JP6519134B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition.

  In the field of printed wiring board manufacture, forming a permanent mask resist on a printed wiring board is performed. The permanent mask resist has a role of preventing the corrosion of the conductor layer and maintaining the electrical insulation between the conductor layers when the printed wiring board is used. In recent years, permanent mask resist prevents solder from adhering to an unnecessary portion of a conductor layer of a printed wiring board in a process of flip chip mounting, wire bonding mounting, etc. of a semiconductor element on a printed wiring board via solder. It also has a role as a solder resist film.

  Heretofore, permanent mask resists in printed wiring board production have 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, bleeding occurs at the time of printing and sagging occurs, so it is difficult to produce a high definition pattern. Therefore, in the conventional method using screen printing of a resin composition, a permanent mask according to the high definition of the wiring pattern and the insulating pattern in the printed wiring board accompanying the recent miniaturization, weight reduction, and high performance of electronic devices. It has become difficult to form a resist, and it has become impossible to sufficiently meet the demand for high definition.

  Therefore, a method of forming a permanent mask resist by photolithography has been developed. Specifically, the method of forming the permanent mask resist is a method of thermocompression bonding a dry film type photocurable resist on a substrate, or curtain coating or spray coating a liquid type photocurable resist on a substrate. A layer is formed, and the resist layer is selectively irradiated with active light such as ultraviolet light through a negative mask to be cured, and only an unirradiated portion is removed by a developer to form an image.

  In the case of using a dry film type photocurable resist, air is entrained during the thermocompression bonding to the base material, air bubbles are easily generated, adhesion between the resist layer and the base material is reduced, or disturbance of the resist pattern is generated, There is a concern for decline. Therefore, the use of a liquid type photocurable resist instead of a dry film type has been studied. Liquid photocurable resists are roughly classified into solvent developing resists and alkali developing resists, but alkali developing resists are mainly used from the viewpoints of working environment preservation and global environment preservation. Among such alkali-developable liquid photocurable resists, those which improve the heat resistance, chemical resistance and electrical properties of the coating have been proposed (for example, Patent Document 1).

  However, in the case of a liquid photocurable resist of an alkali development type proposed in Patent Document 1, heat resistance and PCT resistance (pressure cooker test resistance) required to have further excellent performance in recent years (hereinafter referred to as pressure cooker test) The practical characteristics such as “moisture and heat resistance” may not be fully satisfactory. Liquid developing photocurable resists of alkali development type are mainly composed of ones having a hydrophilic group in order to enable alkaline development, and therefore, it is easy for chemical solutions, water, etc. to penetrate the resist layer, and sufficient. It is considered that the practical characteristics of the excellent resist layer can not be obtained.

  By the way, with the miniaturization, weight reduction, and high performance of electronic devices, the miniaturization of semiconductor packages, the practical use of multiple pins, and mass production are also urgently needed. For example, high reliability is required for semiconductor package substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) mounted on electronic components. In addition, in order to achieve high reliability, PCT resistance (moisture and humidity resistance) is required. However, the conventional liquid photocurable resists proposed in Patent Document 1 and the like can withstand practical use for only several hours to several tens of hours under severe environments (high temperature and high humidity environments) used in PCT resistance evaluation. In addition, there is a need for further improvement of the PCT resistance (moisture and heat resistance).

Also, the mounting method has been changed from conventional insertion mounting to surface mounting such as FC (Flip Chip), TAB (Tape Automated Bonding), COF (Chip On Film), etc. Such temperature tends to be high. In the case of surface mounting, more specifically, the solder is reflowed and fixed, that is, cream solder is printed beforehand on the necessary part, and the entire printed solder is heated by a high temperature furnace such as infrared rays to melt the solder and surface Since the mounting component and the substrate are soldered, the ultimate temperature inside and outside the package becomes extremely high at 220 to 280 ° C. (for example, Patent Document 2).
However, when exposed to high temperature as described above, the conventional liquid photo-curable resist is deteriorated in the reflow resistance that a crack is generated in the coating due to a thermal shock or the coating is separated from the substrate or the sealing material. And there is a need for further improvement. Also, from the viewpoint of preservation of the global environment, lead-free solder is in progress. Lead-free solders have higher melting temperatures than conventional solders. Therefore, excellent solder heat resistance is also required for permanent mask resists.

Since the pitch between the wires is finer along with the high definition of the wiring pattern and the insulating pattern (permanent mask resist) in the printed wiring board, the excellent electrical insulation between the wires (in particular, the electrical insulation after moisture absorption) (HAST resistance)) is required.
And in the manufacture, the electroless-plating method which does not require a lead wire is adopted (for example, patent document 3). The electroless plating method has features such as uniform plating film thickness and high smoothness. However, since the pH of the plating solution is large and strongly alkaline, and the temperature of the solution is increased to about 90 ° C. to improve the plating deposition rate, damage to the permanent mask resist tends to increase. Therefore, the permanent mask resist is also required to be further improved in the electroless plating resistance, which is resistant to the damage by the plating solution used for the electroless plating.

Unexamined-Japanese-Patent No. 1-141904 JP 2005-250004 A JP, 2006-190848, A

The object of the present invention is made in view of such a subject, can form a pattern excellent in resolution, and in addition to heat resistance, adhesion, mechanical characteristics, and electrical characteristics, it is possible to make the pitch finer. It is to provide a photosensitive resin composition excellent in PCT resistance (wet heat resistance), reflow resistance, electrical insulation (HAST resistance), resistance to electroless plating, solder heat resistance, etc., which are required along with the above.
In addition, by using the photosensitive resin composition of the present invention, the size of the miniaturized hole diameter and the formation stability of the interval pitch between holes are improved along with the recent miniaturization and high performance of electronic devices. It is an object of the present invention to provide a permanent mask resist that can be patterned and a printed wiring board provided with the same.

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

1. (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, (C) an inorganic filler, (D) a photopolymerizable compound, and (E) an alkoxypolysiloxane; The photosensitive resin composition whose siloxane is shown by following General formula (1).

[R ⁰¹ represents an alkyl group, an aryl group or an aralkyl group, Y ⁰¹ represents an alkyl group, an aryl group, an aralkyl group, or an alkoxy group represented by —OR ⁰² , R ⁰² represents an alkyl group, and m ₀₁ Represents an integer of 2 to 1000. The plurality of R ⁰¹ , R ⁰² and Y ⁰¹ may be the same or different, and at least one of R ⁰¹ is an alkyl group. ]
2. Furthermore, the photosensitive resin composition of said 1 containing the (F) pigment.
3. A photosensitive element comprising: a support; and a photosensitive layer comprising the photosensitive resin composition described in 1 or 2 above on the support.
4. A permanent mask resist formed of the photosensitive resin composition according to 1 or 2 or the photosensitive element according to 3 above.
5. A printed wiring board comprising the permanent mask resist as described in 4 above.

  According to the present invention, a pattern having excellent resolution can be formed, and in addition to heat resistance, adhesion, mechanical properties, and electrical properties, PCT resistance (moisture and humidity resistance) required with the miniaturization of pitch, Photosensitive resin composition excellent in reflow resistance, electrical insulation (HAST resistance), resistance to electroless plating, solder heat resistance, etc., photosensitive element using the same, permanent mask resist, and the permanent mask resist Printed wiring board can be obtained.

It is a figure which shows the pattern shape of the negative mask used in the Example.

[Photosensitive resin composition]
The photosensitive resin composition according to an embodiment of the present invention (hereinafter sometimes referred to simply as the present embodiment) may be (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, (C) It contains an inorganic filler, (D) photopolymerizable compound, and (E) alkoxypolysiloxane, and the (E) alkoxypolysiloxane has a specific structure. Each component is described below. In the present specification, these components may be simply referred to as (A) component, (B) component, (C) component, (D) component, and (E) 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 the component (A). The acid-modified vinyl group-containing epoxy resin (A) is not particularly limited as long as the epoxy resin is modified with a vinyl group-containing organic acid, and an epoxy resin (a) and a vinyl group-containing monocarboxylic acid (b) An epoxy resin (a ′) obtained by reacting, and an epoxy resin (a ′ ′) obtained by reacting the epoxy resin (a ′) with a polybasic acid anhydride containing a saturated or unsaturated group (c) preferable.

  As an epoxy resin (a), the epoxy resin which has a structural unit shown by following General formula (11)-(15) is mentioned preferably, It is preferable that it is at least 1 type chosen from these. The epoxy resin which has a structural unit shown by these general formula is demonstrated.

  First, as the epoxy resin (a), an epoxy resin having a structural unit represented by the following general formula (11) is preferably mentioned, and as a novolac epoxy resin having such a structural unit, for example, a general formula The novolac epoxy resin represented by 11 ') is preferably mentioned.

In formulas (11) and (11 ′), R ¹¹ represents a hydrogen atom or a methyl group, Y ¹¹ represents a hydrogen atom or a glycidyl group, and the molar ratio of hydrogen atom to glycidyl group is 0/100 to 30 / 70, preferably 0/100 to 10/90, and n ₁₁ represents an integer of 1 or more. As can be seen from the molar ratio of hydrogen atom to glycidyl group, at least one Y ¹¹ represents glycidyl group. In addition, a plurality of R ¹¹ may be the same or different, and when n ₁₁ is 2 or more, a plurality of Y ¹¹ may be the same or different.

n ₁₁ is an integer of 1 or more as described above, preferably 10 to 200, more preferably 30 to 150, more preferably from 30 to 100. When n ₁₁ is within the above range, the resist shape, resolution, heat resistance, adhesion, and resist pattern excellent in balance of electrical insulation resistance.
In the epoxy resin having a structural unit represented by the general formula (11), the content of the structural unit is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more .

  As a novolak-type epoxy resin shown by General formula (11 ') which has a structural unit shown by General formula (11), a phenol novolak-type epoxy resin and a cresol novolak-type epoxy resin are mentioned preferably, for example. These novolac type epoxy resins can be obtained, for example, by reacting a phenol novolak resin, a phenolic resin such as cresol novolac resin with an epihalohydrin such as epichlorohydrin by a known method.

  As the novolac epoxy resin represented by the general formula (11 ′), for example, YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (all Nippon Steel Sumitomo Metal Corporation) Chemical Co., Ltd., trade name), DEN-431, DEN-439 (all, Dow Chemical Co., trade name), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012 , EOCN-1025, EOCN-1027, BREN (above, Nippon Kayaku Co., Ltd., trade name), EPN-1138, EPN-1235, EPN-1299 (above, BASF Japan Ltd. trade name), N-730, N-770, N-865, N-665, N-673, VH-4150, VH- 240 (or more, DIC (Ltd.), trade name) and the like are commercially available.

  As the epoxy resin (a), an epoxy resin having a constitutional unit represented by the general formula (12) is preferably mentioned, and as an epoxy resin having such a constitutional unit, for example, a bisphenol represented by a general formula (12 ′) A-type epoxy resin and bisphenol F-type epoxy resin are preferably mentioned.

