JP2012198361A - Photosensitive composition, photosensitive film, method for forming permanent pattern, permanent pattern, and printed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which is excellent in all of resolution, embedding property, thermal shock resistance, and electric insulation; and a photosensitive film, a method for forming a permanent pattern, a permanent pattern, and a printed board using the photosensitive composition.SOLUTION: A photosensitive composition contains a dispersant, an inorganic filler, a binder, a polymerizable compound having two or more ethylenically unsaturated groups, a light polymerization initiator, and a heat crosslinking agent, in which the dispersant has a phosphoric ester group.

Description

  The present invention relates to a photosensitive composition, a photosensitive film, a permanent pattern forming method, a permanent pattern, and a printed board.

  In order to cope with downsizing and higher density of electronic component modules in recent years, a wiring conductor layer is formed by a thin film formation method using copper or gold, which is a low resistance metal, on the surface of an insulating substrate made of glass fiber and epoxy resin. A so-called printed circuit board formed with the above has been used for electronic component modules. In addition, this printed board is also changing to a build-up wiring board capable of higher density wiring.

  For example, such a build-up wiring board is formed by laminating a film made of a thermosetting resin on an insulating board made of glass fiber and epoxy resin, and thermosetting the film to form an insulating layer. An opening is formed, and then the surface of the insulating layer is chemically roughened and a copper film is deposited using an electroless copper plating method and an electrolytic copper plating method, thereby forming a conductor layer in the opening and insulating. The wiring conductor layer is formed on the layer surface, and the insulating layer and the wiring conductor layer are repeatedly formed.

  In addition, a solder resist layer having a thickness of 20 μm to 50 μm is deposited on the surface of the wiring board in order to prevent oxidation and corrosion of the wiring conductor layer and to protect the insulating layer from heat when mounting electronic components on the wiring board. Is formed. This solder resist layer is generally composed of an alkali-soluble photocrosslinkable resin having good adhesion to the wiring conductor layer and the insulating layer, and a flexible resin, and has a coefficient of thermal expansion determined by the heat of the insulating layer and the wiring conductor layer. In order to match the expansion coefficient, the inorganic filler is contained in an amount of 5 to 75% by mass.

  Since the material used for the solder resist layer is required to have thermal shock resistance (TCT) and electrical insulation (HAST), these improvements are required.

In order to improve thermal shock resistance (TCT) and electrical insulation (HAST), a technique of highly filling an inorganic filler has been proposed (for example, see Patent Document 1).
However, when the inorganic filler is highly filled, the coating solution is thickened, so that the coating suitability is not sufficient and screen printing cannot be performed. In some cases, the inorganic filler cannot be dispersed, and instead the thermal shock resistance (TCT) and the electrical insulation (HAST) may be lowered. Further, when the film is laminated on the wiring conductor layer, there is a problem that the melt viscosity of the film is high and the embedding property between the wirings is not sufficient.

Therefore, it has been studied to disperse the inorganic filler with a dispersant. For example, a main agent containing an epoxy resin, silica and aluminum hydroxide, a curing agent containing an acid anhydride curing agent, a curing accelerator, a phosphate ester type wetting and dispersing agent, and no inorganic filler. A casting epoxy resin composition has been proposed (see, for example, Patent Document 2).
However, this proposed technique is not cured by light, and the resolution required for the photosensitive composition used in the solder resist cannot be obtained.

Also, an ultraviolet curable resin obtained by reacting a reaction product of a bisphenol type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride, a polyfunctional epoxy resin, and a double molecule remaining in the molecule For multilayer printed wiring boards containing polybutadiene with epoxidized part of the binding site, epoxy compound having both photocuring component and thermosetting component, photopolymerization initiator, filler, and phosphate ester dispersant An insulating resin composition has been proposed (see, for example, Patent Document 3). In the proposed technique, 3,4-epoxycyclohexylmethyl methacrylate is used as the epoxy compound.
However, this proposed technique has a problem that the resolution required for the photosensitive composition used in the solder resist is not sufficient.

  Accordingly, a photosensitive composition excellent in resolution, embedding property, thermal shock resistance, and electrical insulation, and a photosensitive film, a permanent pattern forming method, a permanent pattern, and a print using the photosensitive composition At present, the provision of a substrate is required.

JP 2006-188622 A Japanese Patent No. 3872038 Japanese Patent Laid-Open No. 11-214813

  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 photosensitive composition excellent in all of resolution, embedding property, thermal shock resistance, and electrical insulation, and a photosensitive film, a permanent pattern forming method, a permanent pattern using the photosensitive composition. An object is to provide a pattern and a printed circuit board.

Means for solving the problems are as follows. That is,
<1> A dispersant, an inorganic filler, a binder, a polymerizable compound having two or more ethylenically unsaturated groups, a photopolymerization initiator, and a thermal crosslinker,
The photosensitive composition is characterized in that the dispersant is a dispersant having a phosphate group.
<2> The photosensitive composition according to <1>, wherein the inorganic filler is silica.
<3> The photosensitive agent according to any one of <1> to <2>, wherein the dispersant having a phosphate ester group is at least one of a phosphate ester represented by the following general formula (I) and a salt thereof. Composition.
However, in the general formula (I), R represents a group having at least one of a carboxylic acid ester group and a urethane group and at least one ether oxygen atom. n is an integer of 1-2. When n is 2, R may be the same or different.
<4> The photosensitive composition according to <3>, wherein R in the general formula (I) is a group represented by the following general formula (II).
In the general formula (II), _{R 1} represents an alkyl group having 1 to 4 carbon atoms. x represents an integer of 4 to 5. y represents an integer of 2 to 15. z represents an integer of 3 to 15.
<5> A phosphor having a phosphate group is produced by reacting a phosphoric acid equivalent of an ester-forming phosphorus compound with 1 to 2 equivalents of a compound represented by the following general formula (III). The photosensitive composition according to any one of <1> to <3>, which is at least one of an acid ester and a salt thereof.
R-OH general formula (III)
However, in the general formula (III), R represents a group having at least one of a carboxylic acid ester group and a urethane group and at least one ether oxygen atom.
<6> The photosensitive composition according to <5>, wherein R in the general formula (III) is a group represented by the following general formula (II).
In the general formula (II), _{R 1} represents an alkyl group having 1 to 4 carbon atoms. x represents an integer of 4 to 5. y represents an integer of 2 to 15. z represents an integer of 3 to 15.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the dispersant having a phosphate ester group is a phosphate ester salt.
<8> The photosensitive composition according to any one of <1> to <7>, wherein the binder is an acid-modified ethylenically unsaturated group-containing polyurethane resin.
<9> The photosensitive composition according to <8>, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a structural unit represented by the following general formula (G-1).
However, in said general formula (G-1), R < ¹ > -R < ³ > represents either a hydrogen atom and monovalent organic group each independently, A represents a bivalent organic residue, X is oxygen atom, a sulfur atom, and -N ^{(R 12)} - represents one of the ^{R 12} represents a hydrogen atom or a monovalent organic group.
<10> A support and at least a photosensitive layer on the support,
The photosensitive layer is a photosensitive film comprising the photosensitive composition according to any one of <1> to <9>.
<11> A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <9>.
<12> A permanent pattern formed by the method for forming a permanent pattern according to <11>.
<13> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to <11>.

  According to the present invention, it is possible to solve the conventional problems and achieve the object, and a photosensitive composition excellent in resolution, embedding property, thermal shock resistance, and electrical insulation, and the The photosensitive film using the photosensitive composition, the permanent pattern formation method, a permanent pattern, and a printed circuit board can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least a dispersant, an inorganic filler, a binder, a polymerizable compound having two or more ethylenically unsaturated groups, a photopolymerization initiator, and a thermal crosslinking agent, Furthermore, other components are contained as necessary.

<Dispersant>
The dispersant is a dispersant having a phosphate ester group.
The dispersant having a phosphate group is not particularly limited and may be appropriately selected depending on the intended purpose. However, in terms of excellent embedding properties, the phosphate ester represented by the following general formula (I) and At least one of the salts is preferred.

-Phosphate ester represented by general formula (I) and its salt-
However, in the general formula (I), R represents at least one of a carboxylic acid ester group (—COO—) and a urethane group (—NHCOO—), and at least an ether oxygen atom (—O—). A group having one is represented. n is an integer of 1-2. When n is 2, R may be the same or different.

  Examples of the R group include groups obtained by removing terminal hydroxyl groups from polyether-polyesters, polyether-polyurethanes, polyether-polyester-polyurethanes, and the like. Each group can be arranged in blocks or randomly. A block structure is preferable because it is easy to produce and can exhibit wide compatibility.

