WO2012169385A1 - Composition, photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed board - Google Patents

Abstract

A composition which comprises at least one acrylic resin and silica fine particles, wherein the acrylic resin has tertiary amino groups and has an amine value of 1.1mmol/g or more; a photosensitive film; a photosensitive laminate; a method for forming a permanent pattern; and a printed board.

Description

Composition, photosensitive film, photosensitive laminate, permanent pattern forming method and printed circuit board

The present invention relates to a composition suitably used for a solder resist or the like, a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board.

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

Recently, with the miniaturization of devices, development of solder resists such as semiconductor package substrates having a small L / S (line / space) has been promoted. Therefore, in order to improve impact resistance and insulation, it is required to increase the packing of silica fine particles.
On the other hand, in a solder resist composition, it is known to use a polymer dispersant as a dispersant for inorganic fine particles. For example, a commercially available specific dispersant is diverted for silica fine particles (see, for example, Patent Document 1). However, it is known to use a styrene / maleic anhydride / butyl acrylate copolymer for dispersion of barium sulfate (see Patent Document 2).

However, when silica fine particles are highly filled with a photosensitive resin composition such as a solder resist or a photosensitive film, the film physical properties change, and the performance as a solder resist is impaired. For example, when the silica fine particles are highly filled, the melt viscosity increases, and the transferability and developability deteriorate.
For this reason, the development of a dispersant capable of stably and densely dispersing silica fine particles and its dispersant composition, especially when the silica fine particles are highly filled with a photosensitive resin composition such as a solder resist or a photosensitive film, Development of a dispersion composition having excellent transferability, developability, impact resistance, and insulating properties has been desired.

JP 2003-234439 A International Publication No. 2005-124462 Pamphlet

The present invention aims to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides a dispersing agent or composition capable of stably dispersing high density inorganic fine particles, particularly silica fine particles, or embedding, thermal shock resistance, developability, and insulating properties even when the silica fine particles are highly filled. An object of the present invention is to provide an excellent high performance cured film, and to provide a silica dispersion composition suitable for a photosensitive composition or a photosensitive film, particularly for a solder resist.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, in the silica dispersion composition, the amine value and acid value of the dispersant, especially the amine value, are important, and polymers having a specific amine value are also used. The present inventors have found that the above problems can be effectively solved in the resin and resin structure, and have made the present invention based on this finding. Usually, when a basic group and an acidic group coexist in a polymer, a salt is formed and the solubility in a solvent is lowered. This point has also been solved in a specific polymer resin and resin structure.

Means for solving the problems of the present invention are as follows.
(1) A composition comprising at least one acrylic resin and silica fine particles, the acrylic resin having a tertiary amino group and an amine value of 1.1 mmol / g or more.
(2) The composition according to (1), wherein the acrylic resin has a graft chain at a side chain of the resin or at a main chain terminal.
(3) The composition according to (1) or (2), wherein the acrylic resin further has an acidic group.
(4) The composition according to (1) or (2), wherein the acrylic resin further has a carboxyl group.
(5) The composition according to any one of (1) to (4), wherein the acrylic resin has an acid value of 0.3 mmol / g or more.
(6) The composition according to any one of (1) to (5), wherein the silica fine particles have an average particle size (d50) of 0.02 μm to 3.0 μm.
(7) The composition according to any one of (1) to (6), which contains a thermal crosslinking agent.
(8) The composition according to any one of (1) to (7), comprising a binder, a polymerizable compound, and a photopolymerization initiator.
(9) The composition according to any one of (1) to (8), wherein the composition is for a solder resist.
(10) The composition according to any one of (1) to (9), wherein the composition contains a resin containing an acid-modified ethylenically unsaturated group as a binder.
(11) The composition according to any one of (1) to (9), wherein the composition contains an acid-modified ethylenically unsaturated group-containing polyurethane resin as a binder.
(12) A photosensitive film having a photosensitive layer containing the composition according to any one of (1) to (11) on a support.
(13) A photosensitive laminate having a photosensitive layer containing the composition according to any one of (1) to (11) on a substrate.
(14) A method for forming a permanent pattern comprising at least exposing a photosensitive layer formed of the composition according to any one of (1) to (11).
(15) A printed board formed by the permanent pattern forming method according to (14).

According to the present invention, a dispersing agent or composition capable of stably dispersing high-density inorganic fine particles, particularly silica fine particles, or a silica fine particle having a high filling property, excellent embedding properties, thermal shock resistance, developability, and insulating properties. A high-performance cured film can be obtained, and a silica dispersion composition suitable for a photosensitive composition or a photosensitive film, particularly for a solder resist can be provided.

(Composition)
The composition of the present invention is a composition comprising at least one acrylic resin and silica fine particles, and includes a thermal crosslinking agent, a binder, a polymerizable compound, a photopolymerization initiator, and other components as necessary. It contains. In addition, content of each component is solid content (For example, solid content in the total solid of a silica dispersion composition) unless there is particular notice.

<Acrylic resin>
The acrylic resin of the present invention used in the composition of the present invention has a tertiary amino group and an amine value of 1.1 mmol / g or more. This acrylic resin is useful as a dispersant for inorganic or organic fillers and pigments. In the present invention, it particularly acts as a dispersant for silica fine particles.

The acrylic resin is a resin containing repeating units of acrylic acid, methacrylic acid and derivatives thereof such as acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide components, and preferably has the following general formula ( Having a repeating unit represented by P).

In the general formula (P), R ^P1 represents a hydrogen atom or a methyl group, and X ^P1 represents —CO ₂ R ^P2 , CON (R ^P3 ) (R ^P4 ), or —CN. Here, R ^P2 represents a hydrogen atom or an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group. R ^P3 and R ^P4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.
Each of these groups may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, and an aryloxy group. , Alkylthio group, arylthio group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamido group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy Group, carbamoyl group, sulfamoyl group, hydroxyl group, mercapto group, cyano group, nitro group, carboxyl group, sulfo group, ureido group, urethane group and the like.
Moreover, the said acrylic resin may also contain a different repeating unit within the range represented by general formula (P) among the repeating units represented by the said general formula (P). Moreover, you may include repeating units other than the repeating unit represented by the said general formula (P).

In general formula (P), R ^P1 is preferably a methyl group. X ^P1 is preferably —CO ₂ R ^P2 . ^{Also, R P2} is preferably a hydrogen atom or an alkyl group, an acrylic resin used in the present invention, ^{X P1} of the general formula (P) is within the range of the partial structure is a _-CO 2 ^{R P2,} different two or more It is preferable that the repeating unit is included.

The acrylic resin used in the present invention has a tertiary amino group.
The tertiary amino group contained in the acrylic resin is adsorbed on the surface of the inorganic or organic filler or pigment, particularly the surface of the silica fine particles, for example, by ionic interaction.
The tertiary amino group is preferably represented by the following general formula (M).

General formula (M)
-N (R ^M1 ) (R ^M2 )

In General Formula (M), R ^M1 and R ^M2 each independently represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and each of these groups has a substituent. Also good. R ^M1 and R ^M2 may be bonded to each other to form a ring.
The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, isopropyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and n-decyl. The alkenyl group preferably has 2 to 10 carbon atoms, and examples thereof include vinyl, allyl and 2-butenyl. The alkynyl group preferably has 2 to 10 carbon atoms, and examples thereof include ethynyl, 2-propynyl, and 2-butynyl. The cycloalkyl group preferably has 3 to 10 carbon atoms, and examples thereof include cyclopropyl, cyclopentyl, and cyclohexyl. The aryl group preferably has 6 to 12 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group having at least one oxygen atom, sulfur atom or nitrogen atom as a hetero atom constituting the ring skeleton, and the atom bonded to the N atom is carbon. Those that are atoms are preferred. Examples of the heterocyclic group include a tetrahydrofuran ring, a pyrrolidine ring, a piperazine ring, a piperidine ring, a morpholine ring, a dioxane ring, a furan ring, a thiophene ring, a pyridine ring, and a pyrazole ring.

