JP4711208B2 - Photosensitive thermosetting resin composition, resist film-coated smoothed printed wiring board, and method for producing the same. - Google Patents

Description

  The present invention relates to a photosensitive thermosetting resin composition, a resist film-coated smoothed printed wiring board, and a method for producing the same. More specifically, the present invention relates to a printed wiring board, in particular, a printed wiring board for LEDs (especially large liquid crystal backlight LEDs), a printed wiring board for LED illumination, a printed wiring board for LED headlights for automobiles, and an ultraviolet (UV) ) It is coated with solder resist such as printed wiring board for LED and high heat dissipation printed wiring board, interlayer insulating material, photosensitive thermosetting resin composition useful for rewiring layer of semiconductor package, and its resist film. The present invention relates to a smoothed printed wiring board and a method for manufacturing the same.

  Resist films, particularly solder resist films, are required to have excellent characteristics such as HAST (High Accelerated Temperature and Humidity Stress Test) resistance and gold plating resistance as protective films for printed wiring boards. .

  In addition, in the solder resist film of the printed wiring board used for the LED of the light source for illumination and the LED of the backlight for the display element, in addition to the above required characteristics, the light emission of the light emitting diode can be effectively utilized as much as possible. It has been demanded.

  Therefore, as the solder resist film of the LED printed wiring board, a white solder resist film that effectively uses the light emission of the light emitting diode by improving the reflectance of light is desirable. However, there is a limit to the effective use of light emission of the light emitting diode only by improving the light reflectance, and further effective use is desired.

  By the way, the following are disclosed as curable ink used for a printed wiring board etc. That is, Patent Document 1 describes a thermosetting epoxy resin composition containing an alkoxy group-containing silane-modified epoxy resin (A) and an epoxy resin curing agent (B). Patent Document 1 describes that an object is to provide an epoxy resin composition that provides a cured product having excellent heat resistance.

  Patent Document 2 describes an epoxy resin composition containing a silane-modified hydrogenated bisphenol type epoxy resin (A) and an epoxy curing agent (B). Patent Document 2 describes that an object is to provide a thermosetting epoxy resin composition excellent in heat resistance and yellowing resistance.

  Patent Document 3 discloses a heat-resistant feeling containing (1) an unsaturated group-containing polycarboxylic acid resin, (2) an epoxy compound, (3) a photopolymerizable monomer, and (4) a photopolymerization initiator. A light-sensitive resin composition is described. Patent Document 3 discloses a heat-resistant photosensitive resin composition having excellent solder heat resistance, flame resistance, plating resistance, and chemical resistance, electrical insulation, adhesion to a substrate, stability over time, and developability. It is described that it is intended to be provided.

  Patent Document 4 describes a photosensitive resin composition containing an ethylenically unsaturated group-containing polycarboxylic acid resin (A), a photopolymerization initiator (B), a crosslinking agent (C), and a curing agent (D). ing. Patent Document 4 provides a photosensitive resin composition having no tackiness and excellent photosensitivity, and a cured product having excellent adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, and the like. It is described that it aims at.

  Patent Document 5 discloses a resist ink for a photosensitive flexible printed wiring board containing an unsaturated group-containing polycarboxylic acid resin (A), a photopolymerization initiator (B), a diluent (C), and a curing component (D). A composition is described. Patent Document 5 discloses a resist ink composition for a flexible printed wiring board, which can be developed with a dilute alkaline aqueous solution, and the cured film has excellent flexibility, folding resistance, adhesion, chemical resistance, heat resistance, and the like. The object is to provide a product.

  Patent Document 6 describes a photosensitive resin composition containing an unsaturated group-containing polycarboxylic acid resin, a polyfunctional photopolymerizable acrylate monomer, an aminosilane-modified epoxy resin, a photopolymerization initiator, and an organic solvent. Patent Document 6 describes that a transparent thin film that can be patterned and has high smoothness is provided, and that a resin composition useful for forming a protective film or a smooth layer on a colored resin film is provided.

  However, none of the cured products obtained from the curable inks described in Patent Documents 1 to 6 have sufficient HAST resistance. Furthermore, it cannot be said that the cured product obtained from the curable inks described in Patent Documents 1, 2, and 6 has sufficient resistance to gold plating.

JP 2001-59013 A. JP-A-2005-179401. JP-A-6-230571. JP-A-2005-115187. Japanese Patent No. 3281473. JP-A-6-73160.

  In view of the above circumstances, an object of the present invention is to provide a photosensitive thermosetting resin composition that gives a cured product excellent in HAST resistance, gold plating resistance, and the like. In particular, the invention of the present application is excellent in not only the above-mentioned excellent characteristics but also the gloss as well as the light reflectance, and as a result, for LED printed wiring boards that can further effectively utilize the light emission of the diode. It aims at providing the photosensitive thermosetting resin composition which can give a soldering resist film.

In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, have reached the following present invention.
That is, the first invention of the present application is
[I] The following formula:

［式（化Ｉ／Ｅ）中、Ｇはグリシジル基を表す。ａ_１１個のＡ_１１及びａ_１２個のＡ_１３並びにＡ_１５は、それぞれ同一でも異なってもよく、それぞれ独立に２価の芳香族残基若しくは２価の水添芳香族残基を表す。ａ_１１個のＡ_１２とａ_１２個のＡ_１４は、同一でも異なってもよく、それぞれ独立にＨ（「水素原子」を表す。以下、同様。）若しくはＧを表す。但し、ａ_１１個のＡ_１２及びａ_１２個のＡ_１４の内、少なくとも１つはＨであり、総てが同時にＨであってもよい。平均繰り返し単位数ａ_１１及びａ_１２は、同一でも異なってもよく、それぞれ独立に０以上の数を表すがａ_１１とａ_１２とは同時に０ではなく、且つａ_１１とａ_１２との総和は、２０以下である。］

[In the formula (Chemical I / E), G represents a glycidyl group. a ₁₁ A ₁₁ and a ₁₂ A _{13 and} A ₁₅ may be the same or different and each independently represents a divalent aromatic residue or a divalent hydrogenated aromatic residue. a ₁₁ A ₁₂ and a ₁₂ A ₁₄ may be the same or different and each independently represents H (represents “hydrogen atom”; the same shall apply hereinafter) or G. However, at least one of a ₁₁ A ₁₂ and a ₁₂ A ₁₄ may be H, and all may be H at the same time. The average repeating unit numbers a ₁₁ and a ₁₂ may be the same or different, and each independently represents a number of 0 or more, but a ₁₁ and a ₁₂ are not 0 at the same time, and the sum of a ₁₁ and a ₁₂ is , 20 or less. ]

An alkoxy group-containing silane-modified epoxy resin obtained by dealcoholizing a hydrolyzable alkoxysilane with an epoxy resin represented by

[II] An unsaturated group-containing polycarboxylic acid resin having an ethylenically unsaturated group and two or more carboxyl groups in the molecule and having a solid content acid value (mgKOH / g) of 50 to 150,
[III] Diluent,
[IV] Photopolymerization initiator, and [V] Curing adhesion imparting agent

The weight ratio of component [I] to component [II] is 2/100 to 50/100, and the total amount of component [I] and component [II] is 100 parts by weight, 5 to 500 parts by weight of component [III], 0.1 to 30 parts by weight of component [IV], and 0.1 to 20 parts by weight of component [V] A composition is provided.

［式（化Ｉ／Ｅ−１−１）中、Ｇは、グリシジル基を表す。ａ_６１１個のＡ_６１１は、同一でも異なってもよく、それぞれ独立にＨ若しくはＧを表すが、少なくとも一つはＨであり、総てが同時にＨであってもよい。平均繰り返し単位数ａ_６１１は、２０以下の数である。］、In the second invention of the present application, the epoxy resin (Chemical I / E) is represented by the following formula:

[In the formula (Formula I / E-1-1), G represents a glycidyl group. a ₆₁₁ A _611s may be the same or different and each independently represents H or G, but at least one of them may be H, and all may be H at the same time. The average repeating unit number a ₆₁₁ is a number of 20 or less. ],

［式（化Ｉ／Ｅ−１−２）中、Ｇは、前記と同義である。ａ_６２１個のＡ_６２１は、同一でも異なってもよく、それぞれ独立にＨ若しくはＧを表すが、少なくとも一つはＨであり、総てが同時にＨであってもよい。平均繰り返し単位数ａ_６２１は、２０以下の数である。］、及び

[In the formula (Chemical I / E-1-2), G has the same meaning as described above. a ₆₂₁ A ₆₂₁ may be the same or different and each independently represents H or G, but at least one of them may be H, and all may be H at the same time. The average repeating unit number a ₆₂₁ is a number of 20 or less. ],as well as

［式（化Ｉ／Ｅ−Ｓ）中、Ｇは、前記と同義である。ａ_８個のＡ_８は、同一でも異なってもよく、それぞれ独立にＨ若しくはＧを表すが、少なくとも一つはＨであり、総てが同時にＨであってもよい。平均繰り返し単位数ａ_８は、２０以下の数である。］
にて表されるものの１種以上であり、

[In the formula (Chemical I / ES), G has the same meaning as described above. a The _eight A _{8 s} may be the same or different and each independently represents H or G, but at least one of them may be H and all may be H at the same time. The average number of repeating units _{a 8} is the number of 20 or less. ]
One or more of those represented by

［式（化Ｉ／Ｓｉ−２）中、Ｂ_２１〜Ｂ_２６は、同一でも異なってもよくそれぞれ独立に、アルキル基、アリール基、若しくは不飽和脂肪族残基を表す。平均繰り返し単位数ｂ_２１は、２〜１１の数である。］、及びThe hydrolyzable alkoxysilane has the following formula:

[In the formula (Formula I / Si-2), B _{21 to} B ₂₆ may be the same or different and each independently represents an alkyl group, an aryl group, or an unsaturated aliphatic residue. The average number of repeating units _{b 21} is the number of 2 to 11. ],as well as

［式（化Ｉ／Ｓｉ−３）中、Ｂ_３１〜Ｂ_３６は、同一でも異なってもよくそれぞれ独立に、アルキル基、アリール基、若しくは不飽和脂肪族残基を表す。平均繰り返し単位数ｂ_３１は、２〜１１の数である。］

[In the formula (Chemical I / Si-3), B _{31 to} B ₃₆ may be the same or different and each independently represents an alkyl group, an aryl group, or an unsaturated aliphatic residue. The average repeating unit number b ₃₁ is a number from 2 to 11. ]

The photosensitive thermosetting resin composition according to the first invention of the present application is characterized in that it is one or more of those represented by formula (1).

  The third invention of the present application is a resin obtained by reacting an epoxy group-containing unsaturated monomer with a copolymer of an ethylenically unsaturated acid and an ethylenically unsaturated bond-containing monomer as the component [II], And / or a reaction product obtained by reacting an ethylenically unsaturated acid with a copolymer of an epoxy group-containing unsaturated monomer and an ethylenically unsaturated bond-containing monomer, to a saturated and / or unsaturated group Provided is a photosensitive thermosetting resin composition according to the first or second invention of the present application, which is a resin obtained by reacting a contained polybasic acid anhydride.

  The fourth invention of the present application further comprises 10 to 500 parts by weight of a white pigment and 10 to 1200 parts by weight of a filler with respect to 100 parts by weight of the total amount of the components [I] and [II]. A photosensitive thermosetting resin composition according to any one of the first to third aspects of the present invention is provided.

  In the fifth invention of the present application, the photosensitive thermosetting resin composition according to any one of the first to fourth inventions of the present application is applied onto the surface of the smoothed printed wiring board, and the applied resin is photocured, and further 100- Provided is a method for producing a resist film-coated smoothed printed wiring board, which is heated to 190 ° C. and thermally cured.

