CN115677939A - Photosensitive graft polymer and photosensitive resin composition containing same - Google Patents
Photosensitive graft polymer and photosensitive resin composition containing same Download PDFInfo
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- CN115677939A CN115677939A CN202211496428.0A CN202211496428A CN115677939A CN 115677939 A CN115677939 A CN 115677939A CN 202211496428 A CN202211496428 A CN 202211496428A CN 115677939 A CN115677939 A CN 115677939A
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Abstract
The invention belongs to the technical field of photosensitive resin, and relates to a photosensitive graft polymer and a photosensitive resin composition containing the same, wherein the photosensitive graft polymer is obtained by the reaction of (methyl) acrylic acid and glycidyl methacrylate to generate a side chain with an ethylenic bond, and in addition, a macromonomer forms another side chain polymer, and the macromonomer is obtained by the copolymerization of a polymerizable monomer with C8-20 bridged cyclic hydrocarbon groups and a polymerizable monomer without the bridged cyclic hydrocarbon groups. The photosensitive resin composition containing the photosensitive graft polymer, an active monomer, a leveling agent, a coupling agent, a photopolymerization initiator and a solvent can form a cured coating film with excellent pigment dispersion stability and excellent transparency, has alkali developability, has no residual gum after development, is resistant to high temperature, has high residual film rate after development after forming a photoresist, and can provide the photosensitive graft polymer blended in the photosensitive resin composition.
Description
Technical Field
The invention belongs to the technical field of photosensitive resin, and relates to a photosensitive graft polymer and a photosensitive resin composition containing the same.
Background
In recent years, from the viewpoint of resource saving and energy saving, active energy ray-curable resins curable by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of paints, adhesives and the like.
Color filters used in color liquid crystal display devices and solid-state image sensors are formed by forming colored coating films of three colors of red (R), green (G), and blue (B) in a predetermined pattern on a substrate, and forming black matrices between the colored coating films of the three colors of R, G, and B. Such a color filter is usually produced by forming a black matrix on a transparent substrate such as glass, and then sequentially forming colored coating films of R, G, and B in a predetermined pattern, by the following method.
As a method for forming a pattern of a colored coating film, it is now common to form a three-color R, G, and B plus black matrix by repeating the steps of slit coating a photocurable resin composition mainly composed of an alkali-soluble binder polymer, a reactive monomer, a photopolymerization initiator, a pigment, and a solvent on a transparent substrate, exposing by MASK using a high-pressure mercury lamp, developing, and post-curing. A colored coating film formed by such a method is excellent in light resistance and heat resistance and has few defects such as pinholes, and thus is now the mainstream.
Further, in recent years, there has been an increasing demand for high definition of color displays. In order to obtain a clear color tone by the above method, it is necessary to finely divide pigment particles, but if the pigment is excessively finely divided, the dispersibility and stability of the pigment deteriorate with time, and problems occur in thickening the photocurable resin composition and preventing a uniform film thickness and resolution of the formed resist, so that the pigment particle diameter needs to be controlled within a certain range and can be brought into a stable state with the resin.
Therefore, in order to improve the dispersion stability of the pigment, a method of grafting a binder resin polymer has been proposed. This is considered to be because the dispersion stability is improved by grafting the binder resin polymer to form steric hindrance in the side chain polymer to prevent the pigments from aggregating with each other, and on the other hand, by using a cyclic side chain, the compatibility with the pigment molecule is increased. The following compositions have been proposed: a photosensitive sensitive composition using a binder polymer formed of a monomer having an alcoholic hydroxyl group, a macromonomer of styrene and/or methyl methacrylate; a photosensitive sensitive composition using a binder polymer formed from a quaternary ammonium salt monomer and a macromonomer of styrene and/or methyl methacrylate; a colored photosensitive composition using a binder resin polymer formed from a monomer containing a nitrogen atom and a macromolecular polymer of styrene and/or methyl methacrylate. However, the binder polymers using these proposals have poor compatibility with pigment molecules and low steric hindrance due to the absence of cyclic hydrocarbon groups, so that the dispersion stability of the pigment is not satisfactory, and in the post-baking process, the pigment molecules are easily aggregated with the rise of temperature and the evaporation of the solvent, thereby causing the occurrence of blooming in the film layer.
Disclosure of Invention
Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to provide a photosensitive resin composition which can form a cured coating film having excellent dispersion stability of a pigment and excellent transparency, and which can form a three-dimensional structure by crosslinking a resin and an active monomer after exposure to light, and can wrap pigment molecules to prevent aggregation of the pigment molecules during postbaking, thereby preventing the occurrence of a blooming phenomenon, and which has a relatively high molecular weight and serves as a skeleton in a film layer to prevent a colloidal sagging phenomenon caused by a decrease in viscosity at a high postbaking temperature, thereby thinning the film layer. And has alkali developability, no residual gum after development, and a high residual film rate at high temperatures, and provides a photosensitive graft polymer incorporated in the photosensitive resin composition.
In order to solve the above problems, the present inventors have first considered that the steric hindrance effect due to the monomer structure can improve the dispersibility of the pigment, and therefore have required selecting a macromonomer having a structure having a larger volume than that of a macromonomer having an alkyl group (meth) acrylate such as styrene and/or methyl methacrylate, which has been used in large amounts so far. The present inventors have therefore studied various macromonomers, and as a result, have found that a photosensitive graft polymer having a side chain polymer formed from a macromonomer obtained by copolymerizing a polymerizable monomer having a bridged cyclic hydrocarbon group having 8 to 20 carbon atoms and a polymerizable monomer having no bridged cyclic hydrocarbon group at a specific ratio can solve the above problems, and have completed the present invention.
The invention relates to a photosensitive graft polymer, which is a side chain polymer formed by macromonomer, wherein the macromonomer is obtained by copolymerizing 20-60 mol% of a polymerizable monomer having a C8-20 bridged cyclic hydrocarbon group and 30-80 mol% of a polymerizable monomer having no bridged cyclic hydrocarbon group.
The present invention also relates to a photosensitive resin composition containing the photosensitive graft polymer, an active monomer, a leveling agent, a coupling agent, a photopolymerization initiator, and a solvent.
According to the present invention, there can be provided a photosensitive resin composition which can form a cured coating film having excellent dispersion stability of a pigment and excellent transparency, has alkali developability, is free from residual gum after development, is resistant to high temperature, and has a high residual film ratio after development after forming a resist, and a photosensitive graft polymer blended in the photosensitive resin composition.
Detailed Description
The present invention will be described in detail below.
First, a macromonomer forming a side chain polymer in the photosensitive graft polymer of the present invention will be described.
