JP4671016B2 - Thermosetting composition, antihalation film for solid-state imaging device and method for forming the same, and solid-state imaging device - Google Patents

Description

  The present invention relates to a thermosetting composition, an antihalation film for a solid-state imaging device, a method for forming the same, and a solid-state imaging device.

  Solid-state imaging devices include a MOS (Metal Oxide Semiconductor) type, a CCD (Charge Coupled Device) type, and the like, each of which includes a one-dimensional solid-state imaging device and a two-dimensional solid-state imaging device. An example of the former is a facsimile, for example, and an example of the latter is a video camera.

  In recent years, such a solid-state imaging device has been digitized, and further higher image quality is being demanded in combination with high-quality orientation of users. An example is an increase in the number of pixels of a digital camera.

  Solid-state imaging devices include those for black and white and color. Among them, color solid-state imaging devices are manufactured by forming three color filters on a substrate on which a solid-state imaging device is formed. The solid-state image sensor is used as it is, but the surface (corresponding to each solid-state image sensor) is further provided with a convex lens (microlens) to increase the sensitivity (condensing ability) (Patent Literature). 1).

  In order to equip a solid-state image sensor with a color filter and / or a microlens, a fine pattern is formed by using a lithography technique using a photosensitive material.

  The microlens is formed by forming a solid-state image sensor and, if necessary, applying a transparent resin on a substrate on which a color filter is formed to flatten the surface, and then forming a microlens material made of a photosensitive resin. Is applied, the pattern of the lens is exposed, developed and rinsed, and the remaining transparent resin block is heated to slightly melt and contract, thereby forming each block into the shape of a convex lens.

  When exposing and patterning a photosensitive material in the color filter and microlens formation processes, the part that you do not want to expose is exposed to diffusely reflected light from the underlying substrate, and the actual pattern size is different from the target size. There is a problem that a phenomenon that becomes a thing, that is, "halation" occurs.

  When such a phenomenon occurs in the case of a microlens, the shape of the lens becomes uneven, flickering occurs, and the image quality is adversely affected. This has become a more serious problem as the cell size of the solid-state imaging device becomes smaller as recently.

  With respect to this problem, there is known a method for preventing halation by forming an antireflection film that absorbs radiation used for lithography on a solid-state imaging device substrate to suppress reflection. In this example, a CCD protective film containing polyglycidyl methacrylate as a main component and trimellitic acid as a curing agent is blended with a dye (see Patent Document 2). However, such an anti-reflective coating is not a non-volatile material because the anti-halation effect is remarkably reduced due to sublimation of a part of the dye from the anti-reflective coating during the baking process performed to crosslink and solidify the applied material. However, this dye has a drawback that the dye floats on the protective film and the microlens formed on the antihalation film is not formed in a desired shape.

  Further, a halation containing a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, an epoxy group-containing radical polymerizable compound, a mono and / or diolefin unsaturated compound, and a radiation absorbing compound A prevention film has been proposed (see Patent Document 3). This antihalation film assumes a process with a temperature history after formation of 150 ° C. or less, and has not been verified for heat resistance at temperatures exceeding 150 ° C.

However, in a color solid-state image pickup element, a color filter material using a dye substrate has been conventionally used, so that the color filter can be cured at a relatively low temperature of about 150 ° C. However, with the recent demand for higher precision, pigment-based materials have been generally used, and thus a curing temperature of 180 ° C. or higher is required in the forming process (see Patent Documents 4 to 6). .) Therefore, in the solid-state image pickup device for color, the antihalation film formed prior to the color filter is exposed to a higher temperature than ever before.
In recent years, technologies for mounting a CCD camera in an automobile and assisting driving have been studied. However, since the CCD camera used for that purpose is used under severer usage conditions than the conventional one, An anti-halation film capable of withstanding a high temperature of 230 ° C. or higher is required because a high-temperature molding process is required.

It is known that conventionally known antihalation film materials do not function as an antihalation film when exposed to such a high temperature. This phenomenon is presumed to be caused by the fact that in a high temperature region exceeding 150 ° C., the radiation absorbing agent blended in the antihalation film material sublimates and dissipates, so that the radiation absorbing ability is remarkably lowered.
Japanese Patent Laid-Open No. 3-223702 Japanese Patent No. 2956210 Japanese Patent Laid-Open No. 06-289201 JP-A-11-211911 JP-A-11-258415 JP 2000-111172 A

  The present invention has been made in view of the circumstances as described above, and its purpose is to effectively suppress irregular reflection light from the base substrate in an exposure process when forming a color filter or a microlens in a solid-state imaging device. Thermosetting composition suitable for forming antihalation film having high heat resistance, method for forming antihalation film using the same, antihalation film formed by the method, and antihalation An object of the present invention is to provide a solid-state imaging device having a film.

  Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above object of the present invention, first, (1) an epoxy group, (2) a radiation absorbing group and (3) months acetal ester structure of carboxylic acid, ketal ester structure Contact carboxylic acid And a thermosetting composition comprising a polymer having at least one structure selected from the group consisting of thioacetal ester structures of carboxylic acids.

The above object of the present invention is secondly achieved by a method for forming an antihalation film of a solid-state imaging device, characterized in that it includes at least the following steps [1] and [2].
[1] A step of forming a coating film of the thermosetting composition on a substrate.
[2] A step of heat-treating the coating film.

  Furthermore, the object of the present invention is achieved thirdly by the antihalation film of the solid-state image sensor formed by the above method, and fourthly by the solid-state image sensor having the antihalation film.

  According to the present invention, in the exposure process when forming a color filter or a microlens in a solid-state imaging device, irregularly reflected light from the base substrate can be effectively suppressed, the visible light transmittance is high, and high heat resistance is achieved. A thermosetting composition suitable for forming an antihalation film, a method for forming an antihalation film using the composition, an antihalation film formed by the method, and a solid-state imaging device having the antihalation film Provided.

  The antihalation film of the present invention can effectively suppress irregularly reflected light from the base substrate in the exposure process when forming a color filter or a microlens on the antihalation film, and has high heat resistance. Therefore, the color filter and microlens formed on the antihalation film of the solid-state imaging device of the present invention can have a desired shape and size.