  The sixth invention of the present application provides a resist film-covered smoothed printed wiring board manufactured by the manufacturing method according to the fifth invention of the present application.

  By this invention, the photosensitive thermosetting resin composition which gives the hardened | cured material excellent in HAST tolerance, gold plating resistance, etc. can be provided. In particular, according to the present invention, in addition to the above-described excellent characteristics, it is excellent not only in light reflectance but also in glossiness, and as a result, for LED printed wiring boards that can further effectively utilize light emission of diodes. A photosensitive thermosetting resin composition capable of providing a solder resist film can be provided.

Hereinafter, the present invention will be described in detail based on the best embodiment.
The photosensitive thermosetting resin composition according to the present invention contains an alkoxy group-containing silane-modified epoxy resin (hereinafter also referred to as “component [I]”). Component [I] includes those obtained by dealcoholizing an epoxy resin represented by the following formula (Chemical I / E) and a hydrolyzable alkoxysilane described below.

式（化Ｉ／Ｅ）中、Ｇはグリシジル基であり、次式、

In the formula (Chemical I / E), G is a glycidyl group,

にて表されるものである。

It is represented by.

  In the formula (Chemical I / E), the order of arrangement in the resin skeleton of each repeating unit represented by the following formulas (Chemical I / E-U1) and (Chemical I / E-U2) is defined as anything ( Not limited).

  Therefore, when the repeating unit (Chemical I / E-U1) and (Chemical I / E-U2) are not the same, as the resin (Chemical I / E), for example, the repeating unit (Chemical I / E-U1) and (Chemical I / E-U2) may be a block polymerization type, an alternating polymerization type, a random polymerization type, or the like, and one or more of these may be used.

In the formula (Chemical I / E), a ₁₁ A ₁₁ and a ₁₂ A _{13 and} A ₁₅ may be the same or different, and are each independently a divalent aromatic residue or divalent water. Represents an aromatic residue, and preferably A ₁₅ is A ₁₁ or A ₁₃ .

In A ₁₁ , A ₁₃ , and A ₁₅ , examples of the divalent aromatic residue include a divalent group represented by the following formula (Chemical I / E-Ar1), a phenylene group, or a naphthylene group. Can be mentioned.

［式（化Ｉ／Ｅ−Ａｒ１）中、Ａ_２１は（シクロ）アルキレン基、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ−、−ＳＯＯ−、若しくは次式（化Ｆ）、

[In the formula (Chemical I / E-Ar1), A ₂₁ represents a (cyclo) alkylene group, —O—, —CO—, —COO—, —S—, —S—S—, —SO—, —SOO—. Or the following formula (Formula F),

にて表される２価基を表し、ａ_２１は０若しくは１である。］

And a ₂₁ is 0 or 1. ]

In the aromatic residue, examples of the divalent group (Chemical I / E-Ar1) include those in which A ₂₁ is a (cyclo) alkylene group. Examples of the (cyclo) alkylene group include C1-C8. (Cyclo) alkylene group, a substituent [e.g., C1 -C6 (cyclo) alkyl group, an aryl group, -CF _3, etc.] may have. In the formula (Formula I / E-Ar1), one or both benzene rings may further have one or more substituents (for example, a C1-C6 alkyl group, a halogen atom, etc.). Specifically, examples of such aromatic residues include those represented by the following formulas (Chemical I / E-Ar1-1) to (Chemical I / E-Ar1-5).

In the aromatic residue, as another divalent group (Chemical I / E-Ar1), A ₂₁ represents —O—, —CO—, —COO—, —S—, —S—S—, —SO—. Or -SOO-. In the formula (Formula I / E-Ar1), one or both benzene rings may have one or more substituents (for example, a C1-C6 alkyl group, a halogen atom, etc.). Specifically, examples of such aromatic residues include those represented by the following formulas (Chemical I / E-Ar1-6) and (Chemical I / E-Ar1-7).

In the aromatic residues, as yet another divalent group (of _{I / E-Ar1), A} 21 is the following formula (Formula F),

The thing etc. which are represented by are mentioned. In the formula (Chemical I / E-Ar1), one or both benzene rings may have one or more substituents (for example, a C1-C6 alkyl group). Specifically, such aromatic residues include the following formula (Formula I / E-Ar1-F),

にて表されるもの等が挙げられる。

The thing etc. which are represented by are mentioned.

In the aromatic residues, as yet another divalent group (of I / _E-Ar1), include those _{a 21} is 0. In the formula (Formula I / E-Ar1), one or both benzene rings may have one or more substituents (for example, a C1-C6 alkyl group, a halogen atom, etc.). Specifically, examples of such aromatic residues include those represented by the following formulas (Chemical I / E-Ar1-8) and (Chemical I / E-Ar1-9).

  In the aromatic residue, the phenylene group may have one or more substituents (for example, a C1-C6 alkyl group, a halogen atom, etc.) on the aromatic ring. Specifically, as the phenylene group, the following formula (Formula I / E-Ar2-1),

にて表されるもの等が挙げられる。

The thing etc. which are represented by are mentioned.

  In the aromatic residue, as the naphthylene group, specifically, the following formula (Formula I / E-Ar3-1),

にて表されるもの等が挙げられる。

The thing etc. which are represented by are mentioned.

  Aromatic residues include groups (Chemical I / E-Ar1-1), (Chemical I / E-Ar1-4), (Chemical I / E-Ar1-8), and (Chemical I / E-Ar1-). 9) is preferred.

In A ₁₁ , A ₁₃ , and A ₁₅ , examples of the divalent hydrogenated aromatic residue include those obtained by hydrogenating (hydrogenating) an aromatic ring in the aromatic residue. At least a part of A ₁₁ , A ₁₃ , and A ₁₅ may be a hydrogenated aromatic residue instead of the aromatic residue. When hydrogenated aromatic residues are used instead of aromatic residues, there are advantages such as prevention of discoloration due to thermal history (especially yellowing resistance), weather resistance, and compatibility with acrylic copolymer resins. is there.

  Examples of hydrogenated aromatic residues include fully hydrogenated and partially hydrogenated residues. Specifically, hydrogenated aromatic residues include those in which unsaturated bonds (double bonds, etc.) in the aromatic residues are completely hydrogenated to saturated bonds, and hydrogenated to the middle stage. And those in which all unsaturated bonds in the aromatic ring are hydrogenated, and those in which only some unsaturated bonds in the aromatic ring are hydrogenated.

  When an epoxy resin having a hydrogenated aromatic residue (Chemical I / E) is used, yellowing resistance, weather resistance, compatibility with an acrylic copolymerizable resin, and the like can be improved.

  The hydrogenation conditions are appropriately selected according to the degree of hydrogenation (for example, 40 to 100% hydrogenation). For example, using a fixed bed flow reactor filled with a ruthenium-supported molded catalyst, it is dissolved in an ether solvent. Using a flooded bed method in which the raw material solution and hydrogen are circulated to the reactor in a gas-liquid upward cocurrent flow, the reaction temperature is in the range of 10 to 150 ° C., the reaction pressure (hydrogen pressure) is in the range of 0.5 to 15 MPa, Hydrogenation is possible within a flow rate (LHSV) range of 0.2 to 10 / h.

In A ₁₁ , A ₁₃ and A ₁₅ , specific examples of the hydrogenated aromatic residue include those represented by the following formulas (Chemical I / ES-1) to (Chemical I / ES-12). And those in which some or all of these cyclohexane rings are cyclohexene rings.

In the formula (Chemical I / E), the average repeating unit numbers a ₁₁ and a ₁₂ may be the same or different and each independently represents a number of 0 or more, but a ₁₁ and a ₁₂ are not 0 at the same time. The sum (a ₁₁ + a ₁₂ ) of a ₁₁ and a ₁₂ is preferably 20 (particularly 15) or less, for example. When the sum (a ₁₁ + a ₁₂ ) is too large, gelation may be caused by reaction with a polyfunctional hydrolyzable alkoxysilane.

In the formula (Chemical I / E), a ₁₁ A ₁₂ and a ₁₂ A ₁₄ may be the same or different and each independently represents H or G. However, at least one of a ₁₁ A ₁₂ and a ₁₂ A ₁₄ may be H, and all may be H at the same time. Preferably, when a ₁₁ is not 0, at least one of a ₁₁ A ₁₂ is G. Similarly, _preferably, if _{a 12} is not _0, among _{a 12} amino _{A 14,} at least one is G.

  Furthermore, the epoxy resin (Chemical I / E) preferably has a softening point of 50 ° C. or higher (particularly 60 to 100 ° C.). By setting the softening point to 50 ° C. or higher, there are advantages of improved touch drying properties and improved photosensitivity.

  Examples of the epoxy resin (Chemical I / E) include homopolymer resins and copolymer resins, and one or more of these may be used. Examples of the “resin” include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A / F combined type epoxy resin, novolac type epoxy resin, and bisphenol A (or F). Novolac type epoxy resin, triphenylmethane type epoxy resin, bixylenol type epoxy resin, dicyclopentadiene phenolic type epoxy resin, naphthalene skeleton epoxy resin, fluorein type epoxy resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin, etc. One or more of these may be used.

  Preferably, as the epoxy resin (Chemical I / E), a homopolymer resin represented by the following formula (Chemical I / E-1) and an alternating represented by the following formula (Chemical I / E-2) Examples thereof include a copolymer resin and a block copolymer resin represented by the following formula (Chemical I / E-3), and one or more of these may be used.

In formulas (Chemical I / E-1) to (Chemical I / E-3), G has the same meaning as described above.
In the formula (Chemical I / E-1), A ₃₁ and A ₃₃ each independently represent a divalent aromatic residue or a divalent hydrogenated aromatic residue. Preferably, A ₃₃ is A ₃₁ is there. In A ₃₁ and _{A 33,} the divalent aromatic residue or a divalent hydrogenated aromatic residues, may be obtained by Setsuji in the _{A 11, A 13,} and _{A 15.} In the formula (Formula I / E-1), the average number of repeating units a ₃₁ is preferably 20 (particularly 15) or less. In the formula (Chemical I / E-1), a ₃₁ A _{32 s} may be the same or different and each independently represents H or G, but at least one of them is H, and all are H at the same time. There may be.

In the formula (Chemical I / E-2), A ₄₁ , A ₄₃ and A ₄₅ each independently represents a divalent aromatic residue or a divalent hydrogenated aromatic residue, preferably A ₄₅ is _{a 41} or _{a 43.} In A ₄₁ , A ₄₃ , and A ₄₅ , the divalent aromatic residue or the divalent hydrogenated aromatic residue is the same as those explained and exemplified in the above A ₁₁ , A ₁₃ , and A ₁₅ . It's okay. In formula (Formula _{I / E-2), a} 41 has _the same meaning as _{a 31.} In the formula (Chemical I / E-2), a ₄₁ , A ₄₂ and A ₄₄ may be the same or different and each independently represents H or G, but at least one is H, H may be H at the same time.

In the formula (Chemical I / E-3), A ₅₁ , A ₅₃ , and A ₅₅ each independently represent a divalent aromatic residue or a divalent hydrogenated aromatic residue. ₅₅ is _A51 or _A53 . In A ₅₁ , A ₅₃ , and A ₅₅ , the divalent aromatic residue or the divalent hydrogenated aromatic residue is the same as those described and exemplified in the aforementioned A ₁₁ , A ₁₃ , and A ₁₅ . Good. In the formula (Chemical I / E-3), a ₅₁ and a ₅₂ have the same meanings as a ₁₁ and a ₁₂ , respectively. In the formula (Chemical I / E-3), A ₅₂ and A ₅₄ may be the same or different and each independently represents H or G, but at least one is H, and all are H at the same time. There may be.

  The copolymerization type epoxy resin (Chemical I / E-2) or (Chemical I / E-3) exhibits an effect as if each homopolymeric epoxy resin (Chemical I / E-1) was combined.

