KR101473511B1 - Photosensitive graft polymer, and photosensitive resin composition comprising the same - Google Patents
Photosensitive graft polymer, and photosensitive resin composition comprising the same Download PDFInfo
- Publication number
- KR101473511B1 KR101473511B1 KR1020107009457A KR20107009457A KR101473511B1 KR 101473511 B1 KR101473511 B1 KR 101473511B1 KR 1020107009457 A KR1020107009457 A KR 1020107009457A KR 20107009457 A KR20107009457 A KR 20107009457A KR 101473511 B1 KR101473511 B1 KR 101473511B1
- Authority
- KR
- South Korea
- Prior art keywords
- mass
- meth
- acrylate
- graft polymer
- parts
- Prior art date
Links
Classifications
-
- 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
- C08F290/02—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 end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The photosensitive graft polymer according to the present invention is obtained by copolymerizing 30 mol% to 80 mol% of a polymerizable monomer having a crosslinkable cyclic hydrocarbon group having 10 to 20 carbon atoms, such as dicyclopentenyl (meth) acrylate, (A) obtained by copolymerizing 20 mol% to 70 mol% of a polymerizable monomer having no crosslinked cyclic hydrocarbon group as a branched polymer. The polymerizable monomers having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl methacrylate, adamantyl (meth) Is preferably at least one member selected from the group consisting of compounds represented by the following formulas (1) and (2).
[Chemical Formula 1]
(Wherein R < 1 > represents hydrogen or a methyl group)
Description
The present invention relates to a photosensitive graft polymer which can be preferably used for a solder resist, various coatings, an adhesive, a binder for printing ink, a binder for a color filter, and a photosensitive resin composition containing the photosensitive graft polymer.
In recent years, in view of resource saving and energy saving, active energy ray-curable resins that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of printing, paints and adhesives. In the field of electronic materials such as printed wiring boards, a solder resist using a resin cured by an active energy ray is used as a resin for a semiconductor substrate.
A color filter used in a color liquid crystal display device or a solid-state image pickup device includes a colored coating film in which three colors of red (R), green (G) and blue (B) And a black black matrix formed between colored coating films of RGB three colors. Such a color filter is usually manufactured by forming a black matrix on a transparent substrate such as glass and then successively forming colored coating films of R, G and B in a predetermined pattern.
As a method for forming a pattern of a colored coating film, a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method and the like can be mentioned generally. Among them, a pigment using a photolithographic method in which a photocurable resin composition mainly composed of an alkali-soluble binder polymer, a reactive diluent, a photopolymerization initiator, a pigment and a solvent is applied on a transparent substrate, and exposure, The dispersion method is excellent in light resistance and heat resistance of the formed colored coating film, and has become mainstream at present due to few defects such as pinholes.
In recent years, there has been a growing demand for high definition display of color displays. In order to obtain a clear color tone by the pigment dispersion method, it is effective to make the pigment particles finer, but when the pigment is excessively fine, the dispersibility and stability of the pigment deteriorate with time, and the photo- Can not be obtained, or there is a problem in dimensional accuracy.
Thus, in order to improve the dispersion stability of the pigment, a method of grafting the binder polymer has been proposed. It is believed that by grafting the binder polymer, steric hindrance of the branched polymer prevents the aggregation of the pigments, thereby improving dispersion stability. Conventionally, a radiation-sensitive composition using a binder polymer composed of a monomer having an alcoholic hydroxyl group, a macromonomer of styrene or methyl methacrylate (for example, Patent Documents 1 and 2) or a quaternary ammonium salt monomer and styrene or methyl methacrylate (For example, Patent Document 3), a colored photosensitive composition using a binder polymer comprising a monomer mixture of a nitrogen atom-containing monomer and styrene or methyl methacrylate For example, Patent Document 4) has been proposed, but the dispersion stability of the pigment by these binder polymers is not satisfactory.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a curable coating film excellent in dispersion stability of pigments and excellent in transparency, It is an object of the present invention to provide a resin composition and a photosensitive graft polymer blended therewith.
In order to solve the above problems, the inventors of the present invention have found that (meth) acrylate having an alkyl group such as styrene or methyl methacrylate, which has been widely used so far in order to enhance the dispersibility of the pigment by the steric hindrance effect by the monomer structure, It is necessary to select a macromonomer having a bulkier structure than the macromonomer of the rate. The inventors of the present invention have conducted extensive studies on conventional macromonomers. As a result, they have found that a macromonomer obtained by copolymerizing a polymerizable monomer having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable monomer having no crosslinked cyclic hydrocarbon group The present inventors have found that a photosensitive graft polymer comprising a polymer of the present invention solves the above problems, and has accomplished the present invention.
That is, the present invention relates to a process for preparing a macromonomer obtained by copolymerizing 30 to 80 mol% of a polymerizable monomer having a crosslinkable cyclic hydrocarbon group having 10 to 20 carbon atoms and 20 to 70 mol% of a polymerizable monomer having no crosslinked cyclic hydrocarbon group, By weight of the photosensitive graft polymer.
Further, the present invention is a photosensitive resin composition comprising the photosensitive graft polymer, a reactive diluent, a photopolymerization initiator, and a solvent.
According to the present invention, there is provided a photosensitive resin composition which is excellent in dispersion stability of a pigment and which is excellent in transparency and which can form a cured coating film and which further has alkali developability and does not contain residues after development and a photosensitive graft polymer can do.
Hereinafter, the present invention will be described in detail.
First, the macromonomer (a) to be a branched polymer in the photosensitive graft polymer according to the present invention will be described.
The macromonomer (a) in the present invention can be obtained by a conventional radical polymerization method. For example, in the organic solvent, the polymerizable monomer (a-1) having a crosslinkable cyclic hydrocarbon group having 10 to 20 carbon atoms as the first component of the macromonomer and the polymerizable monomer (a-1) having no crosslinked cyclic hydrocarbon group as the second component of the macromonomer The polymerizable monomer (a-2) is dissolved in a predetermined ratio, and a chain transfer agent having a functional group such as a carboxyl group or a hydroxyl group and a polymerization initiator are mixed and subjected to solution polymerization at about 50 to 130 ° C for about 1 to 20 hours, A prepolymer having functional groups such as a carboxyl group and a hydroxyl group at the terminal thereof is obtained. By introducing a polymerizable unsaturated group at the end of the prepolymer thus obtained, a macromonomer (a) which can be introduced as a branch polymer into the photosensitive graft polymer can be obtained. As a method of introducing a polymerizable unsaturated group, for example, when a compound having two functional groups capable of reacting with a functional group such as a carboxyl group or a hydroxyl group at the end of the prepolymer and a polymerizable unsaturated group is reacted with the prepolymer do. As a compound having two groups of a functional group capable of reacting with a prepolymer having a terminal functional group and a polymerizable unsaturated group, glycidyl (meth) acrylate having an epoxy group and alicyclic epoxy (Meth) acrylate having an isocyanate group (e.g., methacrylate having an isocyanate group (e.g., methacrylate) having an isocyanate group (e.g., methacrylate having an isocyanate group (AOI, MOI, manufactured by Showa Denko K.K.) can be used.
