JP4655928B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a resin composition for resist inks that is particularly sensitive to active energy rays, has good alkali developability, and has a wide thermal management range during preliminary drying.

  Solder resist pattern formation method for printed wiring boards is widely used alkali development method from the point of excellent chemical resistance and solvent resistance of the cured film, alkali development resist ink used in this alkali development method, In general, an acid pendant type epoxy vinyl ester compound obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride is used as a main agent.

  In recent years, a direct exposure method using a laser beam (laser direct imaging method) has been proposed and attracted attention as an exposure system employed in such a solder resist pattern forming method using an alkali development method. Compared with the conventional UV exposure method using a mask pattern, the direct exposure method using a laser beam has a feature that a pattern with higher accuracy can be formed, and is very useful for downsizing and high integration of a substrate. It is an exposure method.

  However, the exposure energy obtained by laser light is very small, about 1/10 to 1/100 of UV light, and sufficient curing properties cannot be obtained with conventionally used alkaline development resist inks. . Therefore, there is a need for a resist ink with ultra-high sensitivity that can support such a direct exposure method using laser light.

  Furthermore, even in a system that is cured by a UV exposure method using a conventional mask pattern, the exposure energy at the time of forming a solder resist pattern tends to decrease due to the speedup of the production line in recent years. In addition, there is an increasing demand for an ultrasensitive resist ink that exhibits excellent curability.

  In response to the growing needs for higher sensitivity, for example, glycidyl methacrylate is an acid pendant type epoxy vinyl ester compound obtained by reacting an epoxy resin, an unsaturated monocarboxylic acid and a dibasic acid anhydride. There is known a technique for increasing the sensitivity of a photosensitive resin by reacting an epoxy group-containing radical polymerizable unsaturated monomer to introduce more unsaturated double bonds into the polymer structure (for example, Patent Document 1).

However, when a vinyl ester resin is produced by reacting an epoxy group-containing radical polymerizable unsaturated monomer with an acid pendant type epoxy vinyl ester compound, the epoxy group containing radical polymerizable unsaturated monomer is an acid pendant type epoxy. Since it reacts with a carboxyl group in the vinyl ester compound and consumes an acid group, a decrease in alkali developability is inevitable. Furthermore, in the vinyl ester resin, when the addition amount of the epoxy group-containing radical polymerizable unsaturated monomer is increased with the aim of further increasing the sensitivity, not only the development speed is significantly reduced, but also the preliminary drying. There was annoyance that the heat management width at the time would be extremely narrow. Here, the thermal management width at the time of preliminary drying is allowed within a range in which the thermal allowable limit of the heat drying when developing the unexposed portion after the coating film is dried by heating, that is, the developability can be maintained. This refers to the control range of heating and drying conditions. Therefore, when the thermal management width is narrow, the resin composition of the coating film is cured by the time or temperature conditions exceeding the allowable range in the drying process of applying the alkali developing resist ink to the printed wiring board and removing the solvent. Even after development, after exposure and development, the unexposed part is difficult to be removed by the developer, so that sufficient drying cannot be performed, so the solvent remains even after development, and tackiness remains. It was causing problems.
Thus, the vinyl ester resin of the type obtained by reacting a conventional epoxy group-containing radical polymerizable unsaturated monomer with an acid pendant type epoxy vinyl ester compound has an acid value and sensitivity required for alkali developability. The number of unsaturated double bonds that contribute is contradictory to each other, and the amount of modification of the radically polymerizable unsaturated monomer containing an epoxy group is increased in order to achieve the ultra-high sensitivity required in recent years. In this case, the alkali developability is lowered, and the thermal management width during preliminary drying is reduced. On the other hand, when the amount of modification is suppressed in order to increase the alkali developability and the thermal management range during preliminary drying, it is naturally impossible to achieve the ultra-high sensitivity required in recent years.

  Therefore, in the field of alkali-developable resist inks so far, it can be applied to a direct exposure method using laser light, and has ultra-high sensitivity that exhibits excellent curability even with low exposure energy, excellent developability and wide heat resistance. The current situation is that the management width cannot be combined.

JP-A-10-282665 (page 3-5)

  The problem to be solved by the present invention is that it can be applied to a direct exposure method using a laser beam, and has an extremely high sensitivity that exhibits excellent curability even with low exposure energy, excellent developability, and wide heat. An object of the present invention is to provide a composition for an alkali developing resist ink that also has a control width, and to provide a vinyl ester resin that can impart such characteristics to the composition for an alkali developing resist ink.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reacted an acid pendant type epoxy vinyl ester compound with an epoxy group-containing radically polymerizable unsaturated monomer and a polybasic acid anhydride to produce vinyl. By making the molecular structure of the ester resin multi-stage and highly branched, it is possible to secure a sufficient acid value for alkali development and introduce unsaturated double bonds at a high concentration at the end of the branched structure. Therefore, the present inventors have found that the sensitivity of the vinyl ester resin is dramatically improved and completed the present invention.
That is, the present invention is a photosensitive resin composition comprising an acid group-containing vinyl ester resin (A) and a photopolymerization initiator (B) as essential components, the acid group-containing vinyl ester resin ( A)
A polybasic acid anhydride (a3) is reacted with an epoxy vinyl ester resin (v1) which is a reaction product of an aromatic epoxy resin (a1) and a radically polymerizable unsaturated double bond-containing monocarboxylic acid (a2). Next, the acid group formed by the reaction is reacted with a radical polymerizable unsaturated double bond-containing monoepoxy compound (a4), and the secondary hydroxyl group generated by the reaction is further reacted with a polybasic acid anhydride (a3). An acid group-containing vinyl ester resin having a multi-branched molecular structure obtained by reacting with a radical polymerizable unsaturated double bond per aromatic ring in the acid group-containing vinyl ester resin, It has a ratio of 1.75 to 3.5 and contains acid groups in a range where the acid value of the acid group-containing vinyl ester resin (A) is 30 to 150 mgKOH / g. Relates to a photosensitive resin composition characterized and.

  Further, in the present invention, a polybasic acid anhydride (a3) is reacted with an epoxy vinyl ester resin obtained by reacting a novolac type epoxy resin with (meth) acrylic acid or an aliphatic cyclic ester compound modified product thereof, A radical polymerizable unsaturated double bond-containing monoepoxy compound (a4) is reacted with the acid group formed by the reaction, and a polybasic acid anhydride (a3) is further reacted with the secondary hydroxyl group generated by the reaction. The resulting acid group-containing vinyl ester resin having a multi-branched molecular structure, and 1 radical polymerizable unsaturated double bond (b4) per aromatic ring in the acid group-containing vinyl ester resin. .75 to 3.5, and the acid group contains an acid group in the range where the acid value of the acid group-containing vinyl ester resin is 30 to 150 mgKOH / g. Novel vinyl ester resin to.

According to the present invention, it is possible to correspond to a direct exposure method using a laser beam, and it has ultra-high sensitivity that exhibits excellent curability even with low exposure energy, excellent developability, and a wide thermal management range. It is possible to provide a composition for an alkali developing resist ink that has both, and a vinyl ester resin that can impart such characteristics to the composition for an alkali developing resist ink.
Therefore, the alkali developing resist ink composition of the present invention is excellent in sensitivity to active energy rays, so that it can be applied to a direct exposure method using a laser beam and an energy-saving curing system excellent in productivity. , Alkali developability and wide thermal management range at the time of pre-drying, so the dryness is good, and the balance of properties such as adhesion of the coating film obtained after thermosetting, solder heat resistance, chemical resistance, solvent resistance, etc. A good cured product can be provided.

  The acid group-containing vinyl ester resin (A) used in the present invention is obtained by reacting an aromatic epoxy resin (a1) with a radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) to produce an epoxy vinyl ester resin (v1 Then, the secondary hydroxyl group produced by the reaction is reacted with a polybasic acid anhydride (a3) to form an acid group, and then the radical polymerizable unsaturated double bond is formed on the acid group. The bond-containing monoepoxy compound (a4) is reacted to introduce a radical polymerizable unsaturated double bond at the molecular end, and then the polybasic acid anhydride (a3) is further reacted with the secondary hydroxyl group produced by this reaction. And adopt a molecular structure in which a new acid group is formed in the molecule. As described above, since the secondary hydroxyl group in the epoxy vinyl ester resin (v1) becomes a branching point and increases in molecular weight, the acid group vinyl ester resin (A) forms a highly branched structure as a whole. Yes.

  Further, the vinyl ester resin having a multi-branched structure having a radically polymerizable unsaturated double bond and an acid group formed by the method as described above further comprises a radically polymerizable unsaturated double bond-containing monoepoxy. The compound (a4) reacts, and then the polybasic acid anhydride (a3) reacts. These react alternately and sequentially several times to form a high-dimensional acid group-containing vinyl ester resin. It is possible.

