WO2010074289A1 - α-アリルオキシメチルアクリル酸系共重合体、樹脂組成物及びその用途 - Google Patents
α-アリルオキシメチルアクリル酸系共重合体、樹脂組成物及びその用途 Download PDFInfo
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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
- 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
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
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- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
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- 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
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Definitions
- the present invention relates to an ⁇ -allyloxymethylacrylic acid copolymer, a resin composition containing the copolymer, its use, and a method for producing the polymer. More specifically, ⁇ -allyloxymethylacrylic acid-based copolymers that can be suitably used for various applications such as radical curable resin compositions, colorant dispersion compositions, photosensitive resin compositions, and the like, and resin compositions thereof And a method for producing the polymer.
- Resins (polymers) with a ring structure in the main chain are useful materials that are used in various fields, from engineering plastics to optical materials and resist materials, because of their excellent durability, especially heat resistance.
- various resin compositions such as a radical curable resin composition, a color material dispersion composition, and a photosensitive resin composition have been studied and applied to coating materials, high-performance inks, and resist materials.
- the curable resin composition is used in various industrial fields.
- the radical curable resin composition comprising a radical polymerizable monomer and a binder resin has a high curing speed and durability of a chemical bond to be formed. It is excellent in terms of economy and has a wide range of applications and is used in various applications such as coating materials, adhesives, sealing materials, adhesives, paints, inks, resists, dental materials, lenses, molding materials, etc. .
- alkali-soluble resins are materials used in various industrial fields from civil engineering and building materials to electronic information materials, and one of the main uses is an alkali development type resist.
- An alkali development type resist (hereinafter sometimes simply referred to as a resist) is generally a resin composition containing an alkali-soluble resin, a curing component, a photoinitiator for curing the curing component, and a solvent. It is an industrial material that is indispensable and useful in lithography technology, and there are various resists such as solder resists, etching resists, interlayer insulating materials, plating resists, and color filter resists. Among them, the color filter resist is one of the most advanced and various resists required.
- the color filter is a main member constituting a color liquid crystal display panel and a color image pickup tube element, and has a fine colored layer for separating colors, thereby enabling colorization of the liquid crystal display panel and the image pickup tube element. It becomes possible.
- an alkali-developable photosensitive resin composition containing an alkali-soluble resin, a radical polymerizable monomer, a photoinitiator, a coloring material as a coloring component, and a dispersing agent for the coloring material (
- a method of forming by a photolithography technique is sometimes used.
- the radical polymerizable monomer and the alkali-soluble resin have to be reduced by that amount. Properties (heat-resistant decomposability, heat-resistant transparency, etc.) tend to be significantly reduced.
- the alkali-soluble resin is a component that imparts coating film forming property and developer solubility to the resist and makes the resist resist. expressed. Furthermore, it is also a component that affects various performances such as curability, adhesion, heat resistance, dry re-dissolvability, and heat resistance.
- a binder resin is often devised as a solution.
- a number of methods for devising binder resins have also been proposed in solving the problems associated with color filter resists as described above, and as one of them, as a binder resin, the main chain is known for its excellent durability and particularly heat resistance.
- a method using a resin having a ring structure has been proposed (see, for example, Patent Document 1 and Patent Document 2).
- Patent Document 1 when the resin described in Patent Document 1 is used, a colored resist having excellent curability, solvent solubility, developability, dispersibility, adhesion, and the like is obtained, which is effective for the above-described problems.
- a resin having a ring structure in the main chain is excellent in durability and heat resistance and is used for various applications.
- a method for obtaining such a resin a monomer having a ring structure is used.
- examples of the resin having a ring structure in the main chain produced by the polycondensation mechanism include polycarbonate, polyimide, polyphenylene sulfide and the like.
- Such resins have extremely high heat resistance and are mainly used in engineering plastics, but they are manufactured under extremely severe conditions such as high temperature and high pressure conditions and conditions where hydrochloric acid is generated. There is also a problem that it is difficult to adjust the physical properties and make it multifunctional.
- the addition polymerization mechanism is easy to adjust the molecular weight, and can be copolymerized with various vinyl monomers under mild conditions, so it can adjust physical properties according to the application and provide various functions other than heat resistance. Easy to do. Therefore, it is used as a method for synthesizing resins for applications that require advanced and diverse functions such as optical materials and resist materials.
- Resins having a ring structure in the main chain obtained by such an addition polymerization mechanism include cycloolefin polymers synthesized by coordination polymerization of cycloolefins and maleimide polymers synthesized by radical polymerization of N-substituted maleimides. Etc.
- a method for synthesizing a resin having a ring structure in the main chain there is a method in which a monomer having no ring structure is polymerized while being cyclized simultaneously with addition polymerization.
- a method in which 1,6-dienes are polymerized by a radical polymerization mechanism to obtain a resin having a 5-membered or 6-membered ring structure in the main chain for example, Non-Patent Document 1, Non-Patent Document 2 and Non-Patent Document 3).
- the resin having a ring structure in the main chain used in various compositions, the resin composition, and a method for producing the resin have been studied, but each has a problem, There was room for further ingenuity. That is, a radically curable resin composition using a radically polymerizable monomer having a tetrahydrofurfuryl group or a binder resin having a tetrahydrofurfuryl group in the side chain is curable in air (oxygen scavenging property). It has excellent adhesion and transparency, but there is still room for improvement in heat resistance.
- the resins described in Non-Patent Document 1 and Patent Document 1 are prone to abnormally high molecular weight during polymerization (molecular weight distribution becomes very wide) or gelation, and are stable in production. There was a problem in quality and quality control. In addition, there is still room for improvement in achieving both dispersibility and other performance at a high level.
- the binder resin and the colored resist described in Patent Document 2 are excellent in heat resistance and plate-making property, but cannot sufficiently cope with the increase in the concentration of the coloring material.
- the present invention has been made in view of the above situation, and a resin that can be suitably used for various applications such as a radical curable resin composition, a colorant dispersion composition, and a photosensitive resin composition, and a resin.
- An object is to provide a composition and a means for producing the resin.
- it is an object of the present invention to provide a radical curable binder resin for a composition that is excellent in adhesion and transparency and also has excellent heat resistance, and a radical curable composition using the binder resin.
- the present invention provides a resin for a color material dispersion composition capable of achieving both dispersibility and other properties such as adhesion and curability at a high level, and a color material dispersion composition using the resin.
- a novel alkali-soluble resin having a ring structure in the main chain that has high heat resistance, excellent colorant dispersion stability, and excellent platemaking properties, and a photosensitive resin composition using the resin as a binder resin are provided. To do. Also provided are a color filter formed using the photosensitive resin composition, and a liquid crystal display panel comprising the color filter.
- This inventor earnestly examined about the polymer which has a structural unit represented by following formula (1) in a principal chain. As a result, it has been found that curability in air (oxygen scavenging), and good adhesion and transparency are expressed in a structure having a tetrahydrofuran ring (THF ring) in the main chain and is excellent in heat resistance. It discovered that it could use suitably for the radical curable resin composition used for various uses. And this polymer is not only very excellent in colorant dispersibility, but also found to be particularly excellent in adhesion and curability, and is suitably used for highly functional colorant dispersion compositions used in various inks, paints, etc. I found that I can do it. Furthermore, it has been found that this polymer not only has excellent heat resistance and colorant dispersibility, but also has excellent platemaking properties and can be suitably used for a photosensitive resin composition.
- this polymer not only has excellent heat resistance and colorant dispersibility, but also has excellent platemaking properties and can be suitably used
- the present inventor has conducted various studies on methods for producing a polymer having a ring structure in the main chain by cyclopolymerizing 1,6-diene monomers, and is usually used for adjusting the molecular weight. It has been found that the chain transfer agent exhibits a specific effect that the branching of the polymer can be suppressed in the cyclopolymerization of specific 1,6-dienes. That is, since it is possible to suppress crosslinking by suppressing branching, the chain transfer agent acts as a so-called crosslinking inhibitor, and the molecular weight distribution of the resulting polymer can be narrow, It was found that a polymer can be obtained without gelation even under economically advantageous conditions.
- the chain transfer agent not only adjusts the molecular weight at the time of polymerization by the chain transfer action, but also has the action of suppressing branching and the action of preventing crosslinking and gelation associated therewith. That is, the above-mentioned action and effect is a phenomenon that occurs when a specific 1,6-diene monomer is polymerized, and the purpose of the chain transfer agent used for adjusting the normal molecular weight is the purpose. In contrast, this is a new finding found by the present inventors. Moreover, the heat resistance of the polymer obtained can be improved by suppressing branching.
- the production method of the present invention it is possible to prevent branching of the polymer even in industrially advantageous conditions, for example, conditions with a high conversion rate or polymerization using a high concentration of monomer components.
- the present inventors have found that a polymer having a ring structure in the main chain and having better heat resistance can be produced.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms
- the present invention also includes the ⁇ -allyloxymethylacrylic acid copolymer of the present invention, and is used in at least one application selected from the group consisting of photosensitive applications, colorant dispersibility applications, and radical curable applications. It is also a resin composition.
- the present invention further includes the following formula (1):
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms
- a step of polymerizing a monomer component including an ⁇ -allyloxymethylacrylic acid monomer represented by It is also a method for producing an ⁇ -allyloxymethylacrylic acid copolymer.
- the present invention is described in detail below.
- the ⁇ -allyloxymethylacrylic acid copolymer of the present invention is a copolymer having a structural unit represented by the formula (1) in the main chain (hereinafter referred to as “AMA copolymer (b)”).
- AMA copolymer (b) a copolymer having a structural unit represented by the formula (1) in the main chain
- R in formula (1) is the same as R in formula (2) described later.
- the ⁇ -allyloxymethylacrylic acid copolymer is represented by the following formula (2):
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms
- R is preferably obtained by a production method including a step of polymerizing a monomer component containing a monomer represented by .
- a monomer component containing a monomer represented by .
- AMA monomer (a) As the ⁇ -allyloxymethylacrylic acid monomer represented by the above formula (2) (also referred to herein as “AMA monomer (a)”), one kind may be used, and a plurality of kinds may be used. May be used.
- the said monomer component contains an AMA monomer (a) and another radically polymerizable monomer.
- the AMA monomer (a) will be described in detail. Since the AMA monomer (a) is polymerized to produce a structural unit represented by the above formula (1) at a high ratio, it is heavy compared with other 1,6-diene monomers. It is difficult for branching of coalescence to occur, and accordingly, it is difficult to cause abnormal high molecular weight and gelation.
- R in the formula (2) showing the structure of the AMA monomer (a) is a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the effect of suppressing the branching of the polymer that appears when a chain transfer agent is used is the allyl of the AMA monomer (a). Since it is thought to be due to the ether group, even if R is changed, the effect is sufficiently exhibited.
- each performance of the obtained ⁇ -allyloxymethylacrylic acid-based copolymer is such that in the structural unit represented by the above formula (1), the THF ring in the main chain and the methylenes on both sides of the THF ring Since it is caused by the group, R may be appropriately selected according to the purpose and application.
- R in the formula (2) is a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- organic group having 1 to 30 carbon atoms include, for example, chain saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyloctyl, 2-ethylhexyl, lauryl and stearyl; methoxyethyl, An alkoxy-substituted chain saturated hydrocarbon group in which part of the hydrogen atoms of a chain saturated hydrocarbon group such as methoxyethoxyethyl is replaced with an alkoxy group; a chain saturated hydrocarbon group such as hydroxyethyl, hydroxypropyl, hydroxybutyl, etc.
- chain saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyloctyl, 2-ethylhexyl, lauryl and stearyl
- methoxyethyl An alkoxy-substituted chain saturated hydrocarbon group in which part of the hydrogen atoms of
- Chain unsaturated hydrocarbon groups such as vinyl, allyl, methallyl, crotyl, propargyl, etc., and chain unsaturated hydrocarbon groups in which part of the hydrogen atoms are replaced with alkoxy groups, hydroxy groups or halogens; cyclopentyl, cyclohexyl, 4 -Alicyclic hydrocarbon groups such as methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentadienyl, etc., and part of the hydrogen atoms are alkoxy groups, hydroxy groups or halogens Substituted alicyclic hydrocarbon groups;
- Aromatic hydrocarbon groups such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-t-butylphenyl, benzyl, etc., and aromatic hydrocarbon groups in which some of the hydrogen atoms are replaced with alkoxy groups, hydroxy groups or halogens
- organic groups organic residues
- a substituent may be further bonded to these organic groups.
- the R of the AMA monomer (a) contained in the monomer component may be the same or two or more different. That is, structural units derived from a plurality of types of AMA monomers (a) having different R may be contained in the AMA copolymer (b).
- R in the above formula (2) is a hydrogen atom, a chain saturated hydrocarbon group, an alkoxy-substituted chain saturated hydrocarbon group, a hydroxy-substituted chain saturated hydrocarbon group, a halogen-substituted chain saturated hydrocarbon group.
- Chain unsaturated hydrocarbon group alkoxy-substituted chain unsaturated hydrocarbon group, hydroxy-substituted chain unsaturated hydrocarbon group, halogen-substituted chain unsaturated hydrocarbon group, alicyclic hydrocarbon group, alkoxy-substituted alicyclic ring Hydrocarbon group, hydroxy-substituted alicyclic hydrocarbon group, halogen-substituted alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy-substituted aromatic hydrocarbon group, hydroxy-substituted aromatic hydrocarbon group, or halogen-substituted fragrance It is also a preferred embodiment of the present invention to be a group hydrocarbon group.
- the AMA copolymer (b) obtained by radical polymerization of the monomer component containing the AMA monomer (a) will be described in detail.
- the AMA copolymer (b) has a high heat resistance because it has a structure containing a structural unit represented by the formula (1) in the main chain and a ring structure in the main chain.
- a resin having a ring structure in the main chain has high heat resistance, but in most cases lacks flexibility.
- the repeating unit having a THF ring represented by the above formula (1) is a THF ring. Since it has a methylene group on both sides, it is excellent in flexibility.
- R in the formula (1) may be different for each structural unit or the same.
- tetrahydrofurfuryl group which is a functional group having a THF ring is represented by the following formula (3);
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the oxygen scavenging performance is exhibited, for example, in the radical curable resin composition etc.
- the AMA copolymer (b) of the present invention can be suitably used for a radical curable resin composition, and can improve surface curability and thin film curability.
- it since it has an oxygen scavenging property, it can also be suitably used as an oxygen-absorbing film, a protective material for organic electroluminescent elements, and the like.
- the THF ring acts as a so-called Lewis base (a donor of a lone electron pair). Therefore, for example, when the resin composition using the AMA copolymer (b) and another member are attached, the THF ring and the functional group on the surface of the other member are likely to interact with each other. Expresses adhesion. From such a viewpoint, it can be suitably used for various resin compositions that are used in close contact with a substrate or the like.
- the AMA copolymer (b) has excellent transparency because the THF ring does not contain nitrogen (N). Thereby, it can use suitably as optical materials, such as a lens and a color filter.
- the AMA copolymer (b) has excellent colorant dispersion stability. This is presumably because the THF ring which is a Lewis base interacts with the color material (pigment, dye) surface and the functional group of the color material dispersant. Therefore, the AMA copolymer (b) obtained by the production method of the present invention is suitably used for applications in which coloring materials (pigments, dyes) are added as other components such as paints, colored inks, and colored resists. . From such a viewpoint, the AMA copolymer (b) of the present invention can be suitably used for a colorant dispersion composition.
- the average functional group number is preferably 0.5 or more. More preferably, it is 1.0 or more, More preferably, it is 2.0 or more.
- the average number of functional groups is represented by the following formula.
- Average number of functional groups A / P
- A Number of moles of the structural unit represented by the formula (1) included in the unit mass [mol / g]
- P Number of moles of AMA copolymer (b) contained in unit mass [mol / g]
- A can be calculated as the following equation, including the case where there are two or more types of structural units represented by the equation (1).
- AX unit mass ⁇ (CX / 100) /
- the average number of functional groups is represented by the following formula using CX, FX, and Mn.
- the AMA monomer (a) represented by the formula (2) is represented by the cyclization rate (from the monomer represented by the formula (2) to the formula (1). Therefore, CX and FX can be approximated as follows.
- CX can be approximated as follows.
- said Mn can be measured with the measuring method used in the Example mentioned later.
- the AMA copolymer (b) has excellent compatibility and dry redissolvability. This compatibility and dry redissolvability are considered to be due to the THF ring structure and the methylene groups adjacent to the THF ring structure. This is also inferred from the fact that tetrahydrofuran is a solvent that is often used not only for industrial use but also for analysis and research as a substance capable of dissolving a very wide range of substances.
- the AMA copolymer (b) since the AMA copolymer (b) has various excellent properties, it can be suitably used for various applications.
- the performance derived from the above-mentioned THF ring can be expressed by, for example, a (meth) acrylic copolymer having a tetrahydrofurfuryl group in the side chain, such as a (meth) acrylic acid tetrahydrofurfuryl copolymer, Like the ⁇ -allyloxymethylacrylic acid copolymer of the invention, it is difficult to develop high heat resistance and durability.
- the AMA copolymer (b) when used in a curable resin composition, it can be suitably used for a sealing material for electronic parts, an overcoat, etc., but both oxygen scavenging properties and high heat resistance are achieved. Therefore, the element and the like can be protected from oxidation and deterioration due to heat.
- the AMA copolymer (b) is an ⁇ -allyloxymethylacrylic acid copolymer obtained by polymerizing the AMA monomer (a) and another radical polymerizable monomer.
- the properties derived from other polymerizable monomers can be imparted, so that the ⁇ -allyl obtained can be obtained depending on the intended use.
- the characteristics of the oxymethylacrylic acid copolymer can be adjusted.
- the type of the other radical polymerizable monomer and the structure of the structural unit derived from the other radical polymerizable monomer are not particularly limited. Moreover, it is not specifically limited as the form, For example, any forms, such as a random copolymer, an alternating copolymer, a periodic copolymer, a block copolymer, may be sufficient.
- the other radical polymerizable monomer is a radical polymerizable monomer other than the AMA monomer (a) that can be copolymerized with the AMA monomer (a). 1 type may be used for another radically polymerizable monomer, and 2 or more types may be used for it.
- the other radical polymerizable monomer is a monomer having a radical polymerizable unsaturated group that is polymerized by irradiation with heat or active energy ray, etc., and the type and amount of the other radical polymerizable monomer, The molecular weight and the like may be appropriately selected according to the purpose and application.
- a monofunctional radically polymerizable monomer is mentioned.
