CN1755524A - Phototonus thermosetting resin composition and printing plug board coating with resist and its manufacturing method - Google Patents

Abstract

To provide a photosensitive thermosetting resin composition which has excellent storage stability and can give resists having excellent developability, set dryness to contact, flexural resistance, adhesiveness, coating film transparency, HAST (highly accelerated temperature and humidity stress test) resistance (especially HAST resistance in electric insulating property), heat shock resistance, and the like, to provide a smoothed printed circuit board having excellent resist, and to provide a method for producing the same. This photosensitive thermosetting resin composition is characterized by comprising an unsaturated group-containing polycarboxylic acid resin [I], a diluent [II], a photopolymerization initiator [IV], a crystalline epoxy resin [V] represented by formula (V), and a hardening adhesiveness-imparting agent [VI].

Description

Photosensitive heat curing resin combination and printing distributing board and its manufacturing method coated with resist

Technical field

The present invention relates to the photosensitive heat curing resin combination useful for etchingresistant printing material (especially solder mask ink) etc. and the printing distributing board coated with the resist smoothing printing distributing board etc. of solder resist (especially be coated with) and its manufacturing method.

Technical background

As photosensitive printing distributing board resin against corrosion or print material composition, it is known to use the polycarboxylic acid resin for containing unsaturated group for reacting the reactant of the epoxy resin of specific structure and (methyl) acrylic acid with polybasic carboxylic acid (acid anhydrides) is as active energy ray-curable resin.

Such as, the polycarboxylic acid resin containing unsaturated group by specific structure is described in Patent Documents 1 to 3, diluent [trimethylolpropane tris (methyl) acrylate, 2- ethoxy (methyl) acrylate etc.], Photoepolymerizationinitiater initiater, epoxide [phenol novolak epoxy resin, cresol-novolac epoxy resin, bisphenol-type epoxy resin, three (2, 3- glycidyl) isocyanuric acid ester etc.] or cure component (bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, brominated bisphenol a type epoxy resin, novolac epoxy resin, the novolac epoxy resin of bisphenol-A, bisphenol-s epoxy resin, union II toluene phenol-type epoxy resin, bisphenol-type epoxy resin triglycidyl group isocyanuric acid ester etc.) and epoxy curing agent (dicyandiamide etc.) structure At printing distributing board welding resistance resin combination or flexible printed wiring board etchingresistant printing material composition.

Being designed to provide of patent document 1 gives the printing distributing board welding resistance resin combination of excellent developability and the excellent solder resist of adhesiveness, welding rod heat resistance, resistance to chemical reagents, resistance to gold-plated attribute, electrical insulating property.

Patent document 2 and being designed to provide for patent document 3 are given and can be developed with dilute alkaline aqueous solution, and the flexible printed wiring board etchingresistant printing material composition of the excellent resist such as pliability, folding resistance, adhesiveness, resistance to chemical reagents, heat resistance.

But the problem that resin against corrosion-print material composition of Patent Documents 1 to 3 has the dry to touch of film not so good.In addition, resin against corrosion-print material composition of Patent Documents 1 to 3 has the problem of storage stability (shelf life) difference due to almost using solvent soluble resin.In addition, there is HAST (Highly Acce1erated Temperature and Humidity Stress Test: unsaturated steam under pressure test) patience (the HAST patience especially in electrical insulating property) and thermal shock resistance deficiency by the resist that the resin against corrosion-print material composition obtains.

As other photosensitive printing distributing boards resin against corrosion-print material composition, it is known to use reactant-polymer-resin with acidic group (carboxyl), ester group and (methyl) acryloyl group etc. in side chain (or as side group).

Such as, the alkali developable photosensitive heat curing solder mask ink composition being made of the reactant of the polycarboxylic acid resin containing unsaturated group of other specific structure, epoxy (methyl) acrylate, the polymer with carboxyl or acid anhydride and (methyl) acrylate containing hydroxyl, three (2,3- glycidyl) isocyanuric acid esters, diluent (dipentaerythritol polyacrylate etc.), Photoepolymerizationinitiater initiater and epoxy curing agent (dicyandiamide etc.) is described in patent document 4.

Patent document 4 is designed to provide alkali developable photosensitive heat curing solder mask ink composition, thermal stability, alkali-developable, photonasty when it gives storage-stable, predrying etc. are excellent, and the excellent solder resist such as adhesiveness, electrical insulating property, welding rod heat resistance, resistance to chemical reagents, resistance to gold-plated attribute.

But the resist obtained by the etchingresistant printing material composition of patent document 4, the film transparency are low.Therefore, in the printing distributing board being coated with the resist, there are problems that being difficult to directly visually observing and checing printed wiring plate surface from outside.In addition, the HAST patience (the HAST patience especially in electrical insulating property) and thermal shock resistance of the resist of patent document 4 are insufficient, and film resistance to bend(ing) etc. can not sufficiently meet.Furthermore, the etchingresistant printing material composition for having used liquid epoxy resin is also disclosed in patent document 4, but when using liquid epoxy resin, compared with the case where having used Cristalline epoxy resin, there is a problem of storage stability (shelf life) difference of etchingresistant printing material composition.

Photocurable composition is described in patent document 5; it is made of base polymer, photopolymerization monomer [2- ethoxy (methyl) acrylate etc.], photoinitiator, which is that will import (methyl) acryloyl group after a part of addition of the anhydride rings in copolymer-maleic anhydride, open loop with fatty alcohol to obtain.

Being designed to provide for patent document 5 is capable of forming fine pattern and the excellent covering of position precision with photoetch method, and it can be developed with aqueous alkali, and there is adhesiveness substantially resistant to water-soluble flux, while heat resistance, engineering properties and chemical property also excellent Photocurable composition.

But the Photocurable composition of patent document 5 is identical as the patent document 4, there is a problem of that storage stability is not so good.Furthermore, the resist obtained by the etchingresistant printing material composition of patent document 5 is identical as the Patent Documents 1 to 4, and the film transparency, HAST patience (the HAST patience especially in electrical insulating property), thermal shock resistance and film resistance to bend(ing) etc. cannot sufficiently meet.

It is described in patent document 6 by with carboxyl, the active energy ray-curable resin of ester group and (methyl) acryloyl group etc., diluent (2- hydroxy ethyl methacrylate, pentaerythrite, dipentaerythritol, the polyalcohols such as tris(2-hydroxy ethyl)isocyanurate or the multicomponent methacrylate class of their ethylene oxide or propylene oxide adduct etc.), Photoepolymerizationinitiater initiater, curability bonds imparting agent (S- triaizine compounds etc.), compound (bisphenol-s epoxy resin with epoxy group, o-phthalic acid diglycidyl ester resin, heterocyclic epoxy resin, union II toluene phenol-type epoxy resin, four glycidyl group dimethylbenzene acyl group ethane resin etc.) constitute optical polymerism compositions of thermosetting resin.

Being designed to provide for patent document 6 is excellent as workability (coating, drying property, adherence, photo-curable, developability, Thermocurable, storage stability-shelf life), printing distributing board can be made with the short time, the excellent optical polymerism compositions of thermosetting resin that can be useful with the liquid photoresist of alkali development of cured film characteristic (the lower electrical characteristic of welding rod heat resistance, solvent resistance, resistance to chemical reagents, adhesiveness, electrical insulating property, electric erosion resistance, humidification, resistance to plating property, the adhesiveness on antirust treatment substrate).

But, the resist obtained by the optical polymerism compositions of thermosetting resin of patent document 6, identical as the Patent Documents 1 to 5, the film transparency, HAST patience (the HAST patience especially in electrical insulating property), thermal shock resistance and film resistance to bend(ing) etc. cannot sufficiently meet.

In present invention applicant's earlier application cured film bubble-free remaining and the easy compositions of thermosetting resin of surface grinding and the recess portion on substrate is filled it into the flat runner and its manufacturing method (patent document 7) of the surface smoothness with height.

Patent document 1: Japanese Laid-Open Patent Publication 5-32746 bulletin.

Patent document 2: Japanese Laid-Open Patent Publication 7-207211 bulletin.

Patent document 3: Japanese Laid-Open Patent Publication 8-134390 bulletin.

Patent document 4: Japanese Laid-Open Patent Publication 3-250012 bulletin.

Patent document 5: tekiaki 63-72710 bulletin.

Patent document 6: Japanese Laid-Open Patent Publication 10-20493 bulletin.

Patent document 7: special open 2003-26765 bulletin.

Summary of the invention

In view of the situation, the purpose of the present invention is to provide photosensitive heat curing resin combinations, can give the excellent resist such as excellent storage stability and developability, dry to touch, resistance to bend(ing), adhesiveness, the film transparency, HAST patience (the HAST patience especially in electrical insulating property) and thermal shock resistance.

In addition, the object of the invention is also to provide printing distributing boards (especially smoothing printing distributing board) and its manufacturing method with the excellent resist.

In order to reach the purpose, sharp study is carried out, result completes the present invention.

That is, the present invention provides photosensitive heat curing resin combination, contain:

[I]: the polycarboxylic acid resin containing unsaturated group is the reactant of epoxy resin and monocarboxylic reactant and polybasic carboxylic acid or its acid anhydrides containing unsaturated group shown in following formula (changing I/E),

(changing I/E)

In formula (changing I/E), G is following formula

The group of expression, A₁₁、A₁₃And A₁₅Indicate the aromatic residue or hydrogenated aromatic residue of divalent that can be identical or different, A₁₂And A₁₄Can be identical or different, H or G is each independently represented, wherein A₁₂And A₁₄The two is not H, a simultaneously₁₁And a₁₂Indicate 0 or more integer that can be identical or different, but a₁₁And a₁₂It is not simultaneously 0；

[III]: diluent；

[IV]: Photoepolymerizationinitiater initiater；

[V]: the Cristalline epoxy resin that following formula (changing V) indicates,

(changing V)

In formula (changing V), G and described synonymous, E₁₁~E₁₃And E₁₅~E₁₇Indicate H or C1~C5 alkyl that can be identical or different, e₁₁And e₁₂Indicate 0~3 integer that can be identical or different, E₁₄Indicate S, O ,-CH₂-、-C(CH₃)₂Or the divalent group that following formula (changing V/X) or (changing F) indicate,

(changing V/X)

(changing F)

In formula (changing V/X), E₂₁~E₂₄Can be identical or different, each independently represent C1~C6 alkyl；With

[VI]: solidification adhesiveness imparting agent.

The present invention provides the photosensitive heat curing resin combination; the photosensitive heat curing resin combination also contains [II]: having carboxyl and (methyl) acryloyl group, the polymer that acid value (mgKOH/g) is 20~160 and average molecular weight is 3000~70000.

The present invention provides the photosensitive heat curing resin combination; wherein polymer [II] is [II-1]: the reactant of the polymer with carboxyl or acid anhydride and (methyl) acrylate containing hydroxyl, and/or [II-2]: at least part of the carboxyl in the polymer with carboxyl reacts to have imported the reactant of (methyl) acryloyl group with the unsaturated monomer containing epoxy group.

The present invention provides any one of described photosensitive heat curing resin combination, and wherein the softening point of epoxy resin shown in formula (changing I/E) is 50 DEG C or more, and the fusing point of Cristalline epoxy resin [V] is 110~135 DEG C.

The present invention provides any one of described photosensitive heat curing resin combination, wherein epoxy resin shown in formula (changing I/E) is more than one chosen from block polymerization type resin shown in alternating polymerization type resin shown in homopolymerization type resin shown in following formula (changing I/E-1), following formula (changing I/E-2) and following formula (changing I/E-3)

(changing I/E-1)

(changing I/E-2)

(changing I/E-3)

In formula (change I/E-1)~(changing I/E-3), G with it is described synonymous,

In formula (changing I/E-1), A₃₁And A₃₃Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, in formula (changing I/E-1), a₃₁Indicate 1 or more integer, in formula (change I/E-1), A₃₂Indicating H or G, at least one is G,

In formula (changing I/E-2), A₄₁、A₄₃And A₄₅Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, in formula (changing I/E-2), a₄₁Indicate 1 or more integer, in formula (change I/E-2), A₄₂And A₄₄Can be identical or different, each independently represent H or G, but A₄₂And A₄₄The two is not H simultaneously,

In formula (changing I/E-3), A₅₁、A₅₃And A₅₅Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, in formula (changing I/E-3), a₅₁And a₅₂Each independently represent 1 or more integer, in formula (changing I/E-3), A₅₂And A₅₄Can be identical or different, each independently represent H or G, but A₅₂And A₅₄The two is not H simultaneously.

The present invention provides the photosensitive heat curing resin combination, wherein resin (changing I/E-1) is following formula (changing I/E-1-1) and/or the resin that (changing I/E-1-2) indicates, resin (changing I/E-2) is more than one selected from the resin indicated respectively by following formula (changing I/E-2-1)~(changing I/E-2-4), resin (changing I/E-3) is more than one selected from the resin indicated respectively by following formula (changing I/E-3-1)~(changing I/E-3-4)

(changing I/E-1-1)

(changing I/E-1-2)

(changing I/E-2-1)

(changing I/E-2-2)

(changing I/E-2-3)

(changing I/E-2-4)

(changing I/E-3-1)

(changing I/E-3-2)

(changing I/E-3-3)

(changing I/E-3-4)

In the formula, G and described synonymous, A₆₁₁And A₆₂₁Respectively with the A₃₂It is synonymous, a₆₁₁And a₆₂₁Respectively with a₃₁It is synonymous, A₆₃₁、A₆₄₁、A₆₅₁And A₆₆₁Respectively with the A₄₂It is synonymous, A₆₃₂、A₆₄₂、A₆₅₂And A₆₆₂Respectively with the A₄₄It is synonymous, a₆₃₁、a₆₄₁、a₆₅₁And a₆₆₁Respectively with a₄₁It is synonymous, A₇₁₁、A₇₂₁、A₇₃₁And A₇₄₁Respectively with the A₅₂It is synonymous, A₇₁₂、A₇₂₂、A₇₃₂And A₇₄₂Respectively with the A₆₄It is synonymous, a₇₁₂、a₇₂₂、a₇₃₂And a₇₄₂Respectively with a₅₂It is synonymous,

In the formula, A₆₃₃、A₆₃₄、A₆₄₃、A₆₄₄、A₆₅₃、A₆₅₄、A₆₆₃、A₆₆₄、A₇₁₃、A₇₁₄、A₇₂₃、A₇₂₄、A₇₃₃、A₇₃₄、A₇₄₃And A₇₄₄It is each independently H or CH₃。

The present invention provides any one of described photosensitive heat curing resin combination, and wherein Cristalline epoxy resin [V] is more than one selected from the resin indicated respectively by following formula (changing V/1)~(changing V/9),

(changing V/1)

(changing V/2)

(changing V/3)

(changing V/4)

(changing V/5)

(changing V/6)

(changing V/7)

(changing V/8)

(changing V/9)

In formula (change V/1)~(changing V/9), G and described synonymous, in formula (change V/8), E₃₁~E₃₄Can be identical or different, each independently represent H or C1~C6 alkyl.

