JP2012242653A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition, which is excellent in photosensitivity, alkali developability, adhesiveness and plate making property and excellent in dispersibility with respect to an organic pigment, thereby, which can be suitably used for manufacturing a color filter, a liquid crystal panel or the like.SOLUTION: The photosensitive resin composition comprises: an alkali-soluble resin; a polymerizable monomer; and a photopolymerization initiator. The alkali-soluble resin comprises, as essential components, an alkali-soluble resin having a vinyl phenol monomer unit; and other alkali-soluble resin.

Description

The present invention relates to a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, and a color filter.
More specifically, as a so-called negative photosensitive resist, it is used in the field of various electronic information materials, and in particular, color filter pixels, overcoats, and photolithographic spacers used in color liquid crystal display panels and color imaging tube elements in the field of electronic information materials. The present invention relates to a photosensitive resin composition that can be suitably used for the production of the product, and a cured product thereof.

The photosensitive resin changes its shape when light is applied to the coated film. For example, the photosensitive resin has characteristics such that a portion irradiated with light is cured and other portions are soluble. Utilizing such characteristics, it is used to manufacture optical members for displays and circuit boards of other electronic devices, and the importance of the usefulness increases with the development of so-called IT technology. Industrial material. One important member for which such a photosensitive resin is used is a color filter. The color filter is an indispensable member for a color liquid crystal display device and a color image pickup tube element, and has a fine colored resin layer for separating colors. Various types of photosensitive resin compositions for forming color filters have been proposed, but the current mainstream is to use an acrylic photosensitive resin composition as an alkali development type resist. Usually, an alkali-soluble resin is included as an essential component as a component that affects the plate-making characteristics in processing.
Alkali-soluble resins are materials that are used in various industrial fields, but can be suitably used as alkali-developing resists in the field of electronic information materials.
In this field, for example, in the case of a color filter application, the photosensitivity is good, the development speed with respect to alkali is fast, the basic performance that contributes to the plate-making property when producing the color filter, such as the pattern shape and the adhesion performance, and the solvent resistance. It is required to have excellent basic performance that contributes to the reliability and spectral characteristics of the color filter, such as performance, heat resistance, and transparency. In other words, the alkali-soluble resin greatly affects the plate-making performance when producing a color filter and the performance of the color filter itself, and development research for satisfying and improving these characteristics is being actively conducted. is there.
As a conventional alkali-soluble photosensitive resin, (meth) acrylic acid ester (a) having a specific structure, (meth) acrylic acid (b), and (meth) acrylic acid ester (c) other than (a) An active energy ray-curable resin comprising a modified copolymer (B) obtained by adding an epoxy group-containing unsaturated compound (d) to a part of the acid groups of the obtained copolymer (A) is disclosed. (For example, refer to Patent Document 1). In this active energy ray curable resin, excellent pattern formability for accurately forming a high-definition pattern is required. In order to satisfy the pattern formability and prevent the resist pattern from collapsing, It is intended to increase the mechanical strength of the pattern itself.

JP2009-203320A (page 1-2)

As described above, the alkali-soluble resin is a component that renders the resist an alkali-developable resist by imparting coating film formability and developer solubility, and is also curable, adhesive, heat resistant, and dry re-dissolvable. It is a component that affects various performances. In particular, in a negative alkaline developing resist containing a coloring material such as a color resist for a color filter, in a cleaning step after pixel formation, when the substrate is washed with a highly polar solvent such as N-methylpyrrolidone, In this case, there is a problem that the color material is dissolved and dispersed, and the color characteristics are deteriorated.
Incidentally, Patent Document 1 describes that an active energy ray-curable resin is used as a component of a color filter for a liquid crystal display or a pigment resist for a black matrix. However, sufficient studies on solvent resistance against organic solvents are sufficient. Therefore, further improvement in solvent resistance as a colored resist has been demanded while improving photosensitivity, alkali developability, adhesion and the like.
The present invention has been made in view of the above situation, and is excellent in photosensitivity, alkali developability, adhesion, plate-making property, and excellent in solvent resistance to organic solvents, and is suitably used in the production of liquid crystal panels and the like. It aims at providing the photosensitive resin composition which can be performed.

The inventor conducted various studies on a negative photosensitive resin composition containing a radical polymerizable monomer, a radical polymerizable photopolymerization initiator, and an alkali-soluble resin. By using an alkali-soluble resin having a phenol monomer unit, it is possible to obtain a cured product that has high solvent resistance, in particular, high solvent resistance to highly polar solvents such as N-methylpyrrolidone and little elution into the solvent. I found. For example, when used in a color filter for a liquid crystal panel, this characteristic can prevent color material from elution / dispersion in the substrate cleaning process and suppress deterioration in color characteristics, Can be prevented from contaminating the liquid crystal and lowering the electrical insulation, and a high-quality liquid crystal display or liquid crystal television can be manufactured.
That is, the present invention is a negative photosensitive resin composition comprising (A) a photopolymerizable monomer, (B) a radical polymerizable photopolymerization initiator, and (C) an alkali-soluble resin.
The alkali-soluble resin comprises (C-1) 5% by weight to 95% by weight of an alkali-soluble polymer having a vinylphenol monomer unit, and (C-2) 5% by weight to 95% by weight of another alkali-soluble resin. % Or less. Furthermore, it is a negative photosensitive resin composition containing a polymer containing an N-substituted maleimide monomer unit together with an alkali-soluble polymer having a vinylphenol monomer unit.
The present invention is described in detail below.
The negative photosensitive resin composition of the present invention comprises (A) a radical polymerizable monomer, (B) a radical polymerizable photopolymerization initiator, and (C) an alkali-soluble resin. One type of photopolymerization initiator may be included, or two or more types may be included. Moreover, the other component may be included.
Since the main feature of the present invention is (C) alkali-soluble resin, the alkali-soluble resin will be described first, followed by (A) radical polymerizable monomer and (B) initiation of radical polymerizable photopolymerization. The agent will be described.
The (C) alkali-soluble resin used in the present invention contains (C-1) a vinylphenol monomer unit as an essential component.
The alkali-soluble resin containing the vinylphenol monomer unit needs to be contained in an amount of 5% by mass to 95% by mass with respect to the entire alkali-soluble resin. More preferably, they are 10 mass% or more and 80 mass% or less, Most preferably, they are 20 mass% or more and 60 mass% or less. If the blending amount of the alkali-soluble resin containing the vinylphenol monomer unit is less than 5% by mass, the effect of improving the solvent resistance may not be exhibited sufficiently. Moreover, when it exceeds 95 mass%, there exists a possibility that developability and adhesiveness may fall.
The vinylphenol monomer unit has ortho, meta and rose positions as the positions of the substituents of the phenolic hydroxyl group. However, the paravinylphenol monomer is highly reactive and easily available from the industrial viewpoint. Units are particularly preferred.
(C-1) The content of the vinylphenol monomer unit in the polymer containing the vinylphenol monomer unit is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably vinylphenol. It is a homopolymer (polyvinylphenol).
The polymer containing a vinylphenol monomer unit has a weight average molecular weight of preferably 50,000 or less, more preferably 30,000 or less, and most preferably 20,000 or less.
(C-2) Other alkali-soluble resins used together with the polymer containing the vinylphenol monomer unit include an acid group and a polymerizable double bond, particularly for adjustment of development characteristics and pigment dispersibility. Alkali-soluble resins containing monomer units are preferred. As the monomer having an acid group and a polymerizable double bond, (meth) acrylic acid and itaconic acid are preferable. Among these, (meth) acrylic acid is preferable and acrylic acid is most preferable from the viewpoint of industrial availability and high alkali solubility. As a copolymerization ratio of the monomer unit having an acid group and a polymerizable double bond, 5 to 50% by mass is preferable, and 10 to 30% by mass is preferable. If the monomer unit having an acid group and a polymerizable double bond is outside the above range, developability and adhesion may be reduced.
As other radical polymerizable monomers to be copolymerized with a monomer monomer having an acid group and a polymerizable double bond, (meth) acrylic acid ester, aromatic vinyl, and N-substituted maleimide monomer are preferable. Used for. In particular, a resin containing an N-substituted maleimide monomer unit is excellent in pigment dispersibility, heat resistant colorability, and heat distortion resistance, and has a high degree of freedom in the molecular weight, acid value, and copolymerization ratio of the resin, and required development characteristics and pigment dispersibility. It is very preferable because of its excellent controllability.
As the N-substituted maleimide monomer unit, N-benzylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide are preferable, and N-benzylmaleimide is particularly preferable in terms of less coloring and excellent pigment dispersibility.
The copolymerization amount of the N-substituted maleimide monomer unit is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. If the copolymerization amount of the N-substituted maleimide monomer unit is less than 1% by mass, heat resistance and pigment dispersibility may be inferior. If it exceeds 50% by mass, alkali solubility and solvent solubility may be reduced. is there.
(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethyl (meth) acrylate Hydroxyl-containing (meth) acrylic esters such as cyclodecanyl, (meth) acrylic esters such as isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and glycerol (meth) acrylate are preferred. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate are particularly preferred because of excellent heat resistance colorability.
As the aromatic vinyl monomer, aromatic vinyl compounds such as styrene, vinyltoluene, and α-methylstyrene are preferable. Of these, styrene and vinyltoluene are preferable from the viewpoint of heat resistance coloring property and heat decomposition property of the resin.
20-80 mass% is preferable and, as for the total copolymerization amount of a (meth) acrylic acid ester and an aromatic vinyl monomer, 30-70 mass% is still more preferable. If it is out of the above range, heat resistance colorability, pigment dispersibility, and alkali solubility may be lowered.
In addition, for the purpose of adjusting alkali solubility and pigment dispersibility, acid anhydride monomers such as maleic anhydride and itaconic anhydride, and nitrogen-containing single monomers such as N-vinylpyrrolidone, N-vinylimidazole and N-vinylcarbazole The body or the like is preferably used. The copolymerization amount of these other monomer units is preferably less than 20% by mass.