Each of these groups may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, and an aryloxy group. , Alkylthio group, arylthio group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamido group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy Group, carbamoyl group, sulfamoyl group, hydroxyl group, mercapto group, cyano group, nitro group, carboxyl group, sulfo group, ureido group, urethane group and the like.

As the ring formed by combining R ^M1 and R ^M2 with each other, a 5- or 6-membered ring is preferable, and a saturated ring is preferable, and examples thereof include a pyrrolidine ring, a piperazine ring, a piperidine ring, and a morpholine ring.

R ^M1 and R ^M2 are preferably an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and more preferably an alkyl group. As the alkyl group, an unsubstituted alkyl group is preferable, and the number of carbon atoms is preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, and most preferably a methyl group. It is also preferred that R ^M1 and R ^M2 are bonded to each other to form a pyrrolidine ring, piperazine ring, piperidine ring, or morpholine ring.

The amine value of the acrylic resin used in the present invention is 1.1 mmol / g or more, preferably 1.2 mmol / g or more, and more preferably 1.5 mmol / g or more. The upper limit of the amine value is not particularly limited, but is preferably 4.5 mmol / g or less, more preferably 3.5 mmol / g or less. If the amine value is less than 1.1 mmol / g, the melt viscosity may increase and the embedding property may deteriorate.
Here, the amine value is measured, for example, by weighing a sample in a beaker, adding acetic acid, stirring and dissolving, adjusting the measurement temperature to 25 ° C., and then adding 0.1N perchloric acid acetic acid as a titration reagent. And can be determined by titrating with a titration apparatus.
The amine value is the amount of perchlorate consumed when titrated, expressed in moles per gram of acrylic resin.

The acrylic resin used in the present invention has a tertiary amino group, preferably a group represented by the general formula (M), and this tertiary amino group is represented by the general formula (P). Even if it is incorporated in a part of the repeating unit, the repeating unit obtained from a different monomer may have a tertiary amino group.
In the present invention, it is preferably incorporated in the general formula (P), in any of R ^{P2 ~} R ^P4, and more preferably are incorporated as substituents of the groups defined in R ^{P2 ~} R ^P4 .
Specifically, for example, an alkyl group substituted with a tertiary amino group, an aryl group substituted with a tertiary amino group, and the like.
The tertiary amino group is preferably contained in the repeating unit as represented by the following general formula (P1).

In general formula (P1), ^RP1 is synonymous with ^RP1 of general formula (P), and its preferable range is also the same. R ^M1 and ^{R M2} have the same meanings as ^{R M1} and ^{R M2} of the general formula (M), and their preferable ranges are also the same.
X ^P2 represents —O— or —N (R ^P3 ) —. ^{Here, R P3} has the same meaning as ^{R P3} in Formula (P). L ^P1 represents an alkylene group, an alkenylene group, a cycloalkylene group, a phenylene group, a divalent heterocyclic group, a group in which these groups are combined, or these groups and other divalent groups (for example, —O—, A group in which —S—, —C (═O) —, —SO ₂ —, —SO—, —N (R ^P5 ) — and the like are combined (however, other divalent groups are directly bonded to X ^P1 It is not bound). Here, R ^P5 represents a group represented by R ^P3 , an acyl group, an alkyl or arylsulfonyl group, an alkoxy group, or an aryloxy group. Note that each group of L ^P1 may have a substituent, and examples of such a substituent include the substituents that the groups R ^P3 and R ^P4 in the general formula (P) may have.

Of the repeating units represented by the general formula (P1), X ^P2 is preferably —O—, L ^P1 is preferably an alkylene group, and preferably has 1 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. 4 is more preferable, and 2 is most preferable.

The acrylic resin used in the present invention preferably further has an acidic group. Having a tertiary amino group and an acidic group is preferable not only from developability but also from the viewpoint of insulation.
The acidic group is not particularly limited, and examples thereof include a carboxyl group, a sulfo group, a phosphonyl group, —COCH ₂ CO—R ^B , —CONHCO—R ^B , —COCH ₂ CN, a phenolic hydroxyl group, and —R _F CH ₂ OH. , — (R _F ) ₂ CHOH, an alkyl or arylsulfonamido group, and the like. Here, R ^B represents a hydrocarbon group having 1 to 10 carbon atoms, and R _F represents a perfluoroalkyl group. The hydrocarbon group is a saturated, unsaturated or cyclic hydrocarbon group, preferably an alkyl group.
Of the acidic groups, a carboxyl group is particularly preferable from the viewpoint of developability.

Such an acidic group may be incorporated into the repeating unit represented by the general formula (P) or may be incorporated into another repeating unit. To incorporate these acid groups in the repeating unit represented by Formula (P), and R ^P2 X ^P1 is a -CO ₂ R ^P2 are those containing as a repeating unit of the hydrogen atom. Specifically, it is copolymerized with acrylic acid or methacrylic acid. On the other hand, when incorporating by copolymerizing with other monomers having an acidic group, such monomers include, for example, crotonic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, itaconic acid. Itaconic acid monoalkyl ester, p-hydroxystyrene, p-sulfostyrene, p-carboxystyrene and the like.
In the present invention, it is preferable to incorporate an acidic group by copolymerization with acrylic acid or methacrylic acid.

The acid value of the acrylic resin used in the present invention is preferably 0.3 mmol / g or more, and more preferably 0.45 mmol / g or more.
The acid value of the acrylic resin used in the present invention is preferably 0.3 mmol / g or more, more preferably 0.5 mmol / g or more. Although the upper limit of an acid value is not specifically limited, Preferably it is 3.5 mmol / g or less, More preferably, it is 2.5 mmol / g or less. In the acrylic resin used in the present invention, if the acid value is less than 0.3 mmol / g, the developability deteriorates and a residue may be generated in the unexposed area.
Here, for the measurement of the acid value, for example, a sample is weighed in a beaker, a solution of THF / water = 5/1 (volume ratio) is added, dissolved by stirring, and the measurement temperature is adjusted to 25 ° C. Thereafter, the acid value can be determined by titrating with a titration apparatus using a 0.1N NaOH aqueous solution as a titration reagent.
The acid value is the amount of NaOH consumed when titrated, expressed in moles per gram of acrylic resin.

-Graft chain-
The acrylic resin used in the present invention preferably has a graft chain on the side chain or at least one of the ends of the main chain.
Examples of the graft chain include a polyester chain, a polyalkyl acrylate chain, a polyalkyl methacrylate chain, a polyalkylene oxide chain (preferably a polyethylene oxide chain, a polypropylene oxide chain), a polycarbonate chain, a polystyrene chain, or a combination thereof. The chain | strand of which is included in partial structure is mentioned. Among these, a graft chain having a polyester moiety (polyester graft chain) is preferable in terms of resolution.
The chain length of the graft chain is such that the degree of polymerization is preferably 1 to 100, more preferably 1 to 80, and particularly preferably 1 to 60.
The content of the graft is preferably 10% by mass to 60% by mass and more preferably 20% by mass to 50% by mass with respect to the entire acrylic resin.
In the graft chain, the acrylic resin preferably has a repeating unit represented by the following general formula (PG).

