JP2007241312A - Photosensitive insulating resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive insulating resin composition giving a cured product excellent in resolution, electric insulation and thermal shock resistance and also having good heat and chemical resistances. <P>SOLUTION: The photosensitive insulating resin composition comprises an alkali-soluble resin (A) having phenolic hydroxyl groups, a compound (B) having at least two or more alkyl-etherified amino groups per molecule, crosslinked fine particles (C), a light-sensitive acid generator (D) and an organic solvent (E). A cured product of the invention is obtained by heat-curing such a photosensitive insulating resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive insulating resin composition used for a printed wiring board and the like and a cured product obtained by curing the same. More specifically, a cured product having excellent resolution, electrical insulation, thermal shock, heat resistance, chemical resistance, and the like, and a photosensitive resist for a solder resist from which such a cured product can be obtained. The present invention relates to an insulating resin composition.

  Solder resist used in the field of printed wiring board processing is intended to prevent solder adhesion to parts other than necessary when soldering, or to open a conductor pad on which an IC chip is mounted, and It is used for the purpose of protecting other conductor circuits.

Along with the recent trend toward miniaturization of electronic equipment, adhesion, electrical insulation, solder heat resistance, solvent resistance, impact resistance, and resolution to meet the demand for higher density printed wiring boards and surface mounting of components. There is a demand for solder resists that are excellent in various properties such as properties. As the solder resist, an epoxy-based thermosetting type has been conventionally used, but there are problems in chemical resistance and solder heat resistance. In addition, ultraviolet curable types are often used to improve workability and productivity. For example, JP-A-6-180501 (Patent Document 1) discloses a polyfunctional epoxy resin, an unsaturated monocarboxylic acid, A reaction product of an esterified product and a polybasic acid anhydride, a guanamine resin obtained by adding formaldehyde to a part or all of the amino group and further alkylating part or all with an alcohol having 4 or less carbon atoms (the following formula (See (1)),
Although a solder resist composition having a photopolymerization initiator has been disclosed, the properties required for a high-density printed circuit board have not been fully satisfactory.

(Wherein R represents a divalent hydrocarbon group having 2 to 8 carbon atoms)
JP-A-9-316173 discloses a resin composition containing an epoxy resin, an allyl nadiimide compound, and a photocationic polymerization initiator. However, although the resin composition described in JP-A-9-316173 is excellent in heat resistance, adhesion, and chemical resistance, impact resistance and resolution have not been sufficiently studied. Also, it was not always satisfactory.
Furthermore, Japanese Patent Application Laid-Open No. 2000-7886 discloses a solder resist composition that is excellent in crack resistance under heat cycle conditions mainly composed of an acrylate of a novolak type epoxy resin and a thermoplastic resin. Various characteristics such as resolution are not described. Conventionally, the printed wiring board used a subtractive method of forming a circuit by removing unnecessary portions of the copper foil of the copper-clad laminate by etching. It is difficult to form wiring with high accuracy. Therefore, a full additive method for forming a circuit by electroless plating has attracted attention. As an insulating material suitable for such a method, it must have excellent resolution, electrical insulation, solder heat resistance, solvent resistance, and thermal reliability during lamination. is there. JP-A-11-60895 discloses a permanent resist resin composition excellent in solder heat resistance and solvent resistance, comprising a phenol resin, an ethylenically unsaturated group-containing compound, a photopolymerization initiator, and a compound having a carbodiimide group. However, no mention is made of thermal shock and resolution.
The appearance of a photosensitive insulating resin composition having further excellent resolution and heat resistance has been desired.
JP-A-6-180501 JP-A-9-316173 JP 2000-7886 A Japanese Patent Laid-Open No. 11-60895

  The present invention solves the problems associated with the prior art as described above, and can provide a cured product excellent in various properties such as resolution, electrical insulation, thermal shock resistance, and chemical resistance. It aims at providing the photosensitive insulating resin composition suitable for a use or a fine wiring formation use.