  Therefore, when the terminal unsaturated double bond in the epoxy vinyl ester resin (v1) is a first generation radical polymerizable unsaturated double bond, a polybasic acid anhydride (a3) is bonded to the secondary hydroxyl group in the resin. ), And then the radical polymerizable unsaturated double bond-containing monoepoxy compound (a4) reacts with the acid group formed by ring opening of the polybasic acid anhydride (a3). The unsaturated double bond introduced by the unsaturated double bond-containing monoepoxy compound (a4) becomes a second generation radically polymerizable unsaturated double bond. Further, when the polybasic acid anhydride (a3) reacts with the secondary hydroxyl group in the resin in the same manner and then the radical polymerizable unsaturated double bond-containing monoepoxy compound (a4) reacts, The introduced radically polymerizable unsaturated double bond becomes a third generation radically polymerizable unsaturated double bond.

  Here, the aromatic epoxy resin (a1) is an epoxy resin having a structure in which a glycidyloxy group is nucleus-substituted on an aromatic ring such as a benzene ring or a naphthalene ring, and such an epoxy resin is used as a starting material. Thus, the cured product when the finally obtained acid group-containing vinyl ester resin (A) is cured is excellent in heat resistance, coating strength, and chemical resistance. Specifically, the aromatic epoxy resin (a1) includes a phenol novolak resin, a cresol novolak resin, a halogenated phenol novolak resin, a phenol novolak resin having a C 2-4 alkyl group as a substituent, and a naphthol novolak. A novolak epoxy resin obtained by reacting a novolak resin such as a resin with epichlorohydrin, methyl epichlorohydrin, etc .; reacting a bisphenol such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A with epichlorohydrin, methyl epichlorohydrin, etc. Diglycidyl ether of bisphenols obtained by mixing the above-mentioned diglycidyl ether of bisphenols with bisphenol A, bisphenol F, bisphenol Bisphenol-type epoxy resin polymerized with tetrabromobisphenol A, etc .; modified bisphenol obtained by polymerizing diglycidyl ether of the above bisphenols with carboxyl group-terminated butyronitrile rubber, carboxyl group-terminated polyester, dibasic acid, etc. Type epoxy resin; naphthalene type epoxy resin such as diglycidyl ether of dihydroxynaphthalene and tetraglycidyl ether of bis (2,7-dihydroxynaphthyl) methane; reacting trisphenolmethane, tris-resolemethane, etc. with epichlorohydrin, methyl epichlorohydrin, etc. Trisphenol methane type epoxy resin obtained by the above; biphenyl diglycidyl ether and the like.

  Among these, since it is possible to efficiently increase the number of double bonds in one molecule, a polyfunctional epoxy resin having a repeating structure is preferable, and the resulting cured product has good heat resistance and chemical resistance. Therefore, novolak type epoxy resin is particularly preferable. Such a novolak type epoxy resin is a resist ink in which the finally obtained branched vinyl ester resin easily has a spherical structure and easily exhibits excellent sensitivity, and the viscosity of the branched vinyl vinyl ester resin is moderately low. It is preferable that the average number of nuclei is 4 to 11 from the viewpoint of excellent workability at the time of drying and drying at the time of preliminary drying. Among the novolak type epoxy resins, phenol novolak resins, cresol novolak resins, and phenol novolak resins having 2 to 4 carbon atoms as substituents are particularly preferable because of excellent balance between fluidity and heat resistance. .

  In addition, the aromatic epoxy resin (a1) preferably has a softening point in the range of 50 to 105 ° C., and particularly has a drying property at the time of preliminary drying when used as a resist ink and a heat resistance of a cured product to be obtained. It is more preferable that the temperature is in the range of 65 to 100 ° C. from the point of improvement.

  The radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) is, for example, (meth) acrylic acid (a2-1), or has two or more ester bonds in one molecule, and is a molecule. The unsaturated compound (a2-2) which has a carboxyl group at one terminal is mentioned. (Meth) acrylic acid (a2-1) is preferred from the viewpoint of increasing the concentration of the radical polymerizable unsaturated double bond and improving the sensitivity. On the other hand, the latter unsaturated compound (a2-2) having two or more ester bonds in one molecule and having a carboxyl group at one end of the molecule is the final obtained acid group-containing vinyl ester resin. This is preferable from the viewpoint that the polarity becomes high and the alkali developability becomes good. As the unsaturated compound (a2-2), for example, an aliphatic polyester polyol is reacted with a dibasic acid anhydride such as succinic acid anhydride, maleic acid anhydride, or tetrahydrophthalic acid anhydride to obtain a half ester. , A compound obtained by reacting this with (meth) acrylic acid, and the following structural formula (1)

（式中、Ｒ_１は水素原子又はメチル基、Ｒ_２は炭素原子数２〜６の芳香族炭化水素基を表し、ｎは１〜６の整数を表す。）
で表される化合物が挙げられる。前記一般式（１）で表される化合物としては、（メタ）アクリル酸にε−カプロラクトンを反応させ分子伸長したポリラクトン（メタ）アクリレートや、（メタ）アクリル酸ダイマーが挙げられる。

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an aromatic hydrocarbon group having 2 to 6 carbon atoms, and n represents an integer of 1 to 6).
The compound represented by these is mentioned. Examples of the compound represented by the general formula (1) include polylactone (meth) acrylate obtained by reacting (meth) acrylic acid with ε-caprolactone and molecular extension, and (meth) acrylic acid dimer.

  Among the unsaturated compounds (a2-2), the compound represented by the general formula (1) is preferable from the viewpoint of particularly good alkali developability, and in the general formula (1), n is preferably 1 to 1. When it is 6, sufficient flexibility is imparted to the cured product, and it becomes possible to apply to a flexible substrate whose demand is increasing in recent years.

  Further, the compound represented by the general formula (1) and n in the general formula (1) is preferably 1 to 6 is preferably used in combination with (meth) acrylic acid. When the ratio is 20:80 to 99: 1, the final acid group-containing vinyl ester resin (A) used as a resist ink has sensitivity, developability, and drying property during preliminary drying. From the point of being excellent in balance with.

  Next, the polybasic acid anhydride (a3) is, for example, maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride Acid, 3-butenyl-5,6-dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride, benzophenone tetracarboxylic anhydride, etc. Aliphatic acid anhydrides; phthalic anhydride, tetrachlorophthalic anhydride , Tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, aromatic monoacid anhydride such as benzophenone tetracarboxylic acid anhydride.

  Among these, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is preferable from the viewpoint of good solvent solubility of the acid group-containing vinyl ester resin (A). In addition, succinic anhydride is preferable from the viewpoint that the thermal management width and alkali developability when used as a resist ink are particularly excellent. Therefore, in the present invention, it is preferable to use succinic anhydride in combination with tetrahydrophthalic anhydride or hexahydrophthalic anhydride as the polybasic acid anhydride (a3). In particular, succinic anhydride is an acid group-containing vinyl ester resin. The effect of improving the thermal management width and alkali developability is that the acid group derived from succinic anhydride is located at the last stage of the multi-stage molecular structure after reacting at the final stage when synthesizing (A). It is preferable from the point which becomes.

  To the epoxy vinyl ester resin (v1) obtained by reacting the aromatic epoxy resin (a1) detailed above with the radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2), a polybasic acid is further added. The acid group-containing vinyl ester resin (v2) obtained by reacting the anhydride (a3) is, for example, when a novolak type epoxy resin is used as the aromatic epoxy resin (a1), for example, the following general formula (2 ).

ここで、一般式（２）中、Ｒ_１及びＲ_２は、一般式（１）と同義であり、ｌはそれぞれ独立的に０〜６の整数を表す。Ｒ_３は炭素原子数２〜１０の直鎖脂肪族炭化水素基又は脂環式炭化水素基を表わし、Ｒ_４は水素原子、ハロゲン原子、炭素原子数１〜４のアルキル基を表し、ｍは０〜９の整数を表す。
また、ビスフェノール型エポキシ樹脂を芳香族系エポキシ樹脂（ａ１）として用いる場合には、酸基含有エポキシビニルエステル樹脂（ｖ２）は下記一般式（３）で表すことができる。

Here, in the general formula (2), _{R 1} and _{R 2} are as in formula (1) synonymous, l represents an integer of independently 0-6. R ₃ represents a linear aliphatic hydrocarbon group or alicyclic hydrocarbon group having 2 to 10 carbon atoms, R ₄ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, m is The integer of 0-9 is represented.
When a bisphenol type epoxy resin is used as the aromatic epoxy resin (a1), the acid group-containing epoxy vinyl ester resin (v2) can be represented by the following general formula (3).

ここで、一般式（３）中、Ｒ_１及びＲ_２は、一般式（１）と同義であり、ｌはそれぞれ独立的に０〜６の整数を表す。Ｒ_３は炭素原子数２〜１０の直鎖脂肪族炭化水素基又は脂環式炭化水素基を表わし、Ｒ_６は水素原子、ハロゲン原子、炭素原子数１〜４のアルキル基を表し、ｐは０〜４の整数を表す。

Here, in the general formula (3), _{R 1} and _{R 2} are as in formula (1) synonymous, l represents an integer of independently 0-6. R ₃ represents a linear aliphatic hydrocarbon group or alicyclic hydrocarbon group having 2 to 10 carbon atoms, R ₆ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, p is Represents an integer of 0 to 4;

  Among these, in particular, an epoxy vinyl ester resin using a novolac type epoxy resin as the aromatic epoxy resin (a1), particularly an acid pendant type epoxy vinyl ester resin represented by the above general formula (2) is a radical polymerization. It is preferable from the point that the acid group-containing vinyl ester resin (A) that is finally obtained can have a good sensitivity, because it is possible to introduce a larger amount of the polymerizable unsaturated double bond into the polymer structure.