  The R is preferably a residue of an oxyalkylated monohydric alcohol containing at least one of a carboxylic ester group and a urethane group, and is a C1-C4 oxyalkylated carboxylic acid ester group and a urethane group. A residue of a monohydric alcohol containing any one is more preferable, and a residue of an ethoxylated monohydric alcohol containing at least one of a carboxylic acid ester group and a urethane group is particularly preferable.

  The R group may further contain smaller amounts of other oxygen and nitrogen containing groups such as, for example, carboxylic acid amide groups or urea groups. Basically, however, it is preferred that there are no more such additional groups per R group.

  The ratio of the number of ether oxygen atoms to the number of carboxylic acid ester groups and / or urethane groups is not particularly limited and may be appropriately selected depending on the intended purpose. 20: 1 is preferable, 1:10 to 10: 1 is more preferable, and 1: 5 to 5: 1 is particularly preferable.

  There is no restriction | limiting in particular as an average molecular weight of the said R group, Although it can select suitably according to the objective, 200-10,000 are preferable, 300-5,000 are more preferable, 400-2,000 are especially preferable. preferable. The average molecular weight of the R group can be determined by the molecular weight of the starting material used in the production of the phosphate ester represented by the general formula (1) or a salt thereof. It can also be determined from the final material by hydrolytic cleavage of the ROH group.

  The phosphoric acid ester represented by the general formula (I) is preferably a phosphoric acid ester having 1 or less urethane groups per 10 ether oxygen atoms and carboxylic acid ester groups in total in the R group. In addition, a phosphate ester having 1 or less urethane group per 20 total carboxylic acid ester groups is more preferable, and a phosphate ester in which the R group does not substantially contain a urethane group is particularly preferable.

Further, R is particularly preferably a group represented by the following general formula (II).
In the general formula (II), _{R 1} represents an alkyl group having 1 to 4 carbon atoms. x represents an integer of 4 to 5. y represents an integer of 2 to 15. z represents an integer of 3 to 15.

There is no restriction | limiting in particular as the salt of the said phosphate ester, According to the objective, it can select suitably, For example, amine salt, sodium salt, potassium salt, lithium salt, magnesium salt, calcium salt etc. are mentioned.
Among these, a magnesium salt and a calcium salt are preferable in terms of excellent embedding properties, and a mixed salt of a magnesium salt and a calcium salt is more preferable.

-Manufacturing method of phosphate ester or its salt represented by general formula (I)-
The phosphoric acid ester represented by the general formula (I) is obtained by, for example, reacting an ester-forming phosphorus compound having 1 phosphoric acid equivalent with 1 to 2 equivalents of a compound represented by the following general formula (III). Can be manufactured.
R-OH general formula (III)
In the general formula (III), R represents at least one of a carboxylic acid ester group (—COO—) and a urethane group (—NHCOO—), and at least an ether oxygen atom (—O—). A group having one is represented.
In the phosphate ester represented by the general formula (I), different R groups may be included. That is, when n in the general formula (I) represents 2, the R groups may be the same or different.
When preparing the phosphate ester having a different R group or a salt thereof, first, to produce a monoester, 1 equivalent of an ester-forming phosphorus compound is converted into 1 equivalent of the general formula (III). Reaction with the first compound which is the compound represented, followed by the monoester and an additional equivalent of the second compound which is a compound represented by the general formula (III) Is different). By doing so, the phosphate ester having the different R group can be produced. Further, it is also different from reacting an ester-forming phosphorus compound of 1 phosphoric acid equivalent with a mixture of various compounds represented by the general formula (III) and having the structure in which R is different. The phosphate ester having an R group can be produced.

  In the production of the phosphoric acid ester represented by the general formula (I), when polyphosphoric acids are used as starting materials, various amounts of pyrophosphoric monoesters and polyphosphoric monoesters in addition to the phosphoric monoesters Are produced as primary products. This is especially true when excess, higher condensed polyphosphates are used (see Hoven-Well, XII / 2, page 147). These often react with water or moisture present in a powdered solid to form a phosphate ester represented by the general formula (I).

--Ester-forming phosphorus compound--
The ester-generating phosphorus compound refers to a phosphorus compound that can generate a phosphate ester by reaction with a hydroxy compound. Examples of the ester-generating phosphorus compound include phosphorus oxychloride, phosphorus pentoxide (anhydrous phosphoric acid), polyphosphoric acid, acetyl phosphate, and the like. Moreover, what is described in the West German patent publication 2,726,854 specification is mentioned. As the ester-generating phosphorus compound, phosphorus pentoxide and polyphosphoric acid are preferable.

--Compound represented by formula (III)-
There is no restriction | limiting in particular as a compound represented by the said general formula (III), According to the objective, it can select suitably, However, The said R is group represented by the said general formula (II). preferable.

  Examples of the compound represented by the general formula (III) include polyether-polyesters, polyether-polyurethanes, and polyether-polyester-polyurethanes. Each group can be arranged in blocks or randomly. A block structure is preferable because it is easy to produce and can exhibit wide compatibility.

--- Polyether-Polyesters ---
Examples of the polyether-polyesters include polyether-polyesters obtained by polymerizing with monohydroxy polyethers using lactones such as propiolactone, valerolactone, caprolactone, substituted derivatives thereof, and mixtures thereof as starting materials. Are preferred.
The starting material for alkoxylation to obtain the monohydroxy polyether is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monohydric alcohol having 1 to 30 carbon atoms may be used. it can. Examples of the monohydric alcohol having 1 to 30 carbon atoms include methanol, ethanol, propanol, n-butanol, cyclohexanol, phenylethanol, neopentyl alcohol, and fluorinated alcohol.
The molecular weight of the monohydroxy polyether is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 to 5,000. The polymerization of the lactone is, for example, European Patent Publication No. 154,678. It is carried out by known methods as described in the specification, for example initiated by p-toluenesulfonic acid or dibutyltin dilaurate at a temperature of about 80 ° C. to 180 ° C.

Other examples of the polyether-polyesters include those obtained by condensation of glycol and dibasic acid in the presence of the monohydroxy polyether. The production of dihydroxy compounds can be suppressed by using corresponding stoichiometric amounts of the monohydroxy polyether.
Compounds conventionally used to produce polyesters, such as those described in West German Patent Publication No. 2,726,854, include diols (glycols) and dibasic carboxylic acids (dibasic acids). Can be used as
When dihydric alcohols containing ether groups such as di-, tri- or polyalkylene glycols are used, for example, polyether groups as described in EP 154,678 are included. It is also possible to use no starting alcohol.
Other examples include polyether-polyesters that can be prepared by condensation of oxycarboxylic acids in the presence of the monohydroxy polyether to control molecular weight. Polyester-polyethers obtainable by alkoxylation of monohydroxy-functional polyesters can also be used.

--- Polyether-polyurethanes and polyether-polyester-polyurethanes ---
The compound represented by the general formula (III) is a polyether-polyurethane or polyether-polyester-polyurethane that can be obtained by addition reaction of a diisocyanate compound to a dihydroxy compound in the presence of the monohydroxy polyether. It may be a kind. The reaction occurs, for example, according to the formula shown below.
CH ₃ (OCH ₂ CH ₂ ) ₁₀ OH +
5OCN— (CH ₂ ) ₆ —NCO +
5HO— (CH ₂ ) ₄ —OH →
_{CH 3 (OCH 2 CH 2)} 10 [OOCNH- (CH 2) 6 -NHCOO- (CH 2) 4] 5 OH

  Examples of the dihydroxy compound for producing the urethane group-containing compounds as described above include diols, preferably those having 2 to 12 carbon atoms, as described in EP 270,126, for example. Diols are mentioned. Also preferred are polyoxyalkylene glycols and / or dihydroxy functional polyesters having a molecular weight of up to 2,000.

  When dihydroxy compounds containing an ether group such as di-, tri- or polyalkylene glycols are used, instead of the monohydroxy polyether, the starting alcohols may be monohydroxy functional polyesters, preferably molecular weights. Is 2,000 or less. In addition, other aliphatic monohydric alcohols, cycloaliphatic monohydric alcohols, aromatic monohydric alcohols and the like can be mentioned, and those having 1 to 20 carbon atoms are preferable.

Examples of the diisocyanate compound include aliphatic diisocyanate compounds having 4 to 15 carbon atoms, cyclic aliphatic diisocyanate compounds having 4 to 15 carbon atoms, and aromatic diisocyanate compounds having 4 to 15 carbon atoms. Is mentioned.
Specific examples of the diisocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and diphenylmethane. Diisocyanate, methylene-bis- (4-cyclohexyl diisocyanate), 1,4-cyclohexane-bis- (methyl isocyanate) and the like can be mentioned.

--Reaction--
The reaction between the ester-forming phosphorus compound and the compound represented by the general formula (III) is preferably carried out at a temperature up to about 100 ° C. without a solvent. However, the reaction can also be carried out in the presence of a suitable inert solvent, for example as described in EP 193 019.

