KR102284557B1 - Photosensitive-resin composition - Google Patents

Abstract

[Problem] In addition to the excellent resist shape and the ability to form a pattern with excellent resolution, PCT resistance (moisture and heat resistance), reflow resistance, electrical insulation (HAST resistance), and electroless plating resistance, heat resistance, content To provide a photosensitive resin composition capable of forming a pattern excellent in agent resistance, chemical resistance (alkali resistance, acid resistance) and adhesion, a permanent mask resist using the same, and a printed wiring board comprising the permanent mask resist. [Solution means] containing (A) acid-modified vinyl group-containing epoxy resin, (B) photoinitiator, (C) nitrogen-containing heterocyclic compound, and (D) photopolymerizable compound, and (C) nitrogen-containing heterocyclic compound A photosensitive resin composition having an average particle diameter of 0.01 to 10 µm, a permanent mask resist using the same, and a printed wiring board.

Description

Photosensitive resin composition {PHOTOSENSITIVE-RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition, a photosensitive element using the photosensitive resin composition, a permanent mask resist, and a printed wiring board.

In the manufacturing field of a printed wiring board, forming a permanent mask resist on a printed wiring board is performed. A permanent mask resist has the role of preventing corrosion of a conductor layer at the time of use of a printed wiring board, or maintaining the electrical insulation between conductor layers. In recent years, a permanent mask resist is a solder resist that prevents solder from adhering to unnecessary portions of a conductor layer of a printed wiring board in a process of flip-chip mounting, wire bonding mounting, etc., via solder on a printed wiring board. It also had a role as a membrane.

Conventionally, the permanent mask resist in printed wiring board manufacture has been produced by screen printing using a thermosetting resin composition or an ultraviolet curable resin composition. In the method by screen printing of this resin composition, since smearing, sinking, etc. generate|occur|produce at the time of printing, preparation of a high-precision pattern is difficult. Therefore, in the conventional method by screen printing of a resin composition, the formation of a permanent mask resist according to the high precision of wiring patterns and insulating patterns in printed wiring boards accompanied by recent miniaturization, weight reduction, and high performance of electronic devices is difficult. It became difficult, and it became impossible to fully respond to the request|requirement for high precision.

Then, the formation method of the permanent mask resist by photolithography came to be developed. Specifically, in this method of forming a permanent mask resist, a resist layer is formed by thermocompression bonding a dry film type photocurable resist onto a substrate, or applying a curtain or spray coating of a liquid type photocurable resist onto the substrate to form a resist layer. The layer is cured by selectively irradiating actinic rays such as ultraviolet rays through a negative mask, and forming an image by removing only the unirradiated portion with a developer solution.

When a dry film-type photocurable resist is used, air is drawn in during thermocompression bonding to the substrate and bubbles are easily generated, and the adhesion between the resist layer and the substrate is lowered or the resist pattern is disturbed, resulting in resist performance. is concerned about the decline of Therefore, the use of a liquid type photocurable resist rather than a dry film type is being considered. As a liquid type photocurable resist, although it is divided roughly into a solvent developing type and an alkali developing type, From a viewpoint of working environment preservation and global environmental preservation, the alkali developing type is becoming mainstream. It has been proposed to improve the heat resistance, chemical resistance, and electrical properties of a coating film in such an alkali developing liquid type photocurable resist (for example, Patent Documents 1 to 3).

However, as an alkali developing liquid type photocurable resist proposed in Patent Document 1, heat resistance and PCT resistance (pressure cooker test resistance) (hereinafter referred to as moisture and heat resistance), which have recently been demanded for more excellent performance, are sometimes referred to as It cannot be said that practical characteristics such as .) have been sufficiently satisfactory. Alkali-developing liquid-type photocurable resists have a hydrophilic group as a main component to enable alkali development. Therefore, chemicals, water, etc. easily penetrate into the resist layer, and sufficiently excellent practical properties of the resist layer are obtained. i don't think it can be

By the way, along with the miniaturization, weight reduction, and high performance of electronic devices, miniaturization of semiconductor packages, practical use of multi-pin, and mass production are also urgently needed. For example, high reliability is calculated|required in semiconductor package board|substrates, such as BGA (Ball Grid Array) and CSP (Chip Dimension Package) mounted on electronic components. Moreover, in order to achieve high reliability, PCT resistance (heat-and-moisture resistance) is calculated|required. However, the conventional liquid photocurable resist proposed in Patent Document 1 and the like tends to be practically only lasting for several hours to several tens of hours under a severe environment (high temperature, high humidity environment) as used in PCT resistance evaluation. The improvement of PCT property (moisture and heat resistance) is calculated|required further.

In addition, as a mounting method, surface mounting such as FC (Flip 　 Chip), TAB (Tape 　 Automated Bonding), COF (Chip On Film), etc. has been adopted from the conventional insertion mounting method. There is a tendency for the temperature to increase. In the case of surface mounting, more specifically, the solder is reflowed and fixed. That is, cream solder is printed on the required part in advance, the entire printed solder is heated in a high temperature furnace using infrared rays or the like, and the solder is melted. Since the surface-mounted components and the board are soldered, the temperature reached inside and outside the package is extremely high at 220-280°C.

When exposed to high temperature in this way, in the conventional liquid photocurable resist, cracks are generated in the coating film due to thermal shock, and there is also a problem that the reflow resistance is lowered, which peels off from the substrate or the encapsulant.

In addition, as the wiring patterns and insulating patterns (permanent mask resists) in the printed wiring board are highly precise, the spacing pitch between the wirings is being made finer. this is required

And in the manufacture, the electroless-plating method which does not require a lead wire has come to be employ|adopted. The electroless plating method has characteristics such as a uniform plating film thickness and high smoothness. However, when the pH of the plating solution is large and exhibits strong alkalinity, and when the temperature of the liquid is set to a high temperature of about 90° C. in order to improve the plating deposition rate, the damage to the permanent mask resist tends to increase. Therefore, the electroless plating resistance which is strong in the damage by the plating liquid used for electroless plating is also calculated|required by a permanent mask resist.

Furthermore, it is calculated|required that a permanent mask resist has a favorable resist shape. For example, in the case of forming a thick permanent mask resist with a thickness of 20 to 40 µm or more, the photocuring of the photocurable resist at the bottom cannot be sufficiently photocured, and the undercut of the bottom part is cut out after development, or the photocurability of the bottom is improved. If the exposure amount of ultraviolet irradiation is increased to increase the exposure amount of ultraviolet irradiation to Since this becomes large, it is easy to generate|occur|produce the problem that the deterioration of a resist shape generate|occur|produces or the resolution falls. In addition, there is also a problem that the resist top is missing and the resist shape is deteriorated due to insufficient photocuring in a region extending from the surface to about 3 µm in the resist depth direction due to oxygen inhibition.

Patent Document 1: Japanese Patent Laid-Open No. Hei 1-141904 Patent Document 2: Japanese Patent Laid-Open No. 2009-300532 Patent Document 3: Japanese Patent Laid-Open No. 2010-014767

The object of the present invention was made in view of these problems, and it is possible to form a pattern having excellent resist shape and excellent resolution, PCT resistance (moisture and heat resistance), reflow resistance, electrical insulation (HAST resistance), and to provide a photosensitive resin composition capable of forming a pattern excellent in heat resistance, solvent resistance, chemical resistance (alkali resistance, acid resistance), and adhesion in addition to resistance to electroless plating.

In addition, by using the photosensitive resin composition of the present invention, a permanent mask resist capable of forming a pattern, which is excellent in the formation stability of the size of the pore diameter and the pitch between the holes, which has been miniaturized due to the recent miniaturization and high performance of electronic devices, It is to provide the provided printed wiring board, and a photosensitive element.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the following invention could solve, as a result of repeating earnest research in order to solve the said subject. That is, this invention provides the following photosensitive resin composition, the photosensitive element using this photosensitive resin composition, a permanent mask resist, and a printed wiring board.

1. (A) acid-modified vinyl group-containing epoxy resin, (B) photoinitiator, (C) nitrogen-containing heterocyclic compound and (D) photopolymerizable compound, and (C) average particles of the nitrogen-containing heterocyclic compound A photosensitive resin composition having a diameter of 0.01 to 10 µm.

2. (E) The photosensitive resin composition as described in said 1 which further contains an inorganic filler.

3. (F) The photosensitive resin composition according to Fig. 2, further containing a pigment.

4. A photosensitive element provided with a support body and the photosensitive layer which uses the photosensitive resin composition in any one of said 1-3 on the support body.

5. The permanent mask resist formed with the photosensitive resin composition in any one of said 1-3.

6. Printed wiring board provided with said 5 permanent mask resist.

According to the present invention, it is possible to form a pattern having excellent resist shape and excellent resolution, and in addition to PCT resistance (moisture and heat resistance), reflow resistance, electrical insulation (HAST resistance), and electroless plating resistance, heat resistance , a photosensitive resin composition capable of forming a pattern excellent in solvent resistance, chemical resistance (alkali resistance, acid resistance), and adhesion, a permanent mask resist using the same, and a printed wiring board comprising the permanent mask resist can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross section of the resist formed using the photosensitive resin composition of this invention.
It is a figure which shows the pattern shape of the negative mask used in the Example.
It is a figure which shows the reflow profile employ|adopted in evaluation of reflow property.

[Photosensitive resin composition]

The photosensitive resin composition which concerns on embodiment in this invention (it may simply call this embodiment hereafter) which concerns on embodiment in this invention is (A) acid-modified vinyl group containing epoxy resin, (B) photoinitiator, (C) nitrogen-containing It contains a heterocyclic compound and (D) a photopolymerizable compound, The average particle diameter of this (C) nitrogen-containing heterocyclic compound is 0.01-10 micrometers, It is characterized by the above-mentioned. Each component is demonstrated below. In addition, in this specification, these components may only be called (A) component, (B) component, (C)component, and (D)component.

((A) Acid-modified vinyl group-containing epoxy resin)

The photosensitive resin composition of this embodiment contains an acid-modified vinyl group containing epoxy resin as (A) component. (A) The acid-modified vinyl group-containing epoxy resin is not particularly limited as long as the epoxy resin is modified with an organic acid containing a vinyl group, and an epoxy resin obtained by reacting the epoxy resin (a) with a vinyl group-containing monocarboxylic acid (b) ( A'), furthermore, an epoxy resin (a'') obtained by reacting the epoxy resin (a') with a saturated or unsaturated group-containing polybasic acid anhydride (c) is preferable.

As an epoxy resin (a), the epoxy resin which has structural units represented by the following general formula (I) - (V) is mentioned preferably, It is preferable that it is at least 1 sort(s) chosen from these. The epoxy resin which has a structural unit represented by these general formulas is demonstrated.