As the polymerization method of the monomer component, bulk polymerization, solution polymerization, emulsion polymerization and the like are usually used.
The polymerization method may be used, and may be appropriately selected according to the purpose and application.
This is preferable because it is industrially advantageous and the structure such as molecular weight can be easily adjusted. In addition, the monomer component
The polymerization mechanism includes radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization.
Polymerization methods based on radical polymerization mechanisms can be used.
It is preferable because it is advantageous.
As a polymerization initiation method in the polymerization reaction, heat and electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.),
If the energy necessary to start polymerization is supplied to the monomer component from an active energy source such as an electron beam
Well, if you use a polymerization initiator together, the energy required to start the polymerization can be greatly reduced.
This is preferable because the reaction can be easily controlled.
In addition, as a method for controlling the molecular weight of the polymer obtained by polymerizing the monomer components,
It can be controlled by adjusting the amount and type of the initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.
When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is a polymerization reaction.
It is not particularly limited as long as it is inert, and the polymerization mechanism and the type of monomer used
May be appropriately set according to the polymerization conditions such as type and amount, polymerization temperature, polymerization concentration, etc.
When using a solvent when preparing a fat composition, the solvent containing the solvent is used for solution polymerization of the monomer component.
It is efficient and preferable to use.
Examples of the solvent include methanol, ethanol, isopropanol, and n-butanol.
And monoalcohols such as s-butanol; ethylene glycol, propylene glycol
Glycols such as tetrahydrofuran; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol
Cole monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol
Dimonobutyl ether, diethylene glycol monomethyl ether, diethylene glycol
Rumonoethyl ether, diethylene glycol monobutyl ether, propylene glycol
Rumonomethyl ether, propylene glycol monoethyl ether, propylene glycol
Glycol monoethers such as dimethyl monobutyl ether and 3-methoxybutanol;
Glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol
Allyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol
Diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol
Glycol ethers such as dimethyl ether and propylene glycol diethyl ether
Class: Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl
Ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol
Recall monomethyl ether acetate, diethylene glycol monoethyl ether acetate
Tate, diethylene glycol monobutyl ether acetate, propylene glycol
Nomethyl ether acetate, propylene glycol monoethyl ether acetate,
Lopylene glycol monobutyl ether acetate, dipropylene glycol monomethyl
Ether acetate, dipropylene glycol monoethyl ether acetate, dipropy
Gren such as lenglycol monobutyl ether acetate, 3-methoxybutyl acetate
Esters of coal monoether; methyl acetate, ethyl acetate, propyl acetate, isopate
Lopyr, butyl acetate, methyl propionate, ethyl propionate, butyl propionate,
Methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, 3-methoxy
Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate
, Alkyl esters such as methyl acetoacetate and ethyl acetoacetate; acetone, methyl ether
Ketones such as tilketone, methylisobutylketone, cyclohexanone; benzene, tolu
Aromatic hydrocarbons such as ene, xylene, and ethylbenzene; hexane, cyclohexane,
Aliphatic hydrocarbons such as kutan; dimethylformamide, dimethylacetamide, N-methyl
Preferable examples include amides such as lupyrrolidone. Even if these are used alone, two or more
You may use together.
Among these solvents, solubility of the resulting polymer, surface smoothness when forming a coating film, human body
Propylene glycol monomethyl due to its low environmental impact and industrial availability
Ether, propylene glycol monomethyl ether acetate, diethylene glycol
Dimethyl ether, diethylene glycol ethyl methyl ether, and ethyl lactate are more preferable.
As the usage-amount of the said solvent, it is 50-500 mass% with respect to 100 mass% of said monomer components.
It is preferable that it is 100-300 mass% more preferably.
When the above monomer components are polymerized by a radical polymerization mechanism, heat generated radicals are generated.
It is industrially advantageous and preferable to use a combined initiator together. Such polymerization initiators include thermal energy.
As long as it generates radicals by supplying energy, it is not particularly limited.
If appropriate, depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc.
Good.
Examples of the polymerization initiator include cumene hydroperoxide and diisopropyl benzene.
Zen hydroperoxide, di-t-butyl peroxide, lauroyl peroxide
Benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-
Butyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1 '
-Azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethyl)
Valeronitrile), dimethyl 2,2'-azobis (2-methylpropionate), peroxide
Peroxides and azo compounds that are usually used as polymerization initiators such as hydrogen and persulfate
These may be used alone or in combination of two or more. Also transition with polymerization initiator
You may use reducing agents, such as metal salt and amines, together.
The amount of the polymerization initiator used depends on the polymerization conditions such as the type and amount of the monomer used, the polymerization temperature, and the polymerization concentration.
May be appropriately set according to the molecular weight of the target polymer and the like, and is not particularly limited.
In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, with respect to 100% by mass of the monomer component,
0.1-20 mass% is preferable and 0.5-15 mass% is more preferable.
When the above monomer components are polymerized by a radical polymerization mechanism, they are usually used as necessary.
A chain transfer agent may be used, and it is more preferable to use it together with the polymerization initiator. Continuous during polymerization
When a chain transfer agent is used, it tends to suppress an increase in molecular weight distribution and gelation.
Examples of the chain transfer agent include mecaptoacetic acid and 3-mercaptopropionic acid.
Lucaptocarboxylic acids; methyl mercaptoacetate, methyl 3-mercaptopropionate, 3
-2-ethylhexyl mercaptopropionic acid, n-octyl 3-mercaptopropionic acid
, Methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate
, Trimethylolpropane tris (3-mercaptopropionate), pentaerythri
Tall tetrakis (3-mercaptopropionate), dipentaerythritol hexaki
Mercaptocarboxylic acid esters such as ethyl (3-mercaptopropionate);
Captan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercapto
Alkyl mercaptans such as ethane; 2-mercaptoethanol, 4-mercapto-1-
Mercapto alcohols such as butanol; benzenethiol, m-toluenethiol, p
-Aromatic mercaptans such as toluene thiol and 2-naphthalene thiol; Tris [(3
-Mercaptopropionyloxy) -ethyl] isocyanurate
Rates; 2-hydroxyethyl disulfide, tetraethylthiuram disulfide, etc.
Disulfides; dithiocarbamates such as benzyldiethyldithiocarbamate; α-
Monomer dimers such as methylstyrene dimer; halogenated alkyls such as carbon tetrabromide
Is mentioned. These may be used alone or in combination of two or more.
Among these, in terms of availability, ability to prevent crosslinking, and the degree of decrease in polymerization rate is small,
Ptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, merca
Mercaps such as ptoalcohols, aromatic mercaptans, mercaptoisocyanurates
A compound having a benzoyl group, alkyl mercaptans, mercaptocarboxylic acids,
More preferred are lucaptocarboxylic acid esters. Particularly preferred is n-dodecyl mercap
Tan, mercaptopropionic acid.
The amount of the chain transfer agent used depends on the polymerization conditions such as the type and amount of monomers used, the polymerization temperature, and the polymerization concentration.
May be appropriately set according to the molecular weight of the target polymer and the like, and is not particularly limited.
In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, with respect to 100% by mass of the monomer component,
0.1-20 mass% is preferable and 0.5-15 mass% is more preferable.
The polymerization temperature when polymerizing the monomer component using a polymerization initiator by radical polymerization mechanism and
Therefore, it can be set appropriately according to the type and amount of the monomer used and the type and amount of the polymerization initiator.
However, 50-150 degreeC is preferable and 70-120 degreeC is more preferable. The polymerization time is also the same.
However, 1 to 5 hours are preferable, and 2 to 4 hours are more preferable.
In the present invention, the polymer obtained by polymerizing the monomer component is a polymer containing a side chain double bond.
It is preferable that it is a body. More preferably, the side chain double bond-containing polymer is the monomer.
The polymer obtained by polymerizing the components further has a functional group capable of bonding with an acid group and a polymerizable double bond.
It is a thing obtained by making it react with the compound which has.
That is, the alkali-soluble resin used in the present invention is bonded to the above polymer and an acid group.
Containing side chain double bonds obtained by reacting a compound having a functional group capable of undergoing polymerization and a compound having a polymerizable double bond.
The inclusion of a polymer is also one preferred embodiment of the present invention.
As a method for obtaining the side chain double bond-containing polymer, after polymerizing the monomer component containing (meth) acrylic acid, the obtained polymer and a functional group capable of reacting with the carboxylic acid of the polymer. Group X and polymerizable double
A two-step synthesis method in which a monomer having a linking group is reacted is preferable.
Examples of the polymerizable double bond group include acryloyl group, methacryloyl group, and vinyl group.
, An allyl group, a methallyl group, etc.
You may have more than one seed. Among these, in terms of reactivity, acryloyl group, methacryloyl group
The ru group is preferred.
Examples of the functional group X include a hydroxy group, an epoxy group, an oxetanyl group, and an
Examples include socyanate groups. Among these, the speed of the transformation treatment reaction, heat resistance, transparency
From this point, an epoxy group is preferable.
Even if the monomer having the functional group X and the polymerizable double bond group has only one of these, 2
You may have more than one seed.
Examples of the monomer having an epoxy group and a polymerizable double bond group include (meth) acrylate.
Glycidyl phosphate, β-methylglycidyl (meth) acrylate, β-methacrylate (meth) acrylate
Til glycidyl, vinyl benzyl glycidyl ether, allyl glycidyl ether,
T) Acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxy
Sid etc. are mentioned, These may be used independently or may use 2 or more types together.
When using a monomer having an epoxy group as the functional group X, the carboxyl of the polymer
The process of reacting groups with epoxy groups is to ensure good reaction rate and prevent gelation
, Preferably in a temperature range of 50 to 160 ° C., more preferably in a temperature range of 70 to 140 ° C.
Good. More preferably, it is performed at 90 to 130 ° C.
In order to improve the reaction rate in the step of reacting the carboxyl group and the epoxy group
Basic catalysts and acid catalysts for esterification or transesterification that are usually used as catalysts
Of these, basic catalysts are preferred because side reactions are reduced.
Examples of the basic catalyst include dimethylbenzylamine, triethylamine, tri-
Tertiary amines such as n-octylamine and tetramethylethylenediamine; tetramethylan
Monium chloride, tetramethylammonium bromide, tetrabutylammonium
Quaternary ammonium salts such as bromide and n-dodecyltrimethylammonium chloride;
Urea compounds such as tetramethylurea; alkylguanidines such as tetramethylguanidine;
Amide compounds such as methylformamide and dimethylacetamide; triphenylphosphine
Tertiary phosphine such as tributylphosphine; tetraphenylphosphonium bromide,
Examples include quaternary phosphonium salts such as benzyltriphenylphosphonium bromide.
it can. These catalysts may be used alone or in combination of two or more.
Among these, in terms of reactivity, handling and halogen-free, dimethylbenzylamine,
Triethylamine, tetramethylurea and triphenylphosphine are preferable.
The amount of the catalyst used may be combined with the monomer component used in the present invention and an acid group.
0.01% with respect to 100% by mass of the total mass of the functional group and the compound having a polymerizable double bond
It is preferable to use -5.0 mass%. More preferably 0.1 to 3.0% by mass
It is to be used for.
The step of reacting the carboxyl group and the epoxy group is a polymerization inhibitor in order to prevent gelation.
Is preferably performed in the presence of a molecular oxygen-containing gas. As a molecular oxygen-containing gas
Usually, air or oxygen gas diluted with an inert gas such as nitrogen is used, and the reaction vessel
Be blown into.
As a polymerization inhibitor, a polymerization inhibitor for a radically polymerizable compound that is usually used should be used.
For example, hydroquinone, methyl hydroquinone, trimethyl hydroquinone,
t-butyl hydroquinone, methoquinone, 6-t-butyl-2,4-xylenol, 2,
6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2
, 2'-methylenebis (4-methyl-6-tert-butylphenol)
Agents, organic acid copper salts and phenothiazines. These polymerization inhibitors are used alone
It may be used, or two or more types may be mixed and used.
Among these, phenolic inhibitors are preferred in terms of low coloring and ability to prevent polymerization, and availability,
2,2'-methylenebis (4-methyl-6-tert-butylphenol)
, Methoquinone, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butylpheno
Is preferred.
As the use amount of the polymerization inhibitor, ensuring sufficient polymerization prevention effect, and photosensitive resin composition and
From the viewpoint of curability, the monomer component used in the present invention can bind to the acid group.
For a total mass of 100% by mass with the compound having a functional group and a polymerizable double bond, 0.00
It is preferable to use 1 to 1.0% by mass. More preferably 0.005 to 0.5% by mass
It is to be used.
When using a monomer having an epoxy group as the functional group X, the side chain double bond-containing polymerization
As a method for obtaining the body, for example, after the monomer component used in the present invention is polymerized,
When the obtained polymer is reacted with the monomer having the epoxy group and polymerizable double bond group
In addition, in the present invention, the method of making the amount of the carboxyl group of the polymer excessive from the amount of the monomer,
After polymerizing the monomer components used, the resulting polymer, the epoxy group and the polymerizable double
After reacting with a monomer having a linking group, further reacting with a compound having a polybasic acid anhydride group
And the like.
Specific examples of the compound having a polybasic acid anhydride group include succinic anhydride,
Decenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydro
Hydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhex
Sahydrophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, Methylendomethyle
Tetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, anhydride
Examples include rutaric acid, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc.
These 1 type (s) or 2 or more types can be used.
The side chain double bond-containing polymer preferably has a double bond equivalent of 300 to 10,000.
Yes. More preferably, it is 350-5000, More preferably, it is 400-2000
The By adopting such a range, the alkali-soluble resin used in the present invention
Sufficient storage stability of the contained polymer, sensitivity and pattern shape of the photosensitive resin composition of the present invention
It can be expected that good plate-making characteristics such as the above are compatible at a higher level.
The double bond equivalent means the weight of the solid content of the polymer solution per 1 mol of the polymer double bond.
It is. The weight of the solid content of the polymer solution here means the weight of the constituent component of the monomer component.
This is the total of the weight of the polymerization inhibitor. The weight of the solids in the polymer solution is
It can be determined by dividing by the total amount. The amount of double bonds in the polymer
It can be determined from the amount of the compound having a functional group capable of bonding to a group and a polymerizable double bond.
The (C-2) other alkali-soluble polymer has an acid value of 60 to 200 mgKOH / g.
Is. By setting the acid value of the polymer in such a range, sufficient alkali solubility is expressed, and when it is used for an alkali development type resist, it is possible to exhibit good plate making properties. The acid value of the polymer is preferably 70 to 180 mgKOH / g, more preferably 80 to 150 mgKOH / g, and still more preferably 90 to 120 mgKOH / g. Especially preferably, it is 95-110 mgKOH / g.
The acid value of the polymer is determined by measuring the acid value of the polymer solution with an automatic titration apparatus (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 N aqueous KOH solution as a titrant. It can be obtained by calculating the solid content acid value from the acid value of the solution and the solid content of the solution. Here, the solid content of the polymer solution can be determined as follows. About 1 g of the polymer solution is weighed in an aluminum cup, dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by Espec Corp.), after drying at 160 ° C. for 3 hours under vacuum, the product is allowed to cool in a desiccator and the weight is measured. From the weight loss, the solid content of the polymer solution is calculated.
When the polymer has a high molecular weight, a higher acid value gives better plate making properties, and when it has a low molecular weight, good plate making properties tend to be obtained even with a low acid value. is there.
The weight average molecular weight of the polymer obtained by polymerizing the monomer components is appropriately determined according to the purpose and application.
What is necessary is just to set, but in order to obtain favorable plate-making property, it is 2000-250,000, preferably
It is 3000-100000, More preferably, it is 4000-50000.
The weight average molecular weight of the polymer is, for example, polystyrene as a standard substance and tetrahydro
HLC-8120GPC (manufactured by Tosoh Corporation), column TSKgel using orchid as the eluent
GPC (gel permeation chromatography) method by SuperHZM-M (Tosoh Corporation)
It can be obtained more.
The (C) alkali-soluble resin used in the present invention is contained in the photosensitive resin composition of the present invention.
10 to 60% by mass is contained with respect to 100% by mass of the total solid content of the photosensitive resin composition.
preferable. By such content, the effect of the present invention can be more remarkably exhibited.
It becomes possible. More preferably, it is 20-50 mass%, More preferably, it is 25-45 quality
%.
The “total solid content” means all components other than the solvent.