--Phosphate salt--
The phosphate ester salt can be generated via an acid group remaining in the phosphate ester.
The phosphate ester salt can be obtained by an esterification reaction by neutralization with an organic base, an inorganic base or the like.
Examples of the organic base include primary amines, secondary amines, tertiary amines, and amino alcohols as described in US Pat. No. 4,698,099.
Examples of the inorganic base include NH ₃ , NaOH, KOH, LiOH, Mg (OH) ₂ , and Ca (OH) ₂ .

  A commercial item can be used as said phosphate ester and its salt. Examples of the commercially available products include Disper BYK-103, Disper BYK-110, Disper BYK-111, Disper BYK-180 (all manufactured by Big Chemie), Solsperse 41000 (manufactured by Lubrizol), Efka-8512 (manufactured by BASF) ) And the like.

There is no restriction | limiting in particular as content with respect to the said inorganic filler of the dispersing agent which has the said phosphate ester group, Although it can select suitably according to the objective, 0.1 mg-per 1 m < ² > of surface area of the said inorganic filler 10 mg is preferable and 1 mg to 3 mg is more preferable.
When the content is less than 0.1 mg, the dispersibility of the inorganic filler may be insufficient, and when it exceeds 10 mg, the tackiness of the film may be deteriorated. On the other hand, when the content is within the more preferable range, it is advantageous in terms of both dispersibility and tackiness.

<Inorganic filler>
There is no restriction | limiting in particular as said inorganic filler, According to the objective, it can select suitably, For example, a silica etc. are mentioned. When the inorganic filler is silica, the heat resistance of the cured film is improved, the dispersibility is improved, the viscosity of the photosensitive composition can be maintained in a suitable range, and suitable coating suitability is obtained. It is done.

  There is no restriction | limiting in particular as said silica, According to the objective, it can select suitably, For example, vapor phase method silica, crystalline silica, fused silica etc. are mentioned.

There is no restriction | limiting in particular as an average particle diameter (d50) of the said inorganic filler, Although it can select suitably according to the objective, 0.05 micrometer-5 micrometers are preferable, 0.1 micrometer-2 micrometers are more preferable, and 0.1. 2 μm to 1 μm is particularly preferable.
When the average particle diameter (d50) of the inorganic filler is less than 0.05 μm, the coating viscosity may be high, and when it exceeds 5 μm, the smoothness may not be maintained. On the other hand, when the average particle diameter (d50) of the inorganic filler is within the particularly preferable range, it is advantageous in terms of coating viscosity, smoothness of a cured film and heat resistance.
The average particle size (d50) of the inorganic filler is defined as a particle size of an integrated value of 50% when expressed as an integrated (cumulative) weight percentage, and is defined as d50 (D ₅₀ ) 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. be able to.

There is no restriction | limiting in particular as content in the photosensitive composition of the said inorganic filler, Although it can select suitably according to the objective, 30 mass% or more is preferable, 30 mass%-95 mass% are more preferable, 35% by mass to 80% by mass is particularly preferable.
If the content is less than 30% by mass, the thermal shock resistance and solder heat resistance may be insufficient. When the content is within the particularly preferable range, it is advantageous in that a balance between dispersibility, TCT characteristics, and solder heat resistance can be maintained.

<Binder>
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acid-modified ethylenically unsaturated group-containing polyurethane resins, acid-modified ethylenically unsaturated group-containing epoxy resins, and ethylenically unsaturated groups. And an acrylic resin containing a carboxyl group and a polyimide precursor. Among these, an acid-modified ethylenically unsaturated group-containing polyurethane resin is preferable in that it is excellent in embedding property, electrical insulating property, and thermal shock resistance. This is considered to be because the compatibility between the acid-modified ethylenically unsaturated group-containing polyurethane resin and the dispersant having a phosphate group is good.

-Acid-modified ethylenically unsaturated group-containing polyurethane resin-
The acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited as long as it is a polyurethane resin having a carboxyl group that is an acid group and an ethylenically unsaturated group, and can be appropriately selected according to the purpose. .
There is no restriction | limiting in particular as said acid group, According to the objective, it can select suitably, For example, a carboxyl group is mentioned.
There is no restriction | limiting in particular as said ethylenically unsaturated group, According to the objective, it can select suitably, For example, a vinyl group etc. are mentioned.
Examples of the functional group having an ethylenically unsaturated group include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinylphenyl group, vinyl ester group, vinyl ether group, allyl ether group, and allyl ester group. .

  Examples of the acid-modified ethylenically unsaturated group-containing polyurethane resin include (i) a polyurethane resin having an ethylenically unsaturated group in the side chain, (ii) a carboxyl group-containing polyurethane, and an epoxy group and an ethylenically unsaturated group in the molecule. Examples thereof include a polyurethane resin obtained by reacting with a compound having a saturated group.

-(I) Polyurethane resin having an ethylenically unsaturated group in the side chain--
There is no restriction | limiting in particular as a polyurethane resin which has an ethylenically unsaturated group in the said side chain, According to the objective, it can select suitably, For example, the following general formula (1)-(3) is given to the side chain. What has at least 1 among the functional groups represented is mentioned.

In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group.
Examples of R ^1, is not particularly limited and may be appropriately selected depending on the purpose, for example, a hydrogen atom, 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, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a 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 intended 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. Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo 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, 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, an arylsulfonyl group which may have a substituent, and the like Can be mentioned. 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 ) —. Wherein ^{R 12} has the same meaning as ^{R 12} in the general formula (1), and preferred examples are also the same.

In the general formula (3), R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a monovalent organic group.
Examples of R ^9, is not particularly limited and may be appropriately selected depending on the purpose, for example, an alkyl group which may have a hydrogen atom or a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
R ¹⁰ and R ¹¹ are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo 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, 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, an arylsulfonyl group which may have a substituent, and the like Can be mentioned. 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 include those similar to those in the general formula (1). Moreover, in the said General formula (3), Z represents the phenylene group which may have an oxygen atom, a sulfur atom, -N (R < ¹³ >)-, or a substituent. R ¹³ 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 methyl group, an ethyl group, and an isopropyl group are preferable in terms of high radical reactivity.

The polyurethane resin having an ethylenically unsaturated group in the side chain preferably has a structural unit represented by the following general formula (G-1) from the viewpoint of resolution and insulation reliability.
However, in said general formula (G-1), R < ¹ > -R < ³ > represents either a hydrogen atom and monovalent organic group each independently, A represents a bivalent organic residue, X is oxygen atom, a sulfur atom, and -N ^{(R 12)} - represents one of the ^{R 12} represents a hydrogen atom or a monovalent organic group.

Examples of the monovalent organic group R ¹ in the general formula (G-1), not particularly limited and may be appropriately selected depending on the intended purpose, e.g., an alkyl group which may have a substituent, Etc. R ¹ in the general formula (G-1) is preferably a hydrogen atom or a methyl group.

The monovalent organic group of R ² and R ^{3 in} the general formula (G-1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the monovalent organic group may have a substituent. And a good alkyl group.
As R < ² > and R < ³ > in the said general formula (G-1), a hydrogen atom is preferable.

  A in the general formula (G-1) is not particularly limited as long as it is a divalent organic residue, and can be appropriately selected according to the purpose. For example, A may have a substituent. Examples thereof include a good divalent alkylene group. Specific examples of the divalent organic residue include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, a methylene group is preferable.

  X in the general formula (G-1) is preferably an oxygen atom.

The monovalent organic group is not particularly limited and may be appropriately selected depending on the intended purpose, e.g., an alkyl group which may have a substituent R ¹² in the general formula (G-1), Etc. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable.

The method for introducing the structural unit represented by the general formula (G-1) into the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. And a method of reacting a diisocyanate compound with a compound represented by the following general formula (G).
In the general formula ^{(G), R 1 ~R 3} , A, and X are the same as ^R 1 ^{to R} 3, A, and X in the general formula (G-1).

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

OCN-X ⁰ -NCO: General formula (4)
^HO-Y 0 -OH ··· the general formula (5)
In the general formula (4) and the general formula (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, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain as a reaction product of the diisocyanate compound and the diol compound Generated. According to the method, rather than substituting and / or introducing a desired side chain after reaction of the polyurethane resin, the polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain Can be easily manufactured.

  The diisocyanate compound represented by the general formula (4) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monofunctional alcohol or a monofunctional alcohol having a triisocyanate compound and an ethylenically unsaturated group may be used. Examples thereof include diisocyanate compounds that can be obtained by addition reaction with 1 equivalent of a functional amine compound.

  The triisocyanate compound is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include compounds described in paragraphs “0034” to “0035” of JP-A-2005-250438. Is mentioned.

