KR20110030336A - Photosensitive composition, photosensitive film, photosensitive laminate, method for forming permanent pattern and printed board - Google Patents

Abstract

PURPOSE: A photo-sensitive composition, a photo-sensitive film using the same, a photo-sensitive laminate, a method for forming a permanent pattern, and a printed board are provided to include the superior insulation reliability and to be used as solder resist for packages. CONSTITUTION: A photo-sensitive composition includes a binder, a polymeric compound, a photo-polymerization initiator, and an ion absorber. The ion absorber includes one or more of a bismuth compound, a zirconium compound, and an antimony oxide compound. The bismuth compound is a bismuth oxide. The zirconium compound is a zirconium phosphate. The antimony oxide compound is an antimony penta-oxide. The binder is selected from an epoxy (meta)acrylate resin, a (meta)acrylate resin, and a urethane resin.

Description

Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board {PHOTOSENSITIVE COMPOSITION, PHOTOSENSITIVE FILM, PHOTOSENSITIVE LAMINATE, METHOD FOR FORMING PERMANENT PATTERN AND PRINTED BOARD}

The present invention relates to a photosensitive composition, a photosensitive film, a photosensitive laminate, a method of forming a permanent pattern, and a printed board, which are suitable as solder resist materials for forming an image by laser exposure.

Conventionally, the photosensitive film which formed the photosensitive layer by apply | coating and drying a photosensitive composition on a support body when forming permanent patterns, such as a soldering resist, is used. As a method of forming a permanent pattern, such as a soldering resist, a photosensitive film is laminated | stacked on the support body, such as a copper clad laminated board in which a permanent pattern is formed, and a photosensitive laminated body is formed, for the photosensitive layer in the said photosensitive laminated body, For example, a method of forming a permanent pattern by performing exposure, developing a photosensitive layer after the exposure to form a pattern, and then performing a curing treatment or the like is known.

Although the said solder resist is used for manufacture of a printed wiring board etc., in recent years, it is used for semiconductor packages, such as BGA (ball grid array), CSP (chip size package), and TCP (tape carrier package). Such a package solder resist is strongly required to improve the high-speed accelerated life test (HAST test), which is an accelerated evaluation of insulation reliability, and various studies have been made.

For example, Japanese Patent Application Laid-Open No. 1-259591 discloses a coating material for electronic circuits having a large effect of preventing migration phenomenon. The examples include epoxy resins containing a mixture of zirconium phosphate and lead hydroxyapatite, antimony acid and bismuth oxide. The mixture which mix | blended the mixture and the mixture of titanium antimony acid and lead hydroxyapatite is used. Further, specific examples of the inorganic ion exchanger are disclosed in the lower right column of the third page to the upper right column of the fourth page of Japanese Patent Laid-Open No. 1-259591.

Japanese Unexamined Patent Application Publication No. 8-176242 discloses a highly reliable resin composition for an interlayer insulating material, in which an antimony acid or titanium hydroxide is added to the acrylate resin. Further, paragraphs [0044] to [0046] of Japanese Patent Laid-Open No. 8-176242 disclose specific compounds of inorganic ion exchangers.

In addition, Japanese Unexamined Patent Publication No. 2000-159859 discloses a photosensitive resin composition having excellent insulation and corrosion resistance, and examples thereof include at least any one of antimony pentoxide, antimony trioxide, and hydrotalcite in an epoxy (meth) acrylate resin. A mixture of these is used. Further, in the attic of the Japanese Unexamined Patent Application Publication No. 2000-159859, examples of inorganic ion exchangers that adsorb negative ions, inorganic ion exchangers that adsorb cations, and inorganic ion exchangers adsorbing anions Compounds are described.

However, all of the technologies described in the above prior art documents do not have sufficient performances to satisfy characteristics such as insulation reliability, thermal shock resistance, storage stability, high quality, substrate adhesion, and heat resistance, and further improvement and development This is what is desired.

The present invention combines excellent insulation reliability, thermal shock resistance, storage stability, high quality, substrate adhesion, and heat resistance, and is particularly preferable as a soldering resist for a package, a photosensitive film using the photosensitive composition, photosensitive laminate, permanent pattern formation It aims at providing a method and a printed circuit board.

In order to solve the above problems, the present inventors earnestly examined, and in particular, in order to improve insulation reliability, thermal shock resistance, storage stability, high quality, substrate adhesion, surface hardness, heat resistance, etc. required for a soldering package for resist, It has been found that the above problem can be effectively solved by using at least one of a bismuth compound, a zirconium compound and an antimony oxide compound together as an adsorbent.

This invention is based on the said knowledge by the present inventors, As a means for solving the said subject, it is as follows. In other words,

As a photosensitive composition containing at least a <1> binder, a polymeric compound, a photoinitiator, and an ion adsorption agent,

The ion adsorbent is a photosensitive composition comprising a bismuth compound, at least one of a zirconium compound and an antimony oxide compound.

<2> In <1>, a bismuth compound is a photosensitive composition which is bismuth oxide.

<3> In <1>, a zirconium compound is a photosensitive composition which is zirconium phosphate.

<4> In <1>, the antimony oxide compound is a photosensitive composition which is antimony pentoxide.

<5> The photosensitive composition as described in <1> whose mass ratio (A: B) of a bismuth compound (A), and a zirconium compound and an antimony oxide compound (B) is 1: 0.2-1: 5.

<6> In <1>, a binder is the photosensitive composition chosen from an epoxy (meth) acrylate resin, a (meth) acrylate resin, and a urethane resin.

<7> In <6>, a binder is the photosensitive composition which is an acid-modified vinyl-group containing polyurethane resin.

<8> a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent at least

The ion adsorbent is a photosensitive film comprising a photosensitive layer containing a bismuth compound and a photosensitive composition containing at least one of a zirconium compound and an antimony oxide compound on a support.

At least a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent on the <9> substrate,

The said ion adsorption agent is a photosensitive laminated body which has a photosensitive layer containing a bismuth compound and the photosensitive composition containing at least any one of a zirconium compound and an antimony oxide compound.

<10> a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent at least;

The ion adsorbent is a permanent pattern forming method comprising at least exposing a photosensitive layer formed of a photosensitive composition containing a bismuth compound and at least one of a zirconium compound and an antimony oxide compound.

<11> a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent at least

The ion adsorbent is a permanent pattern is formed by a permanent pattern forming method comprising at least exposing a photosensitive layer formed of a photosensitive composition containing a bismuth compound and at least one of a zirconium compound and an antimony oxide compound. It is a printed circuit board made into.

INDUSTRIAL APPLICABILITY According to the present invention, various problems in the related art can be solved, and a photosensitive composition having excellent insulation reliability, thermal shock resistance, storage stability, high quality, substrate adhesion, and heat resistance, and particularly preferred as a soldering resist for a package, the photosensitive property A photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed board using the composition can be provided.

(Photosensitive composition)

The photosensitive composition of this invention contains a binder, a polymeric compound, a photoinitiator, and an ion adsorption agent at least, and further contains a thermal crosslinking agent and other components as needed.

<Ion Adsorbent>

There is no restriction | limiting in particular as said ion adsorbent, Although it can select suitably according to the objective, It is preferable to use the combination of an anion adsorbent and a cationic adsorbent, and anion, such as free Cl <^-> or hydrolyzable Cl <^-> , and free Na <^+> or Cu <^2+> It is preferable in view of synergistically improving the insulation reliability by replenishing the positive and negative ions.

As an ion adsorbent which adsorbs yin-yang positive ions, a combination of yin-yang ion adsorbents or beryllium oxide hydrate, gallium oxide hydrate, lanthanum oxide hydrate, iron oxide hydrate, aluminum oxide hydrate, titanium oxide hydrate, zirconium oxide hydrate, tin oxide hydrate, and oxidation And hydrous oxides of metals such as germanium hydrate and thorium oxide hydrate.

Moreover, the positive ion exchanger IXE-1100 (calcium system), IXE-1320 (antimony, magnesium, aluminum system), IXE-600 (antimony, bismuth system), IXE-633 (antimony) marketed by Toagosei Co., Ltd. , Bismuth type), IXE-680 (antimony, bismuth type), IXE-6107 (zirconium, bismuth type), IXE-6136 (zirconium, bismuth type), IXE-2116 (yttrium, zirconium type), IXE-7107 (magnesium) , Aluminum, zirconium series) can also be used.

As said anion adsorbent, a bismuth compound, antimony trioxide hydrate, hydrotalcites, etc. are mentioned, for example.

Moreover, the anion exchanger IXE-500 (bismuth system) marketed by Toagosei Co., Ltd .. IXE-530 (bismuth), IXE-550 (bismuth), IXE-700 (magnesium, aluminum), IXE-700F (magnesium, aluminum), IXE-770 (magnesium, aluminum), IXE-770D ( Magnesium, aluminum), IXE-702 (aluminum), IXE-800 (zirconium), IXE-1000 (lead), and the like.

Examples of the ion adsorbent include hydrous oxides and phosphoric acids of metals such as zirconium compounds, antimony oxide compounds, manganese oxide hydrates, silicon oxide hydrates, niobium oxide hydrates, tantalum oxide hydrates, tantalum oxide hydrates, molybdenum oxide hydrates, and tungsten oxide hydrates. Zirconium, zirconium tungstate, antimony molybdate, phosphorus antimonic acid, zirconium molybdate, titanium molybdate, titanium tungsten, tin molybdate, tin tungstate, titanium antimonate, zirconium selenium, zirconium tellurium, zirconium silicate, Zirconium phosphate, zirconium polyphosphate, chromium tripolyphosphate, antimony triphosphate, and the like.

Moreover, cation exchanger IXE-100 (zirconium system), IXE-150 (zirconium system), IXE-200 (tin system), IXE300 (antimony system), IXE-400 (titanium system) marketed from Toagosei Co., Ltd. ), And the like.

In this invention, at least one of a bismuth compound, a zirconium compound, and an antimony oxide compound is used together as said ion adsorbent.

As said bismuth compound, bismuth oxide, bismuth titanate, bismuth nitrate, bismuth salicylate, bismuth carbonate, etc. are mentioned, for example. Among these, bismuth oxide is especially preferable at the point which specifically adsorbs Cl <^-> .

Examples of the zirconium compound include zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium selenate, zirconium tellurium and the like. Among these, zirconium phosphate is particularly preferable because cations such as Na ⁺ and K ⁺ can be selectively ion exchanged and the ion exchange capacity is also excellent.

Examples of the antimony oxide 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 which can selectively adsorb | suck Na <^+> .