The present invention provides any one of described photosensitive heat curing resin combination, it also contains selected from [VII-1]: the Cristalline epoxy resin that 135~170 DEG C of fusing point, [VII-2]: single poly- carbodiimide, [VII-3] shown in following formula (changing VII-2): compound and [VII-4] containing allyl: more than one of the compound containing oxazoline group are as thermosetting component

(changing VII-2)

In formula (changing VII-2), G₂₁And G₂₃Each independently represent the aromatic residue, aliphatic residue or ester ring type residue of 1 valence, G₂₂Indicate aromatic residue, aliphatic residue or the ester ring type residue of divalent, g₂₁Indicate 0~30 number.

The present invention provides the photosensitive heat curing resin combination, wherein Cristalline epoxy resin [VII-1] is more than one selected from resin shown in following formula (changing VII-1/1)~(changing VII-1/3), compound [VII-3] containing allyl is the prepolymer containing allyl selected from average molecular weight 400~30000, diallyl 3 shown in (different) cyanurate three (first generation) allyl ester and following formula (changing VII-3/1), 6- methylene tetrahydric phthalimide (bisallylnadiimide) compound more than one, compound [VII-4] containing oxazoline group is 2, 2- (1, 3- phenylene) two -2- oxazolines and/or the polymer containing oxazoline group,

(changing VII-1/1)

(changing VII-1/2)

(changing VII-1/3)

In formula (change VII-1/1)~(changing VII-1/3), G and described synonymous, in formula (change VII-1/1), g₁₁Indicate 0~2 number,

(changing VII-3/1)

In formula (changing VII-3/1), G₇₁Indicate the divalent group that following formula (changing VII-3/1-R1), (changing VII-3/1-R2) or (changing VII-3/1-R3) indicates,

(changing VII-3/1-R1)

(changing VII-3/1-R2)

(changing VII-3/1-R3)

In formula (changing VII-3/1-R3), g₈₁Indicate 4~8 integer.

The present invention provides the printing distributing board for being coated with resist, and wherein resist contains any one of described photosensitive heat curing resin combination.

The present invention provides the printing distributing board for being coated with resist, and wherein printing distributing board is the recess portion resin filling of printed wiring plate surface to make the smoothing printing distributing board of smooth surface.

The present invention provides the manufacturing method of any one of described printing distributing board coated with resist, wherein in the manufacturing method of printing distributing board for being coated with resist, dry film photoresist using the liquid photosensitive resist agent containing any one of described photosensitive heat curing resin combination or containing any one of described photosensitive heat curing resin combination in photoresist, coats resist in printed wiring plate surface.

Using the present invention, the photosensitive heat curing resin combination that can give excellent storage stability and developability, dry to touch, resistance to bend(ing), adhesiveness, the film transparency, HAST patience (the HAST patience especially in electrical insulating property) and the excellent resist of thermal shock resistance can be provided.

In addition, smoothing printing distributing board and its manufacturing method with the excellent resist can be provided using the present invention.

Detailed description of the invention

Fig. 1 is the cross-section diagram of the smoothing printing distributing board for being coated with resist of the invention.

The cross-section diagram of printing distributing board of the Fig. 2 between circuit with recess portion.

Fig. 3 is the cross-section diagram for smoothing printing distributing board.

Fig. 4 is the cross-section diagram of dry film photoresist according to the present invention.

Symbol description

1: resist

2: photoresist

3: recess portion

4: solidified resin

5: insulating substrate

6: conductor circuit

7: antistatic layer

8: carrier film

9: water-soluble resin layer

10: protective film

Specific embodiment

The present invention is described in detail below.

In photosensitive heat curing resin combination of the invention, contain the polycarboxylic acid resin of [I] containing unsaturated group.By containing the polycarboxylic acid resin of [I] containing unsaturated group, the storage stability of photosensitive heat curing resin combination and the developability of resist, resistance to bend(ing) and adhesiveness etc. can be improved.

The polycarboxylic acid resin of [I] containing unsaturated group is then made obtained from the reactant and polybasic carboxylic acid or its anhydride reaction by making epoxy resin shown in following formula (changing I/E) and the monocarboxylic acid reaction containing unsaturated group.

(changing I/E)

In formula (changing I/E), G is glycidyl, the group indicated for following formula.

In formula (changing I/E), any regulation (restriction) is not carried out to each repetitive unit putting in order in resin matrix shown in following formula (changing I/E-U1) and (changing I/E-U2).

(changing I/E-U1)

(changing I/E-U2)

Therefore, when repetitive unit (changing I/E-U1) and not identical (changing I/E-U2), as resin (changing I/E), the resin that the resin of block polymerization type is arranged in can enumerate such as repetitive unit (changing I/E-U1) and (changing I/E-U2), be arranged in the resin of alternating polymerization type and be arranged in atactic polymerization type, can be used these more than one.

In formula (changing I/E), A₁₁、A₁₃And A₁₅Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, preferably A₁₅For A₁₁Or A₁₃。

In A₁₁、A₁₃And A₁₅In, as the aromatic residue of divalent, divalent group, phenylene or naphthylene such as shown in following formula (changing I/E-Ar1) can be enumerated.

(changing I/E-Ar1)

In formula (changing I/E-Ar1), A₂₁Indicate (ring) alkylidene ,-O- ,-CO- ,-COO- ,-S- ,-S-S- ,-SO- ,-SOO- or following formula (changing F)

(changing F)

The divalent group of expression, a₂₁It is 0 or 1.

In aromatic residue, as divalent group (changing I/E-Ar1), A can be enumerated₂₁For the group of (ring) alkylidene.As (ring) alkylidene, the group of such as C1~C8 can be enumerated.(ring) alkylidene can have substituent group [such as C1~C6 (ring) alkyl, aryl ,-CF₃Base etc.].In addition, can also have 1 or more substituent group (such as C1~C6 alkyl, halogen atom etc.) on the phenyl ring of a side or two sides in formula (changing I/E-Ar1).Specifically, group shown in following formula (changing I/E-Ar1-1)~(changing I/E-Ar1-5) etc. can be enumerated as the aromatic residue.

(changing I/E-Ar1-1)

(changing I/E-Ar1-2)

(changing I/E-Ar1-3)

(changing I/E-Ar1-4)

(changing I/E-Ar1-5)

In aromatic residue, as other divalent groups (changing I/E-Ar1), A can be enumerated₂₁For the group of-O- ,-CO- ,-COO- ,-S- ,-S-S- ,-SO- or-SOO-.In addition, can have 1 or more substituent group (such as C1~C6 alkyl, halogen atom etc.) on the phenyl ring of a side or two sides in formula (changing I/E-Ar1).Specifically, group shown in following formula (changing I/E-Ar1-6) and (changing I/E-Ar1-7) etc. can be enumerated as the aromatic residue.

(changing I/E-Ar1-6)

(changing I/E-Ar1-7)

In aromatic residue, as other divalent groups (changing I/E-Ar1), A can be enumerated₂₁For following formula (changing F)

(changing F)

Shown in group etc..In addition, can have 1 or more substituent group (such as C1~C6 alkyl etc.) on the phenyl ring of a side or two sides in formula (changing I/E-Ar1).Specifically, group shown in following formula (changing I/E-Ar1-F) etc. can be enumerated as the aromatic residue.

(changing I/E-Ar1-F)

In aromatic residue, as other divalent groups (changing I/E-Ar1), a can be enumerated₂₁For 0 group.In addition, can have 1 or more substituent group (such as C1~C6 alkyl, halogen atom etc.) on the phenyl ring of a side or two sides in formula (changing I/E-Ar1).Specifically, group shown in following formula (changing I/E-Ar1-8) and (changing I/E-Ar1-9) etc. can be enumerated as the aromatic residue.

(changing I/E-Ar1-8)

(changing I/E-Ar1-9)

In aromatic residue, as phenylene, 1 or more substituent group (such as C1~C6 alkyl, halogen atom etc.) can have on aromatic rings.Specifically, group shown in following formula (changing I/E-Ar2-1) etc. can be enumerated as phenylene.

(changing I/E-Ar2-1)

In aromatic residue, as naphthylene, group shown in following formula (changing I/E-Ar3-1) etc. can be specifically enumerated.

(changing I/E-Ar3-1)

As aromatic residue, preferred group (changing I/E-Ar1-1), (changing I/E-Ar1-4), (changing I/E-Ar1-8) and (changing I/E-Ar1-9).

In A₁₁、A₁₃And A₁₅In, as the hydrogenated aromatic residue of divalent, can enumerate the group etc. of fragrant hydrogenated (adding hydrogen) in the aromatic residue.Instead of the aromatic residue, A can be made₁₁、A₁₃And A₁₅In at least part be hydrogenated aromatic residue.When replacement aromatic residue is hydrogenated aromatic residue, with the advantages of compatibility raising for closing property resin with acrylic acid copolymer, weatherability also improves.

As hydrogenated aromatic residue, completely hydrogenated and partially hydrogenated aromatic residue can be enumerated.Specifically, as hydrogenated aromatic residue, group etc. that the is unsaturated bond (double bond etc.) in aromatic residue is completely hydrogenated and becoming the group of saturated bond and be hydrogenated to the group in in-between stage and the group for all hydrogenating unsaturated bond all in aromatic rings and only hydrogenate unsaturated bond a part of in aromatic rings can be enumerated.

When using epoxy resin (change I/E) with hydrogenated aromatic residue, weatherability can be made and improved with the compatibility of acrylic copolymer etc..

Hydrogenation conditions are suitably selected according to the degree (such as hydrogenation 40~100%) of hydrogenation, such as, it can be used and be filled with the fixed bed flow through reactors of the preformed catalyst of appendix ruthenium, use makes the material solution being dissolved in ether solvent and hydrogen be passed to the fluidized bed process in reactor with the upward cocurrent of gas-liquid, is hydrogenated under 10~150 DEG C of reaction temperature of ranges, the range of reaction pressure (hydrogen pressure) 0.5~15MPa, the range of the velocity of liquid assets of material solution (LHSV) 0.2~10/h.

In A₁₁、A₁₃And A₁₅In, as hydrogenated aromatic residue, part or all that can specifically enumerate group shown in following formula (change I/E-S-1)~(changing I/E-S-12) and their cyclohexane ring becomes the group etc. of cyclohexene ring.

In formula (changing I/E), a₁₁And a₁₂Indicate 0 or more integer that can be identical or different, but a₁₁And a₁₂It is not simultaneously 0.a₁₁And a₁₂Summation (a₁₁+a₁₂) it can be such as 1~30.Work as a₁₁And a₁₂Summation (a₁₁+a₁₂) it is big when, dry to touch is excellent.

In formula (changing I/E), A₁₂And A₁₄Can be identical or different, each independently represent H or G.Particularly, a₁₁A A₁₂Can be identical or different, each independently represent H or G.Similarly, a₁₂A A₁₄Can be identical or different, each independently represent H or G.But all A₁₂And A₁₄It is not simultaneously H.It is preferred that a₁₁When not being 0, a₁₁A A₁₂In at least 1 be G.Similarly, preferably a₁₂When not being 0, a₁₂A A₁₄In at least 1 be G.

In addition, epoxy resin (changing I/E) preferably 50 DEG C of softening point or more (particularly preferred 60~100 DEG C).By making 50 DEG C of softening point or more, have the advantages that dry to touch improves and photonasty improves.

As epoxy resin (changing I/E), equal poly resin and copolymer resins etc. can be enumerated, these more than one can be used.Type as " resin ", it can enumerate such as bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-A/F and with type epoxy resin, novolac epoxy resin, the novolac epoxy resin of bisphenol-A (or F), triphenylmethane type epoxy resin, union II toluene phenol-type epoxy resin, dicyclopentadiene phenolic aldehyde type ring oxygen resin, naphthalene skeleton epoxy resin, fluorenes type epoxy resin, silicone-modified epoxy resin and 6-caprolactone modified epoxy, they more than one can be used.

As epoxy resin (changing I/E), it is preferred that homopolymerization type resin shown in following formula (changing I/E-1), block copolymerization type resin shown in alternating copolymerization type resin and following formula (changing I/E-3) shown in following formula (changing I/E-2) etc., can be used they more than one.

(changing I/E-1)

(changing I/E-2)

(changing I/E-3)

In formula (change I/E-1)~(changing I/E-3), G with it is described synonymous.

In formula (changing I/E-1), A₃₁And A₃₃Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, but preferred A₃₃For A₃₁.In A₃₁And A₃₃In, it can be the A as the aromatic residue of divalent or the hydrogenated aromatic residue of divalent₁₁、A₁₃And A₁₅In cited group.In formula (changing I/E-1), a₃₁Indicate the integer of 1 or more (such as 1~30).In formula (changing I/E-1), A₃₂Indicate H or G, but at least one is G.

In formula (changing I/E-2), A₄₁、A₄₃And A₄₅Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, preferably A₄₅For A₄₁Or A₄₃.In A₄₁、A₄₃And A₄₅In, it, can be in the A as the aromatic residue of divalent or the hydrogenated aromatic residue of divalent₁₁、A₁₃And A₁₅The middle group for illustrating to illustrate.In formula (changing I/E-2), a₄₁Indicate the integer of 1 or more (such as 1~15).In formula (changing I/E-2), A₄₂And A₄₄Can be identical or different, each independently represent H or G.Particularly, a₄₁A A₄₂Can be identical or different, each independently represent H or G.Similarly, a₄₁A A₄₄Can be identical or different, each independently represent H or G.But all A₄₂And A₄₄It is not simultaneously H.It is preferred that a₄₁A A₄₂In at least 1 be G.Similarly, preferably a₄₁A A₄₄In at least 1 be G.