  The acid group vinyl ester resin (v2) is then reacted with a radical polymerizable unsaturated double bond-containing monoepoxy compound (a4) and then a polybasic acid anhydride (a3) to form a branched structure. Then, double bonds of the second generation, further three generations or more are formed, and the acid group-containing vinyl ester resin (A) is obtained. In the present invention, since the acid group-containing vinyl ester resin (A) has such a multi-branched structure, it has both ultrahigh sensitivity, excellent developability, and a wide thermal management width.

As described above, the total number of radically polymerizable unsaturated double bonds introduced into the acid group-containing vinyl ester resin (A) is as described above per aromatic ring in the acid group-containing vinyl ester resin (A). The ratio is 1.75 to 3.5 radical polymerizable unsaturated double bonds. In the present invention, extremely high supersensitivity is expressed by introducing more radical polymerizable unsaturated double bonds into the resin structure as compared with conventional acid group-containing vinyl ester resins. Here, the number of radically polymerizable unsaturated double bonds per aromatic ring is the total number of the radically polymerizable unsaturated double bonds divided by the total number of aromatic rings constituting the resin (A). Value. Therefore, for example, when a novolak type epoxy resin is used as the aromatic epoxy resin (a1), a radical polymerizable unsaturated double bond per benzene ring or naphthalene ring constituting the novolak resin. Means the number of For example, when the acid group-containing epoxy vinyl ester resin (v2) represented by the general formula (2) is used, the radically polymerizable unsaturated group in the finally obtained acid group-containing vinyl ester resin (A) is used. It is a value obtained by dividing the total number of double bonds by [m + 2]. On the other hand, when a bisphenol type epoxy resin is used as the aromatic epoxy resin (a1), for example, when an acid group-containing epoxy vinyl ester resin (v2) represented by the general formula (3) is used, Since there are two aromatic rings in the repeating unit of bisphenol, the value is obtained by dividing the total number of radical polymerizable unsaturated double bonds by [2p + 2].
Thus, in the present invention, “a ratio of 1.75 to 3.5 radical polymerizable unsaturated double bonds per aromatic ring” means the molecule of the acid group-containing vinyl ester resin (A). It means that more radically polymerizable unsaturated double bonds are contained in the molecular structure compared to the size. On the other hand, when the radical polymerizable unsaturated double bond exceeds 3.5 per aromatic ring, the heat resistance and hardness of the cured coating achieved due to the aromatic skeleton And chemical resistance cannot be obtained. From this point of view, in order to achieve particularly excellent ultrahigh sensitivity, 2.0 to 3.5 radical polymerizable unsaturated double bonds per aromatic ring in the acid group-containing vinyl ester resin are used. It is preferable that the ratio is

  The acid value of the acid group-containing vinyl ester resin (A) is 30 to 150 mgKOH / g, particularly preferably 40 to 120 mgKOH / g, from the viewpoint of realizing excellent developability and a wide thermal management range. .

  The specific structure of the acid group-containing vinyl ester resin (A) includes the above-described aromatic epoxy resin (a1), radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2), polybasic acid anhydride (a3). ), And the type of radically polymerizable unsaturated double bond-containing monoepoxy compound (a4), and the reaction sequence thereof. For example, when a novolak type epoxy resin is used as the aromatic epoxy resin (a1) and glycidyl methacrylate is used as the radical-polymerizable unsaturated double bond-containing monoepoxy compound (a4), Theoretical structure of a radical polymerizable unsaturated double bond up to the next generation, having a ratio of two radical polymerizable unsaturated double bonds per aromatic ring in the acid group-containing vinyl ester resin (A) Can be represented by the following general formula (4).

  Furthermore, when the number of terminal double bonds is 3 as having a third generation double bond, the theoretical structure can be represented by the following general formula (5).

ここで、上記一般式（４）及び（５）中、Ｒ_１及びＲ_２は、一般式（１）と同義であり、ｌはそれぞれ独立的に０〜６の整数を表す。Ｒ_３は炭素原子数２〜１０の直鎖脂肪族炭化水素基又は脂環式炭化水素基を表わし、Ｒ_４は水素原子、ハロゲン原子、炭素原子数１〜４のアルキル基を表し、ｍは０〜９の整数を表す。

Here, in the above general formula (4) and (5), _{R 1} and _{R 2} are as in formula (1) synonymous, l represents an integer of independently 0-6. R ₃ represents a linear aliphatic hydrocarbon group or alicyclic hydrocarbon group having 2 to 10 carbon atoms, R ₄ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, m is The integer of 0-9 is represented.

  In addition, when a bisphenol type epoxy resin is used as the aromatic epoxy resin (a1), glycidyl methacrylate is used as the radical polymerizable unsaturated double bond-containing monoepoxy compound (a4). Examples of those having a generation double bond include a theoretical structural formula represented by the following general formula (5). In the general formula (6), p represents an integer, and the value thereof is 1.75 to 3 for the radical polymerizable unsaturated double bond per aromatic ring in the acid group-containing vinyl ester resin (A). It can be appropriately selected so as to be included at a ratio of 5 pieces.

  Moreover, as an example of what has a 3rd generation double bond, the theoretical structural formula represented by following General formula (7) is mentioned. In the general formula (6), p is an integer, and the value is 1.75 to 3.5 of the radical polymerizable unsaturated double bond per aromatic ring in the acid group-containing vinyl ester resin. It can select suitably so that it may be contained in the ratio which becomes a piece.

  Among the acid group-containing vinyl ester resins (A) detailed above, those using novolak type epoxy resins as aromatic epoxy resins (a1) as described above are excellent in the activity of radical polymerizable unsaturated double bonds. The supersensitivity can be increased, and it is preferable from the viewpoint of excellent heat resistance and chemical resistance. Therefore, the acid group-containing vinyl ester resin (A) is a novel compound of the present invention, which is a novolak type epoxy resin. Acid pendant type epoxy vinyl ester obtained by reacting (meth) acrylic acid or its modified aliphatic cyclic ester compound and then reacting the secondary hydroxyl group produced by the reaction with polybasic acid anhydride (a3) An acid group-containing vinyl resin obtained by reacting a resin with a radical polymerizable unsaturated double bond-containing monoepoxy compound (a4) and a polybasic acid anhydride (a3). It is an ester resin, has 1.75 to 3.5 radical polymerizable unsaturated double bonds per aromatic ring in the acid group-containing vinyl ester resin, and has an acid group. The acid group-containing vinyl ester resin is preferably an acid group-containing vinyl ester resin characterized in that the acid value in the acid group-containing vinyl ester resin is 30 to 150 mgKOH / g.

  Specifically, the acid group-containing vinyl ester resin (A) described in detail above can be produced by the following method 1 or 2.

First, Method 1
Step 1: Aromatic epoxy resin (a1) is reacted with the above-mentioned radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) in the presence of an esterification catalyst as necessary to produce an epoxy vinyl ester resin (v1 )
Step 2: A step of reacting the obtained epoxy vinyl ester resin (v1) with a polybasic acid anhydride (a3) to obtain an acid group-containing vinyl ester resin (v2) having an acid group bonded in a pendant shape,
Step 3: A vinyl ester compound in which a radical polymerizable unsaturated group is further introduced by reacting an acid group in the acid group-containing vinyl ester resin (v2) with an epoxy group-containing radical polymerizable unsaturated monomer (a2). obtaining v3), and
Step 4: A step of obtaining a target acid group-containing vinyl ester resin (A) by reacting the polybasic acid anhydride (a3) again with the secondary hydroxyl group in the vinyl ester resin (v3) obtained in Step 3, Consists of

  That is, first, in step 1, the aromatic epoxy resin (a1) is reacted with the radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) in the presence of an esterification catalyst, if necessary. An ester resin (v1) is obtained. At this time, the reaction ratio between the aromatic epoxy resin (a1) and the radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) is usually 1 mol of the epoxy group of the aromatic epoxy resin (a1). It is preferable that the radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) has a ratio of 0.8 to 1.1 mol. That is, by reacting the radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) in the range where the ratio is 0.8 mol or more, the reaction with the polybasic acid anhydride (a3) in the next step is performed. Can be suppressed, and by reacting in a range of 1.1 mol or less, the drying property at the time of preliminary drying when the acid group-containing vinyl ester resin (A) finally obtained is used as a resist ink In addition, the heat resistance, chemical resistance, plating resistance and the like of the cured product are improved. The ratio is more preferably in a range of 0.90 to 1.05 mol in terms of excellent performance balance and excellent sensitivity to active energy rays and storage stability of the resin composition.

  Examples of the esterification catalyst that can be used here are tertiary such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol, diazabicyclooctane and the like. Amines; quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride; phosphines such as triphenylphosphine and tributylphosphine; 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole And imidazoles such as triphenylstibine.

  In the reaction in Step 1, it is preferable to use a diluent because the viscosity in the system can be reduced. Diluents that can be used here include, for example, ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether. Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha And organic solvents such as petroleum solvents. Among these, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate are used alone, propylene glycol monomethyl ether acetate, since the operability during the reaction is particularly good and the drying speed is excellent when used as a resist ink. And a combination of ketones or diethylene glycol monoethyl ether acetate and a petroleum solvent are preferred.

