JP5403545B2 - Solder resist composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

  The present invention provides a photosensitive solder resist composition that is excellent in photocurability by ultraviolet exposure or direct exposure and that can be developed with an alkaline aqueous solution, a dry film and a cured product thereof, and a print having a cured film formed using them. It relates to a wiring board.

Recently, in the exposure of solder resists for printed wiring boards, active energy beam scanning exposure (direct exposure) such as ultraviolet rays and laser light has become widespread from the viewpoint of excellent alignment accuracy.
Direct exposure is a pattern exposure method that forms an image while directly scanning the solder resist on the wiring board without using a photomask, so the solder resist that supports direct exposure is required to have very high sensitivity. The However, in the case of a conventionally known solder resist, the appropriate exposure amount is 200 mJ / cm ² or more, which has a drawback that it takes a very long time for exposure.

  Against this background, various proposals have been made for photosensitive compositions that can exhibit high photopolymerization ability (see, for example, Patent Document 1 and Patent Document 2). In Patent Document 1, as a photosensitive resin, acrylic acid is added to an epoxy group-containing polymer such as a copolymer of glycidyl methacrylate and methyl methacrylate, and an acid anhydride is further added. Photosensitive resins reacted with hydroxybutyl glycidyl acrylate are exemplified, but these photosensitive resins have very long side-chain molecules with respect to the main chain, and are further branched, so that they are extremely dry to the touch. There was a drawback of being bad. On the other hand, Patent Document 2 exemplifies, as a photosensitive resin, a carboxyl group-containing photosensitive resin obtained by reacting a copolymer of styrene derivative, (meth) acrylic acid, and (meth) acrylate with glycidyl methacrylate. However, although it is excellent in dryness to the touch, the effect of increasing the sensitivity is not sufficient, and it is insufficient for applications requiring ultrahigh sensitivity such as direct exposure.

JP 2004-264773 A (Claims, Synthesis Example) JP 2003-295435 A (Claims, Synthesis Example)

The present invention has been made in view of the prior art as described above, has high sensitivity, particularly high sensitivity to direct exposure, etc., and has excellent workability, such as surface curability, solder heat resistance, and electroless gold plating resistance. An object of the present invention is to provide a photosensitive solder resist composition capable of alkali development and capable of forming an excellent cured film.
Furthermore, an object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a solder resist composition, and a cured film such as a solder resist by the dry film and the cured product. An object of the present invention is to provide a printed wiring board formed.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２は

のいずれか又はそれらの混合物を表し、ｒ、ｓ、ｔはそれぞれ独立に１〜９の整数である。） In order to achieve the object, according to the present invention,
A compound (d) having a structure represented by the following general formula (I) is added to a copolymer (c) having (A) (a) styrene or a styrene derivative and (b) (meth) acrylic acid as essential components. Carboxyl group-containing photosensitive resin obtained by reaction,
(B) an oxime ester photopolymerization initiator,
Provided is a photosensitive solder resist composition developable with an alkaline solution, comprising (C) a compound having two or more ethylenically unsaturated groups in the molecule and (D) a thermosetting compound. Is done.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents

Or a mixture thereof, and r, s, and t are each independently an integer of 1 to 9. )

In a preferred embodiment, in the unit of the copolymer (c) of the carboxyl group-containing photosensitive resin (A), the styrene or styrene derivative (a) portion is 20 to 75 mol% with respect to the main chain unit. Included as a percentage. Further, the component (b) of the copolymer (c) of the carboxyl group-containing photosensitive resin (A) is preferably acrylic acid, and further, the double bond equivalent of the carboxyl group-containing photosensitive resin (A). Is preferably in the range of 500-1000.
In another preferred embodiment, in addition to the carboxyl group-containing photosensitive resin (A), (A ′) a carboxyl group-containing photosensitive resin having a novolak structure is further contained.

Further, according to the present invention, a photocurable dry film obtained by applying and drying the solder resist composition on a carrier film, or a cure obtained by curing the solder resist composition or the dry film. A cured product obtained by photocuring on a product, particularly copper, and a cured product obtained by photocuring in a pattern are also provided.
Furthermore, according to the present invention, there is also provided a printed wiring board having a cured film obtained by photocuring the solder resist composition or the dry film with ultraviolet rays and then thermally curing.

The solder resist composition of the present invention comprises, as a photosensitive resin, a copolymer (c) having (a) styrene or a styrene derivative and (b) (meth) acrylic acid as essential components represented by the general formula (I). While using the carboxyl group-containing photosensitive resin (A) obtained by reacting the compound (d) having the structure represented, an oxime ester photopolymerization initiator (B) as a photopolymerization initiator, preferably an oxime ester Because it contains a combination of photopolymerization initiator and other photopolymerization initiators, it has high sensitivity, especially high sensitivity to direct exposure, etc., good workability, surface curability, solder heat resistance, electroless gold plating resistance A cured film excellent in the above can be formed. In addition, since the styrene or styrene derivative (c) portion of the carboxyl group-containing photosensitive resin (A) is effective as a compatibilizing agent, it is excellent in uniform dispersibility and does not deteriorate touch dryness. Furthermore, in a preferred embodiment in which the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing photosensitive resin (A ′) having a novolac structure are used in combination as the photosensitive resin, solder heat resistance, electroless gold Film characteristics such as plating resistance can be further improved.
Therefore, the solder resist composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.

The exposure time when the solder resist film obtained by applying a solder resist on one side of the substrate of various sizes and drying at 80 ° C. for 30 minutes using a laser direct exposure device (Paragon 8000 manufactured by Orbotech) is measured. It is a graph which shows the relationship between exposure time and the time (exposure tact) required to irradiate the exposure amount with respect to each exposure area.