In formula (changing I/E-3), A₅₁、A₅₃And A₅₅Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, preferably A₅₅For A₅₁Or A₅₃.In A₅₁、A₅₃And A₅₅In, it, can be in the A as the aromatic residue of divalent or the hydrogenated aromatic residue of divalent₁₁、A₁₃And A₁₅The middle group for illustrating to illustrate.In formula (changing I/E-3), a₅₁And a₅₂Each independently represent the integer of 1 or more (such as 1~15).In formula (changing I/E-3), A₅₂And A₅₄Can be identical or different, each independently represent H or G.Particularly, a₅₁A A₅₂Can be identical or different, each independently represent H or G.Similarly, a₅₂A A₅₄Can be identical or different, each independently represent H or G.But all A₅₂And A₅₄It is not simultaneously H.It is preferred that a₅₁A A₅₂In at least 1 be G.Similarly, preferably a₅₂A A₅₄In at least 1 be G.

Copoly type epoxy resin (changing I/E-2) or (changing I/E-3) embody the composite effect of each homopolymerization type epoxy resin (changing I/E-1).

For example, resin properties-feature of resin (changing I/E-1) is because of basic framework A₃₁Difference and it is different.Specifically, working as A₃₁When middle importing bisphenol-f type, there is flexible, adhesiveness resin properties-feature.Work as A₃₁When middle importing group (changing I/E-Ar1-9), there is crystallinity, resin properties-feature of low water absorption.It therefore, can be by the epoxy blend of various homopolymerization types for the feature both obtained.On the other hand, by using the copoly type epoxy resin for being directed respectively into the skeleton in same intramolecular, the characteristic-feature resin for having two resins concurrently can also be synthesized.Therefore, by using the epoxy resin of copoly type, situation present in the relationship cancelled out each other can be made balanced and additional function as resin properties.

In epoxy resin (changing I/E), as resin (changing I/E-1), resin shown in following formula (changing I/E-1-1) and (changing I/E-1-2) can be specifically enumerated.As resin (changing I/E-2), the resin indicated respectively by following formula (changing I/E-2-1)~(changing I/E-2-4) can be specifically enumerated.As resin (changing I/E-3), the resin indicated respectively by following formula (changing I/E-3-1)~(changing I/E-3-4) can be specifically enumerated.As epoxy resin (changing I/E), these more than one can be used.

(changing I/E-1-1)

(changing I/E-1-2)

(changing I/E-2-1)

(changing I/E-2-2)

(changing I/E-2-3)

(changing I/E-2-4)

(changing I/E-3-1)

(changing I/E-3-2)

(changing I/E-3-3)

(changing I/E-3-4)

In the formula, G with it is described synonymous.A₆₁₁And A₆₂₁Respectively with the A₃₂It is synonymous.a₆₁₁And a₆₂₁Respectively with a₃₁It is synonymous.A₆₃₁、A₆₄₁、A₆₅₁And A₆₆₁Respectively with the A₄₂It is synonymous.A₆₃₂、A₆₄₂、A₆₅₂And A₆₆₂Respectively with the A₄₄It is synonymous.a₆₃₁、a₆₄₁、a₆₅₁And a₆₆₁Respectively with a₄₁It is synonymous.A₇₁₁、A₇₂₁、A₇₃₁And A₇₄₁Respectively with the A₅₂It is synonymous.A₇₁₂、A₇₂₂、A₇₃₂And A₇₄₂Respectively with the A₆₄It is synonymous.a₇₁₂、a₇₂₂、a₇₃₂And a₇₄₂Respectively with a₅₂It is synonymous,

In the formula, A₆₃₃、A₆₃₄、A ₆₄₃、A₆₄₄、A₆₅₃、A₆₅₄、A₆₆₃、A₆₆₄、A₇₁₃、A₇₁₄、A₇₂₃、A₇₂₄、A₇₃₃、A₇₃₄、A₇₄₃And A₇₄₄It is each independently H or CH₃.It is preferred that respectively A₆₃₃And A₆₃₄It is identical, A₆₄₃And A₆₄₄It is identical, A₆₅₃And A₆₅₄It is identical, A₆₆₃And A₆₆₄It is identical, A₇₁₃And A₇₁₄It is identical, A₇₂₃And A₇₂₄It is identical, A₇₃₃And A₇₃₄It is identical, A₇₄₃And A₇₄₄It is identical.

The epoxy resin of alternating copolymerization type, such as epoxy resin (changing I/E-2-1) is to make bisphenol A type epoxy resin and 4 first, after 4 '-dihydroxydiphenyl methane addition copolymerizations, is modulated and carrying out epoxidation to remaining hydroxyl.

The epoxy resin of block copolymerization type, such as epoxy resin (changing I/E-3-1) is after for example making homopolymer (n is 1 or more) connection addition of the homopolymer (1 or more n) and bisphenol f type epoxy resin of bisphenol A type epoxy resin, to be modulated and carrying out epoxidation to remaining hydroxyl.

As the monocarboxylic acid containing unsaturated group reacted with epoxy resin (changing I/E), the monocarboxylic acid that intramolecular has ethylenic bond unsaturated bond and carboxyl (including carboxylic acid group-COOH) can be enumerated.In addition, ethylenic bond unsaturated bond and carboxyl can mutually be conjugated (adjoining), (adjoining) can not also be conjugated.

Specifically, as the monocarboxylic acid containing unsaturated group, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, monomethyl maleate, ethyl maleate, maleic acid list propyl ester, sorbic acid etc. can be enumerated, these more than one can be used.

In epoxy resin (change I/E) is reacted with monocarboxylic containing unsaturated group, the epoxy group of every 1 equivalent epoxy resin (changing I/E) can be made to have 0.8~1.3 mole of the monocarboxylic acid containing unsaturated group to react.

Then, it reacts the epoxy resin (changing I/E) obtained in this way with the monocarboxylic reactant (hereinafter sometimes referred to " initial reaction object ") containing unsaturated group with polybasic carboxylic acid or its acid anhydrides (hereinafter sometimes referred to " polybasic carboxylic acid (acid anhydride) "), modulates the polycarboxylic acid resin [I] containing unsaturated group.

As polybasic carboxylic acid (acid anhydride), such as C1~C8 dicarboxylic acids (acid anhydride) can be enumerated.Succinic acid (acid anhydride), maleic acid (acid anhydride), fumaric acid (acid anhydride), itaconic acid (acid anhydride), four or hexahydrophthalic acid (acid anhydride) etc. can specifically be enumerated.

In the early stage in the reaction of reactant and polybasic carboxylic acid (acid anhydride), relative to the hydroxyl in initial reaction object, preferably every 1 equivalent of hydroxyl groups reacts 0.05~1.00 equivalent polybasic carboxylic acid.In the early stage in the reaction of reactant and polybasic carboxylic acid (acid anhydride), relative to the hydroxyl in initial reaction object, preferably every 1 equivalent of hydroxyl groups makes 0.1~0.9 equivalent polybasic carboxylic acid anhydride reactant.

40~150 (particularly preferred 50~120) polycarboxylic acid resin [I] preferred acid number (mgKOH/g) containing unsaturated group.If acid value is too low, development residue increases sometimes, if opposite excessively high, the moisture-proof of film reduces sometimes.

In photosensitive heat curing resin combination of the invention, as ingredient [II], can contain has carboxyl and (methyl) acryloyl group, the polymer that acid value is 20~160 and average molecular weight is 3000~70000.If the acid value of polymer [II] is less than 20, alkali-developable reduces sometimes, and opposite if it exceeds 160, the moisture-proof of film reduces sometimes.It is opposite if it exceeds 70000 if the average molecular weight of polymer [II], less than 3000, dry to touch, envelope developability reduce sometimes, it is reduced sometimes with the compatibility of resin, adhesiveness.

In addition, preferably every 1000 molecular weight is 0.2~5.0 and 0.2~4.0 respectively for carboxyl number and (methyl) acryloyl radix in polymer [II].

Particularly, aftermentioned reactant [II-1] preferred acid number is 20~160, and average molecular weight is 3000~30000, and carboxyl number is every 1000 molecular weight 0.2~5.0, and (methyl) acryloyl radix is every 1000 molecular weight 0.2~4.0.Reactant [II-2] preferred acid number is 20~160, and average molecular weight is 3000~30000, and carboxyl number is every 1000 molecular weight 0.2~5.0, and (methyl) acryloyl radix is every 1000 molecular weight 0.2~4.0.

By containing polymer [II], the dry to touch of film can be made to improve.When making photosensitive dry film resist, the fissility of protective film can be improved.

As polymer [II], from use safety and being easy to get property, the viewpoints, preferably [II-1] such as convieniently synthesized property: the reactant of the polymer with carboxyl or acid anhydride and (methyl) acrylate containing hydroxyl.

In reactant [II-1], as the polymer with carboxyl of brewable material, can enumerate for example make as must monomer the homopolymerization of ethylenic bond unsaturated acids or obtained (methyl) acrylic resin of copolymerization.It is preferred that (methyl) acrylic resin is the copolymer of ethylenic bond unsaturated acids and the monomer containing ethylenic bond unsaturated bond.

In (methyl) acrylic resin, as ethylenic bond unsaturated acids, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, monomethyl maleate, ethyl maleate, maleic acid list propyl ester, sorbic acid etc. can be specifically enumerated, these more than one can be used.

In (methyl) acrylic resin, as the monomer containing ethylenic bond unsaturated bond, C1~C8 alkyl (methyl) acrylate [(methyl) methyl acrylate can specifically be enumerated, (methyl) ethyl acrylate etc.], 2- hydroxyl C1~C18 alkyl (methyl) acrylate [2- methylol (methyl) acrylate, 2- ethoxy (methyl) acrylate, 2- hydroxypropyl (methyl) acrylate etc.], ethylene glycol methacrylate, ethylene glycol monomethyl methacrylate, ethylene glycol list ethyl propylene acid esters, ethylene glycol list ethylmethyl acrylate, glyceryl acrylate, glycerol methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl 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-EHA, 2-Ethylhexyl Methacrylate, benzyl acrylate, benzyl methacrylate, carbitol acrylate, methacrylic acid carbitol ester, 6-caprolactone modified acroleic acid tetrahydrochysene chaff ester, 6-caprolactone modified methacrylic acid tetrahydrochysene chaff ester, diethylene glycol (DEG) ethoxy acrylate, isodecyl acrylate, isodecyl methacrylate, 2-ethyl hexyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, Tridecyl methacrylate base ester, stearyl acrylate, stearyl methacrylate etc., these more than one can be used.

Specifically, (methyl) acrylic resin can enumerate copolymer, methacrylic acid and the copolymer of methyl acrylate of methacrylic acid and Isobutyl methacrylate etc., these more than one can be used.

The preferred average molecular weight of polymer with carboxyl is 3000~30000, and the carboxyl number in resin is every 1000 molecular weight 0.2~5.0, and acid value is 20~160.

In reactant [II-1], as the polymer with acid anhydride, polymer shown in following formula (changing II-1/An) can be enumerated.

(changing II-1/An)

[in formula (changing II-1/An), B₁₁And B₁₂Each independently represent H, C₁~C₃Alkyl or aromatic group (phenyl, phenol etc.).b₁₁And b₁₂Indicate the integer of 10~500 (preferably 15~300)].

In formula (changing II-1/An), to put in order no any regulation (restriction) of each repetitive unit shown in following formula (changing II-1/An-U1) and (changing II-1/An-U2) in polymer (changing II-1/An) skeleton containing anhydride group.

(changing II-1/An-U1)

(changing II-1/An-U2)

[in formula (changing II-1/An-U2), B₁₁And B₁₂With it is described identical].

Therefore, when repetitive unit (changing II-1/An-U1) and different (changing II-1/An-U2), as the polymer (changing II-1/An) containing anhydride group, the polymer that the polymer of block polymerization type is arranged as can enumerate such as repetitive unit (changing II-1/An-U1) and (changing II-1/An-U2), be arranged as the polymer of alternating polymerization type and be arranged as atactic polymerization type, can be used these more than one.

As the polymer (changing II-1/An) containing anhydride group, the preferably polymer of alternating polymerization type shown in following formula (changing II-1/An-1).

(changing II-1/An-1)

[in formula (changing II-1/An-1), B₂₁And B₂₂Respectively with the B₁₁And B₁₂It is identical.b₂₁Indicate the integer of 5~400 (preferably 10~300)].

Specifically, styrene and Malaysia can be enumerated as the polymer with acid anhydride

The copolymer of acid anhydrides, the copolymer of α-isobutene and maleic anhydride, the copolymer of styrene and maleic anhydride and reactant of alkylol etc., can be used these more than one.

The preferred average molecular weight of polymer with acid anhydride is 3000~30000, and the acid anhydrides radix in resin is every 1000 molecular weight 0.2~5.0, and acid value is 20~160.

In reaction equation [II-1], as (methyl) acrylate containing hydroxyl, substance shown in following formula (changing II-1/Ac) etc. can be enumerated.

(changing II-1/Ac)

[in formula (changing II-1/Ac), B₃₁Indicate C1~C6 alkylidene].

Specifically, as (methyl) acrylate (changing II-1/Ac) containing hydroxyl, 2- ethoxy (methyl) acrylate, 2- hydroxypropyl (methyl) acrylate, 4- hydroxyl butyl (methyl) acrylate, 2- ethoxy (methyl) acrylate and reactant, the pentaerythrite three (methyl) acrylate of 6-caprolactone etc. can be enumerated, these more than one can be used.

In the reaction of the polymer with carboxyl and (methyl) acrylate containing hydroxyl (changing II-1/Ac), relative to 1 equivalent of carboxyl in polymer, the hydroxyl for preferably comprising (methyl) acrylate (changing II-1/Ac) of hydroxyl is 0.1~0.75 equivalent.

In the reaction of the polymer with acid anhydride and (methyl) acrylate containing hydroxyl (changing II-1/Ac), relative to 1 equivalent of acid anhydride in polymer, the hydroxyl for preferably comprising (methyl) acrylate (changing II-1/Ac) of hydroxyl is 0.4~0.6 equivalent.

As reactant [II-1], preferably substance shown in following formula (changing II-1).

(changing II-1)

[in formula (changing II-1), B₄₁、B₄₂And B₄₃Respectively with the B₃₁、B₁₁And B₁₂It is synonymous.b₄₁And b₄₂Indicate the integer of 10~500 (preferably 15~300)].

