JP2013036034A - Curable resin composition and application of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition using a fluorine-containing compound that is excellent in solubility to the system and controlled in generation of pinholes, wherein the fluorine-containing compound uses a well-known common fluorine-containing monomer, but uses neither a heavy metal nor a long-chain perfluoroalkyl group.SOLUTION: The curable resin composition includes a block copolymer (A) the below, a solvent (B) and a resin (C), wherein a transparent liquid without getting cloudy is obtained when 1 mass% of the block copolymer (A) is mixed with propylene glycol monomethyl ether acetate.

Description

  The present invention relates to a curable resin composition containing a block copolymer and use thereof.

  Photocurable resin compositions that are polymerized by ultraviolet rays or visible rays are used in various applications such as paints, adhesives, and coating agents. Among them, the resist composition is used as a photoresist composition or a color resist composition for a color filter of a liquid crystal display device, and is required to form a particularly uniform coating film during coating.

In order to improve the uniformity of the coating film, it is necessary that the leveling property of the composition is excellent.
In order to impart leveling properties, a fluorine-containing compound containing a perfluoroalkyl group is added to the composition. At that time, in order to further improve the leveling property, the ratio of the monomer containing the perfluoroalkyl group is increased, the structure of the monomer containing the perfluoroalkyl group is devised (Patent Document 1), or block polymerization is performed. In order to strengthen the function of fluorine, patent documents 2 and 3 have been developed.

  However, when a fluorine-containing compound is added for the purpose of imparting leveling properties, the fluorine-containing compound remains on a part of the uniformly coated surface due to the leveling properties. The presence of the fluorine-containing compound on the surface after coating causes the fluorine to be repelled by the influence of the function of the fluorine, so that uniformity may not be maintained and pinholes may occur.

When the function of fluorine is increased by increasing the ratio of the monomer containing a perfluoroalkyl group, the solubility in the composition itself is deteriorated. In addition, there is a problem that the player plays as described above.
In addition, a device in which a structure of a monomer containing a perfluoroalkyl group is devised has a problem in terms of cost because its synthesis route is complicated.
In addition, when performing block polymerization, first of all, there is a problem when following a synthetic route including heavy metals in the method, and even if another route is used, the property of the block polymerization method In addition, when the perfluoroalkyl group is gathered in the copolymer, there is a tendency that repelling tends to occur and the solubility in the composition itself is deteriorated.
In addition, the block copolymer described in Patent Document 3 using another route does not use heavy metal and has a good surface tension reducing ability, but in this document, there is a perfluoropolymer among the copolymers. There is no description about dealing with deterioration in solubility due to alkyl grouping, no specific description about the curable resin composition, particularly about the solubility in the curable resin composition There is no description.

JP 2008-115258 A JP 2006-063132 A JP 2008-297522 A

  The present invention is a fluorine-containing compound that does not use a heavy metal, does not use a long-chain perfluoroalkyl group, and uses a generally known fluorine-containing monomer, and has excellent solubility in the system and suppresses repelling. It aims at providing the curable resin composition using this.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by adding a specific block copolymer to the curable resin composition, and have completed the present invention.

The present invention provides the following curable resin composition.
A curable resin composition comprising the following block copolymer (A), solvent (B) and resin (C).
Block copolymer (A): This is a block copolymer that, when mixed with propylene glycol monomethyl ether acetate at a concentration of 1% by mass, yields a transparent liquid without clouding, and is represented by the following formula (2). A structural unit derived from the compound represented by formula (3), a structural unit derived from the compound represented by formula (3) below, and a residue of the compound represented by formula (1) below.
The symbols in the formula have the following meanings.
X ¹ : hydrogen atom, halogen atom, amino group, P (O) (OH) ₂ group or monovalent organic group.
Y ¹ : hydrogen atom, halogen atom, alkali metal atom, NH ₄ group or monovalent organic group.
R ¹ : a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms.
R ² : a hydrogen atom or a monovalent group.
A: —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
R ^4: a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group having 1 to 5 carbon atoms of 1 to 5 carbon atoms.
B: —O— or —NR ⁷ —.
R ⁵ , R ⁶ , R ⁷ : each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula (r).
−Q ² −Rf ² (r)
Rf ¹ and Rf ² : each independently a C 1-6 perfluoroalkyl group.
Q ¹ and Q ^{2 are} each independently a single bond or a divalent linking group.

About the said block copolymer (A), what is Fn calculated | required by the following formula ((alpha)) is 1-120.
Formula (α) Fn = Mw × (Fw / Fm) × Cn
The symbols in the formula have the following meanings.
Mw: mass average molecular weight of the block copolymer (A).
Fw: Fa / (Fa + Fb)
Fm: molecular weight of the compound represented by formula (3).
Fa: Use amount of the compound represented by the formula (3).
Fb: the amount of the compound represented by formula (2) used.
Cn: carbon number of Rf ¹ of the compound represented by formula (3). However, in the case of Rf ² is present, this is also including.

This invention can also provide the solution which contains the said block copolymer (A) in a solvent (B) as curable resin composition.
In the present invention, the solvent (B) preferably contains propylene glycol monomethyl ether acetate.

  The present invention also provides a resist composition using the curable resin composition.

  Moreover, this invention provides the said resist composition as a color resist material used for a color filter.

  The present invention also provides a color filter prepared using the resist composition.

  By including the specific block copolymer, the surface tension of the curable resin composition of the present invention is greatly reduced. From this, it is considered that the leveling property of the composition is improved, unevenness at the time of application is less likely to occur, and a uniform coating film can be formed. In addition, since the specific block copolymer exhibits good solubility in propylene glycol monomethyl ether acetate, the composition does not cause white turbidity or the like, and has an effect that it does not repel after application. Since the resist composition using the curable resin composition of the present invention can form a uniform coating film without white turbidity, it can be suitably used as a color filter.

  In the present specification, the compound represented by the formula (1) is also referred to as a compound (1). The compounds represented by other formulas may be expressed similarly.

  The curable resin composition of this invention is characterized by including a block copolymer (A). The block copolymer (A) according to the present invention comprises a block unit containing a structural unit derived from the compound (2), that is, a repeating unit derived from the compound (2), and a structural unit derived from the compound (3), that is, a compound ( It has a block segment containing a repeating unit derived from 3) and a residue of compound (1).

  In the present specification, the compound represented by the formula (1) is also referred to as a compound (1). The compounds represented by other formulas may be expressed similarly.

[Compound (1)]
Compound (1) is a compound having a thiocarbonylthio group (thiocarbonylthio compound). By using the compound (1) as a chain transfer agent, the residue of the compound (1) is introduced at the end of the main chain of the block copolymer (A).
In the formula (1), X ¹ is a hydrogen atom, a halogen atom, an amino group, a P (O) (OH) ₂ group or a monovalent organic group.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

In the present invention, the “organic group” means a group containing a carbon atom.
The monovalent organic group for X ¹ is not particularly limited. Preferred organic groups include alkyl groups, alkylthio groups, alkoxy groups, dialkylamino groups, saturated hydrocarbon ring groups, unsaturated hydrocarbon ring groups, aromatic hydrocarbon ring groups, aromatic heterocyclic groups and the like.
The carbon atom in each organic group may have a substituent. Here, that a carbon atom has a substituent means that an atom or group other than a hydrogen atom is bonded to the carbon atom. Examples of the substituent include a halogen atom, an alkyl group, a hydroxy group, a carbonyl group, a carboxy group, an alkoxy group, an alkylthio group, a dialkylamino group, an amide group, and a nitro group.