  In the reaction of Step 1, it is desirable to use a polymerization inhibitor from the viewpoint of suppressing gelation during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, tertiary butylhydroquinone, methoquinone, toluhydroquinone, and tolquinone. 1,4-naphthoquinone, phenothiazine, ditertiarybutylhydroxytoluene, aluminum salt of N-nitrosophenylhydroxyamine, and the like.

  The reaction temperature in step 1 can be selected in the range of 60 to 130 ° C. regardless of the addition timing of the esterification catalyst. In particular, in order to suppress thickening of the reaction product to be obtained, it is preferable to suppress side reactions at the initial stage of reaction as much as possible. For this purpose, the reaction temperature should be a relatively low temperature range of 60 to 110 ° C. preferable. Moreover, although the total reaction time of the process 1 changes with scales, it is preferable that it is 5 to 40 hours.

  In step 1, the esterification catalyst may be added all at once when the aromatic epoxy resin (a1) and the radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) are reacted. A method of adding an esterification catalyst in a multistage manner after adding a part and allowing the reaction to proceed is preferable because side reactions are suppressed and the reaction time is shortened. Although it does not specifically limit as the catalyst amount at the time of using by primary addition and secondary addition, It is preferable to add 50 to 90 weight% of the total catalyst amount by primary addition, and to add the remainder by secondary addition.

  Next, the resulting epoxy vinyl ester resin (v1) is reacted with a polybasic acid anhydride (a3) to obtain an acid group-containing vinyl ester resin (v2) in which acid groups are bonded in a pendant form (step 2). ).

  At this time, the number of reaction moles of the polybasic acid anhydride (a3) is not particularly limited, but the polybasic acid anhydride (a3) with respect to 1.0 mole of the secondary hydroxyl group of the epoxy vinyl ester resin (v1). It is preferable from the point of the gelation prevention in the said reaction that it is a ratio used as 0.75-1.0 mol of acid anhydride groups of.

  In Step 2, if the polybasic acid anhydride (a3) remains in the system after completion of the reaction, there is a possibility that gelation may occur in the subsequent production process or product. The reaction temperature is preferably in the range of 60 to 130 ° C., and the reaction time is preferably in the range of 1 to 10 hours.

Next, the carboxyl group in the acid group-containing vinyl ester resin (v2) is reacted with the epoxy group-containing radical polymerizable unsaturated monomer (a2) to further introduce a radical polymerizable unsaturated group ( v3) is obtained (step 3).
At this time, the epoxy group-containing radical polymerizable unsaturated monomer (a2) is added in an amount of 0.75 to 1.0 mol per 1.0 mol of 2-oxypropylene group bonded to the aromatic ring in the acid group-containing vinyl ester resin (v2). It is preferable to make it react in the quantity used as 1.0 mol. In addition, when using the bisphenol type represented by General formula (3) as acid group containing vinyl ester resin (v2), 2-oxypropylene couple | bonded with the aromatic ring in acid group containing vinyl ester resin (v2). The ratio is preferably 0.8 to 1.0 mol with respect to 1.0 mol of the group.

  The reaction temperature in such a reaction is preferably in the range of 90 to 130 ° C., and the reaction time is preferably in the range of 1 to 10 hours.

  Next, the secondary hydroxyl group in the vinyl ester resin (v3) obtained in step 3 is reacted with the polybasic acid anhydride (a3) again to obtain the target acid group-containing vinyl ester resin (A). (Step 4). The ratio of the polybasic acid anhydride (a3) in the reaction is a ratio of 0.1 to 0.9 mol with respect to 1 mol of 2-oxypropylene group bonded to the aromatic ring in the vinyl ester resin (v3). It is preferable that The reaction temperature in this reaction is not particularly limited, but is preferably in the range of 90 to 130 ° C., and the reaction time is preferably in the range of 1 to 10 hours.

  In the present invention, through the above-described Step 3 and Step 4, and further by repeating these reactions, the polybasic acid anhydride (a3) and the epoxy group-containing radical polymerizable unsaturated monomer ( A molecular structure in which a4) reacts alternately is formed.

  Further, as described above, in Step 2, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is used as the polybasic acid anhydride (a3), and in Step 4, succinic anhydride is used as the polybasic acid anhydride (a3). ), The acid group-containing vinyl ester resin (A) can be given excellent solvent solubility, and the acid group derived from succinic anhydride is located at the last stage of the multi-stage molecular structure. The effect of improving the control width and alkali developability becomes remarkable.

  The method 1 described in detail above is preferable because the reaction can be easily controlled and the degree of freedom in designing the polymer structure is increased.

On the other hand, in Method 2, the epoxy vinyl ester resin (v1) obtained in Step 1 of Method 1, the epoxy group-containing radical polymerizable unsaturated monomer (a2), and the polybasic acid anhydride (a3) are collected together. This is a method of charging and reacting. This method 2 is preferable because a double bond of the third generation or higher can be easily introduced into the acid group-containing vinyl ester resin structure.
Specifically, the reaction ratio of the epoxy vinyl ester resin (v1), the epoxy group-containing radical polymerizable unsaturated monomer (a2), and the polybasic acid anhydride (a3) in Method 2 is as follows. The epoxy group-containing radically polymerizable unsaturated monomer (a2) is 0.75 to 2.5 mol and the polybasic acid anhydride (a3) is 0.1 mol with respect to 1.0 mol of the secondary hydroxyl group in v1). It is preferable that it is the range used as 75-3.5 mol. In addition, when using a bisphenol type thing as acid group containing vinyl ester resin (v1), it is 0.8 with respect to 1.0 mol of 2-oxypropylene groups couple | bonded with the aromatic ring in epoxy vinyl ester resin (v1). It is preferable that it is the ratio used as -1.0 mol.

  Furthermore, from the viewpoint of alkali developability, radical polymerization with respect to 1.0 mol of the secondary hydroxyl group from the number of moles of the polybasic acid anhydride (a3) with respect to 1.0 mol of the secondary hydroxyl group in the epoxy vinyl ester resin (v1). It is preferable that it is resin obtained by making it react in the ratio from which the value which pulled the number-of-moles of the monounsaturated double bond containing monoepoxy compound (a4) becomes 0.4-0.95.

  The reaction temperature in this case is not particularly limited, but is preferably in the range of 90 to 130 ° C., and the reaction time is preferably in the range of 4 to 24 hours.

  Further, in the present invention, the polybasic acid anhydride (a3) and the epoxy are used for the acid group-containing vinyl ester resin (v2) obtained through, for example, the step 1 and the step 2 regardless of the method 1 or the method 2 described above. A method may be used in which a predetermined amount of the group-containing radically polymerizable unsaturated monomer (a2) is charged and reacted together. Under the present circumstances, the usage-amount of polybasic acid anhydride (a3) is 1.0-4.0 mol with respect to 1 mol of 2-oxypropylene groups couple | bonded with the aromatic ring in this acid group containing vinyl ester resin (v2). Moreover, the usage-amount of an epoxy-group-containing radically polymerizable unsaturated monomer (a2) is a ratio used as 0.75-2.5 mol with respect to 1 mol of this 2-oxypropylene groups. It is preferable from the viewpoint of sensitivity and developability. Furthermore, from the number of moles of the polybasic acid anhydride (a3) with respect to 1 mole of the 2-oxypropylene group, a radical polymerizable unsaturated double bond-containing monoepoxy compound (a4) with respect to 1 mole of the 2-oxypropylene group. From the viewpoint of developability, the reaction is preferably carried out at a ratio such that the value obtained by subtracting the number of moles of 0.4 to 0.95.

  In the acid group-containing vinyl ester resin (A) synthesized in this way, a large number of radical polymerizable unsaturated double bonds derived from the epoxy group-containing radical polymerizable unsaturated monomer (a4) are arranged at the terminal portion of the molecule. Therefore, the three-dimensional structure has high active energy ray sensitivity. Furthermore, the resin having such a structure has a high content of pendant-bonded acid groups compared to conventional epoxy vinyl ester resins, and a relatively low chloride ion concentration derived from aromatic epoxy resins. Thus, the insulation reliability during a durability test or the like is also excellent.

  Next, the photopolymerization initiator (B) used in the present invention is, for example, acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, cycloacetophenone, 2-methyl-1- [ Acetophenones such as 4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; benzophenone, 2-chlorobenzophenone, benzophenones such as p, p-bisdiethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isobutyl ether; Ketals such as tilketal; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone; anthraquinone, 2,4,5-triarylimidazole dimer, 2,4,6- Examples include tris-S-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Is preferred because of its high reactivity. These photopolymerization initiators (B) can be used alone or in combination of two or more.

  It is preferable that the compounding quantity of the said photoinitiator (B) is the range of 0.5-50 weight part normally with respect to 100 weight part of acid group containing vinyl ester resin (A). That is, at 0.5 parts by weight or more, the photocuring reaction of the acid group-containing vinyl ester resin (A) proceeds well, and at 50 parts by weight or less, the mechanical properties of the cured product are good. From the viewpoint of excellent sensitivity to active energy rays, mechanical properties of the cured product, and the like, the more preferable blending amount of the photopolymerization initiator (B) is 2 to 30 with respect to 100 parts by weight of the acid group-containing vinyl ester resin (A). The range is parts by weight.

