KR20140049983A - Photosensitive resin composition, and photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed substrate using same - Google Patents

Abstract

At least one ion trapping agent, a radical polymerizable monomer, a photopolymerization initiator, and a thermal crosslinking agent of an inorganic compound having at least one metal of an acid-modified ethylenically unsaturated group-containing resin, an inorganic filler, Zr, Bi, or Sb, respectively; As a photosensitive resin composition, the photosensitive resin composition whose content of the said inorganic filler is 20 volume% or more in the non volatile component total capacity of the said photosensitive resin composition, the photosensitive film, the photosensitive laminated body, the permanent pattern formation method, and the printed circuit board using the same.

Description

PHOTOSENSITIVE RESIN COMPOSITION, AND PHOTOSENSITIVE FILM, PHOTOSENSITIVE LAMINATE, METHOD FOR FORMING PERMANENT PATTERN, AND PRINTED SUBSTRATE USING SAME}

This invention relates to the photosensitive resin composition used suitably for a soldering resist, etc., the photosensitive film, the photosensitive laminated body, the permanent pattern formation method, and the printed circuit board using the same.

Conventionally, in forming permanent patterns, such as a soldering resist, the photosensitive film which formed the photosensitive layer by apply | coating and drying a silica dispersion composition on a support body has been used. As a method of forming a permanent pattern, such as a soldering resist, a laminated body is formed by laminating | stacking a photosensitive film on base materials, such as a copper clad laminated board in which a permanent pattern is formed, and exposing exposure to the photosensitive layer in this laminated body. The method of forming a permanent pattern by carrying out, developing the photosensitive layer after exposure, and forming a pattern, and performing a hardening process etc. after that are known.

In recent years, with the miniaturization of devices, development of soldering resists, such as a semiconductor package substrate with small L / S (line space), is progressing. Therefore, in order to improve impact resistance and insulation, high-impedance of an inorganic filler is required.

In recent years, Ba having a refractive index of 1.50 to 1.65 in order to match the coefficient of linear expansion of the substrate which is the base of the solder resist and the solder resist to suppress cracking and peeling of the solder resist generated at the time of a cold-heat cycle, It is proposed to contain 25-40 volume% of Mg or Al type inorganic fillers with respect to the non volatile component whole quantity of the photosensitive resin composition (refer patent document 1). Moreover, in order to make smooth the shape of the inner wall surface at the time of forming thermal cycle test tolerance, storage stability, and via, it is proposed to use spherical silica surface-treated with a silane coupling agent as an inorganic filler ( See Patent Document 2).

On the other hand, it is known to use a specific ion adsorbent in the photosensitive composition (refer patent documents 3 to 5).

However, in the photosensitive resin composition, photosensitive film, etc. which are used for a soldering resist etc., when high filling an inorganic filler to a photosensitive layer, melt viscosity will become high and transferability and developability will fall.

Japanese Patent Laid-Open No. 2011-75923 Japanese Patent Laid-Open No. 2011-95731 Japanese Patent Laid-Open No. 2000-159859 Japanese Patent Publication No. 2009-186510 Japanese Patent Laid-Open No. 11-288090

The present invention provides a high-performance cured film containing an inorganic filler at a high density, excellent in dispersion stability of the inorganic filler, good resolution, less development residue, and excellent in all of insulation, heat resistance, and plating resistance. It is a subject to provide a composition. Moreover, this invention makes it a subject to provide the photosensitive laminated body, the permanent pattern formation method, and the printed circuit board which used the said photosensitive resin composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject of this invention could be solved by the following means.

That is, the means for solving the said subject of this invention are as follows.

<1> Photosensitive resin composition which contains at least 1 type of acid-modified ethylenically unsaturated group containing resin, an inorganic filler, an ion trapping agent, a radically polymerizable monomer, a photoinitiator, and a thermal crosslinking agent, respectively, The nonvolatile component of the photosensitive resin composition The photosensitive resin composition whose content of the said inorganic filler in a total capacity is 20 volume% or more, and the said ion trapping agent is an inorganic compound which has at least 1 sort (s) of Zr, Bi, or Sb in a constituent atom.

<2> The ion trapping agent is zirconium phosphate, zirconium tungsten, zirconium molybdate, zirconium selenium, zirconium tellurium, bismuth oxide, bismuth titanate, bismuth nitrate, bismuth nitrate, bismuth carbonate, antimony pentoxide, antimony trioxide, phosphorus antimony The photosensitive resin composition as described in said <1> which is an inorganic compound chosen from antimony zirconium and titanium antimonate.

<3> Photosensitive resin composition as described in said <1> or <2> containing at least 1 sort (s) of the inorganic compound which has Zr in a structural atom, and at least 1 sort (s) of the inorganic compound which has Bi in a structural atom as said ion trapping agent.

The photosensitive resin composition in any one of said <1>-<3> which has the group which interacts with the surface of a <4> inorganic filler, and contains the polymeric dispersing agent which does not have an ethylenically unsaturated group.

<5> Photosensitive resin composition as described in said <4> whose said dispersing agent is a dispersing agent which has a basic group or an acidic group.

<6> Photosensitive resin composition as described in said <4> or <5> in which the said dispersing agent has a primary amino group or a secondary amino group.

<7> Photosensitive resin composition in any one of said <4>-<6> in which the said dispersing agent has a graft chain.

<8> Photosensitive resin composition in any one of said <4>-<7> whose amine value of the said dispersing agent is 0.65 mmol / g or more.

<9> Photosensitive resin composition in any one of said <4>-<8> whose acid value of the said dispersing agent is 0.1 mmol / g or more.

<10> Photosensitive resin composition in any one of said <1>-<9> in which the said inorganic filler contains a silicon in a constituent atom.

The photosensitive resin composition in any one of said <1>-<10> whose <11> above-mentioned acid-modified ethylenically unsaturated group containing resin is a polyurethane resin.

<12> The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and in any one of the above <1> to <11> having a structure of any one of the following general formulas (1) to (3). The photosensitive resin composition described.

In General Formulas (1) to (3), R ¹ to R ¹¹ each independently represent a hydrogen atom or a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom or -N (R ¹² )-. Here, R ¹² represents a hydrogen atom or a monovalent organic group. Z represents an oxygen atom, a sulfur atom, -N (R ¹³ )-or a phenylene group which may have a substituent. R <^13> represents a hydrogen atom or monovalent organic group here.

<13> The photosensitive resin composition according to any one of <1> to <12>, in which the acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and the proportion of the aromatic moiety in the resin is 30% by mass or more. .

<14> The photosensitive resin composition according to any one of <1> to <13>, wherein the acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin and has a partial structure represented by the following General Formula (UB). .

In formula (UB), X ^L1 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or- C (= O) ^-is represented and R ^u1 to R ^u8 each independently represent a hydrogen atom or a substituent.

<15> The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, has a partial structure represented by the following general formula (UB), and the proportion of the aromatic moiety of the general formula (UB) in the resin is The photosensitive resin composition in any one of said <1>-<14> which is 30 mass% or more.

In formula (UB), X ^L1 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or- C (= O) ^-is represented and R ^u1 to R ^u8 each independently represent a hydrogen atom or a substituent.

<16> Photosensitive resin composition as described in said <14> or <15> whose R ^u1 -R ^u8 are all hydrogen atoms in said general formula (UB).

<17> The photosensitive resin composition according to any one of <1> to <16>, wherein the acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin and has a partial structure represented by the following General Formula (UNCO). .

In general formula (UNCO), X ^L1 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or- C (= 0)-. R ^u1 to R ^u8 each independently represent a hydrogen atom or a substituent.

<18> The photosensitive resin composition according to the above <17>, wherein in the general formula (UNCO), R ^u1 to R ^u8 are all hydrogen atoms, and X ^L1 is —CH ₂ —.

<19> Photosensitive resin composition as described in said <17> or <18> whose ratio of the aromatic part of the said general formula (UNCO) to the acid-modified ethylenically unsaturated group containing polyurethane resin is 30 mass% or more.

<20> The photosensitive resin composition according to any one of <1> to <19>, wherein the acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin and has a partial structure represented by the following General Formula (UE1). .

In the general formula (UE1), the L ^UE does not include -NHC (= 0) O- or -OC (= 0) NH- at the bond of the main chain, and also has an ethylenically unsaturated group or an ethylenically unsaturated group as a substituent. The divalent linking group which has one group is shown.

<21> The photosensitive resin composition according to any one of <1> to <20>, wherein the acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin and has a partial structure represented by the following General Formula (G1). .

In General Formula (G1), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group. A represents a divalent organic residue. X represents an oxygen atom, a sulfur atom, or -N (R ¹² )-, and R ¹² represents a hydrogen atom or a monovalent organic group.

<22> The photosensitive resin composition according to any one of <1> to <21>, wherein the acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin and has a partial structure represented by the following General Formula (U1). .

In General Formula (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group.

<23> The photosensitive resin composition according to any one of <1> to <22>, in which the acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin and has a group having a carboxyl group at a polymer terminal.

<24> Photosensitive resin composition in any one of said <1>-<23> whose ethylenically unsaturated group equivalent of acid-modified ethylenically unsaturated group containing resin is 1.00 mmol / g or more.

The photosensitive film which has a photosensitive layer containing the photosensitive resin composition in any one of said <1>-<24> on a <25> support body.

The photosensitive laminated body which has a photosensitive layer containing the photosensitive resin composition in any one of said <1>-<24> on a <26> base body.

<27> The permanent pattern formation method which includes at least exposing the photosensitive layer formed with the photosensitive resin composition in any one of said <1>-<24>.

<28> A printed circuit board formed by forming a permanent pattern by the permanent pattern forming method according to <27>.

INDUSTRIAL APPLICATION According to this invention, an inorganic filler can be disperse | distributed stably and with high density, and it is especially suitable for soldering resists, etc., It is a high performance hardening excellent in image development residue reduction, insulation, flatness, resolution, heat resistance, and developability and transferability. The photosensitive resin composition, the photosensitive film, the photosensitive laminated body, the permanent pattern formation method, and the printed circuit board which can obtain a film can be provided.

These and other features and advantages of the present invention will become more apparent from the following description.

(Photosensitive resin composition)

The photosensitive resin composition (henceforth only a photosensitive composition or composition hereafter) of this invention contains an acid-modified ethylenically unsaturated group containing resin, an inorganic filler, an ion trapping agent, a radically polymerizable monomer, a photoinitiator, and a thermal crosslinking agent, respectively. It is a composition containing a species. The photosensitive resin composition of this invention may contain the dispersing agent, the elastomer, and other components as needed.

The acid-modified ethylenically unsaturated group-containing resin of the present invention is an acid-modified resin having at least an ethylenically unsaturated group, and examples of the acid-modified ethylenically unsaturated group-containing resin include the following resins.

1) polyurethane resin

2) (meth) acrylic resin

3) polyether resin

4) novolac resin

5) polyester resin

6) polyamide or polyimide resin

Among these, the polyether resin of 3) and the novolak-type resin of 4) are resin obtained from an epoxy resin. In addition, the (meth) acrylic resin of 2) is a generic term of resin containing an acrylic resin and methacryl resin. In this specification, acid-modified ethylenically unsaturated group containing resin other than said 1) is named generically, and it is called acid-modified ethylenically unsaturated group containing non-polyurethane resin.

The acid-modified ethylenically unsaturated group-containing resin used in the present invention is an acid-modified resin, and examples of the acid group of the acid include a carboxyl group, a sulfo group and a phospho group, but a carboxyl group is preferable.

Moreover, although any group may be sufficient as an ethylenically unsaturated group, group represented by General formula (1)-(3) mentioned later is preferable, and group represented by General formula (1) mentioned later is more preferable.

Among the above-mentioned resins 1) to 6), the resins of 1) to 4) are preferable, and the resin of 1) is particularly preferable.

First, an acid-modified ethylenically unsaturated group containing polyurethane resin is demonstrated in detail.

<< acid-modified ethylenically unsaturated group containing polyurethane resin >>

There is no restriction | limiting in particular as acid-modified ethylenically unsaturated group containing polyurethane resin, According to the objective, it can select suitably, Especially in this invention, the acid-modified polyurethane resin which has an ethylenically unsaturated bond in a side chain is preferable. In the present invention, the side chain is a chain connected by substituting a branch or a main constituent atom from the chain of the atom constituting the main chain of the polyurethane resin, and having an ethylenically unsaturated group on the side chain includes an ethylenically unsaturated group in such side chain. Or, the ethylenically unsaturated group is directly substituted by the atom which comprises a main chain. For example, the polyurethane resin obtained only by reaction of a diol of HOCH ₂ CH = CHCH ₂ OH and OCN (CH ₂ ) ₆ NCO contains an ethylenically unsaturated group in the main chain. In addition, the sealed part of a polymer terminal by an ethylenically unsaturated group containing compound is not a side chain.

In addition, an ethylenically unsaturated group is a group which has an ethylene bond consumed by the measurement of bromine and iodine number, and is not a group which shows aromatics like benzene. The vinyl group in which an ethylenically unsaturated group may have a substituent is preferable.

Preferable molecular weight, acid value, and ethylenically unsaturated group equivalent of a acid-modified ethylenically unsaturated group containing polyurethane resin used by this invention, and preferable content of the photosensitive resin composition are demonstrated below.

≪Molecular weight≫

There is no restriction | limiting in particular as mass mean molecular weight of acid-modified ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 3,000-60,000 are preferable as a mass mean molecular weight, 3,000-50,000 are more preferable, 4,000 -30,000 are especially preferable. When the photosensitive resin composition of this invention is used for the photosensitive soldering resist, it is excellent in the dispersibility of an inorganic filler, being excellent also in crack resistance and heat resistance, if it is the range of this mass average molecular weight, and the developability of the non-image part by alkaline developing solution is excellent.

Moreover, when the mass average molecular weight is too small, sufficient low modulus at the time of high temperature of a cured film may not be obtained, and when too large, application aptitude and developability may deteriorate.

Here, the said mass average molecular weight uses a high-speed GPC apparatus (HLC-802A by Toyo Sodatsu Co., Ltd., HLC-802A), for example, makes 0.5 mass% THF solution a sample solution, and the column is TSKgel HZM-M Using one, 200 μL of sample was injected, eluted with the THF solution, measured by a refractive index detector or UV detector (detection wavelength 254 nm) at 25 ° C., and a mass average molecular weight from a molecular weight distribution curve corrected with standard polystyrene. Can be obtained.

≪Sanga≫

There is no restriction | limiting in particular as an acid value of acid-modified ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 20 mgKOH / g-120 mgKOH / g is preferable, 30 mgKOH / g-110 mgKOH / g is more preferable , 35 mgKOH / g to 100 mgKOH / g are particularly preferred. If the acid value is too low, developability may become insufficient. On the contrary, if the acid value is too high, the development speed may be too high, which may make it difficult to control the development.

Here, an acid value can be measured based on JISK0070, for example. In addition, when a sample does not melt, dioxane, tetrahydrofuran, etc. are used as a solvent. In addition, an acid value is a solid content (non-volatile component) acid value of the said resin.

≪Ethylenically unsaturated group equivalents≫

There is no restriction | limiting in particular as ethylenically unsaturated group equivalent of acid-modified ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 0.05 mmol / g-3.0 mmol / g are preferable, and 0.5 mmol / g- 2.7 mmol / g is more preferable, 0.75 mmol / g-2.5 mmol / g are more preferable, and 1.00 mmol / g or more (preferably 1.00 mmol / g-2.5 mmol / g) is especially preferable. When ethylenically unsaturated group equivalent is too small, the heat resistance of a cured film may fall.

Here, ethylenically unsaturated group equivalent can be calculated | required by measuring bromine number, for example. The said bromine value can be measured based on JISK2605, for example.

In addition, where the ethylenically unsaturated equivalent weight is typically a vinyl group equivalent weight, and the number of grams of bromine (Br ₂₎ is appended to the resin 100g of measurements obtained from the bromine number (gBr ₂ / 100g) the additional resin 1g sugars from bromine It is the value converted into the number-of-moles of (Br ₂ ).

<< content rate of aromatic part >>

In this invention, it is preferable that the ratio of the aromatic part which an acid-modified ethylenically unsaturated group containing polyurethane resin occupies in the said polyurethane resin is 30 mass% or more, 30 mass%-60 mass% are more preferable, 33 mass %-55 mass% are more preferable, 35% mass%-50 mass% are especially preferable. When the ratio of the aromatic part to polyurethane resin is too low, the hardness of the film | membrane after hardening may fall.

Here, the term aromatic refers to the concept of tolerance of aromatics as defined in the literature, in particular Jerry MARCH, MARCH'S Advanced Organic Chemistry, Fifth Edition, John Wiley and Sons, 2001, p. 37. It is preferable that an aromatic shows aromaticity in a hydrocarbon ring and a heterocyclic ring, and, in this invention, a hydrocarbon ring is more preferable.

The mass of the said aromatic part in this invention means the total mass of the atom which comprises the skeleton of an aromatic ring, and the hydrogen atom couple | bonded with this atom. In addition, two aromatic rings are connected by -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or -C (= O)- If so, it means the total mass plus the mass of this connection part.