The weight average molecular weight of the macromonomer (a) is preferably 2,000 to 20,000, more preferably 7,000 to 18,000. If the weight average molecular weight of the macromonomer (a) is less than 2,000, the dispersion stability of the pigment may not be sufficiently obtained. On the other hand, if the weight average molecular weight exceeds 20,000, the dispersion stability of the pigment is not further improved, There is a case in which the property is deteriorated and a residue is generated.
The copolymerization ratio of the polymerizable monomer (a-1) and the polymerizable monomer (a-2) is preferably from 20 mol% to 20 mol% based on 30 mol% to 80 mol% of the polymerizable monomer (a- , More preferably from 20 mol% to 50 mol% of the polymerizable monomer (a-2) relative to 50 mol% to 80 mol% of the polymerizable monomer (a-1). If the copolymerization ratio of the polymerizable monomer (a-1) is less than 30 mol%, the dispersion stability of the pigment can not be sufficiently obtained. On the other hand, if the copolymerization ratio of the polymerizable monomer (a-1) exceeds 80 mol%, the hydrophobicity of the macromonomer becomes excessively high, the solubility of the photosensitive graft polymer in the solvent decreases and the photosensitive graft polymer solution becomes turbid, As a result, transparency of the photosensitive resin composition is impaired.
The polymerizable monomer (a-1) which is the first component of the macromonomer can be a polymerizable monomer having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms. From the viewpoint of improving the heat resistance, the glass transition temperature (Tg) of the homopolymer is 120 Lt; 0 > C or more. Specific examples of such a polymerizable monomer (a-1) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl methacrylate, adamantyl (meth) , Compounds represented by the following formulas (1) and (2), and the like. These may be used singly or in combination of two or more kinds.
[Chemical Formula 1]
(Wherein R < 1 > represents hydrogen or a methyl group)
The polymerizable monomer (a-2) which is the second component of the macromonomer can be any polymerizable monomer that does not have a crosslinked cyclic hydrocarbon group and can be copolymerized with the polymerizable monomer (a-1), and the photosensitive graft polymer solution is turbid It is preferable that the hydrophobicity is not so high and compatibility with the solvent used in the graft polymer synthesis is high. In order to increase the dispersibility of the pigment by the steric hindrance effect due to the monomer structure, the polymerizable monomer (a-2) preferably has a cyclic structure, for example, an aromatic ring, a heterocyclic ring or an alicyclic structure. Specific examples of such a polymerizable monomer (a-2) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, rosin (meth) acrylate, phenoxy Ethyl (meth) acrylate, and the like. These may be used singly or in combination of two or more kinds.
Examples of the polymerization initiator used in the radical polymerization include azobisisobutyronitrile, azobisisobalonitrile, azobisisobutylate, azobiscyano valeric acid, azobiscyanopentanol, benzoyl peroxide, t- Butyl peroxy-2-ethyl hexanoate, and the like. The amount of the polymerization initiator to be used is generally 0.5 parts by mass to 20 parts by mass, preferably 1.0 parts by mass to 10 parts by mass, per 100 parts by mass of the total amount of the polymerizable monomer (a-1) and the polymerizable monomer (a-2) .
As the chain transfer agent to be used in the radical polymerization, thiol is preferable from the value of the chain transfer constant in the case of using an acrylic monomer in order to efficiently introduce a functional group to the terminal, and specifically, thioglycolic acid, mercaptopropionic acid , Mercaptoethanol, and the like. The amount of the chain transfer agent to be used is generally 0.3 parts by mass to 20 parts by mass, preferably 0.5 parts by mass to 10 parts by mass, per 100 parts by mass of the total amount of the polymerizable monomer (a-1) and the polymerizable monomer (a-2) .
Examples of the organic solvent include glycol ester solvents such as propylene glycol monomethyl ether acetate, hydrocarbon solvents such as toluene and xylene, and organic solvents having no functional groups such as ethyl acetate.
It is also possible to perform bulk polymerization by using only the polymerizable monomer (a-1), the polymerizable monomer (a-2), the polymerization initiator and the chain transfer agent without using an organic solvent, In order to promote a stable polymerization reaction, it is preferable to add the organic solvent as described above. The macromonomer solution synthesized by adding an organic solvent may be used as it is, or may be used after removing the solvent. In this case, the macromonomer solution is reprecipitated in a poor solvent to obtain a macromonomer.
Next, the photosensitive graft polymer (A) according to the present invention will be described.
The photosensitive graft polymer (A) according to the present invention is characterized by using the macromonomer (a) as the branched polymer. In the present invention, the photosensitive graft polymer (A) is classified into four copolymers (A-1) to can do.
The copolymer (A-1) according to the present invention is obtained by copolymerizing the macromonomer (a), the unsaturated monobasic acid (b) and the radical polymerizable compound (c) other than the macromonomer (a) and the unsaturated monobasic acid ). The copolymerization ratio of the component (a), the component (b) and the component (c) is 2% by mass to 20% by mass, preferably 4% by mass to 20% (B) is 3 mass% to 35 mass%, preferably 10 mass% to 35 mass%, more preferably 10 mass% to 30 mass%, and (c) Is 30% by mass to 90% by mass, preferably 35% by mass to 85% by mass, and more preferably 40% by mass to 85% by mass. If the copolymerization ratio of the component (a) is less than 2 mass%, the dispersion stability of the pigment may not be sufficiently obtained. On the other hand, even if the copolymerization ratio of the component (a) exceeds 20 mass% The alkali developability is deteriorated and a residue is sometimes generated.
The unsaturated monobasic acid (b) is used to have a carboxyl group in the side chain of the copolymer (A-1) to have an acid value. The unsaturated monobasic acid as the component (b) of the present invention is not particularly limited, and examples of the compound having a carboxyl group include (meth) acrylic acid, crotonic acid, cinnamic acid and the like. In addition, polyfunctional (meth) acrylates having one hydroxyl group and at least one (meth) acryloyl group (for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (Meth) acrylate, trimethylolpropane di (meth) acrylate, etc.) with a polybasic acid anhydride may also be used. Among them, (meth) acrylic acid is preferable in view of reactivity and ease of obtaining water. These may be used singly or in combination of two or more kinds.
The radically polymerizable compound (c) other than the component (a) and the component (b) is not particularly limited as long as it has an ethylenic unsaturated group. Specific examples thereof include styrene, styrene
The method of radical polymerization in producing the copolymer (A-1) is not particularly limited, but the amount of the polymerization initiator or the like used may be the same as that in producing the macromonomer. In addition, bulk polymerization may be carried out using only the component (a), the component (b) and the component (c) and the polymerization initiator without using an organic solvent, but it is preferable to add an organic solvent for the same reason as in the production of the macromonomer.
