JP2011197310A - Curable composition, and curable film, curable laminate, permanent pattern forming method and printed board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excelling in surface smoothness, heat resistance, toughness, developability and insulation, and to provide a curable film, a curable laminate, a permanent pattern forming method and a printed board that uses the curable composition.SOLUTION: The curable composition contains inorganic fine particles coated with a compound, having a functional group capable of forming a hydrogen bond. The inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond are represented by formula (1): M-X-Y-Z, wherein M represents a metal atom in each inorganic fine particle; X represents a substituent bonding to a metallic atom surface constituting the inorganic fine particle; Y represents the compound having a functional group capable of forming a hydrogen bond; and Z represents a crosslinkable group.

Description

  The present invention relates to a curable composition suitable as a solder resist material, and a curable film, a curable laminate, a permanent pattern forming method, and a printed board using the curable composition.

  Conventionally, when forming a permanent pattern such as a solder resist, a curable film (photosensitive film) in which a photosensitive layer is formed by applying a photosensitive composition on a support and drying it has been used. As a method for forming a permanent pattern such as a solder resist, for example, a curable film is laminated on a substrate such as a copper-clad laminate on which a permanent pattern is formed to form a laminate, and the photosensitive layer in the laminate is formed. There is known a method of forming a permanent pattern by performing exposure on the substrate, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like.

  The solder resist is used in the production of printed wiring boards and the like, but has recently been used in new LSI packages such as BGA and CSP. The solder resist is a material required as a protective film for preventing the solder from adhering to unnecessary portions in the soldering process and as a permanent mask.

  Such solder resists are required to have excellent properties such as surface smoothness, heat resistance, toughness, developability, and insulating properties. In particular, recently, the density of printed circuit boards has been increased. Accordingly, there is a tendency that the density of wiring is improved and the number of input / output terminals is further increased. Therefore, higher delicate developability is required. In addition, as the density of printed circuit boards increases, it is required to reduce the thickness of printed circuit boards and to reduce the distance between components connected to the printed circuit boards. There was a problem that the surface smoothness of the substrate was lowered. If the surface smoothness of the printed circuit board is insufficient, the distance between the printed circuit board and the components may not be maintained uniformly, resulting in a connection failure, and the distance between the printed circuit board and the connected components may be reduced. Can not.

  For this reason, as an attempt to improve surface smoothness, for example, a curable composition containing an alkali-soluble resin, a photopolymerization initiator, and a colorant, and containing a specific alkaline resin as the alkali-soluble resin. An article (photosensitive composition) has been proposed (Patent Document 1).

  However, this curable composition is for suppressing the generation of wrinkles in the black matrix of the color filter, and cannot sufficiently solve problems such as poor connection due to the decrease in the surface smoothness, Further, there is a problem that various characteristics required for the solder resist cannot be satisfied.

  For the purpose of improving heat resistance and toughness, for example, a curable composition containing a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, and further comprising silica or the like. A curable composition to which inorganic fine particles are added has been proposed (Patent Document 2).

  However, when inorganic fine particles made of silica or the like are added, there is a problem that high-definition development cannot be performed because developability deteriorates.

  Therefore, there is a need for a curable composition that can provide excellent characteristics in all of surface smoothness, heat resistance, toughness, developability, and insulation.

JP 2007-286478 A JP 2009-086376 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention relates to a curable composition excellent in surface smoothness, heat resistance, toughness, developability and insulation, and a curable film, a curable laminate, and a permanent pattern using the curable composition. It is an object to provide a forming method and a printed circuit board.

Means for solving the problems are as follows. That is,
<1> A curable composition comprising inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond.
<2> The curable composition according to <1>, wherein the inorganic fine particles are silica.
<3> The curable composition according to any one of <1> to <2>, wherein the inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond are represented by the following general formula (1): It is.
Where M represents a metal atom in the inorganic fine particle, X represents a substituent bonded to the surface of the metal atom constituting the inorganic fine particle, and Y represents a compound having a functional group capable of forming a hydrogen bond. Z represents a crosslinkable group.
<4> The curable composition according to any one of <1> to <3>, further including a photopolymerization initiator and a polymerizable compound.
<5> The curable composition according to any one of <1> to <4>, further including a binder.
<6> The curable composition according to any one of <1> to <5>, further including a thermal crosslinking agent and a curing catalyst.
<7> The curable composition according to any one of <1> to <6>, which is used as a curable composition for a printed circuit board.
<8> A curable film comprising a photosensitive layer containing the curable composition according to any one of <1> to <7> on a support.
<9> A curable laminate having a photosensitive layer containing the curable composition according to any one of <1> to <7> on a substrate.
<10> A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the curable composition according to any one of <1> to <7>.
<11> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to <10>.

  According to the present invention, the conventional problems can be solved and the object can be achieved, and a curable composition excellent in surface smoothness, heat resistance, toughness, developability and insulation, and Providing a curable film, a curable laminate, a method for forming a permanent pattern, and a printed board using the curable composition can be provided.

(Curable composition)
The curable composition of the present invention contains inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond, and if necessary, a binder, a thermal crosslinking agent, a chain transfer agent, a photopolymerization initiator, Contains a polymerizable compound and other components.

<Inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond>
The inorganic fine particles coated with the compound having a functional group capable of forming a hydrogen bond are not particularly limited as long as they are inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond. It is preferably formed by surface modification with a silane coupling agent and then coating with a compound having a functional group capable of forming a hydrogen bond.
In this case, the inorganic fine particles are reacted with the silane coupling agent to modify the surface of the inorganic fine particles. Next, by reacting a functional group that reacts with an organic compound included in the silane coupling agent modified on the surface of the inorganic fine particle and a compound having a functional group capable of forming a hydrogen bond, the inorganic fine particle is Inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond, which is coated with a compound having a functional group capable of forming a hydrogen bond, can be formed.

  Alternatively, it may be formed by preparing a silane coupling agent capable of forming a hydrogen bond in advance and coating with the silane coupling agent.

There is no restriction | limiting in particular as an average particle diameter of the inorganic fine particle coat | covered with the compound which has the functional group which can form the said hydrogen bond, Although it can select suitably according to the objective, 0.05 micrometer-5 .. 0 μm is preferable, 0.1 μm to 3.0 μm is more preferable, and 0.1 μm to 2.0 μm is particularly preferable.
When the average particle size is less than 0.05 μm, the applicability of the curable composition may be inferior, and when it exceeds 5.0 μm, the pattern flatness may be deteriorated. The average particle size is defined as a particle size having an integrated value of 50% when the average particle size (d50) of the silica particles is expressed as an integrated (cumulative) weight percentage, and is defined as d50 (D50) or the like. For example, using a dynamic light scattering photometer (trade name DLS7000, manufactured by Otsuka Electronics Co., Ltd.), the measurement principle is a dynamic light scattering method, and the size distribution analysis method is a cumulant method and / or a histogram method. can do.

-Inorganic fine particles-
The inorganic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose, e.g., for example, silica _(SiO 2), alumina _{(Al 2 O} 3), titania _(TiO 2), zirconia (ZrO ₂ ) And the like, and metal hydroxides. Of these, silica and alumina are preferable.
There is no restriction | limiting in particular as an average particle diameter of the said inorganic fine particle, Although it can select suitably according to the objective, For example, 0.05 micrometer-5.0 micrometers are preferable, 0.1 micrometer-3.0 micrometers are more preferable, 0.1 μm to 2.0 μm is particularly preferable.
When the average particle size is less than 0.05 μm, the applicability of the curable composition may be inferior, and when it exceeds 5.0 μm, the pattern flatness may be deteriorated.