  A heat-reactive curing agent (C) and a diluent (D) can be blended in the photosensitive resin composition of the present invention. When using especially as a resin composition for resist inks, it is preferable to mix | blend a heat-reactive hardener (C) and a diluent (D).

  Examples of the heat-reactive curing agent (C) include amino resins such as epoxy resins, butoxylated melamine resins, methoxylated melamine resins, and benzoguanamine-based cocondensation resins. Among these, an epoxy resin is preferable from the viewpoint that heat resistance and solvent resistance after thermosetting are particularly good. Examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, alicyclic epoxy resins, trisphenol methane type epoxy resins, rubber-modified epoxy resins, Examples include tris (2,3-epoxypropyl) isocyanurate, diphenyldiglycidyl ether, tetramethyldiphenyldiglycidyl ether, and an epoxy resin containing an oxazolidone ring.

  Among these, a cresol novolac type epoxy resin and an epoxy resin containing an oxazolidone ring are preferable from the aspect of excellent thermal management width when used as a resist ink and heat resistance of a cured product after heat curing, and used as a resist ink. In view of excellent sensitivity and reactivity, bisphenol A type epoxy resin and tris (2,3-epoxypropyl) isocyanurate are preferably used. These resins can be used alone or in combination of two or more according to the application.

  The epoxy resin containing the oxazolidone ring is not particularly limited, and examples thereof include an epoxy resin obtained by reacting a polyfunctional epoxy resin with aromatic monoisocyanates.

  Moreover, when using the said epoxy resin as a heat-reactive hardener (C), it is preferable to use a hardening accelerator. Examples of the curing accelerator include various epoxy resin curing accelerators such as melamine derivatives, imidazole derivatives, dicyandiamide, and phenol derivatives.

  The amount of the heat-reactive curing agent (C) is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the acid group-containing vinyl ester resin (A). In other words, by using 5 parts by weight or more, the cured product finally obtained has excellent physical properties such as heat resistance, solvent resistance, acid resistance, adhesion, and sufficient electrical properties such as insulation resistance. On the other hand, when the content is 40 parts by weight or less, the sensitivity to active energy rays is excellent, and the photosensitivity and developability when used as a resist ink are excellent.

  Although it does not specifically limit as said diluent (D), For example, Ketones, such as ethyl methyl ketone and cyclohexanone; Aromatic hydrocarbons, such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether; ethyl acetate, butyl acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Esters such as acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; Octane, decane, etc. Aliphatic hydrocarbons; organic solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinyl Pyrrolidone, N-vinylcaprolactam, acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethylacrylamide, melamine (meth) acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, glyce Polyglycidyl ether di (meth) acrylate, isobornyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, or these ethylene oxides, And photopolymerizable reactive diluents such as polyvalent (meth) acrylates of propylene oxide adducts. Among these, from the point that the smoothness after preliminary drying when used as a resist ink is good, the use of esters alone, the combined use of esters and petroleum solvents are preferred, and these are photopolymerizable reactive diluents The combined product is more preferable. Among the esters, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate are preferably used.

  The diluent (D) is used alone or as a mixture of two or more thereof, and the blending amount thereof is preferably 30 to 300 parts by weight, particularly 50 parts per 100 parts by weight of the acid group-containing vinyl ester resin (A). It is preferable that it is -200 weight part.

  In order to make the photosensitive resin composition of the present invention a resin composition for resist ink, the acid group-containing vinyl ester resin (A), photopolymerization initiator (B), heat-reactive curing agent (C), and It can be obtained by mixing the diluent (D) and mixing it uniformly by means such as a three-roll or rotation / revolution stirrer.

  Here, the blending amount of the acid group-containing vinyl ester resin (A) is not particularly limited, but the sensitivity of the resist ink and the effect of improving the drying property after preliminary drying become favorable, and further thermosetting. From the point which is excellent in the heat resistance of the coating film obtained later, and solvent resistance, it is preferable that it is 10 to 70 weight% in the resin composition for resist ink, and it is especially preferable that it is the range used as 30 to 60 weight%.

  In the photosensitive resin composition of the present invention, pigments, fillers, additives and the like that are commonly used in the technical field as shown below can be used. For example, organic pigments such as quinacridone, azo, and phthalocyanine; inorganic pigments such as titanium oxide, metal foil pigments, rust preventive pigments; barium sulfate, calcium carbonate, spherical fused silica, crushed fused silica, crystalline silica, alumina Fillers such as silicon nitride, aluminum hydroxide, carbon black, talc and clay; UV absorbers such as hindered amines, benzotriazoles and benzophenones; oxidations such as hindered phenols, phosphoruss, sulfurs and hydrazides Inhibitors; coupling agents such as silanes and titaniums; leveling agents such as fluorosurfactants; rheology control agents such as aerosils; pigment dispersants: anti-repellent agents; additives such as antifoaming agents . Moreover, reinforcing materials, such as glass fiber, glass cloth, and carbon fiber, can be contained as needed. Moreover, a flame retardant imparting agent can be added as necessary. Various flame retardants can be used as the flame retardant, such as halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A; phosphorus atom-containing compounds such as red phosphorus and various phosphate compounds; melamine or derivatives thereof Nitrogen atom-containing compounds; inorganic flame retardant compounds such as aluminum hydroxide, magnesium hydroxide, zinc borate and calcium borate can be exemplified.

  The photosensitive resin composition thus obtained can obtain a cured product by irradiation with active energy rays such as ultraviolet rays or electron beams, and is not limited in its usage or application. . In particular, when a resin composition for resist ink is used, it is applied to a thickness of 10 to 150 μm (liquid film thickness) on a printed board by screen printing, curtain coating, roll coating, spin coating, dip coating, or the like. After that, it is pre-dried at 60-90 ° C. for 15-90 minutes to volatilize volatile components such as organic solvents (the coating and pre-drying steps may be repeated several times) and a desired mask is applied to the dried coating film. A pattern negative film is brought into close contact with the surface and exposed to radiation such as ultraviolet rays or an electron beam (or the pattern may be directly exposed using laser light, etc. In this case, a mask pattern is not required. ), And then developing with a dilute alkaline aqueous solution as a developer, the coating film in the non-exposed area is removed and the coating film in the exposed part is photocured. By remaining without being removed, it is possible to form a pattern. In this case, the dilute alkaline aqueous solution is generally 0.5 to 5% by weight of sodium carbonate aqueous solution or sodium hydroxide aqueous solution, but other alkaline solutions can also be used. Subsequently, the cured coating film excellent in heat resistance, solvent resistance, etc. can be obtained by thermosetting with a hot air dryer etc. for 20 to 90 minutes at 130 to 160 ° C.

  The resin composition described above is, for example, a solder resist for circuit boards such as printed wiring boards, interlayer insulating layers, resist materials for liquid crystal color filters, such as overcoats, liquid crystal spacers, color filter pigment resists, black matrix resists, etc. Are preferably used.

  Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise indicated, the middle part and% in the examples are based on mass.

  The number of radically polymerizable unsaturated double bonds per molecule of the acid group-containing vinyl ester resin (A) described in the following examples and tables is the total number of aromatic rings and unsaturated monobases of the aromatic epoxy resin (a1). It is a calculated value from the number of moles charged of the acid and epoxy group-containing unsaturated monomer. The number of radically polymerizable unsaturated double bonds is determined based on the number average molecular weight calculated by the GPC measurement shown below and the measured value of the double bond equivalent, etc., per radical of the acid group-containing vinyl ester resin (A). A method of actually measuring the number of polymerizable unsaturated double bonds may be employed.

The analysis conditions of gel permeation chromatography (GPC) at the time of number average molecular weight measurement are shown.
GPC device: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSG-GUARDCOLUMN + TSG-GEL G2000HXL × 2 + TSG-GEL G3000HXL + TSG-GEL G4000HXL (all manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran 1ml / min Detector: RI detector

Example 1 [Preparation of resin solution (A-1) containing acid group-containing vinyl ester resin (A)]
Ortho-solole novolak-type epoxy resin [Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 2140 g (diglycol group number (fragrance) The total number of rings): 10.0 mol), 720 g (10.0 mol) of acrylic acid, and 2.9 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 8.6 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, then 2.3 g of triphenylphosphine was further added, the temperature was raised to 120 ° C., and the reaction was further performed for 12 hours. The resulting reaction solution was charged with 1923 g of aromatic hydrocarbon (Sorvesso 150) and 1368 g (9.0 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 4 hours. Furthermore, 1136 g (8.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was performed at 115 ° C. for 4 hours. Next, 912 g (6.0 mol) of tetrahydrophthalic anhydride was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 70 mgKOH / g and a solid content of 62%. This is designated as resin solution A-1.

Example 2 [Preparation of resin solution (A-2) containing acid group-containing vinyl ester resin (A)]
197 g of diethylene glycol monoethyl ether acetate, 214 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 0.86 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 0.23 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for further 12 hours. The obtained reaction solution was charged with 197 g of Solvesso 150 and 144 g (0.95 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 4 hours. Furthermore, 121 g (0.85 mol) of glycidyl methacrylate was added to the resulting reaction solution and reacted at 115 ° C. for 4 hours. Next, 91.2 g (0.6 mol) of tetrahydrophthalic anhydride was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 64 mgKOH / g and a solid content of 62%. It was. This is designated as resin solution A-2.