As described above, the solder resist composition of the present invention is characterized in that, as a photosensitive resin, (a) a copolymer (c) containing styrene or a styrene derivative and (b) (meth) acrylic acid as essential components, While using the carboxyl group-containing photosensitive resin (A) obtained by reacting the compound (d) having the structure represented by the general formula (I), an oxime ester photopolymerization initiator (B ), Preferably an oxime ester photopolymerization initiator and another photopolymerization initiator in combination.
According to the study by the present inventors, the carboxyl group-containing photosensitive resin (A) is converted into an oxime ester photopolymerization initiator (B) as a photopolymerization initiator, preferably an oxime ester photopolymerization initiator and others. It has been found that when the photopolymerization initiators are used in combination, as shown in Table 2 to be described later, the sensitivity is high, and particularly the sensitivity to direct exposure and the like is high. When only the photopolymerization initiator other than the oxime ester photopolymerization initiator is used as the photopolymerization initiator, the sensitivity does not increase even when the carboxyl group-containing photosensitive resin (A) is contained. That is, high sensitivity can be achieved only by using the carboxyl group-containing photosensitive resin (A) and the oxime ester photopolymerization initiator (B) in combination. It was surprising that could not be predicted at all.

Hereinafter, each component of the soldering resist composition of this invention is demonstrated in detail.
First, the carboxyl group-containing photosensitive resin (A) used in the solder resist composition of the present invention comprises (a) a styrene derivative and (b) (meth) acrylic acid synthesized by a conventionally known copolymerization reaction as essential components. It can be obtained by reacting the copolymer (c) with a compound (d) having a structure represented by the general formula (I). By this reaction, the carboxyl group derived from (meth) acrylic acid (b) in the copolymer (c) reacts with the epoxy group of the compound (d) having the structure represented by the general formula (I), The epoxy group is cleaved to form a hydroxyl group and an ester bond. This reaction itself is preferably a conventionally known reaction using an esterification catalyst (see Patent Documents 1 and 2 above), and a conventionally known method can also be applied in the present invention.

The ratio of units of styrene or styrene derivatives in the copolymer (c) is preferably in the range of 20 to 75 mol%. More preferably, it is in the range of 30 mol% to 70 mol%.
When the ratio is less than 20 mol%, in addition to poor touch dryness, compatibility with thermosetting resins such as epoxy resins and carboxyl group-containing photosensitive resins having a novolak structure described later is poor. Thus, the cured coating film has a matte state as described in International Publication WO 01/058977. In particular, an acid anhydride is added to the above carboxyl group-containing photosensitive resin (A) and a carboxyl group-containing photosensitive resin (A ′) having a novolak structure, particularly a cresol novolak type epoxy acrylate, which is preferable in terms of further improving film properties. In addition, when a carboxyl group-containing photosensitive resin (A ′) to which a compound having an epoxy group and an ethylenically unsaturated group is added is used in combination, the resin component based on the copolymer becomes particles even after uniform dispersion. Precipitation occurred. This is considered to have caused a solvent shock state in which when one of the resins having poor compatibility is mixed, the solvent is absorbed in one of them and the other is precipitated. That is, it has been found that the presence of styrene or a styrene derivative is effective as a compatibilizing agent.
On the other hand, when the amount of styrene units is more than 75 mol%, the acid value and double bond equivalent required for alkali development cannot be obtained, which has an effect on the developability and sensitivity.

  Moreover, it is preferable that the said (b) component used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A) is acrylic acid. It has been found that when acrylic acid is used as the acid component instead of methacrylic acid, the sensitivity is extremely improved. Although this acid component is effective for development, since the (d) component such as 4-hydroxybutyl glycidyl ether acrylate reacts with this to introduce an ethylenically unsaturated double bond, it is photosensitive. Become a unit. Here, it is considered that acrylic acid has a higher degree of freedom than methacrylic acid in the main chain portion of the photosensitive unit, resulting in higher sensitivity.

  Furthermore, it is preferable that the double bond equivalent of the said carboxyl group-containing photosensitive resin (A) is the range of 500-1000. In general, the smaller the double bond equivalent, the higher the reactive group concentration, and thus the higher the sensitivity. However, the sensitivity of this resin can be increased even if the concentration is increased to a double bond equivalent of less than 500. On the contrary, it is not preferable because the result is that the dryness to touch is extremely deteriorated. On the other hand, when the double bond equivalent exceeds 1000, not only the sensitivity is lowered, but also the development resistance is lowered, the surface is dropped by development, and the surface becomes dull.

Moreover, since compatibility with other resin can be raised by making content of the styrene or styrene derivative unit of the said carboxyl group-containing photosensitive resin (A) into the range of 20-75 mol%, it is photosensitive. If the acid value of the resin is secured to such an extent that it can be developed, the conventional conflicting relationship that the double bond equivalent increases and the sensitivity decreases can be solved.
The above phenomenon was a surprising result that cannot be easily imagined.

Examples of styrene or styrene derivative (a) used for the synthesis of the carboxyl group-containing photosensitive resin (A) include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, indene, 4- Examples thereof include carboxystyrene and 4-t-butoxystyrene.
Moreover, as (b) component, although acrylic acid and methacrylic acid are mentioned, acrylic acid is preferable as mentioned above. For the purpose of adjusting the acid value, it is also possible to copolymerize conventionally known unsaturated group-containing compounds copolymerizable with other styrene derivatives.

  Examples of the compound (d) having the structure represented by the general formula (I) used for the synthesis of the carboxyl group-containing photosensitive resin (A) include 2-hydroxyethyl glycidyl ether acrylate, 2-hydroxypropyl glycidyl ether acrylate, 3-hydroxypropyl glycidyl ether acrylate, 4-hydroxybutyl glycidyl ether acrylate, 1,4-butanediol glycidyl ether acrylate, diethylene glycol glycidyl ether acrylate, triethylene glycol glycidyl ether acrylate, dipropylene glycol glycidyl ether acrylate, tripropylene glycol glycidyl ether Acrylate, ditetramethylene glycol glycidyl ether acrylate, tritetramethyl Glycol glycidyl ether acrylate, polyethylene glycol glycidyl ether acrylate, polypropylene glycidyl ether acrylate, and polyethylene polypropylene glycidyl ether acrylate. Among these, a preferable compound (d) is 4-hydroxybutyl glycidyl ether acrylate. Those having no oxymethylene group such as glycidyl methacrylate and methacrylates cannot obtain the effect of improving the sensitivity described in the present invention.

