DE102006043357B4 - A photosensitive thermosetting resin composition and use thereof for manufacturing a circuit board - Google Patents

Abstract

(Chemische Formel I/E) wobei G eine Glycidylgruppe ist; A₁₁ und A₁₃ und A₁₅ jeweils untereinander gleich oder untereinander verschieden sein können und unabhängig voneinander ein zweiwertiger aromatischer Rest oder eine zweiwertige, hydrierte, aromatische Restgruppe umfassend eine vollständig hydrierte Gruppe sein können; A₁₂ und A₁₄ jeweils zueinander gleich oder unterschiedlich sein können und unabhängig voneinander gleich H oder G sein können; wenigstens eines von A₁₂ und A₁₄ ferner H ist, und alle diese gleichzeitig H sein können; die durchschnittlichen Wiederholungs-Einheitszahlen all und a₁₂ zueinander gleich oder unterschiedlich sein können und unabhängig davon...A photosensitive, thermosetting resin composition, characterized in that the composition contains:
(I) An alkoxy group-containing silane-modified epoxy resin obtained by a dealcoholization reaction of the epoxy resin represented by the following chemical formula (Chemical Formula I / E) with hydrolyzable alkoxysilane:

(Chemical formula I / E) wherein G is a glycidyl group; A ₁₁ and A ₁₃ and A _{15 may} each be the same or different from each other and may independently be a divalent aromatic radical or a divalent, hydrogenated, aromatic radical group comprising a fully hydrogenated group; A ₁₂ and A _{14 may} each be the same or different and may independently be H or G; at least one of A ₁₂ and A _{14 is} further H, and all of these may be H at the same time; the average repetition unit numbers all and a ₁₂ can be the same or different from each other and regardless of ...

Description

The invention of the present invention relates to a photosensitive thermosetting resin composition and the use thereof for producing a resist film coated, smoothed printed circuit board.

More particularly, the present invention relates to a photosensitive thermosetting resin composition (photosensitive thermoplastic composition) used as solder resist, layer to layer insulating material, wiring layer of a semiconductor device, etc. particularly for a printed circuit board, particularly a printed circuit board for LED (especially a printed circuit board) LED for a larger size liquid crystal backlight), a printed circuit board for LED lighting, a printed vehicle LED headlamp circuit board, a UV LED printed circuit board, and a high heat printed circuit board, and a smooth printed circuit board; which is coated with its resist film, and also to a method for producing the same.

It is required that a resist film, particularly a solder resist film, as protective films for printed circuit boards have excellent characteristics such as HAST (Highly Accelerated Temperature and Humidity Stress Test) resistance and gold coating resistance.

Besides the above-described characteristics, it is required that a solder resist film of a printed circuit board used for an LED as a light source for illumination or a LED of a backlight for a display element should utilize the light emission of an LED as effectively as possible.

Therefore, a white solder resist film as a solder resist film for a printed circuit board used for an LED is preferable because it can improve white light resist film light reflection, thereby effectively utilizing the light emission of the LED. However, by taking advantage of only the improvement in the light reflection factor, there is a limit to the effective utilization of the light emission of the LED. As a result, it has been demanded to make more efficient use of the light emission of the LED.

Therefore, a white solder resist film as a solder resist film for a printed circuit board used for an LED is preferable because it can improve white light resist film light reflection, thereby effectively utilizing the light emission of the LED. However, by taking advantage of only the improvement in the light reflection factor, there is a limit to the effective utilization of the light emission of the LED. It was clearly demanded to use the light emission of the LED more effectively.

Incidentally, the describes JP-A1-2001-59013 (Japanese Unexamined Patent Publication (Kokai) No. 2001-59013) as a curable ink used for a printed circuit board, a thermosetting epoxy resin composition comprising (A) an alkoxy group-containing silane-modified epoxy resin, and (A) a curing agent for the epoxy resin. Patent No. 1 describes that it is an object to provide an epoxy resin composition having a cured product having excellent heat resistance.

The JP-A1-2005-179401 (Japanese Unexamined Patent Publication (Kokai) No. 2005-179401) describes a thermosetting epoxy resin composition comprising (A) a silane-modified hydrogenated bisphenol epoxy resin and (A) an epoxy curing agent. Patent No. 2 describes that it is an object to provide a thermosetting epoxy resin composition that provides a cured product that has excellent heat resistance and resistance to yellowing.

The JP-A1-6-230571 (Japanese Unexamined Patent Publication (Kokai) No. 6-230571) describes a heat-resistant photosensitive resin composition comprising (1) an unsaturated group-containing polycarboxylic acid resin, (2) an epoxy compound, (3) a photopolymerizable monomer, and (4) a photopolymerization -Trigger. Patent No. 3 describes that it is an object to provide a heat-resistant photosensitive resin composition whose cured product is excellent in solder heat resistance, flame resistance, plating resistance, chemical resistance Resistance, the electrical insulation properties and the adhesion properties on a board, and which is also excellent in terms of stability over time and the development properties.

The JP-A1-2005-115187 (Japanese Unexamined Patent Publication (Kokai) No. 2005-115187) describes a photosensitive resin composition comprising (A) an unsaturated ethylene group-containing polycarboxylic acid resin, (B) a photopolymerization initiator, (C) a crosslinking agent, and (D) a curing agent. It describes that it is an object to provide a photosensitive resin composition excellent in photosensitivity and having no initial tack and capable of giving a cured product having excellent adhesion properties, pencil hardness, solvent resistance, acid resistance, heat resistance and has resistance to gold plating.

There is also known a photosensitive resist dye composition for a flexible printed circuit board comprising (A) an unsaturated group-containing polycarboxylic acid resin, (B) a photopolymerization initiator, (C) a diluent, and (D) a curing component, wherein it is an object is to provide a resist dye composition for a flexible printed circuit board which can be developed in a dilute alkaline aqueous solution and which is capable of giving a cured film excellent in flexibility, bendability, adhesion properties, chemical resistance , Heat resistance, etc. has.

The JP-A1-6-73160 (Japanese Unexamined Patent Publication (Kokai) No. 6-73160) describes a photosensitive resin composition comprising an unsaturated group-containing polycarboxylic acid resin, a polyfunctional acrylate-photopolymerizable monomer, an aminosilane-modified epoxy resin, a photopolymerization initiator, and an organic solvent, which is an object is to provide a resin composition capable of being subjected to patterning and capable of giving a transparent film having high flatness and useful for forming a protective layer or a flat layer on a color resist film is.

The JP 2002-179762 A is concerned with providing a silane-modified epoxy resin composition capable of obtaining a cured product having good heat resistance, which does not cause voids or cracks, and a cured product of the composition. To this end, the silane-modified epoxy resin composition has an alkoxy-group-containing silane-modified epoxy resin (A), which is thereby obtained dealcoholization-concentration reaction of an alkoxysilane partial condensation product with a bisphenol-type epoxy resin mixture, and an epoxy resin curing agent (B) wherein the bisphenol type epoxy resin mixture is a bisphenol type epoxy resin (1) having an epoxy equivalent of> 400 g / equivalent and <10,000 g / equivalent and a bisphenol type epoxy resin (2) having an epoxy equivalent of> 170 g / Equivalent and <400 g / equivalent, wherein the weight ratio in use ((1) / (2)) is between 0.1 and 1.0. A cured epoxy resin-silica hybrid product is obtained by curing the epoxy resin composition.

However, the cured products obtained from the curable ink described in the prior art do not have sufficient HAST resistance. Further, the cured products obtained from the thermosetting dye described in the prior art do not have sufficient resistance to gold plating.

It is an object of the present invention to provide a photosensitive thermosetting resin composition capable of giving a cured product excellent in HAST resistance and gold-plating resistance. In particular, it is an object of the present invention to provide a photosensitive thermosetting resin composition capable of giving a solder resist film for a printed LED circuit board which is excellent not only in light reflection factor but also in glossiness to the above-mentioned excellent properties, and thereby can more effectively use the light emission of the diode.

To this end, the present invention relates to a resin composition according to claim 1. Advantageous embodiments of the resin composition are characterized in the subclaims 2 to 4.

The invention further relates to the use of the resin composition of the above-mentioned type for producing a flat, resist-coated, printed circuit board according to claim 5.

According to the present invention, there is provided a photosensitive thermosetting resin composition capable of being a cured product having excellent HAST resistance and gold plating resistance. In particular, according to the present invention, there is provided a photosensitive thermosetting resin composition capable of giving a solder resist film for a printed LED circuit board having the above-described excellent characteristics, and further not only in terms of the light reflection factor but also in FIG In terms of the gloss factor is excellent, so that the light emission of the diode is used more effectively.

Embodiments of the invention will be described with reference to the detailed description of the drawings.

1 Fig. 10 is a cross-sectional view showing a process for producing a flat solder resist-coated printed circuit board.

(Chemische Formel I/E) (worin G eine Glycidylgruppe ist, die durch die folgende chemische Formel dargestellt wird:

A photosensitive thermosetting resin composition of the present invention comprises an alkoxy group-containing silane-modified epoxy resin (hereinafter sometimes referred to as "Component [I]"). An example of the component [I] is a substance obtained by a dealcoholization reaction of the epoxy resin represented by the following chemical formula (Chemical Formula I / E) with hydrolyzable alkoxysilane which will be described later.

(Chemical formula I / E) (wherein G is a glycidyl group represented by the following chemical formula:

(Chemische Formel I/E-U1)

(Chemische Formel I/E-U2) In the chemical formula I / E, the arrangement sequence of a resin skeleton of each repeating unit represented by the following chemical formulas (Chemical Formula I / E-U1) and (Chemical Formula I / E-U2) is not limited or specified.

(Chemical formula I / E-U1)

(Chemical formula I / E-U2)

Thus, in the case where the repeating units (Chemical Formula I / E-U1) and (Chemical Formula I / E-U2) are not the same, the resin (Chemical Formula I / E) is represented by a resin in FIG the repetitive units. (Chemical formula I / E-U1) and (Chemical formula I / E-U2) are arranged in a block copolymerization type, an alternating copolymerization type and a random copolymerization type, and at least one of these resin types can be used.

In the chemical formula I / E, Au in the repeats a ₁₁ , A ₁₃ in the repeats a ₁₂ and A _{15 may be the} same or different from each other, and they may independently and A _{15 be the} same or different from each other, and they may be independent from each other be a divalent aromatic radical group or a divalent, fully hydrogenated, aromatic radical group. [Preferably, A ₁₅ is A ₁₁ or A _13. ]

(Chemische Formel I/E-An): wobei A₂₁ eine (Cyclo)-Alkylengruppe, -O-, -CO-, -COO-, -S-, -S-S-, -SO-, -SOO- oder eine zweiwertige Gruppe, die durch die folgende chemische Formel (Chemische Formel F) dargestellt wird, ist und a₂₁ gleich 0 der 1 ist

(Chemische Formel F) In A ₁₁ , A ₁₃ and A ₁₅ , a divalent group represented by the following chemical formula (Chemical Formula I / E-AM), a phenylene group or a naphthylene group, etc. are exemplified:

(Chemical formula I / E-An): wherein A _{21 is} a (cyclo) alkylene group, -O-, -CO-, -COO-, -S-, -SS-, -SO-, -SOO- or a divalent A group represented by the following chemical formula (Chemical Formula F) is and a ₂₁ is 0 of 1

(Chemical formula F)

(Chemische Formel I/E-Ar1-2)

(Chemische Formel I/E-Ar1-3)

(Chemische Formel I/E-Ar1-4)

(Chemische Formel I/E-Ar1-5) In an aromatic residual group, an example of a divalent group (Chemical Formula I / E-Ar1) is one in which A _{21 is} a (cyclo) alkylene group. An example of a (cyclo) -alkylene group is one such that C1 ~ has C8. A (cyclo) alkylene group may have a substituent (for example, a C 1 -C 6 (cyclo) alkyl group, aryl group, -CF ₃ , etc.). In the chemical formula I / E-Ar1, one benzene ring or both benzene rings may have at least one substituent (for example, C1-C6 alkyl group, halogen atom, etc.). In particular, an example of such an aromatic residual group is one represented by the following chemical formulas (Chemical Formula I / E-Ar1-1 to Chemical Formula I / E-Ar1-5).

(Chemical formula I / E-Ar1-2)

(Chemical formula I / E-Ar1-3)

(Chemical formula I / E-Ar1-4)

(Chemical formula I / E-Ar1-5)

(Chemische Formel I/E-Ar1-6)

(Chemische Formel I/E-Ar1-7) In an aromatic radical group, another bivalent group (Chemical Formula I / E-Ar1) becomes, for example, one in which A _{21 is} -O-, -CO-, -COO-, -S-, -SS-, -SO-, or -SOO- is. In the chemical formula I / E-Ar1, a benzene ring or both benzene rings may have at least one substituent (for example, a C1-C6 alkyl group, a hologen atom, etc.). In particular, such an aromatic residual group is, for example, one shown in the following chemical formulas (Chemical Formula I / E-Ar1-6) ~ (Chemical Formula I / E-Ar1-7).

(Chemical formula I / E-Ar1-6)

(Chemical formula I / E-Ar1-7)

(Chemische Formel F) Further, in an aromatic residual group, another divalent group (Chemical Formula I / E-Ar1) is, for example, one in which A _{21 is represented} by the following Chemical Formula F:

(Chemical formula F)

(Chemische Formel I/E-Ar1-F). In the chemical formula I / E-Ar1, a benzene ring or both benzene rings may have at least one substituent (for example, a C1-C6 alkyl group, etc.). In particular, such an aromatic residual group is, for example, one represented by the following chemical formula (Chemical Formula I / E-Ar1-F):

(Chemical formula I / E-Ar1-F).

(Chemische Formel I/E-Ar1-8)

(Chemische Formel I/E-Ar1-9) In an aromatic residual group, another divalent group (Chemical Formula I / E-Ar1) is, for example, one in which a ₂₁ is 0. In the chemical formula I / E-Ar1, one benzene ring or both benzene rings may have at least one substituent (for example, C1-C6 alkyl group, halogen atom, etc.). In particular, such an aromatic residual group is, for example, those represented by the following chemical formulas (Chemical Formula I / E-Ar1-8) and (Chemical Formula I / E-Ar1-9):

(Chemical formula I / E-Ar1-8)

(Chemical formula I / E-Ar1-9)

(Chemische Formel I/E-Ar2-1): In an aromatic residual group, a phenylene group may have at least one substituent (for example, C1-C6 alkyl group, halogen atom, etc.) on the aromatic ring. In particular, such a phenylene group is, for example, one represented by the following chemical formula (Chemical Formula I / E-Ar2-1):

(Chemical formula I / E-Ar2-1):

(Chemische Formel I/E-Ar3-1) For example, in an aromatic residual group, the naphthylene group is one represented by the following chemical formula (I / E-Ar3-1):

(Chemical formula I / E-Ar3-1)

The aromatic radical group used are groups (Chemical Formula I / E-Ar1-1), (Chemical Formula I / E-Ar1-4), (Chemical Formula I / E-Ar1-8) and (Chemical Formula I / E-Ar1-4). 9) is preferred.

The aromatic radical group used are groups (Chemical Formula I / E-Ar1-1), (Chemical Formula I / E-Ar1-4), (Chemical Formula I / E-Ar1-8) and (Chemical Formula I / E-Ar1-4). 9) is preferred.

In A ₁₁ , A ₁₃ and A ₁₅ , a divalent fully hydrogenated aromatic residual group is, for example, one in which one aromatic ring of the above-described aromatic residual group is fully hydrogenated. At least a part of A ₁₁ , A ₁₃ and A ₁₅ may be a hydrogenated one be aromatic radical group instead of the above-described aromatic radical group. According to such a case, there are advantages that a color change due to the heat treatment history is suppressed to improve the resistance to yellowing and the weather resistance and the compatibility with copolymerizable acrylic resins. A hydrogenated, aromatic residual group comprises a fully hydrogenated group. In particular, a hydrogenated aromatic residual group includes one in which unsaturated bonds, for example, a double bond in an aromatic residual group, are fully hydrogenated so as to be changed into saturated bonds.

When an epoxy resin having a hydrogenated aromatic residual group (Chemical Formula I / E) is used, yellowing resistance, weather resistance and compatibility with copolymerizable acrylic resin will be improved.

The conditions for the hydrogenation are suitably selected. For example, the hydrogenation may be carried out under conditions such that the reaction temperature is 10~150 ° C, the reaction pressure (hydrogen pressure) is 0.5 to 15 MPa, and the flow rate of the raw material solution (LHSW) is 0.2 to 10 / h Use of a fluidized bed process wherein the raw material solution is prepared by dissolving the crude material in an ether family solvent and introducing hydrogen into the reactor in a gas-liquid parallel flow in which a packed bed fluid Type reactor is used in which ruthenium-supported, formulated catalysts are loaded.

(Chemische Formel I/E-S-1)

(Chemische Formel I/E-S-2)

(Chemische Formel I/E-S-3)

(Chemische Formel I/E-S-4)

(Chemische Formel I/E-S-5)

(Chemische Formel I/E-S-6)

(Chemische Formel I/E-S-7)

(Chemische Formel I/E-S-8)

(Chemische Formel I/E-S-9)

(Chemische Formel I/E-S-10)

(Chemische Formel I/E-S-11)

(Chemische Formel I/E-S-12) In particular, the hydrogenated aromatic residual groups in A ₁₁ , A ₁₃ and A _{15 are} those represented by the following formulas (Chemical Formula I / ES-1) to (Chemical Formula I / ES-12) and those such as they are represented by the chemical formulas in which either part or all of the cyclohexane rings have been changed to cyclohexene rings:

(Chemical formula I / ES-1)

(Chemical formula I / ES-2)

(Chemical formula I / ES-3)

(Chemical formula I / ES-4)

(Chemical formula I / ES-5)

(Chemical formula I / ES-6)

(Chemical formula I / ES-7)

(Chemical formula I / ES-8)

(Chemical formula I / ES-9)

(Chemical formula I / ES-10)

(Chemical formula I / ES-11)

(Chemical formula I / ES-12)

In the chemical formula I / E, the averaged repeating unit numbers a ₁₁ and a _{12 may} each be the same or different, and a number is independently more than 0 but not 0 at the same time. The sum of a ₁₁ and a ₁₂ (a ₁₁ + a ₁₂ ) is preferably 20 and below, more preferably 15 and below. When the sum of a ₁₁ and a _{12 is} larger, the possibility of gel formation by reaction with the polyfunctional hydrolyzable alkoxysilane occurs.

In the chemical formula I / E, A ₁₂ of a ₁₁ and A ₁₄ of a _{12 may be the} same or different and independently equal to H or G, provided that at least one of A ₁₂ of a ₁₁ and A ₁₄ of a ₁₂ is H and they can be H at the same time. Preferably, when all other than 0, at least one of A ₁₄ of a ₁₂ is G. Similarly, if a _{12 is} not 0, at least A ₁₄ of a _{12 is} preferably G.

The softening point of the epoxy resin (Chemical Formula I / E) is preferably 50 ° C and above, especially 60 ~ 100 ° C. This has the advantages of improving dry tack and photosensitivity.

An epoxy resin (Chemical Formula I / E) includes homopolymer resin and copolymer resin, and more than one of these resins may be used. Examples of "resin" are bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A / F combination type epoxy resin, novolac epoxy resin, bisphenol A novolac epoxy resin (or F-type epoxy resin). Type), triphenylmethane epoxy resin, bixylenol epoxy resin, dicyclopentadiene phenol epoxy resin, epoxy resin having a naphthalene skeleton, fluorine epoxy resin, silicone-modified epoxy resin, ε-caprolactone-modified epoxy resin, etc. More than one of these resins may be used.

(Chemische Formel I/E-1)

(Chemische Formel I/E-2)

(Chemische Formel I/E-3) Preferably, an epoxy resin (Chemical Formula I / E) includes a homopolymer resin represented by the following formula (Chemical Formula I / E-1), an alternating copolymerization type resin represented by the following formula (Chemical formula I / E -2), and a block copolymerization type resin represented by the following formula (Chemical Formula I / E-3). More than one of these resins can be used.

(Chemical formula I / E-1)

(Chemical formula I / E-2)

(Chemical formula I / E-3)

G in the chemical formula I / E-1, the chemical formula I / E-2 and the chemical formula I / E-3 has the same meaning as defined above. Each of A ₃₁ and A ₃₃ in Chemical Formula I / E-1 is a divalent aromatic group or a divalent, hydrogenated, aromatic group independently, but preferably A ₃₃ is A ₃₁ . In A ₃₁ and Aas, the divalent aromatic residual group or the divalent hydrogenated aromatic residual group may be those as described above in A ₁₁ , A ₁₃ and A ₁₅ . The number of the average repeating unit number A ₃₁ in the chemical formula I / E-1 is preferably 20 and below, more preferably 15 and below. A ₃₂ of a ₃₁ in the chemical formula I / E-1 may be the same or different, and is independently H or G, where at least one H and all of them may be H at the same time.

Each of A ₄₁ , A ₄₃ and A ₄₅ in the chemical formula I / E-2 is a divalent aromatic group or a divalent, hydrogenated, aromatic group independently, but preferably A ₄₅ is A ₄₁ or A ₄₃ . The divalent aromatic residual group or the divalent hydrogenated aromatic residual group in A ₄₁ , A ₄₃ and A ₄₅ may be those as described and shown above for A ₁₁ , A ₁₃ and A ₁₅ . In the chemical formula I / E-2, a _{41 has} the same meaning as a ₃₁ . In the chemical formula I / E-2, A ₄₂ and A ₄₄ of a _{41 may} each be the same or different from each other, and they may independently be H or G, at least one being H and all at the same time being H.

Each of A ₅₁ , A ₅₃ and A ₅₅ in Chemical Formula I / E-3 is a divalent aromatic group or a divalent, hydrogenated, aromatic group independently, but preferably A ₅₅ is A ₅₁ or A ₅₃ . The divalent aromatic residual group or the divalent hydrogenated aromatic residual group in A ₅₁ , A ₅₃ and A ₅₅ may be those described and shown above in A ₁₁ , A ₁₃ and A ₁₅ . In the chemical formula I / E-3, a ₅₁ and a _{52 may have} the same meanings as al _l and a _12, respectively. In the chemical formula I / E-3, A s and A _{54 may} each be the same or different from each other, and may independently be H or O, at least one being H and all being H at the same time.

Copolymer epoxy resins (Chemical Formula I / E-2) or (Chemical Formula I / E-3) exhibit an effect as a combined effect of each homopolymer epoxy resin (Chemical Formula I / E-1).

For example, the resin properties and the characteristics of the resin (Chemical Formula I / E-1) differ depending on their basic skeleton A ₃₁ . In particular, when a bisphenol F epoxy resin is introduced at A ₃₁ , there are resin properties and characteristics such as flexibility and adhesion properties. When a group according to the chemical formula I / E-1-9 is introduced at A ₃₁ , resin properties and characteristics such as crystallizability and low water absorption occur. Therefore, in order to obtain the characteristics of both, it is preferable to mix a homopolymer epoxy resin of each of them. Also, by using the copolymer epoxy resin obtained by introducing both of the skeletons described above into the same molecule, on the other hand, it is possible to synthesize a resin having properties and characteristics of each of the two resins. Thus, by using a copolymeric epoxy resin, it is possible to ensure that they complement each other, thereby improving their inherent properties and characteristics or adding new functions and giving rise to new excellent resin properties and characteristics.

(Chemische Formel I/E-1-1)

(Chemische Formel I/E-1-2)

(Chemische Formel I/E-2-1)

(Chemische Formel I/E-2-2)

(Chemische Formel I/E-2-3)

(Chemische Formel I/E-2-4)

(Chemische Formel I/E-3-1)

(Chemische Formel I/E-3-2)

(Chemische Formel I/E-3-3)

(Chemische Formel I/E-3-4) In the epoxy resin (Chemical Formula I / E), the resin (Chemical Formula I / E-1) comprises those represented by the following formulas (Chemical Formula I / E-1-1) and (Chemical Formula I / E) 1-2). The resin (Chemical Formula I / E-2) includes those represented by the following formulas (Chemical Formula I / E-2-1) to (Chemical Formula I / E-2-4). The resin (Chemical Formula I / E-3) includes those represented by the following formulas (Chemical Formula I / E-3-1) to (Chemical Formula I / E-3-4). More than one of these epoxy resins can be used.

(Chemical formula I / E-1-1)

(Chemical formula I / E-1-2)

(Chemical formula I / E-2-1)

(Chemical formula I / E-2-2)

(Chemical formula I / E-2-3)

(Chemical formula I / E-2-4)

(Chemical formula I / E-3-1)

(Chemical formula I / E-3-2)

(Chemical formula I / E-3-3)

(Chemical formula I / E-3-4)

G in the above-described formulas (Chemical formula I / E-1-1) to (Chemical formula I / E-2-4) and (Chemical formula I / E-3-1) to (Chemical formula I / E-3 -4) has the same meaning as defined above. A ₆₁₁ and A ₆₂₁ each have the same meaning as A ₃₂ . Each of the average repeat unit numbers a ₆₁₁ and a ₆₂₁ is a number of 20 and below. Each of A ₆₃₁ , A ₆₄₁ and A ₆₅₁ has the same meaning as A ₄₂ . Each of A ₆₃₂ , A ₆₄₂ , A ₆₅₂ and A ₆₆₂ have the same meaning as A ₄₄ . Each of a ₆₃₁ , a ₆₄₁ , a _651, and a ₆₆₁ has the same meaning as a ₄₁ . Each of the A _711, A _721, A ₇₃₁ and A ₇₄₁ have the same meaning as A _52nd Each of the A ₇₁₂ , Am, A ₇₃₂ and A ₄₇₄₂ have the same meaning as A ₆₄ . Each of a ₁₁ , a ₂₁ , a ₃₁ and a ₇₄₁ has the same meaning as a ₅₁ . Each of a ₇₁₂ , a ₇₂₂ , a _732, and a ₇₄₂ has the same meaning as a ₅₂ .

Each of A ₆₃₃ , A ₆₃₄ , A ₆₄₃ , A ₆₄₄ , A ₆₅₃ , A ₆₅₄ , A ₆₆₃ , A ₆₆₄ , A ₇₁₃ , A ₇₁₄ , A ₇₂₃ , A ₇₂₄ , A ₇₃₃ , A ₇₃₄ , A ₇₄₃ and A ₇₄₄ in _FIG the above-described formulas (Chemical Formula I / E-1-1) to (Chemical Formula I / E-2-4) and (Chemical Formula I / E-3-1) to (Chemical Formula I / E-3-4 ) H or CH _{3 is} independent of each other. Preferably, A _{633 is} equal to A ₆₃₄ . A ₆₄₃ is equal to A ₆₄₄ . A ₆₅₃ is equal to A ₆₅₄ . A ₆₆₃ is equal to A ₆₆₄ . A ₇₁₃ is equal to A ₇₁₄ . A ₇₂₃ is equal to A ₇₂₄ . A ₇₃₃ is equal to A ₇₃₄ . And A ₇₄₃ is equal to A ₇₄₄ . equal to A ₇₁₄ . A ₇₂₃ is equal to A ₇₂₄ . A ₇₃₃ is equal to A ₇₃₄ . And A ₇₄₃ is equal to A ₇₄₄ .

An alternating copolymerization type epoxy resin, for example, the epoxy resin (Chemical Formula I / E-2-1) is synthesized by subjecting a bisphenol A epoxy resin and 4,4'-dihydroxydiphenylmethane to an additional polymerization reaction and then dissolving the remaining Hydroxyl group is epoxidized.

A block copolymer epoxy resin, for example, the epoxy resin of chemical formula I / E-3-1 is synthesized, for example, by sequentially adding a homopolymer of bisphenol A epoxy resin (n = 1 and above) with a homopolymer of bisphenol-F Epoxy resin (n = 1 and above) are joined together, and that then the remaining hydroxyl group is epoxidized.

(Chemische Formel I/E-S) wobei G die gleiche Bedeutung hat, wie oben definiert wurde. A₈ von a₈ kann gleich oder unterschiedlich sein, und es kann unabhängig H oder G sein, wobei jedoch wenigstens eines H ist und alle H sein können. Die gemittelte Wiederholungseinheitszahl ist eine Zahl von 20 oder darunter. Als Epoxydharz (Chemische Formel I/E) können mehr als eines der oben gezeigten Epoxydharze verwendet werden. Das hydrolisierbare Alkoxysilan, welches das andere Rohmaterial für den Bestandteil [I] ist, ist ein solches das durch die nachstehenden Formeln (Chemische Formel I/Si-2) und (Chemische Formel I/Si-3) ausgedrückt wird.

(Chemische Formel I/Si-2)

(Chemische Formel I/Si-3) As the epoxy resin (Chemical Formula I / E), those represented by the above-described formulas (Chemical Formula I / E-1-1) and (Chemical Formula I / E-1-2) and also (Chemical Formula I) are most preferred / ES) described below.

(Chemical formula I / ES) where G has the same meaning as defined above. A ₈ of a ₈ may be the same or different, and it may independently be H or G, but at least one is H and all of them may be H. The average repeat unit count is a number of 20 or less. As the epoxy resin (Chemical Formula I / E), more than one of the epoxy resins shown above can be used. The hydrolyzable alkoxysilane which is the other raw material for the component [I] is one expressed by the following formulas (Chemical formula I / Si-2) and (Chemical formula I / Si-3).

(Chemical formula I / Si-2)

(Chemical formula I / Si-3)

In the formulas (Chemical Formula I / Si-2) and (Chemical Formula I / Si-3), B ₂₁ to B ₂₆ and B ₃₁ to B _{36 may be} the same or different, and each independently denotes an alkyl group with C ₁ to 8, an aryl group or an unsaturated aliphatic radical group. B ₂₂ and B ₂₆ of unit b ₂₁ and B ₃₂ and B ₃₆ of unit b ₃₁ may each be the same or different and are each independent. B ₂₁ and B ₂₄ to B ₂₆ and B ₃₁ to B ₃₆ are concretely preferably alkyl groups (methyl groups, ethyl groups, isopropyl groups, etc.) with C1 to 8, aryl groups, etc. B ₂₂ and B ₂₃ are concretely preferably alkyl groups (Methlygruppen, ethyl groups, isopropyl groups etc.) with C1 to 3 etc.

In the formulas (Chemical Formula I / Si-2) and (Chemical Formula I / Si-3), the average repeating unit numbers b ₂₁ and b _{31 are} each preferably 0 to 20, and more preferably 1 to 10.

(Chemische Formel I/Si-4) (Wobei die durchschnittliche Wiederholungseinheitszahl b₄₁ gleich 1 bis 7 ist).An alkoxysilane condensate (Chemical Formula I / Si-3) includes compounds represented by the following formula

(Chemical formula I / Si-4) (Where the average repeat unit number b ₄₁ is 1 to 7).

Hydrolyzable alkoxysilanes are those expressed by the formulas (Chemical Formula I / Si-2) and (Chemical Formula I / Si-3), and the substances expressed by the formula (Chemical Formula I / Si-4).

The component [I] is obtained by a dealcoholization reaction of at least one kind of epoxy resin (Chemical Formula I / E) with at least one kind of hydrolyzable alkoxysilane. In the reaction, the weight ratio of the hydrolyzable alkoxysilane to the epoxy resin (Chemical Formula I / E) (Silica conversion weight of the hydrolyzable alkoxysilane / weight of the epoxy resin (Chemical formula I / E)) of 0.01 to 1.2 is preferable.

In the dealcoholization reaction, the equivalent mass ratio of the equivalent molecular weight of the hydroxyl groups of the epoxy resin (Chemical Formula I / E) and the equivalent molecular weight of the alkoxy groups of the hydrolyzable alkoxysilane is preferably less than 0.8 or at least 1.2.

In the dealcoholization reaction, the reaction solution is preferably organic tin, organic acid tin, and especially dibutyltin dilaurate.

The dealcoholization reaction may typically be carried out at a reaction temperature of 70 to 110 ° C and with a reaction time of 1 to 20 hours.

In this way, an alkoxy group-containing, silane-modified epoxy resin is prepared, which modification may be partial, but also complete. The alkoxy group-containing silane-modified epoxy resin itself may be used as the component [I] but may be used instead of the epoxy resin (Chemical Formula I / E). That is, even the product obtained by an alcohol withdrawal reaction of such partially modified epoxy resin with a hydrolyzable alkoxysilane can be used as component [I].

(Chemische Formel I/U-1)

(Chemische Formel I/U-2)

(Chemische Formel I/U-3)

(Chemische Formel I/U-4) und insbesondere nach einer der nachstehenden Formeln haben

(Chemische Formel I/U-5)

(Chemische Formel I/U-6) ausgedrückte Struktur aufweisen.The component [I] may have a structure of any one of the following formulas

(Chemical formula I / U-1)

(Chemical formula I / U-2)

(Chemical formula I / U-3)

(Chemical formula I / U-4) and in particular have one of the following formulas

(Chemical formula I / U-5)

(Chemical formula I / U-6) have expressed structure.

In the formulas (Chemical formula I / U-1) to (Chemical formula I / U-6), A ₃₁ , B ₂₂ to B ₂₆ , B ₃₂ to B ₃₆ , b ₂₁ , b ₃₁ and b _{41 have} the same meaning as on top.

The photosensitive thermosetting resin composition of the present invention contains an unsaturated group-containing polycarboxylic acid resin (hereinafter also referred to as component [II]). For the component [II], preferred is a resin having in the molecules unsaturated ethylenic groups and at least two carboxyl groups, and whose solid acid value (mg KOH / g) is from 30 to 160 (especially 60 to 130). With a lower solid acid number than 30, the heat stability is poor and it may be that in the alkali development no solution is possible and a residue is formed. On the other hand, if a value of 160 is exceeded, the moisture resistance decreases, and the insulating properties, HAST resistance and reliability decrease.

Such a component [II] is, for example, a resin (hereinafter referred to as Resin IIA) obtained by reacting a copolymer (hereinafter also referred to as copolymer IIA) of an ethylenically unsaturated acid and a monomer containing ethylenic unsaturated bonds with a Epoxy group-containing unsaturated monomer is obtained. The weight-average molecular weight of the resin IIA is preferably 3,000 to 60,000 (especially 5,000 to 30,000).

Specifically, for the ethylenically unsaturated acid, there may be mentioned, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, fumaric monomethyl, fumaric acid monoethyl, fumaric monopropyl, maleic monomethyl, maleic monoethyl, maleic monopropyl or sorbic acid, etc. More than one such ethylenically unsaturated acid can be used.

Examples of a monomer containing ethylenic unsaturated bonds are C 1 -C 8 alkyl (meth) acrylates (methyl (meth) acrylate, ethyl (meth) acrylate, etc.), 2-hydroxy-C 1 -C 8 alkyl (meth) acrylates (2- Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.), ethylene glycol monomethyl acrylate, ethylene glycol monomethyl methacrylate, ethylene glycol monoethyl acrylate, ethylene glycol monoethyl methacrylate, glycerol acrylate, glycerol methacrylate, dimethyl acrylate, methacrylaminoethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylamide, methacrylamide, acrylonitrile , methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, Acrylsäurecarbitol, Methacrylsäurecarbitol, ε-caprolactone Tetrafurfurylacrylat, ε-caprolactone Tetrafurfurylmethacrylat, Diethylenglykolethoxylacrylat, isodecyl acrylate, Isodecylmethycrylaf , Octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate ylate, stearyl acrylate, stearyl methacrylate, or reaction products of saturated or unsaturated dibasic acid anhydrides with (meth) acrylates having a hydroxyl group in one molecule (for example, reaction products of succinic anhydride, phthalic anhydride or tetrahydrophthalic anhydride with 2-hydroxyethyl or -propyl (meth) acrylate, etc .). More than one such monomer containing ethylenic unsaturated bonds may be used.

As copolymer IIA, copolymers of methacrylic acid and methyl methacrylate or copolymers of methacrylic acid and butyl methacrylate are specifically preferred, and more than one kind thereof may be used.

The copolymer IIA preferably has an average molecular weight of 3,000 to 30,000, and preferably, the number of carboxyl groups in the resin is 0.5 to 5.0 pieces per molecular weight of 1,000 and the acid value is 20 to 160.

(Chemische Formel II/E) Wobei C₁₁ eine einwertige Gruppe, die einen Epoxydring enthält, der auch geschrumpft sein kann. C₁₂ bis C₁₄ können gleich oder unterschiedlich und H, eine C1 bis 6 Alkylgruppe oder eine Arylgruppe (beispielsweise eine Phenylgruppe usw.) sein.An epoxy group-containing unsaturated monomer includes compounds represented by the following formula

(Chemical formula II / E) Where C _{11 is} a monovalent group containing an epoxide ring which may also have shrunk. C ₁₂ to C ₁₄ may be the same or different and H, a C 1 to 6 alkyl group or an aryl group (for example, a phenyl group, etc.).

In particular, examples of an epoxy group-containing unsaturated monomer are: glycidyl (meth) acrylate, C 1 -C 6 -alkyl-2,3-epoxypropyl (meth) acrylate (2-methyl-2,3-epoxypropyl (meth) acrylate, Ethyl-2,3-epoxypropyl (meth) acrylate, etc.), fatty-ring epoxy group-having chemical formulas (3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylaminoacrylate, etc.). More than one of these monomers can be used.

(Chemische Formel II/E-1)

(Chemische Formel II/E-2)

(Chemische Formel II/E-3)

(Chemische Formel II/E-4)

(Chemische Formel II/E-5) Preferably, the epoxy group-containing unsaturated monomer is a compound expressed by the following formulas.

(Chemical formula II / E-1)

(Chemical formula II / E-2)

(Chemical formula II / E-3)

(Chemical formula II / E-4)

(Chemical formula II / E-5)

In the above formula (Chemical Formula II / E-5), C ₂₁ denotes an alkylene group having C 1 to C 6, and C denotes C 2 H or an alkyl group having C 1 to C ₃ . Preferably, C _{21 is} a methylene group. C ₂₂ is a methyl group.

In the reaction of the copolymer IIA with the epoxy group-containing unsaturated monomer, an equivalent weight of the epoxy groups of the epoxy group-containing unsaturated monomer of 0.1 to 0.9 with respect to an equivalent weight of the carboxyl groups in the copolymer IIA of 1 is preferable.

Another component [II] is, for example, a resin (hereinafter also referred to as Resin IIB) obtained by reacting a reaction product (hereinafter also referred to as Reaction Product IIB) by a reaction of a copolymer (hereinafter also referred to as Copolymer IIB). from an epoxy group-containing unsaturated monomer and a monomer containing ethylenically unsaturated bonds with an ethylenically unsaturated acid, with a polybasic acid anhydride containing saturated and / or unsaturated groups (hereinafter also referred to as a polybasic acid anhydride having saturated / unsaturated groups is called) is reacted. The weight-average molecular weight of the resin IIB is preferably 3,000 to 60,000 (especially 5,000 to 30,000).

For the epoxy group-containing unsaturated monomer, the monomer containing ethylenic unsaturated bonds, and the ethylenically unsaturated acid, the examples given above may be given.

As an epoxy group-containing unsaturated monomer, glycidyl (meth) acrylate or aryl glycidyl ether is preferable.

Monomers containing ethylenically unsaturated bonds are styrene, chlorostyrene, α-methylstyrene, acrylate or methacrylate substitution group with methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, 2-ethylhexyl, octyl, capryl , Nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isobornyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-chloro-2-hydroxypropyl as a substitution group, mono (meth) acrylate of polyethylene glycol, or mono (meth) acrylate of Polypropylene glycol, vinyl acetate, vinyl butyrate or vinyl benzoate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, or acrylonitrile.

An ethylenic unsaturated acid is acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, fumaric monomethyl, fumaric acid monoethyl, fumaric monopropyl, maleic monomethyl, maleic monoethyl, maleic monopropyl or sorbic acid.

Examples of polybasic acid anhydride with saturated / unsaturated groups are in particular maleic anhydride, succinic anhydride, phthalic anhydride, methyl-hexa or - Tetrahydrophthalic anhydride, di-, tetra- or hexahydrophthalic anhydride, itaconic anhydride, trimellitic anhydride or pyromellitic anhydride, with succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride.

In the reaction of the copolymer IIB with the ethylenically unsaturated acid, an equivalent weight of the epoxy groups in the copolymer IIB is preferably from 0.8 to 1.3, more preferably 0.9 to 1.1, in terms of an equivalent weight of the carboxyl groups in the ethylenically unsaturated acid of 1.

In the reaction of the reaction product IIB with the polybasic acid anhydride having saturated / unsaturated groups, an equivalent mass of the anhydride groups of the polybasic acid anhydride having saturated / unsaturated groups of preferably from 0.05 to 1.0, more preferably from 0.1 to 0.95, with respect to an equivalent mass of the hydroxyl groups in reaction product IIB of FIG.

Another component [II] is, for example, a resin (hereinafter also referred to as resin IIC) obtained by a reaction (1) of a polybasic carboxylic acid or its anhydride (hereinafter also referred to as a polybasic carboxylic acid (anhydride) with the reaction product (hereinafter also called the reaction product IIC) of an epoxy resin (hereinafter also referred to as epoxy resin IIC) having at least two epoxy groups in the molecules and a monocarboxylic acid containing unsaturated groups. The weight-average molecular weight of the resin IIC is preferably 3,000 to 30,000 (especially 5,000 to 20,000).

The epoxy resin IIC comprises the above epoxy resin (Chemical Formula I / E). Examples of the epoxy resin IIC are: bisphenol A epoxy resin, hydrobisphenol A epoxy resin, bisphenol F epoxy resin, bisophenol S epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, novolak epoxy resin of bisphenol A, eiphenol epoxy resin, Biphenol novolac epoxy resin, bixylenol epoxy resin, trisphenol methane epoxy resin, N-glycidyl epoxy resin, etc. More than one of these epoxy resins IIC can be used.

The monocarboxylic acid containing unsaturated groups includes acids having in the molecules ethylenic unsaturated bonds and a carboxyl group (including carboxylic acid group -COOH). The ethylenically unsaturated bonds and the carboxyl group may be mutually conjugated (adjacent), but this need not be the case.

Examples of the monocarboxylic acid containing unsaturated groups are: acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, fumaric monomethyl, fumaric acid monoethyl, fumaric acid monopropyl, monomethyl maleate, maleic acid monopropyl, maleic monopropyl, sorbic acid, β-carboxyethyl acrylate, etc. More than one monocarboxylic acid, the unsaturated groups contains, can be used.

In the reaction of the epoxy resin IIC with the monocarboxylic acid containing unsaturated groups, from 0.8 to 1.3 moles of the monocarboxylic acid containing unsaturated groups can be reacted per equivalent mass of the epoxy groups in the epoxy resin IIC of FIG.

Subsequently, the reaction product IIC thus obtained is reacted with a polybasic carboxylic acid (its anhydride) to prepare the resin IIC.

The polybasic carboxylic acid (anhydride) is, for example, a dibasic carboxylic acid (its anhydride) having C1 to C8, for example succinic acid (anhydride), maleic acid (anhydride), pthalic acid (anhydride), itaconic acid (anhydride), tetra- or hexahydrophthalic acid (anhydride), etc For the polybasic carboxylic acid (anhydride), a polybasic carboxylic acid anhydride is preferred.

In the reaction of the reaction product IIC with the polybasic carboxylic acid (anhydride), it is preferable to have an equivalent mass of 0.05 to 1.00 for the polybasic carboxylic acid and an equivalent weight of 0.1 to 0.9 for the polybasic carboxylic acid anhydride in terms of equivalent mass of the hydroxyl groups in the reaction product 110 of FIG.

When the photosensitive thermosetting resin composition of the present invention is prepared as a white solder resist ink for printed circuit boards for light-emitting diodes, etc., for the component [II], from the viewpoint of yellowing resistance, the resin IIA and the resin IIB are preferred.

The photosensitive thermosetting resin composition of the present invention comprises a diluent (hereinafter also referred to as component [III]). By containing the component [III], the crosslinking efficiency can be enhanced, the heat resistance can be improved, and the application viscosity of the composition can be controlled.

As the component [III], an organic solvent and / or a photopolymerizable monomer can be used. In the component [III], examples of organic solvents are: ketones such as ethyl methyl ketone or cyclohexanone, aromatic hydrocarbons such as toluene, xylene or tetramethylbenzene, glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether or triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate and esterification products the above glycol ethers, alcohols such as ethanol, propanol, ethylene glycol or propylene glycol, aliphatic hydrocarbons such as octane or decane, or petroleum based solvents such as petroleum ether, petroleum naphtha, hydropetrol naphtha, solvent naphtha, etc., and more than one such organic solvent may be used.

For the component [III], examples of the photopolymerizable monomer are: hydroxyalkyl (meth) acrylates, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc., mono- or diacrylates of glycol, for example, ethylene glycol, methoxytetraethylene glycol, polyethylene glycol , Propylene glycol, etc., (meth) acrylamides, for example, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc., aminoalkyl (meth) acrylates. For example, N, N-dimethylaminoethyl (meth) acrylate, etc., Polyhydroxyalcohole, for example hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc., or polyvalent (meth) acrylates of ethylene oxide or a propylene oxide adduct thereof, (meth) acrylates, such as phenoxy (meth) acrylate, bisphenol A di (meth) acrylate and ethylene oxide or propylene oxide adduct of phenol thereof (meth) acrylates of glycidyl ether, for example, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. and melamine (meth) acrylate, etc. More than one of these components 111] can be used.

The photosensitive thermosetting resin composition of the present invention comprises a photopolymerization initiator (hereinafter also referred to as constituent [IV]). For the component [IV], a substance is preferable in which the storage stability of the resin composition is good after blending the individual components whose solubility is good, and no steam in the course of various heat treatments (predrying, thermosetting, molding, assembly soldering) arises from unreacted initiator.

Specifically, examples of the component [IV] are: benzoins such as benzoin, benzyl, benzoin methyl ether or benzoin isopropyl ether, acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dicycloacetophenone , 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-monopholinopropan-1-one, or N, N-dimethylaminoacetophenone, anthraquinones, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert. Butyl anthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone or 2-aminoanthraquinone, thioxanthones, such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone or 2,4-diisopropylthioxanthone, ketals, such as acetophenone dimethyl ketal or benzyldimethyl ketal, benzophenones, such as benzophenone, Methylbenzophenone, 4,4'-dicyclobenzophenone or 4,4'-bis-diethylaminobenzophenone, as well as xanthones, and benzoic acid esters such as ethyl 4-dimethyl-monobenzoate or 2- (dimethylamino) -ethyl benzoate, or tertiary amines such as triethylamine or triethanolamine, or light sensitizers such as 7-amino-4-methylcoumarin, 1-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6- Dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-diethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin or 4,6-dimethyl-7-ethylaminocoumarin may be used singly or in combinations of two or more kinds.

From the viewpoint of the environment, the constituent [IV] is preferably: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4- morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholinophenyl) -butanone-1, 2,4-diethylthioxanthone, 4-benzoyl-4'-methyldiphenylsulfide, 4- Phenylbenzophenone, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) -phenyl) -2-methyl-propan-1-one, poly (oxy (methyl-1, 2-ethanediol)), α- (4- (dimethylamino) benzoyl-ω-butoxy, 9-phenylacridine, 1,7-bis (9-acridinil) heptane, 1,5-bis (9-acridinil) pentane, 1, 3-bis (9-acridinil) propane, N-phenylglycine, N-phenylglycine derivatives, coumarin family compounds, etc. More than one of these components [IV] can be used.

Another ingredient [IV] is a photoacid generator. Photo acid generators are chemical compounds that generate acid by light (electron receptors). Photoacid generators include, in particular, iodonium salt compounds, sulfonium salt compounds, ammonium salt compounds, phosphonium salt compounds, arsonium salt compounds, antimony salt compounds, oxonium salt compounds, selenonium salt compounds, stannonium salt compounds, etc. More than one such photoacid generator can be used. An iodonium salt compound, a sulfonium salt compound and an ammonium salt compound are preferred.

Examples of the above iodonium salt compounds are: diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphinate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroantimonate, bis (4,4'-t-butylphenyl) iodonium hexafluoroborate, bis (4,4'-t-butylphenyl) iodonium hexafluorophosphinate, bis (4,4'-t. butylphenyl) iodonium hexafluoroantimonate, bis (4,4'-t.butylphenyl) iodonium hexafluoroarsenate, diphenyliodonium trifurate, bis (4,4'-t.butylphenyl) iodonium trifurate, etc. More than one of these iodonium salt compounds can be used.

Examples of sulfonium salt compounds are: triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphinate, triphenylsulfonium hexafluoranemonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifurate, etc. More than one of these sulfonium salt compounds can be used.

The photo-acid generator can be used together with a sensitizer (thioxanthone derivatives such as diethylthioxanthone or isopropylthioxanthone, anthracene, pyrene, phenothiazine, etc.).

In the photosensitive thermosetting resin composition of the present invention, a hardening adhesive agent (hereinafter also referred to as component [V]) is contained. The fact that the component [V] is included can improve adhesiveness, chemical resistance, heat resistance or moisture resistance.

Examples of the component [V] are in particular: dicyandiamide, S-triazines (such as melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-tolyl-S-triazine or 2,4-diamino-6-xylyl-S-triazine), guanamines (such as guanamine, acetoguanamine, benzoguanamine or 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2, 4,8,10tetraoxaspiro [5,5] undecane), imidazolic chemical formulas (such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl4,5-dihydroxymethylimidazole or isocyanuric acid adducts of 2-methylimidazole (" 2MZ-OK "from Shikoku Chemicals Corporation, etc.), 1- (4,5-diamino-2-triazinyl) -2- (2-methyl-1-imidazolyl) ethane (" 2MZ-AZINE "from Shikoku Chemicals Corporation), etc , 1,8-diazabicyclo [5,4,0] undecene-7 ("DBU" (registered trademark) of San-Apro Ltd.)), and organic acid salts and epoxide adducts thereof, imidazolecoxysilane derivatives (such as N, midazolmethyltrimethoxysilane, N-2 -Methylimidazolmethyltrimethoxysilane, N-2-ethylimidazole-ethyltrimethoxy silane, N-2-iso-propylimidazolmethyltrimethoxysilane, N-2-ethyl-4-methylimidazolemethyltrimethoxysilane, N-2-undecylimidazolmethyltrimethoxysilane, N-2-heptadecylimidazolmethyltrimethoxysilane, N-imidazolemethyltriethoxysilane, N-2-methylimidazolyltrimethoxysilane, N-2-ethylimidazolmethyltriethoxysilane, N- 2-iso-propylimidazolmethyltriethoxysilane, N-2-ethyl-4-methylimidazolmethyltriethoxysilane, N-2-undecylimidazolmethyltriethoxysilane, N-2-heptadecylimidazolmethyltriethoxysilane, 2- (N-imidazole) ethyltrimethoxysilane, 2- (N-2-methylimidazole) ethyltrimethoxysilane, 2- (N-2-ethylimidazole) ethyltrimethoxysilane, 2- (N-2-iso -propylimidazole) ethyltrimethoxysilane, 2- (N-2-ethyl-4-methylimidazole) ethyltrimethoxysilane, 2- (N-2-undecylimidazole) ethyltrimethoxysilane, 2- (N-2-heptadecylimidazole) ethyltrimethoxysilane, 2- (N-imidazole) ethyltriethoxysilane, 2- (N-2-methylimidazole) ethyltriethoxysilane, 2- (N-2-ethylimidazole) ethyltriethoxysilane, 2- (N-2-iso-propylimidazole ) ethyltriethoxysilane, 2- (N-2-ethyl-4-methylimidazole) ethyltrieth oxysilane, 2- (N-2-undecylimidazole) ethyltriethoxysilane, 2- (N-2-heptadecylimidazole) ethyltriethoxysilane, 3- (N-imidazole) propyltrimethoxysilane, 3- (N-2-methylimidazole) propyltrimethoxysilane, 3- (N-2 Ethylimidazole) propyltrimethoxysilane, 3- (N-2-isopropylimidazole) propyltrimethoxysilane, 3- (N-2-ethyl-4-methylimidazole) propyltrimethoxysilane, 3- (N-2-undecylimidazole) propyltrimethoxysilane, 3- (N-2 -Heptadecylimidazole) propyltrimethoxysilane, 3- (N-imidazole) propyltriethoxysilane, 3- (N-2-methylimidazole) propyltriethoxysilane, 3- (N-2-ethylimidazole) propyltriethoxysilane, 3- (N-2-iso -propylimidazole) propyltriethoxysilane, 3 - (N-2-ethyl-4-methylimidazole) propyltriethoxysilane, 3- (N-2-undecylimidazole) propyltriethoxysilane or 3- (N-2-heptadecylimidazole) propyltriethoxysilane), quaternary imidazolium salt derivatives (such as 1-ethyl-3-methylimidazolium trifluoromethylsulfate, N-methyl, N'-n-butylimidazolium hexafluorophosphate or N-alkyl-N'-alkoxyalkylimidazolium salt (wherein the anions are at least one species selected from bis (trifluoromethylsu lfonyl) imide salt, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, tris (trifluoromethylsulfonyl) carboxylic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or organic carboxylic acids or halogen ions)), diaminodimethylmethane, m-phenylenediamine, diaminodiphenylsulfone, cyclohexylamine, m-xylylenediamine, 4,4'-diamino- 3,3'-diethyldiphenylmethane, diethylenetriamine, tetraethylenepentamine, N-aminoethylpiperazine, isophoronediamine, dicyandiamine, ureas (such as urea itself), polyamines (such as polybasic hydrazide), organic acid salts and / or epoxide adducts thereof, amine complexes of boron trifluoride, tertiary amines (such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, N, N-dimethylaniline, N-benzylmethylamine, pyridine, N-methylpyridine, N- Methylmorpholine, hexamethoxymethylmelamine, 2,4,6-tris (dimethylaminophenol), N-cyclohexyldimethylamine, tetramethylguanidine, or m-aminophenol), organic phosphines (such as tributylphosphine, triphenylphosphine, or tris-2-cyanoethylphosphine), phosphonium salts (such as tri-n-butyl). butyl (2,5-dihydroxyphenyl) phosphonium bromide or hexadecyltributylphosphonium chloride), quaternary ammonium salts (such as benzyltrimethylammonium chloride, phenyltributylammonium chloride or benzyltrimethylammonium bromide), diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, thermo-cationic polymerization catalysts, styrene-maleic acid resins, silane coupling agents, etc. More than one the stock hurry [V] can be used.

When imidazole alkoxysilane derivatives and / or quaternary imidazolium salt derivatives are used as constituent [V], an increase in adhesiveness of the resist film is expected, and in addition, gold plating resistance, soldering heat resistance, moisture resistance and peeling strength can also be improved.

Preferably, the component [V] is, for example, a diaminediamide, an S-triazine derivative such as melamine, ethyldiamino-S-triazine or 2,4-diamino-S-triazine, an imidazolecarboxysilane derivative such as N-imidazolmethyltrimethoxysilane or 3- (N- 2-methylimidazole) propyltrimethoxysilane) or a quaternary imidazolium salt derivative (such as 1-ethyl-3-methylimidazolium trifluoromethylsulfate, N-methyl, N'-n-butylimidazolium hexafluorophosphate, N-alkyl-N'-alkoxyalkylimidazolium phthalate), etc.

The photosensitive thermosetting resin composition of the present invention may also be added with colorants, fillers, defoaming agents, epoxy resins, mold release agents, surface treatment agents, flame retardants, viscosity modifiers, plasticizers, antimicrobial agents, antibacterial agents, leveling agents, stabilizers, coupling agents, antioxidants or phosphors.

Especially, when the photosensitive thermosetting resin composition of the present invention is prepared as a white solder resist ink for printed circuit boards for light-emitting diodes, etc., it is preferable to add a white pigment as a colorant. Examples of white pigment are, for example, titanium oxide, zinc oxide, basic carbonates, basic lead sulfate, lead sulfate, zinc sulfide, antimony oxide, titanium nitride, cerium fluoride, cerium oxide, etc., although titanium oxide is preferred because of its tinting strength and nontoxicity. The average particle size of the white pigment is preferably 0.01 to 1.0, more preferably 0.1 to 0.5 μm.

Examples of the filler are: talc, barium sulfate, barium titanate, silica powder, micropowdered silica, amorphous silica, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, zinc hydroxide, aluminum nitride, silicon nitride, boron nitride, diamond powder, zirconium silicate, zirconium oxide, magnesium hydroxide, mica, mica powder, Silicone powder, organic resin filling materials (such as polystyrene, poly (meth) acrylate, (benzo) guanamine, acrylic rubber, rubber resin filling materials, etc.), etc.)

A defoaming agent is, for example, polydimethylsiloxane, silicone-modified, fluorine or high molecular surface activators, emulsion-type defoaming agents, and the like.

Examples of the epoxy resin are: bisphenol epoxy resins, novolak epoxy resins (such as orthocresol novolak epoxy resins or phenolic novolac epoxy resins), glycidyl ester epoxy resins obtained by reaction of a polybasic acid (e.g., phthalic acid or dimer acid) with epichlorohydrin, glycidylamine Epoxy resins obtained by reacting a polyamine (eg, diaminophenylmethane or isocyanuric acid) with epichlorohydrin, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with a peracid such as peracetic acid, fatty ring epoxy resins, etc.

The compounding weight ratio of component [I] and component [II] (compounding weight of component [I] / compounding weight of component [II]) is preferably 2/100 to 50/100, more preferably 5/100 to 40/100. With respect to total of 100 parts by weight of the component [I] and the component [II], the component [III] preferably comprises 5 to 500 parts by weight, more preferably 20 to 300 parts by weight. With respect to together 100 parts by weight of the component [I] and the component [II], the component [IV] preferably comprises 0.1 to 30 parts by weight, more preferably 2 to 20 parts by weight. With respect to the total of 100 parts by weight of the component [I] and the component [II], the component (V) preferably comprises 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

If the compounding weight in the above compounding composition is less than 2/100, the soldering heat resistance, adhesiveness and weathering resistance may become insufficient, while if more than 50/100, the heat resistance of the ink may decrease and the developability may be hindered. If the component [III] is less than 5 parts by weight, the application ability may become poor and the application tiring, and moreover the photopolymerizability may decrease, while if more than 500 parts by weight, the applicability, the dry feeling property, and the resolving power may decrease. If the component [IV] is less than 0.1 part by weight, insufficient light polymerization and development may occur, while if more than 30 parts by weight, the light absorption becomes large, the thick film curing becomes difficult, and the resolving power may become difficult. If the component (V) is less than 0.1 part by weight, the adhesion with the substrate (such as copper, a composite material, a glass epoxy resin or a make coat) may become insufficient and the reliability may decrease, while if it exceeds 20 parts by weight, the heat stability of the ink can decrease and the developability can be made more difficult.

The amount of the colorant added is preferably 0 to 500 parts by weight, more preferably 0.1 to 200 parts by weight, relative to 100 parts by weight of each of Component [I] and Component [II]. The amount of the filler added is preferably 0 to 1200 parts by weight, more preferably 10 to 500 parts by weight, with respect to 100 parts by weight of Component [I] and Component [II] together. The amount of the defoaming agent added is preferably 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, in terms of total of 100 parts by weight of Component [I] and Component [II].

Particularly, when the photosensitive thermosetting resin composition of the present invention is prepared as a white solder resist for printed circuit boards for light emitting diodes, etc., 10 to 50 parts by weight (especially 20 to 300 parts by weight) of the white pigment and 0 to 1200 parts by weight (especially 10 to 1200 , and especially 10 to 800 parts by weight) of the filler with respect to together 100 parts by weight of component [I] and. Component [II] preferred.

The photosensitive thermosetting resin composition of the present invention prepared as described above generally has a photosensitivity of the step 8 (on the 21-stage plate of Stouffer) and is also remarkable in its developability.

Next, a printed circuit board having a solder resist layer made of the photosensitive thermosetting resin composition of the present invention will be described.

The printed circuit board as the material motherboard for the solder resist coating is preferably a smoothed printed circuit board. In particular, a smoothed printed circuit board is preferred in which pits, etc. on the surfaces of the printed circuit board are filled with a resin and the surfaces of the printed circuit board have been smoothed. By using a smooth printed circuit board, the coating properties for circuits become good, and the reliability and hiding ability (the hiding ability of the copper circuits) can be improved.

Of course, in the present invention, other printed circuit boards, for example, conventional printed circuit boards in which bumps are present on the surfaces of the printed circuit board, may also be used. In addition, the printed circuit boards can printed on one side printed circuit boards and also on both sides. Circuit boards.

Smoothed printed circuit boards can be used, for example, according to the methods described in Unexamined Patent Publication No. 2003-26765 (US Pat. Japanese Patent Application 2001-253678 SAN-EI KAGAKU CO., LTD.), In Unexamined Patent Publication No. 2003-105061 ( Japanese Patent Application 2001-337180 , SAN-EI KAGAKU CO., LTD.) And in the description of Japanese Patent Application 2004-311541 cited methods are produced.

Specifically, a smoothed printed circuit board can be made by first applying a filling resin to the recesses on the surfaces of the printed circuit board and performing a primary cure at a low temperature by polishing the surfaces and then making a secondary Curing is done at a high temperature.

Here, the "recesses" described above are not particularly limited, but include a depression between circuits on the surfaces of the printed circuit board, those of Contact holes (vias) or those for the embedding of components. Further, a "recess" also includes holes, for example, through-holes, blind vias, cavities, build-up vias, conformal vias, stack vias, padless holes, or hole-embedment base vias, etc. *** "

As the filling resin, thermosetting resin compositions can be used. However, in the present invention, any other curable resins, for example, photo-curable or light-heat-curable resin compositions may be used.

According to the invention, a thermosetting resin composition [A] comprises an adduct of an epoxy resin and an unsaturated fatty acid, [B] a (meth) acrylate, [C] a radical polymerization initiator, [D] a crystalline epoxy resin, and [E] a latent curing agent.

The component [A] is preferably about 20 to 80% (in particular 40 to 60%) adduct of a novolak epoxy resin and (meth) acrylic acid (specifically about a 20 to 80% (in particular 40 to 60%) adduct cresol novolak epoxy resin and acrylic acid), a 20 to 80% (especially 40 to 60%) adduct of bisphenol A epoxy resin and (meth) acrylic acid), etc. More than one of these thermosetting resin compositions may be contained.

The component [B] includes, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, etc., mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol, etc., acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide etc., aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, etc., polyhydric acrylates of polyhydric alcohols or ethylene oxide or propylene oxide adducts thereof such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol or tris-hydroxyethyl isocyanurate, acrylates such as phenoxyacrylate, bisphenol A diacrylate and ethylene oxide or propylene oxide adducts of such phenols, glycidyl ether acrylates such as glycerol diglycidyl ether, trimethylolpropane triglycidyl ether or triglycidyl isocyanurate, as well as melamine acrylate, isoboronyl acrylate, dicyclopentanyl methacrylate and / or methacrylates corresponding to the above acrylates. More than one of the components [B] may be added to the thermosetting resin composition.

The component [C] may preferably be t-butyl peroxybenzoate, t-butylperoxy-2-ethylhexanoate, dicumyl peroxide, etc. More than one of these components [C] may be added to the thermosetting resin composition.

The component [D] may be preferable: bisphenol S epoxy resins such as "BPS-200" (trade name) of Nippon Kayaku Co., Ltd., or "EPX-30" (trade name) of ACR Co., or "Epiclon EXA-151) (trade name) of Dainippon Ink and Chemicals, Inc., diglycidyl phthalate resins such as "Blemmer DGT" (trade name) of NOF Corporation, heterocyclic epoxy resins such as "TEPIC" (trade name) of Nissan Chemical Industries, Ltd. or "Araldite PT810" (trade name) by Ciba Geigy, bixylenol epoxy resins such as "YX-4000" (trade name) of Japan Epoxy Resin Co., eiphenol epoxy resins such as "YL-6121H" (trade name) of Japan Epoxy Reson Co. or tetraglycidylxylenoilethane resins such as "ZX-1063" (trade name) of Tohto Kasei Co., Ltd. More than one of the components [D] may be added to the thermosetting resin composition.

The component [E] is preferably dicyandiamide (DICY), imidazole, a BF ₃ -amine complex, an amine adduct curing agent, an amine acid anhydride (polyimide) adduct curing agent, a hydrazidic curing agent, a carboxylic acid salt of amine curing agent, or onium salt. More than one of the components [E] may be added to the thermosetting resin composition. The amount of the component [B] added with respect to 100 parts by weight of the component [A] is preferably 50 to 300 parts by weight, more preferably 150 to 250 parts by weight. The amount of the ingredient [C] added with respect to 100 parts by weight of the ingredient [A] is preferably 5 to 20 parts by weight, more preferably 8 to 15 parts by weight. The amount of the ingredient [D] added with respect to 100 parts by weight of the ingredient [A] is preferably 50 to 200 parts by weight, more preferably 60 to 120 parts by weight. The amount of the ingredient [E] added with respect to 100 parts by weight of the ingredient [A] is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight.

A method for applying the thermosetting resin composition is, for example, screen printing, curtain coating, roll coating or spray coating.

Subsequently, a primary curing is carried out at a low temperature. "Low temperature" means a temperature lower than the secondary one discussed below Curing temperature is. Concretely, the primary curing temperature may be, for example, 100 to 150 ° C. If the primary curing temperature is too low, the component [D] will not be sufficiently dissolved and, as a result, air bubbles may remain in the applied film. On the other hand, if the primary cure temperature is too high, a secondary cure reaction will occur and the cured film may become too hard. As a result, the polishability may decrease.

For the primary curing time, for example, 30 to 120 minutes are preferable. If the primary curing time is too short, component [D] will not be sufficiently dissolved and, as a result, air bubbles may remain in the application film. On the other hand, if the primary cure time is too long, the work efficiency may decrease.

Subsequently, the surfaces containing the primary curing film as prepared above are polished and smoothened. As a polishing method, for example, mechanical polishing (such as belt grinding, polishing wheel grinding, sand blasting, abrasion polishing, etc.), chemical polishing (such as using persulfates, a hydrogen peroxide-sulfuric acid mixture, or inorganic or organic acids) may be cited.

Thereafter, a secondary cure is carried out at a high temperature. "High temperature" means a temperature higher than the above primary curing temperature. Concretely, the secondary curing temperature may be, for example, 150 to 200 ° C. If the secondary curing temperature is too low, the reaction involving the epoxy groups does not proceed sufficiently and may decrease the heat resistance and the moisture resistance of the curing film. On the other hand, if the secondary cure temperature is too high, the motherboard itself may suffer heat damage.

For the secondary curing time, for example, 30 to 180 minutes are preferable. If the secondary curing time is too short, the heat resistance and moisture resistance of the curing film may be insufficient. On the other hand, if the secondary cure time is too long, the work efficiency may decrease.

In this way, the recesses on the surfaces of the circuit board are filled by the cured resin of the thermosetting resin composition, thereby obtaining a smoothed printed circuit board whose surfaces are smoothed.

The above secondary heat-curing may be carried out simultaneously with the thermosetting of a solder resist film discussed below. That is, the secondary heat-curing of the filling resin in the recesses between the circuits and the secondary heat-curing of the solder resist ink may be performed after heating the photosensitive thermosetting resin composition of the present invention on the surfaces of the polished mother board by heating to the secondary heat-curing temperature carried out with a light irradiation or after a light irradiation.

Subsequently, the photosensitive thermosetting resin composition of the present invention is applied to the surfaces of the smoothed printed circuit board, and the coating resin is photohardened, followed by heating to 100 to 190 ° C and heat curing, whereby the resist film coated smoothed printed circuit board after of the present invention.

More concretely, first, the photosensitive thermosetting resin composition of the present invention is applied on the surfaces of the smoothed printed circuit board obtained as discussed above, and a coating is formed. Subsequently, after a selective exposure to active light rays via a photomask forming a predetermined pattern, development of the unexposed light areas with a developing liquid is made, and a photo-curing film of the solder resist is formed. Thereafter, heat-curing (complete cure) of the photo-cured film of the solder resist is performed by heating, whereby the resist-film-coated smoothed printed circuit board according to the present invention can be produced.

For application, the above-mentioned coating methods can be used. The amount of application should be such that the film thickness after curing reaches, for example, 7 to 100 μm.

The source of active light rays may be, for example, UV light having a wavelength of 300 to 450 nm. The exposure may be made, for example, with a low pressure mercury lamp, a high pressure mercury lamp, an extra high pressure mercury lamp, an arc lamp, a xenon lamp, a UV light emitting diode, and so on. In addition to UV rays, irradiation with an excimer laser, X-rays, electron beams, etc. can also be used. The exposure light amount should be 5 to 2000 mJ / cm ² .

Examples of the developing liquid are: buffer solutions containing hydroxides of alkali metals such as lithium, sodium, potassium, etc., carbonates, bicarbonates, phosphates, pyrophosphates, primary amines such as benzylamine, butylamine, monoethanolamine, etc., secondary amines such as dimethylamine, dibenzylamine, diethanolamine, etc , tertiary amines such as trimethylamine, triethylamine, triethanolamine, etc., cyclic amines such as morpholine, piperazine, pyridine, etc., polyamines such as ethylenediamine, hexamethylenediamine, etc., ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide, etc., Sulfonium hydroxides such as trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide or dimethylbenzylsulfonium hydroxide, etc., choline or silicate-containing buffer solution, etc.

Also, if necessary, alcoholic solvents (butyl cellosolve, butyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propanol, propylene glycol, etc.) or surface activators (such as dipolar surface activators or nonionic surface activators) may be used.

The heat curing (complete curing) can be carried out for example for 0.1 to 3 hours at 120 to 180 ° C. The alkoxy group-containing silane-modified epoxy resin causes methanol removal upon heat-curing by a condensation reaction of the alkoxy groups. Therefore, gradual heating in multiple stages or with a temperature gradient is preferred so that no voids, cracks, etc. are formed. Of course, for example, heat curing in a train is not a problem with a thin application film.

In order to complete the light reaction and increase the reliability, after the development or after the heat-curing, light irradiation (with UV rays, etc.) may be repeated.

The solder resist film of the present invention prepared in the above manner normally has a glass transition temperature (Tg) of 140 to 165 ° C.

The solder resist film according to the present invention is characterized in that its HAST resistance is extremely good. Concretely, the value of the electrical insulation resistance (× 10 ¹⁰ Ω) under HAST conditions after the lapse of 168 hours is typically 100 to 900.

The solder resist film according to the present invention also has the peculiarity that the appearance according to a HAST story and a gold coating resistance test shows no irregularity.

In addition, the white solder resist film of the present invention has the peculiarity of having a gloss (%) of generally at least 40, and typically 81 to 95, in excess of the above specifics, which far surpasses conventional films. Since the white solder resist film according to the present invention effectively utilizes luminance of a light emitting diode not only by light reflection as above, but also gloss by light reflection, an increase in luminous efficiency of light emitting diode backlight modules, light modules for light emitting diode illumination or light emitting diode headlight modules is achieved ,

In addition, the solder resist film of the present invention not only excels in extremely excellent coating film adhesiveness and heat shock resistance, but also excellent in solvent resistance, acid resistance, soldering heat resistance, flexing resistance, coating film transparency, yellowing resistance, weather resistance and so on.

By coating a smoothed printed circuit board with the solder resist film of the present invention, effects such as easy penetration into joints, aggravation of occurrence of positional shifts or aggravation of occurrence of cracks are also obtained, and therefore a variety of component packaging problems can be solved ,

embodiments

Hereinafter, the invention of the present application will be explained concretely with reference to the drawings.

Preparation of the silane-modified epoxy resin

Synthetic Example 1

300 parts by weight of bisphenol A epoxy resin (1) ("EPOTOHTO YD-011" (trade name) manufactured by TOHTO KASEI CO., LTD., Epoxy equivalent 475 g / eq, average repeating unit number 2.2) and (2) 1250 parts by weight of bisphenol A epoxy resin ("EPOTOHTO YD-127" (trade name) manufactured by TOHTO KASEI CO., LTD., Epoxy equivalent mass 190 g / eq, average repeating unit number 0.11) was charged in a reaction apparatus equipped with an agitator, a water separator, a , Thermometer and a Stickstoffeinblaseöffnung was provided, and dissolved at 80 ° C. Then, 581.2 parts by weight of poly (methyltrimethoxysilane) ("MTMS-A" (trade name) manufactured by TAMA CHEMICAL CO., LTD., Average repeating unit number 3.5) and 2.0 parts by weight of dibutyltin laurate as a catalyst were added thereto. Under a nitrogen gas flow, an alcohol withdrawal reaction was carried out at 100 ° C for 8 hours. After cooling to 60 ° C, the pressure was reduced to 13 kPa, and dissolved methanol was completely removed, thereby obtaining 2050 parts by weight of silane-modified epoxy resin (Synthesis Example 1).

The mixing ratio of the epoxy resins (1) and (2) (epoxy resin (1) / epoxy resin (2)) at the time of introduction was 0.24. The epoxy equivalent mass of the epoxy resin mixture (a mixture of epoxy resin (1) with epoxy resin (2)) was 245 g / eq. The weight reduced by SiO _{2 of} the polymethyltrimethoxysilane divided by the weight of the epoxy resin mixture (usage weight ratio) was 0.20.

It was found by 1H-NMR measurement (solvent CDCl ₃ ) of the obtained silane-modified epoxy resin (Synthesis Example 1) that the methine peak of the epoxy rings (near 3.3 ppm) was maintained 100% while the peak of the epoxide rings Hydroxyl groups in the epoxy resin (near 3.85 ppm) had disappeared. The epoxy equivalent mass of the silane-modified epoxy resin (Synthesis Example 1) was 280 g / eq.

Synthesis Example 2

950 parts by weight of bisphenol A epoxy resin ("EPOTOHTO" YD-127 "(trade name) manufactured by TOHTO KASEI CO., LTD., Epoxy equivalent 185 g / eq) and 950 parts by weight of dimethylformamide were placed in a 2-liter three-necked flask. which was provided with a stirrer, a water separator and a thermometer. Then, 304.6 parts by weight of tetramethoxysilane condensate ("METHYLSILICATE 51" (trade name) manufactured by TAMA CHEMICAL CO., LTD.) And 2 g of dibutyltin dilaurate as a catalyst were added. At 90 ° C, an alcohol removal reaction was carried out for 6 hours, whereby 2080 parts by weight of a silane-modified epoxy resin solution (Synthesis Example 2) having 50% of the effect components (after the curing) were obtained. For complete completion of the alcohol withdrawal reaction, an ester exchange reaction was carried out during the reaction while removing the formed methanol from the reaction system.

As a result of comparison of 1 H-NMR (solvent CDCl ₃ ) of the obtained silane-modified epoxy resin solution (Synthesis Example 2) and bisphenol A epoxy resin (as base material), it was found that in the silane-modified epoxy resin solution (Synthesis Example 2), the methine peak of the epoxy rings (near 3.3 ppm) was maintained to 100% while the peak of the hydroxyl groups in the epoxy resin (near 3.8 ppm) had disappeared. A new peak of methoxysilyl groups (near 3.6 ppm) appeared. The epoxy equivalent mass of the obtained silane-modified epoxy resin solution (Synthesis Example 2) was 431 g / eq.

Synthesis Example 3

400 parts by weight of novolak epoxy resin ("EPOTOHTO YDPN-638P" (trade name) manufactured by TOHTO KASEI CO., LTD, epoxy equivalent 177 g / eq, average repeating unit number 5.2) and 21.2 parts by weight of bisphenol A were mixed at 150 ° C in a Reaction apparatus provided with an agitator, a water separator, a thermometer and a nitrogen injection port was, solved. As a catalyst for ring-opening modification, 0.1 part by weight of N, N-dimethylbenzylamine was added. By a two-hour reaction, bisphenol-modified novolak epoxy resin, a hydroxyl group-containing ring-opening-modified epoxy resin was obtained. The number of moles of the ring opening modifying active hydrogen divided by the number of moles of the novolak epoxy resin was 0.4.

To this resin was added 215.2 parts by weight of poly (methyltrimethoxysilane) ("MTMS-A" (trade name) manufactured by TAMA CHEMICAL CO., LTD., Average number of Si per molecule 3.5), 350 parts by weight of methyl ethyl ketone, 30.99 parts by weight of glycidol and 1 part by weight of dibutyltin dilaurate added as a catalyst. Under a nitrogen gas flow, an alcohol removal reaction using the water separator was carried out at 100 ° C for 5 hours to obtain 980 parts by weight of a methoxy group-containing silane-modified epoxy resin (Synthesis Example 3).

Synthesis Example 4

300 parts by weight of a glycidyl etherification product of phenol novolac resin ("EPIKOTE 154" (trade name) manufactured by JAPAN EPDXY RESIN CO, epoxy equivalent 178, average molecular weight 700) and 450 parts by weight of ethyl cellosolve acetate were placed in a flask equipped with a refrigerator and blowing nitrogen gas at 100 ° C C heated and dissolved. When a uniform solution was formed, 37.5 parts by weight of a solution containing 15 parts by weight of an aminosilicon compound ("X-12-16606-3" (trade name) manufactured by SHIN-ETSU CHEMICAL CO., LTD , average molecular weight 4000) were dissolved in Ethylcellosolveacetat dripped. Thereafter, a reaction was carried out for three hours, followed by reaction at 120 ° C for one hour to obtain 780 parts by weight of an ethylcellosolve acetate solution of an aminosilane-modified epoxy resin (Synthesis Example 4).

The degree of conversion of the terminal amino groups in the aminosilicon compound was 95%. The solid concentration of the obtained ethylcellosolve acetate solution of the aminosilane-modified epoxy resin (Synthesis Example 4) was 40%, and the epoxy equivalent mass was 467.5, and the epoxy equivalent mass of the solid content after the elimination of the ethylcellosolve acetate was 187.

Preparation of the unsaturated group-containing polycarboxylic acid resin

Synthesis Example 5

220 parts by weight of cresol novolac epoxy resin ("ECON-104" (trade name) manufactured by NIPPON KAYAKU CO., LTD, epoxy equivalent mass 220 g / eq) was placed in a four-ported flask equipped with an agitator and a reflux condenser. 206 parts by weight of carbitol acetate were added and dissolved with heating. Then, 0.1 part by weight of hydroquinone as a polymerization inhibitor and 2.0 parts by weight of triphenylphosphine as a reaction catalyst were added thereto. This mixture was heated to 95 to 105 ° C, added dropwise 72 parts by weight of acrylic acid, and made a twenty-hour reaction. The obtained reaction product was cooled to 80 to 90 ° C, added with 91.2 parts by weight of tetrahydrophthalic anhydride, and reacted for eight hours and cooled to obtain 590 parts by weight of a solution of an unsaturated group-containing polycarboxylic acid resin (Synthesis Example 5).

The thus obtained solution of the unsaturated group-containing polycarboxylic acid resin (Synthesis Example 5) had a nonvolatile content of 65% and a solid acid value (mg KOH / g) of 87.8 mg KOH / g.

Synthetic Example 6

250 parts by weight of dipropylene glycol monomethyl ether and 10 parts by weight of t-butylperoxy-2-ethylhexanoate were placed in a separable flask equipped with an agitator, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube. After a temperature increase to 95 ° C., a mixture of 170 parts by weight of methacrylic acid, 130 parts by weight of methyl methacrylate, 250 parts by weight of dipropylene glycol monomethyl ether and 10 parts by weight of azobisdimethylvaleronitrile was added dropwise over a period of 4 hours. Then, by a five-hour ripening, a carboxyl group-containing methylacrylic acid-methyl methacrylate copolymer solution was obtained.

Then, to this resin solution was added 200 parts by weight of (3,4-epoxycyclohexyl) methyl methacrylate, 2 parts by weight of triphenylphosphine and 1 part by weight of hydroquinone monomethyl ether while passing a mixed gas (7% oxygen and 93% nitrogen) and an addition reaction at 100 ° C for 19 hours to obtain 1020 parts by weight of a solution of an unsaturated group-containing polycarboxylic acid resin (Synthesis Example 6).

When measuring the resin material properties of this solution of the unsaturated group-containing polycarboxylic acid resin (Synthesis Example 6), a solid content of 51%, an acid value (mg KOH / g) of 105, a double bond equivalent of 490 g / mol and a weight average molecular weight ( polystyrene reduced weight) of 13,000.

Synthesis Example 7

140 parts by weight of glycidyl methacrylate, 60 parts by weight of methyl methacrylate, 200 parts by weight of carbitol acetate, 0.4 parts by weight of lauryl mercaptan, and 6 parts by weight of azobisisobutyronitrile were placed in a separable flask equipped with a reflux condenser, a thermometer, a nitrogen substitution glass tube, and a stirrer under a nitrogen gas stream was heated and polymerized at 75 ° C for 5 hours to obtain a 50% copolymer solution.

To this 50% copolymer solution was added 0.1 part by weight of hydroquinone, 74 parts by weight of acrylic acid and 0.4 part by weight of dimethylbenzylamine. At 100 ° C an addition reaction was carried out for 24 hours. Thereafter, 90 parts by weight of tetrahydrophthalic anhydride and 158 parts by weight of carbitol acetate were added, and a reaction of three hours was carried out at 100 ° C. to obtain 725 parts by weight of a solution of an unsaturated group-containing polycarboxylic acid resin (Synthesis Example 7).

When measuring the resin material properties of this solution of the unsaturated group-containing polycarboxylic acid resin (Synthesis Example 7), a solid content of 50%, a double bond equivalent mass of 350 g / mol, an acid value (mg KOH / g) of 91 and a weight average molecular weight (Um Polystyrene reduced weight) of 26,000.

<Preparation of photosensitive thermosetting resin composition>

Embodiment 1 to 5 and comparative form 1 to 6

After the individual compounding ingredients were stirred and mixed according to the compounding compositions shown in Table 1, three-roller uniform dispersion was carried out to prepare photosensitive thermosetting resin compositions (Embodiments 1 to 5 and Comparative Forms 1 to 6).

In Table 1, 1) stands for solution weight Preparation of Resist Film-Coated Smooth Printed Circuit Board Production Embodiment 1 to 5 and Production Comparative Form 1 to 6 A printed circuit board of 0.8 mm thick (copper circuit thickness 40 μ, line / space ( L / S) = 75 μm / 75 μm) was used as the board material. A thermosetting resin composition having the following composition was masked using a 250 mesh polyester screen and applied to the above board. Subsequently, the plate was heated to 150 ° C with a heating furnace and subjected to primary curing at this temperature for 60 minutes. Then, the surface of the primary hardening film side was polished once with a belt grinder (No.400) and then polished four times with a polishing wheel (No.600). Finally, a 90 minute secondary cure at 180 ° C was performed in a box-shaped dryer.

In this way, a smoothed printed circuit board ( 1A ), in which the recesses between the circuits ( 1A . 2 ) on an insulating motherboard ( 1A . 1 ) by a secondary cured resin ( 1A . 3 ) were filled. The height difference of the bumps on the surface of this smoothed printed circuit board ( 1A ) was not more than 2 μm.

Mixture composition of the thermosetting resin composition (parts by weight):

75% Acrylic Acid adduct of a phenolic novolac epoxy resin (100), isoboronyl acrylate (40), tricyclodecanedimethanol acrylate (100), trimethylolpropane triacrylate (10), t-butyl peroxybenzoate (10), tetramethyl biphenyl epoxy resin (100), dicyandiamide (16), barium sulfate (120) , Polydimethylsiloxane (0.1).

The above photosensitive thermosetting resin compositions (Embodiments 1 to 5 and Comparative Examples 1 to 6) were applied to the smoothed surface of smoothed printed circuit boards as above by the screen printing method (100 mesh polyester) so that the dry film thickness would be 20 reached on the surface of the motherboard a Lötresisttintenschicht ( 1B . 4 ) was formed.

Subsequently, to remove the solvent in the Lötresisttintenschicht ( 1B . 4 ) was pre-dried at 80 ° C on the mother board surface for 20 minutes, whereby a dried film having a film thickness of 20 μm was obtained.

Then, using a UV exposure apparatus ("HMW-680C" (model number) of ORC MANUFACTURING CO., LTD.), Exposure was carried out in which the thus-obtained dried film having ultraviolet rays of 500 mJ / cm ² through a solder resist negative film ( 1C . 5 ) was irradiated.

Thereafter, the unexposed portions of the dried film after the exposure process were removed by developing with a developing liquid (1% aqueous sodium carbonate solution) to form an exposure-cured (primary-cured) resist film pattern on the motherboard. 1D . 6 ) train.

Thereafter, after a predrying at 100 ° C for 30 minutes, the motherboard was cured at 150 ° C for 60 minutes, irradiated again with ultraviolet rays of 500 mH / cm ² , and fully cured, thereby forming one with a solder resist film. 1E . 7 ), smoothed, printed circuit board (Manufacturing Embodiment 1 to 5 and Comparative Production Form 1 to 6).

Tests to evaluate the resist film coated, smoothed printed circuit board

The resist film-coated smoothed printed circuit boards (Production Embodiments 1 to 5 and Comparative Production Forms 1 to 6) of the above preparation were subjected to the below-mentioned evaluation tests. The evaluation results are shown in Table 2.

Dry feeling on touch

O:

keine Klebrigkeit und keine Fingerabdruckspuren

Ω:

geringfügige Klebrigkeit und Fingerabdruckspuren

x:

stark klebrige Oberfläche und Fingerabdruckspuren

After application, it was placed in a hot air circulating oven and dried at 80 ° C for 20 minutes. Thereafter, the application area was strongly pressed with the finger, the tackiness was examined, and the condition of the application film was judged.

O:

no stickiness and no fingerprint marks

Ω:

slight stickiness and fingerprint marks

x:

very sticky surface and fingerprint marks

development properties

O:

bei der Entwicklung wurde die Tinte vollständig beseitigt, Entwicklung war möglich

x:

bei der Entwicklung gab es nicht entwickelte Bereiche

Using a UV exposure device (model HMW-680C from ORC Manufacturing Co., Ltd.), ultraviolet rays of 500 mJ / cm ^{2 were} irradiated through a solder resist negative film. Then, with a developing liquid of a 1% sodium carbonate aqueous solution at a spray pressure of 2.0 × 10 ⁵ Pa, a development was performed for 60 seconds, after which the removal of the undeveloped portions was judged by visual inspection.

O:

During development, the ink was completely eliminated, development was possible

x:

There were undeveloped areas during development

photosensitivity

A 21-stage density panel (manufactured by Stouffer) was adhered to the applied film after drying and irradiated with ultraviolet rays with a total amount of light of 500 mJ / cm ² . Then, development was carried out for 60 seconds with a 1% sodium carbonate aqueous solution at a spray pressure of 2.0 × 10 ⁵ Pa, and the number of stages of the non-developed portions was determined.

pencil hardness

The evaluation was made according to JIS K5600.

adhesiveness

O:

es kam zu keinem Ablösen von Kreuzschnittbereichen

Ω:

beim Abziehen des Klebebands kam es zu einem Ablösen von Kreuzschnittbereichen

x:

es kam auch ohne Vornahme des Kreuzschnittversuchs zu einem Schwellen und Ablösen des Resistfilms

According to JIS K5600, on a test piece, a checkerboard pattern having 100 fields of 1 mm was prepared and a peeling test was made by means of an adhesive tape. The peeling state of the checkerboard pattern was visually evaluated and evaluated according to the following standards.

O:

there was no detachment of cross-cut areas

Ω:

When removing the adhesive tape, there was a detachment of cross-cut areas

x:

It also came without making the cross-cut test to a swelling and peeling of the resist film

Solvent Resistance

O:

das Aussehen des Auftragefilms wies keine Unregelmäßigkeiten auf, und es gab keine Schwellungen und Ablösungen

x:

der Auftragefilm wies Schwellungen und Ablösungen auf

The test piece was immersed in isopropyl alcohol at room temperature for 30 minutes. After checking whether the appearance was irregular, a peel-off (R) peeling test was conducted and evaluated according to the following standards.

O:

the appearance of the application film showed no irregularities and there was no swelling and peeling

x:

the application film showed swelling and detachment

acid resistance

O:

das Aussehen des Auftragefilms wies keine Unregelmäßigkeiten auf, und es gab keine Schwellungen und Ablösungen

x:

der Auftragefilm wies Schwellungen und Ablösungen auf

The test piece was immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After checking whether the appearance had any irregularities, a peel-off attempt was made and evaluated according to the following standards.

O:

the appearance of the application film showed no irregularities and there was no swelling and peeling

x:

the application film showed swelling and detachment

soldering heat resistance

O:

das Aussehen des Auftragefilms wies keine Unregelmäßigkeiten auf, und es gab keine Schwellungen und Ablösungen

x:

der Auftragefilm wies Schwellungen und Ablösungen auf

The flattening flux W-2704 (manufactured by MEC Co., Ltd.) was applied to the test piece, followed by immersion in a solder pot of 288 ° C for 10 seconds. This cycle was repeated three times. After cooling to room temperature, an adhesive tape (R) peel test was performed and evaluated according to the following standards.

O:

the appearance of the application film showed no irregularities and there was no swelling and peeling

x:

the application film showed swelling and detachment

O:

keine Gleichung erkennbar

Ω:

Gleichung erkennbar

x:

deutliche Gleichung erkennbar

In addition, the evaluation of the surface bleaching after the soldering heat resistance test was conducted as follows.

O:

no equation recognizable

Ω:

Equation recognizable

x:

clear equation recognizable

O:

keine Verfärbung erkennbar

Ω:

geringe Verfärbung erkennbar

x:

deutliche Verfärbung erkennbar

In addition, the evaluation of the discoloration after the soldering heat resistance test was made as follows.

O:

no discoloration visible

Ω:

slight discoloration visible

x:

noticeable discoloration

Gold coating resistance

After being immersed in an acid degreasing solution (20% by volume aqueous solution of "Metex L-56" (trade name) manufactured by NIPPON MCDERMID CO., LTD.) Having a temperature of 30 ° C for 3 minutes, it became the test motherboard washed with water. After being immersed in a 14.4 wt.% Ammonium persulfate aqueous solution for three minutes, it was washed with water. Subsequently, the test motherboard was immersed in a 10% by volume aqueous sulfuric acid solution at room temperature for 1 minute, and then washed with water.

Then, this test motherboard was immersed in a catalyst solution (10 vol.% Aqueous solution of "Metalplate Activator 350" (trade name) manufactured by MELTEX INC.) At a temperature of 30 ° C for 7 minutes, washed with water for 20 minutes in a nickel plating solution (20 vol% aqueous solution of "Melplate Ni-865M" (trade name) manufactured by MELTEX INC., pH 4.6) at a temperature of 85 ° C, and a nickel plating was carried out, followed by the plate at Room temperature was immersed in a 10 vol% aqueous sulfuric acid solution for 1 minute and washed with water.

O:

keinerlei Unregelmäßigkeiten

Ω:

geringfügige Ablösungen erkennbar

x:

starke Ablösungen

Then, the experimental motherboard was immersed in a gold plating solution (15% by volume "Aurolectroless UP" aqueous solution (trade name) made by MELTEX INC., And 3% by volume of gold potassium cyanide, pH 6) at a temperature of 95 ° C for 10 minutes immersed and made an electroless gold plating, then washed with water, immersed in warm water at 60 ° C dipped with water for three minutes, and dried. A cellophane adhesive tape was stuck on the obtained electroless gold-plated evaluation base board and the state after peeling was evaluated.

O:

no irregularities

Ω:

slight detachment recognizable

x:

strong detachments

HAST resistance

After a solder resist film was carried out on the test motherboards at 130 ° C in an 85% unsaturated pressure vessel, a DC voltage of 5 V was applied between comb-shaped electrodes having an L / S of 50 μm / 50 μm, and immobilized for 168 hours after which it was checked whether the appearance had irregularities. In addition, a measurement of the insulation resistance was carried out before and after the experiment.

O:

das Aussehen des Auftragefilms wies keine Unregelmäßigkeiten auf

Ω:

an den Elektroden waren Verfärbungen erkennbar, doch gab es keine Schwellungen oder Ablösungen

x:

der Auftragefilm wies Schwellungen oder Ablösungen auf

The insulation resistance was measured by using a digital ultrahigh resistance / small current measurer "R8340A" according to the insulation resistance test specifications of "JPCA-HD01" after applying a direct current of 10 V for one minute at this application state.

O:

the appearance of the application film showed no irregularities

Ω:

discoloration was visible on the electrodes, but there was no swelling or detachment

x:

the application film had swelling or detachment

Thermal shock resistance

O:

keine Entstehung von Rissen im Auftragefilm

x:

im Auftragefilm sind Risse entstanden

The test piece was exposed to a heat history with one cycle at -40 ° C for 30 minutes and 125 ° C for 30 minutes. The test piece was observed with a microscope after the lapse of 100 cycles and evaluated according to the following standards.

O:

no formation of cracks in the commissioned film

x:

cracks have been created in the commissioned film

surface gloss

O:

Glanzwert mindestens 81

Ω:

Glanzwert von 51 bis 80

x:

Glanzwert höchstens 50

The specular surface gloss at an angle of incidence of "JIS 28741" of 60 ° was measured using the apparatus "Micro-gloss" (trade name, manufactured by BYK-Labotron INC.) And evaluated according to the following evaluation standards.

O:

Gloss value at least 81

Ω:

Gloss value from 51 to 80

x:

Gloss value at most 50

Glass transition temperature Tg

A hardening film having a thickness of 40 μm was machined to 10 mm x 30 mm with a viscoelastic measuring device ("DMS6100", manufactured by Seiko Electronic Works), and to a measuring frequency of 1 Hz at a temperature rising speed of 5 ° C / min measured in a measuring temperature range of 40 to 250 ° C. tanδmax was set as the glass transition point (Tg).

Table 2 shows:
As shown in Production Embodiments 1 to 5, each solder resist film made of a photosensitive thermosetting resin composition of the present invention has excellent HAST resistance. Specifically, under HAST conditions, a high value of the electrical insulation resistance (Ω) is maintained even after the lapse of 168 hours, reaching a value more than about ten times the value of the conventional films (comparative production form 1 to 6).

In addition, in the solder resist films of the present invention, no irregularities in appearance are discernible not only by HAST history but also by the gold plating resistance test. Also, the gloss, the application adhesiveness and the heat shock resistance are far superior to those of the conventional films (comparative production form 1 to 6).

In photosensitive, thermosetting resin compositions in which one of the constituents [I] or [II] is missing (Comparative Form Manufacturing 1 to 6), HAST resistance, gold coating resistance, gloss, film adhesiveness and heat shock resistance are extremely poor. From this it can be seen that these peculiarities represent peculiarities, which are only brought about by the combination of component [I] and component [II]. As shown in Comparative Production Form 6, it can be seen that an amino group-containing silane-modified epoxy resin is not a substitute for the alkoxy group-containing silane-modified epoxy resin.

As shown in Comparative Production Examples 1 and 2, it can be seen that an unmodified epoxy resin (that is, only an epoxy resin itself) is not a substitute for the alkoxy group-containing silane-modified epoxy resin. As shown in Preparation Comparative Form 6, it can be seen that an amino group-containing silane-modified epoxy resin is not a substitute for the alkoxy group-containing silane-modified epoxy resin.

Glass transition temperature Tg

A hardening film having a thickness of 40 μm was machined to 10 mm x 30 mm with a viscoelastic measuring device ("DMS6100", manufactured by Seiko Electronic Works), and to a measuring frequency of 1 Hz at a temperature rising speed of 5 ° C / min measured in a measuring temperature range of 40 to 250 ° C. tanδmax was used as the glass transition point (Tg).

Simple explanation of the drawing

1 Fig. 10 is a sectional view of the manufacturing processes showing the process for producing the solder resist coated smooth printed circuit board.

LIST OF REFERENCE NUMBERS

1

insulating motherboard

2

circuit

3

secondarily cured resin

4

Lötresisttintenschicht

5

negative film

6

Pattern of resist application film

7

solder resist

Claims (5)

A photosensitive thermosetting resin composition, characterized in that the composition contains: (I) an alkoxy group-containing silane-modified epoxy resin obtained by a dealcoholization reaction of the epoxy resin represented by the following chemical formula (Chemical Formula I / E) with hydrolyzable Alkoxysilane is obtained:

(Chemical formula I / E) wherein G is a glycidyl group; A ₁₁ and A ₁₃ and A ₁₅ is a divalent aromatic radical or a divalent, hydrogenated, aromatic residual group can be a fully hydrogenated each group to each other may be identical or different from one another and independently of each other comprising; A ₁₂ and A _{14 may} each be the same or different and may independently be H or G; at least one of A ₁₂ and A _{14 is} further H, and all of these may be H at the same time; the average repetition unit numbers all and a ₁₂ may be the same or different from each other and regardless of the repetition unit number is greater than 0, and the total number of a ₁₁ and a ₁₂ is 20 and less, and wherein the hydrolyzable alkoxysilane at least one of Substances which are represented by the formula I / Si-2:

(Chemical formula I / Si-2) wherein B ₂₁ to B _{26 may be the} same or different and are an alkyl group, an aryl group or an unsaturated aliphatic residual group; an average repeating unit number b _{21 is} a number from 2 to 11, and one of the substances represented by formula I / Si-3 is:

Chemical Formula I / Si-3) (wherein B ₃₁ to B _{36 are} each the same or different and are an alkyl group, an aryl group or an unsaturated aliphatic residual group, and the average repeating unit number b _{31 is} a number from 2 to 11; an unsaturated group-containing polycarboxylic acid resin having in the molecules unsaturated ethylenic groups and two carboxyl groups and more and a solid acid number (mg KOH / g) of 50 to 150, (III) a diluent, (IV) a photopolymerization initiator, and (V) a curing adhesion promoter characterized in that the weight ratio of the contents of the component [I] and the component [II] is 2/100 to 50/100 and that the photosensitive thermosetting resin composition respectively contains 50 to 500 parts by weight of the component [III], 0 , 1 to 30 parts by weight of the component [IV] and 0.1 to 20 parts by weight of the component [V] in relation to the total amount of 100 parts by weight of ingredient [I] and ingredient [II]. Resin composition according to claim 1, characterized in that the epoxy resin represented by the chemical formula I / E is at least one of the substances represented by the formula I / E-1-1

(Chemical formula I / E-1-1) wherein G is a glycidyl group; the molecules A ₆₁₁ in the repeats a ₆₁₁ may be the same or different from each other and independently of one another H or G, where at least one is H, but all of them may also be H at the same time; and the average repeating unit number a _{611 is} a number of 20 or less, and is one of the substances represented by the formula I / E-1-2

(Chemical formula I / E-1-2) wherein G is a glycidyl group; A _{621 of} the repetitions 8621 may be the same or different from each other and independently of one another H or G, where at least one H is, but all at the same time H may be H; and the average repeat unit number a _{621 is} a number of 20 or less; and one of the substances represented by the formula I / E-1-S

(Chemical formula I / S) wherein G is a glycidyl group; A _{8 of} the repetitions a ₈ can be the same or different from each other and can independently of one another be H or G, where at least one H is, but all H can also be H at the same time; and the average repeat unit number a _{8 is} a number of 20 or less. A resin composition according to claim 1 or 2, wherein the component [II] is a resin obtained by a reaction of (1) a copolymer of an unsaturated ethylenic acid and a monomer containing ethylenically unsaturated bonds with (2) an epoxy group, unsaturated monomer, and / or a resin obtained by a reaction of (1) a reaction product obtained by a reaction of a copolymer of an epoxy group-containing unsaturated monomer and a monomer containing ethylenic unsaturated bonds with an ethylenically unsaturated one Acid is obtained with (2) a polybasic acid anhydride containing saturated and / or unsaturated groups. A resin composition according to any one of claims 1 to 3, further containing 10 to 500 parts by weight of a white pigment and 10 to 1200 parts by weight of a filler with respect to the total amount of the components (I) and component [II]. Use of the resin composition according to any one of claims 1 to 4 for producing a flat resist film coated printed circuit board, comprising the steps of: applying the photosensitive thermosetting resin composition according to any one of the above-described embodiments to the surface of a flat printed circuit board; Photohardening the applied resin, and then heating to a temperature of 100 to 190 ° C for the heat curing.

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