JP2002040633A - Halogen-free photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a halogen-free photosensitive resin composition which will not generate hydrogen bromide as a harmful gas in combustion and is superior in heat and moisture resistances, adhesion and fire retardancy. SOLUTION: The photosensitive resin composition contains (A) an epoxy acrylate resin, (B) epoxy resin, (C) diluent, (D) curing agent, (E) curing accelerator, (F) sensitizer, (G) crosslinked phenoxyphosphazene compound prepared by crosslinking a cyclic or chain phenoxyphosphazene compound with m- phenylene groups, etc., and (H) an inorganic filler as essential components. The component (G) is contained by 2-20 wt.% with respect to the amount of the entire resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as an interlayer insulating resin for a printed wiring board, a solder resist, etc., and does not contain a halogen compound and has excellent heat resistance, moisture resistance, adhesion, and flame retardancy. The present invention relates to a halogen-free photosensitive resin composition.

[0002]

2. Description of the Related Art Flame-retardant regulations required for electric and electronic parts have been focused on low-pollution, low-toxicity, and safety, along with increasing interest in global environmental issues and human safety issues. Transfer, not only flammable but also toxic gas,
There is a demand for a reduction in smoke emission. Conventionally, most of halogen compounds used as flame retardants in interlayer insulating resins for printed wiring boards and solder resists on which electric and electronic components are mounted are bromine-based, and derivatives mainly containing tetrabromobisphenol A (bromine) Epoxy resins and the like) are widely used, and the demand for dehalogenation of photosensitive resin compositions used therein is also increasing. Non-halogen flame retardants include nitrogen-based, phosphorus-based, and inorganic compounds. When used as an interlayer insulating resin for printed wiring boards, nitrogen-based resins generally have an effect on resin curing, and phosphorus-based compounds have moisture resistance. There is a problem such as lowering and it is difficult to put it to practical use.

[0003] In addition to the halogen-free flame retardancy, the use of lead-free solder in printed wiring boards has also become important. The problem here is that the mainstream composition of lead-free solder is mainly Sn / Sn in terms of reliability.
Because of the Ag / (Bi) system and the Sn / Zn / (Bi) system, the flow or reflow temperature is the general flow and reflow temperature of the conventional Pb / Sn eutectic solder (mp: 183 ° C.). It means that the temperature rises from about 240 ° C to 10 to 20 ° C. For this reason, the substrate material is also required to have higher heat resistance than before.

[0004] Although such a brominated epoxy resin has good flame retardancy, it can generate harmful hydrogen halide (hydrogen bromide) gas upon combustion, and can also generate brominated dioxins and furans. Therefore, its use is being suppressed.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is halogen-free and has good flame retardancy (halogen-free). Make it applicable to the soldering process,
Halogen-free photosensitive resin composition used for interlayer insulation resins for printed wiring boards and solder resists that does not generate hydrogen bromide, which is a harmful gas during combustion, and has excellent heat resistance, moisture resistance, adhesion, and flame retardancy It is intended to provide.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a crosslinked phenoxyphosphazene compound was added to a resin composition without using a halogen compound as a flame retardant. Epoxide compounds,
With a novel formulation that is appropriately combined with others, while showing good flame retardancy without halogen,
The inventors have found that the above objects can be achieved with improved moisture resistance and heat resistance, and the present invention has been completed.

That is, the present invention provides (A) an epoxy acrylate resin, (B) an epoxy resin, (C) a diluent, (D)
A curing agent, (E) a curing accelerator, (F) a sensitizer, (G) a cross-linked phenoxyphosphazene compound and (H) an inorganic filler are essential components.
A halogen-free photosensitive resin composition comprising a crosslinked phenoxyphosphazene compound at a ratio of 2 to 20% by weight.

Hereinafter, the present invention will be described in detail.

Each component of the photosensitive resin composition of the present invention will be described.