  The weight average molecular weight of the carboxyl group-containing photosensitive resin (A) is preferably in the range of 6,000 to 500,000, and more preferably in the range of 8,000 to 100,000. The solid content acid value of the carboxyl group-containing photosensitive resin (A) is preferably in the range of 50 to 150 mgKOH / g, and more preferably in the range of 60 to 125 mgKOH / g.

The solder resist composition of the present invention can use other commonly known carboxyl group-containing resins in addition to the carboxyl group-containing photosensitive resin (A). It is preferable to contain in combination the carboxyl group-containing photosensitive resin (A ′).
The carboxyl group-containing photosensitive resin (A ′) having a novolak structure is a carboxyl group-containing photosensitive resin having a novolak structure and having an ethylenically unsaturated double bond in the molecule, and the following can be used.
(1) a carboxyl group-containing photosensitive resin obtained by reacting (e) a novolak epoxy resin with (f) an unsaturated monocarboxylic acid and adding (g) a dibasic acid anhydride to a hydroxyl group present in the side chain,
(2) The carboxyl group-containing photosensitive resin of (1) above, further comprising (h) a compound having an ethylenically unsaturated group such as a cyclic ether group and (meth) acryloyl group in one molecule. Examples thereof include photosensitive resins.
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  As the novolak epoxy resin (e) used for the synthesis of the carboxyl group-containing photosensitive resin of the above (1) and (2), various known and commonly used epoxy resins such as bisphenol A type novolac epoxy resin, phenol novolac type epoxy resin, Examples include cresol novolac epoxy resins and biphenyl novolac epoxy resins. Among these, cresol novolac epoxy resins are preferable because they can provide a cured coating film with high sensitivity and excellent heat resistance. Furthermore, a cresol novolac type epoxy resin having a softening point of 60 ° C. or higher is more preferable because it is excellent in dryness to touch. These novolac epoxy resins can be used alone or in combination of two or more.

  Examples of the unsaturated monocarboxylic acid (f) used in the synthesis of the carboxyl group-containing photosensitive resin (1) and (2) include acrylic acid, methacrylic acid or its caprolactone adduct, and one hydroxy group in the molecule. An acid anhydride adduct of (meth) acrylate having Examples of commercially available products include Aronix (registered trademark) M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.). These unsaturated monocarboxylic acids can be used alone or in combination of two or more.

  Examples of the dibasic acid anhydride (g) used for the synthesis of the carboxyl group-containing photosensitive resin of (1) and (2) above include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Examples include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride, and the like. These can be used alone or in combination of two or more.

  Moreover, as a compound (h) which has a cyclic ether group and an ethylenically unsaturated group in 1 molecule used for the synthesis | combination of the carboxyl group-containing photosensitive resin of said (2), 2-hydroxyethyl (meth) acrylate glycidyl ether is included. 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl ( Examples thereof include epoxy group-containing ethylenically unsaturated monomers such as (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether, and glycidyl (meth) acrylate. Or in combination of two or more can be used.

  The carboxyl group-containing photosensitive resin (A ′) having the novolak structure as described above is 0 to 9 times by weight, more preferably 0.25 to 4 times the weight of the carboxyl group-containing photosensitive resin (A). Can be used in a range. The effect of using the carboxyl group-containing photosensitive resin (A ′) having a novolak structure is improvement of dryness to touch, improvement of heat resistance of solder, improvement of electrical insulation, etc. It is effective in peeling off electroplated Ni, Sn, Pd and other metal plating.

Since the carboxyl group-containing photosensitive resin (A ′) having the novolak structure as described above has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
The acid value of the carboxyl group-containing photosensitive resin (A ′) having the novolak structure is in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing photosensitive resin (A ′) having a novolak structure is less than 40 mg KOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mg KOH / g, dissolution of the exposed portion by the developer proceeds. For this reason, the lines are unnecessarily thinned, or in some cases, the resist is dissolved and peeled with a developer without distinction between the exposed and unexposed areas, which makes it difficult to draw a normal resist pattern.

  The weight average molecular weight of the carboxyl group-containing photosensitive resin (A ′) having the novolak structure varies depending on the resin skeleton, but is generally 2,000 to 150,000, more preferably 5,000 to 100,000. Those in the range are preferred. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  Mixing amount of the carboxyl group-containing photosensitive resin (A) as described above, and a mixture thereof when the carboxyl group-containing photosensitive resin (A) and the carboxyl group-containing photosensitive resin (A ′) having a novolak structure are used in combination. As for the compounding quantity, 20-60 mass% in the whole composition, Preferably the ratio of 30-50 mass% is suitable. When the amount is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity becomes high and the coating property and the like deteriorate, which is not preferable.

As described above, the solder resist composition of the present invention has an oxime ester photopolymerization initiator (B) as a photopolymerization initiator, preferably an oxime ester photopolymerization initiator (B) and another photopolymerization initiator ( B ') is contained in combination.
As the oxime ester photopolymerization initiator (B), an oxime ester photopolymerization initiator having a group represented by the following general formula (II) can be preferably used, and other photopolymerization initiators ( B ′) has an α-aminoacetophenone photopolymerization initiator (B′-1) having a group represented by the following general formula (III), and / or a group represented by the following formula (IV). It is preferable to use one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators (B′-2).

式中、Ｒ^３は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^４は、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^５及びＲ^６は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ^７及びＲ^８は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、
Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基若しくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^９及びＲ^１０の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。

In the formula, R ³ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ⁴ is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R ⁹ and R ¹⁰ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group. And one of R ⁹ and R ¹⁰ may represent a R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).