If the two are connected by a linking group of the aromatic rings it is, for example, is represented by the formula 2 (UB) of the benzene ring Whanin place, following one direction, X ^L1 is _{-CH 2 -, -CH (CH 3} ) - , —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —O— or —C (═O) —. R ^u1 to R ^u8 are hydrogen atoms or substituents.

For example, the X ^L1 of the connecting -CH (CH ₃₎ In the case of (A) - is more the mass of - a -CH (CH ₃₎ because it is. On the contrary, in the case of (B), X ^L1 of the connecting portion is -C (= 0) -O-, which does not satisfy the requirements of X ^L1 , so that this mass is not added to the mass of the aromatic moiety. In addition, the substituent substituted by an aromatic ring is not added to the mass of an aromatic part other than said linking group.

Therefore, in the case of (A), the mass of the aromatic moiety is that one benzene ring portion has 6 carbon atoms, 3 hydrogen atoms, 2 connection carbon atoms, 4 hydrogen atoms, and the remaining benzene ring portion is carbon atoms. 6 and 3 hydrogen atoms. As a result, what is considered as the mass of an aromatic part is a part with 14 carbon atoms and 10 hydrogen atoms.

On the other hand, in the case of (B), since the -C (= O) -O- portion is not added, the mass of the aromatic portion is 12 carbon atoms and 6 hydrogen atoms.

The aromatic moiety in the acid-modified ethylenically unsaturated group-containing polyurethane resin preferably has at least a partial structure represented by the general formula (UB) above all, and it is preferable that all of R ^u1 to R ^u8 are hydrogen atoms, It is preferable that X ^L1 is -CH _2- .

Moreover, it is more preferable that the content rate of the partial structure (partial structure of the aromatic part mentioned above) represented by the said general formula (UB) in acid-modified ethylenically unsaturated group containing polyurethane resin is 30 mass% or more.

It is more preferable that the partial structure represented by this general formula (UB) is a partial structure represented by the following general formula (UNCO).

Below, the acid-modified polyurethane resin which has an ethylenically unsaturated bond in the preferable side chain in this invention is demonstrated.

There is no restriction | limiting in particular as acid-modified polyurethane resin which has an ethylenically unsaturated bond in a side chain, It can select suitably according to the objective, For example, at least among the functional groups represented by following General formula (1)-(3) in the side chain. The thing which has one is mentioned.

In General Formulas (1) to (3), R ¹ to R ¹¹ each independently represent a hydrogen atom or a monovalent organic group. Here, as the monovalent organic group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, alkyl Amino group, arylamino group, acylamino group, sulfonamide 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, etc. are mentioned, These groups may be further substituted by these substituents. Moreover, the group same as the monovalent organic group or substituent in each subsequent group and each general formula is mentioned.

R ¹ is preferably an alkyl group which may have a hydrogen atom or a substituent, and among them, a hydrogen atom and a methyl group are more preferable in view of high radical reactivity. In addition, R <^2> , R <^3> , R <^4> -R <^8> , R <^10> and R <^11> are a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, the alkyl group which may have a substituent, and a substituent An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent The arylsulfonyl group which may have a preferable is preferable, and among these, the hydrogen atom, the carboxyl group, the alkoxycarbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are more preferable at the point of high radical reactivity.

R ⁹ is preferably an alkyl group which may have a hydrogen atom or a substituent, and among them, a hydrogen atom and a methyl group are more preferable in view of high radical reactivity.

X and Y each independently represent 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 preferably an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group is more preferable in view of high radical reactivity.

Z represents an oxygen atom, a sulfur atom, -N (R ¹³ )-or a phenylene group which may have a substituent. R ¹³ represents a hydrogen atom or a monovalent organic group. R ¹³ is preferably an alkyl group which may have a substituent, and among them, a methyl group, an ethyl group, and an isopropyl group are more preferable in view of high radical reactivity.

Here, there is no restriction | limiting in particular as a substituent (each substituent which may have in the alkyl group etc. which may have a substituent) which each said group may have, It can select suitably according to the objective, For example, the said monovalent oil Groups exemplified in the apparatus include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, alkylamino groups, arylamino groups, acylamino groups, and carboxes. A barmoyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carboxyl group, a sulfo group, a nitro group, and a cyano group are preferable.

Of the groups represented by the general formulas (1) to (3), the group represented by the general formula (1) is preferable, and in view of the crosslinked cured film formability, R ¹ in the general formula (1) is a methyl group and R ² and R ³ is the group of formula (1) of R ¹ ~R ³ is hydrogen atom in the group, and that in the formula (3) phenylene group Z styryl groups are preferred, hydrogen atom, the formula ( 1) R ¹ is a methyl group and also R ² and R ³ is the group of all the R ¹ ~R ³ in the formula (1), more preferred groups are a hydrogen atom, and the cross-linked cured film is formed and a hydrogen atom at the Particularly preferred is a group in which R ¹ in general formula (1) is a methyl group and R ² and R ³ are hydrogen atoms in terms of compatibility with biopreservation. Here, X in General formula (1) has an oxygen atom, As a ethylenically unsaturated group, a methacryloyloxy group or an acryloyloxy group is especially preferable, and a methacryloyloxy group is the most preferable.

In order to introduce an ethylenically unsaturated group into the side chain, (i) a method of obtaining an ethylenically unsaturated group by a polymerization reaction with a compound having a diisocyanate compound or a diol compound, (ii) a carboxyl group-containing polyurethane, an epoxy group and an ethylenic compound in a molecule There is a method obtained by reacting a compound having an unsaturated group.

Hereinafter, the polyurethane resin obtained by the method of (i) is also called polyurethane resin (i), and the polyurethane resin obtained by the method of (ii) is also called polyurethane resin (ii). In addition, the polyurethane resin which has an ethylenically unsaturated bond in a side chain is what contains both polyurethane resin (i) and (ii).

In this invention, the polyurethane resin (i) obtained by the method of (i) is preferable.

Polyurethane resin (i)

Polyurethane resin is synthesize | combined by reaction of a diisocyanate compound and a diol compound (compound which has at least 2 hydroxyl group), Polyurethane resin (i) is at least 1 sort (s) of the diisocyanate compound represented by following General formula (4), It is a polyurethane resin which makes a structural skeleton represented by at least 1 sort (s) of reaction product of the diol compound represented by following General formula (5) as a basic skeleton.

OCN-X ⁰ -NCO... In general formula (4)

HO-Y ⁰ -OH. General formula (5)

In General Formula (4) and General Formula (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

If at least one of the diisocyanate compound represented by the said General formula (4) or the diol compound represented by the said General formula (5) has at least 1 of the groups represented by the said General formula (1)-(3), As a reaction product of the diisocyanate compound and the diol compound, a polyurethane resin having a group represented by the general formulas (1) to (3) introduced into the side chain is produced. According to this method, the polyurethane resin in which the group represented by the said General formula (1)-(3) was introduce | transduced into the side chain rather than replacing and introducing a desired side chain after reaction reaction of a polyurethane resin can be manufactured easily.

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 a unsaturated group or a monofunctional amine compound 1 The product obtained by addition-reacting equivalent is mentioned.

It does not restrict | limit especially as said triisocyanate compound, According to the objective, it can select suitably, For example, the compound etc. of Paragraph [0034]-[0035] of Unexamined-Japanese-Patent No. 2005-250438 are mentioned.

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

There is no restriction | limiting in particular as a diisocyanate compound in the method of using the diisocyanate compound containing an ethylenically unsaturated group in a side chain, According to the objective, it can select suitably, The monofunctional alcohol or monofunctional which has a triisocyanate compound and an unsaturated group The diisocyanate compound obtained by addition reaction of 1 equivalent of the amine compound of the compound, For example, the compound which has an unsaturated group in the side chain of Unexamined-Japanese-Patent No. 2005-250438, etc. are mentioned. .

Polyurethane resin (i) can also copolymerize diisocyanate compounds other than the diisocyanate compound containing the said ethylenically unsaturated group from a viewpoint of improving compatibility with other components in a polymeric composition, and improving storage stability.

There is no restriction | limiting in particular as a diisocyanate compound to copolymerize, According to the objective, it can select suitably, For example, it is a diisocyanate compound represented by following General formula (6).

OCN-L ¹ -NCO... General formula (6)

In General formula (6), L <^1> represents the bivalent aliphatic or aromatic hydrocarbon group which may have a substituent. As needed, L <^1> may have another functional group which does not react with an isocyanate group, for example, ester group, urethane group, amide group, and ureido group.

There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (6), According to the objective, it can select suitably, For example, the dimer of 2, 4- tolylene diisocyanate and 2, 4- tolylene diisocyanate, 2 , 6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'- dimethyl biphenyl- Aromatic diisocyanate compounds such as 4,4'-diisocyanate; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatemethyl) cyclohexane compound; Diisocyanate compounds which are reactants of diols and diisocyanates such as adducts of 1 mole of 1,3-butylene glycol and 2 moles of tolylene diisocyanate; And the like.

Although the diisocyanate compound represented by General formula (4) or General formula (6) (especially the diisocyanate compound represented by General formula (6)) may be used in combination of another kind, it is excellent in abrasion resistance It is preferable that at least 1 sort (s) is an aromatic diisocyanate compound from the point which can be improved. As an aromatic diisocyanate compound, it is preferable that it is a diisocyanate compound which has a skeleton of bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, or anthracene type, for example, and it is bisphenol A type or bisphenol F, for example. It is more preferable that it is a diisocyanate compound which has a skeleton of a type | mold, and the diisocyanate compound which has a bisphenol F type | mold skeleton is the most preferable.

The skeleton of each of these types is represented by the following general formula.

In the above, R ^a and R ^b each independently represent a substituent, and as the substituent, an alkyl group having 2 to 5 carbon atoms is preferable. l ₁ and l ₂ each independently represent an integer of 0 to 4; l ₁ and l ₂ is 0 or 1 are preferred. l ₃ represents an integer of zero to six. l ₄ represent an integer of 0 to 8. l ₃ is 0 to 2 are preferred, l ₄ is a 0 or 2 is preferred. l ₁ ~l ₄ The second plurality of R ^a, R ^b is present at greater than may be the same or different.

It is more preferable to combine an aromatic diisocyanate compound and an aliphatic diisocyanate compound with the said diisocyanate compound from a viewpoint of suppressing the curvature after hardening and improving cut resistance. As an aromatic diisocyanate compound, it is preferable that it is a diisocyanate compound which has a skeleton of bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, or anthracene type, for example, and it is bisphenol A type or bisphenol F type It is more preferable that it is a diisocyanate compound which has a frame | skeleton of. As an aliphatic diisocyanate compound, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate is preferable, for example, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate are more preferable.

As for the said diisocyanate compound, the compound represented with the following general formula (UB1) is especially preferable, and the polyurethane resin obtained has a partial structure of general formula (UNCO).

In formula (UB1) and formula (UNCO), X ^L1 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S- , -O- or -C (= O) ^-is represented, and R ^u1 to R ^u8 each independently represent a hydrogen atom or a substituent.

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

Here, as a method of introducing an ethylenically unsaturated group into the side chain of a polyurethane resin, the method of using the diol compound containing an ethylenically unsaturated group in a side chain as a raw material of polyurethane resin manufacture other than the above-mentioned method is preferable. The diol compound which contains an ethylenically unsaturated group in the said side chain may be marketed like trimetholpropane monoallyl ether, for example, Compounds, such as a halogenated diol compound, a triol compound, an aminodiol compound, and an unsaturated group The compound manufactured by reaction of compounds, such as carboxylic acid, acid chloride, an isocyanate, alcohol, an amine, a thiol, and a halogenated alkyl compound, may be sufficient.

As a diol compound which has such an ethylenically unsaturated group, the compound represented by the following general formula (UE) is preferable, and it has a partial structure represented by the following general formula (UE1) in a polyurethane resin.

In formula (UE) and formula (UE1), the L ^UE is a divalent linking group that does not include -NHC (= 0) O- or -OC (= 0) NH- in the bond of the main chain, and also in the side chain. The divalent linking group which has one ethylenically unsaturated group is shown.

It is preferable that L ^UE does not contain an aromatic ring in the shortest coupling chain which combines two hydroxyl groups (HO group), and it is more preferable that it is a bivalent aliphatic group which may contain -O- and -S- in the shortest coupling chain. It is preferable that it is a divalent aliphatic group, and it is especially preferable that it is an alkylene group. Moreover, 2-12 are preferable, as for carbon number in the shortest coupling chain which couples two hydroxyl groups (HO group), 2-6 are more preferable, 2-4 are more preferable, and 2 is the most preferable. The divalent linking group L of the ^UE is gatjiman one an ethylenic unsaturated group as the substituent, which in addition may have a substituent group other than unsaturated, examples of the substituent of the general formula (1) to (3) of R ¹ ~R ^The monovalent organic group illustrated by ¹¹ is mentioned.

If date which group the represented by formula (1) having an In unsaturated to the invention, if the α position or β position on the main chain of L ^UE does not bind to the alkyloxycarbonyl group having a hydroxyl group or an acyl group are preferred.

As for the compound represented by general formula (UE), the compound represented by the following general formula (UE-1) (UE-6)-is preferable. In addition, the compound represented by the following general formula (UE-7) is a preferable compound other than the compound represented by the said general formula (UE).

In General Formulas (UE-1) to (UE-7), E ¹ represents a single bond or a divalent linking group (bivalent organic residue), and E ² represents a single bond or a divalent linking group other than -CH _2- . Indicates. A represents a divalent linking group. Q represents any of the groups of the general formulas (1) to (3). As the divalent linking group in E ¹ , E ² , for example, -O-, -S-, -OCH (CH ₂ -Q) CH _2- , -CO ₂ -CH _2- , -OCH ₂ C (CH ₂ -Q) ₂ CH _2- , -O-CONHCH ₂ CH _2- , -OC (= O)-, -CONHCH ₂ CH _2- , -CH ₂ C (CH ₂ -Q) ₂ CH _2- , -CH _2- , -NHCONHCH ₂ CH _2- , -NHCH (CH ₂ -Q) CH _2- , -NCH (CH ₂ -Q) CH _2- , -NHCH ₂ C (CH ₂ -Q) ₂ CH ₂ -,- NH-CH (CH ₂ -Q) CH _2- , -C (= 0)-, -CO ₂ -CH ₂ CH _2- , -CO ₂ -CH ₂ CH ₂ CH ₂ -and the like. In addition, Q represents the group in any one of general formula (1)-(3) here.

As these specific compounds, the compound of Paragraph "0057"-"0060" of Unexamined-Japanese-Patent No. 2005-250438 is mentioned.

Among the compounds represented by general formulas (UE-1) to (UE-7), compounds represented by general formulas (UE-1) to (UE-6) are preferable, and the general formula (UE-6) The compound represented by is more preferable. Moreover, the compound represented by the following general formula (G) is especially preferable among the compound represented by general formula (UE-6). In addition, the compound represented by general formula (G) becomes a partial structure represented by the following general formula (G1) in a polyurethane resin.

In General Formula (G) and General Formula (G1), each of R ¹ to R ³ independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, X is an oxygen atom, a sulfur atom, or- N (R ¹² )-is represented, and R ¹² represents a hydrogen atom or a monovalent organic group.

Further, the above-mentioned formula (G), in the general formula (G1), R ¹ ~R ³ and X are synonymous with X and R ¹ ~R ³ in the general formula (1), as a preferred form.

As a compound represented by general formula (G), the compound of Paragraph [0064]-[0066] of Unexamined-Japanese-Patent No. 2005-250438 is mentioned, It is preferable for this invention.

By using the polyurethane resin derived from the diol compound represented by the said General formula (G), the improvement of the film | membrane strength of a layer is suppressed by the effect which suppresses the excessive molecular movement of the polymer main chain resulting from the secondary alcohol with a big steric hindrance. I think it can be achieved.

The polyurethane resin (i) of the present invention is acid modified, and the definition of acid modified herein indicates that the polymer of the polyurethane resin has an acid group. There is no restriction | limiting in particular as an acidic radical here, A carboxyl group, a sulfo group, etc. are mentioned. It is preferable to have a carboxyl group from a developable viewpoint. It is preferable to acid-modify by using the diol compound which has a carboxyl group for the synthesis | combination of a polyurethane resin (i). As a diol compound which has the said carboxyl group, what is represented by the following general formula (17)-(19) is contained, for example.

In formulas (17) to (19), R ¹⁵ represents a hydrogen atom or a substituent [for example, a halogen atom such as cyano group, nitro group, -F, -Cl, -Br, -I, -CONH ₂ ,- COOR ¹⁶ , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR ¹⁶ , -NHCOR ¹⁶ , -OCONHR ¹⁶ (wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) Group is included.] As long as it represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group which may have any of the above compounds, there is no particular limitation, and a hydrogen atom and an alkyl group having 1 to 8 carbon atoms can be selected as appropriate. And an aryl group having 6 to 15 carbon atoms is preferable.

