at the end of the copolymerization reaction is not separated from the polymer (A) but can be used as it is as the composition of the present invention. Furthermore, other desired solvents may be further added to the composition as necessary. Moreover, the solvent contained in the other component used when preparing a curable composition can also be used and / or added as a component of a solvent (B).
  • the reactive diluent (C) (polymerizable monomer) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule. Among these, it is preferable to have a plurality of polymerizable functional groups. Such a reactive diluent is not necessarily an essential component of the curable composition. However, by using this together with the curable (meth) acrylate polymer (A), the film strength of the coating film formed from the composition and the adhesion to the substrate can be improved.
  • the monofunctional monomer used as the reactive diluent can be arbitrarily selected.
  • (Meth) acrylate compounds aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene and vinyltoluene; carboxylic acid esters such as vinyl acetate and vinyl propionate. Moreover, these can be used individually or in combination of 2 or more types.
  • the polyfunctional monomer used as the reactive diluent can be arbitrarily selected.
  • tris (hydro (Meth) acrylate compounds such as tri (meth) acrylate of (ethyl) isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallylphthalate and diallylbenzenephosphonate; dicarboxylic acid ester compounds such as divinyl adipate; triallyl cyanurate, methylenebis Examples include (meth) acrylamide, (meth) acrylamide methylene ether, condensates of polyhydric alcohol and N-methylol (meth) acrylamide. Moreover, these can be used individually or in combination of 2 or more types.
  • the compounding quantity of the polymer (A) in a curable composition, a solvent (B), and a reactive diluent (C) is selected suitably the compounding quantity of the polymer (A) in a curable composition, a solvent (B), and a reactive diluent (C) according to the intended purpose.
  • the curable polymer (A) is 10 to 100 parts by mass and the solvent (B) is 30 to 1,000 parts by mass.
  • the reactive diluent (C) is 0 to 90 parts by mass.
  • the curable polymer (A) is 20 to 80 parts by mass
  • the solvent (B) is 50 to 800 parts by mass
  • the reactive diluent (C) is 20 to 80 parts by mass.
  • the polymer (A) is 30 to 75 parts by mass
  • the solvent (B) is 100 to 700 parts by mass
  • the reactive diluent (C) is 25 to 70 parts by mass. If it is the compounding quantity of this range, the curable composition which has suitable viscosity will be obtained, and it can use preferably in order to prepare the photosensitive polymer composition mentioned later.
  • various coatings, adhesives, printing ink binders, and the like can be preferably used.
  • the photosensitive polymer composition of the present invention preferably contains a curable (meth) acrylate polymer (A), a solvent (B), and a photopolymerization initiator (D component, hereinafter may be referred to as D).
  • the composition may preferably contain a reactive diluent (C) and / or a colorant (E component, hereinafter may be referred to as E) as required.
  • the curable (meth) acrylate polymer (A), the solvent (B), and the reactive diluent (C) are the same as those contained in the curable composition containing the curable (meth) acrylate polymer.
  • Photopolymerization initiator (D) It does not specifically limit as a photoinitiator (D), It can select arbitrarily.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1- Methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
  • Acetophenone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like; xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2, -Xanthone compounds such as diisoprop
  • the compounding quantity of the photoinitiator (D) in a photosensitive polymer composition is selected arbitrarily, when it is 100 mass parts in total of (A) component and (C) component, generally 0.1% -30 parts by mass, preferably 0.5-20 parts by mass, more preferably 1-15 parts by mass. If it is the compounding quantity of this range, the photosensitive polymer composition which has suitable photocurability can be obtained.
  • the colorant (E) is not particularly limited as long as it dissolves or disperses in the solvent (B), and can be arbitrarily selected. Examples thereof include dyes and pigments.
  • the dye acidic groups such as carboxylic acid and sulfonic acid are used from the viewpoints of solubility in the solvent (B) and the alkaline developer, interaction with other components in the photosensitive polymer composition, and heat resistance. It is preferable to use the acid dye selected from the acid dyes, salts with the nitrogen compounds of the acid dyes, sulfonamides of the acid dyes, and the like.
  • dyes include: acid alizarin violet N; acid black1,2,24,48; acid blue1,7,9,25,29,40,45,62,70,74,80,83,90, 92, 112, 113, 120, 129, 147; acid chrome violetolK; acid Fuchsin; acidacgreen1, 3, 5, 25, 27, 50; acid range6, 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 yellow1, 3, 9, 11, 17,
  • pigments examples include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I.
  • Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as CI Pigment Green 7, 36, 58; I. Brown pigments such as CI Pigment Brown 23 and 25; I. And black pigments such as CI pigment blacks 1 and 7, carbon black, titanium black, and iron oxide.
  • Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60
  • I. Violet color pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38
  • Green pigments such as CI Pigment Green 7, 36, 58
  • Brown pigments such as
  • the blending amount of the colorant (E) can be arbitrarily selected.
  • the total of component (A) and component (C) is 100 parts by mass, it is generally 5 to 80 parts by mass, preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass.
  • a known dispersant may be added to the photosensitive polymer composition from the viewpoint of improving the dispersibility of the pigment.
  • the dispersant it is preferable to use a polymer dispersant excellent in dispersion stability over time.
  • the polymer dispersant can be arbitrarily selected. For example, urethane dispersant, polyethyleneimine dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene glycol diester dispersant, sorbitan aliphatic ester dispersant, aliphatic modified ester dispersion Agents and the like.
  • EFKA registered trademark, manufactured by BASF Japan
  • Disperbyk registered trademark, manufactured by Big Chemie
  • Disparon registered trademark, manufactured by Enomoto Kasei Co., Ltd.
  • SOLPERSE registered trademark, manufactured by Geneca
  • the amount of each component is arbitrarily selected as necessary.
  • the composition contains a curable (meth) acrylate polymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D), and a colorant (E), these compounds The amount is preferably as follows.
  • the curable (meth) acrylate polymer (A) is 10 to 90 parts by mass
  • the solvent (B) is 30 to 1,000 parts by weight
  • the reactive diluent (C) is 10 to 90 parts by weight
  • the photopolymerization initiator (D) is 0.1 to 30 parts by weight
  • the colorant (E) is 5 to 80 parts by mass.
  • the curable (meth) acrylate polymer (A) is 20 to 80 parts by mass
  • the solvent (B) is 50 to 800 parts by mass
  • the reactive diluent (C) is 20 to 80 parts by mass
  • a photopolymerization initiator ( D) is 0.5 to 20 parts by mass
  • the colorant (E) is 5 to 70 parts by mass.
  • the curable (meth) acrylate polymer (A) is 30 to 75 parts by mass
  • the solvent (B) is 100 to 700 parts by mass
  • the reactive diluent (C) is 25 to 70 parts by mass
  • D) is 1 to 15 parts by mass
  • the colorant (E) is 10 to 60 parts by mass.
  • the photosensitive polymer composition does not contain the colorant (E), the curable (meth) acrylate polymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (
  • the above numerical range can be preferably used for the blending amount of D).
  • the curable composition and photosensitive polymer composition of the present invention are blended with known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors in order to impart predetermined characteristics. Also good.
  • the amount of these additives 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 an arbitrarily selected method. For example, it can manufacture by mixing said component using a well-known mixing apparatus. If desired, after preparing a curable composition containing the curable (meth) acrylate polymer (A) and the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and It is also possible to add the colorant (E), which is an optional component, and mix them.
  • the photosensitive polymer composition of the present invention is preferably used as a resist used for various purposes. It is particularly suitable as a resist used in the manufacture of organic EL displays, liquid crystal display devices, and color filters incorporated in solid-state imaging devices such as CCD and CMOS. Further, the photosensitive polymer composition of the present invention gives a cured film excellent in heat resistance, solvent resistance, dispersibility of dyes and pigments, and the like. Therefore, it can also be preferably used for various coatings, adhesives, binders for printing inks, and the like.
  • the color filter of this invention has a coloring pattern formed using said photosensitive polymer composition.
  • the color filter is usually composed of a substrate, RGB pixels formed on the substrate, a black matrix formed at the boundary between the pixels, and a protective film formed on the pixels and the black matrix. .
  • known configurations can be adopted as the other configurations except that the pixels and the black matrix (colored pattern) are formed using the above-described photosensitive polymer composition of the present invention.
  • a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate.
  • the material of the base material is not particularly limited. For example, 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 substrate, an array substrate, or the like can be used as appropriate.
  • the colored pattern can be formed by a photolithography method. Specifically, it can be obtained as follows. First, the photosensitive polymer composition is applied onto a substrate to form a coating film. Thereafter, the coating film is exposed through a photomask having a predetermined pattern, and the exposed portion is photocured. Then, the unexposed portion is developed with an alkaline aqueous solution and then baked. In this way, a predetermined pattern can be formed.