In general formula (PG), ^RP1 is synonymous with ^RP1 of general formula (P), and its preferable range is also the same. X ^P2 has the same meaning as ^{X P1} of the general formula (P1), and the preferred range is also the same. L ^P2 represents a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a phenylene group, a divalent heterocyclic group, a group in which these groups are combined, or these groups and other divalent groups (for example,- Groups in which O—, —S—, —C (═O) —, —SO ₂ —, —SO—, —N ( ^{RP 5} ) —, etc.) are combined (other divalent groups are directly ^Does not bind to ^XP2 ). Here, R ^P5 represents a group represented by R ^P3 , an acyl group, an alkyl or arylsulfonyl group, an alkoxy group, or an aryloxy group. Note that each group of L ^P2 may have a substituent, and examples of such a substituent include substituents that the groups R ^P3 and R ^P4 may have. R ^P6 represents a hydrogen atom or a substituent, and examples of the substituent include substituents that the groups R ^P3 and R ^P4 in the general formula (P) may have.

X ^P2 is preferably —O—.
L ^P2 is preferably a divalent group having a partial structure of polyoxyalkylene, polyacrylic ester, polymethacrylic ester, polyester, polycarbonate, and polystyrene.
The polyoxyalkylene is preferably polyoxyethylene or polyoxypropylene. Polyester is represented by — [(CH ₂ ) m ^P1 —COO] n ^p1 —, and polycarbonate is represented by — [(CH ₂ ) m ^p2 —OCOO] n ^p2 —, wherein n ^P1 and n ^P2 are each independently 1 to 50 is preferable, and m ^P1 and m ^P2 each independently preferably represent 1 to 10.
The polyester, polycarbonate moiety, upon binding to X ^P1, polyesters via a divalent linking group, those polycarbonate binds preferable. As the divalent linking group in this case, for example, an alkylene group, an alkenylene group, a cycloalkylene group, a phenylene group, a divalent heterocyclic group, a group in which these groups are combined, or —O—, — And a group in which S—, —C (═O) —, —SO ₂ —, —SO—, and —N (R ^P5 ) — are combined. Among them, an -alkylene-NHC (═O) O— group is preferable, and a —CH ₂ CH ₂ —NHC (═O) O— group is particularly preferable.

When adjusting the molecular weight of the acrylic resin, it is preferable to use a chain transfer agent containing a thiol group. The acrylic resin used in the present invention has a mass average molecular weight of preferably 3000 to 30000, and more preferably 5000 to 18000.

The acrylic resin used in the present invention may have a repeating unit other than the repeating unit represented by the general formula (P) throughout the resin, but in the present invention, the acrylic resin is represented by the general formula (P). The unit content is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more.
Further, the acrylic resin used in the present invention contains 20 mol% to 70 mol% of the repeating unit represented by the general formula (P1) and 3 mol% to 25 mol of the repeating unit represented by the general formula (PG). It is preferable to contain 2 mol% to 40 mol% of a repeating unit obtained from a monomer having an mol group and an acidic group.
In addition, as a repeating unit different from the repeating unit represented by the general formula (P) and obtained from the general formula (P1), (PG), and a monomer having an acidic group, an acrylic ester or a methacrylic ester may be used. The obtained repeating unit is preferred, and the alcohol part of the ester preferably has 1 to 20 carbon atoms, more preferably 1 to 12 and even more preferably 1 to 8.

Specific examples of the acrylic resin used in the present invention are shown below, but the present invention is not limited thereby. The numerical value is% by mass and x is the degree of polymerization, which is 1 to 50.

The acrylic resin used in the present invention can be easily synthesized by a general polymerization reaction using a corresponding monomer. Specific synthesis examples are shown in the examples.

<Silica fine particles>
There is no restriction | limiting in particular as a silica of the silica particle used by this invention, According to the objective, it can select suitably, For example, vapor phase method silica, crystalline silica, fused silica, etc. are mentioned.

The average particle diameter (d50) of the silica fine particles used in the present invention is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.02 μm to 3.0 μm, preferably 0.1 μm to 2.0 μm. Is more preferable, and 0.2 μm to 1.5 μm is particularly preferable.
If the average particle diameter (d50) of the silica particles is less than 0.02 μm, the coating viscosity may be high, and if it exceeds 3.0 μm, smoothness may not be maintained. On the other hand, when the average particle diameter (d50) of the silica particles is within the particularly preferable range, it is advantageous in terms of coating viscosity, smoothness of the cured film and heat resistance.
Here, the average particle size (d50) of the silica particles is defined as a particle size of an integrated value of 50% when expressed as an integrated (cumulative) mass percentage, and is defined as d50 (D ₅₀ ) or the like. Yes, for example, using a dynamic light scattering photometer (trade name: DLS7000, manufactured by Otsuka Electronics Co., Ltd.), using the measurement principle as the dynamic light scattering method, and the size distribution analysis method using the cumulant method, histogram method, etc. Can do.

As the silica fine particles, those appropriately synthesized may be used, or commercially available products may be used. Examples of the commercially available product include SO-C2 (manufactured by Admatechs).

The solid content of the silica fine particles in the mixture of the silica fine particles and the silica fine particle dispersant is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 70% by mass.
When the content is less than 5% by mass, impact resistance may be inferior, and when it exceeds 80% by mass, dispersibility may be insufficient.
The acrylic resin of the present invention is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of silica fine particles.

<Thermal crosslinking agent>
The composition used in the present invention preferably contains a thermal crosslinking agent.
There is no restriction | limiting in particular as a thermal crosslinking agent, According to the objective, it can select suitably, For example, an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned.
Among these, an epoxy resin compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule are preferable.

The epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0095] of JP-A-2007-2030, and JP-A-2010-72340. And the compounds described in paragraph [0130].

The polyfunctional oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the compounds described in paragraph [0096] of JP-A-2007-2030.

The content of the thermal crosslinking agent in the silica dispersion composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 50% by mass, and 2% by mass to 40% by mass. Is more preferable, and 3% by mass to 30% by mass is particularly preferable.
When the content is less than 1% by mass, heat resistance may be inferior, and when it exceeds 50% by mass, developability and crack resistance may be inferior. 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.

The other thermal crosslinking agent can be added separately from the epoxy resin and the polyfunctional oxetane compound. The other thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0098] to [0100] of JP-A-2007-2030. Is mentioned.

<< 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, ethylenically unsaturated group-containing polycarboxylic acid resins, and acid-modified ethylenically unsaturated resins. Examples thereof include a saturated group-containing epoxy resin, a resin containing an ethylenically unsaturated group and a carboxyl group, and a polyimide precursor.

-Acid-modified ethylenically unsaturated group-containing polyurethane resin-
The acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose. For example, (i) a polyurethane having an ethylenically unsaturated bond (vinyl group) in the side chain And (ii) a 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.

-(I) Polyurethane resin having an ethylenically unsaturated group in the side chain--
The urethane resin having an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the purpose. For example, the side chain may be represented by the following general formulas (1) to (3). What has at least 1 among the functional groups represented is mentioned.