The amount of the organic solvent used is usually 30 parts by mass to 1000 parts by mass, preferably 50 parts by mass to 800 parts by mass, based on 100 parts by mass of the total amount of the components (a), (b) and (c). When the amount of the organic solvent used is 1000 parts by mass or less, the molecular weight of the copolymer can be prevented from decreasing due to the chain transfer action, and the solid content concentration of the finally obtained copolymer can be controlled within an appropriate range.
Since the copolymer (A-1) according to the present invention is a photosensitive resin composition mixed with a reactive diluent (B), a photopolymerization initiator (C) and a solvent (D) to be described later and is mainly used as an electronic material such as a resist, When the co-polymer (A-1) is prepared by radical copolymerization as described above, a glycol ester-based solvent such as propylene glycol monomethyl ether acetate is preferably used.
The copolymer (A-2) according to the present invention is obtained by reacting a radical polymerizable compound (d) having an epoxy group or alicyclic epoxy group with a carboxyl group present in the side chain of the copolymer (A-1) . The amount of the radically polymerizable compound having an epoxy group or alicyclic epoxy group as the component (d) is 5 to 80 moles, preferably 10 to 65 moles, per 100 moles of carboxyl groups present in the side chain of the copolymer (A-1) desirable. By using the amount as described above, the balance between the carboxyl group and the unsaturated group becomes good, and the curability of the copolymer (A-2) and developability due to alkali are suitably maintained.
The reaction of the radical polymerizable compound having an epoxy group or alicyclic epoxy group as the component (d) to the carboxyl group in the copolymer (A-1) is carried out as follows. That is, in order to prevent the gelation of the unsaturated monobasic acid or the resulting unsaturated group-containing copolymer by polymerization, it is preferable to use a polymerization initiator in the presence of a polymerization inhibitor such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, The reaction is carried out usually at 50 ° C to 150 ° C, preferably at 80 ° C to 130 ° C in the presence of a phosphorous compound such as a quaternary ammonium salt such as triethylamine, or a tertiary amine such as triethylamine, or a phosphorous compound such as triphenylphosphine. When an organic solvent is obtained by the radical copolymerization reaction to obtain the copolymer (A-1), it can be used in the subsequent reaction in the state of the organic solvent solution of the copolymer (A-1).
The radically polymerizable compound having an epoxy group or alicyclic epoxy group as the component (d) is not particularly limited, and examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) 3-vinylcyclohexane (Cellocide 2000 manufactured by Daicel Chemical Industries, Ltd.), 3, 4-vinylcyclohexane (manufactured by Daicel Chemical Industries, Ltd.) Mono (meth) acrylic acid esters of 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, epoxides of dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) (Meth) acrylate, 1,2-epoxy-4-vinylcyclohexane and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable because of the ease of obtaining raw materials. desirable. These may be used singly or in combination of two or more kinds.
The copolymer (A-3) according to the present invention is a copolymer (A-1) obtained by reacting a radically polymerizable compound (d) having an epoxy group or an alicyclic epoxy group with a carboxyl group present in the side chain of the copolymer And further reacting the anhydride (e). The amount of the polybasic acid anhydride as the component (e) is 5 to 100 moles relative to 100 moles of the hydroxyl group generated by the reaction of the carboxyl group in the component (b) with the epoxy group or alicyclic epoxy group in the side chain derived from the component (d) , Preferably 10 to 90 moles, and more preferably 20 to 90 moles. By setting the amount as described above, the acid value of the obtained copolymer (A-3) can be controlled within the range of 20 mgKOH / g to 180 mgKOH / g.
The reaction of the hydroxyl group in the copolymer (A-2) with the polybasic acid anhydride as the component (e) is carried out as follows. That is, after a radical polymerizing compound having an epoxy group or alicyclic epoxy group as the component (d) is reacted with the carboxyl group of the side chain derived from the component (b) in the copolymer (A-1), the component (e) And the reaction is carried out usually at 50 ° C to 150 ° C, preferably at 80 ° C to 130 ° C. There is no need to add a new catalyst.
The polybasic acid anhydride as the component (e) is not particularly limited and includes, for example, anhydrous succinic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Phthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferable in view of reactivity and ease of access. These may be used singly or in combination of two or more kinds.
The copolymer (A-4) according to the present invention is obtained by copolymerizing the component (a), the component (d) and the component (c), reacting the component (b) with an epoxy group or an alicyclic epoxy group in the resulting copolymer, (E) is further reacted with the hydroxyl group produced by the above-mentioned reaction. The carboxyl group of the component (b) reacts with an epoxy group or an alicyclic epoxy group of a side chain derived from the component (d) to open an epoxy group, and a hydroxyl group is generated in the copolymer and an unsaturated group is imparted to the terminal. The polybasic acid anhydride as the component (e) reacts with the hydroxyl group generated by the reaction of the carboxyl group in the component (b) and the epoxy group of the side chain derived from the component (d), and the acid anhydride group is converted into a carboxyl group. The copolymerization ratio of the component (a), the component (d) and the component (c) is 2% by mass to 20% by mass, preferably 4% by mass to 20% by mass, more preferably 4% (C) is 6 mass% to 55 mass%, and the component (d) is 10 mass% to 50 mass%, preferably 20 mass% to 45 mass%, more preferably 25 mass% By mass, preferably 10% by mass to 50% by mass, and more preferably 10% by mass to 45% by mass. If the copolymerization ratio of the component (a) is less than 2 mass%, the dispersion stability of the pigment may not be sufficiently obtained. On the other hand, even if the copolymerization ratio of the component (a) exceeds 20 mass% It is not improved and alkali developability is deteriorated and a residue is sometimes generated.
The radically polymerizable compound (d) having an epoxy group or an alicyclic epoxy group is used for introducing an epoxy group or an alicyclic epoxy group into the side chain of the copolymer and introducing an unsaturated group by reacting with the carboxyl group of the component (b). In addition, the component (e) is reacted with the hydroxyl group generated at that time to thereby be used for the introduction of the acid value. Therefore, the same epoxy compound can be used although the function is different from that of the component (d) introduced into the side chain of the copolymer (A-3) and the amount of introduction is different.
(A) can be controlled by adjusting the amount of the epoxy group or alicyclic epoxy group introduced, that is, the amount of the unsaturated group derived from the unsaturated monobasic acid as the component (b), to 10 to 50 mass% -4) can be controlled. By setting the components (a) and (d) in the above-mentioned proportions, the component (c) can be appropriately selected within a range of 6% by mass to 55% by mass.
The amount of the unsaturated monobasic acid to be used as the component (b) is 10 to 100 mol, preferably 30 to 100 mol, per 100 mol of the epoxy group or alicyclic epoxy group of the side chain derived from the component (d) Is from 50 moles to 100 moles.
When the amount of the unsaturated monobasic acid to be used is 10 mol or more, the minimum amount of the unsaturated group necessary for curing the resin can be introduced. When the amount of the unsaturated monobasic acid is 100 mol or less, the unreacted unsaturated monobasic copolymer (A- The amount of acid can be reduced.