The negative photosensitive resin composition of the present invention further comprises (A) a radical polymerizable compound.
The radical polymerizable compound is a low molecular compound having a radical polymerizable unsaturated group that is polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and the like. The photosensitive resin composition can be made more excellent in curability. radical
The polymerizable compound can be classified into a monofunctional radical polymerizable compound having only one radical polymerizable unsaturated group in the same molecule and a polyfunctional radical polymerizable compound having two or more.
As such a radically polymerizable compound, those usually used can be used,
It does not restrict | limit in particular, What is necessary is just to select 1 type (s) or 2 or more types suitably according to the objective and a use.
Examples of the monofunctional radically polymerizable compound include methyl (meth) acrylate, (
(Meth) ethyl acrylate, (meth) acrylic acid n-propyl, (meth) acrylic acid i-propyl
Lopyl, n-butyl (meth) acrylate, s-butyl (meth) acrylate, (meth) acrylic
T-butyl laurate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, (
Meth) acrylic acid t-amyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid 2
-Ethylhexyl, isodecyl (meth) acrylate, tridecyl (meth) acrylate, (
(Meth) acrylic acid cyclohexyl, (meth) acrylic acid cyclohexylmethyl, (meth)
Octyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (
Benzyl (meth) acrylate, phenyl (meth) acrylate, isobol (meth) acrylate
Nyl, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth
T) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (
(Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl,
(Meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl,
(Meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth)
T) Phenoxyethyl acrylate, Tetrahydrofurfuryl (meth) acrylate, (Meth
) Glycidyl acrylate, β-methylglycidyl (meth) acrylate, (meth) acrylic
Acid β-ethylglycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl
, N, N-dimethylaminoethyl (meth) acrylate, α-hydroxymethylacrylic
(Meth) acrylic acid esters such as methyl acrylate and ethyl α-hydroxymethyl acrylate;
N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc.
(Meth) acrylamides; (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl benzoate
Unsaturated monocarboxylic acids such as acids; maleic acid, fumaric acid, itaconic acid, citraconic acid,
Unsaturated polycarboxylic acids such as saconic acid; succinic acid mono (2-acryloyloxyethyl)
, Between unsaturated groups such as mono (2-methacryloyloxyethyl) succinate and carboxyl groups
Unsaturated monocarboxylic acids in which is chain-extended; unsaturated compounds such as maleic anhydride and itaconic anhydride
Wadic anhydrides such as styrene, α-methylstyrene, vinyltoluene, methoxystyrene, etc.
Aromatic vinyls: methylmaleimide, ethylmaleimide, isopropylmaleimide, siku
Rohexyl maleimide, phenyl maleimide, benzyl maleimide, naphthyl maleimide
N-substituted maleimides such as 1,3-butadiene, isoprene, chloroprene and other conjugated die
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc.
Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl
Vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, laur
Ril vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypoly
Ethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydro
Vinyl ethers such as xylbutyl vinyl ether; N-vinyl pyrrolidone, N-vinyl carbonate
Prolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetoa
N-vinyl compounds such as amide; isocyanatoethyl (meth) acrylate, allyl isocyanate
And unsaturated isocyanates such as nates.
Examples of the polyfunctional radically polymerizable compound include ethylene glycol di (meth).
Acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol
Di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol
Cold di (meth) acrylate, hexanediol di (meth) acrylate, cyclohex
Sandimethanol di (meth) acrylate, bisphenol A alkylene oxide di (me
) Acrylate, bisphenol F alkylene oxide di (meth) acrylate, tri
Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth)
) Acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (
(Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentae
Lithritol hexa (meth) acrylate, ethylene oxide-added trimethylol prop
Tritri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (
(Meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acryl
Rate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate,
Lopylene oxide-added trimethylolpropane tri (meth) acrylate, propylene glycol
Koxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide
Addition pentaerythritol tetra (meth) acrylate, propylene oxide addition dipen
Taerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylol
Propane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane
Tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (me
Acrylate), ε-caprolactone-added dipentaerythritol hexa (meth) acrylate
Polyfunctional (meth) acrylates such as relate; ethylene glycol divinyl ether, di
Ethylene glycol divinyl ether, polyethylene glycol divinyl ether, pro
Pyrene glycol divinyl ether, butylene glycol divinyl ether, hexane di
All divinyl ether, bisphenol A alkylene oxide divinyl ether, bis
Phenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl
Ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether
Ter, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl
Ether, dipentaerythritol hexavinyl ether, ethylene oxide addition tri
Methylolpropane trivinyl ether, ethylene oxide-added ditrimethylol propylene
Tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether
And polyfunctional vinyls such as dipentaerythritol hexavinyl ether
Nyl ethers; 2- (vinyloxyethyl) (meth) acrylate, 3-bi (meth) acrylate
Nyloxypropyl, 1-methyl-2-vinyloxyethyl (meth) acrylate, (meth) a
2-vinyloxypropyl crylate, 4-vinyloxybutyl (meth) acrylate, (meth)
4-vinyloxycyclohexyl acrylate, 5-vinyloxypentyl (meth) acrylate
, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethy (meth) acrylate
Lucyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth) acrylate, (
2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinylo) (meth) acrylate
(Meth) acrylic acid containing vinyl ether groups such as xyloxyethoxyethoxy) ethyl
Stealth; ethylene glycol diallyl ether, diethylene glycol diallylate
Polyethylene glycol diallyl ether, propylene glycol diallyl ether
, Butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol
Nord A alkylene oxide diallyl ether, bisphenol F alkylene oxide di
Allyl ether, trimethylol propane triallyl ether, ditrimethylol prop
Tetraallyl ether, glyceryl triallyl ether, pentaerythritol tetra
Allyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol
L-hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether
Ter, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene
Oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipen
Polyfunctional allyl ethers such as taerythritol hexaallyl ether; (meth) acrylic
Allyl group-containing (meth) acrylic acid esters such as allyl acid; tri (acryloyloxye)
Chill) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, al
Xylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene
Multifunctional (meth) aldehyde such as trioxide (methacryloyloxyethyl) isocyanurate
Cryroyl group-containing isocyanurates; polyfunctional allyl groups such as triallyl isocyanurate
Containing isocyanurates; tolylene diisocyanate, isophorone diisocyanate, key
Polyfunctional isocyanates such as silylene diisocyanate and 2-hydroxy (meth) acrylic acid
Hydroxyl-containing (meth) acrylic such as ciethyl and 2-hydroxypropyl (meth) acrylate
Polyfunctional urethane (meth) acrylates obtained by reaction with acid esters;
Polyfunctional aromatic vinyls such as Zen; and the like.
Among the above radical polymerizable compounds, from the viewpoint of curability, a multifunctional radical polymerizable compound is used.
Things are preferred. Furthermore, among the polyfunctional radically polymerizable compounds, reactivity, economy,
Multifunctional (meth) acrylates and polyfunctional urethane (meth) acrylates due to availability
, (Meth) acryloyl group-containing isocyanurates, (meth) acryloyl group
More preferred are polyfunctional monomers. More preferably, dipentaerythritol penta (medium
) Acrylate, dipentaerythritol hexa (meth) acrylate, trimethylo
Rupropane tri (meth) acrylate.
When the polyfunctional monomer having the (meth) acryloyl group is exemplified by a trade name, KAYAR
AD R-526, NPGDA, PEG400DA, MANDA, R-167, HX-2
20, HX-620, R-551, R-712, R-604, R-684, GPO-30
3, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T
-1420 (T), DPHA, DPHA-2C, D-310, D-330, DPCA-2
0, DPCA-30, DPCA-60, DPCA-120, DN-0075 (above, Japan
Manufactured by Kayaku Co., Ltd.); Aronix M-203S, M-208, M-211B, M-215, M-
220, M-225, M-270, M-240, M-309, M-310, M-321,
M-350, M-360, M-370, M-313, M-315, M-325, M-32
7, M-306, M-305, M-451, M-450, M-408, M-403, M-
400, M-402, M-404, M-406, M-405, M-510, M-520 (
Above, manufactured by Toagosei Co., Ltd.); Light acrylate 3EG-A, 4EG-A, 9EG-A, DC
PA, BP-4EA, BP-4PA, HPP-A, PTMGA-250, G201PT
MP-A, TMP-6EO-3A, TMP-3EO-A (manufactured by Kyoeisha Chemical Co., Ltd.),
Toester EG, 2EG, 3EG, 4EG, 9EG, G101P, G201P, BP-2
EM, BP-6EM, TMP (above, manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 295, 300, 3
60, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.
Among these, TMPTA and DPHA are preferably used.
The molecular weight of the radical polymerizable compound may be appropriately set according to the purpose and application, but 2000 or less is preferable in terms of handling.
In addition, the amount of the radical polymerizable compound used may be appropriately set according to the type, purpose, and use of the radical polymerizable compound and alkali-soluble resin to be used. It is preferable to use 3 to 90% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition. More preferably, it is 5-80 mass%, More preferably, it is 10-70 mass%.
The negative tourism resin composition of the present invention further contains (B) a radical polymerizable photopolymerization initiator.