  The monofunctional alcohol having the ethylenically unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraph “Japanese Patent Application Laid-Open No. 2005-250438” And compounds described in “0037” to “0040”.

  Here, the method for introducing an ethylenically 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 a polymerizable unsaturated group is preferred. There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, A triisocyanate compound and the monofunctional alcohol which has an ethylenically unsaturated group, or 1 equivalent of monofunctional amine compounds are made to react. The diisocyanate compound which can be obtained by this, Comprising: The compound etc. which have an ethylenically unsaturated group in the side chain described in Paragraph "0042"-"0049" of Unexamined-Japanese-Patent No. 2005-250438 are mentioned, for example.

  The polyurethane resin having an ethylenically unsaturated group in the side chain contains the ethylenically unsaturated group from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. It is also possible to copolymerize diisocyanate compounds other than the diisocyanate compound.

The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a diisocyanate compound represented by the following general formula (6).
^OCN-L 1 -NCO ··· general formula (6)
In the general formula (6), L ¹ may have a substituent (for example, any one 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 group. If necessary, L 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.

  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 acid 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 Examples thereof include a diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate. These may be used individually by 1 type and may use 2 or more types together.

  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, high molecular diols, such as a polyether diol compound, a polyester diol compound, and a polycarbonate diol compound Compounds: Low molecular diol compounds such as ethylene glycol and neopentyl glycol; diol compounds having an ethylenically unsaturated group; diol compounds having a carboxylic acid group.

  Here, as a method for introducing an ethylenically unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a diol compound containing an ethylenically unsaturated group in the side chain is used as a raw material for producing the polyurethane resin. A method is also preferred. The diol compound containing an ethylenically unsaturated group in the side chain may be a commercially available compound such as trimethylolpropane monoallyl ether, or a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound. And compounds that are easily produced by reaction with a compound containing an ethylenically unsaturated group, such as a carboxylic acid, an acid chloride, an isocyanate, an alcohol, an amine, a thiol, or a halogenated alkyl compound.

The diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs “0057” to “0060” of JP-A-2005-250438. , A compound obtained by ring-opening a tetracarboxylic dianhydride described in paragraphs “0095” to “0101” of JP-A-2005-250438 with a diol compound, represented by the following general formula (G) Examples thereof include compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438. Among these, the compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G) are preferable.
However, in said general formula (G), R < ¹ > -R < ³ > represents either a hydrogen atom and a monovalent organic group each independently, A represents a bivalent organic residue, and X is an oxygen atom. , sulfur atom, and -N ^{(R 12)} - represents one of the ^{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 group in the side chain is, for example, ethylenic in the side chain from the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. A diol compound other than a diol compound containing an unsaturated group can be copolymerized.
The diol compound other than the diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol Compound etc. are mentioned.

  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 group 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 of the polyurethane resin having an ethylenically unsaturated group in the side chain, a diol compound having a carboxyl group can be used in combination with the diol compound described above. The diol compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds represented by the following general formulas (8) to (10).

In the general formulas (8) to (10), R ¹⁵ is a hydrogen atom, a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—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 7 carbon atoms) Represents an aralkyl group of ˜15.), And the like may represent an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group that may have. Among these, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable.
In the general formulas (8) to (10), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl). A divalent aliphatic or aromatic hydrocarbon group optionally having a group, an alkoxy group, or a halogeno group. 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, the L ^{9 to} L ¹¹ may have other functional groups that do not react with the isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, and an 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 general formula (9), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and may be appropriately selected according to the purpose. 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 General formula (8)-(10), 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- Hydroxyphenyl) 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 in that 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 group in the side chain is a resin further having a carboxyl group in the side chain, and more specifically, the ethylenically unsaturated group in the side chain is 0. It is preferably 0.05 mmol / g to 3.0 mmol / g, more preferably 0.5 mmol / g to 2.7 mmol / g, and particularly preferably 0.75 mmol / g to 2.4 mmol / g. Preferably, the side chain 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 mg KOH / g is particularly preferred.
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 polyurethane resin having an ethylenically unsaturated group 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 corresponding to each 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.

  Moreover, as a polyurethane resin which has an ethylenically unsaturated group in the said side chain, what has an ethylenically unsaturated group in a polymer terminal and a principal chain is used suitably. By having an ethylenically unsaturated group at the polymer terminal and main chain, it further has an ethylenically unsaturated group between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated group in the side chain, or in the side chain. Crosslinking reactivity is improved between polyurethane resins, and the strength of the photocured product is increased. As a result, when a polyurethane resin having an ethylenically unsaturated group in the side chain is used for a lithographic printing plate, a material having excellent toughness can be provided.

Examples of the method for introducing an ethylenically unsaturated group at the polymer terminal include the following methods. That is, in the process of synthesizing a polyurethane resin having an ethylenically unsaturated group in the side chain as described above, in the step of treating with a residual isocyanate group at the polymer end and an alcohol or amine, the ethylenically unsaturated group is contained. Alcohols or amines 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 ethylenically unsaturated group.
The ethylenically unsaturated group is preferably introduced into the polymer side chain rather than the polymer end from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and the crosslinking reaction efficiency is improved. .

The ethylenically unsaturated group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a methacryloyl group, an acryloyl group or a vinylphenyl group from the viewpoint of forming a crosslinked cured film, and is preferably 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 ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 3.0 mmol / g, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.

  As a method for introducing an ethylenically unsaturated group into the main chain, there is a method in which a diol compound having an ethylenically unsaturated group in the main chain direction is used for the synthesis of the polyurethane resin. The diol compound having an ethylenically unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-2-butene-1,4-diol and trans-2-butene. -1,4-diol, polybutadiene diol and the like.

  The polyurethane resin having an ethylenically unsaturated group 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 group 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 (i) polyurethane resin having an ethylenically unsaturated group in the side chain include, for example, P-1 to P— shown in paragraphs “0293” to “0310” of JP-A-2005-250438. And 31 polymers. 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 an ethylenically unsaturated 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, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule. . Depending on the purpose, a low molecular diol having a weight average molecular weight of 300 or less or a low molecular diol having a weight average molecular weight of 500 or more may be added as a copolymer component as a diol 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 containing a carboxylic acid-containing diol as an essential component, and reacting the obtained reaction product with a compound having an epoxy group and an ethylenically unsaturated group in the molecule through a —COO— bond. It may be obtained.

Moreover, as said polyurethane resin, at least 1 sort (s) chosen from the diisocyanate shown by the following general formula (11), and the carboxylic acid group containing diol shown by the following general formula (12-1)-(12-3), Is obtained by reacting a reaction product having an essential component with a compound having an epoxy group and an ethylenically unsaturated group in the molecule represented by the following general formulas (13-1) to (13-16). May be.
However, in the general formula (11), 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 (12-1), 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 (where R ₆ is an alkyl group having 1 to 10 carbon atoms, aralkyl having 7 to 15 carbon atoms) Each group is included), which may have 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 (12-1), (12-2) and (12-3), 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, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group are preferable), and may represent a divalent aliphatic or aromatic hydrocarbon. 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.

In the general formula _{(13-1) ~ (13-16),} 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.

  As the polyurethane resin, in particular, a reaction between a diisocyanate represented by the general formula (11) and at least one selected from carboxylic acid group-containing diols represented by the general formulas (12-1) to (12-3) It is obtained by further reacting a compound having one epoxy group and at least one (meth) acryl group in the molecule represented by any of the general formulas (13-1) to (13-16), An alkali-soluble photocrosslinkable polyurethane resin having an acid value of 20 mgKOH / g to 120 mgKOH / g is preferred.

  These polymer compounds may be used alone or in combination of two or more.

--- Synthesis method of polyurethane resin obtained by reacting carboxyl group-containing polyurethane with compound having epoxy group and ethylenically unsaturated 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, the molar ratio of the diisocyanate and diol compound can be reduced by treatment with alcohols or amines. It is synthesized in such a way that no isocyanate groups remain entangled.

---- Diisocyanate ----
There is no restriction | limiting in particular as a diisocyanate compound shown by the said General formula (11), According to the objective, it can select suitably, For example, the compound described in Paragraph "0021" of Unexamined-Japanese-Patent No. 2007-2030 etc. Is mentioned.

---- Carboxylic acid group-containing diol ----
In addition, the diol compound having a carboxyl group represented by the general formulas (12-1) to (12-3) 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.

---- Low molecular weight diol containing no carboxylic acid group ----
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 JP2007-2030A. It is done.
The copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80 mol% or less, and particularly preferably 50 mol% 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 an ethylenically unsaturated group in the molecule include, for example, paragraph “ Glycidyl acrylate as a compound containing an epoxy group and an ethylenically unsaturated group in the polymers of U1 to U13, U1 to U4 and U6 to U11 shown in "0314" to "0315" is converted into glycidyl methacrylate, 3,4-epoxycyclohexylmethyl. Examples thereof include polymers in place of acrylate (trade name: Cyclomer A400 (manufactured by Daicel Chemical Industries)) and 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (manufactured by Daicel Chemical Industries)).

