JP2006291188A - (meth)acryloyl group-containing aromatic isocyanate compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monomer having excellent reactivity, imparting high heat resistance and high refractive index and having two or more polymerizable functional groups having different polymerization characteristics and an aromatic ring in the molecule and to provide an industrially advantageous method for producing the monomer. <P>SOLUTION: The monomer is an acryloyl or a methacryloyl group-containing aromatic isocyanate compound represented by formula (I) (wherein, R<SP>1</SP>represents a single bond or a 1-5C straight-chain or a 1-5C branched alkylene group; R<SP>2</SP>represents a hydrogen atom or a methyl group; R<SP>3</SP>represents a single bond or a 1-3C straight-chain or a 1-3C branched alkylene group; X represents a halogen atom or an electron attractive group; m represents an integer of 0-4; n represents an integer of 1-3; and 1≤m+n≤5). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel (meth) acryloyl group-containing aromatic isocyanate compound having two or more polymerizable functional groups having different polymerization characteristics and sufficient reactivity to an isocyanate group, and a process for producing the same, and further to the isocyanate The present invention relates to a reactive monomer obtained from a compound and particularly suitable for an optical material, a curable composition containing the same, and a cured product thereof.

  As monomers having polymerizable functional groups having different polymerization characteristics in one molecule, for example, compounds having an unsaturated group and an isocyanate group in the molecule, 2-isocyanatoethyl methacrylate (Karenz MOI, Showa Denko) are known. . Such a functional group having two different polymerization characteristics, that is, a monomer having an unsaturated group and an isocyanate group in the molecule is a coating material, an ultraviolet curable paint, a thermosetting paint, a molding material, an adhesive, an ink, a resist, In the fields of optical materials, stereolithography materials, printing plate materials, dental materials, polymer battery materials, etc., they are useful compounds as raw material monomers for resins.

  As a method for producing such a compound, US Pat. No. 2,821,544 (Patent Document 1) discloses a method for producing an aliphatic compound having an unsaturated group and an isocyanate group in one molecule. Specifically, unsaturated carboxylic acid aminoalkyl ester hydrochloride is synthesized by reaction of unsaturated carboxylic acid chloride with amino alcohol hydrochloride, and then reacted with carbonyl chloride to produce unsaturated carboxylic acid isocyanatoalkyl ester. How to get.

  However, since the method described in Patent Document 1 contains a large amount of by-products (such as HCl adducts with respect to unsaturated groups) that are considered to be based on unsaturated groups, the reaction yield is low, and much effort is required for purification. Problem.

  On the other hand, in the optical field and the like, in recent years, there is a demand for high refractive index and high heat resistance, and a monomer having an aromatic ring in the molecule is demanded. As such a compound, Japanese Patent Application Laid-Open No. 2003-12632 (Patent Document 2) discloses 3-isopropenyl-isopropenyl-α having an unsaturated group and an isocyanate group in one molecule and further having an aromatic ring. , Α-dimethylbenzyl isocyanate compounds are disclosed.

  However, since the compound described in Patent Document 2 has an unsaturated group at the benzyl position, there is a problem that the cured product made of the compound has low weather resistance, and further, the reaction rate of the isocyanate group is slow.

  In addition, regarding an adduct of an isocyanate compound as typified above, for example, JP-A-2000-086302 (Patent Document 3) discloses a polyester polyol obtained by a reaction between a specific diol component and a polybasic acid component, By using a polyester polyurethane (meth) acrylate oligomer obtained by subjecting a (meth) acrylate having a hydroxy group and a polyisocyanate to a urethanation reaction, an acrylic monomer having high water absorption such as N-vinylpyrrolidone can be used in combination. A composition having high photocurability and heat resistance even when the concentration of urethane groups is increased is disclosed.

Also, JP-A-2000-204125 (Patent Document 4), JP-A-2001-200007 (Patent Document 5), and JP-A-2004-014327 (Patent Document 6) also have urethane having a specific chemical structure. It is disclosed that acrylate compounds provide high heat resistance.

However, in the above description, when synthesizing a urethane compound, any of the elements such as a high reaction temperature, a long-time reaction is indispensable, and an environment-friendly tin-based catalyst is used. There is room for further improvement.
U.S. Pat. No. 2,821,544 JP 2003-012632 A JP 2000-086302 A JP 2000-204125 A JP 2001-200007 A JP 2004-014327 A

  An object of the present invention is to provide a monomer having two or more polymerizable functional groups having different polymerization characteristics and an aromatic ring in the molecule, which is excellent in reactivity and can impart high heat resistance and high refractive index, and the monomer. An object of the present invention is to provide an industrially advantageous production method of a monomer, and to provide an adduct of the monomer obtained under mild conditions, and further a cured product having high heat resistance and curability.

  The present inventors diligently studied to solve the above problems. As a result, a (meth) acryloyl group-containing aromatic isocyanate compound having an aromatic ring in the molecular skeleton and two or more polymerizable functional groups having different polymerization characteristics in the molecule, and a method for producing the same, have been found. It came to complete.

That is, the present invention includes the following matters.
[1] A (meth) acryloyl group-containing aromatic isocyanate compound represented by the following formula (I).

(In the formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 represents a linear or branched alkylene group, X independently represents a halogen atom or an electron withdrawing group, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5. .)

[2] The (meth) acryloyl group-containing aromatic isocyanate compound according to [1], wherein R ³ in the formula (I) is a single bond.
[3] n in said formula (I) is 1, [1] or [2]
(Meth) acryloyl group-containing aromatic isocyanate compound.

[4] The (meth) acryloyl group-containing aromatic isocyanate compound according to any one of [1] to [3], wherein R ¹ in the formula (I) is a single bond.
[5] The (meth) acryloyl group-containing aromatic isocyanate compound according to [1] represented by the following formula (II).

(Formula (in II), R ^1, R ^2, R ³ and n have the formula (R ¹ in I), R ^2, represent the R ³ and n the same as those.)
[6] The (meth) acryloyl group-containing aromatic isocyanate compound according to [1] represented by the following formula (III).

(In the formula (III), R ² represents a hydrogen atom or a methyl group.)
[7] The (meth) acryloyl group-containing aromatic isocyanate compound according to [1] represented by the following formula (IV).

(In formula (IV), R ² represents a hydrogen atom or a methyl group.)
[8] In the above formula (I), for the group containing an isocyanate on the aromatic ring, (meth)
The (meth) acryloyl group-containing aromatic isocyanate compound according to [1], wherein a substituent constant σ of a substituent containing an acryloyloxy group is −0.2 <σ <0.8.

[9] A process for producing a (meth) acryloyl group-containing aromatic isocyanate compound represented by the following formula (I), comprising the following steps (1) to (4):

(In the formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 represents a linear or branched alkylene group, X independently represents a halogen atom or an electron withdrawing group, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5. .)
(1) A step of obtaining a hydroxyphenylamino mineral acid salt compound represented by the following formula (VI) from a hydroxyphenylamine compound represented by the following formula (V) and a mineral acid;

(Formula (in ^{V), R 1, R 3} , X, m and n are. Representing those of formulas (R ¹ in I), R ^3, X, the same as m and n)

(In the formula ^{(VI), R 1, R} 3, X, m and n are, R ^1, R ³ in formula (I), X, represents the same as m and n, W ¹ is a mineral acid To express.)
(2) A step of obtaining a hydroxyphenyl isocyanate compound represented by the following formula (VIII) from the hydroxyphenylamino mineral acid compound obtained in the step (1) and a compound represented by the following formula (VII): ;

(In Formula (VII), Z ¹ and Z ² each independently represent a fluorine atom, a chlorine atom, a bromine atom, an imidazole, a pyrazole, or R′O—, wherein R ′ is a C 1-6 carbon atom. An alkyl group or alkenyl group which may have a branch or an aryl group which may have a substituent.

(In the formula ^{(VIII), R 1, R} 3, X, m and n are, R ¹ in formula ^{(I), R 3, X} , m and n
Represents the same thing. )
(3) A step of obtaining an isocyanate group-containing phenyl ester compound represented by the following formula (X) from the hydroxyphenyl isocyanate compound obtained in the step (2) and a compound represented by the following formula (IX);

(In the formula (IX), R ² represents the same as R ² in formula (I).)

(Formula (X) in, R ¹ to R ^3, X, m and n have the formula (R ¹ to R ³ in I), X, represents those same m and n.)
(4) A step of dehydrochlorinating the isocyanate group-containing phenyl ester compound obtained in the step (3) in the presence of a basic nitrogen compound.

  [10] The (meth) acryloyl group-containing aromatic isocyanate compound according to [9], wherein the mineral acid is at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, carbonic acid and phosphoric acid. Manufacturing method.

[11] The process for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to [9], wherein the reactions in the steps (1) to (4) are performed in a solvent.
[12] The solvent used in the step (1) is selected from the group consisting of water, alcohols, esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. It is at least 1 type, The manufacturing method of the (meth) acryloyl group containing aromatic isocyanate compound as described in [11] characterized by the above-mentioned.

  [13] The solvent used in the steps (2) to (4) is at least selected from the group consisting of esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. It is 1 type, The manufacturing method of the (meth) acryloyl group containing aromatic isocyanate compound as described in [11] characterized by the above-mentioned.

  [14] The production of a (meth) acryloyl group-containing aromatic isocyanate compound according to [12], wherein the step (2) is carried out after the solvent is distilled off after completion of the step (1). Method.

[15] The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to [9], wherein the basic nitrogen compound in the step (4) is triethylamine.
[16] The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to [9], wherein a basic nitrogen compound is added as a catalyst in the step (3).

[17] A process for producing a (meth) acryloyl group-containing aromatic isocyanate compound represented by the following formula (I), comprising the following steps (1 ′) to (3 ′):

(In the formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 represents a linear or branched alkylene group, X independently represents a halogen atom or an electron withdrawing group, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5. .)
(1 ′) a step of obtaining a hydroxyphenylamino mineral acid salt compound represented by the following formula (VI) from a hydroxyphenylamine compound represented by the following formula (V) and a mineral acid;

(Formula (in ^{V), R 1, R 3} , X, m and n are. Representing those of formulas (R ¹ in I), R ^3, X, the same as m and n)

(In the formula (VI), R ¹ , R ³ , X, m and n represent the same as R ¹ , R ³ , X and n, m in the formula (I), and W ¹ represents a mineral acid. To express.)
(2 ′) A hydroxyphenyl isocyanate compound represented by the following formula (VIII) is obtained from the hydroxyphenylamino mineral acid salt compound obtained in the step (1 ′) and the compound represented by the following formula (VII). Obtaining step;

(In Formula (VII), Z ¹ and Z ² each independently represent a fluorine atom, a chlorine atom, a bromine atom, an imidazole, a pyrazole, or R′O—, wherein R ′ is a C 1-6 carbon atom. An alkyl group or alkenyl group which may have a branch or an aryl group which may have a substituent.

(In the formula ^{(VIII), R 1, R} 3, X, m and n are, R ¹ in formula ^{(I), R 3, X} , m and n
Represents the same thing. )
(3 ′) A step of reacting the hydroxyphenyl isocyanate compound obtained in the step (2 ′) with a compound represented by the following formula (XI).

(In the formula (XI), R ² represents the same as R ² in formula (I).)
[18] The (meth) acryloyl group-containing aromatic isocyanate compound according to [17], wherein the mineral acid is at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, carbonic acid and phosphoric acid. Manufacturing method.

  [19] The process for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to [17], wherein the reaction in the steps (1 ′) to (3 ′) is carried out in a solvent.

  [20] The solvent used in the step (1 ′) is selected from the group consisting of water, alcohols, esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. [19] The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to [19].

  [21] The solvent used in the steps (2 ′) and (3 ′) is selected from the group consisting of esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. [19] The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to [19].

  [22] The (meth) acryloyl group-containing aromatic isocyanate compound according to [20], wherein the step (2 ′) is performed after the solvent is distilled off after the step (1 ′) is completed. Manufacturing method.

  [23] The process for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to [17], wherein a basic nitrogen compound is added as a catalyst in the step (3 ′).

  [24] A (meth) acryloyl group-containing urethane compound represented by the following formula (XII).

(In the formula (XII), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 linear or branched alkylene groups, R ⁴ represents an ether group, a thioether group or an NH group,
X independently represents a halogen atom or an electron withdrawing group, Y represents an aliphatic group, a group containing an aromatic ring, a group containing a heterocyclic ring, a polycarbonate residue, a polyurethane residue, a polyester residue or a polyhydroxy compound having a repeating unit Represents a residue, 1 represents an integer of 1 to 50, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5. )
[25] The (meth) acryloyl group-containing urethane compound as described in [24], wherein R ³ in the formula (XII) is a single bond.

[26] The (meth) acryloyl group-containing urethane compound as described in [24] or [25], wherein n in the formula (XII) is 1.
[27] The (meth) acryloyl group-containing urethane compound according to any one of [24] to [26], wherein R ¹ in the formula (XII) is a single bond.

  [28] The (meth) acryloyl group-containing urethane compound according to [24] represented by the following formula (XIII).

(In the formula (XIII), R ¹ , R ² , R ³ , R ⁴ , Y, l and n are the same as R ¹ , R ² , R ³ in the formula (XII)).
, R ⁴ , Y, l and n are the same. )
[29] The (meth) acryloyl group-containing urethane compound according to [24] represented by the following formula (XIV).

(Formula (XIV) in, R ^2, R ^4, Y and l are. Representing those of formulas (XIII) in R ^2, R ^4, Y and l the same as the)
[30] The (meth) acryloyl group-containing urethane compound according to [24] represented by the following formula (XV).

(Formula (XV) in, R ^2, R ^4, Y and l are. Representing those of formulas (XIII) in R ^2, R ^4, Y and l the same as the)
[31] The substituent of the substituent containing a (meth) acryloyloxy group with respect to the group containing a urethane bond on the aromatic ring, represented by the formula (XII) according to [24] A reactive monomer, wherein the constant σ is −0.2 <σ <0.8.

[32] represented by the formula (XII) according to [24], wherein R ⁴ is an ether group, Y is an alkyl group, a xylylene group, a fluorine-containing group or a norbornane group. , L = 1 or 2, a reactive monomer.

[33] Y of the formula (XII) is _{- (CH 2) p (CF} 2) a group represented by _q F (p represents an integer of 0 to 2, q is an integer of 0 to 8, p And q are not 0 at the same time.) The reactive monomer as described in [32].

[34] represented by the formula (XII) described in [24], wherein in the formula (XII), R ⁴ is an ether group, Y is a group having a fluorene skeleton, and n = 2. Reactive monomer characterized.

[35] represented by the formula (XII) according to [24], wherein R ⁴ is an NH group, Y is an alkyl group, a xylylene group, a fluorine-containing group or a norbornane group. , N is 1 or 2, a reactive monomer.

[36] In the formula (XII), Y is a group represented by —CH ₂ (CF ₂ ) ₈ F, or —R ⁴ —Y is a residue of 2,6-difluoroaniline. [35]
The reactive monomer described in 1.

[37] represented by the formula (XII) described in [24], wherein in the formula (XII), R ⁴ is a thioether group, and Y is a linear or branched saturated aliphatic group or phenyl group. Reactive monomer characterized.

[38] A (meth) acryloyl group-containing aromatic isocyanate compound represented by the formula (I) according to [1] is reacted with a compound to which a functional group having active hydrogen is bonded [31] -The manufacturing method of the reactive monomer as described in [37].

[39] In the formula (XII),
Y has a structure composed of a polycarbonate skeleton having a molecular weight of 500 to 5000,
An aliphatic dihydric alcohol residue in which the alkylene group is a trimethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a tetramethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a pentamethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a hexamethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a heptamethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is an octamethylene group; and
At least one selected from 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,20-eicosanediol and 1,4-cyclohexanedimethanol residue Having species residues,
The (meth) acryloyl group-containing urethane compound according to [24], wherein n is 2.

[40] The aliphatic dihydric alcohol residue in which the alkylene group is a trimethylene group is 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl. -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4 -Selected from trimethyl-1,3-pentanediol and 2-butyl-2-ethyl-1,3-propanediol residues;
The aliphatic dihydric alcohol residue in which the alkylene group is a tetramethylene group is a 1,4-butanediol residue;
The aliphatic dihydric alcohol residue in which the alkylene group is a pentamethylene group is selected from 1,5-pentanediol, 3-methyl-1,5-pentanediol and 1,5-hexanediol residue;
The aliphatic dihydric alcohol residue in which the alkylene group is a hexamethylene group is selected from 1,6-hexanediol and 2-ethyl-1,6-hexanediol residues;
The aliphatic dihydric alcohol residue in which the alkylene group is a heptamethylene group is a 1,7-heptanediol residue;
[39] The aliphatic dihydric alcohol residue in which the alkylene group is an octamethylene group is selected from 1,8-octanediol and 2-methyl-1,8-octanediol residues. (Meth) acryloyl group-containing urethane compound.

[41] A (meth) acryloyl group-containing aromatic isocyanate compound represented by the formula (I) described in [1] is reacted with the (meth) acryloyl group-containing urethane compound described in [24]. A method for producing a reactive (meth) acrylate polymer.

[42] A (meth) acryloyl group-containing aromatic isocyanate compound represented by the formula (I) according to [1] is reacted with a polymer compound having a repeating unit to which a functional group having active hydrogen is bonded. A method for producing a reactive (meth) acrylate polymer.

[43] The method for producing a reactive (meth) acrylate polymer as described in [42], wherein the polymer compound is a polyhydroxy compound having a repeating unit.
[44] The [meth] acryloyl group-containing aromatic isocyanate compound is represented by the formula (III) described in [6] or the formula (IV) described in [7]. 42]. The process for producing a reactive (meth) acrylate polymer as described in 42].

  [45] The polyhydroxy compound having the repeating unit is a polyester polyol compound, a polycarbonate polyol compound, a polyether polyol compound, a polyurethane polyol compound, a hydroxyalkyl (meth) acrylate homopolymer or copolymer, or an epoxy (meth). It is an acrylate compound, The manufacturing method of the reactive (meth) acrylate polymer as described in [43].