Example 3 [Preparation of resin solution (A-3) containing acid group-containing vinyl ester resin (A)]
213 g of diethylene glycol monoethyl ether acetate, 214 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 0.86 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 0.23 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for further 12 hours. 213 g of Solvesso 150, 274 g (1.8 mol) of tetrahydrophthalic anhydride and 135 g (0.95 mol) of glycidyl methacrylate were added to the resulting reaction solution, and the reaction was carried out at 115 ° C. for 8 hours, with a solid content acid value of 71 mg KOH / g, A resin solution having a solid content of 62% was obtained. This is designated as resin solution A-3.

Example 4 [Preparation of resin solution (A-4) containing acid group-containing vinyl ester resin (A)]
258 g of diethylene glycol monoethyl ether acetate, 214 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 0.86 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 0.23 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for further 12 hours. 258 g of Solvesso 150, 357 g (2.35 mol) of tetrahydrophthalic anhydride, and 199 g (1.4 mol) of glycidyl methacrylate were charged into the resulting reaction solution, and the reaction was carried out at 115 ° C. for 8 hours, with a solid content acid value of 65 mg KOH / g, A resin solution having a solid content of 62% was obtained. This is designated as Resin Solution A-4.

Example 5 [Preparation of resin solution (A-5) containing acid group-containing vinyl ester resin (A)]
Orthocresol novolac type epoxy resin “EPICLON N-695” 2140 g (number of glycidyl groups (total number of aromatic rings): 10.0 mol), acrylic acid 720 g (10.0 mol), and hydroquinone 2.9 g Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 8.6 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, then 2.3 g of triphenylphosphine was further added, the temperature was raised to 120 ° C., and the reaction was further performed for 12 hours. To the resulting reaction solution, 1828 g of Solvesso 150 and 1368 g (9.0 mol) of tetrahydrophthalic anhydride were charged, and the reaction was performed at 110 ° C. for 4 hours. Furthermore, 1136 g (8.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was performed at 115 ° C. for 4 hours. Next, 600 g (6.0 mol) of succinic anhydride was added to the obtained reaction solution, and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 71 mgKOH / g and a solid content of 62%. This is designated as Resin Solution A-5.

Example 6 [Preparation of resin solution (A-6) containing acid group-containing vinyl ester resin (A)]
186 g of diethylene glycol monoethyl ether acetate, 214 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 0.86 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 0.23 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for further 12 hours. The obtained reaction solution was charged with 186 g of Solvesso 150 and 137 g (0.9 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 4 hours. Furthermore, 121 g (0.85 mol) of glycidyl methacrylate was added to the resulting reaction solution and reacted at 115 ° C. for 4 hours. Next, 65.0 g (0.65 mol) of succinic anhydride was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 67 mgKOH / g and a solid content of 62%. . This is designated as Resin Solution A-6.

Example 7 [Preparation of resin solution (A-7) containing acid group-containing vinyl ester resin (A)]
200 g of diethylene glycol monoethyl ether acetate, 214 g of orthocresol novolak epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 0.86 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 0.23 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for further 12 hours. 200 g of Solvesso 150, 152 g of tetrahydrophthalic anhydride (1.0 mol), 80.0 g (0.8 mol) of succinic anhydride, and 135 g (0.95 mol) of glycidyl methacrylate were charged into the obtained reaction solution at 115 ° C. Reaction was carried out for 8 hours to obtain a resin solution having a solid content acid value of 76 mgKOH / g and a solid content of 62%. This is designated as Resin Solution A-7.

Example 8 [Preparation of resin solution (A-8) containing acid group-containing vinyl ester resin (A)]
243 g of diethylene glycol monoethyl ether acetate, 214 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 72 g (1.0 mol) of acrylic acid, and 0.29 g of hydroquinone Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 0.86 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 0.23 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for further 12 hours. Into the obtained reaction solution, 243 g of Solvesso 150, 213 g (1.4 mol) of tetrahydrophthalic anhydride, 95.0 g (0.95 mol) of succinic anhydride, and 199 g (1.4 mol) of glycidyl methacrylate were charged at 115 ° C. Reaction was carried out for 8 hours to obtain a resin solution having a solid content acid value of 69 mgKOH / g and a solid content of 62%. This is designated as Resin Solution A-8.

（表中の原料組成は、モル比を示し、また、各略号の内容は下記のとおりである。
Ｎ６９５ ： オルソクレゾールノボラック型エポキシ樹脂
〔大日本インキ化学工業株式会社製、ＥＰＩＣＬＯＮ Ｎ−６９５、
軟化点９５℃、エポキシ当量２１４、平均官能基数７．６〕
ＡＡ ： アクリル酸
Ｍ５３００ ： ε−カプロラクトン２モル変性アクリル酸
〔東亞合成化学工業株式会社製、アロニックスＭ−５３００、
分子量３００〕
ＴＨＰＡ１ ： 工程１又は方法２で用いたテトラヒドロ無水フタル酸
ＧＭＡ ： グリシジルメタクリレート
ＳＡ ： 無水コハク酸
ＴＨＰＡ２ ： 工程４で用いたテトラヒドロ無水フタル酸
ＤＢｅｑ ： 芳香環１個に対するラジカル重合性不飽和二重結合の個数
二重結合世代数 ： ラジカル重合性不飽和二重結合の世代数 ）

(The raw material composition in the table indicates the molar ratio, and the contents of each abbreviation are as follows.
N695: Orthocresol novolac type epoxy resin
[Dainippon Ink & Chemicals, EPICLON N-695,
Softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6]
AA: acrylic acid M5300: ε-caprolactone 2 molar modified acrylic acid
[Aronix M-5300, manufactured by Toagosei Chemical Industry Co., Ltd.
Molecular weight 300]
THPA1: Tetrahydrophthalic anhydride GMA used in Step 1 or Method 2: Glycidyl methacrylate SA: Succinic anhydride THPA2: Tetrahydrophthalic anhydride used in Step 4 DBeq: Radiation polymerizable unsaturated double bond for one aromatic ring Number of double bond generations: Number of radical polymerizable unsaturated double bond generations)

Example 9 [Preparation of resin solution (A-9) containing acid group-containing vinyl ester resin (A)]
2063 g of diethylene glycol monoethyl ether acetate, 2140 g of orthocresol novolak type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 10.0 mol), 2 mol of ε-caprolactone modified acrylic acid [Toagosei Co., Ltd. Manufactured by Aronics M-5300, molecular weight 300] 600 g (2.0 mol), 576 g of acrylic acid (8.0 mol), and 3.3 g of hydroquinone were heated and stirred at 100 ° C. to be uniformly dissolved. Next, 10.0 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours. Then, 2.7 g of triphenylphosphine was further added, the temperature was raised to 120 ° C., and the reaction was further performed for 12 hours. To the obtained reaction liquid, 2063 g of aromatic hydrocarbon (Sorvesso 150) and 1368 g (9.0 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. Furthermore, 1136 g (8.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was performed at 115 ° C. for 4 hours. Next, 912 g (6.0 mol) of tetrahydrophthalic anhydride was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 63 mgKOH / g and a solid content of 62%. This is designated as Resin Solution A-9.

Example 10 [Preparation of resin solution (A-10) containing acid group-containing vinyl ester resin (A)]
211 g of diethylene glycol monoethyl ether acetate and 214 g of orthocresol novolak type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 2 mol of ε-caprolactone 60.0 g of modified acrylic acid (0.2 Mol), 57.6 g (0.8 mol) of acrylic acid, and 0.33 g of hydroquinone were added, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.0 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and then 0.27 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. Into the obtained reaction solution, 211 g of Solvesso 150 and 144 g (0.95 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. Furthermore, 121 g (0.85 mol) of glycidyl methacrylate was added to the resulting reaction solution and reacted at 115 ° C. for 4 hours. Next, 91.2 g (0.6 mol) of tetrahydrophthalic anhydride was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 60 mgKOH / g and a solid content of 62%. It was. This is designated as Resin Solution A-10.

Example 11 [Preparation of resin solution (A-11) containing acid group-containing vinyl ester resin (A)]
227 g of diethylene glycol monoethyl ether acetate and 214 g of orthocresol novolac epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 2 mol of ε-caprolactone, 60.0 g of modified acrylic acid (0.2 Mol), 57.6 g (0.8 mol) of acrylic acid, and 0.33 g of hydroquinone were added, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.0 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and then 0.27 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. 227 g of Solvesso 150, 274 g (1.8 mol) of tetrahydrophthalic anhydride and 135 g (0.95 mol) of glycidyl methacrylate were charged into the obtained reaction solution, and the reaction was performed at 115 ° C. for 8 hours, with a solid content acid value of 67 mg KOH / g, A resin solution having a solid content of 62% was obtained. This is designated as Resin Solution A-11.