The macromolecular polymer in the present invention can be obtained by a conventional radical polymerization method. For example, a polymerizable monomer having a C8-20 bridged cyclic hydrocarbon group as the component 1 of a macromonomer and a polymerizable monomer having no bridged cyclic hydrocarbon group as the component 2 of a macromonomer are dissolved in a predetermined ratio in an organic solvent, and a monomer having a functional group such as a carboxyl group or a hydroxyl group, a chain transfer agent, and a polymerization initiator are mixed and solution polymerization is carried out at about 80 to 130 ℃ for about 2 to 10 hours, thereby obtaining a prepolymer having a functional group such as a carboxyl group or a hydroxyl group at the end. By introducing a polymerizable unsaturated group into the terminal of the prepolymer thus obtained, a macromonomer capable of forming a side chain polymer by introducing a photosensitive graft polymer can be obtained. As a method for introducing the polymerizable unsaturated group, for example, a compound having two groups as follows: a functional group capable of reacting with a functional group such as a carboxyl group or a hydroxyl group at the end of the prepolymer; and a polymerizable unsaturated group. As the compound having both a functional group capable of reacting with the prepolymer having a functional group at the end and a polymerizable unsaturated group, for the prepolymer having a carboxyl group at the end, glycidyl (meth) acrylate having an epoxy group and/or (meth) acrylate having an alicyclic epoxy group; for the prepolymer having a hydroxyl group at the end, a (meth) acrylate having an isocyanate group can be used.
The number average molecular weight of the macromonomer is preferably 5000 to 20000, more preferably 8000 to 15000. If the number average molecular weight of the macromonomer is less than 5000, sufficient pigment dispersion stability may not be obtained and the resist may easily fall off during development, while if the number average molecular weight exceeds 20000, the pigment dispersion stability may not be further improved, and the alkali developability may be lowered to cause residual gum and lower the resolution of the resist.
The copolymerization ratio of the polymerizable monomer (a-1) and the polymerizable monomer (a-2) is from 30 to 80 mol% based on the polymerizable monomer (a-l), and the copolymerization ratio of the polymerizable monomer (a-2) is from 20 to 70 mol%; preferably, the amount of the polymerizable monomer (a-2) is 20 to 50 mol% based on 50 to 80 mol% of the polymerizable monomer (a-1). If the copolymerization ratio of the polymerizable monomer (a-1) is less than 30 mol%, sufficient dispersion stability of the pigment cannot be obtained, while if the copolymerization ratio of the polymerizable monomer (a-1) exceeds 80 mol%, the solubility of the macromolecular polymer in the solvent is poor, the solubility of the photosensitive graft polymer in the solvent is lowered, and turbidity is likely to occur in the photosensitive graft polymer solution, which consequently results in impaired transparency of the photosensitive resin composition and occurrence of blooming and blooming in the photoresist.
The polymerizable monomer (a-1) as the component 1 of the macromonomer may be any polymerizable monomer having a bridged cyclic hydrocarbon group having 8 to 20 carbon atoms, and the glass transition temperature (Tg) of the homopolymer is preferably 100 ℃ or higher from the viewpoint of improving heat resistance. Specific examples of the polymerizable monomer (a-1) include dicyclopentadienyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate, and isobornyl (meth) acrylate is preferable, and compounds represented by the following formulae are preferable.
(wherein R represents a hydrogen atom or a methyl group.)
The polymerizable monomer (a-2) as the component 2 of the macromonomer may be any polymerizable monomer which does not have a bridged cyclic hydrocarbon group and is copolymerizable with the polymerizable macromonomer (a-1), and is preferably a polymerizable monomer which has not so high hydrophobicity and high compatibility with a solvent used in the synthesis of a graft polymer in order to avoid turbidity of a graft polymer solution. Further, the polymerizable monomer (a-2) preferably has a cyclic structure such as an aromatic ring, a heterocyclic ring or an alicyclic ring structure because the pigment dispersibility can be improved by the steric hindrance effect due to the monomer structure. Specific examples of the polymerizable monomer (a-2) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, rosin (meth) acrylate, phenyl (meth) acrylate, and the like. These compounds may be used alone in 1 kind or in combination of 2 or more kinds, and phenyl (meth) acrylate is preferable. Examples of the compound (b) having a carboxyl group include (meth) acrylic acid, crotonic acid, and cinnamic acid. In addition, a reaction product of a polyfunctional (meth) acrylate having one hydroxyl group and one or more (meth) acryloyl groups (e.g., hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, etc.) and a polybasic acid anhydride, and the like can also be used. Among them, (meth) acrylic acid is preferable in view of reactivity and easy availability.
Examples of the polymerization initiator used in the radical polymerization include azobisisobutyronitrile, azobisisopentonitrile, azobisisobutyrate, benzoyl peroxide, tert-butyl peroxy (2-ethylhexanoate), and di-tert-butyl peroxide. The amount of the polymerization initiator used is usually 0.5 to 20g, preferably 2.0 to 8g, based on 100g of the total amount of the polymerizable monomer (a-1) and the polymerizable monomer (a-2).
When an acrylic monomer is used as the chain transfer agent used for radical polymerization in order to efficiently introduce a functional group to the terminal, the chain transfer agent is preferably a thiol group from the viewpoint of the chain transfer constant, and n-dodecyl mercaptan is generally used. The amount of the chain transfer agent to be used is usually 0.3 to 10g, preferably 2 to 5g, based on 100g of the total amount of the polymerizable monomer (a-1) and the polymerizable monomer (a-2).
Examples of the organic solvent include glycol ester solvents such as propylene glycol monomethyl ether acetate, and organic solvents having no functional group such as hydrocarbon solvents such as toluene and xylene.
Further, the bulk polymerization can be carried out by merely adding the initiator and the chain transfer agent to the polymerizable macromonomer (a-1), the polymerizable cyclic monomer (a-2), and the (meth) acrylic acid (b) without using an organic solvent, but it is preferable to add the organic solvent as described above in order to prevent an abnormal polymerization reaction and to carry out a stable polymerization reaction. The macromonomer solution synthesized by adding an organic solvent can be used as it is.
Next, the photosensitive graft polymer (A) of the present invention will be described.
The photosensitive graft polymer (a) of the present invention is characterized in that the side chain polymer is formed by copolymerizing a macromonomer (a) with other monomers, and in the present invention, the photosensitive graft polymer (a) can be classified into four graft copolymers (a-1) to (a-4) described later.
The graft copolymer (A-1) of the present invention is obtained by copolymerizing the macromonomer (a), the unsaturated monobasic acid (b), the radical polymerizable compound (c) other than the macromonomer and the unsaturated monobasic acid, and styrene, and the copolymerization ratio of the component (a), the component (b), and the component (c) is as follows: the component (a) is 2 to 20 mass%, preferably 5 to 15 mass%; the component (b) is 5 to 35 mass%, preferably 10 to 30 mass%; the component (c) is 30 to 90% by mass, more preferably 40 to 80% by mass, and the styrene content is 1 to 5%. If the copolymerization ratio of the component (a) is less than 5% by mass, good stability cannot be obtained for DPP-based pigments having a large conjugation range, while if the copolymerization ratio of the component (a) exceeds 20% by mass, the solubility in a solvent decreases, and on the contrary, the pigment molecules are precipitated and aggregated, and the alkali developability is lowered to form a residual gum in some cases.
