JP5043516B2 - Photocurable / thermosetting resin composition and printed wiring obtained using the same - Google Patents

Description

  The present invention relates to a photocurable / thermosetting resin composition that can be developed with a dilute alkaline aqueous solution, a cured product thereof, and a printed wiring board having a resist pattern obtained using the same.

Recently, in the exposure of solder resists for printed wiring boards, laser scanning exposure has become widespread from the viewpoint of excellent alignment accuracy.
Since laser exposure forms an image while scanning a solder resist on a patterned wiring board without using a photomask, when a commercially available solder resist is used, the appropriate exposure amount is 200 mJ / cm ^2. As described above, there is a drawback that exposure takes a very long time. Therefore, the solder resist corresponding to laser exposure is required to have very high sensitivity.

  From the above points, proposals have been made for oxime-based photopolymerization initiators that can exhibit high photopolymerization ability and compositions using the photopolymerization initiators (for example, Patent Document 1 and Patent Documents). 2). However, these technologies can certainly exhibit sufficient photopolymerization ability, but due to the deactivation of the photopolymerization initiator on the circuit after heat treatment (due to the reaction of oxime ester and copper metal), In particular, there is a problem that the photoreaction is remarkably lowered and the coating film is peeled off on the copper circuit.

On the other hand, as a technique for accelerating the photoreaction, a technique for increasing the sensitivity of a photoresist by using a chain transfer reaction of a mercapto compound has been proposed (see Patent Document 3 and Patent Document 4). However, since the disclosed mercaptopropionic acid derivative is very active against copper wiring existing on a printed wiring board and reacts with copper, a residue is present even in a portion that should be developed originally. It was confirmed that the phenomenon of remaining would occur. In addition, even during resist storage, the mercapto group derived from mercaptopropionic acid used in these documents is rich in reactivity, so it has been confirmed that it reacts with a compound having an unsaturated double bond. Has been confirmed to significantly reduce the.
JP 2001-235858 A (Claims) International Publication WO02 / 096969 (Claims) JP 2006-10793 A (Claims) JP 2006-259150 A (Claims)

The present invention has been made to solve the above-mentioned problems of the prior art, and its main purpose is high sensitivity in ultraviolet and laser exposure, good curing depth, and further conventional storage. An object of the present invention is to provide a photocurable / thermosetting resin composition that is excellent in stability and workability, is excellent in developability with a dilute alkaline aqueous solution, and is suitable for a solder resist.
Furthermore, the objective of this invention is providing the printed wiring board which has a resist pattern excellent in the cured | curing material excellent in various characteristics obtained by using such a photocurable thermosetting resin composition, and excellent in pattern accuracy. It is in.

In order to achieve the above object, according to the present invention, (A) a carboxyl group-containing resin, (B) mercaptobutanoic acid or a derivative thereof, (C) an oxime ester photopolymerization initiator as a photopolymerization initiator , (D There is provided a photocurable / thermosetting resin composition comprising a compound having two or more ethylenically unsaturated groups in the molecule and (E) a thermosetting component.

In a preferred embodiment, the carboxyl group-containing resin (A) is a carboxyl group-containing resin (A1) having an unsaturated double bond capable of radical polymerization, and in particular, part or all of the unsaturated double bond is a meta group. It is preferably derived from acrylic acid or a derivative thereof. Further, the photopolymerization initiator (C) is a rear predicate general formula (I) represented by an oxime ester-based photopolymerization initiator (C1), or, the oxime ester-based photopolymerization initiator (C1), It is a mixture with an aminoacetophenone photopolymerization initiator (C2) represented by the general formula (II) and / or an acylphosphine oxide photopolymerization initiator (C3) represented by the general formula (III). Is preferred.

In another preferred embodiment, the mercaptobutanoic acid or derivative (B) thereof preferably has two or more 2-mercaptoisobutanoic acid or 3-mercaptobutanoic acid or derivatives thereof in one molecule.
In addition, the two-component composition in which the thermosetting component (E) is blended in a mixture different from the blend in which the mercaptobutanoic acid or derivative (B) is blended, or at least the carboxyl group-containing resin (A ) And the mercaptobutanoic acid or its derivative (B), and a two-component composition comprising a mixture of the oxime ester photopolymerization initiator (C) and the thermosetting component (E). In addition, the compound (D) which has a 2 or more ethylenically unsaturated group in a molecule | numerator may be added to any said mixture.
Furthermore, a solder resist containing a colorant, particularly a green or blue solder resist is preferred.