Example 12 [Preparation of resin solution (A-12) containing acid group-containing vinyl ester resin (A)]
272 g of diethylene glycol monoethyl ether acetate and 214 g of orthocresol novolac epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 2 mol of ε-caprolactone 60.0 g of modified acrylic acid (0.2 Mol), 57.6 g (0.8 mol) of acrylic acid, and 0.33 g of hydroquinone were added, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.0 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and then 0.27 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. The resulting reaction solution was charged with 272 g of Solvesso 150, 357 g (2.35 mol) of tetrahydrophthalic anhydride, and 199 g (1.4 mol) of glycidyl methacrylate, reacted at 115 ° C. for 8 hours, and a solid content acid value of 62 mgKOH / g, A resin solution having a solid content of 62% was obtained. This is designated as Resin Solution A-12.

Example 13 [Preparation of resin solution (A-13) containing acid group-containing vinyl ester resin (A)]
1967 g of diethylene glycol monoethyl ether acetate and 2140 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 10.0 mol), ε-caprolactone 2 mol modified acrylic acid 600 g (2.0 mol) , 576 g (8.0 mol) of acrylic acid, and 3.3 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 10.0 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours. Then, 2.7 g of triphenylphosphine was further added, the temperature was raised to 120 ° C., and the reaction was further performed for 12 hours. The obtained reaction solution was charged with 1967 g of Solvesso 150 and 1368 g (9.0 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 4 hours. Furthermore, 1136 g (8.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was performed at 115 ° C. for 4 hours. Next, 600 g (6.0 mol) of succinic anhydride was added to the obtained reaction solution, and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 66 mgKOH / g and a solid content of 62%. This is designated as Resin Solution A-13.

Example 14 [Preparation of resin solution (A-14) containing acid group-containing vinyl ester resin (A)]
200 g of diethylene glycol monoethyl ether acetate, 214 g of orthocresol novolak type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 2 mol of ε-caprolactone, 60.0 g of modified acrylic acid (0.2 Mol), 57.6 g (0.8 mol) of acrylic acid, and 0.33 g of hydroquinone were added, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.0 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and then 0.27 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. Into the obtained reaction solution, 200 g of Solvesso 150 and 137 g (0.9 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. Furthermore, 121 g (0.85 mol) of glycidyl methacrylate was added to the resulting reaction solution and reacted at 115 ° C. for 4 hours. Next, 65.0 g (0.65 mol) of succinic anhydride was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 63 mgKOH / g and a solid content of 62%. . This is designated as Resin Solution A-14.

Example 15 [Preparation of resin solution (A-15) containing acid group-containing vinyl ester resin (A)]
214 g of diethylene glycol monoethyl ether acetate and 214 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 2 mol of ε-caprolactone 60.0 g of modified acrylic acid (0.2 Mol), 57.6 g (0.8 mol) of acrylic acid, and 0.33 g of hydroquinone were added, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.0 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and then 0.27 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. Into the obtained reaction liquid, 214 g of Solvesso 150, 152 g of tetrahydrophthalic anhydride (1.0 mol), 80.0 g (0.8 mol) of succinic anhydride, and 135 g (0.95 mol) of glycidyl methacrylate were charged at 115 ° C. The reaction was carried out for 8 hours to obtain a resin solution having a solid content acid value of 71 mgKOH / g and a solid content of 62%. This is designated as Resin Solution A-15.

Example 16 [Preparation of resin solution (A-16) containing acid group-containing vinyl ester resin (A)]
257 g of diethylene glycol monoethyl ether acetate and 214 g of orthocresol novolac epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 1.0 mol), 2 mol of ε-caprolactone 60.0 g of modified acrylic acid (0.2 Mol), 57.6 g (0.8 mol) of acrylic acid, and 0.33 g of hydroquinone were added, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.0 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and then 0.27 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. Into the obtained reaction solution, 257 g of Solvesso 150, 213 g (1.4 mol) of tetrahydrophthalic anhydride, 95.0 g (0.95 mol) of succinic anhydride, and 199 g (1.4 mol) of glycidyl methacrylate were charged at 115 ° C. The reaction was carried out for 8 hours to obtain a resin solution having a solid content acid value of 66 mgKOH / g and a solid content of 62%. This is designated as Resin Solution A-16.

（表中の原料組成は、モル比を示し、また、各略号の内容は下記のとおりである。
Ｎ６９５ ： オルソクレゾールノボラック型エポキシ樹脂
〔大日本インキ化学工業株式会社製、ＥＰＩＣＬＯＮ Ｎ−６９５、
軟化点９５℃、エポキシ当量２１４、平均官能基数７．６〕
ＡＡ ： アクリル酸
Ｍ５３００ ： ε−カプロラクトン２モル変性アクリル酸
〔東亞合成化学工業株式会社製、アロニックスＭ−５３００、
分子量３００〕
ＴＨＰＡ１ ： 工程１又は方法２で用いたテトラヒドロフタル酸無水物
ＧＭＡ ： グリシジルメタクリレート
ＳＡ ： 無水コハク酸
ＴＨＰＡ２ ： 工程４で用いたテトラヒドロフタル酸無水物
ＤＢｅｑ ： 芳香環１個に対するラジカル重合性不飽和二重結合の個数
二重結合世代数 ： ラジカル重合性不飽和二重結合の世代数 ）

(The raw material composition in the table indicates the molar ratio, and the contents of each abbreviation are as follows.
N695: Orthocresol novolac type epoxy resin
[Dainippon Ink & Chemicals, EPICLON N-695,
Softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6]
AA: acrylic acid M5300: ε-caprolactone 2 molar modified acrylic acid
[Aronix M-5300, manufactured by Toagosei Chemical Industry Co., Ltd.
Molecular weight 300]
THPA1: Tetrahydrophthalic anhydride GMA used in Step 1 or Method 2: Glycidyl methacrylate SA: Succinic anhydride THPA2: Tetrahydrophthalic anhydride used in Step 4 DBeq: Radical polymerizable unsaturated double for one aromatic ring Number of bonds Double bond generations: Generation number of radically polymerizable unsaturated double bonds

Comparative Example 1 (Production of Comparative Photosensitive Resin)
1080 g of diethylene glycol monoethyl ether acetate and 2080 g of orthocresol novolak type epoxy resin [Dainippon Ink Chemical Co., Ltd., EPICLON N-665, softening point 65 ° C., epoxy equivalent 208, average functional group number 4.6] Total number of rings): 10.0 mol), 720 g (10.0 mol) of acrylic acid, and 1.4 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 8.5 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours. Then, 2.8 g of triphenylphosphine was added, and the reaction was further performed for 10 hours. 1091 g of Solvesso 150 and 760 g (5.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and the reaction was performed at 110 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 84 mgKOH / g and a solid content of 62%. It was. This is designated as resin solution A′-1.

Comparative Example 2 (same as above)
1,109 g of diethylene glycol monoethyl ether acetate, 2080 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 10.0 mol), 720 g of acrylic acid (10.0 mol), and 1.4 g of hydroquinone The mixture was heated and stirred at 100 ° C. to dissolve uniformly. Next, 8.5 g of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours. Then, 2.8 g of triphenylphosphine was added, and the reaction was further performed for 10 hours. 1109 g of Solvesso 150 and 760 g (5.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction solution, and reacted at 110 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 82 mgKOH / g and a solid content of 62%. It was. This is designated as resin solution A′-2.

Comparative Example 3 (same as above)
1336 g of diethylene glycol monoethyl ether acetate 2140 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 10.0 mol), 720 g of acrylic acid (10.0 mol), 1.4 g of hydroquinone The mixture was heated and stirred at 100 ° C. to dissolve uniformly. Next, 8.6 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 2.9 g of triphenylphosphine was added, heated to 120 ° C., and further reacted for 10 hours. The obtained reaction solution was charged with 1336 g of Solvesso 150 and 1216 g (8.0 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 4 hours. Furthermore, 284 g (2.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was continued at 110 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 81 mgKOH / g and a solid content of 62%. This is designated as resin solution A′-3.

Comparative Example 4 (same as above)
2140 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 10.0 mol), 720 g of acrylic acid (10.0 mol) and 1.4 g of hydroquinone to 1510 g of diethylene glycol monoethyl ether acetate The mixture was heated and stirred at 100 ° C. to dissolve uniformly. Next, 8.6 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 2.9 g of triphenylphosphine was added, heated to 120 ° C. and further reacted for 10 hours. The obtained reaction solution was charged with 16624 g of Solvesso 150 and 1216 g (8.0 mol) of tetrahydrophthalic anhydride, and reacted at 115 ° C. for 4 hours. Further, 852 g (6.0 mol) of glycidyl methacrylate was added to the obtained reaction liquid, and subsequently reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 26 mgKOH / g and a solid content of 62%. This is designated as resin solution A′-4.

Comparative Example 5 (same as above)
2140 g of orthocresol novolac type epoxy resin “EPICLON N-695” (number of glycidyl groups (total number of aromatic rings): 10.0 mol), 720 g of acrylic acid (10.0 mol) and 1.4 g of hydroquinone to 1515 g of diethylene glycol monoethyl ether acetate The mixture was heated and stirred at 100 ° C. to dissolve uniformly. Next, 8.6 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours. Then, 2.9 g of triphenylphosphine was added, heated to 120 ° C. and further reacted for 10 hours. 1515 g of Solvesso 150 and 1444 g (9.5 mol) of tetrahydrophthalic anhydride were charged into the obtained reaction solution, and the reaction was performed at 115 ° C. for 4 hours. Furthermore, 639 g (4.5 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was continued at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 60 mgKOH / g and a solid content of 62%. This is designated as resin solution A′-5.