The content of the inorganic fine particles coated with the compound having a functional group capable of forming a hydrogen bond in the curable composition is not particularly limited and may be appropriately selected depending on the intended purpose. -80 mass% is preferable, 5 mass%-60 mass% is more preferable, 10 mass%-50 mass% is especially preferable.
When the said content rate is less than 1 mass%, heat resistance may be inferior, and when it exceeds 80 mass%, pattern formation property may be inferior.

-Silane coupling agent-
The silane coupling agent is a silicon compound having a functional group that reacts with an inorganic compound and a functional group that reacts with an organic compound, and the silicon compound is not particularly limited and may be appropriately selected.
Examples of the functional group of the silane coupling agent include a mercapto group, a hydroxy group, an amino group, an isocyanato group, a glycidyl group, a vinyl group, a methacryloyl group, an acrylic group, and a styryl group. Those having an amino group are preferable from the viewpoints of ease of formation and imparting hydrogen bonding. If it is a vinyl group, a methacryloyl group, etc., it may be inferior in heat resistance and toughness.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltrichlorosilane, vinyltriacetoxysilane, and N- (β-aminoethyl) -γ-amino. Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltris (β-methoxyethoxy) silane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxylane, methyltrie Xylan, hexamethyldisilazane, .gamma. anilino trimethoxysilane, N- [beta-(N-vinyl benzal amino) ethyl] -γ- aminopropyltrimethoxysilane hydrochloride and the like. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as a method of performing the surface treatment by the said silane coupling, For example, the aqueous solution method, the organic-solvent method, an air layer method etc. are mentioned.
The amount of the silane coupling agent added in the surface treatment is not particularly limited, but is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the inorganic fine particles. Mass parts to 10 parts by mass are more preferable, and 0.2 parts to 5 parts by mass are particularly preferable.
When the addition amount is less than 0.1 parts by mass, the surface may not be sufficiently covered, and when it exceeds 20 parts by mass, the particles may aggregate.

-Compounds having functional groups capable of forming hydrogen bonds-
The compound having a functional group capable of forming a hydrogen bond is not particularly limited as long as it has at least a functional group capable of forming a hydrogen bond, and can be appropriately selected depending on the purpose.
The functional group capable of forming a hydrogen bond is not particularly limited as long as it can form a hydrogen bond, and can be appropriately selected according to the purpose. For example, an isocyanide group, a hydroxyl group, a urethane group, a urea Group, amide group, sulfonamide group, imide group, thiourethane group, thiourea group, and derivatives thereof.

The compound having a functional group capable of forming a hydrogen bond preferably has a crosslinkable group at the terminal in terms of imparting interaction with a polymerizable compound, a binder, a thermal crosslinker and the like.
Examples of the crosslinkable group include a vinyl group, a carboxyl group, an amino group, and a cyclic ether group.

  Examples of the compound having a functional group capable of forming a hydrogen bond include a reaction product of a vinyl group-containing isocyanate compound and an amino group, a reaction product of an acid anhydride and an amino group, a vinyl group-containing acid chloride and an amino group. Examples thereof include a reaction product, a reaction product of a vinyl group-containing acid anhydride compound and an amino group, a reaction product of a vinyl group-containing isocyanate compound and a hydroxy group, and a reaction product of a vinyl group-containing acid chloride and a hydroxy group.

The amount of the compound having a functional group capable of forming a hydrogen bond is not particularly limited, but is preferably 0.1 parts by mass to 100 parts by mass with respect to 100 parts by mass of the inorganic fine particles, and 0.2 parts by mass. -50 mass parts is more preferable, 0.2 mass part-20 mass parts is especially preferable.
When the added amount is less than 0.1 parts by mass, the coating may not be sufficiently performed, and when it exceeds 100 parts by mass, the particles may aggregate.

  In the curable composition containing the inorganic fine particles formed by coating with a compound having a functional group capable of forming a hydrogen bond, surface smoothness and crack resistance are particularly improved. The reason for this is that by coating with a compound having a functional group capable of forming a hydrogen bond, the inorganic particles are sufficiently dispersed in the binder without agglomeration, and aggregates of inorganic fine particles hardly appear on the surface. it is conceivable that.

The inorganic fine particles coated with the compound having a functional group capable of forming a hydrogen bond are preferably represented by the following general formula (1).
Where M represents a metal atom in the inorganic fine particle, X represents a substituent bonded to the surface of the metal atom constituting the inorganic fine particle, and Y represents a compound having a functional group capable of forming a hydrogen bond. Z represents a crosslinkable group.

  Examples of M in the general formula (1) include Si, Al, Ti, and Zr. Si and Al are preferable in terms of easy particle size control.

Examples of MX- in the general formula (1) include a linker of a silane coupling agent. Specifically, for _{example, M- (CH 2) n NH-} , M- (CH 2) n NH- (CH 2) n N -, - (CH 2) such as n N-Ph and the like, of the processing M- (CH ₂ ) _n NH— is preferable in terms of ease. As said n, 2-10 are preferable.

  Examples of Y in the general formula (1) include a functional group capable of forming the hydrogen bond. Specific examples include a urethane group, an amide group, a urea group, a sulfonamide group, a thiourea group, and the like, and a urethane group, an amide group, and a urea group are preferable in terms of ease of synthesis.

Examples of Z in the general formula (1) include the crosslinkable group. Specific examples include a vinyl group, a carboxyl group, an amino group, and a cyclic ether group, and a vinyl group and a carboxyl group are preferable from the viewpoint of reactivity with a polymerizable compound, a binder, a thermal crosslinking agent, and the like.
Y and Z are one compound and have a functional group capable of forming the hydrogen bond.

  The inorganic fine particles formed by coating with a compound having a functional group capable of forming a hydrogen bond may be coated with the compound having a functional group capable of forming a hydrogen bond and the resin.

-Resin-
There is no restriction | limiting in particular as said resin, According to the objective, it can select suitably, For example, a thermoplastic resin is mentioned.

  There is no restriction | limiting in particular as said thermoplastic resin, Although it can select suitably according to the objective, The resin obtained by either polycondensation and addition polymerization is preferable.

  The resin obtained by any of the polycondensation and addition polymerization is not particularly limited and can be appropriately selected depending on the purpose. For example, polyether, polyester, polyurethane, polyamide, polyimide, polyamic acid, polycarbonate, Examples include polyurea and polyallylamine. Of these, polyether, polyester, polyurethane, and polyamic acid are preferable.

Although there is no restriction | limiting in particular as addition amount of the said resin, 0.1 mass part-100 mass parts are preferable with respect to 100 mass parts of compounds which have the functional group which can form the said hydrogen bond, 0.2 mass parts- 50 mass parts is more preferable, and 0.2 mass part-20 mass parts are especially preferable.
When the added amount is less than 0.1 parts by mass, the coating may not be sufficiently performed, and when it exceeds 100 parts by mass, the particles may aggregate.

The thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferably excellent in compatibility with the binder, and the SP value in the thermoplastic resin The SP value in the binder is preferably a predetermined difference.
The SP value in the thermoplastic resin is not particularly limited, but the difference from the SP value in the binder is preferably 5 MPa ^1/2 or less, more preferably 4 MPa ^1/2 or less, and 3 MPa ¹ It is particularly preferred that the ratio is ≦ ² .
When the difference in SP value exceeds 5 MPa ^1/2 , the compatibility between the coating resin and the binder resin deteriorates, and sufficient heat resistance, toughness, and flatness may not be exhibited.
The SP value is an index indicating the mutual solubility of substances, and a solubility parameter that can be calculated from the molecular structure is defined. For example, the Okitsu method is defined as the solubility parameter, and can be calculated from the parameter.

<Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, For example, the compound which has one or more ethylenically unsaturated bonds is preferable.

  Examples of the ethylenically unsaturated bond include (meth) acryloyl groups, (meth) acrylamide groups, styryl groups, vinyl groups such as vinyl esters and vinyl ethers; and allyl groups such as allyl ethers and allyl esters.