In formula (changing II-1), to put in order no any regulation (restriction) of each repetitive unit in polymer backbone shown in following formula (changing II-1/U1) and (changing II-1/U2).

(changing II-1/U1)

(changing II-1/U2)

[in the formula, B₄₁、B₄₂And B₄₃Respectively with it is described synonymous].

Therefore, when repetitive unit (changing II-1/U1) and different (changing II-1/U2), as reactant (changing II-1), the polymer that the polymer of block polymerization type is arranged as can enumerate such as repetitive unit (changing II-1/U1) and (changing II-1/U2), be arranged as the polymer of alternating polymerization type and be arranged as atactic polymerization type, can be used these more than one.

As reactant (changing II-1), preferably substance shown in following formula (changing II-1/1).

(changing II-1/1)

[in formula (changing II-1/1), B₅₁、B₅₂And B₅₃Respectively with the B₃₁、B₁₁And B₁₂It is synonymous.b₅₁Indicate the integer of 5~400 (preferably 10~300)].

As other polymer [II]; the viewpoints, preferably for example [II-2] such as it is easy to get, is convieniently synthesized from raw material: making at least part for the carboxyl for having in the polymer of carboxyl and unsaturated monomer reaction containing epoxy group and importing the reactant of (methyl) acryloyl group.Reactant [II-2] can replace reactant [II-1] or be used together with reactant [II-1].

In reactant [II-2], as the polymer with carboxyl of brewable material, the polymer illustrated in the reactant [II-1] can be enumerated.

Unsaturated monomer reaction of the reactant [II-2] by making at least part of the carboxyl in the polymer with carboxyl and containing epoxy group obtains.Its result imports (methyl) acryloyl group in resin.

As the unsaturated monomer containing epoxy group, (methyl) glycidyl acrylate can specifically be enumerated, C1~C6 alkyl -2, 3- glycidyl (methyl) acrylate [2- methyl -2, 3- glycidyl (methyl) acrylate, 2- ethyl -2, 3- glycidyl (methyl) acrylate etc.], compound [3 with ester ring oxygroup, 4- epoxycyclohexyl-methyl (methyl) acrylate, 3, 4- epoxycyclohexylethyl (methyl) acrylate, 3, 4- epoxycyclohexyl butyl (methyl) acrylate, 3, 4- epoxycyclohexyl methylamino acrylate etc.] etc., these more than one can be used.

In addition, in order to obtain required acid value, hydroxyl and acid anhydrides in resin can also be made to carry out addition reaction as needed in the modulation of reactant [II-2].As acid anhydrides, phthalic anhydride, two, four or hexahydrophthalic anhydride, maleic anhydride, succinic anhydride etc. can be specifically enumerated, these more than one can be used.

In the reacting of polymer and the unsaturated monomer containing epoxy group with carboxyl, relative to 1 equivalent of carboxyl in polymer, the epoxy group for preferably comprising the unsaturated monomer of epoxy group is 0.1~0.9 equivalent.

In photosensitive heat curing resin combination of the invention, contain diluent as ingredient [III].By containing diluent [III], cross-linking efficiency can be improved, improve heat resistance, the application viscosity of regulation composition.

As diluent [III], organic solvent and/or photopolymerization monomer can be used.In diluent [III], as organic solvent, the ketones such as ethyl methyl ketone, cyclohexanone can be specifically enumerated；Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon；The dihydric alcohols ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene monoethylether, triethylene glycol list ether；The esters such as the carboxylate of ethyl acetate, butyl acetate and the dihydric alcohol ethers；The alcohols such as ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；Petroleum series solvent such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha etc., can be used these more than one.

In diluent [III], as photopolymerization monomer, hydroxyalkyls (methyl) esters of acrylic acid such as 2- ethoxy (methyl) acrylate, 2- hydroxyl butyl (methyl) acrylate can be specifically enumerated；The list or diacrylate esters of the dihydric alcohols such as ethylene glycol, methoxyl group tetraethylene glycol, polyethylene glycol, propylene glycol；(methyl) acrylic amides such as N, N- dimethyl (methyl) acrylamide, N- methylol (methyl) acrylamide；N, N- dimethylaminoethyl (methyl) acrylate etc. aminoalkyls (methyl) esters of acrylic acid；The polyalcohols such as hexylene glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or its etc. ethylene oxide or propylene oxide adduct polynary (methyl) esters of acrylic acid；Phenoxy group (methyl) acrylate, (methyl) acrylate of bisphenol-A two and its etc. phenols ethylene oxide or propylene oxide adduct etc. (methyl) esters of acrylic acid；(methyl) esters of acrylic acid of the glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester；With melamine (methyl) acrylate etc., these more than one can be used.

In photosensitive heat curing resin combination of the invention, contain Photoepolymerizationinitiater initiater as ingredient [IV].As Photoepolymerizationinitiater initiater [IV], it is preferred that the storage-stable of resin combination is good after each components matching, dissolubility is good, and various heat treatment procedures (predrying, heat cure, molding, actual load welding) in do not generate unreacted initiator mist initiator.

As the Photoepolymerizationinitiater initiater [IV], the benzoin class such as benzoin, benzoin benzylic ether, benzoin methylether, benzoin iso-propylether and benzoin alkyl ethers can specifically be used singly or two or more kinds in combination；Acetophenone, 2,2- dimethoxy-2- phenyl acetophenone, 2,2- diethoxy-2- phenyl acetophenone, 1,1- dichloroacetophenone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-(4- methyl mercapto) phenyl)-2- morpholinyl-propane-1- ketone, N, the acetophenones such as N- dimethylamino acetophenone；The Anthraquinones such as 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone, 2- amyl anthraquinone, 2- amino anthraquinones；The thioxanthene ketone class such as 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone；The ketals such as acetophenone dimethyl ketone acetal, benzyl dimethyl ketal；Benzophenone, methyl benzophenone, 4,4 '-dichloro benzophenones, 4, the benzophenones and xanthene ketone etc. such as 4 '-lignocaine benzophenone；And the benzoates such as ethyl 4- dimethylaminobenzoic acid ester, 2- (dimethylamino) ethylamino benzonitrile acid esters；Or the various light sensitizers of the tertiary amines such as triethylamine, triethanolamine.

As from the preferred Photoepolymerizationinitiater initiater of environmental problem, 2 can be enumerated, 4, 6- trimethylbenzoy-dipheny-phosphine oxide, two (2, 4, 6- trimethylbenzoyl)-phenyl phosphine oxide, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1, 2- dimethylamino -2- (4- methylbenzyl) -1-4- morphlinophenyl)-butanone -1, 2, 4- diethyl thioxanthone, 4- benzoyl -4 '-dimethyl diphenyl sulfide, 4- phenyl benzophenone, 2- hydroxyl -1- (4- (4- (2- hydroxy-2-methyl-propiono)-benzyl)-phenyl) -2- methyl-propan -1- ketone, poly- (oxygen (methyl-1, 2- ethane diyl)), α-(4- (dimethylamino) benzoyl-ω-fourth oxygen Base, 9- phenylacridine, 1,7- bis- (9- acridinyl) heptane, 1,5- bis- (9- acridinyl) pentane, 1,3- bis- (9- acridinyl) propane etc., can be used these more than one.

In photosensitive heat curing resin combination of the invention, contain Cristalline epoxy resin shown in following formula (changing V) as ingredient [V].By the way that the polycarboxylic acid resin [I] containing unsaturated group and Cristalline epoxy resin [V] to be used in combination, the film transparency, HAST patience (the HAST patience especially in electrical insulating property) and the thermal shock resistance of resist can be made to embody and improve.In addition, the HAST patience in electrical insulating property can be made to improve significantly by the way that the polycarboxylic acid resin [I] containing unsaturated group, polymer [II] and Cristalline epoxy resin [V] to be used in combination.

(changing V)

In formula (change V), G with it is described synonymous.E₁₁~E₁₃And E₁₅~E₁₇Indicate H or C1~C5 alkyl that can be identical or different.e₁₁And e₁₂Indicate 0~3 integer that can be identical or different.If e₁₁And e₁₂More than 3, crystallinity, storage stability reduce sometimes.

E₁₄Indicate S, O ,-CH₂-、-C(CH₃)₂Or the divalent group that following formula (changing V/X) or (changing F) indicate.

(changing V/X)

(changing F)

In formula (changing V/X), E₂₁~E₂₄Can be identical or different, each independently represent C1~C6 alkyl.

Cristalline epoxy resin [V] preferably fusing point 40~140 (especially 110~135) DEG C, 20 μm of maximum particle diameter or less (especially 0.5~15 μm) of powder body.If fusing point is too low, dry to touch reduces sometimes or storage stability reduces sometimes, if opposite excessively high, sometimes the compatibility of light reactive resin and Cristalline epoxy resin declines, and the transparency of film is deteriorated, or the Physical properties of coating film such as heat resistance, moisture-proof reduce sometimes.If partial size is excessive, flatness, the heat resistance of film reduce sometimes.

Specifically, as Cristalline epoxy resin [V], resin and 2 shown in following formula (changing V/1)~(changing V/9) can be enumerated, 2 '-dimethyl -5,5 '-di-t-butyls -4, the diglycidyl ether of 4 '-dihydroxydiphenyl methane, 1, the diglycidyl ether of 4- bis- (3- methyl -4- hydroxyl cumyl) benzene, 1,4- bis- (3,5- dimethyl -4- hydroxyl cumyl) benzene diglycidyl ether etc., these more than one can be used.Wherein, resin, most preferably resin shown in formula (change V/1) shown in preferred formula (change V/1) and (changing V/6).

(changing V/1)

(changing V/2)

(changing V/3)

(changing V/4)

(changing V/5)

(changing V/6)

(changing V/7)

(changing V/8)

(changing V/9)

In (change V/1)~(changing V/9), G with it is described synonymous.In formula (changing V/8), E₃₁~E₃₄Can be identical or different, each independently represent H or C1~C6 alkyl (methyl, ethyl, isopropyl, tert-butyl etc.).

In photosensitive heat curing resin combination of the invention, contain solidification adhesiveness imparting agent as ingredient [VI].By can further make the characteristics such as adhesiveness, resistance to chemical reagents, heat resistance, moisture-proof improve containing solidification adhesiveness imparting agent [VI].

Specifically, as solidification adhesiveness imparting agent [VI], S- triazines [melamine can be enumerated, ethyl diamino-S- triazine, 2, 4- diamino-S- triazine, 2, 4- diamino -6- tolyl-S- triazine, 2, 4- diamino -6- xylyl-S- triazine etc.], guanamines [guanamines, acetylguanamine, benzoguanamine, 3, [the 2- (3 of 9- bis-, 5- diamino -2, 4, 6- triazine base) ethyl] -2, 4, 8, tetra- oxaspiro [5 of 10-, 5] hendecane etc.], glyoxaline compound [2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2- phenyl -4, 5- bishydroxymethyl imidazoles, isocyanuric acid adduct (four countries' chemical conversion industry of 2-methylimidazole, " 2MZ-OK " etc.), 1 (4, 5- diamino-2- triazine radical)-2- (2- methyl-1-imidazole radicals) ethane (four countries' chemical conversion industry, " 2MZ-AZINE " etc.)], imidazoles alkoxy silane derivative [TMSIM N imidazole methyltrimethoxysilane, N-2- methylimidazole methyltrimethoxysilane, N-2- ethyl imidazol(e) methyltrimethoxysilane, N-2- isopropylimdazole methyltrimethoxysilane, N-2- ethyl -4-methylimidazole methyltrimethoxysilane, N-2- undecyl imidazole methyltrimethoxysilane, N-2- heptadecyl imidazole methyltrimethoxysilane, TMSIM N imidazole methyltriethoxysilane, N-2- methylimidazole ethyl trimethoxy silane, N-2- ethyl imidazol(e) methyltriethoxysilane, N-2- isopropylimdazole methyltriethoxysilane , N-2- ethyl -4-methylimidazole methyltriethoxysilane, N-2- undecyl imidazole methyltriethoxysilane, N-2- heptadecyl imidazole methyltriethoxysilane, 2- (TMSIM N imidazole) ethyl trimethoxy silane, 2- (N-2- methylimidazole) ethyl trimethoxy silane, 2- (N-2- ethyl imidazol(e)) ethyl trimethoxy silane, 2- (N-2- isopropylimdazole) ethyl trimethoxy silane, 2- (N-2- ethyl -4-methylimidazole) ethyl trimethoxy silane, 2- (N-2- undecyl imidazole) ethyl trimethoxy silane, 2- (N-2- heptadecyl imidazole) ethyl trimethoxy silane, 2- (TMSIM N imidazole) ethyl triethoxysilane, 2- (N-2- methylimidazole) ethyl triethoxysilane, 2- (N - 2- ethyl imidazol(e)) ethyl triethoxysilane, 2- (N-2- isopropylimdazole) ethyl triethoxysilane, 2- (N-2- ethyl -4-methylimidazole) ethyl triethoxysilane, 2- (N-2- undecyl imidazole) ethyl triethoxysilane, 2- (N-2- heptadecyl imidazole) ethyl triethoxysilane, 3- (TMSIM N imidazole) propyl trimethoxy silicane, 3- (N-2- methylimidazole) propyl trimethoxy silicane, 3- (N-2- ethyl imidazol(e)) propyl trimethoxy silicane, 3- (N-2- isopropylimdazole) propyl trimethoxy silicane, 3- (N-2- ethyl -4-methylimidazole) propyl trimethoxy silicane, 3- (N-2- undecyl imidazole) propyl trimethoxy silicane, 3- (N-2- heptadecyl imidazole) third Base trimethoxy silane, 3- (TMSIM N imidazole) propyl-triethoxysilicane, 3- (N-2- methylimidazole) propyl-triethoxysilicane, 3- (N-2- ethyl imidazol(e)) propyl-triethoxysilicane, 3- (N-2- isopropylimdazole) propyl-triethoxysilicane, 3- (N-2- ethyl -4-methylimidazole) propyl-triethoxysilicane, 3- (N-2- undecyl imidazole) propyl-triethoxysilicane, 3- (N-2- heptadecyl imidazole) propyl-triethoxysilicane etc.], season imidazolium derivative [1- ethyl-3-methylimidazole trifluoromethyl sulfate, N- methyl-N '-butylimidazolium hexafluorophosphate, (anion is from two (trifluoromethyl sulfonyl) imidic acids to N- alkyl-N '-alkoxyalkyl imidazole salts, perchloric acid, tetrafluoro boron Acid, hexafluorophosphoric acid, three (trifluoromethyl sulfonyl) carbonic acid, trifluoromethanesulfonic acid, chosen in trifluoroacetic acid or organic carboxyl acid or halide ion at least one kind of) etc.], diaminodiphenyl-methane, m-phenylene diamine (MPD), diamino diphenyl sulfone, cyclohexylamine, m-xylene diamine, 4, 4 '-diamino -3, 3 '-diethyl diphenyl methanes, diethylenetriamines, tetren, N- aminoethyl piperazine, isophorone diamine, dicyandiamide, urea class [urea itself etc.], polyamines class [polynary hydrazides etc.], these equal acylates and/or epoxy adduct, the amine complex of boron trifluoride, tertiary amines [trimethylamine, triethanolamine, N, N- dimethyl octylame, N, accelerine, N- benzyl dimethylamine, pyridine, N- picoline, N-methylmorpholine, hexamethoxy methyl cyanuramide, 2, 4, 6- tri- (Dimethylaminophenol), N- cyclohexyldimethylamine, tetramethylguanidine, m-aminophenol etc.], organic phosphine [tributylphosphine, triphenylphosphine, three -2- cyanoethyl phosphines etc.], phosphonium salt class [three normal-butyls (2, 5- dihydroxyphenyl) phosphonium bromide, phosphonium hexadecanyl-3-butyl chloride etc.], quaternary ammonium salt [benzyltrimethylammonium chloride, phenyl tributyl ammonium chloride, benzyltrimethylammonium bromide etc.], tetrafluoro boric acid diphenyl iodine, hexafluoro-antimonic acid triphenylsulfonium, 2, 4, 6- triphenyl thiopyridine hexafluorophosphate, light cationic polymerization catalyst, styrene-maleic acid resin, silane coupling agent etc., these more than one can be used.