The unsaturated monoacid (b) is used to impart a carboxyl group to the side chain of the graft copolymer (A-1) while maintaining the acid value. The unsaturated monobasic acid as the component (b) of the present invention is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid, and the like as compounds having a carboxyl group. In addition, a reaction product of a polyfunctional (meth) acrylate having one hydroxyl group and one or more (meth) acryloyl groups (for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and the like) and a polybasic acid anhydride, and the like can also be used. Among them, (meth) acrylic acid is preferable in view of reactivity and easy availability.
The radical polymerizable compound (c) other than the component (a) and the component (b) is not particularly limited as long as it has an ethylenically unsaturated group. Specific examples thereof include styrene, a-alkyl derivatives of styrene, o-alkyl derivatives of styrene, m-alkyl derivatives of styrene, p-alkyl derivatives of styrene, nitro derivatives of styrene, and amide derivatives of styrene; dienes such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecenyl (meth) acrylate, tricyclodecenyloxyethyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, hexyl (meth) acrylate, anthranoyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furanyl (meth) acrylate, and furyl (meth) acrylate, (meth) acrylate esters such as tetrahydrofurfuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, methylphenyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-N-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, isopropylphenyl (meth) acrylate, (N, N-dimethylamino) ethyl (meth) acrylate, (N, N-diethylamino) ethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, rosin (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2, 3-dihydroxypropyl (meth) acrylate; (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, and (meth) acrylic acid (such as anthraamide); vinyl compounds such as (meth) acryloylaniline, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinylsulfonic acid, and vinyl acetate; unsaturated dicarboxylic acid diethyl esters such as citraconic acid diethyl ester, maleic acid diethyl ester, fumaric acid diethyl ester, and itaconic acid diethyl ester; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-dodecylmaleimide and N- (4-hydroxyphenyl) maleimide; n- (meth) acryloylphthalimide, and the like. Among them, styrene, vinyl toluene, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, rosin (meth) acrylate, and 2, 3-dihydroxypropyl (meth) acrylate are preferable from the viewpoint of further improving the transparency of the cured coating film. These compounds may be used singly or in combination of two or more, and benzyl (meth) acrylate is preferred.
The method of radical polymerization for producing the graft copolymer (A-1) is not particularly limited, and solution polymerization is generally selected.
The amount of the organic solvent used is usually 30g to 1000g, preferably 200g to 800g, based on 100g of the total amount of the component (a), the component (b), the component (c) and styrene. By setting the amount of the organic solvent to 800g or less, the molecular weight of the graft copolymer can be prevented from being lowered by chain transfer, and the solid content concentration of the polymer finally obtained can be controlled within an appropriate range.
Since the graft copolymer (a-1) of the present invention is a photosensitive resin composition obtained by mixing with the active monomer (B), photopolymerization initiator (C), solvent (D), leveling agent and coupling agent (E), and pigment dispersion liquid (F) described later, and is mainly used as an electronic material such as a resist, it is preferable to use a glycol ester-based solvent such as propylene glycol methyl ether acetate when producing the graft copolymer (a-1) by the above-mentioned radical polymerization.
The graft copolymer (A-2) of the present invention is obtained by reacting a carboxyl group present in a side chain of the graft copolymer (A-1) with a radical polymerizable compound (d) having an epoxy group or an alicyclic epoxy group to convert a part of the carboxyl group into an unsaturated group. The amount of the radical polymerizable compound having an epoxy group or an alicyclic epoxy group used as the component (d) is usually 5 to 80 moles, preferably 20 to 60 moles, based on 100 moles of the carboxyl group present in the side chain of the graft copolymer (A-1). By using the above-mentioned amount, the balance between the carboxyl group and the unsaturated group can be made good, and the graft copolymer (A-2) can maintain appropriate curability and alkali developability.
The reaction of the carboxyl group in the graft copolymer (A-1) with the radical polymerizable compound having an epoxy group or an alicyclic epoxy group as the component (d) proceeds as follows. That is, in order to prevent gelation caused by polymerization of the unsaturated monoacid and/or the resulting graft copolymer containing an unsaturated group, the reaction is usually carried out at 50 to 150 ℃ and preferably at 80 to 130 ℃ in the presence of a polymerization inhibitor such as a phenol such as p-methoxyphenol and in the presence of a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride or tetrabutylammonium bromide, or a phosphorus compound such as triphenylphosphine. When an organic solvent is used in the radical copolymerization reaction for obtaining the graft copolymer (A-1), the subsequent reaction can be carried out while keeping the state of the organic solvent solution of the graft copolymer (A-1) unchanged.
The radical polymerizable compound having an epoxy group or an alicyclic epoxy group as the component (d) is not particularly limited, and examples thereof include glycidyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate and lactone adducts thereof, l, 2-epoxy-4-vinylcyclohexane, mono (meth) acrylate of 3, 4-epoxycyclohexylmethyl-3 \\4, -epoxycyclohexane carboxylate, epoxide of tricyclodecenyl (meth) acrylate, and epoxide of (tricyclodecenyloxy) ethyl methacrylate, and these compounds may be used alone in 1 kind or in combination of 2 or more kinds, and glycidyl (meth) acrylate is preferable from the viewpoint of easy availability of raw materials.
The graft copolymer (A-3) of the present invention is obtained by reacting a hydroxyl group, which is generated when a carboxyl group present in a side chain of the graft copolymer (A-1) reacts with the radical polymerizable compound (d) having an epoxy group or an alicyclic epoxy group, with the polybasic acid anhydride (e). The amount of the polybasic acid anhydride of the component (e) to be used is 5 to 100 mol, preferably 40 to 80 mol, based on 100 mol of the hydroxyl group formed by the reaction of the carboxyl group of the component (b) with the side chain epoxy group or the alicyclic epoxy group derived from the component (d). By using the above-mentioned amount, the acid value of the resulting graft copolymer (A-3) can be controlled within the range of 60mgKOH/g to 180mgKOH/g.
The reaction of the hydroxyl group in the graft copolymer (A-2) with the polybasic acid anhydride of the component (e) is carried out as follows. That is, after the side chain carboxyl group derived from the component (b) in the graft copolymer (A-1) is reacted with the radical polymerizable compound having an epoxy group or an alicyclic epoxy group as the component (d), a predetermined amount of the component (e) is directly added thereto, and the reaction is usually carried out at 50 to 150 ℃ and preferably at 80 to 130 ℃. No new catalyst needs to be added.
The polybasic acid anhydride as the component (e) is not particularly limited, and examples thereof include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 1,2, 4-trimellitic anhydride, and 1,2,4, 5-pyromellitic anhydride. Among these compounds, tetrahydrophthalic anhydride and phthalic anhydride are preferable from the viewpoints of reactivity and easy availability. These compounds may be used alone in 1 kind, or 2 or more kinds in combination, preferably tetrahydrophthalic anhydride.