In General Formulas (17) to (19), L ⁹ , L ¹⁰ , and L ¹¹ may be the same as or different from each other, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group, or an alkoxy group). It is not particularly limited as long as it represents a divalent aliphatic or aromatic hydrocarbon group which may have a halogen atom). Although it can select suitably according to the objective, it is a C1-C20 alkylene group and C6-C15 arylene A group is preferable and a C1-C8 alkylene group is more preferable. Moreover, you may have other functional groups which do not react with an isocyanate group in said L <^9> -L <^{11> as} needed, for example, carbonyl group, ester group, urethane group, amide group, ureido group, and ether group. In addition, you may form a ring by two or three of said R <^15> , L <^9> , L <^10> , L <^11> .

In General Formula (18), there is no restriction | limiting in particular as long as it represents the trivalent aromatic hydrocarbon group which may have a substituent as Ar, Although it can select suitably according to the objective, A C6-C15 aromatic group is preferable.

There is no restriction | limiting in particular as a diol compound which has a carboxyl group represented by said General Formula (17)-(19), According to the objective, it can select suitably, For example, 3, 5- dihydroxy benzoic acid, 2, 2- Bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxy Phenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2 -Hydroxyethyl) -3-carboxy-propionamide, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a diol compound which has a carboxyl group, According to the objective, it can select suitably, For example, the compound etc. which were described in Unexamined-Japanese-Patent No. 2007-2030 are mentioned.

Since the presence of such a carboxyl group can give a polyurethane resin the characteristics of hydrogen bondability and alkali solubility, it is preferable. By introducing a carboxyl group in this way, an acid value can be adjusted to a preferable range in this invention as mentioned above.

Since the presence of such a carboxyl group can give a polyurethane resin the characteristics of hydrogen bondability and alkali solubility, it is preferable. By introducing a carboxyl group in this way, an acid value can be adjusted to a preferable range in this invention as mentioned above.

In addition, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in a side chain, you may use together the compound which ring-opened tetracarboxylic dianhydride to a diol compound other than the diol compound mentioned above.

There is no restriction | limiting in particular as a compound which ring-opened the said tetracarboxylic dianhydride with a diol compound, According to the objective, it can select suitably, For example, Paragraph [0095]-[0101] of Unexamined-Japanese-Patent No. 2005-250438 The compound described in the above can be mentioned.

Polyurethane resin (i) contains the diol compound and carboxyl group which contain an ethylenically unsaturated group in the said side chain from a viewpoint of improving compatibility with other components in a polymeric composition, and improving storage stability, for example. Diol compounds other than a diol compound can be copolymerized, and in this invention, it is especially preferable to copolymerize such a diol compound.

There is no restriction | limiting in particular as such a diol compound, According to the objective, it can select suitably, For example, the polyether diol compound, polyester diol compound, polycarbonate diol compound, m-dihydroxy which are a low molecular diol compound and a polymer diol compound Polycarbonate compounds of benzene and the like can be exemplified.

Such a diol compound is represented by the following general formula (U), and when introduced as a polyurethane resin, is represented by a partial structure represented by the following general formula (U1).

In general formula (U) and general formula (U1), L ^U1 represents a bivalent coupling group which does not contain an ethylenically unsaturated group and a carboxyl group.

L ^U1 includes, for example, an alkylene group, an arylene group, a divalent heterocyclic group, and the alkylene group is -O-, -OCOO-, phenylene group, carbon-carbon double bond, carbon- in the chain of the alkylene group. A carbon triple bond and -OCO-Z ¹ -COO- (Z ¹ represents an alkylene group, an alkenylene group, an arylene group) may be included.

Among the diol compounds represented by the general formula (U), those having a low molecular weight diol compound are preferably those having a mass average molecular weight of less than 400, and examples thereof include the compounds described in paragraph [0048] of JP 2007-2030A. .

In this invention, a polymer diol compound is preferable and it demonstrates in detail below.

Polymer Diol Compound

There is no restriction | limiting in particular as said polymer diol compound, According to the objective, it can select suitably, For example, polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, the block copolymer or random copolymer of ethylene oxide / propylene oxide, Polyether diols such as block copolymers or random copolymers of polytetramethylene glycol, tetramethylene glycol and neopentyl glycol; Polyester diols which are condensates of polyhydric alcohols or polyether diols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, terephthalic acid and isophthalic acid; Polycarbonate diols obtained by reaction of glycol or bisphenol and carbonate ester or reaction of phosgene in the presence of alkali in glycol or bisphenol; And polybutadiene-based polymer diols such as caprolactone-modified polymer diols such as caprolactone-modified polytetramethylene diols, polyolefin-based polymer diols, and hydrogenated polybutadiene diols, and silicone-based polymer diols. These may be used individually by 1 type and may use 2 or more types together.

In addition, in the present invention, preferred compounds and partial structures of the compounds represented by the general formula (U) and (U1) ^include- (CH ₂ CH ₂ O) n ^U1 CH ₂ CH ₂ -,-[CH ₂ CH (CH ₃ ) O] n ^U1 -CH ₂ CH (CH ₃ )-,-(CH ₂ CH ₂ CH ₂ O) n ^U1 -CH ₂ CH ₂ CH ₂ -,-[(CH ₂ ) n ^U2 -OC (= O)-(CH ₂ ) n ^U3 -C (= O) O] n ^U4 -O (CH ₂ ) n ^U2 -or-[(CH ₂ ) n ^U5 -OC (= O) O] n ^U6- (CH ₂ ) n ^U7- . Here, n ^{U1 to} n ^U7 each independently represent one or more numbers. n ^U1 ~n ^U7 is to be preferred, more preferably 500 or less, and more preferably the number of 1,000 or less is a number of not more than 100.

Moreover, as for the compound represented by general formula (U), the diol compound represented by general formula (III-1)-(III-6) mentioned later is also preferable.

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

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

There is no restriction | limiting in particular as said polycarbonate diol compound, According to the objective, it can select suitably, For example, Paragraph [0080]-[0081] of Unexamined-Japanese-Patent No. 2005-250438, and No. in paragraph [0084] are mentioned. The compound of 9-9 can be mentioned.

Moreover, you may use together the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above.

There is no restriction | limiting in particular as a diol compound which has a substituent which does not react with the said isocyanate group, According to the objective, it can select suitably, For example, the compound as described in Paragraph [0087]-[0088] of Unexamined-Japanese-Patent No. 2005-250438, etc. Can be mentioned.

It is preferable that the mass mean molecular weight of such a polymer diol compound is 400-8,000, It is more preferable that it is 500-5,000, It is further more preferable that it is 600-3,000, It is especially preferable that it is 800-2,000. If the mass average molecular weight is less than 400, the fracture resistance may not be sufficiently obtained. If the mass average molecular weight is more than 8,000, the glass transition temperature (Tg) of the obtained polyurethane resin may be excessively lowered, so that the insulation reliability may be lowered.

Here, the mass mean molecular weight uses 0.5 mass% THF solution as a sample solution using the high-speed GPC apparatus (Toyo Sodatsu Co., Ltd., HLC-802A), for example, and one column of TSKgel HZM-M 200 μL of sample can be injected, eluted with the THF solution, and measured at 25 ° C. by a refractive index detector or UV detector (detection wavelength 254 nm).

10-60% is preferable, as for the mass ratio of the partial structure represented by the said general formula (U1) in acid-modified ethylenically unsaturated group containing polyurethane resin, it is more preferable that it is 20-60%, 25-55 It is more preferable that it is%, and it is more preferable that it is 30-50%. When the said mass ratio is less than 10%, curvature suppression after hardening may become difficult, and when it exceeds 60%, the sensitivity of photocuring may fall too much and resolution may worsen.

Moreover, as a polyurethane resin which has an ethylenically unsaturated bond in the side chain used by this invention, the thing which has an unsaturated group in a polymer terminal and a main chain is used suitably. Crosslinking reactivity is improved by having a polymer terminal, an unsaturated group in the main chain, and between the photosensitive resin composition and a polyurethane resin having an ethylenically unsaturated bond in the side chain, or a polyurethane resin having an ethylenically unsaturated bond in the side chain, thereby increasing the photocuring strength. Increases. Herein, as the unsaturated group, one having a carbon-carbon double bond is particularly preferable because crosslinking reaction is likely to occur.

As a method of introducing an unsaturated group into a polymer terminal, there exists a method shown below. In other words, alcohols or amines having an unsaturated group may be used in the step of treating the remaining isocyanate groups at the polymer end with alcohols or amines in the step of synthesizing a polyurethane resin having an ethylenically unsaturated bond in the side chain described above. As such a compound, specifically, the same thing as the exemplary compound listed as a monofunctional alcohol or a monofunctional amine compound which has an unsaturated group first is mentioned.

Moreover, it is preferable to introduce an unsaturated group into a polymer side chain rather than a polymer terminal from a viewpoint that the introduction amount can be controlled easily, an introduction amount can be increased, and crosslinking reaction efficiency improves.

There is no restriction | limiting in particular as an ethylenically unsaturated bond group introduce | transduced, Although it can select suitably according to the objective, From a point of crosslinking cured film formation property, a methacryloyl group, an acryloyl group, a styryl group is preferable, and a methacryloyl group and an acryl A diary is more preferable, and a methacryloyl group is especially preferable at the point of the compatibility of the formation property of a crosslinked cured film, and biopreservation.

There is no restriction | limiting in particular as an introduction amount of a methacryloyl group, Although it can select suitably according to the objective, As ethylenically unsaturated group equivalent, 0.05 mmol / g-3.0 mmol / g are preferable, and 0.5 mmol / g-2.7 mmol / g is more preferable, 0.75 mmol / g-2.5 mmol / g are still more preferable, and 1.00 mmol / g or more (preferably 1.00 mmol / g-2.5 mmol / g) is especially preferable.

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

In the present invention, as the acid-modified polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention, an acid-modified polyurethane resin having at least one carboxyl group at the terminal of the polymer main chain is also suitable in view of excellent developability of the non-image portion by the alkaline developer. Is used. It is preferable to have at least 1 carboxyl group at the terminal of a polymer main chain, and to have 2 or more and 5 or less carboxyl groups, and having two carboxyl groups is especially preferable at the point of developability and fine pattern formation property.

In addition, although the terminal of the main chain in the said polyurethane resin has two, it is preferable to have at least 1 carboxyl group at the one end, and may have at least 1 carboxyl group at both ends.

It is preferable to have a structure represented by the following general formula (AD) at the terminal of the main chain of the said polyurethane resin.

General formula (AD)

-L ^100- (COOH) _n

In the formula (AD), L ¹⁰⁰ is (n + 1) represents a monovalent organic connecting chain, n represents an integer of 1 or more, and is preferably 1 to 5, is 2 are particularly preferred.

The organic linking group represented by L ¹⁰⁰ comprises one or more atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, and specifically constitutes the main skeleton of the organic linking groups represented by L ¹⁰⁰ . 1-30 are preferable, as for atomic number, 1-25 are more preferable, 1-20 are more preferable, and 1-10 are especially preferable.

In addition, the said "main skeleton of an organic linking group" means the atom or atom group used only for connecting the main chain and terminal COOH of the said polyurethane resin, and when there are multiple connection paths, it comprises the path which has the smallest number of atoms used. Refers to an atom or group of atoms.

There is no restriction | limiting in particular as a method of introduce | transducing at least 1 carboxyl group into the terminal of the principal chain of the said polyurethane resin, According to the objective, it can select suitably, For example, the carboxyl which has at least 1 carboxyl group as a raw material of polyurethane resin manufacture. The method of using an acid compound, etc. are mentioned.

Examples of the carboxylic acid compound include monocarboxylic acid compounds having one carboxyl group, dicarboxylic acid compounds having two carboxyl groups, tricarboxylic acid compounds having three carboxyl groups, tetracarboxylic acid compounds having four carboxyl groups, Pentacarboxylic acid compound etc. which have five carboxyl groups are mentioned. Among these, the dicarboxylic acid compound which has two carboxyl groups is especially preferable at the point which is excellent in developability and a fine pattern formation property.

There is no restriction | limiting in particular if it has at least 1 carboxyl group as said carboxylic acid compound, Although it can select suitably according to the objective, The compound represented by the following general formula (ADH) is suitable.

General formula (ADH)

HOL ²⁰⁰ -Y ¹⁰⁰ -L ^100- (COOH) n

In General Formula (ADH), L ¹⁰⁰ and n have the same meanings as those of General Formula (AD). Y ¹⁰⁰ represents a divalent or higher atom. L ²⁰⁰ represents an alkylene group which may have a single bond or a substituent.

As the two or more atoms of the Y ^100, for example, an oxygen atom, a nitrogen atom, a carbon atom, a silicon atom. Among these, a nitrogen atom and a carbon atom are especially preferable. Here, the valence divalent or higher represented by Y ¹⁰⁰ means that at least Y ¹⁰⁰ has two bonds to which the terminal —COOH bonds through L ¹⁰⁰ and L ²⁰⁰ , but Y ^{100 further} represents a hydrogen atom or a substituent You may have it.

Examples of the substituent that can be introduced into Y ¹⁰⁰ include a substituent including an atom selected from a hydrogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom. Among these, a hydrocarbon group having 1 to 50 carbon atoms is preferable, a hydrocarbon group having 1 to 40 carbon atoms is more preferable, and a hydrocarbon group having 1 to 30 carbon atoms is particularly preferable.

As an alkylene group in L ²⁰⁰ , an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 2 to 10 carbon atoms is more preferable. As a substituent which can be introduce | transduced into the said alkylene group, the halogen atom (-F, -Br, -Cl, -I), the alkyl group which may have a substituent, etc. are mentioned, for example.

There is no restriction | limiting in particular as a carboxylic acid compound represented by said general formula (ADH), According to the objective, it can select suitably, For example, the reaction material of lactic acid, malic acid, hydroxyhexanoic acid, a citric acid, a diol compound, an acid anhydride, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, malic acid is especially preferable.

As a specific example of the polyurethane resin (i) used by this invention, the polymer of P-1-P-31 shown by stage of Unexamined-Japanese-Patent No. 2005-250438, etc. are mentioned, for example. Can be. Among these, polymers of P-27 and P-28 shown in paragraphs [0308] and [0309] are preferable.

The polyurethane resin which has an ethylenically unsaturated bond in the side chain used by this invention is synthesize | combined by heating the said diisocyanate compound and a diol compound by adding the well-known catalyst of the activity according to each reactivity in an aprotic solvent. And treated with 1 are preferred, alcohols or amines, such as the molar ratio of diisocyanate and diol compounds used in synthesis (M _a: M _b) it is not particularly limited and can be suitably selected according to the purpose, 1: 1 to 1.2 As a result, a product having a desired physical property such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains.

The polyurethane resin which has an ethylenically unsaturated bond in the side chain used by this invention especially has the above-mentioned diisocyanate compound, the (meth) acrylate compound which has two hydroxyl groups in a molecule as a diol compound, and has two hydroxyl groups in a molecule | numerator. It is preferable to obtain by making a carboxylic acid and the above-mentioned polymer diol compound react, and in addition, it is preferable to react by obtaining the compound which has one hydroxyl group and carboxyl group represented by general formula (ADH).

Polyurethane resin (ii)

The polyurethane resin (ii) is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in a molecule.

Polyurethane resin (ii) is a polyurethane resin obtained by making the carboxyl group-containing polyurethane resin which has diisocyanate and carboxyl group-containing diol as an essential component, and the compound which has an epoxy group and ethylenically unsaturated group in a molecule | numerator react. According to the objective, as a diol component, you may add the low molecular weight diol of the mass mean molecular weight 300 or less, and the low molecular weight diol of the mass mean molecular weight 500 or more as a copolymerization component.

Polyurethane resin (ii) is excellent in the stable dispersibility, crack resistance, or impact resistance with an inorganic filler, and it improves heat resistance, moisture heat resistance, adhesiveness, mechanical characteristics, and electrical characteristics by using this.

As the polyurethane resin (ii), a diisocyanate of a divalent aliphatic and aromatic hydrocarbon which may have a substituent and a carboxyl group-containing diol having a COOH group and two OH groups through either C atom or N atom as essential components As one reactant, the obtained reactant may be obtained by reacting a compound having an epoxy group and an ethylenically unsaturated group in a molecule via a -COO- bond.

Moreover, as said polyurethane resin (ii), the diisocyanate represented by the following general formula (I) and the carboxyl group-containing diol compound represented by General formula (17)-(19) demonstrated in the above-mentioned polyurethane resin (i) At least one selected from polymeric diols having as essential components at least one member selected from and having a mass average molecular weight represented by the following general formulas (III-1) to (III-6) in the range of 800 to 3,000 according to the purpose. As a reactant, what is obtained by making the obtained reactant react with the compound which has an epoxy group and ethylenically unsaturated group in the molecule | numerator represented by following General formula (IV-1)-(IV-16) may be sufficient.

OCN-R ₁ -NCO general formula (I)

In general formula (I), R <_1> represents the bivalent aliphatic or aromatic hydrocarbon group which 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). . As needed, R <_1> may have another functional group which does not react with an isocyanate group, for example, ester group, urethane group, amide group, and ureido group.