- Esters are examples of esters;
- (Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; Unsaturated polyvalent carboxylic acids such as acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; styrene, ⁇ -methylstyrene, vinyltoluene, methoxystyrene Aromatic vinyls such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, and the like; and the like.
- the weight average molecular weight (Mw) of the AMA copolymer (b) may be appropriately set according to the purpose and application, but when used for liquid applications such as a radical curable resin composition and a colorant dispersion composition. In order to achieve good fluidity, it is preferably 100000 or less, more preferably 70000 or less, and still more preferably 50000 or less. Moreover, in order for the characteristic as a polymer to fully be exhibited, it is preferable that it is 1000 or more, More preferably, it is 3000 or more.
- the AMA copolymer (b) preferably has a polydispersity (Mw / Mn) representing a molecular weight distribution of 5.0 or less, more preferably 4.0 or less, and still more preferably 3 0.0 or less.
- Mw / Mn polydispersity
- branching of the polymer can be suppressed, Mw / Mn can be reduced.
- Mw weight average molecular weight
- Mw / Mn polydispersity
- a conventional method can be used as a method for controlling the molecular weight of the AMA copolymer (b). For example, the amount and type of a polymerization initiator, the polymerization temperature, and the type and amount of a chain transfer agent are adjusted. Can be controlled.
- the AMA copolymer (b) of the present invention has an oxygen scavenging property, adhesion property, colorant dispersibility, compatibility, dry resolubility, transparency and other properties derived from the THF ring and its adjacent methylene groups, Heat resistance and durability can be achieved at a high level.
- the alkali-soluble resin of the present invention is an alkali-soluble resin having a structural unit represented by the above formula (1) in the main chain.
- the content of the structural unit represented by the formula (1) in the alkali-soluble resin of the present invention may be appropriately set according to the purpose, application, and molecular weight of the alkali-soluble resin of the present invention. In the unit, it is 1 to 99 mol%, preferably 2 to 98 mol%, more preferably 5 to 95 mol%.
- the alkali-soluble resin of the present invention has a high molecular weight, performance tends to develop even if the content of the structural unit represented by the formula (1) is small, and when the content is low, the content is large. There is a tendency that performance is easy to express.
- the average number of functional groups is 0.5 or more. Preferably, it is 1.0 or more, more preferably 2.0 or more.
- the average number of functional groups can be obtained in the same manner as described above.
- the alkali-soluble resin of the present invention has an acid group for becoming alkali-soluble.
- the acid value of the alkali-soluble resin of the present invention is set to a preferable value depending on the purpose and application, but is preferably 10 to 300 mgKOH / g, more preferably 15 to 250 mgKOH / g, and still more preferably. 20-200 mg KOH / g.
- the alkali-soluble resin of the present invention has a high molecular weight, the higher the acid value, the better plate-making property can be obtained, and when the molecular weight is low, the good plate-making property tends to be obtained even when the acid value is low. There is.
- Examples of the acid group for becoming alkali-soluble include functional groups that neutralize with alkaline water, such as carboxyl group, phenolic hydroxyl group, carboxylic acid anhydride group, phosphoric acid group, and sulfonic acid group. You may have only a seed
- Examples of the method for introducing an acid group include a one-step introduction method for polymerizing a monomer component containing a monomer represented by the above formula (2) and a monomer having an acid group, and the above formula. There are two or more stages of introduction methods in which a modification treatment is performed after obtaining a resin having the structural unit represented by (1) in the main chain.
- the monomer having an acid group in the one-step introduction method can be polymerized with a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, or a sulfonic acid group. And a compound having an unsaturated group.
- a functional group that neutralizes with alkaline water such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, or a sulfonic acid group.
- a compound having an unsaturated group such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, or a sulfonic acid group.
- unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid
- unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid Carboxylic acids
- unsaturated monocarboxylic acids such as succinic acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryloyloxyethyl) in which the chain between the unsaturated group and the carboxyl group is extended
- maleic anhydride And unsaturated acid anhydrides such as itaconic anhydride
- phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.).
- Carboxylic acid monomers unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids
- the introduction method having two or more steps is not particularly limited as long as the structural unit represented by the formula (1) is not lost during the modification treatment.
- a monomer having a functional group p is used.
- the modification treatment is performed as many times as necessary to convert the functional group r into the functional group p, and then the compound having the functional group q is reacted.
- the introduction method may be used.
- Examples of such a functional group p include an active hydrogen group such as a hydroxy group and an amino group
- examples of the functional group q include a polybasic acid anhydride group.
- Specific examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.
- Acid hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, anhydrous Trimellitic acid, pyromellitic anhydride and the like can be mentioned, and one or more of these can be used.
- a two-stage introduction method of reacting a compound having a functional group q that reacts with the functional group p to generate an acid group after polymerizing a monomer component containing the monomer having the functional group p for example, ( Examples thereof include a method of reacting succinic anhydride after polymerizing a monomer component containing 2-hydroxyethyl (meth) acrylate.
- the modification process is performed as many times as necessary to convert the functional group r into the functional group p, and then the compound having the functional group q is reacted.
- the introduction method include a method in which a monomer component containing glycidyl (meth) acrylate is polymerized and then reacted with (meth) acrylic acid and further reacted with succinic anhydride.
- the alkali-soluble resin of the present invention preferably has a radical polymerizable unsaturated group.
- the content of the radically polymerizable unsaturated group may be appropriately set according to the purpose and application, but in order to obtain good platemaking properties, the radically polymerizable unsaturated bond equivalent (radical polymerizable unsaturated bond 1 chemistry).
- the molecular weight per equivalent is preferably 200 to 5000, more preferably 250 to 4000, and still more preferably 300 to 3000.
- radical polymerizable unsaturated group examples include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a methallyl group.
- the radical polymerizable unsaturated group may have only one kind or two or more kinds. Among these, an acryloyl group and a methacryloyl group are preferable in terms of reactivity.
- a method for introducing a radically polymerizable unsaturated group there may be mentioned a two-step or more introduction method in which a modification treatment is performed after obtaining a resin having a structural unit represented by the formula (1) in the main chain.
- the introduction method having two or more steps is not particularly limited as long as the structural unit represented by the formula (1) is not lost during the modification treatment.
- a monomer having a functional group s is used.
- There is a two-stage introduction method in which a monomer having a functional group t capable of reacting with the functional group s is reacted after the monomer component to be polymerized is reacted. Further, after polymerizing the monomer having the functional group u, the modification process is performed as many times as necessary to convert the functional group u into the functional group s, and then the monomer having the functional group t is reacted. It may be an introduction method of more than stages.
- Examples of such combinations of functional groups s and t include, for example, carboxyl group and hydroxy group, carboxyl group and epoxy group, carboxyl group and oxetanyl group, carboxyl group and isocyanate group, hydroxy group and isocyanate group, and acid anhydride group.
- Examples include a hydroxy group, an acid anhydride group, and an amino group.
- a combination of a carboxyl group and an epoxy group is preferable in terms of the speed of the modification treatment reaction, heat resistance, and transparency.
- the monomer having a carboxyl group examples include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, and itaconic acid.
- unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, and itaconic acid.
- Unsaturated polyvalent carboxylic acids such as citraconic acid and mesaconic acid
- chain extension between unsaturated group and carboxyl group such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate
- Unsaturated monocarboxylic acids which can be used alone or in combination of two or more.
- the monomer having an epoxy group examples include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, Examples include allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, and vinylcyclohexene oxide. These may be used alone or in combination of two or more.
- a two-stage introduction method for reacting a monomer having a functional group t capable of reacting with the functional group s after polymerizing a monomer component containing the monomer having the functional group s specifically, for example, there is a method of reacting (meth) acrylic acid after polymerizing a monomer component containing glycidyl (meth) acrylate.
- the modification treatment is performed as many times as necessary to convert the functional group u into the functional group s, and then the monomer having the functional group t is reacted.
- a monomer component containing 2-hydroxyethyl (meth) acrylate is polymerized and then reacted with succinic anhydride, and further glycidyl (meth) acrylate is added.
- the method of making it react is mentioned.
- the alkali-soluble resin of the present invention is a resin having an acid group.
- the acid group When a radical polymerizable unsaturated bond is introduced, the acid group must also be introduced by some method.
- the amount of the carboxyl group is excessively larger than the amount of the epoxy group when reacting the carboxyl group and the epoxy group, or the polybasic acid anhydride is added after reacting the carboxyl group and the epoxy group. If it is made to react, it can be set as resin which has an acid group and a radically polymerizable unsaturated bond.
- an epoxy group is used as the functional group s and a carboxyl group is used as the functional group t, the polybasic acid anhydride may be reacted after reacting the carboxyl group and the epoxy group.
- the step of reacting the carboxyl group and the epoxy group is preferably 50 to 160 ° C. in order to ensure a good reaction rate and prevent gelation. It is carried out at a temperature range, more preferably 70 to 140 ° C, still more preferably 90 to 130 ° C.
- a basic catalyst and an acid catalyst for esterification or transesterification which are usually used as a catalyst can be used, but there are few side reactions.
- To basic catalysts are preferred.
- dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handling properties, and halogen-free. These catalysts may be used alone or in combination of two or more.
- the amount of the catalyst used is 0.01 to 5.0% by mass, preferably 0.1 to 3.0% by mass, based on the alkali-soluble resin of the present invention into which a radical polymerizable unsaturated bond is introduced. It is preferable to use for.
- a polymerization inhibitor in the presence of a molecular oxygen-containing gas in order to prevent gelation.
- a molecular oxygen-containing gas air or oxygen gas diluted with an inert gas such as nitrogen is usually used and blown into the reaction vessel.
- the polymerization inhibitor commonly used polymerization inhibitors for radically polymerizable monomers can be used, and examples thereof include phenolic inhibitors, organic acid copper salts, and phenothiazines. Of these, phenol-based inhibitors are preferred from the viewpoint of low coloration and ability to prevent polymerization.
- the alkali-soluble resin of the present invention into which a radically polymerizable unsaturated bond has been introduced from the viewpoint of ensuring sufficient polymerization prevention effect and curability when a photosensitive resin composition is used.
- it is preferably used in an amount of 0.001 to 1.0 mass%, preferably 0.005 to 0.5 mass%.
- the alkali-soluble resin of the present invention may have an epoxy group and / or an oxetanyl group and / or an alkoxysilyl group.
- an epoxy group and / or an oxetanyl group and / or an alkoxysilyl group By having an epoxy group and / or an oxetanyl group and / or an alkoxysilyl group, the crosslinking density can be improved in the thermosetting step.
- it is particularly suitable as a binder resin for resists for photospacers, transparent resists for protective films and resists for interlayer insulation films. be able to.
- the weight average molecular weight of the alkali-soluble resin of the present invention may be appropriately set according to the purpose and use. In order to obtain good plate-making properties, it is 2000 to 250,000, preferably 3000 to 200000, more preferably 4000 to 150,000. In addition, the weight average molecular weight can use the measuring method used in the Example mentioned later, for example.
- an ⁇ -allyloxymethylacrylic acid copolymer is produced by polymerizing a monomer component containing the AMA monomer (a). Is the method.
- the AMA copolymer (b) can be produced by cyclopolymerizing the AMA monomer (a).
- the AMA copolymer (b) is excellent in heat resistance because it has a ring structure (THF ring) in the main chain, and further has a methylene group on both sides of the THF ring. It is excellent in solubility and solvent solubility.
- the content of the AMA monomer (a) may be appropriately set according to the purpose, application, and molecular weight of the AMA copolymer (b), but is preferably 1 to 99 mol in all monomer components. %, More preferably 2 to 98 mol%, still more preferably 5 to 95 mol%.
- the AMA copolymer (b) can exhibit the outstanding characteristic derived from the structural unit represented by Formula (1).
- the said structural unit is a repeating unit which comprises a polymer, and a several polymer will be contained in one polymer.
- the AMA monomer (a) is more easily cyclized by radical polymerization than ionic polymerization, and radical polymerization is an industrially advantageous polymerization method. It is preferable to include a step of radical polymerization. Furthermore, in the case where the content of the AMA monomer (a) is large or the polymerization concentration is very high, the production method described above is carried out under the condition that the polymer is easily branched or gelled. It is more preferable to include a step of radical polymerization in the presence of a chain transfer agent. By using a chain transfer agent, branching of the polymer can be more effectively suppressed. As the branching proceeds, crosslinking occurs and the polydispersity (Mw / Mn) representing the molecular weight distribution increases.
- the crosslinking When the crosslinking further proceeds, it becomes a solvent swell that is insoluble in the solvent (gels). By suppressing the branching, such a phenomenon can be suppressed. Moreover, although the branch part of an AMA copolymer tends to be inferior in heat resistance, heat resistance can be improved by suppressing branching.
- the chain transfer agent is used to adjust the molecular weight, but when the AMA monomer (a) is polymerized, it is also obtained because it works to suppress the branching of the polymer. The molecular weight distribution of the polymer can be narrowed, or the polymer can be obtained without gelation even under industrially and economically advantageous conditions.
- the molecular weight distribution becomes large, and in some cases, gelation may occur.
- the branch part of an AMA copolymer is somewhat inferior in heat resistance, the heat resistance of the AMA copolymer manufactured by suppressing branching also improves.
- the chain transfer agent exerts a crosslinking inhibitory effect (an effect of inhibiting branching) specifically on the AMA monomer (a) among the 1,6-diene monomers is not clear.
- the reason is that one of the two double bonds of the AMA monomer (a) is an allyl ether group.
- the polymer branching occurs in the following formula (5);
- the allyl ether structure of the AMA monomer (a) interacts with the chain transfer agent through some mechanism to improve the cyclization rate.
- the chain transfer agent mainly prevents the polymerization of double bonds (allyl ether groups) of unclosed units.
- R is the same or different and represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the double bond easily reacts with the double bond of the monomer or other unclosed unit, and particularly under industrially and economically advantageous conditions (for example, conditions where the polymerization concentration is high or the conversion rate is high). Unusual high molecular weight and gelation are likely to occur.
- polymerization is performed using the AMA monomer (a) as in the reaction represented by the above formula (5), and the double bond of the unclosed unit becomes an allyl ether group.
- the radical generated in the allyl ether group reacts preferentially with the chain transfer agent to generate a chain transfer agent-derived radical, and the chain transfer agent-derived radical is sufficient. It is presumed that it has a sufficient ability to initiate polymerization and has a function of preferentially reacting with the monomer.
- the amount of the chain transfer agent used is the type of chain transfer agent, the content of the AMA monomer (a) contained in the monomer component, the target molecular weight, the polymerization concentration, the amount of initiator used together, the polymerization Although it may be appropriately selected according to the temperature or the like, it is preferably used in an amount of 0.03% by mass or more based on 100% by mass of the monomer component. By using in such a range, the effect acquired by using a chain transfer agent is fully exhibited, and the branching of a polymer can be suppressed more effectively.
- the amount of the chain transfer agent used is more preferably 0.05% by mass or more. More preferably, it is 0.1 mass% or more.
- the upper limit of the amount used is not particularly high, and the effect of the present invention will be more exhibited if the amount of the chain transfer agent is large, but it is uneconomical even if used more than necessary, and odor may be a problem. Therefore, it is preferably 20% by mass or less with respect to 100% by mass of the monomer component.
- the chain transfer agent may be any compound that causes a chain transfer reaction in the polymerization of a radical polymerizable vinyl monomer, and is a compound that is industrially used as a so-called chain transfer agent.
- Mercapto groups such as mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanurates, etc. in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. (Also referred to as “mercaptan compound” or “mercaptan chain transfer agent”) is preferred. That is, the chain transfer agent is preferably a compound having a mercapto group.
- the compound having a mercapto group include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and 3-mercaptopropion.
- N-octyl acid methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis Mercaptocarboxylic acid esters such as (3-mercaptopropionate); ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane, etc.
- Rumel mercaptans mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3 And mercaptan chain transfer agents such as mercaptoisocyanurates such as -mercaptopropionyloxy) -ethyl] isocyanurate.
- mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol
- aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol
- tris [(3 And mercaptan chain transfer agents such as mercaptoisocyanurates such as -mercaptopropionyloxy) -eth
- chain transfer agents other than the compound which has a mercapto group can also be used.
- chain transfer agents other than compounds having a mercapto group include disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; monomer dimers such as ⁇ -methylstyrene dimer And alkyl halides such as carbon tetrabromide.
- 1 type may be used and 2 or more types may be used together.
- AMA monomer (a) and radicals capable of initiating polymerization exist as an addition method in the case of adding the chain transfer agent.
- AMA monomer (a) and radicals capable of initiating polymerization exist as an addition method in the case of adding the chain transfer agent.
- the chain transfer agent is added in the period.
- a method of adding all at once before the start of polymerization, adding all at once during the polymerization, starting the addition at the same time as the start of polymerization, and continuing the addition until the polymerization is completed can be mentioned. From the viewpoint of reducing the amount of the chain transfer agent used and maximizing the effect, a method of starting the addition simultaneously with the start of polymerization and continuing the addition until the polymerization is completed is preferable.
- a residue of the chain transfer agent (a group forming a part of the chain transfer agent) is bonded to the terminal of the obtained polymer.
- the chain transfer agent residue is not bonded to all of the ⁇ -allyloxymethylacrylic acid copolymer obtained by polymerization, but at least a polymer having a chain transfer agent residue bonded to the terminal is present.
- One is manufactured.
- the use of a chain transfer agent is determined by detecting elements and functional groups peculiar to the residue of the chain transfer agent by elemental analysis or spectroscopic techniques (NMR, IR, UV, etc.). be able to.
- the polymerization step can be carried out at a monomer component concentration (polymerization concentration) of 15% by mass or more, the polymerization conversion rate can be increased or the polymerization time can be shortened. Is preferable.
- a monomer component concentration polymerization concentration of 15% by mass or more
- the polymerization conversion rate can be increased or the polymerization time can be shortened. Is preferable.
- the polymerization concentration is increased, there is a tendency that the polymer is likely to be branched.
- branching of the polymer can be suppressed even if the polymerization concentration is increased.
- the polymerization concentration in the polymerization step is more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more.
- concentration made 100 mass% what added the monomer component and chain transfer agent which are used for a superposition
- the amount of the chain transfer agent and polymerization initiator used in the polymerization step is small. Therefore, when performing polymerization using a solvent, for the sake of convenience, the concentration of the monomer component when the sum of the monomer component used in the polymerization step and the solvent is 100% by mass may be defined as the polymerization concentration. .
- the polymerization step is preferably performed with the monomer component concentration (polymerization concentration) of 15 mass% or more with respect to a total of 100 mass% of the polymerization solvent and the monomer component.