The graft copolymer (a-4) of the present invention is obtained by copolymerizing the component (a), the component (d), styrene and the component (c), reacting the component (b) with an epoxy group or an alicyclic epoxy group in the obtained graft copolymer, and further reacting the component (e) with a hydroxyl group formed by the reaction. The carboxyl group of the component (b) reacts with the side chain epoxy group or the alicyclic epoxy group derived from the component (d) to open the ring of the epoxy group, thereby forming a hydroxyl group in the graft copolymer and at the same time, providing an unsaturated group at the terminal. The polybasic acid anhydride of the component (e) reacts with the hydroxyl group formed by the reaction of the hydroxyl group of the component (b) with the side chain epoxy group derived from the component (d) to open the ring of the acid anhydride group and convert it into a carboxyl group. The copolymerization ratios of the component (a), the component (d) and the component (c) are as follows: the component (a) is 5 to 18 mass%, preferably 6 to 16 mass%, more preferably 6 to 14 mass%; the component (d) is 10 to 50 mass%, preferably 25 to 45 mass%; the component (c) is 1 to 55% by mass, preferably 15 to 45% by mass. If the copolymerization ratio of the component (a) is less than 5% by mass, sufficient pigment dispersion stability cannot be obtained for a DPP-based dye having a high degree of conjugation, and if the copolymerization ratio of the component (a) exceeds 18% by mass, the solubility of the colloid in a solvent is lowered, whereby the pigment dispersion stability is lowered, and further, the alkali developability is lowered to form a residual gum.
The radical polymerizable compound (d) having an epoxy group or an alicyclic epoxy group is used for introducing an epoxy group or an alicyclic epoxy group into a side chain of the graft copolymer, and then reacts with a carboxyl group of the component (b) to introduce an unsaturated group. And further for introducing an acid value by reacting the hydroxyl group formed at this time with the component (e). Therefore, the function and the amount of the component (d) introduced into the side chain of the graft copolymer (A-3) are different from each other, but the same epoxy compound can be used.
By setting the component (d) to 10 to 50% by mass, the amount of the epoxy group or the alicyclic epoxy group introduced, that is, the amount of the unsaturated group derived from the unsaturated monobasic acid of the component (b) introduced can be controlled, and the curability of the graft copolymer (a-4) can be controlled. By making the component (a) and the component (b) in the above-described ratio, the component (c) can be appropriately selected within the range of 10% by mass to 50% by mass.
The amount of the unsaturated monobasic acid of the component (b) to be used is 10 to 100 moles, preferably 60 to 100 moles, based on 100 moles of the side chain epoxy group or the alicyclic epoxy group derived from the component (d).
The minimum amount of unsaturated groups required for curing the resin can be introduced by adjusting the amount of the unsaturated monobasic acid to 10 moles or more, and the amount of the unreacted unsaturated monobasic acid in the resulting graft copolymer (A-4) can be reduced by adjusting the amount of the unsaturated monobasic acid to 100 moles or less.
The amount of the polybasic acid anhydride of the component (e) used is 5 to 100 moles, preferably 40 to 90 moles, based on 100 moles of the hydroxyl group formed by the reaction of the carboxyl group of the component (b) with the side chain epoxy group or the alicyclic epoxy group derived from the component (d). By the above amount, the acid value of the graft copolymer (A-4) obtained can be controlled within the range of 60mgKOH/g to 180mgKOH/g.
The acid value of the photosensitive graft polymer (A) (graft copolymers (A-1) to (A-4)) is preferably from 20mgKOH/g to 180mgKOH/g, more preferably from 60mgKOH/g to 150mgKOH/g. If the acid value is outside this range, sufficient alkali developability is not obtained. That is, if the acid value is less than 20mgKOH/g, the solubility in an alkaline developer is sometimes insufficient, a developed pattern is not perfectly developed, and a residual gum remains, and if it exceeds 180mgKOH/g, the cured portion may be dissolved in the alkaline developer, and the entire film layer may be peeled off.
The acid value of the photosensitive graft polymer (A) in the present invention is the number of mg of potassium hydroxide required for neutralizing lg of the photosensitive resin, and can be measured by an automatic potentiometric titrator using a potassium hydroxide ethanol titration solution.
The number average molecular weight (a value in terms of polystyrene obtained by GPC) of the photosensitive graft polymer (a) is preferably 3000 to 80000, more preferably 5000 to 20000. When the weight average molecular weight is less than 3000, the heat resistance may be low and the entire film layer may easily flake off during development, and when it exceeds 20000, the solubility in an alkaline developer may be insufficient, and the film may be easily unclearly developed or may be easily lumpy off.
The number average molecular weight (Mn) of the photosensitive graft polymer (a) in the present invention is measured by Gel Permeation Chromatography (GPC) under the following conditions, and calculated in terms of polystyrene.
Column: shodex GPCKF800 (Showa electrician)
Column temperature: 40 deg.C
Mobile phase: tetrahydrofuran (THF)
A detector: differential refractometer RID-20A (Shimadzu)
Flow rate: 1 mL/min
The photosensitive graft polymer (a) obtained as described above is added with the active monomer (B), the photopolymerization initiator (C), the solvent (D), the pigment dispersion (E), the leveling agent, the coupling agent (F), and the like to obtain a photosensitive resin composition.
The reactive monomer (B) that can be used is not particularly limited as long as it is a compound that can react with the photosensitive graft polymer (a). Specific examples of the active monomer (B) include aromatic vinyl monomers such as styrene, a-methylstyrene, a-chloromethylstyrene, vinyltoluene, divinylbenzene and diallyl phthalate; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These compounds can be used alone in 1, also can be more than 2 combined use.
The amount of the reactive monomer (B) added is usually 40 to 200g, preferably 80 to 150g, based on 100g of the photosensitive graft polymer (A). By setting the amount of addition to the above range, the photocurability can be maintained within an appropriate range, and the viscosity can be adjusted.
As the photopolymerization initiator (C), a known compound used in photocuring with active light such as ultraviolet rays can be used without limitation. Specific examples of the photopolymerization initiator (C) include benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ester, and alkyl esters thereof; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone > 4- (1-t-butylperoxy-1-methylethyl) acetophenone and the like; the method comprises incubating flos anthraquinones, 2-amylanthrax, 2-tert-butylanthrax, and 1-chloro anthrax; 2, 4-dimethyl yether, 2, 4-diisopropyl yether, 2-chloro yether, etc. yether; ketals such as acetophenone dimethyl ketal and 2, 2-dimethoxy-2-phenylacetophenone; benzophenones such as benzophenone > 4- (1-t-butylperoxymethylethyl) benzophenone, 3', 4' -tetrakis (t-butylperoxy \31478yl) benzophenone and the like; 2-methylmercapto) phenyl ] -2-alunite-HE-propan-1-one and/or 2-mer-yl-2-dimethylamino-1- (4-alunite-phenyl) -1-T-ketone; acyl phosphorus oxides and xanthones, OXE-1, OXE-2, and the like. These compounds can be used alone in 1 kind, also can be 2 or more combined use, preferably OXE-1 (powerful new material).
The amount of the photopolymerization initiator (C) added is usually 0.1 to 20g, preferably 1 to 15g, based on 100g of the solid content in the photosensitive resin composition. By setting the amount of addition to the above range, photocurability can be maintained within an appropriate range.