A radical polymerizable photopolymerization initiator is one that generates a polymerization initiating radical upon irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or more commonly used ones can be used.
The Moreover, you may add 1 type, or 2 or more types of the photosensitizer normally used, photoradical polymerization accelerator, etc. as needed.
Examples of the radical polymerizable photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone,
2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy -1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopro Pan 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ Alkylphenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone; benzophenone, 4,4′-bis (dimethylamino) benzophenone, 2-carboxy Benzophenone compounds such as cibenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone and 2,4-diethylthioxanthone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2
-(4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2
-(4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2
-(4-Ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-to
Halomethylated triazine compounds such as lyazine; 2-trichloromethyl-5- (2′-be
Nzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2
'-Benzofuryl) vinyl] -1,3,4-oxadiazole, 4-oxadiazole,
Halomethylated esters such as 2-trichloromethyl-5-furyl-1,3,4-oxadiazole
Xadiazole compounds; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ′
-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophen
Nyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-
Bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,
Biimidazole compounds such as 2′-biimidazole; 1,2-octanedione, 1- [4
-(Phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-eth
6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-a)
Oxime ester compounds such as cetyl oxime; bis (η5-2,4-cyclopentadi)
En-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -fur
Phenyl) titanium and the like; p-dimethylaminobenzoic acid, p-diethi
Benzoic acid ester-based compounds such as ruaminobenzoic acid; Acrid such as 9-phenylacridine
And the like.
Sensitivity and curability can be improved by using a photosensitizer and a photoradical polymerization accelerator together with the radical polymerizable photopolymerization initiator. Examples of such photosensitizers and photoradical polymerization accelerators include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; ethyl 4-dimethylaminobenzoate, 4-dimethylamino Examples include dialkylaminobenzene compounds such as 2-ethylhexyl benzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole.
The total addition amount of the radical polymerizable photopolymerization initiator may be set as appropriate according to the purpose and application, and is not particularly limited. It is preferable that it is 0.1-30 mass% with respect to 100 mass% of total solid of the photosensitive resin composition of this, More preferably, it is 0.5-25 mass%, More preferably, it is 1-20 mass. %.
The total amount of the photosensitizer and radical photopolymerization accelerator is appropriately set according to the purpose and application.
Although it is not particularly limited, it may be a balance between curability, adverse effects of degradation products, and economic efficiency.
Further, 0.001 to 20% by mass with respect to 100% by mass of the total solid content of the photosensitive resin composition of the present invention.
%, More preferably 0.01 to 15% by mass, still more preferably
Is 0.05-10 mass%.
It is preferable that the photosensitive resin composition of the present invention also contains a solvent. Solvents reduce viscosity and handle
Used for improving colorability, forming a coating film by drying, making it a dispersion medium for coloring materials, etc.
It is a low-viscosity organic solvent that can dissolve or disperse each component in the photosensitive resin composition.
As the solvent, those usually used can be used, and are appropriately selected according to the purpose and application.
Although not particularly limited, for example, methanol, ethanol, isopropanol
Monoalcohols such as ethylene, n-butanol and s-butanol; ethylene glycol, pro
Glycols such as pyrene glycol; cyclic ethers such as tetrahydrofuran and dioxane
, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, di
Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Lopylene glycol monomethyl ether, propylene glycol monoethyl ether, prop
Glycol monoethers such as propylene glycol monobutyl ether and 3-methoxybutanol
Ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether
, Ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether,
Propylene glycol dimethyl ether, propylene glycol diethyl ether, etc.
Recall ethers; ethylene glycol monomethyl ether acetate, ethylene glycol
Cole monoethyl ether acetate, ethylene glycol monobutyl ether acetate
Diethylene glycol monomethyl ether acetate, diethylene glycol monoe
Chill ether acetate, diethylene glycol monobutyl ether acetate, propylene
Lenglycol monomethyl ether acetate, propylene glycol monoethyl ether
Acetate, propylene glycol monobutyl ether acetate, dipropylene glycol
Cole monomethyl ether acetate, dipropylene glycol monoethyl ether acetate
Tate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate
Esters of glycol monoethers such as cetate; methyl acetate, ethyl acetate, acetic acid pro
Pill, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate,
Butyl pionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate
, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy
Alkyl esters such as ethyl propionate, methyl acetoacetate and ethyl acetoacetate;
Ketones such as seton, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; hexane,
Aliphatic hydrocarbons such as chlorohexane and octane; dimethylformamide, dimethylacetate
Amides, amides such as N-methylpyrrolidone, water and the like can be mentioned. Use these alone
Moreover, you may use 2 or more types together.
The amount of the solvent used may be set as appropriate according to the purpose and application, and is not particularly limited.
However, it is preferably 10 to 90% by mass with respect to 100% by mass of the photosensitive resin composition of the present invention.
More preferably, it is 20-80 mass%.
The negative photosensitive resin composition of the present invention is a thermosetting resin such as a coloring material, a pigment dispersant, a filler, an epoxy resin, and a phenol resin, pigment dispersion, in addition to the components described above, depending on the required characteristics of each application. Agent, heat resistance improver, development aid, plasticizer, polymerization inhibitor, UV absorber, antioxidant, matting agent, antifoaming agent, leveling agent, antistatic agent, slip agent, surface modifier, shaking change Components such as an agent, a thixotropic agent, a coupling agent such as silane, aluminum, and titanium, a quinonediazide compound, a polyhydric phenol compound, a cationic polymerizable compound, and an acid generator may be blended. Below, other components suitable when using the photosensitive resin composition of this invention as a resist for color filters are demonstrated.
<Color material>
As the color material used in the present invention, pigments and dyes are preferably used.
As the above pigment, those usually used as organic pigments can be used, and are not particularly limited. For example, azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, Preferable examples include isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complex, diketopyrrolopyrrole, and dye lake pigments. Examples of pigment colors that can be used include yellow, red, purple, blue, green, brown, black, white, and azo dyes.
The pigment 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 and the like according to the purpose and application.
Further, as the dye, for example, organic dyes described in JP 2010-9033 A, JP 2010-211198 A, JP 2009-51896 A, and JP 2008-50599 A are used. Can do. These dyes may be used alone or in combination of two or more. Furthermore, a combination of a pigment and a dye can also be used.
These pigments and dyes may be used alone or in combination of two or more.
The amount of the pigment or dye used can be appropriately set according to the purpose and application. In the negative photosensitive resin composition of the present invention, the total solid content of the photosensitive resin composition is 100% by mass. It is preferable that 3-70 mass% is contained with respect to. With such a content, the effect of the present invention can be more remarkably exhibited. More preferably, it is 5-60 mass%, More preferably, it is 10-50 mass%.
<Dispersant>
Dispersant is an interaction site to pigment and an interaction site to dispersion medium (solvent or binder resin).
And has a function of stabilizing the dispersion of the pigment in the dispersion medium.
Type dispersants (polymer dispersants), surfactants (low molecular dispersants), and pigment derivatives. This
As such a dispersant, a commonly used dispersant can be used.
Examples of the resin-type dispersant include polycarboxylic acids such as polyurethane and polyacrylate.
Acid ester, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarbohydrate
Ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyamido
Noamide phosphate, hydrogen group-containing polycarboxylic acid ester, poly (lower alkyleneimine)
) And a polyester having a free carboxyl group,
Salt, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid
Ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl
Pyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene
Examples include adducts of lenoxide.
The resin-type dispersant has a structure in which the main chain has an interaction site with the pigment.
The graft structure is such that the graft chain is a compatible chain having an interaction property with the dispersion medium.
A resin or a resin in which an anchor chain and a compatible chain have a block structure is particularly preferably used.
It is.
Examples of the surfactant include polyoxyethylene alkyl ether sulfate and dodecy.
Sodium benzenesulfonate, sodium alkylnaphthalenesulfonate, alkyl
Sodium diphenyl ether disulfonate, monoethanolamine lauryl sulfate, laur