The epoxy acrylate resin (A) used in the present invention includes a reaction product obtained by reacting an unsaturated monocarboxylic acid with an epoxy resin, or a reaction product obtained by reacting an unsaturated monocarboxylic acid with an epoxy resin, and further comprising a polybasic anhydride. Any reaction product to which a substance is added may be used, and is not particularly limited and can be widely used. As the epoxy resin used here, bisphenol A type epoxy resin,
Examples include bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolak type epoxy resin, polyfunctional epoxy resin and the like. As the unsaturated carboxylic acid used herein, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid And polybasic acid anhydrides used herein include maleic anhydride and the like,
These epoxy acrylate resins can be used alone or in combination of two or more.

The epoxy resin (B) used in the present invention may be any compound having at least two epoxy groups in the molecule. Examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin. Resins, novolak-type epoxy resins, polyfunctional epoxy resins, and the like can be used, and are not particularly limited and can be widely used. These epoxy resins can be used alone or in combination of two or more.

The diluent (C) used in the present invention may be any unsaturated compound or organic solvent having at least two ethylene bonds in the molecule, and is not particularly limited and may be used widely. it can. It is desirable to use an unsaturated compound and an organic solvent in combination. Specific examples of the unsaturated compound include trimethylolpropane triacrylate, hexanediol acrylate, diallyl phthalate, triallyl cyanurate, diallyl isophthalate and the like, and these can be used alone or in combination of two or more. . Further, specific organic solvents include ethylene glycol monoalkyl ethers,
Diethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, petroleum naphtha, and the like. These may be used alone or in combination of two or more. can do.

The curing agent (D) used in the present invention is not particularly limited as long as it is a compound usually used for curing an epoxy resin. As a specific curing agent,
Examples of amines include dicyandiamide and aromatic amines, and examples of phenolic resins include phenol novolak resins, cresol novolak resins, and bisphenol A-type novolak resins. These can be used alone or in combination of two or more. .

The (E) curing accelerator used in the present invention is not particularly limited as long as it is a compound which is usually used for accelerating the curing of an epoxy resin. Specific curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole,
Examples thereof include phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole and the like, and these can be used alone or in combination of two or more.

The sensitizer (F) used in the present invention is not particularly limited as long as it is a compound usually used for photocuring an epoxy acrylate resin. Specific sensitizers include, for example, benzoin ethers,
Benzophenone type, ketal type, acetophenone type, thioxanthone type and the like can be mentioned, and these can be used alone or in combination of two or more.

The phenoxyphosphazene compound before crosslinking in (G) used in the present invention is not particularly limited as long as it can be obtained by reacting a dichlorophosphazene compound with an alkali metal salt of a phenol. Can be widely used. Specific examples of the phenoxyphosphazene compound include a cyclic phenoxyphosphazene compound represented by the following structural formula and

Embedded image (Wherein, m represents an integer of 3 to 25). A chain phenoxyphosphazene compound represented by the following structural formula is exemplified.

[0017]

Embedded image (Wherein, X ¹ represents a group —N （P (OC ₆ H ₅ ) ₃ or a group —N （P (O) OC ₆ H ₅ , and Y ¹ represents a group —P (O
C ₆ H ₅ ) ₄ or a group —P (O) (OC ₆ H ₅ ) ₂
Represents an integer of 3 to 10000) The cross-linked phenoxyphosphazene compound is such that at least one phosphazene compound selected from the above-mentioned cyclic phenoxyphosphazene compound and chain phenoxyphosphazene compound is an o-phenylene group, an m-phenylene group, a p- Phenylene group and bisphenylene group represented by general formula

Embedded image (Where A is -C (CH ₃ ) _2- , -SO _2- ,
Represents a compound represented by —S— or —O—, and a represents 0 or an integer of 1 or more).