In the general formulas (12) and (12 ′), R ¹² represents a hydrogen atom or a methyl group, Y ¹² represents a hydrogen atom or a glycidyl group, and the molar ratio of hydrogen atom to glycidyl group is 0/100 to 30. / 70, preferably 0/100 to 10/90, and n ₁₂ represents an integer of 1 or more. As can be seen from the molar ratio of hydrogen atom to glycidyl group, at least one Y ¹² represents glycidyl group. In addition, a plurality of R ¹² may be the same or different, and when n ₁₂ is 2 or more, a plurality of Y ¹² may be the same or different.

n ₁₂ is an integer of 1 or more as described above, preferably from 10 to 100, more preferably 10 to 80, still more preferably 15 to 60. When n ₁₂ is within the above range, the resist shape, resolution, heat resistance, adhesion, and resist pattern excellent in balance of electrical insulation resistance.
Moreover, in the epoxy resin which has a structural unit shown by General formula (12), content of this 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. .

The bisphenol A epoxy resin and bisphenol F epoxy resin represented by the general formula (12 ′) and Y ¹² having a glycidyl group are, for example, bisphenol A epoxy resin represented by the following general formula (16), bisphenol F type It can be obtained by reacting the hydroxyl group of the epoxy resin with an epihalohydrin such as epichlorohydrin.

In the general formula (16), R ¹² and n ₁₂ are the same as above.

  Considering that the amount of epihalohydrin used is superior in balance between resist shape, resolution, coating film strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, and resolution, a resist pattern can be obtained, It is preferable to set it as 2-10 mol with respect to 1 mol of hydroxyl groups in the epoxy resin shown by General formula (16).

  From the same viewpoint, it is preferable to use a basic catalyst in the reaction of the epoxy resin represented by the general formula (16) with the epihalohydrin. Preferred examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides, and alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide are preferred. More preferred 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 shown by General formula (16).

  From the viewpoint of increasing the reaction rate in the reaction of the epoxy resin represented by the general formula (16) with an epihalohydrin, as an organic solvent, for example, alcohols such as methanol and ethanol; Cellosolves such as methyl cellosolve and ethyl cellosolve; It is preferable to use an ether such as dioxane, or a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide. From among these, one type can be used alone, or two or more types can be used in combination, and from the viewpoint of adjusting the polarity, it is preferable to use two or more types in combination.

  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 side reactions are less likely to occur.

After the above reaction, preferably, the unreacted epihalohydrin, the organic solvent and the like are distilled off by distillation under heating under reduced pressure to obtain an epoxy resin represented by the general formula (12 ').
Further, from the viewpoint of obtaining an epoxy resin with higher purity, the obtained epoxy resin can be redissolved in an organic solvent, and a basic catalyst such as the above-mentioned alkali metal hydroxide can be added and reacted. Under the present circumstances, it is preferable to use phase transfer catalysts, 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 reaction rate. In this case, an epoxy resin having high purity can be obtained by removing salts and the like generated after completion of the reaction by filtration, water washing and the like and further distilling off the organic solvent and the like under heating and pressure reduction.

  As the bisphenol A epoxy resin or bisphenol F epoxy resin represented by the general formula (12 ′), for example, Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (all, Mitsubishi Chemical Corporation) (Trade name), DER-330, DER-301, DER-361 (above, Dow Chemical Co., Ltd., trade name), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (trade names, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like) are commercially available.

  As an epoxy resin (a), the epoxy resin which has a structural unit shown by following General formula (13) is mentioned preferably, As an epoxy resin which has such a structural unit, for example, General formula (13 ') The triphenolmethane type epoxy resin shown is preferably mentioned.

In the general formulas (13) and (13 ′), Y ¹³ represents a hydrogen atom or glycidyl group, and the molar ratio of hydrogen atom to glycidyl group is preferably 0/100 to 30/70, and n ₁₃ is 1 Indicates an integer greater than or equal to. As can be seen from the molar ratio of hydrogen atom to glycidyl group, at least one Y ¹³ represents glycidyl group. In addition, a plurality of Y ³ may be the same or different.

n ₁₃ is an integer of 1 or more as described above, preferably 10 to 100, more preferably 15 to 80, and still more preferably 15 to 70. When n ₁₃ is within the above range, the resist shape, resolution, heat resistance, adhesion, and resist pattern excellent in balance of electrical insulation resistance.
Moreover, in the epoxy resin which has a structural unit shown by General formula (13), content of this 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 .

  As the triphenolmethane type epoxy resin represented by the general formula (13 ′), for example, FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) are commercially available. It is available.

  As an epoxy resin (a), the bisphenol novolak-type epoxy resin which has a structural unit shown by General formula (14) is mentioned preferably.

In general formula (14), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ¹⁴ represents a hydrogen atom or a glycidyl group, and n ₁₄ represents an integer of 1 or more Indicates At least one Y ¹⁴ represents a glycidyl group, and a plurality of R ¹³ may be the same or different.

As an alkyl group of R ¹³ , one having 1 to 20 carbon atoms is preferable, one having 1 to 12 carbon atoms is more preferable, and one having 1 to 3 carbon atoms is more preferable. The alkyl group may be linear or branched, and may be substituted by 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 methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, isopentyl, neopentyl and the like. Among them, preferred is a methyl group.
Examples of the aryl group include phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group and the like, preferably an aryl group having 6 to 20 ring carbon atoms, more preferably an aryl group having 6 to 14 ring carbon atoms. It is. The aryl group may be substituted by a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amido group, an alkoxy group or the like.
The aralkyl group is not particularly limited as long as one of the hydrogen atoms of the above-mentioned alkyl group is substituted by the above-mentioned aryl group, and an aralkyl group having 7 to 20 carbon atoms is preferable. Examples thereof include an ethyl group, a phenylpropyl group and a naphthylmethyl group, and may be one substituted by a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amido group, an alkoxy group or the like.

n ₁₄ is, as described above, an integer of 1 or more, preferably 10 to 100, more preferably 15 to 80, and still more preferably 15 to 70. When n ₁₄ is within the above range, the resist shape, resolution, heat resistance, adhesion, and resist pattern excellent in balance of electrical insulation resistance.
Moreover, in the epoxy resin which has a structural unit shown by General formula (14), content of this 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. .

  Moreover, as epoxy resin (a), the bisphenol novolak-type epoxy resin which has a structural unit shown by General formula (15) is mentioned preferably.

In the general formula (15), R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ¹⁵ represents a hydrogen atom or a glycidyl group, and n ₁₅ represents an integer of 1 or more Indicates At least one Y ¹⁵ represents a glycidyl group, and a plurality of R ¹⁴ may be the same or different. Moreover, as the alkyl group, aryl group and aralkyl group of R ^14, the same as those described for R ¹³ can be preferably exemplified.

n ₁₅ is an integer of 1 or more as described above, preferably from 10 to 100, more preferably 15 to 80, more preferably from 15 to 70. When n ₁₅ is within the above range, the resist shape, resolution, heat resistance, adhesion, and resist pattern excellent in balance of electrical insulation resistance.
Moreover, in the epoxy resin which has a structural unit shown by General formula (15), content of this 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. .

In the general formula (15), one in which R ¹⁴ is a hydrogen atom and Y ¹⁵ is a glycidyl group is as EXA-7376 series (trade name of DIC Corporation), and R ¹⁴ is a methyl group, Y ¹⁵ is one of glycidyl group, EPON SU8 series (Mitsubishi Chemical Co., Ltd., trade name) is commercially available as.

  The bisphenol novolac epoxy resin having a structural unit represented by the general formulas (14) and (15) is, for example, a hydroxyl group of a bisphenol novolac resin represented by the general formulas (17) and (18) and an epihalohydrin such as epichlorohydrin. It can be obtained by reaction.

In the general formula (17), R ^13, n ₁₄ is the same as R ^13, n ₁₄ in the general formula (14), in the general formula (18), R ^14, n _15, the above general It is the same as R ¹⁴ and n ₁₅ in the formula (15).

  The bisphenol novolac resin having a structural unit represented by these general formulas (17) and (18) preferably has, for example, a bisphenol compound and an aldehyde compound or a ketone compound, an alkyl group having 1 to 4 carbon atoms in the molecular structure It can be obtained by reacting in the presence of the sulfonic acid of

  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, Preferred are bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, bisphenol Z and the like.

  Preferred examples of the aldehyde compound to be reacted with the above-mentioned bisphenol compound include formaldehyde, acetaldehyde, benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde, and naphthylaldehyde, and the ketone compound includes benzophenone, fluorenone, Indanone etc. are mentioned preferably.

  Moreover, as a sulfonic acid which has a C1-C4 alkyl group in molecular structure, alkanesulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and a fluorine atom to the alkane part to this Preferred examples include perfluoroalkanesulfonic acid having

  More specifically, bisphenol novolac epoxy resins having the structural units represented by the general formulas (14) and (15) are obtained as follows. The above bisphenol compound and aldehyde compound or ketone compound are charged into a reaction vessel, and sulfonic acid is continuously or intermittently added so as to maintain a range of 20 to 200 ° C. while stirring under an inert gas atmosphere. Then, the bisphenol compound is reacted with an aldehyde compound or a ketone compound to obtain a crude bisphenol novolac resin. Then, the crude bisphenol novolak resin is extracted with a non-water-soluble organic solvent to form a bisphenol novolak resin solution, which is washed with water, neutralized, and further distilled off the non-water-soluble organic solvent to obtain bisphenol novolac epoxy A resin is obtained.

  Here, as the non-water-soluble organic solvent, one having a boiling point of 100 to 130 ° C. is preferable from the viewpoint of improving the work efficiency of extraction, water washing and neutralization, for example, butanol, pentyl alcohol, methoxyethanol, ethoxyethanol , Diethylene glycol, methyl isobutyl ketone and the like.

The above-mentioned water washing is carried out until the crude bisphenol novolak resin solution has a pH of 3 to 7, more preferably 5 to 7 and, if necessary, a basic substance such as sodium hydroxide, sodium carbonate, ammonia or triethylenetetramine. May be neutralized.
The above-mentioned distillation is preferably carried out by heating under reduced pressure under the conditions of, for example, a temperature of 170 to 200 ° C. and a pressure of 3 kPa or less. By performing under such conditions, bisphenol novolac resin having high purity can be obtained. .

The epoxy resin (a) is an epoxy resin having a structural unit represented by the general formula (I), a structural unit represented by the general formula (II), from the viewpoint of being able to improve the solvent resistance while being excellent in process latitude. The epoxy resin having the following formula, the bisphenol novolac epoxy resin having the structural unit represented by the general formula (IV) is preferable, the novolac epoxy resin represented by the general formula (I ′), the bisphenol A represented by the general formula (II ′) Type epoxy resin, and bisphenol F-type epoxy resin represented by general formula (II '), and bisphenol novolac A-type epoxy resin having a structural unit represented by general formula (IV), and composition represented by general formula (IV) More preferred is a bisphenol novolac F-type epoxy resin having units.
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 (14) and a structural unit represented by the general formula (15) It is preferable to use together with the epoxy resin which it has.

  Examples of vinyl group-containing monocarboxylic acid (b) to be reacted with the above epoxy resin (a) include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfuryl acrylic acid, β-styryl acrylic acid And acrylic acid derivatives such as cinnamic acid, crotonic acid and α-cyanocinnamic acid, a half ester compound which 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 A half ester compound which is a reaction product of an ester and a dibasic acid anhydride is preferably mentioned.