To solidify adhesiveness imparting agent [VI], when using imidazoles alkoxy silane derivative and/or season imidazolium derivative, the adhesiveness that resist may be implemented, which improves, and can make resistance to gold-plated attribute, welding rod heat resistance, moisture-proof, peel strength etc., to be improved.

As solidification adhesiveness imparting agent [VI], it is preferred that dicyandiamide, S- pyrrolotriazine derivatives [specially melamine, ethyl diamino-S- triazine, 2,4- diamino-S- triazine etc.], imidazoles alkoxy silane derivative [specially TMSIM N imidazole methyltrimethoxysilane, 3- (N-2- methylimidazole) propyl trimethoxy silicane etc.], season imidazolium derivative [1- ethyl-3-methylimidazole trifluoromethyl sulfate, N- methyl-N '-butylimidazolium hexafluorophosphate, N- alkyl-N '-alkoxyalkyl imidazoles phthalate] etc..

In photosensitive heat curing resin combination of the invention, preferably also contain thermosetting component.As thermosetting component, such as [VII-1] can be enumerated: the Cristalline epoxy resin (but not including Cristalline epoxy resin [V]) that 135~170 DEG C of fusing point.By using Cristalline epoxy resin [VII-1], storage stability can further be made to stablize.

Cristalline epoxy resin [VII-1] is preferably with 135~170 DEG C of fusing point, preferably 140~170 DEG C, 20 μm of maximum particle diameter or less (especially 0.5~15 μm) of powder body.If fusing point is less than 135 DEG C, storage stability reduces sometimes, opposite if it exceeds 170 DEG C, sometimes results in the reduction of compatibility, the film transparency and heat resistance of resin etc..

As Cristalline epoxy resin [VII-1], the resin as shown in following formula (changing VII-1/1), (changing VII-1/2) and (changing VII-1/3) respectively can be specifically enumerated, these more than one can be used.

(changing VII-1/1)

(changing VII-1/2)

(changing VII-1/3)

In formula (change VII-1/1)~(changing VII-1/3), G with it is described synonymous.In formula (changing VII-1/1), g₁₁Indicate 0~2 number.If g₁₁It is excessive, then do not show crystallinity, result storage stability reduces sometimes.

As other thermosetting components, can enumerate [VII-2]: following formula (changes single poly- carbodiimide (single carbon diimine and/or poly- carbodiimide) shown in VII-2.By that hydrolytic resistance and cold-resistant thermal impact can be made to improve containing single poly- carbodiimide [VII-2].

(changing VII-2)

In formula (changing VII-2), G₂₁And G₂₃Each independently represent the aromatic residue, aliphatic residue or ester ring type residue of 1 valence.G₂₂Indicate aromatic residue, aliphatic residue or the ester ring type residue of divalent.g₂₁Indicate the number of 0~30 (preferably 2~15).

In G₂₁And G₂₃In, as the aromatic residue of 1 valence, phenyl, tolyl, o-tolyl, 3,5- xylyl, naphthalene etc. can be enumerated, as aliphatic residue, cyclohexyl, butyl etc. can be enumerated.

In G₂₂In, aromatic residue as divalent, 4 can be enumerated, the suitable group of the divalent of 4 '-diphenyl methanes, to phenylene, 4, the suitable group of the divalent of 4 '-diphenyl ether, 3,3 '-dimethoxy-4 's, the suitable group of the divalent of 4 '-biphenyl, naphthylene etc., as aliphatic residue, 1 can be enumerated, 6- hexylidene, 2,2,4- trimethyls -1,6- hexylidene, 4,4 '-two cyclohexylidenes, xylylene, tetramethyl xylylen, isophorone the suitable group of divalent, the suitable group of divalent of cyclohexylidene, lysine, suitable group of the divalent of hexahydrotoluene etc..

Poly- carbodiimide [VII-2] for example by the way that polymerizable monomer is polymerize after, with end-capping reagent by the polymerizable end sealing end be modulated.

In the modulation of poly- carbodiimide [VII-2], as the polymerizable monomer of brewable material, organic diisocyanate shown in following formula (changing VII-2/D1) and (changing VII-2/D2) can be enumerated, these more than one can be used.

(changing VII-2/D1)

(changing VII-2/D2)

In formula (changing VII-2/D1), G₃₁Indicate C1~C6 alkyl, halogen atom etc..In formula (changing VII-2/D2), G₄₁And G₄₃Each independently represent 1 valence group (such as C1~C6 alkyl, halogen atom etc.).G₄₂It indicates divalent group (such as C1~C6 alkylidene, phenylene, naphthylene ,-O- ,-S- ,-Si- etc.).g₄₁Indicate 0~6 number.If g₄₁More than 6, heat resistance declines sometimes.

Specifically, as organic diisocyanate (changing VII-2/D1) and (changing VII-2/D2), p- phenylene diisocyanate can be enumerated, 2, 4- toluene di-isocyanate(TDI), 2, 6- toluene di-isocyanate(TDI), 1- anisyl -2, 4- diisocyanate, 4, 4 '-methyl diphenylene diisocyanates, 4, 4 '-diphenyl ether diisocyanates, 3, 3 '-dimethyl -4, 4 '-diphenyl ether diisocyanates, ortho-tolidine diisocyanate, 3, 3 '-dimethoxy-4 's, 4 '-biphenyl diisocyanates etc., these any or two or more (such as 4 can be used, 4 '-methyl diphenylene diisocyanates and the mixture of toluene di-isocyanate(TDI) etc.).

In the modulation of poly- carbodiimide [VII-2], as end-capping reagent, organic single-isocyanate [phenyl isocyanate, isocyanic acid (o-, m-, to) toluene ester, isocyanic acid dimethyl phenyl ester, NSC 87419, methyl isocyanate, isocyanic acid chlorobenzene ester, isocyanic acid trifluoromethyl phenyl ester, naphthyl isocyanate etc.] can be enumerated, these more than one can be used.

In the modulation of poly- carbodiimide [VII-2], polymerization can be homopolymerization or copolymerization, can carry out as described below.I.e., in polymer solvent [tetrachloro-ethylene etc.], under inert atmosphere [nitrogen etc.], as needed in the presence of carbodiimidization catalyst [3- methyl-1-phenyl-2- phosphorane-1- oxide etc.], to organic diisocyanate [4 at 120~200 DEG C, 4 '-methyl diphenylene diisocyanates and the mixture of toluene di-isocyanate(TDI) etc.] and end-capping reagent [phenyl isocyanate etc.] heating stirring, carry out the condensation reaction with carbon dioxide removal, available poly- carbodiimide.

From viewpoints such as the storage stability of resin combination, HAST patience, single poly- carbodiimide [VII-2] preferably softening point 100~150 (especially 105~140) DEG C, 20 μm of maximum particle diameter or less (especially 1~15 μm) of powder body.If softening point is too low, can cause to deteriorate sometimes with the addition reaction of the polycarboxylic acid resin [I] containing unsaturated group, the storage stabilities such as storage stability of resin combination at low temperature sometimes.If partial size is excessive, the flatness of film declines sometimes, since generation of pinprick etc. reduces heat resistance sometimes.

As other thermosetting components, [VII-3] can be enumerated: the compound containing allyl.By containing the compound of [VII-3] containing allyl, the solidification physical property such as heat resistance, resistance to chemical reagents can be made to improve.

As the compound [VII-3] containing allyl, the prepolymer containing allyl can be enumerated.

In the compound [VII-3] containing allyl, the preferred average molecular weight 400~30000 of the prepolymer containing allyl, particularly preferred 1000~20000.If average molecular weight, less than 400, dry to touch, heat resistance reduce sometimes, opposite if it exceeds 30000, the viscosity of resin increases and is difficult to handle, and the compatibility of resin declines sometimes.

In the compound [VII-3] containing allyl, as the prepolymer containing allyl, the diallyl phthalate prepolymer that triallyl isocyanurate prepolymer and repetitive unit following formula (changing VII-3/U1) indicate and the diallyl isophthalate prepolymer etc. that following formula (changing VII-3/U2) indicates can be specifically enumerated, these more than one can be used.

(changing VII-3/U1)

(changing VII-3/U2)

In formula (changing VII-3/U1), g₅₁Indicate 2~50 integer.In formula (changing VII-3/U2), g₆₁Indicate 2~50 integer.If g₅₁Or g₆₁Too small, dry to touch, heat resistance reduce sometimes, if opposite excessive, the viscosity of resin can be increased, and processing becomes difficult, and the compatibility of resin declines sometimes.

Contain the compound [VII-3] of allyl as other, triallyl isocyanurate, triallyl cyanurate, three methallyl of isocyanuric acid etc. can be specifically enumerated, these more than one (hereinafter sometimes referred to " (different) cyanurate three (first generation) allyl esters ") can be used.

In addition, containing the compound [VII-3] of allyl as other, diallyl 3 shown in following formula (changing VII-3/1), 6- methylene tetrahydric phthalimide compound etc. can be enumerated.

(changing VII-3/1)

In formula (changing VII-3/1), G₇₁Indicate divalent group shown in following formula (changing VII-3/1-R1), (changing VII-3/1-R2) or (changing VII-3/1-R3).

(changing VII-3/1-R1)

(changing VII-3/1-R2)

(changing VII-3/1-R3)

In formula (changing VII-3/1-R3), g₈₁Indicate 4~8 integer.If g₈₁Too small, processing becomes difficult sometimes, if opposite excessive, heat resistance declines sometimes.

As the compound [VII-3] containing allyl, can be used the prepolymer containing allyl, (different) cyanurate three (first generation) allyl ester and diallyl 3,6- methylene tetrahydric phthalimide compound (VII-3/1) more than one.These compounds carry out thermal response at high temperature, but the influence to the storage stability of resin combination, developability is few, and can make the heat resistance of cured film, welding rod heat resistance etc. and improve.

As other thermosetting components, [VII-4] can be enumerated: the compound etc. containing oxazoline group.From the viewpoint of the storage stability of resin combination, HAST patience, the compound [VII-4] containing oxazoline group preferably softening point 100~150 (especially 110~140) DEG C, 20 μm of maximum particle diameter or less (especially 0.5~15 μm) of powder body.Compound [VII-4] containing oxazoline group if softening point it is too low, it can cause to deteriorate sometimes with the addition reaction of the polycarboxylic acid resin [I] containing unsaturated group, the storage stabilities such as storage stability of resin combination at low temperature sometimes.If partial size is excessive, the flatness of film declines sometimes, since generation of pinprick etc. reduces heat resistance sometimes.By containing the compound of [VII-4] containing oxazoline group, can make to improve with the compatibility of resin, and improve adhesiveness.

In thermosetting component, as the compound [VII-4] containing oxazoline group, 2,2- (1,3- phenylene), two -2- oxazoline and polymer containing oxazoline group etc. can be specifically enumerated, these more than one can be used.

In the compound [VII-4] containing oxazoline group, the preferred average molecular weight of the polymer containing oxazoline group is 1000~10000.If average molecular weight is too small, dry to touch, heat resistance reduce sometimes, if opposite excessive, the viscosity of resin can be increased, and processing becomes difficult, and the compatibility of resin declines sometimes.

As the polymer containing oxazoline group, can enumerate has polymer of the oxazoline group as side group on polymer chain, it is specifically included in the polymer etc. in a part of the copoly types such as acrylic resin, styrene/acrylic resin, polystyrene with side group, these more than one can be used.

In photosensitive heat curing resin combination of the invention, can be used the thermosetting component [VII-1]~[VII-4] more than one.

In addition, in photosensitive heat curing resin combination of the invention, silane coupling agent, organic/inorganic alkoxysilane polymer, defoaming agent, colorant (dyestuff, pigment, inorganic), filler etc. can be optionally added as adding ingredient.

In the composition of photosensitive heat curing resin combination of the invention, relative to 100 parts by weight of polycarboxylic acid resin [I] containing unsaturated group, polymer [II] preferably 0~60 (especially 2~40) parts by weight.If polymer [II] is very few, sometimes referred to as touching drying property can be deteriorated, and the developability of envelope can be deteriorated, if opposite excessive, reduce sometimes with the compatibility of resin, adhesiveness can be deteriorated.

In the composition of photosensitive heat curing resin combination of the invention, relative to 100 parts by weight of polycarboxylic acid resin [I] containing unsaturated group, diluent [III] preferably 10~300 (especially 30~200) parts by weight.If diluent [III] is very few, coating can deteriorate and be difficult to be coated with sometimes, and optical polymerism can reduce, if opposite excessive, dry to touch, resolution reduce sometimes.