Rilsulfuric acid triethanolamine, ammonium lauryl sulfate, sodium stearate,
Anionic surfactants such as sodium lauryl sulfate; polyoxyethylene oleyl ether
, Polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether
, Polyoxyethylene sorbitan monostearate, polyethylene glycol monolaure
Nonionic surfactants such as alkylates; alkyl quaternary ammonium salts and their ethylene oxide
Id adducts and other cationic surfactants; alkyldimethylaminoacetic acid betaines and the like
Amphoteric surfactants such as rubetaine and alkylimidazolines; and the like.
The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include
For example, sulfonic acid group, sulfonamide group and quaternary salt thereof, dialkylamino group, hydroxyl group,
Examples include the carboxyl group, amide group, phthalimide group, etc.
Is, for example, azo, anthraquinone, quinophthalone, phthalocyanine, quinacrine
Don, benzimidazolone, isoindoline, dioxazine, indanthrene
Perylene, diketopyrrolopyrrole and the like.
Examples of the trade name of the dispersant include the following. However, with the above dispersant
However, it is not limited to these.
For example, EFKA-46, 47, 48, 745, 1101, 1120, 1125, 400
8, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 401
0, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 433
0, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 504
4, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 121
0, 2150, KS860, KS873N, 7004, 1813, 1860, 1401,
1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE
131, 1525070, 5207 (above, EFKA ADDI
TIVES), Anti-Terra-U, Anti-Terra-U100, A
anti-Terra-204, Anti-Terra-205, Anti-Terra-
P, Disperbyk-101, 102, 103, 106, 108, 109, 110,
111, 112, 151, 160, 161, 162, 163, 164, 166, 182,
P-104, P-104S, P105, 220S, 203, 204, 205, 2000,
2001, 9075, 9076, 9077 (above, manufactured by Big Chemie), SOLPER
SE3000, 5000, 9000, 12000, 13240, 13940, 17000
20000, 22000, 24000, 24000GR, 26000, 28000 (hereinafter
Top, manufactured by Nippon Lubrizol), Disperlon 7301, 325, 374, 234
1220, 2100, 2200, KS260, KS273N, 152MS
Manufactured by Kasei Co., Ltd.), Ajisper PB-711, 821, 822, 880, PN-411, PA-
111 (above, Ajinomoto Fine Techno Co., Ltd.), KP series (Shin-Etsu Chemical Co., Ltd.), Poly
Flow series (manufactured by Kyoeisha Chemical Co., Ltd.), Megafuck series (DIC (DIC))
And Dispersaid series (manufactured by San Nopco).
These dispersants can be used alone or in combination of two or more.
The amount of the dispersant used may be appropriately set according to the purpose and application, but the dispersion stability, durability
In order to balance the transparency (heat resistance, light resistance, weather resistance, etc.) and transparency, the photosensitive tree of the present invention is used.
It is preferably 0.01 to 60% by mass with respect to 100% by mass of the total solid content of the fat composition.
More preferably, it is 0.1-50 mass%, More preferably, it is 0.5-40 mass%
.
<Heat resistance improver>
The photosensitive resin composition of the present invention has an N- (alkoxymethyl) medium for improving heat resistance and strength.
Adding a lamin compound, a compound having two or more epoxy groups or oxetanyl groups
it can. In particular, a resist for a photospacer, a transparent resist for a protective film, and a resist for an interlayer insulating film.
In the case of a strike, these are preferred.
<Leveling agent>
In the photosensitive resin composition of the present invention, a leveling agent should be added to improve leveling properties.
Can do. As the leveling agent, a fluorine-based or silicon-based surfactant is preferable.
<Coupling agent>
In the photosensitive resin composition of the present invention, a coupling agent can be added to improve adhesion.
Yes. As the coupling agent, a silane coupling agent is preferable.
Si-, methacryl- and amino-based silane coupling agents are mentioned.
Silane coupling agents are preferred.
<Development aid>
In order to improve developability, the photosensitive resin composition of the present invention is, for example, (meth) acrylic acid, acetic acid.
, Monocarboxylic acids such as propionic acid; maleic acid, fumaric acid, succinic acid, tetrahydro
Polycarboxylic acids such as phthalic acid and trimellitic acid; maleic anhydride, succinic anhydride, teto
Development aids such as carboxylic acid anhydrides such as lahydrophthalic anhydride and trimellitic anhydride;
Can be added as
In the photosensitive resin composition of the present invention, the components are mixed and dispersed using various mixers and dispersers.
In particular, when the photosensitive resin composition of the present invention contains a pigment,
It is manufactured through a pigment dispersion treatment process. Examples of the pigment dispersion treatment step include:
First, weigh each predetermined amount of organic pigment, dispersant, binder resin, and solvent,
Conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer,
Using a disperser such as a kneader or blender, the pigment is dispersed in fine particles to form a liquid colorant dispersion (
Base). Preferably, kneading and dispersing treatment is performed with a roll mill, kneader, blender, etc.
And then finely disperse with a media mill such as a bead mill filled with 0.01 to 1 mm beads.
Make sense. The radically polymerizable compound, light, which was separately stirred and mixed with the obtained mill base.
Add and mix a transparent resist solution containing a polymerization initiator, binder resin, solvent, leveling agent, etc.
A uniform dispersion solution is obtained to obtain a photosensitive resin composition. The obtained photosensitive resin composition is
It is desirable to remove fine dust by filtration using a filter.
When forming the photosensitive resin composition of the present invention as a color filter, a liquid crystal panel, etc.
First, the composition is applied onto a substrate. As a substrate on which the composition is applied, glass
Polyester, polycarbonate, polyolefin, polysulfone, cyclic
Thermoplastic sheets such as ring-opening polymers of fins and their hydrogenated products, epoxy resins,
Examples thereof include thermosetting plastic sheets such as unsaturated polyester resins. Among these
From the viewpoint of heat resistance, a glass plate or a heat-resistant plastic sheet is preferable. Also, the above substrate
If necessary, chemicals using corona discharge treatment, ozone treatment, silane coupling agent, etc.
Processing or the like may be performed.
That is, a cured product obtained by curing the photosensitive resin composition is also one aspect of the present invention.
As a method of applying the photosensitive resin composition of the present invention to a substrate, spin coating, slit coating,
Roll coating, casting coating, etc., and any method is preferred in the composition of the present invention.
Can be used.
The coating after drying on the substrate can be dried using a hot plate, IR oven, or convection oven.
Use a bun or the like. The drying conditions include the boiling point of the solvent component, the type of curing component, the film thickness,
Although it is appropriately selected depending on the performance of the dryer, it is usually 50 to 160 ° C. for 10 seconds to 3 seconds.
Perform for 00 seconds.
The exposure for curing the photosensitive resin composition is applied to the coating film through a predetermined pattern mask.
A step of irradiating with a characteristic light. Examples of active light sources include xenon lamps and halos.
Gen lamp, tungsten lamp, high pressure mercury lamp, super high pressure mercury lamp, metal halide lamp,
Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp, argon ion
Laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser
Laser light sources such as lasers and semiconductor lasers are used. As a method of exposure machine, professional
Examples include the proximity method, mirror projection method, and stepper method.
A proximity method is preferably used.
After the exposure, the film is developed with a developer to remove unexposed portions and form a pattern. Present
Any image liquid can be used as long as it dissolves the photosensitive resin composition of the present invention.
Usually, an organic solvent or an alkaline aqueous solution is used. Al as developer
When a caustic aqueous solution is used, it is preferable to wash with water after development. Arca
In addition to alkaline agents, surfactants, organic solvents, buffers, dyes,
A pigment or the like can be contained. Alkaline agents include sodium silicate and potassium silicate
Sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, secondary lithium
Inorganic alkenyl such as sodium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate
Reagents: trimethylamine, diethylamine, isopropylamine, n-butylamine,
Noethanolamine, diethanolamine, triethanolamine, tetramethylammo
And amines such as nium hydroxide and tetraethylammonium hydroxide,
These may be used alone or in combination of two or more.
Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene
Ethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl
Non-ionic surfactants such as ruesters; alkylbenzene sulfonates, alkyl naphthalates
Phthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid
Anionic surfactants such as ester salts; amphoteric interfaces such as alkylbetaines and amino acids
An activator etc. are mentioned, These may be individual or may combine 2 or more types.
Examples of the organic solvent include isopropanol, benzyl alcohol, and ethylene glycol.
Coal monoethyl ether, ethylene glycol monobutyl ether, propylene glycol
Alcohols such as alcohol may be mentioned, and these may be used alone or in combination of two or more. Present
Image processing is usually performed at a development temperature of 10 to 50 ° C., such as immersion development, spray development, brush development, and supersonic.
It is performed by a method such as wave development.
After development, usually at a temperature of 150 to 250 ° C. for 5 to 60 minutes, hot plate, convection
Heat using a heating device such as a microwave oven or a high-frequency heating machine, and perform a thermosetting treatment.

