JP5449688B2 - Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

The present invention is developable photocurable thermosetting resin composition by a dilute aqueous alkaline solution, a solder resist composition to photocuring in particular ultraviolet exposure or laser exposure, the dry film and cured, and formed by them The present invention relates to a printed wiring board having a cured film.

  With recent rapid progress in semiconductor components, electronic devices tend to be smaller, lighter, higher performance, and multifunctional. Following this trend, printed wiring boards are also becoming increasingly dense and surface-mounted. In the production of high-density printed wiring boards, photo solder resist is generally employed, and dry film type photo solder resist and liquid photo solder resist have been developed. Among these, in consideration of environmental problems, an alkali developing type photosensitive composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been proposed (Patent Document 1). -3 etc.)

Alkali development type photosensitive compositions are currently used in large quantities as solder resists in the production of actual printed wiring boards. As a method for forming a solder resist using the same, contact exposure, in which a solder resist layer is applied to a circuit-formed substrate and dried, and then exposed in a vacuum contact with a photo tool, has become the mainstream.
At this time, if the dry touch of the dry paint film is poor, the photo tool is in close contact with the paint film, and the photo tool cannot be peeled off, or the dry paint film is peeled off from the substrate. . As a method for improving the dryness to touch of the dried coating film, it is known to add a resin other than the photocurable resin, for example, a phenoxy resin to the photosensitive composition (for example, see Patent Document 4). . However, when such a resin is added to the photosensitive composition, the dryness to touch of the dried coating can be improved, but on the other hand, it is inferior in developability, and the time until drying and exposure / development ( There was a problem that the drying control width was short.

Further, in the case of a dry film type solder resist in which a dry coating film is formed on a carrier film, since the photo tool is overlaid and exposed over the carrier film, there is no problem of being in close contact with the photo tool as described above. However, when a dry film type solder resist is laminated by heating under vacuum on a circuit board with unevenness formed on a circuit, those with poor touch-drying properties will stick to the substrate in a state where the vacuum pressure is not sufficient. As a result, bubbles remained between the circuits after lamination.
JP 61-243869 (Claims) JP-A-11-288091 (Claims) JP-A-5-32746 (Claims) JP-A-6-138655 (Claims)

The present invention has been made in view of the problems of the prior art as described above, and its main purpose is that the coating film after drying is excellent in dryness to touch, and even if contact exposure is performed, the phototool is exposed at the time of exposure. An object of the present invention is to provide a photocurable thermosetting resin composition free from problems such as sticking.
Further object of the present invention, the dry film and cured product excellent in various properties as described above obtained by using such a photocurable thermosetting resin composition, and the solder resist by the dry film and cured An object of the present invention is to provide a printed wiring board on which a cured film such as the above is formed.

In order to achieve the above object, according to the present invention, there is provided a photocurable thermosetting resin composition comprising a cellulose ester derivative, a carboxyl group-containing resin, a photopolymerization initiator, and a thermosetting component. And the compounding ratio of the said cellulose-ester derivative is 1-50 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, The photocurable thermosetting resin composition characterized by the above-mentioned is provided.
In a preferred embodiment, the cellulose ester derivative is soluble in a solvent, and the glass transition temperature Tg of the cellulose ester derivative is preferably 70 ° C. or higher. Further, the photocurable thermosetting resin composition is preferably alkali developable.

The photocurable thermosetting resin composition may be in liquid form, or may be in the form of a dry film. Dry film of the photocurable thermoset, the photocurable thermosetting resin composition obtained by coating and drying the carrier film.

Moreover, according to this invention, the hardened | cured material obtained by photocuring the said photocurable thermosetting resin composition or a dry film is provided.
Furthermore, according to the present invention, there is also provided a printed wiring board characterized by having a cured film obtained by photocuring the photocurable thermosetting resin composition or dry film and then thermosetting. . Alternatively, it is a printed wiring board having a cured film containing a cellulose ester derivative and a carboxyl group-containing resin, and the blending ratio of the cellulose ester derivative is 1 to 50 masses per 100 parts by mass of the carboxyl group-containing resin. A printed wiring board characterized by being a part is provided. In the present invention, the printed wiring board refers to a board in which a conductor pattern is formed on the surface of an electrically insulating board using a printing technique such as a screen printing method or a photo-etching method. There is a wiring board.

Photocurable thermosetting resin composition of the present invention, by containing the cellulose ester derivative, excellent tack of the coating film after drying, be subjected to contact exposure, the phototool during exposure Unlike the case of adding a phenoxy resin, there is no problem such as sticking, and it has an advantage of excellent developability and a long time (drying control width) until drying and exposure / development after drying.
Accordingly, photocurable thermosetting resin composition of the present invention can be advantageously applied to formation of a cured film of the solder resist of the printed wiring board.

As described above, the photocurable thermosetting resin composition of the present invention eliminates problems such as sticking of a photo tool during contact exposure so that a dry coating film excellent in dryness to touch can be obtained. Therefore, although it is characterized by containing a cellulose ester derivative, other photocuring components and the like can contain conventionally known various components. Hereinafter, each component of the photocurable thermosetting resin composition of the present invention will be described.

(A) Cellulose ester derivative The cellulose ester derivative (A) used in the present invention is preferably soluble in an organic solvent and has a high glass transition temperature (Tg). The cellulose ester derivatives, and the like cellulose ester as described below.

（式中、Ｒは水素又は有機酸エステル基を表し、水素及び有機酸エステルの中から選ばれる少なくとも２種以上から構成される。ｎは１以上の整数であり、その上限は後述する分子量から規制される。）
上記式（１）で示されるセルロースエステルにおいて、セルロース樹脂に対するヒドロキシル基含有量は０〜６ｗｔ％、有機酸エステルとして、アセチル基含有量は０〜４０ｗｔ％、プロピオニル基又は／及びブチリル基含有量は０〜５５ｗｔ％の範囲が好ましい。ここでいう「ｗｔ％」とは、セルロースの重量に対する水素又は有機酸エステルの重量％である。 A more preferable cellulose ester derivative is a cellulose ester obtained by esterifying a hydroxyl group of cellulose with an organic acid, and specifically includes a compound represented by the following formula (1).

(In the formula, R represents hydrogen or an organic acid ester group, and is composed of at least two kinds selected from hydrogen and organic acid esters. N is an integer of 1 or more, and the upper limit is from the molecular weight described later. Regulated.)
In the cellulose ester represented by the above formula (1), the hydroxyl group content relative to the cellulose resin is 0 to 6 wt%, and the organic acid ester has an acetyl group content of 0 to 40 wt%, a propionyl group and / or a butyryl group content of The range of 0-55 wt% is preferable. Here, “wt%” is the weight% of hydrogen or organic acid ester relative to the weight of cellulose.

  Examples of such commercially available cellulose esters include cellulose acetate butyrate such as CA-398-3, CA-398-6, CA-398-10, CA-398-30, and CA-394-60S. CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-531-1, CAB-500-5, CAB-381-0.1, CAB-381- 0.5, CAB-381-2, CAB-381-20, CAB-381-20BP, CAB-321-0.1, CAB-171-15, etc., as cellulose acetate propionate, CAP-504-0. 2, CAP-482-0.5, CAP-482-20 (all of the above cellulose derivatives are trade names manufactured by Eastman), etc. And the like. Among these, cellulose acetate butyrate and cellulose acetate propionate are preferable from the viewpoint of solubility in a solvent, and cellulose acetate propionate is more preferable from the viewpoint of odor.

The number average molecular weight of the cellulose ester derivative is not particularly limited, but is preferably 5000 to 500,000, and more preferably 10,000 to 100,000. When the molecular weight is smaller than the above range, it is difficult to obtain the desired touch drying property (tack-free property). On the other hand, when the molecular weight is larger than the above range, the solubility in the solvent and the compatibility are likely to be deteriorated.

The glass transition temperature Tg of the cellulose ester derivative is preferably 70 ° C. or higher and lower than 200 ° C., more preferably 100 ° C. or higher and lower than 180 ° C. When the glass transition temperature is less than 70 ° C., it is difficult to obtain sufficient tack-free properties. On the other hand, when the glass transition temperature is 200 ° C. or more, the folding resistance of the cured coating film may be impaired.
The glass transition temperature Tg referred to in the present invention refers to a glass transition temperature measured by thermomechanical analysis (DSC) according to the method described in “5.17.5 DSC method” of JIS C 6481: 1996. .

The cellulose ester derivative used in the present invention is preferably derived from a natural product from the viewpoint of fossil fuel depletion. Furthermore, the starting material used for the cellulose ester derivative of the present invention can be produced from a recycled product such as recycled pulp, and a preferable composition can be provided from the environmental aspect of CO ₂ reduction.