For example, the resin (of I / E-1), the resin properties and characteristics by the basic skeleton _{A 31} differ. Specifically, in the case of introducing bisphenol F type A _31, flexibility, having resin properties and features such adhesion. _Further, in the case of introducing group (of I / E-Ar1-9) to _{A 31,} having a crystalline, resin properties and characteristics and low water absorption. Therefore, in order to obtain the characteristics of both, each homopolymerized epoxy resin may be blended. On the other hand, it is possible to synthesize a resin combining the characteristics and features of both resins by using a copolymer type epoxy resin in which the skeleton is introduced into the same molecule. Therefore, by using a copolymerization type epoxy resin, it is possible to add functions in a well-balanced manner that are in a trade-off relationship as resin characteristics.

  In the epoxy resin (Chemical I / E), the resin (Chemical I / E-1) specifically includes the following formulas (Chemical I / E-1-1) and (Chemical I / E-1-2). The resin represented by is mentioned. Specific examples of the resin (Chemical I / E-2) include resins represented by the following formulas (Chemical I / E-2-1) to (Chemical I / E-2-4), respectively. . Specific examples of the resin (Chemical I / E-3) include resins represented by the following formulas (Chemical I / E-3-1) to (Chemical I / E-3-4), respectively. . One or more of these may be used as the epoxy resin (Chemical I / E).

In the above formulas (Chemical I / E-1-1) to (Chemical I / E-2-4) and (Chemical I / E-3-1) to (Chemical I / E-3-4), G represents It is synonymous with. A ₆₁₁ and A ₆₂₁ have the same _{meanings as} A ₃₂ , respectively. The average repeating unit numbers a ₆₁₁ and a ₆₂₁ are numbers of 20 or less, respectively. A ₆₃₁ , A ₆₄₁ , A ₆₅₁ , and A ₆₆₁ are each synonymous with A ₄₂ . A ₆₃₂ , A ₆₄₂ , A ₆₅₂ , and A ₆₆₂ have the same _{meaning as} A ₄₄ . a ₆₃₁ , a ₆₄₁ , a ₆₅₁ , and a ₆₆₁ each have the same meaning as the a ₄₁ . A ₇₁₁ , A ₇₂₁ , A ₇₃₁ , and A ₇₄₁ have the same _{meaning as} A ₅₂ . A ₇₁₂ , A ₇₂₂ , A _732, and A ₇₄₂ have the same _{meaning as} A ₆₄ . a ₇₁₁ , a ₇₂₁ , a ₇₃₁ , and a ₇₄₁ are respectively synonymous with the a ₅₁ . a ₇₁₂ , a ₇₂₂ , a ₇₃₂ , and a ₇₄₂ have the same _{meanings as the} a ₅₂ , respectively.

In the above formulas (Chemical I / E-1-1) to (Chemical I / E-2-4) and (Chemical I / E-3-1) to (Chemical I / E-3-4), A ₆₃₃ , A ₆₃₄ , A ₆₄₃ , A ₆₄₄ , A ₆₅₃ , A ₆₅₄ , A ₆₆₃ , A ₆₆₄ , A ₇₁₃ , A ₇₁₄ , A ₇₂₃ , A ₇₂₄ , A ₇₃₃ , A ₇₃₄ , A ₇₄₃ , and A ₇₄₄ are each independently H or CH ₃ . Preferably, A ₆₃₃ and A ₆₃₄ are the same, A ₆₄₃ and A ₆₄₄ are the same, A ₆₅₃ and A ₆₅₄ are the same, A ₆₆₃ and A ₆₆₄ are the same, A ₇₁₃ and A ₇₁₄ are the same, respectively. A ₇₂₃ and A ₇₂₄ are the same, A ₇₃₃ and A ₇₃₄ are the same, and A ₇₄₃ and A ₇₄₄ are the same.

  An alternating copolymerization type epoxy resin, for example, an epoxy resin (Chemical I / E-2-1) is obtained by first copolymerizing a bisphenol A type epoxy resin and 4,4′-dihydroxydiphenylmethane and then an epoxy having a residual hydroxyl group. Prepared by

  The block copolymer type epoxy resin, for example, epoxy resin (Chemical I / E-3-1) is, for example, a homopolymer of bisphenol A type epoxy resin (n is 1 or more) and a homopolymer of bisphenol F type epoxy resin. (N is 1 or more) is added by linking and then prepared by epoxidation of the remaining hydroxyl group.

［式（化Ｉ／Ｅ−Ｓ）中、Ｇは、前記と同義である。ａ_８個のＡ_８は、同一でも異なってもよく、それぞれ独立にＨ若しくはＧを表すが、少なくとも一つはＨであり、総てが同時にＨであってもよい。平均繰り返し単位数ａ_８は、２０以下の数である。］
で表されるものが、最も好ましい。As the epoxy resin (Chemical I / E), the above formulas (Chemical I / E to 1-1) and (Chemical I / E-1-2), and the following formula,

[In the formula (Chemical I / ES), G has the same meaning as described above. a The _eight A _{8 s} may be the same or different and each independently represents H or G, but at least one of them may be H and all may be H at the same time. The average number of repeating units _{a 8} is the number of 20 or less. ]
Those represented by are most preferred.

  In addition, as an epoxy resin (chemical I / E), 1 or more types of the epoxy resin illustrated above can be used.

にて表されるものが挙げられる。As the hydrolyzable alkoxysilane which is the other preparation raw material of component [I], the following formula:

The thing represented by is mentioned.

In the formula (Chemical I / Si-1), B ₁₀ and B ₁₁ represent an alkyl group, an aryl group, an allyl group, or an unsaturated aliphatic residue, which may be the same or different, and b ₁₁ B ₁₀ And (4-b ₁₁ ) B ₁₁ is at least one alkyl group. _{Preferably, B 10} is an alkyl group, or an aryl group of _{C1-8, B 11} is C1~4 alkyl group. b ₁₁ represents an integer of 0 to 3. B ₁₀ and B ₁₁ may further have a functional group.

  Specific examples of the hydrolyzable alkoxysilane (Chemical I / Si-1) include tetraalkoxysilanes [tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, etc.], alkyltri Alkoxysilanes [methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltri Methoxysilane, isopropyltriethoxysilane, etc.], aryltrialkoxysilanes [phenyltrimethoxysilane, phenyltriethoxysilane, etc.], functional group-containing trialkoxysilanes [vinyl] Limethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, isocyanatepropyltriethoxysilane, alkoxypropyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, triethoxysilyl-N- (1,3dimethyl-butylidene), p-styryltrimethoxysilane, hexamethyldisilazane, etc.], dialkoxysilanes [dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxy Silane etc.] may be used, and one or more of these may be used. Tetraalkoxysilanes are preferable.

  Another hydrolyzable alkoxysilane includes an alkoxysilane condensate, such as a hydrolyzable alkoxysilane (Chemical I / Si-1) condensate. Specifically, examples of the alkoxysilane condensate include those represented by the following formulas (Chemical I / Si-2) and (Chemical I / Si-3), respectively.

In the formulas (Chemical I / Si-2) and (Chemical I / Si-3), B _{21 to} B ₂₆ and B _{31 to} B ₃₆ may be the same or different, and are each independently a C1-8 alkyl group, Represents an aryl group or an unsaturated aliphatic residue. Note that b ₂₁ B ₂₂ and B ₂₆ and b ₃₁ B ₃₂ and B ₃₆ may be the same or different, and are independent. The B ₂₁ and _B 24 _{.about.B 26} and _B 31 _{.about.B 36,} specifically, C1~8 alkyl group (methyl group, an ethyl group, an isopropyl group, etc.), an aryl group are preferable. As B ₂₂ and B ₂₃ , specifically, a C1-3 alkyl group (methyl group, ethyl group, isopropyl group, etc.) and the like are preferable.

In formula (Formula I / Si-2) and (of I / Si-3), the average number of repeating units _{b 21} and _{b 31} are each 0-20 (especially 1-10) are preferable.

［式中、平均繰り返し単位数ｂ_４１は、１〜７である。］
で表されるものが挙げられる。As the alkoxysilane condensate (Chemical I / Si-3), the following formula:

[Wherein, the average number of repeating units b ₄₁ is 1 to 7. ]
The thing represented by is mentioned.

  As the hydrolyzable alkoxysilane, those represented by the formulas (Chemical I / Si-2) and (Chemical I / Si-3) are preferable, and in particular, represented by the formula (Chemical I / Si-4). Is most preferred.

  Component [I] is obtained by subjecting one or more types of epoxy resins (chemical I / E) and one or more types of the above hydrolyzable alkoxysilanes to a dealcoholization reaction. In the dealcoholization reaction, the weight ratio of hydrolyzable alkoxysilane and epoxy resin (Chemical I / E) [weight of hydrolyzable alkoxysilane converted to silica / weight of epoxy resin (Chemical I / E)] is 0.01. -1.2 is preferred.

  In the dealcoholization reaction, the equivalent ratio of the hydroxyl group equivalent of the epoxy resin (Chemical I / E) to the alkoxy group equivalent of the hydrolyzable alkoxysilane is preferably less than 0.8 or 1.2 or more.

  As a reaction catalyst in the dealcoholization reaction, organic tin, organic acid tin, particularly dibutyltin dilaurate is preferable.

  The dealcoholization reaction can be typically performed at a reaction temperature of 70 to 110 ° C. and a reaction time of 1 to 20 hours.

  As described above, the alkoxy group-containing silane-modified epoxy resin is prepared, and the modification may be partial modification or complete modification. The alkoxy group-containing silane partially modified epoxy resin itself can be used as component [I], but can also be used in place of the epoxy resin (Chemical I / E). That is, what is obtained by dealcoholizing such partially modified epoxy resin and hydrolyzable alkoxysilane can also be used as component [I].

特に、下記式、As component [I], in the resin structure, for example, the following formula:

In particular, the following formula:

にて表される構造の何れか１種以上を有するものであってよい。

It may have any one or more of the structures represented by:

In formula (Formula I / U-1) ~ (of _{I / U-6), A} 31, B 22 ~B 26, B 32 ~B 36, b 21, b 31 and _{b 41} is a as defined above .

  The photosensitive thermosetting resin composition according to the present invention contains an unsaturated group-containing polycarboxylic acid resin (hereinafter also referred to as “component [II]”). Component [II] preferably has an ethylenically unsaturated group and two or more carboxyl groups in the molecule and a solid content acid value (mgKOH / g) of 30 to 160 (particularly 60 to 130). If the solid content acid value is less than 30, the thermal stability is poor and may not be dissolved during alkali development, resulting in a residue. Conversely, if it exceeds 160, the moisture resistance decreases, and the reliability such as insulation, HAST resistance, etc. May decrease.

  Examples of such component [II] include, for example, an epoxy group-containing unsaturated compound in a copolymer of an ethylenically unsaturated acid and an ethylenically unsaturated bond-containing monomer (hereinafter also referred to as “copolymer IIA”). Examples thereof include resins obtained by reacting monomers (hereinafter also referred to as “resin IIA”). The weight average molecular weight of the resin IIA is preferably 3000 to 60000 (particularly 5000 to 30000).

  Specific examples of the ethylenically unsaturated acid include acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate and maleic acid. Examples thereof include monoethyl acid, monopropyl maleate, and sorbic acid, and one or more of these may be used.