- any polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization, and precipitation polymerization can be used as long as it is a polymerized by a radical polymerization mechanism.
- These polymerization methods may be appropriately selected depending on the purpose and application.
- solution polymerization is preferable because it is industrially advantageous and structural adjustments such as molecular weight are easy.
- polymerization is performed by dissolving the AMA monomer (a) in a polymerization solvent.
- a solution in which polymerizable monomers as raw materials are collectively dissolved in a polymerization solvent may be used, or the polymerizable monomers as raw materials may be used with respect to the polymerization solvent.
- a method of adding stepwise may be used.
- the polymerizable monomer is added stepwise to the polymerization solvent.
- the polymerizable monomer may be added continuously or intermittently.
- a monomer may be added. This is the same as the method for adding the chain transfer agent.
- the polymerization concentration is determined by the polymerization solvent, the polymerizable monomer and the chain transfer agent that are collectively added, and The mass percentage (% by mass) of the polymerizable monomers added in a lump when the total mass with other components added as necessary is 100% by mass.
- the polymerization concentration is a step when the total amount of the polymerization solvent and the total amount of polymerizable monomers added stepwise is 100% by mass. It becomes the mass percentage (mass%) of the sum total of the polymerizable monomer added automatically.
- the amount of chain transfer agent and polymerization initiator used in the polymerization step is small, and for convenience, the monomer when the total of the monomer components and solvent used in the polymerization step is 100% by mass.
- the concentration of the component may be the polymerization concentration.
- the type and amount of the solvent used for the polymerization are not particularly limited as long as they are inert to the polymerization reaction, and the polymerization mechanism is used. What is necessary is just to set suitably according to polymerization conditions, such as a kind and quantity of a monomer, polymerization temperature, polymerization concentration, and the use for which an ⁇ -allyloxymethylacrylic acid type copolymer is used later.
- alcohols examples include alcohols, glycols, cyclic ethers, glycol ethers, esters of glycol monoethers, alkyl esters, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, dimethylformamide, Examples include amides such as dimethylacetamide and N-methylpyrrolidone, and water. These may be used alone or in combination of two or more.
- energy necessary for initiating polymerization may be supplied to the monomer component from an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and the like.
- an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and the like.
- the method for producing the ⁇ -allyloxymethylacrylic acid copolymer preferably includes a step of polymerizing a monomer component containing the AMA monomer (a) in the presence of a radical polymerization initiator. Furthermore, in the case where the content of the AMA monomer (a) is large or the polymerization concentration is very high, the polymer containing the AMA monomer (a) is easily included under conditions where the polymer is likely to be branched or gelled. It is more preferable to include a step of polymerizing the monomer component in the presence of a chain transfer agent and a radical polymerization initiator. Examples of the radical polymerization initiator include polymerization initiators that generate radicals by heat or light.
- thermal radical polymerization initiators are advantageous and preferable.
- the thermal radical polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy. Depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. It may be selected as appropriate.
- thermal radical polymerization initiator a peroxide, an azo compound, etc. are mentioned, These may be used independently or may use 2 or more types together. Moreover, you may use together reducing agents, such as a transition metal salt and amines, with a polymerization initiator.
- the amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.05 to 20% by mass is preferable with respect to 100% by mass of all monomer components, and 0.1 to 15% by mass is more preferable. .
- the preferred polymerization temperature and polymerization time in the above cyclopolymerization vary depending on the type of polymerizable monomer used, the use ratio, etc., but are preferably 50 to 200 ° C., more preferably 70 to 150 ° C.
- the polymerization time is preferably 20 hours or less, more preferably 10 hours or less, and still more preferably 8 hours or less.
- the cyclopolymerization may be performed so that the conversion rate of the AMA monomer is 70% or more in order to reduce the adverse effects on the performance due to the remaining monomer when used in various applications. preferable. That is, in the polymerization step, the conversion rate of the AMA monomer (a) is preferably 70% or more.
- the conversion rate is more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.
- the method for producing the AMA copolymer (b) may further include a step of performing a modification treatment after polymerizing the monomer component containing the AMA monomer (a) represented by the formula (2).
- a modification treatment By performing the modification treatment, it is possible to introduce radically polymerizable unsaturated groups, graft chains, and the like.
- the AMA copolymer (b) having a radical polymerizable unsaturated group is obtained by a modification treatment, for example, when the AMA copolymer (b) is used in a radical curable resin composition, the curability is improved. This is preferable. That is, the AMA copolymer (b) may be one that has been subjected to modification treatment after polymerizing the monomer component containing the AMA monomer (a) represented by the formula (2).
- the modification treatment method is not particularly limited as long as it is a treatment method in which the structural unit represented by the formula (1) in the AMA copolymer (b) is not lost.
- a single monomer having a functional group x examples include a method of reacting a compound having a functional group y capable of reacting with the functional group x after polymerizing the monomer component containing the body.
- Examples of the combination of the functional groups x and y include, for example, carboxyl group and hydroxy group, carboxyl group and epoxy group, carboxyl group and isocyanate group, hydroxy group and isocyanate group, acid anhydride group and hydroxy group, acid anhydride group and An amino group etc. are mentioned.
- an AMA copolymer (b) having a radically polymerizable unsaturated group is obtained by reacting glycidyl (meth) acrylate after polymerizing a monomer component containing (meth) acrylic acid.
- an AMA copolymer (b) having a polycaprolactone in the graft chain is obtained by polymerizing a monomer component containing glycidyl (meth) acrylate and then reacting with one terminal carboxyl group polycaprolactone. be able to.
- the present invention is also an ⁇ -allyloxymethylacrylic acid copolymer (AMA copolymer (b)) produced by the above production method.
- AMA copolymer (b) ⁇ -allyloxymethylacrylic acid copolymer
- Such an ⁇ -allyloxymethylacrylic acid-based copolymer may be obtained by polymerizing one kind of AMA monomer (a), or may polymerize a plurality of kinds of AMA monomers (a). It may be what was done.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms
- a step of polymerizing a monomer component consisting only of an ⁇ -allyloxymethylacrylic acid monomer is also one aspect of the present invention.
- the resin composition of the present invention that is, the radical curable resin composition, the color material dispersion composition, and the photosensitive resin composition will be described in order.
- the radical curable resin composition of the present invention is a radical curable resin composition containing a radical polymerizable monomer and a binder resin, wherein the binder resin has a structural unit represented by the formula (1) in the main chain.
- a radically curable resin composition is binder resin used for the radical curable resin composition of this invention, Comprising:
- the said binder resin is resin which has the structural unit represented by Formula (1) in a principal chain,
- the radical curable resin composition is also one of this invention.
- each component of the radical curable resin composition of this invention is demonstrated.
- the essential components of the radical curable resin composition of the present invention are (A) a radical polymerizable monomer and (B) a binder resin, and (B) the binder resin is a structural unit represented by the formula (1).
- the radical curable resin composition of the present invention preferably contains (C) a radical polymerization initiator for improving curability in addition to the above essential components, and further includes types of radical polymerizable monomers and binder resins, and various uses.
- D Diluent and
- E Other components may be blended according to the purpose and required characteristics.
- each component which comprises the radical curable resin composition of this invention is demonstrated.
- the radical polymerizable monomer is a low molecular weight compound having a radical polymerizable unsaturated group that is polymerized by heat, irradiation of active energy rays, or the like. Gives radical curability.
- a liquid having a low viscosity at room temperature is also called a reactive diluent because it also has a function as a diluent for adjusting viscosity, and is particularly preferably used in applications where use of a solvent is disliked.
- a radically polymerizable monomer those usually used as a radically polymerizable monomer can be used, and one or more kinds may be appropriately selected according to the purpose and application.
- the radical polymerizable monomer is classified into a monofunctional radical polymerizable monomer having only one radical polymerizable unsaturated group in the same molecule and a polyfunctional radical polymerizable monomer having two or more. can do.
- a monofunctional radical polymerizable monomer those similar to the other radically polymerizable monomers shown in the method for producing the ⁇ -allyloxymethylacrylic acid copolymer can be used.
- polyfunctional (meth) acrylates polyfunctional urethane (meth) acrylates, and (meth) acryloyl group-containing isocyanates are considered due to reactivity, economy, and availability.
- Polyfunctional monomers having a (meth) acryloyl group such as nurates can be preferably used.
- the molecular weight of the radical polymerizable monomer may be appropriately set according to the purpose and application, but 2000 or less is preferable in terms of handling.
- the amount of the radical polymerizable monomer used may be appropriately set according to the type, purpose, and use of the radical polymerizable monomer and binder resin to be used, but exhibits good radical curability and binder resin characteristics. From this point, it is 5 to 1000% by mass, preferably 15 to 700% by mass, and more preferably 20 to 500% by mass with respect to the binder resin.
- Binder resin is a polymer compound that mainly affects the properties of the coating film after drying and the physical properties of the coating film after curing, and is a component that contributes to radical curability.
- the binder resin for a radical curable resin composition of the present invention the above-mentioned ⁇ -allyloxymethylacrylic acid copolymer can be used. Such a resin can reduce radical polymerization inhibition by oxygen, is excellent in adhesion and transparency, and is excellent in heat resistance.
- the expression of the characteristics as described above in the binder resin for a radical curable resin composition of the present invention is attributed to the THF ring contained in the structural unit represented by the formula (1) and the methylene group on both sides of the THF ring.
- the binder resin of the present invention also exhibits the effect of reducing radical curing inhibition by oxygen, and further, the THF ring and the functional group on the base material surface are likely to interact with each other, so that it is considered that good adhesion is expressed. It is done.
- a coloring radical curable resin composition by adding a coloring material (pigment, dye) as other components such as paint, colored ink, and colored resist.
- a coloring material pigment, dye
- the binder resin for a radical curable resin composition of the present invention has excellent colorant dispersion stability as described later. This is presumably because the THF ring which is a Lewis base interacts with the color material (pigment, dye) surface and the functional group of the color material dispersant.
- the binder resin for a radical curable resin composition of the present invention is considered to exhibit the above-described performances effectively due to the structure in which the methylene group is present on both sides of the THF ring in the structure.
- the performance derived from these THF rings can be expressed to some extent even in a (meth) acrylic copolymer having a tetrahydrofurfuryl group in the side chain, but like the binder resin for a radical curable resin composition of the present invention. It is difficult to develop high heat resistance.
- One of the preferred modes of use of the radical curable resin composition of the present invention is a sealing material or an overcoat for electronic parts. This is because the radical curable resin composition of the present invention has an oxygen scavenging property ( That is, both the antioxidant ability and high heat resistance can be achieved, and the elements and the like can be protected from oxidation and deterioration due to heat.
- the weight average molecular weight of the binder resin for a radical curable resin composition of the present invention may be appropriately set according to the purpose and application, but is usually 2000 to 250,000, preferably 3000 to 200000, and more preferably 4000 to 150,000. is there.
- the weight average molecular weight can use the measuring method used in the Example mentioned later, for example.
- the ratio of the binder resin for the radical curable resin composition of the present invention in the radical curable resin composition of the present invention may be appropriately set according to the type, purpose, and use of the radical polymerizable monomer and binder resin to be used.
- the preferred amount used is as shown in the radical polymerizable monomer.
- the binder resin for the radical curable resin composition may be the same as the ⁇ -allyloxymethylacrylic acid copolymer as described above, but in addition, the AMA monomer (a An ⁇ -allyloxymethylacrylic acid polymer obtained by polymerizing a monomer component consisting only of ()) can also be used. Even in this case, the same effect as when the ⁇ -allyloxymethylacrylic acid copolymer is used can be expected. That is, the use of the ⁇ -allyloxymethylacrylic acid polymer as a binder resin for a radical curable resin composition is also one aspect of the present invention.
- the radical curable resin of the present invention is used from an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. What is necessary is just to supply energy required for radical polymerization start to a composition, and also using a radical polymerization initiator together can reduce significantly energy required for radical polymerization start, and can improve sclerosis
- an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc.
- radical polymerization initiators there are thermal radical polymerization initiators that generate polymerization initiating radicals by heating, and photo radical polymerization initiators that generate polymerization initiating radicals by irradiation of energy rays such as electromagnetic waves and electron beams. 1 type or 2 types or more can be used. Moreover, it is also preferable to add one or more kinds of heat radical polymerization accelerators, photosensitizers, photoradical polymerization accelerators and the like that are usually used as necessary.
- the total amount of the radical polymerization initiator added may be appropriately set according to the purpose and application, and is not particularly limited. However, from the viewpoint of balance between curability, adverse effects of decomposition products, and economy, radical curable resin composition
- the content is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and still more preferably 0.1 to 15% by mass with respect to the entire product.
- the total amount of the thermal radical polymerization accelerator, photosensitizer, and photoradical polymerization accelerator added may be appropriately set according to the purpose and application, and is not particularly limited. From the viewpoint of the balance of properties, the content is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.05 to 10% by mass with respect to the entire radical curable resin composition. 10% by mass.
- (D) Diluent In the radically curable resin composition of the present invention, the viscosity is lowered and the handleability is improved, the coating film is formed by drying, the dispersion medium of the coloring material, etc., as necessary.
- a low viscosity organic solvent or water capable of dissolving or dispersing each component in the radical curable resin composition may be added as a diluent.
- those similar to the polymerization solvent shown in the method for producing an ⁇ -allyloxymethylacrylic acid copolymer can be used. These may be used alone or in combination of two or more.
- the amount of the diluent used may be appropriately set according to the purpose and application, and is not particularly limited, but is usually preferably 0 to 90% by mass with respect to the whole radical curable resin composition, more The content is preferably 0 to 80% by mass.
- the radical curable resin composition of the present invention comprises a filler, a resin other than the binder resin for the radical curable resin composition of the present invention, and a coloring material (pigment) according to the purpose and required characteristics of each application.
- a coloring material pigment
- Dyes Dyes
- dispersants plasticizers
- polymerization inhibitors UV absorbers
- antioxidants matting agents
- antifoaming agents leveling agents
- antistatic agents dispersants
- slip agents surface modifiers
- shaking change Components other than the above essential components such as an agent, a thixotropic agent, a coupling agent such as silane, aluminum, and titanium, a cationic polymerizable compound, and an acid generator may be blended.
- the radical curable resin composition of the present invention when used for adhesives or pressure-sensitive adhesives, adhesives such as resins and tackifiers other than the binder resin for the radical curable resin composition of the present invention are used as necessary.
- a property-imparting agent, various fillers, a colorant, a dispersant, and the like can be blended.
- a use mode in which the adhesive or pressure-sensitive adhesive thus obtained is applied on a metal, glass, paper, resin, or other substrate and cured by heating or irradiation with active energy rays is one of the preferred embodiments of the present invention. One.
- the radical curable resin composition of the present invention When the radical curable resin composition of the present invention is used for inks or paints, a resin other than the binder resin for the radical curable resin composition of the present invention, various fillers, a coloring material, a dispersant, a drying oil, if necessary. A dryer or the like can be blended.
- the use mode in which the ink or paint thus obtained is applied onto a metal, glass, paper, resin, or other base material and cured by heating or irradiation with active energy rays is one of the preferred embodiments of the present invention. is there.
- the radical curable resin composition of the present invention is used for a curable molding material
- a resin other than the binder resin for the radical curable resin composition of the present invention various fillers, a coloring material, a dispersant, an ultraviolet ray, if necessary.
- An absorbent etc. can be mix
- the curable molding material thus obtained is used as it is or impregnated in a reinforcing fiber such as glass fiber, carbon fiber or aramid fiber, and cured by heating or irradiation with active energy rays.
- a reinforcing fiber such as glass fiber, carbon fiber or aramid fiber
- an alkali-soluble binder resin, an epoxy resin, various fillers, a colorant, a dispersant, and the like can be blended as necessary.
- the use mode in which the resist material thus obtained is applied on a metal, glass, resin, or other substrate, cured by irradiation with active energy rays, developed with an alkaline developer, and image formation is suitable for the present invention. It is one of the embodiments.
- the radical curable resin composition of the present invention can be obtained by blending, mixing, dissolving, or dispersing blending components such as a radical polymerizable monomer, a binder resin, and other additives.
- the radical curable resin composition of the present invention includes an adhesive, an adhesive, a biomaterial, a dental material, an optical member, an information recording material, an optical fiber material, a color filter resist, a solder resist, a plating resist, an insulator, and a sealing material.
- Inkjet ink, printing ink, paint, casting material, decorative plate, WPC, coating material, photosensitive resin plate, dry film, lining material, civil engineering and building material, putty, repair material, flooring material, paving material gel coat, overcoat It can be used in a wide range of applications such as molding materials such as hand lay-up, spray-up, pultrusion, filament winding, SMC, BMC, and polymer solid electrolytes.
- the color material dispersion composition of the present invention is a color material dispersion composition containing a color material, a dispersant, a binder resin, and a liquid medium, wherein the binder resin has a structural unit represented by formula (1) in the main chain.
- a colorant-dispersed composition Moreover, it is binder resin used for the color material dispersion composition of this invention, Comprising: For the color material dispersion composition whose said binder resin is resin which has the structural unit represented by Formula (1) in a principal chain. A binder resin is also one aspect of the present invention.
- each component of the color material dispersion composition of the present invention will be described.
- the essential components of the color material dispersion composition of the present invention are (F) a color material, (G) a dispersant, (H) a binder resin, and (I) a liquid medium, and (H) the binder resin has the above formula. It is a resin having the structural unit represented by (1) in the main chain. Further, other components (J) other than those described above may be further blended according to the purpose and required characteristics of each application.
- each component constituting the color material dispersion composition of the present invention will be described.
- the coloring material coloring material is used for coloring the coloring material dispersion composition of the present invention, and dyes and pigments that are usually used as coloring materials can be used. And inorganic pigments).
- the color materials can be used alone or in combination of two or more, and those having an appropriate average particle diameter can be used according to the purpose and application. For example, when transparency is required, a small average particle size of 0.1 ⁇ m or less is preferable, and when concealability is required, a large average particle size of 0.5 ⁇ m or more is preferable.
- the color material may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application. Good.
- the proportion of the color material in the color material dispersion composition of the present invention may be appropriately set according to the purpose and application, but in the color material dispersion composition in terms of balancing the coloring power and dispersion stability,
- the content is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass.
- the dispersant has an interaction site with the color material and an interaction site with the dispersion medium (liquid medium or binder resin), and functions to stabilize the dispersion of the color material into the dispersion medium.
- a dispersant that is usually used as a dispersant can be used. Generally, it is classified into a resin type dispersant (polymer dispersant), a surfactant (low molecular dispersant), and a pigment derivative.