The amount of the polybasic acid anhydride as the component (e) is 5 to 100 moles relative to 100 moles of the hydroxyl group generated by the reaction of the carboxyl group in the component (b) and the side chain derived from the component (d) with the alicyclic epoxy group , Preferably 10 to 90 moles, and more preferably 20 to 90 moles. By using such an amount as described above, the acid value of the obtained copolymer (A-4) can be controlled within the range of 20 mgKOH / g to 180 mgKOH / g.
The acid value of the above-mentioned photosensitive graft polymer (A) (copolymers (A-1) to (A-4)) is preferably from 20 mgKOH / g to 180 mgKOH / g, more preferably from 20 mgKOH / g to 150 mgKOH / g Is more preferable. If the acid value is out of this range, sufficient alkali developing property can not be obtained. That is, if the acid value is less than 20 mgKOH / g, the solubility in an alkali developing solution may be insufficient. When the acid value is more than 180 mgKOH / g, the cured portion may be dissolved or swollen in an alkali developing solution.
The acid value of the photosensitive graft polymer (A) in the present invention is the number of mg of potassium hydroxide necessary for neutralizing 1 g of the photosensitive resin, and is measured according to the method described in the acid value of JIS K 6901: 1999, 5.3 .
The photosensitive graft polymer (A) preferably has a weight average molecular weight (polystyrene conversion value by GPC method) of 5,000 to 80,000, more preferably 7,000 to 50,000. If the weight average molecular weight is less than 5,000, the heat resistance and flexibility may be lowered. If the weight average molecular weight is more than 80,000, the solubility in an alkaline developer may become insufficient.
The value of the weight average molecular weight (Mw) of the photosensitive graft polymer (A) in the present invention is measured by gel permeation chromatography (GPC) under the following conditions and calculated by polystyrene conversion.
Column: Shodex LF-804 + LF-804
Column temperature: 40 DEG C
Developing solvent: tetrahydrofuran
Detector: Differential refractometer (Shodex RI-71S)
Flow rate: 1 ml / min
A photosensitive resin composition is obtained by adding the reactive diluent (B), the photopolymerization initiator (C) and the solvent (D) to the photosensitive graft polymer (A) thus obtained.
The reactive diluent (B) that can be used is not particularly limited as long as it can react with the photosensitive graft polymer (A). Specific examples of the reactive diluent (B) include, for example, styrene,
The amount of the reactive diluent (B) to be added is usually 10 parts by mass to 200 parts by mass, preferably 20 parts by mass to 150 parts by mass, based on 100 parts by mass of the photosensitive graft polymer (A). By setting the amount in the above range, the photocurability can be maintained in an appropriate range and the viscosity can be adjusted.
As the photopolymerization initiator (C) that can be used, any known photopolymerization initiator (C) can be used without limitation as long as it is cured by active light such as ultraviolet rays. Specific examples of the photopolymerization initiator (C) include benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan- One ; Acylphosphine oxides, xanthones, and the like. These may be used singly or in combination of two or more kinds.
The addition amount of the photopolymerization initiator (C) is usually 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the solid content in the photosensitive resin composition Mass part. By setting the amount in the above range, the photo-curability can be maintained in an appropriate range.
As the solvent (D) which can be used, any inert solvent which does not react with the graft polymer and the photopolymerizable monomer (B) can be used without limitation.
Examples of the usable solvent (D) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol mono Methyl ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, etc. . Of these, propylene glycol monomethyl ether acetate preferably used in the radical polymerization reaction is preferred. These may be used singly or in combination of two or more kinds.
The amount of the solvent (D) to be added is usually 30 parts by mass to 1000 parts by mass, preferably 50 parts by mass to 800 parts by mass, per 100 parts by mass of the photosensitive graft polymer (A). By setting the viscosity in the above range, the viscosity can be appropriately maintained.
In the photosensitive resin composition of the present invention, a coloring material (E) may be added as needed. As the coloring material (E), known coloring materials such as inorganic pigments, organic pigments, and dyes can be used. The photosensitive resin composition of the present invention can be used for a liquid crystal photo spacer, a liquid crystal seal, and the like, and a known pigment can be added to form a photosensitive resin composition for forming a color filter.
Specific examples of usable pigments include, for example, C.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 , 147, 148, 150, 153, 154, 166, 173, 194 and 214; C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ; C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16 and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments such as Pigment Green 7, 36; C.I. Brown pigments such as Pigment Brown 23 and 25; C.I. Pigment black 1, black pigment such as carbon black, titanium black and iron oxide, and the like. These pigments may be used singly or in combination of two or more kinds depending on the color of a target pixel.
In order to improve the dispersibility of the pigment, a known dispersant may be further added. As the dispersing agent, the use of a polymer dispersing agent is preferable because it provides excellent dispersion stability over time. As the polymer dispersing agent, for example, a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, an aliphatic modified ester- . Specific examples of such dispersants include, but are not limited to, EFKA (manufactured by EFKA), Disperbyk (manufactured by Bigkema), Disperon (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (manufactured by Geneca) .
In addition, known sensitizers, antifoaming agents, coupling agents, leveling agents and the like may be added to the photosensitive resin composition of the present invention as necessary.
The photosensitive resin composition of the present invention is applied, for example, on a printed wiring board by a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, etc., (Un) cured (unexposed) portion is rinsed with an aqueous alkali solution.
Examples of the aqueous alkali solution used in the development include aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide and potassium hydroxide, and aminophenol compounds in the case of tetramethylammonium hydroxide, tetraethylammonium hydroxide and amine. However, p-phenylenediamine-based compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N -? - methoxyethylaniline, and 3-methyl-4-amino-N-ethyl-N -? - methanesulfonamide ethyl aniline, Sulfate, hydrochloride or p-toluenesulfonate.
A low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a meta-halide lamp, or the like is used as a light source used for curing a coated surface by light irradiation.
Example
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
≪ Macromonomer Synthesis Example 1 >
46.2 parts by mass of propylene glycol monomethyl ether acetate, 11.1 parts by mass (about 0.050 mole) of dicyclopentanyl methacrylate, and 8.9 parts by mass of benzyl methacrylate were added to a flask equipped with a stirrer, a dropping funnel, a condenser, (About 0.051 mol) was added and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Then, 44.4 parts by mass (about 0.202 mole) of dicyclopentanyl methacrylate, 35.6 parts by mass (about 0.202 mole) of benzyl methacrylate, 1.9 parts by mass of thioglycolic acid, and t-butylperoxy-2-ethylhexanoate 6.0 Was added dropwise to the flask over 2 hours from the dropping funnel, and further reacted at 120 DEG C for 0.5 hour.