  The alkyl group, alkylthio group, and alkoxy group each preferably have 1 to 10 carbon atoms, and particularly preferably have 1 to 5 carbon atoms. These groups may be linear or branched.

The alkyl group in the dialkylamino group preferably has 1 to 10 carbon atoms, and particularly preferably has 1 to 5 carbon atoms. The alkyl group may be linear or branched, and is preferably linear.
In the dialkylamino group, the two alkyl groups substituted with a nitrogen atom may have the same structure or different structures, and the ends may be bonded to each other to form a ring together.

Among the above organic groups, the ring in the ring group (saturated hydrocarbon ring group, unsaturated hydrocarbon ring group, aromatic hydrocarbon ring group, aromatic heterocyclic group) may be a single ring or 2 It may be a condensed ring in which two or more rings are condensed.
These cyclic groups preferably have 4 to 12 carbon atoms, and particularly preferably have 4 to 10 carbon atoms.
Examples of the saturated hydrocarbon ring group include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the unsaturated hydrocarbon ring group include a cyclopentenyl group and a cyclohexenyl group.
Examples of the aromatic hydrocarbon ring group include a phenyl group, a naphthyl group, and an anthranyl group.
Examples of the aromatic heterocyclic group include a pyrrolyl group, a thienyl group, a furyl group, and a pyridyl group.

In the present invention, X ¹ in the formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, an aromatic carbon It is preferably a hydrogen ring group or an aromatic heterocyclic group (however, the carbon atom in each of the above groups may have a substituent).

In the present invention, the atom bonded to carbon of the thiocarbonyl group in X ¹ is preferably a hetero atom.
Examples of the hetero atom include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and a silicon atom, and among them, an oxygen atom or a nitrogen atom is preferable.

In the present invention, X ¹ is preferably a group represented by the following formula (4) or the following formula (5).
R ⁸ —O— (4)

[Wherein, R ⁸ is an alkyl group having 1 to 10 carbon atoms; R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

The alkyl group in R ⁸ , R ⁹ and R ¹⁰ may be linear or branched. 1-10 are preferable and, as for carbon number of this alkyl group, 1-5 are more preferable.
At least one of R ⁹ and R ¹⁰ is preferably an alkyl group, and more preferably both are alkyl groups.

Y ^{1 in the} compound (1) is a hydrogen atom, a halogen atom, an alkali metal atom, an NH ₄ group or a monovalent organic group.
Examples of the halogen atom for Y ¹ include the same as those mentioned for X ¹ above.
Examples of the alkali metal atom in Y ¹ include a lithium atom, a sodium atom, and a potassium atom, and a sodium atom is preferable.
When Y ¹ is an alkali metal atom or NH ₄ group, compound (1) exists as a salt.
The monovalent organic group for Y ¹ is not particularly limited, and examples thereof include the same organic groups as those described for X ¹ .
In the present invention, Y ¹ is preferably a monovalent organic group having a thiocarbonyl group, and particularly preferably a group represented by the following formula (6) or the following formula (7).

[Wherein, X ² and X ³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, or an aromatic hydrocarbon. A cyclic group or an aromatic heterocyclic group (however, the carbon atom in each of the aforementioned groups may have a substituent); ]

As the halogen atom, alkyl group, alkylthio group, alkoxy group, dialkylamino group, saturated hydrocarbon ring group, unsaturated hydrocarbon ring group, aromatic hydrocarbon ring group or aromatic heterocyclic group in X ² and X ³ , the same as those mentioned above for X ¹ can be mentioned.

In the present invention, X ¹ in the formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, an aromatic carbonization. A hydrogen ring group or an aromatic heterocyclic group (wherein the carbon atom in each group may have a substituent), and Y ¹ is represented by the formula (6) or the formula (7). It is preferable that it is group represented.
That is, the compound (1) is preferably represented by the following formula (1 ′) or the following formula (1 ″).

[Wherein, X ^{11 to} X ¹³ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, or an aromatic hydrocarbon. A cyclic group or an aromatic heterocyclic group (however, the carbon atom in each of the aforementioned groups may have a substituent); ]

Examples of X ^{11 to} X ¹³ include the same as X ² and X ³ .

Particularly preferred as the compound (1) is a compound represented by the following formula (1-1), the following formula (1-2) or the following formula (1-3).

[Wherein, R ⁸ is an alkyl group having 1 to 10 carbon atoms; R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

R ⁸ in the formula (1-1) is the same as R ⁸ in the formula (4), the two R ⁸ may be the same, respectively, may be different.
R ^9, R ¹⁰ in the formula (1-2) to (1-3) is the same as R ^9, R ¹⁰ of each of the formulas (5), the two R ^9, R ¹⁰ are the same respectively May be different or different.

[Compound (2)]
The compound (2) is a polymerizable compound having at least one polymerizable group.
R ¹ in Formula (2) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms.
The halogen atom, the same groups in the X ¹ can be mentioned.
The alkyl group in R ¹ may be linear or branched. 1-4 are preferable and, as for carbon number of this alkyl group, 1 is especially preferable.
The fluoroalkyl group is a group in which one or more hydrogen atoms of the alkyl group are substituted with a fluorine atom.
R ¹ is preferably a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

A in Formula (2) is —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
The alkyl group in —NR ³ — may be linear or branched.
A is preferably -O-.

R ² in the formula (2) is a hydrogen atom or a monovalent group.
The monovalent group is not particularly limited, and for example, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, an aromatic hydrocarbon ring group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a silyl group (trialkyl) Silyl group, etc.), alkoxy group, isocyanate group and the like.

Examples of the compound (2) include the following compounds (2-1) to (2-8).
_{CH 2 = C (R) -COO} -R '... (2-1)
_{CH 2 = C (R) -COO-} (Ak) m - (O) l -Cyc ... (2-2)
_{CH 2 = C (R) -COO-} (Ak) m - (AkO) n -R '... (2-3)
_{CH 2 = C (R) -COO-} (Ak) m - (AkO) n -Cyc ... (2-4)
_{CH 2 = C (R) -COO-} (Ak) m - (AkO) n - (Ak) m -OCO-C (R) = CH 2 ... (2-5)
_{CH 2 = C (R) -COO-} (Ak) m -OP (O) (OH) 2 ... (2-6)
_{CH 2 = C (R) -COO-} (Ak) m -Si ((O) p R ') 3 ... (2-7)
_{CH 2 = C (R) -CONR} -R '... (2-8)

In the above formulas (2-1) to (2-8), R and R ′ are each independently a hydrogen atom or a chain aliphatic hydrocarbon group having 1 to 22 carbon atoms.
The aliphatic hydrocarbon group may be linear or branched. The hydrogen atom in the group may be substituted with a hydroxy group, a halogen atom, a carboxy group or an isocyanate group. The carbon atom in the group may be substituted with -O-, -NR- (R is as defined above) or -CO-.
Cyc is a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group or an aromatic hydrocarbon ring group. The carbon atom in each of these groups may be substituted with —O— or —NR— (R is as defined above).
Ak is an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear or branched. When a plurality of Ak are present in one molecule, each Ak may be the same or different.
l is an integer of 0 or 1.
m is an integer of 0 or 1.
n is an integer of 1-50.
p is an integer of 0 or 1.