The mass ratio (A: B) of the bismuth compound (A) and at least one of the zirconium compound and the antimony oxide compound (B) is preferably from 1: 0.2 to 1: 5, more preferably from 1: 0.5 to 1: 2. Do. If one of the yin-yang ion adsorbents is shifted to increase, the adsorption action of the yin-ion ion adsorbent may be inhibited in the resin matrix.

When there are too many said bismuth compounds (A), adsorption inhibition will be inhibited with respect to a cation adsorbent, and when at least one (B) of the said zirconium compound and antimony oxide compound is too large, it may become adsorption inhibition with respect to an anion adsorbent.

0.5 mass%-10 mass% are preferable, and, as for the total content in the said photosensitive composition solid content of the said ion adsorbent, 1 mass%-5 mass% are more preferable. When the said total content exceeds 10 mass%, hardening defect, resolution, and adhesiveness may fall, and when it is less than 0.5 mass%, the effect of the insulation reliability improvement may become small.

<Binder>

There is no restriction | limiting in particular if it is a compound which introduce | transduced the photosensitive group and the acidic radical for giving alkali developability as said binder, According to the objective, it can select suitably, For example, an epoxy (meth) acrylate resin and a (meth) acrylate resin A polymer obtained by further reacting a polybasic acid anhydride after reacting a urethane resin, an epoxy resin having two or more epoxy groups, and an unsaturated (meth) acrylic acid; A modified copolymer in which glycidyl (meth) acrylate is added to a part of an acid group of a copolymer obtained from a compound containing a (meth) acrylic acid ester and an unsaturated group and having at least one acid group; The polymer etc. which are obtained by reaction of a carboxyl group-containing (meth) acrylic-type copolymer resin and an alicyclic epoxy group containing unsaturated compound are mentioned.

Among these, the acid groups of some of the copolymers obtained from a compound containing an epoxy (meth) acrylate resin, a (meth) acrylate resin, a urethane resin, a (meth) acrylic acid ester and an unsaturated group, and having at least one acid group More preferred is a modified copolymer to which cydyl (meth) acrylate is added.

As said urethane resin, the acid-modified vinyl-group containing polyurethane resin demonstrated below is preferably illustrated from the point which is excellent in heat shock resistance.

<< acid-modified vinyl group containing polyurethane resin >>

There is no restriction | limiting in particular as said acid-modified vinyl-group containing polyurethane resin, According to the objective, it can select suitably, For example, (i) polyurethane resin which has ethylenically unsaturated bond in a side chain, (ii) carboxyl group-containing polyurethane, Polyurethane resin etc. which are obtained by making the compound which has an epoxy group and a vinyl group react in a molecule | numerator are mentioned.

-(i) polyurethane resin having a vinyl group in the side chain-

There is no restriction | limiting in particular as a urethane resin which has a vinyl group in the said side chain, According to the objective, it can select suitably, For example, what has at least 1 of the functional groups represented by following General formula (1)-(3) in the side chain Can be mentioned.

In the said General formula (1), R <^1> -R <^3> represents a hydrogen atom or monovalent organic group each independently. There is no restriction | limiting in particular as said R <^1> , According to the objective, it can select suitably, For example, a hydrogen atom, the alkyl group which may have a substituent, etc. are mentioned. Among these, a hydrogen atom and a methyl group are preferable at the point of high radical reactivity. In addition, there is no restriction | limiting in particular as said R <^2> and R <^3> , According to the objective, it can select suitably, Each independently, for example, a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyan Furnace group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, The alkylsulfonyl group which may have a substituent, the arylsulfonyl group which may have a substituent, etc. are mentioned. Among these, in view of high radical reactivity, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

In the general formula (1), X represents an oxygen atom, a sulfur atom, or -N (R ¹² )-, and R ¹² represents a hydrogen atom or a monovalent organic group. There is no restriction | limiting in particular as said R <^12> , According to the objective, it can select suitably, For example, the alkyl group etc. which may have a substituent are mentioned. Among these, a hydrogen atom, a methyl group, an ethyl group, and isopropyl group are preferable at the point of high radical reactivity.

There is no restriction | limiting in particular as said substituent which can be introduce | transduced here, According to the objective, it can select suitably, For example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, Alkylamino group, arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group, etc. are mentioned.

In the said General formula (2), R <^4> -R <^8> represents a hydrogen atom or monovalent organic group each independently. Wherein R ⁴ ~R ⁸ is not particularly limited and can be suitably selected according to the purpose, take a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, and a substituent may have Alkylsulfonyl group, the arylsulfonyl group which may have a substituent, etc. are mentioned. Among these, in view of high radical reactivity, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

As a substituent which can be introduce | transduced, the thing similar to the said General formula (1) is mentioned. In addition, Y is an oxygen atom, a sulfur atom, or -N (R ¹²⁾ - represents a. Said R <^12> is synonymous with the case of R <^12> of the said General formula (1), and its preferable example is also the same.

Wherein in the formula (3), R ⁹ ~R ^l1, independently represent a hydrogen atom or a monovalent organic, respectively. There is no restriction | limiting in particular as said R <^{9> in the} said General formula (3), It can select suitably according to the objective, The alkyl group etc. which may have a hydrogen atom or a substituent are mentioned. Among these, a hydrogen atom and a methyl group are preferable at the point of high radical reactivity. There is no restriction | limiting in particular as said R <^10> and R <^{11> in the} said General formula (3), According to the objective, it can select suitably, A hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro Group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, and may have a substituent An arylamino group, the alkylsulfonyl group which may have a substituent, the arylsulfonyl group which may have a substituent, etc. are mentioned. Among these, in view of high radical reactivity, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

Here, as a substituent which can be introduce | transduced, the thing similar to the said General formula (1) is illustrated. Z represents an oxygen atom, a sulfur atom, -N (R ¹³ )-, or a phenylene group which may have a substituent. There is no restriction | limiting in particular as said R <^13> , According to the objective, it can select suitably, The alkyl group etc. which may have a substituent are mentioned. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable at the point of high radical reactivity.

The urethane resin which has an ethylenically unsaturated bond in the said side chain is represented by at least 1 sort (s) of reaction product of the diisocyanate compound represented by following General formula (4), and the diol compound represented by following General formula (5). It is a polyurethane resin whose structural unit is a basic skeleton.

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

At least one of the diisocyanate compound represented by the general formula (4) or the diol compound represented by the general formula (5) has at least one of the groups represented by the general formulas (1) to (3) If there exists, the polyurethane resin which introduce | transduced the group represented by the said General formula (1)-(3) into the side chain as a reaction product of the said diisocyanate compound and the said diol compound 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. .

It does not restrict | limit especially as a diisocyanate compound represented by the said General formula (4), According to the objective, it can select suitably, For example, a triisocyanate compound and the monofunctional alcohol which has an 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 method of introduce | transducing an unsaturated group into the side chain of the said polyurethane resin, Although it can select suitably according to the objective, The method of using the diisocyanate compound containing an unsaturated group in a side chain as a raw material of polyurethane resin manufacture. This is preferred. There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, It is a diisocyanate compound obtained by addition-reacting 1 equivalent of monofunctional alcohol or monofunctional amine compound which has a triisocyanate compound and an unsaturated group, For example, the compound etc. which have an unsaturated group in the side chain of Paragraph [0042]-[0049] of Unexamined-Japanese-Patent No. 2005-250438 are mentioned.

Polyurethane resins having ethylenically unsaturated bonds in the side chains include diisocyanate compounds other than the diisocyanate compounds containing the unsaturated groups from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. It can also copolymerize.

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).

In General Formula (6), L ¹ represents a divalent 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, urethane, amide, 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-tolylenedienediisocyanate, p-xylylenediisocyanate, m-xylylenediisocyanate, 4,4 ',-diphenylmethane diisocyanate, 1,5-naphthylenediisocyanate, 3,3',-dimethyl Aromatic diisocyanate compounds such as biphenyl-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; Etc. can be mentioned.

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 polyetherdiol compound, a polyesterdiol compound, a polycarbonate diol compound, etc. are mentioned.

Here, as a method of introducing an unsaturated group into the side chain of a polyurethane resin, the method of using the diol compound containing an unsaturated group in a side chain as a raw material of polyurethane resin manufacture other than the above-mentioned method is also preferable. The diol compound which contains an unsaturated group in the said side chain may be marketed like a trimetholpropane monoallyl ether, for example, and contains compounds, such as a halogenated diol compound, a triol compound, an aminodiol compound, and an unsaturated group The compound may be easily produced by the reaction of a compound such as carboxylic acid, acid chloride, isocyanate, alcohol, amine, thiol, or halogenated alkyl compound. There is no restriction | limiting in particular as a diol compound containing an unsaturated group in the said side chain, According to the objective, it can select suitably, For example, the compound of Paragraph [0057]-[0060] of Unexamined-Japanese-Patent No. 2005-250438, and the following general And the compounds described in paragraphs [0064] to [0066] of JP 2005-250438 A shown by the formula (G). Among them, the compounds described in paragraphs [0064] to [0066] of JP 2005-250438 A represented by the following general formula (G) are preferable.

In the above general formula (G), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or -N (R). ¹² )-, and R ¹² represents a hydrogen atom or a monovalent organic group.

Further, the above-mentioned general formula R ¹ ~R ^3, and X in (G) is an R ¹ ~R ^3, and X and agreement in the general formula (1), as a preferred form.

By using the polyurethane resin derived from the diol compound represented by the said General formula (G), the film strength of a layer is improved 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 that can be achieved.

The polyurethane resin having an ethylenically unsaturated bond in the side chain is, for example, other than a diol compound containing an unsaturated group in the side chain from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. The diol compound of can be copolymerized.

There is no restriction | limiting in particular as diol compounds other than the diol compound which contains an unsaturated group in the said side chain, According to the objective, it can select suitably, For example, a polyetherdiol compound, a polyesterdiol compound, a polycarbonate diol compound, etc. are mentioned. .

There is no restriction | limiting in particular as said polyetherdiol 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 polyesterdiol 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 described in 9-12., Etc. are mentioned.

In addition, the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in the said side chain can also 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.

In addition, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in the said side chain, you may use together the diol compound which has a carboxyl group other than the diol compound mentioned above. As a diol compound which has the said carboxyl group, what is shown by following formula (17)-(19) is contained, for example.