-Weight average molecular weight of acid-modified ethylenically unsaturated group-containing polyurethane resin-
There is no restriction | limiting in particular as a weight average molecular weight of the said acid-modified ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 2,000-60,000 are preferable, 3,000-50 3,000 is more preferable, and 3,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 2,000, 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. . On the other hand, when the photosensitive composition is used for a photosensitive solder resist having a weight average molecular weight of 2,000 to 60,000, it is excellent in crack resistance and heat resistance, and has a non-image area formed by an alkaline developer. Excellent developability.
The weight average molecular weight is, for example, a high-speed GPC device (HLC-802A manufactured by Toyo Soda Kogyo Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column of one TSKgel HZM-M. 200 μL of sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm).

-Acid value of acid-modified ethylenically unsaturated group-containing polyurethane resin-
The acid value of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 20 mgKOH / g to 120 mgKOH / g, preferably 30 mgKOH / g to 110 mgKOH / g is more preferable, and 35 mgKOH / g to 100 mgKOH / 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.

--Equivalent ethylenically unsaturated group equivalent of acid-modified ethylenically unsaturated group-containing polyurethane resin--
The ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.05 mmol / g to 3.0 mmol / g. Preferably, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable. When the ethylenically unsaturated group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 3.0 mmol / g, the brittleness of the cured film may increase.
The said ethylenically unsaturated group equivalent can be calculated | required by measuring a bromine number, for example. The bromine number can be measured according to, for example, JIS K2605.

-Acid-modified ethylenically unsaturated group-containing epoxy resin-
The acid-modified ethylenically unsaturated group-containing epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least two or more per molecule described in Japanese Patent No. 2877659 An epoxy compound having an epoxy group (a), a compound (b) having at least two hydroxyl groups in one molecule and one reactive group other than a hydroxyl group that reacts with an epoxy group, and an ethylenically unsaturated group-containing monocarboxylic acid Acid-modified ethylenically unsaturated group-containing epoxy resin which is a reaction product of the reactant (I) of the acid (c) and the polybasic acid anhydride (d), an epoxy having at least two epoxy groups in one molecule Compound (a), compound (b) having one reactive group other than a hydroxyl group that reacts with at least two hydroxyl groups and an epoxy group in one molecule, and an ethylenically unsaturated group-containing monomer Acid-modified ethylenically unsaturated group-containing epoxy resin, which is a reaction product of reaction product (I) of boric acid (c), polybasic acid anhydride (d) and ethylenically unsaturated group-containing monoisocyanate (e) Can be mentioned.

  A commercially available product can be used as the acid-modified ethylenically unsaturated group-containing epoxy resin. Examples of commercially available acid-modified ethylenically unsaturated group-containing epoxy resins include ZFR series, CCR series, and PCR series (all manufactured by Nippon Kayaku Co., Ltd.).

-Acrylic resin containing ethylenically unsaturated groups and carboxyl groups-
There is no restriction | limiting in particular as an acrylic resin containing the said ethylenically unsaturated group and a carboxyl group, According to the objective, it can select suitably, For example, it contains (meth) acrylic acid ester and an ethylenically unsaturated group. An acrylic resin in which a (meth) acrylate having an epoxy group is added to a part of the acid groups of a copolymer obtained from a compound having at least one acid group.
As such an acrylic resin, for example, obtained from (meth) acrylic acid ester and a compound containing an ethylenically unsaturated group and having at least one acid group described in JP-A-2009-86376. Examples thereof include a modified copolymer obtained by adding glycidyl (meth) acrylate to a part of acid groups of the obtained copolymer.
A commercial item can be used for the acrylic resin containing the said ethylenically unsaturated group and a carboxyl group. As a commercial item of the acrylic resin containing the said ethylenically unsaturated group and a carboxyl group, CyclomerP 200HM (made by Daicel Chemical Industries) etc. are mentioned, for example.

-Polyimide precursor-
There is no restriction | limiting in particular as said polyimide precursor, According to the objective, it can select suitably, For example, what was described in Unexamined-Japanese-Patent No. 2010-6946 etc. is mentioned.

-Binder content-
There is no restriction | limiting in particular as content in the said photosensitive composition of the said binder, Although it can select suitably according to the objective, 5 mass%-80 mass% with respect to solid content of the said photosensitive composition Is preferable, 20 mass%-75 mass% is more preferable, and 30 mass%-70 mass% is especially preferable.
If the content is less than 5% by mass, the crack resistance may not be kept good, and if it exceeds 80% by mass, the heat resistance may be lowered. 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.

<Polymerizable compound having two or more ethylenically unsaturated groups>
There is no restriction | limiting in particular as a polymeric compound which has 2 or more of said ethylenically unsaturated groups, According to the objective, it can select suitably.

  The polymerizable compound having two or more ethylenically unsaturated groups is preferably a polymerizable compound having two or more (meth) acryloyl groups. Here, the (meth) acryloyl group means an acryloyl group and a methacryloyl group.

The polymerizable compound having two or more (meth) acryloyl groups is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, Ethylene oxide for polyfunctional alcohols such as methylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerol tri (meth) acrylate, trimethylolpropane, glycerol and bisphenol And (meth) acrylates after addition reaction with propylene oxide, described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, etc. Urethane acrylates; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; epoxy resin and (meth) Such as multifunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, dicyclopentanyl dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate Is more preferable.
The polymerizable compound having two or more (meth) acryloyl groups is preferably a polymerizable compound having a polycyclic aliphatic group and two or more (meth) acryloyl groups. Examples of the polymerizable compound having a polycyclic aliphatic group and two or more (meth) acryloyl groups include dimethylol tricyclodecane di (meth) acrylate.

  The number of (meth) acryloyl groups in the polymerizable compound having two or more (meth) acryloyl groups is not particularly limited and may be appropriately selected depending on the intended purpose. Is more preferable.

  The polymerizable compound having two or more ethylenically unsaturated groups preferably has no epoxy group.

-Content of polymerizable compound having two or more ethylenically unsaturated groups-
The content of the polymerizable compound having two or more ethylenically unsaturated groups in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. However, the solid content of the photosensitive composition Is preferably 2% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and particularly preferably 4% by mass to 35% by mass. When the content of the polymerizable compound having two or more ethylenically unsaturated groups is less than 2% by mass, pattern formation may not be possible, and when it exceeds 50% by mass, crack resistance may be inferior. On the other hand, when the content of the polymerizable compound having two or more ethylenically unsaturated groups is within the particularly preferable range, it is advantageous in that the pattern formability and crack resistance are improved.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. Examples thereof include halogenated hydrocarbon derivatives, phosphine oxide, hexa Examples include arylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and ketoxime ethers.

Examples of the halogenated hydrocarbon derivative include a halogenated hydrocarbon derivative having a triazine skeleton and a halogenated hydrocarbon derivative having an oxadiazole skeleton.
The halogenated hydrocarbon derivative having a triazine skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. For example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in Japanese Patent Laid-Open No. 53-133428, German Patent No. 3337024 Compounds, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and JP-A-5-34920 And the like.
Examples of the halogenated hydrocarbon derivative having an oxadiazole skeleton include compounds described in US Pat. No. 4,221,976.

  There is no restriction | limiting in particular as said oxime derivative, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0085" of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned.

  There is no restriction | limiting in particular as said ketone compound, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0087" of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned.

  Examples of photopolymerization initiators other than those described above include the compounds described in paragraph “0086” of JP-A-2007-2030.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  There is no restriction | limiting in particular as said sensitizer, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0089" of Unexamined-Japanese-Patent No. 2007-2030 are mentioned.

  The combination of the photopolymerization initiator and the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. (1) Electron donating initiator and sensitizing dye, (2) Electron accepting initiator and sensitizing dye, (3) Electron donating initiator, sensitizing dye and electron accepting initiator (ternary initiation system) ] Etc. are mentioned.

  There is no restriction | limiting in particular as content of the said sensitizer, Although it can select suitably according to the objective, 0.05 mass%-30 mass% are preferable with respect to solid content of the said photosensitive composition. 0.1% by mass to 20% by mass is more preferable, and 0.2% by mass to 10% by mass is particularly preferable. When the content of the sensitizer is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease, exceeding 30% by mass. In some cases, the sensitizer may precipitate from the photosensitive layer during storage.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferable examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which can cope with laser light having a wavelength of 405 nm in the later-described exposure. Examples thereof include a composite photoinitiator in which a hydrogen compound and an amine compound as a sensitizer are combined, a hexaarylbiimidazole compound, and titanocene.