  These compounds are commercially available, Kyoeisha Chemical Co., Ltd. light ester, light acrylate, Kojin Co., Ltd. monomer product, Showa Denko Co., Ltd., Nippon Oil & Fat Co., Bremer, Shin-Nakamura Chemical Co., Ltd. NK ester, Chisso Corporation Each brand product such as Silaplane can be used or its equivalent.

Among these, more specifically preferred structures include the following compounds.
Methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, isostearyl methacrylate, behenyl methacrylate, cyclohexyl methacrylate , T-butylcyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate.

  Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, lauryl acrylate, isomyristyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate , Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, isobornyl acrylate.

  2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, glycerin methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, glycerin acrylate, polyethylene glycol Methacrylate (EO number average 1 to 45), polyethylene glycol acrylate (EO number: average 1 to 45), methoxy polyethylene glycol methacrylate (EO number average 1 to 45), methoxy polyethylene glycol acrylate (EO number average 1 to 45), polypropylene Glycol methacrylate (PO number average 1 to 22), Polypropylene glycol acrylate (PO number average 1 to 1) 2), poly (ethylene glycol-propylene glycol) methacrylate (EO number average 1 to 22, PO number average 1 to 22), poly (ethylene glycol-propylene glycol) acrylate (EO number average 1 to 22, PO number average 1 to 2) 22), polyethylene glycol dimethacrylate (EO number average of 1 to 22), polyethylene glycol diacrylate (EO number average of 1 to 22), poly (ethylene glycol-tetramethylene glycol) methacrylate (EO number average of 1 to 22, BO number average) 1-22), poly (ethylene glycol-tetramethylene glycol) acrylate (EO number average 1-22, BO number average 1-22), poly (propylene glycol-tetramethylene glycol) methacrylate (PO number average 1-22, BO Number average 1-22 , Poly (propylene glycol-tetramethylene glycol) acrylate (PO number average 1-22, BO number average 1-22), ethoxydiethylene glycol monoacrylate octoxypolyethylene glycol polypropylene glycol methacrylate (EO number average 1-22, PO number average 1) -12), octoxy polyethylene glycol polypropylene glycol acrylate (EO number average 1 to 22, PO number average 1 to 12), lauroxy polyethylene glycol methacrylate (EO number average 1 to 22), lauroxy polyethylene glycol acrylate (EO number average) 1 to 22), stearoxy polyethylene glycol methacrylate (EO number average 1 to 22), phenoxy polyethylene glycol acrylate (EO number average 1 to 22), Alkoxy polyethylene glycol methacrylate (EO average number 1-22).

  Glycidyl methacrylate, glycidyl acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl succinic acid, 2-acrylic acid Leuoxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentyl glycol acrylic acid benzoate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate.

  n-butoxyethyl methacrylate, butoxydiethylene glycol methacrylate, phenoxyethyl methacrylate, butoxyethyl acrylate, ethoxy-diethylene glycol acrylate, 2-ethylhexyl-diglycol acrylate phenoxyethyl acrylate, phenoxy polyethylene glycol acrylate (EO number average 1 to 22), 2-hydroxy -3-phenoxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N, N-dimethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropylacrylamide , Acryloylmorpholine, N-isopropyl acrylate Amide, N, N-diethylacrylamide, 2-methacryloyloxyethyl isocyanate, methacrylic acid-2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl, diacetone acrylamide, acryloxymethyltrimethylsilane, (3 -Acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) trichlorosilane.

In the above, EO number average, PO number average, and BO number average are an ethylene oxide repeating unit (—CH ₂ CH ₂ O—), a propylene oxide repeating unit, and a butylene oxide repeating contained in one molecule of the compound, respectively. The average number of moles of units.

  Compound (2) preferably has a molecular weight of less than 10,000, and more preferably less than 5,000. When the molecular weight is less than 10,000, the solubility of the resulting block copolymer in various solvents is improved.

The compound (2) can be appropriately selected from known compounds according to the performance required for the block copolymer.
In particular, it is preferable to use one or more monomers containing an AkO structure as in the above formulas (2-3) to (2-5), and among them, Ak preferably has 2 to 4 carbon atoms. .

[Compound (3)]
The compound (3) is a polymerizable compound having at least one polymerizable group and a perfluoroalkyl group.
Rf ¹ in formula (3) is a perfluoroalkyl group having 1 to 6 carbon atoms. The perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms. The perfluoroalkyl group may be linear or branched, and is preferably linear.
The number of carbon atoms of Rf ¹ is 4-6 are preferable, 6 is more preferable.

R ⁴ in the formula (3) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. Specifically, R 4 in the formula (2) The same thing as ¹ is mentioned.
R ⁴ is preferably a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group.

Q ¹ in the formula (3) is a single bond or a divalent linking group.
If Q ¹ is a single bond, a CR ⁵ R ⁶ on the left end for Q ¹ in formula (3), and the Rf ¹ at the right end for Q ¹ means that directly bonded.

As the divalent linking group, a divalent chain aliphatic hydrocarbon group, a divalent cyclic aliphatic hydrocarbon group, a divalent aromatic ring group, a divalent heterocyclic group, -O-, —S—, —NH—, —NR ¹¹ — (wherein R ¹¹ is an alkyl group having 1 to 5 carbon atoms), —SO ₂ —, —PO ₂ —, —CH═N—, —N Examples include groups such as ═N—, —N (O) ═N—, —CO—, —CH (OH) —, and combinations of these groups. For example, the combination of —CO— and —O— is —COO—, and the combination of —NR ¹¹ — and —SO ₂ — is —NR ¹¹ —SO ₂ —. These groups may be combined with another group.
Moreover, these groups may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a halogen atom, and a cyano group.

Q ¹ is preferably a divalent linking group, and the divalent linking group is preferably a divalent chain aliphatic hydrocarbon group, —COO— or a combination thereof.
The divalent chain aliphatic hydrocarbon group may be linear or branched.
Examples of the divalent chain aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, but an alkylene group is preferable. As the alkylene group, a linear alkylene group having 1 to 5 carbon atoms is preferable.

R ⁵ and R ^{6 in} formula (3) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula (r).
−Q ² −Rf ² (r)
Rf ² is a perfluoroalkyl group having 1 to 6 carbon atoms. Rf ² may be the same as Rf ^1, and may be the same as or different from Rf ² . Also, if there are multiple Rf ² in the compound (3) it can be different even these are respectively the same.
Q ² is a single bond or a divalent linking group. Q ² is, like can be mentioned as the Q ^1, may be the same or different and Q ^1. Also, if there are multiple Q ² 'in the compound (3) it can be different even these are respectively the same.
In the formula (3), R ⁵ and R ⁶ may be the same or different. R ⁵ and R ⁶ are preferably both hydrogen atoms, or one of them is preferably a hydrogen atom and the other is a group represented by the formula (r), and both are particularly preferably hydrogen atoms.

