TWI443454B - Photosensitive composition, solder resist and photosensitive dry film - Google Patents

Description

Photosensitive composition, solder resist and photosensitive dry film

The present invention relates to a photosensitive composition which can form a fine pattern by exposure and development, and uses a solder resist and a photosensitive dry film of the compositions. In particular, the present invention relates to a photosensitive composition which can obtain a cured product excellent in flame retardancy, flexibility, heat resistance, adhesion to metal, and electrical insulation, and uses the solder resist and photosensitive of the compositions. Dry film. The photosensitive composition of the present invention can be used as a photoresist material, and in particular, it can be used as an insulating material and a solder resist material for a printed wiring board, and can be used in the field of electrical and electronic materials.

Recently, with the demand for a large number of functions, high integration, thinning, and reduction in size and weight of electronic devices, wiring patterns have been increasing in density in printed wiring boards, and expansion is required to be thin and flexible. Wiring board (hereinafter referred to as FPC). Along with this, in addition to the higher resolution and high reliability required for the photoresist material used in the manufacture of the wiring board, it is necessary to have flexibility of the photoresist itself in accordance with the FPC.

In addition, most of the components used in electronic equipment are obligated to impart flame retardancy in accordance with UL specifications in order to ensure safety. In particular, in FPC, since the fire extinguishing effect of the substrate is small compared with the printed wiring board, the photoresist used in the FPC itself requires high flame retardancy.

A flame retardant solder used in the manufacture of printed wiring boards has been proposed so far. A brominated epoxy compound and a ruthenium compound are produced as a flame retardant (Patent Document 1).

However, although a composition containing a halogen such as bromine exhibits a high flame retarding effect, on the other hand, since harmful dioxin compounds are generated during combustion, in recent years, non-halogenation of materials has been demanded.

An inorganic hydroxide (Patent Document 2), a phosphorus-based flame retardant composed of a phosphate ester (Patent Document 3), and a hydrated metal compound and a nitrogen compound are known as a non-halogen-based flame retardant composition (Patent Literature) 4). However, the inorganic filler component such as an inorganic hydroxide (hydrated metal compound) has a lower flame retarding effect than a halogen-based flame retardant or a phosphorus-based flame retardant, and if it is formulated to sufficiently obtain a flame retardant effect, There is a problem of reduced insulation reliability. Further, especially when used in FPC applications, if the filler component is large, the cured product loses flexibility and the substrate is bent. On the other hand, the phosphorus-based flame retardant composed of a phosphate ester has a relatively high flame retarding effect, and generally, a sufficient flame retardancy can be obtained with a smaller amount than the inorganic hydroxide. However, a flame retardant such as a phosphate ester also has a problem of lowering heat resistance or insulation reliability. Further, in particular, the resolution at the time of exposure development is greatly lowered.

Phosphonates are also known as phosphorus-based flame retardants (Patent Document 5).

Patent Document 1: Japanese Patent Publication No. 11-242331 Patent Document 2: JP-A-2006-194968 Patent Document 3: JP-A-2001-183819 Patent Document 4: JP-A-2004-12810 Patent Document 5: JP-A-2003-301013

As described above, the conventional solder resist composition is still problematic in that it is suitable for a thin printed wiring board or FPC while maintaining flame retardancy.

The inventors of the present invention have been found to have sufficient flame retardancy, and are excellent in resolution and storage stability, and the properties necessary for the solder resist, the heat resistance and the electrical insulating properties are maintained, and the flexibility is also excellent. Further, it can be widely used for a photosensitive composition containing a non-halogen-based flame retardant on a thin printed wiring board or an FPC board.

In order to solve the above problem, the photosensitive composition of the present invention described in claim 1 contains the compound (A) having a carboxyl group derived from an epoxy compound skeleton and having a carboxyl group and a radical polymerizable group, and an urethane amide ( B) A polymerizable compound (C) other than (A) and (B) having a radical polymerizable group, a filler (D) containing a phosphorus atom, and a photopolymerization initiator (E).

The photosensitive composition of the present invention described in claim 2 is the invention of claim 1, wherein the composition of the component (A) and the component (B) is 100 parts by mass based on 100 parts by weight. Parts by mass (A), 10 to 80 parts by mass of component (B), and 5 to 50 parts by mass of component (C).

The photosensitive composition of the present invention according to the third aspect of the invention is the invention of claim 1, wherein the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass. As a standard, it contains 1 to 150 parts by mass of the component (D).

The photosensitive composition of the present invention according to claim 4, which is the invention of claim 1, wherein the compound having a skeleton derived from an epoxy compound and having a carboxyl group and a radical polymerizable group (A) A compound obtained by subjecting an epoxy compound to an unsaturated monocarboxylic acid to an addition reaction and subjecting the produced hydroxyl group to a polybasic acid anhydride.

The photosensitive composition of the present invention according to claim 5, wherein the urethane urethane (B) is a compound having a polycarbonate polyol skeleton.

The photosensitive composition of the present invention according to claim 6 is the invention of claim 1, wherein the urethane acrylate (B) is a polycarbonate polyol skeleton having no carboxyl group. Compound.

The photosensitive composition of the present invention described in claim 7 is the invention of claim 6, wherein the urethane amide having a compound of a polycarbonate polyol skeleton having no carboxyl group ( B) has a mass average molecular weight of 2,000 to 50,000.

The photosensitive composition of the present invention described in claim 8 is the invention according to the first aspect of the invention, wherein the polymerizable compound other than (A) and (B) having a radical polymerizable group is C) is a compound having three or more (meth) acrylonitrile groups in one molecule.

The photosensitive composition of the present invention described in claim 9 is the invention according to the first aspect of the invention, wherein the filler (D) containing a phosphorus atom is a metal salt of an oxyacid of phosphorus.

The photosensitive composition of the present invention as set forth in claim 10 is the invention of claim 1, wherein the filler (D) containing a phosphorus atom is a metal salt of a phosphonic acid.