In General Formulas (III-1) to (III-3), each of R ₇ to R ₁₁ independently represents a divalent aliphatic or aromatic hydrocarbon group. R ₇ , R ₉ , R ₁₀ and R ₁₁ are each preferably a C2-C20 alkylene group or a C6-C15 arylene group, each having a C2-C10 alkylene group or a C6-C10 aryl group. More preferably. R <_8> represents a C1-C20 alkylene group or a C6-C15 arylene group, and its C1-C10 alkylene group or a C6-C10 arylene group is more preferable. Moreover, in R <_7> -R <_11> , another functional group which does not react with an isocyanate group, for example, an ether group, a carbonyl group, ester group, cyano group, an olefin group, a urethane group, an amide group, a ureido group, or a halogen atom may be sufficient.

In 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. Hydrogen atom, C1-C10 alkyl group, C6-C15 aryl group, C7-C15 aralkyl group, cyano group, or a halogen atom is preferable, A hydrogen atom, C1-C6 alkyl group, and C6 More preferably, 10 to 10 aryl groups are used. In addition, in R _12, there may be other functional groups that do not react with isocyanate groups, for example, alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms. m represents the integer of 2-4.

In general formula (III-5), R <_13> represents an aryl group or a cyano group, and a C6-C10 aryl group or cyano group is preferable.

In formulas (III-1) to (III-6), n ₁ , n ₂ , n ₃ , n ₄ , n ₅ , n ₇ , n _8, and n ₉ each represent a number of 2 or more, and 2 The number of -100 is preferable. In said general formula (III-5), n <_6> represents the number of 0 or 2 or more, and the number of 0 or 2-100 is preferable.

In 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 hydrocarbon group having 1 to 10 carbon atoms. . p represents 0 or the number of 1-10.

In addition, when a carboxyl group-containing polyurethane and a compound having an epoxy group or an oxetane group are reacted in a molecule, X, Y or Z is a hydroxyl group or acyl at a -CO _2- (β or γ position in a partial structure connected to the polyurethane main chain. It becomes a structure which has an oxy group substituted aliphatic group)-(*). Here, the partial structure of General formula (1)-(3) exists in (*) side.

Further, the polyurethane resin (ii) may further copolymerize a carboxyl group-free low molecular weight diol as a fifth component, and the low molecular weight diol compound is represented by the above general formulas (III-1) to (III-6). The mass average molecular weight is 500 or less. The said carboxyl group-free low molecular weight diol can be added in the range which can maintain sufficiently low the elasticity modulus of a cured film, as long as alkali solubility does not fall.

As said low molecular weight diol compound, the compound etc. which were described in Paragraph [0048] of Unexamined-Japanese-Patent No. 2007-2030 are mentioned, for example.

Especially as said polyurethane resin (ii), at least 1 sort (s) chosen from the diisocyanate represented by the said General formula (I) and the carboxyl group-containing diol represented by the said General formula (17)-(19) as an essential component And at least one selected from polymer diols having a mass average molecular weight represented by the formulas (III-1) to (III-6) in the range of 800 to 3,000, depending on the purpose, or the formulas (III-1) to (III) One epoxy group in the molecule | numerator represented by either of the general formula (IV-1)-(IV-16) to the reaction product with the low molecular weight diol which does not contain a carboxyl group of 500 or less mass mean molecular weight represented by -6) Alkali-soluble photocrosslinkable polyurethane resin whose acid value is 20 mgKOH / g-120 mgKOH / g obtained by making the compound which has at least 1 (meth) acryl group react is suitable.

Moreover, also in the said polyurethane resin (ii), General formula (U) demonstrated by the above-mentioned polyurethane resin (i) instead of or in combination with the compound represented by said general formula (III-1)-(III-6). It is preferable to use the diol compound represented by), and the mass ratio of the partial structure represented by said general formula (U1) in the acid-modified ethylenically unsaturated group containing polyurethane resin is the polyurethane resin (i) mentioned above. Same as

These high molecular compounds may be used individually by 1 type, and may use 2 or more types together.

Also in the polyurethane resin (ii), it is preferable to have at least one carboxyl group at the terminal of the polymer main chain in order to obtain the same effect as that of the polyurethane resin (i), and to obtain the polymer main chain as described in the polyurethane resin (i). The group represented by the terminal sealing method and general formula (A) is preferable, and its preferable range is also the same as a polyurethane resin (i).

As said polyurethane resin (ii), the epoxy group and vinyl group containing compound in the polymer of U1-U4, U6-U11 shown, for example by Unexamined-Japanese-Patent No. 2007-2030, Paragraph-[0314]-[0315]. Glycidyl acrylate as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400, Daicel Kagaku Co., Ltd.), 3,4-epoxycyclohexylmethyl The polymer etc. which changed into methacrylate (brand name: cyclomer M400, the Daicel Kagaku Co., Ltd. product) are mentioned.

Synthesis method of polyurethane resin (ii) obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in a molecule-

As the synthesis method of the said polyurethane resin (ii), the said diisocyanate compound and the diol compound are synthesize | combined by adding the well-known catalyst of the activity according to each reactivity in an aprotic solvent, and heating. The molar ratio of the diisocyanate to be used and the diol compound is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the polymer terminal, the molar ratio of the diisocyanate and diol compound to be used is synthesized in the form in which the isocyanate group does not finally remain by treatment with alcohols or amines.

<< content of acid-modified ethylenically unsaturated group containing polyurethane resin >>

In addition to the acid-modified ethylenically unsaturated group-containing polyurethane resin, the photosensitive resin composition of this invention uses together alkali-soluble polymer which contains the polyurethane resin which has a structure different from the acid-modified ethylenically unsaturated group-containing polyurethane resin. It is possible. For example, it is possible to use together the polyurethane resin which has an aromatic group in a main chain and / or a side chain together with the polyurethane resin which has an ethylenically unsaturated bond in the said side chain.

There is no restriction | limiting in particular as content of the acid-modified ethylenically unsaturated group containing polyurethane resin in solid content of the photosensitive resin composition of this invention, Although it can select suitably according to the objective, 5 mass%-80 mass% are preferable, and 20 mass % -75 mass% is more preferable, and 30 mass%-70 mass% are especially preferable.

When the said content is too low, it may not be able to maintain favorable cut resistance, On the contrary, when too high, heat resistance may cause breakage. If the said content is in the said range, it is advantageous at the point of favorable compatibility of heat resistance and heat resistance.

`` (Meth) acrylic resin containing an acid group and an ethylenically unsaturated group≫

As an acidic group, a carboxyl group is preferable and as an ethylenically unsaturated group, an acryloyl group, a methacryloyl group, an allyl group, a vinyl ether group, and a vinylphenyl group are preferable.

As (meth) acrylic resin containing an acidic group and an ethylenically unsaturated group, the copolymer (henceforth "copolymer") obtained from the (meth) acrylic acid ester and the compound which has an ethylenically unsaturated group and has at least 1 acidic group may be called. It is preferable from the point which is excellent in heat resistance that it is a modified copolymer (henceforth a "modified copolymer" may be called) obtained by making some acidic groups of) react with the compound which has an epoxy group and ethylenically unsaturated group in a molecule | numerator. In addition, as mentioned above, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester.

The raw material of each reaction in the above is demonstrated below.

(Meth) acrylic acid ester

As said (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth), for example (Meth) acrylic-acid alkylesters, such as an acrylate; (Meth) which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone modified 2-hydroxyethyl (meth) acrylate Acrylic esters; Benzyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, meth (Meth) acrylates, such as methoxy triethylene glycol (meth) acrylate and methoxy polyethyleneglycol (meth) acrylate, etc. are mentioned. Among these, benzyl (meth) acrylate is preferable at the point of low water absorption.

A compound containing an ethylenically unsaturated group and having at least one acid group

Examples of the compound containing the ethylenically unsaturated group and having at least one acid group include acrylic acid, methacrylic acid, vinylphenol, a modified unsaturated monocarboxylic acid extending in chain between ethylenically unsaturated group and carboxyl group, and the like. .

Here, as a modified unsaturated monocarboxylic acid, (beta) -carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxy ethyl phthalic acid, 2-acryloyloxy ethyl hexa, for example And unsaturated monocarboxylic acids having ester bonds such as hydrophthalic acid and lactone modification, and modified unsaturated monocarboxylic acids having ether bonds.

These may be used individually by 1 type and may use 2 or more types together.

In addition to the above, you may further copolymerize with the monomer which has an ethylenically unsaturated group for copolymerization with (meth) acrylic acid ester and / or (meth) acrylic acid. Examples of such monomers include (meth) acrylic acid amide, (meth) acrylonitrile, styrene, styrene in which a sulfo group and a carboxyl group are substituted with a benzene ring, vinyl chloride, vinyl acetate, ethylene, butadiene, and the like.

As said lactone modified unsaturated monocarboxylic acid, it is a compound which specifically modified (meth) acrylic acid by lactone, for example, The compound represented by the following general formula (AC-1) is mentioned, A terminal hydroxyl group is used for an acid anhydride. Examples of the lactone-modified unsaturated monocarboxylic acid acid-modified by the compound include compounds represented by the following General Formula (AC-2), and examples of the modified unsaturated monocarboxylic acid having an ether bond are represented by the following General Formula (AC-3). Losing compound is mentioned.

In General Formulas (AC-1) to (AC-3), R ^AC1 represents a hydrogen atom or a methyl group, R ^AC2 and R ^AC3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m ^ac1 to m ^ac3 respectively independently represents the integer of 4-8, n ^ac1- n ^ac3 represents the integer of 1-10 each independently. Here, some R <^AC2> and R <^AC3> may mutually be same or different. L ^AC1 is a C1-C10 divalent aliphatic saturated hydrocarbon group, a C2-C10 divalent unsaturated hydrocarbon group, a C3-C6 divalent alicyclic saturated hydrocarbon group, a divalent aromatic group (preferably a phenylene group) Or a bivalent heterocyclic group (preferably a 5 or 6 membered ring and having a oxygen atom, a sulfur atom, or a nitrogen atom in a ring constituent atom). Each group in L ^AC1 may have a substituent. As these substituents, the group illustrated by the organic group or substituent of R <^1> -R <^11> in above-mentioned general formula (1)-(3) is mentioned.

In formula (AC-2), R ^AC2 and R ^AC3 are preferably a hydrogen atom, a methyl group or an ethyl group. In formula (AC-2), R ^AC2 and R ^AC3 are a hydrogen atom, a methyl group, an ethyl group, or a propyl group. Group or butyl group is preferred.

-Compound which has epoxy group and ethylenically unsaturated group in molecule-

There is no restriction | limiting in particular as a compound which has an epoxy group and ethylenically unsaturated group in a molecule | numerator, It can select suitably according to the objective, In the polyurethane resin (ii) in the above-mentioned acid-modified ethylenically unsaturated group containing polyurethane resin The compound which has an epoxy group and ethylenically unsaturated group in a molecule | numerator is preferable, and a preferable range is also the same.

Specifically, the above general formulas (IV-1) to (IV-16) are preferable, and glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are more preferable. Among these, glycidyl (meth) acrylate is especially preferable.

-Method for producing (meth) acrylic resin containing acid group and ethylenically unsaturated group-

As a manufacturing method of the (meth) acrylic resin containing an acidic radical and an ethylenically unsaturated group, the example is demonstrated below about the manufacturing method of the said modified copolymer.

First, the copolymer is prepared. There is no restriction | limiting in particular as a manufacturing method of the said copolymer, According to the objective, it can select suitably, For example, the manufacturing method of well-known acrylic resins, such as solution polymerization, is mentioned.

Subsequently, it produces by adding the compound which has an epoxy group and ethylenically unsaturated group in a molecule | numerator to some acidic groups of the said copolymer.

There is no restriction | limiting in particular as said addition amount, According to the objective, it can select suitably.

In the said addition, it is preferable to use a solvent and a catalyst.

There is no restriction | limiting in particular as a solvent, According to the objective, it can select suitably, For example, the solvent of Paragraph [0020] of Unexamined-Japanese-Patent No. 2009-086376, etc. are mentioned.

There is no restriction | limiting in particular as a catalyst, According to the objective, it can select suitably, For example, the catalyst as described in Paragraph [0021]-[0025] of Unexamined-Japanese-Patent No. 2009-086376 is mentioned.

Examples of the (meth) acrylic resin containing an acid group and an ethylenically unsaturated group include the exemplified compounds described in Japanese Patent Application Laid-Open No. 2010-128275, the compounds used, and the production method described in the patent publication or this. It can manufacture by a standard manufacturing method.

<< acid-modified ethylenically unsaturated group containing epoxy resin >>

In the present application, the acid-modified ethylenically unsaturated group-containing epoxy resin is a resin obtained from an epoxy resin as described above, and the chemical structure is a polyether resin of 2) described above and a novolak resin of 3). For convenience, these are called epoxy resins.

The acid-modified ethylenically unsaturated group-containing epoxy resin may be any epoxy number as long as it has an acid group and an ethylenically unsaturated group.

The acid-modified ethylenically unsaturated group-containing epoxy resin is preferably a resin having a partial structure represented by the following general formula (EP).

In general formula (EP), R <^A1> and R <^A2> represent an unsaturated aliphatic group in which one is unsaturated, and the other shows the aromatic group which has a saturated or unsaturated aliphatic group or carboxyl group which has a carboxyl group. R ^EP1 to R ^EP3 each independently represent a hydrogen atom or a substituent.

The partial structure represented by said general formula (EP) is obtained by reaction of (a) epoxy resin, (b) unsaturated group containing monocarboxylic acid, and (c) polybasic acid anhydride.

That is, the unsaturated aliphatic group in general formula (EP) is group derived from an unsaturated group containing monocarboxylic acid, and is group obtained by removing -COOH from this unsaturated group containing monocarboxylic acid. On the other hand, a saturated or unsaturated aliphatic group having a carboxyl group or an aromatic group having a carboxyl group is a group obtained from a polybasic acid anhydride, for example, a group in a rectangular frame as described below.

Examples of the unsaturated aliphatic group in the formula ^{(EP), -C (R 1} ) = C (R 2 in the general formula (1) in the polyurethane resins containing ethylenically unsaturated groups of the acid modification of the above (R ³ ) is preferred. Here, R ¹ ~R ³ is R ¹ ~R ³ and agreed in the general formula (1) Also, the preferable range is the same.

Examples of the above unsaturated aliphatic group include vinyl group, α-methylvinyl group, β-methylvinyl group, β-furfurylvinyl group, β-styrylvinyl group, β-phenylvinyl group and α-cyano-β-phenylvinyl And 1,3-pentadienyl group.

Moreover, when illustrated as unsaturated group containing monocarboxylic acid in said (b), For example, acrylic acid, a dimer of acrylic acid, methacrylic acid, (beta) -furfuryl acrylic acid, (beta) -styryl acrylic acid, cinnamic acid, crotonic acid , α-cyano cinnamic acid, sorbic acid and the like can be used. In addition, a semiester compound which is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated group-containing dibasic anhydride, an unsaturated group-containing monoglycidyl ether or an unsaturated group-containing monoglycidyl ester and a saturated or unsaturated group-containing dibasic acid anhydride The half ester compound which is a reaction product can be used. Here, a semiester compound means the compound in which only one of two carboxyl groups was esterified, for example. These (b) unsaturated group containing monocarboxylic acids can be used individually or in combination of 2 or more types.

The semiester compound can be obtained by reacting a hydroxyl group-containing acrylate or an unsaturated group-containing mono glycidyl ether or an unsaturated group-containing monoglycidyl ester with a saturated or unsaturated group-containing dibasic anhydride in an equimolar ratio.

As the hydroxyl group-containing acrylate, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol Monoacrylate, polyethylene glycol monomethacrylate, trimetholpropanediacrylate, trimetholpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipenta Erythritol hexamethacrylate, glycidyl acrylate, glycidyl methacrylate and the like can be used.

As unsaturated group containing monoglycidyl ether or unsaturated group containing monoglycidyl ester, glycidyl (meth) acrylate etc. can be used.

As an aromatic group which has a saturated or unsaturated aliphatic group or carboxyl group which has a carboxyl group in general formula (EP), As a saturated or unsaturated aliphatic group which has a carboxy group, it is an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and a carboxyl group. The group which substituted is mentioned, As an aromatic group which has a carboxy group, the group by which the carboxyl group was substituted by the phenyl group is mentioned.

Illustrating as polybasic acid anhydride, as saturated or unsaturated group containing dibasic anhydride, for example, succinic anhydride, maleic anhydride, tetrahydro phthalic anhydride, phthalic anhydride, methyltetrahydro phthalic anhydride, ethyl tetrahydro phthalic anhydride, hexahydro phthalic anhydride , Methyl hexahydro phthalic anhydride, ethyl hexahydro phthalic anhydride, itaconic anhydride and the like can be used.

R ^EP1 to R ^EP3 in General Formula (EP) each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

It is preferable that the acid-modified ethylenically unsaturated group containing epoxy resin in this invention is an epoxy resin represented by either of the following general formula (P1)-(P3).