In the production of optical members such as a color filter and a liquid crystal panel, the present invention has the above-described configuration, and is excellent in photosensitivity, alkali developability, adhesion, plate-making property, and pigment dispersibility. It is the photosensitive resin composition which can be used conveniently.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “
It means “mass%”.
In the following Examples and Comparative Examples, various physical properties and the like were measured as follows.
<Weight average molecular weight>
HLC-8220GP with polystyrene as standard and tetrahydrofuran as eluent
The weight average molecular weight was measured by a GPC (gel permeation chromatography) method using C (manufactured by Tosoh Corp.), column TSKgel SuperHZM-M (manufactured by Tosoh Corp.).
<Solid content>
About 1 g of the polymer solution is weighed into an aluminum cup, about 3 g of acetone is added and dissolved,
It was naturally dried at room temperature. And hot air dryer (Espec Co., Ltd., trade name: PHH-
101) and dried at 160 ° C. under vacuum for 3 hours, and then allowed to cool in a desiccator, and the weight was measured. From the weight loss, the solid content of the polymer solution was calculated.
<Acid value>
3 g of the resin solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and 0.1 N KOH aqueous solution is used as a titrant, and an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) The acid value of the polymer solution was measured, and the acid value per gram of solid content was determined from the acid value of the solution and the solid content of the solution.
Synthesis example 1
(Synthesis of (C-2) alkali-soluble resin solution 1)
A separable flask with a cooling tube as a reaction vessel was charged with 80 parts of propylene glycol monomethyl ether acetate (PGMEA) and 80 parts of propylene glycol monomethyl ether (PGME), and the temperature was raised to 90 ° C. in a nitrogen atmosphere. 1 as benzylmaleimide 5 parts, cyclohexyl methacrylate 13 parts, acrylic acid 62 parts, PGMEA 10 parts, PGME 10 parts, perbutyl O (trade name, manufactured by NOF Corporation) 1.2 parts, dropping system 2 as n-dodecyl mercaptan 2 parts, 5 parts of PGMEA, and 5 parts of PGME were each continuously fed over 4 hours. Then, after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours. Once cooled to room temperature, 100 parts of glycidyl methacrylate, 0.27 parts of Antage W400 (manufactured by Kawaguchi Chemical Co., Ltd.), 0.54 parts of triethylamine, 150 parts of PGMEA, 150 parts of PGME are added, and the oxygen concentration is 7%. The temperature was raised to 110 ° C. while bubbling the oxygen-nitrogen mixed gas adjusted to, and the reaction was continued for 14 hours to obtain an alkali-soluble resin (C-2) solution 1.
When various physical properties of the obtained resin solution 1 were measured, the weight average molecular weight was 13,000, the solid content obtained by drying at 160 ° C. under vacuum was 25%, and the solid content obtained by the titration method was The acid value was 85 mgKOH / g.
(Creation of pigment dispersion)
12.9 parts of PGMEA, 0.4 parts of Disparon DA-7301 as a dispersant, C.I. I. Pigment Green 36 (Monastral Green 6Y-CL, manufactured by Heubach) 1.5 parts, and C.I. I. Pigment Yellow 150 (Yellow Pigment E4GN-GT, manufactured by Lanxess) (1.0 part) was mixed and dispersed with a paint shaker for 3 hours to obtain Pigment Dispersion 1.