Furthermore, according to this invention, the photocurable and thermosetting dry film obtained by apply | coating and drying the said photocurable thermosetting resin composition to a carrier film is provided.
Furthermore, in another aspect of the present invention, the photocurable / thermosetting resin composition or dry film is obtained by photocuring on copper, and is patterned with a laser oscillation light source of 350 nm to 410 nm. There is provided a cured product obtained by photocuring into a shape. Furthermore, it has a resist pattern obtained by photocuring the photocurable / thermosetting resin composition or dry film in a pattern by direct drawing of ultraviolet rays having a wavelength of 350 nm to 410 nm and then thermosetting. A printed wiring board is provided.

The photocurable / thermosetting resin composition of the present invention comprises (A) a carboxyl group-containing resin, (C) an oxime ester photopolymerization initiator as a photopolymerization initiator , and (D) two or more ethylenes in the molecule. Since it contains (B) mercaptobutanoic acid or a derivative thereof together with a compound having a polymerizable unsaturated group, and (E) a thermosetting component, photocuring and heat using the chain transfer reaction of this compound High sensitivity of the coating film of the curable resin composition can be achieved. In particular, when used in combination with an oxime ester- based initiator as a photopolymerization initiator, a high photopolymerization ability can be exhibited, and mercaptobutanoic acid or a derivative thereof can be used for copper wiring existing on a printed wiring board. Since it reacts mildly, the deactivation of the photopolymerization initiator (by the reaction of the oxime ester and metallic copper) on the circuit after the heat treatment can be suppressed. Therefore, it has high sensitivity in ultraviolet and laser exposure, has a good curing depth, is excellent in storage stability and workability, and is excellent in developability with a dilute alkaline aqueous solution. It does not occur.
Further, by using such a photocurable / thermosetting resin composition, it is possible to provide a cured product having various characteristics and a printed wiring board having a resist pattern having excellent pattern accuracy.

  As a result of diligent research to achieve the above-described problems, the present inventors have found that a mercaptopropionic acid derivative and a mercaptobutanoic acid or a derivative thereof (B ) And a compound having a copper wiring and an unsaturated double bond present on the printed wiring board. That is, the mercaptopropionic acid derivative is very active against copper wiring and reacts with copper, so that a phenomenon that a residue remains even if it should be originally developed occurs. The mercaptobutanoic acid or its derivative (B) used in the present invention reacts mildly with respect to the copper wiring, so that such problems can be suppressed, and mercaptopropionic acid-derived mercapto can also be stored during resist storage. Since the group is highly reactive, it reacts with a compound having an unsaturated double bond, and the developability of the resist is remarkably lowered. However, such a problem is caused by using mercaptobutanoic acid or its derivative (B). The present inventors have found that it can be suppressed and have completed the present invention.

Hereinafter, each component of the photocurable / thermosetting resin composition of the present invention will be described in detail.
First, the mercaptobutanoic acid or derivative (B) used in the present invention is 2-mercaptoisobutanoic acid or 3-mercaptobutanoic acid or a derivative thereof, and more specifically a compound in which the acid is esterified or amidated. It is. It is preferable that two or more mercapto groups exist in one molecule by esterification. Specifically, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate) as listed in JP-A-2004-149755. , Butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa Kiss (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. Is mentioned. Among these, alicyclic structures such as 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione By using one having a photocurable / thermosetting resin composition excellent in solder heat resistance, electroless gold plating and storage stability.

  Here, the effects of these mercaptobutanoic acids or their derivatives are as follows: (1) improvement of sensitivity, (2) prevention of peeling due to reduction of deactivation of oxime initiator on copper, (3) development life of resist There is improvement (extension) of (developable drying time). In particular, the effects (2) and (3) are novel effects that have not been known at all.