In formulas (17) to (19), R ^{15 is a} hydrogen atom, a substituent [for example, a cyano group, a nitro group, a halogen atom such as -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). Each 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 them, it is not particularly limited and may be appropriately selected depending on the purpose. An alkyl group and a C6-C15 aryl group are preferable. In Formulas (17) to (19), L ⁹ , L ¹⁰ , and L ¹¹ may be the same or different from each other, and may be a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, or halogeno). Each group of is preferable.) As long as it represents a divalent aliphatic or aromatic hydrocarbon group which may have, there is no restriction | limiting in particular, Although it can select suitably according to the objective, C1-C20 alkylene group and C6-C15 aryl A benzene group is preferable and a C1-C8 alkylene group is more preferable. Moreover, as needed, you may have other functional groups which do not react with an isocyanate group in said L <^9> -L <^11> , for example, carbonyl, ester, urethane, amide, ureido, ether group. In addition, you may form a ring by two or three of said R <^15> , L <^7> , L <^8> , L <^9> .

There is no restriction | limiting in particular as long as it represents the trivalent aromatic hydrocarbon group which may have a substituent as Ar in said Formula (18), 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 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-hydroxyphenyl ) Acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2- Hydroxyethyl) -3-carboxy-propionamide, and the like.

Since the presence of such a carboxyl group can give a polyurethane resin the characteristics of hydrogen bondability and alkali solubility, it is preferable. More specifically, it is preferable that the polyurethane resin which has an ethylenically unsaturated bond group in the said side chain is resin which has a carboxyl group in a side chain, More specifically, it is preferable that the vinyl group of a side chain is 0.05 mmol / g-1.80 mmol / g, and 0.5 It is more preferable that it is mmol / g-1.80 mmol / g, It is especially preferable that it is 0.75 mmol / g-1.60 mmol / g, It is preferable to have a carboxyl group in a side chain, It is preferable that an acid value is 20 mgKOH / g-120 mgKOH / g. It is more preferable that it is 30 mgKOH / g-110 mgKOH / g, and 35 mgKOH / g-100 mgKOH / g are especially preferable.

In addition, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in a side chain, the compound which ring-opened tetracarboxylic dianhydride to a diol compound can also be used together in addition to 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 is mentioned.

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

There is no restriction | limiting in particular as the introduction amount in the polyurethane resin which has an ethylenically unsaturated bond in the said side chain of the said ethylenically unsaturated bond group, Although it can select suitably according to the objective, As a vinyl group equivalent, it is 0.05 mmol / g-1.80 mmol / g This is preferable, 0.5 mmol / g-1.80 mmol / g are more preferable, 0.75 mmol / g-1.60 mmol / g are especially preferable. Moreover, it is preferable that the carboxyl group is introduce | transduced in the side chain with the said ethylenically unsaturated bond group in the polyurethane resin which has an ethylenically unsaturated bond in the said side chain. As acid value, 20 mgKOH / g-120 mgKOH / g are preferable, 30 mgKOH / g-110 mgKOH / g are more preferable, 35 mgKOH / g-100 mgKOH / g are especially preferable.

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

Moreover, as a polyurethane resin which has an ethylenically unsaturated bond in the said side chain, what has an unsaturated group in a polymer terminal and a main chain is used preferably. Crosslinking reactivity is improved by having a polymer terminal and an unsaturated group in a main chain, and also between the photosensitive composition and the polyurethane resin which has an ethylenically unsaturated bond in a side chain, or between the polyurethane resin which has an ethylenically unsaturated bond in a side chain, Cargo strength increases Here, as an unsaturated group, what has a carbon-carbon double bond is especially preferable from the tendency of a crosslinking reaction to occur.

As a method of introducing an unsaturated group into a polymer terminal, there exists a method shown below. That is, in the process of synthesis | combining the polyurethane resin which has an ethylenically unsaturated bond in the above-mentioned side chain, the alcohol or amines etc. which have an unsaturated group are used in the process of processing with the residual isocyanate group of a polymer terminal, alcohol, amines, etc. Do it. As such a compound, the thing similar to the exemplary compound illustrated previously as monofunctional alcohol or monofunctional amine compound which has an unsaturated group is mentioned specifically ,.

Moreover, it is preferable that an unsaturated group is introduce | transduced 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 both the formation of a crosslinked cured film, and a biopreservation property.

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 vinyl group equivalent, 0.05 mmol / g-1.80 mmol / g are preferable, and 0.5 mmol / g-1.80 mmol / g are More preferably, 0.75 m mo1 / g-1.60 mmol / g are 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, trans-2-butene-1,4-diol And polybutadiene diols.

The polyurethane resin which has an ethylenically unsaturated bond in the said side chain can also use together alkali-soluble polymer containing the polyurethane resin which has a structure different from the said specific polyurethane resin. For example, the polyurethane resin which has an ethylenically unsaturated bond in the said side chain can use together the polyurethane resin which contained the aromatic group in the main chain and / or the side chain.

As a specific example of the polyurethane resin which has an ethylenically unsaturated bond in said (i) side chain, For example, P-1-P-31 of Paragraph [0293]-[0310] of Unexamined-Japanese-Patent No. 2005-250438 are mentioned. Polymers; Among these, polymers of P-27 and P-28 shown in paragraphs [0308] and [0309] are preferable.

-(ii) polyurethane resin obtained by making a compound which has an epoxy group and a vinyl group react in a carboxyl group-containing polyurethane and a molecule |

The said polyurethane resin is a polyurethane resin obtained by making the carboxyl group-containing polyurethane which makes a diisocyanate and carboxylic acid group containing diol an essential component, and the compound which has an epoxy group and a vinyl group in a molecule | numerator react. According to the objective, you may add the low molecular weight diol of a weight average molecular weight 300 or less and the low molecular weight diol of 500 or more of weight average molecular weight as a copolymerization component as a diol component.

By using the polyurethane resin, it is excellent in stable dispersibility, crack resistance, and impact resistance with the inorganic filler, so that heat resistance, moisture heat resistance, adhesion, mechanical properties, and electrical properties are improved.

As the polyurethane resin, a diisocyanate of a divalent aliphatic and aromatic hydrocarbon which may have a substituent and a carboxylic acid-containing diol having a COOH group and two OH groups via any one of C and N atoms as essential components As one reactant, the obtained reactant may be obtained by reacting a compound having an epoxy group and a vinyl group in a molecule through a -CO0- bond.

Moreover, as said polyurethane resin, at least 1 sort (s) chosen from diisocyanate represented by the following general formula (I) and carboxylic acid group containing diol represented by the following general formula (II-1)-(II-3) is an essential component. According to the objective, the weight average molecular weight represented by following General formula (III-1)-(III-5) is a reactant with at least 1 sort (s) chosen from the polymeric diol in the range of 800-3,000, and the obtained reactant, What is obtained by making the compound which has an epoxy group and a vinyl group react in the molecule | numerator represented by following General formula (IV-1)-(IV-16) may be sufficient.

However, in said general formula (I), R <_1> represents the bivalent aliphatic or aromatic hydrocarbon which may have a substituent (for example, any one of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Indicates. As needed, said R <_1> may have any other functional group which does not react with an isocyanate group, for example, ester group, urethane group, amide group, and ureido group. In General Formula (I), R ₂ represents a hydrogen atom, a substituent [for example, a cyano group, a nitro group, a halogen atom (-F, -Cl, -Br, -I), -CONH ₂ , -COOR ₆ ,- OR ₆ , -NHCONHR ₆ , -NHCOOR ₆ , -NHCOR ₆ , -OCONHR ₆ , CONHR ₆ (wherein R ₆ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) Each group is included]. It represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group which may have. Among these, a hydrogen atom, a C1-C3 alkyl group, and a C6-C15 aryl group are preferable. In said general formula (II-1) and general formula (II-2), R <_3> , R <_4> and R <_5> may be the same respectively, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group, The divalent aliphatic or aromatic hydrocarbon which may have an alkoxy group and a halogeno group is preferable). Among these, a C1-C20 alkylene group and a C6-C15 arylene group are preferable, and a C1-C8 alkylene group is more preferable. Moreover, as needed, you may have other functional groups which do not react with an isocyanate group in said R <_3> , R <_4> and R <_5> , for example, a carbonyl group, ester group, a urethane group, an amide group, a ureido group, and an ether group. In addition, you may form a ring by two or three of said R <_2> , R <_3> , R <_4> and R <_5> . Ar represents the trivalent aromatic hydrocarbon which may have a substituent, and a C6-C15 aromatic group is preferable.

However, in General Formulas (III-1) to (III-3), R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ may be the same as or different from each other and represent a divalent aliphatic or aromatic hydrocarbon. . R ₇ , R ₉ , R ₁₀ and R ₁ are each preferably a C 2-20 alkylene group or a C 6-15 arylene group, each having 2 to 10 alkylenes or 6 to 10 carbon atoms. Arylene group is more preferable. R <_8> represents a C1-C20 alkylene group or a C6-C15 arylene group, and its C1-C10 alkylene or a C6-C10 arylene group is more preferable. In addition, in R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , other functional groups which do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups, amide groups, and urea Pottery, a halogen atom, etc. 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, C6-C15 aralkyl, cyano group, or halogen atom is preferable, Hydrogen atom, C1-C6 alkyl, and C6 More preferably, 10 to 10 aryl groups are used. Moreover, in said R <_12> , another functional group which does not react with an isocyanate group, for example, an alkoxy group, a carbonyl group, an olefin group, an ester group, or a halogen atom may be sufficient.

In said 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. M represents the integer of 2-4 in the said General formula (III-4). In the general formulas (III-1) to (III-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represent an integer of 2 or more, and an integer of 2 to 100 is preferable. In said general formula (III-5), n <_6> represents the integer of 0 or 2 or more, and the integer of 0 or 2-100 is preferable.

In the 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 having 1 to 10 carbon atoms. Group. p represents the integer of 0 or 1-10.

Further, the polyurethane resin may further copolymerize a low molecular weight diol containing no carboxylic acid group as the fifth component, and are represented by the general formulas (III-1) to (III-5) as the low molecular weight diol, The weight average molecular weight is 500 or less. The said carboxylic acid group-containing low molecular weight diol can be added in the range which can maintain the elasticity modulus of a cured film sufficiently low, as long as alkali solubility does not fall.