In the composition of photosensitive heat curing resin combination of the invention, relative to 100 parts by weight of polycarboxylic acid resin [I] containing unsaturated group, Photoepolymerizationinitiater initiater (IV) preferably 0.5~40 (especially 2~30) parts by weight.

In the composition of photosensitive heat curing resin combination of the invention, relative to 100 parts by weight of polycarboxylic acid resin [I] containing unsaturated group, Cristalline epoxy resin [V] preferably 1~100 (especially 4~70) parts by weight.If very few, the Physical properties of coating film such as heat resistance, resistance to chemical reagents, adhesiveness, moisture-proof reduce Cristalline epoxy resin [V] sometimes, if opposite excessive, alkali-developable declines sometimes.

In the composition of photosensitive heat curing resin combination of the invention, relative to 100 parts by weight of polycarboxylic acid resin [I] containing unsaturated group, solidify adhesiveness imparting agent [VI] preferably 0.1~20 (especially 0.5~10) parts by weight.If solidified, adhesiveness imparting agent [VI] is very few, and adhesiveness, resistance to gold-plated attribute reduce sometimes, if opposite excessive, storage stability declines sometimes.

In the composition of photosensitive heat curing resin combination of the invention, relative to 100 parts by weight of polycarboxylic acid resin [I] containing unsaturated group, Cristalline epoxy resin [VII-1] preferably 0.1~50 (especially 2~40) parts by weight, single poly- carbodiimide [VII-2] preferably 0.1~50 (especially 2~40) parts by weight, compound [VII-3] preferably 0.1~50 (especially 2~30) parts by weight containing allyl, compound [VII-4] preferably 0.1~50 (especially 2~30) parts by weight containing oxazoline group.

But, Cristalline epoxy resin [V] and the thermosetting component [VII-1]~[VII-4] total amount (i.e. [V]+[VII-1]+[VII-2]+[VII-3]+[VII-4]) are relative to 100 parts by weight of polycarboxylic acid resin [I] containing unsaturated group, preferably 2~100 (especially 5~80) parts by weight.

If the thermosetting component is very few, the Physical properties of coating film such as heat resistance, resistance to chemical reagents, adhesiveness, moisture-proof reduce sometimes, if opposite excessive, alkali-developable, storage stability decline sometimes.

In addition, relative to 100 parts by weight of Cristalline epoxy resin [V], Cristalline epoxy resin [VII-1] preferably 0~200 (especially 5~150) parts by weight.[VII-1] relative to Cristalline epoxy resin [V] if excessive, the transparency of film declines sometimes.

Photosensitive heat curing resin combination of the invention usually has acid value 40~120.If acid value is too low, alkali-developable reduces sometimes, if opposite excessively high, the moisture-proof of film reduces sometimes.

As described above, it can modulate excellent suitable for the transparency of storage stability, pre-dried thermal stability, dry to touch, the developability aqueous alkali, photonasty and cured film, adhesiveness, electrical insulating property, welding rod thermal shock resistance, resistance to chemical reagents, resistance to gold-plated attribute, resistance to bend(ing), long-term reliability (resistance to migration, HAST patience), be not easy vapour discharge and take into account the photosensitive heat curing resin combination of the invention of the solder resist of environment.The photosensitive heat curing resin combination of the invention is particularly useful with print material, such as the photic solder mask ink of alkali developable liquid, alkali developable dry film solder resist etc. for various resists (solder resist, interlayer dielectic etc.).

It is illustrated below to the resist obtained by the photosensitive heat curing resin combination of the invention is coated to the printing distributing board coated with resist obtained on the surface of printing distributing board.As printing distributing board, preferably smoothing printing distributing board.As smoothing printing distributing board, the smoothing printing distributing board of printing distributing board smooth surface is filled and made to the through-hole section of particularly preferred printing distributing board, the recess portion resin of printed wiring plate surface.Certainly other any printing distributing boards [such as there is concave-convex previous printing distributing board (hereinafter sometimes referred to " embossing distributing board ") etc. in printed wiring plate surface] also can be used in the present invention, the printing distributing board coated with resist being achieved in that also belongs to technology scope of the invention.

It as " recess portion ", is not particularly limited, the recess portion that can enumerate such as the recess portion of recess portion, through-hole between the circuit in wiring plate surface and fill part.

The resin for filling of recess portion as printed wiring plate surface, it is preferred that the compositions of thermosetting resin recorded in for example described patent document 7, but other thermosetting resins also can be used in the present invention, any printing distributing board coated with resist obtained in this way also belongs to technical scope of the invention.

The smoothing printing distributing board is obtained using the method recorded in for example described patent document 7.That is, being first applied to compositions of thermosetting resin on the recess portion of printed wiring plate surface, one-step solidification is carried out at low temperature, carries out surface grinding, carries out secondary curing at high temperature then to manufacture smoothing printing distributing board.

The manufacturing method that printing distributing board is smoothed when being below the recess portion between the circuit in wiring plate surface with regard to " recess portion ", is illustrated using attached drawing.Firstly, to recess portion 3 (Fig. 2) filling formed between the conductor circuit on the printing distributing board being made of insulating substrate 5 (Fig. 2) and conductor circuit 6 (Fig. 2), being coated with compositions of thermosetting resin.

As compositions of thermosetting resin, the composition recorded in the preferably described patent document 7.That is, preferably comprise the addition product of [A] epoxy resin and unsaturated fatty acid, [B] (methyl) esters of acrylic acid, [C] radical polymerization initiator, [D] Cristalline epoxy resin and [E] potentiality curing agent compositions of thermosetting resin.

As ingredient [A], specifically, it is preferred that addition product is [specifically for 20~80% (especially 40~60%) of novolac epoxy resin and (methyl) acrylic acid, cresol-novolac epoxy resin and 20~80% (especially 40~60%) addition products of acrylic acid etc.], bisphenol A type epoxy resin and 20~80% (especially 40~60%) addition products of (methyl) acrylic acid etc., can be containing these more than one in thermoset composition.

As ingredient [B], in particular, it is preferred that the hydroxyalkyl acrylates class such as acrylic acid 2- hydroxy methacrylate, acrylic acid 2- hydroxybutyl；The list or diacrylate esters of the dihydric alcohols such as ethylene glycol, methoxyl group tetraethylene glycol, polyethylene glycol, propylene glycol；The acrylic amides such as N,N-DMAA, N hydroxymethyl acrylamide；The acrylates class such as N, N- dimethylamino ethyl acrylate；The polyalcohols such as hexylene glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or its etc. ethylene oxide or propylene oxide adduct multicomponent methacrylate class；Acrylic acid benzene oxygen ester, bisphenol a diacrylate and its etc. phenols ethylene oxide or propylene oxide adduct etc. esters of acrylic acid；The esters of acrylic acid of the glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl isocyanurate；It, can be containing these a kind or more in thermoset composition with melamine acrylate, isobornyl acrylate, two ring pentyl ester of methacrylic acid, and/or methyl acrylic ester corresponding with the esters of acrylic acid etc..

It, can be containing these a kind or more in thermoset composition in particular, it is preferred that t-butyl peroxybenzoate, peroxide-the 2 ethyl hexanoic acid tert-butyl ester, dicumyl peroxide etc. as ingredient [C].

As ingredient [D], in particular, it is preferred that Japanese chemical drug corporation makes the bisphenol-s epoxy resins such as mono- シ of BPS-200, エ, mono- ア, mono- Le company manufacture EPX-30, big Japanese ink chemical industrial company manufacture エ ピ Network ロ Application EXA-1514；Nof Corp. manufactures the o-phthalic acid diglycidyl esters resins such as mono- DGT of Block レ Application マ；Nissan Chemical company manufactures the heterocyclic epoxy resins such as TEPIC, mono- ガ イ ギ of チ バ, mono- company manufacture ア ラ Le ダ イ ト PT810；Oiling シ エ Le company manufactures the union IIs toluene phenol-type epoxy resins such as YX-4000；Oiling シ エ Le company manufactures the bisphenol-type epoxy resins such as YL-6056；Dongdu is melted into company's manufacture four glycidyl groups dimethylbenzene acyl group ethane resin such as ZX-1063 etc., can be containing these a kind or more in thermoset composition.

As ingredient [E], preferably such as dicyandiamide (DICY) class, imidazoles, BF₃Amine complex, amine add-on type curing agent, amine-acid anhydrides (polyamide) add-on type curing agent, hydrazides system curing agent, the carboxylate of amine system curing agent, salt etc., can be containing these a kind or more in thermoset composition.

In the composition of the compositions of thermosetting resin, relative to 100 parts by weight of ingredient [A], ingredient [B] preferably 50~300 parts by weight (especially 150~250 parts by weight), ingredient [C] preferably 5~20 parts by weight (especially 8~15 parts by weight), ingredient [D] preferably 50~200 parts by weight (especially 60~120 parts by weight), ingredient [E] preferably 5~30 parts by weight (especially 10~20 parts by weight).

As the coating method of the compositions of thermosetting resin, can enumerate such as screen printing method, rolling method.

Then, one-step solidification is carried out at low temperature.So-called " low temperature " refers to the temperature lower than aftermentioned secondary curing temperature.Specifically, can be such as 100~150 DEG C as one-step solidification temperature.

Then, carrying out grinding to the surface of the one-step solidification film containing the formation keeps it smooth.As grinding method, mechanical lapping (abrasive band polishing grinding, sandblasting, brushes grinding etc. at emery wheel grinding), chemical grinding (grinding using persulfate, hydrogen peroxide-sulfuric acid mixture, inorganic-organic acid etc. etc.) etc. can be enumerated.

Then, secondary curing is carried out at high temperature.So-called " high temperature " refers to the temperature higher than the one-step solidification temperature.It can be such as 150~200 DEG C as secondary curing temperature.

The recess portion between the circuit in wiring plate surface is filled using the solidified resin 4 (Fig. 3) of the compositions of thermosetting resin in this way, to obtain the smoothing printing distributing board (Fig. 3) of smooth surface.

Then, resist 1 (Fig. 1) is coated on the smooth surface of the smoothing printing distributing board obtained as described above.As coating method, the method for example using liquid photosensitive resist agent can be enumerated.Specifically, firstly, liquid photosensitive resist agent is applied on the smooth surface of the smoothing printing distributing board.Then, after selectively using active ray to expose by being formed with the photomask of predetermined pattern, make unexposed portion development to forming corrosion-resisting pattern with developer solution.Then, the heat curable component heat cure is made by heating, the smoothing printing distributing board coated with resist of the invention can be manufactured.

As liquid photosensitive resist agent, contain photosensitive heat curing resin combination of the invention.In addition it is possible to use organic solvent [the ketones such as ethyl methyl ketone, cyclohexanone；Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon；The dihydric alcohols ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene monoethylether, triethylene glycol list ether；The esters such as the acetate compound of ethyl acetate, butyl acetate and the dihydric alcohol ethers；The alcohols such as ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；Petroleum series solvent such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha etc.], known usual inorganic filler, furthermore can contain known usual additive kind as the adhesiveness imparting agent such as known usual colorant, known usual heat polymerization inhibitors, known usual tackifier, defoaming agent, silane coupling agent etc..

Coating can be carried out using such as screen printing, curtain coating, print roll coating, spraying.

As active ray, ultraviolet light (300~450nm etc.) can be enumerated.Exposure can be carried out using such as Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, arc lamp, xenon lamp.In addition it is also possible to be exposed by excimer laser, X-ray, the electron ray etc. except irradiation ultraviolet light.

As developer solution, lithium can be enumerated, sodium, the hydroxide of the alkali metal such as potassium, carbonate, bicarbonate, phosphate, pyrophosphate, benzylamine, butylamine, the primary amine such as monoethanolamine, dimethylamine, dibenzylamine, the secondary amine such as diethanol amine, trimethylamine, triethylamine, the tertiary amines such as triethanolamine, morpholine, piperazine, the cyclic amines such as pyridine, ethylenediamine, the polyamines such as hexamethylene diamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium, benzyltrimethyl ammonium hydroxide, the ammonium hydroxide classes such as hydroxide phenylbenzyl ammonium, hydroxide sulfonium, hydroxide diethylmethyl sulfonium, the sulfonium hydroxides classes such as dimethyl benzyl sulfonium, and choline, buffer etc. containing silicate.

In addition, alcohols solvent (butyl cellosolve, butyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propyl alcohol, propylene glycol), surfactant (amphoteric surfactant, nonionic surfactant etc.) also can be used as needed.

Heat cure can carry out 0.1~3 hour at such as 120~180 DEG C.

As other coating methods, the method for example using dry film photoresist can be enumerated.As dry film photoresist, the dry film photoresist being at least made of carrier film, photoresist (photosensitive layer) and protective film can be enumerated.

As carrier film, synthetic resin films such as polyester film, polyethylene terephthalate film, poly (ethylene naphthalate) film, polyethylene, polypropylene, polycarbonate, polyvinyl chloride etc. can be specifically enumerated.

Photoresist can be by the way that photosensitive heat curing resin combination of the invention to be diluted in the organic solvents such as ethyl acetate, methyl ethyl ketone, and being coated using applicator, metering bar coater, roll coater, curtain coater, flow coater etc. is made dry film thickness reach 10~100 μm and formed.Furthermore, known usual inorganic filler can be used in photoresist, furthermore can contain known usual additive kind as the adhesiveness imparting agents such as known usual colorant, known usual heat polymerization inhibitors, known usual tackifier, defoaming agent, silane coupling agent etc..In addition, photoresist can make two or more difference stratification of photosensitive heat curing resin combination of the invention, become 2 layers or more of multilayered structure.

As protective film, synthetic resin films such as polyethylene film, polypropylene, polyvinyl chloride etc. can be specifically enumerated.

In addition, can have water-soluble resin layer, antistatic layer etc. in dry film photoresist as needed.

It, can be easily by carrier film stripping by the way that water-soluble resin layer is arranged.In water-soluble resin layer, as water-soluble resin, it can enumerate from the cellulose derivatives such as natural starch, gelatin, semi-synthetic carboxymethyl cellulose (CMC), methylcellulose (MC), the synthetic water soluble polymers such as polyvinyl alcohol (PVA), partly-hydrolysed polyvinyl alcohol resin, polyacrylic polymer, polyacrylamide (PAM), polyethylene oxide (PEO) etc..