[46] The process for producing a reactive (meth) acrylate polymer as described in [43], wherein the polyhydroxy compound having a repeating unit contains a carboxyl group.
[47] Obtained by reacting the (meth) acryloyl group-containing aromatic isocyanate compound represented by the formula (I) according to [1] with a polymer compound having a repeating unit to which a functional group having active hydrogen is bonded. Reactive (meth) acrylate polymer.

[48] The reactive (meth) acrylate polymer as described in [47], wherein the polymer compound is a polyhydroxy compound having a repeating unit.
[49] The reactivity according to [47] or [48], wherein the (meth) acryloyl group-containing aromatic isocyanate compound is represented by the formula (III) according to [6]
(Meth) acrylate polymer.

  [50] The reactive (meth) acrylate according to [47] or [48], wherein the (meth) acryloyl group-containing aromatic isocyanate compound is represented by the formula (IV) according to [7] polymer.

  [51] The polyhydroxy compound having the repeating unit is a polyester polyol compound, polycarbonate polyol compound, polyether polyol compound, polyurethane polyol compound, hydroxyalkyl (meth) acrylate homopolymer or copolymer, or epoxy (meth) The reactive (meth) acrylate polymer according to [48], which is an acrylate compound.

[52] The reactive (meth) acrylate polymer as described in [48], wherein the polyhydroxy compound having a repeating unit contains a carboxyl group.
[53] The reaction according to [48], wherein the polyhydroxy compound is an acrylic copolymer having a repeating unit represented by the following general formula (XVI) or (XVII) having a molecular weight of 5,000 to 50,000. (Meth) acrylate polymer.

[54] A curable composition comprising the reactive monomer according to any one of [31] to [37] and a polymerization initiator.
[55] A cured product formed by curing the curable composition according to [54].

[56] The curable composition as described in [54], wherein the polymerization initiator is a photopolymerization initiator.
[57] The curable composition according to [56], further comprising an ethylenically unsaturated monomer.

  [58] 10 to 40% by mass of the reactive (meth) acrylate polymer (A) according to any one of [47] to [53], 25 to 60% by mass of the pigment (B), and 2 to 25% by mass % Of a photopolymerization initiator (D), 5 to 20% by mass of an ethylenically unsaturated monomer (F), and an organic solvent (G).

  [59] 10 to 40% by mass of the reactive (meth) acrylate polymer (A) according to any one of [47] to [53], 25 to 60% by mass of the pigment (B), and 2 to 20% by mass % Photopolymerization initiator (D), 5 to 20% by mass of ethylenically unsaturated monomer (F), organic solvent (G), and 2 to 20% by mass of polyfunctional thiol (H). A curable composition characterized by that.

[60] The curable composition as described in any one of [57] to [59], which is used for forming a color filter.
[61] The curable composition according to [58] or [59], wherein the pigment (B) is carbon black.

  [62] The reactive (meth) acrylate polymer (A) according to any one of [47] to [53], a thermosetting polymer (C), a photopolymerization initiator (D), a thermal polymerization catalyst ( E) and curable composition characterized by the above-mentioned.

[63] The curable composition as described in [62], which is used as a solder resist.
[64] An insulating protective film formed using the curable composition according to [62].

  [65] A printed wiring board having the insulating protective film according to [64].

The (meth) acryloyl group-containing aromatic isocyanate compound of the present invention is excellent in reactivity and can be expected to impart functions such as high heat resistance and high refractive index. Therefore, coating material, UV curable paint, thermosetting paint, molding material, adhesion, ink, resist,
It can be used as a raw material monomer in a wide range of fields such as optical materials, stereolithography materials, printing plate materials, dental materials, and polymer battery materials.

  In addition, the reactive monomer synthesized using the (meth) acryloyl group-containing aromatic isocyanate compound of the present invention is obtained in a short time under mild conditions, and further does not use a catalyst for promoting the reaction. A cured product in which elements such as coloring and impurities are suppressed can be provided.

Hereinafter, the (meth) acryloyl group-containing aromatic isocyanate compound according to the present invention, the production method thereof, and the synthesis of the urethane compound will be described in detail. In addition, in all general formulas in this specification, all stereoisomers such as cis and trans are included.

(I) (Meth) acryloyl group-containing aromatic isocyanate compound The (meth) acryloyl group-containing aromatic isocyanate compound of the present invention is represented by the following formula (I).

In the formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, and specifically includes a single bond, a methylene group, an ethylene group, a propylene group, an isopropylene group, butylene. Group and isobutylene group. In these, a single bond, a methylene group, and an ethylene group are preferable. R ² represents a hydrogen atom or a methyl group. R ³ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms, and specific examples include a single bond, a methylene group, an ethylene group, a propylene group, and an isopropylene group. In these, a single bond, a methylene group, and an ethylene group are preferable. X independently represents a halogen atom or an electron withdrawing group. m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 is particularly preferable. However, 1 ≦ m + n ≦ 5.

  Preferable examples of the compound represented by the above formula (I) (hereinafter also referred to as “compound (I)”) include compounds represented by the following formula (III) or (IV).

Preferred specific examples of the compound (I) include 4-acryloyloxyphenyl isocyanate, 3-acryloyloxyphenyl isocyanate, 2-acryloyloxyphenyl isocyanate, 4-methacryloyloxyphenyl isocyanate, 3- (acryloyloxymethyl) phenyl isocyanate, Examples include 2- (acryloyloxymethyl) phenyl isocyanate, 3,5-bis (methacryloyloxyethyl) phenyl isocyanate, and 2,4-bis (acryloyloxy) phenyl isocyanate.

  In particular, the substituent containing a reactive (meth) acryloyl group is preferably an electron withdrawing group having a substituent constant of −0.2 <σ <0.8 with respect to the group containing isocyanate on the aromatic ring. Specific examples include a methacryloyloxy group and an acryloyloxy group.

The isocyanate compounds exemplified as preferred specific examples of the compound (I) are reactive (
The reactivity of the isocyanate group can be controlled by the substituent constant of the substituent containing the (meth) acryloyl group, and the addition reaction can be performed under conditions such as room temperature and no catalyst.

(Ii) First production method of (meth) acryloyl group-containing aromatic isocyanate compound The first production method of the compound (I) is:
(1) From a hydroxyphenylamine compound represented by the above formula (V) (hereinafter also referred to as “compound (V)”) and a mineral acid, a hydroxyphenylamino mineral salt compound represented by the above formula (VI) ( (Hereinafter also referred to as “compound (VI)”),
(2) From the compound (VI) obtained in the step (1) and the compound represented by the above formula (VII), a hydroxyphenyl isocyanate compound represented by the above formula (VIII) (hereinafter referred to as “compound (VIII)”) ))), And
(3) From the compound (VIII) obtained in the step (2) and the compound represented by the above formula (IX), an isocyanate group-containing phenyl ester compound represented by the above formula (X) (hereinafter referred to as “compound ( X) ")), and
(4) A step of dehydrochlorinating the compound (X) obtained in the step (3) in the presence of a basic nitrogen compound. Hereinafter, each step will be described.

<Step (1)>
In step (1), as shown in the following reaction scheme, compound (VI) represented by formula (VI) is synthesized from compound (V) represented by formula (V) and mineral acid (W ¹ ). It is a process to do.

  Examples of the compound (V) used as a raw material in the step (1) include 4-aminophenol, 3-aminophenol, 2-aminophenol, 4- (aminomethyl) phenol, 3- (aminomethyl) phenol, 2 -(Aminomethyl) phenol, 4- (1-aminoethyl) phenol, 3- (1-aminoethyl) phenol, 2- (1-aminoethyl) phenol, 4- (1-aminopropyl) phenol, 3- ( 1-aminopropyl) phenol, 2- (1-aminopropyl) phenol, 4- (2-aminopropyl) phenol, 3- (2-aminopropyl) phenol, 2- (2-aminopropyl) phenol, 4- ( 3-aminopropyl) phenol, 3- (3-aminopropyl) phenol, 2- (3-aminopropyl) phenol Lumpur,

  4- (1-amino-1-methylethyl) phenol, 3- (1-amino-1-methylethyl) phenol, 2- (1-amino-1-methylethyl) phenol, 4- (2-amino-1) -Methylethyl) phenol, 3- (2-amino-1-methylethyl) phenol, 2- (2-amino-1-methylethyl) phenol, 4-amino-1,2-benzenediol, 3-amino-1 , 2-benzenediol, 5-amino-1,3-benzenediol, 4-amino-1,3-benzenediol, 2-amino-1,3-benzenediol, 3-amino-1,4-benzenediol, 2-amino-1,4-benzenediol, 5-aminomethyl-1,3-benzenediol, 4-aminomethyl-1,3-benzenediol, 2-aminomethyl-1,3 Benzenediol, 4-aminomethyl-1,2-benzenediol, 3-aminomethyl-1,2-benzenediol,

  4- (2-aminoethyl) -1,2-benzenediol, 3- (2-aminoethyl) -1,2-benzenediol, 5- (2-aminoethyl) -1,3-benzenediol, 4- (2-aminoethyl) -1,3-benzenediol, 2- (2-aminoethyl) -1,3-benzenediol, 3- (3-aminopropyl) -1,4-benzenediol, 2- (3 -Aminopropyl) -1,4-benzenediol, 4- (3-aminopropyl) -1,2-benzenediol, 3- (3-aminopropyl) -1,2-benzenediol, 3- (2-amino) Propyl) -1,4-benzenediol, 2- (2-aminopropyl) -1,4-benzenediol, 4- (2-aminopropyl) -1,2-benzenediol, 3- (2-aminopropyl) − , 2-benzenediol, 4- (2-amino-1-methylethyl) -1,2-benzenediol, 3- (2-amino-1-methylethyl) -1,2-benzenediol,

2-amino-1,3,5-benzenetriol, 6-amino-1,2,4-benzenetriol, 5-amino-1,2,4-benzenetriol, 3-amino-1,2,4-benzene Triol, 5-amino-1,2,3-benzenetriol, 4-amino-1,2,3-benzenetriol, 5-aminomethyl-1,2,3-benzenetriol, 4-aminomethyl-1,2 , 3-benzenetriol, (4-aminophenyl) methanol, (3-aminophenyl) methanol, (2-aminophenyl) methanol, 2- (4-aminophenyl) ethanol, 2- (3-aminophenyl) ethanol, 2- (2-aminophenyl) ethanol, 2- [4- (aminomethyl) phenyl] ethanol, 2- [2- (
Aminomethyl) phenyl] ethanol, 3,5-bis (1-aminophenyl) ethanol and the like.

  Among these, 5-amino-1,3-benzenediol, 3,5-bis (1-aminophenyl) ethanol, 2- [4- (aminomethyl) phenyl] ethanol, 4- (aminomethyl) phenol, 2- (aminomethyl) phenol, 4-aminophenol, 3-aminophenol and 2-aminophenol are preferred.

  Although the mineral acid used at the said process (1) is not specifically limited, For example, a sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, phosphoric acid etc. can be used. Hydrochloric acid, carbonic acid and dry hydrogen chloride gas are preferred, hydrochloric acid and dry hydrogen chloride gas are more preferred, and dry hydrogen chloride gas is particularly preferred.

The amount of the mineral acid used varies depending on the type of the amine compound (V) and is not particularly limited, but is usually 1 to 5 mol, preferably 1 with respect to 1 mol of the amine compound (V).
-1.2 mol. If the amount of mineral acid used is less than the above range, the yield may decrease and the next step may be adversely affected. On the other hand, if the above range is exceeded, it is not preferable because it imposes a burden on the waste liquid treatment and the exclusion device.

The solvent used in the step (1) varies depending on the type of the amine compound (V) and is not particularly limited. Usually, it is preferable to use a solvent, but if the starting amine compound (V) and / or the resulting amino mineral salt compound (VI) is liquid or melts, it is not necessary to use a solvent. Good.

  Examples of the solvent that can be used include water; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and n-hexanol; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and the like. Esters; chain ethers such as diethyl ether, dipropyl ether and dibutyl ether; cyclic ethers such as dioxane, dioxolane and tetrahydrofuran; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene and cumene; propane Aliphatic hydrocarbons such as hexane, heptane and cyclohexane; and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane and 1,2-dichlorobenzene. Among these, dioxane, dioxolane, tetrahydrofuran, ethyl acetate and the like are preferable because of their high polarity.

As the usage-amount of the said solvent, it is 2-100 normally with respect to 1 mass part of amine compound (V).
It is 3 parts by mass, preferably 3-20 parts by mass, more preferably 5-10 parts by mass. If the amount of the solvent is less than the above range, it may be difficult to control the reaction, and if it is more than the above range, the reaction rate may be remarkably reduced, which is not preferable.

  Although reaction temperature changes with kinds of compound to be used and is not specifically limited, For example, it is 0-150 degreeC normally, Preferably it is 15-120 degreeC, More preferably, it is 30-100 degreeC. If the reaction temperature is lower than the above range, the reaction rate may be slow, and if it exceeds the above range, the generated salt may be decomposed by heat, which is not preferable.

The amino mineral acid compound (VI) obtained in the step (1) can be used in the next step (2) as it is, but it is preferably used in the next step (2) after distilling off the solvent. . Further, it may be used after being purified by a usual purification method such as extraction or recrystallization.

<Step (2)>
As shown in the following reaction scheme, the step (2) is represented by the formula (VIII) from the compound (VI) obtained in the above step (1) and the compound (VII) represented by the formula (VII). This is a step of synthesizing Compound (VIII).

Preferred examples of Z ¹ and Z ^{2 in} the above formula (VII) include fluorine atom; chlorine atom; bromine atom; methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, pentaoxy group, hexaoxy group, cyclohexyl group. Alkyloxy groups such as saoxy groups; alkenyloxy groups such as vinyloxy groups and allyloxy groups; phenyloxy groups, tolyloxy groups, xylyloxy groups, biphenyloxy groups, naphthyloxy groups, anthryloxy groups, phenanthryloxy groups, etc. Aryloxy group; imidazoles such as imidazole, 2-imidazoline, 3-imidazoline, 4-imidazoline, imidazolidine, imidazolidone, ethyleneurea, ethylenethiourea; pyrazole, 1-pyrazoline, 2-pyrazoline, 3-pyrazoline, pyrazolidone And pyrazoles. In these, a chlorine atom and a fluorine atom are more preferable, and especially a chlorine atom is preferable.

Moreover, the dimer or trimer of the said compound can also be used. The dimer is composed of two molecules of compound (VII). For example, when Z ¹ and Z ² are chlorine atoms, the dimer is represented by the following formula (XVIII).

The trimer is composed of three molecules of compound (VII). For example, when Z ¹ and Z ² are chlorine atoms, the trimer is represented by the following formula (XIX).

The amount of compound (VII) used relative to the amino mineral salt compound (VI) varies depending on the type of compound (VII) used and is not particularly limited. Theoretically, the reaction between compound (VI) and compound (VII) proceeds at a molar ratio of 1: 1, but in order to carry out the reaction smoothly,
It is preferred to use an excess of compound (VII). For example, compound (VII) is 1-10 mol normally with respect to 1 mol of compound (VI), Preferably it is 1-5 mol. Compound (VII
When the amount of) is less than the above range, the unreacted amino mineral acid compound (VI) increases, the yield decreases, and the impurities may increase. On the other hand, if the above range is exceeded, the reaction is not affected at all, but an exclusion device or the like is required, which is not preferable because there is a possibility that the load on the environment is increased.

The solvent used in the above step (2) varies depending on the type of raw material amine compound (V),
It is not particularly limited. Usually, it is preferable to use a solvent, but when the amino mineral acid compound (VI) is liquid or melts, it is not necessary to use a solvent. As a solvent which can be used, various organic solvents except water and alcohol are mentioned among the solvents illustrated by the said process (1).

  As a usage-amount of a solvent, it is 1.5-200 mass parts with respect to 1 mass part of amino mineral salt compound (VI), Preferably it is 2-20 mass parts. If the amount of the solvent is less than the above range, the reaction may not be performed smoothly. If the amount exceeds the above range, the amount of the solvent to be discarded increases, which may increase the burden on the environment. .

Although the reaction temperature in a process (2) changes with kinds of compound to be used, it is 30-150 degreeC normally, Preferably it is 50-120 degreeC. If the reaction temperature is lower than the above range, the reaction rate may be slow, and if it exceeds the above range, the mineral acid salt may be liberated from the amine mineral salt compound (VI), which may cause impurity generation. This is not preferable.
The obtained isocyanate compound (VIII) can be used as it is for the reaction in the next step (3), but may be used after being purified by a purification operation such as extraction, recrystallization or distillation.

<Step (3)>
Step (3) is represented by the formula (X) from the compound (VIII) obtained in the step (2) and the compound (IX) represented by the formula (IX) as shown in the following reaction scheme. In this step, compound (X) is synthesized.

  The above compound (IX), for example, 3-chloropropionic acid chloride is obtained by reacting methacrylic acid and phosgene using dimethylformamide as a solvent. These compounds can generally be purchased as reagents.

  Although the usage-amount of compound (IX) with respect to isocyanate compound (VIII) changes with kinds of compound to be used, it is generally 1-10 mol with respect to 1 mol of compound (VIII), Preferably it is 3-6 mol. If the amount of compound (IX) used is less than the above range, the yield may decrease and impurities may increase, and if it exceeds the above range, waste increases, which may increase the burden on the environment. That is not preferable.

In the step (3), it is usually preferable to use a solvent, but when the isocyanate compound is liquid or melts, it is not necessary to use a solvent. Examples of the solvent that can be used include the same solvents as those used in the above step (2).

  As a usage-amount of a solvent, it is 1.5-200 times mass with respect to 1 mass part of isocyanate compound (VIII), Preferably it is 2-20 times mass. If the amount of the solvent is less than the above range, the reaction may not be performed smoothly. If the amount exceeds the above range, the amount of the solvent to be discarded increases, which may increase the burden on the environment. .