Especially as said polyurethane resin, at least 1 sort (s) chosen from the diisocyanate represented by said general formula (I) and the carboxylic acid group containing diol represented by general formula (II-1)-(II-3) as an essential component According to the purpose, the weight average molecular weight represented by the general formulas (III-1) to (III-5) is at least one selected from polymer diols in the range of 800 to 3,000, or general formulas (III-1) to ( 1 in the molecule represented by any one of general formulas (IV-1) to (IV-16) in a reaction product with a low molecular weight diol having a weight average molecular weight of III-5) and a carboxylic acid group-free group having 500 or less. The alkali-soluble photocrosslinkable polyurethane resin whose acid value is 20 mgKOH / g-120 mgKOH / g obtained by reacting the compound which has two epoxy groups and at least 1 (meth) acryl group is preferable.

These high molecular compounds may be used independently and may use 2 or more types together. As content of the said acid-modified vinyl-group containing polyurethane resin contained in total solids, such as a photosensitive composition, 2 mass%-30 mass% are preferable, and 5 mass%-25 mass% are more preferable. When the said content is less than 2 mass%, sufficient low modulus at the time of high temperature of a cured film may not be obtained, and when it exceeds 30 mass%, developability deterioration and toughness fall of a cured film may occur.

Synthesis method of polyurethane resin obtained by reacting carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in a molecule-

As a synthesis method of the said polyurethane resin, the said diisocyanate compound and a 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 treating with an alcohol or an amine. .

--Diisocyanate--

There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (I), According to the objective, it can select suitably, For example, the compound etc. of Paragraph [0021] of Unexamined-Japanese-Patent No. 2007-2030 are mentioned. have.

--High molecular weight diols--

There is no restriction | limiting in particular as a high molecular weight diol compound represented by said general formula (III-1)-(III-5), According to the objective, it can select suitably, For example, Paragraph of Unexamined-Japanese-Patent No. 2007-2030 [ The compound described in 0022]-[0046], etc. are mentioned.

--Carboxylic acid group-containing diols--

Moreover, there is no restriction | limiting in particular as a diol compound which has a carboxyl group represented by said general formula (I1-1)-(II-3), According to the objective, it can select suitably, For example, Unexamined-Japanese-Patent No. 2007-2030. The compound described in paragraph [0047], etc. are mentioned.

Low molecular weight diols containing no carboxylic acid groups

There is no restriction | limiting in particular as said carboxylic acid group-containing low molecular weight diol, According to the objective, it can select suitably, For example, the compound etc. of Paragraph [0048] of Unexamined-Japanese-Patent No. 2007-2030 are mentioned.

As a copolymerization amount of the said carboxylic acid group free diol, 95 mol% or less in a low molecular weight diol is preferable, 80 mol% or less is more preferable, 50 mol% or less is especially preferable. When the said copolymerization amount exceeds 95 mol%, the urethane resin with favorable developability may not be obtained.

As a specific example of the polyurethane resin obtained by making the said (ii) carboxyl group-containing polyurethane react with the compound which has an epoxy group and a vinyl group in a molecule | numerator, it shows, for example in Paragraph [0314]-[0315] of Unexamined-Japanese-Patent No. 2007-2030. Glycidyl acrylate as the epoxy group and the vinyl group-containing compound in the polymers of U1 to U4 and U6 to U11, glycidyl methacrylate and 3,4-epoxycyclohexylmethyl acrylate (trade name: cyclomer A400 And polymers substituted by Daicel Kagaku Co., Ltd., 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cycler M400, manufactured by Daicel Kagaku Co., Ltd.), and the like.

Content of acid-modified vinyl group-containing polyurethane resin

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

If the said content is less than 5 mass%, crack resistance may not be maintained favorable, and when it exceeds 80 mass%, heat resistance may cause breakage. On the other hand, when the said content is in the said especially preferable range, it is advantageous at the point of compatible both crack resistance and heat resistance.

Weight-average molecular weight of acid-modified vinyl group-containing polyurethane resin

There is no restriction | limiting in particular as a weight average molecular weight of the said acid-modified vinyl-group containing polyurethane resin, Although it can select suitably according to the objective, 5,000-60,000 are preferable, 5,000-50,000 are more preferable, 5,000-30,000 are especially preferable. . When the said weight average molecular weight is less than 5,000, sufficient low elastic modulus at the time of high temperature of a cured film may not be obtained, and when it exceeds 60,000, applicability and developability may deteriorate.

In addition, the said weight average molecular weight uses a high-speed GPC apparatus (made by Toureda Co., Ltd., HLC-802A), for example, 0.5 mass% THF solution as a sample solution, and uses 1 TSKgel HZM-M as a column. , 200 μL of sample can be injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm). Subsequently, the weight average molecular weight was calculated | required from the molecular weight distribution curve corrected with standard polystyrene.

Acid value of acid-modified vinyl group-containing polyurethane resin

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

In addition, the said acid value can be measured based on JISK0070, for example. However, when the sample is not dissolved, dioxane or tetrahydrofuran is used as the solvent.

Vinyl group equivalent of acid-modified vinyl group-containing polyurethane resin

There is no restriction | limiting in particular as vinyl group equivalent of the said acid-modified vinyl-group containing polyurethane resin, Although it can select suitably according to the objective, 0.05 mmol / g-1.8 mmol / g are preferable, and 0.5 mmol / g-1.8 mmol / g This is more preferable, and 0.75 mmol / g-1.6 mmol / g are especially preferable. If the vinyl group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be lowered, and if it exceeds 1.8 mmol / g, the crack resistance may deteriorate.

The said vinyl group equivalent can be calculated | required, for example by measuring a bromine value. In addition, the said bromine value can be measured based on JISK2605, for example.

5 mass%-80 mass% are preferable, and, as for content in the said photosensitive composition solid content of the said binder, 30 mass%-60 mass% are more preferable. If the said content is 5 mass% or more, developability and exposure sensitivity will become favorable, and if it is 80 mass% or less, it can prevent that the adhesiveness of a photosensitive layer becomes too strong.

<Polymeric Compound>

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

As said ethylenically unsaturated bond, For example, vinyl groups, such as a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, a vinyl ester, and a vinyl ether; And allyl groups such as allyl ether and allyl ester.

There is no restriction | limiting in particular as a compound which has one or more of said ethylenically unsaturated bonds, Although it can select suitably according to the objective, For example, at least 1 sort (s) chosen from the monomer which has a (meth) acryl group is mentioned suitably.

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, trimetholol (Meth) acrylate after addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols such as propane, glycerin and bisphenol Urethane acrylates described in each publication such as yttrate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates, methacrylates, etc., such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among these, trimetholpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

5 mass%-50 mass% are preferable, and, as for content in the said photosensitive composition solid content of the said polymeric compound, 10 mass%-40 mass% are more preferable. If the said content is 5 mass% or more, developability and exposure sensitivity will become favorable, and if it is 50 mass% or less, it can prevent that the adhesiveness of a photosensitive layer becomes too strong.

<Photoinitiator>

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

The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm. As for the said wavelength, 330 nm-500 nm are more preferable.

As said photoinitiator, a neutral photoinitiator is used. Moreover, you may contain the other photoinitiator as needed.

There is no restriction | limiting in particular as said neutral photoinitiator, Although it can select suitably according to the objective, It is preferable that it is a compound which has an aromatic group at least, and it is preferable that it is (bis) acylphosphine oxide or its ester, an acetophenone type compound, and a benzophenone type It is more preferable that they are a compound, a benzoin ether type compound, a ketal derivative compound, and a thioxanthone compound. The said neutral photoinitiator may use 2 or more types together.

As said photoinitiator, it is (bis) acylphosphine oxide or its ester, acetophenone type compound, a benzophenone type compound, a benzoin ether type compound, a ketal derivative compound, a thioxanthone compound, an oxime derivative, an organic peroxide, for example. And thio compounds. Among these, oxime derivatives, (bis) acylphosphine oxides or esters thereof, acetophenone compounds, benzophenone compounds, and benzo Preference is given to inether compounds, ketal derivative compounds and thioxanthone compounds.

As said (bis) acyl phosphine oxide, 2, 6- dimethyl benzoyl diphenyl phosphine oxide, 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide, 2, 4, 6- trimethyl benzoyl phenyl phosphinic acid Methyl ester, 2,6-dichlorobenzoylphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide And bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

As said acetophenone type compound, for example, acetophenone, methoxyacetophenone, 1-phenyl 2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-diphenoxydichloro Acetophenone, diethoxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, etc. are mentioned.

As said benzophenone type compound, for example, benzophenone, 4-phenylbenzophenone, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxy benzophenone, 3,3'- dimethyl- 4-methoxy benzophenone, diphenoxy Cibenzophenone etc. are mentioned.

As said benzoin ether type compound, benzoin ethyl ether, benzoin propyl ether, etc. are mentioned, for example.

As said ketal derivative compound, benzyl dimethyl ketal etc. are mentioned, for example.

As said thioxanthone compound, 2-chloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, isopropyl thi, for example Orcanthone etc. are mentioned.

As an oxime derivative used preferably by this invention, it is represented by following General formula (1), for example.

In the general formula (1), R ¹ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group, and R ² is each independently. Represents a substituent. m represents the integer of 0-4, and when two or more, you may connect with each other and form a ring. A represents any of 4, 5, 6, and a 7-membered ring. Moreover, it is preferable that A is either 5 or 6 membered ring.

Moreover, as an oxime derivative (oxime compound) used by this invention, what is represented by following General formula (2) is more preferable.

However, in said General formula (2), R <^1> represents either a hydrogen atom, the acyl group which may have a substituent, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group, and R <^2> is respectively independent Represents a substituent. m represents the integer of 0-4, and when two or more, you may connect with each other and form a ring. X represents any one of CH ₂ , O, and S. A represents either 5 or 6 membered ring.

As the acyl group represented by R ¹ in the general formulas (1) and (2), any of aliphatic, aromatics, and heterocycles may be used, and further have a substituent.

Examples of the aliphatic group include acetyl group, propanoyl group, butanoyl group, hexanoyl group, decanoyl group, phenoxyacetyl group, and chloroacetyl group. As an aromatic group, a benzoyl group, a naphthoyl group, a methoxy benzoyl group, a nitro benzoyl group, etc. are mentioned. Examples of the heterocyclic group include furanoyl group and thiophenoyl group.

As a substituent, any one of an alkoxy group, an aryloxy group, and a halogen atom is preferable. As an acyl group, it is preferable that it is C2-C30, It is more preferable that it is C2-C20, It is especially preferable that it is C2-C16. As such an acyl group, for example, an acetyl group, propanoyl group, methyl propanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, Benzylcarbonyl group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, pyridyl Carbonyl group, methacryloyl group, acryloyl group, etc. are mentioned.

The alkyloxycarbonyl group may have a substituent, preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 16 carbon atoms. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group and ethoxyethoxycarbonyl group. Can be.