  Specific examples of the ethylenically unsaturated bond-containing monomer include C1-C8 alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, etc.], 2-hydroxy C1-C18 alkyl (meth). Acrylate [2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.], ethylene glycol monomethyl acrylate, ethylene glycol monomethyl methacrylate, ethylene glycol monoethyl acrylate, ethylene glycol mono Ethyl methacrylate, glycerol acrylate, glycerol methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tetrahydrofurf Le acrylate, tetrahydrofurfuryl methacrylate,

Acrylic amide, methacrylic amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate , Benzyl methacrylate, carbitol acrylate, carbitol methacrylate, ε-caprolactone modified tetrafurfuryl acrylate, ε-caprolactone modified tetrafurfuryl methacrylate, diethylene glycol ethoxyl acrylate, isodecyl acrylate, isodecyl methacrylate, octyl acrylate, octyl methacrylate, Lauril Reaction product of acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, saturated or unsaturated dibasic acid anhydride and (meth) acrylate having one hydroxyl group in one molecule [ For example, a reaction product of succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and the like with 2-hydroxyethyl or propyl (meth) acrylate] may be used, and one or more of these may be used.

  As the copolymer IIA, specifically, a copolymer of methacrylic acid and methyl methacrylate and a copolymer of methacrylic acid and butyl methacrylate are preferable, and one or more of these may be used.

  The copolymer IIA preferably has an average molecular weight of 3000 to 30000, the number of carboxyl groups in the resin is 0.2 to 5.0 per 1000 molecular weight, and an acid value of 20 to 160.

［式（化ＩＩ／Ｅ）中、Ｃ_１１は、縮環していてもよいエポキシ環を有する一価基を表す。Ｃ_１２〜Ｃ_１４は、同一でも異なってもよく、それぞれ独立にＨ、Ｃ１〜６アルキル基、又はアリール基（フェニル基等）を表す。］
にて表されるものが挙げられる。As an epoxy group-containing unsaturated monomer, the following formula,

[In the formula (Formula II / E), C ₁₁ represents a monovalent group having an epoxy ring which may be condensed. C _{12 to} C ₁₄ may be the same or different and each independently represents H, a C 1-6 alkyl group, or an aryl group (such as a phenyl group). ]
The thing represented by is mentioned.

  Specifically, as the epoxy group-containing unsaturated monomer, glycidyl (meth) acrylate, C1-C6 alkyl-2,3-epoxypropyl (meth) acrylate [2-methyl-2,3-epoxypropyl (meth) ) Acrylate, 2-ethyl-2,3-epoxypropyl (meth) acrylate, etc.], a compound having an alicyclic epoxy group [3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) ), Acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylamino acrylate, etc.], and the like using one or more of these, and the like using one or more of these. Good.

にて表される化合物である。Preferably, the epoxy group-containing unsaturated monomer has the following formula:

It is a compound represented by these.

In the formula (Formula _{II / E-5), C} 21 represents a C1~6 alkylene group. C ₂₂ represents H or C1~3 alkyl. Preferably, C ₂₁ is a methylene group and C ₂₂ is a methyl group.

  In the reaction between the copolymer IIA and the epoxy group-containing unsaturated monomer, the epoxy group-containing unsaturated monomer has an epoxy group content of 0.1 to 0.9 per 1 equivalent of the carboxyl group in the copolymer IIA. Equivalents are preferred.

  As another component [II], for example, a copolymer of an epoxy group-containing unsaturated monomer and an ethylenically unsaturated bond-containing monomer (hereinafter also referred to as “copolymer IIB”) is ethylenically unsaturated. A saturated and / or unsaturated group-containing polybasic acid anhydride (hereinafter referred to as “saturated / unsaturated group-containing polybasic acid anhydride”) is added to a reaction product obtained by reacting an acid (hereinafter also referred to as “reaction product IIB”). Resin ”(hereinafter also referred to as“ resin IIB ”). The weight average molecular weight of the resin IIB is preferably 3,000 to 60,000 (particularly 5,000 to 30,000).

  Examples of the “epoxy group-containing unsaturated monomer”, “ethylenically unsaturated bond-containing monomer”, and “ethylenically unsaturated acid” include those exemplified above.

  As the epoxy group-containing unsaturated monomer, glycidyl (meth) acrylate and allyl glycidyl ether are preferable.

  Examples of the ethylenically unsaturated bond-containing monomer include styrene, chlorostyrene, α-methylstyrene, and methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, 2-ethylhexyl, octyl as substituents. Acrylate or methacrylate having a substituent such as, capryl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isobornyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl; Mono (meth) acrylate of polyethylene glycol or mono (meth) acrylate of polypropylene glycol; vinyl acetate, vinyl butyrate or vinyl benzoate; (meth) acrylamide, N-hydroxymethyl (meth) acrylate Riruamido, N- methoxymethyl (meth) acrylamide, N- ethoxymethyl (meth) acrylamide, N- butoxymethyl (meth) acrylamide; acrylonitrile preferable.

  Ethylenically unsaturated acids include acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate, monoethyl maleate, maleic acid Monopropyl and sorbic acid are preferred.

  Specific examples of saturated / unsaturated polybasic acid anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, methyl-hexa or tetrahydrophthalic anhydride, di-, tetra- or hexahydrophthalic anhydride, Examples thereof include maleic acid, itaconic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, preferably succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride.

  In the reaction between the copolymer IIB and the ethylenically unsaturated acid, the epoxy group in the copolymer IIB is 0.8 to 1.3 (especially 0.9 to 1.1) Equivalents are preferred.

  In the reaction of the reaction product IIB with the saturated / unsaturated group-containing polybasic acid anhydride, the anhydride group 0 of the saturated / unsaturated group-containing polybasic acid anhydride is equivalent to 1 equivalent of the hydroxyl group in the reaction product IIB. 0.05-1.0 (especially 0.1-0.95) equivalent is preferable.

  As another component [II], for example, a reaction product of an epoxy resin having two or more epoxy groups in the molecule (hereinafter also referred to as “epoxy resin IIC”) and an unsaturated group-containing monocarboxylic acid (hereinafter “ Reaction product IIC ”) and a resin (hereinafter“ resin IIC ”) obtained by reacting polybasic carboxylic acid or its anhydride (hereinafter also referred to as“ polybasic carboxylic acid (anhydride) ”). Also called). The weight average molecular weight of the resin IIC is preferably 3000 to 30000 (particularly 5000 to 20000).

  Examples of the epoxy resin IIC include the epoxy resin (Chemical I / E). Specifically, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy Resins, biphenol type epoxy resins, biphenol novolac type epoxy resins, bixylenol type epoxy resins, trisphenol methane type epoxy resins, N-glycidyl type epoxy resins, and the like can be used, and one or more of these can be used.

  Examples of the unsaturated group-containing monocarboxylic acid include those having an ethylenically unsaturated bond and one carboxyl group (including a carboxylic acid group —COOH) in the molecule. The ethylenically unsaturated bond and the carboxyl group may or may not be conjugated (adjacent) to each other.

  Specifically, the unsaturated group-containing monocarboxylic acid includes acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate , Monoethyl maleate, monopropyl maleate, sorbic acid, β-carboxyethyl acrylate and the like, and one or more of these may be used.

  In the reaction between the epoxy resin IIC and the unsaturated group-containing monocarboxylic acid, 0.8 to 1.3 mol of the unsaturated group-containing monocarboxylic acid may be reacted per equivalent of the epoxy group in the epoxy resin IIC.

  The reaction product IIC thus obtained is then reacted with a polybasic carboxylic acid (anhydride) to prepare resin IIC.

  Examples of the polybasic carboxylic acid (anhydride) include C1-C8 dibasic carboxylic acid (anhydride). Specific examples include (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) phthalic acid, (anhydrous) itaconic acid, tetra- or hexahydro (anhydride) phthalic acid, and the like. As the polybasic carboxylic acid (anhydride), a polybasic carboxylic acid anhydride is preferable.

  In the reaction between the reaction product IIC and the polybasic carboxylic acid (anhydride), 0.05 to 1.00 equivalent of the polybasic carboxylic acid per equivalent of the hydroxyl group with respect to the hydroxyl group in the reaction product IIC, The polybasic carboxylic acid anhydride is preferably reacted in an amount of 0.1 to 0.9 equivalent.

  When preparing the photosensitive thermosetting resin composition according to the present invention as a white solder resist ink such as a printed wiring board for LED, from the viewpoint of yellowing resistance and the like, as the component [II], resin IIA and resin IIB Is preferred.

  The photosensitive thermosetting resin composition according to the present invention contains a diluent (hereinafter also referred to as “component [III]”). By containing component [III], the crosslinking efficiency can be increased, the heat resistance can be improved, and the coating viscosity of the composition can be adjusted.

  As component [III], an organic solvent and / or a photopolymerizable monomer can be used. In Component [III], specific 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, Glycol ethers such as butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate and esterified products of the above glycol ethers; ethanol, propanol, Alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha Include petroleum solvents such may be used those of one or more.

  In Component [III], as the photopolymerizable monomer, specifically, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate: ethylene glycol, Mono- or diacrylates of glycols such as methoxytetraethylene glycol, polyethylene glycol and propylene glycol; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; N, N-dimethyl Aminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyhydric alcohol or polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts; addition of phenoxy (meth) acrylate, bisphenol A di (meth) acrylate, and these phenols to ethylene oxide or propylene oxide (Meth) acrylates such as products; (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and melamine (meth) acrylate, etc. One or more may be used.

  The photosensitive thermosetting resin composition according to the present invention contains a photopolymerization initiator (hereinafter also referred to as “component [IV]”). As component [IV], the storage stability of the resin composition after blending each component is good, the solubility is good, and unreacted in various heat treatment steps (pre-drying, thermosetting, molding, mounting soldering) What does not generate | occur | produce the mist of an agent is preferable.

  Specific examples of component [IV] include benzoins such as benzoin, benzyl, benzoin methyl ether, and benzoin isopropyl ether, and benzoin alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2 -Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-monoforino-propan-1-one, N, N Acetophenones such as dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone Anthraquinones such as 2,4-dimethylthiosantone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, thioxanthones such as 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, Benzophenones such as methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, and xanthones, and benzoic acid such as ethyl 4-dimethylaminobenzoate and 2- (dimethylamino) ethylbenzoate Esters or tertiary amines such as triethylamine and triethanolamine,

7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7- Dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethyl Aminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-diethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 4 , 6-dimethyl-7-ethylaminocoumarin, etc. alone or in combination It can be used in combination on.

  From the environmental viewpoint, the component [IV] includes 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-benzyl-2-dimethyl. Amino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholinophenyl) -butanone-1,2,4-diethyl Thioxanthone, 4-benzoyl-4'-methyldiphenyl sulfide, 4-phenylbenzophenone, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) -phenyl) -2- Methyl-propan-1-one, poly (oxy (methyl-1,2-ethanediyl)), α- (4- (di Tilamino) benzoyl-ω-butoxy, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, N -Phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like are preferred, and one or more of these may be used.

  Another component [IV] includes a photoacid generator. The photoacid generator is a compound that generates an acid (electron pair acceptor) by light. Specific examples of the photoacid generator include iodonium salt compounds, sulfonium salt compounds, ammonium salt compounds, phosphonium salt compounds, arsonium salt compounds, stibonium salt compounds, oxonium salt compounds, selenonium salt compounds, and stannonium salt compounds. One or more of them may be used. Preferred are iodonium salts, sulfonium salts, ammonium salts and the like.

  Specifically, as the iodonium salt, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphinate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroantimonate, bis (4,4′-t.butylphenyl) Iodonium hexafluoroborate, bis (4,4′-t.butylphenyl) iodonium hexafluorophosphinate, bis (4,4′-t.butylphenyl) iodonium hexafluoroantimonate, bis (4,4′-t. Butylphenyl) iodonium hexafluoroarsenate, diphenyliodonium triflate, bis (4,4′-t.butylphenyl) iodonium triflate, etc. It may be.

  Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphinate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium triflate. More than seeds may be used.

  As the photoacid generator, a sensitizer [thioxanthone derivatives such as diethylthioxanthone and isopropylthioxanthone, anthracene, pyrene, phenothiazine and the like] can be used in combination.

  The photosensitive thermosetting resin composition according to the present invention contains a curing adhesion imparting agent (hereinafter also referred to as “component [V]”). By including component [V], properties such as adhesion, chemical resistance, heat resistance, and moisture resistance can be further improved.

  Specifically, the component [V] includes dicyandiamide, S-triazines [melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-tolyl-S-. Triazine, 2,4-diamino-6-xylyl-S-triazine, etc.], guanamines [guanamine, acetoguanamine, benzoguanamine, 3,9-bis [2- (3,5diamino-2,4,6-triaza Phenyl) ethyl] 2,4,8,10 tetraoxaspiro [5,5] undecane, etc.], imidazole compounds [2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl4, Isocyanuric acid adduct of 5-dihydroxymethylimidazole and 2-methylimidazole (Shikoku Kasei Kogyo, “2MZ-O Etc.), 1- (4,5-diamino-2-triazinyl) -2- (2-methyl-1-imidazolyl) ethane (Shikoku Kasei Kogyo, “2MZ-AZINE” etc.)], 1,8-diazabicyclo [ 5,4,0] Undecen-7 [DBU, manufactured by San Apro Co., Ltd.] and their organic acid salts and epoxy adducts,

Imidazolealkoxysilane derivatives [N-imidazolemethyltrimethoxysilane, N-2-methylimidazolemethyltrimethoxysilane, N-2-ethylimidazolemethyltrimethoxysilane, N-2-iso-propylimidazolemethyltrimethoxysilane, N- 2-ethyl-4-methylimidazolemethyltrimethoxysilane, N-2-undecylimidazolemethyltrimethoxysilane, N-2-heptadecylimidazolemethyltrimethoxysilane, N-imidazolemethyltriethoxysilane, N-2-methyl Imidazole ethyltrimethoxysilane,

N-2-ethylimidazolemethyltriethoxysilane, N-2-iso-propylimidazolemethyltriethoxysilane, N-2-ethyl-4-methylimidazolemethyltriethoxysilane, N-2-undecylimidazolemethyltriethoxysilane N-2-heptadecylimidazole methyltriethoxysilane, 2- (N-imidazole) ethyltrimethoxysilane, 2- (N-2-methylimidazole) ethyltrimethoxysilane, 2- (N-2-ethylimidazole) Ethyltrimethoxysilane, 2- (N-2-iso-propylimidazole) ethyltrimethoxysilane, 2- (N-2-ethyl-4-methylimidazole) ethyltrimethoxysilane, 2- (N-2-undecyl) Imidazole) ethyltrimethoxysilane

2- (N-2-heptadecylimidazole) ethyltrimethoxysilane, 2- (N-imidazole) ethyltriethoxysilane, 2- (N-2-methylimidazole) ethyltriethoxysilane, 2- (N-2- Ethylimidazole) ethyltriethoxysilane, 2- (N-2-iso-propylimidazole) ethyltriethoxysilane, 2- (N-2-ethyl-4-methylimidazole) ethyltriethoxysilane, 2- (N-2) -Undecylimidazole) ethyltriethoxysilane, 2- (N-2-heptadecylimidazole) ethyltriethoxysilane, 3- (N-imidazole) propyltrimethoxysilane, 3- (N-2-methylimidazole) propyltri Methoxysilane, 3- (N-2-ethylimidazole) propylto Silane, 3- (N-2-iso- propyl-imidazole) propyl trimethoxysilane,

3- (N-2-ethyl-4-methylimidazole) propyltrimethoxysilane, 3- (N-2-undecylimidazole) propyltrimethoxysilane, 3- (N-2-heptadecylimidazole) propyltrimethoxysilane 3- (N-imidazole) propyltriethoxysilane, 3- (N-2-methylimidazole) propyltriethoxysilane, 3- (N-2-ethylimidazole) propyltriethoxysilane, 3- (N-2- iso-propylimidazole) propyltriethoxysilane, 3- (N-2-ethyl-4-methylimidazole) propyltriethoxysilane, 3- (N-2-undecylimidazole) propyltriethoxysilane, 3- (N- 2-heptadecylimidazole) propyltriethoxysilane, etc.]

Quaternary imidazolium salt derivatives [1-ethyl-3-methylimidazolium trifluoromethyl sulfate, N-methyl, N′-n-butylimidazolium hexafluorophosphate, N-alkyl-N′-alkoxyalkylimidazole Lilium salt (anion is bis (trifluoromethylsulfonyl) imidic acid, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, tris (trifluoromethylsulfonyl) carbonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or At least one selected from organic carboxylic acids or halogen ions)],

Diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, cyclohexylamine, m-xylylenediamine, 4,4'-diamino-3,3'diethyldiphenylmethane, diethylenetriamine, tetraethylenepentamine, N-aminoethylpiverazine, Isophorone diamine, dicyandiamide, ureas [urea itself, etc.], polyamines [polybasic hydrazide, etc.], organic acid salts and / or epoxy adducts thereof, amine complexes of boron trifluoride,

Tertiary amines [trimethylamine, triethanolamine, N, N-dimethyloctylamine, N, N-dimethylaniline, N-benzyldimethylamine, pyridine, N-methylpyridine, N-methylmorpholine, hexamethoxymethylmelamine, 2 , 4,6-tris (dimethylaminophenol), N-cyclohexyldimethylamine, tetramethylguanidine, m-aminophenol, etc.], organic phosphines [tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, etc.],

Phosphonium salts [tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, etc.], quaternary ammonium salts [benzyltrimethylammonium chloride, phenyltributylammonium chloride, benzyltrimethylammonium bromide, etc.], diphenyl Examples include iodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, thermal cationic polymerization catalyst, styrene-maleic acid resin, silane coupling agent, etc. One or more of the above may be used.

  When an imidazole alkoxysilane derivative and / or a quaternary imidazolium salt derivative is used as component [V], the adhesion of the resist film is improved, and further, metal plating resistance, solder heat resistance, moisture resistance, peel Strength etc. can also be improved.

  Preferably, component [V] includes dicyandiamide, S-triazine derivatives [specifically melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, etc.], imidazole alkoxysilane derivatives [specifically N-imidazolemethyltrimethoxysilane, 3- (N-2-methylimidazole) propyltrimethoxysilane, etc.], quaternary imidazolium salt derivatives [1-ethyl 3-methylimidazolium trifluoromethyl sulfate, N -Methyl, N'-n-butylimidazolium hexafluorophosphate, N-alkyl-N'-alkoxyalkylimidazolium phthalate] and the like.

  The photosensitive thermosetting resin composition according to the present invention further includes a colorant, a filler, an antifoaming agent, an epoxy resin, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, and an antibacterial agent. Antifungal agents, leveling agents, stabilizers, coupling agents, antioxidants, phosphors and the like may be added.

  In particular, when the photosensitive thermosetting resin composition according to the present invention is prepared as a white solder resist ink such as a printed wiring board for LED, it is preferable to add a white pigment as a colorant. Examples of white pigments include titanium oxide, zinc oxide, basic carbonate, basic lead sulfate, lead sulfate, zinc sulfide, antimony oxide, titanium nitride, cerium fluoride, and cerium oxide. From this point, titanium oxide is preferable. As an average particle diameter of a white pigment, 0.01-1.0 (especially 0.1-0.5) micrometer is preferable, for example.

  In the additive, fillers include talc, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, zinc hydroxide, Aluminum nitride, silicon nitride, boron nitride, diamond powder, zirconium silicate, zirconium oxide, magnesium hydroxide, mica, mica powder, silicone powder, organic resin filler (polystyrene, polymeta (a) acrylate, (benzo) guanamine , Acrylic rubber-based, rubber-based, etc.).

  Examples of the antifoaming agent include polydimethylsiloxane, modified silicone type, fluorine type, polymer type, surfactant, emulsion type antifoaming agent, and the like.

  Epoxy resins include bisphenol type epoxy resins, novolak type epoxy resins (orthocresol novolak type epoxy resins, phenol novolak type epoxy resins, etc.), polybasic acids (phthalic acid, dimer acid, etc.) and epichlorohydrin. Glycidyl ester type epoxy resin obtained by reacting polyamines (diaminodiphenylmethane, isocyanuric acid, etc.) with epichlorohydrin, and oxidizing the olefin bond with peracid such as peracetic acid. Examples thereof include linear aliphatic epoxy resins and alicyclic epoxy resins.

  The blending weight ratio of component [I] to component [II] (blending weight of component [I] / blending weight of component [II]) is 2/100 to 50/100 (preferably 5/100 to 40/100). ). Furthermore, with respect to 100 parts by weight of the total amount of the component [I] and the component [II], the component “III” is 5 to 500 (preferably 20 to 300) parts by weight, and the component [IV] is 0.1 to 30 parts, respectively. (Preferably 2 to 20) parts by weight, component [V] is 0.1 to 20 (preferably 0.5 to 10) parts by weight.

  In the above blending composition, if the blending weight ratio is less than 2/100, the solder heat resistance, adhesion, and weather resistance may be insufficient. Conversely, if it exceeds 50/100, the thermal stability of the ink will decrease. , Developability may be difficult. If the component [III] is less than 5 parts by weight, the coating property may be deteriorated and it may be difficult to apply or the photopolymerization property may be decreased. , The resolution may decrease. If the component [IV] is less than 0.1 parts by weight, photopolymerization may not occur sufficiently, resulting in poor development. Conversely, if it exceeds 30 parts by weight, light absorption is large, and thick film curing is difficult. Resolution may also be difficult. When the component [V] is less than 0.1 parts by weight, the adhesion with the base (copper, laminated material, glass epoxy resin, build-up layer, etc.) may not be sufficient, and the reliability may decrease. If it exceeds the parts by weight, the thermal stability of the ink may be reduced, making it difficult to develop.

  As a compounding composition of the additive, 0 to 500 (particularly 0.1 to 200) parts by weight of a coloring agent and 0 to 1200 (particularly, filler) with respect to 100 parts by weight of the total amount of the component [I] and the component [II]. 10 to 500) parts by weight and 0 to 10 (particularly 0.1 to 5) parts by weight of the antifoaming agent are preferred.

  In particular, when the photosensitive thermosetting resin composition according to the present invention is prepared as a white solder resist ink such as a printed wiring board for LED, the total amount of component [I] and component [II] is 100 parts by weight. , 10 to 500 (particularly 20 to 300) of white pigment and 0 to 1200 parts (particularly 10 to 1200, especially 10 to 800) parts by weight of filler are preferred.

  The photosensitive thermosetting resin composition according to the present invention prepared as described above generally has 8 or more photosensitivities (21-step tablet manufactured by Stoffer) and has excellent developability. .

  Hereinafter, the solder resist film-coated printed wiring board produced from the photosensitive thermosetting resin composition of the present invention will be described.

  The printed wiring board of the material substrate that covers the solder resist film is preferably a smoothed printed wiring board. In particular, a smoothed printed wiring board in which concave portions on the surface of the printed wiring board are filled with resin and the surface of the printed wiring board is smoothed is preferable. By using a smoothed printed wiring board, the coverage of the circuit is improved, and further improvements in reliability and concealment (copper circuit concealment) can be achieved.

  Of course, in the present invention, any other printed wiring board, for example, a conventional printed wiring board having irregularities on the surface of the printed wiring board, can be used. Furthermore, the printed wiring board may be a single-sided printed wiring board or a double-sided printed wiring board.

  The smoothed printed wiring board can be manufactured, for example, according to the methods described in Japanese Patent Application Nos. 2001-253678, 2001-337180, and 2004-311541.