  Furthermore, since the solid-state imaging device of the present invention has the antihalation film described above, and the color filter and microlens formed on the antihalation film have a desired shape and size, the solid-state imaging of the present invention The element is excellent in reliability.

  The present invention will be described below. First, each component of the thermosetting composition of this invention is explained in full detail.

Copolymer [A]
Polymer used in the present invention, (1) an epoxy group, (2) a radiation absorbing group, and (3) months acetal ester structure of carboxylic acid, thioacetal ester structure ketal ester structure Contact and carboxylic acid of the carboxylic acid It has at least one structure selected from the group consisting of:

The polymer is preferably [A] (a1) an epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “compound (a1)”), (a2) a radiation-absorbing radical polymerizable compound (hereinafter referred to as “compound”). (a2) "may be referred to.), and (a 3-2) polymerizable with at least one structure selected from the ketal ester structure or Ranaru group acetal ester structure and a carboxylic acid of the carboxylic acid- Or a monomer mixture copolymer (hereinafter also referred to as “copolymer [A]”) containing a saturated compound (hereinafter sometimes referred to as “compound (a3)”), or Or [B] Copolymerization of a monomer mixture containing (a1) an epoxy group-containing unsaturated compound, (a2) a radiation-absorbing radical polymerizable compound and (a3-1) a polymerizable unsaturated polycarboxylic anhydride Coalescence It is an addition copolymer having an acetal structure or a thioacetal structure of carboxylic acid, obtained by adding a vinyl ether compound or a vinyl thioether compound to the acid anhydride group of [A].

Copolymer [A] is a structural unit derived from the compound (a1), 10 to 70 wt%, good Mashiku is contained 20 to 60 wt%. A copolymer having this constitutional unit of less than 10% by weight tends to lower the moisture and heat resistance of the resulting antihalation film. On the other hand, when it exceeds 70 weight%, it exists in the tendency for the storage stability of a curable composition to fall.

  The compound (a1) is a compound having an epoxy group and a polymerizable carbon-carbon double bond in one molecule. Specifically, for example, glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, α-ethyl Glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxy acrylate Examples include heptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.

  Among these, glycidyl methacrylate, methyl glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are copolymerizable and reactive. The antihalation film obtained is preferably used from the viewpoint of increasing the heat resistance and hardness. These (a1) epoxy group-containing unsaturated compounds are used alone or in combination.

Copolymer used in the present invention [A] is a structural unit derived from the compound (a2), 1 to 40 wt%, good Mashiku is contained 3-30 wt%. If this structural unit is less than 1% by weight, the antihalation performance may be insufficient. On the other hand, when this structural unit exceeds 40% by weight, the film formability of the coating film tends to deteriorate.

Radiation absorbing structure compound (a2) has is, 400 nm or less wavelength, particularly absorbing light of a wavelength of 365 nm, and light in the visible light region not substantially absorbed,

Under following formula (1)

A skeleton having a benzotriazole structure represented by :

The radical polymerizable compound having such a radiation absorbing structure, under following formula (2), (3) and (4) of the compounds represented by the

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, a hydroxy group, a halogen atom, a carboxyl group or an alkoxycarbonyl group. R ³ represents an alkylene group having 2 to 10 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group. ]

[Wherein, R ^{4 is} as defined above and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[Wherein, R ³ , R ⁴ and R ⁵ are the same as defined above, and R ⁶ represents an alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group. ]
Is used .

In the above formula (2), examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso group. -Butyl group, tert-butyl group, n-pentyl group, tert-pentyl group (amyl group), n-hexyl group, tert-hexyl group, n-heptyl group, tert-heptyl group, n-octyl group, di-tert -A linear or branched alkyl group having 1 to 8 carbon atoms such as an octyl group can be exemplified. Among these, a tert-alkyl group having 4 to 8 carbon atoms such as a methyl group, a tert-butyl group, a tert-pentyl group, a tert-heptyl group, and a ditert-octyl group is preferable.

Examples of the alkoxyl group having 1 to 8 carbon atoms represented by R ¹ and R ² include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, and a tert-butoxy group. And a linear or branched alkoxyl group having 1 to 8 carbon atoms such as a group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group and n-octyloxy group.

Examples of the halogen atom represented by R ¹ and R ² include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Of these, a chlorine atom is preferred.

Examples of the alkylene group having 2 to 10 carbon atoms represented by R ³ include an ethylene group, trimethylene group, propylene group, tetramethylene group, 1,1-dimethyltetramethylene group, butylene group, octamethylene group, octylene group, Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms such as a decamethylene group and a decylene group. Among these, an ethylene group, a propylene group, and the like are preferable.

In the above formulas (3) and (4), the alkyl group having 1 to 8 carbon atoms represented by R ⁵ is the same as the alkyl group having 1 to 8 carbon atoms represented by R ¹ and R ² in the above (2). The same thing is preferable.

In the above formula (4), examples of the alkylene group having 1 to 4 carbon atoms which may be substituted with the hydroxyl group represented by R ⁶ include a methylene group, an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group, 1 A linear or branched alkylene group having 1 to 4 carbon atoms such as a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group or a 1,1-dimethylethylene group, and these groups substituted with a hydroxyl group; Can be mentioned. Among these, those having 2 to 3 carbon atoms such as ethylene group, trimethylene group and 2-hydroxytrimethylene group are preferable.

  In the present invention, among the radiation absorbing radical polymerizable compounds represented by the above formulas (2) to (4), the radiation absorbing radical polymerizable compound represented by the formula (2) is particularly preferably used.