-Content of photopolymerization initiator-
There is no restriction | limiting in particular as content in the said photosensitive composition of the said photoinitiator, Although it can select suitably according to the objective, 0.5 mass% with respect to solid content of the said photosensitive composition -20% by mass is preferable, 0.5% by mass to 15% by mass is more preferable, and 1% by mass to 10% by mass is particularly preferable. When the content of the photopolymerization initiator is less than 0.5% by mass, the exposed area tends to be eluted during development, and when it exceeds 20% by mass, the heat resistance may be lowered. On the other hand, when the content of the photopolymerization initiator is within the particularly preferable range, it is advantageous in that a good pattern can be formed and heat resistance is also improved.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but has at least one functional group selected from a cyclic ether group, a blocked isocyanate group, an oxazolyl group, and an ethylene carbonate group. Compounds are preferred.

  Examples of the thermal crosslinking agent include a compound having a cyclic ether group, a compound having a blocked isocyanate group, a compound having an oxazolyl group, and a compound having an ethylene carbonate group.

Examples of the compound having a cyclic ether group include a compound having an oxirane group and a compound having an oxetanyl group.
Examples of the compound having an oxirane group include an epoxy compound having at least two oxirane groups in one molecule.
Examples of the compound having an oxetanyl group include an oxetane compound having at least two oxetanyl groups in one molecule.

  There is no restriction | limiting in particular as said epoxy compound, According to the objective, it can select suitably, For example, the epoxy resin etc. which were described in Paragraph "0095" of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned. Examples of the epoxy compound include bisphenol type epoxy resins. Examples of the bisphenol type epoxy resin include a bisphenol F type epoxy resin.

  There is no restriction | limiting in particular as said oxetane compound, According to the objective, it can select suitably, For example, the polyfunctional oxetane compound etc. which were described in Unexamined-Japanese-Patent No. 2007-2030 paragraph "0096" etc. are mentioned.

  There is no restriction | limiting in particular as a compound which has the said block isocyanate group, According to the objective, it can select suitably, For example, the compound obtained by making a blocking agent react with the isocyanate group of polyisocyanate and its derivative (s) is mentioned. Examples of such a compound include the blocked polyisocyanate described in paragraph “0023” of JP-A-5-9407.

  The compound having an oxazolyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is obtained by polymerizing an unsaturated monomer having an oxazolyl group with another unsaturated monomer as necessary. Resin etc. are mentioned. Examples of the unsaturated monomer having an oxazolyl group include vinyl oxazoline compounds such as 2-isopropenyl-2-oxazoline. A commercial item can be used as a compound which has the said oxazolyl group. Examples of the commercially available product include EPOCROS RPS-1005 manufactured by Nippon Shokubai Co., Ltd.

  The compound having an ethylene carbonate group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an acrylic resin having an ethylene carbonate group. Examples of the acrylic resin having an ethylene carbonate group include a carbonate group-containing copolymer described in JP-A-1-146968.

These may be used individually by 1 type and may use 2 or more types together.
Among these, a compound having an oxirane group is preferable in terms of the smoothness of the pattern side surface and electrical insulation.

-Content of thermal crosslinking agent-
There is no restriction | limiting in particular as content in the said photosensitive composition of the said thermal crosslinking agent, Although it can select suitably according to the objective, 1 mass%-50 with respect to solid content of the said photosensitive composition % By mass is preferable, 2% by mass to 40% by mass is more preferable, and 3% by mass to 30% by mass is particularly preferable. When the content of the thermal crosslinking agent is less than 1% by mass, heat resistance may be deteriorated, and when it exceeds 50% by mass, developability and crack resistance may be deteriorated. On the other hand, when the content is within the particularly preferable range, a cured film can be produced with good sensitivity, and the formed cured film is advantageous in that both heat resistance and crack resistance can be achieved.

<Other ingredients>
Examples of the other components include thermoplastic elastomers, thermosetting accelerators, adhesion promoters, thermal polymerization inhibitors, colorants, organic solvents, thixotropic agents, antifoaming agents, and leveling agents.

-Thermoplastic elastomer-
By adding the thermoplastic elastomer to the photosensitive composition, heat resistance, flexibility and toughness can be imparted to the photosensitive composition.
There is no restriction | limiting in particular as said thermoplastic elastomer, According to the objective, it can select suitably, For example, styrene-type elastomer, olefin-type elastomer, urethane-type elastomer, polyester-type elastomer, polyamide-type elastomer, acrylic-type elastomer, silicone And elastomers and rubber-modified epoxy resins. These may be used individually by 1 type and may use 2 or more types together.
These thermoplastic elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. Moreover, there is no restriction | limiting in particular as a characteristic of the said elastomer, According to the objective, it can select suitably, For example, it is preferable that it is alkali-soluble or swellable in terms of the production efficiency of a image development process.
Examples of the styrene-based elastomer, olefin-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic-based elastomer, silicone-based elastomer, and rubber-modified epoxy resin include, for example, paragraph “ And the like described in “0087” to “0095”.

--- The content of thermoplastic elastomer--
There is no restriction | limiting in particular as content in the said photosensitive composition of the said thermoplastic elastomer, Although it can select suitably according to the objective, 1 mass%-50 with respect to solid content of the said photosensitive composition % By mass is preferable, 2% by mass to 20% by mass is more preferable, and 3% by mass to 10% by mass is particularly preferable. If the content is less than 1% by mass, the crack resistance may be inferior, and if it exceeds 50% by mass, the unexposed part may not be eluted with the developer. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of improving developability and crack resistance.

-Thermosetting accelerator-
There is no restriction | limiting in particular as said thermosetting accelerator, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0101" of Unexamined-Japanese-Patent No. 2007-2030 are mentioned.

--Content of thermosetting accelerator--
There is no restriction | limiting in particular as content in the said photosensitive composition of the said thermosetting accelerator, Although it can select suitably according to the objective, 0.01 mass with respect to solid content of the said photosensitive composition % To 20% by mass is preferable, 0.05% to 15% by mass is more preferable, and 0.1% to 10% by mass is particularly preferable. If the content of the thermosetting accelerator is less than 0.01% by mass, the toughness of the cured film may not be expressed. If the content exceeds 20% by mass, the storage stability of the photosensitive composition may be reduced. May get worse. On the other hand, when the content of the thermosetting accelerator is within the particularly preferred range, it is advantageous in that the storage stability and the cured film properties of the photosensitive composition are improved.

-Adhesion promoter-
There is no restriction | limiting in particular as said adhesion promoter, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0108" of Unexamined-Japanese-Patent No. 2007-2030 are mentioned.

--Content of adhesion promoter--
There is no restriction | limiting in particular as content in the said photosensitive composition of the said adhesion promoter, Although it can select suitably according to the objective, 0.01 mass% with respect to solid content of the said photosensitive composition -20% by mass is preferable, 0.05% by mass to 15% by mass is more preferable, and 0.1% by mass to 10% by mass is particularly preferable. When the content of the adhesion promoter is less than 0.01% by mass, the toughness of the cured film may not be expressed. When the content exceeds 20% by mass, the preservability of the photosensitive composition is deteriorated. There are things to do. On the other hand, when the content is within the particularly preferred range, it is advantageous in that the storage stability and the cured film physical properties of the photosensitive composition are improved.

-Thermal polymerization inhibitor-
There is no restriction | limiting in particular as said thermal polymerization inhibitor, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0113" of Unexamined-Japanese-Patent No. 2007-2030 are mentioned.

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, A coloring pigment and the dye suitably selected from well-known dye can be used.
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0106" of Unexamined-Japanese-Patent No. 2007-2030 are mentioned.
There is no restriction | limiting in particular as content in the said photosensitive composition of the said coloring agent, According to the objective, it can select suitably.

-Organic solvent-
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0043” of JP-A No. 11-240930 and paragraphs of JP-A No. 2007-2030. And the compounds described in “0121”.

-Content of organic solvent-
There is no restriction | limiting in particular as content in the said photosensitive composition of the said organic solvent, Although it can select suitably according to the objective, 1 mass%-80 mass with respect to solid content of the said photosensitive composition % Is preferable, 2% by mass to 70% by mass is more preferable, and 3% by mass to 60% by mass is particularly preferable. When the content of the organic solvent is less than 1% by mass, the viscosity of the composition may be high and it may be difficult to form a coating film. When the content exceeds 80% by mass, it is difficult to control the desired film thickness. May be. On the other hand, when the content of the organic solvent is within the particularly preferable range, it is advantageous from the viewpoint of coating film production suitability.