The solvent (D) that can be used is not limited as long as it is an inert solvent that does not react with the graft polymer and the photopolymerizable monomer (B).
Examples of the solvent (D) that can be used include propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ester acetate, and diethylene glycol ethyl ester acetate. Among these solvents, propylene glycol monomethyl ether acetate is preferably used in the radical polymerization reaction. These compounds can be used alone in 1, also can be more than 2 combined use.
The amount of the solvent (D) added is usually 100 to 1000 parts by mass, preferably 300 to 800g, based on 100g of the photosensitive graft polymer (A). By setting the amount to be added within the above range, an appropriate viscosity can be maintained.
The photosensitive resin composition of the present invention may contain a leveling agent and a coupling agent (F) as required, and a fluorine-containing leveling agent such as Efka3227 or Efka3600 of EFKA and a coupling agent such as Dow Corning Z-6040 are generally added, and the amounts of both are in the range of 0.5 to 3% based on the whole photosensitive resin composition.
The photosensitive resin composition of the present invention may contain a color paste (E) as required. As the color paste (E), known color pastes such as inorganic pigments, organic pigments and dyes can be used. The photosensitive resin composition for forming a color filter can be prepared by adding a known pigment.
Specific examples of pigments that can be used include c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; c.i. pigment blue 5, 15: 3. 15: 4. 15:6, 16, 60, etc. blue pigments; c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment; c.i. pigment green 7, 36, and other green pigments; c.i. brown pigments such as pigment brown 23, 25; c.i. pigment black 1, 7, carbon black, titanium black, iron oxide, and other black pigments. These pigments may be used alone or in combination of 2 or more, respectively, depending on the color of the target pixel.
In addition, a known dispersant may be further added to improve the dispersibility of the pigment. The use of a polymeric dispersant is preferable because it is excellent in dispersion stability with time. Examples of the polymer dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ester dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified ester dispersant. Specific examples of such dispersants include trade names of EFKA, disperbyk, SOLSPERSE, afcona, and the like. At present, professional companies knead pigments and disperse the pigments into finished color paste such as Dongyang ink, shanyang pigment and the like by a sand mill.
The photosensitive resin composition of the present invention can be applied to a printed wiring board by, for example, screen printing, bar coating, slit coating, spray coating, etc., and then the necessary portion is photocured, and then the uncured (unexposed) portion is washed with an aqueous alkaline solution to carry out development.
The alkaline aqueous solution used for the development is an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc., and is useful as tetramethylammonium hydroxide or tetraethylammonium hydroxide, with a 0.4% aqueous solution of potassium hydroxide being preferred.
As a light source used when curing the coated surface by light irradiation, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used, and a high-pressure mercury lamp is preferred.
Hereinafter, examples and comparative examples are shown to specifically explain the present invention, but the present invention is not limited to these examples.
< example A-1>
Into a 2000ml four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet tube, 554g of propylene glycol monomethyl ether acetate as a solvent was charged, and the temperature was raised to 85 ℃ while stirring was carried out under nitrogen substitution. Subsequently, a monomer mixture comprising 55.58g (0.25 mol) of isobornyl methacrylate, 123.35g (0.70 mol) of benzyl methacrylate, 56.lg (0.65 mol) of methacrylic acid and 3.33g of styrene (0.032 mol) was weighed, 6.0g of di-tert-butyl peroxide and 6.0 to 500ml of n-dodecyl mercaptan were added to the flask, nitrogen gas was introduced to the flask to expel oxygen for 15 minutes, the mixture was added to a 150ml constant pressure funnel, the mixture was dropped into the flask from the constant pressure funnel within 2 hours, the reaction was stirred at 85 ℃ for 4 hours, and when no monomer was present in the reaction solution by GPC monitoring, the heating and stirring were stopped. A graft copolymer having an acid value of 148.5mgKOH/g as a solid content and a number average molecular weight of 8340 was obtained.
Next, the flask was purged with air, and then 24.93g (0.175 mol) of glycidyl methacrylate, 0.25g of tetrabutylammonium bromide and 0.04g of p-methoxyphenol were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was stopped until the peak of GMA in the reaction mixture disappeared by GPC monitoring. The number average molecular weight of the polymer was 8600, and the acid value of the solid content was 98.58mgKOH/g.
< example A-2>
266.7g of propylene glycol monomethyl ether acetate as a solvent was placed in a 500ml four-necked flask equipped with a stirrer, condenser, thermometer and nitrogen inlet, and the temperature was raised to 85 ℃ while stirring and purging with nitrogen. Subsequently, a monomer mixture comprising 74.67g (0.334 mol) of isobornyl methacrylate, 25.5g (0.145 mol) of benzyl methacrylate, 25.5g (0.296 mol) of methacrylic acid and 1.61g (0.016 mol) of styrene was weighed, 3.1g of di-tert-butyl peroxide and 3.1g of n-dodecyl mercaptan were added to a 250ml flask, nitrogen gas was introduced into the flask to expel oxygen for 15 minutes, the mixture was added to a 150ml constant pressure funnel, the mixture was dropped from the constant pressure funnel into the flask over 2 hours, the reaction was stirred at 85 ℃ for 4 hours, and when no monomer was present in the reaction mixture, the heating and stirring were stopped under the monitoring of GPC. A graft copolymer having a solid acid value of 132.7mgKOH/g and a number average molecular weight of 8720 was obtained.
Next, the flask was purged with air, and then 12.5g (0.088 mol) of glycidyl methacrylate, 0.13g of tetrabutylammonium bromide and 0.02g of p-methoxyphenol were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was stopped until the peak of GMA in the reaction mixture disappeared by GPC monitoring. The polymer had a number average molecular weight of 8930 and an acid value of 84.9mgKOH/g as a solid content.
< example A-3>
266.7g of propylene glycol monomethyl ether acetate as a solvent was placed in a 500ml four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet, and the temperature was raised to 85 ℃ while stirring was carried out under nitrogen substitution. Subsequently, a monomer mixture comprising 74.67g (0.334 mol) of isobornyl methacrylate, 25.5g (0.145 mol) of benzyl methacrylate, 25.5g (0.296 mol) of methacrylic acid and 3.22g (0.032 mol) of styrene was weighed, 3.1g of di-tert-butyl peroxide and 3.1g of n-dodecyl mercaptan were added to a 250ml flask, nitrogen gas was introduced to the flask to expel oxygen for 15min, the mixture was added to a 150ml constant pressure funnel, the mixture was dropped from the constant pressure funnel into the flask over 2 hours, the reaction was further stirred at 85 ℃ for 4 hours, and when no monomer was present in the reaction solution as monitored by GPC, the heating and stirring were stopped. A graft copolymer having a solid acid value of 131.5mgKOH/g and a number average molecular weight of 8720 was obtained.
Next, the flask was purged with air, and then 12.5g (0.088 mol) of glycidyl methacrylate, 0.13g of tetrabutylammonium bromide and 0.02g of p-methoxyphenol were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was stopped until the peak of GMA in the reaction mixture disappeared by GPC monitoring. The polymer had a number average molecular weight of 8930 and an acid value of 84.9mgKOH/g as a solid content.