First, as an epoxy resin (a), the epoxy resin which has a structural unit represented by the following general formula (I) is mentioned preferably, As a novolak-type epoxy resin which has such a structural unit, For example, general formula ( The novolak-type epoxy resin represented by I') is mentioned preferably.

In general formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ represents a glycidyl group. Moreover, in the novolak-type epoxy resin which has a structural unit represented by general formula (I), content of the structural unit becomes like this. Preferably it is 70 mass % or more, More preferably, it is 90 mass % or more, More preferably, 95 mass % or more. mass % or more.

In the general formula (I'), R ¹¹ ' represents a hydrogen atom or a methyl group, Y ¹ ' represents a hydrogen atom or a glycidyl group, and the molar ratio of a hydrogen atom to a glycidyl group is preferably 0 :100-30:70, More preferably, it is 0:100-10:90, More preferably, it is 0:100. As can be seen from the molar ratio of the hydrogen atom to the glycidyl group, at least one Y ¹ ′ represents a glycidyl group. n ₁ represents an integer of 1 or more. In addition, a plurality of R ¹¹ 'are each may be the same or different, and a plurality of Y ^1' is may be the same or different.

n ₁ is an integer of 1 or more as described above, preferably 10 to 200, more preferably 30 to 150, still more preferably 30 to 100. When n ₁ is within the above range, a resist pattern with more excellent balance of resist shape, resolution, heat resistance, adhesiveness, and electrical insulation can be obtained.

As a novolak-type epoxy resin represented by general formula (I'), a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc. are mentioned preferably, for example. These novolak-type epoxy resins can be obtained, for example by making phenol resins, such as a phenol novolak resin and cresol novolak resin, react with epihalohydrin, such as epichlorohydrin, by a well-known method.

As a novolak-type epoxy resin represented by general formula (I'), For example, YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (above, New Nippon Chemicals Co., Ltd., brand name), DEN-431, DEN-439 (above, Dow Chemical, Ltd., brand name), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN -1012, EOCN-1025, EOCN-1027, BREN (above, manufactured by Nippon Kayaku Co., Ltd., brand name), EPN-1138, EPN-1235, EPN-1299 (above, manufactured by BASF Japan, brand name), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (above, manufactured by DIC Corporation, trade name) and the like are commercially available.

As the epoxy resin (a), an epoxy resin having a structural unit represented by the general formula (II) is preferably mentioned, and the epoxy resin having such a structural unit is, for example, an epoxy resin represented by the general formula (II') A bisphenol A epoxy resin and a bisphenol F type epoxy resin are mentioned preferably.

In general formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ² represents a glycidyl group. Moreover, in the epoxy resin which has a structural unit represented by general formula (II), content of the structural unit becomes like this. Preferably it is 70 mass % or more, More preferably, it is 90 mass % or more, More preferably, it is 95 mass % or more. am.

In the general formula (II'), R ¹² ' represents a hydrogen atom or a methyl group, Y ² ' represents a hydrogen atom or a glycidyl group, and the molar ratio of a hydrogen atom to a glycidyl group is preferably 0 :100-30:70, More preferably, it is 0:100-10:90, More preferably, it is 0:100. As can be seen from the molar ratio of the hydrogen atom to the glycidyl group, at least one Y ² ′ represents a glycidyl group. n ₂ represents an integer of 1 or more. In addition, a plurality of R ¹² 'may be the same or are different and, if n ₂ is 2 or more, plural Y ^2' is may be the same or different.

n ₂ is an integer of 1 or more as described above, preferably 10 to 100, more preferably 10 to 80, still more preferably 15 to 60. When n ₂ is within the above range, an excellent resist shape and a pattern excellent in resolution can be obtained, and excellent adhesion, heat resistance, and electrical insulation properties can be obtained.

The bisphenol A type epoxy resin represented by the general formula (II') and Y ² ' is a glycidyl group, the bisphenol F type epoxy resin is, for example, a bisphenol A type epoxy resin represented by the following general formula (VI); It can obtain by making the hydroxyl group of a bisphenol F-type epoxy resin react with epihalohydrin, such as epichlorohydrin.

In general formula (VI), R ¹² and n ₂ are the same as above.

The amount of epihalohydrin used is determined by the general formula ( It is preferable to set it as 2-10 mol with respect to 1 mol of hydroxyl groups in the epoxy resin represented by VI).

From the same viewpoint, it is preferable to use a basic catalyst in the reaction between the epoxy resin represented by the general formula (VI) and epihalohydrin. As the basic catalyst, for example, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides and the like are preferable, and alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide are more preferable from the viewpoint of catalytic activity. . Moreover, it is preferable that the usage-amount is 0.9-2 mol with respect to 1 mol of hydroxyl groups in the epoxy resin represented by general formula (VI).

In the reaction between the epoxy resin represented by the general formula (VI) and epihalohydrin, from the viewpoint of further increasing the reaction rate, examples of the organic solvent include alcohols such as methanol and ethanol; cellosolves such as methyl cellosolve and ethyl cellosolve; ethers such as tetrahydrofuran and dioxane; It is preferable to use a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide. Among these, it can be used individually by 1 type or in combination of 2 or more type, It is preferable to use 2 or more types combining from a viewpoint of polarity adjustment.

The reaction temperature is preferably 20 to 120°C, more preferably 50 to 120°C, and the reaction time is preferably 0.5 to 10 hours. When the reaction temperature and the reaction time are within the above ranges, the reaction is less likely to be delayed, and a side reaction product is less likely to be generated.

After the above reaction, unreacted epihalohydrin, an organic solvent, etc. are distilled off by distillation, preferably under heating and reduced pressure, to obtain an epoxy resin represented by the general formula (II'). .

Moreover, from a viewpoint of obtaining a higher purity epoxy resin, the obtained epoxy resin is made to dissolve again in an organic solvent, and basic catalysts, such as said alkali metal hydroxide, can be added and made to react. At this time, it is preferable to use the phase transfer catalyst, such as a quaternary ammonium salt and a crown ether, in 0.1-3 mass % with respect to an epoxy resin from a viewpoint of raising a reaction rate. In this case, a high-purity epoxy resin can be obtained by removing salts or the like generated after completion of the reaction by filtration or washing with water, and further distilling off an organic solvent or the like under heating and reduced pressure.

As the bisphenol A epoxy resin or bisphenol F epoxy resin represented by the general formula (II'), for example, Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (above, Mitsubishi Chemical Co., Ltd. product name), DER-330, DER-301, DER-361 (above, Dow Chemical Co., Ltd. product name), YD-8125, YDF-170, YDF-175S, YDF-2001 , YDF-2004, YDF-8170 (above, manufactured by Shin-Nittetsu Sumikingaku Co., Ltd., trade name) and the like are commercially available.

As an epoxy resin (a), the epoxy resin which has a structural unit represented by the following general formula (III) is mentioned preferably, As an epoxy resin which has such a structural unit, the following general formula (III') A triphenolmethane type epoxy resin represented by is preferably mentioned.

In general formulas (III) and (III'), Y ³ represents a hydrogen atom or a glycidyl group, and the molar ratio of a hydrogen atom to a glycidyl group is preferably 0:100 to 30:70. As can be seen from the molar ratio of the hydrogen atom to the glycidyl group, at least one Y ³ represents a glycidyl group. n ₃ represents an integer of 1 or more. In addition, some Y<^3> may be same or different.

n ₃ is an integer of 1 or more as described above, preferably 10 to 100, more preferably 15 to 80, still more preferably 15 to 70. When n ₃ is within the above range, a resist pattern with more excellent balance of resist shape, resolution, heat resistance, adhesiveness, and electrical insulation can be obtained.

Moreover, in the epoxy resin which has a structural unit represented by general formula (III), content of the structural unit becomes like this. Preferably it is 70 mass % or more, More preferably, it is 90 mass % or more, More preferably, it is 95 mass % or more. am.

As a triphenolmethane type epoxy resin represented by general formula (III'), FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd. product, brand name) etc. are obtained commercially, for example. possible.

As an epoxy resin (a), the bisphenol novolak-type epoxy resin which has a structural unit represented by General formula (IV) is mentioned preferably.

In general formula (IV), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, and Y ⁴ represents a hydrogen atom or a glycidyl group. At least one Y ⁴ represents a glycidyl group, and a plurality of R ¹³ may be the same or different.

As an alkyl group of R<^13> , a C1-C20 thing is preferable, A C1-C12 thing is more preferable, A 1-3 thing is more preferable. The alkyl group may be linear or branched, and may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a sec-pentyl group, an isopentyl group, and a neopentyl group. etc. are mentioned preferably, Among these, a methyl group is preferable.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group, preferably an aryl group having 6 to 20 ring carbon atoms, more preferably 6 ring carbon atoms It is an aryl group of ~14. The aryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.

The aralkyl group is not particularly limited as long as one of the hydrogen atoms of the alkyl group is substituted with the aryl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group. It may be substituted with an atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.

Moreover, in the epoxy resin which has a structural unit represented by general formula (IV), content of the structural unit becomes like this. Preferably it is 70 mass % or more, More preferably, it is 90 mass % or more, More preferably, it is 95 mass % or more. am. If it is in the said range, the resist pattern more excellent in the balance of a resist shape, resolution, heat resistance, adhesiveness, and electrical insulation can be obtained.

Moreover, as an epoxy resin (a), the bisphenol novolak-type epoxy resin which has a structural unit represented by the following general formula (V) is mentioned preferably.

In the general formula (V), R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, and Y ⁵ represents a hydrogen atom or a glycidyl group. At least one Y ⁵ represents a glycidyl group, and a plurality of R ¹⁴ may be the same or different. Further, as the alkyl group, an aryl group, an aralkyl group of R ^14, it may be mentioned the same as those described in R ^13, and a preferred embodiment is also the same.

Moreover, in the epoxy resin which has a structural unit represented by general formula (V), content of the structural unit becomes like this. Preferably it is 70 mass % or more, More preferably, it is 90 mass % or more, More preferably, it is 95 mass % or more. am. If it is in the said range, the resist pattern more excellent in the balance of a resist shape, resolution, heat resistance, adhesiveness, and electrical insulation can be obtained.

In the general formula (V), R ¹⁴ is a hydrogen atom and Y ⁵ is a glycidyl group, EXA-7376 series (manufactured by DIC Corporation, brand name), R ¹⁴ is a methyl group, and Y ⁵ is The glycidyl group is commercially available as EPON SU8 series (manufactured by Mitsubishi Chemical Co., Ltd., trade name).