  The compound having one or more ethylenically unsaturated bonds is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from monomers having a (meth) acryl group is Preferably mentioned.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  The solid content of the polymerizable compound in the solid content of the curable composition is preferably 2% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass. If the solid content is 2% by mass or more, developability (resolution) and exposure sensitivity are good, and if it is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. Those having photosensitivity are preferable, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of monomer. May be.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm. The wavelength is more preferably 330 nm to 500 nm.
As the photopolymerization initiator, a neutral photopolymerization initiator is used. Moreover, the other photoinitiator may be included as needed.

  The neutral photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a compound having at least an aromatic group, such as (bis) acylphosphine oxide or an ester thereof. More preferred are acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds. Two or more neutral photopolymerization initiators may be used in combination.

  Examples of the photopolymerization initiator include (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime derivatives, organic peroxides, thiols, and the like. Compounds, and the like. Among these, from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, oxime derivatives, (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone Of these compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are preferred.

Examples of the (bis) acylphosphine oxide include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6 -Dichlorobenzoylphenylphosphine oxide, 2,6-dimethylmethyoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethyl) And benzoyl) -phenylphosphine oxide.
Examples of the acetophenone compounds include acetophenone, methoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and the like.
Examples of the benzophenone compounds include benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, and diphenoxybenzophenone.
Examples of the benzoin ether compounds include benzoin ethyl ether and benzoin propyl ether.
Examples of the ketal derivative compound include benzyldimethyl ketal.
Examples of the thioxanthone compound include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, and the like.

As an oxime derivative used suitably by this invention, it represents with following General formula (1), for example.

However, in the general formula (1), R ¹ represents any ^one of a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. , R ² each independently represents a substituent. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. A represents any of 4, 5, 6, and 7-membered rings. A is preferably either a 5- or 6-membered ring.

  The matters described in JP-A-2008-249857, JP-A-2008-242372, JP-A-2008-122546, JP-A-2008-122545 and the like of the oxime compound can be applied.

<Binder>
The binder is not particularly limited as long as it is a compound into which a photosensitive group and an acid group for imparting alkali developability are introduced, and can be appropriately selected according to the purpose. For example, an acid group is introduced. Examples thereof include poly (meth) acrylic resin, polyester, polyurethane, polyamide, polyamic acid, polyether, polyurea, and polycarbonate. Further, a polymer obtained by reacting an epoxy resin having two or more epoxy groups with a vinyl group-containing organic acid, and further reacting with a polybasic acid anhydride; at least a part of the acid of the carboxyl group-containing resin Modified copolymer in which a vinyl compound having a glycidyl group or an alicyclic epoxy group is added to a group; a vinyl compound having an isocyanato group or an acid anhydride group is added to at least a part of hydroxyl groups of a hydroxyl group-containing resin Modified copolymer; modified copolymer obtained by adding a vinyl compound having an isocyanate group or an acid anhydride group to at least a part of amino groups of an amino group-containing resin; a copolymer of a vinyl group-containing diol or a diamine; a glycidyl group Or a ring-opening polymer of a vinyl compound having an oxetanyl group or an alicyclic epoxy group.

  Among these, a polymer obtained by reacting an epoxy resin having two or more epoxy groups with a vinyl group-containing organic acid and further reacting with a polybasic acid anhydride, a polyurethane comprising polyisocyanate and polyisocyanate Is preferred.

  The polyurethane has a structure derived from polyisocyanate and polyisocyanate, and as the polyurethane, an acid-modified vinyl group-containing binder is preferably used from the viewpoint of alkali developability and toughness of a cured film.

<< Binder containing acid-modified vinyl group >>
The acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (i) a polyurethane resin having an ethylenically unsaturated bond in the side chain, (ii) a carboxyl group And polyurethane resin obtained by reacting the containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule.

-(I) Polyurethane resin having a vinyl group in the side chain-
There is no restriction | limiting in particular as urethane resin which has a vinyl group in the said side chain, According to the objective, it can select suitably, For example, it represents with the following general formula (1)-(3) in the side chain. The thing which has at least 1 among functional groups is mentioned.

In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group. R ¹ is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity. The R ² and R ³ are not particularly limited and may be appropriately selected depending on the purpose. For example, each of R ² and R ³ is independently a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group. Group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryl which may have a substituent An oxy group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent , Etc. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.
In the general formula (1), X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. R ¹² is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent. Among these, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
Here, the substituent that can be introduced is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom. Amino group, alkylamino group, arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group, and the like.

In the general formula (2), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group. The R ^{4 to} R ⁸ are not particularly limited and may be appropriately selected depending on the intended purpose. Hydrogen atoms, halogen atoms, amino groups, dialkylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, nitro groups , A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, substituted An alkylamino group which may have a group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like It is done. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

Examples of the substituent that can be introduced include the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Said R < ¹² > is synonymous with the case of R < ¹² > of General formula (1), and its preferable example is also the same.

In the general formula (3), R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a monovalent organic group. In the general formula (3), R ⁹ is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom or an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity. In the general formula (3), R ¹⁰ and R ¹¹ are not particularly limited and may be appropriately selected depending on the intended purpose. A hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxy group A carbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent An aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. And a good arylsulfonyl group. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced are the same as those in the general formula (1). Further, Z is an oxygen atom, a sulfur atom, -N ^{(R 13)} -, or a phenylene group which may have a substituent. There is no restriction | limiting in particular as said R < ¹³ >, According to the objective, it can select suitably, The alkyl group etc. which may have a substituent are mentioned. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable in terms of high radical reactivity.

  The urethane resin having an ethylenically unsaturated bond in the side chain is at least one diisocyanate compound represented by the following general formula (4), at least one diol compound represented by the general formula (5), and A polyurethane resin having a structural unit represented by the reaction product as a basic skeleton.

OCN-X ⁰ -NCO (4)
^HO-Y 0 -OH (5)

In the general formulas (4) and (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

  At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If it has at least one of them, as a reaction product of the diisocyanate compound and the diol compound, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is provided. Generated. According to this method, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is easier than substitution and introduction of a desired side chain after the reaction of the polyurethane resin is generated. Can be manufactured.

The diisocyanate compound represented by the general formula (4) is not particularly limited and can be appropriately selected depending on the purpose. For example, a triisocyanate compound and a monofunctional alcohol having an unsaturated group Or the product obtained by addition-reacting with 1 equivalent of monofunctional amine compounds is mentioned.
The triisocyanate compound is not particularly limited and can be appropriately selected depending on the purpose. For example, compounds described in paragraphs “0034” to “0035” of JP-A-2005-250438, Etc.

  The monofunctional alcohol having an unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs of JP-A-2005-250438 Examples thereof include compounds described in “0037” to “0040”.

  Here, the method for introducing an unsaturated group into the side chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. A method using a diisocyanate compound containing is preferable. There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, By carrying out addition reaction of the monoisocyanate which has a triisocyanate compound, and a monofunctional amine compound or monofunctional amine compound. Examples of the diisocyanate compound that can be obtained include compounds having an unsaturated group in the side chain described in paragraphs “0042” to “0049” of JP-A-2005-250438.

  The polyurethane resin having an ethylenically unsaturated bond in the side chain is a diisocyanate containing the unsaturated group from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. Diisocyanate compounds other than the compounds can also be copolymerized.

  The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a diisocyanate compound represented by the following general formula (6).

OCN-L ¹ -NCO (6)

In the general formula (6), L ¹ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L ¹ may have another functional group that does not react with an isocyanate group, for example, an ester, urethane, amide, or ureido group.

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (6), According to the objective, it can select suitably, For example, the dimer of 2, 4- tolylene diisocyanate and 2, 4- tolylene diisocyanate 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4 '-Aromatic diisocyanate compounds such as diisocyanate; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4, 4' Alicyclic diisocyanate compounds such as methylene bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate 2 A diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate;

  There is no restriction | limiting in particular as a diol compound represented by the said General formula (5), According to the objective, it can select suitably, For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound etc. are mentioned. .