B in the formula (3) is —O— or —NR ⁷ —.
R ⁷ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a group represented by the formula (r). R ⁷ is the same groups as those with the R ⁵ and R ^6, may be different even identical to R ⁵ and R ^6.
As B, —O— or —NR ⁷ — in which R ⁷ is a group represented by the formula (r) is preferable, and —O— is particularly preferable.

Examples of the compound (3) include the following compounds, but are not limited thereto.
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 4 -F,
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 6 -F,
_{CH 2 = CH-COO-CH} 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO-CH} 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 3 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 3 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = CH-COO- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F,

_{CH 2 = CH-CONH- (CH} 2) 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH- (CH} 2) 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH- (CH} 2) 3 - (CF 2) 4 -F,
_{CH 2 = CH-CONH- (CH} 2) 3 - (CF 2) 6 -F,
_{CH 2 = CH-CONH-CH} 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH-CH} 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 3 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 3 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = CH-CONH- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F

_{CH 2 = CH-CONH-CH} (COO-C 2 H 4 (CF 2) 6 F) -CH 2 -COO-C 2 H 4 - (CF 2) 6 F
_{CH 2 = C (CH 3)} -CONH-CH (COO-C 2 H 4 (CF 2) 6 F) -CH 2 -COO-C 2 H 4 - (CF 2) 6 F
_{CH 2 = CHCON (CH 2 COOC} 2 H 4 (CF 2) 6 F)
_{CH 2 = CH-CONH-CH} (COO-C 2 H 4 (CF 2) 4 F) -CH 2 -COO-C 2 H 4 - (CF 2) 4 F
_{CH 2 = C (CH 3)} -CONH-CH (COO-C 2 H 4 (CF 2) 4 F) -CH 2 -COO-C 2 H 4 - (CF 2) 4 F
_{CH 2 = CHCON (CH 2 COOC} 2 H 4 (CF 2) 4 F)

As the compound (3), the following compounds are particularly preferable.
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 - (CF 2) 6 -F,

  As a method for producing the block copolymer (A), the compound (2) is polymerized in a state where the compound (1) is present in the system, and the compound (3) is further polymerized to the obtained polymer. Is preferred. JP-A-2008-297522 can be referred to as the production method. At that time, as an index for obtaining a block copolymer (A), that is, a block copolymer in which a transparent liquid can be obtained without clouding when mixed with propylene glycol monomethyl ether acetate at a concentration of 1% by mass, It is desirable to select the compound (2) and the compound (3) so as to satisfy Fn described later. Therefore, the present invention also provides a method for producing the block copolymer (A) by selecting each of the compound (2) and the compound (3) so as to satisfy the Fn related to the molecular weight, the amount used, and the like. it can.

In the production of the block copolymer (A), first, the compound (2) is polymerized in a state where the compound (1) is present in the system.
A compound (1) may be used individually by 1 type, and may use 2 or more types together.
The amount of compound (1) used is preferably 0.01 to 10% by weight, and 0.05 to 5% by weight, based on the total of compound (2) and compound (3) used in the production of the block copolymer. Is more preferable. When using 2 or more types of compounds (1), it is preferable that those sum total exists in the said range.

A compound (2) may be used individually by 1 type, and may use 2 or more types together.
Although the usage-amount of a compound (2) is not specifically limited, It is preferable that it is 50-99 mass% with respect to the sum total of the compound (2) and compound (3) used for manufacture of a block copolymer, 70 More preferably, it is -97 mass%. When using 2 or more types of compounds (2), it is preferable that those sum total exists in the said range.

The polymerization of the compound (2) may be performed in the absence of a solvent or may be performed in the presence of a solvent.
When the polymerization of the compound (2) is carried out in the presence of a solvent, the solvent used is not particularly limited as long as the raw material dissolves, and a solvent containing no fluorine atom in the structure (hereinafter referred to as a fluorine-free solvent). Or a fluorine-containing solvent, and one or more of these may be used as appropriate.
The fluorine-free solvent is not particularly limited as long as the raw material dissolves, and examples thereof include acetone, methanol, ethanol, 2-propanol, ethyl acetate, toluene, tetrahydrofuran and the like.
The fluorine-containing solvent is not particularly limited as long as the raw material dissolves. For example, perfluorocarbon (PFC), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroether (HFE), etc. And a solvent containing a fluorine atom.
Specific examples of fluorine-containing solvents include 3M's HFE series, Fluorinert series, Asahi Glass series, Asahi Glass Co., Ltd., ZEOLA H. Mitsui DuPont Fluorochemicals, Inc. There are series, etc. In addition to these, fluorine-containing aromatic compound derivatives, fluorine-containing alcohols, fluorine-containing ketones, trifluoromethylbenzene and derivatives thereof, hexafluoroxylene and derivatives thereof, and the like can be given.
The fluorine-containing solvent is preferably one that does not have an ozone depletion coefficient, and among them, it has a sufficiently high solubility even for non-fluorinated polymers, so that fluorine-substituted aromatics, fluoroalkyl-substituted aromatics, fluoroalcohols Are preferred.

  The polymerization of the compound (2) is preferably performed in the presence of a solvent in the range of 0.5 to 10 times the mass of the compound (2) or in the absence of a solvent.

A radical polymerization method is used for the polymerization of the compound (2), and the form thereof may be any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
A polymerization initiator is preferably used for the polymerization of the compound (2). The polymerization initiator is not particularly limited. For example, 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2′-azobis-2-methylpropionate, 2,2′-azobisiso Examples thereof include azo compounds such as butyronitrile and organic oxides such as lauroyl peroxide.

The polymerization temperature is preferably 0 to 150 ° C. in terms of ease of control. In particular, when polymerization is performed in the absence of a solvent, it is preferable to perform the polymerization at a temperature equal to or higher than the glass transition temperature of the produced polymer.
The polymerization pressure is preferably normal pressure or, in the case of a closed system, a pressure of about the gas generated by the decomposition of the polymerization initiator from the viewpoint of simplicity.
Examples of the atmosphere during the polymerization include air, a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere. In order not to consume radicals during polymerization, an inert gas atmosphere is preferred.

After the polymerization of the compound (2), the resulting polymer is polymerized with the compound (3).
As the compound (3), one type may be used alone, or two or more types may be used in combination.
Although the usage-amount of a compound (3) is not specifically limited, It is preferable that it is 1-50 mass% with respect to the sum total of the compound (2) used for manufacture of a block copolymer, and a compound (3). More preferably, it is 30 mass%. When 2 or more types of compounds (3) are included, it is preferable that those sum total exists in the said range. When the amount of the compound (3) used is within this range, it becomes easy to prepare the block copolymer (A) in the desired Fn range without adversely affecting the handling properties. Fn will be described later.