In the general formula (1), R ¹ is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom and an alkyl group which may have a substituent. . Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity. The R ² and R ³ are not particularly limited and may be appropriately selected depending on the intended purpose. For example, each independently represents 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 are not particularly limited and may be appropriately selected depending on the intended purpose. The hydrogen atom, halogen atom, amino group, dialkylamino group, carboxyl group, alkoxycarbonyl A group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group, and the like. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

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

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

Here, examples of the substituent that can be introduced include the same as those in the general formula (1). Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. 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 because of high radical reactivity.

The urethane resin having an ethylenically unsaturated bond 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 —General formula (5)
However, in the general formulas (4) and (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If at least one of them is present, a polyurethane resin in which the groups represented by the above general formulas (1) to (3) are introduced into the side chain as a reaction product of the diisocyanate compound and the diol compound is provided. Generated. According to such a method, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain can be easily used, rather than replacing and introducing a desired side chain after the reaction of the polyurethane resin. Can be manufactured.

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

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

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

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

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

The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a diisocyanate compound represented by the following general formula (6).
OCN-L ¹ -NCO General formula (6)
However, in the general formula (6), L ¹ represents an aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L ¹ may have another functional group that does not react with an isocyanate group, for example, an ester, urethane, amide, or ureido group.

The diisocyanate compound represented by the general formula (6) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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 ' An aromatic diisocyanate compound such as diisocyanate; an aliphatic diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4′-me Alicyclic diisocyanate compounds such as lenbis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate 2 A diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate;

Here, as a method for introducing an unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a method using a diol compound containing an unsaturated group in the side chain as a raw material for producing a polyurethane resin is also preferable. . The diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the purpose. For example, a commercially available product such as trimethylolpropane monoallyl ether may be used. By reaction with a compound such as a halogenated diol compound, a triol compound or an aminodiol compound and a compound containing an unsaturated group such as a carboxylic acid, acid chloride, isocyanate, alcohol, amine, thiol or halogenated alkyl compound. It may be a compound that is easily produced. The diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs [0057] to [0060] of JP-A-2005-250438 And the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the following general formula (G). Among these, compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the following general formula (G) are particularly preferable.

In the general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom or a sulfur atom. Or —N (R ¹² ) —, wherein R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, R ¹ ~ R ³ and X in the general formula (G), said a general formula (1) the same meaning as R ¹ ~ R ³ and X in preferred embodiments versa.
By using the polyurethane resin derived from the diol compound represented by the general formula (G), the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.

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

The polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0068] to [0076] of JP-A-2005-250438. Can be mentioned.

The polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paragraphs [0077] to [0079] and paragraphs [0083] to [0085] of JP-A-2005-250438. No. 1-No. 8 and no. 13-No. 18 and the like, and the like.

The polycarbonate diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the paragraphs [0080] to [0081] and paragraph [0084] of JP-A-2005-250438, No. 9-No. 12 and the like, and the like.

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

Furthermore, in the synthesis of a polyurethane resin having an ethylenically unsaturated bond in the side chain, a diol compound having a carboxyl group can be used in combination with the diol compound described above. Examples of the diol compound having a carboxyl group include those represented by the following formulas (X) to (Z).

In the formulas (X) to (Z), R ¹⁵ represents a hydrogen atom, a substituent (for example, a halogen atom such as a cyano group, a nitro group, —F, —Cl, —Br, —I, etc., —CONH ₂ , —COOR ¹⁶ , —OR ¹⁶ , —NHCONHR ¹⁶ , —NHCOOR ¹⁶ , —NHCOR ¹⁶ , —OCONHR ¹⁶ (wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) And any other group that may have an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like. 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 above formulas (X) to (Z), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group). As long as it represents a divalent aliphatic or aromatic hydrocarbon group that may have an alkyl group, and an alkoxy group and a halogen atom are not particularly limited, and can be appropriately selected depending on the purpose. However, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. If necessary, the L ⁹ to L ¹¹ may have other functional groups that do not react with isocyanate groups, such as carbonyl, ester, urethane, amide, ureido, and ether groups. A ring may be formed by two or three of R ¹⁵ , L ⁷ , L ⁸ and L ⁹ .
In the formula (Y), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose. However, an aromatic group having 6 to 15 carbon atoms is preferred.

The diol compound having a carboxyl group represented by the formulas (X) to (Z) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3,5-dihydroxybenzoic acid, 2, 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxy Phenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide, and the like.

It is preferable because the presence of such a carboxyl group can impart properties such as hydrogen bonding and alkali solubility to the polyurethane resin. More specifically, the polyurethane resin having an ethylenically unsaturated bond group in the side chain is a resin having a carboxyl group in the side chain.

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

Further, as the polyurethane resin having an ethylenically unsaturated bond in the side chain, those having an alkali developing group in the polymer terminal and main chain are also preferably used. By having an alkali-developable group at the polymer terminal and main chain, the developability at the time of alkali development is further improved, and excellent pattern forming properties are provided. Furthermore, crosslinking reactivity is improved between the thermal crosslinking agent and the polyurethane resin having an ethylenically unsaturated bond in the side chain, and the cured product strength is increased. As a result, when a polyurethane resin having an ethylenically unsaturated bond in the side chain is used as a printed board material, a material having excellent durability can be provided. Here, the alkali-developable group preferably has a carboxyl group from the viewpoint of imparting developability with a dilute alkali.

Examples of a method for introducing an alkali-developable group at the polymer terminal include the following methods.

-Carboxyl group at the end of the main chain-
The polyurethane resin has at least one carboxyl group at the end of the main chain and preferably has 2 or more and 5 or less carboxyl groups, and having two carboxyl groups is excellent in developability and forms a fine pattern. It is particularly preferable in terms of sex.
The polyurethane resin has two main chain ends, but preferably has at least one carboxyl group at one end, and may have at least one carboxyl group at both ends.
It is preferable that the terminal of the main chain of the polyurethane resin has a structure represented by the following general formula (7): -L ^100- (COOH) _n ... General formula (7)
In the general formula (7), L ¹⁰⁰ represents an (n + 1) -valent organic connecting chain, n represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 2.
The organic linking group represented by L ¹⁰⁰ is configured to include one or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, specifically, represented by L ^100. The number of atoms constituting the main skeleton of the organic linking group is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 1 to 10.
The “main skeleton of the organic linking group” means an atom or an atomic group used only for linking L ²⁰⁰ and the terminal COOH in the general formula (8) described later, and there are a plurality of linking paths. In some cases, it refers to an atom or atomic group that constitutes the path with the least number of atoms used.

The method for introducing at least one carboxyl group at the end of the main chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a raw material for producing a polyurethane resin, at least one Examples include a method using a carboxylic acid compound having a carboxyl group.

-Carboxylic acid compound-
Examples of the carboxylic acid compound include a monocarboxylic acid compound having one carboxyl group, a dicarboxylic acid compound having two carboxyl groups, a tricarboxylic acid compound having three carboxyl groups, a tetracarboxylic acid compound having four carboxyl groups, and a carboxyl group. Examples thereof include pentacarboxylic acid compounds having five groups. Among these, a dicarboxylic acid compound having two carboxyl groups is particularly preferable in terms of excellent developability and fine pattern formability.

The carboxylic acid compound is not particularly limited as long as it has at least one carboxyl group, and can be appropriately selected according to the purpose, but a compound represented by the following general formula (8) is preferable.