  Furthermore, an object of the present invention is to provide a cured product obtained by curing such a photosensitive insulating resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the photosensitive insulating resin composition containing the characteristic component has excellent characteristics, and have completed the present invention. That is, the present invention includes (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound containing at least two alkyl etherified amino groups in the molecule, (C) crosslinked fine particles, (D) light It is characterized by a photosensitive insulating resin composition comprising a sensitive acid generator and (E) a solvent.

  In the photosensitive insulating resin composition, 1 to 100 parts by weight of the compound (B), 1 to 50 parts by weight of the crosslinked fine particles (C), and a photosensitive acid with respect to 100 parts by weight of the alkali-soluble resin (A). The generator (D) is preferably contained in an amount of 0.1 to 10 parts by weight.

  According to the photosensitive insulating resin composition of the present invention, (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound containing at least two alkyl etherified amino groups in the molecule, ( C) Since it contains crosslinked fine particles and (D) a light-sensitive acid generator, it has excellent resolution and heat resistance, as well as various properties such as resolution, electrical insulation, thermal shock resistance, and chemical resistance. An excellent cured product can be obtained.

  Such a photosensitive insulating resin composition is excellent in resolution, and its cured product is excellent in electrical insulation, thermal shock resistance, heat resistance, and chemical resistance. Therefore, the photosensitive insulating resin composition of the present invention can be suitably used particularly as a solder resist for a multilayer circuit board of a semiconductor element, a material for forming a fine wiring, or the like.

Hereinafter, the photosensitive insulating resin composition according to the present invention and the cured product thereof will be specifically described.
[Photosensitive insulating resin composition]
The photosensitive insulating resin composition in the present invention comprises (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound containing at least two or more alkyl etherified amino groups in the molecule, (C) cross-linking Fine particles, (D) a light-sensitive acid generator, and (E) a solvent. Moreover, the photosensitive insulating resin composition of this invention may contain other additives, such as an epoxy resin, an inorganic filler, a coloring agent, a sensitizer, and a leveling agent, as needed.
(A) an alkali-soluble resin having a phenolic hydroxyl group;
The alkali-soluble resin having a phenolic hydroxyl group (hereinafter referred to as “phenol resin (A)”) used in the present invention is not particularly limited, but specifically, phenol / formaldehyde condensation novolak resin, cresol / formaldehyde condensation are used. Novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, polyhydroxystyrene and its copolymer, phenol-xylylene glycol condensed resin, cresol-xylylene glycol condensed resin, phenol-dicyclopentadiene condensed resin, etc. . Two or more kinds of such phenol resins may be mixed and used.

A phenolic low molecular weight compound (hereinafter referred to as “phenol compound (a)”) can be used in combination with the alkali-soluble resin having a phenolic hydroxyl group. For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ) Ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6 -Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) ) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like.

  These phenolic low molecular weight compounds (a) are contained in the alkali-soluble resin (A) having a phenolic hydroxyl group in an amount of 0 to 40% by weight, particularly 0 to 30% by weight, as part of the component (A). It only has to be. The phenol resin (A) is required to have a weight average molecular weight of 2000 or more, particularly in the range of 2000 to 20000, from the viewpoints of resolution, developability, plating solution resistance and the like of the obtained insulating layer. Is preferred.

In the composition of the present invention, the content ratio of the phenol resin (A) (the total amount when the phenol compound (a) is used in combination with the phenol resin (A)) is a ratio at which the obtained insulating layer exhibits sufficient alkali solubility. Usually, it is 30 to 75% by weight of the whole composition, preferably 40 to 70% by weight. When the ratio of the phenol resin (A) is in such a range, the insulating thin film formed using the resulting composition has sufficient developability with an alkaline aqueous solution. Moreover, when it exists in such a range, the insulating layer obtained by further hardening is excellent also in toughness, heat resistance, and plating solution resistance.
(B) Compound having at least two alkyl etherified amino groups in the molecule Compound having at least two alkyl etherified amino groups in the molecule (hereinafter referred to as “crosslinking agent (B)”) .) Acts as a crosslinking component that reacts with the phenol resin (A). The amino group at least alkyl etherified in the molecule is represented by the following formula, for example.