< example A-4>
266.7g of propylene glycol monomethyl ether acetate as a solvent was placed in a 500ml four-necked flask equipped with a stirrer, condenser, thermometer and nitrogen inlet, and the temperature was raised to 85 ℃ while stirring and purging with nitrogen. Subsequently, a monomer mixture comprising 74.67g (0.334 mol) of isobornyl methacrylate, 25.5g (0.145 mol) of benzyl methacrylate, 25.5g (0.296 mol) of methacrylic acid and 2.42g (0.024 mol) of styrene was weighed, 3.1g of di-tert-butyl peroxide and 3.1g of n-dodecyl mercaptan were added to a 250ml flask, nitrogen gas was introduced to the flask to expel oxygen for 15 minutes, the mixture was added to a 150ml constant pressure funnel, the mixture was dropped from the constant pressure funnel into the flask over 2 hours, the reaction was further stirred at 85 ℃ for 4 hours, and when no monomer was present in the reaction solution as monitored by GPC, the heating and stirring were stopped. A graft copolymer having a solid acid value of 132.1mgKOH/g and a number average molecular weight of 8720 was obtained.
Next, the flask was purged with air, and then 12.5g (0.088 mol) of glycidyl methacrylate, 0.13g of tetrabutylammonium bromide and 0.02g of p-methoxyphenol were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was stopped until the peak of GMA in the reaction mixture disappeared by GPC monitoring. The polymer had a number average molecular weight of 8930 and an acid value of 84.9mgKOH/g as a solid content.
< examples A to 5>
Into a 2000ml four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet tube, 554.0g of propylene glycol monomethyl ether acetate as a solvent was charged, and the temperature was raised to 85 ℃ while stirring was carried out under nitrogen substitution. Subsequently, a monomer mixture comprising 54.57g (0.245 mol) of isobornyl methacrylate, 123.35g (0.70 mol) of benzyl methacrylate, 56.lg (0.65 mol) of methacrylic acid and 3.32g (0.032 mol) of styrene was weighed, 6.0g of di-tert-butyl peroxide and 6.0 to 500ml of n-dodecyl mercaptan were added to the flask, nitrogen gas was introduced to the flask to expel oxygen for 15 minutes, the mixture was added to a 150ml constant pressure funnel, the mixture was dropped into the flask from the constant pressure funnel within 2 hours, the reaction was stirred at 85 ℃ for 4 hours, and when no monomer was present in the reaction solution by GPC monitoring, the heating and stirring were stopped. A copolymer having a solid acid value of 148.58mgKOH/g and a number average molecular weight of 8450 was obtained.
Next, the flask was purged with air, and then 92.63g (0.65 mol) of glycidyl methacrylate, 0.92g of tetrabutylammonium bromide and 0.04g of p-methoxyphenol were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was stopped until the peak of GMA in the reaction mixture disappeared by GPC monitoring.
99.15g (0.65 mol) of tetrahydrophthalic anhydride was added to the reaction mixture, and the mixture was reacted at 115 ℃ for 2 hours to obtain a graft copolymer having a number average molecular weight of 9680 and an acid value of 83.50 mgKOH/g.
< example A-6 >
266.7g of propylene glycol monomethyl ether acetate as a solvent was placed in a 500ml four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet, and the temperature was raised to 80 ℃ while stirring was carried out under nitrogen substitution. Then, a monomer mixture comprising 74.0g (0.33 mol) of isobornyl methacrylate, 25.5g (0.145 mol) of benzyl methacrylate, 25.5g (0.296 mol) of methacrylic acid and 1.60g (0.015 mol) of styrene was weighed, 3.1g of di-tert-butyl peroxide and 3.1g of n-dodecyl mercaptan were added to a 250ml flask, nitrogen gas was introduced to the flask to expel oxygen for 15min, the mixture was added to a 150ml constant pressure funnel, the mixture was dropped from the constant pressure funnel into the flask over 2 hours, the reaction was further stirred at 85 ℃ for 4 hours, and when no monomer was present in the reaction solution, the heating and stirring were stopped under the monitoring of GPC. A copolymer having an acid value of 132.7mgKOH/g as a solid content and a number average molecular weight of 9320 was obtained.
Next, the flask was purged with air, and then 42.1g (0.296 mol) of glycidyl methacrylate, 0.42g of tetrabutylammonium bromide and 0.02g of p-methoxyphenol were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was stopped until the peak of GMA in the reaction mixture disappeared by GPC monitoring.
To the reaction mixture was added 45.07g (0.296 mol) of tetrahydrophthalic anhydride, and the mixture was reacted at 115 ℃ for 2 hours to obtain a graft copolymer having a number average molecular weight of 10020 and an acid value of 78.62 mgKOH/g.
Comparative example B-1
Into a four-necked flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an inlet tube, 152g of propylene glycol monomethyl ether acetate was charged, and the temperature was raised to 85 ℃ while stirring and replacing with nitrogen, then, into a 250ml three-necked flask, a solution of 91.24g (0.41 mol) of isobornyl methacrylate, 80.6g (0.457 mol) of benzyl methacrylate, 40.4g (0.47 mol) of methacrylic acid, 2.78g (0.027 mol) of n-dodecyl mercaptan, 5.88g and 2.4g of di-tert-butyl peroxide was charged, and after 15 minutes of passing nitrogen gas, the mixture was dropped into the flask from the constant-pressure dropping funnel over 2 hours, and reacted at 85 ℃ for 2 hours.
Next, the flask was purged with air, and then 20.4g (0.144 mol) of glycidyl methacrylate, 0.2g of tetrabutylammonium bromide and 0.06g of p-hydroxyanisole were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was terminated by monitoring with GPC, and no GMA monomer peak appeared in the reaction solution. A solution of a graft polymer having a solid content acid value of 75.82KOHmg/g and a number average molecular weight of 21040 was obtained.
Comparative example B-2
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an inlet tube, 152.4g of propylene glycol monomethyl ether acetate was charged, the temperature was raised to 85 ℃ while introducing nitrogen gas, and further, a solution of 91.25g (0.41 mol) of isobornyl methacrylate and 8.10g (0.046 mol) of benzyl methacrylate, 35.5g (0.41 mol) of methacrylic acid, 1.8g (0.017 mol) of styrene and 4.1g of n-dodecyl mercaptan and 6.0g of di-t-butyl peroxide was charged into a 250ml flask, introduced with nitrogen gas for 15 minutes, and then charged into a 250ml constant pressure funnel, dropped into the flask over 2 hours, and reacted at 85 ℃ for 2 hours.
Next, the flask was purged with air, and then 22.4g (0.158 mol) of glycidyl methacrylate, 0.22g of tetrabutylammonium bromide and 0.02g of p-methoxyphenol were put into the flask to react at 100 ℃ for 5 hours. A graft polymer solution having a solid acid value of 90.89KOHmg/g and a number average molecular weight of 25430 was obtained.