The polymerization of compound (3) is carried out in the absence of a solvent or in the presence of a fluorinated solvent.
When the polymerization of the compound (2) is carried out in the absence of a solvent and the polymerization of the compound (3) is carried out in the absence of a solvent, the polymerization of the compound (3) is carried out as it is following the polymerization of the compound (2). Can be implemented.
When the polymerization of the compound (2) is performed in the absence of a solvent and the polymerization of the compound (3) is performed in the presence of a fluorinated solvent, after the polymerization of the compound (2), a fluorinated solvent is added. Compound (3) is polymerized.
When the polymerization of the compound (2) is performed in the presence of a solvent and the polymerization of the compound (3) is performed in the absence of a solvent, the compound (3) is removed after the polymerization of the compound (2) and then the solvent is removed. Is polymerized. As a method for removing the solvent, a known method such as using an evaporator such as an evaporator can be used.
When the polymerization of the compound (2) is carried out in the presence of a solvent and the polymerization of the compound (3) is carried out in the presence of a fluorinated solvent, the solvent used for the polymerization of the compound (2) contains a fluorinated solvent. If so, the compound (3) may be polymerized as it is, and a fluorine-containing solvent may be further added. If the solvent used for the polymerization of the compound (2) does not contain a fluorinated solvent, the fluorinated solvent is added to carry out the polymerization of the compound (3).
Preferably, the polymerization of the compound (2) is carried out in the presence of a solvent, and the polymerization of the compound (3) is carried out in the presence of a fluorinated solvent. In particular, the polymerization of the compound (2) is carried out in the presence of a fluorinated solvent. It is preferable to carry out the polymerization of the compound (3) as it is because it is simple.

When the polymerization of the compound (3) is carried out in the presence of a fluorine-containing solvent, examples of the fluorine-containing solvent include the same as those mentioned in the polymerization of the compound (2), and any one of them is used alone. Two or more types may be used in combination.
When the polymerization of the compound (3) is carried out in the presence of a fluorine-containing solvent, only the fluorine-containing solvent may be used as the polymerization solvent, or a fluorine-free solvent may be used in combination with the fluorine-containing solvent.
Examples of the fluorine-free solvent include the same ones as mentioned in the polymerization of the compound (2), and any one of them may be used alone, or two or more may be used in combination.
When the fluorine-containing solvent and the fluorine-free solvent are used in combination, the ratio of the fluorine-containing solvent to the total amount of the fluorine-containing solvent and the fluorine-free solvent is preferably 25% by mass or more, and more preferably 50% by mass or more.

The polymerization of the compound (3) is performed in the presence of a polymerization solvent within a range of 1 to 20 times the total mass of the compound (2) and the compound (3), or in the absence of a solvent. Is preferred.
Here, the polymerization solvent is the total of all solvents present in the system at the time of polymerization. In the polymerization of the compound (3), the polymerization solvent needs to contain a fluorinated solvent.
That is, in the polymerization of the compound (3) in the presence of the fluorine-containing solvent, the total amount of the fluorine-containing solvent and the fluorine-free solvent (the amount of the fluorine-containing solvent when no fluorine-containing solvent is not used) is the compound (2 ) And the total mass of the compound (3) is preferably in the range of 1 to 20 times.

  For the polymerization of the compound (3), a radical polymerization method is used as in the polymerization of the compound (2). The polymerization conditions such as the polymerization temperature, the polymerization pressure, and the atmosphere during the polymerization are the same as those for the polymerization of the compound (2). It may be the same.

The polymerization of the compound (2) is preferably performed until the conversion rate of the compound (2) becomes 80% or more. The conversion is more preferably 90% or more, and particularly preferably 95% or more. Thus, by polymerizing the compound (2) to some extent and then polymerizing the compound (3), the randomness of the block portion in the resulting block copolymer is lowered, and the resulting block copolymer Performance (such as the ability to reduce the liquid surface tension) is improved.
Moreover, it is preferable to perform superposition | polymerization of a compound (3) until the conversion rate of a compound (3) becomes 80% or more. The conversion is more preferably 90% or more, and particularly preferably 95% or more. Thereby, the obtained block copolymer will be excellent in performance such as the ability to reduce the surface tension of the liquid.
Here, the conversion rate is the ratio (%) of the monomer actually used in the polymerization reaction among the used compounds (compound (2) or (3). Collectively referred to as “monomer” in this paragraph). Means.
The conversion rate is determined, for example, by measuring the amount of monomer (mole) in the system before the reaction and the amount of monomer in the system after the reaction (that is, the amount of unreacted monomer) using a gas chromatograph or the like. It can ask for.
Conversion (%) = {(monomer amount in the system before reaction−monomer amount in the system after reaction) / monomer amount in the system before reaction} × 100

When the block copolymer (A) is mixed with propylene glycol monomethyl ether acetate at a concentration of 1% by mass at 25 ° C., the solution is transparent without becoming cloudy. This “transparent” means that which is visually confirmed. By not becoming cloudy, it can be suitably used as an optical material.
The curable resin composition according to the present invention is a propylene glycol monomethyl ether acetate solution of a block copolymer (A) as a particularly preferred form of a solution containing such a block copolymer (A) in a solvent (B). Can also be provided. The concentration of the block copolymer (A) in the solution is usually from 0.001 to 10% by mass, preferably from 0.003 to 3% by mass. Of course, the solution may contain a resin (C) described later.

As for a block copolymer (A), it is preferable that Fn calculated | required by the following formula ((alpha)) is 1-120. 1-100 are especially preferable, More preferably, it is 10-100, More preferably, it is 30-100. Within this range, the amount of the compound having a fluorine atom is not too large, and the uniformity of the coating film is easily maintained. In addition, Fn and formula (α) are the number of carbon atoms of the perfluoroalkyl group in the Fn defined by the formula (α) while the perfluoroalkyl group is continuously arranged in the block copolymer. The inventor has found as an index to indicate that the larger the Fn value, the greater the carbon number.
Formula (α) Fn = Mw × (Fw / Fm) × Cn
Mw: mass average molecular weight of the block copolymer (A).
Fw: Fa / (Fa + Fb)
Fm: molecular weight of the compound represented by formula (3).
Fa: Use amount of the compound represented by the formula (3).
Fb: the amount of the compound represented by formula (2) used.
Cn: carbon number of Rf ¹ of the compound represented by formula (3). However, in the case of Rf ² is present, this is also including.

  In the calculation formula (α), Mw means the mass average molecular weight of the block copolymer (A). Mw in the present invention is a molecular weight in terms of polymethyl methacrylate (standard substance) measured by GPC (gel permeation chromatography, column filler: styrene divinylbenzene copolymer, mobile phase: tetrahydrofuran).

  In the calculation formula (α), Fm is the molecular weight of the compound (3), Fa is the usage amount of the compound (3), and Fb is the usage amount of the compound (2). In addition, when using 2 or more types of compounds (2) together, Fb is the total amount of the usage-amount of each compound (2).