The bisphenol novolak-type epoxy resin having structural units represented by the general formulas (IV) and (V) is, for example, the hydroxyl group and epi of the bisphenol novolac resin represented by the following general formulas (VII) and (VIII), respectively. It can obtain by reacting epihalohydrin, such as chlorohydrin.

In the general formula (VII), R ^{13 is the same as R 13} in the general formula (IV), and in the general formula (VIII), R ¹⁴ is the same as ^{R 14} in the general formula (V).

The bisphenol novolak resin having structural units represented by these general formulas (VII) and (VIII) is preferably, for example, a bisphenol compound and an aldehyde compound or a ketone compound, and an alkyl group having 1 to 4 carbon atoms has a molecular structure. It can be obtained by reacting in the presence of sulfonic acid.

Here, the bisphenol compound is not particularly limited as long as it is a compound having two hydroxyphenyl groups, for example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G , bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, bisphenol Z, etc. are mentioned preferably, and bisphenol A and bisphenol F are more preferable.

Preferred examples of the aldehyde compound to be reacted with the bisphenol compound include formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde, naphthylaldehyde and the like. Benzophenone, fluorenone, indanone, etc. are mentioned preferably, Among them, formaldehyde is preferable.

Examples of the sulfonic acid having an alkyl group having 1 to 4 carbon atoms in its molecular structure include alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid, and perfluoroalkanesulfonic acid having a fluorine atom in the alkane moiety. .

More specifically, the bisphenol novolak-type epoxy resin which has structural units represented by general formula (IV) and (V), Preferably it can be obtained as follows. The bisphenol compound and the aldehyde compound or the ketone compound are placed in a reaction vessel, and while stirring in an inert gas atmosphere, sulfonic acid is continuously or intermittently added to maintain the range of 20 to 200° C., and the bisphenol compound and the aldehyde compound or the ketone compound react to obtain a crude bisphenol novolak resin. Next, the crude bisphenol novolac resin is extracted with a water-insoluble organic solvent to obtain a bisphenol novolak resin solution, washed with water, neutralized, and further distilled off the water-insoluble organic solvent to obtain a bisphenol novolak-type epoxy resin can be obtained.

Here, as the water-insoluble organic solvent, from the viewpoint of improving the working efficiency of extraction, washing with water, and neutralization, a thing having a boiling point of 100 to 130°C is preferable, for example, butanol, pentyl alcohol, methoxyethanol, ethoxyethanol, Diethylene glycol, methyl isobutyl ketone, etc. are mentioned preferably, butanol, methoxyethanol, and methyl isobutyl ketone are more preferable, and methyl isobutyl ketone is more preferable.

The above water washing is carried out until the crude bisphenol novolak resin solution reaches pH 3 to 7, more preferably pH 5 to 7, and, if necessary, a basic substance such as sodium hydroxide, sodium carbonate, ammonia, triethylenetetramine, etc. It may be used to neutralize.

The above-mentioned distillation is preferably carried out by heating and vacuum distillation under the conditions of a temperature of 170 to 200°C and a pressure of 3 kPa or less, so that a bisphenol novolak resin with high purity can be obtained.

As the epoxy resin (a), the epoxy resin having a structural unit represented by the general formula (I), represented by the general formula (II), from the viewpoint of being excellent in process induction and improving the solvent resistance. A bisphenol novolak-type epoxy resin having a structural unit represented by formula (IV) is preferable, and a novolak-type epoxy resin represented by formula (I'), general formula (II') ), a bisphenol A epoxy resin represented by the general formula (II'), a bisphenol F-type epoxy resin represented by the general formula (II'), and a bisphenol novolac A epoxy resin having a structural unit represented by the general formula (IV), and the general formula A bisphenol novolac F-type epoxy resin having a structural unit represented by (IV) is more preferable.

Further, from the viewpoint of being able to further reduce the warpage of the thin film substrate and further improving the thermal shock resistance, an epoxy resin having a structural unit represented by the general formula (IV), and a configuration represented by the general formula (V) It is preferable to use together the epoxy resin which has a unit.

Examples of the vinyl group-containing monocarboxylic acid (b) to be reacted with the epoxy resin (a) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfuryl acrylic acid, β-styryl acrylic acid, cinnamic acid, Acrylic acid derivatives such as crotonic acid and α-cyano cinnamic acid, a half-ester compound that is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester and the half-ester compound etc. which are reaction products of a dibasic acid anhydride are mentioned preferably.

The half-ester compound can be obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. These vinyl group containing monocarboxylic acids (b) can be used individually by 1 type or in combination of 2 or more type.

As the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the above half-ester compound as an example of the vinyl group-containing monocarboxylic acid (b), for example, hydroxy hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) ) acrylate, dipentaerythritol penta (meth) acrylate, vinyl glycidyl ether, glycidyl (meth) acrylate, etc. are preferably mentioned.

As a dibasic acid anhydride used for the synthesis|combination of said half-ester compound, the thing containing a saturated group and the thing containing an unsaturated group can be used. Specific examples of the dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and ethylhexahydrophthalic anhydride. , itaconic anhydride, etc. are preferably mentioned.

In the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) described above, the ratio of the vinyl group-containing monocarboxylic acid (b) to 0.6 to 1.05 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin (a). Preferably, the reaction is carried out in a ratio of 0.8 to 1.0 equivalent, and more preferably in a ratio of 0.9 to 1.0 equivalent. By reacting in such a ratio, since photopolymerization improves, that is, it becomes a thing excellent in photosensitivity, it is preferable.

The reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be carried out by dissolving in an organic solvent.

Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; Petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, etc. are mentioned preferably.

Furthermore, it is preferable to use a catalyst in order to promote the reaction. Examples of the catalyst include preferably triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, and triphenylphosphine. . To [ the usage-amount of a catalyst / a total of 100 mass parts of an epoxy resin (a) and a vinyl group containing monocarboxylic acid (b) ], Preferably it is 0.1-10 mass parts. When it is set as said usage-amount, since reaction of an epoxy resin (a) and a vinyl group containing monocarboxylic acid (b) is accelerated|stimulated, it is preferable.

It is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during reaction. As a polymerization inhibitor, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrrogalol etc. are mentioned preferably, for example. To [ the usage-amount of a polymerization inhibitor / a total of 100 mass parts of an epoxy resin (a) and a vinyl group containing monocarboxylic acid (b)), Preferably it is 0.01-1 mass part. Since the storage stability (self-life) of a composition is improved when it sets it as said usage-amount, it is preferable. The reaction temperature is preferably 60 to 150°C, more preferably 80 to 120°C.

In addition, if necessary, a vinyl group-containing monocarboxylic acid (b), a phenol-based compound such as p-hydroxyphenethyl alcohol, or trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, or biphenyltetracarboxylic acid Polybasic acid anhydrides, such as anhydride, can be used together.

Thus, it is estimated that the epoxy resin (a') obtained has a hydroxyl group formed by the addition reaction of the epoxy group of an epoxy resin (a) with the carboxyl group of a vinyl-group containing monocarboxylic acid (b).

In the present embodiment, as the (A) acid-modified vinyl group-containing epoxy resin, an epoxy resin (a”) obtained by reacting the above-mentioned epoxy resin (a') with a polybasic acid anhydride (c) is also preferably mentioned. Epoxy In the resin (a"), it is presumed that the hydroxyl group of the epoxy resin (a') (including the hydroxyl group originally present in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) are half-esterified.

As polybasic acid anhydride (c), the thing containing a saturated group and the thing containing an unsaturated group can be used preferably. Specific examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydro A phthalic anhydride, itaconic anhydride, etc. are mentioned preferably.

In the reaction between the epoxy resin (a') and the polybasic acid anhydride (c), by reacting 0.1 to 1.0 equivalent of the polybasic acid anhydride (c) with respect to 1 equivalent of the hydroxyl group in the epoxy resin (a'), acid-modified vinyl group-containing epoxy The acid value of the resin can be adjusted.

(A) It is preferable that the acid value of an acid-modified vinyl group containing epoxy resin is 30-150 mgKOH/g, It is more preferable that it is 40-120 mgKOH/g, It is more preferable that it is 50-100 mgKOH/g. The solubility to the dilute alkali solution of the photosensitive resin composition is hard to fall that an acid value is 30 mgKOH/g or more, and the electrical property of a cured film is hard to fall that it is 150 mgKOH/g or less.

It is preferable that the reaction temperature of an epoxy resin (a') and polybasic acid anhydride (c) sets it as 60-120 degreeC.

Moreover, as an epoxy resin (a), a part of hydrogenated bisphenol A epoxy resin can also be used together as needed, for example. Further, as the (A) acid-modified vinyl group-containing epoxy resin, a part of a styrene-maleic acid-based resin such as a hydroxyethyl (meth)acrylate-modified product of a styrene-maleic anhydride copolymer may be used in combination.

(A) As for the weight average molecular weight of an acid-modified vinyl group containing epoxy resin, 3000-30000 are preferable, More preferably, it is 4000-25000, More preferably, it is 5000-18000. (A) A resist pattern more excellent in the balance of a resist shape, resolution, heat resistance, adhesiveness, and electrical insulation as the weight average molecular weight of (A) component is in the said range can be obtained. Here, the weight average molecular weight is a weight average molecular weight in terms of polyethylene measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, it can measure with the following GPC measuring apparatus and measurement conditions, and the value converted using the analytical curve of standard polystyrene can be made into a weight average molecular weight. In addition, preparation of a calibration curve uses 5 sample sets ("PStQuick 　MP-H" and "PStQuick 　B", manufactured by Tosoh Co., Ltd.) as standard polystyrene.

(GPC measuring device)

GPC device: High-speed GPC device "HLC-8320GPC", the detector is a differential refractometer, manufactured by Tosoh Corporation

Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation

(Measuring conditions)

Solvent: tetrahydrofuran (THF)

Measuring temperature: 40℃

Flow: 0.35ml/min

Sample concentration: 10mg/THF5ml

Injection volume: 20 μl

(A) As an acid-modified vinyl group-containing epoxy resin, as an epoxy resin (a), the novolak-type epoxy resin represented by general formula (I'), which has a structural unit represented by general formula (I), general formula ( An epoxy resin (a') obtained by reacting a bisphenol A type epoxy resin represented by the general formula (II'), a bisphenol F type epoxy resin, and a vinyl group-containing monocarboxylic acid (b) having a structural unit represented by II); and an epoxy resin (a'') obtained by reacting an epoxy resin (a') with a saturated or unsaturated group-containing polybasic acid anhydride (c) is preferable, and an epoxy resin (a'') is more preferable.