  Specifically, first, a filling resin is applied to the recesses on the surface of the printed wiring board, primary curing is performed at a low temperature, surface polishing is performed, and then secondary curing is performed at a high temperature, thereby smoothing the printed wiring. A substrate can be manufactured.

  The “recess” is not particularly limited, and examples thereof include a recess between circuits on the surface of the wiring board, a via recess, and a recess for embedding a component. Further, the “concave portion” includes a hole, for example, a through hole, a blind via, a cavity, a build-up via, a conformal via, a stacked via, a landless via, a hole-filled base via, and the like.

  Examples of the filling resin include a thermosetting resin composition. In the present invention, any other curable resin, for example, a photocurable or photothermosetting resin composition can be used.

  Examples of the thermosetting resin composition include [A] an adduct of an epoxy resin and an unsaturated fatty acid, [B] (meth) acrylates, [C] a radical polymerization initiator, [D] a crystalline epoxy resin, and [C] E] A thermosetting resin composition containing a latent curing agent may be mentioned.

  Component [A] is specifically an adduct of 20 to 80% (particularly 40 to 60%) of a novolac type epoxy resin and (meth) acrylic acid [specifically, a cresol novolak type epoxy resin and acrylic acid. 20-80% (especially 40-60%) adducts etc.], 20-20% (especially 40-60%) adducts of bisphenol A type epoxy resin and (meth) acrylic acid, etc. are preferred. One or more kinds may be contained in the thermosetting composition.

  Specific examples of component [B] include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol Acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylamioethyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris- Polyhydric acrylates of polyhydric alcohols such as hydroxyethyl isocyanurate or their ethylene oxide or propylene oxide adducts Acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide or propylene oxide adducts of these phenols; glycidyl such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate Ether acrylates; and melamine acrylate, isobornyl acrylate, dicyclopentanyl methacrylate, and / or methacrylates corresponding to the above acrylates are preferred, and one or more of these are contained in the thermosetting composition. It's okay.

  As the component [C], specifically, t-butyl peroxybenzoate, t-butyl peroxy-2-ethyl hexanate, dicumyl peroxide and the like are preferable, and one or more of these are preferably used in the thermosetting composition. It may contain.

  Specific examples of the component [D] include bisphenol S such as BPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ARC, Inc., Epicron EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Type epoxy resin; diglycidyl phthalate resin such as Bremer DGT manufactured by NOF Corporation; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Co., Ltd., Araldite PT810 manufactured by Ciba-Geigy Corporation; YX manufactured by Japan Epoxy Resins Co., Ltd. -Bixylenol type epoxy resin such as -4000; Biphenol type epoxy resin such as YL-6121H manufactured by Japan Epoxy Resin Co., Ltd .; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. is preferable. One or more of these may be contained in the thermosetting composition.

Examples of the component [E] include dicyandiamides (DICY), imidazoles, BF ₃ -amine complexes, amine adduct type curing agents, amine-acid anhydride (polyamide) adduct type curing agents, hydrazide type curing agents, and amine type curings. Carboxylic acid salts, onium salts, and the like of the agent are preferable, and one or more of these may be contained in the thermosetting composition.

  In the composition of the thermosetting resin composition, the component [B] is 50 to 300 parts by weight (particularly 150 to 250 parts by weight) and the component [C] is 5 to 20 parts by weight with respect to 100 parts by weight of the component [A]. (Especially 8 to 15 parts by weight), component [D] is preferably 50 to 200 parts by weight (particularly 60 to 120 parts by weight), and component [E] is preferably 5 to 30 parts by weight (particularly 10 to 20 parts by weight).

  Examples of the method for applying the thermosetting resin composition include screen printing, curtain coating, roll coating, spray coating, and the like.

  Next, primary curing is performed at a low temperature. “Low temperature” means a temperature lower than the secondary curing temperature described later. Specifically, the primary curing temperature may be, for example, 100 to 150 ° C. When the primary curing temperature is too low, the component [D] is not sufficiently dissolved, and as a result, bubbles may remain in the coating film. On the other hand, when the primary curing temperature is too high, a secondary curing reaction occurs, and the cured film may become too hard. As a result, the polishability may be reduced.

  The primary curing time may be, for example, 30 to 120 minutes. If the primary curing time is too short, the component [D] may not be sufficiently dissolved, and as a result, the primary curing may occur with bubbles remaining in the coating film. Conversely, if the primary curing time is too long, the working efficiency may be reduced.

  Next, the surface including the primary cured film prepared above is polished and smoothed. Examples of the polishing method include mechanical polishing (belt sander, buff polishing, sand blast, scrub polishing, etc.), chemical polishing (persulfate, hydrogen peroxide-sulfuric acid mixture, inorganic and organic acids, etc.), and the like. .

  Thereafter, secondary curing is performed at a high temperature. Note that “high temperature” means a temperature higher than the primary curing temperature described above. The secondary curing temperature may be, for example, 150 to 200 ° C. If the secondary curing temperature is too low, the reaction related to the epoxy group does not proceed sufficiently, and the heat resistance and moisture resistance of the cured film may be lowered. Conversely, if the secondary curing temperature is too high, the substrate itself may be thermally damaged.

  The secondary curing time may be, for example, 30 to 180 minutes. If the secondary curing time is too short, the heat resistance and moisture resistance of the cured film may not be sufficient. Conversely, if the secondary curing time is too long, the working efficiency may be reduced.

  In this way, the concave portion on the surface of the wiring board is filled with the cured resin of the thermosetting resin composition, and a smoothed printed wiring board having a smooth surface is obtained.

  In addition, you may perform the said secondary thermosetting simultaneously with the thermosetting of the soldering resist film mentioned later. That is, after applying the photosensitive thermosetting resin composition of the present invention on the polished substrate surface, heating to the secondary thermosetting temperature while performing light irradiation or after light irradiation, between the circuits The secondary thermosetting of the filling resin in the recess and the secondary thermosetting of the solder resist ink may be performed simultaneously.

  Next, by applying the photosensitive thermosetting resin composition according to the present invention on the smoothed printed wiring board surface, photocuring the coating resin, and further heating to 100 to 190 ° C. to thermally cure. The resist film-coated smoothed printed wiring board according to the present invention can be manufactured.

  More specifically, first, the photosensitive thermosetting resin composition of the present invention is applied and coated on the surface of the smoothed printed wiring board obtained as described above. Next, after selectively exposing with actinic rays through a photomask having a predetermined pattern, the unexposed portion is developed with a developer to form a photocured film of a solder resist. Then, the soldering resist film coat | covering smoothing printed wiring board of this invention can be manufactured by thermosetting (completely hardening) the photocuring film | membrane of a soldering resist by heating.

  As the coating, the above-described coating method can be used. The amount applied may be, for example, an amount that results in a cured film thickness of 7-100 μm.

Examples of the actinic rays include ultraviolet rays (300 to 450 nm, etc.). The exposure can be performed with, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an arc lamp, a xenon lamp, a UV-LED, or the like. Further, in addition to ultraviolet rays, excimer laser, X-ray, electron beam or the like can be irradiated for exposure. The exposure amount may be 5 to 2000 mj / cm ² .

  Developers include alkaline metal hydroxides such as lithium, sodium and potassium, carbonates, bicarbonates, phosphates, pyrophosphates, primary amines such as benzylamine, butylamine and monoethanolamine, dimethylamine Secondary amines such as dibenzylamine and diethanolamine, tertiary amines such as trimethylamine, triethylamine and triethanolamine, cyclic amines such as morpholine, piperazine and pyridine, polyamines such as ethylenediamine and hexamethylenediamine, tetramethylammonium hydro Ammonium such as oxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide Dorokishido acids, trimethyl sulfonium hydroxide, diethyl methyl sulfonium hydroxide, sulfonium hydroxide such as dimethyl benzyl sulfonium hydroxide, other choline, silicate-containing buffers, and the like.

  If necessary, alcohol solvents (butyl cellosolve, butyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propanol, propylene glycol) and surfactants (amphoteric surfactants, nonionic surfactants, etc.) are also used. be able to.

Thermosetting (complete curing) may be performed at 120 to 180 ° C. for 0.1 to 3 hours, for example. The alkoxy group-containing silane-modified epoxy resin undergoes demethanolation by the condensation reaction of the alkoxy group during thermosetting. Therefore, it is preferable to gradually heat cure in multiple stages or with a temperature gradient so as not to generate voids, cracks and the like. Of course, for example, when the coating thickness is thin, there is no problem even if it is thermally cured at once.
In order to complete the photoreaction and improve the reliability, light (ultraviolet ray or the like) irradiation may be performed again after development or after heat curing.

  The solder resist film according to the present invention produced as described above usually has a glass transition point (Tg) of 140 to 165 ° C.

The solder resist film according to the present invention is characterized by extremely excellent HAST resistance. Specifically, the electric insulation resistance value (× 10 ¹⁰ Ω) after 168 hours is typically 100 to 900 under HAST conditions.
Further, the solder resist film according to the present invention is characterized in that no abnormality is observed in the appearance after the HAST history and after the gold plating resistance test.

  Further, the white solder resist film according to the present invention has a gloss (%) of generally 40 or more, typically 81 to 95, in addition to the above-mentioned features, and is far superior to the conventional one. It also has a feature. The white solder resist film according to the present invention differs from the conventional light reflection only, and effectively utilizes the light emission of the light emitting diode not only by the light reflection but also by the gloss, so that the LED backlight module and the LED illumination light module are used. Improvement of the light emission efficiency of the LED headlight module is achieved.

  Furthermore, the solder resist film according to the present invention is not only extremely excellent in coating film adhesion and thermal shock resistance, but also solvent resistance, acid resistance, solder heat resistance, flex resistance, coating film transparency, yellowing resistance, Excellent weather resistance.

  Furthermore, by covering the smoothed printed wiring board with the solder resist film according to the present invention, it is easy to penetrate the underfill, it is difficult to cause displacement, and cracks are less likely to occur. Various problems can be solved.

Hereinafter, the present invention will be specifically described with reference to the drawings.
<Preparation of silane-modified epoxy resin>
Synthesis example 1
In a reactor equipped with a stirrer, a water separator, a thermometer, and a nitrogen blowing port, bisphenol A type epoxy resin (1) [manufactured by Toto Kasei Co., Ltd., trade name “Epototo YD-011”, epoxy equivalent 475 g / eq, Average repeat unit number 2.2] 300 parts by weight and bisphenol A type epoxy resin (2) [manufactured by Toto Kasei Co., Ltd., trade name “Epototo YD-127”, epoxy equivalent 190 g / eq, average repeat unit number 0.11 1250 parts by weight were added and dissolved at 80 ° C. Furthermore, poly (methyltrimethoxysilane) [manufactured by Tama Chemical Co., Ltd., trade name “MTMS-A”, average number of repeating units 3.5] 581.2 parts by weight, and dibutyltin laurate 2.0 parts by weight as a catalyst Was added and allowed to undergo demethanol reaction at 100 ° C. for 8 hours under a nitrogen stream. Further, after cooling to 60 ° C., the pressure was reduced to 13 kPa to completely remove dissolved methanol, thereby obtaining 2050 parts by weight of a silane-modified epoxy resin (Synthesis Example 1).

  The blending weight ratio of the epoxy resins (1) and (2) at the time of preparation [weight of the epoxy resin (1) / weight of the epoxy resin (2)] is 0.24. The epoxy equivalent of the epoxy resin mixture [epoxy resin (1) + epoxy resin (2)] is 245 g / eq. Further, [poly (methyltrimethoxysilane) -silica conversion weight / epoxy resin mixture weight] (use weight ratio) was 0.20.

As a result of 1H-NMR (CDCl ₃ solvent) measurement of the obtained silane-modified epoxy resin (Synthesis Example 1), 100% of the methine peak (near 3.3 ppm) of the epoxy ring is retained, and the hydroxyl groups in the epoxy resin It was confirmed that the peak (near 3.85 ppm) disappeared. The epoxy equivalent of the silane-modified epoxy resin (Synthesis Example 1) was 280 g / eq.

