JP6346228B2 - Photosensitive resin composition - Google Patents

Description

  The present invention covers a photosensitive resin composition suitable for an insulating coating material for coating a coating material, for example, a conductor circuit pattern formed on a substrate such as a printed wiring board, and a cured product obtained by curing the photosensitive resin composition. The present invention relates to a wiring board such as a printed wiring board.

  In accordance with the miniaturization of the conductor circuit pattern of the printed wiring board, there is a problem of causing a solder bridge or the like due to adhesion of solder balls to the surface of the insulating coating during solder flow. In order to prevent this problem, the surface of the insulating coating is roughened and matted, thereby improving the resistance to solder adhesion to the surface of the insulating coating during solder flow and preventing the adhesion of solder balls. Yes. Moreover, aiming at the improvement of the concealment power of insulation coating is also performed by making insulation coating matte.

  As the matting means, for example, a photocurable / thermosetting matte composition in which an organic filler having an average primary particle size in the range of 1 to 30 μm is blended with a carboxyl group-containing photosensitive resin has been proposed ( Patent Document 1).

  However, in Patent Document 1, when the addition amount of the organic filler is increased in order to obtain a good matting effect, thixotropy increases, bubbles and skips are still generated during printing, and sufficient printability is obtained. There was no problem. Moreover, when the addition amount of the organic filler is increased, there is a problem in that the electrical insulating property of the formed insulating coating is lowered.

Further, when an organic filler having a large particle size is used in order to obtain a good matting effect, the organic filler tends to be lifted from the surface of the coating film when an insulating coating pattern is formed. As a result, there has been a problem that water, chemicals and the like permeate along the interface between the organic filler and the resin, and the chemical resistance, electrical insulation and the like are lowered. Moreover, in patent document 1 using an organic filler, there existed a problem that hiding power was not enough.

JP 2006-40935 A

  In view of the above circumstances, an object of the present invention is to provide a solder-resist film that has excellent solder adhesion resistance, insulation characteristics, and hiding power due to a matte effect (low glossiness) without impairing basic characteristics such as solder heat resistance. It is providing the photosensitive resin composition suitable for formation of insulation coatings, such as.

  Embodiments of the present invention include (A) a carboxyl group-containing photosensitive resin, (B) a fatty acid amide, (C) a photopolymerization initiator, (D) a compound having an ethylenically unsaturated group, and (E) an epoxy. A photosensitive resin composition comprising a compound and (F) a colorant.

In an aspect of the present invention, the (B) fatty acid amide is represented by the following general formula (1):
R ¹ —C (═O) —NH— (CH ₂ ) ₁ —NH—C (═O) —R ² (1)
(Wherein R ¹ and R ² are each independently a saturated or unsaturated hydrocarbon group having 14 to 21 carbon atoms, and l represents 0 or an integer of 1 to 10). ,
The following general formula (2)
R ³ —NH—C (═O) — (CH ₂ ) _m —C (═O) —NH—R ⁴ (2)
(Wherein R ³ and R ⁴ each independently represents a saturated or unsaturated hydrocarbon group having 14 to 21 carbon atoms, and m represents 0 or an integer of 1 to 10). ,
And the following general formula (3)
R ⁵ —C (═O) —NH—R ⁶ (3)
(Wherein R ⁵ and R ⁶ each independently represents a saturated or unsaturated hydrocarbon group having 14 to 21 carbon atoms.) Are at least one selected from the group consisting of compounds represented by It is the photosensitive resin composition characterized by the above-mentioned.

  An aspect of the present invention is a photosensitive resin composition, wherein the (B) fatty acid amide has a melting point of 70 ° C to 160 ° C.

  In an embodiment of the present invention, the (B) fatty acid amide is hexamethylenebisoleic acid amide, N-stearyl stearic acid amide, N-oleyl stearic acid amide, N, N′-dioleyl sebacic acid amide, N, N ′. -A photosensitive resin composition characterized by being at least one selected from the group consisting of dioleyl adipic acid amide, N, N'-ethylenebiserucic acid amide and ethylenebisoleic acid amide.

  An aspect of the present invention is the photosensitive resin composition, wherein the (B) fatty acid amide is contained in an amount of 1.0 to 15 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. It is a thing.

  An aspect of the present invention is a photosensitive resin composition, wherein the colorant (F) is a black colorant.

  The aspect of this invention is a printed wiring board which has the photocured film of the said photosensitive resin composition.

  According to the aspect of the present invention, by adding the fatty acid amide, the solder adhesion resistance, the insulation characteristics, and the hiding power due to the matte effect (low glossiness) are obtained without impairing the basic characteristics such as solder heat resistance. An excellent cured product can be obtained. In addition, by blending fatty acid amide instead of blending conventional organic fillers and inorganic fillers, it is excellent in that the surface roughness of the insulating coating can be reduced without impairing the excellent matting effect. Insulation characteristics, that is, insulation reliability can also be obtained.

  According to the aspect of the present invention, the fatty acid amide is at least one selected from the group consisting of the compounds represented by the general formula (1), the general formula (2), and the general formula (3). The matte effect, insulating properties and hiding power are further improved.

  According to the present invention, when the fatty acid amide has a melting point of 70 ° C. to 160 ° C., the matting effect, the insulating properties, and the hiding power are further improved in a balanced manner. The matte effect, insulating properties and hiding power are further improved in a balanced manner because the fatty acid amide is dissolved in the coated photosensitive resin composition in the preliminary drying step after coating the photosensitive resin composition. One reason is considered that the fatty acid amide tends to be uniformly oriented on the surface of the coated photosensitive resin composition.