(Photosensitive film)
Although the photosensitive composition of this invention can be used also as a liquid resist by apply | coating and drying on the board | substrate with which conductor wiring was formed, it is especially useful for manufacture of the photosensitive film.
The photosensitive film has at least a support and a photosensitive layer, and preferably has a protective film. Further, if necessary, the photosensitive film is abbreviated as a cushion layer and an oxygen barrier layer (hereinafter referred to as a PC layer). ) And other layers.
The form of the photosensitive film is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive layer and the protective film are provided in this order on the support, The PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film are provided on the support. The form which it has in order, etc. are mentioned. The photosensitive layer may be a single layer or a plurality of layers.

<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.

  There is no restriction | limiting in particular as said support body, According to the objective, it can select suitably, For example, the support body of Paragraph [0115]-[0117] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

<Photosensitive layer>
The photosensitive layer is formed from the photosensitive composition of the present invention.

  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 a method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive 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 used for the said photosensitive composition solution, According to the objective, it can select suitably.

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, 1 micrometer-100 micrometers are preferable, 2 micrometers-50 micrometers are more preferable, and 4 micrometers-30 micrometers are especially preferable.

There is no restriction | limiting in particular as melt viscosity in 70 degreeC of the said photosensitive layer, Although it can select suitably according to the objective, 5 * 10 < ³ > Pa * s or less is preferable. When the melt viscosity at 70 ° C. of the photosensitive layer exceeds 5 × 10 ³ Pa · s, lamination failure may occur.
There is no restriction | limiting in particular as melt viscosity in 30 degreeC of the said photosensitive layer, Although it can select suitably according to the objective, 1 * 10 < ⁵ > Pa * s or more is preferable. If the melt viscosity at 30 ° C. of the photosensitive layer is less than 1 × 10 ⁵ Pa · s, edge fusion may deteriorate.
The melt viscosity of the photosensitive layer can be measured by using a melt viscosity measuring device such as a rheometer / VAR-1000 type (manufactured by Rheological Co., Ltd.).

  Details are as described in paragraphs “0115” to “0127” of JP2007-2030A.

(Permanent pattern forming method and permanent pattern)
The permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps as necessary.
The permanent pattern of the present invention is formed by the permanent pattern forming method.

<Exposure process>
If the said exposure process is a process of exposing with respect to the photosensitive layer formed with the photosensitive composition of this invention, there will be no restriction | limiting in particular, According to the objective, it can select suitably.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose, but while performing at least one of heating and pressurizing the photosensitive film on the substrate. It is preferable to be performed on a laminated body formed by laminating.

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

<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 developing step is a step of removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as a removal method of the said exposed part, 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, According to the objective, it can select suitably, For example, the developing solution as described in Paragraph [0171]-[0173] of Unexamined-Japanese-Patent No. 2008-250074 is mentioned.

-Curing 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.

  The method for the entire surface exposure treatment and the entire surface heat treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, in paragraphs [0176] to [0177] of JP-A-2008-250074 The method of description is 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 a printed circuit board by the permanent pattern forming method. It can be formed and soldered 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 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. And a semiconductor, components, etc. are mounted in the part which soldered. 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 Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples at all.

In the following synthesis examples, the acid value, weight average molecular weight, and ethylenically unsaturated group equivalent were determined by the following methods.
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 weight average molecular weight was measured using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.). That is, 0.5% by mass of HHF solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 μL of sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
The said ethylenically unsaturated group equivalent was calculated | required by measuring a bromine number based on JISK2605.

(Synthesis Example 1)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin>
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 Kasei) 0.2 g) was added and stirred at 75 ° C. for 5 hours. Thereafter, the solution was diluted with methyl alcohol and stirred for 30 minutes to obtain an acid-modified ethylenically unsaturated group-containing polyurethane resin solution having a solid concentration of 40% by mass.
The acid-modified ethylenically unsaturated group-containing polyurethane resin obtained above has a solid content acid value of 70 mgKOH / g, and a weight average molecular weight (polystyrene standard) of 8, measured by gel permeation chromatography (GPC). And the ethylenically unsaturated group equivalent was 1.5 mmol / g.

(Synthesis Example 2)
<Synthesis of acid-modified ethylenically unsaturated group-containing epoxy resin>
YDF2001 (Toto Kasei Co., Ltd., bisphenol F type epoxy resin) 475 parts by mass, 72 parts by mass of acrylic acid, 0.5 parts by mass of hydroquinone, and 120 parts by mass of carbitol acetate were added to the reaction mixture by heating and stirring to 90 ° C. Was dissolved. Next, the mixture was cooled to 60 ° C., charged with 2 parts by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / g. Next, 98 parts by weight of maleic anhydride and 85 parts by weight of carbitol acetate are added, heated to 80 ° C., reacted and cooled for about 6 hours, and diluted with carbitol acetate to a solid content concentration of 40% by weight. An acid-modified ethylenically unsaturated group-containing epoxy resin was obtained.

(Synthesis Example 3)
<Synthesis of polyimide precursor>
In a flask equipped with a stirrer and a reflux condenser, 10 g of tetracarboxylic dianhydride (M1) having an amide bond (solid content 60% by weight, 0.01 mol), 4,4 ′-[isopropylidenebis ( p-phenyleneoxy)] dianiline (BAPP), 2.87 g (0.007 mol), Jeffamine D400 (Mitsui Chemical Fine) 1.36 g (0.003 mol), and dimethylacetamide 2.82 g were charged at room temperature. Stirring was performed for a time to obtain a polyimide precursor (P2) having an amide bond as component (A). The resulting polyimide precursor had a weight average molecular weight of 30,000 and a solid content concentration of 40% by mass.

Example 1
<Preparation of photosensitive composition coating solution>
The following components were mixed to prepare a photosensitive composition coating solution.
Specifically, the following components were mixed and dispersed for 1.5 hours in a bead mill (Eiger Mill M-50, manufactured by Eiger Japan, media; zirconia beads having a diameter of 1 mm, filling rate 75% by volume), and photosensitive. A composition coating solution was prepared.
Moreover, the viscosity of the photosensitive composition coating liquid was measured using an E-type viscometer (trade name: VISCOMETER RE-80, manufactured by TOKI). The results are shown in Table 1.
―――――――――――――――――――――――――――――――――――――――
Acid-modified ethylenically unsaturated group-containing polyurethane resin synthesized in Synthesis Example 1 (solid content concentration 40% by mass) 32.3 parts by mass Dispersant: Disper BYK-110 (manufactured by BYK Chemie) 0.22 parts by mass Coloring pigment: HELIOGEN BLUE D7086 (manufactured by BASF)
0.021 parts by mass Coloring pigment: Pariotol Yellow D0960 (manufactured by BASF)
0.006 parts by mass Curing agent: Melamine (manufactured by Wako Pure Chemical Industries) 0.16 parts by mass Ion trap agent: IXE-6107 (manufactured by Toagosei Co., Ltd.) 0.82 parts by mass Filler: SO-C2 (manufactured by Admatechs) 16.0 parts by mass Polymerizable compound: DCP-A (dimethylol tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 5.3 parts by mass Thermal crosslinker: Epototo YDF-170 (manufactured by Tohto Kasei Co., Ltd.) 2.9 parts by mass Initiator: IRG907 (manufactured by Ciba Specialty Chemicals) 0.6 parts by mass Sensitizer: DETX-S (manufactured by Nippon Kayaku Co., Ltd.) 0.005 parts by mass Reaction aid: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 0. 019 parts by mass Elastomer: Esper 1612 (manufactured by Hitachi Chemical Co., Ltd.) 2.7 parts by mass Application aid: 0.2 parts by mass of Megafac F-780F (Dainippon Ink Co., Ltd .: 30 parts by mass) Methyl ethyl ketone solution)
Cyclohexanone (solvent) 38.7 parts by mass

-Production of photosensitive film-
Using a polyethylene terephthalate film (PET) having a thickness of 25 μm as a support, the photosensitive composition coating solution was applied onto the support with a bar coater so that the thickness of the photosensitive layer after drying was about 30 μm. It was dried in a hot air circulation dryer at 80 ° C. for 30 minutes to produce a photosensitive film.
About the produced photosensitive film, the measurement of the melt viscosity of a photosensitive layer was measured on condition of the following using rheometer * VAR-1000 type (made by Rheological Co., Ltd.).
--Measurement conditions for melt viscosity--
Melt viscoelasticity was measured using a plate having a diameter of 20 mm at a strain of 0.005 and a frequency of 1 Hz. The temperature range was 25 ° C. to 85 ° C., and the measurement was performed at a rate of temperature increase of 5 ° C./min.

<Formation of permanent pattern>
-Preparation of laminate-
Next, a chemical polishing treatment was applied to the surface of a copper-clad laminate (no through-hole, printed wiring board with a copper thickness of 12 μm) on which wiring was formed as the substrate. On the copper clad laminate, the photosensitive layer of the photosensitive film is in contact with the copper clad laminate, and is laminated using a vacuum laminator (manufactured by Nichigo Morton, VP130), the copper clad laminate, A laminate was prepared in which the photosensitive layer and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressing time of 10 seconds.