Furthermore, among the radiation-absorbing radically polymerizable compounds represented by the formula (2), when R ¹ is a hydrogen atom or a chlorine atom and is a chlorine atom, it is substituted at the 5-position of the benzotriazole ring, ² is a hydrogen atom, a methyl group or a tert-alkyl group having 4 to 8 carbon atoms (more preferably a hydrogen atom, a methyl group or a tert-butyl group), and R ³ is 2 to 10 carbon atoms (more preferably 2 to 2 carbon atoms). The radiation-absorbing radically polymerizable compound which is an alkylene group of 3) and R ⁴ is a hydrogen atom or a methyl group is particularly preferable. Specific examples of such a radiation-absorbing radical polymerizable compound include 2- (2′-hydroxy-5′-acryloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacrylic). Roxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacryloxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -5 -Chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methacryloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3) '-Tert-butyl-5'-acryloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy- '- methacryloxypropyl hexylphenyl) -2H- benzotriazole, and 2- (5'-2'-hydroxy-3'-tert-butyl-methacryloxyethyl phenyl) -2H- benzotriazole.

  Among these, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (hereinafter referred to as “monomer (a2-1)”) represented by the following formula (5) And 2- (2′-hydroxy-3′-tert-butyl-5′-methacryloxyethylphenyl) -2H-benzotriazole represented by the following formula (6) (hereinafter referred to as “monomer ( a2-2) ") is preferably used. In the present invention, the radiation-absorbing radically polymerizable compound may be used alone or in combination of two or more.

Copolymer used in the present invention [A] is a structural unit derived from the compound (a3), 5 to 60 wt%, good Mashiku is contained 10 to 50 wt%. A copolymer having this constitutional unit of less than 5% by weight tends to lower the heat-and-moisture resistance of the resulting antihalation film. On the other hand, when it exceeds 60% by weight, the storage stability of the curable composition tends to be lowered.

The above compound (a3) is a (a 3-2) the polymerizable unsaturated compound having at least one structure selected from the ketal ester structure or Ranaru group acetal ester structure and a carboxylic acid of the carboxylic acid.

  These can be used individually or in mixture of 2 or more types.

The (a3-2), e.g., a norbornene compound having a ketal ester structure acetal ester structure or a carboxylic acid of the carboxylic acid, having acetal or ketal ester structure of a carboxylic acid (meth) and acrylic acid ester compound it can.

Specific examples of the norbornene compound having the acetal ester structure or ketal ester structure include, for example, 2,3-di-tetrahydropyran-2-yloxycarbonyl-5-norbornene,
2,3-di-trimethylsilanyloxycarbonyl-5-norbornene,
2,3-di-triethylsilanyloxycarbonyl-5-norbornene,
2,3-di-t-butyldimethylsilanyloxycarbonyl-5-norbornene,
2,3-di-trimethylgermyloxycarbonyl-5-norbornene,
2,3-di-triethylgermyloxycarbonyl-5-norbornene,
2,3-di-t-butyldimethylgermyloxycarbonyl-5-norbornene,
2,3-di-t-butyloxycarbonyl-5-norbornene,
2,3-di-benzyloxycarbonyl-5-norbornene,
2,3-di-tetrahydrofuran-2-yloxycarbonyl-5-norbornene 2,3-di-tetrahydropyran-2-yloxycarbonyl-5-norbornene 2,3-di-cyclobutyloxycarbonyl-5-norbornene,
2,3-di-cyclopentyloxycarbonyl-5-norbornene,
2,3-di-cyclohexyloxycarbonyl-5-norbornene,
2,3-di-cycloheptyloxycarbonyl-5-norbornene,
2,3-di-1-methoxyethoxycarbonyl-5-norbornene,
2,3-di-1-t-butoxyethoxycarbonyl-5-norbornene,
2,3-di-1-benzyloxyethoxycarbonyl-5-norbornene,
2,3-di- (cyclohexyl) (ethoxy) methoxycarbonyl-5-norbornene,
2,3-di-1-methyl-1-methoxyethoxycarbonyl-5-norbornene,
2,3-di-1-methyl-1-i-butoxyethoxycarbonyl-5-norbornene,
2,3-di- (benzyl) (ethoxy) methoxycarbonyl-5-norbornene and the like;

  Specific examples of the (meth) acrylic acid ester compound having the acetal ester structure or ketal ester structure include 1-ethoxyethyl (meth) acrylate, tetrahydro-2H-pyran-2-yl (meth) acrylate, 1- (Cyclohexyloxy) ethyl (meth) acrylate, 1- (2-methylpropoxy) ethyl (meth) acrylate, 1- (1,1-dimethyl-ethoxy) ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) ) Acrylate and the like.

Of these, (meth) acrylic acid ester compounds having an acetal ester structure or a ketal ester structure of carboxylic acid are preferred, and in particular, 1-ethoxyethyl methacrylate, tetrahydro-2H-pyran-2-yl methacrylate, 1- (cyclohexyloxy) ) ethyl methacrylate, 1- (2-methyl-propoxy) ethyl methacrylate, 1- (1,1-dimethyl - ethoxy) ethyl methacrylate, 1- (cyclohexyloxy) ethyl methacrylate click relay bets are preferred.

  These may be used alone or in combination.

  As described above, the copolymer [A] used in the present invention is a copolymer of a monomer mixture containing the compound (a1), the compound (a2), and the compound (a3) as essential components. The monomer mixture may optionally contain (a4) an olefinically unsaturated compound other than (a1), (a2) and (a3) (hereinafter sometimes referred to as “compound (a4)”). it can.

  By using such a compound (a4) as a copolymerization component together with the compound (a1), the compound (a2), and the compound (a3), the storage stability of the thermosetting composition can be improved, and the resulting antihalation film can be obtained. Advantages such as improved heat resistance can be obtained.

  The copolymer [A] of the present invention can contain a structural unit derived from the compound (a4), preferably 50% by weight or less, more preferably 40% by weight or less.

  When this structural unit exceeds 50% by weight, the antihalation performance and chemical resistance of the resulting antihalation film may be insufficient.

  The olefinic unsaturated compound (a4) is a compound having no epoxy group and no radiation-absorbing group and having a polymerizable carbon-carbon double bond. Acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, dicarboxylic acid diester, indene derivative, dicarbonylimide derivative, hydroxyalkyl ester, aromatic unsaturated compound, conjugated diene And other unsaturated compounds.