  Although the reaction temperature in a process (3) changes with kinds of compound to be used, it is 30-150 degreeC normally, Preferably it is 50-120 degreeC. If the reaction temperature is lower than the above range, the reaction rate may be slow, and if it exceeds the above range, impurities may increase and unsaturated bonds may be polymerized.

  In step (3), it is preferable to add a basic nitrogen compound as a catalyst for accelerating the reaction rate. A basic nitrogen compound is a nitrogen-containing compound that exhibits basicity for the purpose of dehydrochlorination.

  Examples of such basic nitrogen compounds include trimethylamine, triethylamine, tripropylamine, dimethylethylamine, dimethylisopropylamine, diethylmethylamine, dimethylbutylamine, dimethylhexylamine, diisopropylethylamine, dimethylcyclohexylamine, tetramethyldiaminomethane, Dimethylbenzylamine, tetramethylethylenediamine, tetramethyl-1,4-diaminobutane, tetramethyl-1,3-diaminobutane, tetramethyl-1,6-diaminohexane, pentamethyldiethylenetriamine, 1-methylpiperidine, 1-ethyl Piperidine, N, N-methylpiperazine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) 1,5-diazabicyclo [4.3.0] -5-noene (DBN), 2,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethylaniline, N, N-diethylaniline And ion exchange resins containing tertiary nitrogen.

  The basic nitrogen compounds may be used alone or in combination of two or more. Among the basic nitrogen compounds, trimethylamine, triethylamine and tripropylamine are preferable.

The resulting isocyanate group-containing phenyl ester compound (X) is directly used in the next step (
Although it can be used for the reaction of 4), it may be used after further purification by a purification operation such as extraction, recrystallization or distillation.

<Process (4)>
In the step (4), as shown in the following reaction scheme, the compound (X) obtained in the step (3) is dehydrochlorinated in the presence of the above basic nitrogen compound, thereby being represented by the formula (I). This is a step of synthesizing the (meth) acryloyl group-containing aromatic isocyanate compound.

  As a basic nitrogen compound used at a process (4), the basic nitrogen compound illustrated at the said process (3) can be used. In the step (4), a basic nitrogen compound containing a tertiary nitrogen atom is preferable, a tertiary nitrogen atom is contained, and the tertiary nitrogen atom is a group other than an aromatic ring group, such as an alkyl group. A basic nitrogen compound having at least one is more preferable. Moreover, it is preferable that the aromatic ring group couple | bonded with this tertiary nitrogen atom is 1 or less. Specifically, trimethylamine, triethylamine and tripropylamine are preferable, and triethylamine is particularly preferable.

  The amount of the basic nitrogen compound used varies depending on the type of compound used, but the alkali-decomposable chlorine in the reaction solution after the completion of the step (3) is measured, and the amount of the basic nitrogen compound is determined by the measured value. It is desirable to decide. Specifically, the amount of the basic nitrogen compound is 0.5 to 10 mol, preferably 0.8 to 5.0 mol, more preferably 0.9 to 1 mol per 1 mol of the alkali-decomposable chlorine measured. 2.0 moles.

  If the amount of basic nitrogen compound used is less than the above range, the yield may decrease, and if it exceeds the above range, the stability of the resulting compound may be deteriorated and the cost will increase. It is not preferable.

  The amount of the alkali-decomposable chlorine is determined by diluting the reaction solution obtained in the step (3) with a methanol / water mixed solvent, adding a sodium hydroxide aqueous solution and heating it, and then using a silver nitrate solution. This value is obtained by potentiometric titration, and details will be described later.

The solvent used in the step (4) varies depending on the type of compound used and is not particularly limited. Usually, it is preferable to use a solvent, but when the ester compound (X) is liquid or melts, it is not necessary to use a solvent. Examples of the solvent that can be used include the same solvents as those in the above step (2).

The usage-amount of a solvent is 1.5-200 with respect to 1 mass part of ester compound (X), for example.
Part by mass, preferably 2 to 20 parts by mass. If the amount of the solvent is less than the above range, the reaction may not be performed smoothly, and it is difficult to remove the generated salt. If the amount exceeds the above range, the amount of the solvent to be discarded increases, so the burden on the environment is high. It is not preferable because there is a possibility of becoming.

  The reaction temperature in the step (4) varies depending on the kind of the compound to be used and is not particularly limited, but is, for example, 0 to 150 ° C, preferably 20 to 100 ° C. If the reaction temperature is lower than the above range, the reaction rate may be slow, and if it exceeds the above range, the unsaturated bond produced by the dehydrochlorination reaction may be polymerized.

The compound (I) of the present invention obtained by the above step (4) can be purified by general operations, that is, filtration, extraction, recrystallization, distillation and the like.
(Iii) Second method for producing (meth) acryloyl group-containing aromatic isocyanate compound Next, a second method for producing the (meth) acryloyl group-containing aromatic isocyanate compound of the present invention will be described. The second manufacturing method is
(1 ′) the same step as step (1) of the first production method,
(2 ′) the same step as step (2) of the first production method,
(3 ′) From the isocyanate compound (VIII) obtained in the step (2 ′) and a compound represented by the formula (XI) (hereinafter also referred to as “compound (XI)”), the compound represented by the formula (I) Synthesizing the (meth) acryloyl group-containing aromatic isocyanate compound. The reaction scheme of the step (3 ′) is shown below.

  For example, in the case of methacrylic acid chloride, the compound (XI) used in the step (3 ') can be obtained by reacting methacrylic acid and phosgene using dimethylformamide as a solvent. Compound (XI) can also be purchased from a reagent company.

  Although the usage-amount of the said compound (XI) changes with kinds of compound to be used, it is 1-10 mol with respect to 1 mol of hydroxyphenyl isocyanate compounds (VIII), Preferably it is 3-6 mol. If the amount of compound (XI) used is less than the above range, the yield may decrease and impurities may increase, and if it exceeds the above range, waste may increase and processing costs may increase. It is not preferable.

  The solvent used in the above step (3 ′) varies depending on the type of compound used and is not particularly limited. Usually, it is preferable to use a solvent, but when the isocyanate compound (VIII) is liquid or melts, it is not necessary to use a solvent. Examples of the solvent that can be used include those exemplified in the step (2) of the first production method.

  The usage-amount of a solvent is 1.5-200 mass parts with respect to 1 mass part of compounds (VIII), Preferably it is 2-20 mass parts. If the amount of the solvent is less than the above range, the reaction may not be carried out smoothly. If the amount exceeds the above range, the amount of the solvent to be discarded increases, which may increase the burden on the environment.

  Although the reaction temperature in a process (3 ') changes with kinds of compound to be used, it is 30-150 degreeC normally, Preferably it is 50-120 degreeC. If the reaction temperature is lower than the above range, the reaction rate may be slow, and if it exceeds the above range, impurities may increase and unsaturated bonds may be polymerized.

Compound (I) of the present invention obtained by the above step (3 ′) is subjected to a general procedure, that is,
It can be purified by filtration, extraction, recrystallization, distillation and the like.
The (meth) acryloyl group-containing aromatic isocyanate compound of the present invention has a function of imparting high heat resistance, a high refractive index and the like, and thus is useful in the field of functional resins. For example, by copolymerizing the compound (I) of the present invention with a (meth) acrylate such as methyl methacrylate or methyl acrylate, or a compound having a vinyl group such as vinyl ether or styrene, it has high heat resistance and high resistance. A functional polymer material having a function such as a refractive index can be manufactured.

(Iv) Reactive monomer By reacting the compound (I) of the present invention with a monomer, oligomer or polymer having active hydrogen such as hydroxyl group, amino group or carboxyl group, the monomer, oligomer or polymer is reacted. A material having functions such as high heat resistance and a high refractive index can be manufactured.

Furthermore, by using the compound (I) of the present invention, there is a possibility that a composition having a high curing speed and functions such as high heat resistance and high refractive index can be obtained.
By reacting the compound (I) of the present invention with a compound having a hydroxyl group in the molecule, a (meth) acryloyl group-containing urethane compound represented by the following formula (XII) can be obtained.

In the above formula (XII), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, specifically, a single bond, a methylene group, an ethylene group, a propylene group, an isopropylene group, Examples include butylene group and isobutylene group. In these, a single bond, a methylene group, and an ethylene group are preferable.

R ² represents a hydrogen atom or a methyl group.
R ³ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms, and specific examples include a single bond, a methylene group, an ethylene group, a propylene group, and an isopropylene group. In these, a single bond, a methylene group, and an ethylene group are preferable.

R ⁴ represents an ether group, a thioether group or an NH group.
X independently represents a halogen atom or an electron withdrawing group.
l represents an integer of 1 to 50, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 is particularly preferable. However, 1 ≦ m + n ≦ 5.

  Y is an aliphatic group, a group containing an aromatic ring, a group containing a heterocyclic ring, a polycarbonate residue, a polyurethane residue, a polyester residue or a polyhydroxy compound residue having a repeating unit.

  The aliphatic group of the substituent Y is a group having a linear, branched or cyclic carbon chain and having 1 to 4 substitutable positions. Specific examples thereof include a linear or branched alkyl group, a linear or branched alkylene group, and a cyclic alkyl group.

The aliphatic group of the substituent Y may further have a substituent. Specific examples of such a substituent include an ethyl group, an n-butyl group, an n-hexyl group, —CH ₂ CH ₂ (CF ₂ ) ₈ F, —CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF. ₂ An alkyl group such as CH ₃ ; and a cyclic alkyl group such as a cyclohexyl group, a cycloalkenyl group, and a norbornyl group.

  The aromatic group of the substituent Y is an aromatic group having 1 to 4 substitutable positions, and specific examples thereof include a phenyl group, a xylylene group, a bisphenol group, and a fluorene group.

The heterocyclic group of the substituent Y is a heterocyclic group having 1 to 4 substitutable positions, and specific examples thereof include pyridyl group, thienyl group, furyl group, piperidyl group, imidazolyl group, quinolyl group and the like. Can be mentioned.

  Particularly preferred examples of the compound represented by the above formula (XII) include compounds represented by the following formula (XIV) or (XV).

(Formula (XIV) in, R ^2, Y and l. Representing the the same as R ^2, Y and l in formula (XII))

(Formula (XV) in, R ^2, Y and l. Representing the the same as R ^2, Y and l in formula (XII))
The reactive monomer of the present invention is cured by radical polymerization or cationic polymerization in an ethylenically unsaturated group by light or heat.
Hereinafter, preferred specific examples of the reactive monomer of the present invention will be described for each of the case where R ⁴ is an ether group, a thioether group, and an NH group.

<Reactive monomer in which R ⁴ is an ether group>
In the reactive monomer in the first example, R ^{4 in} the formula (XII) is an ether group, Y is a group containing fluorine, and l = 1. Specific examples of such a fluorine-containing group having one substitution position include a fluoroalkyl group. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a linear structure (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (
CF ₂ ) ₄ H, —CH ₂ CH ₂ (CF ₂ ) ₈ F, etc.), and branched structures (eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH ( _{CH 3) CF 2 CF 3,} -CH (CH 3) (
CF ₂ ) ₅ CF ₂ H and the like, and an alicyclic structure (preferably a 5- or 6-membered ring,
For example, it may be a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond. Specific examples of the fluoroalkyl group having an ether bond include —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , such as _{-CH 2 CH 2 OCF 2 CF 2} OCF 2 CF 2 H and the like.

A plurality of the above fluoroalkyl groups may be contained in the same molecule.
Preferable examples of Y in the formula (XII) are groups represented by — (CH ₂ ) _p (CF ₂ ) _q F (p represents an integer of 0 to 2, and q represents an integer of 0 to 8. p and q are not 0 at the same time.).

  The fluorine content is preferably 30% by weight or more, more preferably 40% by weight or more, and still more preferably 50% by weight or more based on the total amount of reactive monomers. When the fluorine content is low, the value of the refractive index increases, and when used as an antireflection film or a cladding material, the characteristics as a low refractive material may not be exhibited. For example, when the fluorine content is less than 40% by weight, the refractive index may be 1.45 or more, but such a refractive index is not suitable as a low refractive material. However, a fluorine content can be 50 weight% or more with respect to the whole quantity of a composition by preparing a composition by using a reactive monomer as one component.

In the reactive monomer in the second example, R ^{4 in} the formula (XII) is an ether group, Y is a group containing fluorine, and l = 2. Such a fluorine-containing group having two substitution positions is preferably a group obtained from a fluorine-containing diol. Specific examples of the fluorine-containing diol include 2,2,3,3,4,4-hexafluoro- 1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6 , 6,7,7-dodecafluoro-1,8-octanediol and the like; perfluoroalkylene glycols such as perfluorotriethylene glycol and perfluorotetraethylene glycol; α- (1,1-difluoro- 2-hydroxyethyl) -ω- (2,2-difluoroethanol) poly (oxy-1,1,2,2-tetrafluoroethylene), α- (1,1-diph Oro-2-hydroxyethyl) -ω- (2,2-difluoroethanol) poly (oxy-difluoromethylene), α- (1,1-difluoro-2-hydroxyethyl) -ω- (2,2-difluoroethanol ) Polyperfluoroalkylene ether diols such as poly (oxy-difluoromethylene) (oxy-1,1,2,2-tetrafluoroethylene); 3-perfluorobutyl-1,2-epoxypropane, 3-perfluorooctyl Examples include ring-opening diols of fluoroalkyl epoxides such as -1,2-epoxypropane and 3-perfluorobutyl-1,2-epoxypropane; 2,2-bis (4-hydroxycyclohexyl) hexafluoropropane and the like. Further, it may be a group obtained from a diol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to these fluorine-containing diols.

The preferred range of the fluorine content with respect to the total amount of reactive monomers is the same as in the first example described above.
In the reactive monomer in the third example, R ^{4 in} the formula (XII) is an ether group, Y is a group having a fluorene skeleton, and l = 2. Examples of the group having a fluorene skeleton include a group represented by the following formula (XX).

In the above formula (XX), h is preferably 1 to 4, more preferably 1 to 2.
<Reactive monomer in which R ⁴ is NH group>
In the reactive monomer in the first example, R ^{4 in} formula (XII) is an NH group, Y is a group containing fluorine, and l = 1. Examples of the fluorine-containing group having one substitution position include the same groups as those in the case where R ⁴ is an ether group, and preferred specific examples include F (CF ₂ ) ₃ CH ₂ —. , F (CF ₂ ) ₆ CH ₂ —, F (CF ₂ ) ₇ CH ₂ —, F (CF ₂ ) ₈ CH ₂ —, an aromatic group such as a residue of 2,6-difluoroaniline.

In the reactive monomer in the second example, R ^{4 in} the formula (XII) is an NH group, Y is a saturated aliphatic group or an aromatic group, and l = 2. Examples of the saturated aliphatic group include a group consisting of a linear, branched or cyclic carbon chain having two substitution positions. Specific examples include groups having an alkylene linear structure such as ethylene, propylene, butylene, hexamethylene and polyoxyalkylene, and groups having an alicyclic structure such as cyclohexyl and norbornane.

  In addition, aromatic groups include phenylene group, xylylene group, 4,4'-methylenebis (phenylamine) group, 2,3,5,6-tetrafluoro-phenyl group, 2,3,5,6-tetrafluoro. Examples include a -1,4-xylylenyl group.

<Reactive monomer in which R ⁴ is a thioether group>
Examples of the substituent Y when R ⁴ is a thioether group include the same groups as those described above in which R ⁴ is an ether group or an NH group. Specific examples of the substituent Y include those obtained by adding the isocyanate group of the (meth) acryloyl group-containing isocyanate compound of the formula (I) to the following compound having one or more mercapto groups. It is done.

  Specific examples of such compounds having one or more mercapto groups include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, Furfuryl mercaptan, thiophenol, thiocresol, ethylthiophenol, benzyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexane Dithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, bicyclo [2,2,1] Puta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopro Pionate), trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate),

1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (2-mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, 1,4-bis (2-mercaptoethyl) benzene, 1,2- Bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1, 2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) ben 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (2-mercaptoethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3
, 5-Tris (2-mercaptoethyl) benzene, 1,2,3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercaptoethyleneoxy) benzene, 1,3,5- Tris (2-mercaptoethyleneoxy) benzene,

  1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyl) benzene, 2,3,5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2-mercaptoethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) Benzene, 2,2′-dimercaptobiphenyl, 4,4′-thiobis-benzenethiol, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4 -Toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethyl Benzene-1,3-dithiol, 9,10-anthracene dimethanethiol,

  1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2-mercaptoethylthio) benzene, 1,2-bis (2-mercaptoethylthiomethyl) benzene, 1,3-bis (2 -Mercaptoethylthiomethyl) benzene, 1,4-bis (2-mercaptoethylthiomethyl) benzene, 1,2,3-tris (2-mercaptoethylthio) benzene, 1,2,4-tris (2-mercapto Ethylthio) benzene, 1,3,5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) benzene, 1,2,3,5-tetrakis (2 -Mercaptoethylthio) benzene, 1,2,4,5-tetrakis (2-mercaptoethylthio) benzene, bis (2-mercaptoethyl) sulfide Bis (2-mercaptoethylthio) methane, 1,2-bis (2-mercaptoethylthio) ethane, 1,3-bis (2-mercaptoethylthio) propane, 1,2,3-tris (2-mercaptoethyl) Thio) propane, tetrakis (2-mercaptoethylthiomethyl) methane, 1,2-bis (2-mercaptoethylthio) propanethiol, 2,5-dimercapto-1,4-dithiane, bis (2-mercaptoethyl) disulfide 3,4-thiophenedithiol, 1,2-bis (2-mercaptoethyl) thio-3-mercaptopropane, bis- (2-mercaptoethylthio-3-mercaptopropane) sulfide, and the like.