HO-L ²⁰⁰ -L ^100- (COOH) n General formula (8)

However, the general formula ^{(8), L 100} and n represent the same meaning as the general formula (7).
L ²⁰⁰ in the general formula (8) represents an alkylene group which may have a single bond or a substituent. As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 2 to 10 carbon atoms is more preferable. Examples of the substituent that can be introduced into the alkylene group include a halogen atom (—F, —Br, —Cl, —I), an alkyl group which may have a substituent, and the like.

There is no restriction | limiting in particular as a carboxylic acid compound represented by the said General formula (8), According to the objective, it can select suitably, For example, lactic acid, malic acid, hydroxyhexanoic acid, a citric acid, a diol compound, Examples include a reaction product of an acid anhydride. These may be used individually by 1 type and may use 2 or more types together. Among these, malic acid is particularly preferable.
Examples of the reaction product of the diol compound and the acid anhydride include compounds represented by the following structural formulas.

Further, as the polyurethane resin having an ethylenically unsaturated bond in the side chain, those having an unsaturated group in the polymer terminal and main chain are also preferably used. Polyurethane resin having an ethylenically unsaturated bond in the side chain, or between the silica dispersion composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain, by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved, and the strength of the photocured product is increased. As a result, when a polyurethane resin having an ethylenically unsaturated bond in the side chain is used for the printed board material, the durability is excellent. Here, as an unsaturated group, it is especially preferable to have an unsaturated group from the ease of a crosslinking reaction.

Examples of the method for introducing an unsaturated group at the polymer terminal include the following methods. That is, in the step of synthesizing the polyurethane resin having an ethylenically unsaturated bond in the side chain as described above, in the step of treating with the residual isocyanate group at the polymer end and the alcohol or amine, the alcohol having an unsaturated group. Alternatively, amines or the like may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.

The ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The 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 unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. The diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, cis-2-butene-1,4-diol, trans-2-butene 1,4-diol, polybutadiene diol, and the like.

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

Specific examples of the polyurethane resin (i) having an ethylenically unsaturated bond in the side chain include, for example, P-1 to P— shown in paragraphs [0293] to [0310] of JP-A-2005-250438. 31 polymers, and the like. Among these, 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 mass average molecular weight of 300 or less and a high molecular diol having a mass average molecular weight of 500 or more may be added as a diol component as a copolymer component.
By using the polyurethane resin, it is excellent in stable dispersibility with an inorganic filler, crack resistance and impact resistance, so that heat resistance, moist heat resistance, adhesion, mechanical properties and electrical properties are improved.
The polyurethane resin includes a divalent aliphatic or aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups via any one of a C atom and an N atom. A reaction product comprising a carboxylic acid-containing diol as an essential component, and reacting the obtained reaction product with a compound having an epoxy group and an ethylenically unsaturated group in the molecule via a —COO— bond. It may be obtained.
Further, the polyurethane resin includes at least one selected from diisocyanates represented by the following general formula (I) and carboxylic acid group-containing diols represented by the following general formulas (II-1) to (II-3): Is a high molecular weight diol having a mass average molecular weight of 80 to 8,000, preferably 80 to 3,000, represented by the following general formulas (III-1) to (III-5) depending on the purpose A reaction product of at least one selected from the group consisting of an epoxy group and an ethylenically unsaturated group in a molecule represented by the following general formulas (IV-1) to (IV-16): It may be obtained by reacting a compound having

However, in the general formula (I), R ₁ may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom 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 (II-1), R ₂ represents a hydrogen atom, a substituent (for example, a cyano group, a nitro 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 and an aralkyl group having 7 to 15 carbon atoms) Or an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable.
In the general formulas (II-1) and (II-2), R ₃ , R ₄ and R ₅ may be the same or different from each other, and may be a single bond, a substituent (for example, an alkyl group or an aralkyl group). , An aryl group, an alkoxy group, and a halogeno group are preferable). Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, any one of other functional groups that do not react with the isocyanate group in the R ₃ , R ₄ and R ₅ , for example, any one of a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, and 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 is preferably an aromatic group having 6 to 15 carbon atoms.

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

In the general formulas (IV-1) to (IV-16), R ₁₄ represents a hydrogen atom or a methyl group, R ₁₅ represents an alkylene group having 1 to 10 carbon atoms, and R ₁₆ represents a carbon atom. This represents a hydrocarbon group having a number of 1 to 10. p represents 0 or an integer of 1 to 10.

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

As the polyurethane resin, in particular, at least one selected from diisocyanates represented by the general formula (I) and carboxylic acid group-containing diols represented by the general formulas (II-1) to (II-3) And at least one selected from polymer diols having a mass average molecular weight of 800 to 3,000 represented by the general formulas (III-1) to (III-5) according to the purpose In addition, the reaction product of the general formulas (III-1) to (III-5) with the low molecular weight diol containing no carboxylic acid group having a mass average molecular weight of 500 or less is further added to the general formulas (IV-1) to (IV). IV-16), which is obtained by reacting a compound having one epoxy group and at least one (meth) acrylic group in the molecule represented by any one of the molecules, and has an acid value of 20 mgKOH / g to 120 mgK An alkali-soluble photocrosslinkable polyurethane resin that is OH / g is preferred.

The polyurethane resin is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent, and adding a known catalyst having an activity corresponding to the reactivity thereof, followed by heating. The molar ratio (Ma: Mb) of the diisocyanate and diol compound used in the synthesis is not particularly limited and can be appropriately selected according to the purpose, preferably 1: 1 to 1.2: 1, and alcohols Alternatively, by treating with an amine or the like, a product having a desired physical property such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.

The amount of ethylenically unsaturated bonds introduced into the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. The ethylenically unsaturated group equivalent is 0.05 mmol / g to 3.0 mmol. / G is preferable, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.5 mmol / g is particularly preferable. Furthermore, the polyurethane resin having an ethylenically unsaturated bond in the side chain preferably has a carboxyl group introduced in the side chain together with the ethylenically unsaturated bond group. The acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and particularly preferably 35 mgKOH / g to 100 mgKOH / g.

The molecular weight of the polyurethane resin having an ethylenically unsaturated bond in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3,000 to 60,000 in terms of mass average molecular weight. More preferably, 4,000 to 50,000, particularly preferably 4,000 to 30,000. In particular, when the composition is used for a photosensitive solder resist, it is excellent in dispersibility with an inorganic filler, excellent in crack resistance and heat resistance, and excellent in developability of non-image areas with an alkaline developer.

-Synthesis 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. If an isocyanate group remains at the end of the polymer, the molar ratio can be reduced by treatment with alcohols or amines. It is synthesized in such a way that no isocyanate groups remain entangled.

--Diisocyanate--
The diisocyanate compound represented by the general formula (I) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0021] of JP-A-2007-2030, Etc.

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

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

--Low molecular weight diol containing no carboxylic acid groups--
The carboxylic acid group-free low molecular weight diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0048] of JP-A-2007-2030. Can be mentioned.
The copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80 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, paragraphs of JP-A-2007-2030. 0314] to [0315], glycidyl acrylate as a compound containing an epoxy group and an ethylenically unsaturated group in the polymers U1 to U4 and U6 to U11 is replaced with glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name). : Cyclomer A400, manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (produced by Daicel Chemical Industries, Ltd.)), and the like.

-Content of acid-modified ethylenically unsaturated group-containing polyurethane resin-
The content of the acid-modified ethylenically unsaturated group-containing polyurethane resin in the silica dispersion composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass to 80% by mass, 10 mass% to 75 mass% is more preferable, and 15 mass% to 70 mass% is particularly preferable.
If the content is less than 5% by mass, good crack resistance may not be maintained, and if it exceeds 80% by mass, the heat resistance may fail. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of both good crack resistance and heat resistance.

