JP6582804B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition.

  In the field of manufacturing a printed wiring board, a permanent mask resist is formed on the printed wiring board. The permanent mask resist has a role of preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers when the printed wiring board is used. In recent years, permanent mask resists prevent solder from adhering to unnecessary portions of a conductor layer of a printed wiring board in a process of flip chip mounting, wire bonding mounting or the like of a semiconductor element on the printed wiring board via solder. It also has a role as a solder resist film.

  Conventionally, the permanent mask resist in printed wiring board manufacture has been produced by screen printing using a thermosetting resin composition and an ultraviolet curable resin composition. In the method by screen printing of this resin composition, bleeding, sagging and the like occur during printing, and thus it is difficult to produce a high-definition pattern. Therefore, in the conventional method by screen printing of the resin composition, the permanent mask according to the high-definition of the wiring pattern and the insulating pattern in the printed wiring board accompanying the downsizing, weight reduction and high performance of the electronic equipment in recent years It is difficult to form a resist, and it is not possible to sufficiently meet the demand for higher definition.

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

  When using a dry film type photo-curing resist, air is easily engulfed during thermocompression bonding to the base material, air bubbles are likely to be generated, the adhesion between the resist layer and the base material is reduced, or the resist pattern is disturbed. There is concern about the decline. Therefore, the use of a liquid type photocurable resist instead of a dry film type has been studied. The liquid-type photocurable resist is roughly classified into a solvent development type and an alkali development type, but the alkali development type is mainly used from the viewpoints of work environment conservation and global environment conservation. Such an alkali development type liquid photocurable resist has been proposed which improves the heat resistance, chemical resistance and electrical properties of the coating film (for example, Patent Document 1).

  However, in the alkali development type liquid photocurable resist proposed in Patent Document 1, heat resistance and PCT resistance (pressure cooker test resistance) (hereinafter referred to as pressure cooker test resistance) (hereinafter referred to as “high pressure cooker resistance”) have been demanded. In some cases, practical characteristics such as resistance to moisture and heat are not sufficiently satisfied. Alkaline development type liquid photo-curable resists are mainly composed of a hydrophilic group in order to enable alkali development. Therefore, chemicals and water easily penetrate into the resist layer, It is considered that practical characteristics of an excellent resist layer cannot be obtained.

  By the way, along with the downsizing, weight reduction, and high performance of electronic devices, there is an urgent need for downsizing of semiconductor packages, practical application of high pin count, and mass production. For example, semiconductor package substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) mounted on electronic components are required to have high reliability. Moreover, in order to achieve high reliability, PCT resistance (moisture heat resistance) is required. However, the conventional liquid-type photocurable resist proposed in Patent Document 1 and the like can withstand practical use only for several hours to several tens of hours under a severe environment (high temperature and high humidity environment) used for PCT resistance evaluation. Therefore, further improvement in PCT resistance (moisture heat resistance) is demanded.

Also, the mounting method is changed from the conventional insertion mounting to surface mounting such as FC (Flip Chip), TAB (Tape Automated Bonding), COF (Chip On Film), etc. Such temperature tends to increase. In the case of surface mounting, more specifically, the solder is reflowed and fixed, that is, cream solder is printed in advance on the necessary part, and the entire printed solder is heated in a high-temperature furnace such as infrared rays to melt the solder and surface Since the mounting component and the substrate are soldered, the temperature reached inside and outside the package is extremely high at 220 to 280 ° C. (for example, Patent Document 2).
However, when exposed to a high temperature in this way, the conventional liquid-type photo-curable resist has reduced reflow resistance, in which the coating film is cracked or peeled off from the substrate or the sealing material due to thermal shock. There is a problem of further improvement, and further improvement is required. In addition, lead-free solder is being promoted from the viewpoint of global environmental conservation. Lead-free solder has a higher melting temperature than conventional solder. Therefore, excellent solder heat resistance is required for the permanent mask resist.

As the wiring pattern and insulation pattern (permanent mask resist) on the printed wiring board become more precise, the spacing pitch between the wirings has become finer, so excellent electrical insulation between the wirings (especially 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 employ | 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 exhibits strong alkalinity, and the temperature of the solution is increased to about 90 ° C. in order to improve the plating deposition rate, damage to the permanent mask resist tends to increase. Therefore, the permanent mask resist is required to further improve the electroless plating resistance, which is resistant to damage by the plating solution used for electroless plating.

JP-A-1-141904 JP 2005-250004 A JP 2006-190848 A

The object of the present invention has been made in view of such problems, and can form a pattern having excellent resolution, and in addition to heat resistance, adhesion, mechanical properties, and electrical properties, the pitch can be made finer. It is to provide a photosensitive resin composition excellent in PCT resistance (moisture heat resistance), reflow resistance, electrical insulation (HAST resistance), electroless plating resistance, solder heat resistance, and the like that are required.
In addition, by using the photosensitive resin composition of the present invention, it was excellent in the miniaturization of electronic devices in recent years, and the formation stability of the finer hole diameter and the pitch between the holes due to higher performance, It is an object of the present invention to provide a permanent mask resist capable of pattern formation and a printed wiring board having the permanent mask resist.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problem can be solved by the following invention. 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) a siloxane bond-containing vinyl polymer, ) A photosensitive resin composition in which the siloxane bond-containing vinyl polymer is obtained from the monomer 1 represented by the following general formula (1).

[In the formula (1), R ⁰¹ represents a hydrogen atom or a methyl group, R ⁰² and R ⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and R ⁰³ represents a hydrogen atom or a halogen atom. Or an alkoxy group, Z ⁰¹ represents a —COO— bond or an arylene group, Z ⁰² represents a divalent organic group, m ₀₁ represents an integer of 1 to 20, and m ₀₂ represents an integer of 1 to 3. R ⁰³ when m ₀₂ is 1 is an alkoxy group, and at least one R ⁰³ when m ₀₂ is 2 or 3 is an alkoxy group. A plurality of R ^{02 to} R ⁰⁴ may be the same or different. ]
2. Furthermore, the photosensitive resin composition of said 1 containing (F) pigment.
3. A photosensitive element provided with a support body and the photosensitive layer which uses the photosensitive resin composition of said 1 or 2 on this support body.
4). 3. A permanent mask resist formed by the photosensitive resin composition described in 1 or 2 above or the photosensitive element described in 3 above.
5. 5. A printed wiring board comprising the permanent mask resist as described in 4 above.

  According to the present invention, it is possible to form a pattern with excellent resolution, and in addition to heat resistance, adhesion, mechanical properties, and electrical properties, PCT resistance (moisture heat resistance) required along with finer pitches, Photosensitive resin composition excellent in reflow resistance, electrical insulation (HAST resistance), electroless plating resistance, solder heat resistance, etc., photosensitive element using the same, permanent mask resist, and permanent mask resist A 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 the embodiment of the present invention (hereinafter may be simply referred to as the present embodiment) includes (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, and (C). It contains an inorganic filler, (D) a photopolymerizable compound, and (E) a siloxane bond-containing vinyl polymer, and the (E) siloxane bond-containing vinyl polymer has a specific structure. Each component will be 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). (A) The acid-modified vinyl group-containing epoxy resin is not particularly limited as long as the epoxy resin is modified with a vinyl group-containing organic acid, and the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) are used. Epoxy resin (a ′) obtained by reaction, and epoxy resin (a ″) obtained by reacting the epoxy resin (a ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c) Is preferred.

  As an epoxy resin (a), the epoxy resin which has a structural unit shown by the 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 formulas is demonstrated.

  First, as an epoxy resin (a), the epoxy resin which has a structural unit shown by following General formula (11) is mentioned preferably, As a novolak-type epoxy resin which has such a structural unit, general formula ( The novolak type epoxy resin shown by 11 ') is mentioned preferably.

In the general 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 the hydrogen atom to the 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 a glycidyl group. The plurality of R ¹¹ may be the same or different, and when n ₁₁ is 2 or more, the 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 the 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, and further preferably 95% by mass or more. .

  Preferred examples of the novolac type epoxy resin represented by the general formula (11 ′) having the structural unit represented by the general formula (11) include a phenol novolac type epoxy resin and a cresol novolac type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting a phenol resin such as a phenol novolak resin or a cresol novolak resin with an epihalohydrin such as epichlorohydrin by a known method.

  Examples of the novolak type epoxy resin represented by the general formula (11 ′) include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, and YDPN-602 (and above, NSSMC). Chemical Co., Ltd., trade name), DEN-431, DEN-439 (Dow Chemical Co., Ltd., 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 structural unit represented by the general formula (12) is preferably exemplified. As the epoxy resin having such a structural unit, for example, a bisphenol represented by the general formula (12 ′) A type epoxy resin and bisphenol F type epoxy resin are preferably mentioned.

In 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 the hydrogen atom to the glycidyl group is 0/100 to 30 / 70, preferably 0/100 to _{10/90, n 12} represents an integer of 1 or more. As can be seen from the molar ratio of hydrogen atoms to glycidyl groups, at least one Y ¹² represents a glycidyl group. The plurality of R ¹² may be the same or different, and when n ₁₂ is 2 or more, the 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, a resist pattern that is superior in the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.
In the epoxy resin having the structural unit represented by the general formula (12), the content of the structural unit is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. .

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

In General Formula (16), R ¹² and n ₁₂ are the same as described above.

  The amount of epihalohydrin used is such that the resist pattern, resolution, coating strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, and excellent resist pattern due to the balance of resolution 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 between the epoxy resin represented by the general formula (16) and epihalohydrin. Preferred examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, and the like, and alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide are preferable. More preferable from the viewpoint of catalytic activity. Moreover, it is preferable that the usage-amount is 0.9-2 mol with respect to 1 mol of hydroxyl groups in the epoxy resin shown by General formula (16).