  The effect of the above (2) will be explained. The oxime photopolymerization initiator has poor stability against contact with metal, and when used for a solder resist, the sensitivity of the portion in contact with the copper wiring on the circuit board is low. May be. It is confirmed that this phenomenon becomes more prominent as heating is performed, and further, a portion where the solder resist becomes thin (circuit wrinkles) or the like is peeled off after development. This is considered to be due to the decomposition of the oxime compound due to contact between copper and the oxime compound, and the decrease (deactivation) of the photopolymerization initiation ability due to the decomposition of the oxime compound was a serious problem for the solder resist. However, the presence of a mercapto group derived from mercaptobutanoic acid that reacts or coordinates relatively mildly with copper acts as a kind of protective film to prevent deactivation of the oxime compound and prevent peeling of the solder resist. I guess that.

  The effect of the above (3) will be described. In particular, when the thermosetting component used for the solder resist is an epoxy resin, the effect was observed. In other words, when the epoxy resin is present in the solder resist composition and when both the epoxy resin and the mercaptobutanoic acid derivative are present in the solder resist composition, the composition in which mercaptobutanoic acid is clearly present. Had a longer development life. Although the detailed reason for this is not always clear, the reduction in development life is generally caused by the gradual reaction of the carboxyl group of the carboxyl group-containing resin and the epoxy group of the epoxy resin. If a mercaptobutanoic acid derivative is added here, it is likely that the mercapto group starts to react with the epoxy group before the reaction between the carboxyl group and the epoxy group. Therefore, it is presumed that the carboxyl group that affects the developability is not consumed.

  The appropriate blending amount of the mercaptobutanoic acid or its derivative (B) is a ratio of 0.05 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (A) described below. The ratio is more preferably 0.1 parts by mass or more and 2.0 parts by mass or less.

  Next, as the carboxyl group-containing resin (A) contained in the photocurable / thermosetting resin composition of the present invention, a known and commonly used resin compound containing a carboxylic acid in the molecule can be used. Furthermore, a carboxylic acid-containing photosensitive resin (A ′) having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoints of photocurability and development resistance. The unsaturated group is preferably derived from acrylic acid or methacrylic acid or derivatives thereof, and those derived from methacrylic acid are effective from the viewpoint of storage stability. (Mercaptobutanoic acid or its derivative (B) tends to undergo a Michael addition reaction with an ethylenically unsaturated double bond derived from acrylic acid, but reacts with an ethylenically unsaturated double bond derived from methacrylic acid. Because it is difficult). However, since those derived from methacrylic acid are inferior in sensitivity to those derived from acrylic acid, compounds having both those derived from acrylic acid and those derived from methacrylic acid are preferred. According to the study by the present inventors, the partial introduction of acrylic acid was able to increase the sensitivity without significantly affecting the storage stability. In addition, partial introduction of methacrylic acid was effective in storage stability with little decrease in sensitivity, so ethylenically unsaturated double bonds derived from methacrylic acid and ethylenically unsaturated double bonds derived from acrylic acid It is considered that the structure having each of the above is most preferable. In this case, from the balance of sensitivity and stability, the ratio of ethylenically unsaturated double bonds derived from acrylic acid: ethylenically unsaturated double bonds derived from methacrylic acid is a ratio of 95-50: 5-50. Is preferred.

Specific examples of the carboxyl group-containing resin (A) include the resins listed below.
(1) a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
(2) Glycidyl (meth) acrylate or 3,4-epoxycyclohexyl is a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond. A photosensitive carboxyl group-containing resin obtained by adding an ethylenically unsaturated group as a pendant by a compound having an epoxy group and an unsaturated double bond, such as methyl (meth) acrylate, or (meth) acrylic acid chloride,
(3) Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that A photosensitive carboxyl group-containing resin obtained by reacting an unsaturated carboxylic acid such as (meth) acrylic acid with the coalescence and reacting the generated secondary hydroxyl group with a polybasic acid anhydride,
(4) To a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than that, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; A photosensitive carboxyl group-containing resin obtained by reacting a compound having an unsaturated double bond;
(5) a photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) After reacting a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is reacted with an epoxy group and a compound having an unsaturated double bond in one molecule. Photosensitive hydroxyl and carboxyl group-containing resins obtained by
(7) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A photosensitive carboxyl group-containing resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride,
(8) Saturated or unsaturated polybasic with respect to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule. A photosensitive carboxyl group-containing resin obtained by reacting an acid anhydride, and (9) (a) a polyfunctional epoxy resin reacted with (b) an unsaturated monocarboxylic acid, and (c) a polybasic acid anhydride. And (f) a photosensitive carboxyl group obtained by reacting a compound having one oxirane ring and one or more ethylenically unsaturated groups in the molecule. Examples thereof include, but are not limited to, a containing resin.