—NHR ¹ —O—R ²
(In the formula, R ¹ represents an alkylene group (a divalent hydrocarbon group), and R ² represents an alkyl group.)
As such a crosslinking agent (B), active polymethylol groups (CH ₂ OH) in nitrogen compounds such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, etc. Examples thereof include compounds in which all or part (however, at least two) of the groups are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and the alkyl groups constituting the alkyl ether contained in the crosslinking agent (B) at least two are the same as each other. Or different. Moreover, in such a crosslinking agent (B), when the methylol group which is not alkyl-etherified is contained in the compound, even if the methylol groups are self-condensed, the methylol groups of two or more compounds are The oligomer component may be formed by condensation.

Specific examples of the crosslinking agent (B) used in the present invention include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, and the like. These crosslinking agents (B) may be used alone or in combination of two or more. The blending amount of the crosslinking agent (B) in the present invention is 100 parts by weight of the phenol resin (A) [when the phenol compound (a) is used in combination with the phenol resin (A), the total amount thereof is 100 parts by weight, which will be described later (C 1 to 100 parts by weight, preferably 5 to 50 parts by weight with respect to the same for the components)) to (E)]. If the blending amount is less than 1 part by weight, curing by exposure becomes insufficient, patterning may become difficult, and the heat resistance of the resulting cured product may decrease. If the amount exceeds 100 parts by weight, the resolution will decrease. In some cases, electrical insulation may be reduced.
(C) crosslinked fine particles;
As the crosslinked fine particles (C) according to the present invention, those having a Tg of 0 ° C. or less are used. Such crosslinked fine particles (C) are present in a state of being uniformly dispersed in the composition of the present invention, act as a buffer material against thermal shock resistance, and exhibit excellent characteristics.

  Such a crosslinked fine particle (C) is not particularly limited as long as Tg is within the above range and is compatible to some extent with other components. One or more crosslinkable monomers (hereinafter referred to as “crosslinkable monomers”) and one or more other monomers (hereinafter referred to as “other monomers”) selected so that the Tg of the crosslinked fine particles (C) is 0 ° C. or less. In particular, crosslinked fine particles obtained by copolymerizing a monomer having a functional group other than a polymerizable group, for example, a functional group such as a carboxyl group, an amino group, and a hydroxyl group, with a crosslinkable monomer as the other monomer. (C) is preferably used.

  Examples of cross-linkable monomers include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol di Examples thereof include compounds having a plurality of polymerizable unsaturated groups such as (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, divinylbenzene is preferable.

Examples of other monomers include butadiene, isoprene, dimethylbutadiene, chloroprene, 1,3-pentadiene, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid Unsaturated nitrile compounds such as nitrile, cinnamate nitrile, itaconic dinitrile, maleic dinitrile, fumarate dinitrile, (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis ( (Meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (
2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide,
Unsaturated amides such as amide group-containing unsaturated compounds such as dimethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth ) Hexyl acrylate, (meth) acrylate lauryl, polyethylene glycol (meth) acrylate, (meth) acrylates such as polypropylene glycol (meth) acrylate, styrene, α-methylstyrene, o-methoxystyrene, p-hydroxy Aromatic vinyl compounds such as styrene and p-isopropenylphenol, epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxyl-containing unsaturated compounds such as loxybutyl (meth) acrylate, (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β -Unsaturated acid compounds such as (meth) acryloxyethyl and hexahydrophthalic acid-β- (meth) acryloxyethyl, and amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate It can be illustrated.

  Among these other monomers, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth) acrylic acid Hydroxyalkyl (meth) acrylates and the like are preferably used.

  The crosslinked fine particles (C) used in the present invention preferably have a crosslinkable monomer and other monomers in a range of 1 to 20% by weight of the crosslinkable monomer with respect to the total of the crosslinkable monomer and other monomers. More preferably, a copolymer having a composition in the range of 2 to 10% by weight is desirable. Further, a method for producing the crosslinked fine particles (C) will be described in detail.