  The half ester compound is 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 singly or in combination of two or more.

  Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the above-mentioned half ester compound which is an example of the vinyl group-containing monocarboxylic acid (b) include, for example, 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) Preferred are acrylate, vinyl glycidyl ether, glycidyl (meth) acrylate and the like.

  As a dibasic acid anhydride used for the synthesis | combination of said half ester compound, what contains 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, methyl hexahydrophthalic anhydride Preferred are acid, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the above-mentioned epoxy resin (a) with the vinyl group-containing monocarboxylic acid (b), the vinyl group-containing monocarboxylic acid (b) is 0.6 to 6 per equivalent of epoxy group of the epoxy resin (a). It is preferable to make it react by the ratio which will be 1.05 equivalent, and it is more preferable to make it react by the ratio which becomes 0.8-1.0 equivalent. The reaction at such a ratio is preferable because the photopolymerization property is improved, that is, the photosensitivity becomes more excellent.

The reaction of the epoxy resin (a) with 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; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate; aliphatic carbonization such as octane and decane Hydrogens; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like are preferably mentioned.

  Furthermore, it is preferable to use a catalyst to accelerate the reaction. Preferred examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine and the like. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The above amount is preferable because the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) is promoted.

  It is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Preferred examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like. The amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The above amount is preferable because the storage stability (shelf life) of the composition is improved. Moreover, the reaction temperature is preferably 60 to 150 ° C., more preferably 80 to 120 ° C.

  In addition, if necessary, vinyl group-containing monocarboxylic acid (b) and a phenolic compound such as p-hydroxyphenethyl alcohol, or trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, biphenyltetracarbonide. It can be used in combination with a polybasic acid anhydride such as an acid anhydride.

  The epoxy resin (a ') thus obtained has a hydroxyl group formed by the addition reaction of the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b) It is guessed.

  In the 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 used. Preferably mentioned. In the epoxy resin (a ′ ′), the hydroxyl group in the epoxy resin (a ′) (including the hydroxyl group originally contained in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) It is presumed to be semi-esterified.

  As the polybasic acid anhydride (c), those containing a saturated group and polybasic acid anhydrides containing an unsaturated group can be preferably used. Specific examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like are preferably mentioned.

  In the reaction of the epoxy resin (a ') with the polybasic acid anhydride (c), the polybasic acid anhydride (c) is added in an amount of 0.1 to 1. per equivalent of hydroxyl group in the epoxy resin (a'). The acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted by reaction with 0 equivalent.

  The acid value of the acid-modified vinyl group-containing epoxy resin (A) is preferably 30 to 150 mg KOH / g, more preferably 40 to 120 mg KOH / g, and still more preferably 50 to 100 mg KOH / g. When the acid value is 30 mgKOH / g or more, the solubility of the photosensitive resin composition in a dilute alkali solution is unlikely to decrease, and when it is 150 mgKOH / g or less, the electrical properties of the cured film are unlikely to decrease.

  The reaction temperature of the epoxy resin (a ′) and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.

  In addition, as the epoxy resin (a), for example, a hydrogenated bisphenol A epoxy resin can be used in combination as required. Furthermore, as the acid-modified vinyl group-containing epoxy resin (A), a styrene-maleic acid resin such as a hydroxyethyl (meth) acrylate modified product of a styrene-maleic anhydride copolymer can be used in combination.

The weight average molecular weight of the acid-modified vinyl group-containing epoxy resin (A) is preferably 3,000 to 30,000, more preferably 4,000 to 25,000, and still more preferably 5,000 to 18,000. When the weight average molecular weight of the component (A) is in the above range, a resist pattern which is more excellent in the balance between the resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained. Here, a weight average molecular weight is a weight average molecular weight of polyethylene conversion measured by the gel permeation chromatography (GPC) method which made tetrahydrofuran the solvent. More specifically, for example, it is possible to use a calibration curve of standard polystyrene and measure using the following GPC measurement apparatus and measurement conditions, and use it as the weight average molecular weight. Moreover, preparation of a standard curve uses five sample sets ("PStQuick MP-H" and "PStQuick B", Tosoh Co., Ltd. product) as standard polystyrene.
(GPC measuring device)
GPC apparatus: high-speed GPC apparatus “HCL-8320GPC”, detector: differential refractometer, manufactured by Tosoh Corp. Column: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Toso (stock Made in (measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40 ° C
Flow rate: 0.35 ml / min Sample concentration: 10 mg / THF 5 ml
Injection volume: 20 μl

  (A) As the acid-modified vinyl group-containing epoxy resin, a novolac epoxy resin represented by the general formula (11 ′), having a structural unit represented by the general formula (11) as the epoxy resin (a), 12) A bisphenol A type epoxy resin represented by the general formula (12 ′), an epoxy resin obtained by reacting a bisphenol F type epoxy resin and a vinyl group-containing monocarboxylic acid (b) a ′) and an epoxy resin (a ′ ′) obtained by reacting an epoxy resin (a ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c) are preferable, and an epoxy resin (a ′ ′) is preferable Is more preferred.

These epoxy resins (a ′) and (a ′ ′) can be used singly or in combination of two or more, and it is preferable to use two or more in combination. As a combination, an epoxy resin (a ′) or (a ′ ′) obtained from a novolac epoxy resin represented by the general formula (11 ′), and a bisphenol A epoxy resin represented by the general formula (12 ′), bisphenol An epoxy resin (a ′ ′) obtained from a novolac epoxy resin represented by the general formula (I ′) is preferable, and a combination of two types with an epoxy resin (a ′) or (a ′ ′) obtained from an F-type epoxy resin And a combination of two types of epoxy resin (a ′ ′) obtained from bisphenol A epoxy resin and bisphenol F epoxy resin represented by the general formula (12 ′) are more preferable.
Epoxy resin (a ′) or (a ′ ′) obtained from novolac epoxy resin represented by the general formula (11 ′), bisphenol A epoxy resin represented by the general formula (12 ′), bisphenol F epoxy resin 95: 5-30: 70 are preferable, and it is more preferable that they are 90: 10-40: 60, and, as for mass mixing ratio with the epoxy resin (a ') or (a'') obtained from, 80:20 More preferably, it is 45:55.

  It is preferable that it is 20-80 mass parts, and, as for content of the (A) component which makes solid content whole quantity of the photosensitive resin composition 100 mass parts, it is more preferable that it is 30-70 mass parts, 35-65. It is particularly preferred that it is part by weight. When the content of the component (A) is in the above range, a coating film excellent in heat resistance, electrical properties, and chemical resistance (alkali resistance, acid resistance) can be obtained. Here, the solid content in the present embodiment refers to a component in the composition other than a volatile substance such as water and a solvent described later. That is, the solid content includes liquid, starch syrup and wax at a room temperature around 25 ° C. and does not necessarily mean that it is solid.

  The photosensitive resin composition of this embodiment contains a photoinitiator as a (B) component. The photopolymerization initiator (B) is not particularly limited and can be appropriately selected from photopolymerization initiators that are usually used. It is preferable to contain the acyl phosphine oxide type photoinitiator which has an acyl phosphine oxide group (= P (= O) -C (= O)-group) from a resist shape and a reflow resistant viewpoint. Examples of the acyl phosphine oxide photopolymerization initiators include (2,6-dimethoxybenzoyl) -2,4,6-pentyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, 4,6-trimethylbenzoyl diphenyl phosphine oxide, ethyl-2,4,6-trimethyl benzoyl phenyl phosphite, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, (2,5-dihydroxyphenyl) diphenyl A phosphine oxide, (p-hydroxyphenyl) diphenyl phosphine oxide, bis (p-hydroxyphenyl) phenyl phosphine oxide, tris (p- hydroxyphenyl) phosphine oxide etc. are mentioned preferably.

In addition, as photopolymerization initiators other than the acyl phosphine oxide photopolymerization initiator, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, N, Acetophenone photopolymerization initiators such as N-dimethylaminoacetophenone; 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-amino anthraquinone Anthraquinone photopolymerization initiators such as laquinone; thioxanthone photopolymerization initiators such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal, benzyl dimethyl Ketal photopolymerization initiators such as ketals; benzophenones, methylbenzophenones, 4,4'-dichlorobenzophenones, 4,4'-bis (diethylamino) benzophenones, benzophenones such as Michler's ketone, 4-benzoyl-4'-methyl diphenyl sulfide; An oxime-based photopolymerization initiator such as 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) is also preferably mentioned.
(B) As a photoinitiator, said thing can be used individually by 1 type or in combination of 2 or more types.

  The content of the photopolymerization initiator (B) is preferably 0.2 to 15 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. When the amount is 0.2 parts by mass or more, the exposed portion is difficult to elute during development, and when the amount is 15 parts by mass or less, the heat resistance is unlikely to be reduced. For the same reason, the content of the component (B) is more preferably 0.2 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass, and particularly preferably 0.5 to 2.5 It is a mass part.

  In addition, photopolymerization assistants such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. The agents may be used alone or in combination of two or more.

The photosensitive resin composition of the present embodiment contains an inorganic filler as the component (C). The inorganic filler (C) is used for the purpose of improving various properties such as adhesion of the photosensitive resin composition, solder heat resistance, and coating film strength. (C) 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 zirconate 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 · 4SiO 2 · H 2} O), aluminum titanate _{(TiO 2 · Al 2 O 3} ), yttria-containing Jill Near _{(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 and the like are preferably mentioned. These (C) inorganic fillers can be used individually by 1 type or in combination of 2 or more types.

  (C) The inorganic filler preferably has a maximum particle diameter of 0.1 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.1 to 5 μm, and 0.1 to 1 μm. Particularly preferable. The fall of electrical insulation (HAST tolerance) can be suppressed as the largest particle diameter is 20 micrometers or less. Here, the largest particle diameter of (C) inorganic filler shall be measured by the laser diffraction method (JISZ8825-1 (2001 year) conformity).

  Among the inorganic fillers, it is preferable to use silica from the viewpoint of being able to improve solder heat resistance, and from the viewpoint of being able to improve solder heat resistance, crack resistance (heat shock resistance) and PCT resistance, barium sulfate It is preferred to use Moreover, it is preferable that the said barium sulfate is surface-treated by the alumina and / or the organic silane type compound from a viewpoint which can improve the aggregation prevention effect.

  The elemental composition of aluminum on the surface of barium sulfate surface-treated with alumina and / or an organic silane compound is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%, More preferably, it is 1.5 to 3.5 atomic percent. The elemental composition of silicon on the surface of barium sulfate is preferably 0.5 to 10 atomic percent, more preferably 1 to 5 atomic percent, and still more preferably 1.5 to 3.5 atomic percent. preferable. The elemental composition of carbon on the surface of barium sulfate is preferably 10 to 30 atomic percent, more preferably 15 to 25 atomic percent, and still more preferably 18 to 23 atomic percent. These elemental compositions can be measured using XPS.

  As barium sulfate surface-treated with an alumina and / or an organic silane type compound, NanoFine BFN40DC (made by Nippon Solvay Co., Ltd. product name) is commercially available, for example.