These epoxy resins (a') and (a'') can be used individually by 1 type or in combination of 2 or more type, and it is preferable to use them in combination of multiple types. As a combination, the epoxy resin (a') or (a'') obtained from the novolak-type epoxy resin represented by general formula (I'), the bisphenol A epoxy resin represented by general formula (II'), and bisphenol A combination of two types with the epoxy resin (a') or (a'') obtained from the F-type epoxy resin is preferable, and the epoxy resin (a'') obtained from the novolac-type epoxy resin represented by the general formula (I') ) and the bisphenol-A epoxy resin represented by general formula (II'), and the epoxy resin (a'') obtained from the bisphenol F-type epoxy resin are more preferable.

Epoxy resin (a') or (a'') obtained from a novolak-type epoxy resin represented by general formula (I'), bisphenol A epoxy resin represented by general formula (II'), and bisphenol F-type epoxy 95:5-30:70 are preferable, as for the mass mixing ratio with the epoxy resin (a') or (a'') obtained from resin, it is more preferable that it is 90:10-40:60, 80:20-45 :55 is more preferable.

It is preferable that content of (A) component which makes solid content whole quantity in the photosensitive resin composition 100 mass parts is 20-80 mass parts, It is more preferable that it is 30-75 mass parts, It is especially preferable that it is 40-75 mass parts. (A) When content of component is in the said range, the coating film which was more excellent in heat resistance, an electrical characteristic, and chemical-resistance (alkali resistance, acid resistance) can be obtained. Here, solid content whole quantity in this embodiment is the total amount of solid content contained in (A)-(D)component, (A)-(E)component, or (A)-(F)component. For example, when the photosensitive resin composition of this embodiment contains (A) - (D) component, the total amount of solid content contained in (A) - (D) component furthermore the photosensitive resin composition of this embodiment When this (E)component is further included, when the total amount of solid content contained in (A)-(E)component further contains (F)component further, it is included in (A)-(F)component The total amount of solid content to be used is the total amount of solid content.

The photosensitive resin composition of this embodiment contains a photoinitiator as (B) component. (B) There is no restriction|limiting in particular as a photoinitiator, It can select suitably from the photoinitiator normally used and can be used. It is preferable to contain the acylphosphine oxide type|system|group photoinitiator which has an acylphosphine oxide group (=P(=O)-C(=O)-group) from a resist shape and a viewpoint of reflow property. As an acylphosphine oxide type|system|group photoinitiator, For example, (2,6-dimethoxybenzoyl)-2,4,6- trimethylbenzoyl- pentyphosphine oxide, bis(2,4,6- trimethylbenzoyl)-phenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, (2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, and tris(p-hydroxyphenyl) ) phosphine oxide etc. are mentioned preferably.

Moreover, as photoinitiators other than an acylphosphine oxide type|system|group photoinitiator, Benzoin type photoinitiators, such as benzoin, benzoin methyl ether, benzoin isopropyl ether; Acetphenone, 2,2-dimethoxy-2-phenylacetphenone, 2,2-diethoxy-2-phenylacetphenone, 1,1-dichloroacetphenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- acetphenone-based photopolymerization initiators such as 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and N,N-dimethylaminoacetphenone; anthraquinone-based photopolymerization initiators such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; thioxanthone-based photopolymerization initiators such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketal-based photopolymerization initiators such as acetphenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenylsulfide; Oxime type photoinitiators, such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime), are also mentioned preferably.

(B) As a photoinitiator, said thing can be used individually by 1 type or in combination of 2 or more type.

Content of (B) photoinitiator which makes solid content whole quantity in the photosensitive resin composition 100 mass parts becomes like this. Preferably it is 0.2-15 mass parts. If it is 0.2 mass part or more, an exposed part will become difficult to elute during image development, and heat resistance will become difficult to fall that it is 15 mass parts or less. Moreover, for the same reason, 0.2-10 mass parts is more preferable, as for content of (B) photoinitiator, 0.5-5 mass parts is still more preferable, 0.5-3 mass parts is especially preferable.

In addition, photopolymerization initiation aids such as tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine It can be used individually by 1 type or in combination of 2 or more type.

The photosensitive resin composition of this embodiment contains a nitrogen-containing heterocyclic compound as (C)component. (C) The nitrogen-containing heterocyclic compound is not particularly limited as long as it is a cyclic compound containing at least carbon and nitrogen having an average particle diameter of 0.01 to 10 µm, and can further improve reflow resistance, heat resistance and chemical resistance. In addition to these properties, from the viewpoint of improving the electroless plating resistance of nickel, gold, palladium and tin, etc., an imidazole compound, a triazine compound, an imidazoline compound, etc. are preferably mentioned, either alone or It can be used in combination of 2 or more types.

Examples of the imidazole compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2- Phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxy Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimeritate, 1-cyanoethyl-2-phenylimidazolium trimeritate, 2-phenyl-4 ,5-dihydroxymethylimidazole, 2,3-dihydro-1H-pyrro[1,2-a]benzimidazole, 2-phenylimidazole isocyanuric acid adduct, etc. are preferable. there is. Among these, 4-methyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, etc. are preferable. You may use these imidazole compounds individually by 1 type or in combination of 2 or more type.

Examples of the triazine compound include triaminotriazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino -6-Xylyl-s-triazine, 2,4-diamino-6-[2'-methylimidazoryl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2,4- Diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazineisocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s- Triazine etc. are mentioned preferably. Among these, 2,4-diamino-6-vinyl-s-triazine, triaminotriazine, etc. are preferable. You may use these imidazole compounds individually by 1 type or in combination of 2 or more type.

Examples of the imidazoline compound include 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-ethylimidazoline, and 2-isopropylimidazoline. , 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline, etc. are mentioned preferably, Among these, 2-methylimidazoline, 2-phenylimidazoline, etc. are preferable. You may use these imidazoline compounds individually by 1 type or in combination of 2 or more type.

The average particle diameter of the (C) nitrogen-containing heterocyclic compound used in the present invention needs to be 0.01 to 10 µm. If the average particle diameter is less than 0.01 μm, secondary agglomeration tends to occur, so handling is difficult. If the average particle diameter exceeds 10 μm, the resist shape deteriorates because excellent curability cannot be obtained, and also excellent HAST resistance and electroless plating resistance. can't get In addition, as the average particle diameter of the (C) nitrogen-containing heterocyclic compound, excellent reflow resistance, heat resistance, and chemical resistance can be obtained, and from the viewpoint of refining the pitch pitch and responding to high precision, 0.5 to 5 μm. it is preferable Here, the average particle diameter was determined to be measured by a laser diffraction method (based on JIS Z8825-1 (2001)).

Content of (C) nitrogen-containing heterocyclic compound which makes solid content whole quantity in the photosensitive resin composition 100 mass parts becomes like this. Preferably it is 0.05-10 mass parts. When it is 0.05 parts by mass or more, excellent electroless plating resistance can be obtained, and when it is 10 parts by mass or less, excellent electrical insulation (HAST resistance) can be obtained. Moreover, for the same reason, 0.1-10 mass parts is more preferable, as for content of (C) nitrogen-containing heterocyclic compound, 0.1-5 mass parts is still more preferable, 0.3-5 mass parts is especially preferable.

The photosensitive resin composition of this embodiment contains a photopolymerizable compound as (D)component. (D) The photopolymerizable compound is a photopolymerizable functional group, for example, a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group, (meth) There will be no restriction|limiting in particular if it is a compound which has ethylenically unsaturated groups, such as an acryloyl group, It is preferable that it is a compound which has a (meth)acryloyl group from a reactive viewpoint.

(D) As a photopolymerizable compound, For example, Hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; mono or di(meth)acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol and polyethylene glycol; (meth)acrylamides, such as N,N- dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and tris-hydroxyethyl isocyanurate, or polyhydric (meth)acrylates of these ethylene oxide or propylene oxide adducts; (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ether, such as glycerin diglycidyl ether, trimethylol propane triglycidyl ether, and triglycidyl isocyanurate; Melamine (meth)acrylate etc. are mentioned preferably. These (D) photopolymerizable compounds can be used individually by 1 type or in combination of 2 or more type.

Content of (D) photopolymerizable compound which makes solid content whole quantity in the photosensitive resin composition 100 mass parts becomes like this. Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts, More preferably, it is 1-15 mass parts . (D) When content of component is 0.1 mass part or more, an exposure part is hard to elute during image development, there exists a tendency for the sensitivity and resolution of the photosensitive resin composition to improve, and heat resistance improves as it is 30 mass parts or less.

It is preferable that the photosensitive resin composition of this embodiment contains an inorganic filler as (E)component. (E) An inorganic filler is used suitably for the purpose of improving characteristics, such as adhesiveness of a photosensitive resin composition, heat resistance, and coating-film intensity|strength. (E) As the inorganic filler, for example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si _{3 )} N ₄ ), barium titanate (BaO·TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate (PbO·TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum titanate ( PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO·Al ₂ O ₃ ), mullite (3Al ₂ O ₃ ·2SiO ₂ ), cordierite (2MgO·2Al ₂ O ₃ ·5SiO ₂ ), talc ( 3MgO·4Al ₂ O ₃ ·H ₂ O), aluminum titanate (TiO ₂ ·Al ₂ O ₃ ), yttria-containing zirconia (Y ₂ O ₃ ·ZrO ₂ ), barium silicate (BaO·8SiO ₂ ), boron nitride ( BN), calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon, etc. are preferably mentioned. These (E) inorganic fillers can be used individually by 1 type or in combination of 2 or more type.

(E) The maximum particle diameter of the inorganic filler is preferably 0.1 to 20 µm, more preferably 0.1 to 10 µm, still more preferably 0.1 to 5 µm, and particularly preferably 0.1 to 1 µm. When the maximum particle diameter is 20 µm or less, a decrease in electrical insulation properties (HAST resistance) can be suppressed. Here, (E) the maximum particle diameter of the inorganic filler was measured by a laser diffraction method (based on JIS Z8825-1 (2001)).

(E) Among inorganic fillers, silica is preferable from the viewpoint of improving heat resistance, and from the viewpoint of improving solder heat resistance, crack resistance (thermal shock resistance), and PCT resistance, it is better to use barium sulfate. desirable. In addition, it is preferable that the said barium sulfate is surface-treated with 1 or more types selected from alumina and an organosilane-type compound from a viewpoint of being able to improve the aggregation prevention effect.

The elemental composition of aluminum on the surface of barium sulfate surface-treated with at least one selected from alumina and organosilane compounds is preferably 0.5 to 10 atomic %, more preferably 1 to 5 atomic %, , more preferably 1.5 to 3.5 atomic%. It is preferable that the elemental composition of the silicon in the surface of barium sulfate is 0.5-10 atomic%, It is more preferable that it is 1-5 atomic%, It is still more preferable that it is 1.5-3.5 atomic%. Moreover, it is preferable that it is 10-30 atomic%, and, as for the elemental composition of carbon in the surface of barium sulfate, it is more preferable that it is 15-25 atomic%, It is more preferable that it is 18-23 atomic%. Such elemental composition can be measured using XPS.

As barium sulfate surface-treated with 1 or more types selected from alumina and an organosilane compound, NanoFine BFN40DC (made by Nippon Sorbey Co., Ltd. product, brand name) is commercially available, for example.

When the photosensitive resin composition of this embodiment contains (E) inorganic filler, it is preferable that content of (E) inorganic filler which makes solid content whole amount in the photosensitive resin composition 100 mass parts is 10-80 mass parts, It is preferable that it is 20-70 It is more preferable that it is a mass part, It is still more preferable that it is 20-50 mass parts, It is especially preferable that it is 20-45 mass parts. Here, (E) When content of an inorganic filler is in the said range, coating film strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, etc. of the photosensitive resin composition can be improved more.

Moreover, (E) It is preferable that it is 5-60 mass parts, and, as for content of barium sulfate which makes 100 mass parts of solid content in the photosensitive resin composition in the case of using barium sulfate as an inorganic filler, it is more preferable that it is 10-50 mass parts And, it is more preferable that it is 10-40 mass parts, and it is especially preferable that it is 10-35 mass parts. When the content of the fine particles of barium sulfate is within the above range, heat resistance and PCT resistance can be further improved.

It is preferable that the photosensitive resin composition of this embodiment contains a pigment as (F)component. (F) As a pigment, when concealing a wiring pattern, etc., it is used suitably according to a desired color. (F) As the pigment, a colorant capable of developing a desired color may be appropriately selected and used. As the colorant, for example, a known colorant such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, and crystal violet is preferable. can be heard

As for content of (F) pigment which makes solid content whole quantity in the photosensitive resin composition 100 mass parts, 0.1-5 mass parts is preferable, More preferably, it is 0.1-3 mass parts. (F) When the content of the pigment is within the above range, the wiring pattern can be hidden.

The photosensitive resin composition of this embodiment can use a diluent in order to adjust a viscosity as needed. As a diluent, an organic solvent, a photopolymerizable monomer, etc. are mentioned preferably, for example. The organic solvent can be appropriately selected from among the solvents exemplified as the organic solvent that can be used in the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b), for example. Moreover, as a photopolymerizable monomer, what was illustrated by said (D) photopolymerizable compound is mentioned preferably.

It is preferable that content of the total amount of solid content in the photosensitive resin composition and solid content other than component (A)-(F) sets the usage-amount of a diluent into the quantity used as 50-90 mass %, The quantity used as 60-80 mass % It is more preferable to set it as 65-75 mass %, and it is still more preferable to set it as 65-75 mass %. That is, 10-50 mass % is preferable, as for content of the diluent in the photosensitive resin composition in the case of using a diluent, 20-40 mass % is more preferable, and its 25-35 mass % is still more preferable. By making the usage-amount of a diluent into the said range, the applicability|paintability of the photosensitive resin composition improves, and formation of a more highly precise pattern becomes possible.

The photosensitive resin composition of this embodiment may contain antioxidant in order to improve heat resistance, reflow resistance, chemical-resistance, etc. As antioxidant, a hindered phenol type antioxidant and a quinone type antioxidant are mentioned preferably.

As a hindered phenolic antioxidant, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF Japan Co., Ltd., Irganox 1010 (brand name)) ), thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionet] (BASF Japan Co., Ltd., Irganox 1035 (trade name)), octadecyl [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF Japan Co., Ltd., Irganox 1076 (trade name)), octyl 1-3,5-di-tert-butyl -4-hydroxy-hydrocinnamic acid (BASF Japan Co., Ltd., Irganox 1135 (trade name)), 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan Co., Ltd., Irganox 1520L) ) etc. are mentioned preferably, and as a quinone type antioxidant, hydroquinone, 2-t- butyl hydroquinone, hydroquinone monomethyl ether, metaquinone, benzoquinone, etc. are mentioned preferably. These antioxidants can be used individually by 1 type or in combination of 2 or more type.

The photosensitive resin composition of this embodiment may contain the hardening|curing agent. As the curing agent, a compound that itself is cured by heat, ultraviolet rays, etc., or (A) acid-modified vinyl group-containing epoxy resin that is a photocurable resin component in the composition of the present embodiment. A compound is preferably mentioned. By using a hardening|curing agent, the heat resistance, reflow resistance, chemical-resistance, etc. of a final cured film can be improved.

As a hardening|curing agent, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound etc. are mentioned preferably as a thermosetting compound, for example. As an epoxy compound, For example, bisphenol-type epoxy resins, such as a bisphenol A epoxy resin, a bisphenol F-type epoxy resin, a hydrogenated bisphenol A-type epoxy resin, a brominated bisphenol A-type epoxy resin, and a bisphenol S-type epoxy resin; novolac-type epoxy resin; biphenyl type epoxy resin; Heterocyclic epoxy resins, such as triglycidyl isocyanurate; A non-xylenol type epoxy resin etc. are mentioned preferably. As a melamine compound, triamino triadine, hexamethoxymelamine, hexabutoxy melamine, etc. are mentioned preferably, for example. As a urea compound, dimethylol urea etc. are mentioned preferably.

As the curing agent, from the viewpoint of further improving heat resistance, it is preferable to include at least one selected from an epoxy compound (epoxy resin) and a block type isocyanate, and it is more preferable to use an epoxy compound and a block type isocyanate together.

As the block type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. As this polyisocyanate compound, tolylene diisocyanate, xylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis(isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl, for example. Polyisocyanate compounds, such as hexamethylene diisocyanate and isophorone diisocyanate, and these adduct bodies, a biuret body, an isocyanurate body, etc. are mentioned preferably.

As an isocyanate blocking agent, For example, Phenol type blocking agents, such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; active methylene-based blocking agents such as ethyl acetoacetate and acetylacetone; Methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycol alcohol-based blocking agents such as butyl acid, diacetone alcohol, methyl lactate, and ethyl lactate; Oxime block agents, such as formaldehyde doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; acid amide blocking agents such as acetate amide and benzamide; imide block agents such as succinimide and maleic acid imide; amine blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine block agents, such as methyleneimine and propyleneimine, etc. are mentioned preferably.

A hardening|curing agent is used individually by 1 type or in combination of 2 or more type. When using a hardening|curing agent, it is preferable that content is 2-50 mass parts with respect to 100 mass parts of solid content in the photosensitive resin composition, 2-40 mass parts is more preferable, 3-30 mass parts is still more preferable, especially Preferably it is 5-20 mass parts. By carrying out content of a hardening|curing agent into the said range, the heat resistance of the cured film formed can be improved more, maintaining favorable developability.

An epoxy resin curing agent can be used together with the photosensitive resin composition of this embodiment in order to further improve various characteristics, such as the heat resistance of a final cured film, adhesiveness, and chemical-resistance.

Specific examples of such an epoxy resin curing agent include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2- imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide; at least one selected from organic acid salts and epoxides thereof; amine complexes of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine; Trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, tertiary amines such as m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyl tributyl phosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate; triphenylsulfonium hexafluoroantimonate; 2,4,6-triphenylthiopyrylium hexafluorophosphate etc. are mentioned preferably.

Epoxy resin curing agent is used individually by 1 type or in combination of 2 or more types, Content of the epoxy resin curing agent contained in the photosensitive resin composition becomes like this. Preferably it is 0.01-20 mass %, More preferably, it is 0.1-10 mass %. am.

The photosensitive resin composition of this embodiment, as needed, Polymerization inhibitors, such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrrogalol; thickeners such as bentone and montmorillonite; Antifoaming agents, such as a silicone type, a fluorine type, and a vinyl resin type; Various well-known and usual additives, such as a silane coupling agent, can be used. Furthermore, flame retardants, such as a brominated epoxy compound, an acid-modified brominated epoxy compound, an antimony compound, and the phosphate compound which are phosphorus compounds, an aromatic condensed phosphoric acid ester, and a halogen-containing condensed phosphoric acid ester, can be used.

The photosensitive resin composition of this embodiment can contain an elastomer. An elastomer is especially used preferably, when using the photosensitive resin composition of this embodiment for manufacture of a semiconductor package board|substrate. By adding the elastomer to the photosensitive resin composition of the present embodiment, the curing reaction proceeds by ultraviolet rays or heat, etc., due to (A) distortion (internal stress) inside the resin due to curing shrinkage of the acid-modified vinyl group-containing epoxy resin As long as it is possible, a decrease in flexibility and adhesiveness can be suppressed.

Preferable examples of the elastomer include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These elastomers consist of a hard segment component and a soft segment component, and in general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

In addition to the above elastomer, an epoxy resin that has been modified with rubber can be used. The rubber-modified epoxy resin is, for example, a part or all of the above-mentioned bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, triphenolmethane-type epoxy resin, phenol novolak-type epoxy resin, and cresol novolak-type epoxy resin. It is obtained by modifying an epoxy group with both terminal carboxylic acid-modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber, or the like. Among these elastomers, from the viewpoint of shear adhesion, carboxyl group-modified butadiene-acrylonitrile copolymer at both ends, ESPEL (Hitachiga Sei Co., Ltd., ESPEL 1612, 1620) which is a polyester-based elastomer having a hydroxyl group is preferable. can be heard

The blending amount of the elastomer is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass, still more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the (A) acid-modified vinyl group-containing epoxy resin. . It becomes the tendency for the elastic modulus in the high temperature region of a cured film to become low that it is 2 mass parts or more, and it becomes the tendency for an unexposed part to elute from a developing solution as it is 30 mass parts or less.

The photosensitive resin composition of this embodiment contains (E) component, (F) component, and other various components which are used according to necessity including said (A)-(D) component, a roll mill, a bead mill, etc. It can be obtained by uniformly kneading and mixing.

Moreover, it is preferable that the photosensitive resin composition of this embodiment is liquid. By setting it as a liquid phase, a permanent mask resist can be formed easily by the various application|coating methods mentioned later.

[Photosensitive element, permanent mask resist and printed wiring board]

The photosensitive resin composition of this embodiment is used suitably for formation of a photosensitive element and a permanent mask resist, The photosensitive element of this embodiment, and a permanent mask resist are formed using the photosensitive resin composition of this embodiment. .

The photosensitive element of this embodiment is provided with a support body and the photosensitive layer formed using the photosensitive resin composition of this embodiment on the support body. As a support body, the resin film which has heat resistance and solvent resistance, such as polyester resin films, such as polyethylene terephthalate, and polyolefin resin films, such as polyethylene and polypropylene, is preferably mentioned, for example, From a viewpoint of transparency, polyethylene terephthalate It is preferred to use a phthalate film. Moreover, 1-100 micrometers is preferable, 1-50 micrometers is more preferable, 1-30 micrometers is still more preferable when mechanical strength, obtaining favorable resolution, etc. are considered as for the thickness of a support body.

The photosensitive element of this embodiment is, for example, the photosensitive resin composition of this embodiment on the said support body by methods, such as a dipping method, a spraying method, a bar coating method, a roll coating method, a spin coating method, the photosensitivity of this embodiment It can be obtained by applying the resin composition to a film thickness according to the use (after drying: 10 to 200 μm) to form a coating film, and drying it at 70 to 150° C. for 5 to 30 minutes to form a photosensitive layer.

The permanent mask resist of this embodiment and the printed wiring board provided with this permanent mask resist are image-formed as follows, for example. First, on a substrate on which a resist is to be formed (for example, a copper-clad laminate for a printed wiring board, etc.), the photosensitivity of this embodiment is performed by a method such as a screen printing method, a spraying method, a roll coating method, a curtain coating method, and an electrostatic coating method. A coating film is formed by applying the resin composition to a film thickness according to the use (after drying: 10 to 200 µm), and the coating film is dried at 60 to 110°C. In addition, instead of the coating film, the photosensitive layer of the photosensitive element may be transferred (laminated) onto the substrate on which the resist is to be formed. In this case, the dried coating film on a support body is affixed on a base material using a normal pressure laminator or a vacuum laminator as needed.

After forming the photosensitive layer (coating film) on the substrate, by directly contacting the negative film or through a transparent film, irradiated with actinic rays such as ultraviolet rays at an exposure dose of ^{preferably 10 to 1,000 mJ/cm 2 , the resin film} When using, the resin film is peeled, and an unexposed part is dissolved and removed (developed) with a dilute alkali aqueous solution.

Next, an exposure part is fully hardened by post-exposure (ultraviolet-ray exposure), post-heating, or post-exposure and post-heating, and a cured film is obtained. As for post-exposure, 800-5,000 mJ/cm<^2> is preferable, for example, and, as for post-heating, 30 minutes - 12 hours at 100-200 degreeC are preferable.

In the permanent mask resist obtained in this way, an undercut in which the bottom part is cut out is less likely to occur, and it is difficult to generate a dropout on the upper part of the resist. Since it is difficult, the linearity of the pattern outline is good, the resist shape is excellent, and it has a pattern excellent in resolution. In addition, this permanent mask resist has a pattern excellent in formation stability of the size of the pore diameter and the pitch of the gap between the holes, which have been miniaturized due to the recent miniaturization and high performance of electronic devices. In addition to PCT resistance (moist and heat resistance), reflow resistance, electrical insulation (HAST resistance), and electroless plating resistance, the pattern has heat resistance, solvent resistance, chemical resistance (alkali resistance, acid resistance), and adhesion. it becomes excellent

Example

Hereinafter, although an Example demonstrates this embodiment more concretely, this embodiment is not limited at all by these Examples.

(Assessment Methods)

(1) Evaluation of surface hardenability

The photosensitive resin composition of each Example and the comparative example was apply|coated to a 35-micrometer-thick PET film with the applicator so that the film thickness after drying might be set to 35 micrometers, and the coating film was formed. Then, using a hot air circulation dryer, it was dried at 80 degreeC for 20 minutes. The infrared absorption spectrum (ATR (Attenuated Total Reflection) method) of the obtained coating film surface was measured under the following conditions.

・Measuring device: "Nicolet　iS50R (brand name)", manufactured by Thermo Fisher Scientific Co., Ltd.

· Number of integrations: 128

Next, it exposed with the exposure amount of ^{600 mJ/cm<2>} using the ultraviolet-ray exposure apparatus ("HTE-5102S (trade name)", manufactured by Hi-Tech Corporation). For the surface of the coating film before and after exposure, infrared absorption spectrum (ATR method) was measured under the same conditions as above, and the rate of change of the carbon-carbon double bond displayed at ^{1470 cm -1 before and after exposure was obtained from the following formula,} The surface hardenability of the coating film was measured, and the average value of three integration times was made into surface hardenability (%).

Change rate of double bond (%) = 100- (Amount of carbon-carbon double bonds after exposure/Amount of carbon-carbon double bonds before exposure x 100)

(2) Evaluation of bottom hardenability

The photosensitive resin composition of each Example and the comparative example was apply|coated to a 35-micrometer-thick PET film with the applicator so that the film thickness after drying might be set to 35 micrometers, and the coating film was formed. Then, using a hot air circulation dryer, it was dried at 80 degreeC for 20 minutes. The infrared absorption spectrum (ATR (Attenuated Total Reflection) method) of the obtained coating film surface was measured under the following conditions.

・Measuring device: "Nicolet　iS50R (brand name)", manufactured by Thermo Fisher Scientific Co., Ltd.

· Number of integrations: 128

Next, it exposed with the exposure amount of ^{600 mJ/cm<2>} using the ultraviolet-ray exposure apparatus ("HTE-5102S (trade name)", manufactured by Hi-Tech Corporation). For the surface of the coating film before and after exposure, infrared absorption spectrum (ATR method) was measured under the same conditions as above, and the rate of change of carbon-carbon double bond displayed at ^{1470 cm -1 before and after exposure was obtained from the following formula,} The surface hardenability of the coating film was measured, and the average value of three integration times was made into surface hardenability (%).

Change rate of double bond (%) = 100- (Amount of carbon-carbon double bonds after exposure/Amount of carbon-carbon double bonds before exposure x 100)

(3) Evaluation of resist shape

The photosensitive resin composition of each Example and Comparative Example was applied to a copper-clad laminated substrate (“MCL-E-67 (trade name)”, manufactured by Hitachi Sei Co., Ltd.) having a size of 50 cm x 50 cm and a thickness of 0.6 mm, and the film after drying. After the coating was applied by screen printing to a thickness of 35 μm to form a coating film, it was dried at 80° C. for 20 minutes using a hot air circulation dryer.

Then, as shown in FIG. 2, a pattern of a predetermined hole diameter size and a gap pitch between holes (a hole diameter size of 100 µm and a gap pitch between holes of 100 µm, or a hole diameter size of 80 µm and an interval between holes of 80 µm) Each of the negative masks was brought into close contact with the coating film, and exposed at an exposure dose of ^{600 mJ/cm 2} using an ultraviolet exposure apparatus (“HTE-5102S (trade name)”, manufactured by Hi-Tech Corporation). Then, spray development was carried out at the pressure of ^{0.18 MPa (1.8 kgf/cm<2>} ) for 60 second with 1 mass % sodium carbonate aqueous solution, and the unexposed part was dissolved and developed. Next, using a UV exposure device ("Conveyor type UV irradiation device (brand name):, manufactured by GS Yuasa Lighting Co., Ltd.) at ^{an exposure dose of 1000 mJ/cm 2} , after exposure at an exposure dose of 1000 mJ/cm 2 , the test piece was heated at 150° C. for 1 hour. produced.

The test piece on which the pattern was formed was molded with an epoxy resin ("Epicoat 828 (trade name), manufactured by Mitsubishi Chemical Co., Ltd.) and a thermosetting resin using triethylenetetramine as a curing agent. After hardening sufficiently, a polishing machine ( The cross section of the pattern was scraped off by grinding with "Refine Polisher (brand name)", manufactured by Refine Tech Co., Ltd., and the resist shape was observed with a metallurgical microscope, and evaluated based on the following criteria. shown negatively.

A (excellent): The resist shape showed a rectangle or trapezoid, and the linearity of the pattern outline was good.

B (defective): In the resist shape, undercut, lower width pulling, or thickening were confirmed, or the linearity of the pattern outline was not good.

(4) Evaluation of via diameter accuracy

The photosensitive resin composition of each Example and Comparative Example was applied to a copper-clad laminated substrate (“MCL-E-67 (trade name)”, manufactured by Hitachi Sei Co., Ltd.) having a size of 50 cm x 50 cm and a thickness of 0.6 mm, and the film after drying. After the coating was applied by screen printing to a thickness of 35 μm to form a coating film, it was dried at 80° C. for 20 minutes using a hot air circulation dryer.

Then, as shown in FIG. 2, a pattern of a predetermined hole diameter size and a gap pitch between holes (a hole diameter size of 100 µm and a gap pitch between holes of 100 µm, or a hole diameter size of 80 µm and an interval between holes of 80 µm) Each of the negative masks was brought into close contact with the coating film and exposed at an exposure dose of ^{600 mJ/cm 2} using an ultraviolet exposure apparatus (“HTE-5102S (trade name)”, manufactured by Hi-Tech Corporation). ^{Then, it spray-developed with the pressure of 0.18 MPa (1.8kgf/cm<2>} ) for 60 second with 1 mass % sodium carbonate aqueous solution, the unexposed part was dissolved and developed, and the test piece was produced. The following criteria evaluated the pattern of the obtained test piece.

A (good): 80% or more of patterns of 100 µm and 80 µm were reproduced.

B (defective): Only less than 80% of patterns of 100 µm and 80 µm were reproduced.

Here, using a microscope, magnify 700 times and observe patterns of 100 μm and 80 μm, and in the case of a 100 μm pattern, the bottom of the pattern is formed in a size of 80 μm or more (80% or more with respect to the pattern diameter), A case where there was a pattern was assumed to be reproduced. In the case of the 80 µm pattern, the pattern was reproduced when the pattern bottom was formed to have a size of 64 µm or more. Moreover, in the judgment of "A" and "B", the case where the total number of patterns formed was 80% or more with respect to the total number of 100 micrometers and 80 micrometers patterns was evaluated as "A".

(5) Evaluation of adhesion

A copper-clad laminate board (“MCL-E-67 (trade name)”, Hitachi A copper-clad laminated board (“MCL-E-67”) with a thickness of 0.6 mm, obtained by roughening 0.5 μm in the depth direction using an abrasive (“CZ8101 (trade name)”, manufactured by Mack Co., Ltd.) and chemical polishing (manufactured by Sei Co., Ltd.) ", Hitachi Sei Co., Ltd.) was applied by a screen printing method so that the film thickness after drying would be 35 µm to form a coating film, and then dried using a hot air circulation dryer at 80° C. for 20 minutes.