  • the coating method of the photosensitive polymer composition is not particularly limited and can be arbitrarily selected. For example, 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.
  • the solvent (B) contained in the coating film is volatilized by heating using a heating means such as a circulation oven, an infrared heater, and a hot plate, if necessary. You may let them.
  • the heating conditions are not particularly limited, and may be set as appropriate according to the type of the photosensitive polymer composition to be used. In general, it is preferable to heat at a temperature of 50 ° C. to 120 ° C. for 30 seconds to 30 minutes.
  • the formed coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask.
  • active energy rays such as ultraviolet rays and excimer laser light
  • What is necessary is just to select the energy dose to irradiate suitably according to the composition of the photosensitive polymer composition.
  • it is preferably 30 to 2,000 mJ / cm 2 , but is not limited to this range.
  • the light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like can be arbitrarily selected and used.
  • the aqueous alkali solution used for development is not particularly limited and is arbitrarily selected.
  • an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc . an aqueous solution of an amine compound such as ethylamine, diethylamine, dimethylethanolamine; tetramethylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl An aqueous solution of a -4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and a p-phenylenediamine compound such as a sulfate, hydrochloride or p-toluene
  • the baking conditions are not particularly limited and can be arbitrarily selected. Depending on the type of the photosensitive polymer composition to be used, preferred conditions may be selected for heat treatment. For example, baking at a temperature of 130 ° C. to 250 ° C. for 10 minutes to 4 hours can be preferably employed, and heating for 20 minutes to 2 hours is more preferable. However, it is not limited to these conditions.
  • the steps of coating, exposing, developing and baking are repeated in order using a photosensitive polymer composition for black matrix and a photosensitive polymer composition for red, green, and blue pixels, thereby obtaining a desired A colored pattern can be formed.
  • a photoinitiator (D) the formation method of the coloring pattern by photocuring of the composition using a photoinitiator (D) was demonstrated until now, this invention is not limited to these methods. If, for example, a composition containing a curing accelerator and a known epoxy resin is used instead of the photopolymerization initiator (D), the composition is applied by an ink jet method and then cured by heating to form a desired colored pattern. It can also be formed. Next, a protective film is formed on the colored pattern (RGB pixels and black matrix). It does not specifically limit as a protective film, What is necessary is just to form using a well-known thing.
  • the color filter thus manufactured is manufactured using a photosensitive polymer composition that gives a colored pattern with excellent sensitivity, developability, solvent resistance, and dispersibility of dyes or pigments. Therefore, it has a high brightness coloring pattern.
  • the image display element of the 4th aspect of this invention is a display element which has said color filter.
  • Specific examples thereof include liquid crystal display elements, organic EL display elements, and solid-state imaging elements such as CCD elements and CMOS elements.
  • the color filter is used, and the image display element can be manufactured according to a conventional method. For example, when manufacturing a liquid crystal display element, the color filter is formed on a substrate, and then electrodes, spacers, and the like are sequentially formed. Then, an electrode or the like is formed on another substrate, the two are bonded together, a predetermined amount of liquid crystal is injected, and sealing is performed.
  • Example 1 Add 93.3 g of propylene glycol monomethyl ether acetate as a solvent to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and stir while replacing the nitrogen gas inside the flask, raising the temperature to 120 ° C. It was.
  • a (meth) acrylate polymer represented by the formula (20) was obtained.
  • the acid value of this polymer was 140 KOH mg / g, and the weight average molecular weight was 8,400.
  • a, b, c, d and e represent the number of monomer units and are integers of 1 or more.
  • 353.1 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid content concentration of 35% of the curable polymer (A). This solution was used for various evaluations shown below for the evaluation of Sample 1.
  • Example 2 To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 124.4 g of propylene glycol monomethyl ether acetate is added as a solvent, and the inside of the flask is stirred while replacing nitrogen gas, and the temperature is raised to 120 ° C. It was. Subsequently, 9.5 g of t was added to a monomer mixture consisting of 33.0 g (0.15 mol) of tricyclodecanyl methacrylate, 31.4 g (0.15 mol) of styrene, and 99.4 g (0.7 mol) of glycidyl methacrylate.
  • a curable (meth) acrylate polymer represented by the formula (21) was obtained.
  • the acid value of this polymer was 100 KOH mg / g, and the weight average molecular weight was 9,400.