  In the reaction of the epoxy resin represented by the general formula (16) and epihalohydrin, from the viewpoint of further increasing the reaction rate, examples of the organic solvent include alcohols such as methanol and ethanol; cellosolves such as methyl cellosolve and ethyl cellosolve; It is preferable to use ethers such as dioxane; polar organic solvents such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide. Among these, one kind can be used alone, or two or more kinds can be used in combination. From the viewpoint of polarity adjustment, two or more kinds are preferably used 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 reaction time are within the above ranges, the reaction is unlikely to be slow and side reactions are unlikely to occur.

After the above reaction, preferably, unreacted epihalohydrin, organic solvent, and the like are distilled off by distillation under heating and reduced pressure to obtain an epoxy resin represented by the general formula (12 ′).
Further, from the viewpoint of obtaining a higher purity epoxy resin, the obtained epoxy resin can be dissolved again in an organic solvent, and a basic catalyst such as the above alkali metal hydroxide can be added and reacted. At this time, from the viewpoint of increasing the reaction rate, it is preferable to use a phase transfer catalyst such as a quaternary ammonium salt or a crown ether in a range of 0.1 to 3% by mass with respect to the epoxy resin. In this case, a high-purity epoxy resin can be obtained by removing the salt and the like generated after completion of the reaction by filtration or washing with water, and further distilling off the organic solvent and the like under heating and reduced pressure.

  Examples of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (12 ′) include, for example, Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (and above, Mitsubishi Chemical). (Trade name), DER-330, DER-301, DER-361 (above, manufactured by Dow Chemical Co., Ltd., trade name), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name) 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, general formula (13 ') is mentioned, for example. The triphenolmethane type epoxy resin shown is preferable.

In the general formulas (13) and (13 ′), Y ¹³ represents a hydrogen atom or a glycidyl group, and the molar ratio of the hydrogen atom to the glycidyl group is preferably 0/100 to 30/70, and n ₁₃ is 1 The above integers are shown. As can be seen from the molar ratio of hydrogen atom to glycidyl group, at least one Y ¹³ represents a glycidyl group. A plurality of Y ³ may be the same or different.

n ₁₃ 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 ₁₃ 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 the structural unit represented by the general formula (13), the content of the structural unit is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by 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) and the like are commercially available. It is available.

  Preferred examples of the epoxy resin (a) include bisphenol novolac type epoxy resins having a structural unit represented by the general formula (14).

In the 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 is 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.

The alkyl group for R ^13, preferably has 1 to 20 carbon atoms, more preferably those having 1 to 12 carbon atoms, more preferably from 1 to 3. The alkyl group may be linear or branched and may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a sec-pentyl group, an isopentyl group, and a neopentyl group. Among them, a methyl group is preferable.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a 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 with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.
The aralkyl group is not particularly limited as long as one of the above alkyl groups is substituted with the above aryl group, and is preferably an aralkyl group having 7 to 20 carbon atoms, such as benzyl group, phenyl Examples thereof include an ethyl group, a phenylpropyl group, a naphthylmethyl group, and the like, which may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.

n ₁₄ 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 ₁₄ 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 the structural unit represented by the general formula (14), the content of the structural unit is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. .

  Moreover, as an 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 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. 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, a resist pattern that is superior in the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained.
In the epoxy resin having the structural unit represented by the general formula (15), the content of the structural unit is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. .

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

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

In general formula (17), R ¹³ and n ₁₄ are the same as R ¹³ and n ₁₄ in general formula (14). In general formula (18), R ¹⁴ and n ₁₅ are the same as those in general formula (14). R ¹⁴ in formula (15) is the same as n ₁₅ .

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

  Here, the bisphenol compound is not particularly limited as long as it is a compound having two hydroxyphenyl groups. For example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, Preferred examples include bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, and bisphenol Z.

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

  Examples of the sulfonic acid having an alkyl group having 1 to 4 carbon atoms in the molecular structure include alkane sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, and butane sulfonic acid, and fluorine atoms in the alkane portion. Preferred are perfluoroalkanesulfonic acids having the following.

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

  Here, the water-insoluble organic solvent preferably has a boiling point of 100 to 130 ° C. from the viewpoint of improving the efficiency of extraction, washing and neutralization, butanol, pentyl alcohol, methoxyethanol, ethoxyethanol, diethylene glycol, And methyl isobutyl ketone.

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

As the epoxy resin (a), an epoxy resin having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) from the viewpoint of excellent process tolerance and improved solvent resistance. Preferred is an epoxy resin having a bisphenol novolac type epoxy resin having a structural unit represented by the general formula (IV), a novolak type epoxy resin represented by the general formula (I '), and a bisphenol A represented by the general formula (II') Type epoxy resin, bisphenol F type epoxy resin represented by general formula (II ′), bisphenol novolak A type epoxy resin having a structural unit represented by general formula (IV), and structure represented by general formula (IV) A bisphenol novolac F type epoxy resin having a unit is more preferable.
Further, from the viewpoint of further reducing 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 has.

  Examples of the vinyl group-containing monocarboxylic acid (b) to be reacted with the epoxy resin (a) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid. , Cinnamic acid, crotonic acid, acrylic acid derivatives such as α-cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing acrylate and dibasic acid anhydride, vinyl group-containing monoglycidyl ether or vinyl group-containing monoglycidyl Preferable examples include a half-ester compound which is a reaction product of an ester and a dibasic acid anhydride.

  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 half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) include 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 examples include acrylate, vinyl glycidyl ether, glycidyl (meth) acrylate and the like.

  As a dibasic acid anhydride used for the synthesis of the half ester compound, one containing a saturated group or one containing an unsaturated group can be used. Specific examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Preferred are acid, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b), the vinyl group-containing monocarboxylic acid (b) is 0.6 to 1 with respect to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to make it react by the ratio used as 1.05 equivalent, and it is more preferable to make it react by the ratio used as 0.8-1.0 equivalent. It is preferable to react at such a ratio because the photopolymerizability is improved, that is, the photosensitivity is further improved.

The reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be performed 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 and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate; aliphatic carbonization such as octane and decane Hydrogen: petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha are preferred.

  Furthermore, it is preferable to use a catalyst to promote the reaction. Preferred examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, and triphenylphosphine. 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 amount used is preferable because the reaction between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) is promoted.

  A polymerization inhibitor is preferably used 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 amount used is preferable because the storage stability (shelf life) of the composition is improved. Moreover, reaction temperature becomes like this. Preferably it is 60-150 degreeC, More preferably, it is 80-120 degreeC.

  If necessary, a vinyl group-containing monocarboxylic acid (b) and a phenolic compound such as p-hydroxyphenethyl alcohol, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic A polybasic acid anhydride such as an acid anhydride can be used in combination.

  The epoxy resin (a ′) thus obtained has a hydroxyl group formed by an addition reaction between 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 present embodiment, the (A) acid-modified vinyl group-containing epoxy resin is also preferably an epoxy resin (a ″) obtained by reacting the above-mentioned epoxy resin (a ′) with a polybasic acid anhydride (c). In the epoxy resin (a ″), the hydroxyl group in the epoxy resin (a ′) (including the original hydroxyl group in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) are included. 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 Preferred examples include hydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  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 one equivalent of the hydroxyl group in the epoxy resin (a ′). By reacting with 0 equivalent, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted.

  (A) The acid value of the acid-modified vinyl group-containing epoxy resin is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g, and still more preferably 50 to 100 mgKOH / 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 characteristics of the cured film are unlikely to decrease.

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

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

(A) It is preferable that the weight average molecular weights of an acid-modified vinyl group containing epoxy resin are 3000-30000, More preferably, it is 4000-25000, More preferably, it is 5000-18000. When the weight average molecular weight of the component (A) is within the above range, a resist pattern that is superior in the balance of resist shape, resolution, heat resistance, adhesion, and electrical insulation can be obtained. Here, the weight average molecular weight is a polyethylene-converted weight average molecular weight measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, a value measured by the following GPC measurement apparatus and measurement conditions and converted using a standard polystyrene calibration curve can be used as the weight average molecular weight. The calibration curve is created using a standard sample of 5 sample sets (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation).
(GPC measuring device)
GPC apparatus: High-speed GPC apparatus “HCL-8320GPC”, detector is a differential refractometer, manufactured by Tosoh Corporation Column: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh Corporation ) Made (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 an acid-modified vinyl group-containing epoxy resin, as the epoxy resin (a), a novolac-type epoxy resin represented by the general formula (11 ′) having a structural unit represented by the general formula (11), 12) The epoxy resin obtained by reacting the bisphenol A type epoxy resin represented by the general formula (12 ′), the bisphenol F type epoxy resin and the vinyl group-containing monocarboxylic acid (b) having the structural unit represented by 12) 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 preferred. ) Is more preferable.

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

  The content of the component (A) in which the total solid content of the photosensitive resin composition is 100 parts by mass is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and 35 to 65 parts. The part by mass is particularly preferred. When the content of the component (A) is within the above range, a coating film excellent in heat resistance, electrical characteristics, 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 moisture and a solvent described later. That is, the solid content includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C., and does not necessarily mean solid.