Among these, octyl mercaptan, 1,6-hexanedithiol, 2-mercaptoethyl sulfide, and 1,4-dimercaptobenzene are preferable.
(V) Method for Producing Reactive Monomer The reactive monomer represented by the formula (XII) in the present invention contains a (meth) acryloyl group-containing aromatic isocyanate compound containing two polymerizable functional groups represented by the formula (I) And a compound to which a functional group having active hydrogen is bonded, for example, a compound containing a hydroxyl group, an amino group, or a mercapto group. The reaction method is not particularly limited. For example, the reactive monomer of the formula (XII) can be obtained simply by mixing.

  As a method for producing the compound of the above formula (XII), when a (meth) acryloyl group-containing aromatic isocyanate compound and a compound containing a hydroxyl group are reacted in a solvent, a urethanization catalyst may be used. Generally done. By using the urethanization catalyst, the reaction can be remarkably accelerated.

  Examples of the urethanization catalyst include dibutyltin dilaurate, copper naphthenate, cobalt naphthenate, and zinc naphthenate. However, since these catalysts all contain heavy metals, it is desirable to avoid using them as much as possible in consideration of environmental considerations.

The reactivity of aromatic isocyanate in the urethanization reaction is greatly influenced by the electron withdrawing property or substituent constant of the substituent on the aromatic ring.
The substituent constant is a parameter that is defined based on Hammett's formula and quantifies the reactivity of a substituent having an active hydrogen on the aromatic ring. When the substituent is a hydrogen atom, the substituent constant is 0. Is defined as Generally, the substituent constant of the electron-donating group is negative and the substituent constant of the electron-withdrawing group is positive. The higher the absolute value, the greater the effect.

  In the aromatic isocyanate represented by the general formula (I) of the present invention, the higher the electron withdrawing property of the substituent, the more desirable in terms of increasing the reactivity of the isocyanate group, and the substituent constant is a positive value. It is desirable in that the reaction can be promoted.

  For example, when unsubstituted phenyl isocyanate or p-methylphenyl isocyanate is used, the reactivity of the isocyanate group tends to be greatly reduced as compared with the aromatic isocyanate represented by the general formula (I). It is in.

  The substituent constant of unsubstituted phenyl isocyanate is 0 as described above, and the substituent constant of p-methylphenyl isocyanate is −0.17, both of which are not positive values, and both are electron-withdrawing groups. not. This supports the result that the reactivity of the isocyanate groups of both compounds is low compared to the isocyanate monomer of general formula (I).

  On the other hand, the compound represented by the general formula (I) has sufficient reactivity with respect to a hydroxyl group, and can complete the reaction for producing the reactive monomer without using a catalyst. is there. The reaction temperature is preferably 0 ° C to 60 ° C, more preferably 25 ° C to 40 ° C. If the reaction temperature is less than 0 ° C., the reaction may not be completed and the raw materials may remain. If the reaction temperature exceeds 60 ° C., side reactions may occur or coloring may occur.

In addition, by using the above method, the reaction composition can be simplified and the burden on the environment can be reduced by eliminating heavy metals, which is very useful industrially.
It is known that the above reaction proceeds even with a group other than a hydroxyl group, an amino group, and a mercapto group. For example, since an isocyanate group also reacts with a carboxyl group or the like, a reactive ethylenically unsaturated group can be introduced by addition by reaction.

Therefore, a hydroxyl group, an amino group, or a combination of such a (meth) acryloyl group-containing aromatic isocyanate compound of formula (I) and an isocyanate compound containing one reactive ethylenically unsaturated group You may make it react with the compound containing a mercapto group. Specific examples of the isocyanate compound containing one reactive ethylenically unsaturated group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2- (2-ethylbutenoyloxy). Ethyl isocyanate, 2- (2-propylbutenoyloxy) ethyl isocyanate, methacryloyloxymethyl isocyanate, acryloyloxymethyl isocyanate, (2-ethylbutenoyloxy) methyl isocyanate, (2-propylbutenoyloxy) methyl isocyanate, 3-methacryloyloxypropyl isocyanate, 3-acryloyloxypropyl isocyanate, 3- (2-ethylbutenoyloxy) propyl isocyanate, 3- (2-propylbutenoyloxy) propyl isocyanate 4-methacryloyloxy-butyl isocyanate, 4-acryloyloxy-butyl isocyanate, 4- (2-ethyl-Bed Tenofovir acetoxyphenyl) butyl isocyanate, such as 4- (2-propyl Bed Tenofovir acetoxyphenyl) butyl isocyanate.

(Vi) Curable composition The curable composition of the present invention contains a reactive monomer of the formula (XII) and a polymerization initiator. As the polymerization initiator, a photopolymerization initiator can be used, and by irradiating active energy rays such as ultraviolet rays or visible rays, the reactive monomer undergoes a polymerization reaction to obtain a cured product. Specific examples of such a photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3- Methyl acetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoylpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy 2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, -Chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino Examples include -1- (4-morpholinophenyl) butan-1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-1-one.

Among these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone are preferable.
Said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, a cured product can be obtained by causing a polymerization reaction of the reactive monomer by heat. That is, it can be set as a thermosetting composition by adding a thermopolymerization initiator to a reactive monomer. Examples of such thermal polymerization initiators include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyesters, azo compounds, and persulfates. These may be used alone or in combination of two or more.

  The amount of the polymerization initiator used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the reactive monomer. When the usage-amount of a polymerization initiator will be less than 0.1 weight part, the polymerization rate of a reactive monomer may become slow. Moreover, it may become easy to receive the polymerization inhibition by oxygen etc. On the other hand, when the usage-amount of a polymerization initiator exceeds 20 weight part, a polymerization reaction will be suppressed conversely and the intensity | strength of a cured film obtained, adhesive strength, and heat resistance may fall. Furthermore, it causes coloring.

The curable composition of the present invention may contain a reactive monomer other than the reactive monomer of the formula (XII). By containing such a reactive monomer, the viscosity of the composition can be adjusted, and the properties of the resulting cured product, for example, mechanical properties such as reactivity, hardness, elasticity and adhesion, optical properties such as transparency, etc. Characteristics can be adjusted.

Specific examples of such reactive monomers include
Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1 , 1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, ethylenically unsaturated pyridine, ethylenically unsaturated imidazole, etc. Aromatic compounds;
Carboxyl group-containing compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid;

  Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl ) Acrylates, alkyl such isostearyl (meth) acrylate (meth) acrylates;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate;
Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate;

Polyethylene glycol (meth) acrylates such as polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate;
Polypropylene glycol (meth) acrylates such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl ( Cycloalkyl (meth) acrylates such as (meth) acrylate and tricyclodecanyl (meth) acrylate;

Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, Sphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) Examples include acrylate and dipentaerythritol hexa (meth) acrylate. These reactive monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

In the curable composition of the present invention, the reactive monomer of formula (XII) and the polymerization initiator are mixed with a mixer such as a mixer, a ball mill, or a three-roller at room temperature or under heating conditions, or reacted. It can be blended and adjusted by adding a soluble monomer or solvent as a diluent and dissolving it. Here, specific examples of the reactive monomer used as the diluent include the reactive monomers described above. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate and isopropyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; N, N-dimethylformamide and the like Amides; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as methylene chloride.

  The curable composition of the present invention can be cured, for example, by applying a curable composition on a substrate and forming a coating film, and then irradiating with radiation or heating. You may perform both irradiation of a radiation and a heating for hardening.

The thickness of the coating film is preferably 1 to 200 μm for evaluation, but is appropriately set depending on the application.
Examples of the coating method include coating by a die coater, spin coater, spray coater, curtain coater, roll coater, etc., coating by screen printing, and coating by dipping.

  The radiation used for curing is preferably an electron beam or light in the ultraviolet to infrared wavelength range. For example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet rays, a metal halide light source or a halogen light source can be used for visible rays, and a halogen light source can be used for infrared rays, but other light sources such as lasers and LEDs can be used. The radiation dose is appropriately set according to the type of light source, the film thickness of the coating film, and the like.

  The curable composition of the present invention comprises resist (solder resist, etching resist, color filter resist, spacer, etc.), sealing (waterproof sealing, etc.), paint (antifouling paint, fluorine-based paint, water-based paint, etc.), adhesive / adhesive Agents (adhesives, dicing tape, etc.), printing plates (CTP plates, offset plates, etc.), printing proofs (color proofs, etc.), lenses (contact lenses, microlenses, optical waveguides, etc.), dental materials, surface treatment (optical fiber coating , Disk coat, etc.) and battery materials (solid electrolyte, etc.).

(Vii) Reactive (meth) acrylate polymer (A)
The reactive (meth) acrylate polymer (A) of the present invention is obtained by reacting an isocyanate compound represented by the following formula (I) with a polymer compound having a repeating unit to which a functional group having active hydrogen is bonded. A compound.

In formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 3 carbon atoms. X represents a halogen atom or an electron-withdrawing group, m represents an integer of 0 to 4, and n represents an integer of 1 to 3. However, 1 ≦ m + n ≦ 5.

  Preferable specific examples of the isocyanate compound include compounds represented by the following formula (III) or (IV).

In the formula (III), R ² represents a hydrogen atom or a methyl group.

In the formula (IV), R ² represents a hydrogen atom or a methyl group.
Here, the above-mentioned polymer compound to be reacted with the isocyanate compound of the formula (I) has a repeating unit to which a functional group having an active hydrogen such as a hydroxyl group, an amino group, or a mercapto group is bonded. These hydroxyl group, amino group or mercapto group react with the isocyanate group of the isocyanate compound of formula (I) to form a urethane bond, a urea bond or a thiourethane bond.

  Here, the repeating unit to which a functional group having active hydrogen is bonded is a repeating unit based on a monomer having such a functional group or capable of forming the functional group by a polymerization reaction. The polymer compound is obtained by polymerization. The polymer compound may be a homopolymer composed of the same type of monomer, or may be a copolymer of monomers different from each other.

As the polymer compound, a polyhydroxy compound having a repeating unit is preferable.
The number average molecular weight of the reactive (meth) acrylate polymer (A) of the present invention (polystyrene conversion value by gel permeation chromatography (mass part PC)) is usually 500 to 100,000, preferably 8,000. ~ 40,000.

(Viii) Method for producing reactive (meth) acrylate polymer (A) The reactive (meth) acrylate polymer is a polymer having a repeating unit in which an isocyanate compound of formula (I) and a functional group having active hydrogen are bonded. Although it can be obtained by reacting with a compound, the reaction method is not particularly limited. For example, a reactive (meth) acrylate polymer can be obtained simply by mixing them.

  When the (meth) acryloyl group-containing aromatic isocyanate compound and the hydroxyl group-containing compound are reacted in a solvent as a method for producing the (meth) acrylate polymer (A), a urethanization catalyst should be used. Is generally done. By using the urethanization catalyst, the reaction can be remarkably accelerated.

  Specific examples of the urethanization catalyst include dibutyltin dilaurate, copper naphthenate, cobalt naphthenate, and zinc naphthenate. However, these catalysts are all heavy metals, and it is desired to avoid using them as much as possible in consideration of environmental considerations.

  The reactivity of aromatic isocyanate in the urethanization reaction is greatly influenced by the electron withdrawing property or substituent constant of the substituent on the aromatic ring. Substituent constant is a parameter defined based on Hammett's formula that quantifies the reactivity of a substituent having an active hydrogen on an aromatic ring. Generally, the substituent constant of an electron donating group is negative. The substituent constant of the electron-withdrawing group is positive, and the higher the absolute value, the greater the effect.

  In the aromatic isocyanate of the formula (I) of the present invention, the higher the electron withdrawing property of the substituent, the more desirable in terms of increasing the reactivity of the isocyanate group, and the reaction is promoted when the substituent constant is a positive value. Is desirable in that it can.

  For example, in the case of using unsubstituted phenyl isocyanate or p-methylphenyl isocyanate, compared with the aromatic isocyanate represented by the general formula (I), a significant decrease in the reactivity of the isocyanate group is observed. .

  When the substituent constant of unsubstituted phenyl isocyanate is 0, the substituent constant of p-methylphenyl isocyanate is -0.17, which supports the above result.

On the other hand, the compound represented by the above formula (I) has sufficient reactivity with respect to a hydroxyl group, and can complete a reaction for producing a reactive (meth) acrylate polymer without using a catalyst. Is possible. The reaction temperature is 0 ° C to 60 ° C, preferably 25 ° C to 40 ° C. If the reaction temperature is less than 0 ° C., the reaction may not be completed and the raw materials may remain. If the reaction temperature exceeds 60 ° C., side reactions may occur or coloring may occur.

(Ix) Polyhydroxy compound having a repeating unit The polyhydroxy compound having a repeating unit used in the present invention is a polyester polyol compound, a polycarbonate polyol compound, a polyether polyol compound, a polyurethane polyol compound, or a single weight of a hydroxyalkyl (meth) acrylate. A combination or copolymer, or an epoxy (meth) acrylate compound.

(Ix-a) Polyester polyol compound The polyester polyol compound used in the present invention is a compound having two or more hydroxyl groups and one or more ester bonds in one molecule. Specific examples thereof include polyhydric alcohols and polyhydric alcohols. Examples thereof include polyester-based polyols obtained from esters of basic acids, polylactone-based diols such as polycaprolactone diol and polybutyrolactone diol. Moreover, the polyester polyol compound synthesize | combined so that a carboxyl group may remain | survive can also be used.

(Ix-b) Polycarbonate polyol compound The polycarbonate polyol used in the present invention is a compound having two or more hydroxyl groups and one or more carbonate bonds in one molecule. Above all, the following formula (XXI)

(In the formula, R ⁸ , R ⁹ and R ¹⁰ are each independently a linear, branched or cyclic carbonization having 2 to 30 carbon atoms which may have a hydroxyl group and / or a carboxyl group. A hydrogen group, i and j each independently represents an integer of 0 to 100).

R ⁸ , R ⁹ and R ¹⁰ are preferably an alkylene group having 2 to 12 carbon atoms, and specific examples thereof include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene Group, 2,2-dimethyl-1,3-propylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group and the like.

  The polycarbonate polyol compound can be obtained, for example, by reacting a diaryl carbonate such as diphenyl carbonate with a polyol such as ethylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylol ethane, trimethylol propane, glycerin, or sorbitol. .

(Ix-c) Polyether Polyol Compound The polyether polyol compound used in the present invention is preferably a compound having a structure in which two or more alkylene glycols are dehydrated and condensed. Such a compound is produced by condensation of alkylene glycol or ring-opening polymerization of alkylene oxide.

  Specific examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, Examples include 1,6-hexanediol and 1,4-cyclohexanedimethanol.

  Specific examples of the alkylene oxide include ethylene oxide, propylene oxide, tetrahydrofuran, styrene oxide, phenyl glycidyl ether and the like.

  Specific examples of the polyether polyol compound include polyethylene glycol, polypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene glycol, polyhexamethylene glycol and the like.

(Ix-d) Polyurethane polyol compound The polyurethane polyol compound used in the present invention has two or more hydroxyl groups and one or more urethane bonds in one molecule. These can be obtained by reacting polyisocyanate and polyol by any method. In this reaction, the reactive (meth) acrylate polymer (A) may be produced by simultaneously charging the isocyanate compound of the formula (I).

  Specific examples of the polyisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, m or p) -xylene diisocyanate, methylene bis (cyclohexyl isocyanate), And diisocyanates such as trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, and 1,5-naphthalene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

  Specific examples of the polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1 Diol compounds such as 1,6-hexanediol and 1,4-cyclohexanedimethanol, triol compounds such as glycerin and trimethylolpropane, pentaerythritol, dipentaerythritol and diglycerin.

  As the polyol compound, a polyol compound having a carboxyl group such as dihydroxy aliphatic carboxylic acid can be used, and alkali developability is imparted by introducing a carboxyl group into the reactive (meth) acrylate polymer (A). It is preferable in that it can be performed.

  Examples of such a polyol compound having a carboxyl group include dimethylolpropionic acid and dimethylolbutanoic acid. These may be used alone or in combination of two or more.

  Further, as the polyol, the polyester polyol compound (ix-a), the polycarbonate polyol compound (ix-b), or the polyether polyol compound (ix-c) may be used.

(Ix-e) Hydroxyalkyl (meth) acrylate homopolymer or copolymer The hydroxyalkyl (meth) acrylate homopolymer or copolymer used in the present invention is one or more hydroxyalkyl (meth) acrylates. Is a polymer obtained by homopolymerization or copolymerization by any method. Specific examples of the hydroxyalkyl (meth) acrylate used here include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin di ( (Meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate, trimethylolpropane-alkylene oxide adduct-mono ( (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, polyethylene glycol (meth) acrylate, 6-hydroxyhexanoyloxyethyl (meth) Acrylate and the like.

  Among these, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable. These (meth) acrylates having a hydroxyl group may be used singly or in combination of two or more.

Constituent components other than the hydroxyalkyl (meth) acrylate constituting the copolymer are unsaturated compounds copolymerizable with these, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth)
Alkyl (meth) acrylates such as acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, bornyl (meth) ) Acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc .; benzyl (meth) acrylate, phenyl (meth) acrylate, phenyl carb Thor (meth) acrylate, nonylphenyl (meth) acrylate, nonylphenyl carbitol (meth) acrylate, nonylphenoxy (meth) acrylate, etc. Group (meth) acrylate; (meth) acrylate having an amino group such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-tert-butylaminoethyl (meth) acrylate; methacryloxyethyl Methacrylate having a phosphorus atom such as phosphate, bis-methacryloxyethyl phosphate, methacryloxyethyl phenyl acid phosphate (phenyl P); glycidyl (meth) acrylate; allyl (meth) acrylate; phenoxyethyl acrylate, and the like.

  Also, carboxyl groups or acid anhydrides such as (meth) acrylic acid, itaconic acid, maleic anhydride, itaconic anhydride, polycaprolactone (meth) acrylate, (meth) acryloyloxyethyl phthalate, (meth) acryloyloxyethyl succinate An unsaturated compound having a group may be used.

In the present specification, expressions such as (meth) acrylate means methacrylate and / or acrylate.
In addition, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide, and vinyl aromatic compounds such as styrene and vinyltoluene can also be suitably used.