  Content of the (C) inorganic filler which makes solid content whole quantity in the photosensitive resin composition 100 mass parts is 1-50 mass parts preferably. (C) If the content of the inorganic filler is within the above range, the coating strength, solder heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, etc. of the photosensitive resin composition are further improved. Good inorganic filler dispersibility can be obtained. Moreover, for the same reason, the content of the component (C) is preferably 3 to 30 parts by mass, and more preferably 5 to 30 parts by mass.

  The photosensitive resin composition of the present embodiment contains a photopolymerizable compound as the component (D). The photopolymerizable compound (D) is a photopolymerizable functional group such as a vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, (meth) acryloyl group, etc. The compound is not particularly limited as long as it is a compound having an ethylene oxide unsaturated group, and from the viewpoint of reactivity, a compound having a (meth) acryloyl group is more preferable.

  (D) As the photopolymerizable compound, for example, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and the like Monoglycols or di (meth) acrylates of glycols; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide and the like; N, N-dimethylaminoethyl (meth) acrylate and the like Aminoalkyl (meth) acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Multivalent (meth) acrylates of these ethylene oxide or propylene oxide adducts; (meth) ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol. Preferred are acrylates; (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate and the like; melamine (meth) acrylates and the like. These (D) photopolymerizable compounds can be used singly or in combination of two or more.

  Among these, from the viewpoint of obtaining a resist pattern that is more excellent in the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation, a polyvalent alcohol or a polyvalent compound of the ethylene oxide or propylene oxide adduct thereof (meta ) Acrylates are preferred.

  The total content of solid content in the photosensitive resin composition is 100 parts by mass, and the content of the (D) photopolymerizable compound is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass. Preferably, it is 1 to 15 parts by mass. When the content of the component (D) is 0.1 parts by mass or more, the light sensitivity is appropriately low, and thus the exposed portion is not easily eluted during development, and the heat resistance is improved when the content is 30 parts by mass or less.

  The photosensitive resin composition of the present embodiment contains an alkoxypolysiloxane as the component (E). (E) Alkoxypolysiloxane is a polysiloxane represented by the following general formula (1) and having an alkoxy group in the molecule, and the polysiloxane represented by the general formula (1) may be used singly or in combination of two or more Can be used in combination. (E) A resist pattern which is more excellent in balance of resolution, coating film strength, heat resistance, adhesion, electrical insulation (HAST resistance), and thermal shock resistance by adopting such a polysiloxane as alkoxypolysiloxane Is obtained. In particular, by using a combination of the (C) inorganic filler and the (E) alkoxypolysiloxane, good dispersibility of the (C) inorganic filler can be obtained, so the coating strength and heat resistance of the photosensitive resin composition can be obtained. , Electrical insulation (HAST resistance), thermal shock resistance, resolution and the like can be further improved.

In formula (1), R ⁰¹ represents an alkyl group, an aryl group or an aralkyl group, Y ⁰¹ represents an alkyl group, an aryl group, an aralkyl group or an alkoxy group represented by —OR ⁰² , and R ⁰² represents an alkyl group And m ₀₁ represents an integer of 2 to 1000. The plurality of R ⁰¹ , R ⁰² and Y ⁰¹ may be the same or different, and at least one of R ⁰¹ is an alkyl group.

Preferred examples of the alkyl group, aryl group and aralkyl group of R ⁰¹ and Y ⁰¹ are the same as those described for R ¹³ . In the general formula (1), at least one of R ⁰¹ is an alkyl group, and in consideration of the drying property of the coating of the photosensitive resin composition, it is more preferably an alkyl group having 1 to 5 carbon atoms.
Y ⁰¹ is preferably an alkyl group, an alkoxy group represented by —OR ⁰² , more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group represented by —OR ⁰² , and drying of the coating of the photosensitive resin composition Considering the nature, more preferably, it is an alkoxy group represented by —OR ⁰² , in which R ⁰² is an alkyl group having 1 to 5 carbon atoms.
In addition, m ₀₁ is preferably an integer of 5 to 500, more preferably an integer of 10 to 300, and still more preferably an integer of 10 to 200.

  The weight average molecular weight of the (E) alkoxypolysiloxane is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and still more preferably 5,000 to 25,000. This weight average molecular weight can be measured by the same method as the weight average molecular weight of the (A) acid-modified vinyl group-containing epoxy resin.

  (E) Alkoxypolysiloxane can be produced according to a conventionally known method for producing alkoxypolysiloxane (for example, JP-B-54-34332 etc.), for example, in an organic solvent, Water is added to the silane compound shown in), and hydrolysis is performed by heating for 1 to 24 hours under the temperature condition of preferably 40 to 150 ° C., more preferably 60 to 100 ° C. in the presence of an acid catalyst. You can get it.

Wherein (2), n ₀₁ is an integer from 2 to 4, R ⁰¹ and Y ⁰¹ are the same as R ⁰¹ and Y ⁰¹ in the above formula (1). Examples of silane compounds represented by the general formula (2) include trimethoxymethylsilane, triethoxymethylsilane, tripropoxymethylsilane, tripropoxyethylsilane, tripropoxybutylsilane, tributoxymethylsilane, tributoxyethylsilane, Trialkoxysilanes such as tributoxypropylsilane, tributoxybutylsilane and tributoxyphenylsilane; and alkoxy groups such as tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and tetrapentoxysilane. Are preferably mentioned in the molecule, and low condensates thereof can also be used as the raw material. Here, the low condensate is one having a polymerization degree of usually 10 or less, preferably 2 to 8, more preferably 2 to 6.

As the acid catalyst, in addition to sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, aluminum chloride, etc., acidic zeolite, supported mineral acid catalyst, silica-alumina, titano-silica-alumina, ion exchange resin, acid-treated clay, heteropoly Preferred examples include solid acid catalysts of the type known as acids.
Further, as the organic solvent, those exemplified as the organic solvent preferably used in the reaction of the above-mentioned epoxy resin and epihalohydrin can be preferably used.

(E) Alkoxypolysiloxane is, for example, a mixture of silicic acid or its low condensate and an alcohol having 1 to 5 carbon atoms, preferably at a temperature of 40 to 150 ° C., more preferably 60 to 100 ° C. It can also be obtained by heating for 1 to 24 hours.
Here, as the alcohol having 1 to 5 carbon atoms, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, Isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol and the like are preferably mentioned.

  It is a reaction product obtained by hydrolyzing the raw material shown by said General formula (2), a reaction product obtained by reaction of a silicic acid or its low condensate and alcohol, Comprising: The said General formula (1) One or more kinds of the group represented by the formula (1) may be present, but any one represented by the above general formula (1) can be used as the (E) alkoxypolysiloxane. Moreover, although the thing which is not shown by the said General formula (1) may produce | generate, such a reaction product is also contained in the photosensitive resin composition as long as the effect of this embodiment is not inhibited. May be

  It is preferable that it is 1-40 mass parts, and, as for content of (E) alkoxypolysiloxane which makes solid content whole quantity of the photosensitive resin composition 100 mass parts, it is more preferable that it is 1-25 mass parts, 3 It is especially preferable that it is -15 mass parts. When the content of the component (E) is within the above range, the dispersibility of the (C) inorganic filler will be more excellent, so the coating strength, heat resistance, electrical insulation (HAST resistance) of the photosensitive resin composition ), Thermal shock resistance, resolution and the like can be further improved.

  The photosensitive resin composition of the present embodiment preferably contains a pigment as the component (F). The pigment (F) is preferably used according to the desired color when the wiring pattern is concealed. (F) The pigment is used as needed according to the desired color, and a coloring agent which produces a desired color may be appropriately selected and used. Examples of the coloring agent include phthalocyanine blue and phthalocyanine. Known colorants such as green, iodine green, diazo yellow, crystal violet and the like are preferably mentioned.

  0.1-5 mass parts is preferable, and, as for content of the (F) pigment which makes solid content whole quantity in the photosensitive resin composition 100 mass parts, More preferably, it is 0.1-3 mass parts. A wiring pattern can be concealed as content of (F) component is in the said range.

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

  The amount of diluent used is preferably such that the content of the total solid content in the photosensitive resin composition is 50 to 90% by mass, and the amount is preferably 60 to 80% by mass. Is more preferable, and it is more preferable that the amount be 65 to 75% by 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 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 higher-definition pattern is attained.

  The photosensitive resin composition of the present embodiment may contain a curing agent. As a curing agent, a compound which is itself cured by heat, ultraviolet light, etc., or a carboxyl group, a hydroxyl group and a heat of the (A) acid-modified vinyl group-containing epoxy resin which is a photocurable resin component in the composition of this embodiment Preferred are compounds that cure with ultraviolet light and the like. By using the curing agent, the heat resistance, adhesion, chemical resistance (alkali resistance, acid resistance) and the like of the final cured film can be improved.

  As a hardening agent, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound etc. are mentioned preferably, for example as a thermosetting compound. As the epoxy compound, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin; novolac type epoxy resin Preferred examples include resins; biphenyl type epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanurate; and bixylenol type epoxy resins. Preferred examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. As a urea compound, dimethylol urea etc. are mentioned preferably.

The curing agent preferably contains an epoxy compound (epoxy resin) and / or a block type isocyanate from the viewpoint of being able to further improve the heat resistance, and it is more preferable to use the epoxy compound and the block type isocyanate in combination.
As a block type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. As this polyisocyanate compound, for example, tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanatomethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, etc. And polyisocyanate compounds thereof, and adducts, burettes and isocyanurates thereof.

  Examples of isocyanate blocking agents include phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; and lactam-based blocking agents such as ε-caprolactam, δ-parellolactam, 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, butyl glycolate, diacetone alcohol, methyl lactate And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde xime, acetoaldoxime, acetoxy, methyl ethyl ketoxime, diacetyl monoxime, cyclohexane oxime, etc. butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan-based blocking agents such as methylthiophenol and ethylthiophenol; acid amide-based blocking agents such as acetic acid amide and benzamide; imido-based blocking agents such as succinimide and maleimide; amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethyl imidazole; imine blocking agents such as methylene imine and propylene imine are preferable Can be mentioned.

  The curing agents may be used alone or in combination of two or more. When a curing agent is used, the content of the curing agent is preferably 2 to 50 parts by mass, more preferably 2 to 40 parts by mass, with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. The amount is more preferably 30 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass. By making content of a hardening agent into the said range, the heat resistance of the cured film formed can be improved more, maintaining favorable developability.

  In the photosensitive resin composition of the present embodiment, an epoxy resin curing agent is used in combination for the purpose of further improving various properties such as heat resistance, adhesion, chemical resistance (alkali resistance, acid resistance) and the like of the final cured film. Can.

  Specific examples of such epoxy resin curing agents include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methyl Imidazoles such as -5-hydroxymethyl imidazole; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivative, melamine, polybasic hydrazide and the like Polyamines of these; organic acid salts and / or epoxy adducts thereof; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl- S-to Triazine derivatives such as azine; trimethylamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol) Tertiary amines such as tetramethylguanidine and m-aminophenol; Polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolak; Organics such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine Phosphines; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributyl phosnium chloride, etc .; Quaternary ammonium salts such as sodium chloride and phenyl tributyl ammonium chloride; the above-mentioned polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate And the like.