Among the carboxyl group-containing resins exemplified above, preferred are the carboxyl group-containing resins of (2), (5) and (7), and particularly the carboxylic acid-containing photosensitive resin of (9) above. It is preferable in terms of photocurability and cured coating film characteristics.
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.
Since the carboxyl group-containing resin (A) as described above has a large 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 resin (A) is in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeleton, generally what is in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, and the film may be reduced during development, and the 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.

  The compounding quantity of such carboxyl group-containing resin (A) is 20-60 mass% in all the compositions, Preferably it is 30-50 mass%. 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.

（式中、Ｒ^１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^２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^３及びＲ^４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^５及びＲ^６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^７及びＲ^８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、炭素数１〜１０の直鎖状又は分岐状のアルコキシ基、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^７及びＲ^８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）。 The photopolymerization initiator (C) includes an oxime ester photopolymerization initiator (C1) having a group represented by the following general formula (I), and an α-amino having a group represented by the following general formula (II). One or more photopolymerization initiators selected from the group consisting of an acetophenone photopolymerization initiator (C2) and an acylphosphine oxide photopolymerization initiator (C3) having a group represented by the following formula (III): It is preferable to use it. In particular, the oxime ester photopolymerization initiator (C1), or the oxime ester photopolymerization initiator (C1), the α-aminoacetophenone photopolymerization initiator (C2) and / or the acylphosphine oxide photopolymerization start. A mixture with the agent (C3) is preferred.

(In the formula, R ¹ 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). Or 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 benzoyl. A group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² 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 ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁵ and R ⁶ 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 ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl Group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that one of R ⁷ and R ⁸ is an R—C (═O) — group (where R is 1 to 20 hydrocarbon groups).

The oxime ester photopolymerization initiator (C1) having a group represented by the general formula (I) is preferably 2- (acetyloxyiminomethyl) thioxanthene-9 represented by the following formula (IV) -On, the compound represented by the following general formula (V), and the compound represented by the following general formula (VI) are mentioned.

（式中、Ｒ^９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^１０、Ｒ^１２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^１１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 ⁹ 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 carbon atoms. To 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 in the middle of the alkyl chain) Or a phenoxycarbonyl group,
R ¹⁰ and R ¹² 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), 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 ¹¹ is 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). Which may be substituted with 1 to 6 alkyl groups or phenyl groups)),

（式中、Ｒ^１３及びＲ^１４は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８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、及び
ｎは０〜５の整数を表す）

(Wherein R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 12 carbon atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 5)

  Among the oxime ester photopolymerization initiators (C1) described above, there are 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the formula (IV) and a compound represented by the formula (V). More preferred. Examples of commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator (C2) having a group represented by the general formula (II), 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 (C3) having the group represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

The blending amount of such a photopolymerization initiator (C) is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Is appropriate. 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 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (C) becomes violent, and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester-based photopolymerization initiator (C1) having the group represented by the formula (I), the blending amount is preferably 0 with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is desirable to select from the range of 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass.

  In addition to the photopolymerization initiator (C), a photopolymerization initiator, a photoinitiator assistant and a sensitizer that can be suitably used for the photocurable / thermosetting resin composition of the present invention include a benzoin compound, Examples include acetophenone compounds, anthraquinone compounds, thioxanthone compounds, 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 isoamylethyl ester (Nippon Kayaku Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl (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 resin (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. A 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 contains a colored pigment as well as a colorless and transparent photocurable / thermosetting resin composition. It is possible to provide a colored solder resist film that reflects the color of the colored pigment itself. 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 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is. When the amount of the tertiary amine compound is 0.1 parts by mass or less, there is a tendency that a sufficient sensitizing effect cannot 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.

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

  The compound (D) having two or more ethylenically unsaturated groups in the molecule used in the photocurable / thermosetting resin composition of the present invention is photocured by irradiation with active energy rays, and unexposed portions. Is insolubilized in an alkaline aqueous solution, or helps insolubilization. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, 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 (D) which has 2 or more ethylenically unsaturated groups in such a molecule | numerator is 5-100 with respect to 100 mass parts of said ethylenically unsaturated group containing carboxyl group-containing resin (A). It is a ratio of 1 to 70 parts by mass, more preferably 1 part by mass. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation 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.

