JP2001302871A - Photocurable/thermosetting resin composition and printed wiring board having solder resist coating film and resin insulating layer formed by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alkali development type photocurable/thermosetting resin composition having a large photo-curing depth in exposure, providing a cured material having a high resolution, excellent heat resistance, chemical resistance, electric characteristics, water vapor absorption resistance and PCT resistance, not causing mist in processes followed by heating. SOLUTION: This composition comprises (A) a photosensitive prepolymer containing two or more unsaturated double bonds and one or more carboxyl groups in one molecule, (B) at least one kind of a compound containing at least one group of an alkoxy, an aryloxy, an alkylthio, an arylthio, an alkylamino or an arylamino substituent group directly bonded to a phenyl or a benzoyl group bonded to an oxime functional group as a photopolymerization initiator, (B') another photopolymerization initiator except the photopolymerization initiator, (C) a reactive diluent and (D) an epoxy compound containing two or more epoxy groups in one molecule. The composition is preferably used as a solder resist and an interlaminar resin insulating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cured product which is sensitive to active energy rays, can be developed with a dilute aqueous alkali solution, and has excellent resolution, heat resistance, chemical resistance, electrical properties, and the like. Resin coating film, especially flexible printed wiring board, solder resist film for BGA (ball grid array), CSP (chip scale package) and high definition printed wiring board, multilayer printed wiring board The present invention relates to a photocurable and thermosetting resin composition useful for forming an interlayer resin insulating layer. The present invention further provides a flexible printed circuit board, especially a BGA, CSP, and high-definition printed wiring board having a solder resist film and an interlayer resin insulating layer formed from such a photocurable and thermosetting resin composition. The present invention relates to wiring boards and their manufacturing techniques.

[0002]

2. Description of the Related Art Solder resist inks are intended to prevent solder bridges and protect circuits when soldering components to a printed wiring board. Various characteristics are required. In recent years, the printed wiring board manufacturing industry has been required to reduce the weight of printed wiring boards and increase the density of conductive circuits, and accordingly, solder resist compositions for photographic development, especially compositions that can be developed with aqueous alkaline solutions, have been developed. It has been developed and used (for example, JP-A-1-141904). However, in the case of the solder resist composition used so far, when forming an image, since the photocuring of the deep part of the coating film at the time of exposure is insufficient, the coating film may be peeled off at the time of development. This is a major factor that makes it impossible to obtain an image with image quality. Therefore, there is an increasing demand for the development of a solder resist composition having excellent deep curability at the time of exposure, high resolution, and high performance, but no satisfactory material has been found to date.

Further, in a solder resist composition obtained by a photographic development method, in a predrying step, an exposure step, a thermosetting step, and a soldering step, a volatile component (mist) generated from a resist ink is supplied to a hot air circulation type drying furnace or an exposure machine. ) Adheres, causing a mounting error in a subsequent soldering step or gold plating step. Therefore, in the pre-drying step, the exposure step, the thermosetting step and the soldering step, the components (mist) volatilized from the resist ink do not adhere to production equipment such as a hot-air circulation drying furnace or an exposure machine and the printed wiring board to be manufactured. There is an increasing demand for the development of resist compositions, but to date no satisfactory materials have been found.

Further, in the field of large-sized computers and the like, as the density of electronic devices and the speed of arithmetic functions increase, the printed circuit boards are also required to have higher densities of conductor circuits. Has become mainstream. As a method of manufacturing a multilayer printed wiring board, a laminating press method is conventionally known, but this method requires a large production facility, increases costs, and has a large copper thickness due to through-hole plating in the outer layer. And it becomes difficult to form a fine pattern. In order to overcome such problems, in recent years, the development of a multilayer printed wiring board in which a resin insulating film is alternately built up on a conductor layer has been actively promoted (build-up method).

In the above build-up method, a liquid resist method has been developed and spread as a method of forming a via hole by a photographic method, that is, a so-called photo via formation method. In this method, first, a liquid photosensitive resin composition is applied to the entire surface of the wiring board on which the conductive circuit is formed by a method such as screen printing, curtain coating, or spray coating so that the conductive circuit is embedded, and dried. After that, a negative film having a predetermined exposure pattern is overlaid on the dried coating film and exposed by irradiating ultraviolet rays, then, after removing the negative film, a developing process is performed to form a cured resin insulating layer of a predetermined pattern, Next, after performing a surface roughening treatment with a roughening agent, a conductor layer is formed by electroless plating, electrolytic plating, or the like. Also in the manufacturing process of such a multilayer printed wiring board, the photosensitive resin composition to be used has a sufficient photocuring depth at the time of exposure, and the adhesiveness to the conductor layer of the formed interlayer resin insulating layer and the electric resistance. Excellent properties such as insulation, heat resistance, and chemical resistance are required. In addition, in the heating step after the formation of the conductor layer by electroless plating, electrolytic plating, etc., volatile components generated from the interlayer resin insulation layer have been a cause of poor adhesion of the conductor layer, but have been sufficiently satisfied to date. No material has been found.

[0006] In addition, a flexible (flexible) solder resist composition for photographic development has been developed and used for flexible substrates which have been increasingly used in recent years (see, for example, JP-A-9-54434). issue). Current,
In a flexible substrate, there is an increasing demand for a solder resist composition that can perform non-contact exposure and has excellent moisture absorption resistance and PCT (pressure cooker test) resistance. However, the solder resist composition currently being developed cannot satisfy the requirements for the non-contact exposure, the moisture absorption resistance and the PCT resistance due to the fact that the crosslinked density of the exposed coating film and the cured coating film do not increase. . In addition, when the cured coating film is heated, volatile components evaporate from the solder resist composition, which is a cause of abnormal mounting in a subsequent soldering step or gold plating step. Therefore, in the pre-drying step, the exposure step, the thermosetting step and the soldering step, components (mist) volatilized from the resist ink do not adhere to production equipment such as a hot-air circulation drying oven or an exposure machine and the printed wiring board to be manufactured. There is an increasing demand for the development of resist compositions.

Further, recently, QFP (quad flat pack package) and SOP (small outline package) using a lead frame and a sealing resin.
Printed wiring boards and sealing resins that have been provided with a solder resist composition have appeared in place of IC packages referred to as such. In these new packages, metal such as ball-shaped solder is arranged in an area on one side of a printed wiring board that has been subjected to solder resist, and the IC chip is directly connected to the other side by wire bonding or bumps. And is called by a name such as BGA (ball grid array) or CSP (chip scale package). These packages have more pins and are easier to miniaturize than packages such as QFPs of the same size. Also, in the implementation,
A low defect rate has been achieved by the self-alignment effect of ball-shaped solder, and its introduction has been rapidly promoted.

However, a printed wiring board to which a commercially available alkali development type solder resist composition has been applied is inferior in PCT resistance, which is a long-term reliability test of a package, and peeling of the solder resist film occurs. Also,
Due to the moisture absorption of the solder resist film, the moisture absorbed in the package boils during reflow at the time of package mounting, and a popcorn phenomenon in which cracks occur in the solder resist film inside the package and its surroundings has been regarded as a problem. Therefore, there is an increasing demand for a solder resist composition having excellent characteristics such as moisture absorption resistance and PCT resistance required for IC packages.

In a printed wiring board for high definition, in the case of a solder resist composition which has been used so far, when forming a high definition image, photocuring of a deep portion of the coating film at the time of exposure is insufficient. The coating may peel off during development,
This is a major factor that a high-resolution image cannot be obtained. Therefore, in printed wiring boards for high definition, there is an increasing demand for the development of a solder resist composition having excellent curability in the deep part at the time of exposure, but no satisfactory material has been found to date.

[0010]

SUMMARY OF THE INVENTION Under the circumstances described above, the present invention can be developed with an aqueous alkali solution, and has a high deep curing property at the time of exposure, so that a high resolution can be obtained.
Excellent heat resistance, chemical resistance, electrical properties, moisture absorption resistance, PCT
A component (mist) volatilized from the solder resist composition in a pre-drying step, an exposure step, a heat curing step, and a soldering step that provides a cured product having resistance and is heated, and is subjected to a hot-air circulation drying oven, an exposure machine, and the like. No problem of sticking to production equipment and printed wiring boards to be manufactured,
To provide a solder resist composition for printed wiring boards for flexible, BGA, CSP, and high definition, and a photocurable and thermosetting resin composition suitably used as an interlayer resin insulating layer of a multilayer printed wiring board. It was made for the purpose.

[0011]

According to the present invention, there is provided a photo-curable / thermo-curable resin composition which can be developed with an aqueous alkali solution. (A) a photosensitive prepolymer having two or more unsaturated double bonds and one or more carboxyl groups in one molecule; (B) a photopolymerization initiator represented by the following formulas (I), (II),
It is characterized by containing at least one compound represented by (III) or (IV), (C) a reactive diluent, and (D) an epoxy compound having two or more epoxy groups in one molecule. . In another embodiment, (A) a photosensitive prepolymer having two or more unsaturated double bonds and one or more carboxyl groups in one molecule, and (B) a photopolymerization initiator represented by the following formula (I) ), (II), (III) or (IV), at least one compound or an acid addition salt thereof,
(B ′) a photopolymerization initiator other than the above photopolymerization initiator,
(C) a reactive diluent; and (D) an epoxy compound having two or more epoxy groups in one molecule.