Comparative examples B-3
Into a four-necked flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an inlet tube, 152g of propylene glycol monomethyl ether acetate was charged, and the temperature was raised to 85 ℃ while stirring under nitrogen substitution, then, into a 250ml three-necked flask, 91.24g (0.41 mol) of isobornyl methacrylate, 80.6g (0.457 mol) of benzyl methacrylate, 40.4g (0.47 mol) of methacrylic acid, 5.88g of n-dodecyl mercaptan and 2.4g of di-t-butyl peroxide were charged, and after introducing nitrogen gas for 15 minutes, the mixture was dropped into the flask from the constant pressure dropping funnel over 2 hours, and reacted at 85 ℃ for 2 hours.
Next, the flask was purged with air, and then 20.4g (0.144 mol) of glycidyl methacrylate, 0.2g of tetrabutylammonium bromide and 0.06g of p-hydroxyanisole were added to the flask, followed by reaction at 100 ℃ for 5 hours. The reaction was terminated by no GMA monomer peak in the reaction mixture monitored by GPC. A solution of a graft polymer having a solid content acid value of 75.86KOHmg/g and a number average molecular weight of 21040 was obtained.
Comparative example B-4
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an inlet tube, 152.4g of propylene glycol monomethyl acetate was charged, the temperature was raised to 85 ℃ while introducing nitrogen gas, and a solution of 91.25g (0.41 mol) of isobornyl methacrylate and 8.10g (0.046 mol) of benzyl methacrylate, 35.5g (0.41 mol) of methacrylic acid, 9.02g (0.087 mol) of styrene, 4.1g of n-dodecyl mercaptan and 6.0g of di-t-butyl peroxide was charged into a 250ml flask, introduced with nitrogen gas for 15 minutes, and then charged into a 250ml constant pressure funnel, dropped into the flask over 2 hours, and reacted at 85 ℃ for 2 hours.
Next, the flask was purged with air, and then 22.4g (0.158 mol) of glycidyl methacrylate, 0.22g of tetrabutylammonium bromide and 0.02g of p-methoxyphenol were added to the flask, followed by reaction at 100 ℃ for 5 hours. A graft polymer solution having a solid content acid value of 88.92KOHmg/g and a number average molecular weight of 25430 was obtained.
The solutions of the graft polymers obtained in examples 1 to 6 and comparative examples 1 to 4 were diluted with propylene glycol monomethyl ether acetate so that the respective solid contents were 30 mass%. The diluted graft polymer solutions were used in examples 1 to 6 and comparative examples 1 to 4, respectively. The physical properties and the like in examples and comparative examples were measured by the following methods.
< evaluation of appearance of graft Polymer solution >
Whether it is transparent or turbid was confirmed by visually observing the appearance of each graft polymer solution used in examples 1 to 6 and comparative examples 1 to 4.
< preparation of Red pigment Dispersion ]
150 parts of P.R254 (Nike), 750 parts of sodium chloride (with the particle size of 2um-10um, obtained by dry grinding or jet milling of reagent-grade sodium chloride, equipment is intelligently manufactured by Shenzhen mountain water) and 75 parts of ethylene glycol, the mixture is added into a 2L kneader (Guangzhou Hengfeng mechanical equipment Co., ltd.) and kneaded at 75 ℃ for 8 hours, then the mixture is poured into 6L pure water at 80 ℃, stirred for 1 hour, then filtered (suction filtration or pressure filtration, centrifugal filtration) by using a 1um aqueous membrane, the stirring, pure water washing and filtering processes are repeated, the conductivity of the filtered water is less than 3us, and then the filter cake is dried at 85 ℃ for 8 hours. The dried pigment is crushed, thereby obtaining a red-colored microfine pigment 254.
The finely divided pigment particles were milled to obtain 12g (30% non-volatile matter) of BYK163 (BYK) 8g (45% solid content) of pigment dispersion, namely pigment dispersant BYK-166, (BYK) synergist BYK2105 (BYK) 0.6g, and PMA59.4g, and these were put into a sand mill having an internal volume of 1000mL and stirred with a dispersion plate for 10 minutes to effect preliminary dispersion. To the predispersion thus obtained, 12g of the red microfine pigment obtained in S-1 was added, followed by stirring for 60 minutes to obtain a pigment dispersion.
To the obtained pigment dispersion, 300g of inorganic particles (zirconia, the oriental zirconium industry) having an average particle diameter of 0.1mm were added and ground with cooling water at 20 ℃ for 2 hours, 8g of the dispersion resin of Synthesis 1 was added and ground for 30 minutes, and after the grinding was finished, the inorganic particles were removed by filtration from the resulting mixed dispersion using a filter (200 mesh stainless steel mesh). Thus, a red 254 color pigment dispersion was obtained.
The red pigment dispersion obtained above was used to prepare a red resin composition at the blending ratio shown in table 1 below, and then mixed for four hours with a hemomixer (xinkang pharmaceutical applications limited) to form a stable dispersion, followed by film formation according to the preparation of a cured film.
Table 1: composition of Red resin composition
| Composition (A) | Compounding amount |
| Red pigment dispersion | 45.16% |
| Graft polymer solution | 18.81% |
| Reactive monomer | 5.64% |
| Photopolymerization initiator 1 | 1.49% |
| Coupling agent | 0.5% |
| Leveling agent | 0.25% |
| PMA | 28.15% |
| Total up to | 100% |
Reactive monomer: dipentaerythritol hexaacrylate (Taiwan Changxing)
Photoinitiator (2): PBG-301 (Strong new material)
Coupling agent: z-6040 (dao kang Ning)
Leveling agent: efka3777 (Basf)
< evaluation of pigment Dispersion stability >
In order to evaluate the pigment dispersion stability, the change in viscosity of the red resin composition was measured. If the pigment dispersion stability is poor, the viscosity increases and the target performance cannot be obtained. The following specifically explains the present invention.
The red resin compositions except for the photopolymerization initiator component 1, the photopolymerization initiator component 2 and PGMEA were prepared, and the viscosity immediately after the preparation and the viscosity after the standing in a thermostatic bath at 40 ℃ for 7 days for accelerating the change with time were measured (brookfiieldvn type viscometer, viscosity at 25 ℃), and evaluated according to the following criteria. The results are shown in Table 2.
Very good: the viscosity change rate was less than 15%, and the pigment dispersion stability was extremely excellent.
O: the viscosity change rate is more than 15% and less than 20%, and the pigment dispersion stability is excellent
And (delta): the viscosity change rate is more than 20% and less than 25%, and the pigment dispersion stability is slightly poor
X: the viscosity change rate is more than 25 percent, and the dispersion stability of the pigment is poor
< preparation of cured coating >
The red resin composition was spin-coated on a 1mm by 10 mm square glass substrate (alkali-free glass) so that the film thickness was 2.2um when dried, the solvent was extracted under vacuum of 133pa for 3 minutes, prebaking was performed at 90 ℃ for 2 minutes, and then a photomask was placed at a position 20um away from the coated film and exposure was performed at 100mJ/cm 2. Subsequently, jet development was performed with a 0.4 mass% KOH aqueous solution under a water pressure of 0.3MPa, followed by postbaking at 230 ℃ for 30 minutes to obtain a cured coating film.