(Ix-f) Epoxy (meth) acrylate compound The epoxy (meth) acrylate compound is an epoxy resin with an unsaturated monocarboxylic acid added to the epoxy group, and in some cases, a polybasic acid anhydride is further reacted. Can be obtained. Specific examples of the epoxy resin that can be used here include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac epoxy resin, (o, m, p-) cresol novolac epoxy resin, phenol novolac epoxy. Examples thereof include resins, naphthol-modified novolac epoxy resins, halogenated phenol novolac epoxy resins, and the like.

Among these, novolak epoxy resins such as novolak epoxy resins, (o, m, p-) cresol novolac epoxy resins, phenol novolac epoxy resins, naphthol-modified novolac epoxy resins, halogenated phenol novolac epoxy resins and the like from the viewpoint of light sensitivity. An epoxy (meth) acrylate resin having a carboxylic acid group used as a raw material is preferred.

  The number average molecular weight of the reactive (meth) acrylate polymer (A) of the present invention (polystyrene conversion value by gel permeation chromatography (mass part PC)) is usually 500 to 100,000, preferably 8,000. ~ 40,000. When the number average molecular weight is less than 500, the film strength is remarkably lowered. On the other hand, when the number average molecular weight exceeds 40,000, developability and flexibility are lowered.

  When the reactive (meth) acrylate polymer (A) of the present invention is used for a resist, the acid value is preferably 5 to 150 mgKOH / g, more preferably 30 to 120 mgKOH / g. If the acid value is less than 5 mgKOH / g, the alkali developability may be lowered. On the other hand, if the acid value exceeds 150 mgKOH / g, the alkali resistance and electrical properties of the cured film may be impaired.

  Among the polyhydroxy compounds having a repeating unit described above, the compound having a carboxyl group reacts with the carboxyl group under the reaction conditions of the isocyanate of formula (I) to form an amide bond. A compound of formula (I) can also be added by such a reaction.

  Further, a polymer compound containing a hydroxyl group (or amino group or mercapto group) in combination with such an isocyanate compound of formula (I) and an isocyanate compound containing one reactive ethylenically unsaturated group And may be reacted. Specific examples of the isocyanate compound containing one reactive ethylenically unsaturated group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2- (2-ethylbutenoyloxy). Ethyl isocyanate, 2- (2-propylbutenoyloxy) ethyl isocyanate, methacryloyloxymethyl isocyanate, acryloyloxymethyl isocyanate, (2-ethylbutenoyloxy) methyl isocyanate, (2-propylbutenoyloxy) methyl isocyanate, 3-methacryloyloxypropyl isocyanate, 3-acryloyloxypropyl isocyanate, 3- (2-ethylbutenoyloxy) propyl isocyanate, 3- (2-propylbutenoyloxy) propyl isocyanate 4-methacryloyloxy-butyl isocyanate, 4-acryloyloxy-butyl isocyanate, 4- (2-ethyl-Bed Tenofovir acetoxyphenyl) butyl isocyanate, such as 4- (2-propyl Bed Tenofovir acetoxyphenyl) butyl isocyanate.

(X) Curable composition A curable composition is obtained by mix | blending another component other than the reactive (meth) acrylate polymer (A) of this invention. This curable composition consists of resist (solder resist, etching resist, color filter resist, spacer, etc.), sealing (waterproof sealing, etc.), paint (antifouling paint, fluorine paint, aqueous paint, etc.), adhesive / adhesive ( Adhesives, dicing tape, etc.), printing plates (CTP plates, offset plates, etc.), printing proofs (color proofs, etc.), lenses (contact lenses, microlenses, optical waveguides, etc.), dental materials, surface treatment (optical fiber coatings, discs) Coating) and battery materials (solid electrolyte, etc.).

  For example, specific examples of a curable composition suitable for a color filter or a curable composition suitable for a solder resist are as follows. Particularly preferred as the reactive (meth) acrylate polymer (A) used in such a curable composition is urethane (meta) obtained by reacting a polyhydroxy compound with an isocyanate compound of formula (I). ) Acrylate polymer.

(Xa) Curable composition suitable for color filter This curable composition comprises a reactive (meth) acrylate polymer (A), a pigment (B), a photopolymerization initiator (D), an ethylenically unsaturated monomer ( F) and an organic solvent (G).

(Xaa) Reactive (meth) acrylate polymer (A)
Content of the reactive (meth) acrylate polymer (A) in said curable composition is 10 mass% or more normally, Preferably it is 20 mass% or more, More preferably, it is 30-90 mass%. The mass ratio of the reactive (meth) acrylate polymer (A) and other curable components such as the ethylenically unsaturated monomer (F) is preferably 30/70 to 90 in terms of the balance between strength and photosensitivity. / 10, more preferably 40/60 to 85/15. When the mass ratio of the reactive (meth) acrylate polymer (A) is smaller than 30/70, the film strength is lowered. On the other hand, when the mass ratio of the reactive (meth) acrylate polymer (A) is larger than 90/10, the curing shrinkage is increased.

(Xab) Pigment (B)
As the pigment (B), red, green, and blue pigments can be used, and examples of the pigment (B) that can shield radiation to the maximum include black pigments. As such pigments, known pigments can be used. Specific examples thereof include carbon black, acetylene black, lamp black, carbon nanotube, graphite, iron black, iron oxide black pigment, aniline black, cyanine. Examples thereof include black and titanium black. In addition, organic pigments of three colors of red, green and blue can be mixed and used as a black pigment.

Among these, carbon black and titanium black are preferable, and carbon black is particularly preferable in terms of light shielding rate and image characteristics.
As the carbon black, commercially available ones can be used, and the preferable particle diameter thereof is 5 to 200 nm, more preferably 10 to 100 nm in consideration of dispersibility and resolution. When the particle size is less than 5 nm, uniform dispersion becomes difficult, and when the particle size exceeds 200 nm, the resolution decreases.

  Specific examples of carbon black include Degussa's Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 4, MA100, MA220, MA230 made by Mitsubishi Chemical Co., Ltd. , RAVEN450, RAVEN500 and the like.

(Xac) Photopolymerization initiator (D)
The photopolymerization initiator (D) is a compound that is excited by actinic rays to generate radicals and initiates polymerization of ethylenically unsaturated bonds. Such a photopolymerization initiator is preferably one having high photosensitivity because it is necessary to generate radicals under high light shielding. Specific examples of the photopolymerization initiator include hexaarylbiimidazole compounds, triazine compounds, aminoacetophenone compounds, combinations of sensitizing dyes and organic boron salt compounds, titanocene compounds, oxadiazole compounds, and the like. It is done.

  Among these, hexaarylbiimidazole compounds, triazine compounds, aminoacetophenone compounds, glyoxyester compounds, bisacylphosphine oxide compounds, and combinations thereof are preferable.

Specific examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,
2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5 , 5'-tetra (o, p-dichlorophenyl) -1,2'-biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetra (o, p -Dichlorophenyl) -1,2'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) -1,2'-biimidazole, Examples include 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  To further increase the sensitivity, benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone Further, thioxanthone compounds such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone may be added as a sensitizer.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-propionyl-4,6- Bis (trichloromethyl) -s-triazine, 2-benzoyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (4-methoxyphenyl) -6-trichloromethyl-s-triazine, 2- (4-methoxyphenyl) -2,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-chlorostyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-aminophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (3-chlorophenyl) -6-trichloromethyl-s-triazine, 2- (4- Aminostyryl) -4,6-bis (dichloromethyl) -s-triazine and the like.

  Specific examples of aminoacetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) -Butanone-1.

  Specific examples of the benzophenone compounds include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4-benzoyl- 4′-methyldiphenyl sulfide, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, (2-acryloyloxyethyl) (4-benzoylbenzyl) dimethylammonium bromide, 4 -(3-Dimethylamino-2-hydroxypropoxy) -benzophenone methochloride monohydrate, (4-benzoylbenzyl) trimethylammonium chloride and the like.

  Specific examples of the thioxanthone compound include thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino- 2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthen-9-one methochloride and the like.

Specific examples of the quinone compound include 2-ethylanthraquinone and 9,10-phenanthrenequinone.
Specific examples of the titanocene compound include JP 59-152396 A, JP 61-151197 A, JP 63-10602 A, JP 63-41484 A, and JP 2-291 A. No. 3, JP-A-3-12403, JP-A-3-20293, JP-A-3-27393, JP-A-3-52050, JP-A-4-221958, JP-A-4-21975. And titanocene compounds described in the above. Specifically, dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-diphenyl, dicyclopentadienyl-Ti-bis (2,3,4,5,6-pentafluorophenyl), Dicyclopentadienyl-Ti-bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-Ti-bis (2,4,6-trifluorophenyl), dicyclopentadienyl- Ti-bis (2,6-difluorophenyl), dicyclopentadienyl-Ti-bis (2,4-difluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,3,4,5) , 6-pentafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,3,5,6-tetrafluorophenyl), bis (methylcyclope). Tajieniru)-Ti-bis (2,6-difluorophenyl), and the like.

  Specific examples of the oxadiazole compound include 2-phenyl-5-trichloromethyl-1,3,4, -oxadiazole having a halomethyl group and 2- (p-methylphenyl) -5-trichloromethyl-1. , 3,4, -oxadiazole, 2- (p-methoxyphenyl) -5-trichloromethyl-1,3,4, -oxadiazole, 2-styryl-5-trichloromethyl-1,3,4, -Oxadiazole, 2- (p-methoxystyryl) -5-trichloromethyl-1,3,4, -oxadiazole, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4, -Oxadiazole and the like.

Specific examples of the glyoxyester compounds include benzyl dimethyl ketal, benzoin ethyl ether, benzoin isopropyl ether, and the like.
Specific examples of the bisacylphosphine oxide compound include bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis ( 2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like.

(Xad) ethylenically unsaturated monomer (F)
The ethylenically unsaturated monomer (F) is a compound that crosslinks with radicals generated from the photopolymerization initiator (D) when irradiated with actinic rays, and has a role of adjusting the viscosity of the composition. Specifically, (meth) acrylic acid esters are preferably used.

As a specific example of (meth) acrylic acid ester,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) Alkyl (meth) acrylates such as acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) ) Acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Alicyclic, such as (meth) acrylate;

Aromatic (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenyl carbitol (meth) acrylate, nonylphenyl (meth) acrylate, nonylphenyl carbitol (meth) acrylate, nonylphenoxy (meth) acrylate, etc. ;
2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, butanediol mono (meth) acrylate, glycerol (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, polyethylene glycol (meth) (Meth) acrylate having a hydroxyl group such as acrylate and glycerol di (meth) acrylate;
(Meth) acrylate having an amino group such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-tert-butylaminoethyl (meth) acrylate;

Methacrylates having a phosphorus atom such as methacryloxyethyl phosphate, bis-methacryloxyethyl phosphate, methacryloxyethyl phenyl acid phosphate (phenyl-P);
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 Diacrylates such as 1,6-hexanediol di (meth) acrylate and bis-glycidyl (meth) acrylate;

Polyacrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate;
Ethylene oxide 4 mol modified diacrylate of bisphenol S, ethylene oxide 4 mol modified diacrylate of bisphenol A, fatty acid modified pentaerythritol diacrylate, propylene oxide 3 mol modified triacrylate of trimethylolpropane, propylene oxide 6 mol modified triacrylate of trimethylolpropane Modified polyol polyacrylates such as;
Polyacrylates having an isocyanuric acid skeleton such as bis (acryloyloxyethyl) monohydroxyethyl isocyanurate, tris (acryloyloxyethyl) isocyanurate, ε-caprolactone modified tris (acryloyloxyethyl) isocyanurate;

polyester acrylates such as α, ω-diaacryloyl- (bisethylene glycol) -phthalate, α, ω-tetraacryloyl- (bistrimethylolpropane) -tetrahydrophthalate;
Glycidyl (meth) acrylate; allyl (meth) acrylate; ω-hydroxyhexanoyloxyethyl (meth) acrylate; polycaprolactone (meth) acrylate; (meth) acryloyloxyethyl phthalate; (meth) acryloyloxyethyl succinate; Examples include hydroxy-3-phenoxypropyl acrylate; phenoxyethyl acrylate.

  Further, as the ethylenically unsaturated monomer (F), N-vinyl compounds such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, polyester acrylate, urethane acrylate, epoxy acrylate, and the like may be used.

Among these, (meth) acrylate having a hydroxyl group, glycidyl (meth)
Preferred are acrylates and urethane acrylates. Moreover, the thing which has 3 or more of ethylenically unsaturated groups is preferable at the point which sclerosis | hardenability and heat resistance become high.

(Xae) Organic solvent (G)
Specific examples of the organic solvent (G) include ethers such as diisopropyl ether, ethyl isobutyl ether and butyl ether; ethyl acetate, isopropyl acetate, butyl acetate (n, sec, tert), amyl acetate, ethyl 3-ethoxypropionate, Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate; methyl ethyl ketone, isobutyl ketone, diisopropyl ketone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl Ketones such as ketone, methyl isoamyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Glycols such as ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, tripropylene glycol methyl ether, Beauty and the like and mixtures thereof.

  The organic solvent (G) can dissolve or disperse other components, and the boiling point thereof is preferably 100 to 200 ° C, more preferably 120 to 170 ° C. The amount of the organic solvent (G) used is such that the solid content concentration in the curable composition is in the range of 5 to 50 mass%, preferably 10 to 30 mass%.

(Xaf) Multifunctional thiol (H)
Said curable composition may contain polyfunctional thiol (H). The polyfunctional thiol (H) is a compound having two or more thiol groups. Specific examples thereof include hexanedithiol, decanedithiol, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycol. Rate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate tris (2- Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimethyl Such as mercaptopurine -s- triazine, and the like.

(Xag) Content of each component In said curable composition, the preferable content rate of each component other than the organic solvent (G) is as follows.

  The content of the reactive (meth) acrylate polymer (A) is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, based on the total amount of the composition. When the content is less than 10% by mass, the film strength may decrease. On the other hand, if the content exceeds 40% by mass, sufficient optical density may not be obtained.

The content of the pigment (B) is preferably 25 to 60% by mass, more preferably 30 to 55% by mass with respect to the total amount of the composition. If the content is less than 25% by mass, sufficient optical density may not be obtained. On the other hand, when the content exceeds 60% by mass, the film strength may decrease.

  The content of the photopolymerization initiator (D) is preferably 2 to 25% by mass, more preferably 5 to 20% by mass, based on the total amount of the composition. If the content is less than 2% by mass, sufficient photosensitivity may not be obtained. On the other hand, if the content exceeds 25% by mass, the photosensitivity is too high and the resolution may be lowered.

  The content of the ethylenically unsaturated monomer (F) is preferably 5 to 20% by mass, more preferably 8 to 18% by mass, based on the total amount of the composition. If the content is less than 5% by mass, sufficient photosensitivity may not be obtained. On the other hand, if the content exceeds 20% by mass, sufficient optical density may not be obtained.

  When adding polyfunctional thiol (H), content of a photoinitiator (D) becomes like this. Preferably it is 2-20 mass% with respect to the composition whole quantity, More preferably, it is 3-15 mass%. If the content is less than 2% by mass, sufficient photosensitivity may not be obtained. On the other hand, if the content exceeds 20% by mass, the photosensitivity is too high and the resolution may be lowered. The content of the polyfunctional thiol (F) is preferably 2 to 20% by mass, more preferably 3 to 15% by mass with respect to the total amount of the composition. If the content is less than 2% by mass, the effect of the polyfunctional thiol may not appear. On the other hand, if the content exceeds 20% by mass, the photosensitivity is too high and the resolution may be lowered.

  In addition to the components described above, a pigment dispersant, an adhesion improver, a leveling agent, a development improver, an antioxidant, a thermal polymerization inhibitor, and the like can be added to the curable composition. Particularly, since it is important for quality stability to finely disperse the coloring material and stabilize the dispersion state, it is desirable to add a pigment dispersant as necessary.

(Xah) Manufacturing method of curable composition Said curable composition can be manufactured by mixing each component mentioned above by arbitrary methods. The mixing method may be either a method of mixing each component at the same time or a method of sequentially mixing each component.

  In addition, when all the components to mix | blend are mixed and a dispersion process is performed, there exists a possibility that a highly reactive component may modify | denature because of the heat_generation | fever at the time of dispersion | distribution. For this reason, a black pigment or the like (B) is predispersed together with a solvent (G) and a pigment dispersant, or a mixture of these with a reactive (meth) acrylate polymer (A), and then the remaining components are mixed. It is preferable to perform mixing by the method to do.

The dispersion treatment can be performed using a paint conditioner, a bead mill, a ball mill, a three roll mill, a stone mill, a jet mill, a homogenizer, or the like.
When dispersed by a bead mill, glass beads or zirconia beads having a diameter of 0.1 to several millimeters are preferably used. The temperature at the time of dispersion is usually from 0 to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time is set to an appropriate time according to the composition of the coloring composition (coloring material, solvent, dispersant, binder polymer), bead mill apparatus size, and the like.

  In the case of dispersing with a three-roll mill, the temperature during dispersion is usually 0 to 60 ° C. When the frictional heat of the roll is large and the temperature exceeds 60 ° C., the inside of the roll is cooled with circulating water. The number of passes of the ink through the three-roll mill depends on conditions such as the linear velocity of the roll, the pressure between the rolls, and the viscosity of the material, but is, for example, 2 to 10 times.

A curable composition is manufactured by mixing the composition obtained by the said dispersion process with the remaining component by arbitrary methods.
(Xai) Color filter manufacturing method The color filter is formed by applying the curable composition described above on a transparent substrate, drying the solvent in an oven or the like, exposing and developing to form a pattern, and then performing post-baking. Is manufactured.

  Specific examples of the transparent substrate include quartz glass, borosilicate glass, inorganic glass such as lime soda glass coated with silica on the surface; polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, Examples include thermoplastics such as polysulfone; films or sheets of thermosetting plastics such as epoxy polymers and polyester polymers. Such a transparent substrate may be subjected in advance to corona discharge treatment, ozone treatment, thin film treatment with various polymers such as silane coupling agents and urethane polymers in order to improve physical properties such as surface adhesion. .