  • f, g, h and i represent the number of monomer units and are integers of 1 or more.
  • a polymer solution having a solid content concentration of 35% was prepared.
  • Example 3 To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 124.4 g of propylene glycol monomethyl ether acetate is added as a solvent, and the inside of the flask is stirred while replacing nitrogen gas, and the temperature is raised to 120 ° C. It was. Subsequently, 9.5 g of t was added to a monomer mixture consisting of 33.0 g (0.15 mol) of tricyclodecanyl methacrylate, 31.4 g (0.15 mol) of styrene and 60.2 g (0.7 mol) of methacrylic acid.
  • the anhydride group of tetrahydrophthalic anhydride was reacted to introduce a carboxy group into the side chain.
  • the acid value of the obtained curable (meth) acrylate polymer represented by the formula (22) (Sample 3) was 90 KOH mg / g, and the weight average molecular weight was 10,000.
  • j, k, l and m represent the number of monomer units and are integers of 1 or more.
  • a polymer solution having a solid content concentration of 35% was prepared.
  • Unsaturated group equivalent The mass of the polymer per mole of polymerizable unsaturated bonds, and is a calculated value calculated based on the amount of monomer used.
  • Hydroxyl value The hydroxyl value of the curable polymer measured according to JIS K0070. When 1 g of the curable polymer is acetylated, it means the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group.
  • Example 7 to 12 and Comparative Examples 4 to 6 Using the samples 1 to 9 prepared in Examples 1 to 6 and Comparative Examples 1 to 3, the transparent photosensitive polymer compositions of Examples 7 to 12 and Comparative Examples 4 to 6 (transparent resists) were prepared by the following composition. ) was prepared.
  • Samples 1 to 9 (polymer only) 25.0 Trimethylolpropane triacrylate (reactive diluent) 3.0 Irgacure (registered trademark) 907 (photopolymerization initiator, manufactured by BASF Japan) 0.2 Hycure (registered trademark) ABP (photopolymerization initiator, manufactured by Kawaguchi Pharmaceutical Co., Ltd.) 0.1 Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (solvent) 31.0
  • the photosensitive polymer composition number No. 1-No. No. 9 corresponds to the sample numbers (No. 1 to No. 9) used.
  • the masses of Samples 1 to 9 do not include the solvent used for preparing the polymer solution. The amount of the solvent contained in the polymer solution is added to the solvent as a blending component.
  • the peeled state of 100 grids was visually observed, and the adhesion was evaluated according to the following criteria.
  • Evaluation of heat-resistant yellowing A coating film formed using the above resist on a glass substrate was prepared, and this coating film was left in a dryer at 230 ° C. for 1 hour. About the said coating film before and after heat processing, the light transmittance in 400 nm was measured with the spectrophotometer.
  • Heat yellowing resistance was evaluated using the obtained light transmittance and the following criteria.
  • a photomask having a predetermined pattern was placed at a distance of 100 ⁇ m from the coating film, and the coating film was exposed (exposure amount 150 mJ / cm 2 ) through this photomask, and the exposed portion was photocured.
  • the unexposed part was melt
  • the predetermined pattern for evaluation containing the line pattern from which size differs was formed by baking at 230 degreeC for 30 minute (s).
  • (2-3) Adhesion The width of the minimum line pattern that can be formed with a pattern was observed with an optical microscope, and the adhesion after baking was evaluated according to the following criteria. In addition, a fine pattern can be formed, so that adhesiveness is favorable.
  • the color resist was spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after exposure was 2.5 ⁇ m. Thereafter, the obtained coating film was heated at 90 ° C. for 3 minutes to volatilize the solvent. Next, the coating film was exposed to light having a wavelength of 365 nm, and the exposed portion was photocured. Then, it was left to stand for 30 minutes in a dryer with a baking temperature of 230 ° C. to prepare a cured coating film. 200 mL of N-methyl-2-pyrrolidone was placed in a 500 mL lidded glass bottle, and the above-mentioned test piece with a cured coating film was immersed therein.
  • the numbers (No. 1 to No. 9) of the photosensitive polymer compositions correspond to the sample numbers (No. 1 to No. 9) used. Further, the masses of Samples 1 to 9 described in the following formulations do not include the solvent used for the preparation of the polymer solution. The amount of the solvent is added to the solvent as a blending component.
  • Viscosity change rate is 15% or more and less than 20%.