Example 1
14 parts of pigment dispersion 1, 3.5 parts of (C-2) alkali-soluble resin solution 1, 0.37 parts of (C-1) polyparavinylphenol (Maruzen Petrochemicals molecular weight 10,000), (A) 1.25 parts of dipentaerythritol hexaacrylate as a radical polymerizable compound, (B) Irgacure 369 (manufactured by Ciba Specialty Chemicals) as a radical polymerizable photopolymerization initiator 0.63 parts, PGMEA 5 parts as solvent, PGM 5 The negative photosensitive resin composition 1 was obtained by mixing the parts. The ratio of (C-1) polyparavinylphenol in the (C) alkali-soluble resin in the photosensitive resin product is 30% by mass.
Subsequently, it spin-coated on the 10 square cm glass substrate, prebaked at 90 degreeC for 3 minute (s), and produced the thin film with a dry film thickness of 2 micrometers.

<Evaluation of solvent resistance>
The substrate on which the thin film has been formed is exposed to 100 mJ / cm 2 with a UV exposure apparatus (manufactured by Topcon, trade name: TME-150RNS), photocured, and further heated at 200 ° C. for 30 minutes to be cured. Was completed. The obtained glass substrate was immersed in 100 g of N-methylpyrrolidone (NMP) at room temperature for 2 hours, and then the glass substrate was taken out and the absorbance of NMP was measured, which was 1.5.
<Development evaluation>
The negative photosensitive resin composition 1 was spin-coated on a 10 cm square glass substrate and prebaked at 90 ° C. for 3 minutes to prepare a thin film having a dry film thickness of 2 μm. Next, exposure is performed at 100 mJ / cm 2 through a 15 μm line & space photomask, and development is performed with 0.05% KOH aqueous solution for 20 seconds using a spin developing machine (product name: ADE-3000S, manufactured by Actes). When the obtained pattern was observed with a laser microscope, no pattern peeling was observed, and no residue was observed in the unexposed area, and a good pattern was formed.