  Application of the curable composition to the transparent substrate can be performed using an application apparatus such as a dip coater, a roll coater, a wire bar, a flow coater, a die coater, a spray coater, or a spin coater.

  The solvent can be dried after application by any method, and a drying device such as a hot plate, an IR oven, or a convection oven can be used. The drying temperature is preferably 40 to 150 ° C., and the drying time is preferably 10 seconds to 60 minutes. Further, the solvent may be dried in a vacuum state.

  The exposure is performed by placing a photomask on the sample and exposing the image through the photomask. Specific examples of light sources used for exposure include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps and other lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers and other laser light sources Etc. In the case where only irradiation light with a specific wavelength is used, an optical filter may be used.

  A developing solution is used for the developing process, and the resist is developed by dipping, showering, paddle method or the like. As the developer, a solvent capable of dissolving the resist film in the unexposed area can be used, and specific examples thereof include organic solvents such as acetone, methylene chloride, trichrene, and cyclohexanone.

  Further, an alkali developer can be used as the developer. Specific examples of such an alkaline developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, diethanolamine, triethanolamine, tetraalkylammonium hydroxide salt An aqueous solution containing an organic alkaline agent such as The alkali developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like as necessary. In particular, many surfactants have an improving effect on developability, resolution, background stains, and the like, and it is preferable to add such surfactants.

  Specific examples of the surfactant for the developer include an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And a cationic surfactant.

The development treatment is usually performed at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C., by a method such as immersion development, spray development, brush development, or ultrasonic development.
The post-bake is usually performed at a temperature of 150 to 300 ° C. for 1 to 120 minutes using the same apparatus as that for solvent drying. The thickness of the matrix thus obtained is preferably 0.1 to 2 μm, more preferably 0.1 to 1.5 μm, and still more preferably 0.1 to 1 μm. In order to fulfill the function as a matrix, the optical density is preferably 3 or more at these film thicknesses.

  The black matrix pattern manufactured by the above method usually has an opening of about 20 to 200 μm between the patterns, and R, G, and B pixels are formed in this space in a later process. Usually, each pixel has three colors of R, G, and B, and a reactive (meth) acrylate polymer (like the formation of a black matrix) using a curable composition colored with the above-described pigment or dye ( It can be formed with a curable composition using A).

(Xb) Curable composition suitable for solder resist This curable composition comprises a reactive (meth) acrylate polymer (A), a thermosetting polymer (C), and a photopolymerization initiator (D). And an ethylenically unsaturated monomer (F) and a thermal polymerization catalyst (E).

(Xba) Thermosetting polymer (C)
The thermosetting polymer (C) is contained in the composition as a thermosetting component, and may itself be cured by heat, and the reactive (meth) acrylate polymer (A) by heat. It may react with a carboxyl group.

  Specific examples of the thermosetting polymer (C) include epoxy polymers; phenol polymers; silicone polymers; melamine derivatives such as hexamethoxymelamine, hexabutoxymelamine and condensed hexamethoxymelamine; urea compounds such as dimethylolurea; tetramethylol bisphenol. Examples thereof include bisphenol A compounds such as A; oxazoline compounds; oxetane compounds. These may be used alone or in combination of two or more.

  Among these, an epoxy polymer is preferable. Specific examples of the epoxy polymer include bisphenol A type epoxy polymer, hydrogenated bisphenol A type epoxy polymer, brominated bisphenol A type epoxy polymer, bisphenol F type epoxy polymer, novolac type epoxy polymer, phenol novolac type epoxy polymer, cresol novolak type. Epoxy polymer, N-glycidyl type epoxy polymer, bisphenol A novolac type epoxy polymer, chelate type epoxy polymer, glyoxal type epoxy polymer, amino group-containing epoxy polymer, rubber modified epoxy polymer, dicyclopentadiene phenolic type epoxy polymer, silicone modified epoxy Polymers having two or more epoxy groups in one molecule such as polymer and ε-caprolactone-modified epoxy polymer Carboxymethyl compound; bisphenol S epoxy polymer, diglycidyl phthalate polymer, heterocyclic epoxy polymer, bixylenol epoxy polymer, biphenyl epoxy polymer, such as tetraglycidyl xylenoyl yl ethane polymers.

  Further, in order to impart flame retardancy, a material in which atoms such as halogen such as chlorine and bromine or phosphorus are introduced into the structure in a bonded state that is difficult to be decomposed by heat or water may be used. These epoxy polymers may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the thermosetting polymer (C) is preferably 10 to 150 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass in total of the photocurable component. Thermosetting polymer (C
) Content of less than 10 parts by mass, the cured film may have insufficient solder heat resistance. On the other hand, when the content of the thermosetting polymer (C) exceeds 150 parts by mass, the amount of shrinkage of the cured film increases, and warpage deformation tends to increase when the cured film is used as an insulating protective film on an FPC board. is there.

(Xbb) Photopolymerization initiator (D)
As a photoinitiator (D), the photoinitiator similar to what is used for the curable composition suitable for the color filter mentioned above can be used.

  The content of the photopolymerization initiator (D) is an epoxy (meth) acrylate compound having a urethane (meth) acrylate polymer (A), an ethylenically unsaturated monomer (F), and a carboxyl group blended as necessary. Is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass in total. When the content of the photopolymerization initiator (D) is less than 0.1 parts by mass, the composition may be insufficiently cured.

(Xbc) Thermal polymerization catalyst (E)
The thermal polymerization catalyst (E) exhibits the action of thermosetting the thermosetting polymer (C). Specific examples thereof include amines; amine salts such as chlorides of the amines or quaternary ammonium. Salts; acid anhydrides such as cycloaliphatic acid anhydrides, aliphatic acid anhydrides, and aromatic acid anhydrides; nitrogen-containing heterocyclic compounds such as polyamides, imidazoles, and triazine compounds; and organometallic compounds It is done. These may be used alone or in combination of two or more.

Specific examples of amines include aliphatic or aromatic primary, secondary and tertiary amines.
Specific examples of the aliphatic amine include polymethylene diamine, polyether diamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, triethylenetetramine, dimethylaminopropylamine, mensendiamine, aminoethylethanolamine, bis (hexamethylene). ) Triamine, 1,3,6-trisaminomethylhexane, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene-7-ene Can be mentioned.

Specific examples of the aromatic amine include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.
Specific examples of acid anhydrides include aromatic acids such as phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), etc. Examples of the anhydride include maleic anhydride, succinic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, polyadipic anhydride, chlorendic anhydride, tetrabromophthalic anhydride, and the like.

  Specific examples of polyamides include polyaminoamides having primary or secondary amino groups obtained by condensation reaction of polyamines such as diethylenetriamine and triethylenetetraamine with dimer acid.

  Specific examples of imidazoles include imidazole, 2-ethyl-4-methylimidazole, N-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, and the like. Is mentioned.

  The triazine compound is a compound having a six-membered ring containing three nitrogen atoms. Specific examples thereof include melamine compounds such as melamine, N-ethylenemelamine, N, N ′, N ″ -triphenylmelamine; Acid, isocyanuric acid, trimethyl cyanurate, isocyanurate, triethyl cyanurate, trisethyl isocyanurate, tri (n-propyl) cyanurate, tris (n-propyl) isocyanurate, diethyl cyanurate, N, N'-diethyl isocyanurate And cyanuric acid compounds such as methyl cyanurate and methyl isocyanurate; and cyanuric acid melamine compounds such as equimolar reaction products of melamine compounds and cyanuric acid compounds.

  Specific examples of the organic metal compound include organic acid metal salts such as dibutyltin dilaurate, dibutyltin maleate and zinc 2-ethylhexanoate; 1,3-diketone metal complex salts such as nickel acetylacetonate and zinc acetylacetonate; titanium Examples thereof include metal alkoxides such as tetrabutoxide, zirconium tetrabutoxide, and aluminum butoxide.

  The amount of the thermal polymerization catalyst (E) used is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the thermosetting polymer (C). If the amount of the thermal polymerization catalyst (E) used is less than 0.5 parts by mass, the curing reaction may not proceed sufficiently and the heat resistance may be lowered. Moreover, since curing at a high temperature is required for a long time, it may cause a reduction in work efficiency. On the other hand, when the usage-amount of a thermal-polymerization catalyst (E) exceeds 20 mass parts, it will react with the carboxyl group in a composition, gelatinization will occur easily, and problems, such as a fall of storage stability, may arise.

(Xbd) ethylenically unsaturated monomer (F)
As the ethylenically unsaturated monomer (F), the same ethylenically unsaturated monomer as that used in the curable composition suitable for the color filter described above can be used.

  The mixing ratio of the reactive (meth) acrylate polymer (A) to the other ethylenically unsaturated monomer (F) is preferably 95: 5 to 50:50, more preferably 90:10 in terms of mass ratio. -60: 40, more preferably 85: 15-70: 30. When the blending ratio of the reactive (meth) acrylate polymer (A) exceeds 95, the heat resistance of the cured film made of the composition may be lowered. On the other hand, when the compounding ratio of the reactive (meth) acrylate polymer (A) is less than 5, the alkali solubility of the composition tends to decrease.

Moreover, you may use the epoxy (meth) acrylate compound which has a carboxyl group as a sclerosing | hardenable component as needed. As the epoxy (meth) acrylate compound having such a carboxyl group, for example, those described in the above (ix-f) can be used. The acid value is preferably 10 mgKOH / g or more, more preferably 45 to 160 mgKOH / g, and still more preferably 50 to 140 mgKOH / g. When such an acid value epoxy (meth) acrylate compound is used, the balance between the alkali solubility of the composition and the alkali resistance of the cured film can be improved. When the acid value is less than 10 mgKOH / g, the alkali solubility is deteriorated. On the other hand, if the acid value is too large, depending on the component composition of the composition, the resist properties such as alkali resistance and electrical properties of the cured film may be lowered. When using the epoxy (meth) acrylate compound which has a carboxyl group, it is preferable to use in the range of 100 mass parts or less with respect to 100 mass parts of the reactive (meth) acrylate polymer (A) which has a carboxyl group. .

(Xbe) Manufacturing method of curable composition The said curable composition can be manufactured by mixing each component mentioned above by a normal method similarly to the curable composition suitable for the color filter mentioned above. The mixing method is not particularly limited, and after mixing some components, the remaining components may be mixed, or all components may be mixed at once.

  Moreover, you may add an organic solvent to a composition as needed for viscosity adjustment. By adjusting the viscosity in this manner, it becomes easy to apply or print on an object by roller coating, spin coating, screen coating, curtain coating, or the like. Examples of the organic solvent include ketone solvents such as ethyl methyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetoacetate, γ-butyrolactone, and butyl acetate; alcohol solvents such as butanol and benzyl alcohol; carbitol acetate, Solvents of cellosolves such as methyl cellosolve acetate, carbitols and their esters and ether derivatives; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, etc. Amide solvents: dimethyl sulfoxide; phenol solvents such as phenol and cresol; nitro compound solvents; toluene, xylene, hexamethylbenzene, cumene aromatic solvents, tetralin, decalin, dipen And aromatic or solvents alicyclic consisting of hydrocarbon such as emissions and the like. These may be used alone or in combination of two or more.

The amount of the organic solvent used is such that the composition has a viscosity of 500 to 500,000 mPa · s, more preferably 1,000 to 500,000 mPa · s (measured at 25 ° C. with a B-type viscometer (Brookfield Viscometer)). An amount is preferred. When the composition has such a viscosity, it is more suitable for application and printing on an object and is easy to use. Moreover, the preferable usage-amount of the organic solvent in order to set it as such a viscosity is 1.5 mass times or less of solid content other than an organic solvent. If the composition exceeds 1.5 mass times, the solid concentration will be low, so when printing this composition on a substrate, etc., a sufficient film thickness will not be obtained with a single print, and a large number of prints will be required. There is.

  Further, a colorant can be further added to such a composition and used as an ink. Specific examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like. Even when used as an ink, the viscosity is preferably 500 to 500,000 mPa · s.

  A flow control agent can be further added to the composition in order to adjust the fluidity. By adding a fluidity modifier, the fluidity of the composition can be appropriately adjusted when the composition is applied to an object by roller coating, spin coating, screen coating, curtain coating, or the like.

  Specific examples of the flow regulator include inorganic or organic fillers, waxes, surfactants, and the like. Specific examples of the inorganic filler include talc, barium sulfate, barium titanate, silica, alumina, clay, magnesium carbonate, calcium carbonate, aluminum hydroxide, and a silicate compound. Specific examples of the organic filler include silicone resin, silicone rubber, and fluorine resin. Specific examples of the wax include polyamide wax and oxidized polyethylene wax. Specific examples of the surfactant include silicone oil, higher fatty acid ester, amide and the like. These fluidity modifiers may be used alone or in combination of two or more.

Moreover, additives, such as a thermal-polymerization inhibitor, a thickener, an antifoamer, a leveling agent, and an adhesive provision agent, can be added to a composition as needed. Specific examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine and the like. Specific examples of the thickener include asbestos, olben, benton and montmorillonite. The antifoaming agent is used for eliminating bubbles generated at the time of printing, coating or curing, and specific examples thereof include acrylic and silicone surfactants. The leveling agent is used to lose unevenness on the surface of the film that occurs during printing and coating, and specific examples thereof include acrylic and silicone surfactants. Specific examples of the adhesion-imparting agent include imidazole-based, thiazole-based, triazole-based, and silane coupling agents.

  Further, as other additives, for example, an ultraviolet ray inhibitor and a plasticizer can be added for storage stability. Further, the above curable composition is applied onto a substrate or the like by screen printing at an appropriate thickness, and is heat-treated and dried to obtain a coating film. Then, it can be set as hardened | cured material by exposing and developing, thermosetting and hardening.

  The above-mentioned curable composition can be used for various applications. In particular, it has excellent photosensitivity and developability, and adhesion to a substrate when cured to form a thin film, insulation, heat resistance, warp deformation. It is also suitable for use as an insulating protective coating on a printed wiring board because of its excellent properties, flexibility and appearance. In the case of forming an insulating protective film, a composition or ink is applied to a substrate on which a circuit is formed in a thickness of 10 to 100 μm, and then heat-treated at a temperature of 60 to 100 ° C. for about 5 to 30 minutes to be dried. And a thickness of 5 to 70 μm. Next, exposure is performed through a negative mask provided with a desired exposure pattern, and unexposed portions are removed with a developer and developed. Thereafter, it is cured by thermosetting at a temperature of 100 to 180 ° C. for about 10 to 40 minutes.

  This curable composition is particularly excellent in flexibility when made into a cured product, and the cured product has good flexibility, so it is particularly suitable for use as an insulating protective film on an FPC board. Therefore, the FPC board can be made excellent in handleability. Further, for example, it may be used as an insulating resin layer between layers of a multilayer printed wiring board.

As the active light source used for the exposure, active light generated from a known active light source such as a carbon arc, a mercury vapor arc, a xenon arc, or the like is used.
As the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.

  Moreover, this curable composition can also be used for the photosensitive layer of a dry film resist. The dry film resist has a photosensitive layer made of a composition on a support made of a polymer film or the like. The thickness of the photosensitive layer is preferably 10 to 70 μm. Specific examples of the polymer film used for the support include films made of polyester resins such as polyethylene terephthalate and aliphatic polyester, and films made of polyolefin resins such as polypropylene and low density polyethylene.

  The dry film resist is obtained by forming a photosensitive layer by applying a curable composition on a support and drying it. In addition, by providing a cover film on the formed photosensitive layer, a support, a photosensitive layer, and a cover film are sequentially laminated, and a dry film resist having films on both sides of the photosensitive layer can be produced. The cover film is peeled off when the dry film resist is used, but by providing the cover film on the photosensitive layer until the time of use, the photosensitive layer can be protected and a dry film resist excellent in pot life can be obtained.

  In order to form an insulating protective film on a printed wiring board using a dry film resist, first, the photosensitive layer of the dry film resist and the substrate are bonded. Here, when using a dry film resist provided with a cover film, the cover film is peeled off to expose the photosensitive layer, and then contacted with the substrate.

  Next, the photosensitive layer and the substrate are thermocompression bonded at about 40 to 120 ° C. using a pressure roller or the like, and the photosensitive layer is laminated on the substrate. Thereafter, the photosensitive layer is exposed through a negative mask having a desired exposure pattern, the support is peeled off from the photosensitive layer, the unexposed portion is removed with a developer and developed, and the photosensitive layer is thermally cured. A printed wiring board having an insulating protective film provided on the surface of the substrate is manufactured. Moreover, you may form an insulating resin layer between the layers of a multilayer printed wiring board using such a dry film resist.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples. The analytical instruments and analysis conditions used in the examples are as follows.

<Gas chromatography>
Analytical instrument: “GC14A” manufactured by Shimadzu Corporation
Column: “DB-1” manufactured by J & W, Inc. 30 m × 0.53 mm × 1.5 μm
Column temperature: raised from 70 ° C. to 250 ° C. at 10 ° C./min, 18 minutes at 250 ° C. Hold integrator: “CR7A” manufactured by Shimadzu Corporation
Injection temperature: 220 ° C
Detector temperature: 270 ° C FID
Detector: FID H ₂ 40 ml / min Air 400 ml / min
Carrier gas: He 10ml / min

<Automatic titrator>
Analytical instrument: “COM-550” manufactured by Hiranuma Sangyo Co., Ltd.
<Infrared spectroscopic analysis>
Analytical instrument: “AVATAR 360 FT-IR” manufactured by Thermo Nicolet Japan
Measurement method: reflection method <nuclear magnetic resonance>
Analytical instrument: “JNM-AL400” manufactured by JEOL

[Step (1)]
In a 300 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 10 g (0.09 mol) of 4-aminophenol (manufactured by Tokyo Chemical Industry, reagent) and 1, 100 ml of 4-dioxane was charged. Then heat to 50 ° C.
Hydrogen chloride gas was supplied at a flow rate of 100 ml / min for 1 hour.