Specific examples thereof include alkyl methacrylate esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate;
Examples of acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate;

Examples of cyclic alkyl esters of methacrylic acid include, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, cyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate (as a common name in the art, methacrylic acid). Acid dicyclopentanyl), dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, etc .;

Examples of cyclic alkyl esters of acrylic acid include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, cyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (a common name in the art, acrylic Acid dicyclopentanyl), dicyclopentanyloxyethyl acrylate, isoboronyl acrylate, etc .;

Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate;
Examples of acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;

Examples of indene derivatives include indene and 1-methylindene;
Examples of dicarbonylimide derivatives include phenylmaleimide, benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N- Succinimidyl-3-maleimidopropionate, N- (9-acridyl) maleimide and the like;

Examples of hydroxyalkyl esters include 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;
Examples of the aromatic unsaturated compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like;
Examples of conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like;

Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

  Of these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid cyclic alkyl esters, aromatic unsaturated compounds, conjugated dienes, and dicarbonylimide derivatives are preferably used, especially styrene, t-butyl methacrylate, and methacrylic acid diesters. Cyclopentanyl, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, phenylmaleimide, and N-cyclohexylmaleimide are particularly preferably used from the viewpoint of copolymerization reactivity and heat resistance of the resulting antihalation film.

  These compounds (a4) are used alone or in combination.

  The copolymer [A] used in the present invention is a monomer mixture containing the compound (a1), the compound (a2) and the compound (a3) and, if necessary, the compound (a4), preferably in a solvent. It can be synthesized by radical polymerization in the presence of a polymerization initiator.

  Examples of the solvent used for the production of the copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol alkyl ether acetates. , Propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters and the like.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethanol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;

Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate;
Examples of diethylene glycol monoalkyl ethers include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Examples of diethylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

Examples of propylene glycol monoalkyl ethers include propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether;
Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate;

Examples of propylene glycol alkyl ether propionates include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, Ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2- Methyl hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propo Methyl cyanoacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxy Butyl lopionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropion Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Among these, alcohols, ethylene glycol alkyl ether acetates, diethylene glycols, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates are preferred, and benzyl alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred.

  As the polymerization initiator used in the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as; benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; dimethylxanthogen Xanthogens such as sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

Preferred examples of the copolymer [A] used in the present invention, For example,

Scan styrene / tetrahydro -2H- pyran-2-yl (meth) acrylate / (meth) acrylic acid tricyclo [5.2.1.0 ^2,6] decan-8-yl / (meth) acrylic acid glycidyl / (single Monomer a2-1 or monomer a2-2) copolymer,

Styrene / 1- (cyclohexyloxy) ethyl (meth) acrylate / (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / (meth) acrylic acid glycidyl / (monomer a2 -1 or monomer a2-2) copolymer,
Styrene / tetrahydro-2H-pyran-2-yl (meth) acrylate / phenylmaleimide / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,

Styrene / 2,3-di-tetrahydropyran-2-yloxycarbonyl-5-norbornene / (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / (meth) acrylic acid Glycidyl / (monomer a2-1 or monomer a2-2) copolymer,
Styrene / 1- (cyclohexyloxy) ethyl (meth) acrylate / cyclohexylmaleimide / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,

Styrene / tetrahydro-2H-pyran-2-yl (meth) acrylate / cyclohexylmaleimide / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,
Styrene / 2,3-di-tetrahydropyran-2-yloxycarbonyl-5-norbornene / cyclohexylmaleimide / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,

Butadiene / styrene / 1- (cyclohexyloxy) ethyl (meth) acrylate / (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / (meth) acrylic acid glycidyl / (single amount) Body a2-1 or monomer a2-2) copolymer,
Butadiene / tetrahydro-2H-pyran-2-yl (meth) acrylate / (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / (meth) acrylic acid glycidyl / (monomer) Body a2-1 or monomer a2-2) copolymer,

t-butyl (meth) acrylate / tetrahydro-2H-pyran-2-yl (meth) acrylate / maleic anhydride / (meth) acrylic acid-6,7-epoxyheptyl / (monomer a2-1 or monomer a2-2) copolymer,
Styrene / tetrahydro-2H-pyran-2-yl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,

p-methoxystyrene / tetrahydro-2H-pyran-2-yl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer etc,

Is mentioned.

And those of them preferred,

Scan styrene / tetrahydro -2H- pyran-2-yl (meth) acrylate / (meth) acrylic acid tricyclo [5.2.1.0 ^2,6] decan-8-yl / (meth) acrylic acid glycidyl / (single Monomer a2-1 or monomer a2-2) copolymer,
Styrene / tetrahydro-2H-pyran-2-yl (meth) acrylate / phenylmaleimide / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,

Styrene / 2,3-di-tetrahydropyran-2-yloxycarbonyl-5-norbornene / (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / (meth) acrylic acid Glycidyl / (monomer a2-1 or monomer a2-2) copolymer,
Styrene / 1- (cyclohexyloxy) ethyl (meth) acrylate / cyclohexylmaleimide / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,

Styrene / tetrahydro-2H-pyran-2-yl (meth) acrylate / cyclohexylmaleimide / glycidyl (meth) acrylate / (monomer a2-1 or monomer a2-2) copolymer,
Styrene / 2,3-di - tetrahydropyran-2-yl-oxy-5- norbornene / cyclohexyl maleimide / (meth) acrylic acid glycidyl / (monomer a2-1 or monomer a2-2) copolymer,
Is mentioned.

Addition copolymer [B]
Further, in the present invention, (a3-1) to anhydride groups in the copolymer obtained by copolymerizing an unsaturated polyvalent carboxylic acid anhydride, a vinyl ether compound or a vinyl thioether compound, the absence of an acid catalyst, The addition copolymer [B] obtained by addition at room temperature to about 100 ° C. can be used as an equivalent of the copolymer [A].