In order to impart heat resistance to the photocurable / thermosetting composition of the present invention, a thermosetting component ( E ) can be added. Particularly preferred as the thermosetting component ( E ) is a thermosetting resin 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 resin having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two kinds thereof. A compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound ( E- 1), having at least two oxetanyl groups in the molecule Examples thereof include a compound, that is, a polyfunctional oxetane compound ( E- 2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin ( E- 3).

Examples of the polyfunctional epoxy compound ( E- 1) include JER828, JER834, JER1001, JER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, Epicron 2055, and Toto, 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. Bisphenol A type epoxy resin such as 664 (all trade names); YL903 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. Brominated epoxy resins such as 714 (all trade names); JER152 and JER154 manufactured by Japan Epoxy Resin, and 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, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Industries Sumi-epoxy ESCN-195X, ESCN- 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 & Chemicals, JER807 manufactured by Japan Epoxy Resin, Epotot YDF-170 manufactured by Toto Kasei Co., YDF- 175, YDF-2001, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST- manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 3000 (trade name); Japan Epoxy Resin JER604, Toto Kasei Epototo YH-434, Ciba Specialty Chemicals Araldide MY720, Sumitomo Chemical Co., Ltd. SUMI-EPOXY ELM Glycidylamine type epoxy resin such as 120 (all trade names); Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty -Alicyclic epoxy resins such as Araldide CY175, CY179, etc. (both trade names) manufactured by Chemicals; YL-933 manufactured by Japan Epoxy Resin; 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; YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. (all trade names) Tetraphenylolethane type epoxy resin; Hexacyclic epoxy resins such as Araldide PT810 manufactured by Ba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (both trade names); Diglycidyl phthalate resins such as Bremer DGT manufactured by NOF Corporation; ZX manufactured by Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as -1063; naphthalene group-containing epoxy resins such as Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, Dainippon Ink and Chemicals, Inc. HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; and cyclohexylmaleimide And glycidyl methacrylate Copolymerized epoxy resin; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries), 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 ( E- 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 novolac resin, poly (p-hydroxystyrene), cardo Bisphenols, 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 ( E- 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 amount of the thermosetting component ( E ) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). -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 ( E ) 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.

When using the thermosetting component ( E ) which has a 2 or more cyclic (thio) ether group in the said molecule | numerator, 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, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and those that are commercially available ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (all dimethylamine block isocyanate compounds manufactured by San Apro) Product names), DBU, DBN, U-CATSA102, U-CAT5002 (both 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. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-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 at a normal quantitative ratio. For example, the thermosetting component ( E ) having a carboxyl group-containing resin (A) or two or more cyclic (thio) ether groups in the molecule. Preferably it is 0.1-20 mass parts with respect to 100 mass parts, More preferably, it is 0.5-15.0 mass parts.

  The photocurable / thermosetting resin composition of the present invention can be blended with 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, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin (D-1), XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) manufactured by Hanse-Chemie, Inc. XP 0516, XP 0525, XP 0314 (all are product grades) Name) can also be used. These may be used alone or in combination of two or more.

  The blending amount of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Part. When the blending amount of the filler exceeds 300 parts by mass, the viscosity of the photocurable / thermosetting resin composition is increased, the printability is lowered, and the cured product becomes brittle.

  Furthermore, the photocurable / thermosetting resin composition of the present invention is used for the synthesis of the carboxyl group-containing resin (A) and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. Organic 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; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  The photocurable / thermosetting resin composition of the present invention may further comprise, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, fine silica, and organic bentonite. , Known and commonly used thickeners such as montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, Known and commonly used additives such as rust preventives can be blended.

The photocurable / thermosetting resin composition of the present invention has a form of a dry film comprising a carrier film and a layer formed of the photocurable / thermosetting resin composition formed on the carrier film. You can also
When forming a dry film, the photocurable / thermosetting resin composition of the present invention is diluted with the above-mentioned organic solvent to an appropriate viscosity, followed by a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer coater. A film can be obtained by applying a uniform thickness on a support with a roll coater, gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After the film is formed on the carrier film, it is desirable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the support is more than What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  The photo-curable / thermosetting resin composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method. It is applied by a screen printing method, a curtain coating method, a spray coating method, a roll coating method, etc. and, for example, the organic solvent contained in the composition is evaporated and dried at a temperature of about 60 to 100 ° C. A coating film can be formed.