As antistatic layer, it can specifically enumerate and vapour deposition method or sputtering method is used to form the layer of metal or metal oxide, at least using the acrylic ester containing quaternary ammonium base as the transparent conductivity polymeric layer of monomer component or aniline system conductive polymer layer etc..

Furthermore, more than one of the conductive materials such as lewis acid, carbon, metal particle, metal oxide and/or cationic, anionic and amphoteric surfactant etc. can be added in carrier film and/or antistatic layer or form it, to assign anti-static function.

As antistatic layer or anti-static function, it is contemplated that electrostatic obstacle when manufacture is led to the problem of, surface intrinsic resistance value preferably 10¹¹(especially 10⁹)Ω/cm²Below.

As dry film photoresist, in particular, it is preferred that the structure that antistatic layer shown in Fig. 47, carrier film 8, water-soluble resin layer 9, photoresist 2 and protective film 10 are laminated in order.

The dry film photoresist is laminated on the smooth surface of the smoothing printing distributing board.At this point, film stripping will be protected using dry film-laminating machine is equilateral, while dry film photoresist is laminated on smooth surface.

In this application, when using previous embossing distributing board as printing distributing board, in order to avoid the bad generation etc. with bubble of lamination that concave-convex influence generates, and for the smoothing etc. of wiring plate surface, preferably it is laminated with vacuum furnace laminating machine, vacuum compacting laminating machine etc..

On the other hand, in this application, when using smoothing printing distributing board as printing distributing board, even if being handled using normal pressure laminating machine dry film photoresist, generation bad, bubble for the lamination and smoothing etc. also can manufacture without problems.It can be such as preheating: 60~70 DEG C, roll temperature: 80~110 DEG C, roller speed: 0.5~2.0m/ points, roller pressure: 2 × 10 as normal pressure lamination⁵Pa(2kgf/cm²) more than.

Furthermore, it is possible to which the liquid photosensitive resist agent is further arranged between smooth surface and dry film.

Then, identical as described in the liquid photosensitive resist agent, after the photomask by being formed with predetermined pattern selectively uses active ray to expose, make unexposed portion development to form corrosion-resisting pattern with developer solution.Then, the heat curable component heat cure is made by heating, the smoothing printing distributing board coated with resist of the invention can be manufactured.

The film thickness of the resist being made of photosensitive heat curing resin combination of the invention obtained as described above can be 7~35 μm.

The resist being made of photosensitive heat curing resin combination of the invention, developability, dry to touch, resistance to bend(ing), adhesiveness, the film transparency, HAST patience (the HAST patience especially in electrical insulating property) and thermal shock resistance etc. are excellent.Furthermore, by the way that the resist being made of photosensitive heat curing resin combination of the invention is coated on smoothing printing distributing board, underfill (underfill) can also be obtained to be not easy to be impregnated with, it is not likely to produce dislocation, it is not likely to produce the effect of cracking, so as to various when solving the problems, such as actual installation.

The present invention is specifically described below.

Embodiment

<synthesis of epoxy resin (changing I/E)>

Synthesis example 1: the synthesis of epoxy resin (changing I/E-1-1)

By raw materials bisphenol A type epoxy resin [h shown in following formula₁₁Average value (i.e. average degree of polymerization) 3.3, epoxide equivalent 650,81.1 DEG C of softening point, melt viscosity (150 DEG C) 12.5 moor] 462.5 parts by weight uniform dissolution of 371 parts by weight, 925 parts by weight of epichlorohydrin and dimethyl sulfoxide.Then, the NaOH of 52.8 parts by weight 98.5% was added in the uniform dissolution object with 100 minutes under stiring, at 70 DEG C.

[in formula, h₁₁Indicate the degree of polymerization].

After addition, then reaction in 3 hours is carried out at 70 DEG C.Then, the more than half of superfluous unreacted epichlorohydrin and dimethyl sulfoxide being distilled under reduced pressure.Then, after being dissolved into the reaction product containing secondary raw salt and dimethyl sulfoxide in 750 parts by weight of methyl iso-butyl ketone (MIBK), 10 parts by weight of 30%NaOH aqueous solution is added, are reacted 1 hour at 70 DEG C.

After reaction, 2 washings are carried out with 200 parts by weight of water.It is distilled to recover methyl iso-butyl ketone (MIBK) from oil reservoir after water-oil separating, obtains 340 parts by weight of epoxy resin (synthesis example 1) shown in formula (changing I/E-1-1).

The epoxy resin (synthesis example 1) is epoxide equivalent 287,64.2 DEG C of softening point, the pool of melt viscosity (150 DEG C) 7.1.In addition, if being calculated by epoxide equivalent, it can be determined that the epoxy resin (synthesis example 1) is that have about 3.1 resins being at least partially epoxidized in the bisphenol A type epoxy resin of the raw material in alcohol hydroxyl group 3.3.

Synthesis example 2: the synthesis of epoxy resin (changing I/E-1-2)

By raw materials bisphenol F type curable type epoxy resin [h shown in following formula₂₁Average value 5.8, epoxide equivalent 800,79 DEG C of softening point] 462.5 parts by weight uniform dissolution of 400 parts by weight, 925 parts by weight of epichlorohydrin and dimethyl sulfoxide.Then, the NaOH of 81.2 parts by weight 98.5% was added in the uniform dissolution object with 100 minutes under stiring, at 70 DEG C.

[in formula, h₂₁Indicate the degree of polymerization].

After addition, then reaction in 3 hours is carried out at 70 DEG C.Then, the more than half of superfluous unreacted epichlorohydrin and dimethyl sulfoxide being distilled under reduced pressure.Then, after being dissolved into the reaction product containing secondary raw salt and dimethyl sulfoxide in 750 parts by weight of methyl iso-butyl ketone (MIBK), 10 parts by weight of 30%NaOH aqueous solution is added, are reacted 1 hour at 70 DEG C.

After reaction, 2 washings are carried out with 200 parts by weight of water.It is distilled to recover methyl iso-butyl ketone (MIBK) from oil reservoir after water-oil separating, obtains 370 parts by weight of epoxy resin (synthesis example 2) shown in formula (changing I/E-1-2).

The epoxy resin (synthesis example 2) is epoxide equivalent 290,62 DEG C of softening point.In addition, if being calculated by epoxide equivalent, it can be determined that the epoxy resin (synthesis example 2) is that have about 5.2 resins being at least partially epoxidized in the bisphenol-f type curable type epoxy resin of raw material in alcohol hydroxyl group 5.8.

Synthesis example 3: the synthesis of epoxy resin (changing I/E-2-1)

It is packed into 4,4 '-dihydroxydiphenyl methane, 96 parts by weight and bisphenol A-type liquid epoxy resin [Dongdu is melted into company manufacture " YD-128 ", epoxide equivalent 186g/eq] 332 parts by weight in flask, melting mixing is carried out at 150 DEG C.The molar ratio of phenolic hydroxyl group and epoxy group at this time is 0.53: 1.

Then, 0.084 parts by weight of triphenyl phasphine are added, continue stirring 4 hours at 150 DEG C, complete addition reaction, obtain raw materials bisphenol A/F shown in following formula and with type epoxy resin [h₃₁Average value 1.6, epoxide equivalent 600].

[in formula, h₃₁Indicate the degree of polymerization].

Then, by raw materials bisphenol A/F and with after the dissolution of 308 parts by weight of type epoxy resin, 925 parts by weight of epichlorohydrin and 462.5 parts by weight of dimethyl sulfoxide, the NaOH of 52.8 parts by weight 98.5% was added with 100 minutes under stiring, at 70 DEG C.After addition, then reaction in 3 hours is carried out at 70 DEG C.

Then, the more than half of superfluous unreacted epichlorohydrin and dimethyl sulfoxide being distilled under reduced pressure.Then, it is dissolved into the reaction product containing secondary raw salt and dimethyl sulfoxide in 750 parts by weight of methyl iso-butyl ketone (MIBK), adds 10 parts by weight of 30%NaOH aqueous solution, reacted 1 hour at 70 DEG C.

After reaction, 2 washings are carried out with 200 parts by weight of water.It is distilled to recover methyl iso-butyl ketone (MIBK) from oil reservoir after water-oil separating, obtains 312 parts by weight of epoxy resin (synthesis example 3) shown in formula (changing I/E-2-1).

The epoxy resin (synthesis example 3) is epoxide equivalent 290,64 DEG C of softening point.In addition, if being calculated by epoxide equivalent, it can be determined that the epoxy resin (synthesis example 3) is raw materials bisphenol A/F and with there is about 3.0 resins being at least partially epoxidized in type epoxy resin alcohol hydroxyl group 3.3.

Synthesis example 3S: the synthesis of hydrogenated epoxy resin

It is packed into 4,4 '-dihydroxydiphenyl methane, 96 parts by weight and hydrogenated bisphenol A type liquid epoxy resin [Dongdu is melted into company manufacture " mono- ト ST-3000 of サ Application ト ", epoxide equivalent 230g/eq] 410 parts by weight in flask, melting mixing is carried out at 150 DEG C.The molar ratio of phenolic hydroxyl group and epoxy group at this time is 0.53: 1.

Then, 0.084 parts by weight of triphenyl phasphine are added, continue stirring 4 hours at 150 DEG C, complete addition reaction, obtain raw material hydrogenated bisphenol A type/F type shown in following formula and with epoxy resin [h₃₂Average value 1.6, epoxide equivalent 580].

[in formula, h₃₂Indicate the degree of polymerization].

Then, by the raw material hydrogenated bisphenol A type/F type and with after the dissolution of 308 parts by weight of epoxy resin, 925 parts by weight of epichlorohydrin and 462.5 parts by weight of dimethyl sulfoxide, the NaOH of 52.8 parts by weight 98.5% was added with 100 minutes under stiring, at 70 DEG C.After addition, then reaction in 3 hours is carried out at 70 DEG C.

Then, the more than half of superfluous unreacted epichlorohydrin and dimethyl sulfoxide being distilled under reduced pressure.Then, it is dissolved into the reaction product containing secondary raw salt and dimethyl sulfoxide in 750 parts by weight of methyl iso-butyl ketone (MIBK), adds 10 parts by weight of 30%NaOH aqueous solution, reacted 1 hour at 70 DEG C.

After reaction, 2 washings are carried out with 200 parts by weight of water.It is distilled to recover methyl iso-butyl ketone (MIBK) from oil reservoir after water-oil separating, obtains 312 parts by weight of epoxy resin (synthesis example 3S).

The epoxy resin (synthesis example 3S) is epoxide equivalent 280,61 DEG C of softening point.In addition, if being calculated by epoxide equivalent, it can be determined that the epoxy resin (synthesis example 3S) is raw material hydrogenated bisphenol A type/F type and with there is about 3.0 resins being at least partially epoxidized in epoxy resin alcohol hydroxyl group 3.3.

Synthesis example 4: the synthesis of epoxy resin (changing I/E-2-2)

It is packed into 9,9 '-two (4- hydroxy phenyl) fluorenes, 168 parts by weight and bisphenol A-type liquid epoxy resin [Dongdu is melted into company manufacture " YD-128 ", epoxide equivalent 186g/eq] 332 parts by weight in flask, melting mixing is carried out at 150 DEG C.The molar ratio of phenolic hydroxyl group and epoxy group at this time is 0.53: 1.

Then, 0.084 parts by weight of triphenyl phasphine are added, continue stirring 4 hours at 150 DEG C, addition reaction is completed, obtains the epoxy resin [h that raw material shown in following formula contains fluorene skeleton₄₁Average value 1.6, epoxide equivalent 720].

[in formula, G and described identical, h₄₁Indicate the degree of polymerization].

Then, after 371 parts by weight of epoxy resin, 925 parts by weight of epichlorohydrin and 462.5 parts by weight of the dimethyl sulfoxide dissolution which is contained to fluorene skeleton, the NaOH of 52.8 parts by weight 98.5% was added with 100 minutes under stiring, at 70 DEG C.After addition, then reaction in 3 hours is carried out at 70 DEG C.

Then, the more than half of superfluous unreacted epichlorohydrin and dimethyl sulfoxide being distilled under reduced pressure.Then, it is dissolved into the reaction product containing secondary raw salt and dimethyl sulfoxide in 750 parts by weight of methyl iso-butyl ketone (MIBK), adds 10 parts by weight of 30%NaOH aqueous solution, reacted 1 hour at 70 DEG C.

After reaction, 2 washings are carried out with 200 parts by weight of water.It is distilled to recover methyl iso-butyl ketone (MIBK) from oil reservoir after water-oil separating, obtains 368 parts by weight of epoxy resin (synthesis example 4) shown in formula (changing I/E-2-2).

The epoxy resin (synthesis example 4) is epoxide equivalent 350,68 DEG C of softening point.In addition, if being calculated by epoxide equivalent, it can be determined that the epoxy resin (synthesis example 4) is that raw material contains and has about 3.0 resins being at least partially epoxidized in the epoxy resin of fluorene skeleton in alcohol hydroxyl group 3.3.

Synthesis example 5: the synthesis of epoxy resin (changing I/E-2-3)

It is packed into 3,3 ', 5,5 '-tetramethyl -4,4 '-dihydroxybiphenyl, 116 parts by weight and bisphenol A-type liquid epoxy resin [Dongdu is melted into company and manufactures " YDF-170 ", epoxide equivalent 172g/eq] 301 parts by weight in flask, melting mixing is carried out at 150 DEG C.The molar ratio of phenolic hydroxyl group and epoxy group at this time is 0.53: 1.

Then, 0.084 parts by weight of triphenyl phasphine are added, continue stirring 4 hours at 150 DEG C, addition reaction is completed, obtains raw material shown in following formula and contain bisphenol-A/union II cresols skeleton epoxy resin [h₅₁Average value 1.6, epoxide equivalent 600].

[in formula, G and described identical, h₅₁Indicate the degree of polymerization].

Then, after which being contained bisphenol-A/union II cresols skeleton 310 parts by weight of epoxy resin, 925 parts by weight of epichlorohydrin and the dissolution of 462.5 parts by weight of dimethyl sulfoxide, the NaOH of 52.8 parts by weight 98.5% was added with 100 minutes under stiring, at 70 DEG C.After addition, then reaction in 3 hours is carried out at 70 DEG C.