Then, as shown in FIG. 2, a pattern of a predetermined hole diameter size and a gap pitch between holes (a hole diameter size of 100 µm and a gap pitch between holes of 100 µm, or a hole diameter size of 80 µm and an interval between holes of 80 µm) Each of the negative masks was brought into close contact with the coating film and exposed at an exposure dose of ^{600 mJ/cm 2} using an ultraviolet exposure apparatus (“HTE-5102S (trade name)”, manufactured by Hi-Tech Corporation). Then, spray development was carried out at the pressure of ^{0.18 MPa (1.8 kgf/cm<2>} ) for 60 second with 1 mass % sodium carbonate aqueous solution, and the unexposed part was dissolved and developed. Next, using an ultraviolet exposure apparatus ("Conveyor type UV irradiation apparatus (brand name):, GS Yuasa Lighting Co., Ltd.)" ^{, exposure at an exposure dose of 1000 mJ/cm 2} , and heating at 150° C. for 1 hour to prepare a test piece did.

With respect to the obtained test piece, according to JIS K5600, 100 1 mm checkerboard scales were prepared, and cellophane tape ("Cellotape (trade name) (registered trademark)", manufactured by Nichiban Co., Ltd.) was applied, followed by a direction of 90°. A peel test for forcibly peeling the cellophane tape was performed. The peeling state of the checkerboard scale was observed, and the following references|standards evaluated it.

A (excellent): There was no peeling at 90/100 or more.

B (good): 50/100 or more and less than 90/100, there was no peeling.

C (defective): 0/100 or more and less than 50/100, and there was no peeling.

(6) Evaluation of solvent resistance

The test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape (3) was immersed in isopropyl alcohol at room temperature for 30 minutes, and it was visually confirmed whether there was any abnormality in the appearance. Next, after affixing a cellophane tape ("Cellophane (trade name) (registered trademark)", manufactured by Nichiban Co., Ltd.), a peel test in which the cellophane tape is forcibly peeled in a direction of 90° is performed, The presence or absence was visually confirmed, and the following reference|standard evaluated.

A (excellent): Abnormality was not recognized in the external appearance of a coating film, and there was no peeling.

B (defective): Abnormality was confirmed in the external appearance of a coating film, or it peeled.

(7) Evaluation of acid resistance

(3) The test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape was immersed in a 10 mass % aqueous hydrochloric acid solution at room temperature for 30 minutes, and it was visually confirmed whether there was any abnormality in the appearance. Next, after affixing a cellophane tape ("Cellophane (trade name) (registered trademark)", manufactured by Nichiban Co., Ltd.), a peel test in which the cellophane tape is forcibly peeled in a direction of 90° is performed, The presence or absence was visually confirmed, and the following reference|standard evaluated.

A (excellent): Abnormality was not recognized by the coating-film external appearance, and there was no peeling.

B (defective): Abnormality was confirmed in the appearance of a coating film, or it peeled.

(8) Evaluation of alkali resistance

The test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape (3) was immersed in a 5 mass % sodium hydroxide aqueous solution at room temperature for 30 minutes, and it was visually confirmed whether there was any abnormality in the appearance. Next, after affixing a cellophane tape ("Cellophane (trade name) (registered trademark)", manufactured by Nichiban Co., Ltd.), a peel test in which the cellophane tape is forcibly peeled in a direction of 90° is performed, The presence or absence was visually confirmed, and the following reference|standard evaluated.

A (excellent): Abnormality was not recognized by the coating-film external appearance, and there was no peeling.

B (defective): Abnormality was confirmed in the appearance of a coating film, or it peeled.

(9)Evaluation of electrical insulation (HAST resistance)

On a bismaleimide triazine substrate (BT substrate) on which comb-shaped electrodes (line/space = 10 µm/10 µm) were formed, the photosensitive resins of Examples and Comparative Examples were screen-printed to a film thickness of 35 µm after drying. After coating the composition to form a coating film, it was dried at 80° C. for 20 minutes using a hot air circulation dryer. Then, using an ultraviolet exposure apparatus (“HTE-5102S (trade name)”, manufactured by Hi-Tech Co., Ltd.) at ^{an exposure dose of 1000 mJ/cm 2} , heated at 150° C. for 1 hour, the photosensitive resin composition on the BT substrate A test piece having a cured coating film was produced. This test piece was put into a high-temperature, high-humidity tank under an atmosphere of 130°C and a humidity of 85%, a voltage of 5 V was charged, and the HAST test in the tank was performed for 168 hours. The following references|standards evaluated the insulation resistance value in a tank at the time of 168-hour lapse.

A: 10 ⁸ Ω or more

B: 10 ⁷ Ω or more and less ^{than 10 8 Ω}

C: 10 ⁶ Ω or more 10 ⁷ Ω or more

D: 10 ⁵ Ω or more 10 ⁶ Ω or more

E: less than ^{10 5 Ω}

(10) Evaluation of electroless plating resistance

With respect to the test piece produced under the same conditions as the test piece used in the evaluation of the resist shape (3) above, a commercially available electroless nickel plating bath and an electroless gold plating bath were used, and the conditions were 5 µm for nickel and 0.05 µm for gold. was plated, and by tape peeling, the presence or absence of peeling of the cured coating film of the photosensitive resin composition and the presence or absence of permeation of the plating were evaluated according to the following criteria, and the presence or absence of peeling of the resist layer by tape peeling was evaluated according to the following criteria. .

A: There was no smearing or peeling.

B: A little smearing was observed after plating, but it did not peel off after peeling the tape.

C: Slight penetration was observed after plating and peeling was also confirmed after tape peeling, but it was practically no problem.

D: Smearing was confirmed after plating, and peeling was also confirmed after tape peeling.

E: Remarkable peeling was confirmed after plating.

(11) Evaluation of PCT resistance

(3) The parts, peeling, and discoloration of the cured coating film of the photosensitive resin composition when a test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape was left in saturated steam at 121°C for 50 hours. evaluated on the basis of

A (excellent): There were no parts, peeling, and discoloration in the coating film.

B (good): Parts, peeling, or discoloration were slightly confirmed in the coating film.

C (defective): A remarkable part, peeling, or discoloration was recognized by the coating film.

(12) Evaluation of reflow resistance

(3) The appearance of the cured coating film of the photosensitive resin composition when a test piece produced under the same conditions as the test piece used in the evaluation of the resist shape was processed based on the reflow profile shown in FIG. evaluated.

A (excellent): There was no change in the appearance of a coating film, and generation|occurrence|production of a crack was not recognized either.

B (good): A few cracks were recognized in the coating film.

C (defective): Cracks, tempering, or peeling were confirmed in the coating film.

(13) Evaluation of solder heat resistance

(3) No-clean flux ("RMA SR-209 (trade name)", manufactured by Senju Kinzoku Kogyo Co., Ltd.) was applied to the test piece prepared under the same conditions as the test piece used in the evaluation of the resist shape above, and heated to 280°C. It was immersed in the set solder tank for 10 second, the coating film external appearance was visually observed, and the following reference|standard evaluated.

A: Even if immersion for 10 seconds was repeated 10 times, the change in the appearance of the coating film of the resist was not confirmed.

B: When immersion for 10 seconds was repeated 10 times, although peeling of the coating film of a resist was confirmed a little, it was a grade without a problem practically.

C: When immersion for 10 seconds was repeated 10 times, the parts or peeling of the coating film of a resist was confirmed.

(Synthesis Example 1; Synthesis of acid-modified vinyl group-containing epoxy resin (I))

220 parts by mass of cresol novolak epoxy resin (manufactured by Nippon Steel Chemicals Co., Ltd., "YDCN704 (brand name", in general formula (I), Y ¹ =glycidyl group, R ¹¹ =methyl group)), acrylic acid 72 mass part, hydroquinone 1.0 mass part, and carbitol acetate 180 mass parts were mixed, and the reaction mixture was dissolved by heating and stirring at 90 ° C. Then, after cooling to 60 ° C., 1 mass part of benzyl trimethylammonium chloride was added, and 100 It was further heated to ° C., and reacted until the solid content acid value became 1 mgKOH/g. Then, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of carbitol acetate were added, heated to 80° C., and stirred for 6 hours. After cooling to , it diluted with carbitol acetate so that solid content concentration might be 60 mass %, and acid-modified vinyl group containing epoxy resin (I) was obtained.

(Synthesis Example 2; Synthesis of acid-modified vinyl group-containing epoxy resin (II))

475 parts by mass of bisphenol F-type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., "YDF2001 (trade name)", in general formula (II), Y ² =glycidyl group, R ¹² =H), 72 mass parts of acrylic acid Part, 0.5 mass parts of hydroquinone, and 120 mass parts of carbitol acetate were mixed, it heated and stirred at 90 degreeC, and melt|dissolved the reaction mixture. Then, after cooling to 60 degreeC, 2 mass parts of benzyl trimethylammonium chlorides were added, it heated further at 100 degreeC, and made it react until an acid value became 1 mgKOH/g. Then, 230 mass parts of tetrahydrophthalic anhydride and 85 mass parts of carbitol acetate were added, it heated at 80 degreeC, and stirred for 6 hours. After cooling to room temperature, it diluted with carbitol acetate so that solid content concentration might be 60 mass %, and the acid-modified vinyl group containing epoxy resin (II) was obtained.

(Synthesis Example 3; Synthesis of acid-modified vinyl group-containing epoxy resin (IV))

272 mass parts of bis(4-hydroxyphenyl)methane melt|dissolved at 80 degreeC was put into the flask provided with the thermometer, the dripping fun, a cooling tube, and a stirrer, and stirring was started at 80 degreeC. 3 mass parts of methanesulfonic acid was added here, and 16.3 mass parts of paraformaldehyde (92 mass %) was dripped over 1 hour so that the temperature of a liquid might maintain the range of 80-90 degreeC. After completion of the dropwise addition, the mixture was heated to 110°C and stirred for 2 hours. Next, 1000 parts by mass of methyl isobutyl ketone was added, and it was transferred to a separation funnel and washed with water. After washing with water was continued until the washing water became neutral, the solvent and unreacted bis(4-hydroxyphenyl)methane were removed from the organic layer under reduced pressure by heating (temperature: 220°C, pressure: 66.7 Pa), and a brown solid 164 parts by mass of phosphorus bisphenol-based novolac resin was obtained. The softening point of the obtained bisphenol-type novolak resin was 74 degreeC, and the hydroxyl equivalent was 154 g/eq.

154 parts by mass of the obtained bisphenol novolac resin, 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol, and tetraethyl 2 parts by mass of benzylammonium chloride was mixed and dissolved. Subsequently, after heating this to 65 degreeC and pressure-reducing to the azeotropic pressure, 90 mass parts of sodium hydroxide aqueous solution (49 mass %) was dripped over 5 hours at a constant dripping rate, and it stirred for 30 minutes. In the meantime, the effluent that flowed out by azeotroping was separated by a Dean-Stock trap, the water layer was removed, and the oil layer was returned to the flask (reaction system) for reaction. Then, to the crude epoxy resin obtained by distilling unreacted epichlorohydrin under reduced pressure (temperature: 22 degreeC, pressure: 1.87 kPa), 590 mass parts of methyl isobutyl ketone, 177 mass of n-butanol parts were added to dissolve. Next, 10 mass parts of sodium hydroxide aqueous solution (10 mass %) was added, and it stirred at 80 degreeC for 2 hours. Moreover, water washing was repeated 3 times with 150 mass parts of water. It confirmed that the pH of the washing|cleaning liquid used by the 3rd water washing was neutral. Next, the inside of the flask (inside the reaction system) was dehydrated by azeotroping and microfiltration was performed, and then the solvent was distilled off under reduced pressure (pressure: 1.87 kPa). In this way, the bisphenol-based novolac-type epoxy resin used in the present embodiment, which is a brown viscous liquid (in the general formula (IV), Y ⁴ = glycidyl group, R ¹³ =H is an epoxy resin having structural units of H). (a)) was obtained. The hydroxyl equivalent of this epoxy resin was 233 g/eq.

To 450 parts by mass of the obtained epoxy resin (a), 124 parts by mass of acrylic acid, 1.5 parts by mass of hydroquinone, and 250 parts by mass of carbitol acetate were mixed, heated to 90° C. and stirred to dissolve the reaction mixture. Then, after cooling to 60 degreeC, 2 mass parts of benzyl trimethylammonium chlorides were added, it heated at 100 degreeC, and was made to react until an acid value became 1 mgKOH/g. Next, 230 mass parts of tetrahydrophthalic anhydride and 180 mass parts of carbitol acetate were added, it heated at 80 degreeC, and was made to react for 6 hours. Then, after cooling to room temperature, it diluted with carbitol acetate so that solid content concentration might be 60 mass %, and the acid-modified vinyl group containing epoxy resin (IV) was obtained.

In addition, the softening point of resin was measured based on the round-ball method prescribed by JIS-K7234:1986 (temperature increase rate: 5 degreeC/min), and the acid value of resin was measured by the neutralization titration method. Specifically, 30 g of acetone is added to 1 g of the acid-modified vinyl group-containing epoxy resin, further dissolved uniformly, and an appropriate amount of phenolphthalein, an indicator, is added to the solution containing the acid-modified vinyl group-containing epoxy resin, 0.1N It was measured by performing titration using the potassium hydroxide aqueous solution of

Examples 1 to 6, and Comparative Examples 1 to 4

According to the compounding composition shown in Table 1, the composition was mix|blended, it knead|mixed with three roll mills, and the photosensitive resin composition was prepared. Carbitol acetate was added so that solid content concentration might be set to 70 mass %, and the photosensitive resin composition was obtained. Using the obtained photosensitive resin composition, it evaluated based on said (evaluation method). An evaluation result is shown in Table 1. In addition, the unit of the compounding quantity of each component in Table 1 is a mass part, and the compounding quantity of (A) component means the quantity containing the epoxy resin and solvent (carbitol acetate) obtained by each said synthesis example.

*1, it is the compounding quantity of the solution (solid content concentration: 60 mass %) containing epoxy resin (I), (II), and (IV).

Note) Details of each material in Table 1 are as follows.

Irgacure 819: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF Japan, trade name)

Darocure TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan, trade name)

Irgacure 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (BASF Japan Co., Ltd. product name)

Nitrogen-containing heterocyclic compound 1: triaminotriazine, average particle diameter: 4 µm

Nitrogen-containing heterocyclic compound 2: 2,4-diamino-6-vinyl-s-triazine, average particle diameter: 4 µm

Nitrogen-containing heterocyclic compound 3: 2-phenyl-4-methylimidazole, average particle diameter: 3 µm

Nitrogen-containing heterocyclic compound 4: 2-phenylimidazoline, average particle diameter: 3 µm

Nitrogen-containing heterocyclic compound 1': triaminotriazine, average particle diameter: 18 µm

Nitrogen-containing heterocyclic compound 2': 2,4-diamino-6-vinyl-s-triazine, average particle diameter: 20 µm

Nitrogen-containing heterocyclic compound 3': 2-phenyl-4-methylimidazole, average particle diameter: 15 µm

Kayarad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., brand name)

Epicoat 828: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name)

From the results shown in Table 1, in the photosensitive resin compositions of the present invention of Examples 1 to 6, the permanent mask resist (solder resist) had the size of the hole diameter and the pitch pitch between the holes (the gap between the holes while the size of the hole was 100 µm) Even with a high-precision pattern with a pitch of 100 µm or a hole diameter of 80 µm and a spacing between holes of 80 µm), excellent surface hardening and bottom hardenability are maintained, and undercut, bottom width pulling, or thickening is confirmed, or the pattern It was confirmed that the linearity of the outline was not bad, an excellent resist shape could be obtained, and that the via diameter accuracy was excellent.

In addition, it was confirmed that it was excellent in various performances including electrical insulation (HAST resistance) and electroless plating resistance.

On the other hand, in Comparative Examples 1 to 4, the surface hardenability and bottom hardenability were low, the problem of the resist shape was not solved, and the thickness around the pattern of the permanent mask resist (solder resist) also occurred, which was an insufficient result.

INDUSTRIAL APPLICABILITY

According to the present invention, a pattern having excellent resist shape and excellent resolution can be formed, and in addition to PCT resistance (moisture and heat resistance), reflow resistance, electrical insulation (HAST resistance), and electroless plating resistance, heat resistance , solvent resistance, chemical resistance (alkali resistance, acid resistance), and a photosensitive resin composition capable of forming a pattern with excellent adhesion, a pattern-forming permanent mask with excellent stability in the formation of fine pore diameter size and spacing pitch register can be obtained. A permanent mask resist is used suitably for a printed wiring board, Especially, it is used suitably for the printed wiring board which has the size of the hole diameter miniaturized with recent miniaturization and performance improvement, and the space|interval pitch between holes.

Claims (17)

(A) acid-modified vinyl group-containing epoxy resin, (B) photoinitiator, (C) nitrogen-containing heterocyclic compound, and (D) photopolymerizable compound are contained, and the average particle diameter of the (C) nitrogen-containing heterocyclic compound As this 0.5-5 micrometers photosensitive resin composition,
The photosensitive resin composition whose said (C) nitrogen-containing heterocyclic compound is at least 1 sort(s) chosen from an imidazole compound and an imidazoline compound. According to claim 1,
The photosensitive resin composition whose content of the (C) nitrogen-containing heterocyclic compound which makes solid content whole quantity in the photosensitive resin composition 100 mass parts is 0.05-10 mass parts. According to claim 1,
(A) the acid-modified vinyl group-containing epoxy resin is an epoxy resin having a structural unit represented by the general formula (I), an epoxy resin having a structural unit represented by the general formula (II), and represented by the general formula (III) At least one selected from an epoxy resin having a structural unit, a bisphenol novolac-type epoxy resin having a structural unit represented by the general formula (IV), and a bisphenol novolac-type epoxy resin having a structural unit represented by the general formula (V) The photosensitive resin composition which is a resin obtained by making resin (a') obtained by making the epoxy resin (a) of a species react with a vinyl group containing monocarboxylic acid (b), and polybasic acid anhydride containing a saturated group or unsaturated group (c).

[In formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ represents a glycidyl group.]

[In formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ² represents a glycidyl group. A plurality of R ¹² may be the same or different.]

[In formula (III), Y ³ represents a hydrogen atom or a glycidyl group, at least one Y ³ represents a glycidyl group, and a plurality of Y ³ may be the same or different.]

[In formula (IV), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ⁴ represents a hydrogen atom or a glycidyl group, and at least one Y ⁴ is A glycidyl group is represented, and a plurality of R ¹³ may be the same or different.]

[In formula (V), R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ⁵ represents a hydrogen atom or a glycidyl group, and at least one Y ⁵ is A glycidyl group is represented, and a plurality of R ¹⁴ may be the same or different.] 4. The method of claim 3,
The epoxy resin (a) has an epoxy resin having a structural unit represented by the general formula (I), an epoxy resin having a structural unit represented by the general formula (II), and a structural unit represented by the general formula (IV) The photosensitive resin composition which is at least 1 sort(s) chosen from bisphenol novolak-type epoxy resin. 5. The method of claim 4,
The photosensitive resin composition in which an epoxy resin (a) is a bisphenol novolak-type epoxy resin which has a structural unit represented by general formula (IV). According to claim 1,
(B) The photosensitive resin composition whose photoinitiator is acylphosphine oxides. According to claim 1,
(D) The photosensitive resin composition whose photopolymerizable compound is a compound containing a (meth)acryloyl group. According to claim 1,
(E) The photosensitive resin composition which further contains an inorganic filler. According to claim 1,
(F) The photosensitive resin composition which further contains a pigment. According to claim 1,
The content of the (A) acid-modified vinyl group-containing epoxy resin with the total solid content in the photosensitive resin composition being 100 parts by mass is 20 to 80 parts by mass, (B) the content of the photoinitiator is 0.2 to 15 parts by mass, and (C) The photosensitive resin composition whose content of a nitrogen heterocyclic compound is 0.05-10 mass parts, and content of (D) a photopolymerizable compound is 0.1-30 mass parts. 9. The method of claim 8,
The content of the (A) acid-modified vinyl group-containing epoxy resin with the total solid content in the photosensitive resin composition being 100 parts by mass is 20 to 80 parts by mass, (B) the content of the photoinitiator is 0.2 to 15 parts by mass, and (C) Content of a nitrogen heterocyclic compound is 0.05-10 mass parts, (D) Content of a photopolymerizable compound is 0.1-30 mass parts, (E) The photosensitive resin composition whose content of an inorganic filler is 10-80 mass parts. 10. The method of claim 9,
The content of the (A) acid-modified vinyl group-containing epoxy resin with the total solid content in the photosensitive resin composition being 100 parts by mass is 20 to 80 parts by mass, (B) the content of the photoinitiator is 0.2 to 15 parts by mass, and (C) Content of a nitrogen heterocyclic compound is 0.2-15 mass parts, (D) content of a photopolymerizable compound is 0.1-30 mass parts, (E) content of an inorganic filler is 10-80 mass parts, (F) of a pigment The photosensitive resin composition whose content is 0.1-5 mass parts. According to claim 1,
A liquid, photosensitive resin composition. 14. The method according to any one of claims 1 to 13,
A photosensitive resin composition used for formation of a permanent mask resist. A photosensitive element comprising: a support; and a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 13 on the support. The permanent mask resist formed with the photosensitive resin composition in any one of Claims 1-13. A printed wiring board provided with the permanent mask resist of Claim 16.

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