Subsequently, the inside of the flask was purged with air, and then 2.9 parts by mass of glycidyl methacrylate, 0.3 part by mass of triphenylphosphine and 0.06 part by mass of methylhydroquinone were charged into a flask, and the mixture was reacted at 120 ° C for 3 hours. This reaction solution was dripped into 2 liters of n-hexane and re-precipitated to obtain 82 parts by mass of a white powdery macromonomer (M-1). The weight average molecular weight of the macromonomer (M-1) was 12,100.
≪ Macromonomer Synthesis Example 2 >
A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 46.2 parts by mass of propylene glycol monomethyl ether acetate, 14.9 parts by mass (about 0.068 mole) of dicyclopentanyl methacrylate, and 5.1 parts by mass of benzyl methacrylate (About 0.029 mol) were charged and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Subsequently, 59.6 parts by mass (about 0.271 mole) of dicyclopentyl methacrylate, 20.4 parts by mass (about 0.116 mole) of benzyl methacrylate, 1.8 parts by mass of thioglycolic acid and 6.0 parts by mass of t-butylperoxy-2-ethylhexanoate 6.0 Was added dropwise to the flask over 2 hours from the dropping funnel, and further reacted at 120 DEG C for 0.5 hour.
Subsequently, the inside of the flask was purged with air, and then 2.8 parts by mass of glycidyl methacrylate, 0.3 part by mass of triphenylphosphine, and 0.06 part by mass of methylhydroquinone were charged into a flask, and the reaction was carried out at 120 ° C for 3 hours. The reaction solution was dripped into 2 liters of n-hexane and re-precipitated to obtain 82 parts by mass of a white powdery macromonomer (M-2). The weight average molecular weight of this macromonomer (M-2) was 13,200.
≪ Macromonomer Synthesis Example 3 >
44.5 parts by mass of propylene glycol monomethyl ether acetate, 11.1 parts by mass (about 0.050 mole) of dicyclopentanyl methacrylate, and 8.9 parts by mass of benzyl methacrylate were added to a flask equipped with a stirrer, a dropping funnel, a condenser, (About 0.051 mol) was added and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Then, 44.4 parts by mass (about 0.202 mole) of dicyclopentanyl methacrylate, 35.6 parts by mass (about 0.202 mole) of benzyl methacrylate, 0.9 part by mass of thioglycolic acid, and t-butylperoxy-2-ethylhexanoate 3.0 Was added dropwise to the flask over 2 hours from the dropping funnel, and further reacted at 120 DEG C for 0.5 hour.
Subsequently, the inside of the flask was purged with air, and then 2.9 parts by mass of glycidyl methacrylate, 0.3 part by mass of triphenylphosphine and 0.06 part by mass of methylhydroquinone were charged into a flask, and the mixture was reacted at 120 ° C for 3 hours. This reaction solution was dropped into 2 liters of n-hexane and re-precipitated to obtain 82 parts by mass of a white powdery macromonomer (M-3). The weight average molecular weight of the macromonomer (M-3) was 17,200.
<Macromonomer Comparative Synthesis Example 1>
46.2 parts by mass of propylene glycol monomethyl ether acetate, 4.8 parts by mass (about 0.022 mole) of dicyclopentanyl methacrylate, and 15.2 parts by mass of benzyl methacrylate were added to a flask equipped with a stirrer, a dropping funnel, a condenser, (About 0.086 mol) were charged and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Then, 19.0 parts by mass (about 0.086 mole) of dicyclopentanyl methacrylate, 61.0 parts by mass (about 0.347 mole) of benzyl methacrylate, 2.0 parts by mass of thioglycolic acid and 6.0 parts by mass of t-butylperoxy-2-ethylhexanoate 6.0 Was added dropwise to the flask over 2 hours from the dropping funnel, and further reacted at 120 DEG C for 0.5 hour.
Next, after flushing the inside of the flask with air, 3.1 parts by mass of glycidyl methacrylate, 0.3 part by mass of triphenylphosphine and 0.06 part by mass of methylhydroquinone were charged into a flask, and the mixture was reacted at 120 ° C for 3 hours. The reaction solution was dripped into 2 liters of n-hexane and re-precipitated to obtain 82 parts by mass of a white powdery macromonomer (M-4). The weight average molecular weight of the macromonomer (M-4) was 14,000.
<Macromonomer Comparison Synthesis Example 2: M-5>
46.2 parts by mass of propylene glycol monomethyl ether acetate, 18.4 parts by mass (about 0.084 mole) of dicyclopentanyl methacrylate, and 1.6 parts by mass of benzyl methacrylate were added to a flask equipped with a stirrer, a dropping funnel, a condenser, (About 0.009 mole) was added thereto, and the mixture was stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Subsequently, 73.5 parts by mass (about 0.334 mole) of dicyclopentyl methacrylate, 6.5 parts by mass (about 0.037 mole) of benzyl methacrylate, 1.7 parts by mass of thioglycolic acid, and t-butylperoxy-2-ethylhexanoate 6.0 Was added dropwise to the flask over 2 hours from the dropping funnel, and further reacted at 120 DEG C for 0.5 hour.
Subsequently, 2.6 parts by mass of glycidyl methacrylate, 0.3 part by mass of triphenylphosphine and 0.06 part by mass of methylhydroquinone were put into a flask, and the mixture was reacted at 120 ° C for 3 hours. This reaction solution was dripped into 2 liters of n-hexane and re-precipitated to obtain 82 parts by mass of a white powdery macromonomer (M-5). The weight average molecular weight of the macromonomer (M-5) was 12,500.
≪ Graft Polymer Synthesis Example 1 &
To the flask, 151.9 parts by mass of propylene glycol monomethyl ether acetate was added and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Then, a solution containing 2.7 parts by mass of the macromonomer (M-1), 72.5 parts by mass of benzyl methacrylate, 24.8 parts by mass of methacrylic acid and 1.3 parts by mass of t-butylperoxy-2-ethylhexanoate was passed through a dropping funnel The solution was added dropwise to the flask over 2 hours, followed by continuous reaction at 120 DEG C for 0.5 hour to obtain a graft polymer solution having a solid acid value of 160 mgKOH / g and a weight average molecular weight of 26,000.
≪ Graft Polymer Synthesis Example 2 &
To the flask, 151.9 parts by mass of propylene glycol monomethyl ether acetate was added and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Then, a solution containing 2.7 parts by mass of the macromonomer (M-1), 72.5 parts by mass of benzyl methacrylate, 24.8 parts by mass of methacrylic acid and 1.3 parts by mass of t-butylperoxy-2-ethylhexanoate was passed through a dropping funnel Was added dropwise to the flask over a period of 2 hours, and the reaction was further continued at 120 DEG C for 0.5 hour.
Subsequently, the inside of the flask was purged with air, 14.9 mass parts of glycidyl methacrylate, 0.3 mass parts of triphenylphosphine and 0.07 mass parts of methylhydroquinone were charged into a flask, and the reaction was continued at 120 ° C for 5 hours to obtain a solid content 89 mgKOH / g, and a weight average molecular weight of 31,400.