- the said dispersing agent can be used individually or in combination of 2 or more types.
- the proportion of the dispersant in the color material dispersion composition of the present invention may be set as appropriate according to the purpose and application, but the dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency
- the content is usually preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 40% by mass with respect to the color material. It is.
- binder resin for the color material dispersion composition of the present invention the same binder resin as that for the radical curable resin composition of the present invention can be used. Since the binder ring resin for radical curable resin composition of the present invention has a THF ring in the structure, its action as a so-called Lewis base is not as strong as amines that are strong bases, and has an appropriate basicity. It is considered that the colorant dispersed with the dispersant is further stabilized by interacting with the colorant and the dispersant without disturbing the action.
- the ratio of the binder resin for the color material dispersion composition of the present invention in the color material dispersion composition of the present invention may be appropriately set according to the purpose and application, but is usually 0.1% in the color material dispersion composition.
- the content is preferably -90% by mass, more preferably 0.5-80% by mass, and still more preferably 1-70% by mass.
- the liquid medium is a dispersion medium that uniformly holds the color material dispersed by the dispersant, and is a liquid that mainly functions to adjust the viscosity, coating characteristics, and drying characteristics of the color material dispersion composition. It is a substance.
- a liquid medium usually used can be appropriately selected and used according to the purpose and application.
- the amount of the liquid medium to be used may be appropriately set according to the purpose and application, but is usually preferably 10 to 95% by mass, more preferably 20 to 90% by mass in the color material dispersion composition. %, And more preferably 30 to 85% by mass.
- the color material-dispersed composition of the present invention may further contain components other than the essential components according to the purpose and required characteristics of each application.
- a photocurable ink it is preferable to add a photopolymerizable monomer and a photoinitiator in addition to the above essential components.
- dryness such as linseed oil is used. It is preferable to blend a dryer such as oil or cobalt octylate.
- alkali developing resist inks such as solder resists and color filter resists
- an alkali-soluble binder resin epoxy resin, radical-curable unsaturated group-containing resin, polyfunctional acrylate, and photoinitiator It is preferable to add an agent.
- blend stabilizers such as antioxidant and a ultraviolet absorber
- a leveling agent coupling agents, such as a silane type
- the color material dispersion composition of the present invention can be prepared by a commonly performed dispersion method, and may be appropriately selected according to the purpose and application.
- the disperser that can be used include a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, and a blender.
- a paint conditioner a bead mill
- a roll mill a ball mill
- a jet mill a homogenizer
- a kneader a blender
- a finely dispersing process with a media mill such as a bead mill. It is preferable to remove fine dust by performing a filtration process or the like.
- the method of adding the constituents of the dispersion to the disperser may be batch or sequential, the order is arbitrary, and may be appropriately selected according to the type of the disperser. In addition, it is not necessary to add all of the components (coloring material, dispersant, binder resin, liquid medium, and other components) to the disperser, but the minimum color required to disperse the coloring material with the coloring material and the disperser. Components other than the colorant may be added to and mixed with components other than the colorant after preparing the colorant dispersion composition containing the colorant at a high concentration by introducing the component other than the material into the disperser.
- the photosensitive resin composition of the present invention is a photosensitive resin composition containing an alkali-soluble resin having a structural unit represented by the above formula (1) in the main chain as a binder resin.
- the present invention is also a color filter having a segment formed using the photosensitive resin composition, and a liquid crystal display panel including the color filter.
- the photosensitive resin composition of the present invention is a photosensitive resin comprising (K) the alkali-soluble resin of the present invention, (L) a radical polymerizable monomer, (M) a photoinitiator, and (N) a solvent as essential components. Because of its excellent heat resistance, the composition is suitable for resists for forming members in the field of electronic information, particularly for color filter resists. Further, since it has excellent colorant dispersion stability, in addition to the above essential components, (O) a colorant is added as an essential component to form a photosensitive colored resin composition. This is one of the usage modes that make the most of the characteristics, and such a photosensitive colored resin composition is particularly suitably used as a colored resist for a color filter. Moreover, according to each use and objective, (P) other components may be mix
- Color filter resists include color resists such as colored resists (red, green, and blue pixels and black matrix forming resists), photospacer resists, protective film transparent resists, and interlayer insulation film resists. There is a resist corresponding to each part.
- each structural component of the photosensitive resin composition of this invention is demonstrated, but this invention is not limited to this.
- Alkali-soluble resin of the present invention imparts film-forming properties and alkali-solubility to a resist, and the photosensitive resin composition of the present invention is used as a photosensitive colored resin composition. Also serves as a dispersion medium for the dispersed color material.
- the alkali-soluble resin of the present invention has excellent colorant dispersibility in addition to high heat resistance, and is very suitable for a photosensitive colored resin composition, particularly suitable for a colored resist for a color filter. is there.
- the color resist for color filters is usually prepared by preparing a colorant dispersion (mill base) composed of a colorant, a dispersant, a binder resin, a solvent, etc., and then a radical polymerizable monomer, photoinitiator, binder resin, solvent. It is prepared by adding a transparent resist solution composed of, etc.
- the alkali-soluble resin of the present invention is suitable as a binder resin for a mill base or a binder resin for a transparent resist solution, and may be used for both or only one of them.
- alkali-soluble resin of this invention may mix and use binder resins other than the alkali-soluble resin of this invention.
- the preferable structure of the alkali-soluble resin of the present invention is as described above, a structure having a radical polymerizable unsaturated group in the side chain is particularly preferable for a colored resist.
- the alkali-soluble resin of the present invention has an effect of improving mechanical properties (restoration rate, etc.) and various plate-making properties in addition to high heat resistance, it can be suitably used for a photospacer resist.
- a preferable structure is as described above, and in particular, a radically polymerizable unsaturated group and / or an epoxy group and / or an oxetanyl group in the side chain, and / or Or the structure which has an alkoxy silyl group is preferable.
- the alkali-soluble resin of the present invention is excellent in adhesion and transparency in addition to high heat resistance, and can be suitably used for a transparent resist for a protective film and a resist for an interlayer insulating film.
- the alkali-soluble resin of the present invention is used for a transparent resist for a protective film or a resist for an interlayer insulating film, the preferred structure is as described above, and in particular, a radically polymerizable unsaturated group and / or an epoxy group in the side chain, and A structure having an oxetanyl group and / or an alkoxysilyl group is preferable.
- the proportion of the alkali-soluble resin of the present invention contained in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and application, but in the component excluding the (N) solvent from the photosensitive resin composition.
- the content is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and still more preferably 5 to 70% by mass.
- a radical polymerizable monomer is a low polymer having a radical polymerizable unsaturated group that is polymerized by irradiation with active energy rays such as electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. It is a molecular compound and imparts curability to the photosensitive resin composition of the present invention.
- the radical polymerizable monomer includes a monofunctional radical polymerizable monomer having only one radical polymerizable unsaturated group in the same molecule and a polyfunctional radical polymerizable monomer having two or more.
- a polyfunctional radically polymerizable monomer is preferable at a sclerosing
- a radical polymerizable monomer the same radical polymerizable monomer contained in the above-mentioned radical curable resin composition of the present invention can be used.
- the molecular weight of the radical polymerizable monomer may be appropriately set according to the purpose and application, but 2000 or less is preferable in terms of handling.
- the amount of the radical polymerizable monomer used may be appropriately set according to the type, purpose, and use of the radical polymerizable monomer and binder resin to be used.
- it is usually preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 70% by mass.
- the photosensitive resin composition of this invention contains the photoinitiator which generate
- the radical curable resin composition of this invention One or two or more of the same radical photopolymerization initiators shown as components that may be contained can be used. Moreover, it is also preferable to add 1 type (s) or 2 or more types of the said photosensitizer, the said photoradical polymerization promoter, etc. similarly to the said photoradical polymerization initiator.
- the total amount of the photoinitiator added may be appropriately set according to the purpose and application, and is not particularly limited, but from the viewpoint of the balance between curability, adverse effects of decomposed products, and economy, from the photosensitive resin composition.
- the content is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and still more preferably 1 to 20% by mass.
- the total amount of the photosensitizer and the radical photopolymerization accelerator may be appropriately set according to the purpose and application, and is not particularly limited, but from the viewpoint of balance between curability, adverse effects of decomposition products, and economic efficiency.
- the content of the photosensitive resin composition excluding the (N) solvent is preferably 0.001 to 20% by mass, more preferably 0.05 to 15% by mass, and still more preferably 0.01 to 10% by mass.
- (N) Solvent Solvent dissolves each component in the photosensitive resin composition used to reduce viscosity and improve handling, form a coating film by drying, use as a colorant dispersion medium, etc. Or a low-viscosity organic solvent or water that can be dispersed.
- the same thing as the said diluent shown as a component which may be contained in the radical curable resin composition of this invention can be used, It may be used independently and 2 or more types may be used. May be used in combination.
- the amount of the solvent used may be appropriately set according to the purpose and application, and is not particularly limited, but is usually preferably 10 to 90% by mass, more preferably based on the entire photosensitive resin composition. 20 to 80% by mass.
- the coloring material coloring material is for coloring the photosensitive resin composition of the present invention to further form a photosensitive coloring resin composition, and is shown as an essential component of the coloring material dispersion composition of the present invention.
- the same color materials as those described above can be used.
- the proportion of the coloring material in the photosensitive resin composition of the present invention may be set as appropriate according to the purpose and application.
- the content is usually preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass.
- the photosensitive resin composition of the present invention comprises a filler, a binder resin other than the alkali-soluble resin of the present invention, a dispersant, a heat improver, and a development aid depending on the purpose and required characteristics of each application.
- Components other than the above essential components such as coupling agents such as silane, aluminum, and titanium, quinonediazide compounds, polyhydric phenol compounds, cationic polymerizable compounds, and acid generators may be blended.
- a binder resin other than the alkali-soluble resin of the present invention can be used for balance adjustment of various properties of the color filter resist, cost reduction of the resist, and the like.
- binder resins include (meth) acrylic acid / (meth) acrylic acid ester copolymers, (meth) acrylic acid / aromatic vinyl copolymers, (meth) acrylic acid / (Meth) acrylic acid ester / aromatic vinyl copolymer, (meth) acrylic acid / (meth) acrylic acid ester copolymer / N-substituted maleimide copolymer, (meth) acrylic acid / aromatic vinyl / N-substituted maleimide Copolymer, (meth) acrylic acid copolymer such as (meth) acrylic acid / (meth) acrylic ester / polystyrene macromonomer copolymer; radical polymerizable non-polymerizable in side chain
- the amount of the binder resin other than the alkali-soluble resin of the present invention may be appropriately set according to the purpose and application as long as the characteristics of the alkali-soluble resin of the present invention are not impaired.
- the ratio of the alkali-soluble resin of the present invention in the total binder resin contained in the composition is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more.
- the dispersing agent is a desirable component to be blended with the above essential components when a coloring material is added to the photosensitive resin composition of the present invention to form a photosensitive colored resin composition.
- the dispersant the same dispersant as the dispersant which is an essential component of the color material dispersion composition of the present invention can be used.
- the proportion of the dispersing agent in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and application, but the dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency
- the content is usually preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 40% by mass with respect to the color material. It is.
- an N- (alkoxymethyl) melamine compound a compound having two or more epoxy groups or an oxetanyl group can be added to improve heat resistance and strength.
- a resist for a photospacer a transparent resist for a protective film, or a resist for an interlayer insulating film is used, these are preferably used.
- a leveling agent can be added to the photosensitive resin composition of the present invention to improve leveling properties.
- a fluorine-based or silicon-based surfactant is preferable.
- a coupling agent can be added to the photosensitive resin composition of the present invention to improve adhesion.
- a silane coupling agent is preferable, and specific examples include epoxy, methacrylic, and amino silane coupling agents. Among these, an epoxy silane coupling agent is preferable.
- the photosensitive resin composition of the present invention is a monocarboxylic acid such as (meth) acrylic acid, acetic acid, propionic acid; maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, trimellitic acid, etc.
- Polycarboxylic acids such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and the like can be added as a development aid.
- the photosensitive resin composition of the present invention requires the alkali-soluble resin, radical polymerizable monomer, photoinitiator, solvent, colorant, dispersant, other binder resin, leveling agent, etc. as necessary. Can be prepared by mixing and dispersing various components using various mixers and dispersers.
- the photosensitive resin composition of the present invention contains a color material
- a color material it is produced through a color material dispersion treatment step. For example, first, a predetermined amount of each of a coloring material, a dispersing agent, a binder resin, and a solvent is weighed, and the coloring material is dispersed in fine particles using a dispersing machine such as a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, and a blender. Thus, a liquid colorant dispersion (mill base) is obtained.
- a dispersing machine such as a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, and a blender.
- the mixture is kneaded and dispersed with a roll mill, kneader, blender, etc., and then finely dispersed with a media mill such as a bead mill filled with 0.01 to 1 mm beads.
- a transparent resist solution containing a radical polymerizable monomer, a photoinitiator, a binder resin, a solvent, a leveling agent, etc., which has been separately stirred and mixed, is added and mixed to obtain a uniform dispersion solution.
- a colored resin composition is obtained.
- the obtained photosensitive colored resin composition is desirably filtered through a filter or the like to remove fine dust.
- the present invention is also a color filter having a segment formed using the photosensitive resin composition.
- methods for forming color filter segments include photolithographic methods, printing methods, electrodeposition methods, and ink jet methods.
- Photolithographic methods include mainstream negative acrylic photosensitive resin composition (photosensitive acrylic method), non-photosensitive polyimide resin composition and positive resist (nonphotosensitive polyimide). Law). Specifically, in the photosensitive acrylic method, a negative photosensitive resin composition is applied onto a support substrate and dried, and then a photomask is overlaid on the formed coating film, and exposure is performed through this photomask.
- the exposed portions are photocured, the unexposed portions are developed, washed as necessary, and further heat-cured or photocured to form segments of each color filter.
- the support substrate is large, coating by a slit coating device is common.
- the photosensitive resin composition of the present invention is used as this negative photosensitive resin composition, high quality color filter segments can be formed with high yield.
- it can also be applied to the formation of color filter segments by the ink jet method, taking advantage of the excellent dry resolubility of the alkali-soluble resin and photosensitive resin composition of the present invention.
- a pixel is formed on a transparent substrate in the case of a liquid crystal display device, and a photoelectric conversion element substrate in the case of an imaging tube element.
- an alignment film and an alignment control structure are formed.
- a black matrix and pixels, and a protective film, a photospacer, and the like are formed on a transparent substrate on which TFTs (thin film transistors) are formed.
- the color filter of the present invention only needs to have at least one segment formed using the photosensitive resin composition of the present invention, but preferably the color of all pixels, more preferably a black matrix. And a pixel is formed using the photosensitive resin composition of this invention.
- the photosensitive resin composition of the present invention is particularly suitable for pixels that need to be colored and black matrix, but is also suitable for forming segments that do not require coloring, such as photo spacers and protective layers.
- Transparent substrates include glass, thermoplastic sheets such as polyesters, polycarbonates, polyolefins, polysulfones, cyclic olefin ring-opening polymers and their hydrogenated products, and thermosetting plastic sheets such as epoxy resins and unsaturated polyester resins. From the viewpoint of heat resistance, a glass plate and a heat resistant plastic sheet are preferable.
- the transparent substrate may be subjected to chemical treatment with a corona discharge treatment, an ozone treatment, a silane coupling agent, or the like, if necessary.
- the black matrix is formed on a transparent substrate using a metal thin film or a photosensitive colored resin composition for black matrix.
- the black matrix using a metal thin film is formed of, for example, a chromium single layer or two layers of chromium and chromium oxide.
- the metal or metal / metal oxide thin film is formed on the transparent substrate by vapor deposition, sputtering, or the like.
- the photomask is exposed and developed using the photomask to form a black matrix image.
- the thin film is etched to form a black matrix.
- a black matrix is formed according to segment formation by said photosensitive acrylic method.
- the pixels are usually three colors of red, green, and blue.
- green pixels are formed according to the above-described segment formation by the photosensitive acrylic method using a green photosensitive coloring composition. This operation is performed for the remaining two colors to form pixels of three colors.
- the order of forming the pixels of each color is not particularly limited.
- the protective film is formed on the pixels according to the above-described segment formation by the photosensitive acrylic method using the transparent photosensitive resin composition for the protective film after forming the pixels as necessary. In some cases, a protective film is not formed in order to reduce costs and simplify processes.
- a transparent electrode When forming a transparent electrode on a pixel or a protective film, sputtering method, vacuum deposition method, CVD using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof.
- ITO indium tin oxide
- ZnO zinc oxide
- SnO tin oxide
- a thin film is formed by a method or the like, and if necessary, a predetermined pattern can be formed by etching using a positive resist or using a jig.
- a transparent electrode may not be formed.
- the photo spacer is formed directly on the black matrix according to the above-mentioned photosensitive acrylic method segment formation using the photosensitive resin composition for the photo spacer, if necessary, or a protective film or a transparent film in accordance with the black matrix region. Or formed on an electrode. In some cases, the cell gap is maintained by a particulate spacer without forming a photospacer.
- Examples of the method for applying the photosensitive resin composition to the substrate include spin coating, slit coating, roll coating, casting coating, and the like. Particularly, when using the photosensitive resin composition of the present invention, a method by slit coating is used. preferable.
- the coating conditions for slit coating vary depending on the slit-and-spin method, the spinless method, the size of the transparent substrate, the target film thickness, and the like, and the ejection amount from the nozzle and the moving speed of the slit head are appropriately selected.
- the lip width at the nozzle tip is usually 30 to 500 ⁇ m, and the distance between the nozzle tip and the substrate is usually 30 to 300 ⁇ m.
- the photosensitive resin composition of this invention is preferably applicable also to the method by spin coating, roll coating, and cast coating.
- the thickness of the coating film is usually 0.3 to 3.5 ⁇ m in the case of a black matrix, a pixel and a protective film, and is usually 1 to 10 ⁇ m in the case of a photospacer.
- the coating film after being applied to the substrate is dried using a hot plate, IR oven, convection oven or the like.
- the drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the dryer, etc., but are usually performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds.
- the exposure is a step of irradiating the coating film with actinic rays through a predetermined mask pattern.
- active light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps, argon ion lasers, YAG Laser light sources such as laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser are used.
- the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
- the film is developed with a developer to remove unexposed portions and form a pattern.
- a developer can be used as long as it dissolves the photosensitive resin composition of the present invention.
- an organic solvent or an alkaline aqueous solution is used.
- an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development.
- the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary.
- Alkaline agents include inorganic alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. ; Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and these may be used alone or in combination of two or more; Also good.
- Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and these may be used alone or in combination of two or more; Also good.
- the surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonates, and the like.
- Anionic surfactants such as alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids. These may be used alone or in combination of two or more. Good.
- organic solvent examples include alcohols such as isopropanol, benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol, and these may be used alone or in combination of two or more.
- the development treatment is usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.
- thermosetting treatment After the development, it is usually heated at a temperature of 150 to 250 ° C. for 5 to 60 minutes using a heating device such as a hot plate, a convection oven, a high-frequency heater, etc., and subjected to a thermosetting treatment.
- a heating device such as a hot plate, a convection oven, a high-frequency heater, etc.
- the color liquid crystal display panel of the present invention is a liquid crystal display panel comprising the color filter of the present invention.
- the liquid crystal display panel of the present invention can be manufactured, for example, by forming an alignment film on the inner surface side of the color filter, and laminating a liquid crystal compound in a gap portion by bonding to a counter substrate.
- a resin film such as polyimide is suitable, and usually a surface treatment is performed by ultraviolet treatment or rubbing treatment after coating and heat baking.
- the liquid crystal compound is not particularly limited, and those usually used can be used.
- the counter substrate is preferably a TFT substrate, and a substrate manufactured by a normal method can be used.
- the bonding gap between the color filter and the counter substrate is usually in the range of 2 to 8 ⁇ m. After the opposing substrates are bonded together, the liquid crystal display panel is completed by sealing with a sealing material.
- the structural unit represented by the formula (1) which exhibits curability in air (oxygen scavenging property), good adhesion, transparency, and excellent heat resistance,
- the AMA copolymer (b) having in the main chain is provided. Furthermore, in the production method of the AMA copolymer (b), it is possible to suppress the branching of the polymer in the radical polymerization of the AMA monomer (a) and prevent abnormal high molecular weight and gelation. It is easy to adjust physical properties and add various functions, and has high manufacturing stability and enables strict quality control. Optical applications and resist materials are fields that require advanced and diverse functions and strict quality control. It is possible to provide an ⁇ -allyloxymethylacrylic acid copolymer suitable for the above.
- the ⁇ -allyloxymethylacrylic acid copolymer obtained by the production method of the present invention contains the structural unit represented by the formula (1) obtained by a method other than the production method of the present invention in the main chain. It has higher heat resistance than the resin it has, and can be more suitable for applications that require heat resistance.
- the radical curable resin composition of the present invention not only the curability in air (oxygen scavenging property) but also the adhesion and transparency are excellent, and the radical curable resin is very excellent in heat resistance. A composition is provided. Therefore, the radical curable resin composition of the present invention is used for applications that require heat resistance among the applications in which the radical curable composition is used, for example, sealing materials for electronic parts, overcoats, and coatings.
- the color material dispersion composition of the present invention a color material dispersion composition capable of achieving both dispersibility and other performances such as adhesion and curability at a high level is provided.
- the binder resin of the present invention which is a constituent component of the composition, has good production stability.
- an alkali-soluble resin having excellent heat resistance and colorant dispersibility and excellent platemaking properties, and a photosensitive resin composition using the resin are provided.
- the photosensitive resin composition is excellent in heat resistance, it is suitable for resists for forming members in the field of electronic information, such as solder resists, etching resists, interlayer insulating materials, plating resists, and color filter resists. Since it is excellent in material dispersibility, it is particularly suitable for forming a colored layer of a color filter.
- FIG. 1 is a 1 H-NMR chart measured using the resin powder obtained in Example 8.
- FIG. 2 is a 1 H-NMR chart measured using the resin powder obtained in Example 16.
- FIG. 3 is a 1 H-NMR chart measured using the resin powder obtained in Reference Example 1.
- a part of the resin solution was diluted with tetrahydrofuran and poured into excess hexane for reprecipitation. The precipitate was taken out by filtration and then vacuum dried at 70 ° C. (for 5 hours or more) to obtain a white resin powder.
- Example 1 As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 213.5 parts of propylene glycol monomethyl ether acetate (PGMEA) was charged into the reaction vessel, and the temperature was raised to 90 ° C. On the other hand, 121.8 parts of AMA-M obtained in Synthesis Example 1 and 78.2 parts of methyl methacrylate (MMA) were added to the dropping tank A, and t-butylperoxy-2-ethylhexanoate was added to the dropping tank B. (PBO) 4.7 parts and 42.0 parts of PGMEA were stirred and mixed. In the dropping tank C, 3.5 parts of methyl 3-mercaptopropionate (MPM) and 44.5 parts of PGMEA were stirred and mixed. Got ready.
- MPM methyl 3-mercaptopropionate
- Example 2 As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, a dropping tank prepared by stirring and mixing 60.9 parts of AMA-M, 39.1 parts of MMA, and 6.0 parts of PBO was prepared.
- Example 3 A resin solution and a white resin powder were obtained in the same manner as in Example 1 except that 60.0 parts of AMA-M and 140.0 parts of MMA were prepared in the dropping tank A. The analysis results are shown in Table 2.
- Example 4 As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 120.1 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, 30.0 parts of AMA-M, 70.0 parts of MMA and 6.0 parts of PBO were stirred and mixed in dropping tank A, and 3-mercaptopropionic acid (MPA) 0.1 was added in dropping tank B. And 29.9 parts of PGMEA were mixed with stirring.
- MPA 3-mercaptopropionic acid
- Example 5 As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, a dropping tank was prepared by stirring and mixing 30.0 parts of AMA-M, 70.0 parts of MMA, and 6.0 parts of PBO.
- Example 6 As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 223.7 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, 180.0 parts of AMA-M obtained in Synthesis Example 1 and 20.0 parts of methacrylic acid (MAA) were stirred and mixed in the dropping tank A, and 4.7 parts of PBO and PGMEA 37 were added in the dropping tank B. A mixture obtained by stirring and mixing 3 parts, and a dropping tank C prepared by stirring and mixing 3.0 parts of MPA and 39.0 parts of PGMEA were prepared.
- MAA methacrylic acid
- Example 7 The liquid mixture prepared in the dropping tank A was changed to a mixture in which 120.0 parts of AMA-M, 50.0 parts of benzyl methacrylate (BZMA), 1.4 parts of MMA, and 28.6 parts of MAA were well mixed. Except for the above, a resin solution and a white resin powder were obtained in the same manner as in Example 6. The analysis results are shown in Table 2.
- Example 8 Example except that the liquid mixture prepared in the dropping tank A was changed to a well-mixed mixture of 60.0 parts AMA-M, 110.0 parts BZMA, 1.4 parts MMA, and 28.6 parts MAA. In the same manner as in 6, a resin solution and a white powder of resin were obtained. The analysis results are shown in Table 2.
- Example 9 Except that the mixed solution prepared in the dropping tank A was changed to a well-mixed mixture of 20.0 parts of AMA-M, 110.0 parts of BZMA, 41.4 parts of MMA, and 28.6 parts of MAA. In the same manner as in 6, a resin solution was obtained. The analysis results are shown in Table 2.
- Example 10 to 13 A resin solution was obtained in the same manner as in Example 8 except that the type of AMA-R, which is a monomer for introducing the ether ring structure prepared in the dropping tank A, was changed to that shown in Table 2. The analysis results are shown in Table 2.
- Example 14 The mixed solution prepared in the dropping tank A was changed to a mixture obtained by thoroughly stirring and mixing 60.0 parts of AMA-M, 110.0 parts of cyclohexyl methacrylate (CHMA), 1.4 parts of MMA, and 28.6 parts of MAA. Except for this, a resin solution was obtained in the same manner as in Example 6. The analysis results are shown in Table 2.
- Example 15 As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 208 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, 96.8 parts of styrene (ST) is added to the dropping tank A, and 60.0 parts of AMA-M, 1.4 parts of MMA, 28.6 parts of MAA, and 5.0 parts of PBO are well stirred into the dropping tank B. In the dropping tank C, a mixture obtained by thoroughly stirring and mixing MPA 3.0 parts and PGMEA 92.0 parts was prepared.
- ST styrene
- Example 16 As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA and 14.0 parts of 2-propanol (IPA) were charged into the reaction vessel, and the temperature was raised to 90 ° C. On the other hand, 48.0 parts of AMA-M, 64.0 parts of BZMA, and 48.0 parts of MAA were mixed in the dropping tank A, and 3.7 parts of PBO and 38.3 parts of PGMEA were added to the dropping tank B. In the dropping tank C, a mixture obtained by stirring and mixing MPA 4.3 parts and PGMEA 37.7 parts was prepared.
- IPA 2-propanol
- the dropping of each mixture was started simultaneously from the dropping tanks A, B, and C, and the internal temperature was adjusted to 90 ° C.
- the polymerization reaction was carried out by dropping over 3.5 hours. Temperature increase was started 30 minutes after the completion of the dropping, the temperature was increased to 115 ° C., maintained at 115 ° C. for 1 hour, and then cooled to room temperature.
- the gas to be introduced is switched from nitrogen to a nitrogen / oxygen mixed gas (oxygen 7%), 0.06 part of 6-t-butyl-2,4-xylenol (TBXL), 52.8 parts of glycidyl methacrylate (GMA), dimethyl
- a nitrogen / oxygen mixed gas oxygen 7%
- TXL 0.06 part of 6-t-butyl-2,4-xylenol
- GMA glycidyl methacrylate
- dimethyl dimethyl
- Example 17 A resin solution was obtained in the same manner as in Example 16 except that the dropping tank A was prepared by stirring and mixing 48.0 parts of AMA-M, 64.0 parts of CHMA, and 48.0 parts of MAA. The analysis results are shown in Table 2.
- Example 18 As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 140.3 parts of PGMEA and 14.0 parts of IPA were charged into the reaction vessel, and the temperature was raised to 90 ° C. On the other hand, 56.3 parts of ST was added to the dropping tank A, and 48.0 parts of AMA-M, 48.0 parts of MAA, and 4.0 parts of PBO were added to the dropping tank C. Prepared MPA 4.3 parts and PGMEA 95.7 parts with good stirring and mixing.
- the gas to be introduced was switched from nitrogen to a nitrogen / oxygen mixed gas (oxygen 7%), and after each substance was charged into the reaction vessel in the order of TBXL 0.06 part, GMA 52.8 part, DMBA 0.6 part, stirring,
- the side chain double bond introduction reaction was performed while starting the temperature rise and adjusting the internal temperature to 110 ° C.
- heating was temporarily stopped, 80.0 parts of PGMEA was added, and the pressure was gradually reduced to 37.3 kPa. Heating was resumed while maintaining this pressure, and simultaneously the solvent containing IPA was distilled off.
- the dropping of each mixture was started simultaneously from the dropping tanks A, B, and C. From the dropping tank A, the dropping tanks B and C were taken over 3 hours. Was added dropwise over 3.5 hours to conduct a polymerization reaction. After 30 minutes from the end of dropping, the temperature was started to evaporate the solvent containing IPA, and at the same time, PGMEA in the same amount as the amount of the distilled solvent was supplied to the reaction vessel. When the internal temperature reached 115 ° C., the heating was temporarily stopped, and the pressure in the system was gradually reduced to 37.3 kPa to maintain this pressure.
- Example 5 The liquid mixture prepared in the dropping tank A was prepared by thoroughly stirring and mixing 60.0 parts of benzylmaleimide (BZMI), 110.0 parts of BZMA, 1.4 parts of MMA, 28.6 parts of MAA, and 60.0 parts of PGMEA. A resin solution and a white resin powder were obtained in the same manner as in Example 6 except for the change. The analysis results are shown in Table 3.
- BZMI is a monomer capable of obtaining a resin having an imide ring structure in the main chain, which is known as a highly heat-resistant resin described in Patent Document 2.
- Table 3 Abbreviations in Table 3 are as follows in addition to the abbreviations in Table 2.
- MD Dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate
- BZMI benzylmaleimide THFM: tetrahydrofurfuryl methacrylate
- the values of the monomer components are the monomer composition
- the content ratio (mass%) is represented, and the numerical values of the initiator, the chain transfer agent, and GMA represent the mass ratio with respect to the total amount of monomers used for the polymerization.
- UV was irradiated using an ultra-high pressure mercury lamp capable of irradiating the coating film with a certain amount of light, and the surface was touched to confirm tackiness. UV irradiation and finger touch were repeated, and the UV integrated irradiation dose [J / cm 2 ] when the surface was tackless was recorded. The smaller the UV integrated irradiation amount, the better the surface curability. The results are shown in Table 4.
- Adhesion is one of the coating film performances after curing that the binder resin greatly contributes. In order to clearly evaluate the effect on the adhesion of the structural unit represented by the formula (1), the evaluation is performed only with the binder resin.
- the resin structure does not include an acid group such as a carboxyl group or a strong base such as an amine.
- the adhesiveness of the resins of Examples 6 to 18 having an acid group was also good.
- the binder resin powder shown in Table 4 was dissolved in IPAC to make a 39% solution. This was applied to a float plate glass using a bar coater, naturally dried at room temperature for 10 minutes, and then dried at 70 ° C. for 5 minutes using a hot air dryer to obtain a binder resin coating film having a thickness of 10 ⁇ m. The adhesion of this coating film was evaluated on a scale of 0 to 5 according to JIS K 5600-5-6 (cross cut method). The results are shown in Table 4. Table 5 shows the criteria for adhesion classification in Table 4.
- Transmittance retention [%] transmittance after heating / transmittance before heating ⁇ 100.
- the binder resin of the present invention is higher in transparency than the binder resin having a tetrahydrofurfuryl group in the side chain and the resin having an imide ring in the main chain. It turns out that it has sex.
- C.I. I. Pigment Green 36 (Monastral Green 6Y-CL: manufactured by Heubach, hereinafter referred to as PG36), 3.75 parts, and C.I. I. Pigment Yellow 150 (Yellow Pigment E4GN-GT: Lanxess, hereinafter referred to as PY150) 2.5 parts, SOLPERSE12000 (manufactured by Japan Lubrizol Corporation, hereinafter referred to as SP12000) 0.2 part as a dispersant, 225 ml mayonnaise Weighed in a bottle.
- Example 33 The mill base was prepared and the dispersion stability was evaluated in the same manner as in Example 25 except that the types and amounts of the components of the mill base filled in the mayonnaise bottle were changed as follows. The results are shown in Table 7.
- C. I. Pigment Blue 15: 6 Heliogen Blue L6700F: manufactured by BASF, hereinafter referred to as PB15: 6): 5.0 parts
- C.I. I. Pigment Violet 23 (Hostaperm Violet RL-NF, manufactured by Clariant, hereinafter referred to as PV23): 1.25 parts SP24000 20% PGMEA solution: 3.75 parts SP12000: 0.2 parts
- the resin solution obtained in Example 8 was used as PGMEA. Diluted to 20% with: 14.0 parts PGMEA: 25.8 parts.
- Example 34 The mill base was prepared and the dispersion stability was evaluated in the same manner as in Example 25 except that the types and amounts of the components of the mill base filled in the mayonnaise bottle were changed as follows. The results are shown in Table 7.
- C. I. Pigment Red 254 (Irgaphor Red BT-CF: manufactured by Ciba Specialty Chemicals, hereinafter referred to as PR254): 4.4 parts
- Pigment Red 177 (Chromophthal Red A3B: Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as PR177): 1.85 parts SP24000 20% PGMEA solution: 5.0 parts 20% PGMEA resin solution obtained in Example 8 Diluted to: 13.75 parts PGMEA: 25.0 parts.
- Example 35 The mill base was prepared and the dispersion stability was evaluated in the same manner as in Example 25 except that the types and amounts of the components of the mill base filled in the mayonnaise bottle were changed as follows. The results are shown in Table 7. Carbon black (MA220: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as CB): 6.25 parts SP24000 in 20% PGMEA solution: 3.75 parts SP12000: 0.2 part The resin solution obtained in Example 8 was replaced with PGMEA. Diluted to 20%: 14.0 parts PGMEA: 25.8 parts.
- Example 36 (Preparation of colored resist) First, each mill base material shown in Table 8 was subjected to a dispersion treatment in a bead mill filled with 0.3 mm zirconia beads to obtain a green mill base. Next, each material for the transparent resist solution shown in Table 8 was stirred and mixed to prepare a transparent resist solution. 240.0 parts of the green mill base thus obtained and 135.0 parts of a transparent resist solution were stirred and mixed, and then filtered through a 1 ⁇ m filter to obtain a green resist.
- Pattern shape A The edge of the line is straight and sharp. O: Some parts of the edge of the line are blurred. ⁇ : The edge of the line is totally blurred. X: The edge of the line is clearly rattling.
- Examples 37 to 42, Comparative Examples 13 to 15 Evaluation was performed in the same manner as in Example 36 except that the binder resin for mill base and the binder resin for transparent resist solution were changed as shown in Table 9. The results are shown in Table 9.
- Example 43 (Preparation of colored resist)
- the photosensitive colored resin composition of Example 41 was used as a green resist. Further, as shown in Table 10, red, blue, and black resists were obtained in the same manner as in Example 41 except that the type and amount of the color material were changed.
- Example 16 preparation of transparent resist for photo spacer and protective film
- the materials shown below were stirred and mixed, and then filtered through a 1 ⁇ m filter to obtain a transparent resist for photospacer and protective film.
- the resin solution obtained in Example 16 diluted to 20% with PGMEA 100.0 parts dipentaerythritol hexaacrylate 20.0 parts Irgacure 907 (manufactured by Ciba Specialty Chemicals) 2.4 parts Irgacure 369 (Ciba Specialty Chemicals) 0.4 parts PGMEA 10.0 parts.
- the black resist was coated on a non-alkali glass substrate having a size of 230 mm ⁇ 300 mm and a thickness of 1.1 mm by a spin coating method to form a coating film, and prebaked (80 ° C., 5 minutes). Thereafter, alignment exposure is performed through a predetermined black matrix photomask at an exposure amount of 500 mJ / cm 2 using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source, and development is performed with an alkaline developer. Then, post-baking (230 ° C., 30 minutes) was performed to form a black matrix (thickness: 1.2 ⁇ m).
- the red resist was applied onto the substrate on which the black matrix was formed by spin coating to form a coating film, and prebaked (80 ° C., 5 minutes).
- alignment exposure is performed through a predetermined photomask for pixels at an exposure amount of 100 mJ / cm 2 using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source, development is performed with an alkaline developer, and pure water is used.
- post baking (220 ° C., 30 minutes) was performed to form a red pixel pattern (thickness 2.0 ⁇ m).
- a green pixel pattern was formed using a green resist
- a blue pixel pattern was formed using a blue resist.