In the crosslinked phenoxyphosphazene compound, (a) the crosslinking group is interposed between the two oxygen atoms from which the phenyl group is eliminated in the phosphazene compound, and (b) the phenyl group in the crosslinked compound is The content ratio is 50 to 99.9 based on the total number of all phenyl groups in the cyclic phenoxyphosphazene compound of the formula (4) and / or the chain phenoxyphosphazene compound of the formula (5).
% And (c) having no free hydroxyl group in the molecule.

The terminal group X in the above general formula (5)
¹And Y¹Changes depending on the reaction conditions, etc.
For example, if a mild reaction is performed in a non-aqueous system,
Is X ¹Is a group -N = P (OC₆H_Five)_Three, Y¹Is the group -P
(OC₆H_Five)_FourStructure of water or alkali
Reaction conditions such that metal hydroxide is present in the reaction system, or
Performs the reaction under severe reaction conditions such that a transfer reaction occurs.
X¹Is a group -N = P (OC₆H_Five)_Three, Y¹
Is a group -P (OC₆H_Five)_FourIn addition to the structure ¹Is based
-N = P (O) OC₆H_Five, Y¹Is a group -P (O) (OC
₆H_Five)_TwoIt is in a state where those having the structure of are mixed.

In the present invention, "having no free hydroxyl group in the molecule" refers to Analytical Chemistry Handbook (Revised 3rd Edition, edited by The Japan Society for Analytical Chemistry, Maruzen Co., Ltd., 1981), No. 353. It means that the amount of free hydroxyl groups is below the detection limit when quantified according to the acetylation method using acetic anhydride and pyridine described on page. Here, the detection limit is 1 g of a sample (the crosslinked phenoxyphosphazene compound of the present invention).
It is a detection limit as a hydroxyl equivalent per unit, more specifically, 1 × 10 ⁻⁶ hydroxyl equivalent / g or less. When the crosslinked phenoxyphosphazene compound of the present invention is analyzed by the above acetylation method, the amount of the remaining hydroxyl groups of the raw phenol is also added.However, since the raw phenol can be quantified by high performance liquid chromatography, Only free hydroxyl groups can be quantified.

The crosslinked phenoxyphosphazene compound of the present invention is prepared by mixing a dichlorophosphazene compound with an alkali metal phenolate and diphenolate and reacting them (first step), and then further reacting the obtained compound with an alkali metal phenolate ( 2nd step).

As the dichlorophosphazene compound, known compounds, for example, a cyclic dichlorophosphazene compound represented by the following general formula 7, a chain dichlorophosphazene compound represented by the general formula 8, and the like can be used.

[0023]

Embedded image (Where m represents an integer of 3 to 25)

Embedded image (Where X ² is a group -N = PCl ₃ or a group -N = P
(O) Cl, Y ² represents a group —P (Cl) ₄ or a group —P
(O) Cl ₂ , n represents an integer of 3 to 10000) These dichlorophosphazene compounds can be used alone or in combination of two or more. Also,
You may use together a cyclic thing and a chain thing.

The production of the dichlorophosphazene compound is described, for example, in H. R. Allcock, “Phosphor
us-Nitrogen Compounds ", Ac
ademic Press, (1972), J. Amer. E. FIG. M
ark, H .; R. Allcock, R.A. By West,
“Inorganic Polymer” Prenti
ce-Hall International In
c. , (1992) and the like.

Examples of the alkali metal phenolate to be reacted with the above-mentioned dichlorophosphazene compound include sodium phenolate, potassium phenolate, lithium phenolate and the like, and these can be used alone or in combination of two or more. .

The diphenolate to be reacted with the above-mentioned dichlorophosphazene compound includes, for example, the following general formula:

Embedded image (Wherein, M represents an alkali metal)
-, M-, p-substituted alkali metal diphenolates,

Embedded image (Where A is -C (CH ₃ ) _2- , -SO _2- ,
Represents -S- or -O-, a represents 0 or an integer of 1 or more,
M represents an alkali metal, respectively), and the like. The substitution position of the phenolate in Chemical formula 10 may be any of ortho, meta and para.