The mass average molecular weight 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 preferably 3,000 to 60,000, and preferably 3,000 to 50 Is more preferable, and 4,000 to 30,000 is particularly preferable. When the mass average molecular weight is less than 3,000, 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 deteriorate. is there.
Here, the mass average molecular weight is determined by using, for example, a high-speed GPC apparatus (manufactured by Toyo Soda Co., Ltd., HLC-802A), a 0.5 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). Next, the mass average molecular weight can be determined from the molecular weight distribution curve calibrated with standard polystyrene.

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, but 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 speed may be too high, and the development control may be difficult.
Here, the said acid value can be measured based on JISK0070, for example. However, if the sample does not dissolve, dioxane or tetrahydrofuran is used as the solvent.

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 2.5 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.
Here, the said ethylenically unsaturated group equivalent (typically vinyl 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. Bromine was added to the resin 100g of measurements obtained by bromine number (Br ₂₎ grams of the _(gBr 2 / 100g), a value obtained by converting the number of moles of the added bromine (Br ₂₎ per resin 1g is there.

-Unsaturated group-containing polycarboxylic acid resin-
There is no restriction | limiting in particular as said unsaturated group containing polycarboxylic acid resin, According to the objective, it can select suitably, For example, what was described in the patent 2877659 etc. is mentioned.

-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, it is described in Japanese Patent No. 4127010 (Japanese Patent Laid-Open No. 2004-133060). And so on.

-Resins containing unsaturated groups and carboxyl groups-
There is no restriction | limiting in particular as resin containing the said unsaturated group and a carboxyl group, According to the objective, it can select suitably, For example, what was described in the international publication 2004/034147 pamphlet etc. are mentioned. .

-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.

<Polymerizable compound>
The composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose. A compound having at least one addition-polymerizable group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Preferable examples include at least one selected from monomers having a (meth) acryloyl group. The polymerizable compound is a compound different from the binder resin described above, and is preferably a monomer or oligomer having a molecular weight of 1000 or less, preferably a monomer.

There is no restriction | limiting in particular as a monomer which has the said (meth) acryloyl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meta) ) Monofunctional acrylate such as acrylate; Monofunctional methacrylate; Polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Trimethylolethane triacrylate, Trimethylolpropane triacrylate, Trimethylolpropane diacrylate, Neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Sa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate , Glycerin tri (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, trimethylolpropane, glycerin, bisphenol and other polyfunctional alcohols after addition reaction of ethylene oxide and propylene oxide to (meth) acrylate Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, and the like; Polyester acrylates described in various publications such as Kokai 48-64183, JP-B 49-43191, and JP-B 52-30490; reaction products of epoxy resin and (meth) acrylic acid And polyfunctional acrylates and methacrylates such as epoxy acrylates. These may be used individually by 1 type and may use 2 or more types together. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tricyclodecane dimethanol (meth) acrylate are particularly preferable. preferable.
As the polymerizable compound, compounds having two or more acryloyloxy groups and methacryloyloxy groups and compounds having an alicyclic ring such as tricyclodecanedimethanol (meth) acrylate are particularly preferable.

The content of the polymerizable compound in the silica dispersion composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2% by mass to 50% by mass, and 3% by mass to 40% by mass. Is more preferable, and 4% by mass to 35% by mass is particularly preferable.
When the content 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 is within the particularly preferable range, it is advantageous in that both good pattern formation and crack resistance can be achieved.

<Photopolymerization initiator>
The composition used in the present invention preferably contains a 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 depending on the purpose. For example, a halogenated hydrocarbon derivative (for example, a triazine skeleton And those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like.

The halogenated hydrocarbon compound 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 compounds described in JP-A-5-34920. Examples of the halogenated hydrocarbon compound having an oxadiazole skeleton include the compounds described in US Pat. No. 4,221,976.

The oxime derivative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0085] of JP-A-2007-2030.

The ketone compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0087] of Japanese Patent Application Laid-Open No. 2007-2030.

The photopolymerization initiator other than the above is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0086] of JP-A-2007-2030. Can be mentioned.

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

The sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0089] of JP-A-2007-2030.

The combination of the photopolymerization initiator and the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an electron transfer type initiation system described in JP-A-2001-305734 [ (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.

The content of the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 0.05% by mass to 30% by mass with respect to all components in the silica dispersion composition. 0.1 mass% to 20 mass% is more preferable, and 0.2 mass% to 10 mass% is particularly preferable. When the content is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

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

The content of the photopolymerization initiator in the silica dispersion composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5% by mass to 20% by mass, and preferably 0.5% by mass. % To 15% by mass is more preferable, and 1% to 10% by mass is particularly preferable.
When the content is less than 0.5% by mass, the exposed portion 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 is within the particularly preferable range, it is advantageous in that a good pattern can be formed and heat resistance is also improved.

<Other ingredients>
The composition used in the present invention may contain other components.
Such a component is not particularly limited and may be appropriately selected depending on the purpose. For example, a thermoplastic elastomer, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, a colorant (color pigment or Dyes) and the like, and further adhesion promoters to the substrate surface, or other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants). , Fragrance, surface tension adjusting agent, chain transfer agent, etc.) may be used in combination.
By appropriately containing these components, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

The thermoplastic elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, acrylic elastomer, and Examples include silicone elastomers.
These 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.
The thermoplastic elastomer is described in paragraphs [0197] to [0207] of JP-A-2007-199532.
The filler is described in detail in, for example, paragraphs [0098] to [0099] of JP-A-2008-250074.
The thermal polymerization inhibitor is described in detail, for example, in paragraphs [0101] to [0102] of JP-A-2008-250074.
The thermosetting accelerator is described in detail, for example, in paragraph [0093] of JP-A-2008-250074.
The plasticizer is described in detail, for example, in paragraphs [0103] to [0104] of JP-A-2008-250074.
The colorant is described in detail, for example, in paragraphs [0105] to [0106] of JP-A-2008-250074.
The adhesion promoter is described in detail, for example, in paragraphs [0107] to [0109] of JP-A-2008-250074.

(Photosensitive film)
The composition used in the present invention can be used as a liquid resist by coating and drying on a substrate on which a conductor wiring is formed, but is particularly useful for the production of a photosensitive film.
The photosensitive film has at least a support and a photosensitive layer, preferably has a protective film, and further, if necessary, a cushion layer, an oxygen barrier layer (hereinafter abbreviated as PC layer). ) And other layers.
There is no restriction | limiting in particular as a form of the said photosensitive film, According to the objective, it can select suitably, For example, the form which has the said photosensitive layer and the said protective film in this order on the said support body. 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 protection are provided on the support. The form which has a film in this order, etc. are mentioned. The photosensitive layer may be a single layer or a plurality of layers.