Here, as a method for introducing an unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a method using a diol compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane resin is also preferable. The diol compound containing an unsaturated group in the side chain may be, for example, a commercially available product such as trimethylolpropane monoallyl ether, and a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound; The compound which is easily manufactured by reaction with compounds, such as a carboxylic acid, an acid chloride, an isocyanate, alcohol, an amine, a thiol, and a halogenated alkyl compound containing an unsaturated group, may be sufficient. The diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0057” to “0060” of JP-A-2005-250438 And the compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G). Among these, the compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G) are preferable.
In the general formula (G), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, wherein R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, ^R 1 to R ³ and X in the general formula (G) has the same meaning as ^R 1 to R ³ and X in the general formula (1), preferred embodiments versa.
By using the polyurethane resin derived from the diol compound represented by the general formula (G), the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.

The polyurethane resin having an ethylenically unsaturated bond in the side chain is unsaturated in the side chain from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability, for example. A diol compound other than a diol compound containing a group can be copolymerized.
The diol compound other than the diol compound containing an unsaturated group in the side chain is not particularly limited and can be appropriately selected according to the purpose. For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, And so on.

  There is no restriction | limiting in particular as said polyether diol compound, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0068"-"0076" of Unexamined-Japanese-Patent No. 2005-250438 etc. are mentioned. It is done.

  There is no restriction | limiting in particular as said polyester diol compound, According to the objective, it can select suitably, For example, Paragraph "0077"-"0079" of Unexamined-Japanese-Patent No. 2005-250438, Paragraph "0083"-"0085" No. 1-No. 8 and no. 13-No. 18 and the like.

  There is no restriction | limiting in particular as said polycarbonate diol compound, According to the objective, it can select suitably, For example, Unexamined-Japanese-Patent No. 2005-250438 Paragraph "0080"-"0081" and Paragraph "0084" No. 9-No. 12 listed compounds.

Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in the said side chain, the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above can also be used together.
The diol compound having a substituent that does not react with the isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0087” to “0088” of JP-A-2005-250438 And the compounds described.

  Furthermore, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in the said side chain, the diol compound which has a carboxyl group other than the diol compound mentioned above can also be used together. Examples of the diol compound having a carboxyl group include those represented by the following formulas (17) to (19).

In the formulas (17) to (19), R ¹⁵ is a hydrogen atom, a substituent (for example, a halogen atom such as a cyano group, a nitro group, -F, -Cl, -Br, -I, -CONH ₂ , -COOR ¹⁶ , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR ¹⁶ , -NHCOR ¹⁶ , -OCONHR ¹⁶ (wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms. As long as it represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group, which may have a group, depending on the purpose. Although it can select suitably, a hydrogen atom, a C1-C8 alkyl group, and a C6-C15 aryl group are preferable. In the above formulas (17) to (19), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different, and each may be a single bond, a substituent (for example, alkyl, aralkyl, aryl, alkoxy, As long as it represents a divalent aliphatic or aromatic hydrocarbon group that may have a divalent aliphatic or aromatic hydrocarbon group, and may be appropriately selected depending on the purpose. An alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. If necessary, the L ^{9 to} L ¹¹ may have another functional group that does not react with an isocyanate group, such as a carbonyl, ester, urethane, amide, ureido, or ether group. In addition, you may form a ring by 2 or 3 of said R < ¹⁵ >, L < ⁷ >, L < ⁸ >, L < ⁹ >.
In the formula (18), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose. However, an aromatic group having 6 to 15 carbon atoms is preferable.

  There is no restriction | limiting in particular as a diol compound which has a carboxyl group represented by the said Formula (17)-(19), According to the objective, it can select suitably, For example, 3, 5- dihydroxy benzoic acid, 2, 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxy Phenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-Carboxy-propionamide and the like.

  The presence of such a carboxyl group is preferable because the polyurethane resin can be provided with characteristics such as hydrogen bonding properties and alkali solubility. More specifically, the polyurethane resin having an ethylenically unsaturated bond group in the side chain is a resin further having a carboxyl group in the side chain, and more specifically, the vinyl group in the side chain is 0.05 mmol. / G to 1.80 mmol / g, preferably 0.5 mmol / g to 1.80 mmol / g, particularly preferably 0.75 mmol / g to 1.60 mmol / g, In addition, the side chain preferably has a carboxyl group, and the acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and 35 mgKOH / g to 100 mgKOH / g. g is particularly preferred.

Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in a side chain, the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
The compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-2005-250438, paragraph "0095" And the compounds described in “0101”.

The polyurethane resin having an ethylenically unsaturated bond in the side chain is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent by adding a known catalyst having an activity depending on the reactivity and heating. Is done. The molar ratio of diisocyanate and diol compound used for synthesis (M _a : M _b ) is not particularly limited and may be appropriately selected depending on the intended purpose, preferably 1: 1 to 1.2: 1. By treating with alcohols or amines, a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.

  The amount of introduction in the polyurethane resin having an ethylenically unsaturated bond in the side chain of the ethylenically unsaturated bond group is not particularly limited and can be appropriately selected according to the purpose. 0.05 mmol / g to 1.80 mmol / g is preferable, 0.5 mmol / g to 1.80 mmol / g is more preferable, and 0.75 mmol / g to 1.60 mmol / g is particularly preferable. Furthermore, in the polyurethane resin having an ethylenically unsaturated bond in the side chain, it is preferable that a carboxyl group is introduced into the side chain together with the ethylenically unsaturated bond group. The acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and particularly preferably 35 mgKOH / g to 100 mgKOH / g.

  There is no restriction | limiting in particular as molecular weight of the polyurethane resin which has an ethylenically unsaturated bond in the said side chain, Although it can select suitably according to the objective, 5,000-50,000 are preferable at a mass mean molecular weight, and 5 30,000 to 30,000 is more preferable. In particular, when the photosensitive composition of the present invention is used for a photosensitive solder resist, it has excellent dispersibility with inorganic fillers, excellent crack resistance and heat resistance, and developability of non-image areas with an alkaline developer. Excellent.

  Further, as the polyurethane resin having an ethylenically unsaturated bond in the side chain, those having an unsaturated group in the polymer terminal and main chain are also preferably used. Polyurethane resin having an ethylenically unsaturated bond in the side chain, or between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain, by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved, and the strength of the photocured product is increased. As a result, when a polyurethane resin having an ethylenically unsaturated bond in the side chain is used for a lithographic printing plate, a plate material having excellent printing durability can be provided. Here, as an unsaturated group, it is especially preferable to have a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.

As a method for introducing an unsaturated group into the polymer terminal, there are the following methods. That is, in the process of synthesizing a polyurethane resin having an ethylenically unsaturated bond in the side chain described above, in the process of treating with a residual isocyanate group at the polymer terminal and an alcohol or an amine, an alcohol having an unsaturated group Alternatively, amines or the like may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.
The ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The vinyl group equivalent is preferably 0.05 mmol / g to 1.80 mmol / g, preferably 0.5 mmol. / G to 1.80 mmol / g is more preferable, and 0.75 mmol / g to 1.60 mmol / g is particularly preferable.

  As a method of introducing an unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. There is no restriction | limiting in particular as a diol compound which has an unsaturated group in the said principal chain direction, According to the objective, it can select suitably, cis-2-butene-1, 4-diol, trans-2-butene-1 , 4-diol, polybutadiene diol, and the like.

  The polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin. For example, the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.

  Specific examples of the polyurethane resin (i) having an ethylenically unsaturated bond in the side chain include, for example, P-1 to P— shown in paragraphs “0293” to “0310” of JP-A-2005-250438. 31 polymers, and the like. Among these, the polymers of P-27 and P-28 shown in paragraphs “0308” and “0309” are preferable.