Embedded image(Where R₁Is phenyl (which is unsubstituted or
Or C1-C6 alkyl, phenyl, halogen, O
R₈, SR₉Or NR_TenR₁₁Replaced by one or more of
Or R₁Is C1-C20 alk
Or a C2-C20 alkyl, which optionally includes -O
-Interrupted by one or more of
Substituted by one or more droxy groups)
Or; R₁Is C5-C8 cycloalkyl or C
2-C20 alkanoyl or benzoyl (this
It can be unsubstituted or C1-C6 alkyl,
Nil, OR₈, SR₉Or NR_TenR₁₁At least one of
Or R)₁Are C2 to C1
2 alkoxycarbonyl, which may optionally be -O-
Interrupted by one or more and / or
Substituted by one or more xy groups);
Is R₁Is phenoxycarbonyl (which is unsubstituted
Or C1-C6 alkyl, halogen, phenyl,
OR₈Or NR_{1 0}R₁₁Replaced by one or more of
Is present); or R₁Is -CONR_TenR ₁₁, C
N, NO_Two, C1-C4 haloalkyl, S (O)_m− (C
1-C6 alkyl), unsubstituted or C1-C12 al
S (O) replaced by kill_m-(C6 ~ C12 Ally
Le) or SO_TwoO- (C1-C6 alkyl), SO_TwoO
-(C6-C10 aryl) or diphenyl-ho
M is 1 or 2;₁′
C2-C12 alkoxycarbonyl (this may be
Interrupted by one or more of -O- and / or
More substituted by one or more hydroxyl groups)
Or R₁'Is phenoxycarbonyl (this
Is unsubstituted or C1-C6 alkyl, halogen
Phenyl, OR₈Or NR_TenR₁₁More than one
Or more substituted); or R₁'Is C5
C8 cycloalkyl, -CONR_TenR₁₁, CN, or
Henil (this is SR ₉Has been replaced by
And optionally a group R_Four', R_Five'And R₆′
By building a bond to the carbon atom of the phenyl ring₉
To form a 5- or 6-membered ring), or R
_Four', R_Five'And R₆'Is at least one -SR₉Is
Then R₁'Further represents a C1-C12 alkyl (this
Is unsubstituted or halogen, OH, OR_Two,
Phenyl, halogenated phenyl, or SR₉Replacement Fe
Substituted by one or more of nyl, and optionally
-Interrupted by -O- or -NH (CO)-)
Yes; R_TwoIs a C2-C12 alkanoyl (this is non-
Is substituted or at least one of halogen or CN
Or more substituted); or R_TwoIs C4-C
6 alkenoyl (provided that the double bond is carbonyl
Not conjugated to a group); or R_TwoIs benzoyl (this
Is unsubstituted or C1-C6 alkyl, halogen
, CN, OR₈, SR₉Or NR_TenR₁₁One or more of
Or R)_TwoIs C2-
C6 alkoxycarbonyl or phenoxycarbonyl
(This can be unsubstituted or C1-C6 alkyl
Or substituted by halogen);_Three,
R_Four, R_Five, R₆And R₇Are independently of each other hydrogen, halo
Gen, C1-C12 alkyl, cyclopentyl, cyclo
Hexyl or phenyl (which may be unsubstituted or
Is OR₈, SR₉Or NR_TenR₁₁By one or more of
Or R)_Three, R_Four, R_Five, R₆as well as
R₇Is benzyl, benzoyl, C2-C12 alkano
Yl or C2-C12 alkoxycarbonyl (this
Is optionally interrupted by one or more of -O-, and
/ Or optionally substituted by one or more hydroxyl groups
Or R_Three, R_Four, R_Five, R₆And R
₇Is phenonoxycarbonyl or a group OR₈, SR₉, S
OR₉, SO_TwoR₉Or NR_TenR₁₁(Where the substituent
OR₈, SR₉And NR_TenR₁₁Is optionally a phenyl ring
A further substituent or one of the carbon atoms of the phenyl ring and the group
R₈, R₉, R_TenAnd / or R₁₁5- or 6-member via
Forming a ring), provided that R_Three, R_Four, R_Five, R₆Passing
And R₇At least one is OR₈, SR₉And NR_TenR
₁₁And R_Four', R_Five'And R₆′ Are independent of each other
Hydrogen, halogen, C1-C12 alkyl, cyclope
Methyl, cyclohexyl, or phenyl (this is
Or OR₈, SR₉Or NR_TenR₁₁By
Or R)_Four', R_Five'And R
₆'Is benzyl, benzoyl, C2-C12 alkano
Yl or C2-C12 alkoxycarbonyl (this
Is optionally interrupted by one or more of -O-, and
/ Or optionally substituted by one or more hydroxyl groups
Or R_Four', R_Five'And R₆′
Is phenonoxycarbonyl or a group OR₈, SR₉, S
OR₉, SO_TwoR₉Or NR_TenR₁₁(Where the substituent
OR₈, SR₉And NR_TenR₁₁Is optionally a phenyl ring
A further substituent or one of the carbon atoms of the phenyl ring and the group
R₈, R₉, R_TenAnd / or R₁₁5- or 6-member via
Forming a ring), provided that R_Four', R_Five'as well as
R₆′ Is OR₈, SR₉And NR_TenR
₁₁And R_Five'Is methoxy and R_Four'as well as
R₆′ Are both hydrogen at the same time;₁'Is CN
R_Two'Is benzoyl or 4- (C1-C10 alkyl
R) not benzoyl; R₈Is hydrogen, C1-C12
Alkyl or C2-C6 alkyl, which is
-OH, -SH, -CN, C1-C4 alkoxy, C3
~ C6 alkeneoxy, -OCH_TwoCH_TwoCN, -OCH
_TwoCH_Two(CO) O (C1-C4 alkyl), -O (C
O)-(C1-C4 alkyl), -O (CO) -phenyl
,-(CO) OH or-(CO) O (C1-C4 alkyl)
Or R) ₈Is C2-C6
Alkyl, which is more interrupted by one or more of -O-
Or R₈Is-(CH_TwoCH_TwoO)_n
H, C2-C8 alkanoyl, C3-C12 alkenyl
, C3-C6 alkenoyl, cyclohexyl, or
Phenyl, which is unsubstituted or halogen, C1
Substituted with -C12 alkyl or C1-C4 alkoxy
Or R₈Is phenyl- (C1
To C3 alkyl), Si (C1 to C8 alkyl)_r(Fe
Nil)_3-rOr the following formula:

Embedded image N is 1 to 20; r is 1,
R ₉ is hydrogen, C1-C12 alkyl, C3-C12 alkenyl, cyclohexyl, or C
2-C6 alkyl, which is -OH, -SH, -CN,
C1-C4 alkoxy, C3-C6 alkeneoxy,-
_{OCH 2 CH 2 CN, -OCH 2} CH 2 (CO) O (C1~
C4 alkyl), -O (CO)-(C1-C4 alkyl), -O (CO) -phenyl,-(CO) OH or-
(Substituted with (CO) O (C1-C4 alkyl))
Or R ₉ is C 2 -C 12 alkyl, which is interrupted by one or more of —O— or —S—; or R ₉ is phenyl, which is unsubstituted Or substituted with halogen, C1-C12 alkyl or C1-C4 alkoxy);
Or R ₉ is phenyl- (C1-C3 alkyl), or the following formula:

Embedded image R ₁₀ and R ₁₁ independently of one another are hydrogen, C 1 -C 12 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 3-
C5 alkenyl, C5-C12 cycloalkyl, phenyl- (C1-C3 alkyl), or phenyl, which is
Unsubstituted or C1-C12 alkyl or C
1-C4 alkoxy));
Or R ₁₀ and R ₁₁ are C2 to C3 alkanoyl, C3 to
Or R ₁₀ and R ₁₁ together are C 2 -C 6 alkylene, which is optionally interrupted by —O— or —NR ₈ — and / or optionally hydroxyl, C 1 ~C4 alkoxy, or is substituted with C2~C4 alkanoyloxy or benzoyloxy); or when R ₁₀ is hydrogen, R ₁₁ is represented by the following formula:

Embedded imageM can be a C1-C12 alky!
Kylene, cyclohexylene, phenylene,-(CO) O
-(C2-C12 alkylene) -O (CO)-,-(C
O) O- (CH_TwoCH_TwoO)_n-(CO)-or-(CO)
-(C2-C12 alkylene)-(CO)-; M
₁Is a direct bond or a C1-C12 alkylene
Oxy (this is optionally 1 to 5 -O-, -S
-And / or -NR_Ten-Has been interrupted by
M;_TwoIs a direct bond or (C1-C12
Alkylene) -S- (this is optionally 1 to 5-
O-, -S-, and / or -NR_TenInterrupted by
M)_ThreeIs a direct bond, a piperazino group, or
(C1-C12 alkylene) -NH- (which is
From 1 to 5 -O-, -S-, and / or -NR_Ten
-Interrupted by-) provided that (i) R_FiveIs methoxy and R_TwoIs benzoyl or acetyl
If chill, R ₁Is not phenyl; (ii) R_FiveIs methoxy and R_TwoIs ethoxycarbonyl
, Then R_TwoIs benzoyl or ethoxycarbonyl
Not (iii) R_FiveIs methoxy and R₁Is 4-methoxybenz
If it is Zoyl, R_TwoIs not ethoxycarbonyl
(Iv) R_FiveIs methacryloylamino, and R₁But
If R_TwoIs not benzoyl; (v) R_FiveAnd R_FourOr R_FiveAnd R₆Are both OR₈Based on
Yes, their OR₈The radicals together form R₈Through the ring
To thereby form -O-CH_Two-O-, R₁But
If chill, R_TwoIs not acetyl; (vi) R_Four, R_FiveAnd R₆Are simultaneously methoxy and R₁But
If it is ethoxycarbonyl, R_TwoIs acetyl
Absent. In the present specification, for example, C1 to C6 alkyl
Represents an alkyl group having 1 to 6 carbon atoms (other similar analogs).
The same applies to expressions).

Further, according to the present invention, there is provided a solder resist film formed by selective exposure, development, and heat curing of a coating film of the photocurable / thermosetting resin composition applied on a circuit board. A printed wiring board characterized by the fact that a resin insulating layer and a conductive layer of a predetermined circuit pattern are sequentially formed on a circuit board. -Provided is a multilayer printed wiring board comprising a cured coating film of a thermosetting resin composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies to develop photocurable and thermosetting resin compositions having preferable characteristics as solder resists and insulating materials. As a photopolymerization initiator for the photosensitive prepolymer (A) having two or more unsaturated double bonds and one or more carboxyl groups, a compound represented by the above formula (I), (II), (III) or (IV) When at least one compound represented by the formula is used, compared with the case where a photopolymerization initiator such as an acetophenone-based, benzophenone-based, benzoin-based, or aminoketone-based photopolymerization initiator generally used in the past is used, irradiation is performed during exposure. It has been found that the photosensitive prepolymer reacts with high sensitivity to the active energy rays, and the photopolymerization rate of the photosensitive prepolymer is high, so that the photocuring depth is increased and the resolution is improved.

Further, according to the study of the present inventors, as a photopolymerization initiator, the above-mentioned formula (I), (II), (III) or (I)
When at least one compound represented by V) is used in combination with other photopolymerization initiators and / or sensitizers, the sensitivity and sensitivity can be improved as compared with the case where each photopolymerization initiator is used alone. It has been found that the light curing depth is further increased, and the resolution is dramatically increased. Although the reason for this is not necessarily clear, as the photopolymerization initiator, the compound represented by the above formula (I), (II), (III) or (IV) and the other photopolymerization initiator can be used for the electronic interaction. This is presumed to be due to the sensitization resulting in an increase in the absorbance of the active energy rays, and the generation of a sufficient amount of active radicals with a relatively small amount of active energy rays. The above-mentioned effects are obtained when the compound represented by the formula (I), (II), (III) or (IV) or another photopolymerization initiator is used alone as the photopolymerization initiator. It is surprising that the effect is completely unexpected.

According to the study of the present inventors, (A)
A photosensitive prepolymer having two or more unsaturated double bonds and one or more carboxyl groups in one molecule; (B) a photopolymerization initiator represented by the formula (I), (II), (III) or (I
V) at least one compound (or (B ′) a photopolymerization initiator and / or a sensitizer other than the above photopolymerization initiator), (C) a reactive diluent, and (D) ) When a photocurable / thermosetting resin composition containing an epoxy compound having two or more epoxy groups in one molecule is used, the composition can be used in a predrying step, an exposure step, a thermosetting step, and a soldering step. It has been found that the volatile components (mist) do not adhere to the production equipment such as a hot-air circulation drying oven and an exposure machine and the printed wiring board to be manufactured, because the components volatilized from the product are significantly reduced.

Further, according to a study by the present inventors, the photo-curable and thermo-curable resin composition according to the present invention is compared with a photosensitive resin composition for a flexible printed wiring board which is conventionally generally used. In addition, the cured coating film subjected to non-contact exposure has excellent flexibility in addition to excellent moisture absorption resistance and PCT resistance.
When compared with the photosensitive resin composition used for a printed wiring board for SP, it has excellent moisture absorption resistance and PCT resistance, and furthermore, a photosensitive resin composition for a high-definition printed wiring board generally used conventionally. It has been found that excellent high-definition patterning can be performed as compared with a product.

Hereinafter, each component of the photocurable and thermosetting resin composition of the present invention will be described in detail. First, the photosensitive prepolymer (A) having two or more unsaturated double bonds and one or more carboxyl groups in one molecule includes a polymer or oligomer having two or more epoxy groups in one molecule. For example, a polyfunctional epoxy compound (D) having two or more epoxy groups in one molecule as described later, a copolymer of alkyl (meth) acrylate and glycidyl (meth) acrylate, hydroxyalkyl (meth) acrylate Is reacted with an unsaturated monocarboxylic acid having an unsaturated double bond, and then an unsaturated or saturated polycarboxylic acid anhydride is added to a copolymer of alkyl (meth) acrylate and glycidyl (meth) acrylate. A photosensitive prepolymer obtained by the reaction, an oligomer or polymer having a carboxyl group, such as an alkyl (meth) acryl Photoreactive prepolymers obtained by reacting an unsaturated compound having an unsaturated double bond and an epoxy group in one molecule, such as glycidyl (meth) acrylate, with a copolymer of methacrylate and (meth) acrylic acid Is mentioned. Here, the term “(meth) acrylate” is a general term for acrylate, methacrylate and mixtures thereof, and the same applies to (meth) acrylic acid.

The above photosensitive prepolymer (A)
Has a large number of free carboxyl groups in the side chain of the backbone polymer, enabling development with a dilute aqueous alkali solution, and at the same time, after exposure and development, the coating film is post-heated to form a separate thermosetting compound. An addition reaction takes place between the epoxy group of the epoxy compound (D) added as a component and the free carboxyl group of the above side chain, resulting in various properties such as heat resistance, solvent resistance, acid resistance, adhesion, and electrical properties. Excellent cured film can be obtained. The acid value of the photosensitive prepolymer (A) is preferably in the range of 45 to 160 mgKOH / g. The acid value of the photosensitive prepolymer is 45
When the amount is less than mgKOH / g, alkali development becomes difficult. On the other hand, when the amount exceeds 160 mgKOH / g, the hydrophilicity of the photosensitive prepolymer becomes too high, which is unfavorable because it adversely affects the electrical properties.

One preferred example of the photosensitive prepolymer (A) is (a) an epoxy compound having two or more epoxy groups in one molecule, for example, a polyfunctional epoxy resin (D) as described below; b) a reaction product with an unsaturated group-containing monocarboxylic acid, and (d) an aromatic polycarboxylic anhydride such as dibasic acid anhydride such as phthalic anhydride or trimellitic anhydride or pyromellitic anhydride. Is obtained by reacting In this case, the polyfunctional epoxy resin (D)
A resin obtained by reacting 0.15 mol or more of a polybasic anhydride (d) with respect to one hydroxyl group of a reaction product of a monocarboxylic acid (b) with an unsaturated group-containing monocarboxylic acid (b) is suitable.

Another preferred photosensitive prepolymer (A-1) used in the present invention is a (meth) acrylic modified resin obtained by subjecting an epoxy resin represented by the following general formula (V) to an esterification reaction of (meth) acrylic acid. And polybasic anhydride (d)
Is a prepolymer soluble in a dilute aqueous alkali solution obtained by the addition reaction of

Embedded image In the formula, E represents CH ₂ , C (CH ₃ ) ₂ or SO ₂ ;
Is 1 to 12, and G represents a hydrogen atom or a glycidyl group. However, when i is 1, G represents a glycidyl group, and when i is 2 or more, at least one of G represents a glycidyl group.

The photosensitive prepolymer (A-
The photo-curable / thermo-curable resin composition containing 1) provides a cured film having excellent flexibility, and thus can be advantageously used particularly for forming a solder resist film of a flexible printed wiring board. The reason why a cured film excellent in flexibility can be obtained is that, as a skeleton resin of the photosensitive prepolymer before being modified with (meth) acrylic acid and adding an acid anhydride to introduce a carboxyl group, the general formula (V) By using a linear epoxy resin containing a large number of ether bonds as represented by, the density of highly rigid aromatic residues is relatively low, thereby contributing to the development of flexibility of the cured film. It is thought that it is. Further, the molecular chain portion between the ether bonds is easily rotated, and the molecular weight between the bridge points between the cured photosensitive prepolymers is increased (that is, the chain length between the bridge points). Is prolonged) is also considered to contribute to the improvement of the flexibility of the cured film. The cured film obtained from the photocurable / thermocurable resin composition containing such a photosensitive prepolymer is rich in flexibility, and therefore, has excellent punching resistance (mechanical impact resistance) at the time of press punching. In addition, other characteristics required for the solder resist, such as electrical insulation, electroless gold plating resistance, acid resistance, and water resistance, are also good. For the same reason as described above, the thermosetting component used in combination with the photosensitive prepolymer (A-1) is an epoxy compound having a structure similar to the general formula (V), for example, a bisphenol A type epoxy resin, Bisphenol F type epoxy resin,
Including diglycidyl ether type epoxy resin such as bisphenol S type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, or diglycidyl ether type epoxy resin modified with dibasic acid Is preferred.

The photosensitive prepolymer (A-1) preferably has an acid value in the range of 60 to 120 mgKOH / g. When the acid value is less than 60 mgKOH / g, the alkali solubility becomes poor, and conversely, 120 mgKOH / g.
If the thickness is too large, it will cause a reduction in the properties of the cured film such as alkali resistance and electrical properties as a resist. The epoxy resin as a starting material preferably has a polymerization degree n of about 1 to 12 in the general formula (V), and more preferably has a polymerization degree n of about 2 to 6. When the degree of polymerization n is 0, the photosensitive prepolymer in the exposed part is easily dissolved in the developing solution during development because of a small molecular weight, and the resolution is deteriorated. The obtained cured film has good properties as a solder resist. Is difficult to obtain. On the other hand, when the degree of polymerization n is larger than 12, the development of unexposed portions becomes difficult due to the high molecular weight and long chain length.

Still another preferred photosensitive prepolymer (A-2) used in the present invention is (a) an epoxy compound having two or more epoxy groups in one molecule, for example, a polyfunctional epoxy resin as described below. (D), (b) an unsaturated group-containing monocarboxylic acid, and (c) one other functional group other than a hydroxyl group having two or more hydroxyl groups in one molecule and reacting with an epoxy group. The reaction product (a) with the compound having
(D) a prepolymer soluble in a dilute aqueous alkali solution obtained by subjecting an unsaturated or saturated polybasic acid anhydride to an addition reaction. The acid value of the photosensitive prepolymer (A-2) is 30.
It is preferably in the range of １００100 mgKOH / g.

In the synthesis reaction of the reaction product (a), the polyfunctional epoxy compound (a) is reacted with the unsaturated group-containing monocarboxylic acid (b) (or the compound (c)), and then the compound (c) ( Alternatively, a first method of reacting an unsaturated group-containing monocarboxylic acid (b)) and a second method of simultaneously reacting a polyfunctional epoxy compound (a), an unsaturated group-containing monocarboxylic acid (b) and a compound (c). There is a method. Either method may be used, but the second method is preferred. In the above reaction, the ratio of the total amount of the unsaturated group-containing monocarboxylic acid (b) and the compound (c) to about 0.8 to 1.3 mol per 1 equivalent of the epoxy group of the polyfunctional epoxy compound (a). Is preferable, and the ratio is particularly preferably about 0.9 to 1.1 mol. The ratio of the unsaturated group-containing monocarboxylic acid (b) to the compound (d) is such that the compound (c) is used with respect to 1 mol of the total amount of the unsaturated group-containing monocarboxylic acid (b) and the compound (d). The reaction ratio is preferably such that the amount is 0.05 to 0.5 mol, particularly preferably 0.1 to 0.3 mol. Next, in the reaction between the reaction product (a) and the polybasic acid anhydride (d), the polybasic acid anhydride (d) is added in an amount of 0.1 per equivalent of the hydroxyl group in the reaction product (a). ~
It is preferable to react 0.9 equivalent. Reaction temperature is 60 ~
The temperature is preferably 150 ° C., and the reaction time is preferably 1 to 10 hours.

Specific examples of the unsaturated group-containing monocarboxylic acid (b) used in the synthesis of the photosensitive prepolymer (A-2) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β -Styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, etc .; and a (meth) acrylate having a saturated or unsaturated dibasic anhydride and one hydroxyl group in one molecule Or half-esters which are the reaction products of saturated or unsaturated dibasic acids with unsaturated monoglycidyl compounds, such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride Or a saturated or unsaturated dibasic acid anhydride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylol Propane di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
A half ester obtained by reacting (meth) acrylates having one hydroxyl group in one molecule such as (meth) acrylate of phenylglycidyl ether in one molecule in an equimolar ratio, or a saturated or unsaturated dibasic acid (for example, Succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, itaconic acid, fumaric acid, etc.) and unsaturated monoglycidyl compounds (eg, glycidyl (meth) acrylate)
And a half ester obtained by reacting them in an equimolar ratio. These can be used alone or in combination of two or more. Particularly preferred are acrylic acid and methacrylic acid, particularly acrylic acid from the viewpoint of photocurability.

The photosensitive prepolymer (A-2)
Compound (c) having at least two or more hydroxyl groups and one other functional group other than a hydroxyl group that reacts with an epoxy group (for example, a carboxyl group or a secondary amino group) in one molecule used for the synthesis of Specific examples include polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid; dialkanolamines such as diethanolamine and diisopropanolamine. be able to. Particularly preferred are, for example, dimethylolpropionic acid.

The photosensitive prepolymers (A-1 and A-
Typical examples of the saturated or unsaturated polybasic anhydride (d) used in the synthesis of 2) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydroanhydride. Phthalic anhydride,
Dibasic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, Aromatic polycarboxylic anhydrides such as benzophenonetetracarboxylic dianhydride; and other accompanying compounds such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Examples thereof include polycarboxylic anhydride derivatives such as acid anhydrides, and particularly preferred are tetrahydrophthalic anhydride and hexahydrophthalic anhydride.

Next, the photopolymerization initiator (B) represented by the general formula (I), (II), (III) or (IV) is directly bonded to a phenyl or benzoyl group bonded to an oxime functional group. Containing at least one of the following substituents: alkoxy, aryloxy, alkylthio, arylthio, alkylamino or arylamino.
Specific examples of the photopolymerization initiator (B) include, for example, 1
-(4-phenylsulfanyl-phenyl) -butane-
1,2-dione 2-oxime-O-benzoate, 1
-(4-phenylsulfanyl-phenyl) -octane-1-oneoxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-
Dione 2-oxime-O-benzoate, 1- (4-
Phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O
-Acetate and the like.
-(4-Phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate and 1- (4-phenylsulfanyl-phenyl) -octane-1-oneoxime-O-benzoate are preferred.
The photopolymerization initiator (B) is described in
Since it is described in detail in Japanese Patent Application Publication No. 00-80068, refer to the publication for details. These photopolymerization initiators (B) may be used alone or in combination of two or more. The content of the photopolymerization initiator (B) is selected in the range of usually 0.5 to 50 parts by mass, preferably 2 to 30 parts by mass, per 100 parts by mass of the photosensitive prepolymer (A).

In the composition of the present invention, another photopolymerization initiator used in combination with the above photopolymerization initiator (B)
(B ′) is a radical photopolymerization initiator such as benzophenone, acetophenone, benzoin ether, benzyl ketal, monoacrylphosphine oxide, perester, titanocene, and the like. For example, specific examples of the other photopolymerization initiator (B ′) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-
2-phenylacetophenone, 2,2-diethoxy-2
Acetophenones such as -phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-
Aminoacetophenones such as (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-
Anthraquinones such as ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone,
Thioxanthones such as 4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide; Phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and ethyl-2,4,6-trimethylbenzoylphenylphosphinate Various peroxides, and these known and commonly used photopolymerization initiators can be used alone or in combination of two or more. The mixing ratio of these photopolymerization initiators (B ′) is 0.1 per 100 parts by mass of the photosensitive prepolymer (A).
A range of from 5 to 5 parts by mass is preferred.

The above-mentioned photopolymerization initiators (B and B ')
And photosensitizers such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine. May be used alone or in combination of two or more. Further, a titanocene-based photopolymerization initiator such as Irgacure 784 manufactured by Ciba Specialty Chemicals, which initiates radical polymerization in the visible region, or a leuco dye may be used in combination as a curing aid.

The reactive diluent (C) used in the photo-curable / thermo-curable resin composition of the present invention adjusts the viscosity of the composition, improves workability, and increases the crosslink density.
It is used to obtain a coating film having heat resistance, chemical resistance and the like. For example, 2-hydroxyethyl (meth)
Hydroxyalkyl (meth) acrylates such as acrylate and 2-hydroxypropyl (meth) acrylate; mono- or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol and polyethylene glycol; N, N-dimethyl (meth) ) Acrylamide, (meth) acrylamides such as N-methylol (meth) acrylamide; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditri Polyhydric alcohols such as methylolpropane, dipentaerythritol, trishydroxyethyl isocyanurate or polyhydric alcohols of these ethylene oxide or propylene oxide adducts ( (T) acrylates; phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, etc., and ethylene oxide or propylene oxide adducts of (meth) acrylates; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether And (meth) acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine (meth) acrylate. These reactive diluents (C) may be used alone or in combination of two or more. The content is preferably in the range of 2 to 50 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer (A).

In the photocurable / thermosetting resin composition of the present invention, the epoxy compound (D) used as the thermosetting component can be thermoset by itself or reacts with other components to form a thermosetting resin. It cures and is used to obtain a sufficiently tough cured film after the film is cured by heating.
Examples of the thermosetting epoxy compound include bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, and propylene glycol. Or diglycidyl ether of polypropylene glycol, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane glycidyl ether, phenyl-
1,3-diglycidyl ether, biphenyl-4,4 '
-Diglycidyl ether, 1,6-hexanediol glycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol glycidyl ether, tris (2,3-epoxypropyl) isocyanurate And compounds having two or more epoxy groups in one molecule, such as triglycidyl tris (2-hydroxyethyl) isocyanurate. These may be used alone or in combination of two or more. Further, a known epoxy curing accelerator such as an S-triazine compound such as melamine as a reaction accelerator, an imidazole compound such as imidazole or 2-ethyl-4-methylimidazole or a derivative thereof, or a phenol compound is used in combination with the curing coating. By heat curing the film, the heat resistance of the cured coating film,
Various properties such as chemical resistance, adhesion, and pencil hardness can be improved. The content of the epoxy compound (D) is
From the point that a sufficiently tough coating film can be obtained after thermosetting,
Per 100 parts by mass of the photosensitive prepolymer (A),
The content is preferably in the range of 0.1 to 50 parts by mass, particularly 0.5 to 3 parts by mass.
A range of 0 parts by weight is preferred.

Among the epoxy compounds used as thermosetting components in the photocurable / thermosetting resin composition of the present invention, the diluent (C) has two or more epoxy groups in one molecule, and When the insoluble epoxy compound (D-1) is used, the resulting composition has improved sensitivity and developability (resolution).
And the development resistance of the coating film and the properties of the cured film are improved. Such an epoxy compound can be dispersed in fine particles in the photosensitive prepolymer (A) having two or more unsaturated double bonds and one or more carboxy groups in one molecule, and can be solidified at room temperature. Or, it must be semi-solid, and at the time of kneading, the above photosensitive prepolymer (A)
And those that do not dissolve in the diluent (C) are preferred. However, as long as the photosensitivity and developability are not adversely affected, partial dissolution may be performed without any problem. An epoxy compound (D-1) preferable as satisfying these conditions is:
Bisphenol S-type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by AC AL Co., Ltd., and Epicron EXA-1514 manufactured by Dainippon Ink & Chemicals, Ltd .; Blenmer manufactured by NOF Corporation Glycidyl terephthalates such as DGT; TEP manufactured by Nissan Chemical Industries, Ltd.
Heterocyclic resins such as IC, TEPIC-H, and Araldide PT810 manufactured by Ciba Specialty Chemicals; YX-400 manufactured by Yuka Shell Epoxy Co., Ltd.
0, YL-6121 or other bixylenol type epoxy resin or biphenyl type epoxy resin; Yuka Shell Epoxy Co., Ltd. YL-6056 or other biphenol type epoxy resin; Nippon Steel Chemical Co., Ltd. ESN-190 or other naphthalene Epoxy resin having a tetramethylbisphenol F structure, such as a backbone epoxy resin, GK-5089L, E
There is a fluorene skeleton epoxy resin such as SF-300.

The hardly soluble epoxy compound (D-
1) pulverizing the epoxy compound at normal temperature and / or breaking and dispersing the epoxy compound with another composition component such as the photosensitive prepolymer (A) by a kneading machine such as a roll mill at the time of preparing the composition; And can be used alone or in combination of two or more. The amount of use is 5 to 50 parts by mass per 100 parts by mass of the photosensitive prepolymer (A).
A suitable range is 10 parts by weight, more preferably 10 to 30 parts by weight. In addition, the hardly soluble epoxy compound (D-1)
Bisphere type A epoxy resin,
A problem in use of an epoxy resin soluble in the diluent (C) such as a biphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin in terms of photosensitivity and elution of an unexposed portion during development. Can be used together within the range without.

When the photocurable / thermosetting resin composition of the present invention is used particularly for forming an interlayer resin insulating layer of a multilayer printed wiring board, the softening point 110 is used as at least one of the thermosetting components. ℃ or less epoxy resin (D-
It is preferable to use 2). Specific examples of such an epoxy resin (D-2) include Epicoat 807, Epicoat 828, Epicoat 1001, Epicoat 1004 manufactured by Yuka Sureppo Co., Ltd., Epicron 840 manufactured by Dainippon Ink and Chemicals, Inc. Epiclone 85
0, Epicron 1055, Epicron 2055, Epototo YD-011, YD-013, manufactured by Toto Kasei Co., Ltd.
YD-127 and YD-128, D.C. E. FIG. R. 317, D. E. FIG. R. 331, D. E. FIG.
R. 661, D. E. FIG. R. 664, Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260 manufactured by Ciba Specialty Chemicals, Sumiepoxy ES manufactured by Sumitomo Chemical Co., Ltd.
A-011, ESA-014, ELA-115, ELA
-128, manufactured by Asahi Chemical Industry Co., Ltd. E. FIG. R. 330,
A. E. FIG. R. 331, A. E. FIG. R. 661, A. E. FIG.
R. Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Yuka Shell Epoxy Co., Ltd., Epicron 152 and Epicron 165 manufactured by Dainippon Ink and Chemicals, Inc .; Epotote YDB-400, YDB-500, D.C. E. FIG. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumiepoxy ESB-400, ESB-5 manufactured by Sumitomo Chemical Co., Ltd.
A.00 manufactured by Asahi Chemical Industry Co., Ltd. E. FIG. R. 711, A.
E. FIG. R. Brominated epoxy resins such as 714 (all trade names); E. FIG. N. 431,
D. E. FIG. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by Dainippon Ink and Chemicals, Inc .; Epototo YDC manufactured by Toto Kasei Co., Ltd.
N-701, YDCN-704, Araldide XPY307 manufactured by Ciba Specialty Chemicals, EPPN-201, EOCN-1025 manufactured by Nippon Kayaku Co., Ltd.
EOCN-104S, RE-306, Sumitomo Chemical Industries, Ltd. Sumiepoxy ESCN-195X, ESCN-
220, manufactured by Asahi Chemical Industry Co., Ltd. E. FIG. R. CN-23
5, novolak-type epoxy resins such as ECN-299 (all trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, Inc .; Epototo YDF-1 manufactured by Toto Kasei Co., Ltd.
70, YDF-175, YDF-2004, Araldide XPY30 manufactured by Ciba Specialty Chemicals
Bisphenol F epoxy resin such as No. 6 (all trade names); hydrogenated bisphenol epoxy resin such as Epototo ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd. Glycidylamine type epoxy resins such as Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., and Sumiepoxy ELM-12 manufactured by Sumitomo Chemical Co., Ltd. Ciba
Araldide CY- manufactured by Specialty Chemicals
Hydantoin epoxy resin such as 350 (trade name); Celloxide 2021 manufactured by Daicel Chemical Industries, Ltd .;
Araldide CY1 manufactured by Specialty Chemicals
75, CY179, T.W. E. FIG.
N. (All trade names) such as trihydroxyphenylmethane type epoxy resin; YX manufactured by Yuka Shell Epoxy Co., Ltd.
-4000, YL-6121 (all trade names) and other bixylenol-type or biphenyl-type epoxy resins; Dainippon Chemical Co., Ltd. EXA-1514 (trade name) and other bisphenol S-type epoxy resins; Bis A novolak type epoxy resin such as Epicoat 157S (trade name) manufactured by Epoxy Co .; Epicoat YL-931 manufactured by Yuka Shell Epoxy Co., Ltd., and Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names are available) Araldide PT810 manufactured by Ciba Specialty Chemicals,
Examples include heterocyclic epoxy resins such as TEPIC and TEPIC-H (all trade names) manufactured by Nissan Chemical Industries, Ltd.

The compounding amount of the epoxy resin (D-2) having a softening point of 110 ° C. or less is the same as that of the photosensitive prepolymer (A).
30 to 60 parts by mass is preferable for 100 parts by mass.
Examples of the epoxy curing agent for the epoxy resin (D-2) include amines, acid anhydrides, amino polyamide resins, polysulfide resins, boron trifluoride amine complex, novolak resins, dicyandiamide, acid hydrazide, and carboxyl group-containing. Compounds and the like can be used.

In the photocurable and thermosetting resin composition of the present invention, the rubber fine particles (E) used together with the epoxy resin (D-2) are dispersed in the cured coating film. Any material can be used as long as it does not dissolve in other components. However, in consideration of heat resistance and the like, it is preferable to use fine particles of crosslinked rubber such as acrylic or butadiene, particularly fine particles of acrylic crosslinked rubber. Further, since processing such as cutting is performed at normal temperature, rubber fine particles having a glass transition point of 2 ° C. or less are desirable at room temperature, and the network density of the rubber fine particles is 0.01 to
1.4 mmol / g is preferred. Furthermore, in order to generally be uniformly dispersed in the insulating resin composition having a thickness of about 20 to 100 μm, rubber fine particles having a particle diameter of 0.01 to 10 μm are preferable. The rubber microparticles can be added to the composition as the rubber microparticles alone or in a form dispersed in an epoxy resin solvent, for example, a rubber microparticle-dispersed epoxy resin varnish, or further dispersed in a diluent (solvent) Can also be used.

Specific examples of the rubber fine particles (E) include XER-91 manufactured by Nippon Synthetic Rubber Co., Ltd. and Takeda Pharmaceutical Co., Ltd.
And Staphyloid AC-3355 manufactured by Toto Kasei Co., Ltd., as epoxy varnishes, such as Epotote YR-528, YR-591 and YR-570, manufactured by Toto Kasei Co., Ltd.
YR-516, Epodine RB manufactured by Reginas Kasei Co., Ltd.
-2000, RB-2010 and the like. Also,
Examples of the component of the rubber fine particles include acrylic rubber, styrene rubber, isoprene rubber, ethylene rubber, propylene rubber, urethane rubber, butyl rubber, silicone rubber, nitrile rubber, fluorine rubber, norbornene rubber, and ether rubber. Among these, acrylic rubber is desirable. The mixing ratio of the rubber fine particles (E) is 2 per 100 parts by mass of the photosensitive prepolymer (A).
An appropriate range is from 30 to 30 parts by mass.

The photo-curable / thermo-curable resin composition of the present invention may further comprise, if necessary, an organic solvent and various additive components such as silica, alumina, talc, Extenders such as barium sulfate, calcium carbonate, calcium sulfate, titanium oxide, phthalocyanine,
An azo type pigment, an antifoaming agent, a leveling agent and the like can be contained.

When the photo-curable and thermo-curable resin composition of the present invention is used for forming a solder resist for a printed wiring board, the viscosity is adjusted to a value suitable for a coating method if necessary.
For example, a screen printing method, a curtain coat method, a spray coat method,
A tack-free coating film can be formed by applying a coating method such as a roll coating method and performing a drying treatment at a temperature of, for example, about 60 to 100 ° C. as necessary. Thereafter, the substrate is selectively exposed to active light through a photomask on which a predetermined exposure pattern is formed. Alternatively, exposure and drawing can be directly performed according to a pattern by a laser beam.
Next, a resist pattern can be formed by developing the unexposed portion with an alkaline aqueous solution.
By heating to a temperature of 80 ° C. and thermally curing, the polymerization of the photosensitive resin component is promoted in addition to the curing reaction of the thermosetting component, and the resulting resist film has heat resistance, solvent resistance, acid resistance, Various properties such as moisture absorption resistance, PCT resistance, adhesion, and electrical properties can be improved.

As the aqueous alkali solution used for the development, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. Further, as an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can also be used as an active light beam for exposure.

When an interlayer insulating resin layer of a multilayer printed wiring board is formed using the photocurable / thermosetting resin composition of the present invention, the viscosity may be adjusted to a value suitable for the coating method as necessary. This is applied, for example, on a conductor layer of a wiring board formed in advance by a conventionally known method as described above,
If necessary, for example, after drying at a temperature of about 60 to 100 ° C. to form a tack-free coating film, the film is selectively exposed to active light through a negative film having a light-opaque portion having a predetermined shape such as a black circle. Then, the unexposed portion is developed with, for example, the above-described alkaline aqueous solution to form a via hole corresponding to the black circle of the negative film. Thereafter, if necessary, a predetermined interlayer conductive hole or the like is drilled, and then a roughening treatment is performed with a roughening agent such as an oxidizing agent, an aqueous alkali solution, or an organic solvent, and the surface of the roughened insulating resin layer is formed. After covering the conductor layer by electroless plating, electrolytic plating, or the like, heat treatment is performed to increase the crosslink density of the insulating resin layer and relieve stress. For example, by heating and curing at a temperature of about 140 to 180 ° C., it is excellent in various properties such as impact resistance, heat resistance, solvent resistance, acid resistance, moisture absorption resistance, PCT resistance, adhesion, and electrical properties. An interlayer insulating resin layer can be formed. Thereafter, the conductor layer on the surface of the insulating resin layer is etched to form a predetermined circuit pattern according to a conventional method, thereby forming a conductor layer on which a circuit is formed. In addition, such an operation can be sequentially repeated as desired, and the insulating resin layer and the conductor layer having a predetermined circuit pattern can be alternately built up to be formed. In addition,
The photocurable / thermosetting resin composition of the present invention is used not only as an insulating resin layer in the method for producing a multilayer printed wiring board by the build-up method as described above, but also for a multilayer printed wiring board by a copper foil laminating method, for example. It can also be used as an insulating resin composition for a prepreg used for forming an insulating resin layer in manufacturing and a lamination press method.

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but it goes without saying that the present invention is not limited to the following examples. In the following, “parts” means “parts by mass” unless otherwise specified.

Synthesis Example 1 One equivalent of a cresol novolak-type epoxy resin having an epoxy equivalent of 217 and having an average of seven phenol nucleus residues per molecule and an epoxy group, and 1.05 of acrylic acid The reaction product obtained by the reaction with the above equivalent was reacted with 0.67 equivalent of tetrahydrophthalic anhydride in a conventional manner using phenoxyethyl acrylate as a catalyst. This was a viscous liquid containing 35 parts of carbitol acetate, and was a carboxylic acid resin containing an unsaturated group having an acid value of 65 mgKOH / g as a mixture.

Example 1 100 parts of the unsaturated group-containing carboxylic acid resin of the component (A) obtained in Synthesis Example 1 was added to the component (B) of 1- (4-phenylsulfanyl) represented by the following formula (VI). 15 parts of phenyl) -octane-1-one oxime-O-benzoate (manufactured by Ciba Specialty Chemicals), diethylthioxanthone (B ') component (manufactured by Nippon Kayaku Co., Ltd .: DET)
XS) 1 part, component (C) dipentaerythritol hexaacrylate 10 parts, component (D) 2,2'-
(3,3 ', 5,5'-Tetramethyl (1,1'-biphenyl) -4,4'-diyl) bis (oxymethylene)) bis-oxirane (Yukaka Epoxy Co., Ltd.)
30 parts, antifoaming agent (AC-300, manufactured by Kyoeisha Yushi Co., Ltd.) 1 part, barium sulfate 80 parts
And 0.5 part of phthalocyanine green, and further mixed and dispersed with a three-roll mill to prepare a photocurable and thermosetting resin composition.

Embedded image

Example 2 A photocurable and thermosetting resin composition was prepared in the same manner as in Example 1 except that the component (B '), diethylthioxanthone, was not used.

Comparative Example 1 In Example 1, the component (B) was not used and instead, 2-methyl-1- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Specialty Chemicals) was used. (Irgacure 907) was used to prepare a photo-curable / thermo-curable resin composition according to exactly the same formulation and method as in Example 1 except that 15 parts were used.

Each of the photo-curable and thermo-curable resin compositions obtained in Examples 1 and 2 and Comparative Example 1 was coated with a copper-clad laminate of a glass epoxy base material on which a copper foil of 35 μm was laminated and etched in advance. Then, the entire surface of the printed wiring board on which the pattern was formed was applied by screen printing. Then, after drying with a hot air circulating dryer at 80 ° C. for 30 minutes, a desired negative film was brought into close contact with the film, and 300 mJ /
After irradiation with ultraviolet rays of ² cm ^2, the film was developed with a 1.0% by mass aqueous solution of sodium carbonate for 60 seconds, and further thermally cured at 150 ° C. for 60 minutes by a hot-air circulation dryer to obtain a cured coating film. Table 1 shows the properties of the obtained cured coating films. In Table 1, the characteristics of each cured coating film were evaluated by the following methods.

(1) Solder heat resistance According to the test method of JIS C-6481,
The state of the coating film was evaluated after a total of three cycles, in which a test of peeling with a cellophane tape after dipping in a solder bath at 260 ° C. for 10 seconds was one cycle. ：: No change in the coating film after 3 cycles. X: Peeling occurs after 3 cycles.

(2) Chemical Resistance The state of the cured coating film after immersion in 10% hydrochloric acid for 30 minutes was evaluated. A: No change was observed. X: The coating film swelled and peeled off.

(3) Solvent resistance The state of the cured coating film after immersion in methylene chloride for 30 minutes was evaluated. A: No change was observed. ：: slightly changed. Δ: Notably changed. X: The coating film swelled and peeled off.

(4) Adhesion In accordance with the test method of JIS D-0202, 100 crosscuts were cut in a cross-cut pattern on the cured coating film of the test piece, and the peeling state after the peeling test with a cellophane tape was visually observed. Judged.

(5) Sensitivity Kodak no. 2 step tablet and 300mJ /
After exposure and development with cm ² , the sensitivity was evaluated from the number of steps obtained from the step tablet.

(6) Resolution A negative pattern of a line of 50 to 130 μm was applied to the coating film after the preliminary drying using an exposure machine of an ultrahigh pressure mercury lamp at 300 mJ / cm.
^{After 2} exposures and development, the formed minimum width line was read and the resolution was evaluated.

[0055]

[Table 1]

Example 3 100 parts of the unsaturated group-containing carboxylic acid resin of the component (A) obtained in Synthesis Example 1 were added to the 1- (4-phenylsulfanyl-) represented by the above formula (VI) of the component (B). 15 parts of phenyl) -octane-1-one oxime-O-benzoate (manufactured by Ciba Specialty Chemicals) and diethylthioxanthone (B ') component (manufactured by Nippon Kayaku Co., Ltd .: DET)
XS) 1 part, component (C) dipentaerythritol hexaacrylate 30 parts, component (D) 2,2'-
(3,3 ', 5,5'-Tetramethyl (1,1'-biphenyl) -4,4'-diyl) bis (oxymethylene)) bis-oxirane (Yuika Shell Epoxy Co., Ltd.)
Manufactured by YX-4000) 20 parts, bisphenol A type epoxy resin dispersed with acrylic rubber fine particles of component (E) (manufactured by Toto Kasei Co., Ltd .: YR-528 (rubber component 20%)) 50
Part, antifoaming agent (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.)
Parts, 30 parts of calcium carbonate, 2 parts of dicyandiamide, and 0.5 part of phthalocyanine green, were further mixed and dispersed by a three-roll mill to prepare a photocurable / thermosetting resin composition.

Example 4 A photocurable / thermosetting resin composition was prepared in the same manner as in Example 3 except that the component (B '), diethylthioxanthone, was not used.

Comparative Example 2 Example 3 was repeated, except that the component (B) was not used and 2-methyl-1- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Specialty Chemicals) was used. (Irgacure 907), a photocurable / thermosetting resin composition was prepared in exactly the same manner as in Example 3 except that 15 parts were used.

Each of the photocurable and thermosetting resin compositions obtained in Examples 3 and 4 and Comparative Example 2 was applied to a copper-clad laminate of a glass epoxy substrate on which a copper foil of 35 μm was laminated, and was previously etched. Then, the entire surface of the printed wiring board on which the pattern was formed was applied by screen printing. Then, after drying for 30 minutes in a hot air circulating dryer at 80 ° C., a desired negative film is adhered to the film, and ultraviolet light is irradiated on the film for 20 minutes.
After irradiating with 0 mJ / cm ^2, development treatment was performed with a 1.0% by mass aqueous sodium carbonate solution for 60 seconds to remove an unexposed portion forming a via hole. Further, it was heat-cured at 150 ° C. for 60 minutes using a hot-air circulating drier to form a cured resin insulating layer, subjected to a roughening treatment with a roughening agent, and then formed a conductor layer by an electroless plating treatment. Table 2 shows the characteristics of the formed cured resin insulating layer. In Table 2, the characteristics of each cured resin insulating layer were evaluated by the following methods.

(7) Peel Strength and Uniformity of Film Thickness The adhesion strength (peel strength) between the insulating resin layer of the multilayer printed wiring board and the conductive pattern of the first layer is determined according to JIS C-6481.
The film thickness was measured according to the method described above, and the thickness uniformity of the insulating layer was determined to be good or bad by measuring the cross section of the film thickness. ：: Uniform thickness ×: Variation in thickness

(8) Sensitivity Kodak no. 2 step tablet and 200mJ /
After exposure and development with cm ² , the sensitivity was evaluated from the number of steps obtained from the step tablet.

[0062]

[Table 2]

Synthesis Example 2 Bisphenol F type epoxy resin in which E is CH ₂ , G is OH and the average degree of polymerization i is 6.2 in the above general formula (V) (epoxy equivalent 950 g / eq, softening point 85 ° C.) 38
0 parts and 925 parts of epichlorohydrin were dissolved in 462.5 parts of dimethyl sulfoxide.
60.9 parts (1.5 equivalents) of 8.5% NaOH were added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the completion of the reaction, 250 parts of water was added and washed. After oil-water separation, most of the dimethyl sulfone oxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, and the remaining by-product salt and the reaction product containing dimethyl sulfone oxide were dissolved in 750 parts of methyl butyl ketone,
Further, 10 parts of 30% NaOH was added and reacted at 70 ° C. for 1 hour. After the completion of the reaction, the resultant was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin having an epoxy equivalent of 310. When the obtained epoxy resin was calculated from the epoxy equivalent, about 5 of 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy resin were epoxidized. This epoxy resin 310
And 282 parts of carbitol acetate were charged into a flask, heated and stirred at 90 ° C. and dissolved. The obtained solution is once cooled to 60 ° C., and 72 parts (1 equivalent) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, and the mixture is heated to 100 ° C. and reacted for about 60 hours. Gave a reaction product of 0.2 mg KOH / g,
To this was added 140 parts (0.92 equivalents) of tetrahydrophthalic anhydride, and the mixture was heated to 90 ° C. and the solid content acid value was 100 mg.
The reaction was carried out until the concentration reached KOH / g to obtain an unsaturated group-containing polycarboxylic acid resin having a solid content of 65%.

Example 5 100 parts of the unsaturated group-containing polycarboxylic acid resin of the component (A-1) obtained in Synthesis Example 2 was added to the above formula (VI) of the component (B).
15 parts of 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-benzoate (manufactured by Ciba Specialty Chemicals) represented by
1 part of diethylthioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.) as the component (B ′) and triacrylate of ethylene oxide adduct of trimethylolpropane as the component (C) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) : TMP-3),
(D) Bisphenol A type epoxy resin (Epicoat # 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) 60
Part, antifoaming agent (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.)
Parts, 10 parts of finely divided silica, 1 part of melamine and 0.5 part of phthalocyanine green, were mixed and dispersed by a three-roll mill to prepare a photocurable / thermosetting resin composition.

Example 6 A photocurable and thermosetting resin composition was prepared in the same manner as in Example 5 except that the component (B '), diethylthioxanthone, was not used.

COMPARATIVE EXAMPLE 2 In Example 5, the component (B) was not used and instead, 2-methyl-1- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Specialty Chemicals) was used. A photocurable / thermosetting resin composition was prepared according to exactly the same formulation and method as in Example 5 except that 15 parts of Irgacure 907) (manufactured by: IRGACURE 907) were used.

Each of the photocurable and thermosetting resin compositions obtained in Examples 5 and 6 and Comparative Example 3 was screen-printed on the entire surface of a printed circuit board (an imide film laminated with a copper foil). Applied. Then, after drying with a hot air circulating dryer at 80 ° C. for 30 minutes, a desired negative film is adhered and irradiated with ultraviolet rays of 300 mJ / cm ² , and then a 1.0 mass% aqueous solution of sodium carbonate for 60 seconds. The film was subjected to a development treatment, and was thermally cured at 150 ° C. for 60 minutes by a hot-air circulation dryer to obtain a cured coating film. Table 3 shows the properties of the obtained cured coating films. In Table 3, the characteristics of each cured coating film were evaluated by the following methods. The sensitivity was evaluated by the same method as in the above (5).

(9) Flexibility Judgment was made in a state where the test substrate was folded at 180 °. ○: No abnormality ×: Peeled

(10) Heat-Resistant Deterioration Resistance The test substrate was left at 125 ° C. for 5 days. ○: No abnormality ×: Peeled

(11) Solder Heat Resistance A rosin-based flux was applied to a test substrate, immersed in a solder bath at 260 ° C. for 10 seconds, and subjected to a peeling test using a cellophane tape to evaluate the state of the coating film. A: No change in the coating film. X: Peeling occurs after 3 cycles.

(12) PCT resistant PCT device (TABAI ESPEC HAST SYS)
Using TEM TPC-412MD), treatment was performed at 121 ° C. and 2 atm for 168 hours, and the state of the cured coating film was evaluated. The criteria are as follows. ◎: Peeling, discoloration and no elution. Δ: Any of peeling, discoloration, and elution was observed. X: Many peeling, discoloration and elution are observed.

[0072]

[Table 3]

Synthesis Example 3 Cresol novolak type epoxy resin (Nippon Kayaku Co., Ltd.)
EOCN104S, softening point 92 ° C, epoxy equivalent 22
0) 2200 parts (10 equivalents), 143 parts (1 mol) of dimethylolpropionic acid and 648.5 parts of acrylic acid (9 moles)
Mol), 4.6 parts of methylhydroquinone, 1131 parts of carbitol acetate and 484.9 of solvent naphtha
The mixture was heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C. and reacted for about 32 hours, and the acid value was 0.5 mg KOH / g.
Was obtained (12 equivalents of hydroxyl groups). Next, 582.5 parts of tetrahydrophthalic anhydride, 219.5 parts of carbitol acetate and 94.2 parts of solvent naphtha were added thereto.
The mixture was heated to 95 ° C., reacted for about 6 hours, cooled, and the acid value of the solid content was 60 mg KOH / g, and the solid content concentration was 6 mg.
A 5% unsaturated group-containing polycarboxylic acid resin was obtained.

Example 7 100 parts of the unsaturated group-containing polycarboxylic acid resin of the component (A-2) obtained in Synthesis Example 3 were added to the component (B) of the above formula (VI).
15 parts of 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-benzoate (manufactured by Ciba Specialty Chemicals) represented by
One part of diethylthioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.) as the component (B ′), 15 parts of dipentaerythritol hexaacrylate as the component (C), and a cresol novolac epoxy resin (Nippon Kayaku) as the component (D) 20 parts of EOCN1020 manufactured by Yakuhin Co., Ltd. and biphenyl epoxy resin (YX-40 manufactured by Yuka Shell Epoxy Co., Ltd.)
00) 5 parts, antifoaming agent (KS-6 manufactured by Shin-Etsu Chemical Co., Ltd.)
6) 1 part, 80 parts of barium sulfate, 1 part of dicyandiamide and 0.5 part of phthalocyanine green were blended and further mixed and dispersed by a three-roll mill to prepare a photocurable / thermosetting resin composition.

Example 8 A photocurable / thermosetting resin composition was prepared in the same manner as in Example 7 except that the component (B '), diethylthioxanthone, was not used.

Comparative Example 4 The procedure of Example 7 was repeated, except that the component (B) was not used and instead, 2-methyl-1- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Specialty Chemicals) was used. (Irgacure 907) was used to prepare a photo-curable / thermo-curable resin composition in exactly the same manner as in Example 7, except that 15 parts were used.

Each of the photocurable and thermosetting resin compositions obtained in Examples 7 and 8 and Comparative Example 4 was coated with a glass-epoxy-based copper-clad laminate obtained by laminating a copper foil of 35 μm and etched in advance. Then, the entire surface of the printed wiring board on which the pattern was formed was applied by screen printing. Then, after drying with a hot air circulating dryer at 80 ° C. for 30 minutes, a desired negative film was brought into close contact with the film, and 300 mJ /
After irradiating with ultraviolet rays of cm ^2, the film was developed with a 1.0% by mass aqueous solution of sodium carbonate for 60 seconds, and further thermally cured at 150 ° C. for 60 minutes by a hot-air circulation dryer to obtain a cured coating film. Table 4 shows the properties of the obtained cured coating film. In Table 4, the characteristics of each cured coating film were evaluated by the following methods. The method of (1) is used for solder heat resistance, the method of (5) for sensitivity, the method of (6) for resolution, and the method of (1) for PCT resistance.
Evaluation was performed by the method of 2).

(13) Electroless Plating Resistance Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the cured coating film is formed by tape peeling. The presence or absence of peeling and the presence of plating soak were evaluated. ◎: no peeling at all △: slight peeling ×: peeled cured coating

(14) Electric Corrosion Resistance An evaluation substrate was prepared under the above-mentioned conditions using a comb electrode B coupon of IPC B-25 instead of the copper foil substrate, and a bias voltage of 100 V DC was applied to the comb electrode. , 85
° C, 85% R.C. H. The presence or absence of migration after 1000 hours was confirmed in a constant temperature and constant humidity bath. ◎: No change at all △: Very slight change ×: Migration occurs

[0080]

[Table 4]

[0081]

As described above, the photocurable composition according to the present invention
The thermosetting resin composition has a photosensitive resin content of 2 per molecule.
Since it contains a photosensitive prepolymer (A) having at least one unsaturated double bond and at least one carboxyl group, it can be developed with an aqueous alkali solution after exposure. Using the compound (B) represented by the above formula (I), (II), (III) or (IV), which reacts with high sensitivity, or using these compounds with another radical photopolymerization initiator (B ′) Because they are used together, the photocuring depth at the time of exposure is large, high resolution is obtained, and together with these components, a reactive diluent (C) which contributes to an increase in crosslink density and a polyfunctional epoxy compound as a thermosetting component Since it also contains (D), a cured film with excellent properties such as heat resistance, chemical resistance, electrical properties, moisture absorption resistance, and PCT resistance is formed by a series of exposure, development, and post-heating treatments. be able to. In addition, the composition according to the present invention basically does not need to contain an organic solvent, and even if it contains a small amount, a preliminary drying step involving heating, an exposure step, a thermosetting step, and a soldering step. Mist does not occur, and there is no problem that mist adheres to and contaminates production equipment used in these steps and printed wiring boards manufactured. Therefore, the flexible printed wiring board, B
Printed circuit board for GA and CSP, resolution 100μm
It can be suitably used for applications such as a solder resist having the following resist pattern, such as a printed wiring board for high definition, and an interlayer resin insulating layer of a multilayer printed wiring board.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/00 C08F 290/00 4J036 299/00 299/00 5E314 C08G 59/14 C08G 59/14 59/20 59/20 59/42 59/42 59/68 59/68 C08L 9/00 C08L 9/00 21/00 21/00 63/00 63/00 A 63/10 63/10 G03F 7/027 515 G03F 7 / 027 515 7/028 7/028 H05K 3/28 H05K 3/28 D (72) Inventor Yutaka Yokoyama No. 388, Okura, Arashiyama-cho, Hiki-gun, Saitama Prefecture Taiyo Ink Manufacturing Co., Ltd. Arashiyama Plant F-term (reference) 2H025 AA01 AA02 AA10 AA14 AB15 AC01 AD01 BC13 BC31 BC74 BC83 BC85 BC86 BJ10 CA07 CB30 CB54 CC20 FA17 4J002 AC06Z AC07Z BB15Z BB18Z BD12Z BG04Z BK00Z BQ00Y CD01X CD02X CD03X CD05X CD06X CD11X CD14X CD20Q03 PA02 CP03 Q02PA03 A06 QA13 QA18 QA22 QA23 QA24 QA33 QA34 QA38 QA39 QA46 QB16 QB19 QB20 RA03 RA05 SA02 SA14 SA16 SA17 SA19 SA20 SA22 SA32 SA34 SA54 SA58 SA63 SA64 SA78 SA84 UA01 VA01 WA01 4J026 AA12 AB14 AA14A17 AB14 BA29 BA30 BA32 BA50 CA02 DB36 GA07 4J027 AC03 AC06 AE02 AE03 AE04 AE05 BA07 BA08 BA13 BA14 BA19 BA20 BA23 BA24 BA26 BA28 CA08 CA10 CB10 CC05 CD10 4J036 AA01 AA05 AA06 AB02 AB03 AB10 AC01 AD04 AD07 AD08 AF21 AF08 AF08 AF21 AF08 FB05 FB06 GA29 HA02 JA10 KA01 5E314 AA25 AA27 AA32 AA47 FF06 GG08 GG10 GG14

Claims (12)

[Claims] (A) two or more unsaturated doubles in one molecule
Photosensitive prepolymer having a bond and one or more carboxyl groups
Rimmer, (B) As photopolymerization initiators, the following formulas (I) and (I)
At least one of the types represented by I), (III) or (IV)
Compound, (C) reactive diluent, and (D) 2 per molecule
Contains an epoxy compound having two or more epoxy groups
A photo-curable / thermo-curable resin composition, characterized in that: Embedded image(Where R₁Is phenyl (which is unsubstituted or
Or C1-C6 alkyl, phenyl, halogen, O
R₈, SR₉Or NR_TenR₁₁Replaced by one or more of
Or R₁Is C1-C20 alk
Or a C2-C20 alkyl, which optionally includes -O
-Interrupted by one or more of
Substituted by one or more droxy groups)
Or; R₁Is C5-C8 cycloalkyl or C
2-C20 alkanoyl or benzoyl (this
It can be unsubstituted or C1-C6 alkyl,
Nil, OR₈, SR₉Or NR_TenR₁₁At least one of
Or R)₁Are C2 to C1
2 alkoxycarbonyl, which may optionally be -O-
Interrupted by one or more and / or
Substituted by one or more xy groups);
Is R₁Is phenoxycarbonyl (which is unsubstituted
Or C1-C6 alkyl, halogen, phenyl,
OR₈Or NR_{1 0}R₁₁Replaced by one or more of
Is present); or R₁Is -CONR_TenR ₁₁, C
N, NO_Two, C1-C4 haloalkyl, S (O)_m− (C
1-C6 alkyl), unsubstituted or C1-C12 al
S (O) replaced by kill_m-(C6 ~ C12 Ally
Le) or SO_TwoO- (C1-C6 alkyl), SO_TwoO
-(C6-C10 aryl) or diphenyl-ho
M is 1 or 2;₁′
C2-C12 alkoxycarbonyl (this may be
Interrupted by one or more of -O- and / or
More substituted by one or more hydroxyl groups)
Or R₁'Is phenoxycarbonyl (this
Is unsubstituted or C1-C6 alkyl, halogen
Phenyl, OR₈Or NR_TenR₁₁More than one
Or more substituted); or R₁'Is C5
C8 cycloalkyl, -CONR_TenR₁₁, CN, or
Henil (this is SR ₉Has been replaced by
And optionally a group R_Four', R_Five'And R₆′
By building a bond to the carbon atom of the phenyl ring₉
To form a 5- or 6-membered ring), or R
_Four', R_Five'And R₆'Is at least one -SR₉Is
Then R₁'Further represents a C1-C12 alkyl (this
Is unsubstituted or halogen, OH, OR_Two,
Phenyl, halogenated phenyl, or SR₉Replacement Fe
Substituted by one or more of nyl, and optionally
-Interrupted by -O- or -NH (CO)-)
Yes; R_TwoIs a C2-C12 alkanoyl (this is non-
Is substituted or at least one of halogen or CN
Or more substituted); or R_TwoIs C4-C
6 alkenoyl (provided that the double bond is carbonyl
Not conjugated to a group); or R_TwoIs benzoyl (this
Is unsubstituted or C1-C6 alkyl, halogen
, CN, OR₈, SR₉Or NR_TenR₁₁One or more of
Or R)_TwoIs C2-
C6 alkoxycarbonyl or phenoxycarbonyl
(This can be unsubstituted or C1-C6 alkyl
Or substituted by halogen);_Three,
R_Four, R_Five, R₆And R₇Are independently of each other hydrogen, halo
Gen, C1-C12 alkyl, cyclopentyl, cyclo
Hexyl or phenyl (which may be unsubstituted or
Is OR₈, SR₉Or NR_TenR₁₁By one or more of
Or R)_Three, R_Four, R_Five, R₆as well as
R₇Is benzyl, benzoyl, C2-C12 alkano
Yl or C2-C12 alkoxycarbonyl (this
Is optionally interrupted by one or more of -O-, and
/ Or optionally substituted by one or more hydroxyl groups
Or R_Three, R_Four, R_Five, R₆And R
₇Is phenonoxycarbonyl or a group OR₈, SR₉, S
OR₉, SO_TwoR₉Or NR_TenR₁₁(Where the substituent
OR₈, SR₉And NR_TenR₁₁Is optionally a phenyl ring
A further substituent or one of the carbon atoms of the phenyl ring and the group
R₈, R₉, R_TenAnd / or R₁₁5- or 6-member via
Forming a ring), provided that R_Three, R_Four, R_Five, R₆Passing
And R₇At least one is OR₈, SR₉And NR_TenR
₁₁And R_Four', R_Five'And R₆′ Are independent of each other
Hydrogen, halogen, C1-C12 alkyl, cyclope
Methyl, cyclohexyl, or phenyl (this is
Or OR₈, SR₉Or NR_TenR₁₁By
Or R)_Four', R_Five'And R
₆'Is benzyl, benzoyl, C2-C12 alkano
Yl or C2-C12 alkoxycarbonyl (this
Is optionally interrupted by one or more of -O-, and
/ Or optionally substituted by one or more hydroxyl groups
Or R_Four', R_Five'And R₆′
Is phenonoxycarbonyl or a group OR₈, SR₉, S
OR₉, SO_TwoR₉Or NR_TenR₁₁(Where the substituent
OR₈, SR₉And NR_TenR₁₁Is optionally a phenyl ring
A further substituent or one of the carbon atoms of the phenyl ring and the group
R₈, R₉, R_TenAnd / or R₁₁5- or 6-member via
Forming a ring), provided that R_Four', R_Five'as well as
R₆′ Is OR₈, SR₉And NR_TenR
₁₁And R_Five'Is methoxy and R_Four'as well as
R₆′ Are both hydrogen at the same time;₁'Is CN
R_Two'Is benzoyl or 4- (C1-C10 alkyl
R) not benzoyl; R₈Is hydrogen, C1-C12
Alkyl or C2-C6 alkyl, which is
-OH, -SH, -CN, C1-C4 alkoxy, C3
~ C6 alkeneoxy, -OCH_TwoCH_TwoCN, -OCH
_TwoCH_Two(CO) O (C1-C4 alkyl), -O (C
O)-(C1-C4 alkyl), -O (CO) -phenyl
,-(CO) OH or-(CO) O (C1-C4 alkyl)
Or R) ₈Is C2-C6
Alkyl, which is more interrupted by one or more of -O-
Or R₈Is-(CH_TwoCH_TwoO)_n
H, C2-C8 alkanoyl, C3-C12 alkenyl
, C3-C6 alkenoyl, cyclohexyl, or
Phenyl, which is unsubstituted or halogen, C1
Substituted with -C12 alkyl or C1-C4 alkoxy
Or R₈Is phenyl- (C1
To C3 alkyl), Si (C1 to C8 alkyl)_r(Fe
Nil)_3-rOr the following formula:N is 1 to 20; r is 1,
2 or 3; R₉Is hydrogen, C1-C12 alkyl
, C3-C12 alkenyl, cyclohexyl, or C
2-C6 alkyl, which is -OH, -SH, -CN,
C1-C4 alkoxy, C3-C6 alkeneoxy,-
OCH_TwoCH_TwoCN, -OCH_TwoCH_Two(CO) O (C1 ~
C4 alkyl), -O (CO)-(C1-C4 alkyl
), -O (CO) -phenyl,-(CO) OH or-
(Substituted with (CO) O (C1-C4 alkyl))
Or R₉Is a C2-C12 alkyl (this
Is interrupted by one or more of -O- or -S-
R) or R₉Is phenyl (which is unsubstituted
Or halogen, C1-C12 alkyl or
Is substituted with C1-C4 alkoxy));
Or R₉Is phenyl- (C1-C3 alkyl), or
The following formula:R;_TenAnd R₁₁Are independent of each other
Hydrogen, C1-C12 alkyl, C2-C4 hydroxy
Cycloalkyl, C2-C10 alkoxyalkyl, C3-
C5 alkenyl, C5-C12 cycloalkyl, phenyl
Ru- (C1-C3 alkyl) or phenyl (which is
Unsubstituted or C1-C12 alkyl or C
1-C4 alkoxy));
Or R_TenAnd R₁₁Is C2-C3 alkanoyl, C3-
C6 alkenoyl or benzoyl; or R_TenPassing
And R₁₁Are together C2-C6 alkylene (this
Is optionally -O- or -NR₈Interrupted by
And / or optionally hydroxyl, C1-C4
Lucoxy, C2-C4 alkanoyloxy or ben
Substituted with zoyloxy); or R_TenBut
When it is hydrogen, R₁₁Is represented by the following formula:M can be a C1-C12 alky!
Kylene, cyclohexylene, phenylene,-(CO) O
-(C2-C12 alkylene) -O (CO)-,-(C
O) O- (CH_TwoCH_TwoO)_n-(CO)-or-(CO)
-(C2-C12 alkylene)-(CO)-; M
₁Is a direct bond or a C1-C12 alkylene
Oxy (this is optionally 1 to 5 -O-, -S
-And / or -NR_Ten-Has been interrupted by
M;_TwoIs a direct bond or (C1-C12
Alkylene) -S- (this is optionally 1 to 5-
O-, -S-, and / or -NR_TenInterrupted by
M)_ThreeIs a direct bond, a piperazino group, or
(C1-C12 alkylene) -NH- (which is
From 1 to 5 -O-, -S-, and / or -NR_Ten
-Interrupted by-) provided that (i) R_FiveIs methoxy and R_TwoIs benzoyl or acetyl
If chill, R ₁Is not phenyl; (ii) R_FiveIs methoxy and R_TwoIs ethoxycarbonyl
, Then R_TwoIs benzoyl or ethoxycarbonyl
Not (iii) R_FiveIs methoxy and R₁Is 4-methoxybenz
If it is Zoyl, R_TwoIs not ethoxycarbonyl
(Iv) R_FiveIs methacryloylamino, and R₁But
If R_TwoIs not benzoyl; (v) R_FiveAnd R_FourOr R_FiveAnd R₆Are both OR₈Based on
Yes, their OR₈The radicals together form R₈Through the ring
To thereby form -O-CH_Two-O-, R₁But
If chill, R_TwoIs not acetyl; (vi) R_Four, R_FiveAnd R₆Are simultaneously methoxy and R₁But
If it is ethoxycarbonyl, R_TwoIs acetyl
Absent. ) 2. The photosensitive prepolymer having (A) two or more unsaturated double bonds and one or more carboxyl groups in one molecule, and (B) a photopolymerization developing agent according to the above (1). At least one compound represented by the formula (I), (II), (III) or (IV), (B ′) a photopolymerization initiator other than the above photopolymerization initiator, and (C) reactive dilution A photo-curable / thermo-curable resin composition comprising: an agent; and (D) an epoxy compound having two or more epoxy groups in one molecule. 3. The photosensitive prepolymer (A)
Unsaturated group-containing prepolymer (A-1) obtained by subjecting an epoxy resin represented by the following general formula (V) to an esterification reaction of (meth) acrylic acid and (meth) acrylic modification, and further adding a polybasic anhydride. The composition according to claim 1, comprising: Embedded image (Wherein E represents CH ₂ , C (CH ₃ ) ₂ or SO ₂ ;
i represents 1 to 12, and G represents a hydrogen atom or a glycidyl group. However, when i is 1, G represents a glycidyl group, and when i is 2 or more, at least one of G represents a glycidyl group. ) 4. The photosensitive prepolymer (A)
(A) an epoxy compound having two or more epoxy groups in one molecule, (b) an unsaturated group-containing monocarboxylic acid,
(C) Addition reaction of (d) polybasic acid anhydride to a reaction product of two or more hydroxyl groups in one molecule and a compound having one functional group other than a hydroxyl group that reacts with an epoxy group The composition according to any one of claims 1 to 3, further comprising an unsaturated polycarboxylic acid resin (A-2) obtained by the reaction. 5. The method according to claim 1, wherein the epoxy compound (D) contains an epoxy compound (D-1) insoluble in the diluent (C). Composition. 6. The epoxy compound (D-1) insoluble in the diluent (C) is 1,3,5-tris (2,3-epoxy-propyl) -1,3,5-triazine-2,4. , 6-
Trione and 2,2 '-[3,3', 5,5'-tetramethyl (1,1'-biphenyl) -4,4'-diyl)
The composition according to claim 5, wherein the composition is at least one of bis (oxymethylene)] bis-oxirane. 7. The method according to claim 1, wherein at least one of the epoxy compounds (D) is an epoxy resin (D-2) having a softening point of 110 ° C. or lower, and further contains (E) rubber fine particles. A composition according to any one of the preceding claims. 8. The rubber fine particle (E) is an acrylic and / or butadiene-based crosslinked rubber, and has a particle size of from 0.01 to 10%.
The composition according to claim 7, having a particle size of μm. 9. A printed wiring board in which a solder resist film as a permanent protective film is formed on a circuit board having a conductor layer of a predetermined circuit pattern, wherein the solder resist film is any one of claims 1 to 8. A printed wiring board comprising a cured coating film of the photo-curable and thermo-curable resin composition according to the above. 10. A flexible printed wiring having a solder resist film formed using the photocurable / thermosetting resin composition containing the unsaturated group-containing prepolymer (A-1) according to claim 3. The printed wiring board according to claim 9, wherein the printed wiring board is a board. 11. A BGA (ball) having a solder resist film formed using the photocurable / thermosetting resin composition containing the unsaturated polycarboxylic acid resin (A-2) according to claim 4. 10. The printed wiring board according to claim 9, wherein the printed wiring board is a printed wiring board for a grid array and a CSP (chip scale package). 12. The photocurable and heat-curable resin according to claim 7, wherein in a multilayer printed wiring board in which a resin insulating layer and a conductor layer having a predetermined circuit pattern are sequentially formed on a circuit board, the resin insulating layer is formed. A multilayer printed wiring board comprising a cured coating film of a curable resin composition.