Specific examples of these alkali metal diphenolates include resorcinol, hydroquinone, catechol, 4,4'-isopropylidene diphenol (bisphenol-A), 4,4'-sulfonyl diphenol (bisphenol-S), Sodium salts and lithium salts such as 4,4'-thiodiphenol, 4,4'-oxydiphenol, and 4,4'-diphenol, which can be used alone or in combination of two or more. .

The content ratio of phenyl groups in the crosslinked phenoxyphosphazene compound is from 50 to 99.9 based on the total number of all phenyl groups in the cyclic phenoxyphosphazene compound and / or the chain phenoxyphosphazene compound.
%, Preferably 70 to 90%.

Among the above crosslinked phenoxyphosphazene compounds, the crosslinked phenoxyphosphazene compound crosslinked by the structure of the above formula (6) has a decomposition temperature in the range of 250 to 350 ° C. and can be preferably used. These crosslinked phenoxyphosphazene compounds can be used alone or in combination of two or more for the treatment of the present invention. In order to maintain heat resistance corresponding to lead-free solder, it is preferable that the crosslinked phenoxyphosphazene compound has a decomposition initiation temperature of 300 ° C. or higher.

In the present invention, the compounding ratio of the crosslinked phenoxyphosphazene compound to the whole resin composition is 2 to 20% by weight.

As the inorganic filler (H) used in the present invention,
There is no particular limitation, and specific examples include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, barium sulfate, and the like. These may be used alone or in combination of two or more. be able to. It is desirable that the inorganic filler is blended so as to be contained in a proportion of 10 to 50% by weight of the whole resin composition. If the compounding ratio is less than 10% by weight, sufficient flame retardancy, heat resistance and moisture resistance cannot be obtained, and 50% by weight
If it exceeds, the resin viscosity increases, coating unevenness and voids occur, and the thickness becomes poor, which is not preferable.

The photosensitive resin composition of the present invention comprises (A) an epoxy acrylate resin, (B) an epoxy resin, (C) a diluent, (D) a curing agent, (E) a curing accelerator, and (F) sensitization. The composition contains (G) a crosslinked phenoxyphosphazene compound and (H) an inorganic filler as essential components, but within a range not inconsistent with the object of the present invention, and if necessary, a coloring pigment, an antifoaming agent, a leveling agent, and an antioxidant. Agents, other additives, and the like. The photosensitive resin composition can be manufactured by uniformly mixing with a three-roll or the like in which the above-described components are blended. The photosensitive resin composition thus obtained is
It is used as interlayer insulation for printed wiring boards, solder resist, and the like.

Since the photosensitive resin composition of the present invention does not contain a halogen compound, it does not generate hydrogen bromide which is a toxic gas during combustion. After applying this photosensitive resin composition to a printed wiring board to a desired thickness, 60 to 8
Heat and dry at 0 ° C. for 15 to 60 minutes to evaporate the organic solvent. Then, after irradiating ultraviolet rays to cure the necessary portions, the unexposed portions are dissolved and removed with an organic solvent or a dilute alkaline aqueous solution, and then thermally cured to form a resin film.

[0034]

Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[Synthesis of Crosslinked Phenoxyphosphazene Compound] Synthesis Example 1 (Synthesis of Phenoxyphosphazene Compound Having Crosslinked Structure with Paraphenylene) 103.5 g of phenol
(1.1 mol), 44.0 g of sodium hydroxide (1.1
Mol), 50 g of water and 500 ml of toluene were heated under reflux to remove only water from the system to prepare a toluene solution of sodium phenolate.