The production of the crosslinked fine particles (C) is not particularly limited, and examples thereof include an emulsion polymerization method. That is, a crosslinkable monomer and other monomers are emulsified in water using a surfactant, and a radical polymerization initiator such as a peroxide catalyst or a redox catalyst is used as a polymerization initiator. In the presence of a molecular weight regulator such as a hydrofluoric acid, polymerization is performed at 0 to 50 ° C., and after reaching a predetermined polymerization addition rate, N,
Crosslinked fine particles can be synthesized by adding a reaction terminator such as N-diethylhydroxylamine to stop the polymerization reaction, and then removing unreacted monomers in the polymerization system by steam distillation or the like.

  The surfactant used when the crosslinked fine particle component is produced by emulsion polymerization is not particularly limited, and examples thereof include anionic surfactants such as alkylnaphthalene sulfonate and alkylbenzene sulfonate, and alkyltrimethylammonium. Nonionic surfactants such as salts, cationic surfactants such as dialkyldimethylammonium salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, and the like Any of amphoteric surfactants, further reactive emulsifiers, or a mixture of a plurality of surfactants can be used.

In addition, it is possible to produce crosslinked fine particles without using a crosslinking monomer, and as a method thereof,
・ A method of adding a peroxide or the like as a crosslinking agent to a latex particle to crosslink the latex particle ・ A method of gelling in the latex particle by increasing the polymerization conversion rate ・ A metal salt using a functional group such as a carboxyl group Examples thereof include a method of crosslinking within the particles by adding a crosslinking agent such as.

The latex containing crosslinked fine particles obtained by such emulsion polymerization can be solidified by a method such as salting out, washed with water and dried to be taken out as a solid crosslinked fine particle component. In addition to the salting-out method for solidifying the crosslinked fine particles, if a nonionic surfactant is used as the surfactant, it is heated above the cloud point of the nonionic surfactant to solidify the crosslinked fine particle component. You can also Furthermore, even when the polymerization is performed using a surfactant other than the nonionic surfactant, the crosslinked fine particle component can be solidified by adding the nonionic surfactant after the polymerization and heating to a cloud point or higher. .

  In the present invention, the particle size of the crosslinked fine particle component is usually 30 to 500 nm, preferably 40 to 200 nm. The method for controlling the particle size of the crosslinked fine particles is not particularly limited. For example, when the crosslinked fine particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is controlled by the amount of the emulsifier used to control the particle size. The method of controlling can be illustrated.

In the resin composition according to the present invention, the crosslinked fine particles (C) are desirably blended in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the phenol resin (A). . If the blending amount is less than 1 part by weight, the thermal shock resistance of the resulting cured film may be lowered, and if it exceeds 50 parts by weight, the heat resistance is lowered or the compatibility with other components is lowered. Such crosslinked fine particles (C) are highly compatible with the component (A) and the like and do not necessarily require modification with an epoxy compound or the like.
(D) a photosensitive acid generator;
The photo-sensitive acid generator (hereinafter referred to as “acid generator (D)”) used in the present invention is a compound that generates an acid upon irradiation with radiation or the like, and a crosslinking agent (B ) And the phenolic resin (A) react with dealcoholization and cure, so that a negative pattern can be formed by using the photosensitive insulating resin composition according to the present invention. .

  The acid generator (D) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation or the like. And so on. Specific examples are shown below.

Onium salt compounds:
Examples of onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.

Specific examples of preferable onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluorochlorosulfonate, Phenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n- Butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate Or the like can be mentioned the door.

Halogen-containing compound: Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-
Mention may be made of s-triazine derivatives such as triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine. it can.

Diazoketone compound: Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like, and specific examples include 1,2-naphthoquinonediazide-4-phenol of phenols. Examples include sulfonic acid ester compounds.

Sulfone compounds: Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone and mesitylphenacyl. Examples include sulfone and bis (phenacylsulfonyl) methane.

  Sulfonic acid compounds: Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and the like. Specific examples include benzoin tosylate, pyrogallol tris-trifluoromethane. Examples thereof include sulfonate, o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, and the like.

Sulfonimide compound: Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide,
N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

  Diazomethane compound: Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane. In this invention, these acid generators (D) can be used individually by 1 type or in mixture of 2 or more types.