-(Ii) Polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule-
The polyurethane resin is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane having a diisocyanate and a carboxylic acid group-containing diol as essential components with a compound having an epoxy group and a vinyl group in the molecule. Depending on the purpose, as the diol component, a low molecular diol having a mass average molecular weight of 300 or less or a low molecular diol having a mass average molecular weight of 500 or more may be added as a copolymer component.
By using the polyurethane resin, it is excellent in stable dispersibility with an inorganic filler, crack resistance and impact resistance, so that heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties are improved.
The polyurethane resin includes a divalent aliphatic or aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups via any one of a C atom and an N atom. A reaction product comprising a carboxylic acid-containing diol as an essential component, which is obtained by reacting the obtained reaction product with a compound having an epoxy group and a vinyl group in the molecule via a —COO— bond It may be.
In addition, as the polyurethane resin, at least one selected from diisocyanates represented by the following general formula (I) and carboxylic acid group-containing diols represented by the following general formulas (II-1) to (II-3): And at least one selected from polymer diols having a weight average molecular weight in the range of 800 to 3,000 represented by the following general formulas (III-1) to (III-5) according to the purpose: A reaction product obtained by reacting the obtained reaction product with a compound having an epoxy group and a vinyl group in a molecule represented by the following general formulas (IV-1) to (IV-16) It may be.
However, in the general formula (I), R ₁ may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Represents an aromatic or aromatic hydrocarbon. If necessary, R ₁ may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group. In the general formula (I), R ₂ represents a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH ₂ , —COOR _6. , —OR ₆ , —NHCONHR ₆ , —NHCOOR ₆ , —NHCOR ₆ , —OCONHR ₆ , —CONHR ₆ (wherein R ₆ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) Represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable. In the general formulas (II-1) and (II-2), R ₃ , R ₄ and R ₅ may be the same or different from each other, and may be a single bond or a substituent (for example, an alkyl group or an aralkyl group). , An aryl group, an alkoxy group, and a halogeno group are preferable). Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, in R ₃ , R ₄ and R ₅ , any other functional group that does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may have. In addition, you may form a ring by 2 or 3 of said R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ >. Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and an aromatic group having 6 to 15 carbon atoms is preferable.

However, in said general formula (III-1)-(III-3), R < ₇ >, R < ₈ >, R < ₉ >, R < ₁₀ > and R < ₁₁ > may be the same respectively, may be different, and are bivalent. Represents an aliphatic or aromatic hydrocarbon. R ₇ , R ₉ , R ₁₀ and R ₁₁ are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon having 2 to 10 carbon atoms. Several to 10 arylene groups are more preferable. R ₈ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms is More preferred. In addition, in R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups , An amide group, a ureido group, or a halogen atom. In the general formula (III-4), R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group, or a halogen atom. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ˜6 alkyl and aryl groups having 6 to 10 carbon atoms. R ₁₂ may have other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms.
In General Formula (III-5), R ₁₃ represents an aryl group or a cyano group, and preferably an aryl group or a cyano group having 6 to 10 carbon atoms. In the general formula (III-4), m represents an integer of 2 to 4. In the general formulas (III-1) to (III-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represents an integer of 2 or more, and an integer of 2 to 100 is preferable. In General Formula (III-5), n ₆ represents 0 or an integer of 2 or more, and 0 or an integer of 2 to 100 is preferable.

In the general formula (IV-1) ~ (IV -16), R 14 represents a hydrogen atom or a methyl _{group, R 15} represents an alkylene group having 1 to 10 carbon _{atoms, R 16} is a carbon The hydrocarbon group of number 1-10 is represented. p represents 0 or an integer of 1 to 10.

  The polyurethane resin may further be copolymerized with a low molecular weight diol that does not contain a carboxylic acid group as a fifth component, and the low molecular weight diol may be any one of the general formulas (III-1) to (III-5). ) Having a mass average molecular weight of 500 or less. The low molecular weight diol containing no carboxylic acid group can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.

  As the polyurethane resin, in particular, a diisocyanate represented by the general formula (I) and at least one selected from carboxylic acid group-containing diols represented by the general formulas (II-1) to (II-3) are essential. As a component, depending on the purpose, at least one selected from polymer diols having a mass average molecular weight of 800 to 3,000, represented by general formulas (III-1) to (III-5), In addition to the reaction product of the carboxylic acid group-free low molecular weight diol having a mass average molecular weight of 500 or less represented by the formulas (III-1) to (III-5), the compounds represented by the general formulas (IV-1) to (IV-16) The acid value obtained by reacting a compound having one epoxy group and at least one (meth) acrylic group in the molecule represented by any of the above) is 20 mgKOH / g to 120 mgKOH / g Alkali-soluble photocrosslinkable polyurethane resins are preferred.

  These polymer compounds may be used alone or in combination of two or more. The content of the acid-modified vinyl group-containing polyurethane resin contained in the total solid content of the photosensitive composition or the like is preferably 2% by mass to 30% by mass, and more preferably 5% by mass to 25% by mass. When the content is less than 2% by mass, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 30% by mass, the developability may deteriorate and the toughness of the cured film may decrease. .

-Synthesis of polyurethane resin obtained by reacting carboxyl group-containing polyurethane with compound having epoxy group and vinyl group in molecule-
As a method for synthesizing the polyurethane resin, the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, it can be treated with alcohols or amines to obtain It is synthesized in such a way that no isocyanate groups remain entangled.

--Diisocyanate--
The diisocyanate compound represented by the general formula (I) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the compound described in paragraph “0021” of JP-A-2007-2030, Etc.

--High molecular weight diol--
The high molecular weight diol compound represented by the general formulas (III-1) to (III-5) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as disclosed in JP-A-2007-2030 And compounds described in paragraphs “0022” to “0046”.

--Carboxylic acid group-containing diol--
The diol compound having a carboxyl group represented by the general formulas (II-1) to (II-3) is not particularly limited and may be appropriately selected depending on the intended purpose. And the compounds described in paragraph “0047” of No. 2030 publication.

--Carboxylic acid group-free low molecular weight diol--
The carboxylic acid group-free low molecular weight diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0048” of JP-A-2007-2030. Can be mentioned.
The copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80% or less, and particularly preferably 50% or less in the low molecular weight diol. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.

  Specific examples of the polyurethane resin obtained by reacting the above (ii) carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule include, for example, paragraphs “0314” to JP-A-2007-2030. Glycidyl acrylate as an epoxy group and vinyl group-containing compound in the polymers U1 to U4 and U6 to U11 shown in “0315” is converted into glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400 (Daicel). Chemical)), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (manufactured by Daicel Chemical)), and the like.

There is no restriction | limiting in particular as content in the said photosensitive composition of the said acid-modified vinyl group containing polyurethane resin, Although it can select suitably according to the objective, 5 mass%-80 mass% are preferable, and 20 mass% -75 mass% is more preferable, and 30 mass%-70 mass% is especially preferable.
If the content is less than 5% by mass, good crack resistance may not be maintained, and if it exceeds 80% by mass, the heat resistance may fail. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of both good crack resistance and heat resistance.

There is no restriction | limiting in particular as a mass average molecular weight of the said acid-modified vinyl group containing polyurethane resin, Although it can select suitably according to the objective, 5,000-60,000 are preferable and 5,000-50,000 are preferable. More preferred is 5,000 to 30,000. When the mass average molecular weight is less than 5,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 60,000, coating suitability and developability may be deteriorated. .
The mass average molecular weight is, for example, a high-speed GPC device (HLC-802A manufactured by Toyo Soda Co., Ltd.), a 0.5% by mass THF solution is used as a sample solution, and a single TSKgel HZM-M column is used. Then, 200 μL of sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength 254 nm). Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.