  • color resists using photosensitive polymer compositions Nos. 1 to 6) using the photosensitive polymer compositions (pigment types) of Examples 19 to 24 of the present invention are alkaline. Good performance was shown in developability, sensitivity, solvent resistance, pigment dispersibility and adhesion. In contrast, the color resists of Comparative Examples 10 to 12 (using photosensitive polymer compositions No. 7 to 9) using the photosensitive polymer compositions of Comparative Examples 1 to 3 have pigment dispersibility and solvent resistance. And adhesion were inferior.
  • a photosensitive polymer composition (dye / pigment type) was prepared by the following composition.
  • the numbers (No. 1 to No. 9) of the photosensitive polymer compositions correspond to the sample numbers (No. 1 to No. 9) used.
  • the amounts of Samples 1 to 9 (polymers) described in the following formulations do not include the solvent used for preparing the polymer solution. The amount of the solvent contained in each polymer solution is added to the following solvent as a blending component.
  • color resists using photosensitive polymer compositions Nos. 1 to 6) using the photosensitive polymer compositions (dye / pigment type) of Examples 25 to 30 of the present invention are as follows. It can be seen that good performance is exhibited in alkali developability, sensitivity, solvent resistance, pigment dispersibility and adhesion. On the other hand, the color resists of Comparative Examples 13 to 15 (using photosensitive polymer composition Nos. 7 to 9) are inferior in performance.
  • the present invention when used as a photosensitive material, it is possible to obtain a curable polymer excellent in sensitivity, developability, solvent resistance as a cured product, adhesion to a substrate, and dispersibility of a colorant. it can. Moreover, the cured coating film formed from the photosensitive polymer composition of this invention is excellent in solvent resistance, adhesiveness with a board
  • a curable polymer excellent in sensitivity, developability, heat-resistant yellowing as a cured product, solvent resistance, adhesion to a substrate and dispersibility of a colorant, and a photosensitive polymer containing the curable polymer are provided.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention concerne : un polymère de (méth)acrylate durcissable contenant une unité répétitive ayant une structure dans laquelle au moins deux groupes carboxy sont directement liés à un squelette alicyclique; une composition durcissable comprenant celui-ci; et un filtre coloré.
PCT/JP2016/065146 2015-07-31 2016-05-23 Polymère de (méth)acrylate durcissable, composition durcissable, filtre coloré et dispositif d'affichage d'image Ceased WO2017022299A1 (fr)

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JP2005036218A (ja) * 2003-06-30 2005-02-10 Mitsubishi Gas Chem Co Inc 熱硬化性樹脂組成物及びその用途
JP2007102109A (ja) * 2005-10-07 2007-04-19 Goo Chemical Co Ltd 感光性樹脂組成物、硬化物及びプリント配線板
JP2008070893A (ja) * 1998-08-26 2008-03-27 Nissan Chem Ind Ltd 液晶配向処理剤及びそれを用いた液晶素子並びに液晶の配向方法
JP2013032495A (ja) * 2011-06-29 2013-02-14 Sumitomo Chemical Co Ltd 硬化性樹脂組成物
JP2014210892A (ja) * 2013-04-22 2014-11-13 昭和電工株式会社 （メタ）アクリレート系ポリマー、該ポリマーを含む組成物及びその用途
JP2015067734A (ja) * 2013-09-30 2015-04-13 昭和電工株式会社 感光性樹脂の製造方法及びカラーフィルター

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008070893A (ja) * 1998-08-26 2008-03-27 Nissan Chem Ind Ltd 液晶配向処理剤及びそれを用いた液晶素子並びに液晶の配向方法
JP2005036218A (ja) * 2003-06-30 2005-02-10 Mitsubishi Gas Chem Co Inc 熱硬化性樹脂組成物及びその用途
JP2007102109A (ja) * 2005-10-07 2007-04-19 Goo Chemical Co Ltd 感光性樹脂組成物、硬化物及びプリント配線板
JP2013032495A (ja) * 2011-06-29 2013-02-14 Sumitomo Chemical Co Ltd 硬化性樹脂組成物
JP2014210892A (ja) * 2013-04-22 2014-11-13 昭和電工株式会社 （メタ）アクリレート系ポリマー、該ポリマーを含む組成物及びその用途
JP2015067734A (ja) * 2013-09-30 2015-04-13 昭和電工株式会社 感光性樹脂の製造方法及びカラーフィルター

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