(Example 2)
(C-2) Alkali-soluble resin solution 1 2.25 parts, (C-1) Polyparavinylphenol Except for changing to 0.69 parts, the same operation as in Example 1 was performed, and the solvent resistance and developability were changed. Evaluation was performed. (C) The ratio of polyparavinylphenol in the alkali-soluble resin is 55% by mass. The absorbance of NMP was 1.4. Further, although slight pattern peeling was observed, no residue was observed in the unexposed area, and the developability was slightly good.

(Comparative Example 1)
(C-2) The same operation as in Example 1 was carried out except that only 5 parts of the alkali-soluble resin liquid 1 was used and (C-1) polyparavinylphenol was not used. Was evaluated. The absorbance of NMP was 3.5, which was inferior to Examples 1 and 2. Further, NMP was clearly colored green, and it was visually confirmed that the coloring material had melted.
No pattern peeling was observed, no residue was observed in the unexposed area, and developability was good.

(Comparative Example 2)
(C-2) The same operation as Example 1 was carried out except that 1 part of (C-1) polyparavinylphenol was used without using the alkali-soluble resin solution 1, and evaluation of solvent resistance and developability. Went. Although the absorbance of NMP was 1.4, pattern peeling was remarkable and developability was poor.

The alkali-soluble resin of the present invention and the photosensitive resin composition using the resin are excellent in photosensitivity, alkali developability and adhesion, and resists for forming members in the field of electronic information, such as solder resists, etching resists, It is suitable for interlayer insulating materials, plating resists, color filter resists, and is excellent in solvent resistance and developability, and is particularly suitable for forming a color filter pixel (colored layer).

Claims (7)

A photosensitive resin composition comprising (A) a radically polymerizable monomer, (B) a radically polymerizable photopolymerization initiator and (C) an alkali-soluble resin, wherein (C) the alkali-soluble resin is (C-1 ) 5% by mass to 95% by mass of a resin having a vinylphenol monomer unit and 5% by mass to 95% by mass of another alkali-soluble resin in the alkali-soluble resin. Negative photosensitive resin composition. (C-1) The negative photosensitive resin according to claim 1, wherein the alkali-soluble resin having a vinylphenol monomer unit is a polymer containing 50% by mass or more of a vinylphenol monomer unit. Resin composition. (C-1) The negative photosensitive resin composition according to claim 1, wherein the alkali-soluble resin having a vinylphenol monomer unit is polyvinylphenol. (C-2) The other alkali-soluble resin is an alkali-soluble resin containing a monomer unit containing an acid group and a polymerizable double bond and another monomer unit capable of copolymerization. The negative photosensitive resin composition of claim | item 1-3. 5. The negative photosensitive resin composition according to claim 4, wherein the (C-2) other alkali-soluble resin is an alkali-soluble resin further containing an N-substituted maleimide monomer unit. A cured product obtained by forming a cured product of the negative photosensitive resin composition according to claim 1 on a substrate. A color filter, wherein a cured product of the negative photosensitive resin composition according to claim 1 is formed on a substrate.