[Step (2)]
The obtained liquid was heated to 55 ° C., 27.1 g (0.27 mol) of carbonyl chloride was supplied over 6 hours, and the temperature was maintained for 3 hours. After completion of the reaction, nitrogen was introduced to remove dissolved carbonyl chloride. A sample was collected and analyzed by gas chromatography (hereinafter referred to as “GC”). As a result, 4-isocyanatephenol was obtained in a yield of 90%.

[Step (3)]
100 ml of o-dichlorobenzene was added to the obtained liquid, and 31.0 g (0.25 mmol) of 3-chloropropionic acid chloride was further added, followed by heating at 130 ° C. for 9 hours. At that time, the reaction was carried out while distilling 1,4-dioxane out of the system. The resulting reaction solution was analyzed for alkali-decomposable chlorine by the following method.

  About 0.5 g of a sample was accurately weighed into a 300 ml conical stoppered flask, 100 ml of a methanol / purified water mixture (volume ratio: 70/30) was added, and then 10 ml of a 30% aqueous sodium hydroxide solution was added. A condensing tube was attached to this Erlenmeyer flask and heated to reflux in an 80 ° C. water bath for 1 hour, and then cooled to room temperature. Subsequently, the obtained solution was transferred to a volumetric flask, and purified water was added to make up a total of 200 ml.

  10 ml of the obtained liquid is accurately taken in a 200 ml beaker, 100 ml of purified water is added, 1 ml of (1 + 1) nitric acid is added, potentiometric titration is performed using a 1/50 normal silver nitrate solution, The concentration was determined. However, in the following formula, A is a silver nitrate titration amount (ml), and B is a factor of the silver nitrate aqueous solution.

Chlorine concentration (%) = A × B × 35.5 / 50 × (sample mass) × 100
The reaction solution obtained by distilling off o-dichlorobenzene from the obtained reaction solution was 29.2 g, and the alkali-decomposable chlorine concentration in the reaction solution was 4.1%. Therefore, the alkali-decomposable chlorine in the reaction solution was calculated to be 1.20 g (0.03 mol).

[Process (4)]
The reaction solution and 90 ml of toluene were charged into a 200 ml flask, and 4.4 g (0.04 mol) of triethylamine was added dropwise over 1 hour. Next, the mixture was stirred at 50 ° C. for 6 hours and then cooled to room temperature. The produced solid content was separated by filtration to obtain 95 g of a filtrate.

[Purification process]
0.02 g of phenothiazine (manufactured by Tokyo Chemical Industry, reagent) and 0.02 g of 2,6-bis-t-butylhydroxytoluene (manufactured by Sigma Aldrich Japan Co., Ltd., reagent) are added to the obtained filtrate, and the pressure is reduced with a vacuum pump. The pressure was reduced to 10 kPa and the solvent was distilled off. The obtained concentrated liquid was charged into a 100 ml flask, distilled under reduced pressure to 0.5 kPa, and 5.0 g of a fraction at 100 to 110 ° C. was obtained.

  The obtained fraction was identified as 4-acryloyloxyphenyl isocyanate by infrared spectroscopic analysis (hereinafter referred to as “IR”) and nuclear magnetic resonance analysis (hereinafter referred to as “NMR”). The IR and NMR charts are shown in FIGS. The yield of 4-acryloyloxyphenyl isocyanate was 24%.

[Step (1)]
A 300 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 15 g (0.14 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry, reagent) and 100 ml of ethyl acetate under a nitrogen atmosphere. It is. Subsequently, it heated at 50 degreeC and hydrogen chloride gas was supplied at the flow volume of 100 ml / min for 1 hour.

[Step (2)]
The obtained liquid was heated to 55 ° C., 40.6 g (0.41 mol) of carbonyl chloride was supplied over 6 hours, and then heating was continued at 60 ° C. for 3 hours. After completion of the reaction, nitrogen was introduced to remove dissolved carbonyl chloride. As a result of collecting a sample and performing GC analysis, 4-isocyanatephenol was obtained with a yield of 90%.

[Step (3)]
To the resulting reaction solution, 100 ml of o-dichlorobenzene was added, and 46.5 g (0.37 mmol) of 3-chloropropionic acid chloride was further added, and heating was continued at 130 ° C. for 1 hour. At that time, the reaction was carried out while distilling off ethyl acetate out of the system. After completion of the reaction, the reaction solution was distilled under reduced pressure to 0.5 kPa, and a fraction at 100 to 110 ° C. was collected to obtain 25 g of 3-chloropropionyloxy-1-isocyanate-benzene.

  As a result of analyzing the alkali-decomposable chlorine of the obtained liquid by the above method, the alkali-decomposable chlorine concentration was 6.4%, and the alkali-decomposable chlorine in 25 g of liquid was 1.60 g (0.04 mol). It was.

[Process (4)]
25 g of the obtained liquid was charged into a 100 ml flask, 50 g of toluene was further charged, and 5.1 g (0.05 mol) of triethylamine was added dropwise over 1 hour. Next, the mixture was stirred at 50 ° C. for 6 hours and then cooled to room temperature. The produced solid content was separated by filtration to obtain 72.5 g of a filtrate.

[Purification process]
To the obtained filtrate, 0.02 g of phenothiazine and 0.02 g of 2,6-bis-t-butylhydroxytoluene were added, the pressure was reduced to 10 kPa with a vacuum pump, and the solvent was distilled off. The concentrated liquid was charged into a 50 ml flask, distilled under reduced pressure to 0.5 kPa, and 6.1 g of a fraction at 100 to 110 ° C. was obtained.

  The resulting fraction was identified as 3-acryloyloxyphenyl isocyanate by IR and NMR. The IR and NMR charts are shown in FIGS. The yield of 3-acryloyloxyphenyl isocyanate was 23.9%.

[Step (1 ′)]
In a 300 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 10 g (0.09 mol) of 4-aminophenol and 100 ml of 1,4-dioxane were charged under a nitrogen atmosphere. Subsequently, it heated at 50 degreeC and hydrogen chloride gas was supplied at the flow volume of 100 ml / min for 1 hour.

[Step (2 ′)]
The obtained liquid was heated to 55 ° C., 27.1 g (0.27 mol) of carbonyl chloride was supplied over 6 hours, and then heating was continued at 60 ° C. for 3 hours. After completion of the reaction, nitrogen was introduced to remove dissolved carbonyl chloride. As a result of collecting a sample and performing GC analysis, 4-isocyanate phenol was obtained in a yield of 90%.

[Step (3 ′)]
After adding 22.3 g (0.25 mmol) of methacrylic acid chloride (manufactured by Tokyo Chemical Industry, reagent) to the resulting liquid, heating was continued at 110 ° C. for 6 hours. At that time, the reaction was carried out while distilling 1,4-dioxane out of the system.

[Purification process]
To the obtained reaction solution, 0.02 g of phenothiazine and 0.02 g of 2,6-bis-t-butylhydroxytoluene were added, the pressure was reduced to 10 kPa with a vacuum pump, and the solvent was distilled off. The concentrated liquid was charged into a 100 ml flask, distilled under reduced pressure to 0.5 kPa, and 6.4 g of a fraction at 100 to 110 ° C. was obtained. The fraction was 4-methacryloyloxyphenyl isocyanate, and the yield was 31%.

[Step (1 ′)]
In a 500 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 30 g (0.275 mol) of 3-aminophenol (manufactured by Mitsui Chemicals, reagent) and 350 ml of 1,4-dioxane were added under a nitrogen atmosphere. Was charged. Subsequently, it heated at 60 degreeC and hydrogen chloride gas was supplied for 70 minutes at the flow volume of 100 ml / min.

[Step (2 ′)]
The obtained liquid was heated to 60 ° C., 54.0 g (0.54 mol) of carbonyl chloride was supplied over 5 hours, and the temperature was maintained for 3 hours. After completion of the reaction, nitrogen was introduced to remove carbonyl chloride. As a result of collecting a sample and performing GC analysis, 3-isocyanatephenol was obtained in a yield of 90%.

[Step (3 ′)]
300 ml of o-dichlorobenzene was added to the obtained liquid, 200 g (1.91 mol) of methacrylic acid chloride and 1.0 g of phenothiazine were further added, and the mixture was heated at 110 ° C. for 48 hours.

[Purification process]
To the obtained reaction liquid, 1.0 g of phenothiazine and 0.5 g of 2,6-bis-tert-butylhydroxytoluene were added, and the solvent was distilled off by reducing the pressure to 10 kPa with a vacuum pump. The concentrated liquid was charged into a 100 ml flask and distilled off under reduced pressure to 0.1 kPa to obtain 13.8 g of a fraction at 123 to 125 ° C. The fraction was 3-methacryloyloxyphenyl isocyanate, and the yield was 25%.

[Examples 5 and 6]
(1) Reactivity of isocyanate group of compound of general formula (I) To a reactor, 0.613 g of 4-methacryloyloxyphenyl isocyanate, 0.721 g of 2-propanol and 5 ml of toluene are added and heated in an oil bath at 60 ° C. Stirring was performed. A small sample was taken at regular intervals, IR measurement was performed using a NaCl plate, the intensity of the absorption peak of the isocyanate group near 2272 cm ⁻¹ was measured, and the time until the peak disappeared was measured. Moreover, the same measurement was performed also about 3-methacryloyloxyphenyl isocyanate. The results are shown in Table 1.

[Comparative Example 1]
(2) Reactivity of isocyanate group of phenyl isocyanate 0.477 g of phenyl isocyanate, 0.721 g of 2-propanol and 5 ml of toluene were added to the reactor, and the mixture was heated and stirred in an oil bath at 60 ° C. A small sample was taken at regular intervals, IR measurement was performed using a NaCl plate, the intensity of the isocyanate absorption peak around 2272 cm ⁻¹ was measured, and an attempt was made to measure the time until the peak completely disappeared. The results are shown in Table 1.

[Example Production Example 1]
(1) Synthesis of urethane (meth) acrylate (U-1) In a reaction vessel equipped with a stirrer, a thermometer and a condenser, polycarbonate diol (manufactured by Kuraray Co., Ltd., C3090, average molecular weight 3000) 3.66 g and 4 -0.521 g of methacryloyloxyphenyl isocyanate was added, 10 mL of methylene chloride was added as a solvent, and the mixture was stirred for 1 hour. Thereafter, 0.0174 g of dibutyltin dilaurate was added. The stirring was further continued, and the reaction was terminated after confirming that the absorption peak (2280 cm ⁻¹ ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, whereby a viscous liquid urethane (meth) acrylate (U-1) was obtained. . The NMR chart of the obtained urethane (meth) acrylate (U-1) is shown in FIG.

[Comparative Production Example 1]
(2) Synthesis of urethane (meth) acrylate (U-2) In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, polycarbonate diol (manufactured by Kuraray Co., Ltd., C3090, average molecular weight 3000) 30.089 g and 2 -3.149 g of methacryloyloxyethyl isocyanate was added, and 100 mL of methylene chloride was added as a solvent. After stirring for 1 hour, 0.133 g of dibutyltin dilaurate was added. The stirring was further continued, and the reaction was terminated after confirming that the absorption peak (2280 cm ⁻¹ ) of the isocyanate group had almost disappeared in the infrared absorption spectrum, thereby obtaining a viscous liquid urethane (meth) acrylate (U-2). . The NMR chart of the obtained urethane (meth) acrylate (U-2) is shown in FIG.

[Example of production 2]
Synthesis of (meth) acrylic copolymer (XVI) In a four-necked flask equipped with a dropping funnel, thermometer, condenser and stirrer, 9.917 g of hydroxyethyl acrylate, 48.533 g of butyl methacrylate, 0.133 g of mercaptoethanol Then, 62.97 g of propylene glycol monomethoxyacetate (hereinafter referred to as “PMA”) was charged, and the atmosphere in the four-necked flask was replaced with nitrogen for 1 hour. Furthermore, after heating to 90 degreeC with an oil bath, the liquid mixture of 0.84g of azobisisobutyronitrile and 62.97g of PMA was dripped over 1 hour. After carrying out the polymerization for 3 hours, a mixed solution of 0.27 g of azobisisobutyronitrile and 7.00 g of PMA was added, and the temperature was further raised to 100 ° C. to carry out the polymerization for 1.5 hours. Then, after cooling at room temperature and removing a certain amount of solvent by vacuum distillation,
. The high molecular weight component was removed in 5 L of methanol, and purification was performed in hexane to obtain 55.29 g of a white (meth) acrylic copolymer (XVI). The weight average molecular weight in terms of polystyrene measured by GPC was 25,000.

[Example Production Example 3]
(1) Synthesis of reactive acrylic copolymer (P1-MPI) In a reactor, 0.215 g of 4-methacryloyloxyphenyl isocyanate, 1.454 g of (meth) acrylic copolymer (XVI), 0.0067 g of dibutyltin dilaurate
And 5 mL of methylene chloride was added and stirred. It was confirmed that the absorption spectrum (2280 cm ⁻¹ ) of the isocyanate group almost disappeared in the infrared absorption spectrum, and the reaction was terminated to obtain a reactive acrylic copolymer (P1-MPI). An NMR chart of the obtained reactive acrylic copolymer (P1-MPI) is shown in FIG.

[Comparative Production Example 2]
(2) Synthesis of Reactive Acrylic Copolymer (P1-MOI) In a reactor, 0.180 g of 2-methacryloyloxyethyl isocyanate, 1.614 g of (meth) acrylic copolymer (XVI), 0. 0067 g and 5 mL of methylene chloride were added and stirred. After confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) almost disappeared in the infrared absorption spectrum, the reaction was terminated to obtain a reactive acrylic copolymer (P1-MOI). An NMR chart of the obtained reactive acrylic copolymer (P1-MOI) is shown in FIG.

[Examples 7 to 12, Comparative Examples 2 to 5]
(1) Preparation of curable composition and preparation of evaluation sample Reactive urethane compounds of the types and amounts shown in Table 2-1 and Table 2-2, and reactions of amounts shown in Table 2-1 and Table 2-2 Bisphenol A type both-end bisacrylate monomer (DPE Kogyo Seiyaku Co., Ltd., BPE4-A) as a photopolymerizable monomer and 1-hydroxy as a photopolymerization initiator in the amounts shown in Tables 2-1 and 2-2 -Cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was stirred and mixed in 20 g of dichloromethane (manufactured by Junsei Chemical Co., Ltd.) at room temperature to uniformly dissolve the curable composition solution. Obtained. The obtained curable composition solution was applied to a glass substrate (size 50 mm × 50 mm) so that the dry film thickness was about 200 μm, and the solvent was dried at 50 ° C. for 30 minutes to obtain an evaluation sample.
In addition, the reactive urethane compound used in Example 12 is the urethane (meth) acrylate (U-1) obtained in Example Production Example 1, and the reactive urethane compound used in Examples 7 to 11 was implemented. Manufactured by changing raw material compounds and the like in Production Example 1. Moreover, the reactive urethane compound used in Comparative Example 5 is the urethane (meth) acrylate (U-2) obtained in Comparative Production Example 1, and the reactive urethane compound used in Comparative Examples 2 to 4 is a comparative example. Manufactured by changing raw material compounds and the like in Production Example 1.

(2) Evaluation of curable composition of reactive monomer <Curability>
The evaluation sample obtained in (1) was exposed with an exposure apparatus (USHIO ELECTRIC MULTILUCILITE ML-251A / B) incorporating an ultrahigh pressure mercury lamp. During this time, an exposure dose of 500 mJ / cm ² is obtained so that the reaction becomes steady by measuring the ethylenically unsaturated group absorption peak (810 cm ⁻¹ ) with an infrared spectrometer (FT / IR7000 manufactured by JASCO Corporation). And exposed. The ethylenically unsaturated group reaction rate was measured from the amount of change in the ethylenically unsaturated group absorption peak (absorption peak intensity after exposure / absorption peak intensity before exposure × 100:%). The results are shown in Table 3.

<Adhesion strength>
The evaluation sample obtained in (1) was exposed at 3 J / cm ² with an exposure apparatus incorporating an ultrahigh pressure mercury lamp. The cured film surface of each cured sample is polished with sandpaper, and a jig of an adhesion tester (Elcomtor Instrument.Std, elcomtor) is cured with an epoxy adhesive (Mitsui Chemicals, HC-1210). The adhesion strength was measured with a fusion tester. The results are shown in Table 3.

<Heat resistance>
The evaluation sample obtained in (1) was exposed at 3 J / cm ² with an exposure apparatus incorporating an ultrahigh pressure mercury lamp. About each hardened sample, the decomposition temperature was measured with the differential scanning calorimeter (The Seiko Instruments make, EXSTAR6000), and the heat resistance was compared. The results are shown in Table 3.

<Refractive index>
The curable composition prepared in (1) was applied on a PET film so that the dry film thickness was about 200 μm, and the solvent was dried at 50 ° C. for 30 minutes to obtain an evaluation sample. The obtained evaluation sample was exposed to 3 J / cm ² with an exposure apparatus incorporating an ultrahigh pressure mercury lamp.
Each cured sample was peeled off as a film, and the refractive index of the cured film was measured using an Abbe refractometer. The results are shown in Table 3.

<Curing shrinkage>
The curable composition prepared in (1) was applied on a glass substrate so that the dry film thickness was about 200 μm, and the solvent was dried at 50 ° C. for 30 minutes to obtain an evaluation sample. After measuring the film thickness of the obtained evaluation sample, it was exposed to 3 J / cm ² with an exposure apparatus incorporating an ultrahigh pressure mercury lamp. The film thickness of each cured sample was measured again, and the curing shrinkage rate was calculated from the film thickness reduction rate. The results are shown in Table 3.