- a transparent resist for a photospacer and protective film was applied on a substrate on which a black matrix and each color pixel were formed by spin coating to form a coating film, and prebaked (80 ° C., 5 minutes). Thereafter, alignment exposure is performed through a predetermined photomask for protective film using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source at an exposure amount of 100 mJ / cm 2 , development is performed with an alkaline developer, and pure water is used. Then, post-baking (220 ° C., 30 minutes) was performed to form a protective film (thickness 1.5 ⁇ m).
- a transparent conductive layer made of acid value indium tin was formed by sputtering.
- a transparent resist for a photospacer and protective film was applied by spin coating on the substrate on which the protective film was formed to form a coating film, and prebaked (80 ° C., 5 minutes). After that, alignment exposure is performed through a predetermined photomask for spacers using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source at an exposure amount of 100 mJ / cm 2 , development is performed with an alkaline developer, and pure water is used. After washing, post-baking (220 ° C., 30 minutes) was performed to form a photospacer (height 4.8 ⁇ m, bottom 12 ⁇ m ⁇ 12 ⁇ m square).
- the polyimide alignment layer is provided on the color filter produced as described above and subjected to alignment treatment (rubbing), it is bonded to the TFT array substrate using an epoxy resin sealant, and TN is applied from the injection port provided in the seal portion. After the liquid crystal was sealed between the color filter and the TFT array substrate, the injection port was sealed, and an optical film such as a polarizing plate was bonded to obtain a simple TN liquid crystal display device.
- the produced liquid crystal display device had high luminance and color purity, and good display quality was obtained without causing color unevenness.
- the radical curable resin composition of the present invention is not only curable in air (oxygen scavenging property) but also excellent in adhesion and transparency, and very excellent in heat resistance.
- the colorant-dispersed composition of the present invention can achieve both high dispersibility and other performances such as adhesion, heat resistance, surface curability, transparency, etc.
- Suitable for paints for example, can be used for automobiles, painted steel sheets, building materials, cans, gravure, flexo, ink jet printers, color filters, and the like.
- the alkali-soluble resin of the present invention and the photosensitive resin composition of the present invention using the resin are excellent in heat resistance, and resists for forming members in the field of electronic information, such as solder resist, etching resist, interlayer insulation It is suitable for materials, plating resists, color filter resists, and is excellent in colorant dispersibility and platemaking properties, and is particularly suitable for forming a colored layer of a color filter.
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Abstract
Description
すなわち、テトラヒドロフルフリル基を有するラジカル重合性単量体、或いは側鎖にテトラヒドロフルフリル基を有するバインダー樹脂を利用したラジカル硬化性樹脂組成物は、空気中での硬化性(酸素捕捉性)に優れ、かつ、密着性、透明性も良好であるが、耐熱性にまだ改良の余地があった。
色材分散組成物用樹脂としては、非特許文献1及び特許文献1に記載の樹脂は、重合時に異常な高分子量化(分子量分布が非常に広くなる)、或いはゲル化を起こし易く、製造安定性、品質管理において課題があった。また、分散性と、その他の性能を高い次元で両立させることに、まだ改良の余地があった。
また感光性樹脂組成物用樹脂としては、特許文献2に記載のバインダー樹脂及び着色レジストは、耐熱性や製版性に優れるものの、色材の高濃度化には十分対応できていなかった。特許文献1に記載のバインダー樹脂及び着色レジストは、色材の高濃度化に対応すべく色材の分散安定性や製版性が改良されているものの、まだ改良の余地があり、また、そのバインダー樹脂を製造する際に異常な高分子量化やゲル化を起こし易く、製造安定性、品質管理の面で課題があった。
そしてまた、環構造を有さない単量体を付加重合と同時に環化させながら重合させる方法においては、環化せずに重合した1,6-ジエン類単量体由来の構成単位(以下、「未閉環単位」ともいう。)が生じ、該未閉環単位に存在する二重結合が基点となり分岐、架橋し、異常な高分子量化(分子量分布が非常に広くなる)やゲル化が生じる場合があった。このような傾向は、特に、単量体の転化率を上げる条件、重合濃度を上げる条件等の工業的、経済的に有利な条件において強く、1,6-ジエン類単量体を原料とした主鎖に環構造を有する樹脂の工業化において大きな障害となっていた。
特に、密着性、透明性にも優れ、かつ耐熱性に非常に優れるラジカル硬化型の組成物用バインダー樹脂、及び該バインダー樹脂を用いたラジカル硬化型の組成物を提供することを目的とする。
また、分散性と、その他の性能、例えば密着性、硬化性等とを、高い次元で両立できる色材分散組成物用樹脂、及び該樹脂を用いた色材分散組成物を提供する。
更に、耐熱性が高く、色材の分散安定性に優れ、かつ製版性に優れる主鎖に環構造を有する新規なアルカリ可溶性樹脂、及び該樹脂をバインダー樹脂として用いた感光性樹脂組成物を提供する。また、該感光性樹脂組成物を用いて形成されて成るカラーフィルター、及び該カラーフィルターを具備する液晶表示パネルを提供する。
すなわち、上述した作用効果は特定の1,6-ジエン類単量体を重合させる場合に発現される現象であって、通常の分子量を調整するために用いられる連鎖移動剤の使用とは目的が異なり、本発明者において見出された新たな知見である。
また、分岐を抑制することにより、得られる重合体の耐熱性を向上させることができる。これらのことより、本発明の製造方法を用いることによって、工業的に有利な条件、例えば、転化率が高い条件や、高濃度の単量体成分を用いた重合においても重合体の分岐を防止して、主鎖に環構造を有する、より優れた耐熱性を有する重合体を製造することができることを見出した。
本発明はまた、本発明のα-アリルオキシメチルアクリル酸系共重合体を含み、感光性用途、色材分散性用途及びラジカル硬化性用途からなる群より選択される少なくとも1つの用途に用いられる樹脂組成物でもある。
本発明は更に、下記式(1);
上記製造方法は、下記式(2);
以下に本発明を詳述する。
なお、式(1)中のRは、後述する式(2)中のRと同様である。
上記式(2)で表されるα-アリルオキシメチルアクリル酸系単量体(本明細書中、「AMA単量体(a)」ともいう。)は1種を用いてもよく、複数種を用いてもよい。また、上記単量体成分は、AMA単量体(a)と、その他のラジカル重合性単量体とを含むものである。
上記AMA単量体(a)は、重合して上記式(1)で表される構成単位を高い割合で生成することから、他の1,6-ジエン類単量体と比較して、重合体の分岐を生じにくく、これに伴い、異常な高分子量化やゲル化を起こし難いものである。
なお上述の通り、式(2)中のRは水素原子、又は、炭素数が1~30の有機基であれば不具合はなく、これらの基が共重合体や樹脂組成物、それらの製法の実施を阻害することはなく、本発明の作用効果が発揮されるものと考えられる。
このように、上記式(2)中のRが、水素原子、鎖状飽和炭化水素基、アルコキシ置換鎖状飽和炭化水素基、ヒドロキシ置換鎖状飽和炭化水素基、ハロゲン置換鎖状飽和炭化水素基、鎖状不飽和炭化水素基、アルコキシ置換鎖状不飽和炭化水素基、ヒドロキシ置換鎖状不飽和炭化水素基、ハロゲン置換鎖状不飽和炭化水素基、脂環式炭化水素基、アルコキシ置換脂環式炭化水素基、ヒドロキシ置換脂環式炭化水素基、ハロゲン置換脂環式炭化水素基、芳香族炭化水素基、アルコキシ置換芳香族炭化水素基、ヒドロキシ置換芳香族炭化水素基、又は、ハロゲン置換芳香族炭化水素基であることもまた、本発明の好適な実施形態の1つである。
上記AMA共重合体(b)は、上記式(1)で表される構成単位を主鎖中に含み、主鎖中に環構造を有する構造であるため耐熱性が高いものである。一般的に主鎖に環構造を有する樹脂は、耐熱性が高い反面、柔軟性に欠ける場合がほとんどであるが、上記式(1)で表されるTHF環を有する繰り返し単位は、THF環の両隣にメチレン基を有するため柔軟性にも優れるものとなる。上記AMA共重合体(b)において、式(1)中のRは、構成単位毎に異なっていてもよいし、同一でもよい。
色材分散組成物においては、上記AMA共重合体(b)が高分子量である場合、式(1)で表される構成単位の含有割合は少なくても性能発現する(色材分散性に優れる)傾向があり、低分子量である場合には含有量を多くした方が性能発現し易い傾向がある。これは、主鎖1本あたりに含まれる式(1)で表される構成単位の個数(以下、「平均官能基数」と表す。)に関係しているためと考えられる。この観点から、平均官能基数は、0.5以上であることが好ましい。より好ましくは1.0以上、更に好ましくは2.0以上である。なお、平均官能基数は、次式のように表されるものである。
A:単位質量に含まれる式(1)で表される構成単位のモル数[mol/g]
P:単位質量に含まれるAMA共重合体(b)のモル数[mol/g]
Aは、式(1)で表される構成単位の種類が2種類以上ある場合も含めると、次式のように算出できる。
A=ΣAX(X=1,2,3,・・・)
AX=単位質量×(CX/100)/FX
AX:単位質量に含まれる、X(X=1,2,3,・・・)種類目の式(1)で表される構成単位のモル数[mol/g]
CX:単位質量に含まれる、X(X=1,2,3,・・・)種類目の式(1)で表される構成単位の質量割合[質量%]
FX:X(X=1,2,3,・・・)種類目の式(1)で表される構成単位の分子量[g/mol]
Pは、AMA共重合体(b)の数平均分子量(Mn)を用いて次式のように近似できる。
P=単位質量/Mn
Mn:AMA共重合体(b)の数平均分子量
したがって、平均官能基数は、CX、FX、Mnを用いて次式のように表される。
平均官能基数=Mn×Σ{(CX/100)×(1/FX)}
(X=1,2,3,・・・)
なお、1,6-ジエン類の中でも、式(2)で表されるAMA単量体(a)は、環化率(式(2)で表される単量体から式(1)で表される構成単位が形成される割合)が高いため、CX及びFXは、次のように近似できる。
CX:反応した全単量体に対する、反応したX(X=1,2,3,・・・)種類目の式(2)で表されるAMA単量体(a)の質量割合[質量%]
FX:X(X=1,2,3,・・・)種類目の式(2)で表されるAMA単量体(a)の分子量[g/mol]
更に、重合に用いる各単量体の反応率(転化率)がいずれも高い(例えば、反応率が90mol%以上)場合、CXは、次のように近似できる。
CX:単量体成分中の、X(X=1,2,3,・・・)種類目の式(2)で表されるAMA単量体(a)の質量割合[質量%]
なお、上記Mnは、後述する実施例で使用した測定方法により測定することができる。
なお、重量平均分子量(Mw)、多分散度(Mw/Mn)の測定方法については特に限定されないが、例えば、後述する実施例で使用した測定方法を用いることができる。
本発明のアルカリ可溶性樹脂は、上記式(1)で表される構成単位を主鎖中に有することを特徴とするアルカリ可溶性樹脂である。
なお、平均官能基数は、上述と同様に求めることができる。
本発明のアルカリ可溶性樹脂は、ラジカル重合性不飽和基を有することがより好ましい。ラジカル重合性不飽和基の含有量としては、目的や用途に応じて適宜設定すればよいが、良好な製版性を得るために、ラジカル重合性不飽和結合当量(ラジカル重合性不飽和結合1化学当量あたりの分子量)が、200~5000であるのが好ましく、250~4000がより好ましく、300~3000であるのが更に好ましい。
なお、重量平均分子量は、例えば、後述する実施例で使用した測定方法を用いることができる。
本発明のα-アリルオキシメチルアクリル酸系共重合体の製造方法は、AMA単量体(a)を含む単量体成分を重合させてα-アリルオキシメチルアクリル酸系共重合体を製造する方法である。AMA単量体(a)は、環化重合することによって、AMA共重合体(b)を製造することができる。上記AMA共重合体(b)は、主鎖に環構造(THF環)を有することで耐熱性に優れ、更に、THF環の両隣にメチレン基を有するものであることから柔軟性が高く、相溶性や溶剤溶解性に優れるものとなる。
上記AMA単量体(a)の含有量は、目的、用途や、AMA共重合体(b)の分子量に応じて適宜設定すればよいが、全単量体成分中、好ましくは、1~99mol%、より好ましくは2~98mol%、更に好ましくは5~95mol%である。このような範囲とすることにより、AMA共重合体(b)は、式(1)で表される構成単位に由来する優れた特性を発揮することができる。また、上記構成単位は、重合体を構成する繰り返し単位であり、一つの重合体中には複数の構成単位が含まれることとなる。
通常、連鎖移動剤は、分子量を調整するために用いられるものであるが、AMA単量体(a)を重合させる際には、重合体の分岐を抑制することにも働くことから、得られる重合体の分子量分布を狭いものとしたり、工業的、経済的に有利な条件下でもゲル化させずに重合体を得たりすることができる。例えば、連鎖移動剤を用いずに、重合開始剤のみを用いて重合を行った場合、分子量分布が大きくなり、場合によってはゲル化するおそれもある。また、AMA共重合体の分岐部分は、耐熱性にやや劣るが、分岐を抑制することにより製造されるAMA共重合体の耐熱性も向上する。
対して、上記連鎖移動剤を用いる場合には、未閉環単位の二重結合からラジカルが失われ、代わりに連鎖移動剤由来のラジカルが生じると考えられる。この連鎖移動剤由来のラジカルに充分な重合開始能があれば重合が停止せず、また未閉環単位の二重結合よりも単量体に対して優先的に反応すれば架橋することなく重合が継続することになる。このような効果は、上記式(2)で表されるAMA単量体(a)を用いた場合に特有の効果である。例えば、2位と6位にエステル基を有する1,6-ジエン類を重合させる場合、環化重合して主に6員環(テトラヒドロピラン環)を生じるとともに、下記式(6);
本発明の製造方法では、上記式(5)で表される反応のように、AMA単量体(a)を用いて重合を行い、未閉環単位の二重結合がアリルエーテル基となる。そして、連鎖移動剤を用いた場合には、アリルエーテル基に生じたラジカルは、連鎖移動剤と優先的に反応して連鎖移動剤由来のラジカルを発生し、なおかつ連鎖移動剤由来のラジカルは充分な重合開始能があり、単量体と優先的に反応する機能を有しているのではないかと推測される。
なお、上記連鎖移動剤としては、1種を用いてもよいし、2種以上を併用してもよい。
上記ラジカル重合開始剤としては、熱又は光によりラジカルを発生する重合開始剤が挙げられ、工業的、経済的には熱によりラジカルを発生する重合開始剤(熱ラジカル重合開始剤)が有利で好ましい。熱ラジカル重合開始剤としては、熱エネルギーを供給することによりラジカルを発生するものであれば特に限定されるものではなく、重合温度や溶媒、重合させる単量体の種類等の重合条件に応じて、適宜選択すればよい。
このようなα-アリルオキシメチルアクリル酸系共重合体は、1種のAMA単量体(a)が重合されたものであってもよいし、複数種のAMA単量体(a)が重合されたものであってもよい。
上記製造方法は、下記式(2);
ラジカル重合性単量体は、熱、又は活性エネルギー線の照射等により重合するラジカル重合性不飽和基を有する低分子化合物であり、ラジカル硬化性樹脂組成物にラジカル硬化性を付与する。特に、常温で低粘度の液状のものは、粘度調整をする希釈剤としての機能も有するため反応性希釈剤とも言われ、特に溶剤使用を嫌う用途において好ましく用いられる。このようなラジカル重合性単量体としては、通常ラジカル重合性単量体として用いられるものを使用することができ、目的、用途に応じて1種または2種以上を適宜選択すればよい。ラジカル重合性単量体は、ラジカル重合性不飽和基を同一分子内にひとつだけ有する単官能性のラジカル重合性単量体と、2個以上有する多官能性のラジカル重合性単量体に分類することができる。
単官能性のラジカル重合性単量体は、上記α-アリルオキシメチルアクリル酸系共重合体の製造方法において示した、他のラジカル重合性単量体と同様のものを用いることができる。