The acid value of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g. 35 mg KOH / g to 100 mg KOH / g is particularly preferable. If the acid value is less than 20 mgKOH / g, the developability may be insufficient, and if it exceeds 120 mgKOH / g, the development rate may be too high, and development control may be difficult.
In addition, the said acid value can be measured based on JISK0070, for example. However, when the sample does not dissolve, dioxane or tetrahydrofuran is used as a solvent.

The vinyl group equivalent of the acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mmol / g to 1.8 mmol / g, 0.5 mmol / g g to 1.8 mmol / g is more preferable, and 0.75 mmol / g to 1.6 mmol / g is particularly preferable. When the vinyl group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 1.8 mmol / g, the crack resistance may be deteriorated.
The vinyl group equivalent can be determined, for example, by measuring the bromine number. In addition, the said bromine number can be measured based on JISK2605, for example.

  In addition to the polyurethane resin, it is preferable to add another resin to the curable composition of the present invention in an amount of 50% by mass or less based on the polyurethane resin as necessary. Examples of the other resin include polyamide resin, epoxy resin, polyacetal resin, acrylic resin, methacrylic resin, polystyrene resin, and novolac type phenol resin.

  The solid content in the solid content of the curable composition of the binder is preferably 5% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass. When the solid content is 5% by mass or more, developability and exposure sensitivity are good, and when it is 80% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the curable film, developability, etc. In the range that does not adversely affect the above, for example, a compound containing an epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), or an oxetane compound having at least two oxetanyl groups in one molecule is used. An epoxy compound having an oxirane group as described in JP-A-2007-47729, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate and derivatives thereof Compounds obtained by reacting a blocking agent with the isocyanate group of It is below.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  1 mass%-50 mass% are preferable, and, as for solid content in the said curable composition solid content of the said thermal crosslinking agent, 3 mass%-30 mass% are more preferable. If the solid content is 1% by mass or more, the film strength of the cured film is improved, and if it is 50% by mass or less, the developability (resolution) and the exposure sensitivity are improved.

  Examples of the epoxy compound include an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule.

  Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resin (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated Bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin) , Brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP- 7200, HP-7200H; manufactured by Dainippon Ink and Chemicals, Inc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (phthalic acid) Diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; Daicel Chemical Industry Co., Ltd. "), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl Ethane resin, naphthalene group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-36” 0; manufactured by Nippon Steel Chemical Co., Ltd. ”,“ HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink and Chemicals Co., Ltd. ”), phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of polyphenol compound obtained by addition reaction and epichlorohydrin, epoxidation of ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid, epoxy resin having linear phosphorus-containing structure, cyclic containing Epoxy resin having phosphorus structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl Metaacryl Copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis Examples thereof include (glycidyloxyphenyl) adamantane type epoxy resin, but are not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred is a compound containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

Examples of the oxetane compound include oxetane compounds having at least two oxetanyl groups in one molecule.
Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group; Novolac resin, poly (p-hydroxystyrene), cardo type bisphenol , Calixarenes, calixresorcinarenes, ether compounds with hydroxyl group-containing resins such as silsesquioxanes, etc. In addition, copolymerization of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates Examples include coalescence.

  Moreover, as the polyisocyanate compound, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is an aliphatic, cycloaliphatic or aromatic group containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

  As an isocyanate group blocking agent in a compound obtained by reacting a blocking agent with the polyisocyanate compound, that is, a compound obtained by reacting a blocking agent with an isocyanate group of polyisocyanate and derivatives thereof, alcohols (for example, isopropanol, tert-butanol etc.), lactams (eg ε-caprolactam etc.), phenols (eg phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol, p -Nonylphenol etc.), heterocyclic hydroxyl compounds (eg 3-hydroxypyridine, 8-hydroxyquinoline etc.), active methylene compounds (eg dialkyl malonate, methyl ethyl ketoxy) , Acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.) and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

As the thermal cross-linking agent, a curing catalyst may be included as necessary in order to promote the cross-linking reaction.
The curing catalyst is a compound that accelerates the polymerization (or crosslinking) reaction of the epoxy compound. The curing catalyst itself forms a network structure by causing a condensation reaction with the epoxy compound or acting as a catalyst to promote the reaction between the epoxy compounds. Examples of the curing catalyst include substituted or unsubstituted amines, imidazoles, mercaptans, acid anhydrides, polyamide resins, organic acid hydrazides, etc. Among them, amine derivatives, acid anhydrides, and imidazole derivatives At least one compound selected from the group consisting of
Examples of the curing catalyst include the compounds exemplified below.

In addition, trimellitic anhydride, maleic anhydride, phthalic anhydride, methyl nadic anhydride, succinic anhydride, polysulfide resin (ThreeBond's Three Bond 2104), ethylene glycol bistrimate, glycerol trismelitate, etc. may be used. it can. These may be used alone or in combination of two or more.
The content of the curing catalyst is preferably 1% to 100%, more preferably 5% to 50%, and particularly preferably 10% to 40% with respect to the mass of the epoxy compound to be used.
When the content is less than 1%, heat curing may not be sufficiently performed and heat resistance may be inferior.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and a colorant (color pigment or dye). Furthermore, adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers. , Chain transfer agent, etc.) may be used in combination.
By appropriately containing these components, properties such as stability, photographic properties, and film physical properties of the target curable film can be adjusted.
The thermal polymerization inhibitor is described in detail, for example, in paragraphs [0101] to [0102] of JP-A-2008-250074.
The thermosetting accelerator is described in detail in paragraph [0093] of JP-A-2008-250074, for example.
The plasticizer is described in detail, for example, in paragraphs [0103] to [0104] of JP-A-2008-250074.
The colorant is described in detail, for example, in paragraphs [0105] to [0106] of JP-A-2008-250074.
The adhesion promoter is described in detail, for example, in paragraphs [0107] to [0109] of JP-A-2008-250074.

(Curable film)
The curable film of the present invention comprises at least a support and a photosensitive layer comprising the curable composition of the present invention on the support, and further comprises other layers as necessary.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2 micrometers-150 micrometers are preferable, 5 micrometers-100 micrometers are more preferable, 8 micrometers-50 micrometers are especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

-Photosensitive layer-
If the said photosensitive layer is a layer which consists of a curable composition, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
Further, the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.

  As the method for forming the photosensitive layer, a curable composition solution is prepared by dissolving, emulsifying or dispersing the curable composition of the present invention in water or a solvent on the support, and the solution is directly applied. The method of laminating | stacking by apply | coating and drying is mentioned.

  There is no restriction | limiting in particular as a solvent of the said curable composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol etc. Alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, and the like ketones; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy Esters such as propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride Halogenated hydrocarbons such as monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. Is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1 micrometer-100 micrometers are preferable, 2 micrometers-50 micrometers are more preferable, and 4 micrometers-30 micrometers are especially preferable.

<Other layers>
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a protective film, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, etc. Layer. The said curable film may have these layers individually by 1 type, and may have 2 or more types.

<< Protective film >>
The curable film may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
There is no restriction | limiting in particular in the thickness of the said protective film, Although it can select suitably according to the objective, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially preferable.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
If the static friction coefficient is 0.3 or more, it is possible to prevent the occurrence of winding misalignment when it is made into a roll shape due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. .

  For example, the curable film is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular in the length of the said elongate curable film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped curable film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is preferable.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 ° C. to 150 ° C. for 1 to 30 minutes. As for the temperature in the case of the said drying, 50 to 120 degreeC is especially preferable.

(Curable laminate)
The curable laminate has at least a substrate and a photosensitive layer provided on the substrate, and is formed by laminating other layers appropriately selected according to the purpose.
The photosensitive layer is transferred from the curable film prepared by the above-described manufacturing method, and has the same configuration as described above.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed or a member to be transferred onto which at least the photosensitive layer of the curable film of the present invention is transferred, and is not particularly limited and may be appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

<Method for producing curable laminate>
Examples of the method for producing the curable laminate include a method in which at least the photosensitive layer in the curable film of the present invention is transferred and laminated while performing at least one of heating and pressing.