<Photosensitive layer>
The photosensitive layer is formed from the silica dispersion composition of the present invention.
The melt viscosity at 70 ° C. of the photosensitive layer is preferably 1.4 × 10 ³ Pa · s or less, more preferably 1.0 × 10 ³ Pa · s or less, and 6.0 × 10 ² Pa · s or less. Further preferred.
When the melt viscosity at 70 ° C. of the photosensitive layer exceeds 1.4 × 10 ³ Pa · s, the embedding property may be deteriorated, and when the melt viscosity at 70 ° C. is in a more preferable range, the embedding property is deteriorated. Is advantageous in that it is sufficiently obtained.
The melt viscosity at 30 ° C. of the photosensitive layer is preferably 1.0 × 10 ⁴ Pa · s or more, more preferably 1.3 × 10 ⁴ Pa · s or more, and 3.0 × 10 ⁴ Pa · s or more. Further preferred.
If the melt viscosity at 30 ° C. of the photosensitive layer is less than 1.0 × 10 ⁴ Pa · s, edge fusion may be deteriorated, and if the melt viscosity at 30 ° C. is in a more preferable range, embedding is performed. It is advantageous in that it can be compatible with edge fusion.

Here, the melt viscosity of the photosensitive layer is measured by, for example, a melt viscosity measuring device such as a rheometer VAR-1000 type (manufactured by Rheological Co., Ltd.), Vibron DD-III type (manufactured by Toyo Baldwin Co., Ltd.) or the like. Can be measured. The details are as described in paragraphs “0115” to “0127” of Japanese Patent Application Laid-Open No. 2007-2030.

<Permanent pattern and permanent pattern forming method>
The permanent pattern used in the present invention is obtained by the permanent pattern forming method.
The permanent pattern is described in paragraphs [0128] to [0283] of Japanese Patent Application Laid-Open No. 2007-2030.

<Printed circuit board>
The printed board used in the present invention has at least a base 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 said base | substrate and the said permanent pattern are mentioned.

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

-Synthesis of polyurethane binder-
The following acid-modified ethylenically unsaturated group-containing polyurethane resin was synthesized.

<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin PU1 and adjustment of resin solution>
To a 1 L 3-neck round bottom flask equipped with a condenser and a stirrer, 9.6 g of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 29.6 of glycerol monomethacrylate (GLM), 4.0 g of malic acid Was dissolved in 76 g of cyclohexanone. To this, 50.1 g of 4,4-diphenylmethane diisocyanate (MDI), 8.4 g of hexamethylene diisocyanate (HMDI), 0.3 g of 2,6-di-t-butylhydroxytoluene, and as a catalyst, trade name: Neostan U 0.3 g of −600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) was added together with 77 g of cyclohexanone, and the mixture was heated and stirred at 75 ° C. for 5 hours.
The mass average molecular weight of the acid-modified ethylenically unsaturated group-containing polyurethane resin PU1 was 12,000. The acid value of the solid content was 68.9 mmol / g, and the ethylenically unsaturated group equivalent of the solid content was 1.82.

<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin PU2 and adjustment of resin solution>
In the synthesis of the acid-modified ethylenically unsaturated group-containing polyurethane resin PU1, 2,2-bis (hydroxymethyl) butyric acid (DMBA), glycerol monomethacrylate (GLM), 4,4-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI) was used, malic acid was removed, and these addition amounts were changed to synthesize modified ethylenically unsaturated group-containing polyurethane resin PU2 in the same manner as acid-modified ethylenically unsaturated group-containing polyurethane resin PU1. .
The acid-modified ethylenically unsaturated group-containing polyurethane resin PU2 had a mass average molecular weight of 13,000, a solid content acid value of 63.3 mmol / g, and a solid content ethylenically unsaturated group equivalent of 1.46. .

-Synthesis of acrylic resin dispersant-
<Synthesis of macromonomer>
250 g of ε-caprolactone, 14.3 g of 2-ethylhexanol, and 0.125 g of monobutyltin oxide were placed in a 500 mL three-necked round bottom flask, stirred at 90 ° C. for 4 hours, stirred at 110 ° C. for 4 hours, and then heated to 80 ° C. The temperature was lowered, and 17.3 g of Showa Denko MOI MOI and 0.07 g of 2,6-di-t-butylhydroxytoluene were added and stirred for 2 hours. Dilution with 650 g of cyclohexanone gave a polyester macromonomer. The molecular weight of the macromonomer was Mn3100.

<Synthesis of Dispersant P-4>
After adding 36 g of cyclohexanone to a three-necked flask, 21.6 g of methacrylic acid 2- (dimethylamino) ethyl ester, 8.0 g of methacrylic acid, 17.6 g of methyl methacrylate, 109 g of a macromonomer solution, Dimethyl 2,2'- A solution obtained by mixing 1.28 g of Azobis (isobutyrate) and 3.2 g of 3-mercaptopropionic acid 2-ethylhexyl ester was added dropwise at 80 ° C. in a nitrogen stream over 1 hour and a half, followed by stirring for 3 hours, and then cyclohexanone. 200 g was added to obtain a dispersant solution P-4.
The solid content concentration of the exemplified polymer P-4 in the dispersant solution P-4 is 20%.

<Synthesis of Dispersant P-11>
After adding 36 g of cyclohexanone to a three-necked flask, 30.4 g of methacrylic acid 2- (dimethylamino) ethyl ester, 8.0 g of methacrylic acid, 8.8 g of methyl methacrylate, Macromonomer AS-6 manufactured by Toa Gosei Co., Ltd. 32.8 g, Dimethyl 2,2′-Azobis (isobutyrate) 1.28 g, 3-mercaptopropionic acid 2-ethylhexyl ester 3.2 g, and cyclohexanone 78 g were mixed at 80 ° C. under nitrogen stream for 1 hour. After dropwise addition over half and stirring for 3 hours, 200 g of cyclohexanone was added to obtain a dispersant solution P-11.
The solid content concentration of the exemplified polymer P-11 in the dispersant solution P-11 is 20%.

Exemplified polymers P-5, P-6 and P-7 were also synthesized by the same method as described above. The solids concentration of these polymers in the dispersion is 20%.
<Synthesis of Elastomer E-1>
699 parts by weight of dimethyl terephthalate, 524 parts by weight of dimethyl isophthalate, 226 parts by weight of dimethyl adipate, 553 parts by weight of dimethyl sebacate, 417 parts by weight of 2,2-dimethylpropanediol, 324 parts by weight of butanediol, 769 parts by weight of ethylene glycol As an antioxidant, 2 parts by mass of Irganox 1330 (manufactured by Ciba Japan Co., Ltd.) and 0.9 parts by mass of tetrabutyl titanate were mixed in the reactor, and the temperature was raised from room temperature to 260 ° C. over 2 hours with stirring. Then, the mixture was heated at 260 ° C. for 1 hour to conduct a transesterification reaction. Next, the pressure in the reactor was gradually reduced and the temperature was raised, and an initial polycondensation reaction was performed at 245 ° C. and 0.5 to 2 torr over 30 minutes. Further, after carrying out the polymerization reaction at 245 ° C. and 0.5 to 2 torr for 4 hours, the pressure was returned to normal pressure over 30 minutes while introducing dry nitrogen, and the polyester was taken out into pellets to obtain polyester resin E-1. Obtained. The obtained polyester resin E-1 was diluted and dissolved in propylene glycol monomethyl ether acetate to a solid content concentration of 60% by mass to obtain a polyester resin E-1 solution.
The obtained polyester resin E-1 had a mass average molecular weight (polystyrene standard) measured by gel permeation chromatography was 34,000.

<Method of measuring amine value>
0.7 g of each silica dispersant was weighed into a 100 mL beaker, and 60 mL of acetic acid was added and dissolved by stirring. After adjusting measurement temperature to 25 degreeC, it titrated with the titration apparatus using 0.1N perchloric acid acetic acid as a titration reagent, and measured the amine titer.