Examples of (a3-1) include unsaturated polycarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4-tetrahydrophthalic anhydride;
Etc.
Of these (a3-1), maleic anhydride is particularly preferable. These preferable (a3-1) have high copolymerization reactivity and are effective in increasing the heat resistance and surface hardness of the protective film obtained. These can be used alone or in admixture of two or more.
Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, 2-pentyl vinyl ether, 3- Examples include pentyl vinyl ether, i-pentyl vinyl ether, neo-pentyl vinyl ether, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, and preferably ethyl vinyl ether and i-propyl vinyl ether. N-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 3,4-dihydro-2H-pyran and the like.

  Examples of the vinyl thioether compound include methyl vinyl thioether, ethyl vinyl thioether, i-propyl vinyl thioether, n-propyl vinyl thioether, n-butyl vinyl thioether, i-butyl vinyl thioether, t-butyl vinyl thioether, and n-pentyl vinyl. Thioether, 2-pentylvinylthioether, 3-pentylvinylthioether, i-pentylvinylthioether, neo-pentylvinylthioether, 3,4-dihydro-2H-thiopyran, 3,4-dihydro-2-methoxy-2H-thiopyran, etc. Preferably, ethyl vinyl thioether, i-propyl vinyl thioether, n-propyl vinyl thioether, n-butyl vinyl thioether, i-butyl vinyl thioether Le, t- butyl vinyl thioether, 3,4-dihydro -2H- thiopyran and the like.

The ratio of vinyl ether or vinyl thioether to be added is 1.8 times to 2.5 times mol, preferably 1.9 times to 2.4 times mol, particularly preferably 2 times to the acid anhydride group. It is 0.0 times mole or more and 2.4 times mole or less.
If the amount of vinyl ether or vinyl thioether is less than 1.8 times mol, the storage stability will be poor, and if it exceeds 2.5 times mol, the hardness of the resulting composition will be low.

  Since this addition copolymer [B] has an acetal structure or a thioacetal structure of a carboxylic acid, it has no or little free carboxyl group. For example, the copolymer [A] in the copolymer [A] It is preferably 20 mol% or less of the acid anhydride group.

As such an addition copolymer [B], for example,
(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with ethyl vinyl ether in double moles relative to the acid anhydride group Added copolymer,
(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with n-propyl vinyl ether to 2 acid anhydride groups Double mole added copolymer,

(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with i-propyl vinyl ether to acid anhydride group Double mole added copolymer,
(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with n-butyl vinyl ether to 2 acid anhydride groups Double mole added copolymer,

(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with i-butyl vinyl ether to acid anhydride group Double mole added copolymer,
(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with t-butyl vinyl ether to 2 acid anhydride groups Double mole added copolymer,

Glycidyl acrylate / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 3,4-dihydro-2H-pyran as acid anhydride A copolymer added twice in moles to the group,
(Meth) acrylic acid glycidyl / itaconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 2-fold moles of ethyl vinyl ether relative to the acid anhydride group Added copolymer,

(Meth) acrylic acid glycidyl / itaconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with i-propyl vinyl ether to 2 acid anhydride groups Double mole added copolymer,
Glycidyl acrylate / Itaconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 3,4-dihydro-2H-pyran as acid anhydride A copolymer added twice in moles to the group,

(Meth) acrylic acid glycidyl / citraconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with ethyl vinyl ether in double moles relative to the acid anhydride group Added copolymer,
(Meth) acrylic acid glycidyl / citraconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with i-propyl vinyl ether to acid anhydride group Double mole added copolymer,

Glycidyl acrylate / citraconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 3,4-dihydro-2H-pyran as acid anhydride A copolymer added twice in moles to the group,
Glycidyl acrylate / cis-1,2,3,4-tetrahydrophthalic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with ethyl A copolymer in which vinyl ether is added in a molar amount of 2 times with respect to the acid anhydride group,

(Meth) acrylate glycidyl / cis-1,2,3,4-tetrahydrophthalic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer i A copolymer obtained by adding 2-fold mol of propyl vinyl ether to an acid anhydride group,
(Meth) acrylic acid glycidyl / cis-1,2,3,4-tetrahydrophthalic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer 3 , 4-Dihydro-2H-pyran, a copolymer obtained by adding a 2-fold mole to the acid anhydride group, and a copolymer obtained by adding a corresponding thioether instead of each vinyl ether in these copolymers

Of these addition copolymers [B], more preferably,
(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with ethyl vinyl ether in double moles relative to the acid anhydride group Added copolymer,
(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with n-propyl vinyl ether to 2 acid anhydride groups Double mole added copolymer,

(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with i-propyl vinyl ether to acid anhydride group Double mole added copolymer,
(Meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with n-butyl vinyl ether to 2 acid anhydride groups Double mole added copolymer,

Glycidyl acrylate / maleic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 3,4-dihydro-2H-pyran as acid anhydride A copolymer added twice in moles to the group,
(Meth) acrylic acid glycidyl / itaconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 2-fold moles of ethyl vinyl ether relative to the acid anhydride group Added copolymer,

(Meth) acrylic acid glycidyl / itaconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with i-propyl vinyl ether to 2 acid anhydride groups Double mole added copolymer,
Glycidyl acrylate / Itaconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 3,4-dihydro-2H-pyran as acid anhydride A copolymer added twice in moles to the group,

Glycidyl acrylate / citraconic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with 3,4-dihydro-2H-pyran as acid anhydride A copolymer added twice in moles to the group,
Glycidyl acrylate / cis-1,2,3,4-tetrahydrophthalic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer with ethyl A copolymer in which vinyl ether is added in a molar amount of 2 times with respect to the acid anhydride group,
(Meth) acrylate glycidyl / cis-1,2,3,4-tetrahydrophthalic anhydride / N-cyclohexylmaleimide / styrene / (monomer a2-1 or monomer a2-2) copolymer i A copolymer obtained by adding 2-fold mole of propyl vinyl ether to the acid anhydride group.

The copolymer [A] and [B] used in the present invention preferably have a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of 2 × 10 ^{3 to} 5 × 10 ⁵ , more preferably 5 × 10. ³ to 1 × 10 ⁵ . If the Mw is less than 2 × 10 ³ , the resulting antihalation film may have insufficient heat resistance and surface hardness. On the other hand, if it exceeds 5 × 10 ⁵ , the flatness of the film surface may be insufficient.