  After forming a coating film on the printed circuit board on which the circuit is formed (when the above dry film is used, after laminating on the printed circuit board on which the circuit has been formed, the support is not peeled off), and then the active energy such as laser light A resist pattern can be formed by directly irradiating a line as a pattern or selectively exposing with an active energy ray through a photomask on which a pattern is formed, and developing an unexposed portion with a dilute alkaline aqueous solution (using the above dry film). If it is, the support is peeled off and developed after exposure). Thereafter, only by heat curing, or by heat curing after irradiation of active energy rays or final curing (main curing) by irradiation of active energy rays after heat curing, electrical insulation, PCT resistance, adhesion, solder heat resistance, A cured film (cured product) excellent in chemical resistance, electroless gold plating resistance and the like is formed.

  The photocurable / thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and the dip coating method, flow coating method, roll coating method, bar coater method on the base material. A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying). . Moreover, in the case of the said dry film form, it bonds together on a base material using a hot roll laminator etc. (It bonds so that the said photocurable thermosetting resin composition layer and a base material may contact). In the case of a dry film provided with a peelable cover film on the photocurable / thermosetting resin composition layer of the film, after the cover film is peeled off, the photocurable / thermosetting resin composition layer Bonding is performed using a hot roll laminator or the like so that the substrate contacts the substrate.

  Then, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film (photocurable and thermosetting resin composition layer). The exposure may be either a contact type (or non-contact type) method of selectively exposing with an active energy ray through a photomask on which a pattern has been formed, or a method of direct pattern exposure using a laser direct exposure machine. By this exposure, the exposed portion (portion irradiated with active energy rays) of the coating film is cured. Next, the unexposed portion is developed with a dilute alkaline aqueous solution (for example, a 0.3 to 3% sodium carbonate aqueous solution) to form a resist pattern. 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) and two or more cyclic ether groups and / or cyclic thioether groups in the molecule are obtained. The thermosetting component which it has reacts and can form the cured coating film excellent in various characteristics, such as heat resistance, chemical resistance, moisture absorption resistance, adhesiveness, and an electrical property.

  As the substrate, 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, fluorine Use copper graded laminates of all grades (FR-4 etc.) using composite materials such as resin, polyethylene, PPO, cyanate ester, polyimide film, PET film, glass substrate, ceramic substrate, wafer plate, etc. it can.

  Volatile drying performed after the photocurable / thermosetting resin composition of the present invention is applied may be a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (having a heat source of an air heating method using steam). It can be performed using a method in which hot air in the dryer is brought into countercurrent contact, or a method in which the hot air in the dryer is blown to the support from the nozzle.

As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can be used. As the active energy ray, either a gas laser or a solid laser may be used as long as laser 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 device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

  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.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Synthesis example 1
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy Equivalent 220) 660 g, carbitol acetate 421.3 g, and solvent naphtha 180.6 g were introduced, heated and stirred at 90 ° C., and dissolved. Next, it is once cooled to 60 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone are added and reacted at 100 ° C. for 12 hours, and a reaction product having an acid value of 0.2 mgKOH / g. Got. This was charged with 241.7 g of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for 6 hours. As a result, a solution of a carboxyl group-containing resin (A) having an acid value of 50 mg KOH / g, a double bond equivalent (g weight of resin per mole of unsaturated groups) of 400, and a weight average molecular weight of 7,000 was obtained. Hereinafter, this carboxyl group-containing resin solution is referred to as A-1 varnish.

Synthesis example 2
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, an o-cresol novolac type epoxy resin (epoxy equivalent 215, 6 phenol nuclei on average in one molecule). ) And acrylic acid 144 g (2 mol). The mixture was heated to 120 ° C. with stirring, and the reaction was continued for 10 hours while maintaining 120 ° C. Once the reaction product was cooled to room temperature, 190 g (1.9 mol) of succinic anhydride was added, heated to 80 ° C., and reacted for 4 hours. Again, the reaction product was cooled to room temperature. The acid value of this product solid was 139 mg KOH / g.
To this solution, 85.2 g (0.6 mol) of glycidyl methacrylate and 45.9 g of propylene glycol methyl ether acetate were added and heated to 110 ° C. with stirring, and the reaction was continued for 6 hours while maintaining 110 ° C. When the reaction product was cooled to room temperature, a viscous solution was obtained. Thus, a solution of a carboxyl group-containing resin (A) having a nonvolatile content of 65% by mass and a solid content acid value of 86 mgKOH / g was obtained. Hereinafter, the solution of this carboxyl group-containing resin is referred to as A-2 varnish.

Synthesis example 3
A solution of the carboxyl group-containing resin (A) was obtained in the same manner except that the acrylic acid of Synthesis Example 1 was replaced with methacrylic acid. Hereinafter, this carboxyl group-containing resin solution is referred to as A-3 varnish.

Examples 1 to 7, Comparative Examples 1 and 2
Using the resin solutions of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photocurable and thermosetting resin composition was prepared. Here, when the degree of dispersion of the obtained photocurable / thermosetting resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.

Performance evaluation:
<Optimum exposure amount>
The photocurable / thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after the circuit pattern substrate with a copper thickness of 35 μm was buffed, washed with water and dried. Dry in a hot air circulating drying oven for 60 minutes. After drying, exposure is performed via a step tablet (Kodak No. 2) using 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 lamp or an exposure apparatus equipped with a high pressure mercury lamp, When the development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) was carried out in 60 seconds, the optimal exposure amount was obtained when the pattern of the step tablet remaining was 7 steps.

<Resolution>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm was applied to the photocurable / thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water, drying and then applying by screen printing. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, exposure was performed using a direct drawing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm. As the exposure pattern, direct drawing data for drawing a 20/30/40/50/60/70/80/90/100 μm line in the space portion was used. The active energy rays were irradiated so that the exposure amount was the optimum exposure amount of the photocurable / thermosetting resin composition. After the exposure, development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes.
It calculated | required using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photocurable and thermosetting resin composition for solder resists 200 times (resolution).

Characteristic test:
The composition of each of the above Examples and Comparative Examples is 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. This substrate is exposed to a solder resist pattern with an optimum exposure amount using a direct writing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied for 60 seconds under a spray pressure of 0.2 MPa. Development was performed 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.

<Color of coating film>
The color of a hardened | cured material was judged visually for the alkali development type solder resist of the said Example and comparative example.

<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>
The evaluation substrate is plated using commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel 0.5 μm and gold 0.03 μm. After evaluating the presence or absence of penetration, 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 characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of a copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type 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.
○: No change at all △: Only a slight change ×: Migration has occurred

<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling by tape beer was confirmed. Judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.

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

尚、比較例１は光重合開始剤の失活によると思われるレジストの剥がれが現像後銅回路上に発生していた。 The results of each evaluation test are summarized in Table 2.

In Comparative Example 1, peeling of the resist, which seems to be caused by deactivation of the photopolymerization initiator, occurred on the copper circuit after development.

Stability test:
In accordance with the formulation example shown in Table 3, the main component and the curing agent are divided into proportions (parts by mass) shown in Table 3, premixed with a stirrer, kneaded with a three-roll mill, and solder resist. A photocurable thermosetting resin composition was prepared. Here, when the degree of dispersion of the obtained photocurable / thermosetting resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.

With respect to the obtained main agent and curing agent, as shown in Table 4, the sensitivity and the maximum development life were evaluated by a 355 nm laser exposure machine. Regarding storage stability, the obtained main agent and curing agent were each put in a polyethylene sealed container and placed in a thermostat at 30 ° C., and evaluation was performed 30 days and 60 days later.
Table 4 shows the obtained results.

Comparative Example 4
In Formulation Example 5 shown in Table 3, after adjusting the main agent and curing agent, they were mixed immediately and stored at 30 ° C. for 60 days, the development life was remarkably shortened to 30 minutes.

Comparative Example 5
In Formulation Example 5 shown in Table 3, (B2) pentaerythritol tetrakis (3-mercaptobutyrate) blended and prepared on the curing agent side was stored at 30 ° C. for 30 days, then mixed and tested. I couldn't develop.