  According to an embodiment of the present invention, the fatty acid amide is hexamethylenebisoleic acid amide, N-stearyl stearic acid amide, N-oleyl stearic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-dioic acid. By being at least one selected from the group consisting of rail adipic acid amide, N, N'-ethylenebiserucic acid amide and ethylenebisoleic acid amide, it has an excellent balance of matting effect, insulating properties and hiding power Can be improved.

  Next, the photosensitive resin composition of the present invention will be described in detail. The photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing photosensitive resin, (B) a fatty acid amide, (C) a photopolymerization initiator, and (D) a compound having an ethylenically unsaturated group, (E) An epoxy compound and (F) a colorant are contained.

(A) Carboxyl group-containing photosensitive resin The carboxyl group-containing photosensitive resin is not particularly limited, and examples thereof include a carboxyl group-containing resin having one or more photosensitive unsaturated double bonds. As an example of a carboxyl group-containing photosensitive resin, acrylic acid or methacrylic acid (hereinafter referred to as “(meth) acrylic acid”) is added to at least a part of the epoxy group of a polyfunctional epoxy resin having two or more epoxy groups in one molecule. A radical polymerizable unsaturated monocarboxylic acid such as epoxy (meth) acrylate to obtain a radical polymerizable unsaturated monocarboxylic oxide epoxy resin, and a polybasic acid or Mention may be made of polybasic acid-modified radical polymerizable unsaturated monocarboxylic oxide epoxy resins such as polybasic acid-modified epoxy (meth) acrylates obtained by reacting the anhydride.

  Any polyfunctional epoxy resin can be used as long as it is a bifunctional or higher functional epoxy resin. Although the epoxy equivalent of a polyfunctional epoxy resin is not specifically limited, 1000 or less are preferable and 100-500 are especially preferable. Examples of the polyfunctional epoxy resin include biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, rubber modified epoxy resin such as silicone modified epoxy resin, ε-caprolactone modified epoxy resin, bisphenol A type, bisphenol. Phenol type novolak type epoxy resin such as F type, bisphenol AD type, cresol novolak type epoxy resin such as о-cresol novolak type, bisphenol A novolak type epoxy resin, cyclic aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, Glycidylamine type polyfunctional epoxy resin, heterocyclic polyfunctional epoxy resin, bisphenol modified novolac type epoxy resin, polyfunctional modified novolak type epoxy resin, phenols and phenolic hydroxyl group Examples thereof include condensate type epoxy resins with aromatic aldehydes. Moreover, what introduce | transduced halogen atoms, such as Br and Cl, to these resin can also be used. These epoxy resins may be used alone or in combination of two or more.

  The radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and acrylic acid and methacrylic acid are preferable. The reaction method of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid is not particularly limited. For example, the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid can be reacted by heating in an appropriate diluent. it can.

  The polybasic acid and the polybasic acid anhydride are those for introducing a free carboxyl group into the resin by reacting with the hydroxyl group generated by the reaction of the epoxy resin and the radical polymerizable unsaturated monocarboxylic acid. The polybasic acid or its anhydride is not particularly limited, and either saturated or unsaturated can be used. Polybasic acids include, for example, succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4- Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydro Examples include phthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid, and diglycolic acid. Examples of polybasic acid anhydrides include these anhydrides. These compounds may be used alone or in combination of two or more.

  The polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin described above can also be used as a carboxyl group-containing photosensitive resin, but if necessary, one carboxyl group is added to the carboxyl group of the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin. By reacting the above glycidyl compound having a radical polymerizable unsaturated group and an epoxy group, a radical polymerizable unsaturated group may be further introduced to provide a carboxyl group-containing photosensitive resin with improved photosensitivity. .

  In this carboxyl group-containing photosensitive resin with improved photosensitivity, the radical polymerizable unsaturated group is bonded to the side chain of the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin skeleton by the reaction of the glycidyl compound. It becomes a resin having high photopolymerization reactivity and having excellent photosensitive properties. Examples of the compound having one or more radically polymerizable unsaturated groups and an epoxy group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, and the like. In addition, you may have multiple glycidyl groups in 1 molecule. The above-mentioned compound having one or more radically polymerizable unsaturated groups and an epoxy group may be used alone or in combination of two or more.

  Further, as the carboxyl group-containing photosensitive resin, for example, a) an epoxy group of an epoxy resin having two or more epoxy groups in one molecule, b) at least 1 carbon number per carboxyl group is 10 or more. A reaction product of a long-chain fatty acid-modified ethylenically unsaturated group-containing modified epoxy resin is obtained by reacting a seed fatty acid with c) an ethylenically unsaturated group-containing carboxylic acid. D) Polybasic acid anhydride is added to the hydroxyl group (mainly secondary) generated by the reaction of the carboxyl group of the unsaturated group-containing carboxylic acid and the epoxy group of the epoxy resin to introduce a free carboxyl group into the resin. Can be mentioned.

a) Epoxy resin having two or more epoxy groups in one molecule Any epoxy resin having two or more epoxy groups in one molecule can be used as long as it is a bifunctional or more epoxy resin. The epoxy equivalent of an epoxy resin having two or more epoxy groups in one molecule is not particularly limited, but prevents deterioration in photosensitivity and flexibility due to a decrease in the ratio of introduction of ethylenically unsaturated group-containing carboxylic acid and long chain fatty acid. From the point which does, 1000 or less are preferable and 100-500 are especially preferable.