<Measurement of acid value>
0.7 g of each silica dispersant was weighed into a 100 mL beaker, and 60 mL of a solution of THF / water = 5/1 (volume ratio) was added and dissolved by stirring. After adjusting measurement temperature to 25 degreeC, it titrated with the titration apparatus using 0.1N NaOH aqueous solution as a titration reagent, and the acid value was measured.

Example 1
-Composition of silica dispersion composition solution-
Polyurethane binder resin solution PU1 synthesized above (40%)
32.3 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 Dispersant: Dispersant P-11 solution 0.22 parts by mass Polymerizable compound: DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 5.3 parts by mass Initiator: Irgacure 907 (manufactured by BASF Corporation) 0 .6 parts by mass Sensitizer: DETX-S (Nippon Kayaku Co., Ltd.) 0.005 parts by mass Reaction aid: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 0.019 parts by mass Curing agent: Melamine (Japanese) 0.16 parts by mass Thermal crosslinking agent: Epototo YDF-170 (manufactured by Toto Kasei Co., Ltd.) 2.9 parts by mass Filler: SO-C2 (manufactured by Admatechs) 16.0 parts by mass Ion trap agent: IXE-6107 (manufactured by Toagosei Co., Ltd.) 0.82 parts by weight Coating aid: 0.2 parts by weight of MegaFuck F-780F (Dainippon Ink Co., Ltd .: 30% by weight methyl ethyl ketone solution)
Elastomer E-1 2.7 parts by mass Cyclohexanone (solvent) 38.7 parts by mass

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

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

Each of the obtained photosensitive films and laminates was evaluated for melt viscosity, embedding property, developability (unexposed portion), insulating property, and thermal shock resistance (TCT) as follows. The results are shown in Table 1 below.

<Measurement of melt viscosity>
Here, the melt viscosity of each photosensitive film was measured using a rheometer VAR-1000 type (manufactured by Rheological Co., Ltd.) under the following conditions.
-Measurement conditions of 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. In addition, the melt viscosity in Table 1 shows a value at 70 ° C.

<Evaluation of embeddability>
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〕
A: When the photosensitive film embeds a step between the pattern circuit and the base film, and no gap is formed between the photosensitive film and the copper-clad laminate with circuit B: The photosensitive film and the circuit When there is a gap between the laminated copper-clad laminate or when air bubbles are generated between the pattern circuit and the photosensitive laminate C: When the melt viscosity is too high to laminate

<Development evaluation>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). From the obtained photosensitive laminate polyethylene terephthalate film (support), 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. The film was exposed at 40 mJ / cm ² .
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as the developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve the uncured region. Removed.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, there is no residue at the bottom of the round hole of the pattern, there are no abnormalities such as blistering / peeling of the pattern, and space The minimum round hole pattern width that can be formed was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution.
[Development evaluation criteria]
Development time: The shortest development time was evaluated visually.
The residue was evaluated according to the following criteria.
A: No residue B: Some residue is seen on the wall and bottom C: Residue is clearly seen

<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. A solder resist layer was formed on the comb-shaped electrode of this substrate by a conventional method, and exposure was performed with 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 Manufacturing. 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 a shield wire made of polytetrafluoroethylene to these comb electrodes by Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation laminate after heating, 50 V is applied to the evaluation laminate. With the voltage applied, the laminate for evaluation was allowed to stand in a super accelerated high temperature and high humidity life test (HAST) bath of 85% RH at 130 ° C. for 200 hours. Thereafter, the degree of migration of the solder resist in the laminate for evaluation was observed with a 100-fold metal microscope. 〔Evaluation criteria〕
A: The occurrence of migration cannot be confirmed, and the insulation is excellent.
B: Occurrence of migration was confirmed, and the insulation was slightly inferior.
C: The electrodes are short-circuited and insulative.

<Thermal shock resistance (crack resistance) (TCT)>
As reliability test items, appearance such as cracks and peeling was evaluated by a temperature cycle test (TCT). TCT uses a gas-phase cold heat tester, and the electronic component module is left in the gas phase at −55 ° C. and 125 ° C. for 30 minutes each, and this is regarded as one cycle under the conditions of 1,000 cycles and 1,500 cycles. The thermal shock resistance was evaluated according to the following criteria.
〔Evaluation criteria〕
A: No crack occurrence B: Shallow crack occurrence C: Deep crack occurrence

Examples 2 to 7 and Comparative Examples 1 to 3
In Example 1, as shown in Table 1 below, the silica dispersant P-11 was replaced with silica dispersants P-4 to P-7 of the present invention and comparative silica dispersants Pa and Pb, respectively. In Example 6, except that the binder was changed to PU2, and in Example 7, the silica content was changed to 16%, the same as Example 1, except that the combinations of Examples 2 to 7 and Comparative Examples 1 to 3 photosensitive films, laminates, and permanent patterns were produced.
About each obtained photosensitive film and laminated body, it carried out similarly to Example 1, and evaluated melt viscosity, embedding property, developability (unexposed part), insulation, and thermal shock resistance (TCT). The results are shown in Table 1.

The acid value of 1 mmol / g is 56.11 KOH mg / g.
Comparative dispersants Pa and Pb have the following structures, and both used a cyclohexanone solution having a solid content concentration of 20%. In the following, the numerical value is% by mass, x represents the degree of polymerization and is 1 to 50.

As apparent from Table 1 above, the dispersant of the present invention exhibits excellent dispersibility, and as a result, the fine particles of silica can be stably and densely dispersed with the dispersant of the present invention, and a composition containing this is used. The resulting photosensitive film exhibits excellent performance in embedding, developing, insulating and thermal shock resistance (TCT) as a photosensitive film such as a solder resist without increasing the melt viscosity. Recognize.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified, but within the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely without conflict.

The present application claims priority based on Japanese Patent Application No. 2011-129644 filed in Japan on June 9, 2011, which is incorporated herein by reference. Capture as.

Claims (15)

A composition comprising at least one acrylic resin and silica fine particles, the acrylic resin having a tertiary amino group and an amine value of 1.1 mmol / g or more. The composition according to claim 1, wherein the acrylic resin has a graft chain at a side chain of the resin or at a main chain terminal. The composition according to claim 1 or 2, wherein the acrylic resin further has an acidic group. The composition according to claim 1 or 2, wherein the acrylic resin further has a carboxyl group. The composition according to any one of claims 1 to 4, wherein the acrylic resin has an acid value of 0.3 mmol / g or more. 6. The composition according to claim 1, wherein the silica fine particles have an average particle size (d50) of 0.02 μm to 3.0 μm. The composition according to any one of claims 1 to 6, further comprising a thermal crosslinking agent. The composition according to any one of claims 1 to 7, further comprising a binder, a polymerizable compound, and a photopolymerization initiator. The composition according to any one of claims 1 to 8, wherein the composition is for a solder resist. 10. The composition according to claim 1, wherein the composition contains a resin containing an acid-modified ethylenically unsaturated group as a binder. 10. The composition according to any one of claims 1 to 9, wherein the composition contains an acid-modified ethylenically unsaturated group-containing polyurethane resin as a binder. A photosensitive film comprising a photosensitive layer containing the composition according to any one of claims 1 to 11 on a support. A photosensitive laminate comprising a photosensitive layer containing the composition according to any one of claims 1 to 11 on a substrate. A method for forming a permanent pattern comprising at least exposing a photosensitive layer formed of the composition according to any one of claims 1 to 11. A printed circuit board formed by the permanent pattern forming method according to claim 14.