≪ Graft Polymer Synthesis Example 3 >
A graft polymer solution having a solid dispersion value of 89 mg KOH / g and a weight average molecular weight of 30,600 was obtained in the same manner as in graft polymer synthesis example 2 except that the macro monomer (M-2) was used instead of the macro monomer (M-1).
≪ Graft Polymer Synthesis Example 4 >
To the flask, 151.9 parts by mass of propylene glycol monomethyl ether acetate was added and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Subsequently, a solution containing 5.3 parts by mass of the macro monomer (M-1), 70.1 parts by mass of benzyl methacrylate, 24.6 parts by mass of methacrylic acid and 1.3 parts by mass of t-butylperoxy-2-ethylhexanoate was added to a dropping funnel Was added dropwise to the flask over a period of 2 hours, and further reaction was continued at 120 ° C for 0.5 hour.
Subsequently, 14.6 parts by mass of glycidyl methacrylate, 0.3 part by mass of triphenylphosphine and 0.07 part by mass of methylhydroquinone were added to the flask, and the mixture was continuously reacted at 120 ° C for 5 hours to obtain a solid content 89 mgKOH / g, and a weight average molecular weight of 29,400.
≪ Graft Polymer Synthesis Example 5 &
To the flask, 151.9 parts by mass of propylene glycol monomethyl ether acetate was added and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Subsequently, a solution containing 10.6 parts by mass of the macromonomer (M-1), 65.3 parts by mass of benzyl methacrylate, 24.1 parts by mass of methacrylic acid and 1.3 parts by mass of t-butylperoxy-2-ethylhexanoate was added to a dropping funnel Was added dropwise to the flask over a period of 2 hours, and further reaction was continued at 120 ° C for 0.5 hour.
Subsequently, the inside of the flask was purged with air, and then 13.9 parts by mass of glycidyl methacrylate, 0.3 part by mass of triphenylphosphine and 0.07 part by mass of methylhydroquinone were added to the flask, and the reaction was continued at 120 ° C for 5 hours to obtain a solid content 89 mgKOH / g, and a weight average molecular weight of 29,200.
≪ Graft Polymer Synthesis Example 6 >
A graft polymer solution having a solid dispersion value of 89 mgKOH / g and a weight average molecular weight of 29,600 was obtained in the same manner as in graft polymer synthesis example 4 except that the macro monomer (M-3) was used instead of the macro monomer (M-1).
≪ Graft Polymer Synthesis Example 7 &
Vinyl-cyclohexane was used in place of glycidyl methacrylate, 13.0 parts by mass of a graft polymer having a solid acid value of 89 mgKOH / g and a weight average molecular weight of 27,000 To obtain a polymer solution.
≪ Graft Polymer Synthesis Example 8 &
The flask was charged with 152.3 parts by mass of propylene glycol monomethyl ether acetate, stirred while replacing nitrogen, and heated to 120 ° C. Subsequently, a solution containing 8.0 parts by mass of the macro monomer (M-1), 31.8 parts by mass of benzyl methacrylate, 60.2 parts by mass of glycidyl methacrylate and 1.5 parts by mass of t-butylperoxy-2-ethylhexanoate Was dropped from the dropping funnel into the flask over 2 hours, and further reacted at 120 DEG C for 0.5 hour.
Subsequently, 29.6 parts by mass of acrylic acid, 0.4 part by mass of triphenylphosphine and 0.08 part by mass of methylhydroquinone were added to the flask, and the reaction was continued at 120 ° C for 5 hours. Then, 41.6 parts by weight of tetrahydrophthalic anhydride was added to the flask and reacted at 115 DEG C for 2 hours to obtain a graft polymer solution having a solid acid value of 89 mgKOH / g and a weight average molecular weight of 30,000.
≪ Graft Polymer Comparative Synthesis Example 1 >
A graft polymer solution having a solid dispersion value of 89 mg KOH / g and a weight average molecular weight of 30,800 was obtained in the same manner as in graft polymer synthesis example 3 except that the macro monomer (M-4) was used instead of the macro monomer (M-2).
≪ Graft Polymer Comparative Synthesis Example 2 >
A graft polymer solution having a solid dispersion value of 89 mg KOH / g and a weight average molecular weight of 31,900 was obtained in the same manner as in graft polymer synthesis example 3 except that the macro monomer (M-5) was used instead of the macro monomer (M-2).
≪ Graft Polymer Comparative Synthesis Example 3 >
Except that a commercially available polystyrene macromonomer (AS-6, manufactured by Toa Seikagaku Kogyo Co., Ltd., Mn = 6,000) was used in place of the macromonomer (M-1) 89 mgKOH / g, and a weight average molecular weight of 28,100.
≪ Graft Polymer Comparative Synthesis Example 4 >
The same operation as in Graft Polymer Synthesis Example 4 was carried out except that a commercially available polymethyl methacrylate macromonomer (AA-6, manufactured by Toa Seikagaku Kogyo Co., Ltd., Mn = 6,000) was used instead of the macro monomer (M-1) To obtain a graft polymer solution having a solid content of 89 mgKOH / g and a weight average molecular weight of 28,400.
[Examples 1 to 8 and Comparative Examples 1 to 4]
Graft polymer The graft polymer solutions obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 4 were each diluted with propylene glycol monomethyl ether acetate (PGMEA) so that the solid content became 30% by mass. The diluted graft polymer solution was used in Examples 1 to 8 and Comparative Examples 1 to 4, respectively. Various physical properties and the like in the examples and comparative examples were measured by the following methods.
≪ Evaluation of Appearance of Graft Polymer Solution &
The appearance of each graft polymer solution used in Examples 1 to 8 and Comparative Examples 1 to 4 was visually observed to determine whether it was transparent or turbid.
<Preparation of Green Pigment Dispersion>
7.58 parts by mass of CI Pigment Green 36 and a PGMEA solution of benzyl methacrylate methacrylic acid copolymer (weight average molecular weight 17,000, solid acid value of 100 mgKOH / g) were added to an SUS container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm 7.58 parts by mass of water, 40 parts by mass of water and 40 parts by mass of solid content), 28.54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 6.31 parts by mass of a dispersant (Disperbyk-161 manufactured by Bigmix) were added and dispersed with a paint shaker for 6 hours to obtain a green pigment dispersion.
Using the green pigment dispersion obtained above, a green resin composition was prepared in the blending ratios shown in Table 1 below.
* 1: Dipentaerythritol hexaacrylate
* 2: Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
* 3: High Cure ABP (manufactured by Kawaguchi Pharmaceutical Co., Ltd.)
≪ Evaluation of Pigment Dispersion Stability &
The viscosity change of the green resin composition was measured to evaluate the pigment dispersion stability. When the stability of the pigment dispersion is poor, the viscosity is increased and the desired performance can not be obtained. Hereinafter, this will be described in detail.