[Examples 13 and 14, Comparative Examples 6 and 7]
(1) Preparation of curable composition and evaluation sample preparation Reactive polymer of the kind and amount shown in Table 4, and 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba) as the photopolymerization initiator of the amount shown in Table 4 Specialty Chemicals Co., Ltd., Irgacure 184) was stirred and mixed at room temperature in 20 g of dichloromethane (manufactured by Junsei Chemical Co., Ltd.) to obtain a curable composition solution. The obtained curable composition solution was applied to a glass substrate (size 50 mm × 50 mm) so that the dry film thickness was about 200 μm, and the solvent was dried at 50 ° C. for 30 minutes to obtain an evaluation sample.
The reactive polymer used in Example 14 is the reactive acrylic copolymer (P1-MPI) obtained in Example Production Example 3, and the reactive polymer used in Example 13 is Example Production Example 3. In Example 1, the raw material compound was changed. The reactive polymer used in Comparative Example 7 is the reactive acrylic copolymer (P1-MOI) obtained in Comparative Production Example 2, and the reactive polymer used in Comparative Example 6 is Comparative Production Example 2. In Example 1, the raw material compound was changed.

(2) Evaluation of curable composition of reactive polymer <Heat resistance>
The evaluation sample obtained in (1) was exposed at 3 J / cm ² with an exposure apparatus incorporating an ultrahigh pressure mercury lamp. About each hardened sample, the decomposition temperature was measured with the differential scanning calorimeter (The Seiko Instruments make, EXSTAR6000), and the heat resistance was compared. The results are shown in Table 5.

2 is an IR chart of the compound obtained in Example 1. 2 is an NMR chart of the compound obtained in Example 1. FIG. 2 is an IR chart of the compound obtained in Example 2. 2 is an NMR chart of the compound obtained in Example 2. 2 is an NMR chart of the compound obtained in Example Production Example 1. 2 is an NMR chart of the compound obtained in Comparative Production Example 1. 4 is an NMR chart of the compound obtained in Example Production Example 3. 3 is an NMR chart of the compound obtained in Comparative Production Example 2.

Claims (65)

A (meth) acryloyl group-containing aromatic isocyanate compound represented by the following formula (I).

(In the formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 represents a linear or branched alkylene group, X independently represents a halogen atom or an electron withdrawing group, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5. .) 2. The (meth) acryloyl group-containing aromatic isocyanate compound according to claim 1, wherein R ³ in the formula (I) is a single bond. N in said Formula (I) is 1, (meth) acryloyl group containing aromatic isocyanate compound of Claim 1 or 2 characterized by the above-mentioned. The (meth) acryloyl group-containing aromatic isocyanate compound according to claim 1, wherein R ¹ in the formula (I) is a single bond. The (meth) acryloyl group-containing aromatic isocyanate compound according to claim 1 represented by the following formula (II).

(Formula (in II), R ^1, R ^2, R ³ and n have the formula (R ¹ in I), R ^2, represent the R ³ and n the same as those.) The (meth) acryloyl group-containing aromatic isocyanate compound according to claim 1 represented by the following formula (III).

(In the formula (III), R ² represents a hydrogen atom or a methyl group.) The (meth) acryloyl group-containing aromatic isocyanate compound according to claim 1 represented by the following formula (IV).

(In formula (IV), R ² represents a hydrogen atom or a methyl group.) In the formula (I), the substituent constant σ of the substituent containing the (meth) acryloyloxy group is −0.2 <σ <0.8 with respect to the group containing isocyanate on the aromatic ring. The (meth) acryloyl group-containing aromatic isocyanate compound according to claim 1. The manufacturing method of the (meth) acryloyl group containing aromatic isocyanate compound represented by following formula (I) characterized by including the following process (1)-(4):

(In the formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 represents a linear or branched alkylene group, X independently represents a halogen atom or an electron withdrawing group, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5. .)
(1) A step of obtaining a hydroxyphenylamino mineral acid salt compound represented by the following formula (VI) from a hydroxyphenylamine compound represented by the following formula (V) and a mineral acid;

(Formula (in ^{V), R 1, R 3} , X, m and n are. Representing those of formulas (R ¹ in I), R ^3, X, the same as m and n)

(In the formula ^{(VI), R 1, R} 3, X, m and n are, R ^1, R ³ in formula (I), X, represents the same as m and n, W ¹ is a mineral acid To express.)
(2) A step of obtaining a hydroxyphenyl isocyanate compound represented by the following formula (VIII) from the hydroxyphenylamino mineral acid compound obtained in the step (1) and a compound represented by the following formula (VII): ;

(In Formula (VII), Z ¹ and Z ² each independently represent a fluorine atom, a chlorine atom, a bromine atom, an imidazole, a pyrazole, or R′O—, wherein R ′ is a C 1-6 carbon atom. An alkyl group or alkenyl group which may have a branch or an aryl group which may have a substituent.

(In the formula ^{(VIII), R 1, R} 3, X, m and n are, R ¹ in formula ^{(I), R 3, X} , m and n
Represents the same thing. )
(3) A step of obtaining an isocyanate group-containing phenyl ester compound represented by the following formula (X) from the hydroxyphenyl isocyanate compound obtained in the step (2) and a compound represented by the following formula (IX);

(In the formula (IX), R ² represents the same as R ² in formula (I).)

(Formula (X) in, R ¹ to R ^3, X, m and n have the formula (R ¹ to R ³ in I), X, represents those same m and n.)
(4) A step of dehydrochlorinating the isocyanate group-containing phenyl ester compound obtained in the step (3) in the presence of a basic nitrogen compound.   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 9, wherein the mineral acid is at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, carbonic acid and phosphoric acid. .   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 9, wherein the reactions in the steps (1) to (4) are performed in a solvent.   The solvent used in the step (1) is at least one selected from the group consisting of water, alcohols, esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 11, wherein:   The solvent used in the steps (2) to (4) is at least one selected from the group consisting of esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. It exists, The manufacturing method of the (meth) acryloyl group containing aromatic isocyanate compound of Claim 11 characterized by the above-mentioned.   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 12, wherein the step (2) is performed after the solvent is distilled off after the step (1) is completed.   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 9, wherein the basic nitrogen compound in the step (4) is triethylamine.   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 9, wherein a basic nitrogen compound is added as a catalyst in the step (3). A method for producing a (meth) acryloyl group-containing aromatic isocyanate compound represented by the following formula (I), comprising the following steps (1 ′) to (3 ′):

(In the formula (I), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 represents a linear or branched alkylene group, X independently represents a hydrogen atom, a halogen atom or an electron withdrawing group, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5)
(1 ′) a step of obtaining a hydroxyphenylamino mineral acid salt compound represented by the following formula (VI) from a hydroxyphenylamine compound represented by the following formula (V) and a mineral acid;

(Formula (in ^{V), R 1, R 3} , X, m and n are. Representing those of formulas (R ¹ in I), R ^3, X, the same as m and n)

(In the formula (VI), R ¹ , R ³ , X, m and n represent the same as R ¹ , R ³ , X and n, m in the formula (I), and W ¹ represents a mineral acid. To express.)
(2 ′) A hydroxyphenyl isocyanate compound represented by the following formula (VIII) is obtained from the hydroxyphenylamino mineral acid salt compound obtained in the step (1 ′) and the compound represented by the following formula (VII). Obtaining step;

(In Formula (VII), Z ¹ and Z ² each independently represent a fluorine atom, a chlorine atom, a bromine atom, an imidazole, a pyrazole, or R′O—, wherein R ′ is a C 1-6 carbon atom. An alkyl group or alkenyl group which may have a branch or an aryl group which may have a substituent.

(In the formula ^{(VIII), R 1, R} 3, X, m and n are, R ¹ in formula ^{(I), R 3, X} , m and n
Represents the same thing. )
(3 ′) A step of reacting the hydroxyphenyl isocyanate compound obtained in the step (2 ′) with a compound represented by the following formula (XI).

(In the formula (XI), R ² represents the same as R ² in formula (I).)   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 17, wherein the mineral acid is at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, and phosphoric acid. .   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 17, wherein the reaction in the steps (1 ') to (3') is performed in a solvent.   The solvent used in the step (1 ′) is at least one selected from the group consisting of water, alcohols, esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. It is a seed | species, The manufacturing method of the (meth) acryloyl-group containing aromatic isocyanate compound of Claim 19 characterized by the above-mentioned.   The solvent used in the steps (2 ′) and (3 ′) is at least one selected from the group consisting of esters, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. It is a seed | species, The manufacturing method of the (meth) acryloyl-group containing aromatic isocyanate compound of Claim 19 characterized by the above-mentioned.   The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 20, wherein the step (2 ') is performed after the solvent is distilled off after the step (1') is completed. . The method for producing a (meth) acryloyl group-containing aromatic isocyanate compound according to claim 17, wherein a basic nitrogen compound is added as a catalyst in the step (3 '). A (meth) acryloyl group-containing urethane compound represented by the following formula (XII).

(In the formula (XII), R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a single bond or 1 to 1 carbon atoms. 3 linear or branched alkylene groups, R ⁴ represents an ether group, a thioether group or an NH group,
X independently represents a halogen atom or an electron withdrawing group, Y represents an aliphatic group, a group containing an aromatic ring, a group containing a heterocyclic ring, a polycarbonate residue, a polyurethane residue, a polyester residue or a polyhydroxy compound having a repeating unit Represents a residue, 1 represents an integer of 1 to 50, m represents an integer of 0 to 4, n represents an integer of 1 to 3, and 1 ≦ m + n ≦ 5. ) The (meth) acryloyl group-containing urethane compound according to claim 24, wherein R ³ in the formula (XII) is a single bond. 26. The (meth) acryloyl group-containing urethane compound according to claim 24 or 25, wherein n in the formula (XII) is 1. The (meth) acryloyl group-containing urethane compound according to any one of claims 24 to 26, wherein R ¹ in the formula (XII) is a single bond. The (meth) acryloyl group-containing urethane compound according to claim 24 represented by the following formula (XIII).

(In the formula (XIII), R ¹ , R ² , R ³ , R ⁴ , Y, l and n are the same as R ¹ , R ² , R ³ in the formula (XII)).
, R ⁴ , Y, l and n are the same. ) The (meth) acryloyl group-containing urethane compound according to claim 24 represented by the following formula (XIV).

(Formula (XIV) in, R ^2, R ^4, Y and l are. Representing those of formulas (XIII) in R ^2, R ^4, Y and l the same as the) The (meth) acryloyl group-containing urethane compound according to claim 24 represented by the following formula (XV).

(Formula (XV) in, R ^2, R ^4, Y and l are. Representing those of formulas (XIII) in R ^2, R ^4, Y and l the same as the)   The substituent constant σ of a substituent containing a (meth) acryloyloxy group with respect to a group containing a urethane bond on the aromatic ring is represented by the formula (XII) according to claim 24. Reactive monomer, characterized in that −0.2 <σ <0.8. It is represented by the formula (XII) according to claim 24, wherein R ⁴ is an ether group, Y is an alkyl group, a xylylene group, a fluorine-containing group or a norbornane group, and l = A reactive monomer characterized by being 1 or 2. A group in which Y in the formula (XII) is represented by — (CH ₂ ) _p (CF ₂ ) _q F (p represents an integer of 0 to 2, q represents an integer of 0 to 8, and p and q are The reactive monomer according to claim 32, which is not 0 at the same time. 25. A reaction represented by formula (XII) according to claim 24, wherein R ⁴ is an ether group, Y is a group having a fluorene skeleton, and n = 2. Monomer. It is represented by the formula (XII) according to claim 24, wherein in the formula (XII), R ⁴ is an NH group,
A reactive monomer, wherein Y is an alkyl group, a xylylene group, a fluorine-containing group or a norbornane group, and n is 1 or 2. In the formula (XII), Y is a group represented by —CH ₂ (CF ₂ ) ₈ F, or —R ⁴ —Y is a residue of 2,6-difluoroaniline, 36. The reactive monomer of claim 35. The formula (XII) according to claim 24, wherein R ⁴ is a thioether group, and Y is a linear or branched saturated aliphatic group or a phenyl group. Reactive monomer. The (meth) acryloyl group-containing aromatic isocyanate compound represented by the formula (I) according to claim 1 is reacted with a compound to which a functional group having active hydrogen is bonded. The manufacturing method of the reactive monomer of description. In the formula (XII),
Y has a structure composed of a polycarbonate skeleton having a molecular weight of 500 to 5000,
An aliphatic dihydric alcohol residue in which the alkylene group is a trimethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a tetramethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a pentamethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a hexamethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is a heptamethylene group;
An aliphatic dihydric alcohol residue in which the alkylene group is an octamethylene group; and
1,9-nonanediol residue, 1,10-decanediol residue, 1,11-undecanediol residue, 1,12-dodecanediol residue, 1,20-eicosanediol and 1,4-cyclohexanedi Having at least one residue selected from methanol residues;
25. The (meth) acryloyl group-containing urethane compound according to claim 24, wherein n is 2. The aliphatic dihydric alcohol residue in which the alkylene group is a trimethylene group is 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1, 3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl- Selected from 1,3-pentanediol and 2-butyl-2-ethyl-1,3-propanediol residues;
The aliphatic dihydric alcohol residue in which the alkylene group is a tetramethylene group is a 1,4-butanediol residue;
The aliphatic dihydric alcohol residue in which the alkylene group is a pentamethylene group is selected from 1,5-pentanediol, 3-methyl-1,5-pentanediol and 1,5-hexanediol residue;
The aliphatic dihydric alcohol residue in which the alkylene group is a hexamethylene group is selected from 1,6-hexanediol and 2-ethyl-1,6-hexanediol residue;
The aliphatic dihydric alcohol residue in which the alkylene group is a heptamethylene group is a 1,7-heptanediol residue;
40. The aliphatic dihydric alcohol residue in which the alkylene group is an octamethylene group is selected from 1,8-octanediol and 2-methyl-1,8-octanediol residues. (Meth) acryloyl group-containing urethane compound. A reactivity comprising reacting the (meth) acryloyl group-containing aromatic isocyanate compound represented by the formula (I) according to claim 1 with the (meth) acryloyl group-containing urethane compound according to claim 24. A method for producing a (meth) acrylate polymer. A reaction comprising reacting a (meth) acryloyl group-containing aromatic isocyanate compound represented by the formula (I) according to claim 1 with a polymer compound having a repeating unit to which a functional group having active hydrogen is bonded. For producing a functional (meth) acrylate polymer.   The method for producing a reactive (meth) acrylate polymer according to claim 42, wherein the polymer compound is a polyhydroxy compound having a repeating unit. 43. The (meth) acryloyl group-containing aromatic isocyanate compound is represented by the formula (III) according to claim 6 or the formula (IV) according to claim 7, A method for producing a reactive (meth) acrylate polymer.   The polyhydroxy compound having the repeating unit is a polyester polyol compound, a polycarbonate polyol compound, a polyether polyol compound, a polyurethane polyol compound, a homopolymer or copolymer of hydroxyalkyl (meth) acrylate, or an epoxy (meth) acrylate compound. 44. The method for producing a reactive (meth) acrylate polymer according to claim 43.   44. The method for producing a reactive (meth) acrylate polymer according to claim 43, wherein the polyhydroxy compound having a repeating unit contains a carboxyl group. A reaction obtained by reacting the (meth) acryloyl group-containing aromatic isocyanate compound represented by formula (I) according to claim 1 with a polymer compound having a repeating unit to which a functional group having active hydrogen is bonded. (Meth) acrylate polymer.   The reactive (meth) acrylate polymer according to claim 47, wherein the polymer compound is a polyhydroxy compound having a repeating unit. The reactive (meth) acrylate polymer according to claim 47 or 48, wherein the (meth) acryloyl group-containing aromatic isocyanate compound is represented by the formula (III) according to claim 6.   The reactive (meth) acrylate polymer according to claim 47 or 48, wherein the (meth) acryloyl group-containing aromatic isocyanate compound is represented by the formula (IV) according to claim 7.   The polyhydroxy compound having the repeating unit is a polyester polyol compound, a polycarbonate polyol compound, a polyether polyol compound, a polyurethane polyol compound, a hydroxyalkyl (meth) acrylate homopolymer or copolymer, or an epoxy (meth) acrylate compound. 49. Reactive (meth) acrylate polymer according to claim 48, characterized in that it is present.   The reactive (meth) acrylate polymer according to claim 48, wherein the polyhydroxy compound having a repeating unit contains a carboxyl group. 49. The reactivity (meta) according to claim 48, wherein the polyhydroxy compound is an acrylic copolymer having a repeating unit represented by the following general formula (XVI) or (XVII) having a molecular weight of 5000 to 50000. ) Acrylate polymer.

  A curable composition comprising the reactive monomer according to any one of claims 31 to 37 and a polymerization initiator.   The hardened | cured material formed by hardening | curing the curable composition of Claim 54.   55. The curable composition according to claim 54, wherein the polymerization initiator is a photopolymerization initiator.   57. The curable composition according to claim 56, further comprising an ethylenically unsaturated monomer.   The reactive (meth) acrylate polymer (A) according to any one of claims 47 to 53, 25 to 60% by mass of the pigment (B), and 2 to 25% by mass of photopolymerization start. A curable composition comprising an agent (D), 5 to 20% by mass of an ethylenically unsaturated monomer (F), and an organic solvent (G).   The reactive (meth) acrylate polymer (A) according to any one of claims 47 to 53, 25 to 60% by mass of pigment (B), and 2 to 20% by mass of photopolymerization start. It contains an agent (D), 5 to 20% by mass of an ethylenically unsaturated monomer (F), an organic solvent (G), and 2 to 20% by mass of a polyfunctional thiol (H). Curable composition.   The curable composition according to any one of claims 57 to 59, which is used for forming a color filter.   60. The curable composition according to claim 58 or 59, wherein the pigment (B) is carbon black.   54. The reactive (meth) acrylate polymer (A) according to any one of claims 47 to 53, a thermosetting polymer (C), a photopolymerization initiator (D), and a thermal polymerization catalyst (E). A curable composition characterized by comprising:   63. The curable composition according to claim 62, which is used as a solder resist.   An insulating protective film formed using the curable composition according to claim 62.   A printed wiring board having the insulating protective film according to claim 64.

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