In the method for producing the curable laminate, the curable film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said curable film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable and 0.2 MPa-0.8 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator Co., Ltd. make, VP-II, Nichigo Morton Co., Ltd. make, VP130) is preferable.

  Since the curable film of the present invention and the curable laminate have a uniform film thickness and an extremely low occurrence rate of planar defects such as pinholes and repellency, they have excellent insulation reliability and high-definition permanent patterns (protection) Film, interlayer insulating film, solder resist pattern, etc.) can be formed efficiently. Therefore, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be suitably used particularly for forming a permanent pattern on a printed circuit board.

(Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps such as a development step appropriately selected as necessary.

<Exposure process>
The said exposure process is a process of exposing with respect to the photosensitive layer in the curable laminated body of this invention. The curable laminate of the present invention is as described above.

  There is no restriction | limiting in particular as long as it is the photosensitive layer in the said curable laminated body as an object of the said exposure, According to the objective, it can select suitably, For example, as above-mentioned, a curable film on a base material. It is preferably performed on a laminate formed by laminating while performing at least one of heating and pressurization.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a development process, a hardening process process, a post exposure process etc. are mentioned.

<< Development process >>
The development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably 8-12, more preferably 9-11. As said weak alkaline aqueous solution, 0.1 mass%-5 mass% sodium carbonate aqueous solution or potassium carbonate aqueous solution etc. are mentioned, for example.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

<< Curing treatment process >>
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the curable composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
The heating temperature in the entire surface heating is preferably 120 ° C to 250 ° C, more preferably 120 ° C to 200 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the resin in the curable composition is decomposed, and the film quality is prevented from becoming weak and brittle.
The heating time in the entire surface heating is preferably 10 minutes to 120 minutes, more preferably 15 minutes to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern is formed on the printed wiring board by the permanent pattern forming method. Further, soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

(Printed board)
The printed circuit board of the present invention comprises at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
There is no restriction | limiting in particular as another structure, According to the objective, it can select suitably, For example, the buildup board | substrate etc. in which the insulating layer was further provided between the base material and the said permanent pattern are mentioned.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
-Preparation of inorganic fine particles coated with a compound having a functional group capable of forming hydrogen bonds-
1 L of propylene glycol monomethyl ether acetate (MFGAc, manufactured by Nippon Emulsifier Co., Ltd.) was added to a 2,000 mL 3-neck flask equipped with a reflux tube and a thermometer. Under strong stirring at 400 rpm, 150 g of silica (particle size 0.5 μm) surface-treated with silica surface-treated with N- (β-aminoethyl) -γ-aminopropylsilane (SC2500-SCJ Admatechs) was added. . Two hours later, 20 g of octyl isocyanate (OctNCO, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 g of MFGAc was added dropwise over 1 hour. The temperature was raised to 80 ° C., and after vigorous stirring was continued for 2 hours, heating was stopped and the mixture was allowed to stand at room temperature, and then 800 mL of MEK was added and stirred for 1 hour. After standing, the solvent was removed by decantation, washed twice with MEK, filtered, and dried in a vacuum oven at 80 ° C. for 6 hours to coat the compound having a functional group capable of forming a hydrogen bond. 145g of inorganic fine particles were obtained.

-Binder synthesis-
A 500 mL three-necked round bottom flask equipped with a condenser and a stirrer was charged with 10.86 g (0.081 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g of glycerol monomethacrylate (GLM). (0.105 mol) was dissolved in 79 mL of propylene glycol monomethyl ether monoacetate. To this, 37.54 g (0.15 mol) of 4,4′-diphenylmethane diisocyanate (MDI), 0.1 g of 2,6-di-t-butylhydroxytoluene, as a catalyst, trade name: Neostan U-600 (Nitto 0.2 g of Kasei Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 75 ° C. for 5 hours. Thereafter, it was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 145 g of a polymer solution.
The acid-modified vinyl group-containing polyurethane resin U1 obtained above has a solid content acid value of 70 mgKOH / g and a mass average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 8,000. The vinyl group equivalent was 1.5 mmol / g.
The acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
The mass average molecular weight was measured using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.). That is, a 0.5 mass% THF solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 μL of a sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
The said vinyl group equivalent was calculated | required by measuring a bromine number based on JISK2605.

-Composition of curable composition solution-
Composition of curable composition solution Binder solid content 45% by mass (acid-modified vinyl group-containing binder): 55 parts by mass Polymerizable compound: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts by mass Initiator: IRG907 ( 1.9 parts by mass: DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.02 parts by mass: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 0.06 parts by mass Curing agent: DICY -7 (manufactured by Yuka Shell Epoxy Co., Ltd.) 2.6 parts by mass Thermal crosslinker: Epototo YDF-170 (manufactured by Toto Kasei Co., Ltd.) 7.5 parts by mass Pigment dispersion: 50 parts by mass Others: Megafac F -780F (Dainippon Ink Co., Ltd. product: 30 mass% methyl ethyl ketone solution) 0.13 mass part Methyl ethyl ketone (solvent): 12.0 mass parts In addition, the said pigment dispersion liquid forms the said hydrogen bond. 30 parts by weight of inorganic fine particles coated with a compound having a functional group, 48.2 parts by weight of a binder solution, 0.34 parts by weight of phthalocyanine blue, 0.11 part by weight of anthraquinone yellow pigment (PY24) In addition, 59.0 parts by mass of normal propyl acetate was mixed in advance, and then dispersed with a motor mill M-250 (manufactured by Eiger) at a peripheral speed of 9 m / s for 3 hours using zirconia beads having a diameter of 1.0 mm. It was prepared.

-Production of curable film-
On a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16FB50) as a support, a curable composition solution having the following composition was applied and dried, and a 30 μm thick photosensitive film was formed on the support. A layer was formed. On the photosensitive layer, a 20 μm-thick polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., Alphan-200) was laminated as a protective layer to produce a curable film.

-Lamination on substrate-
A substrate was prepared by subjecting the surface of a copper-clad laminate (no through holes, copper thickness 12 μm) to chemical polishing treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the curable film so that the photosensitive layer of the curable film was in contact with the copper-clad laminate. A curable laminate in which the copper clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order was prepared.
The pressure bonding conditions were such that the vacuuming time was 40 seconds, the pressure bonding temperature was 70 ° C., the pressure bonding pressure was 0.2 MPa, and the pressure application time was 10 seconds.

(Example 2)
In Example 1, the curing in Example 2 was performed in the same manner as in Example 1 except that the compound having a functional group capable of forming a hydrogen bond was changed from octyl isocyanate to acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). Films and curable laminates were produced.

(Example 3)
The same procedure as in Example 1 was conducted except that the compound having a functional group capable of forming a hydrogen bond in Example 1 was changed from octyl isocyanate to methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko). The curable film and curable laminate in Example 3 were produced.

Example 4
In Example 1, except that the compound having a functional group capable of forming a hydrogen bond was changed from octyl isocyanate to tetrahydrophthalic anhydride (THPA, manufactured by Tokyo Chemical Industry Co., Ltd.), in the same manner as in Example 1, A curable film and a curable laminate in Example 4 were produced.

(Example 5)
In Example 1, except that the compound having a functional group capable of forming a hydrogen bond was changed from octyl isocyanate to trimellitic anhydride methacryloyloxyethyl ester (manufactured by Wako Pure Chemical Industries, Ltd.), as in Example 1. Thus, a curable film and a curable laminate in Example 5 were produced.