バインダー樹脂は、主に乾燥後の塗膜性状や硬化後の塗膜物性を左右する高分子化合物であり、また、ラジカル硬化性にも少なからず寄与する成分である。本発明のラジカル硬化性樹脂組成物用バインダー樹脂としては、上記α-アリルオキシメチルアクリル酸系共重合体を用いることができる。このような樹脂は、酸素によるラジカル重合阻害を低減でき、密着性、透明性に優れ、かつ耐熱性にも優れる。
なお、重量平均分子量は、例えば、後述する実施例で使用した測定方法を用いることができる。
本発明のラジカル硬化性樹脂組成物を硬化させる方法としては、熱や電磁波(赤外線、紫外線、X線等)、電子線などのエネルギー源から本発明のラジカル硬化性樹脂組成物にラジカル重合開始に必要なエネルギーを供給すればよく、さらにラジカル重合開始剤を併用すればラジカル重合開始に必要なエネルギーを大きく下げることができ、かつ硬化性を向上することができ好ましい。ラジカル重合開始剤としては、加熱により重合開始ラジカルを発生する熱ラジカル重合開始剤と、電磁波や電子線などのエネルギー線の照射により重合開始ラジカルを発生する光ラジカル重合開始剤とがあり、通常使用されるものを1種または2種以上使用できる。また、必要に応じて通常用いられる熱ラジカル重合促進剤、光増感剤、光ラジカル重合促進剤等を1種または2種以上添加することも好ましい。
本発明のラジカル硬化性樹脂組成物において、粘度を下げ取扱い性を向上する、乾燥により塗膜を形成する、色材の分散媒とする、等のために、必要に応じて上記必須成分に加え、ラジカル硬化性樹脂組成物中の各成分を溶解、或いは分散できる低粘度の有機溶媒或いは水を希釈剤として添加してもよい。
本発明のラジカル硬化性樹脂組成物は、各用途の目的や要求特性に応じて、フィラー、本発明のラジカル硬化性樹脂組成物用バインダー樹脂以外の樹脂、色材(顔料、染料)、分散剤、可塑剤、重合禁止剤、紫外線吸収剤、酸化防止剤、艶消し剤、消泡剤、レベリング剤、帯電防止剤、分散剤、スリップ剤、表面改質剤、揺変化剤、揺変助剤、シラン系やアルミニウム系、チタン系などのカップリング剤、カチオン重合性化合物、酸発生剤等の上記の必須成分以外の成分が配合されても良い。
本発明の色材分散組成物は、色材、分散剤、バインダー樹脂、及び液媒体を含む色材分散組成物において、上記バインダー樹脂が、式(1)で表される構成単位を主鎖中に有する樹脂、である色材分散組成物である。また、本発明の色材分散組成物に用いられるバインダー樹脂であって、上記バインダー樹脂が、式(1)で表される構成単位を主鎖中に有する樹脂、である色材分散組成物用バインダー樹脂もまた、本発明の1つである。
色材は、本発明の色材分散組成物を着色するものであり、通常色材として用いられる染料や顔料を使用することができるが、耐久性の点から顔料(有機顔料、無機顔料)が好ましい。
分散剤は、色材への相互作用部位と分散媒(液媒体やバインダー樹脂)への相互作用部位とを有し、色材の分散媒への分散を安定化する働きを持つものであり、通常分散剤として用いられる分散剤を使用することができる。一般的には、樹脂型分散剤(高分子分散剤)、界面活性剤(低分子分散剤)、色素誘導体に分類される。
本発明の色材分散組成物用バインダー樹脂としては、本発明のラジカル硬化性樹脂組成物用バインダー樹脂と同様のものを用いることができる。本発明のラジカル硬化性樹脂組成物用バインダー樹脂が構造中に有するTHF環が奏する、いわゆるLewis塩基としての作用は強塩基であるアミン類ほど強くなく、適度な塩基性を有するため、分散剤の作用を妨害することなく色材及び分散剤に相互作用し、分散剤により分散された色材をより安定化すると考えられる。
液媒体は、分散剤により分散された色材を均一に保持する分散媒であり、主に色材分散組成物の粘度、塗布特性や乾燥特性等を調整する働きを持つ液状物質である。このような液媒体としては、目的、用途に応じて、通常用いられる液媒体を適宜選択して使用することができる。
本発明の色材分散組成物は、各用途の目的や要求特性に応じて、更に上記の必須成分以外の成分が配合されても良い。例えば、光硬化型インクにおいては、上記必須成分に加え、光重合性単量体、光開始剤を配合するのが好ましく、空気硬化型塗料においては、上記必須成分に加え、亜麻仁油などの乾性油、オクチル酸コバルトなどのドライヤーを配合するのが好ましい。
本発明の感光性樹脂組成物は、上記式(1)で表される構成単位を主鎖中に有するアルカリ可溶性樹脂をバインダー樹脂として含む感光性樹脂組成物である。本発明はまた、上記感光性樹脂組成物を用いて形成されたセグメントを有するカラーフィルター、及び上記カラーフィルターを具備する液晶表示パネルでもある。
本発明のアルカリ可溶性樹脂は、レジストに塗膜形成性とアルカリ可溶性を付与するとともに、本発明の感光性樹脂組成物を感光性着色樹脂組成物とする場合には、分散された色材の分散媒としての役割も担う。
ラジカル重合性単量体は、電磁波(赤外線、紫外線、X線等)、電子線などの活性エネルギー線の照射等により重合するラジカル重合性不飽和基を有する低分子化合物であり、本発明の感光性樹脂組成物に硬化性を付与する。ラジカル重合性単量体は、上述したように、ラジカル重合性不飽和基を同一分子内にひとつだけ有する単官能性のラジカル重合性単量体と、2個以上有する多官能性のラジカル重合性単量体とに分類することができるが、硬化性の点で多官能性のラジカル重合性単量体が好ましい。このようなラジカル重合性単量体としては、上述した本発明のラジカル硬化性樹脂組成物に含まれるラジカル重合性単量体と同様のものを用いることができる。
本発明の感光性樹脂組成物は、電磁波や電子線などの活性エネルギー線の照射により重合開始ラジカルを発生する光開始剤を含み、本発明のラジカル硬化性樹脂組成物に含まれていてよい成分として示した、上記光ラジカル重合開始剤と同様のものを1種または2種以上使用できる。また、上記光ラジカル重合開始剤と同様、上記光増感剤、上記光ラジカル重合促進剤等を1種または2種以上添加することも好ましい。
溶剤は、粘度を下げ取扱い性を向上する、乾燥により塗膜を形成する、色材の分散媒とする、等のために使用する、感光性樹脂組成物中の各成分を溶解、或いは分散できる低粘度の有機溶媒或いは水である。
色材は、本発明の感光性樹脂組成物を着色して、更に感光性着色樹脂組成物とするものであり、本発明の色材分散組成物の必須成分として示した、上記色材と同様のものを用いることができる。
本発明の感光性樹脂組成物は、各用途の目的や要求特性に応じて、フィラー、本発明のアルカリ可溶性樹脂以外のバインダー樹脂、分散剤、耐熱向上剤、現像助剤、可塑剤、重合禁止剤、紫外線吸収剤、酸化防止剤、艶消し剤、消泡剤、レベリング剤、帯電防止剤、分散剤、スリップ剤、表面改質剤、揺変化剤、揺変助剤、シラン系やアルミニウム系、チタン系などのカップリング剤、キノンジアジド化合物、多価フェノール化合物、カチオン重合性化合物、酸発生剤等の上記の必須成分以外の成分が配合されても良い。以下に、本発明の感光性樹脂組成物をカラーフィルター用レジストとして使用する場合に好適なその他の成分について説明する。
カラーフィルター用レジストの多様な特性のバランス調整や、レジストの低コスト化等のために、本発明のアルカリ可溶性樹脂以外のバインダー樹脂を使用することができる。このようなバインダー樹脂としては、具体的には、例えば、(メタ)アクリル酸/(メタ)アクリル酸エステル共重合体、(メタ)アクリル酸/芳香族ビニル共重合体、(メタ)アクリル酸/(メタ)アクリル酸エステル/芳香族ビニル共重合体、(メタ)アクリル酸/(メタ)アクリル酸エステル共重合体/N置換マレイミド共重合体、(メタ)アクリル酸/芳香族ビニル/N置換マレイミド共重合体、(メタ)アクリル酸/(メタ)アクリル酸エステル/ポリスチレンマクロモノマー共重合体などの(メタ)アクリル酸共重合体;(メタ)アクリル酸共重合体の側鎖にラジカル重合性不飽和基を導入したもの;エポキシ樹脂に(メタ)アクリル酸を付加しさらに多塩基酸無水物を反応させたようなビニルエステル型のアルカリ可溶性樹脂などが挙げられる。
分散剤は、本発明の感光性樹脂組成物に色材を加え感光性着色樹脂組成物とする場合には、上記必須成分とともに配合するのが望ましい成分である。分散剤としては、上記本発明の色材分散組成物の必須成分である分散剤と同様のものを用いることができる。
本発明の感光性樹脂組成物は、耐熱性や強度向上のために、N-(アルコキシメチル)メラミン化合物、2個以上のエポキシ基やオキセタニル基を有する化合物を添加することができる。特に、フォトスペーサー用レジスト、保護膜用透明レジストや層間絶縁膜用レジストとする場合には、これらの使用が好ましい。
本発明の感光性樹脂組成物は、レベリング性向上のために、レベリング剤を添加することができる。レベリング剤としては、フッ素系、シリコン系の界面活性剤が好ましい。
本発明の感光性樹脂組成物は、密着性向上のために、カップリング剤を添加することができる。カップリング剤としては、シラン系のカップリング剤が好ましく、具体的にはエポキシ系、メタクリル系、アミノ系のシランカップリング剤が挙げられ、中でもエポキシ系のシランカップリング剤が好ましい。
本発明の感光性樹脂組成物は、現像性向上のために、(メタ)アクリル酸、酢酸、プロピオン酸などのモノカルボン酸類;マレイン酸、フマル酸、コハク酸、テトラヒドロフタル酸、トリメリット酸などの多価カルボン酸類;無水マレイン酸、無水コハク酸、テトラヒドロフタル酸無水物、トリメリット酸無水物などの、カルボン酸無水物類などを、現像助剤として添加することができる。
また、本発明のラジカル硬化性樹脂組成物によれば、空気中での硬化性(酸素捕捉性)だけでなく、密着性、透明性にも優れ、かつ耐熱性に非常に優れるラジカル硬化性樹脂組成物が提供される。したがって、本発明のラジカル硬化性樹脂組成物は、ラジカル硬化型の組成物が用いられている各用途の中でも、耐熱性を要求される用途、例えば電子部品用の封止材、オーバーコート、コーティング材や接着剤、ソルダーレジスト、カラーフィルターレジスト、電子部品用レンズ、成型材料などに特に好適である。
本発明の色材分散組成物によれば、分散性と、その他の性能、例えば密着性、硬化性などとを、高い次元で両立できる色材分散組成物が提供され、また、当該色材分散組成物の構成成分である本発明のバインダー樹脂は、製造安定性も良好である。
本発明の感光性樹脂組成物によれば、耐熱性及び色材分散性に非常に優れ、かつ製版性に優れるアルカリ可溶性樹脂、及び該樹脂を用いた感光性樹脂組成物が提供される。該感光性樹脂組成物は、耐熱性に優れるため、電子情報分野の部材を形成するためのレジスト、例えばソルダーレジスト、エッチングレジスト、層間絶縁材料、めっきレジスト、カラーフィルター用レジストに好適であり、色材分散性にも優れることから、特にカラーフィルターの着色層形成用として好適である。
<分析>
本実施例の分析は、次のように行った。
(Mw、Mn、Mw/Mn)
樹脂溶液をテトラヒドロフランで希釈し孔径0.45μmのフィルターで濾過したものを、下記ゲルパーミエーションクロマトグラフィ(GPC)装置、及び条件で測定した。
装置:HLC-8220GPC(東ソー社製)
溶出溶媒:テトラヒドロフラン
標準物質:標準ポリスチレン(東ソー社製)
分離カラム:TSKgel SuperHZM-M(東ソー社製)。
(平均官能基数)
平均官能基数=Mn×{(単量体成分中のAMA-Rの重量割合[質量%]/100)×(1/AMA-Rの分子量)}。
(重合濃度)
重合濃度[質量%]=重合に用いた単量体の合計量/(重合に用いた単量体の合計量+重合に用いた溶媒の合計量)×100
(樹脂の取り出し)
樹脂溶液の一部をテトラヒドロフランで希釈し、過剰のヘキサンに投入して再沈殿を行った。沈殿物を濾過により取り出した後、70℃で真空乾燥(5時間以上)することによって樹脂の白色粉末を得た。
上記のように得られた白色粉末200mgをテトラメチルシランを含有する重ジメチルスルホキシド3gに溶解し、核磁気共鳴装置(200MHz、Varian社製)により測定した。
樹脂溶液をアルミカップに約0.3gはかり取り、アセトン約2gを加えて溶解させた後、常温で自然乾燥した。熱風乾燥機を用い、140℃で3時間乾燥した後、デシケータ内で放冷し、重量を測定した。重量減少量から、樹脂溶液の固形分を計算した。
(熱重量分析)
再沈殿により得た重合体(樹脂)粉末を、次の測定機器、及び条件下で測定し、ダイナミックTG曲線を得た。得られたTG曲線から5%重量減少温度を得た。
装置:Thermo Plus TG8120(リガク社製)
雰囲気:窒素フロー 100ml/分
昇温条件:階段状等温制御(SIAモード)、昇温速度=10℃/分、質量変化速度値=0.005%/秒
(樹脂酸価)
0.1規定のKOH水溶液を滴定液として用い、自動滴定装置(平沼産業社製、COM-555)により、重合体(樹脂)溶液の酸価を測定した。溶液の酸価と固形分から固形分酸価を計算し、これを樹脂酸価とした。
[合成例1~5]
表1に示すように、式(2)で表される単量体である各α-アリルオキシメチルアクリル酸エステル(AMA-R)を、特開平10-226669号公報に準じて、触媒として1,4-ジアザビシクロ[2.2.2]オクタンを用い、アリルアルコールと対応する各α-ヒドロキシメチルアクリル酸エステル(HMA-R)とから合成した。
[実施例1]
反応槽として、4口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にプロピレングリコールモノメチルエーテルアセテート(PGMEA)213.5部を仕込み、90℃に昇温した。一方、滴下槽Aには合成例1で得たAMA-M 121.8部とメタクリル酸メチル(MMA)78.2部を、滴下槽Bにはt-ブチルパーオキシ-2-エチルヘキサノエート(PBO)4.7部とPGMEA 42.0部を攪拌混合したものを、滴下槽Cには3-メルカプトプロピオン酸メチル(MPM)3.5部とPGMEA 44.5部を攪拌混合したものを準備した。
反応槽として、3口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 150.0部を仕込み、90℃に昇温した。一方、滴下槽にはAMA-M 60.9部、MMA 39.1部、PBO 6.0部を攪拌混合したものを準備した。
滴下槽AにAMA-M 60.0部とMMA 140.0部を準備したこと以外は、実施例1と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表2に示す。
反応槽として、3口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 120.1部を仕込み、90℃に昇温した。一方、滴下槽AにはAMA-M 30.0部、MMA 70.0部、PBO 6.0部を攪拌混合したものを、滴下槽Bには、3-メルカプトプロピオン酸(MPA)0.1部とPGMEA 29.9部を攪拌混合したものを準備した。
反応槽として、3口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 150.0部を仕込み、90℃に昇温した。一方、滴下槽にはAMA-M 30.0部、MMA 70.0部、PBO 6.0部を攪拌混合したものを準備した。
反応槽として、4口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 223.7部を仕込み、90℃に昇温した。一方、滴下槽Aには合成例1で得たAMA-M 180.0部とメタクリル酸(MAA)20.0部を攪拌混合したものを、滴下槽BにはPBO 4.7部とPGMEA 37.3部を攪拌混合したものを、滴下槽CにはMPA 3.0部とPGMEA 39.0部を攪拌混合したものを準備した。
滴下槽Aに準備する混合液を、AMA-M 120.0部、メタクリル酸ベンジル(BZMA)50.0部、MMA 1.4部、MAA 28.6部をよく攪拌混合したものに変えたこと以外は、実施例6と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表2に示す。
滴下槽Aに準備する混合液を、AMA-M 60.0部、BZMA 110.0部、MMA 1.4部、MAA 28.6部をよく攪拌混合したものに変えたこと以外は、実施例6と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表2に示す。
滴下槽Aに準備する混合液を、AMA-M 20.0部、BZMA 110.0部、MMA 41.4部、MAA 28.6部をよく攪拌混合したものに変えたこと以外は、実施例6と同様にして樹脂溶液を得た。分析結果を表2に示す。
滴下槽Aに準備するエーテル環構造を導入するためのモノマーであるAMA-Rの種類を表2に示すものに変えたこと以外は、実施例8と同様にして樹脂溶液を得た。分析結果を表2に示す。
滴下槽Aに準備する混合液を、AMA-M 60.0部、メタクリル酸シクロヘキシル(CHMA)110.0部、MMA 1.4部、MAA 28.6部をよく攪拌混合したものに変えたこと以外は、実施例6と同様にして樹脂溶液を得た。分析結果を表2に示す。
反応槽として、4口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 208部を仕込み、90℃に昇温した。一方、滴下槽Aにはスチレン(ST)96.8部を、滴下槽BにはAMA-M 60.0部、MMA 1.4部、MAA 28.6部、PBO 5.0部をよく攪拌混合したものを、滴下槽CにはMPA 3.0部とPGMEA 92.0部をよく攪拌混合したものを準備した。
反応槽として、4口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 150.0部と2-プロパノール(IPA)14.0部を仕込み、90℃に昇温した。一方、滴下槽AにはAMA-M 48.0部、BZMA 64.0部、MAA 48.0部を攪拌混合したものを、滴下槽BにはPBO 3.7部とPGMEA 38.3部を攪拌混合したものを、滴下槽CにはMPA 4.3部とPGMEA 37.7部を攪拌混合したものを準備した。
導入するガスを窒素から窒素/酸素混合ガス(酸素7%)に切り替え、6-t-ブチル-2,4-キシレノール(TBXL)0.06部、メタクリル酸グリシジル(GMA)52.8部、ジメチルベンジルアミン(DMBA)0.6部の順に各物質を反応槽へ仕込んだ後、攪拌、昇温を開始し、内温が110℃になるよう調整しながら、側鎖二重結合導入反応を行った。8時間110℃を維持した後、一旦、加熱を停止し、PGMEA 80.0部を加え、徐々に減圧して系内の圧力を37.3kPaとした。この圧力を維持した状態で加熱を再開し、IPAを含む溶媒を留去すると同時に、留去した溶媒の量と同量のPGMEAを反応槽に供給し、反応槽中の溶媒に含まれるIPAを低減した。内温が115℃となってから、冷却を開始、次いで解圧して系内の圧力を常圧に戻し溶媒の留去を停止すると同時にPGMEAの供給も停止した。室温まで冷却を続け、樹脂溶液を得た。分析結果を表2に示す。
滴下槽AにAMA-M 48.0部、CHMA 64.0部、MAA 48.0部を攪拌混合したものを準備したこと以外は、実施例16と同様にして樹脂溶液を得た。分析結果を表2に示す。
反応槽として、4口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 140.3部とIPA 14.0部を仕込み、90℃に昇温した。一方、滴下槽AにはST 56.3部を、滴下槽BにはAMA-M 48.0部、MAA 48.0部、PBO 4.0部をよく攪拌混合したものを、滴下槽CにはMPA 4.3部とPGMEA 95.7部をよく攪拌混合したものを準備した。
滴下槽AにAMA-M 200.0部を準備したこと以外は、実施例1と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表2に示す。なお、重合濃度は、40質量%であった。
また、得られた樹脂粉末を用い、1H-NMRを測定した。1H-NMRチャートを図3に示す。
反応槽として、3口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 170.5部を仕込み、90℃に昇温した。一方、滴下槽AにはAMA-M 50.0部、PBO 1.0部を攪拌混合したものを、滴下槽Bには、MPM 0.45部とPGMEA 29.6部を攪拌混合したものを準備した。
A-M:α-アリルオキシメチルアクリル酸メチル
A-CH:α-アリルオキシメチルアクリル酸シクロヘキシル
A-IB:α-アリルオキシメチルアクリル酸イソボルニル
A-BZ:α-アリルオキシメチルアクリル酸ベンジル
A-PE:α-アリルオキシメチルアクリル酸フェノキシエチル
MMA:メタクリル酸メチル
BZMA:メタクリル酸ベンジル
CHMA:メタクリル酸シクロヘキシル
ST:スチレン
MAA:メタクリル酸
PBO:t-ブチルパーオキシ-2-エチルヘキサノエート
MPM:3-メルカプトプロピオン酸メチル
MPA:3-メルカプトプロピオン酸
GMA:メタクリル酸グリシジル
Mw:重量平均分子量
Mn:数平均分子量
Mw/Mn:分子量分布
また、表2中、単量体成分の数値は、単量体組成物中の含有割合(質量%)を表し、開始剤、連鎖移動剤、及び、GMAの数値は、重合に用いた単量体の合計量に対する質量割合を表している。
滴下槽Aにメタクリル酸テトラヒドロフルフリル(THFM)200.0部を準備したこと以外は、実施例1と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表3に示す。
滴下槽AにMMA 200.0部を準備したこと以外は、実施例1と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表3に示す。
反応槽に仕込むPGMEAの量を163.7部とし、滴下槽Aに準備する混合液を、ジメチル-2,2‘-[オキシビス(メチレン)]ビス-2-プロペノエート(MD)60.0部、BZMA 110.0部、MMA 1.4部、MAA 28.6部、PGMEA 60.0部をよく攪拌混合したものに変えたこと以外は、実施例6と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表3に示す。
なお、MDは、非特許文献1及び特許文献1に記載の主鎖にテトラヒドロピラン環を有する樹脂を得ることができる単量体である。
反応槽として、4口セパラブルフラスコに温度計、冷却管、ガス導入管、攪拌装置を取り付けたものを準備し、反応槽内を窒素置換した。窒素気流下、反応槽にPGMEA 111.8部及びIPA 111.8部を仕込み、IPAが還流し内温が89℃となるまで昇温した。一方、滴下槽AにはMD 20.0部、BZMA 110.0部、MMA 41.4部、MAA 28.6部をよく攪拌混合したものを、滴下槽BにはPBO 4.7部、PGMEA 18.6部、IPA 18.6部を攪拌混合したものを、滴下槽CにはMPA 3.0部、PGMEA 19.5部、IPA 19.5部を攪拌混合したものを準備した。
滴下槽Aに準備する混合液を、ベンジルマレイミド(BZMI)60.0部、BZMA 110.0部、MMA 1.4部、MAA 28.6部、PGMEA 60.0部をよく攪拌混合したものに変えたこと以外は、実施例6と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表3に示す。
なお、BZMIは、特許文献2に記載の耐熱性の高い樹脂として知られている主鎖にイミド環構造を有する樹脂を得ることができる単量体である。
滴下槽Aに準備する混合液を、BZMA 110.0部、MMA 61.4部、MAA 28.6部を攪拌混合したものに変えたこと以外は、実施例6と同様にして樹脂溶液及び樹脂の白色粉末を得た。分析結果を表3に示す。
AMA-M 48.0部の代わりにMMA 48.0部を用いたこと以外は、実施例16と同様にして樹脂溶液を得た。分析結果を表3に示す。
MD:ジメチル-2,2‘-[オキシビス(メチレン)]ビス-2-プロペノエート
BZMI:ベンジルマレイミド
THFM:メタクリル酸テトラヒドロフルフリル
また、表3中、単量体成分の数値は、単量体組成物中の含有割合(質量%)を表し、開始剤、連鎖移動剤、及び、GMAの数値は、重合に用いた単量体の合計量に対する質量割合を表している。
実施例1~9、15、参考例1、2と比較例1から、本発明のバインダー樹脂は、テトラヒドロフルフリル基を側鎖に有するバインダー樹脂よりも耐熱分解性が非常に高く、実施例8と比較例3、比較例5との対比から、そのレベルは既知の耐熱樹脂(比較例3:主鎖にテトラヒドロピラン環を含有する樹脂、比較例5:主鎖にイミド環を含有する樹脂)並の耐熱分解性であることが分かる。
実施例1と実施例2との対比、実施例3、4、8と実施例5との対比から、連鎖移動剤を使用することにより分岐が抑制されて耐熱性が向上していることが分かる。
[実施例19~20、参考例3、比較例6~7]
<酸素による重合阻害を低減する効果の評価(表面硬化性)>
酸素による重合阻害を低減する効果を評価する指標として、光ラジカル硬化における表面硬化性を用いた。式(1)で表される構成単位の表面硬化性に対する効果を明確に評価するため、酸素による重合阻害を起こし易い条件(ラジカル重合性単量体、光ラジカル重合開始剤、配合比、膜厚など)で行った。
表4に記載のバインダー樹脂の粉末1.2部、トリメチロールプロパントリアクリレート(TMPTA)2.8部、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン(ダロキュア1173、チバスペシャリティケミカルズ社製)0.2部、酢酸イソプロピル(IPAC)6.0部を攪拌混合して均一な溶液とし、これをバーコーターを用いてフロート板ガラスに塗布した。室温で10分間自然乾燥した後、熱風乾燥器を用い70℃で5分間乾燥し、厚さ10μmの光ラジカル硬化性の塗膜を得た。次に、この塗膜に一定光量を照射できる超高圧水銀ランプを用いてUVを照射し、表面を指触しタック性を確認した。UV照射と指触を繰り返し、表面がタックレスとなった時のUV積算照射量[J/cm2]を記録した。UV積算照射量が少ないほど、表面硬化性が良好であることになる。結果を表4に示す。
密着性は、バインダー樹脂が大きく寄与する硬化後の塗膜性能の1つであり、式(1)で表される構成単位の密着性に対する効果を明確に評価するため、バインダー樹脂のみで評価し、樹脂構造としては、カルボキシル基などの酸基やアミンなどの強塩基を含まない樹脂構造とした。
なお、酸基を有する実施例6~18の樹脂についても密着性は良好であった。
表4に記載のバインダー樹脂の粉末をIPACに溶解し、39%の溶液とした。これをバーコーターを用いてフロート板ガラスに塗布し、室温で10分間自然乾燥した後、熱風乾燥器を用い70℃で5分間乾燥し、厚さ10μmのバインダー樹脂塗膜を得た。この塗膜の密着性を、JIS K 5600-5-6(クロスカット法)に従い、0~5の6段階に評価した。結果を表4に示す。なお、表4中の密着性の分類の基準を表5に示す。
実施例19、20、参考例3と、比較例7から、式(1)で表される構成単位を有することにより表面硬化性及び密着性が向上し、比較例6より、その効果は表面硬化性においては側鎖にテトラヒドロフルフリル基を有する樹脂と同等、密着性においては側鎖にテトラヒドロフルフリル基を有する樹脂よりも高いことが分かる。
<透明性の評価>
表6に記載のバインダー樹脂の粉末をPGMEAに溶かして30%溶液とし、この溶液の波長400nmにおける透過率[%]を分光光度計(UV-3100、島津製作所社製)で測定し、加熱前の透過率とした。一方、バインダー樹脂の粉末をガラス容器に入れ、230℃で1.5時間加熱してからPGMEAに溶かして30%溶液とし、波長400nmにおける透過率[%]を測定し、これを加熱後の透過率とした。また、加熱前と加熱後の透過率を用い、次式に従って透過率保持率[%]を算出した。結果を表6に示す。
透過率保持率[%]=加熱後透過率/加熱前透過率×100。
実施例21~24、参考例4と比較例8~9から、本発明のバインダー樹脂は、テトラヒドロフルフリル基を側鎖に有するバインダー樹脂、及び主鎖にイミド環を含有する樹脂よりも高い透明性を有していることが分かる。
<色材分散液(ミルベース)の調製、及び分散安定性の評価>
着色レジストにおいて、分散安定性に対するバインダー樹脂の効果を評価をする場合、通常、バインダー樹脂の効果を明確に評価するため、硬化成分を含まない色材分散液(ミルベース)で評価を行うため、ミルベースを調製、ミルベースの分散安定性を評価した。
(ミルベースの調製)
まず、分散剤溶液としてSOLSPERSE24000GR(日本ルーブリゾール社製、以下SP24000と表する)をPGMEAに溶解させ20%としたものと、バインダー樹脂溶液として表7に記載の樹脂溶液を20%にPGMEAで希釈したものを用意した。
分散処理直後のミルベースのメジアン径を、動的光散乱式粒径分布測定装置(LB-500、堀場製作所社製)により測定し、メジアン系が100nm以下となっているものを○、100nmを超えているものを×とした。結果を表7に示す。
分散処理直後の分散状態が良好なもの(メジアン径が100nm以下のもの)を恒温室(23℃)で保存し、分散処理をしてから1日後、2週間後、4週間後の粘度をコーンプレート型回転粘度計(TVE22LT、東機産業社製)を用いて測定した。また、粘度増加率を次式に従って算出した。結果を表7に示す。
粘度増加率[%]=2週間後(または4週間後)の粘度/1日後の粘度×100-100 。
マヨネーズ瓶に充填するミルベースの構成成分の種類と量を次のように変えたこと以外は、実施例25と同様にしてミルベースの調製、及び分散安定性の評価を行った。結果を表7に示す。
C.I.ピグメントブルー15:6(Heliogen Blue L6700F:BASF社製、以下PB15:6と表する):5.0部
C.I.ピグメントバイオレット23(Hostaperm Violet RL-NF、Clariant社製、以下PV23):1.25部
SP24000の20%PGMEA溶液:3.75部
SP12000:0.2部
実施例8で得られた樹脂溶液をPGMEAで20%に希釈したもの:14.0部
PGMEA:25.8部 。
マヨネーズ瓶に充填するミルベースの構成成分の種類と量を次のように変えたこと以外は、実施例25と同様にしてミルベースの調製、及び分散安定性の評価を行った。結果を表7に示す。
C.I.ピグメントレッド254(Irgaphor Red BT-CF:チバスペシャリティケミカルズ社製、以下PR254と表する):4.4部
C.I.ピグメントレッド177(Cromophtal Red A3B:チバスペシャリティケミカルズ社製、以下PR177と表する):1.85部
SP24000の20%PGMEA溶液:5.0部
実施例8で得られた樹脂溶液をPGMEAで20%に希釈したもの:13.75部
PGMEA:25.0部 。
マヨネーズ瓶に充填するミルベースの構成成分の種類と量を次のように変えたこと以外は、実施例25と同様にしてミルベースの調製、及び分散安定性の評価を行った。結果を表7に示す。
カーボンブラック(MA220:三菱化学社製、以下CBと表する):6.25部
SP24000の20%PGMEA溶液:3.75部
SP12000:0.2部
実施例8で得られた樹脂溶液をPGMEAで20%に希釈したもの:14.0部
PGMEA:25.8部 。
樹脂溶液を表7に示すとおりに変えたこと以外は、実施例25と同様にしてミルベースの調製、及び分散安定性の評価を行った。結果を表7に示す。
実施例25、26と比較例12から、式(1)で表される構成単位を有することにより一般的なバインダー樹脂より分散安定性が向上することが分かる。また、実施例25、26と比較例10、11から、その効果は非特許文献1及び特許文献1に記載の主鎖にテトラヒドロピラン環を有する樹脂よりも高いことが分かる。なお、比較例10において分散不良となっているのは、バインダー樹脂(比較例3)が異常な高分子量化を起こしているためと考えられる。さらに、実施例27~32から、その他の共重合成分を変えても、また、式(1)で表される構成単位におけるRを変えても、分散安定性に優れることが分かる。
<製版性の評価>
次のように感光性着色樹脂組成物(着色レジスト)を調製し、その着色レジストを用いて製版性を評価した。製版性の指標としては、現像残渣とパターン形状を用いた。
(着色レジストの調製)
まず、表8に示したミルベース用の各物質を0.3mmのジルコニアビーズを充填したビーズミルで分散処理を行い、緑色ミルベースを得た。次に、表8に示した透明レジスト液用の各物質を攪拌混合し、透明レジスト液を調製した。こうして得られた緑色ミルベース240.0部と透明レジスト液135.0部とを攪拌混合した後、1μmのフィルターで濾過して、緑色レジストを得た。
前記の緑色着色組成物を、スピンコーターを用いて、クロムのブラックマトリクスが形成された100mm×100mmのガラス基板上に、乾燥後の膜厚が1.5μmになるように回転数を調節して塗布した後、90℃で2分間プレベークした。次に、プロキシミティ型露光機と10μm幅のラインアンドスペースを有するパターンマスクにより100mJ/cm2にて露光した。その後、スプレー現像装置を用いて、0.1%炭酸ナトリウム水溶液で現像した。現像時間は、10~100秒までの間で、最も良好な現像性が得られる時間で行った。ついで水洗処理を行い、風乾した。得られた緑色パターン付きガラス基板をレーザー顕微鏡で観察し、現像残渣とパターン形状を次の基準で評価した。結果を表9に示す。
◎:スペース部分に残渣が全く無い
○:スペース部分の一部にごく薄く小さい残渣がある
△:スペース部分に薄い残渣がある
×:スペース部分に濃い残渣がある 。
◎:ラインのエッジが真っ直ぐでシャープ
○:ラインのエッジのところどころがぼやけている
△:ラインのエッジが全体的にぼやけている
×:ラインのエッジがはっきりとガタガタしている 。
ミルベース用のバインダー樹脂と、透明レジスト液用のバインダー樹脂を、表9に示すように変えた以外は、実施例36と同様にして評価した。結果を表9に示す。
本発明のアルカリ可溶性樹脂をバインダー樹脂として用いることで、製版性が向上することが分かる。即ち、カラーフィルターのセグメントを本発明の感光性着色樹脂組成物を用いて形成すれば、歩留まりよくカラーフィルターを製造できる。
[実施例43]
(着色レジストの調製)
緑色レジストとして、実施例41の感光性着色樹脂組成物を用いた。
また、表10に示すように色材の種類と量を変えたこと以外は、実施例41と同様にして赤色、青色、黒色の各色のレジストを得た。
下記に示した各物質を攪拌混合した後、1μmのフィルターで濾過して、フォトスペーサー用、兼保護膜用透明レジストを得た。
実施例16で得られた樹脂溶液をPGMEAで20%に希釈したもの 100.0部
ジペンタエリスリトールヘキサアクリレート 20.0部
イルガキュア907(チバスペシャリティケミカルズ社製) 2.4部
イルガキュア369(チバスペシャリティケミカルズ社製) 0.4部
PGMEA 10.0部 。
230mm×300mm、厚さ1.1mmの無アルカリガラス基板に、上記の黒色レジストをスピンコート法により塗布して塗膜を形成し、プレベーク(80℃、5分間)を行った。その後、超高圧水銀灯を光源とするプロキシミテイ露光機を用いて500mJ/cm2の露光量で、所定のブラックマトリクス用フォトマスクを介してアライメント露光し、アルカリ現像液にて現像を行い、純水で洗浄した後、ポストベーク(230℃、30分間)を行って、ブラックマトリクス(厚み1.2μm)を形成した。
本発明の色材分散組成物は、分散性と、その他の性能、例えば、密着性、耐熱性、表面硬化性、透明性等とを高い次元で両立させることができ、特に、高機能インキ、塗料に好適であり、例えば、自動車、塗装鋼板、建材、缶、グラビア、フレキソ、インクジェットプリンター、カラーフィルター等に使用できる。
本発明のアルカリ可溶性樹脂及び該樹脂を用いた本発明の感光性樹脂組成物は、耐熱性に非常に優れ、電子情報分野の部材を形成するためのレジスト、例えばソルダーレジスト、エッチングレジスト、層間絶縁材料、めっきレジスト、カラーフィルター用レジストに好適であり、色材分散性、製版性にも優れることから、特にカラーフィルターの着色層形成用として好適である。
Claims (6)
- 下記式(1);
- 請求項1又は2に記載のα-アリルオキシメチルアクリル酸系共重合体を含み、感光性用途、色材分散性用途及びラジカル硬化性用途からなる群より選択される少なくとも1つの用途に用いられることを特徴とする樹脂組成物。
- 前記重合工程は、重合溶媒中で連鎖移動剤の存在下にラジカル重合させる工程を含むことを特徴とする請求項4に記載のα-アリルオキシメチルアクリル酸系共重合体の製造方法。
- 前記連鎖移動剤は、メルカプト基を有する化合物であることを特徴とする請求項5に記載のα-アリルオキシメチルアクリル酸系共重合体の製造方法。
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JP2010235546A (ja) * | 2009-03-31 | 2010-10-21 | Nippon Shokubai Co Ltd | α−(不飽和アルコキシアルキル)アクリレートの製造方法 |
EP2415751A1 (en) * | 2009-03-31 | 2012-02-08 | Nippon Shokubai Co., Ltd. | Alpha-(unsaturated alkoxyalkyl) acrylate composition and process for production thereof |
JP2013178407A (ja) * | 2012-02-28 | 2013-09-09 | Nippon Shokubai Co Ltd | フォトスペーサー用硬化性樹脂組成物および柱状スペーサー |
JP2015022175A (ja) * | 2013-07-19 | 2015-02-02 | 株式会社日本触媒 | 硬化性樹脂組成物、及びそのパターン硬化膜 |
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JP5743801B2 (ja) | 2011-08-15 | 2015-07-01 | 富士フイルム株式会社 | 着色組成物、着色感放射線性組成物、重合体の製造方法、パターンの形成方法、カラーフィルタ、及びその製造方法、並びに固体撮像素子 |
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JP2010235546A (ja) * | 2009-03-31 | 2010-10-21 | Nippon Shokubai Co Ltd | α−(不飽和アルコキシアルキル)アクリレートの製造方法 |
EP2415751A1 (en) * | 2009-03-31 | 2012-02-08 | Nippon Shokubai Co., Ltd. | Alpha-(unsaturated alkoxyalkyl) acrylate composition and process for production thereof |
EP2415751A4 (en) * | 2009-03-31 | 2013-02-27 | Nippon Catalytic Chem Ind | ALPHA- (ALCOXYALKYL UNSATURATED) ACRYLATE COMPOSITION AND PROCESS FOR PRODUCING THE SAME |
US8796492B2 (en) | 2009-03-31 | 2014-08-05 | Nippon Shokubai Co., Ltd. | α-(unsaturated alkoxyalkyl) acrylate composition and process for production thereof |
JP2013178407A (ja) * | 2012-02-28 | 2013-09-09 | Nippon Shokubai Co Ltd | フォトスペーサー用硬化性樹脂組成物および柱状スペーサー |
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JPWO2017026187A1 (ja) * | 2015-08-11 | 2018-05-17 | 株式会社ジーシー | 歯科用重合性組成物 |
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KR20110117091A (ko) | 2011-10-26 |
US20110263805A1 (en) | 2011-10-27 |
EP2383317B1 (en) | 2013-10-23 |
EP2383317A4 (en) | 2012-12-12 |
CN102264849B (zh) | 2013-09-25 |
EP2383317A1 (en) | 2011-11-02 |
KR101422327B1 (ko) | 2014-07-22 |
US8497332B2 (en) | 2013-07-30 |
CN102264849A (zh) | 2011-11-30 |
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