The “use amount” in Fa means the ratio of the compound (3) to the total of the compound (2) and the compound (3) used for the production of the block copolymer (A). In the case where the compound (2) is polymerized first and the total amount thereof is used for the polymerization with the compound (3), the amount of the compound (3) relative to the amount of the compound (2) and the amount of the compound (3) charged The ratio of the charged amount is Fa. When the compound (2) is polymerized first and only a part of the obtained polymer is used for the polymerization with the compound (3), the amount of the compound (2) charged is the same as that for the polymerization with the compound (3). It is calculated by multiplying the ratio of the used polymer to the whole obtained polymer. In the case of Fb, the ratio of the compound (2) is also meant. The “charge amount” means parts by mass.
In the polymerization of the above compounds (2) and (3), it is generally considered that all of the charged amount was spent on the polymerization, so the amount used here is substantially derived from the corresponding compound in the copolymer. Corresponds to the amount of constituent units.

In the calculation formula (α), Cn is the carbon number of Rf ¹ of the compound (3). For example, when Rf ¹ is C ₆ F ₁₃ , Cn is 6. Moreover, when several perfluoroalkyl groups exist in one molecule | numerator of Formula (3), what added the carbon number is set to Cn. For example, when Rf ¹ is C ₆ F ₁₃ and Rf ² is C ₄ F ₉ , Cn is 10. If there are a plurality of Rf ² , add them in the same way.
Cn is preferably 1 to 12, more preferably 4 to 12, and particularly preferably 4 to 6 because the surface tension reducing ability of the block copolymer (A) is improved.

When two or more kinds of compounds (3) are used in combination, “Mw × (Fw / Fm) × Cn” is calculated individually for each compound (3), and these are totaled to obtain Fn. For example, the compound (3), two types _{(e.g., CH 2 = CH-COO-} C 2 H 4 -C 6 F 13 and _{(C6FA), CH 2 = CH} -COO-C 2 H 4 -C 4 F 9 When (C4FA)) is used in combination, the following calculation is performed. Similarly, in the case of three or more types, Fn1 + Fn2 + Fn3... Is calculated separately, and finally Fn is obtained by totaling.
Fn = Fn1 + Fn2
Fn1 = Mw × ((Fa1 / (Fa1 + Fa2 + Fb)) / Fm1) × Cn1
Fn2 = Mw × ((Fa2 / (Fa1 + Fa2 + Fb)) / Fm2) × Cn2
(In the formula, Fa1, Fm1, and Cn1 are Fa, Fm, and Cn, respectively, in C6FA, and Fa2, Fm2, and Cn2 are Fa, Fm, and Cn, respectively, in C4FA. The other symbols are the same as in formula (α). Meaning.)

  The curable resin composition of the present invention contains a solvent (B).

Examples of the solvent (B) used in the curable resin composition of the present invention include, as alcohols, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, t- Butyl alcohol, ketones as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, butyrolactone, esters as ethyl formate, ethyl acetate, ethyl propionate, n-propyl propionate , Propionate-i-propyl, acetate-n-butyl, acetate-i-butyl, acetate-t-butyl, ethyl butyrate, ethyl isobutyrate, i-propyl butyrate, n-butyl butyrate, i-butyl butyrate , Ethyl lactate, lactate-n-butyl, 2-oxypropi Methyl onate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropion Acid butyl, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, glycols, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether Teracetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Examples include ethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.
In addition, toluene, xylene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like can be given.

In particular, ketones, esters or glycol ethers are preferred, and among them, cyclohexanone, butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, ethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate are preferred.
A solvent may be used independently and may combine two or more types.
As the solvent (B), propylene glycol monomethyl ether acetate or a mixed solvent containing the same is preferable.

The curable resin composition of the present invention usually contains a resin (C).
The resin (C) is desirably soluble in an alkaline solution.
Examples of the resin (C) include monomers such as acrylic acid, methacrylic acid, itaconic acid, acrylic ester, methacrylic ester, acrylamide, methacrylamide, maleic acid, acrylonitrile, methacrylonitrile, styrene, and vinyl acetate. Homopolymers or copolymers containing, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, polybutylene terephthalate, acetylcellulose, novolac resin, resole resin, polyvinylphenol and the like.

  The resin (C) is preferably a resin having a carboxyl group or a hydroxyl group because development in an alkaline solution is possible. Among them, an acrylic resin containing acrylic acid or methacrylic acid in the composition is preferable. It is a copolymer with an acid ester or a methacrylic acid ester. These resins are excellent in developability and transparency, have a wide range of monomer selection, and can easily control performance.

The curable resin composition of the present invention may contain other components. For example, a polymerizable monomer is mentioned as another component.
The polymerizable monomer is not particularly limited, but a compound having at least one ethylenically unsaturated group is preferable.
For example, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate , Pentaerythritol trimethacrylate, tris (2-acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Hexamethacrylate, 2,2,4,4,6,6-hexa {2- (methacryloyloxy) -ethoxy} -1,3,5-triaza-2,4,6-triphospholine, or ethylene in polyfunctional alcohol Examples of the compound group include acrylated or methacrylated after addition of oxide or propylene oxide.
Among them, an acrylic compound having 3 or more acryloyl groups is preferable.
These polymerizable monomers may be used alone or in combination of two or more.

Examples of other components include polymerization initiators.
A polymerization initiator is not essential because it can be cured by heat, but it is preferable to use it.
The polymerization initiator is preferably a photopolymerization initiator.
Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryes. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine oxide compounds.

In the curable resin composition of the present invention, a surfactant different from the block copolymer (A) may be used in combination. However, when dissolved in propylene glycol monomethyl ether acetate, it is within a range in which a transparent solution can be obtained without becoming cloudy.
As surfactants, in addition to fluorosurfactants, silicone surfactants and hydrocarbon surfactants are raised, and hydrophilic group structures include nonionic, anionic, cationic, betaine, Either can be selected.
Although these are added from a viewpoint of improving applicability | paintability more, since sufficient applicability | paintability can be provided by using the block copolymer (A) of this invention, it is not necessary to add.

As other components, a polymerization inhibitor may be added to impart stability during storage.
As polymerization inhibitors, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, phenothiazine, β-naphthol, nitrobenzene, dinitrobenzene, 4-methoxy-1-naphthol , Cuprous chloride, and the like.

  In addition, various additives such as an antioxidant, an ultraviolet absorber, a filler, an aggregation inhibitor, an adhesion promoter, and the like can be added as necessary.

The curable resin composition of the present invention is preferably used as a resist composition.
A colorant is used for the color resist material using the resist composition of the present invention.
A coloring agent refers to what colors a curable resin composition. Examples of the colorant include red, blue, and green dyes or pigments, dyes or pigments such as yellow, orange, purple, and brown for adjusting chromaticity, or carbon black.
For example, red pigments include quinacridone, perylene, and anthraquinone pigments. More specifically, CI Pigment Red 177, 207, 209, 224, 254, and the like can be given as color index numbers.
Examples of green pigments include halogenated copper phthalocyanine. When expressed by a color index number, CI Pigment 7, 36 and the like can be mentioned.
Examples of blue pigments include phthalocyanine pigments. In terms of color index numbers, CI Pigment Blue 15: 2 15: 3 15: 6 and the like can be mentioned.
Examples of yellow pigments include CI Pigment Yellow 138, 139, 150 and the like when expressed by color index numbers.
Examples of purple pigments include CI Pigment Violet 23 when represented by color index numbers.