In parallel with the above reaction, 16.5 g (0.15 mol) of hydroquinone, 94.1 g (1.0 mol) of phenol, 31.1 g of lithium hydroxide were placed in a 2 l four-necked flask.
g (1.3 mol), 52 g of water and 600 ml of toluene
Was added and heated under reflux to remove only water from the system to prepare a toluene solution of a lithium salt of hydroquinone and phenol. Dichlorophosphazene oligomer (trimer 62%, tetramer 12
%, Pentamer and hexamer 11%, heptamer 3%, octamer or more 12%) 1.0 unit mol (115.9 g)
After 580 g of a 20% chlorobenzene solution containing was added dropwise at 30 ° C. or lower while stirring, the mixture was stirred and reacted at 110 ° C. for 3 hours. Next, the toluene solution of sodium phenolate prepared above was added under stirring, and the reaction was continued at 110 ° C. for 4 hours.

After the completion of the reaction, the reaction mixture was washed three times with 1.0 liter of a 3% aqueous sodium hydroxide solution and then three times with 1.0 liter of water, and the organic layer was concentrated under reduced pressure. The obtained product was heated and vacuum dried at 80 ° C. and 3 mmHg or less for 11 hours to obtain 211 g of a slightly yellow powder (compound X).

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained as described above is 0.04%,
The weight average molecular weight (Mw) is 1080 in terms of polystyrene (by GPC analysis), and the phosphorus content and CHN
From the elemental analysis values, the composition of the final product was [N = P (-Op-
_{C 6 H 4 -O-) 0.15 (} -O-C 6 H 5) 1.7]
Met. The weight average molecular weight (Mw) is 1100 in terms of polystyrene (by GPC analysis), and TG / DTA
The analysis did not show a clear melting point and the decomposition onset temperature was 306
° C, 5% weight loss temperature was 311 ° C. In addition, as a result of quantifying the residual hydroxy group by the acetylation method, it was below the detection limit (hydroxy equivalent per 1 g of sample: 1 × 10 ⁻⁶ equivalent / g or less).

Synthesis Example 2 [Synthesis of a phenoxyphosphazene compound having a crosslinked structure with a 2,2-bis (p-oxyphenyl) isoprolidene group] 65.9 g (0.7 mol) of phenol and 500 ml of toluene in four 1-liter portions In a flask, 0.65 g atom (14.9 g) of sodium metal was cut into small portions and charged while maintaining the internal liquid temperature at 25 ° C. with stirring. After completion of the charging, stirring was continued at 77 to 113 ° C. for 8 hours until the sodium metal completely disappeared.

In parallel with the above reaction, bisphenol A0.
25 mol (57.1 g), phenol 1.1 mol (10
3.5 g) and tetrahydrofuran (THF) 800
Then, 1.6 g atom (11.1 g) of metallic lithium was finely cut and charged while maintaining the internal liquid temperature at 25 ° C. while stirring. After the completion of the charging, stirring was continued at 61 to 68 ° C. for 8 hours until the lithium metal completely disappeared. To this slurry solution, dichlorophosphazene oligomer (concentration: 37%, chlorobenzene solution 313 g, composition: trimer 75%, tetramer 17%, pentamer and hexamer 6%, heptamer 1%, octamer 1.0 mol (115.9) g of the above mixture (1%) was added dropwise with stirring over 1 hour while maintaining the internal liquid temperature at 20 ° C. or lower, and then reacted at 80 ° C. for 2 hours. Next, while stirring, while maintaining the internal liquid temperature at 20 ° C., a separately prepared sodium phenolate solution was added over 1 hour, and the mixture was reacted at 80 ° C. for 5 hours.

After completion of the reaction, the reaction mixture was concentrated, and THF was added.
And 1 l of toluene was newly added. After washing the toluene solution three times with 1 liter of 2% NaOH and then three times with 1 liter of water, the organic layer was concentrated under reduced pressure. The obtained product was heated and vacuum dried at 80 ° C. and 3 mmHg or less for 11 hours to obtain 229 g of a white powder (Compound Y).

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained as described above is 0.07%,
The composition of the phosphorus content and CHN final product elemental analysis values, [N = P (-O- C 6 H 4 -C (CH 3) 2 -C 6
H ₄ -O-) was _{0.25 (-O-C 6 H 5} ) 1.50]. The weight average molecular weight (Mw) was 1130 in terms of polystyrene (by GPC analysis), and TG / DTA
The analysis did not show a clear melting point and the decomposition onset temperature was 308
° C, 5% weight loss temperature was 313 ° C. Further, as a result of quantifying the residual hydroxy group by the acetylation method, it was below the detection limit (1 × 10 ⁻⁶ equivalent / g or less as hydroxy equivalent per 1 g of sample).

Synthesis Example 3 [4,4-sulfonyldiphenylene (bisphenol-
Synthesis of Phenoxyphosphazene Compound Having Cross-Linked Structure with S Residue] Phenol 37.6 g (0.4 mol)
And 500 ml of THF into a 1 l four-necked flask,
Under stirring, 0.45 g atom (9.2 g) of metallic sodium was finely cut and charged while maintaining the internal liquid temperature at 25 ° C. After completion of the charging, stirring was continued for 5 hours at 65 to 72 ° C. until the metallic sodium completely disappeared.

In parallel with the above reaction, 160.0 g (1.70 mol) of phenol and 12.5 g (0.05 mol) of bisphenol-S were added to THF 50 in a 1 l four-necked flask.
0 g, dissolve 1.8 g atom (41.4 g) of metallic sodium at 25 ° C. or lower, raise the temperature to 61 ° C. over 1 hour after completion of the charging, continue stirring at 61-68 ° C. for 6 hours, A phenolate mixed solution was prepared. This solution was treated with dichlorophosphazene oligomer (composition: 62% trimer, 12% tetramer, 11% pentamer and 11% hexamer, 7%
The mixture was added dropwise to 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) under cooling and stirring at 25 ° C. or lower, followed by stirring.
The mixture was stirred and reacted at ７３73 ° C. for 5 hours.

Next, after the sodium phenolate mixed solution prepared above was added dropwise, the reaction was continued at 71 to 73 ° C. for 3 hours.

After completion of the reaction, the reaction mixture was concentrated, redissolved in 500 ml of chlorobenzene, washed three times with 5% aqueous NaOH, washed with 5% sulfuric acid, washed with 5% aqueous sodium bicarbonate, and washed three times with water, and concentrated to dryness. As a result, 218 g of a pale yellow wax (compound Z) was obtained.

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained as described above is 0.01% or less, and the composition of the final product is substantially [N = P ( _{-O-C 6 H 4 -SO 2} -C
_{6 H 4 -O-) 0.05 (-O} -C 6 H 5) 1.90]
It was decided. The weight average molecular weight (Mw) is 1080 in terms of polystyrene (by GPC analysis), and TG / DT
According to A analysis, the melting temperature (Tm) was 103 ° C., the decomposition starting temperature was 320 ° C., and the 5% weight loss temperature was 334 ° C.
Further, as a result of quantifying the residual hydroxy group by the acetylation method, it was below the detection limit (1 × 10 ⁻⁶ equivalent / g or less as hydroxy equivalent per 1 g of sample).

Example 1 Epoxy acrylate resin (Novolak K-48C,
Nippon Kayaku Co., Ltd., acid value 63, solid content 60% by weight) 100
Parts, 40 parts of epoxy resin (CNE200EL, manufactured by Changchun, epoxy equivalent: 200), 10 parts of trimethylolpropane triacrylate, 8 parts of Irgercure 907 (trade name, manufactured by Ciba Geigy), 1 part of dicyandiamide, 2-part
0.25 parts of ethyl-4-methylimidazole, 10 parts of barium sulfate, 10 parts of aluminum hydroxide, and 25 parts of the crosslinked phenoxyphosphazene compound X of Synthesis Example 1 were mixed, and further uniformly mixed by a three-roll mill to form a photosensitive resin composition. Was manufactured.