In General Formulas (P1) to (P3), R ^e1 represents a group or an epoxy group represented by General Formula (EP). R ^e2 and R ^e3 each independently represent a hydrogen atom or a methyl group, and R ^e4 to R ^e9 each independently represent a hydrogen atom, an alkyl group or an aryl group. n ^e1 and n ^e2 each independently represent one or more numbers, and n ^e3 represents zero or one or more numbers. However, all of R ^e1 in the molecule are not epoxy groups. The plurality of R ^e1 's present in the molecule may be the same as or different from each other, and the plurality of R ^e2 and R ^e3 present in the molecule may be the same as or different from each other. R ^e4 in ~R ^e9, each of the plurality of R ^e4 ~R ^e9 present in the molecule may be different, respectively are equal to each other.

As an acid-modified ethylenically unsaturated group containing epoxy resin, the epoxy resin of Paragraph [0107]-[0111] of Unexamined-Japanese-Patent No. 2007-256943, the epoxy resin of Unexamined-Japanese-Patent No. 2006-11395, especially illustrative resin It can be manufactured easily by the manufacturing method described in phosphorus EPA-1-EPA-3, these patent publications, or this.

In addition, acid-modified ethylenically unsaturated group containing epoxy resin is a commercial item, for example, ZAR-1626H (acid-modified bisphenol A type epoxy acrylate), ZAR-2003H (acid-modified bisphenol A type epoxy acrylate, mass average molecular weight: 13000, acid value: 82 mgKOH / g), ZFR-1158 (acid-modified bisphenol F type epoxy acrylate, mass average molecular weight: 10000, acid value: 60 mgKOH / g), ZFR-1492H (bisphenol F type acid-modified ethylenically unsaturated group-containing epoxy Resin), ZCR-1534 (biphenyl aralkyl type acid-modified ethylenically unsaturated group-containing epoxy resin), ZCR-1569H (novolak-type acid-modified vinyl group-containing epoxy resin having a biphenyl skeleton, mass average molecular weight: 4,500, acid value: 98 mgKOH / g). CCR-1219H (cresol novolak type epoxy acrylate), PCR-1050 (acid-modified phenol novolak type epoxy acrylate) [above, Nippon Kayaku Co., Ltd. product], EXP-2811 [containing tricyclodecane structure Acid modified epoxy acrylate containing tricyclodecane structure modified | denatured epoxy resin (EPICLON HP-7200, DIC Corporation make, brand name), EXP-2810 (acid-modified cresol novolak-type epoxy acrylate) [above, all DIC Corporation make, and PR-300P-commercial paper (cresol novolak-type acid-modified ethylenically unsaturated group containing epoxy resin) (the Showa Kobunshi Corporation make) are mentioned.

<< acid-modified ethylenically unsaturated group containing polyester resin >>

There is no restriction | limiting in particular as acid-modified ethylenically unsaturated group containing polyester resin, According to the objective, it can select suitably, In this invention, especially acid-modified polyester resin which has an ethylenically unsaturated bond in a side chain is preferable. In this invention, a side chain is as having demonstrated with the above-mentioned acid-modified ethylenically unsaturated group containing polyurethane resin.

As an acidic group, a carboxyl group is preferable and as an ethylenically unsaturated group, it has at least 1 of the functional groups represented by General Formula (1)-(3) in the above-mentioned acid-modified ethylenically unsaturated group containing polyurethane resin in the side chain. It can be mentioned. These ethylenically unsaturated groups are the same as the preferable range in the above-mentioned acid-modified ethylenically unsaturated group containing polyurethane resin.

In order to introduce an ethylenically unsaturated group into a side chain, (iii) the method of obtaining an ethylenically unsaturated group by the polymerization reaction with the compound which has a dicarboxyl compound or a diol compound, (iv) a carboxyl group-containing polyester, and an epoxy group and ethylene in a molecule | numerator There is a method obtained by reacting a compound having a unsaturated group.

Method (iii) of introducing an ethylenically unsaturated group into the side chain is polymerized with a compound having (i) an ethylenically unsaturated group in a diisocyanate compound or a diol compound in the acid-modified ethylenically unsaturated group-containing polyurethane resin described above. The method (iv) which introduce | transduces an ethylenically unsaturated group into the said side chain corresponding to the method obtained by reaction, The acid-modified ethylenically unsaturated group containing polyester resin in the above-mentioned acid-modified ethylenically unsaturated group containing polyurethane resin is It corresponds to the method obtained by making (ii) carboxyl group-containing polyurethane and acid-modified ethylenically unsaturated group react in the molecule | numerator in said acid-modified ethylenically unsaturated group containing polyurethane resin.

That is, it can manufacture easily only by substituting a diisocyanate compound by a dicarboxyl compound.

In addition, polyester resins containing ethylenically unsaturated groups of the acid-modified is of the polyurethane resin containing ethylenic unsaturated group of the acid-modified of the above general formula, such as -NCO, or the term of "Isocyanate", -CO ₂ H, " By the term "carboxyl", the preferred range of the acid-modified ethylenically unsaturated group-containing polyester resin is the same as the acid-modified ethylenically unsaturated group-containing polyurethane resin.

However, the manufacturing method of a polyester resin can use not only a dicarboxyl compound but an acid anhydride, ester, and an acid halide, and can manufacture it easily by a normal esterification reaction.

The acid-modified ethylenically unsaturated group-containing polyester resins include the polyester resins described in JP-A-2007-128059, especially the resin (1) described in paragraph [0058], and the production method described in the publication or this It can manufacture easily by a manufacturing method according to the above.

<< acid-modified ethylenically unsaturated group containing polyamide or polyimide resin >>

There is no restriction | limiting in particular as acid-modified ethylenically unsaturated group containing polyamide or polyimide resin, According to the objective, it can select suitably. As an acidic group, a carboxyl group is preferable and what has at least 1 of the functional groups represented by General formula (1)-(3) in the above-mentioned acid-modified ethylenically unsaturated group containing polyurethane resin as an ethylenically unsaturated group is mentioned. have. These ethylenically unsaturated groups are the same as the preferable range in the above-mentioned acid-modified ethylenically unsaturated group containing polyurethane resin.

As acid-modified ethylenically unsaturated group containing polyamide resin, what has a partial structure represented by the following general formula (PI-1) is mentioned, for example.

In general formula (PI-1), L ^PI1 represents a tetravalent organic group, L ^PI2 represents a divalent organic group, and R ^PI1 and R ^PI2 each represent a hydroxyl group and the other represents a group having an ethylenically unsaturated group. .

The number of carbon atoms of L ^PI1 is 6-32 are preferred, and a carbon number of 4-30 L ^PI2 are preferred.

The partial structure in general formula (PI-1) is a partial structure obtained by condensing tetracarboxylic acid or its derivative (anhydride, ester or acid halide) and diamine.

L ^PI1 is preferably the following.

In the above, L ^PI3 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O-, -S-,- SO ₂ -or -C (= 0)-.

L ^PI2 is preferably the following.

In the above, L ^PI4 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O-, -S-,- SO ₂ —, —C (═O) —, —CH═CH— or —NHC (═O) —.

R ^PI3 to R ^PI5 each independently represent a hydrogen atom or a substituent, and as the substituent, a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom), an alkyl group (for example, methyl, trifluoromethyl, ethyl, t -Butyl) and an alkoxy group (for example, methoxy and ethoxy).

The acid-modified ethylenically unsaturated group-containing polyamide resin having the partial structure represented by the general formula (PI-1) is easily produced by the production method described in JP-A-2009-230098 or a production method according to the same. can do.

As acid-modified ethylenically unsaturated group containing polyimide resin, what has a partial structure represented by the following general formula (PI-2) is mentioned further.

In general formula (PI-2), A ^PI1 and A ^PI2 each independently represent a tetravalent organic group, and B ^PI1 represents -CO ₂ -CONH-R ^PI3 , -CONH-R ^PI3 , -NHCONH-R ^PI3 or The divalent organic group containing -SCONH-R ^PI3 is shown. Here, R ^PI3 is an ethylenically unsaturated group _{^{or, -L PI5 -NHCO 2 -R PI4,}} -L PI5 -NHCO 2 -CO-R PI4, -L PI5 -NHCO-R PI4, -L PI5 -NHCONH-R ^PI4 or -L ^PI5 -NHCO-SR ^PI4 . Here, ^LPI5 represents a saturated or unsaturated divalent organic group, C1-C20 is preferable and may be substituted by the substituent. R ^PI4 represents a group having an ethylenically unsaturated group, and -C (R ¹ ) = C (R ² ) (R ³ ) is preferable. Where R ¹ ~R ³ is the general formula ⁽¹⁾ R 1 ~R ³ and consent of the polyurethane resins containing ethylenically unsaturated groups of the above-mentioned acid-modified Also, the preferable range is the same.

Specific examples of the acid-modified ethylenically unsaturated group-containing polyimide resin represented by General Formula (PI-2) include the exemplified compounds described in JP-A-2009-167414, in particular the compounds produced in Examples. .

In addition, the acid-modified ethylenically unsaturated group containing polyimide resin represented by general formula (PI-2) can be manufactured easily by the manufacturing method of Unexamined-Japanese-Patent No. 2009-167414, or the manufacturing method according to this. .

Examples of the acid-modified ethylenically unsaturated group-containing non-polyurethane resin include (meth) acrylic resins containing an acid group and an ethylenically unsaturated group, polyether resins of an acid-modified ethylenically unsaturated group-containing epoxy resin [i.e. 2), and 3 Novolak-type resins).

The preferable molecular weight, acid value, and ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing non-polyurethane resin to be used in the present invention, and the content in the photosensitive resin composition solid content are selected from the acid-modified ethylenically unsaturated group-containing polyurethane resin. It is the same as content in preferable molecular weight, acid value, and ethylenically unsaturated group equivalent, and photosensitive resin composition solid content.

Moreover, when using 2 or more types of acid-modified ethylenically unsaturated group containing resin, it is preferable to make the total content of acid-modified ethylenically unsaturated group containing resin into the said preferable content.

<Radical polymerizable monomer>

There is no restriction | limiting in particular as a radically polymerizable monomer, Although it can select suitably according to the objective, The compound which has one or more functional groups which have an ethylenically unsaturated group is preferable.

As a functional group which has the said ethylenically unsaturated group, a (meth) acryloyl group, a (meth) acrylamide group, a vinylphenyl group, a vinyl ester group, a vinyl ether group, an allyl ether group, an allyl ester group, etc. are mentioned, for example.

There is no restriction | limiting in particular as a compound which has one or more functional groups which have the said ethylenically unsaturated group, Although it can select suitably according to the objective, At least 1 sort (s) chosen from the monomer which has a (meth) acryl group is preferable.

There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) Monofunctional acrylates and monofunctional methacrylates, such as a) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimetholethane triacrylate, trimetholpropane triacrylate, trimetholpropane diacrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, dimethrol tree Cyclodecane di (meth) acrylate; (Meth) acrylated after addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols such as trimetholpropane, glycerin and bisphenol; Polyfunctional acrylates, methacrylates, etc., such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among these, trimethol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dimethol tricyclodecane di (meth) ) Acrylates are particularly preferred.

There is no restriction | limiting in particular as content in the said photosensitive resin composition solid content of the said radically polymerizable monomer, Although it can select suitably according to the objective, 3 mass%-50 mass% are preferable, and 5 mass%-40 mass% are more preferable. . If the said content is less than 3 mass%, exposure sensitivity will deteriorate, and when it exceeds 50 mass%, the adhesiveness of a photosensitive layer may become strong too much.

<Heat cross-linking>

There is no restriction | limiting in particular as said thermal crosslinking agent, According to the objective, it can select suitably, In order to improve the film strength after hardening of a photosensitive layer, for example, an epoxy compound (for example, 1) in the range which does not adversely affect developability etc. An epoxy compound having at least two oxirane groups in a molecule), an oxetane compound having at least two oxetanyl groups in one molecule, a polyisocyanate compound, a compound obtained by reacting a blocking agent with an isocyanate group of a polyisocyanate or a derivative thereof (blocking poly Isocyanate compound) etc. are mentioned.

There is no restriction | limiting in particular as content in the said photosensitive resin composition solid content of the said thermal crosslinking agent, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, and 3 mass%-30 mass% are more preferable. The film strength of a cured film improves that the said content is 1 mass% or more, and developability and exposure sensitivity will become favorable when it is 50 mass% or less.

As said epoxy compound, the epoxy compound etc. of Paragraph [0071]-[0073] of Unexamined-Japanese-Patent No. 2010-256399 are mentioned, for example.

As said oxetane compound, the oxetane compound described in Paragraph [0074] of Unexamined-Japanese-Patent No. 2010-256399, etc. are mentioned, for example.

As said polyisocyanate compound, the polyisocyanate compound etc. of Paragraph [0075] of Unexamined-Japanese-Patent No. 2010-256399 are mentioned, for example.

As said blocked polyisocyanate compound, the blocked polyisocyanate compound etc. of Paragraph [0076] of Unexamined-Japanese-Patent No. 2010-256399 are mentioned, for example.

As said melamine derivative, the melamine derivative etc. which were described, for example in Paragraph [0077] of Unexamined-Japanese-Patent No. 2010-256399 are mentioned.

<Photopolymerization initiator>

There is no restriction | limiting in particular as a photoinitiator as long as it has the ability to start superposition | polymerization of the said radically polymerizable monomer, Although it can select suitably according to the objective, For example, what has photosensitivity with respect to visible light from an ultraviolet range, An activator which generates an active radical by generating any action with the excited sensitizer may be used, or an initiator that initiates cationic polymerization depending on the type of monomer.

Examples of the photopolymerization initiator include (bis) acylphosphine oxides or esters thereof, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime derivatives, organic peroxides, Thio compounds, and the like. Among these, an oxime derivative, (bis) acyl phosphine oxide or its ester, an acetophenone type compound, a benzophenone type compound, from a viewpoint of the sensitivity, storage property, and adhesiveness of a photosensitive layer and the board | substrate for printed wiring board formation, etc. among these, Preferred are benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds.

As said (bis) acyl phosphine oxide, the said acetophenone type compound, the said benzophenone type compound, the said benzoin ether type compound, the said ketal derivative compound, and the said thioxanthone compound, For example, Unexamined-Japanese-Patent No. 2010-256399 (Bis) acylphosphine oxide, acetophenone-based compound, benzophenone-based compound, benzoin ether-based compound, ketal derivative compound, thioxanthone compound and the like described in paragraph [0042] of the publication.

A photoinitiator may be used individually by 1 type, and may use 2 or more types together.

There is no restriction | limiting in particular as content in the said photosensitive resin composition solid content of the said photoinitiator, Although it can select suitably according to the objective, 0.1 mass%-30 mass% are preferable, 0.5 mass%-20 mass% are more preferable, 0.5 Mass%-15 mass% are especially preferable.

<Inorganic filler>

The photosensitive resin composition used by this invention contains an inorganic filler. The inorganic filler can be appropriately selected / used from improving the surface hardness of the permanent pattern or lowering the coefficient of linear expansion, increasing the thermal conductivity, or reducing the dielectric constant or dielectric loss tangent of the cured film itself.

Examples of the inorganic fillers include kaolin, barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and the like. As a commercial item of the said barium sulfate, B-30 (made by Sakai Kagaku Kogyo Co., Ltd.) etc. is mentioned, for example.

Among these, compounds having silicon atoms such as silica (compounds containing silicon in the constituent atoms such as silica and talc), barium sulfate and aluminum hydroxide are preferred, and compounds having silicon atoms are more preferred, and silica is particularly preferred. desirable.

There is no restriction | limiting in particular as an average particle diameter of an inorganic filler, Although it can select suitably according to the objective, 5 micrometers or less, Preferably it is 2 micrometers or less, More preferably, 1 micrometer or less corresponds. When the said average particle diameter is 5 micrometers or more, resolution may deteriorate by light confusion.

Content of an inorganic filler is 20 volume% or more in the non volatile component (solid content) total capacity of the photosensitive resin composition in this invention. Thereby, a desired effect can be achieved effectively and a thermal expansion rate can be reduced. The said content of an inorganic filler becomes like this. Preferably it is 25 volume% or more, More preferably, it is 30 volume% or more. The upper limit of the inorganic filler is preferably 60% by volume or less, more preferably 50% by volume or less, still more preferably 40% by volume or less, still more preferably 35% by volume or less, or even 32% by volume or less. When the content of the inorganic filler is too small, the effect of lowering the coefficient of thermal expansion is small, and the effect of improving the impact resistance is insufficient. On the other hand, when content of an inorganic filler is too high, sufficient resolution will not be obtained.

The nonvolatile component of the photosensitive resin composition is a component which does not volatilize, and it corresponds to the component which does not volatilize even if it heats at 150 degreeC under reduced pressure of 20 mm bar, what is called solid content capacity. In addition, relatively high boiling point organic solvents such as low boiling point organic solvents and cellosolve solvents such as propylene glycol monomethyl ether acetate, carbitol and butyl carbitol are known as volatile solvents.

<Dispersant>

It is preferable that a dispersing agent is contained in the photosensitive resin composition used by this invention.