(Example 6)
In Example 1, except that the compound having a functional group capable of forming a hydrogen bond was changed from octyl isocyanate to trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), the same as Example 1 was carried out. 6 produced a curable film and a curable laminate.

(Comparative Example 1)
In Example 1, silica (SO-C2, manufactured by Admatech Co., Ltd., average particle size 0.5 μm) was used in place of the inorganic fine particles coated with the compound having a functional group capable of forming a hydrogen bond. In the same manner as in Example 1, the curable film and curable laminate in Comparative Example 1 were produced.

(Comparative Example 2)
In Example 1, instead of inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond, inorganic fine particles coated with methacryloyl group-modified silica (SC-2500 SMJ, manufactured by Admatechs) were used. Except for the above, a curable film and a curable laminate in Comparative Example 2 were produced in the same manner as in Example 1.

(Comparative Example 3)
In Example 1, the curable film and curable laminate in Comparative Example 3 were the same as Example 1 except that inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond were not included. Manufactured.

(Measurement method and evaluation method)
<Insulation>
Etching was performed on the copper foil of a printed circuit board in which a 12 μm thick copper foil was laminated on a glass epoxy base material, the line width / space width was 50 μm / 50 μm, the lines were not in contact with each other, and the same facing each other A comb electrode on the surface was obtained. The curable laminate was formed on the comb-shaped electrode of this substrate, a solder resist layer was formed by a conventional method, and exposure was performed with an optimum exposure amount (300 mJ / cm ^{2 to 1} J / cm ² ). Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist was formed.
After connecting the polytetrafluoroethylene shield wire to the comb electrodes with Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation laminate after heating, 5 V is applied to the evaluation laminate. The laminate for evaluation was allowed to stand in a super accelerated high temperature and high humidity life test (HAST) bath at 130 ° C. and 85% RH for 200 hours. Thereafter, the degree of migration of the solder resist in the laminate for evaluation was observed with a 100-fold metal microscope. The results are shown in Table 1 below.
〔Evaluation criteria〕
○: The occurrence of migration cannot be confirmed, and the insulation is excellent.
○ Δ: Migration is slightly observed on copper, but insulation is good.
(Triangle | delta): Generation | occurrence | production of migration is confirmed and it is somewhat inferior to insulation.
X: The electrodes are short-circuited and insulative.

<Developability (resolution)>
The curable laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). From the obtained polyethylene terephthalate film (support) of the curable laminate, exposure is performed so that a round hole with a diameter of 50 to 200 μm can be formed using a round hole pattern using the pattern forming apparatus. went.
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the curable film in the sensitivity evaluation. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the curable laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as the developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve the uncured region. Removed.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, there is no residue at the bottom of the round hole of the pattern, there are no abnormalities such as blistering / peeling of the pattern, and space The minimum round hole pattern width that can be formed was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution. The results are shown in Table 1 below.
〔Evaluation criteria〕
A: A round hole having a diameter of 90 μm or less can be resolved, and the resolution is excellent.
(Circle) (triangle | delta): The round hole more than 90 micrometers in diameter and 120 micrometers or less can be resolved, and resolution is favorable.
Δ: A round hole having a diameter exceeding 120 μm and not more than 200 μm can be resolved, and the resolution is slightly inferior.
X: A round hole cannot be resolved and the resolution is inferior.

<Heat resistance>
An evaluation substrate on which a solder resist layer made of each curable composition is formed on a substrate and a rosin-based flux is applied is immersed in a solder bath previously set at 260 ° C. for 30 seconds, and the flux is washed with denatured alcohol. The swelling, peeling, and discoloration of the resist layer due to were evaluated according to the following criteria. The results are shown in Table 1 below.
〔Evaluation criteria〕
○: No change is observed and heat resistance is excellent.
○: Swelling and peeling are slightly seen, but the heat resistance is good.
Δ: Partially swollen, peeled off and inferior in heat resistance.
X: The coating film swells and peels off.

<Toughness>
A solder resist layer is formed on a printed circuit board obtained by laminating a 12 μm-thick copper foil on a glass epoxy base material on the curable laminate, and a HMW-201GX type exposure made by Oak Seisakusho through a 2 mm square photomask. The exposure was performed with an optimum exposure dose (300 mJ / cm ^{2 to 1} J / cm ² ) that can form a 2 mm square pattern. Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist having a 2 mm square opening was formed.
The obtained substrate was exposed to an atmosphere of −65 ° C. for 15 minutes, then exposed to an atmosphere of 150 ° C. for 15 minutes, and then repeatedly exposed to the air of −65 ° C. 1,000 times. The wrinkles and the degree of peeling on the solder resist of the evaluation substrate through the thermal cycle were observed with an optical microscope. The results are shown in Table 1 below.
〔Evaluation criteria〕
○: Solder resist has no wrinkles or peeling and has excellent toughness.
○ Δ: The solder resist has slight wrinkles and good toughness.
Δ: The solder resist has slight wrinkles and peeling, and is slightly inferior in toughness.
X: The solder resist has obvious wrinkles and peeling, and the toughness is inferior.

<Surface smoothness>
A solder resist layer was formed by a conventional method on a printed board obtained by laminating a 12 μm thick copper foil on a glass epoxy base material, and exposed at an optimum exposure amount (300 mJ / cm ^{2 to 1} J / cm ² ).
Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist was formed.
The surface roughness of the film was observed using Surfcom S70A manufactured by Tokyo Seimitsu Co., Ltd. for the formed solder resist. The results are shown in Table 1 below.
〔Evaluation criteria〕
A: The 10-point average roughness is 0.3 μm or less, and the surface smoothness is good.
(Triangle | delta): A 10-point average roughness exceeds 0.3 micrometer and is 0.5 micrometer or less, and is somewhat inferior to surface smoothness.
X: The surface smoothness is inferior.

(In the table, “compound” represents a compound having a functional group capable of forming a hydrogen bond, and “functional group” represents “functional group capable of forming a hydrogen bond”.)

  From Table 1, Comparative Examples 1 to 3 are inferior in any of insulation, developability, heat resistance, toughness, and surface smoothness, but Examples 1 to 6 are insulative, It can be seen that excellent characteristics can be obtained in all of developability, heat resistance, toughness, and surface smoothness.

Since the curable composition of the present invention can achieve high sensitivity and can improve substrate adhesion, surface hardness, heat resistance, and storage stability, it can be suitably used for a film-type solder resist.
Since the curable film of the present invention has improved heat resistance and storage stability and can efficiently form a high-definition permanent pattern, various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern It can be suitably used for forming liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., particularly for forming permanent patterns on printed circuit boards. be able to.
Since the pattern forming method of the present invention uses the curable composition, it is used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of permanent patterns on printed boards.

Claims (11)

  A curable composition comprising inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond.   The curable composition according to claim 1, wherein the inorganic fine particles are silica. The curable composition according to any one of claims 1 to 2, wherein the inorganic fine particles coated with a compound having a functional group capable of forming a hydrogen bond are represented by the following general formula (1).
Where M represents a metal atom in the inorganic fine particle, X represents a substituent bonded to the surface of the metal atom constituting the inorganic fine particle, and Y represents a compound having a functional group capable of forming a hydrogen bond. Z represents a crosslinkable group.   The curable composition according to any one of claims 1 to 3, further comprising a photopolymerization initiator and a polymerizable compound.   The curable composition according to any one of claims 1 to 4, further comprising a binder.   The curable composition according to any one of claims 1 to 5, further comprising a thermal crosslinking agent and a curing catalyst.   The curable composition according to any one of claims 1 to 6, which is used as a curable composition for a printed circuit board.   A curable film comprising a photosensitive layer containing the curable composition according to claim 1 on a support.   A curable laminate comprising a photosensitive layer containing the curable composition according to claim 1 on a substrate.   A method for forming a permanent pattern comprising at least exposing a photosensitive layer formed of the curable composition according to claim 1.   A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 10.