The photosensitive composition of the present invention described in claim 11 is the invention according to claim 1, wherein the filler (D) containing a phosphorus atom is an aluminum salt of a phosphonic acid.

The photosensitive composition of the present invention described in claim 12 is the invention according to the first aspect of the invention, and further contains a phosphorus compound (F) other than the filler (D) containing a phosphorus atom.

The solder resist of the present invention according to claim 13 is characterized in that the photosensitive composition according to any one of claims 1 to 12 is contained.

The photosensitive dry film of the present invention described in claim 14 is characterized in that a coating film containing the photosensitive composition according to any one of claims 1 to 12 is formed on a support film.

The invention is described in detail below.

Further, in the present specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. Further, the propylene group and the methacryl group are collectively referred to as (methyl group). ) propylene based.

According to the present invention, it is possible to obtain a photosensitive composition which is excellent in flame retardancy, flexibility, heat resistance and electrical insulating properties, and which is excellent in resolution and storage stability, without using a flame retardant containing a halogen atom.

In addition, the component (B) and the component (B) and 5 to 50 parts by mass of the component (A) and 10 to 80 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). In the case of the component (C), it is possible to obtain a photosensitive composition which is sufficiently developed by an aqueous alkaline solution and which has sufficient flexibility of the cured coating film.

In addition, when the component (D) is contained in an amount of from 1 to 150 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (C), the flame retardancy improvement effect is sufficiently sufficient. A photosensitive composition in which the physical properties of the cured coating film such as flexibility or insulation reliability are not lowered.

Further, the compound (A) having a carboxyl group and a radical polymerizable group derived from a skeleton of an epoxy compound is subjected to an addition reaction of an epoxy compound and an unsaturated monocarboxylic acid, and the generated hydroxyl group and the polybasic acid anhydride are subjected to an addition reaction. When the compound obtained by the addition reaction is used, it is a photosensitive composition which is excellent in the resolvability and the softness of the cured product.

In addition, when the urethane urethane (B) is a compound having a polycarbonate polyol skeleton, it can be a photosensitive composition excellent in insulation reliability of a cured product.

Further, when the urethane urethane (B) is a compound having a polycarbonate polyol skeleton having no carboxyl group, it can be water resistance of the cured product. And the insulation relies on the 'sensitive sensitization' twin composition.

In addition, when the mass average molecular weight of the urethane urethane (B) having a compound having a polycarbonate polyol skeleton having no carboxyl group is 2,000 to 50,000, it is excellent in the resolution and the softness of the cured product. Sexual composition.

In addition, when the polymerizable compound (C) other than (A) and (B) having a radical is a compound having three or more (meth)acryl fluorenyl groups per molecule, the cured product can be made high. A photosensitive composition that is insulating and reliable.

In addition, when the filler (D) containing a phosphorus atom is a metal salt of phosphorus oxyacid, it can be used as a photosensitive composition which is excellent in resolution and has high flame retardancy and insulation reliability.

In addition, when the filler (D) containing a phosphorus atom is a metal salt of a phosphonic acid, it is excellent in resolution, and the cured product has a photosensitive composition having higher flame retardancy and insulation reliability.

In addition, when the filler (D) containing a phosphorus atom is an aluminum salt of a phosphonic acid, it can become a photosensitive composition which is especially excellent in resolution, and the hardened|cured material has the outstanding high flame retardance and insulation reliability.

In addition, when the phosphorus compound (F) other than the filler (D) containing a phosphorus atom is contained, it is possible to obtain a photosensitive composition which is more effective and has a high flame retardancy.

The solder resist of the present invention can be used for processing of a thin printed wiring board or an FPC substrate.

The photosensitive dry film of the invention is preferably used as an electronic material

[Best Mode for Carrying Out the Invention] 1. (A) ingredients

The component (A) is a compound having a carboxyl group derived from an epoxy compound skeleton and a radical polymerizable group.

As the component (A), various compounds can be used. Preferred examples are, for example, reacting an epoxy compound (epoxy resin) with an unsaturated monocarboxylic acid to produce a compound having a hydroxyl group, or a part of the hydroxyl group of the compound having a hydroxyl group or A reaction product obtained by subjecting all of a saturated or unsaturated polybasic acid anhydride (hereinafter referred to as a polybasic acid anhydride) to an addition reaction.

Examples of the epoxy resin used in this case are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and cresol novolac type epoxy resin. And polyphenol type epoxy resin and the like.

Examples of the unsaturated monocarboxylic acid are acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.

The polybasic acid anhydrides are maleic anhydride, succinoic acid, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride.

The reaction ratio of the polybasic acid anhydride to the compound having a hydroxyl group is not particularly limited, but the polybasic acid anhydride is preferably from 0.1 to 1.0 mol, more preferably from 0.2 to 0.9 mol, based on 1 mol of the hydroxyl group of the compound having a hydroxyl group. If the ratio is less than 0.1 mol, the alkali-developing property of the photosensitive composition is lowered due to insufficient solubility in the lye. On the other hand, if the ratio exceeds 1.0 In the case of the ear, there is a concern that the unreacted polybasic acid anhydride remains, and the unreacted polybasic acid anhydride is crystallized, or in most cases, the composition is preserved due to the reaction between the residual hydroxyl group and the unreacted polybasic acid anhydride during storage. Concerns about reduced stability.

In the above, the component (A) is preferably a bisphenol epoxy (meth)acrylate having a carboxyl group in order to provide excellent resolution and softness of the cured product. The epoxy (meth) acrylate is a compound having a structure obtained by subjecting an epoxy compound and (meth)acrylic acid to an addition reaction.

2. (B) ingredients

The component (B) is a (meth)acrylic acid urethane compound.

As the component (B), various commercially available products can be used, and examples thereof include a reaction product of a polyhydric alcohol with a polyvalent isocyanate and a hydroxyl group-containing (meth) acrylate.

In the above, the component (B) is excellent in insulation reliability of the cured product, and therefore it is preferably a (meth)acrylic acid urethane having a polycarbonate polyol skeleton.