  The color filter produced using the resist composition of the present invention can be produced by forming a black matrix on a transparent substrate and further usually forming red, green and blue pixels thereon. . That is, the resist composition of the present invention is used in at least one of black, red, green, and blue of the black matrix.

Each layer is coated with the resist composition of the present invention on a support by an arbitrary method, exposed through a predetermined mask pattern, and developed with a developing solution, whereby a negative or positive colored resist is formed. A pattern can be formed.
Examples of the arbitrary method include a spinner method, a flow coat method, a roll coat method, a die coat method, and a spray method. In addition, a color filter can be prepared by an ink jet method using the resist composition of the present invention.

The exposure light source used for manufacture of the color filter using the resist composition of this invention will not be specifically limited if it is a light source which has a wavelength of 400 nm or less. For example, xenon lamp, halogen lamp, tungsten lamp, metal halide lamp, carbon arc, low pressure mercury lamp, medium pressure mercury lamp, fluorescent lamp, Ar ion laser, Kr ion laser, ArF laser, laser KrF, XeF laser, N ₂ laser, etc. are used. it can.

  Then, a development process is performed and the part which is not hardened | cured by the light non-irradiation in the said exposure process is eluted among the layers in which the curable resin composition of this invention was apply | coated. An alkaline solution is used for this development process. The alkaline solution may be an inorganic alkali developer or an organic alkali developer.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, silicic acid Sodium, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. It is done.

A surfactant may be added to the alkaline solution in order to improve the wettability. The surfactant is not limited to a hydrocarbon type, silicone type, fluorine type, or anionic, cationic, betaine, nonionic, or ionic.
An organic solvent may be added to the alkaline solution.

After development using an alkaline solution, it is generally pure and washed.
After development and washing, a thermosetting process called post-baking is performed.
The thermosetting treatment is performed in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C.
One-color patterning is performed through these coating, exposure, development, washing, and post-baking steps. This process is sequentially repeated to perform patterning for all colors, thereby creating a color filter.

  In addition, although described about the manufacturing process of a color filter here, this invention is not limited to this, In the range which uses the curable resin composition of this invention, various modifications may be performed.

Specific examples are shown below.
The reagents used are as follows.
AM-230G (trade name): manufactured by Shin Nakamura Chemical Co., Ltd. Polyethylene glycol acrylate _{CH 2 = CH-COO- (C} 2 H 4 O) n -CH 3 (n = average 23)
AM-90G (product name): polyethylene glycol acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. (where n = average 9)
2-ethylhexyl acrylate: Aldrich 2-perfluorohexyl ethyl acrylate: Daikin Chemicals Sales Co., Ltd. Isopropylxanthogen disulfide: Wako Pure Chemical Industries, Ltd. Metaxylene hexafluoride: Tokyo Chemical Industry Co., Ltd. methyl ethyl ketone: Wako Pure Chemical Industries, Ltd. Dimethyl 2,2′-azobis (2-methylpropionate) V-601: Propylene glycol monomethyl ether acetate manufactured by Wako Pure Chemical Industries, Ltd .: Wako Pure Chemical Industries, Ltd. Using GPC-101), polymethyl methacrylate was used as a standard substance.
The surface tension was measured using a static surface tension meter CBVP-A3 type (manufactured by Kyowa Interface Science Co., Ltd.).

[Reference Example 1]
In a 100 ml pressure-resistant glass bottle, 14.2 g of AM-230G, 14.2 g of 2-ethylhexyl acrylate, 0.39 g of isopropylxanthogen disulfide, 71.05 g of metaxylene hexafluoride, 0.21 g of V-601, and sealed, Heated at 70 ° C. for 16 hours. The conversion of 2-ethylhexyl acrylate was 98.6% as measured by gas chromatograph. Let the obtained solution be (S1).

[Synthesis Example 1]
A 25 ml pressure-resistant glass bottle was charged with 24.22 g of the solution (S1) obtained by the method of Reference Example 1, 0.77 g of 2-perfluorohexylethyl acrylate, 0.052 g of V-601, and sealed at 70 ° C. Heated for 16 hours. The conversion of 2-perfluorohexylethyl acrylate measured by gas chromatography was 98.6%. The solvent was distilled off from this solution under reduced pressure at 70 ° C. to recover 6.50 g.
The molecular weight Mw was 28,000.

[Synthesis Example 2]
A 25 ml pressure-resistant glass bottle was charged with 24.62 g of the solution (S1) obtained by the method of Reference Example 1, 0.37 g of 2-perfluorohexylethyl acrylate, 0.024 g of V-601, and sealed at 70 ° C. Heated for 16 hours. The conversion of 2-perfluorohexylethyl acrylate measured by gas chromatography was 94.2%. The solvent was distilled off from this solution under reduced pressure at 70 ° C. to recover 6.50 g.
The molecular weight Mw was 27,200.

[Synthesis Example 3]
In a 25 ml pressure-resistant glass bottle, 17.61 g of the solution (S1) obtained by the method of Reference Example 1, 1.26 g of 2-perfluorohexylethyl acrylate, 6.10 g of metaxylene hexafluoride, 0.039 g of V-601 After charging and sealing, it was heated at 70 ° C. for 16 hours. The conversion of 2-perfluorohexylethyl acrylate measured by gas chromatography was 97.5%. The solvent was distilled off from this solution under reduced pressure at 70 ° C. to recover 6.64 g.
The molecular weight Mw was 30,500.

[Reference Example 2]
In a 100 ml pressure-resistant glass bottle, AM-230G 19.70 g, 2-ethylhexyl acrylate 19.68 g, isopropyl xanthogen disulfide 1.06 g, metaxylene hexafluoride 59.07 g, V-601 0.60 g were charged and sealed. Heated at 70 ° C. for 16 hours. The conversion of 2-ethylhexyl acrylate was 98.6% as measured by gas chromatograph. Let the obtained solution be (S2).

[Synthesis Example 4]
A 25 ml pressure-resistant glass bottle was charged with 24.47 g of the solution (S2) obtained by the method of Reference Example 2, 0.51 g of 2-perfluorohexylethyl acrylate, 0.040 g of V-601 and sealed at 70 ° C. Heated for 16 hours. The conversion of 2-perfluorohexylethyl acrylate measured by gas chromatography was 97.3%. The solvent was distilled off from this solution under reduced pressure at 70 ° C. to recover 9.92 g.
The molecular weight Mw was 15,900.

[Reference Example 3]
A 100 ml pressure-resistant glass bottle was charged with 29.6 g of AM-230G, 29.6 g of 2-ethylhexyl acrylate, 0.40 g of isopropylxanthogen disulfide, and 0.45 g of V-601, and then heated at 70 ° C. for 16 hours. The conversion of 2-ethylhexyl acrylate as measured by gas chromatography was 99.3%. Let the obtained solution be (S3).