The viscosity after standing for 7 days in a thermostatic chamber at 40 ° C was measured (in order to promote the viscosity immediately after preparation of the green resin composition from which the photopolymerization initiator component 1, the photopolymerization initiator component 2 and the PGMEA had been removed and the change with time E-type viscometer RE-80L manufactured by Toki Kikai Co., Ltd., rotor 1 ° 34 '× R 24, measured at 25 ° C., 5 rpm), and evaluated according to the following criteria. The results are shown in Table 2.
?: Less than 15% change in viscosity and excellent stability of pigment dispersion
?: A viscosity change rate of 15% or more and less than 20%, and excellent pigment dispersion stability
?: Change in viscosity of 20% or more and less than 25%, and stability of pigment dispersion is slightly lower
X: Viscosity change rate is 25% or more, and the pigment dispersion stability is poor
≪ Preparation of cured coating film &
A green resin composition was spin-coated on a square glass substrate (non-alkali glass) of 5 cm in thickness to have a thickness of 2.2 탆 upon drying, and was prebaked at 80 캜 for 3 minutes. Then, a photomask was arranged at a distance of 100 탆 from the coating film And exposed at 150 mJ / cm 2. Subsequently, the coating was spray-developed at a water pressure of 0.3 MPa in a 0.1 mass% sodium carbonate aqueous solution, and post-baked at 230 캜 for 30 minutes to obtain a cured coating film.
≪ Evaluation of alkali developing property &
The cured coating film exposed through the mask was spray-developed at 23 占 폚 with a 0.1% by mass aqueous solution of sodium carbonate, and the presence or absence of the coating film after the water rinse was observed and evaluated according to the following criteria. The results are shown in Table 2.
&Amp; cir &: No coating film was observed by visual observation after developing time 50 seconds.
&Amp; cir &: After 70 seconds of developing time, the coating film was observed with naked eyes and no coating film was formed.
X: After 70 seconds of developing time, the coating film was observed with naked eyes.
≪ Evaluation of Developing Residues >
The development glass substrate was visually observed by a light emitter to check for the presence of residues. Further, the surface of the substrate was wiped with ethanol-containing waste, and the presence or absence of residue wiped on the waste was confirmed.
As apparent from the results of Table 2, the graft polymer solutions of Examples 1 to 8 are not opaque and do not affect the transparency of the coating film. In addition, the pigment resin compositions prepared using the graft polymer solutions of Examples 1 to 8 have good viscosity stability over time, and the cured coating film produced using the cured coating film can not only develop alkali but also have no residue after development.
As described above, since the photosensitive graft polymer of the present invention can form a transparent cured coating film which is excellent in dispersion stability of a coloring material such as a pigment and carbon black and can be alkali-developed, it can be used for a pigment dispersion (mill base) Not only is it useful as a binder polymer for resist, but also has a very high utility value in various resist fields.
Claims (12)
(Meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl methacrylate, adamanthyl (meth) acrylate and the like are used as the polymerizable monomer having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms. , And compounds represented by the following formulas (1) and (2): " (1) "
[Chemical Formula 1]
(Wherein R < 1 > represents hydrogen or a methyl group)
Wherein the polymerizable monomer having no crosslinked cyclic hydrocarbon group is selected from the group consisting of cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, rosin (meth) Acrylate, and mixtures thereof. The photosensitive graft polymer according to claim 1, wherein the photosensitive graft polymer is at least one selected from the group consisting of acrylate and acrylate.
Wherein the macromonomer (a) has a weight average molecular weight of 2,000 to 20,000.
Wherein the photosensitive graft polymer has an acid value of 20 mgKOH / g to 180 mgKOH / g.
Wherein the photosensitive graft polymer has a weight average molecular weight of 5,000 to 80,000.
The photosensitive graft polymer is a copolymer (A-1) comprising the macromonomer (a), the unsaturated monobasic acid (b), and the radically polymerizable compound (c) other than the macromonomer (a) and the unsaturated monobasic acid 1). ≪ / RTI >
Wherein the photosensitive graft polymer is a copolymer (A-2) obtained by reacting a radically polymerizable compound (d) having an epoxy group or an alicyclic epoxy group with a carboxyl group of the copolymer (A-1).
Wherein the photosensitive graft polymer is a copolymer (A-3) obtained by reacting a polybasic acid anhydride (e) with a hydroxyl group of the copolymer (A-2).
The photosensitive graft polymer is obtained by copolymerizing the macromonomer (a) with a radically polymerizable compound (d) having an epoxy group or an alicyclic epoxy group and a radically polymerizable compound (c) other than the macromonomer (a) (A-4) obtained by reacting an unsaturated monobasic acid (b) with an epoxy group or alicyclic epoxy group contained in the copolymer and then further reacting a polybasic acid anhydride (e) with the hydroxyl group generated by the reaction Characterized by a photosensitive graft polymer.
And further contains a coloring material (E).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2007-263124 | 2007-10-09 | ||
| JP2007263124 | 2007-10-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20100071092A KR20100071092A (en) | 2010-06-28 |
| KR101473511B1 true KR101473511B1 (en) | 2014-12-16 |
Family
ID=40549097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020107009457A KR101473511B1 (en) | 2007-10-09 | 2008-08-25 | Photosensitive graft polymer, and photosensitive resin composition comprising the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5638243B2 (en) |
| KR (1) | KR101473511B1 (en) |
| CN (1) | CN101821299B (en) |
| TW (1) | TWI421631B (en) |
| WO (1) | WO2009047949A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5584585B2 (en) * | 2010-10-19 | 2014-09-03 | 花王株式会社 | Graft polymer |
| TWI422631B (en) * | 2011-06-30 | 2014-01-11 | Everlight Chem Ind Corp | Black resin composition, black matrix, and light blocking layer |
| JP5358005B2 (en) * | 2011-09-22 | 2013-12-04 | 富士フイルム株式会社 | Positive photosensitive acrylic resin and positive photosensitive resin composition |
| JP5979587B2 (en) * | 2012-05-16 | 2016-08-24 | 荒川化学工業株式会社 | Active energy ray curable resins, active energy ray curable hard coating agents, cured films using them, plastic films on which cured films are laminated, and processed products using plastic films. |
| JP6097029B2 (en) * | 2012-07-25 | 2017-03-15 | 株式会社Ｄｎｐファインケミカル | Energy ray-curable resin composition, protective film using this composition, touch panel member, and method for producing touch panel member |
| TWI603983B (en) * | 2012-08-10 | 2017-11-01 | Nippon Shokubai Co Ltd | Hardening resin composition and its use |
| CN102827526B (en) * | 2012-08-23 | 2015-04-15 | 京东方科技集团股份有限公司 | High-impedance material, and display substrate black matrix and liquid crystal display apparatus containing same |
| JP6230300B2 (en) * | 2013-06-28 | 2017-11-15 | 太陽インキ製造株式会社 | Photocurable composition and cured product thereof |
| JP5915956B2 (en) * | 2013-07-25 | 2016-05-11 | 山栄化学株式会社 | Resin composition for forming solder bumps and solder bump forming method |
| CN105037627B (en) * | 2015-08-21 | 2017-01-25 | 深圳市联深化学技术有限公司 | Oligomeric resin, preparation method thereof and application thereof in color photoresist |
| DE102015119939A1 (en) | 2015-11-18 | 2017-05-18 | ALTANA Aktiengesellschaft | Crosslinkable polymeric materials for dielectric layers in electronic components |
| CN105669892B (en) * | 2016-03-17 | 2019-07-26 | 上海昭和高分子有限公司 | A kind of solvent type copolymer resins and combinations thereof |
| JP7052222B2 (en) * | 2017-05-24 | 2022-04-12 | 三菱ケミカル株式会社 | Curable compositions, cured products and laminates |
| JP7477299B2 (en) * | 2017-12-27 | 2024-05-01 | 富士フイルム株式会社 | Transfer film, electrode protection film, laminate, electrostatic capacitance input device, and method for manufacturing touch panel |
| CN115677939A (en) * | 2022-11-25 | 2023-02-03 | 茂名清荷科技有限公司 | Photosensitive graft polymer and photosensitive resin composition containing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007003945A (en) * | 2005-06-24 | 2007-01-11 | Dainippon Printing Co Ltd | Inkjet ink for color filter, color filter and liquid crystal display device |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3087871B2 (en) * | 1992-06-02 | 2000-09-11 | 東亞合成株式会社 | Method for producing macromonomer having hyperbranched structure |
| JPH08259876A (en) * | 1995-03-24 | 1996-10-08 | Japan Synthetic Rubber Co Ltd | Organic pigment dispersed liquid for color filter |
| JPH09146272A (en) * | 1995-11-27 | 1997-06-06 | Fuji Photo Film Co Ltd | Radiatopm sensitive composition |
| JP3688949B2 (en) * | 1999-09-24 | 2005-08-31 | 昭和高分子株式会社 | Photosensitive resin |
| JP4758652B2 (en) * | 2004-01-19 | 2011-08-31 | 大日精化工業株式会社 | Method for producing graft copolymer having excellent pigment dispersibility, method for producing emulsions using the graft copolymers, and pigment dispersions using the graft copolymers or emulsions |
| JP2005316388A (en) * | 2004-03-30 | 2005-11-10 | Jsr Corp | Radiation sensitive composition for color filter, color filter and color liquid crystal display |
| JP4539165B2 (en) * | 2004-05-12 | 2010-09-08 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, spacer, method for forming the same, and liquid crystal display device |
| JP2006058821A (en) * | 2004-08-24 | 2006-03-02 | Mitsubishi Chemicals Corp | Colored resin composition, color filter and liquid crystal display |
| JP2007070584A (en) * | 2005-09-09 | 2007-03-22 | Hitachi Chem Co Ltd | Coloring composition, photosensitive coloring resin composition, photosensitive liquid for colored image formation, method for making colored image, method for producing color filter, and color filter |
| JP2007199685A (en) * | 2005-12-28 | 2007-08-09 | Fujifilm Electronic Materials Co Ltd | Photocuring coloring composition, color filter, and liquid crystal display device |
| JP2008195768A (en) * | 2007-02-09 | 2008-08-28 | Canon Inc | Liquid composition and ink for inkjet |
-
2008
- 2008-08-25 JP JP2009536952A patent/JP5638243B2/en active Active
- 2008-08-25 KR KR1020107009457A patent/KR101473511B1/en active IP Right Grant
- 2008-08-25 WO PCT/JP2008/065104 patent/WO2009047949A1/en active Application Filing
- 2008-08-25 CN CN2008801106928A patent/CN101821299B/en not_active Expired - Fee Related
- 2008-10-06 TW TW97138406A patent/TWI421631B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007003945A (en) * | 2005-06-24 | 2007-01-11 | Dainippon Printing Co Ltd | Inkjet ink for color filter, color filter and liquid crystal display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101821299B (en) | 2012-10-10 |
| JP5638243B2 (en) | 2014-12-10 |
| TW200933293A (en) | 2009-08-01 |
| WO2009047949A1 (en) | 2009-04-16 |
| JPWO2009047949A1 (en) | 2011-02-17 |
| TWI421631B (en) | 2014-01-01 |
| KR20100071092A (en) | 2010-06-28 |
| CN101821299A (en) | 2010-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101473511B1 (en) | Photosensitive graft polymer, and photosensitive resin composition comprising the same | |
| TWI588162B (en) | (meth)acrylate-based polymer, composition comprising same and use thereof | |
| KR101536500B1 (en) | Copolymer, resin composition and photosensitive resin composition each containing said copolymer, and color filter | |
| KR101405765B1 (en) | Addition copolymer, photosensitive resin composition, and color filter | |
| JP2018123274A (en) | Alkali-soluble resin, photosensitive resin composition and use therefor | |
| CN110998443A (en) | Photosensitive resin composition and method for producing same | |
| TWI430020B (en) | Photosensitive resin composition | |
| CN110073253B (en) | Resin composition for color filter, method for producing resin composition for color filter, and color filter | |
| JP2008088394A (en) | Alkali-developable photosensitive resin and photosensitive resin composition comprising the same | |
| CN109471331B (en) | Resin composition, photosensitive resin composition, resin cured film, and image display element | |
| WO2017204079A1 (en) | Photosensitive resin composition for forming black column spacer, black column spacer and image display device | |
| JP2008143941A (en) | Photosensitive resin and photosensitive resin composition containing the same | |
| CN111615650B (en) | Photosensitive resin composition for color filter, image display element, and method for producing color filter | |
| CN115677939A (en) | Photosensitive graft polymer and photosensitive resin composition containing same | |
| TW202244072A (en) | Polymeric dispersant, pigment dispersion composition, and photosensitive colored composition | |
| JP2019031627A (en) | Alkali-soluble resin, photosensitive resin composition for color filter containing the same, and color filter | |
| CN116490533A (en) | Pigment dispersion composition and photosensitive coloring composition | |
| KR20170139642A (en) | COLOR COMPOSITION FOR COLOR FILTER, COLOR FILTER AND IMAGE DISPLAY DEVICE | |
| KR20230098322A (en) | Photosensitive resin composition and method for producing the photosensitive resin composition | |
| WO2023119900A1 (en) | Photosensitive resin composition and color filter | |
| JP2011099034A (en) | Polycarboxylic acid resin and polycarboxylic acid resin composition | |
| WO2023119898A1 (en) | Pigment dispersion composition, photosensitive colored composition, and color filter | |
| JP2023060757A (en) | Resin composition, photosensitive resin composition, resin cured film, color filter, and image display element | |
| WO2022102367A1 (en) | Polymerizable polymer dispersant, pigment dispersion composition, and photosensitive coloring composition | |
| WO2024111220A1 (en) | Modified polyol compound and photosensitive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| N231 | Notification of change of applicant | ||
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20171120 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20181119 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20191118 Year of fee payment: 6 |