JP6345947B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition, particularly a photosensitive resin composition useful as an insulating coating for circuit boards, and a flexible wiring board having a coating obtained by photocuring the photosensitive resin composition.

  As a material for the insulating coating (for example, solder resist) used for the flexible wiring board, an ultraviolet curable / thermosetting resin composition for forming the insulating coating is applied by a printing method such as screen printing. ing.

  In order to use an ultraviolet curable / thermosetting resin composition for insulation coating of flexible wiring boards, the cured coating film needs to be able to bend freely, that is, to have excellent flexibility. is there.

  Therefore, in Patent Document 1, in order to provide a cured coating film having excellent flexibility, (A) a photosensitive prepolymer having two or more unsaturated double bonds and one or more carboxyl groups in one molecule; A composition containing (B) a photopolymerization initiator, (C) a diluent, (D) an epoxy compound, (E) polybutadiene having one or more internal epoxide groups in one molecule, and (F) polyurethane fine particles. Proposed.

  On the other hand, a substrate for a flexible wiring board is also required to be excellent in flexibility, and a thermoplastic resin such as polyimide is mainly used as a material of a substrate that can be bent freely. However, although the polyimide substrate is excellent in flexibility, it has a characteristic that the shape in the folded state is difficult to be maintained. Therefore, when a polyimide substrate is bent, a large springback occurs, so that when a flexible wiring board is bent and inserted into an electronic device, the work efficiency is inferior and the storage property to the electronic device is insufficient. was there.

  Therefore, in recent years, there has been a demand for a resin composition for insulating coating that can suppress not only the flexibility of a cured coating film but also the spring back of a substrate for a flexible wiring board.

JP 2002-293882 A

  In view of the above circumstances, the object of the present invention is to provide photosensitivity capable of forming a cured coating film that has flexibility while reducing the springback property of the substrate without impairing basic properties such as sensitivity, developability, and tackiness. The object is to provide a resin composition.

  An object of the present invention is to increase the elasticity of a cured coating film by adding an elastic component, that is, to form a cured coating film having a characteristic of small distortion with respect to stress. Reduced.

  An aspect of the present invention includes (A) a carboxyl group-containing photosensitive resin, (B) urethane (meth) acrylate, (C) spherical silica, (D) an epoxy compound, and (E) a photopolymerization initiator. The photosensitive resin composition.

  Aspects of the present invention include: (A) the carboxyl group-containing photosensitive resin is (A-1) a carboxyl group-containing photosensitive resin that is an acid-modified urethanized epoxy (meth) acrylate resin; A-1) A photosensitive resin composition containing a carboxyl group-containing photosensitive resin other than a resin.

  An embodiment of the present invention is characterized in that 20 to 50 parts by mass of the (B) urethane (meth) acrylate is contained with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. It is.

  In an aspect of the present invention, the (B) urethane (meth) acrylate comprises (B-1) one or more aliphatic urethane structures in one molecule and 2 to 4 (meth) acryloyl groups in one molecule. It is the photosensitive resin composition characterized by including the urethane (meth) acrylate which has.

  In an aspect of the present invention, the (B) urethane (meth) acrylate comprises (B-2) one or more aliphatic urethane groups in one molecule and 5 to 7 (meth) acryloyl groups in one molecule. It is the photosensitive resin composition characterized by including the urethane (meth) acrylate which has.

  In the aspect of the present invention, the (B-1) urethane (meth) acrylate is 0.50 to 2.0 parts by mass with respect to 1.0 part by mass of the (B-2) urethane (meth) acrylate. It is a photosensitive resin composition characterized by being contained.

  An aspect of the present invention is a photosensitive resin composition characterized in that the spherical silica (C) is contained in an amount of 25 to 50 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin.

  The aspect of this invention is a flexible wiring board which has a film | membrane obtained by photocuring the said photosensitive resin composition.

  According to the aspect of the present invention, (A) the carboxyl group-containing photosensitive resin contains (B) urethane (meth) acrylate and (C) spherical silica, which are components having appropriate elasticity, so that the sensitivity, It is possible to obtain a cured coating film that has flexibility and can reduce the springback property of the substrate without impairing basic properties such as developability and tackiness.

  According to the aspect of the present invention, the (A) carboxyl group-containing photosensitive resin includes the carboxyl group-containing photosensitive resin that is (A-1) an acid-modified urethanized epoxy (meth) acrylate resin, thereby ensuring more certainty. A cured coating film having flexibility and capable of reducing the spring back property of the substrate can be obtained.

  According to the aspect of the present invention, (B) urethane (meth) acrylate is contained in an amount of 20 to 50 parts by mass with respect to 100 parts by mass of (A) carboxyl group-containing photosensitive resin, thereby providing better flexibility. A cured coating film can be obtained.

  According to an aspect of the present invention, (B) urethane (meth) acrylate comprises (B-1) one or more aliphatic urethane structures in one molecule and 2 to 4 (meth) acryloyl groups in one molecule. By including the urethane (meth) acrylate having, the flexibility of the cured coating film can be improved more reliably.

  According to an aspect of the present invention, (B) urethane (meth) acrylate comprises (B-2) one or more aliphatic urethane groups in one molecule and 5 to 7 (meth) acryloyl groups in one molecule. By including the urethane (meth) acrylate having, the flexibility of the cured coating film can be improved more reliably. Further, by using the urethane (meth) acrylate (B-1) and the urethane (meth) acrylate (B-2) in combination, the flexibility and the characteristic of reducing the spring back property of the substrate (hereinafter referred to as “spring”) The cured coating film can be obtained in a well-balanced manner, and the flexibility can be improved with a smaller amount of (B) urethane (meth) acrylate.

  According to the aspect of the present invention, the urethane (meth) acrylate of (B-1) is 0.50 to 2.0 parts by mass with respect to 1.0 part by mass of the urethane (meth) acrylate of (B-2). By being contained in a proportion, it is possible to obtain a cured coating film that is superior in both flexibility and springback properties.

  According to the aspect of the present invention, the cured coating having a more excellent spring back property can be obtained by including 25 to 50 parts by mass of (C) spherical silica with respect to 100 parts by mass of (A) carboxyl group-containing photosensitive resin. A membrane can be obtained.

  According to the aspect of the present invention, an insulating coating that has flexibility and can reduce the springback property of the substrate is provided by being coated with a coating obtained by photocuring the photosensitive resin composition. A flexible wiring board can be obtained.

  Next, the photosensitive resin composition of the present invention will be described below. The photosensitive resin composition of the present invention includes (A) a carboxyl group-containing photosensitive resin, (B) urethane (meth) acrylate, (C) spherical silica, (D) an epoxy compound, and (E) a photopolymerization initiator. The above components are as follows.

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

  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. These radically polymerizable unsaturated monocarboxylic acids may be used alone or in combination of two or more.

  It is not specifically limited to the reaction method of an epoxy resin and radically polymerizable unsaturated monocarboxylic acid, For example, it can be made to react by heating an epoxy resin and radically polymerizable unsaturated monocarboxylic acid in a suitable diluent. it can.

  The polybasic acid or polybasic acid anhydride is for reacting with a hydroxyl group produced by the reaction between the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid to introduce a free carboxyl group into the resin. 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.

  In the present invention, the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin can also be used as a carboxyl group-containing photosensitive resin. Carboxyl group-containing photosensitivity in which radically polymerizable unsaturated groups are further introduced by reacting a glycidyl compound having one or more radically polymerizable unsaturated groups and an epoxy group, thereby further improving photosensitivity. It is good also as resin.

  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. The photopolymerization reactivity is high, and the photosensitive property can be excellent. 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.

  (A) Acid-modified urethanized epoxy (meth) acrylate resin may be used as the (A) carboxyl group-containing photosensitive resin. In addition, (A) carboxyl group-containing photosensitive resin includes (A-1) acid-modified urethanized epoxy (meth) acrylate resin and (A-2) (A-1) acid-modified urethanized epoxy (meth) acrylate. Carboxy group-containing photosensitive resin other than resin (for example, reacting a glycidyl compound with the carboxyl group of the above-described polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin or the above-mentioned polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin) Thus, a resin in which a radical polymerizable unsaturated group is further introduced to improve the photosensitivity and a photosensitive resin containing a carboxyl group) may be used. The acid-modified urethane-modified epoxy (meth) acrylate resin can further contribute to obtaining a cured coating film that has flexibility and can also reduce the springback property of the substrate.

  (A-1) The acid-modified urethanized epoxy (meth) acrylate resin first obtains an epoxy (meth) acrylate as described above, and in the generated hydroxyl group, the polybasic acid or anhydride thereof and one molecule. It is obtained by reacting with a compound having two or more isocyanate groups.

  The compound having two or more isocyanate groups in one molecule is not particularly limited. For example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), methylene biscyclohexyl isocyanate, Examples of the diisocyanate include trimethylhexamethyl diisocyanate, hexane diisocyanate, hexamethylamine diisocyanate, methylenebiscyclohexyl isocyanate, toluene diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenylpropane diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethyl diisocyanate. These compounds may be used alone or in combination of two or more.

  In the present invention, the above-mentioned acid-modified urethanized epoxy (meth) acrylate resin can also be used as a carboxyl group-containing photosensitive resin, but if necessary, the carboxyl group of the above-mentioned acid-modified urethanized epoxy (meth) acrylate resin. Carboxyl group-containing photosensitivity with further improved photosensitivity by further introducing a radical polymerizable unsaturated group by reacting the glycidyl compound having one or more radical polymerizable unsaturated groups and an epoxy group. It is good also as resin.

  When (A-1) acid-modified urethane-modified epoxy (meth) acrylate resin is used in combination with (A-2) carboxyl group-containing photosensitive resin other than (A-1) acid-modified urethane-modified epoxy (meth) acrylate resin The blending ratio is not particularly limited, but the resin (A-2) is 0.2 to 2.2. 0 parts by mass is preferable, and 0.5 to 1.0 part by mass is particularly preferable.

  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.

  The weight 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 of the weight average molecular weight is preferably 200000 from the viewpoint of smooth alkali developability, and particularly preferably 50000.

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

(B) Urethane (meth) acrylate Urethane (meth) acrylate is blended with spherical silica, which will be described later, thereby contributing to obtaining a cured coating film having flexibility and reducing the spring back property of the substrate. . The urethane (meth) acrylate may be urethane (meth) acrylate obtained by reacting urethane with (meth) acrylic acid, which is a radically polymerizable unsaturated monocarboxylic acid, and is not limited to a specific compound. Urethane is obtained by reacting a compound having two or more isocyanate groups in one molecule with a polyol compound having two or more hydroxyl groups in one molecule.

  The compound having two or more isocyanate groups in one molecule is not particularly limited. For example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), methylene biscyclohexyl isocyanate, Examples of the diisocyanate include trimethylhexamethyl diisocyanate, hexane diisocyanate, hexamethylamine diisocyanate, methylenebiscyclohexyl isocyanate, toluene diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenylpropane diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethyl diisocyanate. These compounds may be used alone or in combination of two or more.

The polyol compound having two or more hydroxyl groups in one molecule is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2 -Butylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2- C ₂ − such as diethyl-1,3-propanediol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, etc. C ₂₂ or alkane diol, 2-butene-1,4-diol, 2,6-dimethyl-1 Aliphatic diols such as alkene diols such as octene-3,8-diol; Alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; Glycerin, 2-methyl-2-hydroxymethyl-1 , 3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol Aliphatic triols such as 2,4-dihydroxy-3- (hydroxymethyl) pentane and 2,2-bis (hydroxymethyl) -3-butanol; and hydroxyl groups such as tetramethylolmethane, pentaerythritol, dipentaerythritol and xylitol Polyols with 4 or more And the like. These compounds may be used alone or in combination of two or more.

  The number of (meth) acryloyl groups in one molecule of urethane (meth) acrylate is not particularly limited, but is preferably 2 to 7 in terms of improving the balance between flexibility and springback property, and flexibility and springback property. And urethane (meth) acrylate having 2 to 4 (meth) acryloyl groups in one molecule and 5 to 7 (meth) acryloyl groups in 1 molecule. It is preferable to use (meth) acrylate in combination.

  From the viewpoint of flexibility, the urethane is preferably an aliphatic urethane. Accordingly, (B-1) urethane (meth) acrylate having one or more aliphatic urethane structures in one molecule and 2 to 4 (meth) acryloyl groups in one molecule, and (B-2) one molecule It is particularly preferred to use urethane (meth) acrylate having one or more aliphatic urethane structures in the molecule and urethane (meth) acrylate having 5 to 7 (meth) acryloyl groups in one molecule.

  Mixing ratio when urethane (meth) acrylate having 2 to 4 (meth) acryloyl groups in one molecule and urethane (meth) acrylate having 5 to 7 (meth) acryloyl groups in one molecule are used in combination Although not particularly limited, 2 to 4 (meth) acryloyl groups per molecule are added to 1.0 part by mass of urethane (meth) acrylate having 5 to 7 (meth) acryloyl groups per molecule. The urethane (meth) acrylate is preferably from 0.30 to 3.0 parts by mass from the viewpoint of surely improving both flexibility and springback property, and from the point of improving both flexibility and springback property in a balanced manner. 50 to 2.0 parts by mass is more preferable, and 1.5 to 2.0 parts by mass from the viewpoint that both flexibility and springback are more balanced and excellent. Particularly preferred.

  Although the compounding quantity of the said urethane (meth) acrylate is not specifically limited, 5 mass parts is the minimum from the point which improves a softness | flexibility and springback property reliably with respect to 100 mass parts of carboxyl group-containing photosensitive resin. Preferably, 20 parts by mass is more preferable, and 25 parts by mass is particularly preferable from the viewpoint of further improving flexibility. On the other hand, the upper limit is preferably 50 parts by mass from the viewpoint of photosensitivity.

(C) Spherical silica Spherical silica functions as a filler (filler) and is blended with the urethane (meth) acrylate described above, so that it has flexibility and can also suppress the spring back property of the substrate. Contributes to Moreover, even if a flexible wiring board is bent, it can prevent that a crack generate | occur | produces in a cured coating film because the shape is a spherical shape which does not have a corner | angular part. The kind of spherical silica is not specifically limited, A well-known thing can be used. Examples of the spherical silica include dry silica (fumed silica), wet silica, and sol-gel silica.

  The average particle diameter of the spherical silica is not particularly limited, but the lower limit is preferably 0.01 μm from the point of kneadability accompanying bulk specific gravity, and particularly preferably 0.5 μm from the point of dispersibility. On the other hand, the upper limit is preferably 5.0 μm from the viewpoint of the flexibility of the cured coating film, and is particularly preferably 1.0 μm from the viewpoint of goby folding that requires more flexibility.

  The blending amount of the spherical silica is not particularly limited, but the lower limit is preferably 15 parts by weight with respect to 100 parts by weight of the carboxyl group-containing photosensitive resin from the viewpoint of surely improving both flexibility and springback property. From the point which improves the property more, 25 mass parts is more preferable, and 35 mass parts is especially preferable. On the other hand, the upper limit value is preferably 50 parts by mass from the viewpoint of reliably preventing a decrease in springback property, and particularly preferably 40 parts by mass from the viewpoint of reliably preventing a decrease in flexibility.

(D) Epoxy compound The epoxy compound is for increasing the cross-linking density of the cured coating film to obtain a cured coating film having sufficient strength. For example, an epoxy resin is added. Examples of the epoxy resin include bisphenol A type epoxy resin, novolak type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, p-tert-butylphenol novolak type, etc.), bisphenol F and bisphenol S with epichlorohydrin. Bisphenol F-type and bisphenol S-type epoxy resins obtained by reaction, alicyclic epoxy resins having cyclohexene oxide groups, tricyclodecane oxide groups, cyclopentene oxide groups, and the like, tris (2,3-epoxypropyl) isocyanurate , Triglycidyl isocyanurate having a triazine ring such as triglycidyl tris (2-hydroxyethyl) isocyanurate, dicyclopentadiene type epoxy resin, Adama It can be exemplified Tan type epoxy resin. 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 a coating film with sufficient intensity | strength after hardening, 10-50 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing photosensitive resin, and 20-40 masses. Part is particularly preferred.

(E) Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it is generally used. For example, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Oxime initiators such as carbazol-3-yl] -1- (0-acetyloxime), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (methylthio) pheny ] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichloro Benzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Examples include diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, and P-dimethylaminobenzoic acid ethyl ester. These may be used alone or in combination of two or more.

  Although the content of the photopolymerization initiator is not particularly limited, it is preferably 5 to 20 parts by mass and particularly preferably 7 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin.

  In the photosensitive resin composition of the present invention, in addition to the above components, various components, for example, various additives, diluents (solvents), ion exchangers (ion catchers), extender pigments, A colorant, a flame retardant, an antifoaming agent, and the like can be appropriately contained.

  Examples of the various additives include latent curing agents such as dicyandiamide and derivatives thereof, melamine and derivatives thereof, antioxidants, and coupling agents.

  A diluent (solvent) is for adjusting the viscosity and drying property of the photosensitive resin composition. Examples of the diluent include an organic solvent that is a non-reactive diluent. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, 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, butyl cellosolve acetate, carbitol acetate, butylcarbi Examples include esters such as tall acetate, ethyl diglycol acetate, and diethylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more.

Ion exchanger (ion catcher)
Ion exchangers (ion catchers), in particular inorganic cation exchangers (cation catchers), take in cations, so they capture cation impurities such as sodium ions remaining in the photosensitive resin composition of the present invention. In addition to fixing, by applying a voltage, metal ions that move and become cations are captured and fixed. Thereby, generation | occurrence | production of the ion migration phenomenon in the hardened | cured material of the photosensitive resin composition can be prevented. By preventing the occurrence of the ion migration phenomenon, for example, a solder resist film formed by applying the photosensitive resin composition of the present invention to a flexible wiring board can exhibit excellent insulation reliability. .

  Examples of the inorganic cation exchanger include oxides of at least one element selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum.

  The extender pigment is for increasing the strength and rigidity of the cured product, and examples thereof include barium sulfate, aluminum hydroxide, alumina, talc, and mica. The colorant is not particularly limited. For example, titanium oxide which is a white colorant, phthalocyanine type such as phthalocyanine green and phthalocyanine blue, anthraquinone type, azo type organic pigments, carbon, etc. Mention may be made of inorganic pigments such as black.

  When the photosensitive resin composition of the present invention contains a flame retardant, flame retardancy can be imparted to the cured product. A flame retardant is not specifically limited, A well-known thing can be used. Examples of the flame retardant include a phosphorus element-containing organic compound. Examples of the phosphorus element-containing organic compound include aluminum trisdiethylphosphinate and aluminum trismethylethylphosphinate. The antifoaming agent is not particularly limited, and examples thereof include silicone polymers, hydrocarbons, and acrylics.

  The manufacturing method of the above-described photosensitive resin composition of the present invention is not limited to a specific method. For example, the above-described components may be mixed and dispersed with a three roll at room temperature after being blended at a predetermined ratio. it can. Moreover, you may pre-mix with a stirrer before the said mixing dispersion | distribution as needed.

  Next, the usage method of the above-mentioned photosensitive resin composition of this invention is demonstrated. Here, a method of applying the photosensitive resin composition of the present invention to a circuit board as an insulating coating such as a solder resist film will be described as an example. The photosensitive resin composition of the present invention obtained as described above is applied to a desired thickness using, for example, a screen printing method on a flexible wiring board having a circuit pattern formed by etching a copper foil. When a diluent (solvent) is added, 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 diluent (solvent) in the photosensitive resin composition. . Then, the negative film which has the pattern which made translucent except the land of the said circuit pattern is closely_contact | adhered on the apply | coated photosensitive resin composition, and an ultraviolet-ray 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, for example, a spray method, a shower method, or the like is used. As the dilute alkaline aqueous solution, for example, a 0.5 to 5% sodium carbonate aqueous solution can be used. Subsequently, by performing post-cure for 20 to 80 minutes with a hot air circulation dryer or the like at 130 to 170 ° C., an intended insulating coating such as a solder resist film can be formed on the flexible wiring board.

  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 1-9, Comparative Examples 1-4
Each component shown in the following Table 1 is blended in the blending ratio shown in the following Table 1, mixed and dispersed at room temperature using three rolls, and used in Examples 1 to 9 and Comparative Examples 1 to 4. A functional resin composition was prepared. And the prepared photosensitive composition was apply | coated as follows and the test piece was created. The numbers in Table 1 below indicate parts by mass. Moreover, the blank in Table 1 below means no blending.

The details of each component in Table 1 are as follows.
(A) Carboxyl group-containing photosensitive resin / FLX-2089, ZAR-2000: Isuzu, manufactured by Nippon Kayaku Co., Ltd.
(B) Urethane (meth) acrylate · KRM-8296, EBECRYL5129: All are manufactured by Daicel Ornex.
(C) Spherical silica / Sciqas 0.05 μm: manufactured by Sakai Chemical Industry.
(D) Epoxy compound EPICRON 860: manufactured by DIC Corporation.
(E) Photopolymerization initiator / chemcure DETX: manufactured by Nippon Shibel Hegner.
・ IRGACURE907: Ciba Specialty Chemicals.

Additives / Melamine: manufactured by Nissan Chemical Industries, Ltd.
-DICY-7: manufactured by Mitsubishi Chemical Corporation.
Diluent / EDGAC: Made by Sanyo Chemical.
Ion catcher IXE-100: manufactured by Toagosei Co., Ltd.
Extender pigment, Heidilite H-42STV: manufactured by Showa Denko K.K.
Colorant / LIONOL BLUE FG7351: Made by Toyo Ink Manufacturing Co., Ltd.
・ Chromophthal yellow: manufactured by Ciba Specialty Chemicals.
Flame retardant, Exolit OP 935: manufactured by Clariant Japan.
Antifoaming agent, KS-66: manufactured by Shin-Etsu Chemical Co., Ltd.

(Meth) acrylates other than (B) M-600: manufactured by Toyo Chemicals.
Fillers other than (C) RHC-730 CLEAR: manufactured by Dainichi Seika Kogyo Co., Ltd.

Test piece preparation process A flexible printed circuit board with a circuit pattern (copper foil) formed on a polyimide film (Kapton 100H, manufactured by Toray DuPont Co., Ltd.) is surface-treated with a 3% dilute sulfuric acid aqueous solution, and then screen-printed. After applying the composition, preliminary drying was performed at 80 ° C. for 20 minutes in a BOX furnace. After the preliminary drying, a negative film having a predetermined pattern is closely adhered to the coating film, and then ultraviolet rays with a main peak wavelength of 365 nm are applied at 200 mJ / cm ² (Oh) by an exposure apparatus (HMW-680GW manufactured by Oak Co.). (Measured using an integrated actinometer manufactured by Kumanu) and irradiated. After irradiation, development is performed with a 1% by weight sodium carbonate developer at 30 ° C. (60 seconds at a spray pressure of 2.0 kg / cm ² ), and post-curing is performed at 150 ° C. for 60 minutes in a BOX furnace. A cured coating film was formed on the flexible wiring board. The thickness of the cured coating film was 20-23 μm.

Evaluation (1) Sensitivity Step sensitivity tablets (21 stages manufactured by Kodak Co., Ltd.) are placed on the coating film on the wiring board that has been subjected to the preliminary drying process in the test piece preparation process. The test piece was obtained by irradiating ultraviolet light having a wavelength of 365 nm with an irradiation light quantity of 200 mJ / cm ² using an integrating light quantity meter manufactured by Oak Manufacturing Co., Ltd. The test piece was developed for 60 seconds at a spray pressure of 2.0 kg / cm ² using a 1% by mass aqueous sodium carbonate solution. After development, the portion of the exposed portion that was not removed was calculated as a number (number of steps). The larger the number of steps, the better the photosensitive characteristics. The evaluation was performed in three stages: ◯: 8 or more stages, Δ: 6 to 7 stages, ×: 5 stages or less.

(2) Springback property Based on the above-mentioned test piece preparation process, it is cured on a flexible wiring board (1.5 cm × 4 cm, single-sided copper foil thickness 18 μm, polyimide thickness 25 μm) on which a circuit pattern (copper foil) is formed. About the test piece which formed the film | membrane, it bent at 180 degrees for 5 second by the goblet folding once with a 500-g load. Thereafter, the load was released and the bending angle was returned to 90 °. Next, the test piece was allowed to stand at room temperature for 30 minutes. After standing, the difference in angle with respect to 90 ° was measured with a protractor. The evaluation was performed in four stages: ◎: less than 5 °, ◯: angle of 5 ° to less than 10 °, Δ: angle of 10 ° to less than 15 °, and x: angle of 15 ° or more.

(3) Bending property About the test piece produced in the above-mentioned test piece production process, 180 ° bending is repeated several times by goby folding, and the crack generation state in the cured coating film at that time is visually observed with an optical microscope of × 200. Observe and measure the number of times cracks did not occur. The evaluation was performed in three stages: ◯: 2 times or more, Δ: 1 time, x: 0 times.

(4) Developability After development in the test piece preparation step, the presence or absence of residue on the copper body and polyimide was visually observed. Evaluation: ○: No residue on copper body and polyimide, △: No residue on copper body, but a little residue on polyimide, ×: Residue on both copper body and polyimide, Performed in three stages.

(5) Tackiness After preliminary drying in the above test piece preparation step, the negative film was brought into close contact with the coating film, and the adhesion of the photosensitive resin composition after exposure to ultraviolet rays was visually observed. Evaluation: ○: After peeling off the negative film, both sticking and sticking marks were left. Δ: After peeling off the negative film, sticking marks remained on the coating film. ×: Photosensitive resin composition on the negative film after peeling off the negative film. Was performed in three stages.

  The evaluation results are shown in Table 2 below.

  As shown in Table 2, in Examples 1 to 9 in which urethane (meth) acrylate and spherical silica were blended, the bendability (flexibility) and the springback property were obtained without impairing the basic characteristics of sensitivity, developability and tackiness. It was possible to obtain a cured coating film having By using together urethane acrylate having 6 acryloyl groups in one molecule and urethane (meth) acrylate having 3 acryloyl groups in one molecule from Examples 1, 3, 4 and Examples 5 and 6, a spring The back property was further improved, and from Examples 7 and 8, the combined use also improved the flexibility.

  Further, from Example 1 and Examples 3 and 4, urethane (meth) acrylate having 3 acryloyl groups in one molecule is obtained with respect to 1.0 part by mass of urethane acrylate having 6 acryloyl groups in one molecule. By being contained at a ratio of 2.0 parts by mass, the spring is compared with the one containing 0.5 to 1.0 parts by mass of urethane (meth) acrylate having three acryloyl groups in one molecule. A cured coating film with better backability could be obtained. From Examples 3 and 7, when about 28 parts by mass of urethane (meth) acrylate is blended with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin, the springback property is more than that of about 19 parts by mass. Improved.

  From Examples 1 and 2, when about 44 parts by mass of spherical silica was blended with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin, the springback property was further improved as compared with the case where about 22 parts by mass was blended.

  On the other hand, from Comparative Examples 1 to 4, when other fillers were blended without blending spherical silica as a filler, the spring back property was not obtained. From Comparative Examples 3 and 4, if the urethane acrylate having 6 acryloyl groups in one molecule and the urethane (meth) acrylate having 3 acryloyl groups in one molecule were not used in combination, the sensitivity was lowered. Moreover, in Comparative Examples 1-4, tackiness fell compared with Examples 1-9.

  Since the present invention provides a photosensitive resin composition capable of obtaining a cured coating film having bendability (flexibility) and springback properties without impairing basic properties such as sensitivity, developability and tackiness, The utility value is particularly high in the field of flexible wiring boards that require a soft structure.

Claims (7)

(A) a carboxyl group-containing photosensitive resin, (B) a urethane (meth) acrylate, a (C) spherical silica, (D) an epoxy compound, (E) including sensitive optical resin composition a photoinitiator ,
The (B) urethane (meth) acrylate is (B-1) urethane (meth) acrylate having one or more aliphatic urethane structures in one molecule and 2 to 4 (meth) acryloyl groups in one molecule. And (B-2) urethane (meth) acrylate having one or more aliphatic urethane groups in one molecule and 5 to 7 (meth) acryloyl groups in one molecule,
The photosensitive resin composition is characterized in that 15 to 50 parts by mass of the (C) spherical silica is contained with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin.   The (A) carboxyl group-containing photosensitive resin is (A-1) a carboxyl group-containing photosensitive resin which is an acid-modified urethanized epoxy (meth) acrylate resin, and (A-2) other than the (A-1) resin. The photosensitive resin composition according to claim 1, comprising a carboxyl group-containing photosensitive resin.   The photosensitive resin according to claim 1, wherein 20 to 50 parts by mass of the (B) urethane (meth) acrylate is contained with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. Composition. The (B-1) urethane (meth) acrylate is contained at a ratio of 0.50 to 2.0 parts by mass with respect to 1.0 part by mass of the (B-2) urethane (meth) acrylate. The photosensitive resin composition according to any one of claims 1 to 3 . Wherein per 100 parts by mass of (A) a carboxyl group-containing photosensitive resin, the (C) photosensitive according to any one of claims 1 to 4 spherical silica is characterized in that it included 25 to 50 parts by weight Resin composition. The photosensitive resin composition according to any one of claims 1 to 5, which is used for a cured coating film having springback properties. The flexible wiring board which has a membrane | film | coat obtained by photocuring the photosensitive resin composition of any one of Claims 1-6 .