  The epoxy resin curing agent is used singly or in combination of two or more, and the content of the epoxy resin curing agent contained in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0. And 1 to 10% by mass.

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

  Preferred examples of the elastomer include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers and silicone elastomers. These elastomers are composed 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 elastomers, rubber-modified epoxy resins can be used. The rubber-modified epoxy resin may be, for example, any or all of the epoxy groups of the above-mentioned bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, triphenolmethane-type epoxy resin, phenol novolac-type epoxy resin or cresol novolac-type epoxy resin It is obtained by modifying with both terminal carboxylic acid modified butadiene-acrylonitrile rubber, terminal amino modified silicone rubber and the like. Among these elastomers, from the viewpoint of shear adhesion, both-terminal carboxyl group-modified butadiene-acrylonitrile copolymer, Espel (Hisshin Kasei Co., Ltd., Espel 1612, 1620), which is a polyester elastomer having hydroxyl groups, is preferable. Can be mentioned.

  The compounding amount of the elastomer is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass with respect to 100 parts by mass of the (A) acid-modified vinyl group-containing epoxy resin. If it is 2 parts by mass or more, the elastic modulus in the high temperature region of the cured film tends to be low, and if it is 30 parts by mass or less, the unexposed area tends to be eluted by the developer.

  The photosensitive resin composition of the present embodiment may optionally contain a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc .; a thickener such as bentone or montmorillonite; silicone, fluorine, vinyl Antifoaming agents such as resin systems, etc .; and various conventional additives such as silane coupling agents can be used. Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, and phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can be used.

In the photosensitive resin composition of the present embodiment, the components (A) to (E) described above, the component (F) used as desired, and other various components are uniformly kneaded using a roll mill, bead mill, etc. , Can be obtained by mixing.
In the present embodiment, by obtaining excellent dispersibility of the (C) inorganic filler, the coating film strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, etc. of the photosensitive resin composition can be obtained. From the viewpoint of further improving the properties, (C) inorganic filler and (E) alkoxypolysiloxane are mixed to obtain an inorganic filler mixture in advance, then (A) component, (B) component, (D) component, and further It is preferable to add and knead | mix and mix the (F) component used as needed, and other various components. That is, the photosensitive resin composition of the present embodiment comprises the steps of mixing the step (1) (C) inorganic filler and the (E) alkoxypolysiloxane to obtain an inorganic filler mixture, and the step (2) (A) acid It is preferable to obtain through a step of mixing a modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, the inorganic filler mixture, and (D) a photopolymerizable compound, and more preferably (F) a pigment.

  This inorganic filler mixture contains (C) inorganic filler and (E) alkoxypolysiloxane, and (E) alkoxypolysiloxane is a resin for dispersing the inorganic filler (also referred to as inorganic filler dispersing resin). Act as. The inorganic filler mixture is preferably in the form of an inorganic filler dispersion liquid in which the inorganic filler (C) is dispersed, from the viewpoint of obtaining good dispersibility of the inorganic filler (C) in the photosensitive resin composition. When the inorganic filler mixture is in the form of an inorganic filler dispersion, the addition effect of the (C) inorganic filler, that is, the adhesiveness of the photosensitive resin composition, various properties such as solder heat resistance, and coating film strength are improved.

As resin for inorganic filler dispersion | distribution, as long as it contains (E) alkoxypolysiloxane, you may contain other resin. As other resin, a hydroxyl group-containing (meth) acrylate compound or a hydroxyl group-containing vinyl polymer which is a resin having a hydroxyl group-containing vinyl ether compound as a monomer is preferably mentioned.
As the hydroxyl group-containing (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like are typically mentioned as a representative, and as the hydroxyl group-containing vinyl ether monomer, hydroxyethyl Typically preferred are vinyl ether, hydroxypropyl vinyl ether, hydroxymethyl propyl vinyl ether, hydroxybutyl vinyl ether, hydroxyethyl allyl ether, glycerol monoallyl ether, trimethylolpropane diallyl ether, diethylene glycol monovinyl ether and the like. Among these, a hydroxyl group-containing (meth) acrylate compound is preferable, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are more preferable.

Further, in consideration of the dispersibility of the (C) inorganic filler, the hydroxyl group-containing vinyl polymer is preferably a copolymer of the above-mentioned hydroxyl group-containing vinyl monomer and another monomer.
The other monomer is not particularly limited as long as it is a monomer having a polymerizable unsaturated group in the molecule, but ethylene such as (meth) acryloyl group, vinyl group or allyl group as the polymerizable unsaturated group Preferred are monomers having a polyunsaturated group.

  As such monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate Alkyl (meth) acrylate compounds such as dicyclopentenyl (meth) acrylate; styrene, methylstyrene, dimethylstyrene, diphenylethylene, vinylnaphthalene, propylstyrene, cyclohexylstyrene, dodecylstyrene, ethylbenzylstyrene, (phenylbutyl) styrene and the like Aromatic vinyl compounds; vinyl halides such as vinyl chloride and vinylidene chloride; nitrogen-containing vinyl compounds such as (meth) acrylonitrile and (meth) acrylamide Mentioned preferred, it can be used individually or in combination of two or more thereof. Further, vinyl compounds having a hydrolyzable silyl group in the molecule such as 3-((meth) acryloyloxyethyl) trimethoxysilane and 3-((meth) acryloyloxypropyl) trimethoxysilane are also preferably mentioned.

When the vinyl polymer having a hydroxyl group is a copolymer of the above-mentioned hydroxyl group-containing vinyl monomer and another monomer, the content of the hydroxyl group-containing vinyl monomer in all the monomers is It is preferably 1 to 30% by weight, and more preferably 5 to 15% by weight. When the content of the hydroxyl group-containing vinyl monomer is in the above range, excellent dispersibility of the inorganic filler is obtained, and excellent weather resistance of the coating film is obtained.
In addition, a vinyl polymer having a hydroxyl group is obtained by a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like, and solution polymerization is adopted from the viewpoint of being able to be used as it is when dispersing the inorganic filler. Is preferred.

  When the resin for inorganic filler dispersion contains (E) alkoxypolysiloxane and another resin, the content of (E) alkoxypolysiloxane in the resin for inorganic filler dispersion is preferably 60% by mass or more, and 75% by mass. % Or more is more preferable, and 80% by mass or more is even more preferable. When the content of the (E) alkoxypolysiloxane is within the above range, good dispersibility of the (C) inorganic filler can be obtained, so the coating strength, heat resistance, electrical insulation (HAST of the photosensitive resin composition) Resistance, thermal shock resistance, resolution and the like can be further improved.

It is preferable that it is 15-80 mass%, as for content of (C) inorganic filler with respect to solid content whole quantity in an inorganic filler mixture, it is more preferable that it is 20-70 mass%, More preferably, it is 25-60 mass% And particularly preferably 30 to 60% by mass. (C) The coating film strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, etc. of the photosensitive resin composition are further improved when the content of the inorganic filler is within the above range. And (C) good dispersibility of the inorganic filler is obtained.
Here, the content of the (C) inorganic filler relative to the total solid content in the inorganic filler mixture is P.I. W. C. Also referred to as (Pigment Weight Concentration), P.I. W. C. (Mass%) = inorganic filler (mass part) / solid content in inorganic filler mixture (mass part) × 100 The value calculated by the formula. In addition, the total solid content in the inorganic filler mixture is the total of the solid content contained in the above-mentioned hydroxyl group-containing vinyl polymer, a curing agent described later, etc. in addition to (C) inorganic filler and (E) alkoxypolysiloxane Amount.

  The content (solid content) of (E) alkoxypolysiloxane in the inorganic filler mixture is preferably 20 to 2000 parts by mass, and 20 to 1000 parts by mass with respect to 100 parts by mass of the (C) inorganic filler. It is more preferable that it is 20-500 mass parts. When the content of the component (E) in the inorganic filler mixture is within the above range, good dispersibility of the (C) inorganic filler can be obtained, and excellent heat resistance can be obtained.

The inorganic filler dispersion liquid is obtained by adding a dispersion aid, a surface treatment agent, etc. to (C) inorganic filler and (E) alkoxypolysiloxane as necessary, and known dispersion treatment such as ball mill, bead mill, ultrasonic dispersion machine, etc. It can obtain by the method etc. which carry out distributed processing using an apparatus. Moreover, in obtaining an inorganic filler dispersion liquid, it is preferable to use an organic solvent.
Here, the organic solvent may be appropriately selected from those described as the organic solvent used in the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). In consideration of the dispersibility of the (C) inorganic filler, glycol ethers or esters are preferred.

  The content of the organic solvent in the inorganic filler mixture is preferably 10 to 50% by mass, and more preferably 15 to 40% by mass. That is, it is preferable that it is 50-90 mass%, and, as for the density | concentration of the solid content whole quantity in an inorganic filler mixture, 60-85 mass% is more preferable. When the content of the organic solvent is within the above range, good dispersibility of the (C) inorganic filler can be obtained.

  In addition, in the inorganic filler mixture, as a curing agent or as a binder (bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type It is preferable to use an epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, or a heterocyclic epoxy resin such as triglycidyl isocyanurate, a bixylenol type epoxy resin, etc. These may be used alone or in combination of two or more. Can be used.

  5-60 mass parts is preferable, and, as for content of the hardening agent which makes solid content whole quantity in an inorganic filler mixture 100 mass parts, 10-50 mass parts is more preferable. When the content of the curing agent is in the above range, good dispersibility of the (C) inorganic filler can be obtained.

  It is preferable that it is 20-80 mass parts, and, as for solid content of the inorganic filler mixture which makes the solid content whole quantity in the photosensitive resin composition 100 mass parts, it is more preferable that it is 20-60 mass parts, Particularly preferred is 25 to 50 parts by mass. When the content of the inorganic filler mixture is in the above range, the coating film strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution and the like of the photosensitive resin composition can be further improved. .

The photosensitive resin composition of the present embodiment obtained in this manner can be supplied as a film or in a liquid depending on the use mode of the supply destination. When forming a permanent mask resist using the composition, the liquid form allows the permanent mask resist to be easily formed by various coating methods described later.
When a curing agent is used and supplied in a liquid state, the curing agent is a resin composition ((A) to (E) components, an optionally added (F) component, and other than the curing agent. It is preferable to supply as a 2 liquid type separately from the resin composition containing an additive, and to mix and use it at a use end. The curing reaction of the resin composition does not accelerate and can be stably supplied as a liquid. When a curing agent is used and supplied as a film, it can be supplied as a film as a resin composition containing the curing agent.

[Photosensitive element, permanent mask resist and printed wiring board]
The photosensitive resin composition of the present embodiment is suitably used for the formation of a photosensitive element and a permanent mask resist, and the photosensitive element and the permanent mask resist of the present embodiment are the photosensitive resin composition of the present embodiment. It is formed using

  The photosensitive element of the present embodiment comprises a support and a photosensitive layer comprising the photosensitive resin composition of the present embodiment on the support. Preferred examples of the support include resin films having heat resistance and solvent resistance such as polyester resin films such as polyethylene terephthalate, and polyolefin resin films such as polyethylene and polypropylene, and from the viewpoint of transparency, polyethylene terephthalate films It is preferable to use The thickness of the support is preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 1 to 30 μm, in consideration of mechanical strength, good resolution, and the like.

  The photosensitive element of the present embodiment is, for example, carried out on the above-mentioned support by the method such as dipping, spraying, bar coating, roll coating, spin method, etc. of the photosensitive resin composition of the present embodiment. The photosensitive resin composition of the form is applied to a film thickness (after drying: 10 to 200 μm) according to the application to form a coating film, and dried at 70 to 150 ° C. for about 5 to 30 minutes to form a photosensitive layer. Can be obtained.

The permanent mask resist of this embodiment and the printed wiring board equipped with the permanent mask resist are imaged, for example, as follows. First, on a substrate on which a resist is to be formed (for example, a copper-clad laminate for a printed wiring board), a method such as screen printing, spraying, roll coating, curtain coating, electrostatic coating, etc. is used. The photosensitive resin composition of the embodiment is applied to a film thickness (after drying: 10 to 200 μm) according to the application to form a coating, and the coating is dried at 60 to 110 ° C. Alternatively, instead of the coating, 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 on the support is attached onto the substrate, using an atmospheric pressure laminator and a vacuum laminator, as necessary.
After forming a photosensitive layer (coated film) on a substrate, a negative film is brought into direct contact or, preferably, 10 to 1,000 mJ / cm ^{2 of} actinic radiation such as ultraviolet light is irradiated through a transparent film. When a film is used, the film is peeled off, and the unexposed area is dissolved and removed (developed) with a dilute aqueous alkali solution.
Next, the exposed portion is sufficiently cured by post-exposure (ultraviolet exposure) and / or post-heating to obtain a cured film. For example, 800 to 5,000 mJ / cm ² is preferable for the post-exposure, and 30 minutes to 12 hours at 100 to 200 ° C. for the post-heating.

  In the permanent mask resist thus obtained, it is difficult to generate an undercut in which the bottom is dulled, a defect in the top of the resist is not easily generated, and the line widths of the middle part (central part) and the deepest part (bottom) of the pattern cross section However, since it is difficult to increase with respect to the line width of the surface portion, the pattern contour has a good linearity, an excellent resist shape, and an excellent resolution. Further, this permanent mask resist has a pattern excellent in the formation stability of the size of the miniaturized hole diameter and the interval pitch between holes accompanying the miniaturization and high performance of electronic devices in recent years. In addition to PCT resistance (moisture resistance), reflow resistance, electrical insulation (HAST resistance), and electroless plating resistance, the pattern also has heat resistance, solvent resistance, chemical resistance (alkali resistance, acid resistance). And adhesion.

  Hereinafter, the present embodiment will be more specifically described by way of examples, but the present embodiment is not limited by these examples.

Synthesis Example 1: Synthesis of (E) Alkoxypolysiloxane 1
The hydrolysis reaction was allowed to proceed by reacting tetraethoxysilane with water under a temperature condition of 80 ° C. under an acid catalyst. Ethyl alcohol as an organic solvent is added to the solution to dilute it, and a solution (solid content; ethoxypolysiloxane (in the formula (1), R ⁰¹ : ethyl group, Y ⁰¹ : ethoxy group, weight average molecular weight: 18000) is contained; It was 30 mass%), and this was made into (E) alkoxypolysiloxane 1 (sometimes called resin 1 for inorganic filler dispersion).

Synthesis Example 2 Synthesis of (E) Alkoxypolysiloxane 2
The hydrolysis reaction was allowed to proceed by reacting tetrabutoxysilane with water under a temperature condition of 80 ° C. under an acid catalyst. Ethyl alcohol is added as an organic solvent to this to dilute, and a solution containing butoxypolysiloxane (in the formula (1), R ⁰¹ : butyl group, Y ⁰¹ : butoxy group, weight average molecular weight: 20000) (solid content; It was set as 30 mass%), and this was obtained (E) alkoxypolysiloxane 2 (sometimes called resin 2 for inorganic filler dispersion | distribution).

Synthesis Example 3: Synthesis of hydroxyl group-containing vinyl polymer 1
In a flask equipped with a stirrer, a reflux condenser, and a thermometer, 250 parts by mass of carbitol acetate was charged. After the temperature was raised to 100 ° C., the monomers shown in Table 1 and a polymerization initiator were dropped over 2 hours.
After completion of the dropwise addition, the mixture was kept for 1 hour, and a solution of 2 g of 2,2'-azobis (isobutyronitrile) dissolved in 20 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the temperature was kept for 1 hour to complete the polymerization reaction. Next, after cooling to room temperature, carbitol acetate is further added to adjust the heating residue to be 50% (solid content 50%), and may be referred to as hydroxyl group-containing vinyl polymer 1 (resin 3 for inorganic filler dispersion) Got.). Here, room temperature refers to 25 ° C. in this specification.

Synthesis Example 4 Synthesis of Hydroxyl Group-Containing Vinyl Polymer 2
A hydroxyl group-containing vinyl polymer 2 (inorganic filler dispersion resin 4 may be referred to as Synthesis Example 3) in the same manner as in Synthesis Example 3 except that in Synthesis Example 3, the monomers and the polymerization initiator are as shown in Table 2. Got).

(Production Example 1: Production of Inorganic Filler Dispersion 1)
100 parts by mass (solid content: 30%) of (E) alkoxypolysiloxane 1 (resin 1 for inorganic filler dispersion) obtained in Synthesis Example 1, 60 parts by mass of (C) inorganic filler (barium sulfate), and binder 60 parts by mass of epoxy resin (Epikote 828, bisphenol A epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd., trade name)) as a resin, bead mill (zirconia bead particle diameter: 0.5 mm, stirring blade circumferential speed: 10 m / s) The mixture was kneaded for 1 hour to obtain an inorganic filler dispersion 1. The solid content concentration in the obtained inorganic filler dispersant 1 is 68.2% by mass, and P.I. W. C. (Pigment Weight Concentration, the concentration of the inorganic filler relative to the total solid content in the inorganic filler mixture) was 40% by mass. Here, P.I. W. C. Is P. W. C. (Mass%) = inorganic filler (mass part) / solid content in inorganic filler mixture (mass part) × 100 The value calculated by the formula. Moreover, about the inorganic filler dispersion liquid 1, the result of having evaluated the following inorganic filler dispersibility, evaluation of dispersion stability, evaluation of storage stability, and evaluation of coating film performance is shown in Table 3.

(Production Examples 2 to 4, Comparative Production Examples 1 to 4)
With respect to Production Examples 2 to 4 and Comparative Production Examples 1 to 4, using the resin for dispersing the inorganic filler, the inorganic filler, and the binder resin shown in Table 3, in the same manner as in the above Production Example 1, each inorganic filler dispersion 2 To 8 were obtained. With respect to the obtained inorganic filler dispersions 2 to 8, solid content concentration, P.I. W. C. The results of evaluation of inorganic filler dispersibility, evaluation of dispersion stability, evaluation of storage stability, and evaluation of coating film performance described below are shown in Table 3.

(Evaluation of inorganic filler dispersibility (measurement of maximum particle size))
Using the same resin for inorganic filler dispersion and inorganic filler as those used in the above production example and comparative production example shown in Table 3, kneading for 1 hour with a bead mill (zirconia bead particle diameter: 0.5 mm, stirring blade circumference Speed: 10 m / s) to obtain a mixture, and the particle size of the dispersed inorganic filler was measured by a laser diffraction scattering method using a nanoparticle size distribution measuring device (SDLA-7100, manufactured by Shimadzu Corporation) . If it is less than 1 μm, it can be said that excellent dispersibility is obtained. Here, the particle size at an integrated value of 99.9% (volume basis) in the particle size distribution measured by the nanoparticle size distribution measuring device was taken as the maximum particle size.

(Evaluation of dispersion stability)
The epoxy resin shown in Table 3 was further added to the mixture obtained by the evaluation of the inorganic filler dispersibility, and the state of sedimentation of the inorganic filler when visually left at room temperature was visually confirmed and evaluated according to the following criteria .
○ (excellent): No sedimentation of the inorganic filler was observed.
Δ (Good): Although the sedimentation of the inorganic filler was slightly confirmed, there was no problem in practical use.
× (Defective) Precipitation of inorganic filler was confirmed.

(Evaluation of storage stability)
The inorganic filler dispersions obtained in Production Examples 1 to 4 and Comparative Production Examples 1 to 4 were left in an atmosphere at 50 ° C., the appearance of the dispersion was visually confirmed, and evaluated according to the following criteria.
○ (excellent): No change was observed in the inorganic filler dispersion.
Δ (Good): Although some thickening or gelling of the inorganic filler dispersion was confirmed, there was no problem in practical use.
X (defect): Thickening or gelation of the inorganic filler dispersion was confirmed.

(Evaluation of coating film performance)
Inorganic materials obtained in Production Examples 1 to 4 and Comparative Production Examples 1 to 4 in a copper-clad laminated substrate ("MCL-E-67 (trade name)" manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 0.6 mm The filler dispersion was applied by an applicator and dried to obtain a coating of 25 to 35 μm in thickness. The coating film was measured for gloss by using a spectrophotometer at 60 ° gloss, and the coating performance was evaluated.

数 値) The numerical value of the compounding ratio of each component in the table includes components other than solid content (organic solvent), and the unit is mass part. Moreover, the detail of the material in Table 3 is as follows.
Binder resin: Epicoat 828 (bisphenol A epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd., trade name))

Next, photosensitive resin compositions of the following examples and comparative examples were obtained using the inorganic filler dispersions 1 to 8 obtained in each production example and comparative production example, and the following evaluation was performed.
(Evaluation method)
(1) Evaluation of photosensitivity The photosensitive resin composition of each Example and Comparative Example was applied to a 35 μm-thick PET film by an applicator so that the film thickness after drying was 35 μm to form a coating film. . Next, it was dried at 80 ° C. for 20 minutes using a hot air circulating dryer. A 41-step step tablet (manufactured by Hitachi Chemical Co., Ltd.) was disposed on the coating film, and exposed with an exposure amount of 500 mJ / cm ² using an ultraviolet exposure device. Next, spray development was carried out with a 1% by mass aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm ² , and the number of steps of the step tablet of the coating film (cured film) left undeveloped was measured. It evaluated by.
○ (excellent): More than 16 steps remained.
Δ (Good): 10 to 15 stages remained.
X (defect): 9 stages or less remained.

(2) Evaluation of resolution A phototool having a 41-step step tablet (manufactured by Hitachi Chemical Co., Ltd.) and a wiring with a line width / space width of 30/30 to 200/200 (unit: μm) as a negative for resolution evaluation A phototool having a pattern was brought into close contact with the evaluation laminate, and exposed with an energy amount such that the number of remaining steps after development of the 41-step tablet was 17 using the above-described exposure machine. Subsequently, the PET film was peeled off by leaving it at room temperature for 1 hour, and then it was developed by spraying a 30% aqueous 1 mass% sodium carbonate solution for 60 seconds for development, and heated (dried) at 80 ° C for 10 minutes. Here, the resolution was evaluated by the smallest value (unit: μm) of the space width between the line widths at which a rectangular resist shape was obtained by the development processing. The resist shape was observed by magnifying 1000 times using a microscope. The smaller this value is, the better the resolution is.

(3) Evaluation of adhesion A copper-clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 0.6 mm obtained by buffing (roughening 5 μm in the depth direction) the copper surface and the copper surface Were chemically polished (roughened in the direction of depth by 0.5 μm using an abrasive (CZ 8101, manufactured by Mec Co., Ltd.)), and the copper-clad laminate substrate (MCL-E-67, Hitachi Chemical Co., Ltd.). The photosensitive resin compositions of Examples and Comparative Examples are applied by screen printing on each of the copper-clad laminate substrates to a dry thickness of 35 μm to form a coating, and then a hot air circulation system is used. It was dried at 80 ° C. for 20 minutes using a drier. Then, it has the pattern shown in FIG. 1 with the size of the hole diameter and the spacing pitch between the holes (hole diameter 100 μm / hole spacing pitch 100 μm or hole diameter 80 μm / hole spacing 80 μm) A negative mask was placed on the coated film, and exposed with an exposure dose of 600 mJ / cm ² using an ultraviolet exposure device. Thereafter, spray development was performed for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) using a 1% by mass aqueous solution of sodium carbonate to dissolve and develop an unexposed area. Next, it exposed by the exposure amount of 1000 mJ / cm < ² > using the ultraviolet exposure device, heated at 150 degreeC for 1 hour, and produced the test piece.
About the obtained test piece, according to JISK5600-5-6 (1999), 100 1-mm grid squares were produced and the peeling test was done by cellophane tape. The peeled state of the grids was visually observed and evaluated according to the following criteria.
○ (excellent): There was no peeling at 90/100 or more.
Δ (Good): No peeling at 50/100 or more and less than 90/100.
X (defect): There was no peeling at less than 0/100 to 50/100.

(4) Evaluation of solder heat resistance Drying on a copper-clad laminate substrate ("MCL-E-67 (trade name)" manufactured by Hitachi Chemical Co., Ltd.) having a size of 50 cm x 50 cm and a thickness of 0.6 mm. The photosensitive resin composition of each of the examples and comparative examples is applied by screen printing to form a coating having a thickness of 35 μm, and then a coating is formed using a hot air circulating dryer for 20 minutes at 80 ° C. It was allowed to dry. Then, it has the pattern shown in FIG. 1 with the size of the hole diameter and the spacing pitch between the holes (hole diameter 100 μm / hole spacing pitch 100 μm or hole diameter 80 μm / hole spacing 80 μm) A negative mask was placed on the coating, and exposed using a UV exposure device at an exposure of 600 mJ / cm ² . Thereafter, spray development was performed for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) using a 1% by mass aqueous solution of sodium carbonate to dissolve and develop an unexposed area. Next, exposure (post-exposure) was performed at an exposure dose of 1000 mJ / cm ² using an ultraviolet exposure apparatus, and heating was performed at 150 ° C. for 1 hour to prepare a test piece.
A non-cleaning type flux ("RMA SR-209 (trade name)", manufactured by Senju Metal Industry Co., Ltd.) was applied to the obtained test piece, and immersed in a solder bath set at 260 ° C for 10 seconds. After immersion for 10 seconds, the test piece was removed from the solder bath and allowed to cool to room temperature. After repeating immersion for 10 seconds and six times, the film appearance was visually observed and evaluated according to the following criteria.
○ (excellent): No change in appearance of the resist coating was observed, and no solder was dripped between the substrate and the mask resist.
Δ (Good): Peeling, blistering of the coating of the resist, or solder pitting was slightly confirmed, but there was no problem in practical use.
X (defect): blistering or peeling of the coating of the resist, or boring of the solder was confirmed.

(5) Thermal shock resistance 1000 cycles of thermal history were added to the test piece obtained in the same manner as the evaluation of solder heat resistance in (4) above, and then the test piece was visually observed and 1000 using a microscope. It observed by magnifying twice. Here, the heat history of one cycle was a heat history of −55 ° C. for 30 minutes and then 125 ° C. for 30 minutes.
○ (excellent): no crack was found at all.
Δ (Good): Although a slight crack was confirmed, it was a practically acceptable level.
X (defect): A crack was confirmed to such an extent that a problem occurs in practical use.

(6) Developability The photosensitive resin composition of each example and comparative example is applied by screen printing on one side of a copper foil substrate on which a copper pattern is formed (pitch: 100 μm), and the temperature is 80 ° C. Dried for 30 minutes. Then, after cooling to room temperature, development was carried out for 30 seconds under the conditions of a spray pressure of 2 kg / cm ^{2 and} a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. The presence or absence of the undeveloped portion of the dried coating was visually confirmed, and the developability was evaluated based on the following criteria.
((Excellent): less than 1% of the coating film remained, but the majority was developed.
Δ (Good): 1 or more and less than 5% of the coating film remained.
X (defect): 5% or more remained as a coating film.

(7) Electroless gold plating solution property The following electroless nickel / gold plating was given to the test piece obtained by carrying out similarly to evaluation of the solder heat resistance of said (4). Electroless nickel / gold plating is a degreasing process (5 minutes immersion), water washing process and soft etching process (2 minutes immersion), water washing process and pickling process (3 minutes immersion), water washing process and pre-dip process (90 seconds immersion) ), Electroless nickel plating step (23 minutes treatment), water washing step and electroless gold plating step (15 minutes treatment), water washing step, and drying step in this order. The materials used for each step of electroless nickel / gold plating are as follows.
Degreasing process: 25% by mass aqueous solution soft etching process of PC-455 (Meltex Co., Ltd., trade name): Aqueous solution pickling process of ammonium persulfate 150 g / L: 5% by volume sulfuric acid aqueous solution electroless nickel plating process: Nimden NPF-2 (Manufactured by Uemura Kogyo Co., Ltd., product name)
Electroless gold plating process: Gobright TIG-10 (made by Uemura Kogyo Co., Ltd., trade name)

Immediately after the drying step, Sellotape (registered trademark) is applied to the surface of a flexible printed substrate (FPC substrate) subjected to electroless nickel / gold plating, and this is peeled off vertically (90 ° peel-off test), permanent The plating resistance (peeling) was evaluated by visually observing the presence or absence of peeling of the mask resist.
In addition, when gold plating is present at the interface between the substrate and the permanent mask resist, gold plating deposited at the interface is observed. After the electroless nickel / gold plating, the interface was visually observed through a transparent permanent mask resist to evaluate the plating resistance.
○ (excellent): Gold plating was not confirmed.
Δ (Good): The gold plating pit was less than 10 μm, and there was no problem in practical use.
X (defect): The gold plating pit became 10 μm or more.

(8) Evaluation of Electrical Insulating Property (HAST Resistance) On a bismaleimide triazine substrate (BT substrate) on which a comb-shaped electrode (line / space = 10 μm / 10 μm) is formed, the film thickness after drying is 35 μm. The photosensitive resin compositions of the respective Examples and Comparative Examples were applied by screen printing to form a coating, and then dried using a hot air circulation drier at 80 ° C. for 20 minutes. Next, it was exposed at an exposure dose of 1000 mJ / cm ² using an ultraviolet exposure device, and heated at 150 ° C. for 1 hour to prepare a test piece having a cured coating of the photosensitive resin composition on a BT substrate. This test piece was placed in a high temperature and high humidity tank under an atmosphere of 130 ° C. and humidity 85%, charged with a voltage of 5 V, and subjected to an in-tank HAST test for 168 hours. The in-tank insulation resistance value after 168 hours was evaluated according to the following criteria.
5:10 ⁸ Omega than 4:10 less ⁷ Omega than 10 ⁸ Ω 3:10 1:10 than ⁵ Omega than ⁶ Omega than 10 ⁷ Omega less than 2:10 ⁵ Omega least 10 ⁶ Omega

Synthesis Example 5 Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Resin 11a
Cresol novolac epoxy resin (manufactured by Toto Kasei Co., Ltd., “YDCN 700-7 (trade name)”, general formula (11), Y ¹¹ = glycidyl group, R ¹¹ = methyl group) 220 parts by mass, acrylic acid 72 parts A part, 1.0 parts by mass of hydroquinone and 180 parts by mass of carbitol acetate were mixed, heated to 90 ° C. and stirred to dissolve the reaction mixture. Then, after cooling to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was mixed, and the mixture was further heated to 100 ° C. to react until the solid content acid value was 1 mg KOH / g. Then, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of carbitol acetate were mixed, heated to 80 ° C., and stirred for 6 hours. After cooling to room temperature, it was diluted with carbitol acetate so that the solid content concentration would be 60% by mass, to obtain an acid-modified vinyl group-containing epoxy resin 11a.

Synthesis Example 6 Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Resin 11b
Phenolic novolac epoxy resin (manufactured by DIC Corporation, "N770 (trade name)", 220 parts by mass of Y ¹¹ = glycidyl group, R ¹¹ = methyl group in the general formula (11), 72 parts by mass of acrylic acid, hydroquinone One part by mass and 180 parts by mass of carbitol acetate were mixed, heated to 90 ° C. and stirred to dissolve the reaction mixture. Then, after cooling to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was mixed and heated to 100 ° C. to react until the acid value became 1 mg KOH / g. Then, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of carbitol acetate were mixed, heated to 80 ° C., and stirred for 6 hours. After cooling to room temperature, it was diluted with carbitol acetate so that the solid content concentration would be 60 mass%, to obtain an acid-modified vinyl group-containing epoxy resin 11 b.

Synthesis Example 7 Synthesis of Acid-Modified Vinyl-Containing Epoxy Resin 12
Bisphenol F type epoxy resin (made by Tohto Kasei Co., Ltd., “YDF 2001 (trade name)”, general formula (12), Y ¹² = glycidyl group, R ¹² = H) 500 parts by mass, acrylic acid 72 parts by mass, hydroquinone 0.5 parts by mass and 150 parts by mass of carbitol acetate were mixed, heated to 90 ° C. and stirred to dissolve the reaction mixture. Then, after cooling to 60 ° C., 2 parts by mass of benzyltrimethylammonium chloride was mixed and heated to 100 ° C. to react until the acid value became 1 mg KOH / g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of carbitol acetate were mixed, heated to 80 ° C., and stirred for 6 hours. After cooling to room temperature, it was diluted with carbitol acetate so that the solid content concentration would be 60% by mass, to obtain an acid-modified vinyl group-containing epoxy resin 12.

Synthesis Example 8 Synthesis of Acid-Modified Vinyl-Containing Epoxy Resin 14
In a flask provided with a thermometer, a dropping funnel, a condenser and a stirrer, 272 parts by mass of bis (4-hydroxyphenyl) methane dissolved at 80 ° C. was charged, and the stirring was started at 80 ° C. To this, 3 parts by mass of methanesulfonic acid was added, and 16.3 parts by mass of paraformaldehyde (92% by mass) was dropped over 1 hour so as to maintain the liquid temperature in the range of 80 to 90 ° C. After the addition was completed, the mixture was heated to 110 ° C. and stirred for 2 hours. Next, 1000 parts by mass of methyl isobutyl ketone was added, transferred to a separatory funnel and washed with water. After continuing washing with water until the wash water shows neutrality, the solvent and unreacted bis (4-hydroxyphenyl) methane are removed from the organic layer under heating and reduced pressure (temperature: 220 ° C., pressure: 66.7 Pa), 164 parts by mass of bisphenol novolac resin as a brown solid was obtained. The softening point of the obtained bisphenol novolak resin was 74 ° C., and the hydroxyl equivalent was 154 g / eq.
154 parts by mass of bisphenol type novolak resin obtained, 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol, and tetraethylbenzyl while purging nitrogen gas in a flask provided with a thermometer, a dropping funnel, a condenser and a stirrer Two parts by mass of ammonium chloride were mixed and dissolved. Next, this was heated to 65 ° C. and depressurized to an azeotropic pressure, and then 90 parts by mass of an aqueous sodium hydroxide solution (49 mass%) was added dropwise over 5 hours with a constant dropping speed, and stirred for 30 minutes. During this time, the azeotropically distilled distillate was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to a flask (reaction system). Thereafter, 590 parts by mass of methyl isobutyl ketone and 177 parts by mass of n-butanol are added to a crude epoxy resin obtained by distilling off unreacted epichlorohydrin by vacuum distillation (temperature: 22 ° C., pressure: 1.87 kPa) It was dissolved. Next, 10 parts by mass of an aqueous solution of sodium hydroxide (10% by mass) was added, and the mixture was stirred at 80 ° C. for 2 hours. Furthermore, water washing was repeated three times with 150 parts by mass of water. It was confirmed that the pH of the washing solution used in the third water washing was neutral. Next, the inside of the flask (inside the reaction system) was dehydrated azeotropically, and after precision filtration was performed, the solvent was distilled off under reduced pressure (pressure: 1.87 kPa). Thus, a bisphenol-based novolac epoxy resin used in this embodiment, which is a brown viscous liquid (epoxy resin having a structural unit of Y ¹⁴ = glycidyl group, R ¹³ = H in the general formula (14) Obtained (a). 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 ° C., 2 parts by mass of benzyltrimethylammonium chloride was mixed and heated to 100 ° C. to react until the acid value became 1 mg KOH / g. Next, 230 parts by mass of tetrahydrophthalic anhydride and 180 parts by mass of carbitol acetate were mixed, heated to 80 ° C., and reacted for 6 hours. Subsequently, after cooling to room temperature, it was diluted with carbitol acetate so that the solid content concentration would be 60 mass%, to obtain an acid-modified vinyl group-containing epoxy resin 14.
In addition, the softening point of resin was measured based on the ring and ball method defined in JIS-K7234: 1986 (temperature rising rate: 5 ° C./min), and the acid value of the resin was measured by neutralization titration method. Specifically, after 30 g of acetone is added to 1 g of acid-modified vinyl group-containing epoxy resin and dissolved uniformly, an appropriate amount of phenolphthalein as an indicator is added to a solution containing the acid-modified vinyl group-containing epoxy resin It measured by performing titration using 0.1 N potassium hydroxide aqueous solution.

Examples 1 to 6 and Comparative Examples 1 to 6
The composition was compounded according to the composition shown in Table 4 and kneaded with a three-roll mill to prepare a photosensitive resin composition. Carbitol acetate was added to a solid content concentration of 70% by mass to obtain a photosensitive resin composition. It evaluated based on said (evaluation method) using the obtained photosensitive resin composition. The evaluation results are shown in Table 4. In addition, the unit of the compounding quantity of each component in Table 4 is a mass part, and the compounding quantity of (A) component contains the epoxy resin and solvent (carbitol acetate) obtained by said each synthesis example. Means quantity.

* 1, Compounding amount of solution containing epoxy resin (solid content concentration: 60% by mass).
数 値) The numerical values of each component in the table include components (organic solvents etc.) other than solid content, and the unit is parts by mass. The total solid content is the total amount (parts by mass) of the solid content contained in components (A) to (F), the binder resin contained in the inorganic filler dispersion, and the epoxy resin contained as a curing agent (epicoat in the table 828) is added. Moreover, the detail of each material in Table 4 is as follows.
Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (manufactured by BASF Japan Ltd., trade name)
Irgacure 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
Kayarad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name)
Epicoat 828: Bisphenol A epoxy resin (product name of Japan Epoxy Resins Co., Ltd.)

From the results shown in Table 4, the photosensitive resin compositions of the present embodiment of Examples 1 to 6 have excellent photosensitivity (photocurability), resolution, and adhesiveness, and a permanent mask resist (solder) Even if it is a high-definition pattern, the size of the hole diameter of the resist and the spacing pitch between the holes (hole size 100 μm / hole spacing 100 μm or hole size 80 μm / hole spacing 80 μm) It was confirmed that the toner was excellent in developability, or various performances such as heat resistance, thermal shock resistance, electroless plating resistance, and electrical insulation (HAST resistance).
On the other hand, Comparative Examples 1 to 4 are inferior in resolution, thermal shock resistance, resistance to electroless gold plating, electrical insulation (HAST resistance), and also tend to deteriorate adhesion and developability. It was confirmed that there is.

  According to the present embodiment, a pattern having excellent resolution can be formed, and in addition to heat resistance, adhesion, mechanical properties, and electrical properties, the PCT resistance (moisture resistance) required along with the miniaturization of the pitch Photosensitive resin composition capable of forming a pattern excellent in reflow resistance, electrical insulation (HAST resistance), resistance to electroless plating, solder heat resistance, etc., size of minute holes and spacing pitch between holes It is possible to obtain a permanent mask resist which is excellent in formation stability and capable of being patterned. The permanent mask resist is suitably used for a printed wiring board, and is particularly suitably used for a printed wiring board having a size of a miniaturized hole diameter and a spacing pitch between holes due to recent miniaturization and high performance.

Claims (14)

(A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, (C) an inorganic filler, (D) a photopolymerizable compound, and (E) an alkoxypolysiloxane; Ri Monodea the siloxane was hydrolyzed silane compound represented by the following general formula (2), the weight average molecular weight of the (E) alkoxy polysiloxane, Ru der 3,000 to 50,000, a photosensitive resin composition object.

[R ⁰¹ represents an alkyl group, an aryl group or an aralkyl group, Y ⁰¹ represents an alkoxy group represented by —OR ⁰² , R ⁰² represents an alkyl group, and n ₀₁ represents an integer of 2 to 4 . The plurality of R ⁰¹ , R ⁰² and Y ⁰¹ may be the same or different, and at least one of R ⁰¹ is an alkyl group. ] The photosensitive resin composition according to claim 1, wherein at least one of R ⁰¹ is an alkyl group having 1 to 5 carbon atoms. (A) The acid-modified vinyl group-containing epoxy resin is an epoxy resin having a constitutional unit represented by the general formula (11), an epoxy resin having a constitutional unit represented by the general formula (12), represented by a general formula (13) At least one epoxy selected from an epoxy resin having a structural unit, a bisphenol novolac epoxy resin having a structural unit represented by General Formula (14), and a bisphenol novolac epoxy resin having a structural unit represented by General Formula (15) Obtained by reacting a resin (a ') obtained by reacting a resin (a) with a vinyl group-containing monocarboxylic acid (b) and a saturated group or unsaturated group-containing polybasic acid anhydride (c) the photosensitive resin composition according to claim 1 or 2 is resin.

[In formula (11), R ¹¹ represents a hydrogen atom or a methyl group, Y ¹¹ represents a hydrogen atom or a glycidyl group, and the molar ratio of hydrogen atom to glycidyl group is 0/100 to 30/70, n ₁₁ represents an integer of 1 or more. In addition, at least one Y ¹¹ represents a glycidyl group, a plurality of R ¹¹ may be the same or different, and when n ₁₁ is 2 or more, a plurality of Y ¹¹ may be the same or different. ]

[In the formula (12), R ¹² represents a hydrogen atom or a methyl group, Y ¹² represents a hydrogen atom or a glycidyl group, and the molar ratio of hydrogen atom to glycidyl group is 0/100 to 30/70, n ₁₂ represents an integer of 1 or more. In addition, at least one Y ¹² represents a glycidyl group, a plurality of R ¹² may be the same or different, and when n ₁₂ is 2 or more, a plurality of Y ¹² may be the same or different. ]

[In formula (13), Y ¹³ represents a hydrogen atom or glycidyl group, and the molar ratio of hydrogen atom to glycidyl group is 0/100 to 30/70, and n ₁₃ represents an integer of 1 or more. In addition, at least one Y ¹³ represents a glycidyl group, and a plurality of Y ¹³ may be the same or different. ]

[In Formula (14), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ¹⁴ represents a hydrogen atom or a glycidyl group, and n ₁₄ represents an integer of 1 or more Indicates At least one Y ¹⁴ represents a glycidyl group, and a plurality of R ¹³ may be the same or different. ]

[In Formula (15), R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a sulfone group, or a trihalomethyl group, Y ¹⁵ represents a hydrogen atom or a glycidyl group, and n ₁₅ is an integer of 1 or more Indicates At least one Y ¹⁵ represents a glycidyl group, and a plurality of R ¹⁴ may be the same or different. ] Epoxy resin (a) has an epoxy resin having a structural unit represented by general formula (11), an epoxy resin having a structural unit represented by general formula (12), and a structural unit represented by general formula (14) The photosensitive resin composition according to claim 3 , which is at least one selected from bisphenol novolac epoxy resins. The photosensitive resin composition according to any one of claims 1 to 4 , wherein the photopolymerizable compound (D) is a compound containing a (meth) acryloyl group. Furthermore, the photosensitive resin composition in any one of the Claims 1-5 containing the (F) pigment. The photosensitivity according to any one of claims 1 to 6 , wherein the content of the photopolymerizable compound (D) is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. Resin composition. The photosensitive resin composition according to any one of claims 1 to 7 , wherein the content of the (E) alkoxypolysiloxane is 1 to 40 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. . The photosensitive resin composition according to any one of claims 1 to 8 , which is liquid. The photosensitive resin composition in any one of the Claims 1-9 used for formation of a permanent mask resist. The photosensitive element provided with a support body and the photosensitive layer which uses the photosensitive resin composition in any one of Claims 1-10 on this support body. The permanent mask resist formed of the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive element according to claim 11. A printed wiring board comprising the permanent mask resist according to claim 12 . Step (1): (C) mixing an inorganic filler and (E) alkoxypolysiloxane to obtain an inorganic filler mixture,
Step (2) mixing the (A) acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, (D) a photopolymerizable compound, and the inorganic filler mixture,
And the (E) alkoxypolysiloxane is a product obtained by hydrolyzing a silane compound represented by the following general formula (2), and the weight-average molecular weight of the (E) alkoxypolysiloxane is 3,000 to 50,000. The manufacturing method of the photosensitive resin composition which is.

[R ⁰¹ Represents an alkyl group, an aryl group or an aralkyl group; ⁰¹ Is -OR ⁰² Represents an alkoxy group represented by ⁰² Represents an alkyl group, n ₀₁ Represents an integer of 2 to 4. Multiple R ⁰¹ , R ⁰² , And Y ⁰¹ May be the same or different, R ⁰¹ Is at least one alkyl group. ]