A (meth)acrylic acid urethane having a polycarbonate polyol skeleton can also be used in various commercial products, for example, a reaction of a polycarbonate polyol with a polyvalent isocyanate and a hydroxyl group-containing (meth) acrylate can be used. Product, etc.

Examples of the polycarbonate polyol are exemplified by a carbonate having an alkyl group, an alkyl group, an aromatic hydrocarbon group, a cycloalkane hydrocarbon group, or the like, and an alkyl group having an alkyl group and an alkyl group. A polycarbonate polyol obtained by reacting a polyhydric alcohol such as an aromatic hydrocarbon group or a cycloalkane hydrocarbon group.

Preferable specific examples of the carbonate are, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, and dicyclohexyl carbonate.

Further, preferred specific examples of the polyhydric alcohol are, for example, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,5-pentane 2 Alcohol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polycaprolactone diol, trimethyl hexane diol, and 1,4-butanediol.

Here, the carbonate and the polyhydric alcohol may be used alone or in combination of two or more kinds of molecular weights or compositions.

Preferred polyvalent isocyanates are toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like.

Preferred (meth) acrylates having a hydroxyl group are hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

In the above, the (B) component is excellent in water resistance and insulation reliability of the cured product, and therefore it is preferably a (meth)acrylic acid urethane having no carboxyl group.

Preferably, the component (B), that is, the aminomethyl (meth)acrylate having no carboxyl group, has a mass average molecular weight of preferably 2,000 to 50,000, more preferably 5,000 to 20,000, and if the mass average molecular weight is less than 2,000, Sometimes hard The softness of the compound is insufficient, and on the other hand, if it exceeds 50,000, the resolution is lowered, which is not preferable.

The preferred blending ratio of the component (A) and the component (B) is 100 parts by mass of the total of the components (A) and (B), and the component (A) is in the range of 20 to 90 parts by mass. When the amount is less than 20 parts by mass, the development property of the alkaline aqueous solution is insufficient, and when it exceeds 90 parts by mass, the softness of the cured product is insufficient. A better range is 40 to 80 parts by mass.

3. (C) ingredients

The component (C) is a polymerizable compound other than (A) and (B) having a free polymerizable group.

The radical polymerizable group which the (C) component has may be preferably a radical polymerizable carbon-carbon double bond, and the most preferred one is an acrylonitrile group, a methacryl fluorenyl group, an allyl group or a vinyl group. Wait.

Specific examples of the polymerizable compound (C) having one radical polymerizable group may, for example, be methyl (meth)acrylate, butyl (meth)acrylate, or 2-ethylhexyl (meth)acrylate, ( A functional group (meth) acrylate such as hydroxyethyl methacrylate or hydroxypropyl (meth) acrylate; a compound having a vinyl group such as styrene; and a compound having an allyl group such as allyl phenol.

Specific examples of the polymerizable compound (C) having two radical polymerizable groups are 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, and poly Ethylene glycol di(meth)acrylate and poly a di(meth)acrylate such as propylene glycol di(meth)acrylate; a vinyl compound such as divinylbenzene; and an allyl compound such as diallyl phthalate.

Specific examples of the polymerizable compound (C) having three or more radical polymerizable groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(methyl). ) acrylate and triallyl isocyanurate.

In order to obtain a cured product having high insulation reliability, a compound having three or more radical polymerizable groups is preferably used as the component (C). More preferably, it is a compound which has three or more (meth) propylene groups in one molecule.

The preferred blending ratio of the component (C) is 5 to 50 parts by mass, particularly in the range of 5 to 20 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When the ratio is less than 5 parts by mass, the crosslinking density of the cured product becomes insufficient, and solder heat resistance or insulation reliability is lowered. When the ratio exceeds 50 parts by mass, the softness of the cured product is lowered.

4. (D) ingredients

(D) The component is a filler containing a phosphorus atom. In the present invention, the filler means that it is insoluble in the photosensitive composition and is dispersed, that is, it is solid at normal temperature (10 to 30 ° C). Ingredient (D) is a component which imparts flame retardancy to the composition.

As a filler containing a phosphorus atom as a flame retardant component, it is incompatible with a resin component, an organic solvent, or the like in the composition, and is used as a microparticle. The physical properties of the composition of the resin [component (A), (B), (C)] or the cured product, especially the photosensitivity or the solubility to the developing solution, may be small, and used as a photoresist. It exhibits high resolution. Further, those having a phosphorus atom can obtain a high flame retardancy at a low dosage compared with an inorganic hydroxide-like filler.

Specific examples of the filler containing a phosphorus atom are exemplified by a phosphonate compound, a diethylphosphonate compound, a dibutylphosphonate compound, a dihydroxymethylphosphonate compound, ammonium polyphosphate, melamine polyphosphate, and phosphoric acid. Hey.

As the component (D), in order to impart high resolution to the photosensitive composition and to have high flame retardancy and insulation reliability of the cured product, it is preferred to use a metal salt of phosphorus oxyacid, and it is preferable to use phosphine. A metal salt of an acid. In the present invention, the phosphonic acid means a group of compounds which are collectively referred to as a phosphonic acid or a compound in which one or two hydrogen atoms bonded to a phosphorus atom of a phosphonic acid are substituted by an alkyl group, an aryl group or a halogen atom. The above alkyl group and aryl group may have a substituent such as a hydroxyl group or an alkoxy group.

Examples of the phosphonic acid can be exemplified by phosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, methylphosphonic acid, dimethylphosphonic acid, ethylphosphonic acid, diethylphosphonic acid, butylphosphonic acid, and dibutyl. Phosphonic acid, phenylchlorophosphonic acid, dihydroxymethylphosphonic acid, and the like.

Examples of the phosphorus oxyacid include, in addition to the above phosphonic acids, hypophosphorous acid, phosphoric acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, peroxyphosphoric acid, peroxydiphosphate, diphosphoric acid, dithiophosphoric acid, and phenyl. Hypophosphorous acid, methyl hypophosphorous acid, ethyl hypophosphorous acid, hydroxymethyl hypophosphorous acid, and the like.

Further, the element constituting the metal salt can be exemplified by an alkali metal such as sodium, magnesium, or the like. An alkaline earth metal, a metal element such as aluminum belonging to Group 13 of the periodic table, and a transition metal element such as iron belonging to Group 8 of the periodic table, as a metal, particularly an aluminum salt, can make the composition have high resolution and easy It is preferably a cured product having high flame retardancy and insulation reliability, and is preferably an aluminum phosphonate salt.

The component (D) preferably has an average particle diameter of 0.5 to 15 μm, especially 1 to 5 μm. If the average particle diameter exceeds 15 μm, the flexibility may be deteriorated. Further, in particular, when a photosensitive dry film which is a film having a film thickness of 50 μm or less is used, the surface state of the film may be deteriorated. On the other hand, when the average particle diameter is less than 0.5 μm, since the bulk density of the film containing a phosphorus atom becomes small, it is difficult to disperse the filler containing a phosphorus atom in other components.

The amount of the component (D) is preferably from 1 to 150 parts by mass, more preferably from 10 to 100 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C). When the amount is less than 1 part by mass, the effect of improving the flame retardancy may be insufficient. On the other hand, when it exceeds 150 parts by mass, physical properties such as flexibility of the cured product or insulation reliability may be lowered.

5. (E) ingredients

The component (E) is a photopolymerization initiator.

(E) The component is a radical polymerization which can be initiated by irradiation with ultraviolet rays or the like, and specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like. Occasion and benzoin alkyl ethers; acetophenone, 2,2-dimethoxy-2-acetophenone, 2,2-diethoxy-2-acetophenone, 1,1-di chlorobenzene An acetophenone such as ethyl ketone; an anthracene such as 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, 1-chloroindole or 2-pentyl hydrazine; Thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-alkylthiothioxanthone, 2,4-dialkylthioxanthone; benzophenone, 4-chlorobenzophenone, 4 , benzophenones such as 4'-dichlorobenzophenone and 4,4'-bisdimethylaminobenzophenone.

The amount of the component (E) is 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C). If it is less than 0.5 part by mass, the reaction does not sufficiently start, and the mechanical strength of the coating film obtained by the exposure is weakened, so that the pattern is serrated after the peeling of the cured coating film in the developing step. On the other hand, when it exceeds 10 parts by mass, the photopolymerization initiator which is not used at the time of exposure may remain in a large amount in the coating film, resulting in deterioration of physical properties such as heat resistance of the cured coating film.

In the present invention, the above component (E) is preferably used in combination with a sensitizer.

The sensitizer may, for example, be N,N-dimethylaminobenzoic acid, isoamyl N,N-dimethylaminobenzoate, triethylamine, diethylthioxanthone or triethanolamine. The sensitizer may be a commercially available product, such as the trade name "Nissocure EPA, EMA, IAMA" manufactured by Shin-Nisho Chemical Co., Ltd., and the product name "Kayajaya EPA, DETX, DMBI" manufactured by Nippon Kayaku Co., Ltd., Osaka, etc. The product name "DABA" made by the organic company.

The blending amount of the sensitizer is preferably 100 parts by mass, preferably 0.5 to 10 parts by mass, based on the total of the components (A), (B) and (C). If it is less than 0.5 part by mass, the reaction rate of curing by ultraviolet rays or the like cannot be sufficiently increased, and when it exceeds 10 parts by mass, the reaction is accelerated to cause the photosensitive group. The storage stability of the adult has deteriorated.

6. (F) ingredients

The photosensitive composition of the present invention may also contain a phosphorus compound (F) other than the filler (D) containing a phosphorus atom. This compound, unlike the filler (D) containing a phosphorus atom, is a phosphorus compound which is soluble in the composition.

(F) The purpose of the composition is to improve the flame retardancy, and the synergistic effect of the component (D) which is a necessary component for imparting flame retardancy can be utilized to more effectively improve the flame retardancy of the composition.

Examples of the component (F) include phosphates such as triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, triethyl phosphate, cresyl phenyl phosphate, and xylylene diphenyl phosphate. Resorcinol bis(diphenyl)phosphate, bisphenol A bis(diphenyl)phosphate, bisphenol A bis(xylenol) phosphate, resorcinol bis (di-2,6-extension Condensation type phosphates such as toluene phosphates, and phosphazene compounds such as propoxyphosphazene, phenoxyphosphazene, and aminophosphazene.

The most preferred (F) component is a condensed phosphate or phosphazene compound.

The amount of the component (F) to be added is preferably from 1 to 50 parts by mass, more preferably from 1 to 30 parts by mass based on 100 parts by mass of the total of the components (A), (B) and (C). It is preferably 1 to 25 parts by mass. When the amount is less than 1 part by mass, the effect of improving the flame retardancy is insufficient. On the other hand, when it exceeds 50 parts by mass, the coating film may be exposed to light to form a pattern, and the resolution of the pattern or the insulation of the cured film may be obtained. Physical properties such as sex are reduced.

In order to suppress the adverse effect on the above-mentioned resolution or insulation reliability, the amount of the component (F) is preferably equal to or less than the amount of the component (D), more preferably 2/3 or less, and most preferably 1 /2 or less.

7. (G) ingredients

The photosensitive composition of the present invention may be a thermal polymerization initiator (G) to which a radical is generated by heating.

The (G) component can be exemplified by, for example, an organic peroxide, an initiator having an azo double structure, and the like. It is preferably a dialkyl peroxide, specifically a di- cumenyl peroxidation, from the viewpoint that storage stability is high due to high decomposition initiation temperature and that low molecular weight volatile components are generated at the time of decomposition. , tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5- (Third butylperoxy)hexane or the like.

In addition, the amount of the component (G) is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (C). If it is less than 0.5 part by mass, the effect of addition is insufficient, and if it exceeds 10 parts by mass, the storage stability of the composition tends to be deteriorated, and at the same time, a large amount of the decomposition product of the initiator is generated, which may impair the heat resistance of the cured product.

The photosensitive composition of the present invention is preferably one which does not substantially contain a compound having an epoxy group (hereinafter referred to as an epoxy compound). When the composition contains an epoxy compound, the stability of storage of the composition may be deteriorated, so that the use is limited.

However, if it is not necessary to have high storage stability, if it is necessary to further improve the heat resistance and chemical resistance of the cured product, an epoxy compound may be added to the photosensitive composition as needed. In this case, it is recommended to use a two-liquid type composition which is mixed before use.

Specific examples of the epoxy compound are cresol novolac epoxy resin, phenol novolac epoxy resin, epoxy resin having an isocyanurate skeleton, and bisphenol A epoxy resin.

As the epoxy compound, a compound having two or more epoxy groups is preferred.

When an epoxy compound is used, an amine-based curing agent, an acid-based curing agent, an acid anhydride-based curing agent, or the like is usually preferably used in combination.

8. Photosensitive composition

The photosensitive composition of the present invention can be produced by stirring and mixing the above-mentioned essential components (A) to (E) and optionally (F), (G) components and other components according to a conventional method.

As a method of using the photosensitive composition of the present invention, when it is used as a coating agent, an adhesive, a photoresist, or the like, for example, after coating a composition on a substrate, the active energy ray is irradiated, followed by Heating method, etc.

As the substrate, wood, stone, and paper such as polycarbonate, polymethyl methacrylate, and polyvinyl chloride, and the like, processed resin (plastic), metal, glass, ceramic, concrete, natural wood, and synthetic wood can be exemplified. Wait.

The active energy ray may be exemplified by electron rays, ultraviolet rays, and visible light. The light source when irradiated with visible light or ultraviolet rays may be appropriately selected depending on the photopolymerization initiator used, but is preferably a high pressure mercury lamp and a metal halide lamp. The conditions of the active energy ray irradiation can be appropriately set depending on the components used and the purpose.

In the above heating, the heating method and conditions can be based on a general method.

The photosensitive composition of the present invention can be used for various purposes. Specifically, it can be exemplified by a coating agent such as a paint, an ink, a photoresist, a molded material, etc., and is preferably used as a photoresist, and is preferably used as a solder resist.

The case where the composition of the present invention is used as a photoresist is described below.

When the photosensitive composition of the present invention is used as a photoresist, an additive such as an inorganic filler, a flow agent, an antifoaming agent, a pigment, and an ion trapping agent which are usually formulated in a photoresist can be added. As the inorganic filler, talc, clay, inorganic hydroxide, cerium oxide or the like can be exemplified. As the pigment, for example, phthalocyanine, phthalocyanine, and carbon black can be exemplified. These blending amounts can be adjusted within a range that does not impair the resolution of the composition, the storage stability, the heat resistance of the cured product, the flexibility, and the electrical insulating properties.

When the photosensitive composition of the present invention is used as a photoresist, it may be used in the form of a liquid photoresist or a dry film photoresist.

When it is used as a liquid photoresist, a high boiling point solvent may be added to the photosensitive composition of the present invention as the case may be. High boiling point solvent used in this case Examples thereof include ethyl cellosolve, butyl solvolysis, butyl carbitol, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl carbitol acetate, and butyl carbene. Alcohol acetate and the like.

The method for using the photosensitive composition of the present invention as a liquid photoresist can be exemplified by coating or printing a composition on a substrate, drying the coating film by heating, and then irradiating an active energy ray such as ultraviolet rays, and then passing through Heating method, etc.

The coating device when the composition is coated on a substrate can be exemplified by a spin coater, a roll coater, a curtain coater, and the like. The film thickness can also be appropriately set depending on the purpose, but is preferably from 1 to 100 μm, preferably from 5 to 50 μm.

The substrate may be exemplified by metals such as bismuth, aluminum, iron, nickel, and copper; glass; substrates such as polyethylene terephthalate, polyimine, and polycarbonate, and glass epoxy substrates. Such as composite substrates.

When a photoresist is formed on a printed wiring board, if the photoresist is formed on the surface of the copper foil on which the oxide film is not formed after the copper surface is polished, it is preferable because higher adhesion can be obtained. Further, when the copper surface is oxidized or roughened to form irregularities, the adhesion is further improved when a photoresist is formed.

When the photosensitive composition contains a solvent, after coating or printing the composition, the solvent in the composition is evaporated by heating. The heating device in this case can be exemplified by an oven, a heating plate, and the like. The heating conditions may be appropriately set depending on the type and purpose of the composition to be used, and the heating temperature is preferably 70 ° C to 120 ° C, and preferably the heating time is 5 to 30 minutes.

The coating film obtained above was irradiated with an active energy ray through a reticle formed with a specific pattern.

As the active energy ray used for hardening the composition, for example, an electron beam, an ultraviolet ray or the like can be exemplified, and from the viewpoint of using an inexpensive device, ultraviolet rays are preferably used.

The irradiation conditions of the active energy rays can also be based on conventional methods. The irradiation conditions may be appropriately used depending on the type and purpose of the photosensitive composition to be used, and are preferably from 10 to 5,000 mJ/cm ² , more preferably from 50 to 500 mJ/cm ² .

After the above-mentioned active energy ray irradiation, the uncured portion is alkali-developed.

The dilute alkaline aqueous solution used for the development may be appropriately selected depending on the type and purpose of the photosensitive composition to be used, and for example, a 0.5 to 2% aqueous solution of sodium carbonate or the like is used.

The development conditions can be appropriately set depending on the type and purpose of the photosensitive composition to be used, and the development temperature is 15 to 50 ° C, preferably 20 to 40 ° C, and the development time is 15 to 180 °, preferably 30 °. 120 seconds.

The photosensitive composition of the present invention can be used as a solder resist, and is preferably used as an alkaline development type photographic solder resist.

In this case, after the active energy ray is irradiated and developed, in order to further improve various physical properties, it is sufficiently cured by heating or active energy ray irradiation. The heating method and conditions may be appropriately set depending on the type and purpose of the composition to be used, and the heating temperature is 100 to 250 ° C, preferably 130 to 230 ° C, and the heating time is 5 minutes to 5 hours, preferably 30 minutes to 2 hours. The irradiation conditions of the active energy rays can be determined according to a conventional method. The irradiation conditions may be appropriately selected depending on the kind and purpose of the composition to be used, and are preferably from 10 to 5,000 mJ/cm ² , more preferably from 500 to 3,000 mJ/cm ² .

When the photosensitive composition of the present invention is used as a photosensitive layer of a dry film, the method for producing a dry film can be exemplified by applying the composition of the present invention to a support film such as polyethylene terephthalate and drying it by heating. After the solvent is removed, a polyolefin film such as polypropylene or the like is laminated as a cover film. The thickness of the composition coating film (photoresist layer) is 1 to 200 μm, preferably 5 to 50 μm.

In this case, a suitable solvent may be added to the coating of the support film used. The solvent in the composition must be volatilized after coating the film at a heating temperature and time which does not allow polymerization of the composition, and thus the solvent can be exemplified by methyl ethyl ketone, ethyl acetate, butyl acetate, methanol, and ethanol. The lower boiling point.

[Examples]

The examples and comparative examples are shown below to more specifically illustrate the present invention.

In the following examples and comparative examples, "parts" means parts by mass, and "%" means mass%.

○ Synthesis Example 1 [Production of (A) component]

Into a 4-neck bottle equipped with a thermometer, a stirrer, and a cooler, 950 g (5.0 epoxy equivalent) of bisphenol A type epoxy resin (manufactured by Oiled Shell Epoxy Co., Ltd., trade name "Epicot 828") and 450 g as a solvent were injected. Toluene, plus Heat to 110 ° C to obtain a homogeneous solution. To the solution, 0.50 g of phenothiazine as a polymerization inhibitor, 10 g of tetrabutylammonium bromide as a catalyst, and 360 g (5.0 carboxy equivalent) of acrylic acid were added, and the reaction was carried out at 110 ° C while blowing air. A compound of an acryloyl group and a hydroxyl group (epoxy acrylate). The acrylic acid consumption rate calculated from the acid value is close to 100%.

220 g (1.5 mol) of phthalic anhydride was added to the solution of the above product, and after heating to 110 ° C to completely dissolve the phthalic anhydride, the reaction was further carried out for 3 hours. After 1040 g of butyl cellosolve was added to the solution, 300 g of toluene was removed under reduced pressure to obtain a solution of 60% of a carboxyl group-containing epoxy acrylate (a-1).

○ Synthesis Example 2 [Manufacture of component (B)]

Into a 4-neck bottle equipped with a thermometer, a stirrer and a cooler, 64 g of toluene diisocyanate and 200 ppm of dibutyltin dilaurate were added while maintaining the temperature at 70 ° C, and slowly adding 390 g of polycarbonate diol under stirring [East Asia A carbonate diol of a reaction product of diethyl carbonate and 1,6-hexanediol produced by Synthetic Co., Ltd. was stirred for 1 hour to cause a reaction. 50 ppm of dibutyltin dilaurate was added to the solution, followed by slowly adding 48 g of 2-hydroxyethyl acrylate while stirring at 70 ° C to carry out a reaction, and the reaction product was analyzed by infrared absorption spectroscopy, and the reaction was continued until it was determined - The absorption of the characteristics of the NCO group disappears.

As a result, 500 g of a rubbery solid of acrylamide (b-1) having a polycarbonate polyol skeleton having no carboxyl group was obtained.

○ Synthesis Example 3 [Manufacture of component (B)]

Into a four-necked flask equipped with a thermometer, a stirrer, and a cooler, 72 g of toluene diisocyanate and 50 ppm of dibutyltin dilaurate were added, and while maintaining at 70 ° C, 280 g of polycarbonate diol was slowly added while stirring [Asahi Kasei Chemical company, trade name "PCDL T6001") and 12 g of dimethylolpropionic acid were stirred for 1 hour to react. 50 ppm of dibutyltin dilaurate was added to the solution, followed by slowly adding 17 g of 2-hydroxyethyl acrylate with stirring at 70 ° C to carry out the reaction, and the reaction product was analyzed by infrared absorption spectroscopy, and the reaction was continued until the -NCO was determined. The absorption of the characteristics of the base disappears.

As a result, 380 g of a rubbery solid of acrylamide (b-3) having a carboxyl group-containing polycarbonate polyol skeleton was obtained.

○ Synthesis Example 4 [Production of Component (B)]

Into a 4-neck bottle equipped with a thermometer, a stirrer and a cooler, 33 g of hexamethylene diisocyanate and 50 ppm of dibutyltin dilaurate were added while maintaining the temperature at 70 ° C while slowly adding 100 g of polycarbonate under stirring. Alcohol (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "PCDL T5650J") was stirred for 30 minutes to react. 50 ppm of dibutyltin dilaurate was added to the solution, followed by slowly adding 24 g of 2-hydroxyethyl acrylate with stirring at 70 ° C to carry out the reaction, and the reaction product was analyzed by infrared absorption spectroscopy, and the reaction was continued until the -NCO was determined. The absorption of the characteristics of the base disappears.

As a result, 156 g of a rubbery solid of an acrylic urethane (b-4) having a polycarbonate polyol skeleton having no carboxyl group was obtained.

○ Synthesis Example 5 [Production of Component (B)]

Into a 4-neck bottle equipped with a thermometer, a stirrer and a cooler, 34 g of hexamethylene diisocyanate and 50 ppm of dibutyltin dilaurate were added while maintaining the temperature at 70 ° C while slowly adding 1000 g of polycarbonate under stirring. An alcohol (manufactured by Toagosei Co., Ltd., trade name "PES-360") and 200 g of polycarbonate diol (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "PCDL T5652") were stirred for 1 hour to cause a reaction. 50 ppm of dibutyltin dilaurate was added to the solution, followed by slowly adding 13 g of 2-hydroxyethyl acrylate with stirring at 70 ° C to carry out the reaction, and the reaction product was analyzed by infrared absorption spectroscopy, and the reaction was continued until the -NCO was determined. The absorption of the characteristics of the base disappears.

As a result, 1246 g of a rubbery solid of acrylamide (b-5) of a polycarbonate polyol skeleton having no carboxyl group was obtained.

○Examples 1 to 11, Comparative Examples 1 to 7

Using 1 part of 2,4-diethyl ketoxime (sensitizer) and methyl ethyl ketone (solvent) and the following ratios in the solid content ratio according to the ratios shown in Table 1 and Table 2, respectively Show the ingredients of (A) ~ (J), which are mixed with a three-axis roll to blend 65% of the solid content.

The numerical values in the column of each component in Tables 1 and 2 mean parts by mass. Further, the abbreviated symbols of the respective components have the following meanings: (a-1): an epoxy acrylate having a carboxyl group prepared in Synthesis Example 1. (b-1): Acrylic urethane having a polycarbonate polyol skeleton having no carboxyl group prepared in Synthesis Example 2 (mass average molecular weight: 8,000) (b-2): Polyester polyol type urethane urethane [U-200AX, manufactured by Shin-Nakamura Chemical Co., Ltd., number average molecular weight 13000] (b-3): Acrylic urethane having a carboxyl group-containing polycarbonate polyol skeleton prepared by Synthesis Example 3 (mass average molecular weight: 10,000) (b-4): Acrylic urethane having a polycarbonate polyol skeleton having no carboxyl group prepared in Synthesis Example 4 (mass average molecular weight: 1800) (b-5): Acrylic urethane having a polycarbonate polyol skeleton having no carboxyl group prepared in Synthesis Example 5 (mass average molecular weight 60000) (c-1): dipentaerythritol [composition composed of amyl acrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name "ARONIXM-400")] (c-2): pentaerythritol diacrylate monostearate [manufactured by Toagosei Co., Ltd., trade name "ARONIXM-233"] (d-1): aluminum diethylphosphonate (manufactured by Clariant's, Japan, trade name "EXOLIT OP-930", average particle size 5 μm, P content 23%] (d-2): melamine polyphosphate (manufactured by Sanwa Chemical Co., Ltd., trade name "MPP-B", average particle size 12 μm, p content 13%] (d-3): Ammonium polyphosphate (manufactured by Suzuka Chemical Co., Ltd., trade name "FCP- 720", average particle size 20μm, P content 13%] (e-1): photopolymerization initiator, 2-methyl-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone (manufactured by Steam Bart Chemical Co., Ltd., trade name " Iregacure907"] (f-1): Aromatic condensed phosphate ester (manufactured by Daiba Chemical Co., Ltd., trade name "PX-200", P content 14%] (f-2): polyphosphazene (manufactured by Otsuka Chemical Co., Ltd., trade name "SPB-100", P content 13%] (g-1): Thermal polymerization catalyst, dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Polkmil D") (h-1): bisphenol A type epoxy resin [trade name "Epicot 828" manufactured by oyster shell epoxy company] (i-1): melamine [hardener of (h-1) epoxy resin described above] (j-1): Magnesium hydroxide [Inorganic hydroxide-based flame retardant, manufactured by Kyowa Chemical Industry Co., Ltd., trade name "Kisma 5A", average particle diameter 1 μm]

The photosensitive composition was applied onto a polyethylene terephthalate film (base film) having a thickness of 25 μm, and heated at 100 ° C for 10 minutes to evaporate volatile components to form a photosensitive composition. Film (thickness about 30 μm). Subsequently, a polyethylene film (cover film) having a thickness of 25 μm was bonded to the film to form a dry film.

The cover film was peeled off in order to evaluate the dry film. The coating film of the photosensitive composition (hereinafter referred to as a photosensitive layer) is attached to a substrate to be described later by heating the dry film of the cover film to 70 ° C, and using a laminator To laminate. The substrate with the photosensitive layer thus obtained is formed by forming a photosensitive layer on the substrate and coating the underlying film thereon.

The resolution, storage stability, flame retardancy, substrate bending, bending resistance, solder heat resistance, and insulation reliability of the photosensitive layer-attached substrate were evaluated by the following methods. The evaluation results are shown in Tables 3 and 4.

(resolution, storage stability)

An FR-4 substrate [manufactured by Sumitomo Backlight Co., Ltd., copper foil thickness of 18 μm] was used as a substrate. On the photosensitive layer with the photosensitive layer substrate formed thereon, a photomask having a pattern of line widths of 60 μm, 80 μm, 100 μm, and 200 μm was used, and exposed at a light amount of 250 mJ/cm ² . The photomask is placed on the base film, and the exposure to the photosensitive layer is performed through the photomask and the base film. After the exposure, the base film was peeled off, and a 1% sodium carbonate aqueous solution having a concentration of 30 ° C at a pressure of 1.5 kg/cm ² was applied for 60 seconds, and the unexposed portion of the photosensitive layer was removed to obtain a test piece for alkali development. . The obtained test piece was observed under a microscope, and the state of the cured film of the photosensitive layer was evaluated in the following three stages.

○...no abnormalities △... observed a part of the abnormality (residue, peeling, snake, etc.) ×... observed all abnormalities (residues, peeling, snakes, etc.)

The evaluation of the storage stability was carried out after the dry film was stored at 15 ° C for one month, and the substrate with the photosensitive layer was formed in the same manner as above, and the test piece after exposure and development was evaluated for resolution.

(flammable)

A 25 μm-thick polyimide film (manufactured by Toray Dupont Co., Ltd., trade name "Capton" was used as a substrate. The substrate with the photosensitive layer was exposed to light at a light amount of 1000 mJ/cm ² . Subsequently, the base film was peeled off, and post-hardened at 160 ° C for 30 minutes to obtain a test piece.

Using the above test piece, the flame retardancy was evaluated in accordance with the UL-94 standard thin material vertical burning test method.

(substrate bending)

A 25 μm-thick polyimide film (manufactured by Toray Dupont Co., Ltd., trade name "Capton") was used as a substrate. The substrate with the photosensitive layer was exposed to light at a light amount of 1000 mJ/cm ² . Subsequently, the base film was peeled off, post-hardened at 160 ° C for 30 minutes, and cut into side lengths of 100 mm to obtain test pieces.

The test piece was placed on a horizontal floor, and the height of each test piece from the floor was measured in mm units, and the average value was used as the evaluation of the bending size.

×...The curvature cannot be measured because it is completely curled

(bending resistance)

A 25 μm-thick polyimide film (manufactured by Toray Dupont Co., Ltd., trade name "Capton") was used as a substrate. The photosensitive layer of the substrate with an exposure light amount to 1000mJ / cm ² of. Subsequently, the base film was peeled off, post-hardened at 160 ° C for 30 minutes, and cut into 100 mm sides to obtain test pieces.

The photosensitive layer of the test piece was bent 90 ∘ or 180 外侧 outside to visually observe damage such as cracks in the photosensitive layer, and was evaluated in the following three stages: ○...the photosensitive layer was not abnormal. △...The surface of the photosensitive layer is abnormal (cracks, etc.) ×...The crack reaches below the photosensitive layer

(solder heat resistance)

As the substrate, an FR-4 substrate [manufactured by Sumitomo Backlight Co., Ltd., copper foil thickness: 18 μm] was used. The substrate with the photosensitive layer was exposed to light at a light amount of 1000 mJ/cm ² . Subsequently, the base film was peeled off and post-hardened at 160 ° C for 30 minutes to obtain a test piece. The test piece was immersed in a molten solder bath of 280 ° C for 10 seconds as a single cycle, and the state of the cured film after 5 cycles was visually observed, and evaluated in the following three stages: ○...the photosensitive layer was not peeled off Δ...photosensitive layer Partial peeling ×... Most of the photosensitive layer is peeled off or completely peeled off

(insulation reliability)

A comb-type test pattern (line width: 100 μm, line pitch: 100 μm) made of a FR-4 substrate (manufactured by Sumitomo Backlight Co., Ltd., copper foil thickness: 18 μm) was used, and the substrate with the photosensitive layer was exposed at a light amount of 1000 mJ/cm ² . . Subsequently, the base film was peeled off and post-hardened at 160 ° C for 30 minutes to obtain a test piece. The obtained test piece was placed in an atmosphere of a temperature of 85 ° C and a relative humidity of 85% to measure the insulation resistance value after leaving the voltage of 50 V for 250 hours, 500 hours, and 1000 hours.

×... Short circuit between wiring lines, resistance value cannot be measured

According to Table 3, any of the results in Examples 1 to 8 of resolution, storage stability, flame retardancy, substrate bending, bending resistance, and solder heat resistance were good, although the insulation reliability was slightly higher after 1000 hours of storage. It is reduced, but it can be understood that it is excellent in the range where there is no problem in practical use. Further, in Example 9 in which an urethane urethane having a polycarbonate polyol skeleton having a carboxyl group was used, the insulation reliability tends to be slightly lowered. Further, in the case of using the urethane urethane having a polycarbonate polyol skeleton having no carboxyl group, in the embodiment 10 having a small mass average molecular weight, the substrate bending and bending resistance were slightly lowered, but the mass average molecular weight was large. In the eleventh embodiment, there is a tendency that the resolution is lowered.

On the other hand, according to Table 4, it can be understood that the plurality of evaluation items in Comparative Examples 1 to 7 are all bad. In particular, the resolution in all the comparative examples was poor, and the insulation reliability was not particularly good except for Comparative Example 6, but the insulation reliability of Comparative Example 6 could not be said to be excellent.

[Industry Utilization]

The photosensitive composition of the present invention is, for example, a coating film formed on a film support material, and a photosensitive dry film can be provided. It can be preferably used as a photoresist, especially as an electronic material such as a solder resist, and can also be used for thin printing. Processing of wiring boards or FPC boards.

Moreover, it can also be used as a coating agent and ink of a coating material.

Claims (8)

A photosensitive composition containing a compound (A) having a carboxyl group and a radical polymerizable group derived from an epoxy compound skeleton, and an urethane urethane having a polycarbonate polyol skeleton having no carboxyl group (B) a polymerizable compound (C) other than (A) and (B) having a radical polymerizable group, a filler (D) containing a phosphorus atom, and a photopolymerization initiator (E), the above urethane carboxylic acid The ester (B) has a mass average molecular weight of 2,000 to 50,000, and the phosphorus atom-containing filler (D) is a phosphonic acid metal salt, and the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass. As a standard, it contains 1 to 70 parts by mass of the component (D). The photosensitive composition of claim 1 which contains 20 to 90 parts by mass of the component (A), 10 to 80 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). Ingredient (B), 5 to 50 parts by mass of component (C). The photosensitive composition of claim 1, wherein the compound (A) having a skeleton derived from an epoxy compound and having a carboxyl group and a radical polymerizable group is added to an epoxy compound and an unsaturated monocarboxylic acid. The reaction is carried out, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to carry out an addition reaction. The photosensitive composition of the first aspect of the invention, wherein the polymerizable compound (C) other than (A) and (B) having a radical polymerizable group has three or more (meth) groups per molecule. Acrylamide Compound. The photosensitive composition of claim 1, wherein the filler (D) containing a phosphorus atom is an aluminum salt of a phosphonic acid. The photosensitive composition of claim 1, which also contains a phosphorus compound (F) other than the filler (D) containing a phosphorus atom. A solder resist comprising the photosensitive composition according to any one of claims 1 to 6. A photosensitive dry film which is formed on a support film to form a coating film containing the photosensitive composition according to any one of claims 1 to 6.