The oxime ester photopolymerization initiator having a group represented by the general formula (II) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V), The compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.

式中、Ｒ^１１は、水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基（アルコキシル基を構成するアルキル基の炭素数が２以上の場合、アルキル基は１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、又はフェノキシカルボニル基を表し、
Ｒ^１２、Ｒ^１３は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^１４は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表す。

In the formula, R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹² and R ¹³ are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹⁴ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted).

式中、Ｒ^１５、Ｒ^１６及びＲ^２１は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、Ｍは、Ｏ、Ｓ又はＮＨを表し、ｐ及びｑは、それぞれ独立に０〜５の整数を表す。

In the formula, R ¹⁵ , R ¹⁶ and R ²¹ each independently represents an alkyl group having 1 to 12 carbon atoms,
R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, M represents O, S or NH, and p and q each independently Represents an integer of 0 to 5;

  Among the oxime ester photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (V) and a compound represented by the formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by ADEKA, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (III), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of the acylphosphine oxide photopolymerization initiator having the group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Examples thereof include oxides and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

The amount of the oxime ester photopolymerization initiator (B) having a group represented by the formula (II) is preferably 0 with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A or A + A ′). The range of 0.01-5 parts by mass, more preferably 0.01-3 parts by mass is desirable.
The amount of the photopolymerization initiator (B + B ′) as described above is 0.01 to 20 parts by mass, preferably 0 with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A or A + A ′). It can be selected from the range of 5 to 15 parts by mass. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 20 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes violent and the deep curability tends to decrease, which is not preferable.
Further, the photopolymerization initiator (B ′) other than the oxime ester-based photopolymerization initiator is preferably 10 parts by mass or less, and more preferably 6 parts by mass or less, because the dryness of the dry film to the touch becomes poor.

  In addition, as a photopolymerization initiator (B′-3), a photoinitiator assistant and a sensitizer that can be suitably used for the solder resist composition of the present invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, Examples include ketal compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A or A + A ′). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A or A + A ′). The ratio is 10 parts by mass. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such a photopolymerization initiator, photoinitiator assistant, and sensitizer is in a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A or A + A ′). Is preferred. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In the solder resist composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity. Specific examples of the chain transfer agent include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclope Tanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.
In particular, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5 as a heterocyclic compound having a mercapto group which is a chain transfer agent that does not impair the developability of the solder resist composition. -Methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These chain transfer agents can be used alone or in combination of two or more.

  The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the solder resist composition of the present invention is photocured by irradiation with active energy rays, and contains the ethylenically unsaturated group-containing carboxyl group. The containing resin (A) is insolubilized in an alkaline aqueous solution, or helps insolubilization. Such compounds (photosensitive monomers) include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxy. Polyhydric alcohols such as ethyl isocyanurate or polyhydric acrylates such as these ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols Multivalent acrylates such as: glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol B pan triglycidyl ether, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of the compound (C) which has 2 or more ethylenically unsaturated groups in such a molecule | numerator is 5-100 mass with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A or A + A '). Part, more preferably, a ratio of 1 to 70 parts by mass. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern development becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

  The solder resist composition of the present invention contains a thermosetting compound (D) in order to impart heat resistance. Examples of thermosetting compounds used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, carbodiimide resins, and bismaleimides. Well-known and commonly used thermosetting compounds such as polyoxazoline can be used. Particularly preferred is a thermosetting compound (D) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  Such a thermosetting compound (D) having two or more cyclic (thio) ether groups in the molecule is either a 3, 4 or 5-membered cyclic ether group or a cyclic thioether group in the molecule. Or a compound having two or more of two types of groups, for example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1), at least two oxetanyl in the molecule A compound having a group, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D-3), and the like.

  Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epitome 2055 manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names) Tetraphenylolethane type epoxy Fatty; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphtalene group-containing epoxy such as HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; Cyclohexylmaleimide and glycidyl methacrylate Relate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound (D-3) having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is 1 equivalent of the carboxyl group of the carboxyl group-containing photosensitive resin (A or A + A ′). Preferably it is 0.6-2.5 equivalent, More preferably, it exists in the range used as 0.8-2.0 equivalent. When the blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in heat resistance, alkali resistance, electricity This is not preferable because the insulating property is lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

    In addition, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule can be added to the solder resist composition of the present invention as a thermosetting component. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two in one molecule. Examples thereof include compounds having the above blocked isocyanate groups, that is, blocked isocyanate compounds.

  As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (above, Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding quantity of the compound which has 2 or more isocyanate group or blocked isocyanate group in 1 molecule like this is 1-100 mass with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A or A + A '). Parts, more preferably a proportion of 2 to 70 parts by weight. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability falls and it is not preferable.

  Furthermore, examples of other thermosetting components include melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM, (above, manufactured by Sanwa Chemical Co., Ltd.) and the like. The said thermosetting component can be used individually or in combination of 2 or more types.

When the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.
The compounding amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, and is preferably 0 with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A or A + A ′) or the thermosetting compound (D), for example. 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

  In the solder resist composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2- Thion, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, etc. is there.

  The solder resist composition of this invention can mix | blend a coloring agent (E). As the colorant, conventionally known colorants such as red (E-1), blue (E-2), green (E-3), yellow (E-4) can be used, and pigments, dyes, Any of pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant (E-1):
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Index (CI; issued by The Society of Dyers and Colorists) number.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant (E-2):
Blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant (E-3):
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant (E-4):
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The blending ratio of the colorant (E) as described above is not particularly limited, but a ratio of 0 to 5% by mass, more preferably 0.01 to 3% by mass in the solid content of the composition is sufficient.

  The solder resist composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler is preferably 75% by mass or less, more preferably 0.1 to 60% by mass of the total amount of the composition. If the blending amount of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition is increased, and the coating and moldability are lowered, and the cured product becomes brittle.