<Other ingredients>
The curable composition of the present invention contains the above-mentioned copolymer [A] or addition copolymer [B] as an essential component, but may contain other components as necessary. Examples of such other components include an adhesion aid, a curing accelerator, a surfactant, and an ultraviolet absorber.

[Adhesion aid]
Adhesion aids can be added to improve the adhesion between the antihalation film to be formed and the substrate.

  As such an adhesion assistant, for example, a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group is preferably used. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

  The use ratio of the adhesion assistant is preferably 30 parts by weight or less, more preferably 0.1 to 25 parts by weight, particularly preferably 100 parts by weight of the copolymer [A] or the addition copolymer [B]. 1 to 20 parts by weight. When the proportion of the adhesion aid used exceeds 100 parts by weight, the heat resistance of the resulting antihalation film may be insufficient.

[Curing accelerator]
A curing accelerator can be added to accelerate the reaction of the copolymer [A] or the addition copolymer [B]. Examples of such a curing accelerator include compounds having a heterocyclic structure containing a secondary nitrogen atom or a tertiary nitrogen atom.

  Specific examples of such compounds include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, benzimidazole, isocyanuric acid, and derivatives thereof. Among these, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methyl- Preferred are imidazole derivatives such as 1- (2′-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 ′-(3 ″, 5 ″ -diaminotriazinyl) ethyl] imidazole, and benzimidazole. Most preferably, 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole and the like are used.

  These compounds can be used as a curing accelerator alone or in combination of two or more.

  The curing accelerator is preferably used in a proportion of 5 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the copolymer [A] or the addition copolymer [B].

[Surfactant]
Surfactant can be added in order to improve the applicability | paintability of a composition.

  Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, and the like.

  Specific examples of these include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like. Examples include ethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Examples of polyoxyethylene dialkyl esters include polyoxyethylene dilaurate and polyoxyethylene distearate.

  As a commercially available product of such a surfactant, as a fluorine-based surfactant, product names manufactured by BM CHIMIE, Inc .: BM-1000, BM-1100, manufactured by Dainippon Ink & Chemicals, Inc. F172, F173, F183, manufactured by Sumitomo 3M Co., Ltd. Trade name: Florard FC-135, FC-170C, FC-430, FC-431, FC4430, FC4432, manufactured by Asahi Glass Co., Ltd. Product Name: Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC -104, SC-105, SC-106, etc., manufactured by Neos Co., Ltd. Trade names: FTX-216D, FTX-218, FTX-20D, etc .;

Product name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, Shin-Etsu manufactured by Toray Dow Corning Silicone Co., Ltd. Product name: KP341 manufactured by Chemical Industry Co., Ltd. Product name: F-top EF301, EF303, EF352, etc. manufactured by Shin-Akita Kasei Co., Ltd .;
As a nonionic surfactant, Kyoeisha Chemical Co., Ltd. brand name: (meth) acrylic acid type copolymer polyflow No.57, the same No.1. 90, no. 95 etc. can be mentioned.

  These surfactants can be used alone or in combination of two or more.

  The proportion of the surfactant used varies depending on the type and the type and ratio of each component constituting the curable composition, but is 100 parts by weight of the copolymer [A] or the addition copolymer [B]. The amount is preferably 5 parts by weight or less, more preferably 0.0001 to 2 parts by weight, and still more preferably 0.001 to 0.5 parts by weight.

Preparation of Thermosetting Composition The thermosetting composition of the present invention is dissolved in an appropriate solvent and used in a solution state. For example, a thermosetting composition in a solution state can be prepared by mixing the copolymer [A] or the addition copolymer [B] and other components added as necessary at a predetermined ratio. it can.

  The thermosetting composition of the present invention is prepared by uniformly dissolving or dispersing each component, preferably in a suitable solvent. As the solvent to be used, those which dissolve or disperse each component of the composition and do not react with each component are used.

  As such a solvent, the thing similar to what was illustrated as a solvent used when manufacturing the above-mentioned copolymer [A] can be used. The amount of the solvent used is preferably the content of the total solid content in the thermosetting composition of the present invention (the total amount of the copolymer [A] and other components added as necessary). The range is 1 to 50 parts by weight, more preferably 5 to 40 parts by weight.

  A high boiling point solvent can be used in combination with the above solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate.

  The amount used when the high boiling point solvent is used in combination is preferably 90 parts by weight or less, more preferably 80 parts by weight or less, based on the total amount of the solvent.

  The solution of the thermosetting composition prepared as described above is filtered, for example, using a Millipore filter having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm. Can also be used.

Next, a method for forming the antihalation film of the solid-state image sensor of the present invention using the thermosetting composition of the present invention will be described.

  The method for forming an antihalation film for a solid-state imaging device according to the present invention includes at least the following steps [1] and [2].

  [1] A step of forming a coating film of the thermosetting composition on a substrate.

  [2] A step of heat-treating the coating film.

Hereinafter, it demonstrates in order.
[1] A step of forming a coating film of the thermosetting composition on a substrate.

  In the method for forming an antihalation film for a solid-state imaging device of the present invention, first, it is subjected to a step of forming a coating film of the thermosetting composition of the present invention on a substrate. The coating film is formed on the substrate by applying the thermosetting composition of the present invention on the substrate.

  In the present invention, a substrate such as glass, quartz, silicon, or resin can be used as the substrate. Examples of the resin include resins such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, and cyclic olefin ring-opening polymers and hydrogenated products thereof.

  As a coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method or the like can be adopted. The slit die coating method is preferable.

  Then, a coating film can be formed on a board | substrate by removing a solvent. In the present invention, it is not necessary to provide the solvent removal step independently, and the solvent may be naturally dissipated during the process, and the solvent removal step may be performed by the following “[2] heat-treating the coating film. You may carry out as one with a process. Note that this does not prevent the adoption of a separate solvent removal step. When carrying out the solvent removal step separately, it can be carried out by holding at a temperature of room temperature to about 150 ° C. for an appropriate time.

  Here, the thickness of the coating film is preferably 0.1 to 5 μm, and more preferably 0.3 to 3 μm. This value should be understood as the film thickness after removal of the solvent.