Example 18
A photocurable / thermosetting resin composition prepared according to Example 3 shown in Table 1 was diluted with methyl ethyl ketone, coated on a carrier film, dried by heating, and a 20 μm thick photocurable / thermosetting resin. A composition layer was formed, and a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film is peeled off, the film is bonded to the patterned copper foil substrate, and then the carrier film is peeled off and dried in a hot air dryer at 80 ° C. for 30 minutes, and then in a hot air dryer at 150 ° C. Heat curing was performed for 60 minutes to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The result was equivalent to Example 3.

Claims (15)

(A) carboxyl group-containing resin, (B) mercaptobutanoic acid or a derivative thereof, (C) an oxime ester photopolymerization initiator as a photopolymerization initiator , and (D) two or more ethylenically unsaturated groups in the molecule. The photocurable thermosetting resin composition characterized by containing the compound which has, and (E) thermosetting component. The photocurable / thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin (A1) having an unsaturated double bond capable of radical polymerization. . The photocurable / thermosetting property according to claim 2 , wherein a part or all of unsaturated double bonds of the carboxyl group-containing resin (A1) are derived from methacrylic acid or a derivative thereof. Resin composition. The mercapto butanoic acid or a derivative thereof (B) is any one of claims 1 to 3, characterized by having two or more 2-mercapto isobutane acid or 3-mercaptobutanoic acid or a derivative thereof in one molecule The photocurable thermosetting resin composition according to one item. The photopolymerization initiator (C) is an oxime ester photopolymerization initiator (C1) represented by the following general formula (I), or the oxime ester photopolymerization initiator (C1) and the following general formula ( It is a mixture with an aminoacetophenone photopolymerization initiator (C2) represented by II) and / or an acylphosphine oxide photopolymerization initiator (C3) represented by the following general formula (III). The photocurable thermosetting resin composition according to any one of claims 1 to 4 .

(In the formula, R ¹ 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). Or 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 benzoyl. A group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² 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 ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁵ and R ⁶ 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 ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl Group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that one of R ⁷ and R ⁸ is an R—C (═O) — group (where R is 1 to 20 hydrocarbon groups). Formula (I) represented by an oxime ester-based photopolymerization initiator (C1), according to claim 5, characterized in that an oxime ester-based photopolymerization initiator represented by the following formula (IV) Photocurable and thermosetting resin composition.

Formula (I) represented by an oxime ester-based photopolymerization initiator (C1), in claim 5, characterized in that an oxime ester-based photopolymerization initiator represented by the following general formula (V) The photocurable thermosetting resin composition as described.

(In the formula, R ⁹ 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 carbon atoms. To 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 in the middle of the alkyl chain) Or a phenoxycarbonyl group,
R ¹⁰ and R ¹² 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), 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 ¹¹ is 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). ) The thermosetting component (E) is a two-part composition blended in a mixture different from the mixture blended with the mercaptobutanoic acid or derivative (B). The photocurable thermosetting resin composition according to any one of 7 above. Two-component type comprising at least a mixture of the carboxyl group-containing resin (A) and the mercaptobutanoic acid or derivative (B), and a mixture of the oxime ester photopolymerization initiator (C) and the thermosetting component (E). It is a composition, The photocurable thermosetting resin composition as described in any one of Claims 1 thru | or 8 characterized by the above-mentioned. Furthermore, it is a soldering resist containing a coloring agent (F), The photocurable and thermosetting resin composition as described in any one of the Claims 1 thru | or 9 characterized by the above-mentioned. It is a green or blue solder resist, The photocurable and thermosetting resin composition as described in any one of Claim 1 thru | or 10 characterized by the above-mentioned. A photocurable / thermosetting dry film obtained by applying and drying the photocurable / thermosetting resin composition according to any one of claims 1 to 11 on a carrier film. The hardened | cured material obtained by photocuring the photocurable thermosetting resin composition as described in any one of the said Claims 1 thru | or 11 , or the dry film of the said Claim 12 on copper. The photocurable / thermosetting resin composition according to any one of claims 1 to 11 or the dry film according to claim 12 is light-patterned with a laser oscillation light source of 350 nm to 410 nm. A cured product obtained by curing. The photocurable / thermosetting resin composition according to any one of claims 1 to 11 or the dry film according to claim 12 is patterned by direct drawing of ultraviolet rays having a wavelength of 350 nm to 410 nm. A printed wiring board having a resist pattern obtained by photocuring into a shape and then thermosetting.