  The amount of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 100 parts by mass of the carboxyl group-containing photosensitive resin (A or A + A ′). 0.1 to 150 parts by mass. When the blending ratio of the filler with respect to the carboxyl group-containing photosensitive resin (A or A + A ′) exceeds 300 parts by mass, the viscosity of the photosensitive composition increases, printability decreases, and the cured product becomes brittle. Therefore, it is not preferable.

  In the solder resist composition of the present invention, a binder polymer can be used for the purpose of improving dryness to touch and improving handling properties. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.

  Furthermore, the solder resist composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.

Furthermore, the solder resist composition of the present invention is organic for the synthesis of the carboxyl group-containing photosensitive resin (A or A + A ′), for the preparation of the composition, or for the adjustment of the viscosity for application to a substrate or carrier film. Solvents can be used.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; methyl lactate, ethyl lactate, butyl lactate, ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol Methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc. Esters; ethanol, propanol, ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, and the like petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  In order to prevent oxidation, the solder resist composition of the present invention includes (1) a radical scavenger that invalidates generated radicals and / or (2) a generated peroxide decomposed into harmless substances, An antioxidant such as a peroxide decomposer that prevents radicals from being generated can be added.

  Specific examples of the antioxidant that acts as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p- Cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4) -Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6) Tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 152, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Special Product name).

  Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilyzer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

In addition to the antioxidant, an ultraviolet absorber can be used in the solder resist composition of the present invention.
Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals, Inc., trade name).
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, stabilization of the molding obtained from the soldering resist composition of this invention can be aimed at. .

  The solder resist composition of the present invention, if necessary, a known and commonly used thixotropic agent such as a known and commonly used thermal polymerization inhibitor, organophosphorous flame retardant, finely divided silica, organic bentonite, montmorillonite, hydrotalcite, Blends well-known and conventional additives such as silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, etc. can do.

  The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The solder resist composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain A tack-free coating film can be formed by coating by a method such as a coating method and volatilizing and drying (temporary drying) an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, the contact type (or non-contact type) is selectively exposed through an active energy ray through a photomask having a pattern formed thereon or directly exposed by a direct exposure machine, and the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 0.3). A resist pattern is formed by development with a 3% sodium carbonate aqueous solution. Furthermore, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin (A or A + A ′), two or more cyclic ether groups and / or cyclic groups in the molecule The thermosetting compound (D) having a thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  Volatile drying performed after the solder resist composition of the present invention is applied is performed using hot air circulation drying furnace, IR furnace, hot plate, convection oven, etc. A method of countercurrent contact and a method of spraying on a support from a nozzle).

  After apply | coating the soldering resist composition of this invention as follows and carrying out volatilization drying, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

As the exposure apparatus used for the active energy ray irradiation, an ultraviolet exposure apparatus equipped with a high-pressure mercury lamp or a metal halide lamp or a direct drawing apparatus (for example, a direct imaging apparatus that directly draws an active energy ray using CAD data from a computer) is used. be able to. The active energy ray may be any one of a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gas laser, a solid state laser, and a semiconductor laser as long as light having a maximum wavelength in the range of 350 to 410 nm is used. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus can be used as long as it oscillates active energy ray light having a maximum wavelength of 350 to 410 nm. Also good.

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The solder resist composition of the present invention is used in the form of a dry film having a solder resist layer formed by previously applying and drying a solder resist on a film of polyethylene terephthalate or the like in addition to a liquid direct coating method on a substrate. You can also The case where the solder resist composition of this invention is used as a dry film is shown below.

  The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by applying and drying the solder resist composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The solder resist layer is formed by uniformly applying the solder resist composition to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, a lip coater, a comma coater, a film coater or the like, and then drying.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the following examples do not limit the present invention, and all modifications may be made without departing from the spirit of the present invention. It is included in the technical scope of the present invention. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.
In the analysis of the compounds synthesized in the following synthesis examples, the viscosity is measured using a BM viscometer manufactured by Toki Sangyo Co., Ltd., and the weight average molecular weight is measured by GPC (gel permeation chromatography). Were measured using TSKgel G7000HXL + TSKgel GMHXL × 2 + TSKgel G2500HXL manufactured by Tosoh Corporation under the conditions of a THF (tetrahydrofuran) eluent, 40 ° C., and a flow rate of 0.5 ml / min. Moreover, the acid value was measured based on the neutralization titration method described in JIS-K0070.

Synthesis example 1
In a 2000 ml flask equipped with a stirrer and a condenser, 590.9 g of dipropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. A flask in which 352 g of styrene, 198 g of acrylic acid, 33 g of dimethyl 2,2′-azobis (2-methylpropionate) (Wako Pure Chemical Industries, Ltd .: V-601) were mixed and dissolved in a flask over 4 hours. It was dripped. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 5.5 g of triphenylphosphine, 0.83 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 297 g of 4-hydroxybutyl acrylate glycidyl ether were added. After stirring and mixing well, the temperature was raised to 90 ° C. over 1 hour, and the reaction was further carried out at 90 to 95 ° C. for 12 hours to obtain a brown viscous liquid (hereinafter referred to as varnish (I) with a double bond equivalent of 571 (calculated value). )). When this varnish (I) was analyzed, it was found that the viscosity was 480 Pa · s / 25 ° C., the weight average molecular weight measured by GPC was 37,500, and the solid content acid value was 82.8 mgKOH / g.

Synthesis example 2
In a 2000 ml flask equipped with a stirrer and a condenser, 590.9 g of dipropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. 332.8 g of styrene, 104.5 g of acrylic acid, 112.8 g of methacrylic acid, 33 g of dimethyl 2,2′-azobis (2-methylpropionate) (Wako Pure Chemical Industries, Ltd .: V-601) were mixed and dissolved. Was added dropwise to the flask over 4 hours. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 5.5 g of triphenylphosphine, 0.83 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 297 g of 4-hydroxybutyl acrylate glycidyl ether were added. After stirring and mixing well, the temperature was raised to 90 ° C. over 1 hour, and the reaction was further carried out at 90 to 95 ° C. for 12 hours to obtain a brown viscous liquid (hereinafter referred to as varnish (II) having a double bond equivalent of 571 (calculated value). )). When this varnish (II) was analyzed, the viscosity was 95.0 Pa · s / 25 ° C., the weight average molecular weight measured by GPC was 39,000, and the solid content acid value was 84.68 mgKOH / g.