（表中の原料組成は、モル比を示し、また、各略号の内容は下記のとおりである。
Ｎ６９５ ： オルソクレゾールノボラック型エポキシ樹脂
〔大日本インキ化学工業株式会社製、ＥＰＩＣＬＯＮ Ｎ−６９５、
軟化点９５℃、エポキシ当量２１４、平均官能基数７．６〕
ＡＡ ： アクリル酸
Ｍ５３００ ： ε−カプロラクトン２モル変性アクリル酸
〔東亞合成化学工業株式会社製、アロニックスＭ−５３００、
分子量３００〕
ＴＨＰＡ１ ： テトラヒドロフタル酸無水物
ＧＭＡ ： グリシジルメタクリレート
ＳＡ ： 無水コハク酸
ＴＨＰＡ２ ： テトラヒドロフタル酸無水物
ＤＢｅｑ ： 芳香環１個に対するラジカル重合性不飽和二重結合の個数
二重結合世代数 ： ラジカル重合性不飽和二重結合の世代数 ）

(The raw material composition in the table indicates the molar ratio, and the contents of each abbreviation are as follows.
N695: Orthocresol novolac type epoxy resin
[Dainippon Ink & Chemicals, EPICLON N-695,
Softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6]
AA: acrylic acid M5300: ε-caprolactone 2 molar modified acrylic acid
[Aronix M-5300, manufactured by Toagosei Chemical Industry Co., Ltd.
Molecular weight 300]
THPA1: Tetrahydrophthalic anhydride
GMA: glycidyl methacrylate SA: succinic anhydride THPA2: tetrahydrophthalic anhydride
DBeq: number of radical polymerizable unsaturated double bonds per aromatic ring double bond generation number: number of radical polymerizable unsaturated double bond generations)

[Preparation of heat-reactive curing agent]
919 g of diethylene glycol monoethyl ether acetate was heated to 100 ° C., and 2140 g of orthocresol novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., EPICLON N-695, softening point 95 ° C., epoxy equivalent 214) was uniformly dissolved to obtain a solid content. A 70% resin solution was obtained. This resin solution is designated as B-1.

Examples 17-32, Comparative Examples 6-10
A photosensitive resin composition was blended according to the blending composition shown in Tables 1 and 2 (numerical values are parts by weight), and mixed with a rotating and rotating stirrer equipped with a cooling device to prepare a resist ink resin solution. . Table 3 shows the drying property, sensitivity, alkali developability, and coating film performance of the resulting resist ink resin composition. The drying property, sensitivity, alkali developability and coating film performance of the resist ink resin composition were evaluated by the methods shown below. However, the coating performance is that the resist ink resin composition is applied to a polyimide film substrate to a thickness of 60 μm (before drying), pre-dried at 80 ° C. for 30 minutes, and then irradiated with ultraviolet rays at an exposure amount of 200 mJ / cm ^2. Then, using a 1% by weight sodium carbonate aqueous solution at 30 ° C. and developing for 60 seconds at a spray pressure of 2.0 kg / cm ² , a cured coating film was prepared by post-curing at 150 ° C. for 30 minutes. Evaluation was performed.

Test Method and Evaluation Method (1) Dryability The coating film was pre-dried at 80 ° C. for 30 minutes. Next, with the coating film cooled to room temperature, the solder mask pattern was brought into contact with the coating film surface, the solder mask pattern was peeled off from the coating film, and the state was evaluated.
○: The film and the pattern do not adhere at all and can be easily peeled. Δ: The film can be peeled without leaving a trace, but has a slight adhesion feeling. ×: The film adheres to the solder mask pattern at the time of peeling.

(2) Sensitivity A 21-step tablet (manufactured by Kodak) was brought into close contact with the coating film after preliminary drying at 80 ° C. for 30 minutes, and an ultraviolet integrated intensity meter manufactured by Igraphic was used using an oak metal halide lamp exposure device. Irradiation exposure was performed with ultraviolet rays of 30 mJ / cm ² and 200 mJ / cm ² . Next, the number of the unexposed portions of the exposed portion after development for 60 seconds at a spray pressure of 2.0 kg / cm ² using a 1 wt% sodium carbonate aqueous solution at 30 ° C. is shown by numeral. Higher numbers indicate higher sensitivity.

(3) Development time A solder mask pattern was brought into close contact with the coating film after preliminary drying at 80 ° C. for 30 minutes, and was exposed to 200 mJ / cm ² of ultraviolet rays. Next, development was performed using a 1% by weight aqueous sodium carbonate solution at 30 ° C. and a spray pressure of 2.0 kg / cm ² . At the time of development, the development state of the unexposed part was visually determined with a magnifying glass every 15 seconds, and the time when the ink was completely removed and development was complete was defined as the development time.

(4) Thermal management width Each coating film whose pre-drying time was changed at intervals of 10 minutes from 80 ° C. 20 minutes to 80 ° C. 90 minutes was subjected to the same evaluation as (5) development time, and the maximum development possible in 60 seconds The pre-drying time (min) was defined as the thermal management width.

(6) Solder heat resistance According to the test method of JIS C 6481, the cured coating film was repeatedly immersed in a solder bath at 260 ° C. for 10 seconds, and the maximum number of times the appearance change did not appear was noted.

(7) Pencil hardness The cured coating film was tested according to the test method of JIS K 5400, and the highest hardness at which the coating film was not damaged was observed.

(8) Adhesiveness A 10 × 10 crosscut with a width of 1 mm was put into the cured coating film, and a peel test was performed with a cellophane tape, and the peeled state was visually observed.
○: No peeling is observed Δ: 1-10 peeling is observed x: 10 or more peeling

(9) Chemical resistance The state of the coating film after the cured coating film was immersed in 10% by weight hydrochloric acid for 30 minutes was evaluated.
○: No change at all ×: The film was swollen and peeled

(10) Solvent resistance The state of the coating film after the cured coating film was immersed in methylene chloride for 30 minutes was evaluated.
○: No change at all ×: The film was swollen and peeled

(11) Number of double bonds D in one molecule
The following calculation formula was used.
D = K × (l + m) / n
K: Number of cores of epoxy resin used l: Number of moles of charged acrylic acid m: Number of moles of charged glycidyl methacrylate n: Number of moles of charged epoxy resin

Claims (7)

A photosensitive resin composition comprising an acid group-containing vinyl ester resin (A) and a photopolymerization initiator (B) as essential components, wherein the acid group-containing vinyl ester resin (A) is:
A polybasic acid anhydride (a3) is reacted with an epoxy vinyl ester resin (v1) which is a reaction product of an aromatic epoxy resin (a1) and a radically polymerizable unsaturated double bond-containing monocarboxylic acid (a2). Next, the acid group formed by the reaction is reacted with a radical polymerizable unsaturated double bond-containing monoepoxy compound (a4), and the secondary hydroxyl group generated by the reaction is further reacted with a polybasic acid anhydride (a3). An acid group-containing vinyl ester resin having a multi-branched molecular structure obtained by reacting with a radical polymerizable unsaturated double bond per aromatic ring in the acid group-containing vinyl ester resin, It has a ratio of 1.75 to 3.5 and contains acid groups in a range where the acid value of the acid group-containing vinyl ester resin (A) is 30 to 150 mgKOH / g. The photosensitive resin composition characterized and. The acid group-containing vinyl ester resin (A) has 2.0 to 3.5 radical polymerizable unsaturated double bonds (b4) per aromatic ring in the multi-branched vinyl ester resin (A). The photosensitive resin composition according to claim 1, having a ratio of The photosensitive resin composition according to claim 1 or 2, wherein the radical polymerizable unsaturated double bond-containing monocarboxylic acid (a2) has a carbonyloxy group in its molecular structure. The photosensitive resin composition according to claim 1, wherein the aromatic epoxy resin (a1) is a novolac type epoxy resin. The photosensitive resin composition according to claim 4, wherein the novolac type epoxy resin has an average number of nuclei of 4 to 11. In addition to the acid group-containing vinyl ester resin (A) and the photopolymerization initiator (B), the thermosetting curing agent (C) and the diluent (D) are further contained in any one of claims 1 to 5. Photosensitive resin composition. A polybasic acid anhydride (a3) was reacted with an epoxy vinyl ester resin obtained by reacting a novolac type epoxy resin with a modified product of (meth) acrylic acid or an aliphatic cyclic ester compound thereof, and then formed by the reaction. A polybranched form obtained by reacting a radical polymerizable unsaturated double bond-containing monoepoxy compound (a4) with an acid group, and further reacting a secondary hydroxyl group produced by this reaction with a polybasic acid anhydride (a3). It is an acid group-containing vinyl ester resin having a molecular structure, and the radical polymerizable unsaturated double bond (b4) is 1.75 to 3.5 per aromatic ring in the acid group-containing vinyl ester resin. And a novel vinyl having an acid group in a range where the acid value of the multi-branched vinyl ester resin is 30 to 150 mgKOH / g Ester resin.