Moreover, the compounding quantity of an acid generator (D) is 0.1-10 weight part with respect to 100 weight part of phenol resin (A) from a viewpoint of ensuring the sensitivity of the resin composition of this invention, resolution, a pattern shape,
Preferably it is 0.3-5 weight part. In this case, if the blending amount of the acid generator (D) is less than 0.1 part by weight, the curing is insufficient, the heat resistance is lowered, and if it exceeds 10 parts by weight, the transparency to radiation is lowered and the pattern shape is reduced. There is a risk of causing deterioration.

Furthermore, in the resin composition according to the present invention, various sensitizers may be blended as necessary in order to increase the acid generation efficiency of the acid generator (D).
(E) solvent;
The organic solvent (E) is added to improve the handleability of the resin composition and to adjust the viscosity and storage stability. The type of the organic solvent is not particularly limited, but examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol mono Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene Glycol monomethyl ether ace Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate,
Aliphatic carboxylic acid esters such as n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, 3-methoxypropionic acid Other esters such as ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-heptanone, 3-heptanone, 4 -Ketones such as heptanone and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolacun. These organic solvents can be used alone or in combination of two or more.

The amount of the solvent used in the present invention is appropriately selected according to the use of the composition and the coating method used, and is not particularly limited as long as the composition can be made uniform. Usually, the obtained liquid composition is used in an amount of 5 to 60% by weight, preferably 10 to 40% by weight.
Other components (F):
The photosensitive resin resin composition of the present invention can contain an epoxy resin as the other additive (F). Specifically, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol Type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin and the like. Moreover, an inorganic filler can also be added, and specific examples include silica, aluminum hydroxide, barium sulfate and the like. Furthermore, polymer additives, reactive diluents, leveling agents, wettability improvers, surfactants, plasticizers, antioxidants, antistatic agents, antifungal agents, humidity control agents, flame retardants, etc. You can also.
Preparation Method of Composition The resin composition according to the present invention may be prepared by dispersing and mixing a predetermined amount of each of the above components using a disperser such as a dissolver, a homogenizer, or a three roll mill. Moreover, you may filter using a mesh membrane filter etc. as needed. The photosensitive insulating resin composition according to the present invention comprises a phenol resin (A), a crosslinking agent (B), a crosslinked fine particle (C), an acid generator (D), a solvent (E), and other additives as required. It contains (F) and is excellent in resolution, and the cured product is excellent in electrical insulation, thermal shock, heat resistance, and chemical resistance.

Therefore, the photosensitive insulating resin composition of the present invention can be suitably used particularly as a solder resist for a multilayer circuit board of a semiconductor element, a material for forming a fine wiring, or the like.
[Cured product]
The cured product according to the present invention is obtained by curing the photosensitive insulating resin composition described above.

  For example, it is used as the following cured product. The photosensitive insulating resin composition according to the present invention described above is applied to a support such as a silicon wafer or an alumina substrate with a copper-clad laminate or a copper sputtered film, and dried to volatilize the solvent and the like to form a coating film. Form. Thereafter, exposure is performed through a desired mask pattern, and heat treatment (hereinafter, this heat treatment is referred to as “PEB”) is performed to promote the reaction between the phenol resin and the crosslinking agent. Subsequently, it develops with an alkaline developing solution, A desired pattern can be obtained by melt | dissolving and removing an unexposed part.

Furthermore, a cured film can be obtained by exposing the entire film after development and performing a heat treatment in order to develop insulating film characteristics. Examples of the method for applying the resin composition to the support include, for example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, an ink jet method, and the like. The coating method can be used. The coating thickness can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the composition solution.

Examples of radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, i-line steppers, and other ultraviolet rays, electron beams, laser beams, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the film thickness is 10 to 50 μm, and 1,000 to 2 is selected.
An exposure of an amount of about 10,000 J / m ² is performed.