[2] Step of heat-treating the coating film The coating film formed on the substrate as described above can be used as an antihalation film of the solid-state imaging device of the present invention by performing a heat-treatment step. .

  The heating temperature is preferably 150 to 250 ° C. The heating time can be appropriately set depending on the type of heating equipment used, etc. For example, when a hot plate is used as the heating equipment, it is about 3 to 15 minutes, and when a clean oven is used, 15 to 30 minutes. Can be about.

  This heat treatment step may be performed in one step, or may be performed by a combination of two or more steps.

Anti-halation film of solid-state image sensor The anti-halation film of the solid-state image sensor of the present invention formed as described above is a base substrate in an exposure process when a color filter or a microlens is formed on the anti-halation film. Can effectively suppress irregular reflection light from the light source and has high heat resistance. Therefore, the color filter and microlens formed on the antihalation film of the solid-state imaging device of the present invention can have a desired shape and size.

  In addition, the thickness of the antihalation film of the solid-state imaging device is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm.

  When this value is less than 0.1 μm, the effect of suppressing irregularly reflected light from the base substrate may be insufficient, while it is not necessary to increase the thickness beyond 5 μm.

Solid-state image sensor A solid-state image sensor of the present invention has the antihalation film described above.

  Since the color filter and microlens formed on the antihalation film have a desired shape and size, the solid-state imaging device of the present invention is excellent in reliability.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 13 parts by weight of styrene, 20 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 40 parts by weight of glycidyl methacrylate and 22 parts by weight of cyclohexylmaleimide, monomer (a2-1) (trade name, manufactured by Otsuka Chemical Co., Ltd.) "RUVA-93") 5 parts by weight were charged and the atmosphere was replaced with nitrogen. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The solid content concentration of the obtained polymer solution was 33.0% by weight. Moreover, the weight average molecular weight (Mw) of the copolymer (A-1) was 6,000.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether, followed by 45 parts by weight of glycidyl methacrylate and anhydrous maleic acid. 15 parts by weight of acid, 15 parts by weight of N-cyclohexylmaleimide and 15 parts by weight of styrene, and 10 parts by weight of monomer (a2-1) (trade name “RUVA-93” manufactured by Otsuka Chemical Co., Ltd.) were substituted with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 70 ° C., and polymerization was carried out for 5 hours while maintaining this temperature. Thereafter, 30 parts by weight of i-propyl vinyl ether was added dropwise and reacted for 2 hours while stirring to obtain a polymer solution containing the copolymer (A-2). The resulting polymer solution had a solid content concentration of 33.2% by weight. Moreover, the weight average molecular weight (Mw) of the copolymer (A-2) was 15,000.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether, followed by 45 parts by weight of glycidyl methyl methacrylate, After charging 15 parts by weight of acid, 15 parts by weight of N-cyclohexylmaleimide and 15 parts by weight of styrene, and 10 parts by weight of monomer (a2-2), and substituting with nitrogen, the mixture was stirred gently to bring the temperature of the reaction solution to 70 ° C. The polymer was polymerized for 5 hours while maintaining this temperature to obtain a polymer solution containing the copolymer (A-3). The resulting polymer solution had a solid content concentration of 33.2% by weight. Moreover, the weight average molecular weight (Mw) of the copolymer (A-3) was 4,000.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether, followed by 45 parts by weight of methyl glycidyl methacrylate, anhydrous After charging 15 parts by weight of maleic acid, 12.5 parts by weight of N-cyclohexylmaleimide, 12.5 parts by weight of styrene, and 15 parts by weight of monomer (a2-2) and substituting with nitrogen, the reaction solution was stirred gently. The temperature was raised to 70 ° C., and this temperature was maintained for polymerization for 5 hours. Thereafter, 30 parts by weight of i-propyl vinyl ether was added dropwise and reacted for 2 hours with stirring to obtain a polymer solution containing the copolymer (A-4). The resulting polymer solution had a solid content concentration of 33.1% by weight. Moreover, the weight average molecular weight (Mw) of the copolymer (A-4) was 10,000.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether, followed by 45 parts by weight of glycidyl methacrylate and acrylic acid. After 15 parts by weight, 15 parts by weight of N-cyclohexylmaleimide and 25 parts by weight of styrene were purged with nitrogen, the mixture was gently stirred to raise the temperature of the reaction solution to 70 ° C., and this temperature was maintained for 5 hours for polymerization. As a result, a polymer solution containing the copolymer (A-3) was obtained. The resulting polymer solution had a solid content concentration of 33.2% by weight. Moreover, the weight average molecular weight (Mw) of the copolymer (R-1) was 6,000.

Example 1
The amount corresponding to 100 parts by weight (solid content) of the copolymer [A-1] of the polymer solution containing the copolymer [A-1] synthesized in Synthesis Example 1 is 100 parts by weight of diethylene glycol ethyl methyl ether. After dilution, 5 parts by weight of γ-glycidoxypropylethoxysilane as an adhesion assistant and 0.075 parts by weight of SH28PA (silicone surfactant, Toray Dow Corning Silicone Co., Ltd.) as a surfactant The thermosetting composition [S-1] was obtained by adding and stirring sufficiently.

Formation of the antihalation film On the glass substrate, the curable composition [S-1] prepared above was applied using a spin coater, and heat-treated at 230 ° C. for 6 minutes using a hot plate to obtain a film thickness of 1.6 μm. An antihalation film was formed.

Evaluation of antihalation film (1) Light transmittance For a substrate having an antihalation film formed as described above, a spectrophotometer 150-20 type double beam (manufactured by Hitachi, Ltd.) was used to measure 365 nm and 400 nm. The transmittance was measured. Next, after additional heating at 180 ° C., 230 ° C. and 250 ° C. for 20 minutes on a hot plate, the transmittances at 365 nm and 400 nm were measured in the same manner. These values are shown in Table 1. When the transmittance of 365 nm is 70% or less, it can be said that the anti-halation performance, that is, the effect of suppressing irregularly reflected light from the base substrate in the exposure process when forming a color filter or a microlens is excellent. Further, when the transmittance at 400 nm is 95% or more, it can be said that the visible light transmittance is good.