Synthesis example 3
In a 2000 ml flask equipped with a stirrer and a condenser, 635.0 g of dipropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. Next, 247.5 g of styrene, 247.5 g of acrylic acid, 55.0 g of methyl methacrylate, dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd .: V-601) A solution in which 0 g was mixed and dissolved was dropped into the flask over 4 hours. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 5.5 g of triphenylphosphine, 0.83 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 363.0 g of 4-hydroxybutyl acrylate glycidyl ether After stirring well, the mixture was heated to 90 ° C. over 1 hour, further reacted at 90 to 95 ° C. for 12 hours, and a brown viscous liquid (hereinafter referred to as varnish) having a double bond equivalent of 504 (calculated value). (III)). When this varnish (III) was analyzed, the viscosity was 132.0 Pa · s / 25 ° C., the weight average molecular weight measured by GPC was 32,000, and the solid content acid value was 105.7 mgKOH / g.

Synthesis example 4
In a 2000 ml flask equipped with a stirrer and a condenser, 760.9 g of dipropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. Next, 157.5 g of styrene, 292.5 g of methacrylic acid, 67.5 g of dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd .: V-601) were mixed and dissolved. Was dropped into the flask over 4 hours. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 4.5 g of triphenylphosphine, 2.25 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 369 g of 4-hydroxybutyl acrylate glycidyl ether were added. After stirring and mixing well, the temperature was raised to 90 ° C. over 1 hour, and the reaction was further carried out at 90 to 95 ° C. for 12 hours, and a brown viscous liquid (hereinafter referred to as varnish (IV) with a double bond equivalent of 502 (calculated value) was obtained. )). When this varnish (IV) was analyzed, the viscosity was 280 Pa · s / 25 ° C., the weight average molecular weight measured by GPC was 24,500, and the solid content acid value was 103.5 mgKOH / g.

Synthesis example 5
In a 2000 ml flask equipped with a stirrer and a condenser, 592.0 g of dipropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. Next, 225.0 g of styrene, 135.0 g of acrylic acid, 90.0 g of methyl methacrylate, dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd .: V-601) A solution in which 0 g was mixed and dissolved was dropped into the flask over 4 hours. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 4.5 g of triphenylphosphine, 2.25 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 130.5 g of 4-hydroxybutyl acrylate glycidyl ether After stirring well, the mixture was heated to 90 ° C. over 1 hour, further reacted at 90 to 95 ° C. for 12 hours, and a brown viscous liquid (hereinafter referred to as varnish) having a double bond equivalent of 891 (calculated value). (Referred to as (V)). When this varnish (V) was analyzed, the viscosity was 220 Pa · s / 25 ° C., the weight average molecular weight was 21,500 measured by GPC, and the solid content acid value was 111.4 mgKOH / g.

Synthesis Example 6
A 2000 ml flask equipped with a stirrer and a condenser was charged with 532.2 g of dipropylene glycol monomethyl ether and 40 g of styrene and heated to 90 ° C. under a nitrogen stream. Subsequently, 356 g of styrene, 154 g of acrylic acid, and 33.0 g of dimethyl 2,2′-azobis (2-methylpropionate) (Wako Pure Chemical Industries, Ltd .: V-601) were mixed and dissolved for 4 hours. Over the flask. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 5.5 g of triphenylphosphine, 0.83 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 209 g of 4-hydroxybutyl acrylate glycidyl ether were added. After stirring and mixing well, the temperature was raised to 90 ° C. over 1 hour, and the reaction was further carried out at 90 to 95 ° C. for 12 hours, and a brown viscous liquid (hereinafter referred to as varnish (VI)) having a double bond equivalent of 727 (calculated value). )). When this varnish (VI) was analyzed, the viscosity was 220 Pa · s / 25 ° C., the weight average molecular weight was 26,400 measured by GPC, and the solid content acid value was 82.0 mgKOH / g.

Comparative Synthesis Example 1
In a 2000 ml flask equipped with a stirrer and a condenser, 650 g of dipropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. Subsequently, 198 g of methyl methacrylate, 352 g of methacrylic acid, and 22.0 g of dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd .: V-601) were mixed and dissolved. It was added dropwise to the flask over 4 hours. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 5.5 g of triphenylphosphine, 0.83 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and 374 g of glycidyl methacrylate were added and mixed well with stirring. Thereafter, the temperature was raised to 90 ° C. over 1 hour, and the reaction was further carried out at 90 to 95 ° C. for 12 hours to obtain a brown viscous liquid (hereinafter referred to as varnish (VII)) having a double bond equivalent 351 (calculated value). It was. When this varnish (VII) was analyzed, the viscosity was 720 Pa · s / 25 ° C., the weight average molecular weight measured by GPC was 24,200, and the solid content acid value was 92.0 mgKOH / g.

Comparative Synthesis Example 2
In a 2000 ml flask equipped with a stirrer and a condenser, 872 g of dipropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. Next, a mixture of 150 g of styrene, 350 g of acrylic acid, 60 g of dimethyl 2,2′-azobis (2-methylpropionate) (Wako Pure Chemical Industries, Ltd .: V-601) was mixed and dissolved over 4 hours. Dropped into the flask. After completion of dropping, the flask was heated to 95 ° C. and held for 4 hours. Once the flask was cooled to room temperature, 5.5 g of triphenylphosphine, 0.83 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and 500 g of glycidyl methacrylate were added and mixed well with stirring. Thereafter, the temperature was raised to 90 ° C. over 1 hour, and the reaction was further carried out at 90 to 95 ° C. for 12 hours to obtain a brown viscous liquid (hereinafter referred to as varnish (VIII)) having a double bond equivalent of 284 (calculated value). . When the varnish (VIII) was analyzed, the viscosity was 20.3 Pa · s / 25 ° C., the weight average molecular weight measured by GPC was 29,000, and the solid content acid value was 91.0 mgKOH / g.

Table 1 summarizes the compounding ratio of the monomer components in each of the synthesis examples and the double bond equivalent (calculated value) of the obtained carboxyl group-containing photosensitive resin.

Examples 1-11 and Comparative Examples 1-5
Using the resin solutions synthesized in each of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 2 or Table 3 together with various components shown in Table 2 or Table 3, and premixed with a stirrer, then 3 A photosensitive resin composition for a solder resist was prepared by kneading with a roll mill. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

Performance evaluation:
<Optimum exposure amount>
The photosensitive resin composition for solder resist of each of the examples and comparative examples was applied to the entire surface by screen printing after applying a circuit pattern substrate having a copper thickness of 35 μm after buffing, washing with water and drying, and heated at 80 ° C. It was dried for 60 minutes in a circulation drying oven. After drying, exposure equipment equipped with a high-pressure mercury lamp (exposure machine manufactured by ORC, equipped with a mercury short arc lamp), direct drawing exposure machine equipped with a high-pressure mercury lamp lamp (direct drawing exposure machine equipped with an ultra-high pressure mercury lamp lamp, Marculex, manufactured by Dainippon Screen) Or exposure through a step tablet (Kodak No. 2) using a direct drawing apparatus (Paragon 8000 manufactured by Orbotech) equipped with a semiconductor laser having a maximum wavelength of 355 nm, and developing (30 ° C., 0.2 MPa, 1 wt% Na _2). When the pattern of the step tablet remaining when the aqueous solution of CO ₃ was performed for 60 seconds was 7 steps, the optimum exposure amount was set.

<Dry touch dryness>
The compositions of the above Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and the film was pressure-bonded under a reduced pressure condition with HMW680-GW20 manufactured by ORC for 1 minute, and then the sticking state of the film was evaluated when the negative film was peeled off.
○: The film peels without resistance.
(Triangle | delta): Although a film peels, a trace is attached to the coating film.
X: There is resistance when the film is peeled off, and the coating film has a clear mark.

<Maximum development life>
The composition of each example and comparative example was applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 10 minutes from 20 to 80 minutes, and allowed to cool to room temperature. did. The substrate was developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under the condition of a spray pressure of 0.2 MPa, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.

Characteristic test:
The compositions of the above Examples and Comparative Examples were applied onto the entire surface of the patterned copper foil substrate by screen printing and allowed to cool to room temperature. The solder resist pattern was exposed at an optimum exposure amount using a direct drawing apparatus (Paragon 8000 manufactured by Orbotech Co., Ltd.) on which a semiconductor laser having a maximum wavelength of 355 nm was mounted on this substrate, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed at a pressure of 0. Development was performed at 2 MPa for 60 seconds to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
A: Peeling is not observed even after 10 seconds of immersion for 6 or more times.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<Electrical insulation characteristics>
The comb type electrode B coupon of IPCB-25 was used for the evaluation board. A bias voltage of DC 100 V was applied to this comb-shaped electrode, and 85 ° C., 85% R.D. H. The presence or absence of migration after 1,000 hours was confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
A: No change is observed at all.
○: Very slightly changed.
Δ: Discoloration is observed.
×: Migration has occurred.

The results of each characteristic test are shown in Tables 4 and 5.

The reference numerals shown in Tables 4 and 5 will be described below.
^{* 1} : A 355 nm laser direct-drawing exposure apparatus (Orbotech Paragon 8000: laser power 4 W; resolution 0.125 mil) was used, but the exposure speed was 500 mm x 600 mm (a common size in printed wiring board manufacturing). The exposure time shown in FIG. 1 is required to expose one side, and it can be said that productivity is remarkably inferior if it cannot be exposed with an exposure amount of about 100 mJ / cm ² or less according to common sense (see FIG. 1). Incidentally, in the case of a general-purpose (not direct drawing) exposure machine using a photomask equipped with a high-pressure mercury lamp, depending on the apparatus, it is 30 if it is about 300 mJ / cm ² for single-side exposure of a 500 mm × 500 mm substrate. Within 2 minutes from the second.
^{* 2} : Although the value of 7 steps of the step tablet, which is an index of the optimum exposure amount, was obtained, the surface of the solder resist film was completely or partially dissolved by the development after the development. (Development erosion occurred.)
^{* 3} : There was no problem immediately after production, but the composition gradually separated and particles of 1 mm or less were generated. The produced substrate was not glossy, and irregularities were generated on the surface.

  As is apparent from the results shown in Table 4 above, in the case of Examples 1 to 11 of the present invention, all are highly sensitive, particularly sensitive to direct exposure, such as solder heat resistance and electroless gold plating resistance. Also excellent in properties. Among them, the sensitivity was particularly high in Examples 1, 3, 5 and 6 using the carboxyl group-containing photosensitive resin (A) whose main chain skeleton was prepared by copolymerization of styrene and acrylic acid. Moreover, the tendency for a sensitivity to fall was seen as it changed from acrylic acid to methacrylic acid (Example 1-> Example 2-> Example 4). When the addition amount of 4-hydroxybutyl glycidyl acrylate, especially expressed in terms of double bond equivalent, no sensitive change was observed in the range of 500 to 1000, but the dryness to touch improved as the double bond equivalent increased. . It was a surprising result that there was no decrease in sensitivity despite the increased double bond equivalent. In the evaluation of dryness to touch, Δ is a level that can be used as a solder resist. When the carboxyl group-containing photosensitive resin (A) of the present invention is used in combination with a carboxyl group-containing photosensitive resin (A ′) having a novolak structure (Examples 7 to 11), the carboxyl group-containing photosensitive resin of the present invention is used. Although the sensitivity was slightly lower than when only (A) was used (Examples 1 to 6), improvement in finger touch drying property and solder heat resistance was observed. In particular, the addition of glycidyl methacrylate to a carboxyl group-containing photosensitive resin having a novolak structure to reduce the double bond equivalent is more effective, and is not limited to touch drying and solder heat resistance. Resistance has also improved.