-Exposure process-
Using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.), the photosensitive layer in the prepared laminate is exposed from the polyethylene terephthalate film (support) side through a photomask at 40 mJ / cm ^2. Then, a part of the photosensitive layer was cured.

-Development process-
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Spray development was performed at 30 ° C. for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the laminate on which the permanent pattern was formed was subjected to heat treatment at 150 ° C. for 1 hour to cure the surface of the permanent pattern, increase the film strength, and prepare a test plate.

  It used for the following evaluation. The results are shown in Table 1.

<Evaluation method>

−Evaluation of embedding−
The embedded state of the photosensitive layer between the wiring patterns of L / S (line / space) = 50 μm / 50 μm was observed at a magnification of 50 to 200 times using an optical microscope and evaluated based on the following criteria.
〔Evaluation criteria〕
○: When there is no gap between the photosensitive layer and the copper clad laminate with circuit △: When there is a gap between the photosensitive layer and the copper clad laminate with circuit, or between the pattern circuit and the tourist layer △ ^× : Melt viscosity is too low and bubbles do not enter when laminated on a copper clad laminate with circuit, but between the copper clad laminate with circuit and the support. When the photosensitive layer is soaked in large quantities ×: When the melt viscosity is too high to be laminated

-Thermal shock resistance (crack resistance) (TCT)-
As a reliability test item, appearance such as cracks and peeling was evaluated by a temperature cycle test (TCT). TCT uses a gas-phase cold-heat tester and is allowed to stand in a gas phase of -55 ° C and 125 ° C for 30 minutes each, and this is performed under the conditions of 1,500 cycles as one cycle. Evaluated.
The test plate was produced by the following method. The photosensitive film was laminated on a copper clad laminate (glass epoxy substrate) from which the copper foil had been removed by etching under the pressure bonding conditions of a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure time of 10 seconds. Subsequently, from the polyethylene terephthalate film (support) side, using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.), exposure is performed at 40 mJ / cm ² through a 5 mm × 5 mm square pattern photomask. A part of the photosensitive layer was cured. Subsequently, in the same manner as in the development step and the curing treatment step, a development treatment and a curing treatment were performed to obtain a test plate.
〔Evaluation criteria〕
◎: Very good with no cracks ○: Slightly cracked but good △: Slightly good with small cracks generated ×: Inferior with large cracks

-Electrical insulation (HAST)-
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. An insulating layer was formed on the comb-shaped electrode of the substrate by a conventional method using the photosensitive film obtained above, and was exposed at an optimum exposure amount (40 mJ / cm ² ). Subsequently, after leaving still at room temperature for 1 hour, spray development was performed for 20 second in 1 mass% sodium carbonate aqueous solution of 30 degreeC. 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 Seisakusho. 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 wires to the comb electrodes with Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation substrate after heating, a voltage of 50 V is applied to the evaluation substrate. In the applied state, the substrate for evaluation was allowed to stand in a super accelerated high temperature high humidity life test (HAST) bath at 130 ° C. and 85% RH for 200 hours. The degree of occurrence of solder resist migration of the subsequent evaluation substrate was observed with a 100-fold metal microscope and evaluated according to the following criteria.
〔Evaluation criteria〕
A: The occurrence of migration cannot be confirmed, and the electrical insulation is excellent.
○: The occurrence of migration is confirmed slightly on the copper, but the electrical insulation is good.
(Triangle | delta): Generation | occurrence | production of migration is confirmed slightly on copper, but electrical insulation is a little good.
X: Between electrodes short-circuited and it is inferior to electrical insulation.

-Solder heat resistance-
A rosin-based flux or a water-soluble flux was applied to the test plate obtained above and immersed in a solder bath at 260 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the coating film was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: There is no abnormality (peeling, swelling) in the appearance of the coating film, and there is no solder peeling.
Δ: Abnormality (peeling, blistering) in the appearance of the coating film, or solder fluffing, but light to the extent ×: Abnormality (peeling, blistering) in the coating film appearance, or solder flakinging Something heavy

-Resolution-
The 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 laminate, using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.), through a photomask having a round hole pattern with a diameter of 50 μm to 200 μm. Exposure was performed at 40 mJ / cm ² .
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate.
The entire surface of the photosensitive layer on the copper clad laminate was sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as a developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove uncured areas. .
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.
〔Evaluation criteria〕
○: A round hole with a diameter of 90 μm or less is resolvable and excellent in resolution. ○ Δ: A round hole with a diameter of 120 μm or less is resolvable and has good resolution. Δ: A round hole with a diameter of 200 μm or less. Can be resolved and resolution is slightly inferior ×: Round hole is not resolvable and resolution is inferior

(Examples 2-4, Comparative Examples 1-3)
In Example 1, the photosensitive composition and the photosensitive property were the same as in Example 1 except that the binder, dispersant, and polymerizable compound were replaced with the binder, dispersant, and polymerizable compound shown in Table 1. A film was obtained.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

However, “M-100” in the table indicates cyclomer M-100 (manufactured by Daicel Chemical Industries, 3,4-epoxycyclohexylmethyl methacrylate).

  The photosensitive compositions of Examples 1 to 4 were all excellent in embeddability, thermal shock resistance, electrical insulation, resolution, and solder heat resistance. When an acid-modified ethylenically unsaturated group-containing polyester resin is used as the binder, the embedding property, thermal shock resistance, and electrical insulation are improved (see Example 1), and the acid-modified ethylenically unsaturated is used as the binder. When a group-containing polyester resin was used and a phosphate ester salt was used as a dispersant, the thermal shock resistance and electrical insulation were very good (see Example 2).

Since the photosensitive composition of the present invention is excellent in resolution, embedding property, thermal shock resistance, and electrical insulation, it can be suitably used for a solder resist.
Since the photosensitive film of the present invention is excellent in resolution, embedding property, thermal shock resistance, and electrical insulation, it can be suitably used for forming a permanent pattern on a printed circuit board.

Claims (13)

Containing a dispersant, an inorganic filler, a binder, a polymerizable compound having two or more ethylenically unsaturated groups, a photopolymerization initiator, and a thermal crosslinking agent,
The photosensitive composition, wherein the dispersant is a dispersant having a phosphate group.   The photosensitive composition according to claim 1, wherein the inorganic filler is silica. The photosensitive composition according to claim 1, wherein the dispersant having a phosphate ester group is at least one of a phosphate ester represented by the following general formula (I) and a salt thereof.
However, in the general formula (I), R represents a group having at least one of a carboxylic acid ester group and a urethane group and at least one ether oxygen atom. n is an integer of 1-2. When n is 2, R may be the same or different. The photosensitive composition according to claim 3, wherein R in the general formula (I) is a group represented by the following general formula (II).
In the general formula (II), _{R 1} represents an alkyl group having 1 to 4 carbon atoms. x represents an integer of 4 to 5. y represents an integer of 2 to 15. z represents an integer of 3 to 15. Phosphate ester produced by reacting a phosphoric acid ester group-containing dispersant with 1 phosphoric acid equivalent of an ester-forming phosphorus compound and 1 equivalent to 2 equivalents of a compound represented by the following general formula (III): The photosensitive composition according to claim 1, which is at least one of the salts.
R-OH general formula (III)
However, in the general formula (III), R represents a group having at least one of a carboxylic acid ester group and a urethane group and at least one ether oxygen atom. The photosensitive composition according to claim 5, wherein R in the general formula (III) is a group represented by the following general formula (II).
In the general formula (II), _{R 1} represents an alkyl group having 1 to 4 carbon atoms. x represents an integer of 4 to 5. y represents an integer of 2 to 15. z represents an integer of 3 to 15.   The photosensitive composition according to claim 1, wherein the dispersant having a phosphate ester group is a salt of a phosphate ester.   The photosensitive composition according to any one of claims 1 to 7, wherein the binder is an acid-modified ethylenically unsaturated group-containing polyurethane resin. The photosensitive composition of Claim 8 in which acid-modified ethylenically unsaturated group containing polyurethane resin has a structural unit represented by the following general formula (G-1).
However, in said general formula (G-1), R < ¹ > -R < ³ > represents either a hydrogen atom and monovalent organic group each independently, A represents a bivalent organic residue, X is oxygen atom, a sulfur atom, and -N ^{(R 12)} - represents one of the ^{R 12} represents a hydrogen atom or a monovalent organic group. Comprising at least a support and a photosensitive layer on the support;
A photosensitive film, wherein the photosensitive layer is made of the photosensitive composition according to claim 1.   A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to claim 1.   It forms with the permanent pattern formation method of Claim 11, The permanent pattern characterized by the above-mentioned.   A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 11.