  The photosensitive resin composition of this embodiment contains a photoinitiator as (B) component. (B) As a photoinitiator, there is no restriction | limiting in particular, It can select from a photopolymerization initiator used normally, and can use it. From the viewpoint of resist shape and reflow resistance, it is preferable to contain an acylphosphine oxide photopolymerization initiator having an acylphosphine oxide group (= P (═O) —C (═O) — group). Examples of the acylphosphine oxide photopolymerization initiator include (2,6-dimethoxybenzoyl) -2,4,6-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (2,5-dihydroxyphenyl) diphenyl Preferred examples include phosphine oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, and tris (p-hydroxyphenyl) phosphine oxide.

Examples of photopolymerization initiators other than acylphosphine oxide photopolymerization initiators include benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, and 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-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthone Anthraquinone photopolymerization initiators such as laquinone; Thioxanthone photopolymerization initiators such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; Acetophenone dimethyl ketal and benzyldimethyl Ketal photopolymerization initiators such as ketals; benzophenones such as benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide; Preferable examples also include oxime photopolymerization initiators such as 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime).
(B) As a photoinitiator, the said thing can be used individually by 1 type or in combination of 2 or more types.

  The content of the photopolymerization initiator (B) in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 0.2 to 15 parts by mass. When the amount is 0.2 parts by mass or more, the exposed portion is hardly eluted during development, and when the amount is 15 parts by mass or less, the heat resistance is not easily lowered. For the same reason, the content of the component (B) is more preferably 0.2 to 10 parts by mass, further preferably 0.5 to 5 parts by mass, and particularly preferably 0.5 to 2.5 parts by mass. Part by mass.

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

The photosensitive resin composition of this embodiment contains an inorganic filler as (C) component. (C) The inorganic filler is used for the purpose of improving various properties such as adhesion of the photosensitive resin composition, solder heat resistance, and coating strength. (C) As an 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 zirconia _{(Y 2 O 3 · ZrO 2} ), barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), barium sulfate (BaSO _4), sulfuric acid Preferable examples include calcium (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon and the like. These (C) inorganic fillers can be used singly or in combination of two or more.

  (C) The inorganic filler preferably has a maximum particle size of 0.1 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.1 to 5 μm, and 0.1 to 1 μm. Particularly preferred. When the maximum particle size is 20 μm or less, it is possible to suppress a decrease in electrical insulation (HAST resistance). Here, the maximum particle diameter of the (C) inorganic filler was measured by a laser diffraction method (based on JIS Z8825-1 (2001)).

  (C) Among inorganic fillers, it is preferable to use silica from the viewpoint of improving solder heat resistance, and from the viewpoint of improving solder heat resistance, crack resistance (thermal shock resistance), and PCT resistance, barium sulfate. Is preferably used. Moreover, it is preferable that the said barium sulfate is what is surface-treated with an alumina and / or an organosilane 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 organosilane compound is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%, More preferably, it is 1.5 to 3.5 atomic%. The elemental composition of silicon on the surface of barium sulfate is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%, and further preferably 1.5 to 3.5 atomic%. preferable. Further, the elemental composition of carbon on the surface of barium sulfate is preferably 10 to 30 atomic%, more preferably 15 to 25 atomic%, and further preferably 18 to 23 atomic%. These elemental compositions can be measured using XPS.

  As barium sulfate surface-treated with alumina and / or an organosilane compound, for example, NanoFine BFN40DC (trade name, manufactured by Nippon Solvay Co., Ltd.) is commercially available.

  The content of the (C) inorganic filler is preferably 1 to 50 parts by mass with the total solid content in the photosensitive resin composition being 100 parts by mass. (C) When 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. And good dispersibility of the inorganic filler can be obtained. 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 this embodiment contains a photopolymerizable compound as (D) component. (D) The photopolymerizable compound is a functional group exhibiting photopolymerization properties such as vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, (meth) acryloyl group, etc. If it is a compound which has an ethylene oxide unsaturated group, there will be no restriction | limiting in particular, From a reactive viewpoint, it is more preferable that it is a compound which has a (meth) acryloyl group.

  (D) As photopolymerizable compounds, 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 Mono- or di (meth) acrylates of glycols; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylate and the like Aminoalkyl (meth) acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate Is a polyvalent (meth) acrylate of these ethylene oxide or propylene oxide adducts; (meth) of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A Preferred are acrylates; (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; melamine (meth) acrylate and the like. These (D) photopolymerizable compounds can be used individually by 1 type or in combination of 2 or more types.

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

  The content of the photopolymerizable compound (D) in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, Preferably it is 1-15 mass parts. When the content of the component (D) is 0.1 part by mass or more, the light sensitivity is moderately low, so that the exposed part is hardly eluted during development, and when it is 30 parts by mass or less, the heat resistance is improved.

  The photosensitive resin composition of this embodiment contains alkoxypolysiloxane as the component (E). (E) A siloxane bond-containing vinyl polymer is a polymer obtained from the monomer 1 which is a vinyl compound having a hydrolyzable silyl group in the molecule represented by the following general formula (1). The body 1 may be a single type or a combination of two or more types. (E) By adopting a siloxane bond-containing vinyl polymer, a resist pattern that is superior in the balance of resolution, coating strength, heat resistance, adhesion, electrical insulation (HAST resistance), and thermal shock resistance can be obtained. . In particular, by using a combination of (C) inorganic filler and (E) siloxane bond-containing vinyl polymer, good dispersibility of the (C) inorganic filler can be obtained, so the coating strength of the photosensitive resin composition , Heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, and the like can be further improved.

In the formula (1), R ⁰¹ represents a hydrogen atom or a methyl group, R ⁰² and R ⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and R ⁰³ represents a hydrogen atom, a halogen atom, Or an alkoxy group, Z ⁰¹ represents a —COO— bond or an arylene group, Z ⁰² represents a divalent organic group, m ₀₁ represents an integer of 1 to 20, and m ₀₂ represents an integer of 1 to 3. R ⁰³ when m ₀₂ is 1 is an alkoxy group, and at least one R ⁰³ when m ₀₂ is 2 or 3 is an alkoxy group. A plurality of R ^{02 to} R ⁰⁴ may be the same or different.

R ⁰¹ is preferably a methyl group in consideration of (C) the dispersibility of the inorganic filler and the curing reactivity of the coating film of the photosensitive resin composition.
Examples of the alkyl group, aryl group, and aralkyl group of R ⁰² and R ⁰⁴ are preferably the same as those described for R ^13. (C) Dispersibility of inorganic filler and coating film of photosensitive resin composition In view of curing reactivity, an alkyl group is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
(C) Considering the dispersibility of the inorganic filler and the curing reactivity of the coating film of the photosensitive resin composition, the monomer 1 needs to be a vinyl compound having a hydrolyzable silyl group in the molecule. R ⁰³ when m ₀₂ is 1 is an alkoxy group. When m ₀₂ is 2 or 3, at least one R ⁰³ needs to be an alkoxy group. R ⁰³ must be an alkoxy group in the above case, and may be any of a hydrogen atom, a halogen atom, and an alkoxy group in other cases, but is preferably an alkoxy group, more preferably 1 to 1 carbon atoms. 5 is an alkoxy group. In this case, _m02 is preferably an integer of 1 to 3, more preferably an integer of 2 or 3, and further preferably 3.
Z ⁰¹ is preferably a —COO— bond in consideration of (C) the dispersibility of the inorganic filler and the curing reactivity of the coating film of the photosensitive resin composition.
M ₀₁ is preferably 1 to 10 in view of the dispersibility of the inorganic filler (C) and the curing reactivity of the coating film of the photosensitive resin composition, more preferably 2 to 8, More preferably, it is 2-5.

  Preferred examples of the divalent organic group include an alkylene group, a cycloalkylene group, a phenylene group, a biphenylene group, a polyether group, a carbonyl group, an ester group, and an amide group. These organic groups may be further substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like. The divalent organic group is preferably an alkylene group considering the dispersibility of the inorganic filler (C) and the curing reactivity of the coating film of the photosensitive resin composition, and an alkylene group having 1 to 5 carbon atoms is preferred. More preferably, an alkylene group having 2 to 4 carbon atoms is particularly preferable.

  As the monomer 1 represented by the general formula (1), which is a vinyl compound having a hydrolyzable silyl group in the molecule, for example, a vinyl compound represented by the following chemical formula is preferable as an example. Can be used alone or in combination of two or more.

Among the above vinyl compounds having a silyl group, (C) In view of dispersibility of inorganic filler, ease of polymerization, and curing reactivity when a coating film is formed, 1 represented by chemical formula (2f) -Methacryloyloxypropyl-1,1,3,3,5,5-hexamethyl-7,7,7-trimethoxytetrasiloxane (R ⁰¹ : methyl group, R ⁰² : methyl group, R ⁰³ : methoxy group, Z ⁰¹ : -COO-bond, Z ⁰² : propylene group, m ₀₁ : 3, m ₀₂ : 3), 1-methacryloyloxypropyl-1,1,3,3,5,5-hexaethyl- represented by the chemical formula (2g) 7,7,7- triethoxy cyclotetrasiloxane ^{(R 01: methyl, R 02: ethyl, R 03:} an ethoxy ^group, Z 01: -COO- ^{bond, Z 02:} propylene _{group, m 01:} , _M 02: 3), represented by the chemical formula (2h) 1-methacryloyloxypropyl -1,1,3,3,5,5,7,7- octamethyl -9,9,9- trimethoxy penta siloxane (R ⁰¹ : methyl group, R ⁰² : methyl group, R ⁰³ : methoxy group, Z ⁰¹ : —COO— bond, Z ⁰² : propylene group, m ₀₁ : 4, m ₀₂ : 3), represented by chemical formula (2i) -Methacryloyloxypropyl-1,1,3,3,5,5,7,7-octaethyl-9,9,9-triethoxypentasiloxane (R ⁰¹ : methyl group, R ⁰² : ethyl group, R ⁰³ : An ethoxy group, Z ⁰¹ : -COO— bond, Z ⁰² : propylene group, m ₀₁ : 4, m ₀₂ : 3) are more preferable.

  (E) The siloxane bond-containing vinyl polymer is a polymer obtained from the monomer 1 which is a vinyl compound having a hydrolyzable silyl group in the molecule represented by the general formula (1). It has a structural unit represented by Formula (2). Moreover, in this embodiment, it is preferable that it is a copolymer of this monomer 1 and another monomer. The other monomer is not particularly limited as long as it can form a copolymer with the monomer 1, but the monomer 2 having an ethylenically unsaturated group and the hydroxyl group-containing monomer 3 Are preferably used in combination.

In General Formula (2), R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , Z ⁰¹ , Z ⁰² , and m ⁰² are the same as those used in General Formula (1).

  Preferred examples of the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, and an allyl group. Examples of the monomer 2 having an ethylenically unsaturated group include methyl (meth) acrylate and ethyl (meth) acrylate. , N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate Alkyl (meth) acrylate compounds such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate; styrene, o-methylstyrene, m Methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- ( Preferred examples include aromatic vinyl compounds such as (phenylbutyl) styrene; halogenated vinyl compounds such as vinyl chloride and vinylidene chloride; nitrogen-containing vinyl compounds such as (meth) acrylonitrile and (meth) acrylamide. As the monomer 2, the above-mentioned monomers can be used alone or in combination of two or more.

Preferred examples of the hydroxyl group-containing monomer 3 include a hydroxyl group-containing (meth) acrylate and a hydroxyl group-containing vinyl ether, and these can be used alone or in combination of two or more.
As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Preferable examples include (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
Examples of the hydroxyl group-containing vinyl ether monomer include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2- Preferable examples include methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, trimethylolpropane diallyl ether, diethylene glycol monovinyl ether and the like.

  Moreover, as a hydroxyl-containing (meth) acrylate compound, the compound shown by the following general formula (21)-(23) is also mentioned preferably.

In the formula, R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a methyl group, Z ²¹ represents an alkylene group having 1 to 8 carbon atoms, and the alkylene group may be linear or branched, Further, it may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group or the like.

  The hydroxyl group-containing monomer 3 is preferably a hydroxyl group-containing (meth) acrylate compound from the viewpoint of obtaining better dispersibility of the (C) inorganic filler, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meta). ) Acrylate and 2-hydroxybutyl (meth) acrylate are more preferred.

When the monomer 1 is used in combination with another monomer, the content of the monomer 1 in all monomers is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. More preferred is ˜25% by mass. When the content of the monomer 1 is within the above range, (C) the dispersibility of the inorganic filler, and (C) the inorganic filler mixture containing the inorganic filler and the (E) siloxane bond-containing vinyl polymer. It is preferable in terms of stability.
From the same viewpoint, the content of the monomer 2 in all monomers is preferably 20 to 80% by mass, more preferably 30 to 75% by mass, and further preferably 40 to 70% by mass. Moreover, 1-40 mass% is preferable, as for content of the monomer 3 in all the monomers 3, 1-30 mass% is more preferable, and 2-25 mass% is further more preferable.

(E) The polymerization of the siloxane bond-containing vinyl polymer may be performed by a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, etc. (C) Viewpoint that can be used as it is when the inorganic filler is dispersed Therefore, it is preferable to employ solution polymerization.
Solution polymerization is performed in an organic solvent. Examples of the organic solvent include linear aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; cycloaliphatics such as cyclohexane, methylcyclohexane, ethylcyclohexane and cycloheptane. Preferred examples of hydrocarbons include aromatic hydrocarbons such as benzene, toluene and xylene. In addition, mineral spirits, mineral thinners, petroleum spirits, white spirits, and mineral terpenes that are mixed solvents can also be used. In addition, esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, and butanol can also be used. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

Moreover, (E) A polymerization initiator can be used for superposition | polymerization of a siloxane bond containing vinyl polymer as needed. As the polymerization initiator, a radical polymerization initiator that generates radicals by heating, ultraviolet rays, or an electron beam is preferably used. As the radical polymerization initiator, a peroxide polymerization initiator, a hydroperoxide polymerization initiator, or an azo type is used. Preferred examples include known thermal polymerization initiators such as polymerization initiators, and known photopolymerization initiators such as benzophenone and benzoin benzoin methyl ether. Among these, one can be used alone, or two or more can be used in combination. .
In the present invention, a thermal polymerization initiator is preferable, and an azo polymerization initiator is more preferable. This is because (C) dispersibility of the inorganic filler and (C) the inorganic filler and (E) the stability when the inorganic filler mixture containing the siloxane bond-containing vinyl polymer is obtained.

  (E) It is preferable that the weight average molecular weights of a siloxane bond containing vinyl polymer are 1000-100000, It is more preferable that it is 3000-50000, It is further more preferable that it is 5000-25000. 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.

  In the present invention, from the viewpoint of obtaining good dispersibility of the inorganic filler (C) and reaction curability of the coating film, inorganic filler dispersants represented by the following general formulas (24) to (29) are preferably used.

In the general formulas (24) to (29), R ^{24 to} R ²⁸ each independently represent an alkyl group, an aryl group or an aralkyl group, R ²⁹ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, Y ²¹ to Y ²⁵ represents a monovalent organic _group, m 21 _{~m 25} represents an integer of 2 to _{4, n 21} represents an integer of 1 to 10. R ²⁶ to R ²⁹ may be the same or ^different, when ^{R 24} and ^{R 25,} and ^Y 21 ^{to Y 25} are a plurality, may be the same or different.

Preferred examples of the alkyl group, aryl group and aralkyl group in R ^{24 to} R ²⁹ are the same as those described for R ¹³ .
Monovalent organic groups include halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, aryl groups, aralkyl groups, alkenyl groups, oxygen-containing organic groups such as glycidyl groups and glycidyloxy groups, amino groups, and amide groups. Preferred are nitrogen-containing organic groups such as isocyanate groups, sulfur-containing organic groups such as mercapto groups and isothiocyanate groups, and organic groups containing these. Preferred examples of the alkyl group, aryl group and aralkyl group are the same as those described for R ¹³ , and preferred examples of the alkyl group in the alkoxy group are the same as those described for R ¹³ . Moreover, as a cycloalkyl group, a C3-C20 cycloalkyl group is preferable, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, 2-methylcyclohexyl group, 2-t-butylcyclohexyl group, and A 4-t-butylcyclohexyl group and the like are exemplified. These groups may be substituted with a halogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, an alkoxy group, or the like.

Examples of the inorganic filler dispersant represented by the general formula (24) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, decyltrimethoxysilane, 3-mercaptopropyltrimethoxylane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) -aminopropyltrimethoxysilane, 3-dimethylaminopropyldiethoxymethylsilane, 3- (2-aminoethylamino) propyl Trimethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, 3-morpholinopropyltrimethoxysilane,
3- (2-aminoethylamino) propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Preferable examples include triethoxysilane and methyltrichlorosilane.

  Examples of the inorganic filler dispersant represented by the general formula (25) include tetraacetoxysilane, methyltriacetoxysilane, triacetoxyvinylsilane, dimethyldiacetoxysilane, 3-mercaptopropyltriacetoxysilane, 3-aminopropyltriacetoxysilane, 3 -Glycidyloxypropyl triacetoxysilane etc. are mentioned preferably.

  Preferred examples of the inorganic filler dispersant represented by the general formula (26) include methyltris (dimethylamino) silane, methyltris (diethylamino) silane, bis (dimethylamino) dimethylsilane, and ethyltris (dimethylamino) silane.

  Examples of the inorganic filler dispersant represented by the general formula (27) include methyltris (N, N-dimethylaminoxy) silane, methyltris (N, N-diethylaminoxy) silane, bis (N, N-diethylaminoxy) dimethoxysilane, Preferred is ethyltris (N, N-diethylaminoxy) silane.

  Examples of the inorganic filler dispersant represented by the general formula (28) include methyltris (ethylmethylketoxime) silane, ethyltris (ethylmethylketoxime) silane, tris (ethylmethylketoxime) vinylsilane, methyltris (dimethylketoxime) silane, Preferable examples include methyltris (diethylketoxime) silane.

  Preferred examples of the inorganic filler dispersant represented by the general formula (29) include those represented by the following chemical formula.

  As the inorganic filler dispersant, (E) inorganic filler dispersion represented by the general formulas (24) and (25) from the viewpoint of compatibility with the siloxane bond-containing vinyl polymer and coating film curability of the photosensitive resin composition. An agent is preferable, and among them, at least one selected from tetramethoxysilane, tetratrimethoxysilane, and tetraacetoxysilane is preferable.

  (E) Since the ratio of the siloxane bond-containing vinyl polymer to the inorganic filler dispersant described above varies depending on the type of (C) inorganic filler used, it cannot be generally specified. It is preferable that it is 0.1-10 mass parts of inorganic filler dispersing agents with respect to 100 mass parts of coalescence, 0.5-5 mass parts is more preferable, and 1-5 mass parts is further more preferable. When the inorganic filler dispersant is within the above range, excellent dispersibility of the inorganic filler (C) can be obtained.

  The content of the (E) siloxane bond-containing vinyl polymer in which the total solid content of the photosensitive resin composition is 100 parts by mass is preferably 1 to 40 parts by mass, and more preferably 1 to 25 parts by mass. The amount is preferably 3 to 15 parts by mass. When the content of the component (E) is within the above range, the dispersibility of the inorganic filler (C) becomes more excellent. Therefore, the coating strength, heat resistance, and electrical insulation (HAST resistance) of the photosensitive resin composition ), Thermal shock resistance, resolution, etc. can be further improved.

  It is preferable that the photosensitive resin composition of this embodiment contains a pigment as (F) component. (F) The pigment is preferably used according to a desired color when the wiring pattern is concealed. (F) The pigment is used as necessary according to the desired color, and a colorant that develops the desired color may be appropriately selected and used. Examples of the colorant include phthalocyanine blue and phthalocyanine. Known colorants such as green, iodine green, diazo yellow, crystal violet and the like are preferable.

  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. When the content of the component (F) is within the above range, the wiring pattern can be concealed.

  In the photosensitive resin composition of the present embodiment, a diluent can be used as necessary to adjust the viscosity. Preferred examples of the diluent include organic solvents or photopolymerizable monomers. For example, the organic solvent can be appropriately selected from the solvents exemplified as the organic solvent that can be used in the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). 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 total solid content in the photosensitive resin composition is 50 to 90% by mass, and 60 to 80% by mass. Is more preferable, and the amount is more preferably 65 to 75% by mass. That is, when the diluent is used, the content of the diluent in the photosensitive resin composition is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and further preferably 25 to 35% by mass. 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 this embodiment may contain a curing agent. Examples of the curing agent include a compound that cures itself by heat, ultraviolet light, and the like, and (A) an acid-modified vinyl group-containing epoxy resin that is a photocurable resin component in the composition of the present embodiment. A compound that is cured by ultraviolet rays or the like is preferable. By using a curing agent, the heat resistance, adhesion, chemical resistance (alkali resistance, acid resistance), etc. 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 as a thermosetting compound, for example. Examples of the epoxy compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins and the like; novolak type epoxy resins 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. Preferred examples of the urea compound include dimethylol urea.

As a hardening | curing agent, from a viewpoint which can improve heat resistance more, it is preferable to contain an epoxy compound (epoxy resin) and / or block type isocyanate, and it is more preferable to use an epoxy compound and block type isocyanate together.
As the block type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. Preferred are polyisocyanate compounds and adducts, burettes and isocyanurates of these.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene 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, lactic acid methyl And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine are preferred Can be mentioned.

  A hardening | curing agent is used individually by 1 type or in combination of 2 or more types. When using a hardening | curing agent, it is preferable that content of a hardening | curing agent is 2-50 mass parts with respect to 100 mass parts of solid content whole quantity of the photosensitive resin composition, 2-40 mass parts is more preferable, 3 -30 mass parts is more preferable, Especially preferably, it is 5-25 mass parts. By making content of a hardening | curing agent in 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) of the final cured film. Can do.

  Specific examples of such an epoxy resin curing agent include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl. Imidazoles such as -5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide, etc. These organic acid salts and / or epoxy adducts; 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 novolac; organic such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine Phosphines; Phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosnium chloride; benzyltrimethylan Quaternary ammonium salts such as nium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate Etc. are preferred.

  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. .1 to 10% by mass.

  The photosensitive resin composition of the present embodiment includes, if necessary, polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; thickeners such as benton and montmorillonite; silicone-based, fluorine-based, vinyl Various known and conventional additives such as resin-based antifoaming agents; silane coupling agents, and the like can be used. Further, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can be used.

  The photosensitive resin composition of this embodiment can contain an elastomer. The elastomer is particularly preferably used when the photosensitive resin composition of the present embodiment is used for manufacturing a semiconductor package substrate. By adding an elastomer to the photosensitive resin composition of the present embodiment, the curing reaction proceeds by ultraviolet rays or heat, so that (A) distortion inside the resin due to curing shrinkage of the acid-modified vinyl group-containing epoxy resin (internal Decrease in flexibility and adhesiveness due to 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. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

  In addition to the above-mentioned elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the above-described bisphenol F type epoxy resin, bisphenol A type epoxy resin, triphenolmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin. It can be obtained by modification with a carboxylic acid-modified butadiene-acrylonitrile rubber or a terminal amino-modified silicone rubber. Among these elastomers, from the viewpoint of shear adhesion, both end carboxyl group-modified butadiene-acrylonitrile copolymers and Espel (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), which is a polyester elastomer having a hydroxyl group, are preferable. Can be mentioned.

  The 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 part tends to be eluted with the developer.

  The photosensitive resin composition of the present embodiment includes, if necessary, polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; thickeners such as benton and montmorillonite; silicone-based, fluorine-based, vinyl Various known and commonly used additives such as resin-based antifoaming agents and silane coupling agents can be used. Further, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, 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 with a roll mill, a bead mill, or the like. Can be obtained by mixing.
In the present embodiment, (C) by obtaining excellent dispersibility of the inorganic filler, coating film strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, etc. of the photosensitive resin composition From the viewpoint of further improving (C) inorganic filler and (E) siloxane bond-containing vinyl polymer to obtain an inorganic filler mixture in advance, (A) component, (B) component, (D) It is preferable to add and knead and mix the component, the component (F) used as desired, and other various components. That is, the photosensitive resin composition of the present embodiment comprises steps (1), (C) a step of mixing an inorganic filler and (E) a siloxane bond-containing vinyl polymer to obtain an inorganic filler mixture, and step (2) ( It is preferable to obtain it through a step of mixing A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator, the inorganic filler mixture, and (D) a photopolymerizable compound, more preferably (F) a pigment. .

  This inorganic filler mixture contains (C) an inorganic filler and (E) a siloxane bond-containing vinyl polymer, and (E) a siloxane bond-containing vinyl polymer is a resin (inorganic filler dispersion) for dispersing the inorganic filler. It is also called resin for use.) The inorganic filler mixture is preferably in the form of an inorganic filler dispersion liquid in which the (C) inorganic filler is dispersed from the viewpoint of obtaining good dispersibility of the (C) inorganic filler in the photosensitive resin composition. When the inorganic filler mixture is in the form of an inorganic filler dispersion, (C) the addition effect of the inorganic filler, that is, various properties such as adhesion of the photosensitive resin composition, solder heat resistance, and coating strength are improved.

  As resin for inorganic filler dispersion, if (E) silyl group containing vinyl polymer is included, other resin may be included. As another resin, a hydroxyl group-containing vinyl polymer which is a resin having a hydroxyl group-containing (meth) acrylate compound or a hydroxyl group-containing vinyl ether compound as a monomer is preferably exemplified. Preferred examples of these monomers include those exemplified as the hydroxyl group-containing monomer 3 described above.

The content of the inorganic filler (C) with respect to the total solid content in the inorganic filler mixture is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 25 to 60% by mass. And particularly preferably 30 to 60% by mass. (C) When the content of the inorganic filler is within the above range, the coating strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, etc. of the photosensitive resin composition are further improved. And (C) good dispersibility of the inorganic filler can be obtained.
Here, the content of the (C) inorganic filler relative to the total solid content in the inorganic filler mixture is W. C. (Pigment Weight Concentration). W. C. (% By mass) = value calculated by the formula of inorganic filler (parts by mass) / solid content in inorganic filler mixture (parts by mass) × 100. The total amount of solids in the inorganic filler mixture is the total of solids contained in the hydroxyl group-containing vinyl polymer, the curing agent described later, etc. in addition to (C) inorganic filler and (E) alkoxypolysiloxane. Amount.

  The content (solid content) of the (E) siloxane bond-containing vinyl polymer in the inorganic filler mixture is preferably 20 to 2000 parts by mass with respect to 100 parts by mass of the (C) inorganic filler, and 20 to 1000 parts by mass. Part is more preferable, and 20 to 500 parts by mass is even more preferable. 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 is known as a ball mill, a bead mill, an ultrasonic disperser or the like by adding a dispersion aid, a surface treatment agent or the like to the (C) inorganic filler and (E) siloxane bond-containing vinyl polymer as necessary. It can be obtained by a distributed processing method using the distributed processing 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 between the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). (C) In consideration of the dispersibility of the 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, the concentration of the total solid content in the inorganic filler mixture is preferably 50 to 90% by mass, and more preferably 60 to 85% by mass. When the content of the organic solvent is within the above range, (C) good dispersibility of the inorganic filler can be obtained.

  In addition, as a curing agent or as a binder (binder), inorganic filler mixtures include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, and novolak types. It is preferable to use an epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, a heterocyclic epoxy resin such as triglycidyl isocyanurate, a bixylenol type epoxy resin, etc., and these may be used alone or in combination of two or more. Can be used in combination.

  5-60 mass parts is preferable and, as for content of the hardening | curing 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 within the above range, (C) good dispersibility of the inorganic filler can be obtained.

  The solid content of the inorganic filler mixture in which the total solid content in the photosensitive resin composition is 100 parts by mass is preferably 20 to 80 parts by mass, more preferably 20 to 60 parts by mass, It is especially preferable that it is 25-50 mass parts. When the content of the inorganic filler mixture is within the above range, the coating film strength, heat resistance, electrical insulation (HAST resistance), thermal shock resistance, resolution, etc. of the photosensitive resin composition can be further improved. .

The photosensitive resin composition of the present embodiment thus obtained can be supplied in the form of a film or in a liquid state depending on the usage mode of the supply destination. When the permanent mask resist is formed using the composition, the permanent mask resist can be easily formed by using various liquid coating methods described later.
When using a hardening | curing agent and supplying with a liquid form, this hardening | curing agent is resin composition ((A)-(E) component, (F) component added as needed, and other than a hardening | curing agent) Apart from the resin composition containing additives), it is preferably supplied as a two-component type and mixed at the point of use. The curing reaction of the resin composition is not accelerated and can be stably supplied as a liquid. Moreover, when using a hardening | curing agent and supplying as a film form, it can supply in a film form as a resin composition containing a hardening | curing agent.

[Photosensitive element, permanent mask resist and printed wiring board]
The photosensitive resin composition of the present embodiment is suitably used for forming 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 this embodiment includes a support and a photosensitive layer formed using the photosensitive resin composition of the present embodiment on the support. As the support, for example, a resin film having heat resistance and solvent resistance, such as a polyester resin film such as polyethylene terephthalate, and a polyolefin resin film such as polyethylene and polypropylene, is preferably mentioned. From the viewpoint of transparency, a polyethylene terephthalate film Is preferably used. The thickness of the support is preferably 1 to 100 μm, more preferably 1 to 50 μm, and further preferably 1 to 30 μm in view of mechanical strength, obtaining good resolution, and the like.

  The photosensitive element of the present embodiment is, for example, carried out by carrying out the photosensitive resin composition of the present embodiment on the support by a method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin method. The photosensitive resin composition of the form is applied at 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 provided with the permanent mask resist are imaged as follows, for example. First, on a base material on which a resist is to be formed (for example, a copper-clad laminate for a printed wiring board), a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, etc. The photosensitive resin composition of the embodiment is applied at a film thickness (after drying: 10 to 200 μm) according to the application to form a coating film, and the coating film is dried at 60 to 110 ° C. Further, instead of the coating film, the photosensitive layer of the photosensitive element may be transferred (laminated) onto the substrate on which the resist is to be formed. In this case, the dried coating film on the support is pasted on the substrate using an atmospheric laminator or a vacuum laminator as necessary.
After the photosensitive layer (coating film) is formed on the substrate, the negative film is directly contacted, or through a transparent film, the active rays such as ultraviolet rays are preferably irradiated at 10 to 1,000 mJ / cm ^2, and the resin When a film is used, the film is peeled off, and the unexposed part is dissolved and removed (developed) with a dilute alkaline aqueous solution.
Next, the exposed portion is sufficiently cured by post-exposure (ultraviolet light exposure) and / or post-heating to obtain a cured film. For example, the post-exposure is preferably 800 to 5,000 mJ / cm ² , and the post-heating is preferably 100 to 200 ° C. for 30 minutes to 12 hours.

  The permanent mask resist thus obtained is less prone to undercuts that cause the bottom to be removed, is less likely to lack the top of the resist, and has a line width at the middle (center) and deepest (bottom) of the pattern cross section. 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 a pattern with excellent resolution. In addition, this permanent mask resist has a pattern that is excellent in the formation stability of the finer hole diameter and the interval pitch between holes due to the recent downsizing and higher performance of electronic devices. In addition to PCT resistance (moisture heat resistance), reflow resistance, electrical insulation (HAST resistance), and electroless plating resistance, the pattern has heat resistance, solvent resistance, and chemical resistance (alkali resistance, acid resistance). Property) and adhesiveness.

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

(Synthesis Example 1: Synthesis of siloxane bond-containing vinyl polymer 1)
A flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 250 parts by mass of carbitol acetate. After heating up to 100 degreeC, the monomer shown in Table 1 and the polymerization initiator were dripped over 2 hours.
After completion of the dropwise addition, the mixture was kept warm for 1 hour, and a solution prepared by dissolving 2 g of 2,2′-azobis (isobutyronitrile) in 20 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was kept warm 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 50% (solid content 50%), and may be referred to as a siloxane bond-containing vinyl polymer 1 (resin 1 for dispersing inorganic fillers). There is.) Here, room temperature in this specification indicates 25 ° C.

* 1,1-Methacryloyloxypropyl-1,1,3,3,5,5-hexamethyl-7,7,7-trimethoxytetrasiloxane (the above chemical formula (2f))

(Synthesis Example 2: Synthesis of siloxane bond-containing vinyl polymer 2)
In Synthesis Example 1, a siloxane bond-containing vinyl polymer 2 (may be referred to as inorganic filler dispersing resin 2) in the same manner as in Synthesis Example 1 except that the monomers and polymerization initiators are those shown in Table 2. .)

* 1,1-Methacryloyloxypropyl-1,1,3,3,5,5,7,7-octamethyl-9,9,9-trimethoxypentasiloxane (the above chemical formula (2h))

(Synthesis Example 3: Synthesis of hydroxyl group-containing vinyl polymer 1)
A flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 250 parts by mass of carbitol acetate. After heating up to 100 degreeC, the monomer shown in Table 3 and the polymerization initiator were dripped over 2 hours.
After completion of the dropwise addition, the mixture was kept warm for 1 hour, and a solution prepared by dissolving 2 g of 2,2′-azobis (isobutyronitrile) in 20 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was kept warm 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 50% (solid content 50%), and may be referred to as hydroxyl group-containing vinyl polymer 1 (resin 3 for dispersing inorganic filler). .)

(Synthesis Example 4: Synthesis of hydroxyl group-containing vinyl polymer 2)
In Synthesis Example 3, except that the monomers and polymerization initiators are those shown in Table 4, they may be referred to as hydroxyl group-containing vinyl polymer 2 (inorganic filler dispersing resin 4) in the same manner as Synthesis Example 3. )

(Production Example 1: Production of inorganic filler dispersion 1)
80 parts by mass (solid content: 30%) of (E) the siloxane bond-containing vinyl polymer 1 (resin 1 for inorganic filler dispersion) obtained in Synthesis Example 1 and (C) 30 parts by mass of barium sulfate as an inorganic filler 30 parts by mass of silica, 20 parts by mass of epoxy resin (Epicoat 828, bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name)) as a binder resin, and 1 part by mass of tetramethoxysilane as an inorganic filler dispersant Then, the mixture was kneaded for 1 hour using a bead mill (zirconia bead particle size: 0.5 mm, stirring blade peripheral speed: 10 m / s) to obtain an inorganic filler dispersion 1. The solid content concentration in the obtained inorganic filler dispersion liquid 1 is 75% by mass. W. C. (Pigment Weight Concentration, the concentration of the inorganic filler relative to the total solid content in the inorganic filler mixture) was 50% by mass. Here, P.I. W. C. P. W. C. (% By mass) = value calculated by the formula of inorganic filler (parts by mass) / solid content in inorganic filler mixture (parts by mass) × 100. Table 5 shows the results of the following inorganic filler dispersion evaluation, dispersion stability evaluation, storage stability evaluation, and coating film performance evaluation of the inorganic filler dispersion liquid 1.

(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 inorganic filler dispersion resin, inorganic filler, and binder resin shown in Table 5, in the same manner as in Production Example 1 above, inorganic filler dispersion 2 ~ 8 was obtained. About obtained inorganic filler dispersion liquids 2-8, solid content concentration, P.I. W. C. Table 5 shows the results of the evaluation of the dispersibility of the inorganic filler, the evaluation of the dispersion stability, the evaluation of the storage stability, and the evaluation of the coating film performance described below.

(Evaluation of inorganic filler dispersibility (measurement of maximum particle size))
Using the same inorganic filler dispersion resin, inorganic filler dispersant, and inorganic filler as those used in the above production examples and comparative production examples shown in Table 5, kneading in a bead mill for 1 hour (zirconia bead particle size: 0.0. 5 mm, stirring blade peripheral speed: 10 m / s) to obtain a mixture, and then using a nanoparticle size distribution measuring device (SDLA-7100, manufactured by Shimadzu Corporation), a laser diffraction scattering method to disperse the dispersed inorganic filler. The particle size was measured. If it is less than 1 μm, it can be said that excellent dispersibility was obtained. Here, the particle size at an integrated value of 99.9% (volume basis) in the particle size distribution measured with the nano particle size distribution measuring device was taken as the maximum particle size.

(Evaluation of dispersion stability)
When the epoxy resin shown in Table 5 was further added to the mixture obtained by the evaluation of the inorganic filler dispersibility and allowed to stand at room temperature, the state of sedimentation of the inorganic filler was visually confirmed and evaluated according to the following criteria. .
○ (excellent): Sedimentation of the inorganic filler was not confirmed at all.
Δ (good): Slight sedimentation of the inorganic filler was confirmed, but there was no practical problem.
X (Poor) Sedimentation 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 of 50 ° C., the appearance of the dispersions were visually confirmed, and evaluated according to the following criteria.
○ (excellent): No change was observed in the inorganic filler dispersion.
Δ (good): Slight thickening or gelation of the inorganic filler dispersion was confirmed, but there was no practical problem.
X (Poor): Thickening or gelation of the inorganic filler dispersion was confirmed.

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

Ii) The numerical value of the blending ratio of each component in the table includes a component (organic solvent) other than the solid content, and its unit is part by mass. The details of the materials in Table 5 are as follows.
Inorganic filler dispersant 1: Tetramethoxysilane inorganic filler dispersant 2: Tetraacetoxysilane binder resin: Epicoat 828 (Bisphenol A type epoxy resin (trade name, manufactured by Japan Epoxy Resin Co., Ltd.))

Next, using the inorganic filler dispersion liquids 1 to 8 obtained in the respective production examples and comparative production examples, photosensitive resin compositions of the following examples and comparative examples were obtained, and the following evaluations were performed.
(Evaluation methods)
(1) Evaluation of photosensitivity The photosensitive resin composition of each Example and Comparative Example was applied to a 35 μm thick PET film with an applicator so that the film thickness after drying was 35 μm to form a coating film. . Subsequently, it was dried at 80 ° C. for 20 minutes using a hot air circulation dryer. A 41-step tablet (manufactured by Hitachi Chemical Co., Ltd.) was placed on the coating film and exposed with an exposure amount of 500 mJ / cm ² using an ultraviolet exposure device. Next, spray development was performed with a 1% by weight 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) that remained without being developed was measured. evaluated.
○ (excellent): 16 steps or more remained.
Δ (good): 10 to 15 stages remained.
X (defect): 9 steps or less remained.

(2) Resolution Evaluation Phototool with 41-step tablet (manufactured by Hitachi Chemical Co., Ltd.) and 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 intimate contact with the evaluation laminate, and the exposure was performed with the above-described exposure apparatus with an energy amount that resulted in 17 steps remaining after development of the 41-step tablet. Then, after leaving still for 1 hour at normal temperature and peeling off a PET film, it developed by spraying 1 mass% sodium carbonate aqueous solution of 30 degreeC for 60 second, and heated (dried) at 80 degreeC for 10 minutes. Here, the resolution was evaluated based on the smallest value (unit: μm) of the space width between the line widths in which a rectangular resist shape was obtained by development processing. The resist shape was observed with a magnification of 1000 times using a microscope. It shows that it is excellent in the resolution, so that this value is small.

(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 Was 0.6 mm thick copper-clad laminate (MCL-E-67, Hitachi Chemical Co., Ltd.) that was chemically polished (polluted 0.5 μm deep in the depth direction using an abrasive (CZ8101, manufactured by MEC Co., Ltd.)). Made by Co., Ltd.). On each copper clad laminated substrate, the photosensitive resin composition of each Example and Comparative Example was applied by screen printing so that the film thickness after drying was 35 μm, and a coating film was formed. It was dried at 80 ° C. for 20 minutes using a dryer. Next, the pattern shown in FIG. 1 of the size of the hole diameter and the pitch between the holes (the size of the hole diameter 100 μm / the spacing pitch between the holes 100 μm, or the size of the hole diameter 80 μm / the spacing between the holes 80 μm) The negative mask which it has was arrange | positioned on a coating film, and it exposed with the exposure amount of 600 mJ / cm < ² > using the ultraviolet-ray exposure apparatus. 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 sodium carbonate solution, and the unexposed portion was dissolved and developed. Next, it exposed with the exposure amount of 1000 mJ / cm < ² > using the ultraviolet exposure apparatus, and 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 grids were produced and the peeling test was done with the cellophane tape. The peeled state of the grid was observed visually and evaluated according to the following criteria.
○ (excellent): 90/100 or more and no peeling.
Δ (good): 50/100 or more and less than 90/100 and no peeling.
X (defect): 0/100 to less than 50/100 and no peeling.

(4) Evaluation of solder heat resistance 50 cm × 50 cm in size and 0.6 mm thick copper-clad laminate (“MCL-E-67 (trade name)” manufactured by Hitachi Chemical Co., Ltd.) After forming the coating film by applying the photosensitive resin composition of each Example and Comparative Example by screen printing method so that the subsequent film thickness becomes 35 μm, using a hot air circulating dryer at 80 ° C. for 20 minutes. Dried. Next, the pattern shown in FIG. 1 of the size of the hole diameter and the pitch between the holes (the size of the hole diameter 100 μm / the spacing pitch between the holes 100 μm, or the size of the hole diameter 80 μm / the spacing between the holes 80 μm) The negative mask which it has was arrange | positioned on a coating film, and it exposed with the exposure amount of 600 mJ / cm < ² > using the ultraviolet-ray exposure apparatus. 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 sodium carbonate solution, and the unexposed portion was dissolved and developed. Next, it exposed with the exposure amount of 1000 mJ / cm < ² > using the ultraviolet exposure apparatus, and heated at 150 degreeC for 1 hour, and produced the test piece.
A non-cleaning 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 dipping for 10 seconds, the test piece was taken out of the solder bath and allowed to cool to room temperature. After repeating immersion for 10 seconds and allowing to cool 6 times, the appearance of the coating film was visually observed and evaluated according to the following criteria.
○ (excellent): No change in the appearance of the resist coating film was confirmed, and no solder was trapped between the substrate and the mask resist.
Δ (good): Peeling or swelling of the resist coating film or solder peeling was confirmed to some extent, but there was no practical problem.
X (Bad): Swelling or peeling of the resist coating film or solder peeling was confirmed.

(5) Thermal shock resistance After adding 1,000 cycles of heat history to the test piece obtained in the same manner as the evaluation of solder heat resistance in (4) above, the test piece was visually observed and 1000 using a microscope. The observation was magnified twice. Here, the thermal history of one cycle was a thermal history of −55 ° C. for 30 minutes and then 125 ° C. for 30 minutes.
○ (Excellent): No cracks were confirmed.
Δ (good): Slight cracks were confirmed, but there was no practical problem.
X (defect): The crack was confirmed to such an extent that a practical problem occurred.

(6) Developability On one surface of a copper foil substrate on which a copper pattern is formed (pitch: 100 μm), the photosensitive resin compositions of the examples and comparative examples are applied by screen printing at 80 ° C. Dry for 30 minutes. Next, after allowing to cool to room temperature, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 30 seconds under a spray pressure of 2 kg / cm ² . The presence or absence of development residue of the dried coating film was visually confirmed, and developability was evaluated according to the following criteria.
○ (excellent): Less than 1% of the coating film remained, but most of the film was developed.
Δ (good): A coating film of 1% or more and less than 5% remained.
X (defect): 5% or more remained as a coating film.

(7) Electroless gold plating solution resistance The following electroless nickel / gold plating was applied to the test piece obtained in the same manner as in the evaluation of solder heat resistance in (4) above. Electroless nickel / gold plating includes 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. The materials used in each process of electroless nickel / gold plating are as follows.
Degreasing process: PC-455 (manufactured by Meltex, trade name) 25% by mass aqueous solution soft etching process: ammonium persulfate aqueous solution pickling process of 150 g / L: 5% by volume sulfuric acid aqueous solution electroless nickel plating process: Nimden NPF-2 (Product name, manufactured by Uemura Kogyo Co., Ltd.)
Electroless gold plating process: Goblite TIG-10 (trade name, manufactured by Uemura Kogyo Co., Ltd.)

Immediately after the drying process, cello tape (registered trademark) is applied to the surface of the flexible printed circuit board (FPC board) subjected to electroless nickel / gold plating, and peeled off in the vertical direction (90 ° peel-off test). The plating resistance (peeling) was evaluated by visually observing the presence or absence of peeling of the mask resist.
Further, when gold plating is stripped at the interface between the substrate and the permanent mask resist, the gold plating deposited on 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 (boring).
○ (excellent): No peeling of gold plating was confirmed.
Δ (good): The plating of the gold plating was less than 10 μm, and there was no practical problem.
X (defect): The plating of the gold plating was 10 μm or more.

(8) Evaluation of electrical insulation (HAST resistance) On a bismaleimide triazine substrate (BT substrate) on which comb-type electrodes (line / space = 10 μm / 10 μm) are formed, the film thickness after drying is 35 μm. The photosensitive resin compositions of the examples and comparative examples were applied by screen printing to form a coating film, and then dried at 80 ° C. for 20 minutes using a hot air circulation dryer. Subsequently, it exposed with the exposure amount of 1000 mJ / cm < ² > using the ultraviolet-ray exposure apparatus, and it heated at 150 degreeC for 1 hour, and produced the test piece which has a cured coating film of the photosensitive resin composition on BT board | 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-chamber HAST test for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.
5:10 ⁸ Ω or more 4:10 ⁷ Ω or more and less than 10 ⁸ Ω 3:10 ⁶ Ω or more and less than 10 ⁷ Ω 2:10 ⁵ Ω or more and less than 10 ⁶ Ω 1:10 ⁵ Ω or less

(Synthesis Example 5: Synthesis of acid-modified vinyl group-containing epoxy resin 11a)
Cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., “YDCN700-7 (trade name)”, in general formula (11), Y ¹¹ = glycidyl group, R ¹¹ = methyl group) 220 parts by mass, acrylic acid 72 mass Parts, 1.0 part by mass of hydroquinone and 180 parts by mass of carbitol acetate were mixed and heated to 90 ° C. and stirred to dissolve the reaction mixture. Subsequently, after cooling to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was mixed, and further heated to 100 ° C. until the solid content acid value reached 1 mgKOH / g. Next, 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 was 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)
Phenol novolac type epoxy resin (manufactured by DIC Corporation, “N770 (trade name)”, in general formula (11), Y ¹¹ = glycidyl group, R ¹¹ = methyl group) 220 parts by mass, acrylic acid 72 parts by mass, hydroquinone 1 part by mass and 180 parts by mass of carbitol acetate were mixed and heated to 90 ° C. and stirred to dissolve the reaction mixture. Subsequently, after cooling to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was mixed, heated to 100 ° C., and reacted until the acid value became 1 mgKOH / g. Next, 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 was 60% by mass to obtain an acid-modified vinyl group-containing epoxy resin 11b.

(Synthesis Example 7; Synthesis of acid-modified vinyl group-containing epoxy resin 12)
Bisphenol F-type epoxy resin (manufactured by Toto Kasei Co., Ltd., “YDF2001 (trade name)”, in 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 and heated to 90 ° C. and stirred to dissolve the reaction mixture. Subsequently, after cooling to 60 ° C., 2 parts by mass of benzyltrimethylammonium chloride was mixed, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / 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 was 60% by mass to obtain an acid-modified vinyl group-containing epoxy resin 12.

(Synthesis Example 8; Synthesis of acid-modified vinyl group-containing epoxy resin 14)
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 272 parts by mass of bis (4-hydroxyphenyl) methane dissolved at 80 ° C., and 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 added dropwise over 1 hour so that the liquid temperature was maintained in the range of 80 to 90 ° C. After completion of dropping, 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 washing with water until the washing 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), As a result, 164 parts by mass of a bisphenol novolac resin as a brown solid was obtained. The obtained bisphenol novolac resin had a softening point of 74 ° C. and a hydroxyl group equivalent of 154 g / eq.
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 154 parts by mass of the obtained bisphenol novolac resin, 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol, and tetraethylbenzyl 2 parts by mass of ammonium chloride was mixed and dissolved. Next, this was heated to 65 ° C., and the pressure was reduced to an azeotropic pressure, and then 90 parts by mass of an aqueous sodium hydroxide solution (49% by mass) was added dropwise over 5 hours at a constant dropping rate, followed by stirring for 30 minutes. During this time, the distillate distilled by azeotropic distillation was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the flask (reaction system). Thereafter, 590 parts by mass of methyl isobutyl ketone and 177 parts by mass of n-butanol were added to a crude epoxy resin obtained by distilling off unreacted epichlorohydrin by distillation under reduced pressure (temperature: 22 ° C., pressure: 1.87 kPa). Dissolved. Subsequently, 10 mass parts of sodium hydroxide aqueous solution (10 mass%) was added, and it stirred at 80 degreeC for 2 hours. Furthermore, washing with water was repeated three times with 150 parts by mass of water. It was confirmed that the pH of the cleaning liquid used in the third water washing was neutral. Next, the inside of the flask (inside the reaction system) was dehydrated by azeotropic distillation and subjected to microfiltration, and then the solvent was distilled off under reduced pressure (pressure: 1.87 kPa). Thus, a bisphenol-based novolak-type epoxy resin used in the present embodiment, which is a brown viscous liquid (an epoxy resin having a constitutional unit of Y ¹⁴ = glycidyl group and R ¹³ = H in the general formula (14)) (A)) was obtained. The epoxy resin had a hydroxyl group equivalent of 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. . Subsequently, after cooling to 60 ° C., 2 parts by mass of benzyltrimethylammonium chloride was mixed, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / 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 diluted with carbitol acetate so that solid content concentration might be 60 mass%, and the acid-modified vinyl group containing epoxy resin 14 was obtained.
The softening point of the resin was measured according to the ring and ball method defined in JIS-K7234: 1986 (temperature increase rate: 5 ° C./min), and the acid value of the resin was measured by a neutralization titration method. Specifically, after adding 30 g of acetone to 1 g of acid-modified vinyl-containing epoxy resin and further uniformly dissolving it, an appropriate amount of indicator, phenolphthalein, is added to the solution containing the acid-modified vinyl group-containing epoxy resin. And it measured by performing titration using 0.1N potassium hydroxide aqueous solution.

Examples 1-6 and Comparative Examples 1-6
A composition was blended according to the blending composition shown in Table 6, and kneaded with a three-roll mill to prepare a photosensitive resin composition. Carbitol acetate was added so that the solid content concentration was 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 6. In addition, the unit of the compounding amount of each component in Table 6 is part by mass, and the compounding amount of the component (A) includes the epoxy resin and the solvent (carbitol acetate) obtained in each of the above synthesis examples. Means quantity.

* 1, It is the compounding quantity of the solution (solid content concentration: 60 mass%) containing an epoxy resin.
Ii) The numerical value of each component in the table includes components (organic solvent etc.) other than the solid content, and the unit is parts by mass. The total amount of solids is the total amount (parts by mass) of solids contained in components (A) to (F), the binder resin contained in the inorganic filler dispersion, and the epoxy resin contained in the curing agent (Epicoat in the table) 828) is added up. The details of each material in Table 4 are as follows.
Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (trade name, manufactured by BASF Japan Ltd.)
Irgacure 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
Kayarad DPHA: Dipentaerythritol pentaacrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.)
Epicoat 828: Bisphenol A type epoxy resin (product name, manufactured by Japan Epoxy Resin Co., Ltd.)

From the results shown in Table 6, the photosensitive resin compositions of the present embodiments of Examples 1 to 6 have excellent photosensitivity (photocurability), resolution, and adhesion, and permanent mask resist (solder Resist) hole diameter size and interval pitch between holes (hole diameter size 100 μm / hole interval pitch 100 μm, or hole diameter size 80 μm / hole interval 80 μm) In addition, it was confirmed that the film was excellent in developability or in various performances such as solder heat resistance, thermal shock resistance, electroless plating resistance, and electrical insulation (HAST resistance).
On the other hand, in Comparative Examples 1 to 4, the resolution, thermal shock resistance, electroless gold plating resistance, and electrical insulation (HAST resistance) are inferior, and adhesion and developability tend to deteriorate. It was confirmed that there was.

  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, PCT resistance (moisture heat resistance) required as the pitch becomes finer. , Photosensitive resin composition capable of forming a pattern excellent in reflow resistance, electrical insulation (HAST resistance), electroless plating resistance, solder heat resistance, etc. It is possible to obtain a permanent mask resist having excellent formation stability and capable of forming a pattern. The permanent mask resist is suitably used for a printed wiring board, and particularly, preferably used for a printed wiring board having a finer hole diameter and a pitch between holes due to recent miniaturization and higher 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) a siloxane bond-containing vinyl polymer, ) A photosensitive resin composition in which the siloxane bond-containing vinyl polymer is obtained from the monomer 1 represented by the following general formula (1).

[In the formula (1), R ⁰¹ represents a hydrogen atom or a methyl group, R ⁰² and R ⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and R ⁰³ represents a hydrogen atom or a halogen atom. Or an alkoxy group, Z ⁰¹ represents a —COO— bond or an arylene group, Z ⁰² represents a divalent organic group, m ₀₁ represents an integer of 1 to 20, and m ₀₂ represents an integer of 1 to 3. R ⁰³ when m ₀₂ is 1 is an alkoxy group, and at least one R ⁰³ when m ₀₂ is 2 or 3 is an alkoxy group. A plurality of R ^{02 to} R ⁰⁴ may be the same or different. ]   The (E) siloxane bond-containing vinyl polymer is obtained from the monomer 1, the monomer 2 having an ethylenically unsaturated group, and the hydroxyl group-containing monomer 3. Photosensitive resin composition.   The monomer 2 having an ethylenically unsaturated group is at least one monomer selected from an alkyl (meth) acrylate compound, an aromatic vinyl compound, a halogenated vinyl compound, and a nitrogen-containing vinyl compound. The photosensitive resin composition according to claim 2, wherein the monomer 3 is at least one monomer selected from a hydroxyl group-containing (meth) acrylate and a hydroxyl group-containing vinyl ether. The photosensitive resin composition according to claim 1, wherein R ⁰³ is an alkoxy group, and m ₀₂ is an integer of 2 or 3. (A) The acid-modified vinyl group-containing epoxy resin is represented by the epoxy resin having the structural unit represented by the general formula (11), the epoxy resin having the structural unit represented by the general formula (12), or the 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 the general formula (14), and a bisphenol novolac epoxy resin having a structural unit represented by the general formula (15) Obtained by reacting the resin (a ′) obtained by reacting the resin (a) with the vinyl group-containing monocarboxylic acid (b) and the saturated or unsaturated group-containing polybasic acid anhydride (c). It is resin, The photosensitive resin composition in any one of Claims 1-4.

[In the 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 the hydrogen atom to the glycidyl group is 0/100 to 30/70, n ₁₁ represents an integer of 1 or more. At least one of Y ¹¹ represents a glycidyl group, a plurality of R ¹¹ may be the same or different, when n ₁₁ is 2 or more, plural Y ¹¹ may be the same or different. ]

In [Equation ^{(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 atoms and a glycidyl group is 0 / 100-30 / 70, n ₁₂ represents an integer of 1 or more. At least one of Y ¹² represents a glycidyl group, the plurality of R ¹² may be the same or different, when n ₁₂ is 2 or more, plural Y ¹² may be the same or different. ]

Wherein ^{(13), Y 13} represents a hydrogen atom or a glycidyl group, and the molar ratio of hydrogen atoms and a glycidyl group is 0 / 100~30 / _{70, n 13} represents an integer of 1 or more. Further, 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 the 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. ]   The epoxy resin (a) has an epoxy resin having a structural unit represented by the general formula (11), an epoxy resin having a structural unit represented by the general formula (12), and a structural unit represented by the general formula (14). The photosensitive resin composition according to claim 5, which is at least one selected from bisphenol novolac type epoxy resins.   (D) The photopolymerizable compound is a compound containing a (meth) acryloyl group, The photosensitive resin composition in any one of Claims 1-6.   Furthermore, the photosensitive resin composition in any one of Claims 1-7 containing (F) pigment.   (E) Content of a siloxane bond containing vinyl polymer is 1-40 mass parts with respect to 100 mass parts of solid content whole quantity in the photosensitive resin composition, The photosensitive property in any one of Claims 1-8. Resin composition.   The photosensitive resin composition in any one of Claims 1-9 which is a liquid form.   The photosensitive resin composition in any one of Claims 1-10 used for formation of a permanent mask resist.   A photosensitive element provided with a support body and the photosensitive layer which uses the photosensitive resin composition in any one of Claims 1-11 on this support body.   A permanent mask resist formed by the photosensitive resin composition according to claim 1 or the photosensitive element according to claim 12.   A printed wiring board comprising the permanent mask resist according to claim 13.