  Examples of the epoxy resin having two or more epoxy groups in one molecule include biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and silicone-modified. Rubber modified epoxy resin such as epoxy resin, ε-caprolactone modified epoxy resin, phenol novolac type epoxy resin such as bisphenol A type, bisphenol F type, bisphenol AD type, cresol novolac type epoxy resin such as о-cresol novolac type, cyclic fat Polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidylamine type polyfunctional epoxy resin, heterocyclic polyfunctional epoxy resin, bisphenol-modified novolac type epoxy resin, polyfunctional modified type Examples thereof include a borac type epoxy resin, a condensate type epoxy resin of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, an epoxy resin containing a fluorene skeleton, and an epoxy resin into which an adamantane skeleton is introduced. Moreover, what introduce | transduced halogen atoms, such as Br and Cl, to these resin can also be used.

  Among these, the sensitivity of the photosensitive resin composition, the flexibility and low warpage of the cured product are excellent, and biphenylaralkyl type epoxy resins and dicyclopentadiene type epoxy resins are preferable from the viewpoint of insulation reliability and heat resistance. .

b) Fatty acid having 10 or more carbon atoms per carboxyl group Fatty acid having 10 or more carbon atoms per carboxyl group is an epoxy group of an epoxy resin having two or more epoxy groups in one molecule. By reacting and introducing the long-chain hydrocarbon structure derived from the fatty acid into the resin, the flexibility (flexibility) and insulation of the cured product of the photosensitive resin composition can be improved. The fatty acid having 10 or more carbon atoms per carboxyl group is not particularly limited, and either saturated or unsaturated can be used, and either linear or branched can be used. Examples of the fatty acid include monobasic acids having 10 or more carbon atoms and dibasic acids having 20 or more carbon atoms. From the viewpoint of the balance between flexibility and dryness to touch, the monobasic acids and dibasic acids are mentioned. Is preferably linear or branched having 2 or less side chains having 2 or less carbon atoms.

  In addition, while introducing a long-chain fatty acid structure into the epoxy resin, different epoxy groups of the epoxy resin are bonded to each other via a fatty acid, so that a relatively rigid skeleton of the epoxy resin is derived from the long-chain fatty acid. The structure can be a structure in which a long-chain hydrocarbon skeleton having high flexibility is covalently cross-linked, and thus the structure contributes to the flexibility of the cured coating film and the solder heat resistance. It is preferable to contain a dibasic acid.

Furthermore, the flexibility and insulation of the cured coating can be further improved by introducing more long-chain hydrocarbon skeletons having high flexibility and insulation properties derived from long-chain fatty acids. In addition to a dibasic acid having 10 or more carbon atoms per unit, a monobasic acid having 10 or more carbon atoms per carboxyl group is used in combination with a fatty acid, a polyfunctional epoxy resin, and an ethylenically unsaturated group. The molecular weight of the reaction product with the group-containing carboxylic acid can be appropriately controlled while improving the composition ratio of the component derived from the long-chain fatty acid. Thus, by appropriately controlling the molecular weight, it is possible to reliably improve the touch-drying property of the coating film after drying, the solubility in weak alkaline developer (that is, developability) and sensitivity in a balanced manner. it can. Moreover, the combined use of a monobasic acid and a dibasic acid can surely contribute to a good improvement in insulation and solder heat resistance.

  It is particularly preferable to include a linear saturated monobasic acid having 18 or more carbon atoms per carboxyl group from the viewpoint of improving the above properties in a more balanced manner by controlling the molecular weight more appropriately.

  The number of carbon atoms per carboxyl group is 8 or more from the viewpoint of imparting flexibility and insulation to the cured coating film, and preferably 10 or more. On the other hand, the upper limit of the number of carbon atoms per carboxyl group is not particularly limited, but is preferably 24 or less, particularly preferably 22 or less, from the viewpoint of maintaining developability.

Specific examples of the fatty acid carbon number per one carboxyl group is 10 or more, as the monobasic acid, capric acid (decanoic acid: C10), undecanoic acid (C11), lauric acid (dodecanoic acid: C12) , tridecane acid (C13), myristic acid (tetradecanoic acid: C14), pentadecylic acid (C15), palmitic acid (hexadecanoic acid: C16), margaric acid (heptadecanoic acid: C17), stearic acid (C18), isostearic acid ( C18), tuberostrostearic acid (C19), arachidic acid (C20), behenic acid (C22), tricosylic acid (C23), tetracosanoic acid (C24), hexacosanoic acid (C26), octacosanoic acid (C28), triacontanoic acid (C30).

  Dibasic acids include eicosane diacid (C20), ethyl octadecanedioic acid (C20), eicosadiene diacid (C20), vinyl octadecaenedioic acid (C20), dimethyl eicosadiene diacid (C22), dimethyleico C36 dimer acid by dimerization reaction of unsaturated fatty acids such as sundioic acid (C22), diphenylhexadecanedioic acid (C28), oleic acid (C18), etc., and hydrogenated olefinic double bond of the dimer acid Examples thereof include hydrogenated C36 dimer acid.