Synthesis example 2
Into a 2 L three-necked flask equipped with a stirrer, a water separator and a thermometer, 950 parts by weight of bisphenol A type epoxy resin [epoxy equivalent 185 g / eq, manufactured by Tohto Kasei, trade name “Epototo YD-127”] and dimethylformamide 950 parts by weight was added and dissolved at 90 ° C. Further, 304.6 parts by weight of tetramethoxysilane condensate [manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 51”] and 2 g of dibutyltin dilaurate as a catalyst were added, followed by demethanol reaction at 90 ° C. for 6 hours to obtain active ingredients. 2080 parts by weight of a silane-modified epoxy resin solution (Synthesis Example 2) with 50% (after curing) was obtained. In addition, in order to perform a complete dealcoholization reaction, transesterification was performed while removing generated methanol from the reaction system during the reaction.

As a result of comparing the obtained silane-modified epoxy resin solution (Synthesis Example 2) and 1H-NMR (CDCl ₃ solvent) of the raw material bisphenol A type epoxy resin, the silane-modified epoxy resin solution (Synthesis Example 2) It was confirmed that the methine peak (near 3.3 ppm) was maintained at 100%, and that the hydroxyl peak (near 3.8 ppm) in the epoxy resin had completely disappeared. A new peak of methoxysilyl group (around 3.6 ppm) appeared. The epoxy equivalent of the obtained silane-modified epoxy resin solution (Synthesis Example 2) was 431 g / eq.

Synthesis example 3
In a reaction apparatus equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet, a novolac type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name “Epototo YDPN-638P”, epoxy equivalent of 177 g / eq, number average phenol nucleus Number of bodies 5.2] 400 parts by weight and 21.2 parts by weight of bisphenol A are dissolved at 150 ° C., and 0.1 part by weight of N, N-dimethylbenzylamine is added as a catalyst for ring-opening modification and reacted for 2 hours. As a result, a bisphenol-modified novolac-type epoxy resin which is a hydroxyl group-containing ring-opening modified epoxy resin was obtained. [Number of moles of active hydrogen to undergo ring-opening modification / number of moles of novolac-type epoxy resin] was 0.4.

  Furthermore, poly (methyltrimethoxysilane) [manufactured by Tama Chemical Co., Ltd., trade name “MTMS-A”, average number of Si per molecule 3.5] 215.2 parts by weight, methyl ethyl ketone 350 parts by weight, A methoxy group-containing silane-modified epoxy resin is prepared by adding 30.99 parts by weight of glycidol and 1 part by weight of dibutyltin dilaurate as a catalyst and performing a demethanol reaction at 100 ° C. for 5 hours using a water separator in a nitrogen stream. (Synthesis Example 3) 980 parts by weight (epoxy equivalent 324 g / eq) was obtained.

Synthesis example 4
300 parts by weight of phenol novolac resin glycidyl ether product [Japan Epoxy Resin Co., Ltd., “Epicoat 154”, epoxy equivalent 178, average molecular weight 700] and 450 parts by weight of ethyl cellosolve acetate are placed in a flask with a condenser, and nitrogen gas is added. It melt | dissolved by heating at 100 degreeC, inject | pouring. When it became a homogeneous solution, 37.5 parts by weight of a solution obtained by dissolving 15 parts by weight of an aminosilicon compound [manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-1660B-3”, average molecular weight 4000] in ethyl cellosolve acetate was added. It was added dropwise over 5 minutes. Thereafter, the mixture was reacted for 3 hours and further reacted at 120 ° C. for 1 hour to obtain 780 parts by weight of an ethyl cellosolve acetate solution of aminosilane-modified epoxy resin (Synthesis Example 4).

  The reaction rate of the terminal amino group in the aminosilicon compound was 95%. The ethyl cellosolve acetate solution (Synthesis Example 4) of the aminosilane-modified epoxy resin obtained had a solid content concentration of 40% and an epoxy equivalent of 467.5 (the epoxy equivalent of the solid after evaporation of ethyl cellosolve acetate was 187). .

<Preparation of unsaturated group-containing polycarboxylic acid resin>
Synthesis example 5
Cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., “EOCN-104”, epoxy equivalent 220 g / eq] 220 parts by weight was put in a four-necked flask equipped with a stirrer and a reflux condenser, and carbitol acetate 206 weights. Part was added and dissolved by heating. Next, 0.1 part by weight of hydroquinone as a polymerization inhibitor and 2.0 parts by weight of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., 72 parts by weight of acrylic acid was added dropwise, and reacted for 20 hours. The obtained reaction product was cooled to 80 to 90 ° C., 91.2 parts by weight of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled, and an unsaturated group-containing polycarboxylic acid resin solution (Synthesis Example 5). 590 parts by weight were obtained.

  The unsaturated group-containing polycarboxylic acid resin solution thus obtained (Synthesis Example 5) had a nonvolatile content of 65% and a solid content acid value (mgKOH / g) of 87.8 mgKOH / g.

Synthesis example 6
A separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube was charged with 250 parts by weight of dipropylene glycol monomethyl ether and 10 parts by weight of t-butylperoxy-2-ethylhexanoate, 95 After raising the temperature to 0 ° C., a mixture of 170 parts by weight of methacrylic acid, 130 parts by weight of methyl methacrylate, 250 parts by weight of dipropylene glycol monomethyl ether, and 10 parts by weight of azobisdimethylvaleronitrile was added dropwise over 4 hours. Furthermore, by aging for 5 hours, a methacrylic acid-methyl methacrylate copolymer solution having a carboxyl group was obtained.

  Next, 200 parts by weight of (3,4-epoxycyclohexyl) methyl methacrylate, 2 parts by weight of triphenylphosphine, and 1 part by weight of hydroquinone monomethyl ether were passed through the resin solution while passing a mixed gas (oxygen 7% + nitrogen 93%). Was added and reacted at 100 ° C. for 19 hours to obtain 1020 parts by weight of an unsaturated group-containing polycarboxylic acid resin solution (Synthesis Example 6).

  When the resin physical properties of this unsaturated group-containing polycarboxylic acid resin solution (Synthesis Example 6) were measured, the solid content was 51%, the acid value (mgKOH / g) 105, the double bond equivalent 490 g / mol, the weight average molecular weight (polystyrene). Conversion) 13000.

Synthesis example 7
In a separable flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution and a stirrer, 140 parts by weight of glycidyl methacrylate, 60 parts by weight of methyl methacrylate, 200 parts by weight of carbitol acetate, 0.4 parts by weight of lauryl mercaptan, 6 parts by weight of azobisisobutyronitrile was added, heated in a nitrogen stream, and polymerized at 75 ° C. for 5 hours to obtain a 50% copolymer solution.

  To the 50% copolymer solution, 0.1 part by weight of hydroquinone, 74 parts by weight of acrylic acid and 0.4 part by weight of dimethylbenzylamine are added, and an addition reaction is performed at 100 ° C. for 24 hours, followed by tetrahydrophthalic anhydride 90 Parts by weight and 158 parts by weight of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain 725 parts by weight of an unsaturated group-containing polycarboxylic acid resin solution (Synthesis Example 7).

  When the resin physical properties of this unsaturated group-containing polycarboxylic acid resin solution (Synthesis Example 7) were measured, the solid content was 50%, the double bond equivalent was 350 g / mol, the acid value (mgKOH / g) 91, the weight average molecular weight (polystyrene). Conversion) was 26000.

<Preparation of photosensitive thermosetting resin composition>
-Examples 1-5 and Comparative Examples 1-6
In accordance with the composition shown in Table 1, each composition component was stirred and mixed, and then uniformly dispersed by three rolls, and a photosensitive thermosetting resin composition (each Example 1-5 and Comparative Examples 1-6). Was prepared.

表１中、１）は溶液重量を表す。

In Table 1, 1) represents the weight of the solution.

<Manufacture of smoothed printed wiring board with solder resist film coating>
Production Examples 1-5 and Production Comparative Examples 1-6
A printed wiring board having a thickness of 0.8 mm [copper circuit thickness is 40 μ, line / space (L / S) = 75 μm / 75 μm] was used as a substrate material. That is, a thermosetting resin composition having the following composition was applied on the substrate by mask printing using a 250 mesh polyester screen. Next, the substrate was heated to 150 ° C. in a heating furnace, and primary curing was performed at this temperature for 60 minutes. Thereafter, the surface including the primary cured film was first polished with a No. 400 belt sander once and then polished four times with a No. 600 buff. Finally, secondary curing was performed at 180 ° C. for 90 minutes with a box-type dryer.

  In this way, the smoothed printed wiring board (FIG. 1A) in which the recesses between the circuits (FIGS. 1A and 2) on the insulating substrate (FIGS. 1A and 1) are filled with the secondary cured resin (FIGS. 1A and 3) is manufactured. did. In addition, the uneven | corrugated height difference of the surface in this smoothing printed wiring board (FIG. 1A) was less than 2 micrometers.

Formulation composition (parts by weight) of the thermosetting resin composition:
75% acrylic acid adduct of phenol novolac type epoxy resin (100), isobornyl acrylate (40), tricyclodecane dimethanol acrylate (100), trimethylolpropane triacrylate (10), t-butyl peroxybenzoate ( 10) Tetramethylbiphenyl type epoxy resin (100), dicyandiamide (16), barium sulfate (120), polydimethylsiloxane (0.1).

  On the smoothed surface of the smoothed printed wiring board (FIG. 1A) produced as described above, the photosensitive thermosetting resin composition (Examples 1 to 5 and Comparative Examples 1 to 6) was dried. The entire surface was coated by a screen (100 mesh polyester) printing method so that the thickness was 20 μm, and a solder resist ink layer (FIGS. 1B and 4) was formed on the substrate surface.

  Subsequently, in order to volatilize the solvent in the resist ink layer (FIGS. 1B and 4) on the substrate surface, preliminary drying was performed at 80 ° C. for 20 minutes to obtain a dry coating film having a thickness of 20 μm.

Next, using an ultraviolet exposure apparatus (Oak Seisakusho, model HMW-680C), exposure was performed by irradiating with ultraviolet light of 500 mj / cm ² through a solder resist negative film (FIGS. 1C and 5).

  Next, the unexposed portion of the dried coating film after the exposure process is developed and removed with a developer (1% aqueous sodium carbonate solution) to remove the pattern of the resist coating film (exposure curing (primary curing) on the substrate) 1D, 6) was formed.

Thereafter, this substrate was pre-cured at 100 ° C. for 30 minutes, then cured at 150 ° C. for 60 minutes, further irradiated with ultraviolet rays of 500 mj / cm ² to be completely cured, and a solder resist film (FIGS. 1E and 7). The coated smoothed printed wiring board (respective production examples 1 to 5 and production comparison examples 1 to 6) was produced.

<Evaluation test of solder resist film coated smoothed printed wiring board>
The soldering resist film-coated smoothed printed wiring board (manufacturing examples 1 to 5 and manufacturing comparative examples 1 to 6) manufactured as described above was subjected to various evaluation tests shown below. The evaluation test results are shown in Table 2.

(Finger dryness)
After the application, it was placed in a hot air circulation drying oven, dried at 80 ° C. for 20 minutes, and then the applied surface was strongly pressed with a finger to examine the sticking property, and the state of the coating film was judged.
○: No stickiness or fingerprint marks are observed.
Δ: The surface is slightly sticky and has fingerprint marks.
X: The surface is markedly sticky and has fingerprint marks.

(Developability)
Using an ultraviolet exposure device (Oak Seisakusho, model HMW-680C), ultraviolet rays of 500 mj / cm ² were irradiated through a solder resist negative film. Then, the state where the unexposed part was removed was visually determined after developing with a developer of 1 wt% aqueous sodium carbonate solution at a spray pressure of 2.0 × 10 ⁵ Pa for 60 seconds.
○: The ink was completely removed during development and development was possible.
X: There is a portion that is not developed during development.

(Light sensitivity)
Stepped tablet 21 steps (made by Stoffer) were brought into close contact with the dried coating film and irradiated with ultraviolet rays with an integrated light amount of 500 mJ / cm ² . Next, the film was developed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 × 10 ⁵ Pa, and the number of coating layers remaining without development was confirmed.

(Pencil hardness)
Evaluation was performed according to JIS K5600.

(Adhesion)
In accordance with JIS K5600, 100 test pieces having a 1 mm size were prepared, and a peeling test was performed using cello tape. The peeled state of the grid was observed and evaluated according to the following criteria.
○: No peeling of the crosscut portion occurred.
(Triangle | delta): Peeling generate | occur | produced in the crosscut part at the time of tape peeling.
X: Swelling or peeling of the resist film occurred without performing a cross-cut test.

(Solvent resistance)
The test piece was immersed in isopropyl alcohol for 30 minutes at room temperature. After confirming that there was no abnormality in the appearance, a peeling test with cello tape (R) was conducted, and evaluation was performed according to the following criteria.
○: Appearance of the coating film is normal and there is no swelling or peeling.
X: The coating film has swelling or peeling.

(Acid resistance)
The test piece was immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there was no abnormality in the appearance, a peeling test using a cello tape was conducted, and evaluation was performed according to the following criteria.
○: Appearance of the coating film is normal and there is no swelling or peeling.
X: The coating film has swelling or peeling.

(Solder heat resistance)
Leveler flux W-2704 [manufactured by MEC Co., Ltd.] was applied to the test piece and immersed in a solder bath at 288 ° C. for 10 seconds. This was defined as 1 cycle and repeated 3 cycles. After being allowed to cool to room temperature, a peeling test with cello tape (R) was performed and evaluated according to the following criteria.
○: Appearance of the coating film is normal and there is no swelling or peeling.
X: The coating film has swelling or peeling.

Moreover, the evaluation method of the surface whitening after a solder heat resistance test was performed as follows.
○: Whitening was not recognized.
Δ: Whitening was observed.
X: Remarkably whitened.

Moreover, the evaluation method of the discoloration after a solder heat resistance test was performed as follows.
○: No discoloration was observed.
Δ: Slight discoloration was observed.
X: Discolored remarkably.

(Gold resistance)
The test substrate was immersed in an acidic degreasing solution (manufactured by McDermit Japan, 20 vol% aqueous solution of “Metex L-5B”) at 30 ° C. for 3 minutes, and then washed with water. Next, the test substrate was immersed in an aqueous 14.4 wt% ammonium persulfate solution at room temperature for 3 minutes and then washed with water. Further, the test substrate was immersed in an aqueous 10 vol% sulfuric acid solution at room temperature for 1 minute and then washed with water.

  Next, the substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 vol% aqueous solution of “Metal Plate Activator 350”) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, “Meltex” The plate was immersed in a 20 vol% aqueous solution of plate Ni-865M, pH 4.6) for 20 minutes, nickel-plated, and then immersed in a 10 vol% sulfuric acid aqueous solution for 1 minute at room temperature and washed with water.

Next, the test substrate was immersed in a gold plating solution at 95 ° C. (Meltex, 15 vol% “Ourolectroles UP” and an aqueous solution of 3 vol% potassium cyanide, pH 6) for 10 minutes, subjected to electroless gold plating, and then washed with water. Further, it was immersed in warm water at 60 ° C. for 3 minutes, washed with water and dried. A cellophane adhesive tape was attached to the obtained electroless gold plating evaluation substrate, and the state when peeled off was observed.
○: No abnormality at all.
Δ: Slightly peeled off.
×: Exfoliated greatly

(HAST resistance)
The test substrate was applied with a DC5V applied voltage between the comb electrodes of L / S = 50 μm / 50 μm each coated with a solder resist film in an unsaturated pressure vessel of 130 ° C. and 85%, and left for 168 hours. In addition to confirming that there was no abnormality in the appearance, the insulation resistance was measured before and after the test.

Insulation resistance was measured by applying a DC voltage of 10 V for 1 minute in accordance with the insulation resistance test standard of JPCA-HD01 (advantest, digital ultra-high resistance / microammeter “R8340A”). The insulation resistance was measured in the applied state.
○: There is no abnormality in the appearance of the coating film.
Δ: Discoloration is observed on the electrode, but there is no swelling or peeling.
X: The coating film has swelling or peeling.

(Heat shock resistance)
The test piece was subjected to thermal history with one cycle of −40 ° C./30 minutes and 125 ° C./30 minutes, and after 100 cycles, the test piece was observed with a microscope and evaluated according to the following criteria.
○: No crack in the coating film.
X: A crack occurred in the coating film.

(Surface gloss)
The specular gloss at an incident angle of 60 ° according to JIS Z8741 was measured using “Micro-gloss” (manufactured by BYK-Labortron) and evaluated according to the following evaluation criteria.
○: Gloss value 81 or more Δ: Gloss value 51-80
X: Gloss value of 50 or less

(Glass transition point Tg)
Using a viscoelasticity measuring instrument [Seiko Denshi Kogyo Co., Ltd., “DMS6100”], a cured film having a thickness of 40 μm is processed to 10 mm × 30 mm, and measured by a synthetic tension wave at a measurement frequency of 1 Hz and a heating rate of 5 ° C./min. The temperature range was measured at 40-250 ° C. Tan δmax was defined as the glass transition point (Tg).

From Table 2 above, the following is clear.
As shown in Production Examples 1 to 5, all the solder resist films prepared from the photosensitive thermosetting resin composition according to the present invention are extremely excellent in HAST resistance. Specifically, even after 168 hours under HAST conditions, the electric insulation resistance value (Ω) is maintained at a high value, which is about 10 times more than the conventional one (Comparative Production Examples 1 to 6). The value is achieved.

  Furthermore, in the solder resist film according to the present invention, there is no abnormality in appearance not only after the HAST history but also after the gold plating resistance test. Furthermore, glossiness, coating film adhesion and thermal shock resistance are far superior to the conventional ones (Comparative Production Examples 1 to 6).

  On the other hand, photosensitive thermosetting resin compositions lacking either component [I] or component [II] (Production Comparative Examples 1 to 6) have HAST resistance, gold plating resistance, gloss, coating film adhesion, and Thermal shock resistance is extremely bad. From these facts, it can be seen that these various properties are properties that are manifested only when the component [I] and the component [II] are combined. In addition, as shown in Production Comparative Example 6, it can be seen that the amino group-containing silane-modified epoxy resin cannot be a substitute for the alkoxy group-containing silane-modified epoxy resin.

  And it turns out that an unmodified | non_denatured epoxy resin (namely, epoxy resin itself) cannot become an alternative of an alkoxy group containing silane modified epoxy resin as shown by manufacture comparative examples 1 and 2. Furthermore, as shown in Production Comparative Example 6, it can be seen that the amino group-containing silane-modified epoxy resin cannot be a substitute for the alkoxy group-containing silane-modified epoxy resin.

It is process sectional drawing which shows the manufacturing method of a soldering resist film coat | covering smoothing printed wiring board.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Insulation board | substrate 2 Circuit 3 Secondary hardening filling resin 4 Solder resist ink layer 5 Negative film 6 Pattern of resist coating film 7 Solder resist film

Claims (6)

[I] The following formula:

[In the formula (Chemical I / E), G represents a glycidyl group. a ₁₁ A ₁₁ and a ₁₂ A _{13 and} A ₁₅ may be the same or different and each independently represents a divalent aromatic residue or a divalent hydrogenated aromatic residue. a ₁₁ A ₁₂ and a ₁₂ A ₁₄ may be the same or different and each independently represents H or G. However, at least one of a ₁₁ A ₁₂ and a ₁₂ A ₁₄ may be H, and all may be H at the same time. The average repeating unit numbers a ₁₁ and a ₁₂ may be the same or different, and each independently represents a number of 0 or more, but a ₁₁ and a ₁₂ are not 0 at the same time, and the sum of a ₁₁ and a ₁₂ is , 20 or less. ]
An alkoxy group-containing silane-modified epoxy resin obtained by dealcoholization reaction of an epoxy resin represented by
[II] An unsaturated group-containing polycarboxylic acid resin having an ethylenically unsaturated group and two or more carboxyl groups in the molecule and having a solid content acid value (mgKOH / g) of 50 to 150,
[III] Diluent,
[IV] A photopolymerization initiator and [V] a curing adhesion-imparting agent are contained, the content weight ratio of the component [I] to the component [II] is 2/100 to 50/100, and the component [I ] And component [II] in an amount of 100 parts by weight, component [III] is 5 to 500 parts by weight, component [IV] is 0.1 to 30 parts by weight, and component [V] is 0.1 A photosensitive thermosetting resin composition containing ˜20 parts by weight. The epoxy resin (Chemical I / E) has the following formula:

[In the formula (Formula I / E-1-1), G represents a glycidyl group. a ₆₁₁ A _611s may be the same or different and each independently represents H or G, but at least one of them may be H, and all may be H at the same time. The average repeating unit number a ₆₁₁ is a number of 20 or less. ],

[In the formula (Chemical I / E-1-2), G has the same meaning as described above. a ₆₂₁ A ₆₂₁ may be the same or different and each independently represents H or G, but at least one of them may be H, and all may be H at the same time. The average repeating unit number a ₆₂₁ is a number of 20 or less. ],as well as

[In the formula (Chemical I / ES), G has the same meaning as described above. a The _eight A _{8 s} may be the same or different and each independently represents H or G, but at least one of them may be H and all may be H at the same time. The average number of repeating units _{a 8} is the number of 20 or less. ]
One or more of those represented by
The hydrolyzable alkoxysilane has the following formula:

[In the formula (Formula I / Si-2), B _{21 to} B ₂₆ may be the same or different and each independently represents an alkyl group, an aryl group, or an unsaturated aliphatic residue. The average number of repeating units _{b 21} is the number of 2 to 11. ],as well as

[In the formula (Chemical I / Si-3), B _{31 to} B ₃₆ may be the same or different and each independently represents an alkyl group, an aryl group, or an unsaturated aliphatic residue. The average repeating unit number b ₃₁ is a number from 2 to 11. ]
It is 1 or more types of what is represented by these, The photosensitive thermosetting resin composition of Claim 1 characterized by the above-mentioned. Component [II] is a resin obtained by reacting an epoxy group-containing unsaturated monomer with a copolymer of an ethylenically unsaturated acid and an ethylenically unsaturated bond-containing monomer, and / or containing an epoxy group A saturated and / or unsaturated group-containing polybasic acid anhydride is obtained by reacting an ethylenically unsaturated acid with a copolymer of an unsaturated monomer and an ethylenically unsaturated bond-containing monomer. 3. The photosensitive thermosetting resin composition according to claim 1, wherein the photosensitive thermosetting resin composition is a resin obtained by reacting.   Furthermore, 10 to 500 parts by weight of a white pigment and 10 to 1200 parts by weight of a filler are contained per 100 parts by weight of the total amount of the component [I] and the component [II]. 4. The photosensitive thermosetting resin composition according to any one of 3 above.   After applying the photosensitive thermosetting resin composition according to any one of claims 1 to 4 onto the surface of the smoothed printed wiring board and photocuring the applied resin, it is further heated to 100 to 190 ° C to be thermoset. A method for producing a smoothed printed wiring board coated with a resist film, comprising:   A resist film-coated smoothed printed wiring board produced by the production method according to claim 5.

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