  As for the antihalation film formed in Example 1, it can be seen that the antihalation performance and the visible light transmittance are excellent both before and after the additional heating.

(2) Patterning of microlens material A microlens material (trade name “MFR-380”, manufactured by JSR Corporation) was applied to the substrate having the antihalation film formed as described above using a spinner. Thereafter, it was pre-baked on a hot plate at 100 ° C. for 90 seconds to form a coating film having a thickness of 2.5 μm. The obtained coating film was subjected to a Nikon NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) through a pattern mask having 4.0 μm dots and 2.0 μm space pattern. Exposure was performed at an exposure amount of 200 J / m ² , and development was performed by a rocking immersion method at 23 ° C. for 1 minute in a 1 wt% aqueous tetramethylammonium hydroxide solution. Next, the substrate was rinsed with running ultrapure water at 23 ° C. for 30 seconds and dried to form a pattern on the antihalation film on the substrate.

  The microlens pattern formed here was observed using a scanning electron microscope (manufactured by Hitachi Sokki Service Co., Ltd., model “S-4200”). The shape of the pattern is shown in Table 1. At this time, if the antihalation performance of the antihalation film (performance for suppressing irregular reflection light from the base substrate) is sufficient, the pattern side surface is formed on a plane as shown in the schematic explanatory view of FIG. The However, if the anti-halation performance is insufficient, a standing wave due to halation influences at the time of exposure, and the pattern side surface is formed in a wave shape as shown in FIG.

  Further, the substrate having the antihalation film formed as described above is further heated at 230 ° C. for 20 minutes on a hot plate, and then, on the antihalation film subjected to the additional heat treatment, in the same manner as described above. Thus, a microlens pattern was formed. Similarly, the observation result of the pattern shape by the electron microscope is shown in Table 1.

Examples 2-4
In Example 1, instead of the solution containing the copolymer [A-1] as the copolymer [A], 100 parts by weight of a solution containing the copolymer described in Table 1 was added in terms of solid content, The addition amount of SH28PA (silicone surfactant, manufactured by Toray Dow Corning Silicone Co., Ltd.), which is a surfactant, and γ-glycidoxypropylethoxysilane, which is an adhesion assistant, is as shown in Table 1, respectively. Otherwise, the same procedure as in Example 1 was performed.
The thickness of the antihalation film formed in each example is shown in Table 1.
The evaluation results are shown in Table 1.

Comparative Example 1
In Example 1, instead of the solution containing the copolymer [A-1], 100 parts by weight of a solution containing the copolymer [R-1] synthesized in Comparative Synthesis Example 1 was added in terms of solid content. In addition, the same procedure as in Example 1 was performed except that 10 parts by weight of Tinuvin 234 (manufactured by Ciba Geigy Co., Ltd.) as a radiation absorber was added. The antihalation film formed here had a thickness of 1.6 μm.
The evaluation results are shown in Table 1.

  The antihalation film of Comparative Example 1 has good antihalation performance before the additional heating, but the antihalation performance after the additional heating is remarkably lowered, and it is understood that the heat resistance is poor.

It is explanatory drawing of the schematic diagram which shows the shape of a micro lens pattern.

Claims (6)

(A1) an epoxy group-containing unsaturated compound, (a2) a radiation-absorbing radical polymerizable compound, and (a3-2) at least one structure selected from the group consisting of an acetal ester structure of a carboxylic acid and a ketal ester structure of a carboxylic acid A copolymer of a monomer mixture containing a polymerizable unsaturated compound having 10 to 70% by weight of a structural unit derived from the epoxy group-containing unsaturated compound (a1) and the radiation absorbing property. A copolymer containing 1 to 40% by weight of a structural unit derived from the radically polymerizable compound (a2) and 5 to 60% by weight of a structural unit derived from the polymerizable unsaturated compound (a3-2). And the radiation-absorbing radically polymerizable compound (a2) is a compound represented by each of the following formulas (2), (3) and (4): That is at least one selected from the group, the thermosetting composition characterized by.

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, a hydroxy group, a halogen atom, a carboxyl group or an alkoxycarbonyl group. It represents a group, R ³ is and R ⁴ represents an alkylene group having 2 to 10 carbon atoms is a hydrogen atom or a methyl group. ]

[Wherein, R ^{4 is} as defined above and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[Wherein, R ³ , R ⁴ and R ⁵ are the same as defined above, and R ⁶ represents an alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group. ] Acid anhydride of copolymer of monomer mixture containing (a1) epoxy group-containing unsaturated compound, (a2) radiation-absorbing radical polymerizable compound and (a3-1) polymerizable unsaturated polyvalent carboxylic acid anhydride An addition copolymer having an acetal structure or a thioacetal structure of a carboxylic acid obtained by adding a vinyl ether compound or a vinyl thioether compound to a physical group, which is derived from the epoxy group-containing unsaturated compound (a1). 10 to 70% by weight of the structural unit, 1 to 40% by weight of the structural unit derived from the radiation-absorbing radical polymerizable compound (a2), and the polymerizable unsaturated polycarboxylic acid anhydride (a3-1). The acetal structure or thioacetate of a carboxylic acid obtained by adding a vinyl ether compound or vinyl thioether compound to the acid anhydride group of Over the structural unit having a Le structure containing addition polymer containing 5 to 60 wt%, and the formula according to the radiation absorbing radical polymerizable compound (a2) is according to claim 1 (2), (3 ) And (4), which is at least one selected from the group consisting of the compounds represented by each of the thermosetting compositions. The thermosetting composition according to claim 1 or 2, which is used for forming an antihalation film of a solid-state imaging device. A method for forming an antihalation film for a solid-state imaging device, comprising at least the following steps [1] and [2].
[1] A step of forming a coating film of the composition according to claim 3 on a substrate,
[2] A step of heat-treating the coating film. An antihalation film for a solid-state imaging device formed by the method according to claim 4. A solid-state imaging device having the antihalation film according to claim 5.

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