[Comparative Synthesis Example 1]
In a 200 ml pressure-resistant glass bottle, 53.8 g of the solution (S3) obtained by the method of Reference Example 3, 13.4 g of 2-perfluorohexylethyl acrylate, 107.5 g of metaxylene hexafluoride, and 0.41 g of V-601 are added. After charging and sealing, it was heated at 70 ° C. for 16 hours. The peak of 2-perfluorohexylethyl acrylate measured by gas chromatography could not be confirmed. The solvent was distilled off from this solution under reduced pressure at 70 ° C. to recover 65.6 g.
The molecular weight Mw was 72,700.

[Reference Example 4]
A 500 ml pressure-resistant glass bottle was charged with 60.0 g of AM-90G, 60.0 g of 2-ethylhexyl acrylate, 120.0 g of methyl ethyl ketone, 0.81 g of isopropylxanthogen disulfide, and 0.90 g of V-601, sealed, and then sealed at 70 ° C. Heated for hours. The conversion of 2-ethylhexyl acrylate as measured by gas chromatography was 99.1%. The solvent was distilled off from this solution at 70 ° C. under reduced pressure to recover a polymer (P1).

[Comparative Synthesis Example 2]
In a 100 ml pressure-resistant glass bottle, 10.0 g of the polymer (P1) obtained by the method of Reference Example 4, 2.51 g of 2-perfluorohexylethyl acrylate, 40.0 g of metaxylene hexafluoride, V-601 0 0.075 g was charged and sealed, and then heated at 70 ° C. for 16 hours. The conversion of 2-perfluorohexylethyl acrylate measured by gas chromatography was 96.7%. The solvent was distilled off from this solution under reduced pressure at 70 ° C. to recover 12.2 g.
The molecular weight Mw was 47,500.

[Comparative Synthesis Example 3]
In a 50 ml pressure-resistant glass bottle, 4.71 g of AM-230G, 4.70 g of 2-ethylhexyl acrylate, 0.50 g of 2-perfluorohexyl ethyl acrylate, 0.048 g of octanethiol, 9.90 g of propylene glycol monomethyl ether acetate, V-601 After 0.15 g was charged and sealed, it was heated at 70 ° C. for 16 hours. The conversion of 2-perfluorohexylethyl acrylate measured by gas chromatography was 99.4%. The solid content concentration of this solution was 50.1%.
The molecular weight Mw was 32,300.

[Comparative Synthesis Example 4]
In a 50 ml pressure-resistant glass bottle, AM-230G 4.46 g, 2-ethylhexyl acrylate 4.46 g, 2-perfluorohexyl ethyl acrylate 0.99 g, octanethiol 0.048 g, propylene glycol monomethyl ether acetate 9.90 g, V-601 After 0.15 g was charged and sealed, it was heated at 70 ° C. for 16 hours. The conversion of 2-perfluorohexylethyl acrylate as measured by gas chromatography was 99.3%. The solid content concentration of this solution was 50.1%.
The molecular weight Mw was 32,900.

The copolymers obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 were dissolved in 10% by mass or 1% by mass in propylene glycol monomethyl ether acetate, and the appearance was confirmed. Moreover, calculation of Fn of each copolymer was also performed. The results are shown in Table 1.
As described above, in the propylene glycol monomethyl ether acetate solution of each copolymer, the 10% by mass solution of the copolymer of the comparative synthesis example was cloudy, and even the 1% by weight solution was cloudy. The block copolymer was colorless and transparent even in a 10% by mass solution.

The copolymers obtained in Synthesis Examples 1 to 4 were dissolved in propylene glycol monomethyl ether acetate to prepare the concentrations shown in Table 2, and the static surface tension was measured. The results are shown in Table 2. Each numerical value in Table 2 means a value of static surface tension (unit “mN / m”). The measured value of the static surface tension of propylene glycol monomethyl ether acetate under the same conditions was 27.6 mN / m.

The photosensitive resin composition was prepared using the copolymer obtained by the synthesis examples 1-4. The surface tension of the photosensitive resin composition was measured. The results are shown in Table 3. In addition, the preparation amount of each raw material in Table 3 is “part by mass”.
In addition, the meaning of the abbreviation of each component in Table 3 is as follows.
PGMEA: propylene glycol monomethyl ether acetate binder: methacrylic acid / benzyl methacrylate / glycidyl methacrylate = 15/80/5 (mass ratio) copolymer PGMEA 40% solution PPZ: manufactured by Kyoeisha Chemical Co., Ltd. 2,2,4,4,6 , 6-Hexa {2- (methacryloyloxy) -ethoxy} -1,3,5-triaza-2,4,6-triphospholine

  From these results, it was found that the surface tension of the curable resin composition of the present invention is greatly reduced by including a specific block copolymer. From this, it is considered that the leveling property of the composition is improved, unevenness at the time of application is less likely to occur, and a uniform coating film can be formed. In addition, since the specific block copolymer exhibits good solubility in propylene glycol monomethyl ether acetate, the composition does not cause white turbidity or the like, and has an effect that it does not repel after application.

Claims (6)

A curable resin composition comprising the following block copolymer (A), solvent (B) and resin (C).
Block copolymer (A): This is a block copolymer that, when mixed with propylene glycol monomethyl ether acetate at a concentration of 1% by mass, yields a transparent liquid without clouding, and is represented by the following formula (2). A structural unit derived from the compound represented by formula (3), a structural unit derived from the compound represented by formula (3) below, and a residue of the compound represented by formula (1) below.
The symbols in the formula have the following meanings.
X ¹ : hydrogen atom, halogen atom, amino group, P (O) (OH) ₂ group or monovalent organic group.
Y ¹ : hydrogen atom, halogen atom, alkali metal atom, NH ₄ group or monovalent organic group.
R ¹ : a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms.
R ² : a hydrogen atom or a monovalent group.
A: —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
R ^4: a hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group having 1 to 5 carbon atoms of 1 to 5 carbon atoms.
B: —O— or —NR ⁷ —.
R ⁵ , R ⁶ , R ⁷ : each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula (r).
−Q ² −Rf ² (r)
Rf ¹ and Rf ² : each independently a C 1-6 perfluoroalkyl group.
Q ¹ and Q ^{2 are} each independently a single bond or a divalent linking group. The curable resin composition according to claim 1, wherein the block copolymer (A) has an Fn calculated by the following calculation formula (α) of 1 to 120.
Formula (α) Fn = Mw × (Fw / Fm) × Cn
The symbols in the formula have the following meanings.
Mw: mass average molecular weight of the block copolymer (A).
Fw: Fa / (Fa + Fb)
Fm: molecular weight of the compound represented by formula (3).
Fa: Use amount of the compound represented by the formula (3).
Fb: the amount of the compound represented by formula (2) used.
Cn: carbon number of Rf ¹ of the compound represented by formula (3). However, in the case of Rf ² is present, this is also including.   The curable resin composition according to claim 1, wherein the solvent (B) contains propylene glycol monomethyl ether acetate.   The resist composition using the curable resin composition in any one of Claims 1-3.   The resist composition according to claim 4, which is a color resist material used for a color filter.   A color filter prepared using the resist composition according to claim 5.