  The above fatty acids having 10 or more carbon atoms per carboxyl group may be used alone or in combination of two or more.

  The reaction method of an epoxy resin having two or more epoxy groups in one molecule and at least one fatty acid having 10 or more carbon atoms per carboxyl group may be a known method, for example, the above epoxy resin And a reaction method in which the fatty acid is heated in a suitable diluent.

  The ratio of fatty acids having 10 or more carbon atoms per carboxyl group in the carboxyl group-containing photosensitive resin (preparation ratio) is not particularly limited. For example, the lower limit is the flexibility and insulation of the cured product. 10 mass% is preferable from the point which improves more, and 15 mass% is especially preferable from the point which improves a softness | flexibility and insulation reliably. On the other hand, the upper limit is preferably 50% by mass and particularly preferably 40% by mass from the viewpoint of maintaining photosensitivity by appropriately maintaining the amount of the ethylenically unsaturated group-containing carboxylic acid introduced.

c) Ethylenically unsaturated group-containing carboxylic acid Ethylenically unsaturated group-containing carboxylic acid reacts with an epoxy group of an epoxy resin having two or more epoxy groups in one molecule, and the epoxy resin is reacted with a photopolymerization initiator. A photocurable group is introduced that can be polymerized by the generated free radicals. The ethylenically unsaturated group-containing carboxylic acid is not particularly limited as long as it imparts photocurability to the epoxy resin, and examples thereof include acrylic acid, methacrylic acid, β-acryloxypropionic acid, and ω-carboxypolycaprolactone. -Carboxylic acid which can introduce | transduce an acryloyl group or a methacryloyl group into an epoxy resin, such as (meth) acrylic acid, crotonic acid, cinnamic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. These may be used alone or in combination of two or more.

  The ratio of the ethylenically unsaturated group-containing carboxylic acid in the carboxyl group-containing photosensitive resin is not particularly limited. For example, the lower limit of the (meth) acrylic equivalent of the carboxyl group-containing photosensitive resin is the flexibility of the cured product. 800 g / eq is preferable from the viewpoint of insulation, and 1000 g / eq is particularly preferable. On the other hand, the upper limit is preferably 3500 g / eq from the viewpoint of photosensitivity and developability, and particularly preferably 3000 g / eq.

  The reaction method of the epoxy resin having two or more epoxy groups in one molecule and the ethylenically unsaturated group-containing carboxylic acid is not particularly limited. For example, the epoxy resin and the ethylenically unsaturated group-containing carboxylic acid are appropriately used. A reaction method of heating in a diluent is mentioned.

d) Polybasic acid anhydride Polybasic acid anhydrides are a hydroxyl group and an ethylenically unsaturated group produced by the reaction of the epoxy resin with at least one fatty acid having 10 or more carbon atoms per carboxyl group. A free carboxyl group is introduced into the epoxy resin by reacting with the hydroxyl group produced by the reaction with the contained carboxylic acid. The polybasic acid anhydride to be used is not particularly limited, and either saturated or unsaturated can be used. Examples of the polybasic acid anhydride include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methyl Examples thereof include anhydrides of polybasic acids such as hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid and diglycolic acid. In addition, these compounds may be used independently and in order to adjust developability moderately, you may mix and use 2 or more types.

  Although the ratio (preparation ratio) of the polybasic acid anhydride in the carboxyl group-containing photosensitive resin is not particularly limited, for example, the lower limit is preferably 5.0% by mass from the viewpoint of improving developability, and 8. 0% by mass is particularly preferred. On the other hand, the upper limit is preferably 20% by mass from the viewpoint of maintaining the flexibility and insulating properties of the cured product by appropriately maintaining the amount of fatty acid having 10 or more carbon atoms per carboxyl group. 15% by mass is particularly preferable.

  Furthermore, as a carboxyl group-containing photosensitive resin, for example, an acid-modified urethanized epoxy (meth) acrylate resin may be used.

  The acid value of the carboxyl group-containing photosensitive resin is not particularly limited, but the lower limit is preferably 30 mg KOH / g, particularly preferably 40 mg KOH / g, from the viewpoint of reliable alkali development. On the other hand, the upper limit of the acid value is preferably 200 mgKOH / g from the viewpoint of preventing dissolution of the exposed area with an alkali developer, and particularly preferably 150 mgKOH / g from the viewpoint of preventing moisture from being cured and preventing deterioration of electrical characteristics.

  Further, the mass average molecular weight of the carboxyl group-containing photosensitive resin is not particularly limited, but the lower limit is preferably 3000 and particularly preferably 5000 from the viewpoint of toughness of the cured product and dryness to touch. On the other hand, the upper limit value of the mass average molecular weight is preferably 200000, particularly preferably 50000, from the viewpoint of smooth alkali developability.

  Examples of commercially available carboxyl group-containing photosensitive resins include ZAR-2000, ZFR-1122, FLX-2089, ZCR-1601H (manufactured by Nippon Kayaku Co., Ltd.), Cyclomer P (ACA). Z-250 (manufactured by Daicel Chemical Industries, Ltd.), lipoxy SP-4621 (manufactured by Showa Polymer Co., Ltd.) and the like can be mentioned. These resins may be used alone or in combination of two or more.