Especially, it is preferable that a dispersing agent is used for dispersion of an inorganic filler. For this reason, the polymer dispersing agent which has a group which interacts with the surface of an inorganic filler, and does not have ethylenically unsaturated group is preferable. Examples of the group which interacts with the surface of the inorganic filler include a basic group, an acidic group or an adsorbent group, and a basic group is particularly preferable. Moreover, it is preferable not to associate between the molecules of a dispersing agent in the state which these interacting groups interacted on the surface of an inorganic filler, and it is preferable that the group which becomes steric hindrance exists in a molecule | numerator in order to suppress this association. Moreover, as for mass average molecular weight, 1,000-100,000 are preferable.

In addition, when a dispersing agent does not contain a basic functional group but contains an acidic functional group and a salt structure, sufficient adsorption amount may not be obtained with respect to inorganic fillers, such as a silica, and when it sets it as a film, The aggregation may not be suppressed so that the viscosity does not decrease.

There is no restriction | limiting in particular as a basic group, For example, a primary amino group, a secondary amino group, a tertiary amino group, a nitrogen-containing heterocyclic group, etc. are mentioned, A tertiary amino group and a nitrogen-containing heterocyclic group are preferable, Tertiary amino groups are particularly preferred.

Basic groups are adsorbed on the surface of inorganic or organic fillers or pigments, in particular on the surface of silica fine particles, for example ionic interactions.

The nitrogen-containing heterocyclic group may be any one as long as the nitrogen atom is included in the ring constituent atom and the nitrogen atom shows basicity. As a hetero ring in a nitrogen-containing heterocyclic group, a 5 or 6 membered heterocyclic group is preferable, and even if it is an aromatic ring or an unsaturated or saturated ring, it is not cared about. The nitrogen-containing heterocycle may further be substituted with an aromatic ring, a heterocycle or an alicyclic ring and may have a substituent on the nitrogen-containing heterocycle. Examples of such substituents include alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, alkylamino groups, arylamino groups, Acylamino group, sulfonamide 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, sia A furnace group, a nitro group, a carboxyl group, a sulfo group, a ureido group, a urethane group, etc. are mentioned.

As a nitrogen-containing heterocyclic ring, a pyrrolidine ring, a pyrroline ring, a piperidine ring, a piperazine ring, a morpholine ring, an imidazolidine ring, an imidazoline ring, an imidazole ring, a pyrazolidine ring, a pyrrolidine ring, And pyrazole ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indole ring, indazole ring, purine ring, quinoline ring, quinoxaline ring, quinazoline ring, indolin ring and quinuclidin ring. .

As the acidic group is not particularly limited, examples of the acid portion of the acid groups groups such as carboxyl group, sulfo group, phospho ^{_{group, -COCH 2 CO-R B,}} -CONHCO-R B, -COCH 2 CN, phenolic there may be mentioned (R _{F) 2} CHOH, alkyl or aryl sulfonamide group, and the like - OH, -R _F CH ₂ OH,. 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 a cyclic hydrocarbon group.

Among the acid groups, a carboxyl group, a sulfo group, and a phosphonyl group are preferable, and a carboxyl group is particularly preferable in view of developability.

The acid portion of the acidic group may have an aliphatic group (alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, cycloalkynyl group, etc.), an aromatic group, a heterocyclic group, and the acid moiety group. The group may be an acidic group directly.

0.65 mmol / g or more is preferable, as for the amine titer of the dispersing agent used preferably in this invention, 0.75 mmol / g or more is more preferable, 0.9 mmol / g or more is more preferable. Although the upper limit of an amine number is not specifically limited, Preferably it is 4 mmol / g or less, More preferably, it is 3 mmol / g or less.

Here, the measurement of the amine value, for example, by measuring the sample in a beaker, by adding and stirring the acetic acid to dissolve, after adjusting the measurement temperature to 25 ℃, titrator using 0.1 N perchloric acid as a titration reagent It can obtain | require by titrating as.

An amine titer shows the quantity of perchlorine consumed at the time of titration by the number-of-moles per 1 g of dispersant resin (solid content).

As for the acid value of the dispersing agent used preferably in this invention, 0.1 mmol / g or more is preferable, 0.2 mmol / g or more is more preferable, More preferably, it is 0.3 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.

Here, the said acid value is measured, for example, by measuring a sample in a beaker, adding a solution of THF / water = 5/1 (volume ratio), stirring and dissolving it, adjusting a measurement temperature to 25 degreeC, and then titrating reagent. The acid value can be obtained by titration with a titration apparatus using a 0.1 N aqueous NaOH solution.

An acid value shows the quantity of NaOH consumed at the time of titration by the number-of-moles per 1 g of dispersant resin (solid content).

As a preferable dispersing agent in this invention, what has at least any one of a basic group and the steric hindrance of a polymer as mentioned above is preferable.

Examples of the steric hindrance group include a branched alkyl group, a bicycloalkyl group, an aryl group, a heterocyclic group (in particular, an aryl group and a heterocyclic group preferably have two or more substituents), and a side chain polymer chain having a number average molecular weight of 500 to 50,000. However, polymer dispersants having graft chains are preferred.

Among these, when the stereoprotective group is not a high molecular weight but has a low molecular weight, sufficient stereoscopic repulsion may not be obtained, and when a film is used, sufficient stereoscopic repulsion may not be obtained with respect to inorganic fillers such as silica. Aggregation of inorganic fillers cannot be suppressed and a viscosity may not fall.

Graft print

The polymer dispersant preferably has a graft chain in the side chain or at least one of the main chain ends.

As the graft chain, for example, polyester chain, polyalkyl acrylate chain, polyalkyl methacrylate chain, polyalkylene oxide chain (preferably polyethylene oxide chain, polypropylene oxide chain), polycarbonate chain, polystyrene chain, Or combination thereof and inclusion of these chains in the substructure. Among these, it is preferable from the point of resolution that it is a graft chain (polyester graft chain) which has a polyester site | part.

The degree of polymerization is preferably 1 to 100, more preferably 1 to 80, and particularly preferably 1 to 60 of the chain length of the graft chain.

10 mass%-60 mass% are preferable with respect to the whole polymer dispersant resin, and, as for content of the said graft, 20 mass%-50 mass% group are more preferable.

In this invention, it is preferable that an amine value, an acid value, or an amine value and an acid value are the said range, It is more preferable that an amine value and an acid value are the above-mentioned range, It is more preferable that an amine value and an acid value are the above-mentioned range, and it has a graft chain. Do.

As a commercial item of the said dispersing agent, for example, Solsper 3000, Solsper 17000, Solsper 20000, Solsper 24000GR, Solsper 24000SC, Solsper 26000, Solsper 27000, Solsper 28000, Solsper 32000, Solsper 33000, Sol Spurs 38500, Solsper 39000, Solsper 41000, Solsper 55000, Solsper 56000, Solsper 71000, Solsper 76500 (all manufactured by Lubrizol); Disperbyk-161, Disperbyk-167, Disperbyk-182, Disperbyk-2155, Disperbyk-102, Disperbyk-111, Disperbyk-106, Disperbyk-108, Disperbyk-112, Disperbyk-2000, Disperbyk-2001, Disperbyk-2008, Disperbyk-2008 2009, Disperbyk-2015, Disperbyk-2020, Disperbyk-2022, Disperbyk-2025 (all manufactured by BYK Chemie); Efka-4008, Efka-4009, Efka-4010, Efka-4015, Efka-4020, Efka-4046, Efka-4047, Efka-4400, Efka-4401, Efka-4002, Efka-4003, Efka-4480, Efka- 4300, Efka-4310, Efka-4320, Efka-4330, Efka-4340, Efka-4061, Efka-5044, Efka-5244, Efka-5054, Efka-5055, Efka-5063, Efka-5065, Efka-5066, Efka-5070, Efka-5071, Efka-5207, Efka-6220, Efka-6225 (all are the BASF Corporation make), etc. are mentioned.

Among these, those having a basic group, those having a steric hindrance group, and the like are preferable.

There is no restriction | limiting in particular as content with respect to the inorganic filler of a dispersing agent, Although it can select suitably according to the objective, 0.1-10 mg per 1 m <2> of surface area of an inorganic filler is preferable, and 1-3 mg is more preferable.

When the said content is less than 0.1 mg, the dispersibility of an inorganic filler is inadequate, and when it exceeds 10 mg, the adhesiveness of a film may deteriorate. On the other hand, when the said content is in the more preferable range, it is advantageous at the point of compatible dispersibility and adhesiveness.

<Elastomer>

By adding an elastomer to the photosensitive resin composition of the present invention, heat resistance, flexibility and toughness can be imparted to the photosensitive resin composition.

There is no restriction | limiting in particular as an elastomer, According to the objective, it can select suitably, For example, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, a silicone elastomer, etc. are mentioned. . These elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance, strength, and the latter to flexibility and toughness. Moreover, there is no restriction | limiting in particular as a property of an elastomer, According to the objective, it can select suitably, For example, it is preferable that it is alkali-soluble or swelling in terms of the production efficiency of a developing process, etc.

There is no restriction | limiting in particular as a styrene-type elastomer, According to the objective, it can select suitably, For example, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene- ethylene-butylene-styrene block copolymer And styrene-ethylene-propylene-styrene block copolymers.

In addition to styrene which is a component constituting the styrenic elastomer, styrene derivatives such as α-methyl styrene, 3-methyl styrene, 4-propyl styrene and 4-cyclohexyl styrene can be used. Specifically, as a commercial item, it is turfren, sorbent T, asaprene T, and tuftec. [Above, Asahi Kasei Co., Ltd.], elastomer AR (Aron Kasei product), Clayton G, guariflex (above, shell Japan product), JSR-TR, TSR-SIS, dynaron [above, Nihon Kosei rubber ( Product], Denka STR [product of Denki Kagaku Kogyo Co., Ltd.], quintech (product of Nippon Xeon), TPE-SB series [product of Sumitomo Kagaku Co., Ltd.], Rabaron [product of Mitsubishi Kagaku Co., Ltd.] , Septon, Hibra (above, Kuraray Co., Ltd.), Smiplex (manufactured by Sumitomo Bakelite Co., Ltd.), rheomer, and actiner (above, Rikenvinyl High School).

There is no restriction | limiting in particular as an olefin elastomer, According to the objective, it can select suitably, For example, the air of C2-C20 alpha olefins, such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl- pentene, Examples of the copolymer include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), and the like. Dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenor And non-conjugated dienes having 2 to 20 carbon atoms and α-olefin copolymers such as bonene, ethylidene norbornene, butadiene and isoprene. Moreover, the carboxy modified NBR which copolymerized methacrylic acid to the butadiene- acrylonitrile copolymer is mentioned. Specific examples include ethylene-α-olefin copolymer rubber, ethylene-α-olefin non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer rubber, and the like.

Specifically, as a commercially available product, a mil- somer [made by Mitsui Kagaku Co., Ltd.], EXACT (made by Exxon Kagaku), ENGAGE (Dow Chemical), hydrogenated styrene-butadiene rubber [DYNABON HSBR, Nippon Kosei Rubber Co., Ltd.] Product], butadiene-acrylonitrile copolymer [NBR series, Nihon Kosei Rubber Co., Ltd.], or both terminal carboxyl group modified butadiene-acrylonitrile copolymer [XER series Nihon Kosei Rubber Co., Ltd.] which has a crosslinking point. Etc. can be mentioned.

There is no restriction | limiting in particular as a urethane elastomer, According to the objective, it can select suitably, For example, it consists of the structural unit of the hard segment which consists of low molecular glycol and diisocyanate, and the soft segment which consists of high molecular (long-chain) diol and diisocyanate, As the polymer (long chain) diol, polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene · 1,4-butylene adipate), polycaprolactone, poly (1,6 -Hexylene carbonate), poly (1, 6- hexylene neopentylene adipate), etc. are mentioned.

The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000, and in addition to ethylene glycol, short chain diols such as propylene glycol, 1,4-butanediol and bisphenol A can be used, and the number average molecular weight of the short chain diol is 48 to 500 is preferred. Commercially available products of the urethane elastomer include PANDEX T-21085, T-2983N (manufactured by DIC Corporation), and cilactran E790.

There is no restriction | limiting in particular as polyester-type elastomer, According to the objective, it can select suitably, For example, what is obtained by polycondensing a dicarboxylic acid or its derivative (s) and a diol compound or its derivative (s) is mentioned.

As said dicarboxylic acid, For example, aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acid in which the hydrogen atom of these aromatic nucleus was substituted by methyl group, ethyl group, phenyl group, etc., Alicyclic dicarboxylic acids, such as C2-C20 aliphatic dicarboxylic acid, such as adipic acid, sebacic acid, and dodecanedicarboxylic acid, and cyclohexanedicarboxylic acid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol; Alicyclic diol, bivalent phenol represented by the following structural formula, etc. are mentioned.

In the above formula, Y ^DO represents any one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, -O-, -S-, and -SO _2- , or a benzene ring. Direct bond (single bond) is shown. R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1;

Specific examples of the polyester elastomer include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, resorcin and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

In addition, as a polyester elastomer, a multi-block air containing an aromatic polyester (eg polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (eg polytetramethylene glycol) portion as a soft segment component Coalescing may also be used.

As a multi-block copolymer, the thing of various grades is mentioned by the difference of the kind, ratio, and molecular weight of a hard segment and a soft segment. Specific examples thereof include Hytrel (manufactured by Dupont-Toray Co., Ltd.), pulprene (manufactured by Toyo Boseki Co., Ltd.), and Espell (manufactured by Hitachi Kasei Kogyo Co., Ltd.).

There is no restriction | limiting in particular as a polyamide-type elastomer, According to the objective, it can select suitably, For example, the polyether block amide type and polyether which used polyamide for a hard phase, and polyether or polyester for a soft phase. It is largely divided into two types of ester block amide type, polyamide-6, 11, 12, etc. are used as polyamide, and polyoxyethylene, polyoxypropylene, polytetramethylene glycol, etc. are used as polyether. Specifically, as a commercial item, UBE polyamide elastomer [manufactured by Ube-Kyosan Co., Ltd.], diamide [manufactured by Daicel Hurus Co., Ltd.], PEBAX [manufactured by Toray Corporation], Glylon ELY [manufactured by MMS Japan Co., Ltd.] ], Nofamid [manufactured by Mitsubishi Kagaku Co., Ltd.], Gleelax [manufactured by DIC Corporation], and the like.

There is no restriction | limiting in particular as an acryl-type elastomer, According to the objective, it can select suitably, For example, an acrylic ester is made into a main component, and ethyl acrylate, butyl acrylate, methoxy ethyl acrylate, an ethoxy ethyl acrylate, etc. are mentioned. Moreover, glycidyl methacrylate, allyl glycidyl ether, etc. are mentioned as a crosslinking point monomer. Moreover, acrylonitrile and ethylene can also be copolymerized. Specifically, an acrylonitrile- butyl acrylate copolymer, an acrylonitrile- butyl acrylate-ethyl acrylate copolymer, an acrylonitrile- butyl acrylate- glycidyl methacrylate copolymer, etc. are mentioned.

There is no restriction | limiting in particular as silicone type elastomer, According to the objective, it can select suitably, For example, it is based on organopolysiloxane, and a polydimethylsiloxane type, a polymethylphenylsiloxane type, polydiphenylsiloxane, etc. are mentioned. As a specific example of a commercial item, KE series (made by Shin-Etsu Kagaku Kogyo Co., Ltd.), SE series, CY series, SH series (above, Toray Die Corning Silicone Co., Ltd. product), etc. are mentioned.

In addition to the elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin is, for example, some or all epoxy groups of the above-mentioned bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylicaldehyde type epoxy resin, phenol novolak type epoxy resin or cresol novolak type epoxy resin. It is obtained by modifying to both terminal carboxylic acid modified type butadiene-acrylonitrile rubber, terminal amino modified silicone rubber, etc. Of these elastomers, Espel [Hitachi Kasei Kogyo Co., Ltd., Espel 1612, 1620], which is a polyester-based elastomer having a hydroxyl group with both terminal carboxyl group-modified butadiene-acrylonitrile copolymers in terms of shear adhesion, is preferable. .

As content of the said elastomer, 1 mass part-50 mass parts are preferable with respect to 100 mass parts of solid content of the said photosensitive resin composition, 2 mass parts-20 mass parts are more preferable, 3 mass parts-10 mass parts are especially preferable.

If the content is less than 2 parts by mass, the modulus of elasticity in the high temperature region of the cured film does not tend to be lowered. If the content exceeds 50 parts by mass, the unexposed portion tends not to elute into the developer.

<Ion Scavenger>

The photosensitive resin composition used by this invention contains the ion trapping agent (ion adsorbent) of the inorganic compound which has at least 1 sort (s) of Zr, Bi, or Sb.

As ions to capture, anions such as free Cl ⁻ or hydrolyzable Cl ⁻ and Na ^{+ of the} glass and Cu ²⁺ in the test are the centers.

Examples of the inorganic compound (zirconium compound) having Zr include zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium selenium, and zirconium tellurium. Among these, zirconium phosphate which can selectively ion-exchange cations, such as Na <^+> and K <^+> , and is excellent also in ion exchange capacity is especially preferable.

As an inorganic compound (bismuth compound) which has Bi, bismuth oxide, bismuth titanate, bismuth nitrate, bismuth salicylate, bismuth carbonate, etc. are mentioned, for example. Among these, bismuth oxide which specifically captures Cl ⁻ is particularly preferable.

As an inorganic compound (antimony compound) which has Sb, an antimony oxide compound is preferable. Examples of the antimony compound include antimony pentoxide, antimony trioxide, phosphorus antimonic acid, zirconium antimonate, titanium antimonate, and the like. Among these, antimony pentoxide is especially preferable at the point of Na <^+> .

In the present invention, the inorganic compound having at least one of Zr, Bi, or Sb is zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium selenium, zirconium tellurium, bismuth oxide, bismuth titanate, bismuth nitrate, bismuth salicylate, Preference is given to inorganic compounds selected from bismuth carbonate, antimony pentoxide, antimony trioxide, antimony phosphate, zirconium antimonate and titanium antimonate.

It is preferable at the point which synergistically improves insulation reliability by capturing negative and positive ions. Especially, it is especially preferable to contain combining at least 1 sort (s) of the inorganic compound (zirconium compound) which has a metal of Zr, and at least 1 sort (s) of the inorganic compound (bismuth compound) which has a metal of Bi.

The mass ratio (A: B) of the bismuth compound (A) and the zirconium compound (B) is preferably from 1: 0.1 to 1:10, more preferably from 1: 0.2 to 1: 5.

0.5 mass%-10 mass% are preferable, and, as for the total content in the said photosensitive resin composition solid content of the said ion trapping agent, 1 mass%-5 mass% are more preferable. If the said content is 10 mass% or more, it will become the case of hardening defect, resolution, and adhesive fall, and if it is 0.5 mass% or less, the effect of the insulation reliability improvement will be small.

In addition, in this invention, you may use another ion trapping agent in combination with the said ion trapping agent. The following are mentioned as another ion trapping agent.

Inorganic ion exchanger (combines Yin-Yang ion scavenger) that adsorbs yin-yang both ions, beryllium oxide hydrate, gallium oxide hydrate, lanthanum oxide hydrate, iron oxide hydrate, aluminum oxide hydrate, titanium oxide hydrate, tin oxide hydrate, germanium oxide Hydrous oxides of metals such as hydrates and thorium oxide hydrates.

Desites etc. are mentioned as an anion trapping agent. Moreover, anion exchanger IXE-700 (magnesium, aluminum type), IXE-700F (magnesium, aluminum type), IXE-770 (magnesium, aluminum type), IXE-770D (magnesium,) marketed by Toagosei Co., Ltd. Aluminum type), IXE-702 (aluminum type), IXE-1000 (lead type), etc. are mentioned.

Examples of the cationic trapping agent include hydrous oxides of metals such as phosphates, manganese oxide hydrates, silicon oxide hydrates, niobium oxide hydrates, tantalum oxide hydrates, tantalum oxide hydrates, molybdenum oxide hydrates, and tungsten oxide hydrates, ammonium phosphide, ammonium and molybdenum Titanium acid, titanium tungstate, tin molybdate, tin tungstate, chromium tripolyphosphate, etc. are mentioned. Moreover, the cation exchanger IXE-200 (tin system), IXE-400 (titanium system) etc. marketed by Toagosei Co., Ltd. are mentioned.

<Color Pigment>

It is preferable to contain a coloring pigment in the photosensitive resin composition of this invention.

There is no restriction | limiting in particular as a coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI 42595), auramine (CI 41000), fact black HB (CI 26150), monolight yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), CI Pigment Yellow 55, Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Postbam Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel pink B spooler (CI pigment red 81), monastral first blue (CI pigment blue 15), monolight first black B (CI pigment black 1), carbon, CI Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment blue 64, and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, the dye suitably selected from well-known dye can be used as needed.

Content in the said photosensitive resin composition solid content of the said coloring pigment can be determined in consideration of exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, and although it changes with kinds of the said coloring pigment, generally it is 0.01-10 mass % Is preferable and 0.05-5 mass% is more preferable.

&Lt; Other components >

There is no restriction | limiting in particular as said other components, According to the objective, it can select suitably, For example, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, a surface treating agent, etc. are mentioned, Adhesion promoter to the surface of a base material, and other Auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination.

By containing these components suitably, the properties, such as stability, photography, film properties, etc. of the target photosensitive resin composition can be adjusted.

As said thermal-polymerization inhibitor, the thermal-polymerization inhibitor as described in Paragraph [0101]-[0102] of Unexamined-Japanese-Patent No. 2008-250074, etc. are mentioned, for example.

As said thermosetting accelerator, the thermosetting accelerator as described in Paragraph [0093] of Unexamined-Japanese-Patent No. 2008-250074, etc. are mentioned, for example.

As said plasticizer, the plasticizer of Paragraph [0103]-[0104] of Unexamined-Japanese-Patent No. 2008-250074, etc. are mentioned, for example.

As said surface treating agent, the silane coupling agent etc. of Paragraph [0017]-[0022] of Unexamined-Japanese-Patent No. 2008-102486 are mentioned.

As said adhesion promoter, the adhesion promoter as described in Paragraph [0107]-[0109] of Unexamined-Japanese-Patent No. 2008-250074, etc. are mentioned, for example.

There is no restriction | limiting in particular as a usage form of the said photosensitive resin composition, According to the objective, it can select suitably, You may use in a liquid form, and you may use as a photosensitive film.

<Photosensitive film>

The said photosensitive film has at least a support body and the photosensitive layer containing the photosensitive resin composition of this invention on this support body, and further has another layer as needed.

- Support -

There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, it is preferable that the said photosensitive layer is peelable, and that light transmittance is favorable, and that surface smoothness is more preferable.

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

- Photosensitive layer -

If the said photosensitive layer is a layer which consists of the said photosensitive resin composition of this invention, there will be no restriction | limiting in particular, According to the objective, it can select suitably.

There is no restriction | limiting in particular as lamination number of the said photosensitive layer, According to the objective, it can select suitably, For example, one layer may be sufficient and two or more layers may be sufficient.

As a formation method of the said photosensitive layer, the said photosensitive resin composition of this invention is melt | dissolved, emulsified, or disperse | distributed in water or a solvent on the said support body, the photosensitive resin composition solution is prepared, and this solution is apply | coated directly and dried and laminated | stacked. Etc. can be mentioned.

There is no restriction | limiting in particular as a solvent used for the said photosensitive resin composition solution, According to the objective, it can select suitably.

There is no restriction | limiting in particular as said coating method, According to the objective, it can select suitably, For example, the method of apply | coating directly to the said support body using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. is mentioned. Can be mentioned.

As said drying conditions, although it changes also with each component, the kind of solvent, a use ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60 degreeC-120 degreeC.

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

-Other Layers-

There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, layers, such as a protective film, a thermoplastic resin layer, a barrier layer, a peeling layer, an adhesive layer, a light absorption layer, and a surface protective layer, are mentioned. . The said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.

--Protective film--

The said photosensitive film may form a protective film on the said photosensitive layer.

There is no restriction | limiting in particular as said protective film, According to the objective, it can select suitably, For example, the protective film etc. of Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 are mentioned.

There is no restriction | limiting in particular as a combination of the said protective film and the said support body, According to the objective, it can select suitably, For example, the combination of Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074, etc. are mentioned.

Moreover, 0.3-1.4 are preferable and, as for the static friction coefficient of the said support body and the said protective film, 0.5-1.2 are more preferable.

If the said static friction coefficient is 0.3 or more, it can prevent that a winding shift | offset | difference arises when it becomes a roll shape by slipping too much, and if it is 1.4 or less, it can wind up to a favorable roll shape.

There is no restriction | limiting in particular as a length and the storage method of the said photosensitive film, According to the objective, it can select suitably, For example, the length as described in Paragraph [0120] of Unexamined-Japanese-Patent No. 2008-250074, a storage method, etc. are mentioned. .

You may surface-treat the said protective film in order to adjust the adhesiveness of the said protective film and the said photosensitive layer. The said surface treatment forms the primer layer which consists of polymers, such as a polyorganosiloxane, a fluorinated polyolefin, polyfluoroethylene, polyvinyl alcohol, on the surface of the said protective film, for example. Formation of this primer layer can be formed by apply | coating the coating liquid of the said polymer on the surface of the said protective film, and then drying at 30 degreeC-150 degreeC for 1 minute-30 minutes. As for the temperature at the time of the said drying, 50 degreeC-120 degreeC is especially preferable.

(Photosensitive laminated body)

The photosensitive laminated body of this invention has at least a base and a photosensitive layer on the said base, and further laminates another layer as needed.

The said photosensitive layer is a layer containing the said photosensitive resin composition of this invention.

The said photosensitive layer is the thing transferred from the said photosensitive film produced by the above-mentioned manufacturing method, for example, and has a structure similar to the above.

<Gas>

The substrate is a target substrate on which the photosensitive layer is formed, or a transfer body on which at least the photosensitive layer of the photosensitive film of the present invention is transferred. There is no particular limitation, and the base can be appropriately selected according to the purpose, for example, surface smoothness. It can select arbitrarily from this high thing to the thing with the uneven surface. A plate-shaped base is preferable and a so-called substrate is used. Specifically, the board | substrate (print board | substrate) for manufacturing a well-known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, a metal plate, etc. are mentioned.

<Method for Producing Photosensitive Laminate>

There is no restriction | limiting in particular as a manufacturing method of the said photosensitive laminated body, According to the objective, it can select suitably, For example, at least the photosensitive layer in the photosensitive film of this invention is transcribe | transferred by carrying out at least any one of heating and pressurization, and lamination | stacking. How to do this.

An example of the manufacturing method of the said photosensitive laminated body is the method of laminating | stacking the photosensitive film of this invention on the surface of the said base, performing at least any one of heating and pressurization. Moreover, when the said photosensitive film has the said protective film, it is preferable to peel off the protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.

There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, For example, 15 degreeC-180 degreeC is preferable, and 60 degreeC-140 degreeC is more preferable.

There is no restriction | limiting in particular as a pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable, and 0.2 MPa-0.8 MPa are more preferable.

There is no restriction | limiting in particular as an apparatus which performs at least one of the said heating, According to the objective, it can select suitably, For example, a laminator (for example, the Daisei Laminator Co., Ltd., VP-II, Nichigomoton Co., Ltd.). Kaisha, VP130) etc. are mentioned suitably.

The photosensitive film and the photosensitive laminate of the present invention can be widely used for forming a high-precision permanent pattern in the field of electronic materials, and in particular, can be suitably used for forming a permanent pattern of a printed board.

(Permanent pattern formation method)

The permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps as necessary.

<Exposure Step>

There is no restriction | limiting in particular if the said exposure process is a process of exposing to the photosensitive layer formed with the photosensitive resin composition of this invention, According to the objective, it can select suitably, For example, the photosensitive in the said photosensitive laminated body of this invention. The process of exposing to a layer is mentioned.

There is no restriction | limiting in particular as long as it is the said photosensitive layer as an object of the said exposure, Although it can select suitably according to the objective, it is performed with respect to the laminated body formed by laminating | stacking and forming the photosensitive film on the base material, performing at least one of heating and pressurization. It is preferable.

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

<Other Processes>

There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process, the image development process, the hardening process process, the post exposure process, etc. are mentioned.

Development Process

The said developing process is a process of removing the unexposed part of the said photosensitive layer.

There is no restriction | limiting in particular as a removal method of the said exposure part, According to the objective, it can select suitably, For example, the method of removing using a developing solution, etc. are mentioned.

There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, the developing solution of Paragraph [0171]-[0173] of Unexamined-Japanese-Patent No. 2008-250074, etc. are mentioned.

Curing treatment process

The said hardening process process is a process of performing hardening process with respect to the photosensitive layer in the formed pattern after the said image development process is performed.

There is no restriction | limiting in particular as said hardening process process, Although it can select suitably according to the objective, For example, a front surface exposure process, a front surface heat treatment, etc. are mentioned suitably.

There is no restriction | limiting in particular as a method of the said front surface exposure process and the said front surface heat processing, According to the objective, it can select suitably, For example, the method of Unexamined-Japanese-Patent No. 2008-250074, Paragraph [0176]-[0177] Etc. can be mentioned.

When the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, a permanent pattern is formed on the printed board by the permanent pattern forming method. Soldering can be performed as follows.

That is, the hardened layer which is the said permanent pattern is formed by the said phenomenon, and a metal layer is exposed on the surface of the said printed circuit board. After performing gold plating with respect to the site | part of the metal layer exposed on the surface of the printed wiring board, soldering is performed. Then, a semiconductor or a component is mounted on the soldering area. At this time, the permanent pattern by the said hardened layer functions as a protective film, an insulating film (interlayer insulation film), and a soldering resist, and the impact from the outside and the conduction of the electrodes of neighbors are prevented.

(Printed board)

The printed circuit board of the present invention has at least a substrate and a permanent pattern formed by the permanent pattern forming method, and has another configuration 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 formed between the base material and the said permanent pattern are mentioned.

Example

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all to these Examples.

In addition, the acid value, mass average molecular weight, and ethylenically unsaturated group equivalent in a synthesis example were measured with the following method.

<Acid value>

The acid value was measured in accordance with JIS K0070. However, when a sample did not melt | dissolve, dioxane, tetrahydrofuran, etc. were used as a solvent.

&Lt; Weight average molecular weight &

The mass average molecular weight was a 0.5 mass% THF solution as a sample solution using a high-speed GPC device (HLC-802A manufactured by Toyo Sodatsu Kogyo Co., Ltd.), and the column was a 200 μL sample using one TSKgel HZM-M. It injected, eluted with the said THF solution, and measured by the refractive index detector or UV detector (detection wavelength 254nm) at 25 degreeC.

<Ethylenically unsaturated group equivalent>

Ethylenic unsaturated group equivalent was calculated | required by measuring bromine value based on JISK2605.

(Synthesis Example 1)

<Synthesis of Polyurethane Resin U1 Containing Acid and Ethylenically Unsaturated Group>

In a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer, 1.9 g (0.01 mol) of malic acid, 8.4 g (0.06 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and glycerol monomethacrylate 12.7 g (0.08 mol), 10.6 g (0.01 mol) of polypropylene glycol (PPG1000), and 10.2 g (0.07 mol) of hexamethylene glycol were dissolved in 60 g of cyclohexanone. To this, 48.1 g (0.19 mol) of 4,4'-diphenylmethane diisocyanate (MDI), 8.1 g (0.05 mol) of hexamethylene diisocyanate (HMDI), and 2,6-di-t-butylhydroxytoluene 0.1 0.2 g of the brand name: Neostane U-600 (made by Nitto Kasei Co., Ltd.) was added as g and a catalyst, and it heated and stirred at 75 degreeC for 5 hours. Then, it diluted with 9.61 mL of methyl alcohol, stirred for 30 minutes, and obtained the polyurethane resin U1 solution (solid content 45 mass%) represented by 165 g of following formula.

Solid polyurethane acid value of the obtained polyurethane resin U1 was 48 mgKOH / g, and the mass mean molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 11,000. In addition, the ethylenically unsaturated group equivalent was 1.3 mmol / g.

(Synthesis Example 2)

<Synthesis of Elastomer Polyester Resin E-1>

699 parts by mass of dimethyl terephthalate, 524 parts by mass of dimethyl isophthalate, 226 parts by mass of dimethyl adipic acid, 553 parts by mass of dimethyl sebacate, 417 parts by mass of 2,2-dimethylpropanediol, 324 parts by mass of butanediol, 769 parts by mass of ethylene glycol, 2 parts by mass of Ilganox 1330 (manufactured by Chiba Japan Co., Ltd.) and 0.9 parts by mass of tetrabutyl titanate were mixed in the reactor as an antioxidant, and the temperature was raised from room temperature to 260 ° C. under stirring for 2 hours, and then at 260 ° C. It heated for 1 hour and transesterified. Subsequently, the inside of the reactor was gradually reduced in pressure and heated up, and the initial polycondensation reaction was performed at 245 ° C and 0.5 to 2 torr over 30 minutes. Furthermore, after performing polymerization reaction at 245 degreeC and 0.5-2 torr for 4 hours, it returned to normal pressure over 30 minutes, introducing dry nitrogen, and pulled out polyester in pellet form and obtained polyester resin E-1. The obtained polyester resin E-1 was diluted and dissolved in propylene glycol monomethyl ether acetate so that it might become 60 mass% solid content concentration, and the polyester resin E-1 solution was obtained.

The mass average molecular weight (polystyrene standard) measured by the gel permeation chromatography of obtained polyester resin E-1 was 340,000.

(Synthesis Example 3)

<Synthesis of Dispersant D-1>

After putting 36 g of cyclohexanone in a three neck flask, 21.6 g of methacrylic acid 2- (dimethylamino) ethyl ester, 24.8 g of hexahydrophthalic acid mono2- (methacryloyloxy) ethyl ester, manufactured by Toagosei Co., Ltd. 80 degreeC and nitrogen were mixed with 33.6 g of macromonomer AS-6, 1.28 g of dimethyl 2,2'-azobis (isobutylate), 3.2 g of 3-mercaptopropionic acid 2-ethylhexyl ester, and 78 g of cyclohexanone. It dripped over 1 hour under airflow. After stirring the reaction solution for 3 hours, 200 g of cyclohexanone was added to obtain a dispersant solution D-1.

Solid content concentration of the dispersing agent polymer D-1 in the dispersing agent solution D-1 is 20 mass%.

(Example 1)

<Production of Photosensitive Film>

On the 16-micrometer-thick polyethylene terephthalate film (16FB50 by Toray Corporation) as a support body, the photosensitive resin composition solution which consists of the following composition was apply | coated, it dried, and the photosensitive layer of thickness 30micrometer was formed on the said support body. A 20-micrometer-thick polypropylene film (manufactured by Oshi Tokushushi, Alpan E-200) was laminated on the photosensitive layer to produce a photosensitive film.

Composition of the photosensitive resin composition solution

Each component below was mixed and the photosensitive composition solution was prepared.

Polyurethane resin U1 solution of the synthesis example 1 (solid content 45 mass%)

                                                           ... 20.3 parts by mass

Polymerizable compound: DCP-A (manufactured by Kyogisha Co., Ltd.). 5.3 parts by mass

Thermal crosslinking agent: Efototo YDF-170 (manufactured by Toto Kasei Co., Ltd.); 2.9 parts by mass

Initiator: monocure 907 (manufactured by BASF); 0.6 parts by mass

· Sensitizer: DETX-S (manufactured by Nippon Kayaku Co., Ltd.). 0.005 parts by mass

Reaction aid: EAB-F (manufactured by Hodogaya Kagaku Co., Ltd.). 0.019 parts by mass

Pigment dispersion (hereinafter referred to as "G-2"). 30.1 parts by mass

· Coating Preparation: Mega Pack F-780F 0.2 parts by mass

  (Dainippon Ink Kagaku Kogyo Co., Ltd .: 30% by mass methyl ethyl ketone solution)

Elastomer: Polyester resin E-1 (60 mass% of solid content)

  (Polyester Resin of Synthesis Example 2). 2.7 parts by mass

In addition, the said pigment dispersion liquid "G-2" is 32.0 mass parts of silica (made by Admatex company, SO-C2), 2.2 mass parts of dispersing agents D-1 solution (20 mass% of solid content) of the synthesis example 3, and a synthesis example 12.0 mass parts of polyurethane resin U1 solution (solid content 45 mass%) of 1, 0.21 mass part of phthalocyanine blue, 0.06 mass part of anthraquinone series yellow pigments (CI PY 24), and IXE-6107 (Doagosei of an ion trapping agent) Moving product) 1.65 parts by mass, melamine (made by Wako Junyakyu Kogyo Co., Ltd.), and 0.3.5 parts by mass of cyclohexanone in advance, and then zirconia of 1.0 mm in motor mill M-250 (manufactured by Iger). It was prepared by dispersing for 3 hours at 9m / s circumference using beads.

Here, IXE-6107 (made by Toagosei Co., Ltd.) of an ion trapping agent is a mixture of bismuth oxide and zirconium phosphate.

Lamination to gas

Chemical polishing was performed on the surface of the copper clad laminated board (no through hole, 12 µm copper thickness) to prepare a base. On the copper-clad laminate, the photosensitive layer of the photosensitive film was brought into contact with the copper-clad laminate and peeled off using a vacuum laminator (Nichigo Motor Co., Ltd., VP130) while peeling off the protective film in the photosensitive film. A photosensitive laminated body in which a copper clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order were prepared.

The crimping conditions were 40 seconds of the time of vacuum processing, 70 degreeC of crimping temperature, 0.2MPa of crimping pressure, and 10 second of pressurization time.

Exposure process

The amount of energy 60mJ / cm 2 so that a predetermined pattern is obtained from the polyethylene terephthalate film (support) side through a glass mask having a predetermined pattern with respect to the photosensitive layer in the prepared photosensitive laminate, using a parallel optical exposure machine (ultra-high pressure mercury lamp). Irradiation was carried out to harden a portion of the photosensitive layer.

Development Process

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

Curing treatment process

The whole surface of the laminated body in which the said permanent pattern was formed was heat-processed at 150 degreeC for 1 hour, after that, post-exposure was performed on 1 J / cm <2> conditions, the surface of the permanent pattern was hardened, and the film strength was raised and the test plate was produced. .

<Evaluation>

Insulation, image development residue, resolution, heat resistance, and plating resistance were evaluated as follows. These results are collectively shown in Table 1 below.

`` Insulation ''

In the lamination to the base, the lamination to the base, the exposure step, the developing step, the curing treatment step were carried out in the same manner as above except that the copper-clad laminate was changed to a comb substrate having a copper thickness of 12 μm and L / S = 25 μm / 25 μm. Was performed, and the board | substrate for evaluation was produced.

The accelerated high temperature and high humidity lifetime test (HAST) was performed on 130 degreeC, 85% RH, 50V, and 200 hours using the board | substrate for evaluation.

The generation | occurrence | production degree of the migration of the soldering resist of the board | substrate for evaluation after that was observed with the optical microscope of 100x.

[Evaluation standard]

AA: No short circuit. In addition, migration cannot be confirmed, and insulation is excellent.

A: No short circuit. However, the occurrence of migration is slightly confirmed on copper

B: There is a short circuit. Occurrence of migration is slightly confirmed on copper

C: There is a short circuit. Occurrence of migration is confirmed, too

≪Residual residue≫

In the above evaluation of the resolution, the residue of the bottom of the round hole of 80 µm and 120 µm was observed by SEM (scanning electron microscope) among the formed round hole patterns, and the surface of the copper-clad laminate having the cured resin pattern obtained in this manner. Was observed with an optical microscope, and there was no abnormality such as no residue at the bottom of the round hole of the pattern, curling and peeling of the pattern portion, and the minimum round hole pattern width capable of forming a space was measured and evaluated according to the following criteria.

[Evaluation standard]

AA: There is no image development residue on the board | substrate of a round hole of 80 micrometers in diameter, and it is excellent in image development residue removal property.

A: There is no image development residue on the board | substrate of a round hole with a diameter of 120 micrometers, and image development residue removal property is favorable.

B: There existed a developing residue slightly on the board | substrate of a round hole of 120 micrometers in diameter, and developing residue removal property is slightly inferior

C: Developing residue exists on the board | substrate of a round hole of 120 micrometers in diameter, and developing residue removal property is inferior

≪Resolution≫

The said photosensitive laminated body was left to stand by 55% RH for 10 minutes at room temperature (23 degreeC). On the polyethylene terephthalate film (support) of the obtained photosensitive laminated body, it was 60 mJ / cm <2> using a pattern forming apparatus so that a round hole of the width of 30 micrometers-100 micrometers of the diameter of a round hole can be formed using a round hole pattern. The exposure was performed.

After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled from the photosensitive laminate.

A 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed at a spray pressure of 0.15 MPa twice as the shortest developing time for the entire surface of the photosensitive layer on the copper clad laminate to dissolve and remove the uncured region.

The surface of the copper-clad laminate having the cured resin pattern thus obtained was observed with an optical microscope, and the minimum round hole pattern width capable of forming a space without abnormalities such as residues, undercuts, and peelings of the pattern portion was measured, and the resolution was measured. It evaluated by the following reference | standard. The smaller the numerical value, the better.

[Evaluation standard]

AA: The round hole of 50 micrometers or less in diameter is resolvable, and is excellent in resolution.

A: The round hole exceeding 50 micrometers in diameter and 70 micrometers or less is resolvable, and resolution is favorable.

B: The round hole exceeding 70 micrometers in diameter and 100 micrometers or less is resolvable, and resolution is inferior

C: Round hole is not resolvable and resolution is inferior

≪Heat resistance≫

The evaluation substrate which formed the soldering resist layer which consists of each photosensitive composition, and apply | coated rosin-type flux was immersed in the solder bath set to 260 degreeC in advance for 30 second, and after wash | cleaning the flux with denatured alcohol, the resist layer visually Expansion, peeling, and discoloration were evaluated by the following criteria.

[Evaluation standard]

AA: No change was observed, especially heat resistance

A: Any one of swelling, peeling, and discoloration is slightly visible, but has excellent heat resistance.

B: Swelling and peeling are seen slightly, but heat resistance is good.

C: Some swelling and peeling are seen, and heat resistance is inferior

D: The coating film has swelling and peeling

`` Plating Resistance ''

The plating resistance with respect to the permanent pattern obtained as follows was evaluated.

Photosensitive laminates newly produced in the same manner as in the case of the above-described photosensitive laminates, not for individual evaluation, except that those obtained by chemically polishing the surface of the copper clad laminate (without holes, copper thickness of 12 μm) were used as the substrate. Was used.

On the photosensitive layer surface of this photosensitive laminated body, the independent wiring pattern of 30 micrometers-1,000 micrometers is formed by the optimal exposure amount beyond a photomask, and it is left still at room temperature for 10 minutes, and then peels the said support body from the said photosensitive laminated body, Spray a 1 mass% aqueous sodium carbonate solution at 30 ° C. at a spray pressure of 0.15 MPa on the entire surface of the photosensitive layer on the laminate to dissolve the uncured region by spraying a time (or 40 seconds to 60 seconds) two to three times the shortest developing time. Removed. Subsequently, the whole surface exposure was performed at 200 mJ / cm <2> with an ultrahigh pressure mercury lamp, and it heat-processed (postbaking) at 150 degreeC for 1 hour, and the permanent pattern was formed.

[Evaluation standard]

A: No peeling at all

B: no delamination in images with a line width of less than 500 μm

C: Exfoliation in an image with a line width of 500 μm or more

(Example 2, Example 3, Comparative Examples 1-3)

In Example 1, except having changed the kind of ion trapping agent and content of the inorganic filler (silica) in the photosensitive resin composition nonvolatile component in the combination of following Table 1, it carried out similarly to Example 1, and the photosensitive film, a laminated body, And permanent patterns. In addition, the ion supplement was added so that the whole quantity of an ion trapping agent might be the same quantity as Example 1.

These were evaluated in the same manner as in Example 1. These results are collectively shown in Table 1 below.

As apparent from Table 1 above, bismuth, zirconium or antimony compounds are used as the ion trapping agent, and the inorganic filler content in the photosensitive resin composition is 20% by volume or more, thereby providing insulation, resolution, heat resistance and plating resistance. It can be seen that it is excellent and the development residue is very small. Moreover, it turns out that a desired effect is not acquired when it is an ion trapping agent like hydrosulfite, or when there is little content of an inorganic filler.

Although the present invention has been described together with the embodiments thereof, we do not intend to limit our invention to any detail in the description unless specifically indicated otherwise, and are broadly interpreted without departing from the spirit and scope of the invention as set forth in the appended claims. I think it should be.

This application claims the priority based on Japanese Patent Application No. 2011-179961 by which the patent application was carried out in Japan on August 19, 2011, These take in the content as a part of description of this specification with reference to here.

Claims (28)

A photosensitive resin composition containing at least one acid-modified ethylenically unsaturated group-containing resin, an inorganic filler, an ion trapping agent, a radical polymerizable monomer, a photopolymerization initiator, and a thermal crosslinking agent, respectively, wherein the nonvolatile component total capacity of the photosensitive resin composition Content of the said inorganic filler is 20 volume% or more, and the said ion trapping agent is an inorganic compound which has at least 1 sort (s) of Zr, Bi, or Sb, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The ion trapping agent is zirconium phosphate, zirconium tungsten, zirconium molybdate, zirconium selenate, zirconium tellurium, zirconium tellurium, bismuth oxide, bismuth titanate, bismuth nitrate, bismuth salicylate, bismuth carbonate, antimony pentoxide, antimony trioxide, antimony acid, antimony acid A photosensitive resin composition, characterized in that it is an inorganic compound selected from zirconium acid and titanium antimonate. 3. The method according to claim 1 or 2,
At least 1 type of the inorganic compound which has Zr and at least 1 type of the inorganic compound which has Bi as said ion trapping agent is contained, The photosensitive resin composition characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
A photosensitive resin composition comprising a polymer dispersant having a group which interacts with the surface of the inorganic filler and not having an ethylenically unsaturated group. 5. The method of claim 4,
Said dispersing agent is a dispersing agent which has a basic group or an acidic group, The photosensitive resin composition characterized by the above-mentioned. The method according to claim 4 or 5,
The said dispersing agent has a primary amino group or a secondary amino group, The photosensitive resin composition characterized by the above-mentioned. 7. The method according to any one of claims 4 to 6,
Said dispersing agent has a graft chain, The photosensitive resin composition characterized by the above-mentioned. 8. The method according to any one of claims 4 to 7,
The amine titer of the said dispersing agent is 0.65 mmol / g or more, The photosensitive resin composition characterized by the above-mentioned. 9. The method according to any one of claims 4 to 8,
The acid value of the said dispersing agent is 0.1 mmol / g or more, The photosensitive resin composition characterized by the above-mentioned. 10. The method according to any one of claims 1 to 9,
The said inorganic filler contains the silicon in the constituent atom, The photosensitive resin composition characterized by the above-mentioned. 11. The method according to any one of claims 1 to 10,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, characterized in that the photosensitive resin composition. 12. The method according to any one of claims 1 to 11,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and further has a structure of any one of the following general formulas (1) to (3).

[In General Formula (1)-(3), R <^1> -R <^11> represents a hydrogen atom or monovalent organic group each independently. X and Y each independently represent an oxygen atom, a sulfur atom or -N (R ¹² )-. Here, R ¹² represents a hydrogen atom or a monovalent organic group. Z represents an oxygen atom, a sulfur atom, -N (R ¹³ )-or a phenylene group which may have a substituent. Wherein R ¹³ represents a hydrogen atom or a monovalent organic group] 13. The method according to any one of claims 1 to 12,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and the ratio of the aromatic moiety in the resin is 30% by mass or more. 14. The method according to any one of claims 1 to 13,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and further has a partial structure represented by the following general formula (UB).

[In Formula (UB), X ^L1 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or -C (= O)-, R ^u1 to R ^u8 each independently represent a hydrogen atom or a substituent.] 15. The method according to any one of claims 1 to 14,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and has a partial structure represented by the following general formula (UB), wherein the proportion of the aromatic moiety of the general formula (UB) in the resin is 30% by mass. The photosensitive resin composition characterized by the above.

[In Formula (UB), X ^L1 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or -C (= O)-, R ^u1 to R ^u8 each independently represent a hydrogen atom or a substituent.] 16. The method according to claim 14 or 15,
In the general formula (UB), R ^u1 to R ^u8 are all hydrogen atoms. 17. The method according to any one of claims 1 to 16,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and further has a partial structure represented by the following general formula (UNCO).

[In general formula (UNCO), X ^L1 is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or -C (= O)-is represented. R ^u1 to R ^u8 each independently represent a hydrogen atom or a substituent] The method of claim 17,
In the general formula (UNCO), all of R ^u1 to R ^u8 are hydrogen atoms, and X ^L1 is —CH ₂ —, wherein the photosensitive resin composition is used. The method according to claim 17 or 18,
The ratio of the aromatic part of the said general formula (UNCO) to the said acid-modified ethylenically unsaturated group containing polyurethane resin is 30 mass% or more, The photosensitive resin composition characterized by the above-mentioned. 20. The method according to any one of claims 1 to 19,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and further has a partial structure represented by the following general formula (UE1).

[In general formula (UE1), L ^UE does not contain -NHC (= O) O- or -OC (= O) NH- at the bond of a principal chain, and, as a substituent, an ethylenically unsaturated group or an ethylenically unsaturated group is used. Represents a divalent linking group having one group] 21. The method according to any one of claims 1 to 20,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and further has a partial structure represented by the following general formula (G1).

[In General Formula (G1), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group. A represents a divalent organic residue. X represents an oxygen atom, a sulfur atom, or -N (R ¹² )-, and R ¹² represents a hydrogen atom or a monovalent organic group.] 22. The method according to any one of claims 1 to 21,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and further has a partial structure represented by the following general formula (U1).

[In General Formula (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group.] 23. The method according to any one of claims 1 to 22,
The acid-modified ethylenically unsaturated group-containing resin is a polyurethane resin, and further has a group having a carboxyl group at the polymer terminal. 24. The method according to any one of claims 1 to 23,
The ethylenically unsaturated group equivalent of the said acid-modified ethylenically unsaturated group containing resin is 1.00 mmol / g or more, The photosensitive resin composition characterized by the above-mentioned. It has a photosensitive layer containing the photosensitive resin composition of any one of Claims 1-24 on a support body, The photosensitive film characterized by the above-mentioned. It has a photosensitive layer containing the photosensitive resin composition of any one of Claims 1-24 on a base body, The photosensitive laminated body characterized by the above-mentioned. A method of forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive resin composition according to any one of claims 1 to 24. A permanent pattern is formed by the permanent pattern formation method of Claim 27, The printed circuit board characterized by the above-mentioned.