  On the other hand, as apparent from the results shown in Table 5, the carboxyl group-containing photosensitive resin (A) of the present invention was used as in Comparative Example 1, and the oxime ester photopolymerization initiator (B) was used. If not, the sensitivity is low even though more photopolymerization initiator (B ′) is added in order to obtain sufficient sensitivity, and further development is performed by exposure with a laser exposure apparatus and a direct drawing exposure apparatus. The phenomenon that the surface was dissolved later was confirmed, and as a result, the electroless gold plating resistance and the electrical insulation characteristics deteriorated. Moreover, the comparative example 1 resulted in extremely bad touch dryness. This is presumably because a large amount of other photopolymerization initiator (B ') was used, which acted as a film plasticizer in the dry film.

  Moreover, although the copolymer resin which does not use a styrene derivative was used as a photosensitive resin in the comparative example 2, the sensitivity was bad, and also melt | dissolution of the coating-film surface was confirmed by the image development by laser exposure. And electroless gold-plating tolerance was not acquired, and also the discoloration was confirmed by the test of the electrical insulation characteristic.

  In the case of Comparative Example 3, although it is a resin by addition of glycidyl methacrylate even though styrene is used for the synthesis of the photosensitive resin, it is the same as Comparative Example 2 even though the double bond equivalent is reduced. In addition, it was confirmed that the surface of the coating film was dissolved during development by laser exposure. And electroless gold-plating tolerance was not acquired, and also the discoloration was confirmed by the test of the electrical insulation characteristic.

  In the case of Comparative Example 4, a carboxyl group-containing resin that does not use a styrene derivative was used for the synthesis of the photosensitive resin, and was used in combination with the carboxyl group-containing photosensitive resin (A ′) having a novolak structure. Due to poor compatibility with (A ') and the epoxy resin used, grains are generated, which causes peeling in the electroless gold plating resistance test, and discoloration in the electrical insulation characteristics test. Was confirmed. In addition, countless irregularities existed in the appearance of the coating film, which was a level of poor appearance.

  In the case of Comparative Example 5 that does not contain the carboxyl group-containing photosensitive resin (A) of the present invention and uses only the carboxyl group-containing photosensitive resin (A ′) having a novolak structure, the oxime ester photopolymerization initiator ( B) and other photopolymerization initiators (B ′) are used in combination, but the sensitivity is low. Both the laser exposure machine and the direct-drawing exposure machine are confirmed to dissolve on the surface, electroless gold plating resistance and electrical insulation. The characteristics were bad.

  In addition, Examples 1 to 6 using only the carboxyl group-containing photosensitive resin (A) as the photosensitive resin, the carboxyl group-containing photosensitive resin (A), and a carboxyl group-containing photosensitive resin having a novolak structure ( As is clear when Examples 7 to 11 used in combination with A ′) are compared, by using these two kinds of carboxyl group-containing photosensitive resins in combination, solder heat resistance, electroless gold plating resistance, etc. It can be seen that the characteristics are improved.

<Dry film production>
After appropriately diluting the photosensitive resin composition for solder resist of Example 1 with methyl ethyl ketone, using an applicator, a PET film (FB-50: 16 μm manufactured by Toray Industries, Inc.) so that the film thickness after drying becomes 20 μm. And dried at 80 ° C. for 30 minutes to obtain a dry film.

<Board fabrication>
Next, after the circuit-formed substrate was buffed, the dry film produced by the above method was pressurized using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.): 0.8 MPa, 70 ° C., Heat lamination was performed for 1 minute under a vacuum degree of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.
When the optimum exposure amount of the obtained substrate was evaluated, 20 mJ / cm ² in a direct drawing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm, a direct drawing exposure machine equipped with a high pressure mercury lamp and an exposure equipped with a high pressure mercury lamp In the apparatus, it was 10 mJ / cm ² . Similarly, the soldering heat resistance and the electroless gold plating resistance were evaluated.

Claims (8)

A compound (d) having a structure represented by the following general formula (I) is added to a copolymer (c) having (A) (a) styrene or a styrene derivative and (b) (meth) acrylic acid as essential components. Carboxyl group-containing photosensitive resin obtained by reaction,
(B) an oxime ester photopolymerization initiator,
(C) A photosensitive solder resist composition developable with an alkaline solution, comprising a compound having two or more ethylenically unsaturated groups in the molecule and (D) a thermosetting compound.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents

Or a mixture thereof, and r, s, and t are each independently an integer of 1 to 9. )   In the copolymer (c) unit of the carboxyl group-containing photosensitive resin (A), a portion of styrene or a styrene derivative (a) is contained in a proportion of 20 to 75 mol% with respect to the main chain unit. The solder resist composition according to claim 1.   The solder resist composition according to claim 1 or 2, wherein the component (b) of the copolymer (c) of the carboxyl group-containing photosensitive resin (A) is acrylic acid.   4. The solder resist composition according to claim 1, wherein the double bond equivalent of the carboxyl group-containing photosensitive resin (A) is in the range of 500 to 1,000. 5.   5. The solder resist composition according to claim 1, further comprising (A ′) a carboxyl group-containing photosensitive resin having a novolak structure.   The dry film obtained by apply | coating and drying the soldering resist composition as described in any one of the said Claims 1 thru | or 5 on a carrier film.   The hardened | cured material obtained by photocuring the soldering resist composition as described in any one of the said Claims 1 thru | or 5, or the dry film of the said Claim 6.   The solder resist composition according to any one of claims 1 to 5 or the dry film according to claim 6 having a cured film obtained by photocuring with ultraviolet rays and then thermosetting. Printed wiring board.

Images