(B) Fatty acid amide By blending the fatty acid amide, it is possible to obtain a cured product having excellent solder resistance, insulating properties, and hiding power due to the matte effect (low glossiness). The fatty acid amide is not particularly limited, but from the viewpoint of further improving the solder adhesion resistance, the insulating properties, and the hiding power due to the matte effect, the following general formula (1)
R ¹ —C (═O) —NH— (CH ₂ ) ₁ —NH—C (═O) —R ² (1)
(In the formula, each of R ¹ and R ² independently represents a saturated or unsaturated hydrocarbon group having 14 to 21 carbon atoms, preferably an unsaturated carbon having one saturated or double bond having 16 to 18 carbon atoms. A hydrogen group, particularly preferably an unsaturated linear hydrocarbon group having one saturated or double bond of 16 to 18 carbon atoms, l is 0 or an integer of 1 to 10, preferably an integer of 4 to 8 A compound represented by:
The following general formula (2)
R ³ —NH—C (═O) — (CH ₂ ) _m —C (═O) —NH—R ⁴ (2)
(In the formula, each of R ³ and R ⁴ independently represents a saturated or unsaturated hydrocarbon group having 14 to 21 carbon atoms, preferably an unsaturated carbon having one saturated or double bond having 16 to 18 carbon atoms. A hydrogen group, particularly preferably an unsaturated linear hydrocarbon group having one saturated or double bond of 16 to 18 carbon atoms, m is 0 or an integer of 1 to 10, preferably an integer of 4 to 8 A compound represented by:
The following general formula (3)
R ⁵ —C (═O) —NH—R ⁶ (3)
(In the formula, each of R ⁵ and R ⁶ independently represents a saturated or unsaturated hydrocarbon group having 14 to 21 carbon atoms, preferably an unsaturated carbon having one saturated or double bond having 16 to 18 carbon atoms. A hydrogen group, particularly preferably an unsaturated linear hydrocarbon group having one saturated or double bond having 16 to 18 carbon atoms).

  Of these, fatty acid amide having a melting point of 70 ° C. to 160 ° C. is more preferable from the viewpoint of further improving the solder adhesion resistance due to the matte effect, the insulating properties and the hiding power in a balanced manner, and hexamethylenebisoleic acid. Amide (melting point 110 ° C.), N-stearyl stearic acid amide (melting point 95 ° C.), N-oleyl stearic acid amide (melting point 74 ° C.), N, N′-dioleyl sebacic acid amide (melting point 113 ° C.), N, N '-Dioleoyl adipic acid amide (melting point 118 ° C), N, N'-ethylenebiserucic acid amide (melting point 120 ° C), ethylenebisoleic acid amide (melting point 119 ° C), methylenebisstearic acid amide (melting point 142 ° C) Ethylene bis lauric acid amide (melting point 157 ° C.) is particularly preferable. In addition, fatty acid amide having a melting point of 70 ° C. to 120 ° C. is more preferable in terms of more excellent matting effect, and hexamethylenebisoleic acid amide (melting point 110 ° C.), N-stearyl stearic acid amide (melting point 95 ° C.). N-oleyl stearamide (melting point 74 ° C.) is particularly preferred. Fatty acid amide may be used individually by 1 type, and may mix and use 2 or more types.

  The amount of the fatty acid amide is not particularly limited. For example, the lower limit value is a carboxyl group-containing photosensitive resin (solid content) from the viewpoint of surely improving solder adhesion resistance, insulation characteristics and hiding power due to the matte effect. ) 1.0 part by mass is preferable with respect to 100 parts by mass, and 2.5 parts by mass is more preferable from the viewpoint of further improving the soldering resistance due to the matting effect, and the soldering resistance due to the particularly excellent matting effect 3.5 parts by mass is particularly preferable from the viewpoint of obtaining the above. On the other hand, the upper limit is preferably 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (solid content) from the viewpoint of surely preventing a decrease in printability. Mass parts are more preferable, and 8.0 parts by mass is particularly preferable from the viewpoint of coating film smoothness.

(C) Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it is generally used. For example, 1,2-octanedione, 1- [4- (phenylthio) -2- ( O-benzoyloxime)], ethanone 1- [9 ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), 2- (acetyloxyiminomethyl) thio Oxime initiators such as xanthen-9-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophene Non, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone 2-tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal Acetophenone dimethyl ketal, P-dimethylaminobenzoic acid ethyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, methyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, 2-ethylhexyl- 4- (dimethylamino) benzoate and the like can be mentioned. These may be used alone or in combination of two or more.

  When the photosensitive resin composition of the present invention is irradiated with ultraviolet light having a wavelength of 300 to 400 nm, the photopolymerization initiator promotes photocuring of the carboxyl group-containing photosensitive resin. The compounding quantity of a photoinitiator is not specifically limited, For example, 2-40 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing photosensitive resin (solid content), and 3-30 mass parts is especially preferable.

(D) Compound having an ethylenically unsaturated group The compound having an ethylenically unsaturated group is, for example, a photopolymerizable monomer and a compound having at least one polymerizable double bond per molecule. The compound having an ethylenically unsaturated group is cured by irradiation with active energy rays such as ultraviolet rays, thereby sufficiently curing the photosensitive resin composition, and having acid resistance, heat resistance, alkali resistance, etc. Used to get things.

  The compound having an ethylenically unsaturated group is not particularly limited. For example, 2-hydroxyethyl methacrylate, phenoxyethyl methacrylate, diethylene glycol monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, stearyl (meth) acrylate Monofunctional (meth) acrylate compounds such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopen Nyldi (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid Modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipenta Risuri Tall hexa (meth) acrylate, polyfunctional (meth) acrylate compounds such as multifunctional urethane (meth) acrylate (e.g., 2 to 6-functional (meth) acrylate compounds). These may be used alone or in combination of two or more.

  The compounding quantity of the compound which has an ethylenically unsaturated group is not specifically limited, For example, 2.0-500 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing photosensitive resin (solid content), and 10-300 masses. Part is particularly preferred.

(E) Epoxy compound The epoxy compound is for increasing the crosslinking density of the cured product to obtain a cured product such as a cured coating film having sufficient mechanical strength. Examples of the epoxy compound include an epoxy resin. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin (biphenyl novolak type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, p-tert-butylphenol novolak). Type), bisphenol F type and bisphenol S type epoxy resin obtained by reacting bisphenol F and bisphenol S with epichlorohydrin, and further cycloaliphatic epoxy resin having cyclohexene oxide group, tricyclodecane oxide group, cyclopentene oxide group, etc. , Triglycerin having triazine ring such as tris (2,3-epoxypropyl) isocyanurate, triglycidyltris (2-hydroxyethyl) isocyanurate Le isocyanurate, can be mentioned dicyclopentadiene type epoxy resins, adamantane type epoxy resins, biphenyl aralkyl type epoxy resins, phenyl aralkyl type epoxy resin, a biphenyl type epoxy resin or the like. These compounds may be used alone or in combination of two or more.

  Although the compounding quantity of an epoxy compound is not specifically limited, From the point which obtains the cured coating film of sufficient mechanical strength reliably, it is 10-150 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin (solid content). Is preferable, and 20-100 mass parts is especially preferable.

(F) Colorant The colorant is not particularly limited, such as a pigment or a dye, and any of a white colorant, a blue colorant, a yellow colorant, and a black colorant can be used. Examples of the colorant include inorganic colorants such as titanium oxide which is a white colorant and carbon black which is a black colorant, organic colorants such as phthalocyanine and anthraquinone such as phthalocyanine green and phthalocyanine blue, and the like. Can be mentioned.

  Although the compounding quantity of a coloring agent is not specifically limited, For example, 1.0-10 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing photosensitive resin (solid content), 2.0-8.0 mass parts Is particularly preferred.

  In the photosensitive resin composition of the present invention, in addition to the components (A) to (F) described above, various additive components such as a non-reactive diluent, an antifoaming agent, and various additives are added as necessary. Etc. can be contained as appropriate.

  The non-reactive diluent is for adjusting the viscosity and drying property of the photosensitive resin composition. Examples of non-reactive diluents include organic solvents. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, Petroleum solvents such as petroleum ether and petroleum naphtha, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butylcellosolve acetate, carbitol acetate and butyl carbitol Examples include esters such as acetate and diethylene glycol monomethyl ether acetate.

  Although an antifoamer is not specifically limited, For example, a silicone type, a hydrocarbon type, an acrylic type etc. can be mentioned. Examples of various additives include latent curing agents such as dicyandiamide (DICY) and its derivatives, melamine and its derivatives, antioxidants, coupling agents, and the like.

  The method for producing the photosensitive resin composition of the present invention described above is not limited to a specific method. For example, after blending the above components at a predetermined ratio, at room temperature, kneading means such as a three roll, ball mill, sand mill, etc. Alternatively, it can be produced by kneading or mixing by a stirring means such as a super mixer or a planetary mixer. Further, prior to the kneading or mixing, if necessary, preliminary kneading or premixing may be performed.

  Next, the usage method of the above-mentioned photosensitive resin composition of this invention is demonstrated. Here, the case where the photosensitive resin composition of the present invention is applied as a solder resist film on a circuit board will be described as an example.

  The photosensitive resin composition of the present invention obtained as described above, for example, on a circuit board such as a printed wiring board or a flexible printed wiring board having a circuit pattern formed by etching a copper foil, screen printing, The coating is applied to a desired thickness using a known coating method such as a spray coater, bar coater, applicator, blade coater, knife coater, roll coater, gravure coater or the like. After coating, when the photosensitive resin composition of the present invention contains an organic solvent, preliminary drying is performed by heating at a temperature of about 60 to 80 ° C. for about 15 to 60 minutes in order to volatilize the organic solvent. To form a tack-free coating.

  Next, the negative film which has the pattern which made translucent except the land of a circuit pattern was stuck on the apply | coated photosensitive resin composition, and an ultraviolet-ray (for example, the range of wavelength 300-400 nm) is irradiated from it. . Then, the coating film is developed by removing the non-exposed areas corresponding to the lands with a dilute alkaline aqueous solution. As the developing method, a spray method, a shower method, or the like is used, and examples of the diluted alkaline aqueous solution used include 0.5 to 5% by mass of an aqueous sodium carbonate solution. Next, a target solder resist film is formed on a circuit board such as a printed wiring board or a flexible printed wiring board by performing post-cure for 20 to 80 minutes with a hot-air circulating dryer at 130 to 170 ° C. Can do.

  Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as it does not exceed the gist thereof.

Examples 1-17, Comparative Examples 1-4
Each component shown in the following Table 1 and Table 2 is blended in the blending ratio shown in the following Table 1 and Table 2, mixed and dispersed at room temperature using three rolls, Examples 1 to 17 and Comparative Examples 1 to 1 The photosensitive resin composition used in No. 4 was prepared. Unless otherwise indicated, the compounding quantity of each component shown in following Table 1 and Table 2 shows a mass part.

In addition, the detail about each component in Table 1 and Table 2 is as follows.
(A) Carboxyl group-containing photosensitive resin / ZFR-1122: Acid anhydride additive (solid content 65% by mass) of bisphenol F type epoxy acrylate, manufactured by Nippon Kayaku Co., Ltd.
-ZAR-2000: Acid anhydride additive of bisphenol A type epoxy acrylate (solid content: 65% by mass), manufactured by Nippon Kayaku Co., Ltd.
FLX-2089: acid-modified urethanized epoxy methacrylate resin (solid content 65% by mass), manufactured by Nippon Kayaku Co., Ltd.
ZCR-1601H: carboxyl group-containing resin having a polyfunctional epoxy having a bisphenol novolac structure (solid content: 65% by mass), manufactured by Nippon Kayaku Co., Ltd.

Synthetic resin A
In a 500 mL separable flask equipped with a stirrer and a reflux condenser, 60 g of diethylene glycol monoethyl ether acetate (EDGAC), 8-ethyloctadecanedioic acid (SB manufactured by Okamura Oil Co., Ltd.) in a nitrogen / air (2: 1) atmosphere. -20) 25.89 g, behenic acid 43.77 g , stearic acid 9.32 g, acrylic acid 13.79 g, triphenylphosphine (TPP) 0.48 g, methoxyhydroquinone (MEHQ) 0.40 g, and a reaction vessel Nitrogen / air (2: 1) was blown into the inside, and the mixture was heated and stirred until dissolved at 110 ° C. Separately, 132.96 g of biphenyl aralkyl type epoxy resin NC-3000 (Epoxy equivalent 277 manufactured by Nippon Kayaku Co., Ltd.) in 70 g of EDGAC solvent was heated to 80 ° C. and uniformly dissolved, and the solution was put into the flask. The mixture was allowed to heat and stir at 15 ° C. for 15 to 17 hours until the acid value of the reaction solution was in the range of 7 to 8 mg KOH / g. Further, a solution in which 37.66 g of hydrogenated trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., HTCan) was dissolved in 10 g of EDGAC solvent was added to this reaction product, and air was blown at 0.3 L / min. Stir at 2-3C for 2-3 hours. The disappearance of the acid anhydride was confirmed by FT-IR (infrared spectrophotometer). As a result, a carboxyl group-containing photosensitive resin (solid content: 65% by mass) (synthetic resin A) having a solid content acid value of 80.7 mgKOH / g and a mass average molecular weight of 7000 to 9000 was obtained.

(B) Fatty acid amide / Slipac ZHO, Nikka Amide S, Nikka Amide OS: manufactured by Nippon Kasei Co., Ltd.

(C) Photopolymerization initiator Irgacure OXE-02: manufactured by BASF
-SPEDCURE EDB: manufactured by LAMBSON.
・ Irgacure 907: manufactured by Ciba Specialty Chemicals Co., Ltd.
SPEEDCURE DETX: manufactured by LAMBSON.

(D) Compound having an ethylenically unsaturated group: KRM8296: manufactured by Daicel Corporation.
DPCA-120: manufactured by Nippon Kayaku Co., Ltd.
・ STA: manufactured by Osaka Organic Chemical Industry Co., Ltd.

(E) Epoxy compound YDF-2004: manufactured by Toto Kasei Co., Ltd.
-EPICLON 860: manufactured by DIC Corporation.
NC-3000: manufactured by Nippon Kayaku Co., Ltd.
YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.

(F) Colorant / carbon black: manufactured by Denki Kagaku Kogyo Co., Ltd.
・ C. I. Pigment Blue 15: 3: manufactured by Toyo Ink Manufacturing Co., Ltd.

Other ingredients Filler OK412: Evonik Degussa.
Non-reactive diluent, diethylene glycol monomethyl ether acetate: manufactured by Sanyo Chemical Industries.

Test piece preparation process A wiring board obtained by forming a circuit pattern of a resin-coated copper foil (Cu thickness: 12.5 μm) of polyimide film (Toray DuPont, “Kapton 100H”, thickness: 25 μm) After the surface treatment with sulfuric acid (5% by mass), the photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 4 prepared as described above were applied by screen printing. After coating, preliminary drying was performed at 80 ° C. for 20 minutes in a BOX furnace. After preliminary drying, the coating film is exposed to UV light having a wavelength of 300 to 400 nm at 250 mJ / cm ² with an exposure device (OMW, HMW-680GW), and a 1 mass% sodium carbonate aqueous solution is used, and the development temperature is 30 ° C. Development was performed at a spray pressure of 0.2 MPa. After the development, a cured coating film was formed on the wiring board by post-curing at 150 ° C. for 60 minutes in a BOX furnace. The thickness of the cured coating film was 20-23 μm.

Evaluation (1) Glossiness The 60 degree glossiness (gross value) of the cured coating film of the above test piece was measured using microtrigloss (manufactured by Big Chemie Japan Co., Ltd.). In addition, 60 degree glossiness was rounded off to the first decimal place and displayed as an integer.

(2) Insulative The wiring board was changed to a comb-shaped electrode of IPC-SM840B B-25 test coupon of IPC-TM-650, and a cured coating film was formed according to the above test piece preparation process. About the obtained test piece, 85 degreeC and 85% R. H. The insulation resistance value after humidifying for 200 hours was measured by applying DC 50 V, and the insulation was evaluated according to the following criteria.
◎: 5 × ^{10 12 Ω} or more ^{○: 1 × 10 12 Ω~5 ×} 10 of less than ^{12 Ω} ×: 1 × less than ^{10 12 Ω}

(3) Solder heat resistance After the cured coating film of the above test piece was immersed in a solder bath at 260 ° C. for 30 seconds in accordance with the test method of JIS C-6481, the peeling test with a cellophane tape was set as one cycle, and this was repeated. The state of the coating film was visually observed and evaluated according to the following criteria.
A: No change is observed in the coating film after 3 cycles.
○: No change is observed in the coating film after 2 cycles, but a change is observed in the coating film after 3 cycles.
(Triangle | delta): Although a change is not recognized by the coating film after 1 cycle repetition, a change is recognized by the coating film after 2 cycles repetition.
X: Change is recognized in the coating film after repeating 1 cycle.

(4) Hiding power The hiding power of the cured coating film with respect to the circuit pattern which is copper foil was observed visually. Evaluation was performed according to the following criteria.
○: The conductor pattern cannot be visually recognized on the cured coating film.
X: A conductor pattern can be visually recognized from on a cured coating film.

  The evaluation results are shown in Tables 1 and 2 above.

  As shown in Tables 1 and 2, in Examples in which fatty acid amides were blended, the glossiness was reduced to 20 or less without deteriorating the solder heat resistance, and solder adhesion resistance due to the matte effect was obtained. . Moreover, in the said Example, in addition to the solder adhesion resistance by a matting effect, the outstanding insulation and hiding power were also obtained. In Examples 4 and 16, in which about 7.7 parts by mass of fatty acid amide was blended with 100 parts by mass of carboxyl group-containing photosensitive resin (solid content), examples in which about 1.5 parts by mass of fatty acid amide were blended. 3, 15 and compared with Examples 1, 2, 5-14, and 17 containing about 4.6 parts by mass of fatty acid amide, the glossiness is further reduced and the solder adhesion resistance due to the matte effect is further improved. I found out that

  Further, from the comparison between Examples 6 to 9 and Examples 10 to 12, a) the epoxy group of the epoxy resin having two or more epoxy groups in one molecule, b) the number of carbon atoms per carboxyl group is 10 Synthetic resin A in which d) a polybasic acid anhydride is added to the hydroxyl group of a long-chain fatty acid-modified ethylenically unsaturated group-containing modified epoxy resin obtained by reacting the above fatty acid with c) an ethylenically unsaturated group-containing carboxylic acid. Insulating properties were further improved. Further, from Example 11, when (A) the synthetic resin A is used as the carboxyl group-containing photosensitive resin and (E) the biphenyl aralkyl type epoxy resin is used as the epoxy compound, not only the insulation properties are further improved but also the solder heat resistance. Also improved. Furthermore, from the comparison between Example 12 and Example 13, as the compound having (D) an ethylenically unsaturated group, the hexafunctional acrylate was further improved in insulation and solder heat resistance than the trifunctional acrylate.

  On the other hand, in Comparative Examples 1 and 3 in which neither a fatty acid amide nor a filler was blended, the glossiness was not reduced, and solder adhesion resistance due to the matte effect was not obtained. In Comparative Examples 1 and 3, the hiding power was not obtained. Further, in Comparative Examples 2 and 4 in which a filler was blended in place of the fatty acid amide, the glossiness was reduced to 10 and solder adhesion resistance due to the matte effect was obtained, but insulation and hiding power were not obtained. It was.

  The photosensitive resin composition of the present invention is a cured product such as an insulation coating having excellent matting effect (low glossiness), solder adhesion resistance, insulation characteristics, and hiding power without impairing basic characteristics such as solder heat resistance. For example, the utility value is high in the field of solder-resist films.

Claims (4)

(A) a carboxyl group-containing photosensitive resin, (B) a fatty acid amide, (C) a photopolymerization initiator, (D) a compound having an ethylenically unsaturated group, (E) an epoxy compound, and (F) A photosensitive resin composition containing a colorant,
The (B) fatty acid amide is at least one selected from the group consisting of hexamethylene bisoleic acid amide and N-stearyl stearic acid amide,
The photosensitive resin composition, wherein the (B) fatty acid amide is contained in an amount of 1.0 to 5.0 parts by mass with respect to 65 parts by mass of the (A) carboxyl group-containing photosensitive resin .   (A) The carboxyl group-containing photosensitive resin is a) an epoxy group of an epoxy resin having two or more epoxy groups in one molecule, and b) at least 1 carbon number per carboxyl group is 10 or more. A fatty acid-modified ethylenically unsaturated group-containing modified epoxy resin is obtained by reacting a seed fatty acid with c) an ethylenically unsaturated group-containing carboxylic acid, and the fatty acid and / or the carboxyl group of the ethylenically unsaturated group-containing carboxylic acid The photosensitive resin composition according to claim 1, which is a resin obtained by adding d) a polybasic acid anhydride to a hydroxyl group generated by a reaction with an epoxy group of the epoxy resin. Wherein (F) the coloring agent, the photosensitive resin composition according to claim 1 or 2 characterized in that it is a black colorant. The printed wiring board which has a photocuring film of the photosensitive resin composition of any one of Claims 1 thru | or 3 .