  After the exposure, PEB treatment is performed to promote the curing reaction of the phenol resin (A) and the crosslinking agent (B) by the generated acid. The conditions vary depending on the blending amount of the resin composition and the used film thickness, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. Then, it develops with an alkaline developing solution, and forms a desired pattern by dissolving and removing an unexposed part (uncured resin composition). Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, a paddle developing method, and the like. The developing conditions are usually 20 to 40 ° C. for about 1 to 10 minutes.

  Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of about 1 to 10% by weight. Can be mentioned. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In addition, after developing with an alkaline developer, it is washed with water and dried.

Furthermore, in order to sufficiently develop the characteristics as an insulating film after development, the entire surface of the film can be exposed and heat-treated to be sufficiently cured. Such curing conditions are not particularly limited, but depending on the use of the cured product, for example, exposure to 10,000 to 50,000 J / m ^{2 by} ultraviolet irradiation of a high-pressure mercury lamp, and 50 to 200 ° C. The composition can be cured by heating at a temperature for about 30 minutes to 10 hours.

  Moreover, in order to fully advance hardening and to prevent the deformation | transformation of the obtained pattern shape, it can also heat in two steps, for example, at the temperature of 50-100 degreeC in a 1st step, 10 minutes-2 It can also be heated for about an hour, and further cured by heating at a temperature of 80 to 200 ° C. for about 30 minutes to 10 hours. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as a heating means.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples.
In the following examples and comparative examples, parts are used in terms of parts by weight unless otherwise specified. Moreover, about each characteristic of hardened | cured material, it implemented in the following way.

Resolution;
A photosensitive insulating resin composition is applied to a copper-clad laminate (substrate thickness: 0.6 mm, size: 10 cm square) whose surface has been roughened, heated in a convection oven at 90 ° C. for 10 minutes, and uniformly 30 μm thick A special coating film was prepared. Thereafter, using an aligner (MA-100 manufactured by Karl Suss), UV light from a high-pressure mercury lamp is exposed through a pattern mask so that the exposure amount at a wavelength of 350 nm is 3,000 to 5,000 J / m ^2. PEB was carried out at 90 ° C. for 15 minutes in an oven, and shower development (pressure; 3 kgf / cm ² ) was performed at 30 ° C. for 3 minutes using a 1 wt% aqueous sodium hydroxide solution. The minimum dimension of the obtained pattern was taken as the resolution.

Electrical insulation (volume resistivity);
The photosensitive insulating resin composition was applied to a SUS substrate and heated in a convection oven at 90 ° C. for 10 minutes to produce a uniform resin film having a thickness of 30 μm. Using a high-pressure mercury lamp for this coating, a wavelength of 350
It exposed so that the exposure amount in nm might be 10,000 J / m < ² >. Thereafter, the film was heated in a convection oven at 150 ° C. for 2 hours and further at 170 ° C. for 2 hours to obtain a cured film. The obtained cured film was subjected to a resistance test for 500 hours under the conditions of temperature: 85 ° C., humidity: 85% using a constant temperature and constant chamber test apparatus (manufactured by Tabai Espec Co., Ltd.). The volume resistivity between the layers before and after the test was measured to confirm the resistance.

Thermal shock resistance;
The resin composition was applied to the substrate shown in FIG. 1 and heated in a convection oven at 90 ° C. for 10 minutes to obtain a uniform resin coating having a thickness of 30 μm. Thereafter, ultraviolet rays of 10,000 J / m ² were exposed using a high-pressure mercury lamp and heated at 150 ° C. for 2 hours and further at 170 ° C. for 2 hours to obtain a cured film. The substrate was subjected to a resistance test using a thermal shock tester (TSA-40L manufactured by Tabai Espec Co., Ltd.) with one cycle of -55 ° C / 30 minutes to 125 ° C / 30 minutes. The number of cycles in which defects such as cracks occurred in the cured film was confirmed.

Heat resistance: A cured film of a resin composition was prepared and 3 mm with a thickness of 50 μm was obtained by DMA
Using a test piece of × 20 mm, the glass transition temperature (Tg) was determined by measuring under the conditions of a load of 3.0 g and a heating rate of 5.0 ° C./min, and used as a heat resistance index. Higher Tg means better heat resistance.

chemical resistance;
The photosensitive insulating resin composition was applied to a SUS substrate and heated in a convection oven at 90 ° C. for 10 minutes to produce a uniform resin film having a thickness of 30 μm. Using a high-pressure mercury lamp for this coating, a wavelength of 350
It exposed so that the exposure amount in nm might be 10,000 J / m < ² >. Thereafter, the film was heated in a convection oven at 150 ° C. for 2 hours and further at 170 ° C. for 2 hours to obtain a cured film. The obtained cured film was immersed in various chemicals (alkali, organic solvent) to confirm the resistance of the film.

The alkali resistance was soaked in a 10% by weight sodium hydroxide aqueous solution (40 ° C.) for 30 minutes, and the organic solvent resistance was soaked in acetone (30 ° C.) for 30 minutes.
○: No change
Δ: Partial membrane whitening,
X: Peeling and film surface roughness The following components were used in Examples and Comparative Examples.
Phenolic resin;
A-1: Cresol novolak resin composed of m-cresol / p-cresol = 60/40 (molar ratio) (weight average molecular weight in terms of polystyrene = 8,700)
A-2: Polyhydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd., trade name: Marcalinker S-2P)
A-3: Phenol-xylylene glycol condensation resin (Mitsui Chemicals, trade name: XLC-3L)
Phenolic compounds;
a-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane crosslinking agent; B-1: hexamethoxymethylmelamine (Mitsui Cytec Co., Ltd., trade name: Cymel 300)
B-2: Tetramethoxymethylglycoluril (Mitsui Cytec Co., Ltd., trade name: Cymel 1174)
Crosslinked fine particles;
C-1: Fine particles copolymerized with butadiene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 67/25/6/2 (% by weight), average particle size = 60 nm
C-2: Butadiene / acrylonitrile / methacrylic acid / divinylbenzene = 62/2
Fine particles copolymerized at 5/10/3 (% by weight), average particle size = 68 nm
Acid generator;
D-1: styryl-bis (trichloromethyl) -s-triazine D-2: 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate
solvent;
E-1: Ethyl lactate E-2: 2-Heptanone
Other additives;
F-1: o-phenol novolak type epoxy resin (Oka Shell, Inc., trade name: EP-152)
F-2: Tetraphenol type epoxy resin (Oilized Shell Co., Ltd., trade name: EP-1031S)
[Example 1]

As shown in Table 1, phenol resin (A-1): 100 parts by weight, crosslinking agent (B-1) 30 parts by weight, crosslinked fine particles (C-1): 10 parts by weight, and acid generator (D-1) 2 parts by weight was mixed with 120 parts by weight of solvent: ethyl lactate (abbreviated as “E-1”) to prepare a photosensitive insulating resin composition.

  The properties of this composition were evaluated according to the evaluation method. The obtained results are shown in Table 2. [Examples 2 to 6]

A photosensitive insulating resin composition having the composition shown in Table 1 was prepared in the same manner as in Example 1, and these characteristics were measured in the same manner as in Example 1. The results are shown in Table 2.
[Comparative Examples 1-4]

  Each composition shown in Table 1 was prepared, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

FIG. 1 is a schematic diagram of cross-sections of base materials prepared in Examples and Comparative Examples. FIG. 2 is a schematic diagram of the substrate surface prepared in Examples and Comparative Examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Board | substrate 3 ... Copper foil

Claims (3)

(A) an alkali-soluble resin having a phenolic hydroxyl group,
(B) a compound containing in the molecule at least two or more alkyl etherified amino groups,
(C) crosslinked fine particles,
A photosensitive insulating resin composition comprising (D) a photosensitive acid generator and (E) a solvent. For 100 parts by weight of the alkali-soluble resin (A),
1 to 100 parts by weight of the compound (B),
1 to 50 parts by weight of the crosslinked fine particles (C),
The photosensitive insulating resin composition according to claim 1, wherein the photosensitive acid generator (D) is contained in an amount of 0.1 to 10 parts by weight.   A cured product obtained by curing the photosensitive insulating resin composition according to claim 1.

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