As an aryloxycarbonyl group, you may have a substituent, the alkoxycarbonyl group of 7-30 total carbons is preferable, It is more preferable that it is 7-20 total carbons, It is especially preferable that it is 7-16 total carbons. Examples of such aryloxycarbonyl groups include phenoxycarbonyl groups, 2-naphthoxycarbonyl groups, paramethoxyphenoxycarbonyl groups, 2,5-diethoxyphenoxycarbonyl groups, parachlorophenoxycarbonyl groups, paranitrophenoxycarbonyl groups, and paracyano. Phenoxycarbonyl group is mentioned.

As an alkylsulfonyl group, you may further have a substituent. Examples of the substituent include phenyl group, halogen atom, alkoxy group, aryloxy group, alkoxycarbonyl group, acyloxy group, acylamino group, carbamoyl group, cyano group, carboxylic acid group, sulfonic acid group and heterocyclic group. have. As the alkylsulfonyl group, methylsulfonyl group, butylsulfonyl group, octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, benzylsulfonyl group and trifluoromethylsulfonyl group are particularly preferably exemplified.

As an arylsulfonyl group, you may further have a substituent. Examples of the substituent include phenyl group, halogen atom, alkoxy group, aryloxy group, alkoxycarbonyl group, acyloxy group, acylamino group, carbamoyl group, cyano group, carboxylic acid group, sulfonic acid group and heterocyclic group. have. As the arylsulfonyl group, benzenesulfonyl group, toluenesulfonyl group, chlorobenzenesulfonyl group, butoxybenzenesulfonyl group, 2,5-dibutoxybenzenesulfonyl group, paranitrobenzenesulfonyl group and perfluorobenzenesulfonyl group are particularly preferably mentioned. Can be.

Examples of the substituents represented by R ² in the general formulas (1) and (2) include aliphatic, aromatic, heteroaromatic, halogen atoms, -OR ³ , -SR ³ , and -NR ³ R ⁴ . R ³ and R ⁴ may be connected to each other to form a ring. R ³ and R ⁴ each independently represent a hydrogen atom or an aliphatic group, an aromatic group or a heteroaromatic group. When m is 2 or more and mutually connects and forms a ring, independent R <^2> may form a ring each independently, and may form a ring through at least one of R <^3> and R <^4> .

When forming a ring through the said substituent R <^2> , the following structures are mentioned.

In the above structural formula, Y and Z represent any one of CH ₂ , -O-, -S-, and -NR-.

Specific examples of the aliphatic group, aromatic group, and heteroaromatic group of R ² , R ³ , and R ⁴ include the same groups as those described above for R ¹ .

Although the compound represented by following structural formula (1)-(51) is mentioned as a specific example of the oxime compound represented by the said General formula (1), This invention is not limited to these.

In addition, the oxime compound used by this invention can be identified by measuring a ¹ H-NMR spectrum and a UV-vis absorption spectrum.

As the method for preparing the oxime compound, in the presence of a base (for example, triethylamine, pyridine) of a corresponding oxime compound and an acyl chloride or anhydride, in an inert solvent such as THF, DMF, acetonitrile, or in a basic solvent such as pyridine It can be synthesize | combined easily by making it react. As said reaction temperature, -10 degreeC-60 degreeC is preferable.

In addition, various oxime ester compounds can be synthesized by using chloroform acid ester, alkylsulfonyl chloride and arylsulfonyl chloride as the acyl chloride.

As a method for synthesizing the oxime compound used as a starting material in preparing the oxime compound, a standard chemistry textbook (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992), or a professional monograph, See, eg, SR Sandler & W. Karo, Organic functional group preparations, Vol. It can obtain by the various methods described in 3, Academic Press.

As a particularly preferable method for synthesizing the oxime compound, a method of reacting an aldehyde or a ketone with a hydroxylamine or a salt thereof in a polar solvent such as ethanol or ethanol water can be mentioned. In this case, the pH of the reaction mixture is controlled by adding a base such as sodium acetate or pyridine. It is well known that the rate of reaction is pH dependent and that the base can be added continuously at the start or during the reaction. Basic solvents such as pyridine may also be used as the base and / or solvent or co-solvent. As said reaction temperature, generally, the reflux temperature of a mixture, ie, about 60 to 120 degreeC is preferable.

As a further preferable synthesis method of the said oxime compound, the method by nitrosation of the "active" methylene group by nitrous acid or alkyl nitrite is mentioned. For example, Organic Syntheses coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp. Alkaline conditions as described in 199 and 840 and, for example, Organic Synthesis coll. Vol. V, pp. 32 and 373, coll. Vol. III, pp. 191 and 513, coll. Vol. II, pp. Both acidic conditions as described in 202, 204 and 363 are preferred for the synthesis of oxime compounds used as starting materials.

The nitrous acid is usually produced from sodium nitrite.

As said alkyl nitrite, methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite, etc. are mentioned, for example.

As group of the said oxime ester, what exists in two types of three-dimensional arrangement (Z) or (E) may be sufficient. An isomer may be isolate | separated by the usual method, and an isomer mixture may be used as it is as a seed for photoinitiation. Therefore, the said oxime compound may be a mixture of the isomers of the steric configuration of the compounds of the structural formulas (1) to (51).

The oxime compound is excellent in storage stability, and is highly sensitive, so that the oxime compound is added to the polymerizable composition so that it is excellent in storage stability without generating polymerization at the time of storage, and generates active radicals by irradiation with energy rays, especially light, thereby initiating polymerization efficiently. Thus, a highly sensitive polymerizable composition capable of efficiently polymerizing the polymerizable compound in a short time can be obtained.

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

0.1 mass%-30 mass% are preferable, as for content in the said photosensitive composition solid content of the said photoinitiator, 0.5 mass%-20 mass% are more preferable, 0.5 mass%-15 mass% are especially preferable.

<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 the photosensitive layer formed using the said photosensitive film, for example, in the range which does not adversely affect developability etc., for example A compound containing an epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), an oxetane compound having at least two oxetanyl groups in one molecule can be used, and JP 2007-47729 A A compound obtained by reacting an isocyanate group of an epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate, and derivatives thereof described in the publication. Etc. can be mentioned.

In addition, a melamine derivative may be used as the thermal crosslinking agent. Examples of the melamine derivatives include methirolmelamine and alkylated methirolmelamine (compounds obtained by etherification of a methrol group with methyl, ethyl, butyl, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated methirolmelamine is preferred, and hexamethylated methirolmelamine is particularly preferable because of its good storage stability, and the effect of improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

1 mass%-50 mass% are preferable, and, as for content in the said photosensitive composition solid content of the said thermal crosslinking agent, 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.

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

As an epoxy compound which has at least 2 oxirane group in the said one molecule, For example, Hexane type | mold or a biphenol type epoxy resin ("YX4000 Japan epoxy resin company make", etc.), or these mixtures, a hetero having an isocyanurate skeleton etc. Cyclic epoxy resin ("TEPIC; Nissan Kagaku Kogyo Co., Ltd.", "Araldite PT810; Chiba Specialty Chemicals", etc.) Bisphenol-A epoxy resin, a novolak-type epoxy resin, a bisphenol F-type epoxy resin, Hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolak type) Epoxy resins, etc.), allyl group-containing bisphenol-A epoxy resin, trisphenol methane-type epoxy resin, diphenyl dimethanol-type epoxy Resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; Dainippon ink Kagaku Kogyo Co., Ltd.", etc.), glycidylamine type epoxy resin (diamino Diphenylmethane type epoxy resin, diglycidyl aniline, triglycidylaminophenol, etc., glycidyl ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycyl) Cydyl ester, dimeric acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin [3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, "GT-300, GT-400, ZEHPE3150; Daicel Kagaku Kogyo KK, etc.], imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenyrolethane type epoxy resin, glycidyl phthalate resin , Tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products "ESN-190, ESN-360; Shinnitetsu Ka. Gaku Kogyo Co., Ltd. "," HP-4032, EXA-4750, EXA-4700; Dainippon ink Kagaku Kogyo Co., Ltd. ", etc.), a phenolic compound, and diolefins, such as divinylbenzene and dicyclopentadiene Epoxy reaction of the polyphenol compound obtained by the addition reaction of the compound, the reaction product of epichlorohydrin, and the ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid, etc. Epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethinephenyl type Liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine epoxy resin, glycidyl methacrylate copolymer type epoxy resin ("CP-50S, CP-50M; the Nippon Yushi Corporation", cyclohexyl maleimide, etc.). Although the copolymerization epoxy resin of a and glycidyl methacrylate, a bis (glycidyl oxyphenyl) fluorene type epoxy resin, a bis (glycidyl oxyphenyl) adamantane type epoxy resin, etc. are mentioned, It is limited to these. no. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing two epoxy groups in at least one molecule having an alkyl group at the β-position can be used, and an epoxy group having a β-position substituted with an alkyl group (more Specifically, the compound containing (beta) -alkyl substituted glycidyl group etc.) is especially preferable.

In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl substituted glycidyl group, and at least one epoxy group is a β-alkyl substituted glyci It may be a deal.

As said oxetane compound, the oxetane compound which has at least 2 oxetanyl group in 1 molecule is mentioned, for example.

Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylic Latex, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methylmethacrylate or these In addition to polyfunctional oxetanes such as oligomers or copolymers, compounds having an oxetane group, novolak resins, poly (p-hydroxystyrenes), cardo-type bisphenols, calixarenes, calyx resorcinylenes, and silses Ether compounds, such as resin which has a hydroxyl group, such as quoxane, are mentioned, In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate etc. are mentioned.

Moreover, as said polyisocyanate compound, the polyisocyanate compound of Unexamined-Japanese-Patent No. 5-9407 can be used, The said polyisocyanate compound is an aliphatic, cyclic aliphatic, or aromatic group substituted aliphatic compound containing at least 2 isocyanate groups. It may be induced. Specifically, difunctional isocyanate (for example, a mixture of 1,3-phenylenediisocyanate and 1,4-phenylenediisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1, 4-xylylene diisocyanate, bis (4-isoisanate-phenyl) methane, bis (4-isocyanate cyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, etc.), the said bifunctional Isocyanates and polyfunctional alcohols such as trimetholpropane, pentaerythritol and glycerin; An alkylene oxide adduct of the polyfunctional acol and an adduct of the difunctional isocyanate; Cyclic trimers such as hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate or derivatives thereof; Etc. can be mentioned.

As an isocyanate group blocking agent in the compound obtained by making a blocking agent react with the said polyisocyanate compound, ie, a compound obtained by making a blocking agent react with the isocyanate group of polyisocyanate and its derivatives, alcohols (for example, isopropanol and tert-butanol) ), Lactams (e.g., epsilon -caprolactam, etc.), phenols (e.g., phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p- Octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (e.g., 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (e.g., dialkylmalonates, methylethylke Toxin, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime and the like). In addition to these, compounds having at least one polymerizable double bond and at least one block isocyanate group in the molecule of JP-A-6-295060 can be used.

Examples of the melamine derivatives include methirolmelamine and alkylated methirolmelamine (compounds obtained by etherification of a methrol group with methyl, ethyl, butyl, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated methirolmelamine is preferred, and hexamethylated methirolmelamine is particularly preferable because of its good storage stability, and the effect of improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

<Other Ingredients>

There is no restriction | limiting in particular as said other components, According to the objective, it can select suitably, For example, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, a coloring agent (colored pigment or dye), etc. are mentioned, The adhesion promoter to the substrate surface and other preparations (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, properties, such as stability, a photographic property, and film | membrane property of the target photosensitive film, can be adjusted.

The filler is described in detail in, for example, paragraphs [0098] to [0099] of JP-A-2008-250074.

The thermal polymerization inhibitor is described in detail in, for example, paragraphs [0101] to [0102] of JP2008-250074A.

The thermosetting accelerator is described in detail in, for example, paragraph [0093] of JP2008-250074A.

The plasticizer is described in detail in, for example, paragraphs [0103] to [0104] of JP2008-250074A.

About the said coloring agent, it describes in detail in paragraphs [0105]-[0106] of Unexamined-Japanese-Patent No. 2008-250074, for example.

The adhesion promoter is described in detail in paragraphs [0107] to [0109] of JP2008-250074A, for example.

(Photosensitive film)

The photosensitive film of this invention consists of at least a support body and the photosensitive layer which consists of the photosensitive composition of this invention on the said support body, and further has other layers 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.

The support is made of a synthetic resin and is preferably transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) Acrylic ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as a low ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is especially preferable. These may be used individually by 1 type and may use 2 or more types together.

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

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

Photosensitive layer

There is no restriction | limiting in particular if the said photosensitive layer consists of a photosensitive composition, According to the objective, it can select suitably.

There is no restriction | limiting in particular as a 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 method of laminating | stacking is prepared by melt | dissolving, emulsifying, or disperse | distributing the said photosensitive composition of this invention in water or a solvent on the said support body, preparing a photosensitive composition solution, and apply | coating and drying the said solution directly. .

There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, alcohol, such as methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, and normal-hexanol ; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, acetate-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethyl formamide, dimethyl acetamide, dimethylene sulfoxide, sulfolane, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Moreover, you may add a well-known surfactant.

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. 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-110 degreeC.

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

<Other floors>

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.

As said protective film, what is used for the said support | support, paper, polyethylene, the paper laminated | stacked polypropylene, etc. are mentioned, for example, Among these, a polyethylene film and a polypropylene film are preferable.

Although the thickness of the said protective film does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially preferable. Do.

As the combination (support / protective film) of the support and the protective film, for example, polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate Etc. can be mentioned. In addition, the interlayer adhesion may be adjusted by surface treatment of at least one of the support and the protective film. The surface treatment of the support may be carried out in order to increase the adhesion with the photosensitive layer, and for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation Treatment, laser beam irradiation treatment, and the like.

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, winding shift | offset | difference can be prevented from occurring when it is made into a roll shape by slipping too much, and if it is 1.4 or less, it can wind up to a favorable roll shape.

It is preferable that the said photosensitive film is wound up and stored in roll shape in elongate shape, for example, by winding in a cylindrical core. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Moreover, you may slit process so that a user may use it, and you may make the elongate body of 100 m-1,000 m range into roll shape. In this case, it is preferable that the support is wound up to the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in sheet form. When storing, it is preferable to provide a separator (particularly moisture-proof and a desiccant containing) on the end surface from the viewpoint of protecting the end surface and preventing edge fusion, and it is preferable to use a material having a low moisture permeability for packing.

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

(Photosensitive laminated body)

The said photosensitive laminated body consists of at least base | substrate and the photosensitive layer provided on the said base | substrate, and is laminated | stacked by the other layer suitably selected according to the objective.

The photosensitive layer is transferred from the photosensitive film produced by the above-described manufacturing method, and has the same configuration as described above.

<Gas>

The substrate is a target gas to which the photosensitive layer is formed, or a transfer body to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and may 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 gas 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>

As a manufacturing method of the said photosensitive laminated body, the method of transferring and laminating | stacking at least any one of a heating and pressurization at least the photosensitive layer in the photosensitive film of this invention is mentioned.

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

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

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

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

Since the photosensitive film and the photosensitive laminate of the present invention have a uniform film thickness and a very low incidence of surface defects such as pinholes and cissing, the photosensitive film has excellent insulation reliability and high definition permanent patterns (protective film, interlayer insulating film, And solder resist patterns) can be efficiently formed. Therefore, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be used especially for permanent pattern formation 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 such as a developing step appropriately selected as necessary.

Exposure process

The said exposure process is a process of exposing to the photosensitive layer in the photosensitive laminated body of this invention. The photosensitive laminated body of this invention is as above-mentioned.

There is no restriction | limiting in particular as an object of the said exposure as long as it is a photosensitive layer in the said photosensitive laminated body, According to the objective, it can select suitably, For example, as mentioned above, at least any of heating and pressurizing a photosensitive film on a base material It is preferable to carry out about the photosensitive laminated body formed by laminating | stacking while doing one.

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

<Other Processes>

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

<< Development Process >>

The development is performed by removing the unexposed portion of the photosensitive layer.

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

8-12 are preferable and, as for pH of the said weakly alkaline aqueous solution, 9-11 are more preferable, for example. As said weak alkaline aqueous solution, 0.1 mass%-5 mass% of sodium carbonate aqueous solution or potassium carbonate aqueous solution, etc. are mentioned, for example.

Although the temperature of the said developing solution can be suitably selected according to the developability of the said photosensitive layer, about 25 degreeC-40 degreeC is preferable, for example.

The developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydrooxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and in order to promote development. You may use together with the organic solvent (for example, alcohol, ketones, ester, ether, amide, lactone, etc.). The developer may be an aqueous developer in which water or an alkali aqueous solution and an organic solvent are mixed, or may be an organic solvent alone.

<< hardening process >>

The said hardening process is a process of hardening | curing 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, 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.

As a method of the said front surface exposure process, the method of exposing the whole surface on the said photosensitive laminated body in which the said permanent pattern was formed after the said image development is mentioned, for example. Curing of resin in the photosensitive composition which forms the said photosensitive layer by the said front surface exposure is accelerated | stimulated, and the surface of the said permanent pattern is hardened.

There is no restriction | limiting in particular as an apparatus which performs the said front surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

As a method of the said front surface heat processing, the method of heating the whole surface on the said photosensitive laminated body in which the said permanent pattern was formed after the said image development is mentioned. The film strength of the surface of the permanent pattern is increased by the front heating.

120 degreeC-250 degreeC is preferable, and, as for the heating temperature in the said front heating, 120 degreeC-200 degreeC is more preferable. When the said heating temperature is 120 degreeC or more, film | membrane intensity | strength improves by heat processing, and when it is 250 degrees C or less, decomposition | disassembly of resin in the said photosensitive composition may arise and it can prevent that a film quality is weakly receded.

10 minutes-120 minutes are preferable, and, as for the heating time in the said whole surface heating, 15 minutes-60 minutes are more preferable.

There is no restriction | limiting in particular as an apparatus which performs said whole surface heating, It can select suitably from a well-known apparatus according to the objective, For example, a dry oven, a hotplate, an IR heater, etc. are mentioned.

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

That is, the hardening 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 wiring board. Soldering is performed after gold plating is performed on the metal layer part exposed on the surface of the printed wiring board. Then, a semiconductor, a component, or the like is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), and a solder resist, thereby preventing external shock and conduction of electrodes between neighbors.

(Printed board)

The printed board of this invention has at least a base | substrate and the permanent pattern formed by the said permanent pattern formation method, and has the other structure suitably selected as needed.

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. which further provided the insulating layer between the base material and the said permanent pattern are mentioned.

[Example]

Hereinafter, although the Example of this invention is described, this invention is not limited to these Examples at all.

Synthesis Example 1

Synthesis of Binder (B-1)

90.6 g of 1-methoxy-2-propanol was put into a 1,000 mL three neck flask, and it heated to 90 degreeC under nitrogen stream. Into this, 105.8 g of benzyl methacrylate and 156 g of 1-methoxy-2-propanol of 120.6 g of methacrylic acid and 7.24 g of 1-methoxy-2-propanol of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Each 50 g solution was dripped over 3 hours. After completion of the dropwise addition, the mixture was heated and reacted for 1 hour. Next, a 20-g solution of 2.00 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 2.00 g was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further heated and reacted for 3 hours, and then the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (30/70 mol% ratio).

Next, 105.2 g of glycidyl methacrylate and 20 g of 1-methoxy-2-propanol were added to the dropping funnel, and 0.34 g of p-methoxyphenol was added to the flask, followed by stirring to dissolve. After dissolution, 0.82 g of triphenylphosphine was added, and after heating to 100 ° C, glycidyl methacrylate was added dropwise from the dropping funnel over 1 hour to conduct an addition reaction. The loss of glycidyl methacrylate was confirmed by gas chromatography and the heating was stopped. 45.8 g of 1-methoxy-2-propanol was added. As mentioned above, the solution (solid content 45 mass%) of the binder (B-1) represented by a following formula was synthesize | combined.

The acid value of the obtained binder (B-1) was 121 mgKOH / g and the weight average molecular weight was 3.10,000.

Synthesis Example 2

Synthesis of Acid-modified Vinyl Group-containing Polyurethane Resin U1

10.86 g (0.081 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g (0.105 mol) of glycerol monomethacrylate (GLM) in a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer. Was dissolved in 79 mL of propylene glycol monomethyl ether monoacetate. 37.54 g (0.15 mol) of 4, 4- diphenylmethane diisocyanate (MDI), 0.1 g of 2, 6- di- t-butylhydroxytoluenes, a brand name as a catalyst: Neostane U-600 (Nitto Kasei Co., Ltd.) 0.2 g of Shikisha Co., Ltd. was added, and it heated and stirred at 75 degreeC for 5 hours. Thereafter, the mixture was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 145 g of a polymer solution.

The obtained acid-modified vinyl-group containing polyurethane resin U1 had a solid acid value of 70 mgKOH / g, the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 8,000, and the vinyl group equivalent was 1.5 mmol / g.

The said acid value was measured based on JISK0070. However, when a sample did not melt | dissolve, dioxane, tetrahydrofuran, etc. were used as a solvent.

The said weight average molecular weight was measured using the high speed GPC apparatus (The HLC-802A by Toyo Chemical Co., Ltd.). That is, 0.5 mass% HHF solution was used as a sample solution, and the column used 62 TSKgelGMH, 200 microliters of samples were injected, eluted in the THF solution, and measured by the refractive index detector at 25 degreeC. Subsequently, the weight average molecular weight was calculated | required from the molecular weight distribution curve corrected with standard polystyrene.

The said vinyl group equivalent was calculated | required by measuring bromine number based on JISK2605.

Synthesis Example 3

Synthesis of Acid-modified Vinyl Group-containing Polyurethane Resin U2

In Synthesis Example 2, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI) was charged with 30.03 g (0.12 mol) of 4,4-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HMDI). ) 5.05 g (0.03 mole), and a combination of 10.86 g (0.081 mole) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g (0.105 mole) of glycerol monomethacrylate (GLM) 10.22 g (0.069 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA), 12.97 g (0.081 mol) of glycerol monomethacrylate (GLM) and 4.80 g of polypropylene glycol (molecular weight 400) (PPG 400) The acid-modified vinyl-group-containing polyurethane resin U2 was synthesized in the same manner as in Synthesis Example 2, except that 79 mL of propylene glycol monomethyl ether monoacetate was changed to 77 mL instead of the combination of (0.012 mol).

The obtained acid-modified vinyl-group containing polyurethane resin U2 had a solid acid value of 65 mgKOH / g, the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 15,000, and the vinyl group equivalent was 1.26 mmol / g.

(Example 1)

Production of Photosensitive Film

The photosensitive composition solution which consists of the following composition was apply | coated on the polyethylene terephthalate film (16FB50 by Toray Industries, Ltd.) of thickness 16micrometer as a support body, and it dried, and formed the photosensitive layer of thickness 30micrometer on the said support body. A photosensitive film was prepared by laminating a polypropylene film (Oji Tokushi Co., Ltd., Alpan E-200) having a thickness of 20 µm as a protective layer on the photosensitive layer.

Composition of Photosensitive Composition Solution

· Binder (B-1) solution of synthesis example 1 (solid content: 45 mass%). 37.2 parts by mass

Polymerizable compound (A-DPH, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.). 11.15 parts by mass

· Thermal crosslinking agent (Efototo YDF-170, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin); 2.0 parts by mass

· Photoinitiator represented by the following structural formula C-1. 1.0 parts by mass

Bismuth oxide (manufactured by Toagosei Co., Ltd., IXE-530). 0.45 parts by mass

Zirconium phosphate (manufactured by Toagosei Co., Ltd., IXE-100). 0.45 parts by mass

Pigment dispersion liquid (Hereinafter, it may be called "G-1"). 36.1 parts by mass

30 mass% methyl ethyl ketone solution of Megapack F-780F (manufactured by Dainippon Ink & Chemicals Co., Ltd.). 0.13 parts by mass

Methyl ethyl ketone (solvent). 12.0 parts by mass

In addition, the said pigment dispersion (G-1) is 30 mass parts of silica (made by Adomatex, SO-C2), 48.2 mass parts of binder (B-1) solutions of the synthesis example 1, and 0.51 mass of phthalocyanine blue After mixing a part, 0.14 mass part of anthraquinone type yellow pigments (CI PY24), and 59.0 mass part of normal propyl acetates previously, zirconia bead of diameter 1.0mm is used with motor mill M-250 (made by Iger company), It was prepared by dispersing at 9 m / s for 3 hours.

Lamination to gas

As the substrate, a chemical polishing treatment was carried out on the surface of a copper clad laminate (without through hole and copper thickness of 12 µm) to prepare. 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 (VP130, manufactured by Nichigo Moton Co., Ltd.) while peeling off the protective film in the photosensitive film. The photosensitive laminated body by which the copper clad laminated board, the said photosensitive layer, and the said polyethylene terephthalate film (support) were laminated | stacked in this order was produced.

The crimping conditions were 40 seconds of vacuum processing, 70 degreeC of pressing temperature, 0.2MPa of pressing pressures, and 10 second of pressurization times.

Evaluation of insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, board | substrate adhesiveness, and surface hardness was performed as follows about the obtained photosensitive laminated body. The results are shown in Table 1.

Insulation Reliability (HAST Test)

A high-speed accelerated life test was performed on the permanent pattern produced in the same manner as the permanent pattern forming method except that the copper-clad laminate having a copper thickness of 12 μm was formed by comb-wiring such that the line / space was 50 μm / 50 μm. (HAST test) was performed to evaluate the dendrite and the insulation resistance (Ω). In the HAST test, a high acceleration tester is used, and the insulation resistance (Ω) of the conductor bumps is measured under the same conditions after applying a voltage of 150 V for 200 hours in an electronic component module at 130 ° C. and a relative humidity of 85%. Then, the dendrite observation of the conductor bump was performed and it evaluated as follows.

[Evaluation standard]

◎: No change in wiring

(Circle): No dendrite is seen but the anode wiring is a little changed.

(Triangle | delta): A dendrite is not seen but an anode wiring is unsightly

×: With dendrites

<Heat resistance (crack resistance)>

As a reliability test item, the appearance and the change rate of resistance value such as cracks and peeling were evaluated by a temperature cycle test (TCT). TCT used a gaseous-phase cold-heat tester, and left the electronic component module in the gaseous phase of temperature of -55 degreeC and 125 degreeC for 30 minutes, performed it on the conditions of 1,000 cycles as this cycle, and evaluated the thermal shock resistance on the following references | standards. .

[Evaluation standard]

○: 10% or less cracking frequency

△: crack occurrence frequency 11% to 20% or less

×: 21% or more crack occurrence frequency

<Sensitivity>

The said photosensitive laminated body was left to stand by 55% RH for 10 minutes at room temperature (23 degreeC). The pattern data of L / S (line / space) = 50 micrometers / 50 micrometers was 0.5 using INPREX IP-3000 (manufactured by Fujifilm Co., Ltd., pixel pitch = 1.0 micrometer) on the photosensitive layer surface of the obtained photosensitive laminated body. The light energy amount from mJ / cm 2 to 500 mJ / cm 2 at different intervals of 2 ^1/2 times was irradiated and exposed, and the line pattern of L / S (line / space) = 50 micrometer / 50 micrometers was hardened. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and 30% of a 1% by mass aqueous solution of sodium carbonate was sprayed at 0.15 MPa on the entire surface of the photosensitive layer on the copper-clad laminate at a rate of 2 to 3 times the shortest development time. Spray development was carried out for a time (or 40 seconds to 60 seconds) to remove and remove the uncured area. The pattern line width of L = 50 μm thus obtained was measured using a laser microscope (VK-9500, manufactured by Gence Co., Ltd .; objective lens 50 times), and the following reference was made based on the exposure amount at which the line width was 50 μm as the sensitivity (optimal exposure amount). Rated by

[Evaluation standard]

◎: Higher sensitivity than 30mj, very excellent sensitivity

(Circle): It is the sensitivity of 39mj-30mj, and is excellent in sensitivity.

(Triangle | delta): It is a sensitivity of 50mj-40mj, and a sensitivity falls slightly

×: lower sensitivity than 50mj and inferior sensitivity

<Developability (shortest development time)>

The polyethylene terephthalate film (support) was peeled off from the photosensitive laminate, and a 30 ° C. 1% by mass aqueous sodium carbonate solution was sprayed at a pressure of 0.15 MPa on the entire surface of the photosensitive layer on the copper clad laminate, and the sodium carbonate aqueous solution was started on the copper clad laminate. The time required until the photosensitive layer was dissolved and removed was measured, and this was evaluated based on the following criteria as the shortest developing time. The shorter the development time, the better the developability.

[Evaluation standard]

(Circle): Developing time is 35 second or less, and developability is favorable.

(Triangle | delta): Developing time is 45 second or less, and developability falls slightly.

X: Developing time exceeds 45 second, and developability is inferior

<Evaluation of Resolution>

The said photosensitive laminated body was left to stand by 55% RH for 10 minutes at room temperature (23 degreeC). Exposure was performed from the polyethylene terephthalate film (support) of the obtained photosensitive laminated body using the said pattern forming apparatus so that a round hole of 50-200 micrometers in diameter width of a round hole could be formed using a round hole pattern.

The exposure amount at this time is an amount of light energy required for curing the photosensitive layer of the photosensitive film in the evaluation of the sensitivity. 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 the time of the shortest developing time on the entire surface of the photosensitive layer on the copper clad laminate to remove and remove the uncured region.

The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and there were no residues at the bottom of the round hole of the pattern, and there was no abnormality such as curling or peeling of the pattern portion, and the smallest round hole pattern capable of forming a space. The width was measured and evaluated as the following reference | standard as the resolution. The smaller the numerical value, the better.

[Evaluation standard]

(Circle): Round hole with a diameter of 120 micrometers or less is resolvable, and resolution is favorable.

(Triangle | delta): A round hole with a diameter of 200 micrometers or less is resolvable, and the resolution falls a little.

×: Round hole is not resolvable and resolution is inferior

<Storage stability>

The said photosensitive film was stored for 5 days on 40 degreeC conditions. It laminated | stacked on the copper clad laminated board and measured the shortest developing time (t _r ). The smaller the ratio (r) = t _r / t ₀ to the shortest developing time (t _o ) before storage, the better the storage stability.

[Evaluation standard]

○: r is 1.5 or less and excellent storage stability

○ △: r is 2.0 or less, and storage stability is good.

Δ ×: r is 2.5 or less and storage stability is slightly inferior

X: r is 2.5 or more and storage stability is inferior

<Heat resistance>

The solder resist film which consists of each photosensitive composition was formed on the board | substrate, the evaluation board | substrate which apply | coated rosin-type flux on the said film was immersed in the solder bath set to 260 degreeC for 30 second, and the flux was wash | cleaned with denatured alcohol. Thereafter, the expansion, peeling, and discoloration of the solder resist film by visual observation were evaluated according to the following criteria.

[Evaluation standard]

(Circle): A change is not confirmed at all and it is excellent in heat resistance.

(Triangle | delta): Although some expansion and peeling are seen, heat resistance is favorable.

×: swelling and peeling in the coating film

<Substrate adhesiveness>

The soldering resist film which consists of each photosensitive composition was formed on the board | substrate. The solder resist film is divided into 1 cm × 1 cm sections with lines of 1 mm vertically and horizontally, and only the cutter knife is cut so that 100 substrates having 1 mm × 1 mm are cut so that the substrate is not broken. Put it. Subsequently, a cellophane tape (Nitto Denko Co., Ltd., a cellophane tape No. 29) was affixed to the insulated resist film, it was pulled up at an angle of 90 degrees, and the number of 1 mm x 1 mm sections was measured at that time. . It is preferable that there is no single peeling and there is no defect in each compartment. Peeling and defect were evaluated by the following reference | standard.

[Evaluation standard]

(Circle): It has no peeling and a defect, and is excellent in board | substrate adhesiveness.

(Triangle | delta): Although not peeling, there exist some defects and a board | substrate adhesiveness falls slightly.

X: Peeling partially occurs, resulting in poor substrate adhesion

<Surface hardness>

The soldering resist film which consists of each photosensitive composition was formed on the board | substrate. According to the test method of JISK-5400, the highest hardness which a scratch does not generate | occur | produce in a resist film at the time of applying a load of 1 kg using a pencil hardness tester was evaluated by the following reference | standard.

[Evaluation standard]

○: more than 4H and excellent surface hardness

(Triangle | delta): It is 3H-4H, and surface hardness falls slightly.

X: 2H or less and surface hardness is inferior

(Example 2)

In Example 1, the photosensitive film, the photosensitive laminated body, and the permanent pattern were produced like Example 1 except having changed the compounding quantity of zirconium phosphate from 0.45 mass part to 0.90 mass part.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 3)

In Example 1, the photosensitive film, the photosensitive laminated body, and the permanent pattern were produced like Example 1 except having changed the compounding quantity of bismuth oxide from 0.45 mass part to 0.90 mass part.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 4)

A photosensitive film, a photosensitive laminate, and a permanent film were prepared in the same manner as in Example 1 except that 0.45 parts by mass of zirconium phosphate in the photosensitive composition solution of Example 1 was changed to 0.45 parts by mass of antimony pentoxide (manufactured by Toagosei Co., Ltd., IXE-300). Made a pattern.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 5)

In Example 4, the photosensitive film, the photosensitive laminated body, and the permanent pattern were produced like Example 4 except having changed 0.45 mass part of antimony pentoxide into 0.90 mass part.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 6)

In Example 4, the photosensitive film, the photosensitive laminated body, and the permanent pattern were produced like Example 4 except having changed 0.45 mass part of bismuth oxide into 0.90 mass part.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 7)

Except having changed 0.45 mass part of bismuth oxides and 0.45 mass part of zirconium phosphates in 0.30 mass part of bismuth oxides, 0.30 mass part of zirconium phosphates, and 0.30 mass part of antimony pentoxide, in the photosensitive composition solution of Example 1, it carried out similarly to Example 1 The photosensitive film, the photosensitive laminated body, and the permanent pattern were produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 8)

Except having changed the binder (B-1) solution (solid content 45 mass%) of the synthesis example 1 into the solution (solid content 45 mass%) of the acid-modified vinyl-group-containing polyurethane resin U1 of the synthesis example 2 in Example 1. In the same manner as in Example 1, a photosensitive film, a photosensitive laminate, and a permanent pattern were produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 9)

Except having changed the binder (B-1) solution (solid content 45 mass%) of the synthesis example 1 into the solution (solid content 45 mass%) of the acid-modified vinyl-group-containing polyurethane resin U1 of the synthesis example 2 in Example 2. In the same manner as in Example 2, a photosensitive film, a photosensitive laminate, and a permanent pattern were produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 10)

Except having changed the binder (B-1) solution (solid content 45 mass%) of the synthesis example 1 into the solution (solid content 45 mass%) of the acid-modified vinyl-group-containing polyurethane resin U2 of the synthesis example 3 in Example 1. In the same manner as in Example 1, a photosensitive film, a photosensitive laminate, and a permanent pattern were produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Example 11)

It carried out except having changed the binder (B-1) solution (solid content 45 mass%) of the synthesis example 1 into the solution (solid content 45 mass%) of the acid-modified vinyl-group-containing polyurethane resin U2 of the synthesis example 3 in Example 2. In the same manner as in Example 2, a photosensitive film, a photosensitive laminate, and a permanent pattern were produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Comparative Example 1)

A photosensitive film, a photosensitive laminate, and a permanent pattern were prepared in the same manner as in Example 1 except that bismuth oxide and zirconium phosphate in the photosensitive composition solution of Example 1 were not added.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Comparative Example 2)

The photosensitive film, the photosensitive laminated body, and the permanent pattern were produced like Example 1 except having changed 0.45 mass part of bismuth oxides and 0.45 mass part of zirconium phosphates into 0.90 mass part of bismuth oxides in the photosensitive composition solution of Example 1.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Comparative Example 3)

The photosensitive film, the photosensitive laminated body, and the permanent pattern were produced like Example 1 except having changed 0.45 mass part of bismuth oxides and 0.45 mass part of zirconium phosphates into 0.90 mass part of zirconium phosphates in the photosensitive composition solution of Example 1.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Comparative Example 4)

The photosensitive film, the photosensitive laminated body, and the same method as in Example 1 except for changing 0.45 parts by mass of bismuth oxide and 0.45 parts by mass of zirconium phosphate in 0.45 parts by mass of zirconium phosphate and 0.45 parts by mass of antimony pentoxide in the photosensitive composition solution of Example 1. A permanent pattern was produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Comparative Example 5)

The photosensitive film, the photosensitive laminated body, and the permanent pattern were produced like Example 1 except having changed 0.45 mass part of bismuth oxides and 0.45 mass part of zirconium phosphates into 0.90 mass part of antimony pentoxide in the photosensitive composition solution of Example 1.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Comparative Example 6)

Photosensitive composition in the same manner as in Example 1 except that 0.45 parts by mass of bismuth oxide and 0.45 parts by mass of zirconium phosphate in the photosensitive composition solution of Example 1 were changed to 0.90 parts by mass of hydrotalcite (IXE-700F, manufactured by Toagosei Co., Ltd.). A film, the photosensitive laminated body, and the permanent pattern were produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

(Comparative Example 7)

The photosensitive film, the photosensitive laminated body, and the like of Example 1 except having changed 0.45 mass part of bismuth oxides and 0.45 mass part of zirconium phosphates into 0.45 mass part of antimony pentoxide and 0.45 mass part of hydrotalcites in the photosensitive composition solution of Example 1 And a permanent pattern was produced.

In the same manner as in Example 1, the obtained photosensitive laminate and the like were evaluated for insulation reliability, sensitivity, thermal shock resistance, developability, resolution, storage stability, heat resistance, substrate adhesion, and surface hardness. The results are shown in Table 1.

Table 1-1

TABLE 1-2

[Table 1-3]

From the results of Table 1, Examples 1-11 are excellent in insulation reliability, thermal shock resistance, a sensitivity, developability, and the resolution compared with Comparative Examples 1-7, and storage stability, heat resistance, board | substrate adhesiveness, and surface hardness are improved. I could see that.

Since the photosensitive composition of the present invention can achieve high sensitivity, and can improve insulation reliability, thermal shock resistance, substrate adhesion, surface hardness, heat resistance, storage stability, and developability, it can be particularly suitably used for film solder resists. .

Since the photosensitive film of the present invention has improved heat resistance and storage stability and can efficiently form a high-definition permanent pattern, various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, and a ball grid array (BGA) ), For manufacturing semiconductor packages such as CSP (chip size package), TCP (tape carrier package), manufacturing of liquid crystal structural members such as color filters, pillars, ribs, spacers, partitions, manufacturing of holograms, micromachines, and proofs It can be used suitably, etc., and especially can be used for formation of semiconductor packages, such as permanent pattern formation of a printed circuit board, BGA (ball grid array), CSP (chip size package), and TCP (tape carrier package).

Since the permanent pattern forming method of the present invention uses the photosensitive composition of the present invention, a protective film and an interlayer insulating film for forming semiconductor packages such as BGA (ball grid array), CSP (chip size package), TCP (tape carrier package), etc. It can be suitably used for forming various patterns such as permanent patterns such as, and solder resist patterns, manufacturing of liquid crystal structural members such as color filters, pillars, ribs, spacers, partitions, holograms, micromachines, and proofs. In particular, it can be suitably used for forming a permanent pattern of a printed board, forming a semiconductor package such as BGA (ball grid array), CSP (chip size package), TCP (tape carrier package), or the like.

Claims (11)

As a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent:
Said ion adsorbent contains a bismuth compound and one or more of a zirconium compound and an antimony oxide compound. The method of claim 1,
The bismuth compound is a photosensitive composition, characterized in that bismuth oxide. The method of claim 1,
The bismuth compound is a photosensitive composition, characterized in that zirconium phosphate. The method of claim 1,
The antimony oxide compound is a photosensitive composition, characterized in that the antimony pentoxide. The method of claim 1,
The mass ratio (A: B) of the bismuth compound (A) and at least one (B) of the zirconium compound and the antimony oxide compound is 1: 0.2 to 1: 5. The method of claim 1,
The binder is selected from epoxy (meth) acrylate resin, (meth) acrylate resin, and urethane resin. The method according to claim 6,
The binder is a photosensitive composition, characterized in that the acid-modified vinyl group-containing polyurethane resin. At least a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent;
Said ion adsorbent has a photosensitive layer containing a bismuth compound and the photosensitive composition containing at least one of a zirconium compound and an antimony oxide compound on a support body, The photosensitive film characterized by the above-mentioned. At least a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent on the substrate;
Said ion adsorbent has a photosensitive layer containing a bismuth compound and the photosensitive composition containing one or more of a zirconium compound and an antimony oxide compound. At least a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent;
And the ion adsorbent comprises at least exposing the photosensitive layer formed by a photosensitive composition containing a bismuth compound and at least one of a zirconium compound and an antimony oxide compound. At least a binder, a polymerizable compound, a photopolymerization initiator, and an ion adsorbent;
The ion adsorbent is characterized in that the permanent pattern is formed by a permanent pattern forming method comprising at least exposing to a photosensitive layer formed of a photosensitive composition containing a bismuth compound and at least one of a zirconium compound and an antimony oxide compound. Printed circuit board.