Further, even if the cellulose ester derivative used in the present invention has a high softening point, the photocurable thermosetting resin composition obtained has no expectation of developability as an alkali developable solder resist. No effect was obtained. Furthermore, there was no problem in sensitivity and solder heat resistance because there was no decrease in sensitivity, and the image was not scratched.

The cellulose ester derivative (A) as described above can be used alone or in admixture of two or more. The blending amount of the cellulose ester derivative (A) is 1 to 50 parts by mass, preferably 2 to 40 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B) described later. When the blending amount of the cellulose ester derivative (A) is less than 1 part by mass, it becomes difficult to form a flexible cured film excellent in tack-free properties and the like. It is not preferable because the characteristics are likely to deteriorate.

The photocurable thermosetting resin composition of the present invention is not limited to a specific component as long as it exhibits the above-described properties, and various types including basically a photocurable component and a thermosetting component. In the case of an alkali-developable solder resist, generally, the cellulose ester derivative (A), the carboxyl group-containing resin (B), the photopolymerization initiator (C), and two or more in the molecule Contains a compound (D) having an ethylenically unsaturated group and a thermosetting component (E) such as an epoxy compound, and further contains a thermosetting catalyst, a filler, an organic solvent, and the like. By combining the amount and the like, a cured product having the characteristics described above can be obtained. For those skilled in the art, by referring to the examples and comparative examples to be described later, it will be confirmed by appropriate tests as to what kind of components, the combination amount, etc. can obtain a cured product having the above-mentioned characteristics. However, although detailed explanation is omitted, main constituent components of the photocurable thermosetting resin composition of the present invention will be briefly described below.

(B) Cal carboxyl resin cellulose derivative-containing light-curable thermosetting resin composition of the present invention, the resin compounds conventionally known having a carboxyl group in the molecule can be used. Examples of the carboxyl group-containing resin include a carboxyl group-containing resin (B-1) that does not itself have an ethylenically unsaturated double bond, and a photosensitive carboxyl group-containing resin (B) having an ethylenically unsaturated double bond. -2) can be used and is not limited to a specific one, but the photosensitive carboxyl group-containing resin (B-2) having an ethylenically unsaturated double bond in the molecule is photocurable and development resistant. From the viewpoint of And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. In addition, when using only carboxyl group-containing resin (B-1) which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, two or more ethylenic in the molecule | numerator mentioned later It is necessary to use together the compound (D) having an unsaturated group.
As specific examples of the carboxyl group-containing resin (B), compounds listed below (any of oligomers and polymers) can be suitably used.

  (1) A carboxyl obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and a compound having an unsaturated double bond such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. Group-containing resin.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate polyols and polyethers Carboxyl group content obtained by polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups Urethane resin.

  (3) Diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin A photosensitive carboxyl group-containing urethane resin obtained by polyaddition reaction of a bifunctional epoxy resin (meth) acrylate or a partially modified anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

  (5) During the synthesis of the resin of (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (6) A photosensitive carboxyl group obtained by reacting (meth) acrylic acid with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and adding a dibasic acid anhydride to the generated hydroxyl group. Containing resin.

  (7) Obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the produced hydroxyl group. A photosensitive carboxyl group-containing resin.

  (8) A carboxyl group-containing polyester resin obtained by reacting a difunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the primary hydroxyl group produced.

(9) A photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in the molecule to the resins (1) to (8).
In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin (B) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin (B) is desirably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. If the acid value of the carboxyl group-containing resin (B) is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds, so the line becomes thinner than necessary. In some cases, 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 form a normal resist pattern.

  Further, the weight average molecular weight of the carboxyl group-containing resin (B) varies depending on the resin skeleton, but is generally preferably in the range of 2,000 to 150,000, more preferably in the range of 5,000 to 100,000. is there. If the weight average molecular weight is less than 2,000, the tack-free performance (touch-drying property) of the coating film may be inferior, the moisture resistance of the coating film after exposure is poor, film loss occurs during development, and the resolution is low It 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 blending amount of such a carboxyl group-containing resin (B) is desirably in the range of 20 to 60% by mass of the total composition, and preferably in the range of 30 to 50% by 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 of the composition is increased or the coating property is lowered, which is not preferable.
In addition, the said carboxyl group-containing resin (B) can be used not only in what was enumerated above, but can be used individually or in combination of 2 or more types.

(C) Photopolymerization initiator The photopolymerization initiator (C) is selected from the group consisting of an oxime ester photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. It is preferable to use one or more photopolymerization initiators.

（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、も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のアルキル基も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、フェニル基も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のアルキル基もしくはフェニル基で置換されていてもよい）を表す。） Examples of the oxime ester photopolymerization initiator include oxime ester photopolymerization initiators having a group represented by the following general formula (2), and commercially available products include CGI-325 and Irga manufactured by Ciba Specialty Chemicals Examples include Cure (registered trademark) OXE01, Irgacure OXE02, and N-1919 manufactured by ADEKA. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

(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. Represents a group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ² is a phenyl group (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, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 ˜8 cycloalkyl groups, Represents an alkanoyl group or a benzoyl group prime 2-20 (carbon atoms may be substituted with 1-6 alkyl or phenyl group).)

  Examples of α-aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethyl Examples include aminoacetophenone. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Acylphosphine oxide photopolymerization initiators 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 desirably in the range of 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts per 100 parts by mass of the carboxyl group-containing resin (B). It is the range of mass parts. 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 coating film surface 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 photopolymerization initiator having a group represented by the general formula (2), the blending amount is preferably 0.01 with respect to 100 parts by mass of the carboxyl group-containing resin (B). It is desirable to be within the range of ˜20 parts by mass, more preferably within the range of 0.01 to 5 parts by mass.

Further photocurable thermosetting resin composition of the present invention, or a photopolymerization initiator other than the above compounds, can be used co-initiator and sensitizer, for example, benzoin compounds, acetophenone compounds, Anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, xanthone compounds, tertiary amine compounds and the like can be mentioned.

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.).

Of the other photopolymerization initiators described above, thioxanthone compounds and tertiary amine compounds are preferred. It is preferable that the thioxanthone compound is contained in the photocurable thermosetting resin composition from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone are preferred.

  The mixing ratio 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 (B). If the blending ratio 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. Dialkylamino group-containing coumarin compounds maximum absorption wavelength in the 350~410nm, since the maximum absorption wavelength is in the ultraviolet region, little discoloration, a colorless transparent light-curable thermosetting resin composition as well, using the colored pigment It is possible to provide a colored solder resist film reflecting 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.

As a mixing ratio of such a tertiary amine compound, a ratio of 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 (B). It is. When the mixing ratio 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 dried coating film by the tertiary amine compound becomes violent, 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.

(D) Compound having two or more ethylenically unsaturated groups in the molecule Compound (D) having two or more ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present invention (D) ) Is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the carboxyl group-containing resin (B) in an alkaline aqueous solution. 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 triglycidyl 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, and further 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 amount of the compound (D) having two or more ethylenically unsaturated groups in the molecule as described above is more preferably 5 to 100 parts by mass, more preferably 100 parts by mass of the carboxyl group-containing resin (B). Is a ratio of 1 to 70 parts 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.

(E) Thermosetting component The thermosetting component (E) can be added to the photocurable thermosetting resin composition of the present invention in order to impart heat resistance. Particularly preferred thermosetting component (E) is a thermosetting compound having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  The thermosetting component (E) having two or more cyclic (thio) ether groups in such a molecule is either a three-, four- or five-membered cyclic ether group or a cyclic thioether group in the molecule. Or a compound having two or more of two kinds of groups, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1), or at least two or more oxetanyl in the molecule Examples thereof include a compound having a group, 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).

  As the polyfunctional epoxy compound (E-1), for example, JER828, JER834, JER1001, JER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, Epicron 2055, 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, 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 & 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. 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 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 (E-3) having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. An episulfide resin in which the oxygen atom of the epoxy group of the novolak type epoxy resin is replaced with a sulfur atom can also be used.

  The blending amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is cyclic (thio) ether with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (B). The group is preferably in the range of 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents. 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 equivalent, carboxyl groups remain in the cured 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 the thermosetting component (E) 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-CAT 3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CAT SA102, U-CAT 5002 (all are bicyclic amidine compounds and salts thereof), etc. It is done. It is not particularly limited to these, as long as it is a thermosetting catalyst for an epoxy resin or an oxetane compound, or a catalyst that promotes the reaction between an epoxy group and / or an oxetanyl group and a carboxyl group, either alone or in combination of two or more. May 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 in the usual quantitative ratio. For example, the thermosetting component (E) having a carboxyl group-containing resin (B) 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 this invention can mix | blend a coloring agent. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes 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.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 , Pigment Blue 15: 6, Pigment Blue 16, 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:
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:
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.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
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.

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 as described above is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). Is sufficient.

The photocurable thermosetting resin 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, at least one selected from the group consisting of known and commonly used inorganic fillers and organic fillers can be used, but inorganic fillers, particularly barium sulfate, spherical silica and talc are preferably used. Furthermore, it is good also as a white resist by adding a titanium oxide as a white filler. These fillers can be blended 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 (B). 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.

Moreover, photocurable thermosetting resin composition of the present invention, for the preparation of synthesis and compositions of the carboxyl group-containing resin (B), or for viscosity adjustment for application to the substrate or 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 photo-curable 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, and phenothiazine, finely divided silica, organic bentonite, Known and commonly used thickeners such as montmorillonite, silicone, fluorine and polymer antifoaming agents and / or leveling agents, imidazole, thiazole and triazole silane coupling agents, antioxidants, Known and commonly used additives such as a rusting agent can be blended.

The photocurable thermosetting resin composition of the present invention is a dry film comprising a carrier film (support) and a layer formed of the photocurable thermosetting resin composition formed on the carrier film. It can also be in the form.
In the dry film of the photocurable thermosetting resin composition of the present invention is diluted with the organic solvent was adjusted to an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, squeeze coater, reverse coater The film can be obtained by applying a uniform thickness on a carrier film with a transfer roll coater, gravure coater, spray coater or the like and drying 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 carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

Moreover, the photocurable thermosetting resin composition or this dry film according to the present invention becomes a cured product by photocuring on copper. Photocuring can be performed by an ultraviolet exposure apparatus, but it can also be cured by laser light having a wavelength of 350 to 410 nm.

Specifically, a dry film, a cured product, and a printed wiring board are formed as follows. That is, the light-curable thermosetting resin composition of the present invention, for example, the adjusted to a viscosity suitable for the coating method with an organic solvent, on a substrate, a dip coating method, flow coating method, a roll coating method, a bar coater A tack-free coating film is formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying). it can. Also, coating the composition on a carrier film, those wound dried as a film, after the photocurable thermosetting resin composition layer is laminated on the substrate so as to contact with the substrate, A resin insulating layer can be formed by peeling off the carrier film. Then, the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask having a pattern formed, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a resist pattern is formed. Furthermore, in the case of the composition containing the thermosetting component (E), for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin (B) and the molecule The thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups reacted with each other, and was excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. A cured coating film can be formed. In addition, even when the thermosetting component (E) is not contained, by performing heat treatment, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Depending on the purpose and application, heat treatment (thermosetting) may be performed.

  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 applying the photocurable thermosetting resin composition of the present invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (equipped with an air heating heat source using steam). , A method in which hot air in the dryer is brought into countercurrent contact, or a method in which the hot air is blown onto a support from a nozzle).

As mentioned above, after apply | coating the photocurable thermosetting resin composition of this invention and evaporating and 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.
The exposure equipment used for the active energy ray irradiation includes a laser direct lithography system (laser direct imaging system), an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, and a mercury short arc lamp. Or a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used. As long as a laser beam having a maximum wavelength in the range of 350 to 410 nm is used as the active energy ray, either a gas laser or a solid laser may be 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. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Resin synthesis example Orthoethylene diol novolak type epoxy resin [Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (diethylene glycol monoethyl ether acetate 600 g) The number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This is referred to as Resin Solution B-1 Varnish.

Examples 1 to 8 and Comparative Examples 1 and 2
The various components shown in Table 1 below are blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and a photocurable thermosetting resin composition for solder resist. Was prepared. Here, when the dispersion degree of the obtained photocurable thermosetting resin composition was evaluated by particle size measurement using a grindometer manufactured by Eriksen, all the compositions were 15 μm or less.
Comparative Examples 1 and 2 are examples in which the cellulose ester derivative used in the present invention is not blended.

Details of each component in Table 1 are as shown in Table 2 below.

Performance evaluation:
<Sensitivity>
A copper solid substrate with a copper thickness of 35 μm is polished with jet scrub, washed with water, dried, and coated with the photocurable thermosetting resin composition shown in Table 1 by a screen printing method. In a hot air circulation drying oven at 80 ° C. Dry for 30 minutes. After drying, when exposed to light with an exposure dose of 50 mJ / cm ² through a step tablet (Kodak No. 2), using a 1 wt% sodium carbonate aqueous solution at 30 ° C. and developing for 60 seconds at a spray pressure of 0.2 MPa. The number of steps of the remaining step tablet was evaluated as sensitivity.

<Dry touch dryness>
Each surface of the photocurable thermosetting resin composition shown in Table 1 was applied onto a patterned copper foil substrate by screen printing, dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. . A negative film made of PET was applied to this substrate, pressure-bonded under a reduced pressure condition by ORC (HMW-GW20) for 1 minute, and then the state of sticking of the film when the negative film was peeled was evaluated.
(Double-circle): When peeling a film, there is no resistance and a trace is not left in a coating film.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

<Dry management width>
Table 1 frontal applied by screen printing the photocurable thermosetting resin composition to each patterned copper foil substrate according were dried in a hot air circulating drying oven at 80 ° C.. After the start of drying, the substrate was taken out every 10 minutes from 20 minutes to 70 minutes and allowed to cool to room temperature. This substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 60 seconds at a spray pressure of 0.2 MPa, and the maximum allowable drying time in which no residue remained was defined as the drying control width.

<Breakpoint>
Table 1 frontal applied by screen printing the photocurable thermosetting resin composition to each patterned copper foil substrate according were dried in a hot air circulating drying oven at 80 ° C.. After drying, it was allowed to cool to room temperature, and the whole surface was exposed with an exposure amount of 50 mJ / cm ² . At this time, half of the substrate was shielded from light by a light shielding film. After exposure, the time required to develop the unexposed portion of the substrate (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) was taken as a breakpoint.

Characteristic test:
Preparation of coating film property evaluation board:
Each photocurable thermosetting resin composition shown in Table 1 was applied onto a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thereafter, the solder resist pattern was exposed at an exposure amount of 50 mJ / cm ² and developed (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) to obtain a resist pattern. This substrate was cured by heating for 60 minutes in a 150 ° C. hot-air circulating drying furnace, and then irradiated with ultraviolet rays in a UV conveyor furnace under the condition of 1000 mJ / cm ² to obtain a coating film property evaluation substrate. The following characteristic evaluation test was performed on the obtained evaluation substrate.

<Solder heat resistance>
The evaluation substrate coated with the rosin flux was immersed in a solder bath at 260 ° C. for 60 seconds, the flux was washed with denatured alcohol, a tape peeling test was performed, and the peeling of the resist layer was evaluated. The judgment criteria are as follows.
○: No peeling is observed.
Δ: The circuit is slightly peeled off.
X: It peels entirely regardless of a circuit.

<Electroless gold plating resistance>
After plating on the evaluation substrate using a commercially available electroless nickel bath and electroless gold plating bath under the conditions of nickel 0.5 μm and gold 0.03 μm, and visually confirming the presence or absence of plating solution penetration The peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Infiltration and peeling are not recognized.
(Triangle | delta): Although there is no peeling, permeation is seen.
X: The circuit is peeled off.

The evaluation results are shown in Table 3.

As can be seen from the results shown in Table 3, the photocurable thermosetting resin composition containing a cellulose ester derivative (A) of the present invention, as compared with conventional photocurable thermosetting resin composition Useful as a photo-curable thermosetting resin composition without sticking to negative film, etc. because it has excellent dryness to touch after drying without causing deterioration in sensitivity, drying control width, solder heat resistance, and gold plating resistance. It is. In the case of Comparative Example 2 containing a phenoxy resin, the dryness to touch was good, but the drying control range was short and the developability was also poor.

Claims (8)

A photocurable thermosetting resin composition comprising a cellulose ester derivative, a carboxyl group-containing resin, a photopolymerization initiator, and a thermosetting component ,
The photo-setting thermosetting resin composition , wherein a blending ratio of the cellulose ester derivative is 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin . Photocurable thermosetting resin composition according to claim 1, wherein the cellulose ester-induced body is a solvent-soluble. Claim 1 or 2 photocurable thermosetting resin composition according to, wherein the glass transition temperature Tg of the cellulose ester-induced body is 70 ° C. or higher. The photocurable thermosetting resin composition according to any one of claims 1 to 3, wherein the photocurable thermosetting resin composition is alkali developable. Photocurable thermosetting resin composition, the photocurable thermosetting dry film obtained by coating and drying the carrier film according to any one of claims 1 to 4. The hardened | cured material obtained by photocuring the photocurable thermosetting resin composition as described in any one of Claims 1 thru | or 4, or the dry film of the said Claim 5. It has a cured film obtained by photocuring the photocurable thermosetting resin composition according to any one of claims 1 to 4 or the dry film according to claim 5 and then thermosetting. Printed wiring board characterized by A printed wiring board having a cured film containing a cellulose ester derivative and a carboxyl group-containing resin ,
The printed wiring board , wherein a blending ratio of the cellulose ester derivative is 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin .