JP2003026762A - Curable resin, curable resin composition, and cured item thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin which gives a curable resin composition which is curable at low temperatures, can be developed with an aqueous dilute alkali solution by a photo method, and is suitable as a solder resist for a printed circuit board or as an interlayer insulation film for a build-up substrate or a chip mounted substrate. SOLUTION: This curable resin comprises a compound represented by formula (1) (wherein R1 to R8 are each H, a halogen or a 1-6C hydrocarbon group; R is H or methyl; X is H, a 1-6C hydrocarbon group or a polybasic acid group represented by-OC-A(COOH)n ; A is a polybasic acid residue; and n is 1, 2 or 3) or its oligomer. The curable resin composition essentially contains the resin and a photoor thermal polymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin, a curable resin composition and a curable resin composition which can be used for an insulating layer such as a circuit protection of a printed circuit board or a build-up board or a chip mounting board. It relates to the obtained cured product.

[0002]

2. Description of the Related Art Solder resist ink is usually used as a coating film forming method from the viewpoint of being used for an insulating protective film of an exposed conductor circuit of a printed wiring board and for preventing solder from adhering to a portion of the circuit where soldering is unnecessary. Is applied to the cured film, and the cured film has solder heat resistance, moisture resistance, adhesion,
Chemical resistance, plating resistance, and electrolytic corrosion resistance are required. There are two types of this type of solder resist, a thermosetting type and an ultraviolet curing type. The former is mainly an epoxy resin, and the latter is an epoxy acrylate resin. However, in recent years, due to the miniaturization of conductor circuit patterns on various printed wiring boards and the improvement of positional accuracy, and further miniaturization of mounted parts,
Insulating film formation by solder resist is changing to screen printing method, and image formation by photo method is becoming mainstream. Although organic solvents have been conventionally used for developing resists by the photo method, it is desired to use a dilute aqueous alkali solution from the viewpoint of air pollution and safety.
Due to such a background, there arises a problem that a conventional solder resin cannot be satisfied with a conventional screen printing-compatible epoxy resin or epoxy acrylate resin.

As a measure for the photo method and the development of a dilute alkaline aqueous solution, for example, a phenol novolac type epoxy acrylate resin or a bisphenol A epoxy acrylate resin, or a half ester compound obtained by a reaction of these epoxy acrylate resins and an acid dianhydride is known. (For example, JP-A-61-243869, JP-B-5
6-40329). However, when these known epoxy acrylate resins or acid anhydride modified products thereof are used as a resin composition for a solder resist, the developability of a dilute alkaline aqueous solution is satisfied, but the curing temperature is at least 180 to stabilize the physical properties. The temperature is required to be higher than 0 ° C., the heating equipment is expensive, and when a glass epoxy substrate is used as the core substrate, for example, the curing temperature is too high, which may cause discoloration or warpage of the substrate. Furthermore, a cured coating obtained from these known epoxy acrylate resins or acid anhydride modified products thereof has solder heat resistance, moisture resistance, adhesion,
There is a problem that chemical resistance, plating resistance, electrolytic corrosion resistance, etc. are not sufficient.

With the recent increase in the density of printed wiring boards,
The insulation layer for the build-up board for MCM (multi-chip module) and the chip mounting board such as CSP (chip size package) is required to have reliability, pressure cooker resistance and thermal cycle resistance. When an acrylate resin or its acid anhydride modified product is used as a solder resist resin composition, there is also a problem that sufficient reliability cannot be exhibited.

As described above, from the viewpoint of heat resistance of the substrate material and manufacturing equipment, low temperature curing is possible, development with dilute alkaline water by the photo method is possible, and solder heat resistance required for the solder resist of the printed wiring board. , Moisture resistance, adhesion, chemical resistance, plating resistance, electrolytic corrosion resistance, and MC
None of them sufficiently satisfies the reliability required for the insulating layer cured film of the high-density mounting substrate such as M.

[0006]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a curable resin which can be cured at a low temperature of 160 ° C. or lower and can be developed with dilute alkaline water by a photo method, and a curable resin composition containing the same as a main resin component. To provide. Further, an object of the present invention is to obtain solder heat resistance, moisture resistance, adhesiveness, chemical resistance, and solder resistance required for a solder resist of a printed wiring board.
(EN) It is intended to provide a curable resin composition excellent in plating resistance, electrolytic corrosion resistance, and reliability required for an insulating layer of a buildup substrate and the like, and a cured product thereof.

[0007]

That is, the present invention is a curable resin comprising a compound represented by the following general formula (1) or the compound and an oligomer thereof.

[Chemical 2] (However, R _{1 to} R ₈ represent hydrogen, halogen or a hydrocarbon group having 1 to 6 carbon atoms, R is hydrogen or a methyl group, X is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms or -OC-A. (COOH) n represents a polybasic acid group represented by A. A is a residue of a polybasic acid, and n represents 1, 2 or 3) Further, the present invention provides a benzene ring with halogen or a carbon number of 1 ~
Obtained by reacting (meth) acrylic acid or a lower alkyl ester of (meth) acrylic acid with an bisphenol F type epoxy compound which may have a hydrocarbon group of 6 or an epoxy resin comprising the compound and an oligomer thereof. It is a curable resin composed of a compound. Further, the present invention, the epoxy resin, a curable resin from a compound obtained by reacting (meth) acrylic acid, a curable resin comprising a compound having an ester bond obtained by reacting a polybasic acid compound is there.

The present invention is also the above-mentioned curable resin containing 5 mol% or more of a compound in which X in the general formula (1) is a polybasic acid group. Furthermore, the present invention is the above curable resin, wherein the ratio of the polybasic acid group in X in the general formula (1) is in the range of 10 to 100 mol%.

The present invention also provides a curable resin composition containing the above-mentioned curable resin and a photo or thermal polymerization initiator as essential components, and a curable resin composition further containing a polyfunctional acrylate in the composition. is there. Further, the present invention provides 120-160.
The above-mentioned curable resin composition has a curing rate of 80 to 95% when the curing time is 1 hour in the entire range of ° C. Further, the present invention is a resin cured product obtained by curing the curable resin composition described above with light or heat.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The curable resin of the present invention comprises a compound represented by the above general formula (1) or an oligomer thereof, and has an average number of repetitions of 1
-10, preferably 1-5. In the general formula (1), R is hydrogen or a methyl group, and R in one molecule may be the same or different. Further, in the general formula (1), R _{1 to} R ₈
Each independently represent hydrogen, halogen or a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group,
Examples thereof include a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group. R _{1 to} R ₈ are preferably a hydrogen atom or a methyl group, and in the case of a hydrocarbon group such as a methyl group, a hydrocarbon group having the same target position such as R ₁ and R ₅ and R ₂ and R _6. Is preferred. Preferred examples include the case where all are hydrogen or a methyl group, R ₁ and R ₅ ,
One, two or three of the three combinations of R ₂ and R ₆ , R ₃ and R ₈ may be a methyl group.

In the above general formula (1), X represents hydrogen, a hydrocarbon group having 1 to 6 carbon atoms or a polybasic acid group represented by -OC-A (COOH) n. Where A is the residue of the polybasic acid and n
Indicates 1, 2 or 3. In the general formula (1), all Xs do not have to be the same, and even if one molecule has hydrogen and a hydrocarbon group or a polybasic acid group, the polybasic acid group and the hydrogen or hydrocarbon group It does not matter even if it has. Further, the curable resin of the present invention is a compound having only hydrogen, a hydrocarbon group having 1 to 6 carbon atoms or a polybasic acid group represented by -OC-A (COOH) n in one molecule, Even if the resin consisting of a compound having hydrogen and a hydrocarbon group or a polybasic acid group, or a compound having a polybasic acid group and hydrogen or a hydrocarbon group alone, some of the above compounds It can also be a resin consisting of a mixture containing. When a part of X is a polybasic acid group, it is often a resin composed of a mixture containing some of the above compounds, and gives a preferable curable resin.

In the above general formula (1), the compound in which X is hydrogen is a bisphenol F type epoxy compound represented by the following general formula (2) or an epoxy resin composed of an oligomer thereof, preferably having an average number of repetitions: It can be produced by reacting 1 to 5, more preferably 1 to 2 epoxy resin with (meth) acrylic acid (meaning acrylic acid, methacrylic acid, or both).

[Chemical 3] (However, R _{1 to} R ₈ represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms) Here, of acrylic acid and methacrylic acid, acrylic acid is preferable. The reaction is usually 50 ° C to 150 ° C
In the range of 1 hour to 20 hours.

In the general formula (1), when X is a hydrocarbon group having 1 to 6 carbon atoms, the epoxy resin and CH ₂ CRCOOX (R represents H or a methyl group)
It can be produced by reacting a (meth) acrylic acid ester represented by

Preferred examples of the (meth) acrylic acid ester include lower alkyl esters such as acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester and methacrylic acid propyl ester. To be The reaction is usually 1 in the range of 50 ° C to 150 ° C.
It is performed in the range of 20 hours to 20 hours.

In the case of the compound of the general formula (1) in which X is a polybasic acid group, a compound of the general formula (1) in which X is H,
It can be produced by reacting with a polybasic acid compound, typically an acid dianhydride represented by the following general formula (3) or an acid dianhydride represented by the following general formula (4). Further, the polybasic acid may be trimellitic anhydride or the like.

[Chemical 4] (However, A represents a residue of an aromatic or aliphatic polybasic acid and may have a substituent)

As the acid dianhydride, diphenyl ether tetracarboxylic acid anhydride, diphenyl sulfone tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid anhydride, anthracene tetracarboxylic acid anhydride, phenanthrene tetracarboxylic acid anhydride Compounds, hexafluoroisopropylidene bis (phthalic anhydride), ethylene glycol bis (anhydrotrimate), methylcyclohexene tetracarboxylic acid anhydride, tetramethyldisiloxane tetracarboxylic acid anhydride and the like. Preferred are biphenyl tetracarboxylic acid anhydride, diphenyl ether tetracarboxylic acid anhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic acid anhydride.

Examples of the acid monoanhydride include maleic anhydride, succinic anhydride, itaconic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylnadic anhydride. Acid, dodecynyl succinic anhydride,
There are chlorendic anhydride and trimellitic anhydride.
Preferably, tetrahydrophthalic anhydride is used.

In the general formula (1), in order to obtain a compound or oligomer having a single X, it is typically selected from (meth) acrylic acid or (meth) acrylic acid ester.
The compound of one kind is reacted with the epoxy compound or oligomer represented by the general formula (2) in a stoichiometric amount, or one kind of polybasic acid compound is represented by the general formula (1). It is obtained by reacting the compound with a theoretical amount. To obtain a compound or oligomer in which X is different,
Two or more kinds of compounds selected from (meth) acrylic acid or (meth) acrylic acid ester are used in combination, or a compound or oligomer in which at least a part of X in the general formula (1) is H and two or more kinds of polybasic acids It is obtained by reacting a compound or by reacting H with a polybasic acid in an amount less than the theoretical amount. For example, as the polybasic acid, it is also possible to use an acid monoanhydride and an acid dianhydride together, preferably 5 mol% or more of X, more preferably 10 to 100 mol%, further preferably 20 to 80 mol. % Is preferably a polybasic acid group, and the ratio of the polybasic acid group generated from the acid monoanhydride and the acid dianhydride is preferably about 10/90 to 90/10. When an acid dianhydride is used, two X's in the general formula (1) may react with an acid dianhydride to form an oligomer, which is also the thermosetting resin of the present invention. is there.

The curable resin composition of the present invention can be obtained by adding a photopolymerization initiator or a radical polymerization initiator to the thermosetting resin of the present invention. In addition, it is also advantageous to blend a polyfunctional acrylate. 3 of resin components (resin and components that become resin after curing) in the curable resin composition of the present invention
0 wt% or more, preferably 50 wt% or more, more preferably 70 wt% or more is the thermosetting resin of the present invention.

As the photopolymerization initiator, various known photopolymerization initiators can be used. Preferred photopolymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether,
Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-
Hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinol propane, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1 -Chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, etc. Can be mentioned. These may be used alone or in combination of two or more.

The amount of the photopolymerization initiator used is 0 to 100 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of the compound represented by the general formula (1). Parts by weight. Further, the curable resin composition 100
It is usually 0 to 50 parts by weight, preferably 1 to 20 parts by weight, based on parts by weight. When using a thermal polymerization initiator, it is not necessary to use a photopolymerization initiator, but the curable resin composition of the present invention is exposed to light and is excellent in developability. It is advantageous to use it as a resin composition.

Further, these photopolymerization initiators and one or more known photosensitizers can be used at the same time. As the photosensitizer, for example, Michler's ketone,
N, N-dimethylaminobenzoic acid ethyl ester, N,
Examples include N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. The amount of the photosensitizer used is 0 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.05, based on 100 parts by weight of the compound represented by the general formula (1).
~ 2 parts by weight. Further, it is usually 0 to 10 parts by weight, and preferably 0.01 to 5 parts by weight, relative to 100 parts by weight of the curable resin composition.

In order to carry out the thermal polymerization, it is preferable to add a radical polymerization initiator, but it is not necessary to mix it when only the photo-curing is carried out. Preferred radical polymerization initiators include, for example, known benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, tert-butylperoxypiperate, and other peroxides. And 1,1′-azobiscyclohexane-1-carbonitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-
Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (methylisobutyrate), α, α-azobis- (isobutyronitrile),
Examples thereof include azo compounds such as 4,4′-azobis- (4-cyanovaleic acid). The amount of the thermal polymerization initiator used is 0 to 100 parts by weight, preferably 0.02 to 6 parts by weight, relative to 100 parts by weight of the compound represented by the general formula (1).
It is 0 part by weight, more preferably 0.05 to 2 parts by weight.
Further, it is 0 to 50 parts by weight, preferably 0.01 to 30 parts by weight, relative to 100 parts by weight of the curable resin composition of the present invention.

In order to improve the adhesiveness, hardness, alkali resistance, flatness and other characteristics of the cured resin product of the present invention, an epoxy resin (phenol) may be added to the resin composition having the above general formula (1), if necessary. Novolac epoxy resin, cresol novolac epoxy resin, trisphenol methane-based epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc.) and epoxy (meta) obtained by reacting these epoxy resins with (meth) acrylic acid. ) Acrylate, a polymer unsaturated group-containing resin such as a reaction product obtained by reacting the epoxy (meth) acrylate with the acid anhydride, a polymerizable monofunctional and polyfunctional (meth) acrylic acid ester Can be blended.

As the polyfunctional (meth) acrylic acid esters, 2-hydroxyethyl (meth) acrylate,
1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol diacrylate, neopentyl glycol adipate diacrylate, hydroxypivalic acid neopentyl glycol acrylate, dicyclopentanyl diacrylate, caprolactan modification Dicyclopentenyl diacrylate, EO-modified phosphoric acid diacrylate,
Allylated cyclohexyl diacrylate, isodyanurate diacrylate, trimethylolpropane triacrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexaacrylate, pentaerythritol tri (meth) acrylate, PO modified trimethylol trimethylol Propane triacrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactan-modified dipentaerythritol hexaacrylate, 1,3-bis (3-
Examples thereof include acryloxypropyl) -1,1,3,3-tetramethyldisiloxane and 1,3-bis (3-acryloxypropyl) -1,1,3,3-tetramethyldisiloxane.

Other inorganic fillers (eg, talc, silica, alumina, barium sulfate, magnesium oxide, etc.)
, Thixotropic agents (eg, Aerosil), thermoplastic elastomers, rubber components (acrylonitrile rubber, nitrile butadiene rubber, etc.), melamine resins (eg, hexamethoxymelamine, hexabutoxymelamine, etc.), leveling agents ( For example, silicone, fluorine-based polymer, acrylic copolymer, etc., silane coupling agent (eg, epoxy group-containing trimethoxysilane, mercapto group-containing trimethoxysilane, etc.), color pigment (eg, cyanine green, cyanine blue) Etc.),
It is possible to add a defoaming agent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a leveling agent and the like.

As the polyfunctional (meth) acrylate used in the resin composition of the present invention, the above polyfunctional (meth) acrylate can be used. Preferably, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxy (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid Neopentyl glycol (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactane-modified dicyclopentenyl di (meth) acrylate,
EO modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isodyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified di Pentaerythritol tri (meth) acrylate, pentaerythritol (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified diester Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactan modified dipentaerythritol hexa (meth) acrylate 1,3-bis (3-acryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (3-acryloxypropyl) -
Examples include 1,1,3,3-tetramethyldisiloxane. These polyfunctional (meth) acrylates are used to further enhance the above-mentioned photo-curing or heat-curing and improve the chemical resistance, acid resistance, heat resistance, mechanical properties, dielectric constant, dielectric loss tangent and the like of the cured product. It may be used alone, or may be used in combination of two or more.

When the polyfunctional (meth) acrylate is blended, the amount used is usually 5 to 100 parts by weight relative to 100 parts by weight of the curable resin of the present invention, and further for improving the dielectric constant and dielectric loss tangent. Preferably, it is selected in the range of 10 to 50 parts by weight. If this amount is less than 5 parts by weight, the photocurability is insufficient, and the effects of improving the chemical resistance, acid resistance, heat resistance, mechanical properties, dielectric properties, etc. of the cured product are not sufficiently exhibited, and 10
If the amount is more than 0 parts by weight, the surface is hardened so well that the surface layer is cracked or hardened to the inside. The amount used is usually 2.5 to 50 parts by weight, and preferably 5 to 100 parts by weight of the curable resin composition.
25 parts by weight.

The curable resin composition for producing the cured resin of the present invention essentially comprises a curable resin comprising a compound or oligomer represented by the general formula (1) as described above,
The composition contains additives such as a photopolymerization initiator, and preferable compositions include the following. Photopolymerization initiator: 1 to 20 relative to 100 parts by weight of the curable resin of the present invention
Parts by weight, preferably 1 to 5 parts by weight, photosensitizer: 0.01
To 5 parts by weight, preferably 0.5 to 2 parts by weight, radical polymerization initiator: 0.01 to 30 parts by weight, preferably 0.05
To 2 parts by weight, trifunctional or higher polyfunctional (meth) acrylate: 5 to 50 parts by weight, preferably 10 to 50 parts by weight, epoxy resin: 5 to 30 parts by weight, preferably 10 to 20 parts by weight, solvent: desired Viscosity and other solid content: 0
-50 parts by weight, preferably 0-20 parts by weight.

Here, as the curable resin of the present invention, X
Is preferably a compound having a polybasic acid residue of 10 to 100%, and the curable resin of the present invention preferably accounts for 50% by weight or more of the solid content. When the resin composition is blended with epoxy acrylate, polyfunctional acrylate, or the like, and when this is also the compound represented by the general formula (1), it is calculated as the compound represented by the general formula (1).

Among the curable resin compositions of the present invention, the preferable one is in the entire range of 120 to 160 ° C.
Examples thereof include those exhibiting a curing rate of 80 to 95% when the curing time is set to 1 hour. In this case, a photo or thermal polymerization initiator may be included as an essential component. The type and addition amount of the photo or thermal polymerization initiator used here are not particularly limited, but it is preferable to use the photo polymerization initiator and the photosensitizer in combination. The content of the photopolymerization initiator is preferably 0.5 to 7 parts by weight and the photosensitizer is 0.01 to 2 with respect to 100 parts by weight of the curable resin of the present invention. . When the curable resin composition is cured, if the curing rate is less than 80%, soldering heat resistance, moisture resistance reliability, etc. at the time of mounting are deteriorated, which is not preferable. This is not preferable because the resolution at that time is lowered.

The curable resin cured product of the present invention can be obtained by a known method. For example, a resin composition is applied to a printed circuit board by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a spin coating method, or a curtain coating method so as to have a thickness of 5 to 100 μm, and the coating film is applied at room temperature to 1
Heating time at 40 ° C for 1 minute to 120 minutes, preferably 60 ° C
A cured product is obtained by drying at ~ 120 ° C for a heating time of 5 minutes to 60 minutes, and further irradiating with ultraviolet light or heating. Thermosetting conditions are usually 100 ° C to 270 ° C, preferably 160 to 250.
At C, the heating time is 30 minutes to 2 hours.

When the resin composition is an alkali developable resin, after coating and drying by the above-mentioned method, a photomask is brought into direct contact with the coating film, followed by irradiation with ultraviolet rays, and a 0.1 to 2% by weight sodium carbonate aqueous solution is further added. The unirradiated portion of the coating film is dissolved and removed with an alkaline aqueous solution such as 0.1 to 2 wt% diethanolamine and 0.1 to 2 wt% tetramethylammonium hydroxide aqueous solution. Further, a cured product is obtained by thermally curing this at 100 ° C. to 270 ° C., preferably 160 to 250 ° C. for a heating time of 30 minutes to 2 hours.

Development with a dilute alkaline aqueous solution is possible,
In order to obtain a cured film patterned by light, a resin composition containing a curable resin having a polybasic acid group as X in the general formula (1) is used. In the general formula (1), the proportion of polybasic acid groups in X is 10 to 100%, preferably 5
It is in the range of 0 to 100%. If the proportion of polybasic acid groups is less than 10, the unexposed areas are unlikely to dissolve in the alkaline aqueous solution.

[0035]

EXAMPLES The present invention will now be described in detail with reference to Examples and Comparative Examples. Example 1 In a 500 ml four-necked flask equipped with a reflux condenser, 4,4 '
-Bis (2,3-epoxypropyloxy) -3,3 ', 5,5'
-Tetramethyldiphenylmethane (epoxy resin A) 6
8.36 g (0.35 equivalent, epoxy equivalent 195.30
g / eq) acrylic acid 25.22 g (0.35 equivalent)
0.04 g of 2,6-tert-butyl-p-cresol, 0.16 g of benzyltriethylammonium chloride, 0.35 g of tetraethylammonium bromide and 23.53 g of propylene glycol monomethyl ether acetate were added, and the mixture was added at 80 to 90 ° C. for 24 hours. The mixture was heated and stirred to obtain an epoxy acrylate solution. Next, 117.65 g of this epoxy acrylate solution (solid content 94.11 g, 0.
352 equivalents), 25.89 g (0.176 equivalents) of biphenyltetracarboxylic dianhydride (abbreviation BPDA), 13.39 g of tetrahydroacid dianhydride (abbreviation THPA)
(0.088 equivalent) and 79.18 g of propylene glycol monomethyl ether acetate (abbreviation PGMEA) were added, and first, the mixture was stirred at 123 to 126 ° C. for 2 hours under heating,
After confirming that there was no undissolved solid, the temperature was lowered and the mixture was heated and stirred at 59 to 62 ° C. for 8 hours. As a result, a pale yellow transparent viscous resin solution was obtained. The resin solid content concentration of this solution was 56.5%, and the solution acid value was 54.0 mgKOH / g. The NMR chart of this resin is shown in FIG.

Example 2 117.65 g of epoxymethacrylate solution obtained in the same manner as in Example 1 (solid content 94.12 g, 0.352)
34.70 g (0.236 equivalent) of BPDA, P
After adding GMEA (75.86 g) and stirring at 123 to 126 ° C. for 2 hours under heating, and confirming that there is no undissolved solid, the temperature is lowered and further heating and stirring at 59 to 62 ° C. for 8 hours. As a result, a pale yellow transparent viscous resin solution was obtained. The resin solid content concentration of this solution was 56.5%, and the solution acid value was 52.0 mgKOH / g.

Comparative Example 1 181.91 g of cresol novolac type epoxy acrylate solution (EX-5000 manufactured by Kyoeisha Chemical Co., Ltd.) (solid content 14
5.53 g, 0.5 equivalent), THPA 76.08 g
(0.5 equivalents), PGMEA 134.57 g, and tetraethylammonium bromide 0.44 g were added, and 90-
After stirring for 2 hours under heating to 100 ° C and confirming that there is no undissolved solid, the temperature was lowered and the mixture was further heated and stirred at 59 to 62 ° C for 8 hours. A resin solution was obtained. The resin solid content concentration of this solution is 56.5.
%, The solution acid value was 56.8 mgKOH / g.

Example 3 58.31 parts by weight of the resin solution obtained in Example 1 was added with 14.12 parts by weight of trimethylolpropane EO-modified triacrylate (M-360 manufactured by Toagosei Co., Ltd.) and 2-methyl-
1.41 parts by weight of 1- (4-methylthiophenyl) -2-morpholinol propane (Irgacure 907),
0.05 parts by weight of 4,4′-bisdiethylaminobenzophenone (also known as Michler's ketone), epoxy resin A or epoxy resin B (YX-40 manufactured by Japan Epoxy Resin)
00H) 10.72 parts by weight, silane coupling agent 0.
54 parts by weight, leveling agent 0.277 parts by weight, propylene glycol monomethyl ether acetate (PEGMEA)
14.67 parts by weight was added, and the mixture was stirred at room temperature for 3 hours and dissolved to obtain a curable resin composition.

[Thermal UV Cured Resin Substrate and Method for Producing Cured Film] The thermal ultraviolet resin composition prepared in Example 3 was spin-coated onto a glass epoxy substrate (FR).
-4), the entire surface was coated on an aluminum vapor-deposited silicon wafer and pre-dried at 110 ° C. for 10 minutes. Next, the coating film was exposed through a photomask to 200 mj / cm ² of light having a wavelength of 365 nm with an ultrahigh pressure mercury lamp, developed in a 1% by weight diethanolamine aqueous solution for 30 seconds, and post-exposed to 1
Irradiation was performed at 800 mj / cm ² , and then heat curing was performed at 160 ° C. for 60 minutes. The obtained cured film had a thickness of 50 μm and was extremely uniform, and the surface was excellent in smoothness. The coating film applied and cured on the aluminum vapor-deposited silicon wafer was immersed in hydrochloric acid to be peeled off from the silicon wafer to obtain a cured film.

[Evaluation Method of Cured Film] Using the thermal ultraviolet resin cured film substrate and the cured film produced by the above method, the characteristics were measured by the following methods.

Dryability of coating film: Evaluated according to JIS-K5400. The evaluation ranks are as follows. ◯: No tack was observed at all Δ: Slight tack was observed x: Significant tack was observed

Developability in alkaline aqueous solution: 1% by weight
Development was carried out by immersing it in the aqueous solution of diethanolamine for 30 seconds. After development, the resin was enlarged 40 times and the remaining resin was visually evaluated. ○: Completely developed △: Thinly undeveloped part ×: Very undeveloped part

Glass transition temperature: A cured film (width 5 mm, length 15 mm) peeled from a silicon wafer was used as a test piece, and its viscoelasticity was measured by a viscoelasticity measuring device (DMA, UBM Co.) to obtain a tan δ peak. The temperature was taken as the glass transition temperature.

Curability: A silicon wafer was coated by spin coating so as to have a thickness of 4 to 6 μm, and dried and cured under the same conditions as above. The spectrum was measured by the transmission method by FT-IR. The curing rate was determined by the rate of change based on the area ratio between the absorption spectrum of the in-plane bending vibration of the double bond (1405 cm ^-1 ) and the stretching vibration of the benzene nucleus (1500 cm ^-1 ) before curing.

Moisture resistance: Glass epoxy substrate (FR-4)
A test piece was obtained by applying and curing to a test piece, and the appearance change of the cured film was visually observed after boiling in boiling water at 100 ° C. for 2 hours. ◯: No change in appearance Δ: Swelling is observed in a part of the cured film x: Swelling and deformation are observed in a considerable part of the cured film

Solder heat resistance: Glass epoxy substrate (FR-
The test piece was coated and cured on 4), and JISC648
According to 1, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds 10 times, and the change in appearance was visually observed. The evaluation ranks are as follows. ◯: No change in appearance Δ: Discoloration is observed in a part of the cured film. X: Floating, peeling, and solder subside are observed in a considerable part of the cured film

Adhesion with a substrate: A cross-cut is made on a coating applied and cured on a copper-clad substrate so as to make at least 100 grids, and then an adhesive tape (cellophane tape,
Peeling test was performed using Sekisui Chemical Co., Ltd., and the peeled state of the cross was visually observed. The evaluation ranks are as follows. ◯: No peeling was observed at all measuring points Δ: Peeling was observed at 1 to 20 points among 100 measuring points ×: Peeling was observed at 21 or more points among 100 measuring points

Alkali resistance: The same test piece as in the adhesion test was immersed in a 5 wt% sodium hydroxide aqueous solution at 25 ° C. for 24 hours, and the appearance after the immersion was visually observed. The evaluation ranks are as follows. ◯: No change in appearance Δ: Part of the cured film peels off ×: Floating is seen in a considerable part of the cured film, and the cured film peels off easily

Acid resistance: 5 wt% of the same test piece as the adhesion test
% Hydrochloric acid aqueous solution at 25 ° C. for 24 hours, and the appearance after the immersion was visually observed. The evaluation ranks are as follows. ◯: No change in appearance Δ: Part of the cured film peels off ×: Floating is seen in a considerable part of the cured film, and the cured film peels off easily

Solvent resistance: The same test piece as the adhesion test was N-
Immerse in methyl-2-pyrrolidone at 40 ° C. for 10 minutes,
The appearance after the immersion was visually observed. The evaluation ranks are as follows. ◯: No change in appearance Δ: Swelling is observed in a part of the cured film X: Swelling and solvent penetration are observed in a considerable part of the cured film

Gold plating resistance: The same test piece as used in the adhesion test was dipped in a 10% sulfuric acid aqueous solution, and then "Autoronex CI" (Gold plating solution manufactured by Cellrex) was used to obtain a liquid temperature of 4
Gold plating was performed for 10 minutes at 0 ° C. and a current density of 1 A / dm ² to deposit a gold plating having a thickness of 2.0 μm, and then the state of the coating film was evaluated in the same manner as acid resistance.