Example 2 Epoxy acrylate resin (Novolak K-48C,
Nippon Kayaku Co., Ltd., acid value 63, solid content 60% by weight) 100
Parts, 40 parts of epoxy resin (CNE200EL, manufactured by Changchun, epoxy equivalent: 200), 10 parts of trimethylolpropane triacrylate, 8 parts of Irgercure 907 (trade name, manufactured by Ciba Geigy), 1 part of dicyandiamide, 2-part
0.25 parts of ethyl-4-methylimidazole, 10 parts of barium sulfate, 10 parts of aluminum hydroxide, and 25 parts of the crosslinked phenoxyphosphazene compound Y of Synthesis Example 2 were mixed, and further uniformly mixed by a three-roll mill to form a photosensitive resin composition. Was manufactured.

Example 3 Epoxy acrylate resin (Novolak K-48C,
Nippon Kayaku Co., Ltd., acid value 63, solid content 60% by weight) 100
Parts, 40 parts of epoxy resin (CNE200EL, manufactured by Changchun, epoxy equivalent: 200), 10 parts of trimethylolpropane acrylate, 8 parts of Irgercure 907 (manufactured by Ciba Geigy, trade name), 1 part of dicyandiamide, 1 part of 2-ethyl-4-methyl 0.25 parts of merimidazole, 10 parts of barium sulfate, 10 parts of aluminum hydroxide, and 25 parts of the crosslinked phenoxyphosphazene compound Z of Synthesis Example 3 were mixed, and further uniformly mixed by a three-roll mill to produce a photosensitive resin composition. .

Comparative Example 1 Epoxy acrylate resin (Novolak K-48C,
Nippon Kayaku Co., Ltd., acid value 63, solid content 60% by weight) 100
Parts, brominated epoxy resin (BREN-S, Nippon Kayaku Co., Ltd., epoxy equivalent: 285) 60 parts, trimethylolpropane triacrylate 10 parts, Irgercure 907
(Ciba Geigy Co., trade name) 8 parts, dicyandiamide 1 part, 2-ethyl-4-methylimidazole 0.25 part,
10 parts of barium sulfate and 10 parts of aluminum hydroxide were mixed, and further uniformly mixed by a three-roll mill to produce a photosensitive resin composition.

Comparative Example 2 Epoxy acrylate resin (triphenolmethane-based T
CR1025, manufactured by Nippon Kayaku Co., Ltd., acid value 103, solid content 60
% By weight), a brominated epoxy resin (BREN-
S, Nippon Kayaku Co., Ltd., epoxy equivalent 285) 60 parts, trimethylolpropane triacrylate 10 parts, Irgercure 907 (Ciba-Geigy, trade name) 8 parts, dicyandiamide 1 part, 2-ethyl-4-methylimidazole 0 .25 parts, 10 parts of barium sulfate, and 10 parts of aluminum hydroxide were mixed, and further uniformly mixed by a three-roll mill to produce a photosensitive resin composition.

The solutions of the photosensitive resin compositions produced in Examples 1 to 3 and Comparative Examples 1 and 2 were applied to a substrate on which a copper foil pattern had been formed in advance by screen printing to a film thickness of 60 μm. Then, it is dried with a hot air circulating dryer at 80 ° C. for 25 minutes to evaporate the organic solvent, and then irradiated with 300 mJ of ultraviolet light through a desired pattern mask, and irradiated with 1% sodium carbonate (30 ° C., spray pressure 1.0 kg). / Cm ² ) for 60 seconds. Then, drying was performed by a hot air circulating dryer at 150 ° C. for 60 minutes to obtain a resin film. Table 1 shows the evaluation results of the developability and the characteristics of the resin film. In each case, the present invention was excellent, and the effects of the present invention could be confirmed.

[0054]

[Table 1] * 1: Measured according to the UL94 flame retardancy test.

* 2: Measured according to IEC-PB112.

* 3: After development, the state of removal of the unexposed portions was evaluated.

◎: Completely developed, 印: Partly developed remaining, Δ: Overall development remaining.

* 4: The sample was floated on the solder bath at 280 ° C. for each time shown in the table, and the presence or absence of swelling was observed. ◎: no swelling, ○: some swelling, Δ: most swelling, ×: all swelling.

* 5: Measured according to JIS-K-5400.

* 6: The sample was treated under the conditions A (boiled for 2 hours) and the condition B (boiled for 4 hours), immersed in a solder bath at 260 ° C. for 30 seconds, and observed for blisters. ◎: no swelling, ○: some swelling, Δ: most swelling, ×: all swelling.

* 7: Each sample was burned in air at 750 ° C. for 10 minutes, the gas generated at that time was absorbed in an absorbing solution, and analyzed by ion chromatography.

[0062]

As is clear from the above description and Table 1, the photosensitive resin composition of the present invention does not contain a halogen compound, so that no toxic gas is generated during combustion, heat resistance,
It is excellent in moisture resistance, adhesion, and flame retardancy, and is suitable for interlayer insulation for printed wiring boards, solder resist, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/5399 C08K 5/5399 C08L 63/00 C08L 63/00 C 63/08 63/08 85/04 85 / 04 G03F 7/027 515 G03F 7/027 515 7/028 7/028 (72) Inventor Tetsuaki Suzuki 9-2 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Toshiba Chemical Corporation Kawasaki Plant (72) Invention Person Yuji Tada 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture F-term (reference) 2H025 AA00 AA10 AA14 AB15 AC01 AD01 BC14 BC74 CC03 CC08 CC17 CC20 FA03 FA17 4J002 CC033 CC043 CD05X CD06X CD20W CQ149 DE0 DG049 DJ019 DJ049 EA016 ED026 EE039 EH076 EH146 EH156 EN057 ER027 EU118 EU196 EV309 FD019 FD134 FD143 FD147 FD158 FD206 FD209 GP03 GQ01 GQ05 4J030 CA02 CB48 CF02 CG22 4J036 AA01 AD08 AD21 AF06 CA20 DA01 DA02 DC10 DC31 DC40 FA01 FB00 FB07 HA02 JA07 JA08 JA10 KA03

Claims (3)

[Claims] (A) an epoxy acrylate resin,
(B) epoxy resin, (C) diluent, (D) curing agent,
(E) a curing accelerator, (F) a sensitizer, (G) and (H)
An inorganic filler is an essential component, and the crosslinked phenoxyphosphazene compound (G) is used in an amount of 2 to 2 with respect to the entire resin composition.
A halogen-free photosensitive resin composition comprising 0% by weight. 2. Components (A) to (H) are essentially non-halogen compounds, and the content of impurity halogens is
0.1% by weight for each of the compounds (A) to (D)
The halogen-free flame-retardant epoxy resin composition according to claim 1, which is: 3. The crosslinked phenoxyphosphazene compound (G) is a cyclic phenoxyphosphazene compound represented by the following structural formula: (Wherein, m represents an integer of 3 to 25) A chain phenoxyphosphazene compound represented by the following structural formula: (Wherein, X ¹ represents a group —N （P (OC ₆ H ₅ ) ₃ or a group —N （P (O) OC ₆ H ₅ , and Y ¹ represents a group —P (O
C ₆ H ₅ ) ₄ or a group —P (O) (OC ₆ H ₅ ) ₂
At least one phosphazene compound selected from the group consisting of an o-phenylene group, an m-phenylene group, a p-phenylene group and a bisphenylene group represented by the general formula: (Where A is -C (CH ₃ ) _2- , -SO _2- ,
-S- or -O-, a represents 0 or an integer of 1 or more), wherein (a) the crosslinking group is a phosphazene compound (B) the content of the phenyl group in the crosslinked compound which is interposed between the two oxygen atoms from which the phenyl group has been eliminated, and the total number of all phenyl groups in the cyclic phenoxyphosphazene compound and / or the chain phenoxyphosphazene compound 50 to 99.9% based on
The halogen-free flame-retardant epoxy resin composition according to claim 2, which is (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule.