JPWO2008140017A1 - Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method - Google Patents

Abstract

The photosensitive resin composition of the present invention comprises (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator containing a compound having an oxime ester bond, and (C) a compound having a thiol group. It contains.

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a resist pattern forming method, and a printed wiring board manufacturing method.

  Conventionally, a permanent mask resist in the production of printed wiring boards has been produced by a method of screen printing a heat or ultraviolet curable resist ink. In recent years, with the high integration of electronic devices, it has become necessary to increase the definition of wiring patterns and insulating patterns in printed wiring boards. However, in the conventional resist forming method by screen printing, bleeding and sagging occur at the time of printing, and it is difficult to form a high-definition resist image. Therefore, in order to form a high-definition resist image, a resist image forming method by photolithography has been developed. Specifically, a dry film type photosensitive resist is thermocompression-bonded on a substrate, or a liquid photosensitive resist is curtain-coated or spray-coated on a substrate, and actinic rays such as ultraviolet rays are passed through a negative mask. After irradiation, development is performed to form a resist image. In the case of a dry film type photosensitive resist, air is easily entrapped at the time of thermocompression bonding to the base material, and bubbles are likely to be generated.

  On the other hand, liquid photosensitive resists are classified into a solvent development type and an alkali development type, but the alkali development type is mainly used from the viewpoint of working environment preservation and global environment preservation. As such an alkali development type photosensitive resist (photosensitive resin composition), those shown in Patent Documents 1 and 2 below are known. In addition, for the purpose of improving the heat resistance, chemical resistance and electrical properties of the coating film, the coating film is further subjected to ultraviolet exposure and heating to promote the crosslinking reaction.

  By the way, as a method for forming a resist pattern, a so-called direct drawing exposure method in which a resist pattern is directly drawn without using a mask pattern has attracted attention. According to this direct drawing exposure method, it is considered possible to form a resist pattern with high productivity and high resolution. In recent years, a gallium nitride blue laser light source that oscillates a laser beam having a wavelength of 405 nm and has a long lifetime has become practically usable as a light source. The use of laser light is expected to enable the formation of a high-density resist pattern that has been difficult to manufacture. As such a direct drawing exposure method, a method using a DLP (Digital Light Processing) system proposed by Texas Instruments has been proposed by Ball Semiconductor, and an exposure apparatus using this method has already been put into practical use. It has begun.

  Furthermore, some photosensitive resin compositions intended to form a resist pattern by a direct drawing exposure method using a laser such as a blue laser as an actinic ray as described above have been proposed so far (for example, Patent Documents). 3 and 4).

JP-A 61-243869 JP-A-1-141904 JP 2002-296664 A JP 2004-45596 A

  However, although the photosensitive resin compositions described in Patent Documents 3 and 4 have good sensitivity to light in the vicinity of a wavelength of 405 nm, they tend to gel with time and have insufficient stability over time. have.

  The present invention has been made in view of the above-described problems of the prior art, and can form a resist pattern using exposure light within a wavelength range of 370 nm to 450 nm with sufficient sensitivity and resolution. To provide a photosensitive resin composition that does not gel even if left for a long period of time and has excellent stability over time, a photosensitive element using the same, a method for forming a resist pattern, and a method for producing a printed wiring board Objective.

  In order to achieve the above object, the present invention provides (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerization initiator containing a compound having an oxime ester bond, and (C) a compound having a thiol group. , A photosensitive resin composition is provided.

  According to such a photosensitive resin composition, it is sufficient to form a resist pattern using exposure light having a wavelength in the range of 370 nm to 450 nm, particularly to form a resist pattern by a direct drawing exposure method using laser light having a wavelength of 405 nm. (C) A compound having a thiol group, together with a photopolymerization initiator including (A) an acid-modified vinyl group-containing epoxy resin, and (B) a compound having an oxime ester bond. By containing the (C) thiol group-containing compound, the photosensitive resin composition can be sufficiently prevented from gelling with time, and good aging stability can be obtained. Can do.

  Furthermore, according to the photosensitive resin composition of the present invention having the above-mentioned configuration, a high-performance cured film excellent in heat resistance, heat and humidity resistance, adhesion, mechanical properties, and electrical properties can be formed. It can be suitably used for the production of high-density multilayer boards and semiconductor packages.

  Moreover, it is preferable that the photosensitive resin composition of this invention further contains the sensitizer which has (D) maximum absorption wavelength in the range of 370 nm-450 nm.

  Gelation of the photosensitive resin composition is likely to occur particularly when a sensitizer is contained. On the other hand, the photosensitive resin composition of the present invention can sufficiently suppress the occurrence of gelation by the (D) sensitizer by containing the compound (C) having the thiol group. . On the other hand, by including (D) a sensitizer having an absorption maximum wavelength in a specific wavelength range, it is possible to improve the photosensitivity with respect to laser light having a wavelength of about 405 nm, and within a wavelength range of 370 nm to 450 nm. Formation of a resist pattern using exposure light, in particular, formation of a resist pattern by a direct drawing exposure method using laser light having a wavelength of 405 nm can be performed with better sensitivity and resolution.

  In the photosensitive resin composition of the present invention, the compound having an oxime ester bond preferably contains at least one compound represented by the following general formula (1) or (2).

［式（１）中、Ｒ^１は炭素数２〜１２の置換若しくは未置換のアルカノイル基、二重結合がカルボニル基と共役していない炭素数４〜６の置換若しくは未置換のアルケノイル基、置換若しくは未置換のベンゾイル基、炭素数２〜６の置換若しくは未置換のアルコキシカルボニル基、又は、置換若しくは未置換のフェノキシカルボニル基を示し、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立に、ハロゲン原子、炭素数１〜１２の置換若しくは未置換のアルキル基、置換若しくは未置換のシクロペンチル基、置換若しくは未置換のシクロヘキシル基、置換若しくは未置換のフェニル基、置換若しくは未置換のベンジル基、置換若しくは未置換のベンゾイル基、炭素数２〜１２の置換若しくは未置換のアルカノイル基、炭素数２〜１２の置換若しくは未置換のアルコキシカルボニル基、又は、置換若しくは未置換のフェノキシカルボニル基を示し、ｍ１は０〜４の整数を示し、ｍ２及びｍ３は各々独立に０〜５の整数を示す。なお、ｍ１が２以上である場合、複数存在するＲ^２はそれぞれ同一でも異なっていてもよく、ｍ２が２以上である場合、複数存在するＲ^３はそれぞれ同一でも異なっていてもよく、ｍ３が２以上である場合、複数存在するＲ^４はそれぞれ同一でも異なっていてもよい。］

[In Formula (1), R ¹ is a substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkenoyl group having 4 to 6 carbon atoms in which a double bond is not conjugated to a carbonyl group, substituted Or an unsubstituted benzoyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, wherein R ² , R ³ and R ⁴ are each independently a halogen atom Substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted Substituted benzoyl group, substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, substituted or unsubstituted group having 2 to 12 carbon atoms Conversion of an alkoxycarbonyl group, or a substituted or indicates unsubstituted phenoxycarbonyl group, m1 represents an integer of 0 to 4, m @ 2 and m3 each show independently an integer of 0-5. In addition, when m1 is 2 or more, a plurality of R ² may be the same or different, and when m2 is 2 or more, a plurality of R ³ may be the same or different, and m3 is When it is 2 or more, a plurality of R ⁴ may be the same or different. ]

［式（２）中、Ｒ^５は置換若しくは未置換のフェニル基、炭素数１〜６の置換若しくは未置換のアルキル基、置換若しくは未置換のフェニル基、炭素数１〜２０の置換若しくは未置換のアルキル基、炭素数５〜８の置換若しくは未置換のシクロアルキル基、炭素数２〜２０の置換若しくは未置換のアルカノイル基、又は、置換若しくは未置換のベンゾイル基を示し、Ｒ^６は炭素数２〜１２の置換若しくは未置換のアルカノイル基、二重結合がカルボニル基と共役していない炭素数４〜６の置換若しくは未置換のアルケノイル基、置換若しくは未置換のベンゾイル基、炭素数２〜６の置換若しくは未置換のアルコキシカルボニル基、又は、置換若しくは未置換のフェノキシカルボニル基を示し、Ｒ^７は水素原子、ハロゲン原子、炭素数１〜１２の置換若しくは未置換のアルキル基、置換若しくは未置換のシクロペンチル基、置換若しくは未置換のシクロヘキシル基、置換若しくは未置換のフェニル基、置換若しくは未置換のベンジル基、置換若しくは未置換のベンゾイル基、炭素数２〜１２の置換若しくは未置換のアルカノイル基、炭素数２〜１２の置換若しくは未置換のアルコキシカルボニル基、又は、置換若しくは未置換のフェノキシカルボニル基を示し、Ｒ^８、Ｒ^９及びＲ^１０はそれぞれ独立に、ハロゲン原子、炭素数１〜１２の置換若しくは未置換のアルキル基、置換若しくは未置換のシクロペンチル基、置換若しくは未置換のシクロヘキシル基、置換若しくは未置換のフェニル基、置換若しくは未置換のベンジル基、置換若しくは未置換のベンゾイル基、炭素数２〜１２の置換若しくは未置換のアルカノイル基、炭素数２〜１２の置換若しくは未置換のアルコキシカルボニル基、又は、置換若しくは未置換のフェノキシカルボニル基を示し、ｍ４及びｍ５はそれぞれ独立に０〜３の整数を示し、ｍ６は０〜５の整数を示す。なお、ｍ４が２以上である場合、複数存在するＲ^８はそれぞれ同一でも異なっていてもよく、ｍ５が２以上である場合、複数存在するＲ^９はそれぞれ同一でも異なっていてもよく、ｍ６が２以上である場合、複数存在するＲ^１０はそれぞれ同一でも異なっていてもよい。］

[In the formula (2), R ⁵ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group having 1 to 20 carbon atoms. A substituted or unsubstituted cycloalkyl group having 5 to 8 carbon atoms, a substituted or unsubstituted alkanoyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted benzoyl group, and R ⁶ represents the number of carbon atoms A substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkenoyl group having 4 to 6 carbon atoms in which the double bond is not conjugated to a carbonyl group, a substituted or unsubstituted benzoyl group, 2 to 6 carbon atoms a substituted or unsubstituted alkoxycarbonyl group, or a substituted or indicates unsubstituted phenoxycarbonyl group, R ⁷ is a hydrogen atom, a halogen atom, a carbon number 1 to 1 Substituted or unsubstituted alkyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted benzoyl group, carbon A substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, and R ⁸ , R ⁹ and R ¹⁰ are Each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group Benzyl group, substituted or unsubstituted benzoyl group, 2 to 1 carbon atoms A substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, m4 and m5 each independently represents an integer of 0 to 3; M6 represents an integer of 0 to 5. In addition, when m4 is 2 or more, a plurality of R ⁸ may be the same or different, and when m5 is 2 or more, a plurality of R ⁹ may be the same or different, and m6 is When it is 2 or more, a plurality of R ¹⁰ may be the same or different. ]

  (B) By containing the compound which has the oxime ester bond represented by the said General formula (1) or (2) as a photoinitiator, the photosensitive resin composition is exposure within the range of wavelength 370nm-450nm. Formation of a resist pattern using light, particularly, formation of a resist pattern by a direct drawing exposure method using a laser beam having a wavelength of 405 nm can be performed with better sensitivity and resolution.

  Moreover, in the photosensitive resin composition of this invention, it is preferable that the compound which has the said (C) thiol group contains the compound represented by following General formula (3).

［式中、Ａｒは、置換基を有していてもよい２価又は３価のアリール基を示し、Ｘは酸素原子、窒素原子又は硫黄原子を示す。］

[Wherein Ar represents a divalent or trivalent aryl group which may have a substituent, and X represents an oxygen atom, a nitrogen atom or a sulfur atom. ]

  (C) By using the compound represented by the general formula (3) as the compound having a thiol group, the photosensitive resin composition can be more sufficiently suppressed from being gelled over time, and is more favorable. Can be obtained.

  In the photosensitive resin composition of the present invention, the (A) acid-modified vinyl group-containing epoxy resin is represented by the following general formula (4), a novolac type epoxy resin, and the following general formula (5). At least one epoxy resin (a) selected from the group consisting of a bisphenol-type epoxy resin and a salicylaldehyde-type epoxy resin represented by the following general formula (6); and a vinyl group-containing monocarboxylic acid (b) It is preferable that it is resin obtained by making these react.

［式中、Ｒ^１１は水素原子又はメチル基を示し、Ｙ^１は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ１は１以上の整数を示す。なお、複数存在するＲ^１１及びＹ^１はそれぞれ同一でも異なっていてもよい。］

[Wherein, R ¹¹ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n1 represents An integer of 1 or more is shown. A plurality of R ¹¹ and Y ¹ may be the same or different. ]

［式中、Ｒ^１２は水素原子又はメチル基を示し、Ｙ^２は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ２は１以上の整数を示す。なお、複数存在するＲ^１２及びＹ^２はそれぞれ同一でも異なっていてもよい。］

[Wherein R ¹² represents a hydrogen atom or a methyl group, Y ² represents a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n2 represents An integer of 1 or more is shown. A plurality of R ¹² and Y ² may be the same or different. ]

［式中、Ｙ^３は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ３は１以上の整数を示す。なお、複数存在するＲ^１１及びＹ^３はそれぞれ同一でも異なっていてもよい。］

[Wherein Y ³ represents a hydrogen atom or a glycidyl group (where hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n3 represents an integer of 1 or more. A plurality of R ¹¹ and Y ³ may be the same or different. ]

  By using the (A) acid-modified vinyl group-containing epoxy resin, the photosensitive resin composition can form a resist pattern using exposure light within a wavelength range of 370 nm to 450 nm, particularly using a laser beam having a wavelength of 405 nm. It is possible to form a resist pattern by the direct drawing exposure method with higher sensitivity and resolution.

  The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention formed on the support.

  According to such a photosensitive element, by providing the photosensitive resin composition layer composed of the above-described photosensitive resin composition of the present invention, formation of a resist pattern using exposure light within a wavelength range of 370 nm to 450 nm, particularly The resist pattern can be formed with sufficient sensitivity and resolution by a direct drawing exposure method using a laser beam having a wavelength of 405 nm.

  The present invention also includes a laminating step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention on a substrate, and exposure by irradiating the photosensitive resin composition layer with actinic rays in an image form. There is provided a resist pattern forming method including an exposure step of photocuring a portion and a development step of removing an unexposed portion of the photosensitive resin composition layer by development.

  Here, the exposure step is preferably a step in which the photosensitive resin composition layer is directly drawn and exposed with a laser beam having a wavelength of 405 nm to photocur the exposed portion.

  According to such a method for forming a resist pattern, since the above-described photosensitive resin composition of the present invention is used, a resist pattern with sufficient resolution can be efficiently formed. Moreover, the resist pattern formed by such a method becomes a high-performance cured film excellent in heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties.

  The present invention further provides a method for producing a printed wiring board, in which a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern of the present invention is etched or plated.

  According to such a method for manufacturing a printed wiring board, since the resist pattern is formed by the resist pattern forming method of the present invention, it is possible to realize a high density of wiring.

  According to the present invention, resist pattern formation using exposure light in a wavelength range of 370 nm to 450 nm, particularly resist pattern formation by direct drawing exposure method using laser light having a wavelength of 405 nm with sufficient sensitivity and resolution. A photosensitive resin composition that does not gel when left for a long period of time and has excellent stability over time, a photosensitive element using the same, a resist pattern forming method, and a printed wiring board A manufacturing method can be provided. Further, according to the photosensitive resin composition and photosensitive element of the present invention, in a direct drawing exposure method using a blue laser beam having a wavelength of 405 nm as a light source, it is possible to form a high-density resist pattern that has been difficult to manufacture. It is possible to obtain a high-performance cured film that is excellent in heat resistance, moist heat resistance (shear adhesiveness), adhesion, mechanical properties, and electrical properties. Therefore, the photosensitive resin composition and photosensitive element of the present invention are suitably used for the production of printed wiring boards, high-density multilayer boards, semiconductor packages, and the like.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive resin composition layer.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present invention, (meth) acryl means acryl and methacryl corresponding thereto, and (meth) acrylate means acrylate and methacrylate corresponding thereto.

  The photosensitive resin composition of the present invention comprises (A) an acid-modified vinyl group-containing epoxy resin (hereinafter sometimes referred to as “component (A)”) and (B) a compound having an oxime ester bond. (Hereinafter referred to as “component (B)” in some cases) and (C) a compound having a thiol group (hereinafter referred to as “(C) component” in some cases), preferably (D) It further contains a sensitizer having a maximum absorption wavelength in the range of 370 nm to 450 nm (hereinafter sometimes referred to as “component (D)”). Hereinafter, each component will be described in detail.

  As the (A) acid-modified vinyl group-containing epoxy resin used in the present invention, a resin obtained by modifying an epoxy resin with a vinyl group-containing monocarboxylic acid is used, and preferably a novolac type epoxy represented by the following general formula (4) At least one selected from the group consisting of a resin, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin represented by the following general formula (5), and a salicylaldehyde type epoxy resin represented by the following general formula (6) A resin obtained by reacting the epoxy resin (a) with the vinyl group-containing monocarboxylic acid (b) is used.

［式中、Ｒ^１１は水素原子又はメチル基を示し、Ｙ^１は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ１は１以上の整数を示す。なお、複数存在するＲ^１１及びＹ^１はそれぞれ同一でも異なっていてもよい。］

[Wherein, R ¹¹ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n1 represents An integer of 1 or more is shown. A plurality of R ¹¹ and Y ¹ may be the same or different. ]

［式中、Ｒ^１２は水素原子又はメチル基を示し、Ｙ^２は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ２は１以上の整数を示す。なお、複数存在するＲ^１２及びＹ^２はそれぞれ同一でも異なっていてもよい。］

[Wherein R ¹² represents a hydrogen atom or a methyl group, Y ² represents a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n2 represents An integer of 1 or more is shown. A plurality of R ¹² and Y ² may be the same or different. ]

［式中、Ｙ^３は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ３は１以上の整数を示す。なお、複数存在するＲ^１１及びＹ^３はそれぞれ同一でも異なっていてもよい。］

[Wherein Y ³ represents a hydrogen atom or a glycidyl group (where hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n3 represents an integer of 1 or more. A plurality of R ¹¹ and Y ³ may be the same or different. ]

  The (A) acid-modified vinyl group-containing epoxy resin used in the present invention is a reaction product of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) (hereinafter referred to as “reactive organism (A ′)”). In addition, an addition reaction product obtained by adding a saturated or unsaturated group-containing polybasic acid anhydride (c) to the reaction product (A ′) can also be used. Here, when the addition reaction product is synthesized, in the first reaction, a hydroxyl group is formed by the addition reaction of the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b), and the next reaction The resulting hydroxyl group (including the hydroxyl group originally contained in the epoxy resin (a)) and the acid anhydride group of the saturated or unsaturated group-containing polybasic acid anhydride (c) undergo a half-ester reaction; Inferred.

  Examples of the novolak type epoxy resin represented by the general formula (4) include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. These novolak type epoxy resins can be obtained by reacting a phenol novolak resin and a cresol novolak resin with epichlorohydrin, respectively, by a known method.

In the compound represented by the general formula (5), the bisphenol A type epoxy resin or bisphenol F type epoxy resin in which Y ² is a glycidyl group is, for example, a bisphenol A type epoxy resin represented by the following general formula (7). Alternatively, it can be obtained by reacting the hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin.

［式中、Ｒ^１２は水素原子又はメチル基を示し、ｎ２は１以上の整数を示す。なお、複数存在するＲ^１２はそれぞれ同一でも異なっていてもよい。］

[Wherein, R ¹² represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more. A plurality of R ¹² may be the same or different. ]

  In order to promote the reaction between the hydroxyl group and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. If the reaction temperature is less than 50 ° C., the reaction is slow, and if the reaction temperature exceeds 120 ° C., many side reactions occur, which is not preferable.

  Specific examples of the salicylaldehyde type epoxy resin represented by the general formula (6) include FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) and the like. .

  Examples of the vinyl group-containing monocarboxylic acid (b) include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α- Cyanocinnamic acid and the like, and a half-ester compound, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester which is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride or The half-ester compound which is a reaction product with an unsaturated dibasic acid anhydride is mentioned. These half ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated 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 acrylate, hydroxyethyl Methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol tris Methacrylate, dipentaerythritol pentaacrylate, Data dipentaerythritol methacrylate, glycidyl acrylate, glycidyl methacrylate and the like.

  Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the epoxy resin (a) with 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). The reaction is preferably performed at a ratio of 05 equivalents, more preferably at a ratio of 0.8 to 1.05 equivalents, and particularly preferably at a ratio of 0.9 to 1.0 equivalents.

  The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) are preferably dissolved and reacted 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 Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Furthermore, it is preferable to use a catalyst to promote the reaction. Examples of the catalyst used 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).

  Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. 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). Moreover, reaction temperature becomes like this. Preferably it is 60-150 degreeC, More preferably, it is 80-120 degreeC.

  Further, 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 acid A polybasic acid anhydride such as an anhydride can be used in combination.

  In the present invention, (A) the acid-modified vinyl group-containing epoxy resin is a resin obtained by reacting the above-mentioned reaction product (A ′) with a saturated or unsaturated group-containing polybasic acid anhydride (c). Are also preferably used.

  Examples of the saturated or unsaturated group-containing polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydro anhydride Examples include phthalic acid, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the reaction product (A ′) with the saturated or unsaturated group-containing polybasic acid anhydride (c), a saturated or unsaturated group-containing polyhydric acid is used with respect to 1 equivalent of the hydroxyl group in the reaction product (A ′). By reacting 0.1 to 1.0 equivalent of the basic acid anhydride (c), the acid value of the acid-modified vinyl group-containing epoxy resin (A) can be adjusted.

  (A) The acid value of the acid-modified vinyl group-containing epoxy resin is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. If the acid value is less than 30 mgKOH / g, the solubility of the photosensitive resin composition in a dilute alkali solution tends to be reduced, and if it exceeds 150 mgKOH / g, the electric properties of the resulting cured film tend to be reduced.

  The reaction temperature between the reaction product (A ′) and the saturated or unsaturated group-containing 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. Further, (A) acid-modified vinyl group-containing epoxy resin, styrene-maleic acid series such as hydroxyethyl acrylate modified product of styrene-maleic anhydride copolymer or hydroxyethyl acrylate modified product of styrene-maleic anhydride copolymer A part of the resin may be used in combination.

  In the photosensitive resin composition, the content of the component (A) is preferably 10 to 60% by mass, more preferably 20 to 40% by mass, based on the total solid content of the photosensitive resin composition. Preferably, it is 20-30 mass%, and it is especially preferable. When this content is less than 10% by mass, the heat resistance tends to be inferior, and when it exceeds 60% by mass, the curability tends to be inferior.

  As the compound having an oxime ester bond contained in the photopolymerization initiator (B) used in the present invention, a compound represented by the following general formula (1) or (2) is preferably used.

In the general formula (1), R ¹ is a substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkenoyl group having 4 to 6 carbon atoms in which a double bond is not conjugated to a carbonyl group, A substituted or unsubstituted benzoyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group is shown. Here, when the alkanoyl group has one or more substituents, the substituent is preferably a halogen atom or a cyano group. When the benzoyl group has one or more substituents, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. When the phenoxycarbonyl group has one or more substituents, the substituent is preferably an alkyl group having 1 to 6 carbon atoms or a halogen atom.

In the general formula (1), R ² , R ³ and R ⁴ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cyclopentyl group, substituted or Unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted benzoyl group, substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, or having 2 to 12 carbon atoms A substituted or unsubstituted alkoxycarbonyl group or a substituted or unsubstituted phenoxycarbonyl group is shown. Here, when the alkoxycarbonyl group has one or more substituents, the substituent is preferably a hydroxyl group or an alkoxy group.

Moreover, in the said General formula (1), m1 shows the integer of 0-4, m2 and m3 show the integer of 0-5 each independently. In addition, when m1 is 2 or more, a plurality of R ² present in the general formula (1) may be the same or different, and when m2 is 2 or more, a plurality of R ² are present in the general formula (1). R ³ may be the same or different, and when m3 is 2 or more, a plurality of R ⁴ present in the general formula (1) may be the same or different.

In the general formula (2), R ⁵ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group having 1 to 20 carbon atoms. A substituted alkyl group, a substituted or unsubstituted cycloalkyl group having 5 to 8 carbon atoms, a substituted or unsubstituted alkanoyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted benzoyl group is shown. Here, when the alkyl group has one or more substituents, the substituent is preferably a hydroxyl group or an alkoxy group. When the benzoyl group has one or more substituents, the substituent is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.

In the general formula (2), R ⁶ is a substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted alkenoyl group having 4 to 6 carbon atoms in which a double bond is not conjugated to a carbonyl group. A group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group; Here, when the alkanoyl group has one or more substituents, the substituent is preferably a halogen atom or a cyano group. When the benzoyl group has one or more substituents, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. When the phenoxycarbonyl group has one or more substituents, the substituent is preferably an alkyl group having 1 to 6 carbon atoms or a halogen atom.

In the general formula (2), R ⁷ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted Or an unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms Group, or a substituted or unsubstituted phenoxycarbonyl group, R ⁸ , R ⁹ and R ¹⁰ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted group. Cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted Is an unsubstituted benzyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted group The phenoxycarbonyl group of is shown. Here, when the alkoxycarbonyl group has one or more substituents, the substituent is preferably a hydroxyl group or an alkoxy group.

Moreover, in said general formula (2), m4 and m5 show the integer of 0-3 each independently, and m6 shows the integer of 0-5. In addition, when m4 is 2 or more, a plurality of R ⁸ may be the same or different, and when m5 is 2 or more, a plurality of R ⁹ may be the same or different, and m6 is When it is 2 or more, a plurality of R ¹⁰ may be the same or different.

  More specifically, the compound having an oxime ester bond contained in the photopolymerization initiator (B) used in the present invention is more specifically 1,2-octanedione-1- [4- represented by the following formula (8). (Phenylthio) phenyl] -2- (O-benzoyloxime) (trade name: OXE-01, manufactured by Ciba Specialty Chemicals), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] ethanone 1- (O-acetyloxime) (trade name: OXE-02, manufactured by Ciba Specialty Chemicals), 1-phenyl-1,2-propanedione-2- [O- (ethoxycarbonyl) oxime ] (Trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.).

  Moreover, in the photosensitive resin composition of this invention, photoinitiators other than the compound which has the said oxime ester bond can be used together as (B) component.

  Examples of the photopolymerization initiator other than the compound having an oxime ester bond include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- Aromatic ketones such as (methylthio) phenyl] -2-morpholino-propanone-1, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroant Anthraquinones such as quinone, 2-amylanthraquinone, 2-aminoanthraquinone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl Benzophenones such as sulfide, 9-phenylacridine, acridine derivatives such as 1,7-bis (9,9′-acridinyl) heptane, 2,4,5-triarylimidazole dimer or derivatives thereof, 2,4, Examples include 6-trimethylbenzoyldiphenylphosphine oxide. These can be used individually by 1 type or in combination of 2 or more types.

  In the photosensitive resin composition, the content of the component (B) is preferably 0.5 to 20% by mass, preferably 2 to 10% by mass, based on the total solid content of the photosensitive resin composition. Is more preferable, and 2 to 5% by mass is particularly preferable. If this content is less than 0.5% by mass, the exposed part tends to be eluted during development, and if it exceeds 20% by mass, the heat resistance of the resulting cured film tends to be reduced.

  The compound (C) having a thiol group used in the photosensitive resin composition of the present invention is preferably a compound that effectively functions as a hydrogen donor. Such a compound is represented by the following general formula (3). Are preferred.

［式中、Ａｒは、置換基を有していてもよい２価又は３価のアリール基を示し、Ｘは酸素原子、窒素原子又は硫黄原子を示す。］

[Wherein Ar represents a divalent or trivalent aryl group which may have a substituent, and X represents an oxygen atom, a nitrogen atom or a sulfur atom. ]

  Specific examples of the compound (C) having a thiol group include, for example, mercaptobenzoxazole (MBO) represented by the following formula (9), mercaptobenzothiazole (MBT) represented by the following formula (10), and the following formula (11) ) Mercaptobenzimidazole (MBI), ethanethiol, benzenethiol, mercaptophenol, mercaptotoluene, 2-mercaptoethylamine, mercaptoethyl alcohol, mercaptoxylene, thioxylenol, 2-mercaptoquinoline, mercaptoacetic acid, α-mercaptopropion Acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thiosalicylic acid, mercaptocyclohexane, α-mercaptodiphenylmethane, C-mercaptotetrazole, mercaptonaphthalene, mercaptonaphth Tol, 4-mercaptobiphenyl, mercaptohypoxanthine, mercaptopyridine, 2-mercaptopyrimidine, mercaptopurine, thiocoumazone, thiocumothiazone, butane-2,3-dithiol, thiocyanuric acid, 2,4,6-trimercapto-s-triazine, Examples include 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, and the like.

  These (C) compounds having a thiol group can be used singly or in combination of two or more. Among these, a compound having a mercapto group in the molecule is preferable from the viewpoint of effectively functioning as a hydrogen donor and further improving the sensitivity and aging stability of the photosensitive resin composition. Oxazole (MBO), mercaptobenzothiazole (MBT) and mercaptobenzimidazole (MBI) are preferred.

  In the photosensitive resin composition, the content of the component (C) is preferably 0.1 to 5% by mass, based on the total solid content of the photosensitive resin composition, and is 0.3 to 3% by mass. More preferably, it is particularly preferably 0.5 to 1.5% by mass. If the content is less than 0.1% by mass, the solution of the photosensitive resin composition tends to gel, and if it exceeds 5% by mass, the sensitivity tends to decrease.

  The photosensitive resin composition of the present invention preferably contains (D) a sensitizer from the viewpoint of further improving photosensitivity.

  Examples of the sensitizer that is component (D) include anthracene such as pyrazolines and dialkoxyanthracene, coumarins, xanthones, thioxanthones, 4,4′-bis (dialkylamino) benzophenones, oxazoles, Examples include benzoxazoles, thiazoles, triazoles, stilbenes, triazines, and thiophenes. These are used individually by 1 type or in combination of 2 or more types.

  The photosensitive resin composition of the present invention preferably contains (D) one or more compounds selected from the group consisting of pyrazoline, anthracene, coumarin and xanthone and / or derivatives thereof as a sensitizer. Moreover, it is more preferable that pyrazoline, anthracene, coumarin, xanthone, and derivatives thereof are compounds having an absorption maximum wavelength in a wavelength range of 370 nm to 450 nm. Further, it is more preferable that pyrazoline, anthracene, coumarin, xanthone, and derivatives thereof are compounds having a maximum absorption wavelength within a wavelength range of 370 nm to 450 nm.

［式（１２）中、Ｒはそれぞれ独立に、炭素数１〜１２のアルキル基、又は、炭素数１〜１０のアルコキシ基を示し、ａ、ｂ及びｃはそれぞれ、ａ、ｂ及びｃの総和が１〜６となるように選ばれる０〜２の整数を示す。なお、ａ、ｂ及びｃの総和が２〜６のとき、同一分子中の複数のＲはそれぞれ同一であっても異なっていてもよい。］Among the sensitizers as the component (D), pyrazolines are preferable from the viewpoint of improving sensitivity, and pyrazoline derivatives represented by the following general formula (12) are particularly preferable.

[In formula (12), each R independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and a, b and c are the sum of a, b and c, respectively. Represents an integer of 0 to 2 which is selected so as to be 1 to 6. When the sum of a, b and c is 2 to 6, a plurality of R in the same molecule may be the same or different. ]

  In addition, from the viewpoint of solubility in an organic solvent, R in the general formula (12) is independently an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. More preferred.

  In the photosensitive resin composition, the content of the component (D) is preferably 0.01 to 5% by mass, and 0.1 to 2% by mass based on the total solid content of the photosensitive resin composition. More preferably, it is particularly preferably 0.2 to 1% by mass. When this content is within the above range, good sensitivity can be obtained.

  In the photosensitive resin composition of the present invention, it is preferable to use the component (B), the component (C) and the component (D) in combination from the viewpoint of sensitivity. In particular, when 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline represented by the following general formula (13) is used as the component (D), The component (C) acts very effectively as a hydrogen donor.

  The presumed reaction mechanism when these (B) component, (C) component, and (D) component are combined and irradiated with an ultraviolet-ray is shown below, giving an example compound. First, (D) the pyrazoline compound (Sens) represented by the above formula (13), which is a sensitizer, absorbs light at 405 nm and becomes a singlet excited state. A doublet excited state is obtained (reaction formula (I)). The following two mechanisms (i) and (ii) are conceivable until the subsequent radical generation.

  (I) One is represented by the above formula (8) having an oxime ester bond which is a photopolymerization initiator (B) by energy transfer from a sensitizer (Sens) excited in a triplet by crossing the system. The compound (OXE-01) is excited (reaction formula (II)), and then the photopolymerization initiator in a triplet excited state is decomposed to generate radicals (reaction formula ( III)).

  (Ii) The other is a sensitization mechanism by electron transfer, and the above formula (B) having an oxime ester bond which is a photopolymerization initiator by electron transfer from (D) sensitizer (Sens) ( This is a mechanism in which an anion radical of the compound (OXE-01) represented by 8) is generated (reaction formula (IV)) and is decomposed to generate a radical (reaction formula (V)).

  The inventors of the present invention examined whether the radical is generated by the mechanism (i) or (ii) described above by quantum chemical calculation. The calculation program uses Gaussian 03, the structure is optimized at the B3LYP / 6-31G (d) level, the molecular orbital (HOMO and LUMO) levels, and the pyrazoline compound represented by the above formula (13), which is a sensitizer The triplet energy of the compound (OXE-01) represented by the above formula (8) having (Sens) and an oxime ester bond was determined by TD calculation.

Here, Rehm-Weller et al. Show an equation represented by the following (A-1) for the ease of photoelectron transfer, and the reaction rate increases as ΔG is negative, from −10 (kcal / mol) It was also shown that the diffusion rate is controlled when the negative value is large.
ΔG = Eox−Ered−hν (eV) (A-1)
[Eox: oxidation potential of electron donor (V vs. Ag / AgCl), Ered: reduction potential of electron acceptor (V vs. Ag / AgCl), hν: excitation energy (eV) by light. ]

If the above formula (A-1) is translated into the formula of quantum chemistry calculation, the standard energy level is determined from Eox (oxidation potential, V) and Ered (reduction potential, V) with respect to the reference electrode to HOMO (maximum) with respect to the vacuum level. It only changes to the energy of the occupied orbit, eV) and LUMO (lowest empty orbit, eV), and can be described by the following equation (A-2) using _εHOMO and _εLUMO , respectively.
_{ΔG = -ε HOMO + ε LUMO -hν} (eV) (A-2)
[Ε _HOMO: electron donor (Sens) of the HOMO level (eV) = - 4.695 (eV ), ε LUMO: LUMO level of the electron acceptor (OXE-01) (eV) = - 2.090 ( eV), hν: excitation energy by light (eV) = 3.062 (eV) at 405 nm. ]

  From the above formula (A-2), ΔG = −0.456 (eV) = − 10.53 (kcal / mol), and this electron transfer reaction is considered to proceed easily.

  Further, the triplet energies of Sens and OXE-01 obtained by TD calculation are T1 (Sens) = 3.02 (eV) and T1 (OXE-01) = 3.19 (eV), respectively. The triplet energy transfer to 01 is unlikely to occur.

  Therefore, it is considered that the radical generation mechanism of OXE-01 when Sens is used is due to the electron transfer reaction (ii).

  When ΔG is a positive value, the efficiency of electron transfer is low, and when ΔG is a negative value, the efficiency of electron transfer is high, and the efficiency of electron transfer is the highest near −10 kcal / mol, and negative efficiency greater than −10 kcal / mol. In the case of the value, it is known that the efficiency of electron transfer is about the same as or lower than that at −10 kcal / mol due to the diffusion rate-limiting of the sensitizer (GJ Kavamos, Hiroshi Kobayashi, “Photoelectron “Migration” Maruzen (1997) p334-337). That is, from the viewpoint of improving the efficiency of electron transfer, ΔG is most preferably in the vicinity of −10 kcal / mol.

  As described above, it is presumed that the sensitivity of the photosensitive resin composition can be further improved when the efficiency of electron transfer is around -10 kcal / mol.

  Table 1 below shows (D) sensitizers of photopolymerization initiators containing various compounds having (B) oxime ester bonds, pyrazoline compounds represented by the above formula (13), and coumarin compounds represented by the following formula (14). The quantum chemistry calculation result at the time of using together is shown.

＊ＮＦ−ＥＯ：上記式（１３）に示すピラゾリン化合物
＊Ｃｏｕｍａｒｉｎ１：下記式（１４）に示すクマリン化合物
＊ＰＤＯ：下記式（１５）に示すオキシムエステル結合を有する化合物

* NF-EO: pyrazoline compound represented by the above formula (13) * Coumarin 1: a coumarin compound represented by the following formula (14) * PDO: a compound having an oxime ester bond represented by the following formula (15)

  On the other hand, regarding the energy transfer of (i) above, as a necessary condition for energy transfer, the triplet energy of (D) sensitizer needs to be higher than the triplet energy of the photopolymerization initiator. It is difficult to predict the efficiency of movement.

  Next, the radical derived from OXE-01 produced by the reaction described above and (C) the compound (MBO) represented by the above formula (9) having a thiol group react to cause chain transfer, resulting in a highly active sulfur radical. (Reaction formulas (VI) and (VII)) can be considered. It is assumed that this sulfur radical becomes an active ingredient that promotes the photopolymerization reaction.

  Moreover, it is preferable that the photosensitive resin composition of this invention contains (E) elastomer from a viewpoint which can improve a thermal shock resistance and shear adhesiveness.

  Examples of (E) elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These (E) 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.

  Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and the like.

  As a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used in addition to styrene. Specifically, Tufprene, Sorprene T, Asaprene T, Tuftec (made by Asahi Kasei Kogyo Co., Ltd.), Elastomer AR (made by Aron Kasei), Clayton G, Over Reflex (made by Shell Japan), JSR-TR , TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.) ), Lavalon (Mitsubishi Chemical Co., Ltd.), Septon, Hibler (above, Kuraray Co., Ltd.), Sumiflex (Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (above, Riken Vinyl Industries).

  The olefin elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, for example, an ethylene-propylene copolymer (EPR). ), Ethylene-propylene-diene copolymer (EPDM) and the like. The olefin-based elastomer includes dicyclopentadiene, 1,4-hexadiene, cyclooctanediene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, and the like. Examples include coalesced and epoxidized polybutadiene. Examples of the olefin-based elastomer include carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymer with methacrylic acid. Further, as the olefin elastomer, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer Rubber etc. are mentioned.

  Specific examples of olefin-based elastomers include milastoma (manufactured by Mitsui Petrochemical), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (manufactured by Nippon Synthetic Rubber) ), Butadiene-acrylonitrile copolymer “NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.), “XER series” of both terminal carboxyl group-modified butadiene-acrylonitrile copolymers having a crosslinking point (manufactured by Nippon Synthetic Rubber Co., Ltd.), polybutadiene A partially epoxidized epoxidized polybudadiene “BF-1000 (manufactured by Nippon Soda Co., Ltd.)” and the like can be mentioned.

  Urethane elastomers are composed of structural units of a hard segment composed of low molecular (short chain) diol and diisocyanate and a soft segment composed of high molecular (long chain) diol and diisocyanate. Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene). Xylene carbonate), poly (1,6-hexylene-neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. Examples of the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48 to 500. Specific examples of the urethane elastomer include PANDEX T-2185, T-2983N (manufactured by Dainippon Ink & Chemicals, Inc.), sylactolan E790, and the like.

  Examples of the polyester elastomer include those obtained by polycondensation of dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, and the like, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used individually by 1 type or in combination of 2 or more types. Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And a dihydric phenol represented by the following general formula (16). These compounds can be used individually by 1 type or in combination of 2 or more types.

［式中、Ｙ^１１は単結合、炭素数１〜１０のアルキレン基、炭素数４〜８のシクロアルキレン基、−Ｏ−、−Ｓ−、又は、−ＳＯ_２−を示し、Ｒ^２１及びＲ^２２はハロゲン原子又は炭素数１〜１２のアルキル基を示し、ｐ及びｑは０〜４の整数を示し、ｒは０又は１を示す。］

[Wherein Y ¹¹ represents a single bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, or —SO ₂ —, and R ²¹ and R ²² represents a halogen atom or an alkyl group having 1 to 12 carbon atoms, p and q represent an integer of 0 to 4, and r represents 0 or 1. ]

  Specific examples of the dihydric phenol represented by the general formula (13) include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. It is done. These compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition, a multiblock copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used. There are various grades depending on the type, ratio, and molecular weight of the hard and soft segments. Specific examples include Hytrel (manufactured by DuPont-Toray Industries, Inc.), Perprene (manufactured by Toyobo Co., Ltd.), Espel (manufactured by Hitachi Chemical Co., Ltd.), and the like.

  Polyamide-based elastomers are roughly classified into two types, polyether block amide type and polyether ester block amide type, in which polyamide is used for the hard phase and polyether or polyester is used for the soft phase. As the polyamide, polyamide-6, 11, 12 or the like is used, and as the polyether, polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used. Specific examples of polyamide-based elastomers include UBE polyamide elastomer (manufactured by Ube Industries, Ltd.), Daiamide (manufactured by Daicel Hyrus Co., Ltd.), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan Co., Ltd.). ), Nopamid (manufactured by Mitsubishi Chemical Co., Ltd.), Glais (manufactured by Dainippon Ink Co., Ltd.)

  The acrylic elastomer is mainly composed of acrylic acid ester, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, or the like is used. Moreover, glycidyl methacrylate, allyl glycidyl ether, etc. are used as a crosslinking point monomer. Furthermore, acrylonitrile and ethylene can be copolymerized. Specific examples of the acrylic elastomer include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

  Silicone elastomers are mainly composed of organopolysiloxane, and can be classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Some are modified with vinyl groups, alkoxy groups, and the like. Specific examples of the silicone elastomer include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

  In addition to the above thermoplastic 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 bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or 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, in terms of shear adhesion, both terminal carboxyl group-modified butadiene-acrylonitrile copolymers and Espel (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), which are polyester elastomers having hydroxyl groups, are used. preferable.

  In the photosensitive resin composition of this invention, when using (E) elastomer, it is preferable that the content is 2-30 mass parts with respect to 100 mass parts of (A) component, 4-20 mass parts. It is more preferable that When the content is in the range of 2 to 30 parts by mass, the elastic modulus in the high temperature region of the cured film can be further reduced.

  It is preferable that the photosensitive resin composition of the present invention further contains (F) a diluent. (F) As a diluent, an organic solvent and / or a photopolymerizable monomer can be used, for example. 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 Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Examples of the photopolymerizable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol. Glycol mono- or di (meth) acrylates, N, N-dimethyl (meth) acrylamide, (meth) acrylamides such as N-methylol (meth) acrylamide, amino such as N, N-dimethylaminoethyl (meth) acrylate Polyhydric alcohols such as alkyl (meth) acrylates, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyethylene (meth) acrylates of these ethylene oxide or propylene oxide adducts, phenoxyethyl (meth) acrylate, (meth) acrylates of phenolic ethylene oxide or propylene oxide adducts such as polyethoxydi (meth) acrylate of bisphenol A And (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and melamine (meth) acrylate.

  These (F) diluents are used individually by 1 type or in combination of 2 or more types.

  (F) Content of the organic solvent which is a diluent can be suitably adjusted in order to adjust the viscosity of the photosensitive resin composition.

  Moreover, it is preferable that content of the photopolymerizable monomer which is (F) diluent is 5-80 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, and it is 10-70 mass%. Is more preferable, and it is especially preferable that it is 15-40 mass%. If this content is less than 5% by mass, the photosensitivity tends to be low and the exposed area tends to be eluted during development, and if it exceeds 80% by mass, the heat resistance tends to decrease.

  In addition, from the viewpoint of further improving heat resistance, the photosensitive resin composition of the present invention can contain (G) a curing agent.

  As the curing agent (G), a carboxyl group or a hydroxyl group of (A) an acid-modified vinyl group-containing epoxy resin that is a compound that is cured by heat or ultraviolet light, or a photocurable resin component in a photosensitive resin composition. And a compound that is cured by reaction with heat or ultraviolet rays. By using this (G) curing agent, the heat resistance, adhesion, chemical resistance, etc. of the finally obtained cured film can be improved.

  (G) As a hardening agent, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound, a block type isocyanate compound etc. can be mentioned as a thermosetting compound, for example. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. Or heterocyclic epoxy resins such as triglycidyl isocyanurate, and bixylenol type epoxy resins. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. Examples of the urea compound include dimethylol urea. These (G) curing agents are used singly or in combination of two or more.

  In the photosensitive resin composition, the content of the (G) curing agent is preferably 2 to 50% by mass, more preferably 10 to 40% by mass based on the total solid content of the photosensitive resin composition. Preferably, it is 15-30 mass%, and it is especially preferable. If this content is less than 2% by mass, the heat resistance of the final cured coating film tends to be low, and if it exceeds 50% by mass, the developability tends to be reduced.

  The photosensitive resin composition of the present invention preferably contains an epoxy resin curing agent for the purpose of further improving various properties such as heat resistance, adhesion and chemical resistance of the cured film.

  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. Imidazole derivatives 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 Triazine derivatives such as triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris ( Tertiary amines such as dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak; tributylphosphine, triphenylphosphine, tris-2-cyanoethyl Organic phosphines such as phosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosnium chloride Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium Examples include hexafluorophosphate.

  These epoxy resin curing agents are used singly or in combination of two or more. When using an epoxy resin hardening | curing agent, it is preferable that the content is 0.01-20 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, and it may be 0.1-10 mass%. More preferred.

  The photosensitive resin composition of the present invention further includes barium sulfate, barium titanate, silica, talc, calcined kaolin, carbonic acid as necessary for the purpose of further improving various properties such as adhesion and coating film hardness. Known inorganic fillers such as magnesium, aluminum oxide, aluminum hydroxide and mica can also be contained. These can be used alone or in combination of two or more. Among these, silica and barium sulfate are preferable from the viewpoint of improving the printability and the hardness of the cured film. Moreover, when using an inorganic filler, it is preferable that the content is 2-80 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, and it is more preferable that it is 5-50 mass%. It is especially preferable that it is -40 mass%.

  In the photosensitive resin composition of the present invention, if necessary, known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, hydroquinone , Polymerization inhibitors such as methyl hydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as benton and montmorillonite, various known and conventional antifoaming agents such as silicone, fluorine and vinyl resins, and silane coupling agents Additives 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 the present invention can be obtained by uniformly kneading and mixing each of the above-described blending components with a roll mill, a bead mill or the like.

  The photosensitive resin composition of the present invention is used in the field of electronic materials such as solder resists in printed wiring boards, interlayer insulating films in high-density multilayer boards, and solder resists for semiconductor packages. It is useful as a permanent mask resist having excellent chemical resistance and electrical characteristics.

  Next, the photosensitive element using the photosensitive resin composition of the present invention described above will be described. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 includes a support 10 and a photosensitive resin composition layer 14 provided on the support 10. The photosensitive resin composition layer 14 is a layer made of the above-described photosensitive resin composition of the present invention. Moreover, the photosensitive element 1 of this invention may coat | cover the surface F1 on the opposite side to the support body 10 on the photosensitive resin composition layer 14 with a protective film.

  The photosensitive resin composition layer 14 is prepared by dissolving the photosensitive resin composition of the present invention in the above solvent or mixed solvent to obtain a solution having a solid content of about 30 to 70% by mass, and then applying the solution onto the support 10. Is preferably formed.

  Although the thickness of the photosensitive resin composition layer 14 varies depending on the application, it is preferably 10 to 100 μm and more preferably 20 to 60 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. preferable.

  Examples of the support 10 included in the photosensitive element 1 include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

  The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm.

  The photosensitive element 1 consisting of two layers of the support 10 and the photosensitive resin composition layer 14 as described above or the photosensitive element consisting of three layers of the support 10, the photosensitive resin composition layer 14 and the protective film is as follows. For example, it may be stored as it is, or it can be wound around a roll core and stored after interposing a protective film.

  Next, the resist pattern forming method of the present invention will be described. The method for forming a resist pattern of the present invention comprises a laminating step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention on a substrate, and actinic rays on the photosensitive resin composition layer in an image form. Is an exposure step in which the exposed portion is photocured and a developing step in which the unexposed portion of the photosensitive resin composition layer is removed by development.

  Lamination of the photosensitive resin composition layer on a substrate (copper-clad laminate, etc.) is performed by, for example, using a photosensitive resin composition by screen printing, spraying, roll coating, curtain coating, electrostatic coating, etc. It can apply by apply | coating on a board | substrate with a film thickness of 10-200 micrometers by the method of this, and drying a coating film at 60-110 degreeC.

Moreover, you may laminate | stack the photosensitive resin composition layer on a board | substrate using the photosensitive element of this invention mentioned above. As a lamination method in that case, when the photosensitive element is provided with a protective film, the protective film is removed, and then the photosensitive resin composition layer is heated to about 70 ° C. to 130 ° C. while being applied to the substrate at 0.1 MPa to 1 MPa. the degree method in which bonding at a pressure of ^{(1kgf / cm 2 ~10kgf / cm} 2 or so) can be mentioned. Such a lamination process may be performed under reduced pressure. The surface of the substrate on which the photosensitive resin composition layer is laminated is usually a metal surface, but is not particularly limited.

  The exposed portion is photocured by irradiating the photosensitive resin composition layer laminated on the substrate in this way with an actinic ray in an image form through a negative or positive mask pattern. At this time, when the photosensitive resin composition layer is laminated using the photosensitive element, a support is present on the photosensitive resin composition layer, but the support is transparent to the actinic ray. In some cases, actinic rays can be irradiated through the support, and when the support is light-shielding against actinic rays, the photosensitive resin composition layer is irradiated with actinic rays after the support is removed. To do.

  As the active light source, a conventionally known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used.

  The photosensitive resin composition and the photosensitive element of the present invention are suitable for use in forming an image by a laser direct drawing exposure method. Therefore, in the resist pattern forming method of the present invention, the exposure step is preferably performed by a laser direct drawing exposure method.

  When exposure is performed by a laser direct drawing exposure method, the exposure step is preferably a step in which the photosensitive resin composition layer is directly drawn and exposed by laser light having a wavelength of 405 nm to photocur the exposed portion. Note that a laser beam having a wavelength of 355 nm can also be used as the laser beam when exposure is performed by the direct drawing exposure method.

In the exposure step, the exposure dose is preferably 10 to 1000 mJ / cm ² .

  After formation of the exposed portion, the photosensitive resin composition layer (unexposed portion) other than the exposed portion is removed by development to form a resist pattern. As a method for removing such an unexposed portion, when a support is present on the photosensitive resin composition layer, the support is removed with an auto peeler or the like, and a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. Examples include a method in which an unexposed portion is removed and developed by wet development or dry development. Examples of the alkaline aqueous solution used for wet development include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1-5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of hydroxide. A dilute solution of sodium and the like can be mentioned. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Moreover, you may mix surfactant, an antifoamer, an organic solvent, etc. in alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.

Next, as a treatment after development, the exposed portion is sufficiently cured by post-exposure (ultraviolet light exposure) and / or post-heating to obtain a cured film. The post-exposure is preferably performed with an exposure amount of 1 to 5 J / cm ² . Post-heating is preferably performed at 100 to 200 ° C. for 30 minutes to 12 hours.

  In the method for producing a printed wiring board of the present invention, the circuit forming substrate on which the resist pattern has been formed by the resist pattern forming method of the present invention is etched or plated. Here, the resist pattern comprising the photosensitive resin composition of the present invention functions effectively as a permanent mask resist having excellent image forming properties, heat resistance, adhesion, mechanical properties, chemical resistance, electrical properties, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Synthesis Example 1]
YDF2001 (Toto Kasei Co., Ltd., bisphenol F type epoxy resin, Y ² = glycidyl group, R ¹² = hydrogen atom compound in the general formula (5)) 475 parts by mass, acrylic acid 72 parts by mass, hydroquinone 0. 5 parts by mass and 120 parts by mass of carbitol acetate were charged and heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of benzyltrimethylammonium chloride was added thereto, heated to 100 ° C., and reacted until the solid content acid value reached 1 mgKOH / g. Furthermore, 98 parts by mass of maleic anhydride and 85 parts by mass of carbitol acetate were added, heated to 80 ° C., and reacted for about 6 hours. Thereafter, it is cooled to room temperature, diluted with carbitol acetate so that the solid content concentration becomes 60% by mass, and carboxylic acid-modified bisphenol F type epoxy acrylate (hereinafter referred to as “epoxy resin A1”) as component (A). Got.

[Synthesis Example 2]
YDCN704 (manufactured by Toto Kasei Co., Ltd., cresol novolak type epoxy resin, Y ¹ = glycidyl group, R ¹¹ = methyl group in general formula (4)) 220 parts by mass, acrylic acid 72 parts by mass, hydroquinone 1. 0 part by mass and 180 parts by mass of carbitol acetate were charged, and the reaction mixture was dissolved by heating and stirring at 90 ° C. Next, the obtained solution was cooled to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was added thereto, heated to 100 ° C., and reacted until the solid content acid value reached 1 mgKOH / g. Further, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of carbitol acetate were added, heated to 80 ° C., and reacted for about 6 hours. Thereafter, it is cooled to room temperature, diluted with carbitol acetate so that the solid content concentration becomes 60% by mass, and carboxylic acid-modified cresol novolac type epoxy acrylate (hereinafter referred to as “epoxy resin A2”) as component (A). Got.

(Examples 1-6 and Comparative Examples 1-4)
After blending the composition according to the blending composition (unit: parts by mass) shown in Table 2 below, kneading with a three-roll mill, adding carbitol acetate so that the solid content concentration becomes 70% by weight, a photosensitive resin composition I got a thing. In addition, the compounding quantity of each component in following Table 2 shows the compounding quantity of solid content.

The details of each component in Table 2 are as follows.
Bisphenol F type epoxy resin (trade name: YSLV-80XY-F, manufactured by Tohto Kasei Co., Ltd.),
DPHA (trade name: Kayrad DPHA, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate),
OXE-01 (trade name, manufactured by Ciba Specialty Chemicals, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) represented by the above formula (8),
IC907 (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd., a compound represented by the following formula (17)),
NF-EO (trade name, manufactured by Nippon Chemical Industry Co., Ltd., 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) represented by the above formula (13) -Pyrazoline, maximum absorption wavelength: 387.2 nm),
Coumarin (C-314T) (trade name: C-314T, manufactured by Acros, compound represented by the following formula (18), maximum absorption wavelength: 435 nm),
MBO (mercaptobenzoxazole represented by the above formula (9)),
MBT (mercaptobenzothiazole represented by the above formula (10)),
MBI (mercaptobenzimidazole represented by the above formula (11)),
NPG (Wako Pure Chemical Industries, N-phenylglycine),
EAB (trade name, manufactured by Hodogaya Chemical Co., Ltd., diethylaminobenzophenone, maximum absorption wavelength: 365 nm).

<Production of evaluation substrate>
The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 6 were applied to a copper-clad laminate using a 120 mesh Tetron screen by screen printing so that the thickness after drying would be about 20 μm. It apply | coated and dried for 30 minutes at 80 degreeC with the hot air circulation type dryer. This obtained the evaluation board | substrate with which the photosensitive resin composition layer which consists of a photosensitive resin composition was laminated | stacked on the copper clad laminated board. Each characteristic was evaluated by the method shown below using the obtained evaluation substrate. The results are summarized in Table 3.

(Light sensitivity)
Spectral filter manufactured by Asahi Spectroscopy Co., Ltd., which is a bandpass filter that disperses light with a wavelength of 405 ± 30 nm on a negative mask (Stofer 41-step step tablet) on the photosensitive resin composition layer of the evaluation substrate (Product name: HG0405) is placed, and in this state, an ultraviolet ray with an exposure amount of 100 mJ / cm ² is used using a parallel light exposure machine (trade name: EXM-1201, manufactured by Oak Manufacturing Co., Ltd.) using a 5 kW short arc lamp as a light source. Was irradiated. Note that the illuminance of the light transmitted through the bandpass filter is determined based on the UV integrated light meter (trade name: UIT-150-A, manufactured by Ushio Electric Co., Ltd., also usable as an illuminometer) and the light receiver “UVD-S405”. (Product name, sensitivity wavelength range: 320 nm to 470 nm, absolute calibration wavelength: 405 nm), and the illuminance × exposure time was defined as the exposure amount. Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution (30 ° C.) for 60 seconds at a pressure of 1.8 kgf / cm ² to dissolve and remove unexposed portions. After removing the unexposed part, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocured film formed on the copper-clad laminate. The light sensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of the step tablet, the higher the light sensitivity.

(Developability)
A spectroscopic filter manufactured by Asahi Spectral Co., Ltd., which is a band-pass filter that disperses light having a wavelength of 405 ± 30 nm on a mask having a via mask opening dimension of 100 μm on the photosensitive resin composition layer of the evaluation substrate (product) Name: HG0405) is mounted, and in this state, an ultraviolet ray with an exposure amount of 100 mJ / cm ² is irradiated using a parallel light exposure machine (trade name: EXM-1201, manufactured by Oak Manufacturing Co., Ltd.) using a 5 kW short arc lamp as a light source. did. Note that the illuminance of the light transmitted through the bandpass filter is determined based on the UV integrated light meter (trade name: UIT-150-A, manufactured by Ushio Electric Co., Ltd., also usable as an illuminometer) and the light receiver “UVD-S405”. (Product name, sensitivity wavelength range: 320 nm to 470 nm, absolute calibration wavelength: 405 nm), and the illuminance × exposure time was defined as the exposure amount. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution (30 ° C.) for 60 seconds at a pressure of 0.18 MPa. Thereafter, the formed via opening was visually observed, and developability was evaluated according to the following criteria.
A: When a via opening having an opening size of 80 μm or more is obtained,
B: When a via opening having an opening size of 60 μm or more and less than 80 μm is obtained,
C: When the opening size of the via opening is less than 60 μm.

<Preparation of test plate>
On the photosensitive resin composition layer of the evaluation substrate, a spectral filter (trade name: HG0405) manufactured by Asahi Spectroscopy Co., Ltd., which is a bandpass filter that splits light with a wavelength of 405 ± 30 nm, is placed, and in this state, a 5 kW short arc lamp Was irradiated with ultraviolet rays having an exposure amount of 100 mJ / cm ² using a parallel light exposure machine (trade name: EXM-1201, manufactured by Oak Manufacturing Co., Ltd.). Note that the illuminance of the light transmitted through the bandpass filter is determined based on the UV integrated light meter (trade name: UIT-150-A, manufactured by Ushio Electric Co., Ltd., also usable as an illuminometer) and the light receiver “UVD-S405”. (Product name, sensitivity wavelength range: 320 nm to 470 nm, absolute calibration wavelength: 405 nm), and the illuminance × exposure time was defined as the exposure amount. Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution (30 ° C.) for 60 seconds at a pressure of 1.8 kgf / cm ² to dissolve and remove unexposed portions. Next, it heated at 150 degreeC for 1 hour, and produced the test board which has the cured film of the photosensitive resin composition layer. Each characteristic was evaluated by the method shown below using the obtained test plate. The results are summarized in Table 3.

(Adhesion)
A peel test was performed on the test plate by a method according to JIS K5400. That is, 100 1 mm grids were prepared on the cured film of the test plate, and the cellophane tape was attached to the grids, and then peeled off. The peeled state after the peeling was observed, and the adhesion was evaluated according to the following criteria.
A: 90/100 or more of the grid pattern is not peeled,
B: 50/100 or more and less than 90/100 of the grid pattern has no peeling,
C: Less than 50/100 of the grid is not peeled.

(Solvent resistance)
After immersing the test plate in isopropyl alcohol at room temperature for 30 minutes, it was visually confirmed whether or not the appearance of the cured film was abnormal. Then, the peeling test which affixes a cellophane tape on a cured film and pulls up was performed, and it was confirmed whether the cured film peeled from a copper clad laminated board. From these results, solvent resistance was evaluated according to the following criteria.
A: There is no abnormality in the appearance of the cured film, and there is no peeling in the peeling test,
B: The appearance of the cured film is abnormal or peeled off in the peel test.

(Solder heat resistance)
After applying the rosin flux to the surface of the cured film of the test plate, it was immersed in a solder bath at 260 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the cured film was visually observed, and the solder heat resistance was evaluated according to the following criteria.
A: There is no abnormality (peeling, swelling) in the appearance of the cured film, and there is no solder peeling,
B: The appearance of the cured film is abnormal (peeling, blistering), or there is solder peeling.

<Preparation of solution for evaluating stability over time and evaluation of stability over time>
In the composition shown in Table 2, the viscosity is adjusted to 50 Pa · s by adding carbitol acetate except for the bisphenol F type epoxy resin as a curing agent and the epoxy resins A1 and A2 as photopolymerizable compounds. A solution for evaluating the day stability was obtained. The obtained solution was allowed to stand at room temperature (25 ° C.), and the time until the solution stopped flowing or gelation occurred was measured. The results are shown in Table 3.

  As is apparent from the results shown in Table 3, according to the photosensitive resin compositions of Examples 1 to 4, the photosensitive resin compositions of Comparative Examples 1 to 6 are superior in photosensitivity and developability. At the same time, it was confirmed that the stability over time was very excellent. In addition, since the photosensitive resin composition of Comparative Examples 3 and 4 had insufficient photosensitivity to light at a wavelength of 405 nm, it was not photocured by exposure and image formation was not possible.

  As described above, according to the present invention, the formation of a resist pattern using exposure light within a wavelength range of 370 nm to 450 nm, particularly the formation of a resist pattern by a direct drawing exposure method using laser light having a wavelength of 405 nm. A photosensitive resin composition that can be performed with sufficient sensitivity and resolution, does not gel when left for a long period of time, and has excellent stability over time, formation of a photosensitive element and a resist pattern using the photosensitive resin composition A method and a printed wiring board manufacturing method can be provided. Further, according to the photosensitive resin composition and photosensitive element of the present invention, in a direct drawing exposure method using a blue laser beam having a wavelength of 405 nm as a light source, it is possible to form a high-density resist pattern that has been difficult to manufacture. It is possible to obtain a high-performance cured film that is excellent in heat resistance, moist heat resistance (shear adhesiveness), adhesion, mechanical properties, and electrical properties. Therefore, the photosensitive resin composition and photosensitive element of the present invention are suitably used for the production of printed wiring boards, high-density multilayer boards, semiconductor packages, and the like.

Claims (9)

(A) an acid-modified vinyl group-containing epoxy resin;
(B) a photopolymerization initiator containing a compound having an oxime ester bond;
(C) a compound having a thiol group;
Containing a photosensitive resin composition.   (D) The photosensitive resin composition of Claim 1 which further contains the sensitizer which has the maximum absorption wavelength in the range of 370 nm-450 nm. The photosensitive resin composition of Claim 1 or 2 in which the compound which has the said oxime ester bond contains at least 1 sort (s) of the compound represented by the following general formula (1) or (2).

[In Formula (1), R ¹ is a substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkenoyl group having 4 to 6 carbon atoms in which a double bond is not conjugated to a carbonyl group, substituted Or an unsubstituted benzoyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, wherein R ² , R ³ and R ⁴ are each independently a halogen atom Substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted Substituted benzoyl group, substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, substituted or unsubstituted group having 2 to 12 carbon atoms Conversion of an alkoxycarbonyl group, or a substituted or indicates unsubstituted phenoxycarbonyl group, m1 represents an integer of 0 to 4, m @ 2 and m3 each show independently an integer of 0-5. In addition, when m1 is 2 or more, a plurality of R ² may be the same or different, and when m2 is 2 or more, a plurality of R ³ may be the same or different, and m3 is When it is 2 or more, a plurality of R ⁴ may be the same or different. ]

[In the formula (2), R ⁵ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group having 1 to 20 carbon atoms. A substituted or unsubstituted cycloalkyl group having 5 to 8 carbon atoms, a substituted or unsubstituted alkanoyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted benzoyl group, and R ⁶ represents the number of carbon atoms A substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkenoyl group having 4 to 6 carbon atoms in which the double bond is not conjugated to a carbonyl group, a substituted or unsubstituted benzoyl group, 2 to 6 carbon atoms a substituted or unsubstituted alkoxycarbonyl group, or a substituted or indicates unsubstituted phenoxycarbonyl group, R ⁷ is a hydrogen atom, a halogen atom, a carbon number 1 to 1 Substituted or unsubstituted alkyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group, substituted or unsubstituted benzoyl group, carbon A substituted or unsubstituted alkanoyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, and R ⁸ , R ⁹ and R ¹⁰ are Each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group Benzyl group, substituted or unsubstituted benzoyl group, 2 to 1 carbon atoms A substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, m4 and m5 each independently represents an integer of 0 to 3; M6 represents an integer of 0 to 5. In addition, when m4 is 2 or more, a plurality of R ⁸ may be the same or different, and when m5 is 2 or more, a plurality of R ⁹ may be the same or different, and m6 is When it is 2 or more, a plurality of R ¹⁰ may be the same or different. ] The photosensitive resin composition as described in any one of Claims 1-3 in which the compound which has the said (C) thiol group contains the compound represented by following General formula (3).

[Wherein Ar represents a divalent or trivalent aryl group which may have a substituent, and X represents an oxygen atom, a nitrogen atom or a sulfur atom. ] The (A) acid-modified vinyl group-containing epoxy resin is a novolac type epoxy resin represented by the following general formula (4), a bisphenol type epoxy resin represented by the following general formula (5), and the following general formula (6 The resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of salicylaldehyde-type epoxy resins represented by (A) and a vinyl group-containing monocarboxylic acid (b), Item 5. The photosensitive resin composition according to any one of Items 1 to 4.

[Wherein, R ¹¹ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n1 represents An integer of 1 or more is shown. A plurality of R ¹¹ and Y ¹ may be the same or different. ]

[Wherein R ¹² represents a hydrogen atom or a methyl group, Y ² represents a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n2 represents An integer of 1 or more is shown. A plurality of R ¹² and Y ² may be the same or different. ]

[Wherein Y ³ represents a hydrogen atom or a glycidyl group (where hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n3 represents an integer of 1 or more. A plurality of R ¹¹ and Y ³ may be the same or different. ]   A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition of any one of Claims 1-5 formed on this support body. A laminating step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on a substrate;
An exposure step of irradiating the photosensitive resin composition layer with an actinic ray in an image shape to photo-cure the exposed portion;
A development step of removing unexposed portions of the photosensitive resin composition layer by development;
A resist pattern forming method including:   The resist pattern forming method according to claim 7, wherein the exposing step is a step of directly drawing and exposing the photosensitive resin composition layer with a laser beam having a wavelength of 405 nm to photocur the exposed portion.   A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 7 or 8.

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