Resistance to pressure cooker: A glass epoxy substrate provided with a copper pattern was subjected to a pressure cooker tester (manufactured by Tabai Espec Co., Ltd.) at 121 ° C.
After testing for 300 hours under the conditions of 100% RH and 2 atm, the state of the cured coating on the copper pattern was observed with a microscope. The evaluation ranks are as follows. ◯: No change in appearance Δ: Bubbles and peeling are observed in a part of the cured film X: Bubbles and peeling are observed in a considerable part of the cured film

Thermal cycle resistance: A glass epoxy substrate provided with a copper pattern was subjected to a temperature cycle between -65 ° C. and 125 ° C. by a vapor phase thermal shock tester (manufactured by Tabai Espec Co., Ltd.), and the cured film was cracked or peeled. The number of cycles until occurrence of was measured.

Examples 4 to 6 Using the resin solutions obtained in Examples 1 to 2 and using the various materials shown in Table 1 in the same manner as in Example 3, the compounding compositions shown in Table 1 (numerical values are weights). Part) to prepare a photosensitive resin composition, a photosensitive resin cured film substrate and a cured film were prepared by the same method as in Example 3, and the characteristics thereof were measured by the same method as in Example 3.

Comparative Example 2 Using the resin solution obtained in Comparative Example 1, various materials shown in Table 1 were used in the same manner as in Example 3, and blended with the blending composition (numerical values are parts by weight) shown in Table 1. Then, a thermal ultraviolet resin composition was produced, a thermal ultraviolet resin cured film substrate and a cured film were produced by the same method as in Example 3, and its characteristics were measured by the same method as in Example 3. The unit of the numbers in Table 1 is parts by weight.

[0056]

【table 1】

[0057]

[Table 2]

[0058]

EFFECTS OF THE INVENTION According to the present invention, it is possible to cure at a low temperature of 160 ° C. or lower and to develop with a dilute alkaline water by a photo method, and to obtain solder heat resistance, moisture resistance, hardness, chemical resistance, plating resistance, and solder resistance. Since it is excellent in electrolytic corrosion resistance, it is suitable not only as a solder resist of a printed wiring board, but also because it is excellent in reliability, it is suitable as an interlayer insulating film for a chip mounting board such as a build-up board or CSP.

[Brief description of drawings]

FIG. 1 NMR chart of curable resin

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Koichi Fujishiro             7-21-11, Nishigotanda, Shinagawa-ku, Tokyo New             Nittetsu Chemical Co., Ltd. F term (reference) 4J027 AE02 BA08 BA19 BA25 BA27                       BA29 CB03 CB10 CC02 CC03                       CD06                 4J036 AD08 CA21 EA04 GA26 JA08                 5E346 CC08 CC09 EE31

Claims (9)

[Claims] 1. A curable resin comprising a compound represented by the following general formula (1) or the compound and an oligomer thereof. [Chemical 1] (However, R _{1 to} R ₈ represent hydrogen, halogen or a hydrocarbon group having 1 to 6 carbon atoms, R is hydrogen or a methyl group, X is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms or -OC-A. (COOH) n represents a polybasic acid group represented by A. A represents a residue of a polybasic acid, and n represents 1, 2 or 3. 2. A halogen atom or a carbon number of 1 to 6 on the benzene ring.
A compound obtained by reacting (meth) acrylic acid or a lower alkyl ester of (meth) acrylic acid with an bisphenol F type epoxy compound which may have a hydrocarbon group or an epoxy resin comprising the compound and an oligomer thereof Curable resin consisting of. 3. A halogen atom or a carbon number of 1 to 6 on the benzene ring.
The curable resin according to claim 2, which comprises a compound obtained by reacting (meth) acrylic acid with the bisphenol F type epoxy compound which may have a hydrocarbon group or an epoxy resin comprising the compound and an oligomer thereof. A curable resin comprising a compound having an ester bond, which is obtained by reacting a polybasic acid compound. 4. The curable resin according to claim 1, containing 5 mol% or more of a compound in which X in the general formula (1) is a polybasic acid group. 5. The curable resin according to claim 1, wherein the proportion of polybasic acid groups in X in the general formula (1) is in the range of 10 to 100 mol%. 6. A curable resin composition comprising the curable resin according to any one of claims 1 to 5 and a photo or thermal polymerization initiator as essential components. 7. The curable resin composition according to claim 6, which further contains a polyfunctional acrylate. 8. The curable resin composition according to claim 6, which has a curing rate of 80 to 95% when the curing time is 1 hour in the entire range of 120 to 160 ° C. 9. A cured resin product obtained by curing the curable resin composition according to claim 6 with light or heat.