< evaluation of alkali developability >
The cured coating exposed through the photomask was subjected to jet development at 23 ℃ using a 0.4% KOH aqueous solution, and the presence or absence of a coating film was observed after washing with water, and evaluated according to the following criteria. The results are shown in Table 2.
Very good: after the development time of 70 seconds, no coating film was visually observed.
O: after a development time of 90 seconds, no coating was visually observed.
X: after the development time of 90 seconds, a coating film was visually observed.
< evaluation of development residue >
The developed glass substrate was visually observed with a metallographic microscope to confirm the presence or absence of a residue. The substrate surface was further wiped with a cleaning cloth dipped with isopropyl alcohol to confirm the presence or absence of the residue wiped off the cleaning cloth.
TABLE 2
| Appearance of the product | Glue just after compounding Degree (cPa. S) | Tack after 7 days at 40 ℃ Degree (cPa. S) | Rate of change of viscosity (%) | Pigment liquid Bulk stability | Alkali developing Shadow property | Development residue | |
| A-1 | Is transparent | 3.65 | 3.86 | 5.7 | O | ◎ | Is free of |
| A-2 | Is transparent | 3.40 | 3.53 | 3.8 | O | O | Is free of |
| A-3 | Is transparent | 3.56 | 3.65 | 2.5 | O | O | Is free of |
| A-4 | Is transparent | 3.78 | 3.93 | 3.97 | O | O | Is composed of |
| A-5 | Is transparent | 3.45 | 3.58 | 3.77 | O | O | Is free of |
| A-6 | Is transparent | 3.58 | 3.72 | 3.91 | O | O | Is composed of |
| B-1 | Is transparent | 4.44 | 5.65 | 27.25 | △ | O | Is free of |
| B-2 | White turbidity | 14.38 | 18.32 | 27.40 | △ | O | Is composed of |
| B-3 | Is transparent | 5.53 | 7.09 | 28.21 | △ | △ | Is free of |
| B-4 | White turbidity | 15.62 | 18.32 | 117.29 | △ | △ | Is provided with |
The results in Table 2 show that the solutions of the graft polymers of examples 1 to 6 were not clouded and had no effect on the transparency of the coating films. Furthermore, the pigment resin compositions prepared using the solutions of the graft polymers of examples 1 to 6 had good viscosity stability with time, and the cured coating films prepared using the solutions were not only alkali-developable but also free from residue after development. It can be seen that the mole number of styrene in the polymer is 1-5% to improve the developing effect, and if no styrene is present, the developing speed is too fast, more than 5%, the developing speed is slow and residual gum is present.
Evaluation of Heat resistance
With respect to the obtained dot pattern, chromaticity coordinate values (x, Y) and stimulus values (Y) in the CIE color system were measured under a C light source and a 2-degree visual field using an intelligent spectroscopic tester (san en shi, shenzhen, ltd). Next, chromaticity coordinate values (x, Y) and stimulus values (Y) after additional baking at 230 ℃ for 90 minutes were measured, and color change before and after additional baking, i.e., Δ E ab, was evaluated. The evaluation results are shown in table 3. The smaller the value of Δ E ab indicates the higher the heat resistance.
In the evaluation of heat resistance, a case where Δ Eab is less than 3.0 was evaluated as "excellent",
the case where the content was 3.0 or more and less than 5.0 was evaluated as "O",
the case where the average particle diameter was 5.0 or more and less than 10 was evaluated as "Δ",
the case of 10 or more was evaluated as "x".
Watch III
| Heat resistance | |
| A-1 | ◎ |
| A-2 | ◎ |
| A-3 | ◎ |
| A-4 | ◎ |
| A-5 | ◎ |
| A-6 | ◎ |
| B-1 | ◎ |
| B-2 | △ |
| B-3 | △ |
| B-4 | △ |
Thus, the color paste such as a photosensitive graft polymer pigment of the present invention is excellent in dispersion stability, can form a transparent cured coating film which can be developed with an alkali, and is heat-resistant, and therefore, is useful not only as a pigment dispersion but also as a binder polymer for a coloring composition. It is understood that the above specific examples are further illustrative of the present invention and are not intended to limit the scope of the invention, and that all other modifications and variations that may occur to those skilled in the art without having the benefit of this disclosure are deemed to be within the scope of the invention.
Claims (10)
1. A photosensitive graft polymer is characterized in that the photosensitive graft polymer is an acrylate polymer and contains a side chain with an ethylenic bond generated by the reaction of (methyl) acrylic acid and glycidyl methacrylate ether and another side chain polymer formed by a macromonomer, wherein the macromonomer is obtained by copolymerizing a polymerizable monomer with a C8-20 bridged cyclic hydrocarbon group and a polymerizable monomer with a naphthenic base without the bridged cyclic hydrocarbon group; the polymerizable monomer having a C8-20 bridged cyclic hydrocarbon group is at least one selected from isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and adamantyl (meth) acrylate compounds; the cycloalkyl polymerizable monomer having no bridged ring type includes styrene, and at least one of cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, rosin (meth) acrylate, and phenoxyethyl (meth) acrylate.
2. The photosensitive graft polymer of claim 1, wherein the structural formula is represented by formula (I),
formula I
Formula II
In the formula I, R 1 Is methyl or is H, R 2 The repeating unit X is derived from at least one of isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate and adamantyl (meth) acrylate, and the repeating unit Y is derived from at least one of cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, rosin (meth) acrylate and phenoxyethyl (meth) acrylate.
3. The photosensitive graft polymer of claim 1, wherein the number average molecular weight of the polymer is 8000 to 15000.
4. The photosensitive graft polymer of claim 1, wherein said photosensitive graft polymer has an acid value of 60 to 180mgKOH/g.
5. The photosensitive graft polymer according to claim 1, wherein the photosensitive graft polymer is a graft copolymer comprising the branch-linked glycidyl methacrylate, another branch-linked bridged hydrocarbon group having 8 to 20 carbon atoms, and (meth) acrylic acid and a cycloalkyl group having no bridge.
6. The photosensitive graft polymer according to claim 1, wherein the photosensitive graft polymer is a graft copolymer obtained by reacting a carboxyl group contained in the graft copolymer with a radical polymerizable compound having an epoxy group or an alicyclic epoxy group, and has an acid value of 80 to 180KOH/g.
7. A photosensitive graft polymer as claimed in claim 1, wherein the mole percentage of styrene used in the polymerization is from 1 to 5%.
8. The photosensitive graft polymer according to claim 1, wherein the photosensitive graft polymer is a graft copolymer in which a carboxyl group in the graft copolymer is reacted with glycidyl (meth) acrylate to form a hydroxyl group, and then reacted with a polybasic acid anhydride to obtain a new carboxyl group.
9. The photosensitive graft polymer of claim 8, wherein said polybasic acid anhydride is tetrahydrophthalic anhydride.
10. A photosensitive resin composition comprising the photosensitive graft polymer according to any one of claims 1 to 9, an active monomer, a photopolymerization initiator, and a solvent.
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