Then, the more than half of superfluous unreacted epichlorohydrin and dimethyl sulfoxide being distilled under reduced pressure.Then, it is dissolved into the reaction product containing secondary raw salt and dimethyl sulfoxide in 750 parts by weight of methyl iso-butyl ketone (MIBK), adds 10 parts by weight of 30%NaOH aqueous solution, reacted 1 hour at 70 DEG C.

After reaction, 2 washings are carried out with 200 parts by weight of water.It is distilled to recover methyl iso-butyl ketone (MIBK) from oil reservoir after water-oil separating, obtains 368 parts by weight of epoxy resin (synthesis example 5) shown in formula (changing I/E-2-3).

The epoxy resin (synthesis example 5) is epoxide equivalent 295,66 DEG C of softening point.In addition, if being calculated by epoxide equivalent, it can be determined that the epoxy resin (synthesis example 5) is that raw material contains in bisphenol-A/union II cresols skeleton epoxy resin and has about 3.0 resins being at least partially epoxidized in alcohol hydroxyl group 3.3.

<synthesis of the polycarboxylic acid resin [I] containing unsaturated group>

Synthesis example 6

It is packed into 2870 parts by weight of the epoxy resin (synthesis example 1) (10 equivalent), 720 parts by weight of acrylic acid (10 equivalent), 2.8 parts by weight of methylnaphthohydroquinone, 1943.5 parts by weight of carbitol acetate, 90 DEG C are heated to, is stirred and dissolves reaction mixture.Then, reaction solution is cooled to 60 DEG C, is packed into 16.6 parts by weight of triphenyl phasphine, be heated to 100 DEG C, reacted about 32 hours, obtain the reactant of acid value 1.0.Then, 783 parts by weight of succinic anhydride (7.83 equivalent), 421.6 parts by weight of carbitol acetate is added to it, 95 DEG C are heated to, reaction is cooled down after about 6 hours, obtains the polycarboxylic acid resin [I] (synthesis example 6) containing unsaturated group.

The polycarboxylic acid resin [I] (synthesis example 6) for containing unsaturated group is acid value 100, solid component concentration 65%, viscosity (25 DEG C) 25Pas of solid component.

Synthesis example 7

It is packed into 2900 parts by weight of the epoxy resin (synthesis example 2) (10 equivalent), 720 parts by weight of acrylic acid (10 equivalent), 2.8 parts by weight of methylnaphthohydroquinone, 1950 parts by weight of carbitol acetate, 90 DEG C are heated to, is stirred and dissolves reaction mixture.Then, reaction solution is cooled to 60 DEG C, is packed into 16.7 parts by weight of triphenyl phasphine, be heated to 100 DEG C, reacted about 32 hours, obtain the reactant of acid value 1.0.Then, 1845 parts by weight of tetrabydrophthalic anhydride and 993.5 parts by weight of carbitol acetate are added, and 974.7 parts by weight of 1810 parts by weight of hexahydrophthalic anhydride and carbitol acetate, it is reacted, obtains the polycarboxylic acid resin [I] (synthesis example 7) containing unsaturated group.

The polycarboxylic acid resin [I] (synthesis example 7) for containing unsaturated group is acid value 90, solid component concentration 65%, viscosity (25 DEG C) 72Pas of solid component.

Synthesis example 8

It is packed into 2900 parts by weight of the epoxy resin (synthesis example 3) (10 equivalent), 720 parts by weight of acrylic acid (10 equivalent), 2.8 parts by weight of methylnaphthohydroquinone, 1950 parts by weight of carbitol acetate, 90 DEG C are heated to, is stirred and dissolves reaction mixture.Then, reaction solution is cooled to 60 DEG C, is packed into 16.7 parts by weight of triphenyl phasphine, be heated to 100 DEG C, reacted about 32 hours, obtain the reactant of acid value 1.0.Then, 1845 parts by weight of tetrabydrophthalic anhydride and 993.5 parts by weight of carbitol acetate are added, is reacted, obtains the polycarboxylic acid resin [I] (synthesis example 8) containing unsaturated group.

The polycarboxylic acid resin [I] (synthesis example 8) for containing unsaturated group is acid value 98, solid component concentration 65%, viscosity (25 DEG C) 30Pas of solid component.

Synthesis example 8S

It is packed into 2800 parts by weight of epoxy resin (synthesis example 3S) (10 equivalent), 720 parts by weight of acrylic acid (10 equivalent), 2.8 parts by weight of methylnaphthohydroquinone, 1950 parts by weight of carbitol acetate, 90 DEG C are heated to, is stirred and dissolves reaction mixture.Then, reaction solution is cooled to 60 DEG C, is packed into 16.7 parts by weight of triphenyl phasphine, be heated to 100 DEG C, reacted about 32 hours, obtain the reactant of acid value 1.0.Then, 1845 parts by weight of tetrabydrophthalic anhydride and 993.5 parts by weight of carbitol acetate are added, is reacted, obtains the polycarboxylic acid resin [I] (synthesis example 8S) containing unsaturated group.

The polycarboxylic acid resin [I] (synthesis example 8S) for containing unsaturated group is acid value 103, solid component concentration 65%, viscosity (25 DEG C) 26Pas of solid component.

Synthesis example 9

It is packed into 3500 parts by weight of the epoxy resin (synthesis example 4) (10 equivalent), 720 parts by weight of acrylic acid (10 equivalent), 2.8 parts by weight of methylnaphthohydroquinone, 1950 parts by weight of carbitol acetate, 90 DEG C are heated to, is stirred and dissolves reaction mixture.Then, reaction solution is cooled to 60 DEG C, is packed into 16.7 parts by weight of triphenyl phasphine, be heated to 100 DEG C, reacted about 32 hours, obtain the reactant of acid value 1.0.Then, 953 parts by weight of succinic anhydride (9.5 equivalent), 513 parts by weight of carbitol acetate is added, it is cooling after being heated to 95 DEG C, reaction about 6 hours, obtain the polycarboxylic acid resin [I] (synthesis example 9) containing unsaturated group.

The polycarboxylic acid resin [I] (synthesis example 9) for containing unsaturated group is acid value 100, solid component concentration 65%, viscosity (25 DEG C) 45Pas of solid component.

Synthesis example 10

It is packed into 2950 parts by weight of the epoxy resin (synthesis example 5) (10 equivalent), 720 parts by weight of acrylic acid (10 equivalent), 2.8 parts by weight of methylnaphthohydroquinone, 1950 parts by weight of carbitol acetate, 90 DEG C are heated to, is stirred and dissolves reaction mixture.Then, reaction solution is cooled to 60 DEG C, is packed into 16.7 parts by weight of triphenyl phasphine, be heated to 100 DEG C, reacted about 32 hours, obtain the reactant of acid value 1.00.Then, 1845 parts by weight of tetrabydrophthalic anhydride and 993.5 parts by weight of carbitol acetate are added, is reacted, obtains the polycarboxylic acid resin [I] (synthesis example 10) containing unsaturated group.

The polycarboxylic acid resin [I] (synthesis example 10) for containing unsaturated group is acid value 96, solid component concentration 65%, viscosity (25 DEG C) 35Pas of solid component.

Synthesis example 11

3300 parts by weight of cresol-novolac epoxy resin (epoxide equivalent 220) are fitted into the flask with gas introduction tube, agitating device, cooling tube and thermometer, 4000 parts by weight of carbitol acetate are added, after heating for dissolving, 4.6 parts by weight of quinhydrones, 13.8 parts by weight of triphenyl phasphine are added.The mixture is heated to 95~105 DEG C, slowly instills 1080 parts by weight of acrylic acid, is reacted 16 hours.Then the reaction product is cooled to 80~90 DEG C, 1630 parts by weight of tetrabydrophthalic anhydride is added, reacted 8 hours, obtain the polycarboxylic acid resin [I] (synthesis example 11) containing unsaturated group.

The polycarboxylic acid resin [I] (synthesis example 11) for containing unsaturated group is acid value 100, the solid component concentration 60% of solid component.

<synthesis of polymer [II]>

Synthesis example 12

It is packed into copolymer (manufacture of ATOCHEM company, SMA-1000, acid value 480) 434 parts by weight, 216 parts by weight of acrylic acid 2- hydroxy methacrylate, 350 parts by weight of diethylene glycol dimethyl ether, 0.5 parts by weight of metoquinone of styrene and maleic anhydride, it is reacted at 90 DEG C about 20 hours, obtains reactant [II-1] (synthesis example 12).

The reactant [II-1] (synthesis example 12) is solid component 65%, resinous acid value 142, number-average molecular weight about 4500.

Synthesis example 13

In a nitrogen atmosphere, the mixed liquor being made of 300 parts by weight of styrene, 350 parts by weight of butyl acrylate, 350 parts by weight of acrylic acid and 30 parts by weight of azodiisobutyronitrile is added dropwise in 400 parts by weight of 500 parts by weight of n-butanol and methyl iso-butyl ketone (MIBK) for having put into the reaction vessel for being maintained at 110 DEG C with 3 hours, it instills post curing 1 hour, instilled the mixed liquor being made of 10 parts by weight of azo two (methyl pentane nitrile) and 100 parts by weight of methyl iso-butyl ketone (MIBK) with 1 hour.Then, it then cures 5 hours, obtains high acid value acrylic resin (acid value 260) solution.

Then, methacrylic acid 3 is added in the solution, 1.4 parts by weight of 780 parts by weight of 4- epoxycyclohexanecarboxylate and hydroquinone monomethyl ether are reacted 5 hours at 80 DEG C of Bian while being blown into air, obtain reactant [II-2] (synthesis example 13).

The reactant [II-2] (synthesis example 13) is solid component 65%, resinous acid value 50, number-average molecular weight about 16000.

<synthesis of Cristalline epoxy resin [V]>

Synthesis example 14

By 2,2 '-dimethyl -5,5 '-di-t-butyl -4,4 '-dihydroxydiphenyl thioether 120g are dissolved into epichlorohydrin 720g, add benzyltriethylammoinium chloride 0.3g, under reduced pressure (about 150mmHg), at 70 DEG C with 4 hours 48% sodium hydrate aqueous solution 55.7g of instillation.The water generated therebetween is discharged to outside system and the azeotropic with epichlorohydrin, and the epichlorohydrin distillated returns in system.After instillation, it is further continued for reaction 1 hour.Then, the salt of generation is removed by filtering, and then distills epichlorohydrin after washing, obtain faint yellow liquid epoxy resin 165g.

Micropowder epoxy resin (changing V/1) [2,2 '-dimethyl -5,5 '-di-t-butyl -4, the diglycidyl ether of 4 '-dihydroxydiphenyl thioethers] 3g in addition modulated as crystallization kind is added in obtained liquid epoxy resin.Then it stands and is crystallized at 30 DEG C.

Its result obtains white crystalline epoxy resin (changing V/1) (synthesis example 14) 149g.The crystalloid epoxy resin (changing V/1) (synthesis example 14) is epoxide equivalent 239,121 DEG C of fusing point.

Synthesis example 15

Be packed into 3,3 '-dimethyl -4 in flask, 4 '-dihydroxydiphenyl thioether 147.6g (0.6 mole), epichlorohydrin 666g, under reduced pressure (about 140mmHg), at 60 DEG C with 4 hours 48% sodium hydrate aqueous solution 97.0g of instillation.Therebetween, water is discharged to outside system and the azeotropic with epichlorohydrin, and the epichlorohydrin distillated returns in system.After instillation, the reaction was continued 1 hour.Then, superfluous epichlorohydrin vacuum distillation remaining in system is fallen, is dissolved into methyl iso-butyl ketone (MIBK) 501.2ml, is then removed the salt of generation by filtering.Then, 24% sodium hydrate aqueous solution 39.3g is added, is reacted 2 hours at 80 DEG C.And then wash, distill methyl iso-butyl ketone (MIBK) after neutralization, obtain epoxy resin (changing V/2) (synthesis example 15) 202g.Epoxide equivalent is 183, and fusing point is 47~51 DEG C.

Synthesis example 16

4,4 '-dihydroxydiphenyl thioether 130.8g (0.6 mole), epichlorohydrin 666g are packed into flask, under reduced pressure (about 140mmHg), at 60 DEG C with 4 hours 48% sodium hydrate aqueous solution 97.0g of instillation.Therebetween, water is discharged to outside system and the azeotropic with epichlorohydrin, and the epichlorohydrin distillated returns in system.After instillation, it is further continued for reaction 1 hour.Then, superfluous epichlorohydrin vacuum distillation remaining in system is fallen, is dissolved into methyl iso-butyl ketone (MIBK) 462ml, is then removed the salt of generation by filtering.Then, 24% sodium hydrate aqueous solution 55.8g is added, is reacted 2 hours at 80 DEG C.And then wash, distill methyl iso-butyl ketone (MIBK) after neutralization, obtain epoxy resin (changing V/3) (synthesis example 16) 184g.Epoxide equivalent is 172, and fusing point is 43~47 DEG C.

Synthesis example 17

It using 4,4 '-dihydroxydiphenyl ether 120g, epichlorohydrin 550g, 48% sodium hydrate aqueous solution 99.0g, is carried out similarly and reacts with synthesis example 16, obtain white crystalline epoxy resin (changing V/4) (synthesis example 17) 169g.Epoxide equivalent is 169, and fusing point is 86 DEG C.

Synthesis example 18

By 2,2 ', 3,3 ', 5,5 '-hexamethyls -4,4 '-dihydroxydiphenyl methane 120g are dissolved into epichlorohydrin 960g, add benzyltriethylammoinium chloride 0.3g, under reduced pressure (about 150mmHg), at 70 DEG C with 4 hours 48% sodium hydrate aqueous solution 81.3g of instillation.The water generated therebetween is discharged to outside system and the azeotropic with epichlorohydrin, and the epichlorohydrin distillated returns in system.After instillation, it is further continued for reaction 1 hour.Then, the salt of generation is removed by filtering, and then distills epichlorohydrin after washing, obtain faint yellow liquid epoxy resin 165g.

The micropowder crystallization (changing V/6) [2,2 ', 3 in addition modulated as crystallization kind is added in obtained liquid epoxy resin, 3 ', 5,5 '-hexamethyls -4, the diglycidyl ether of 4 '-dihydroxydiphenyl methane] 3g, it then stands and is crystallized at 30 DEG C.

160g epoxy resin (changing V/6) (synthesis example 18) [115 DEG C of epoxide equivalent 210, fusing point] is just obtained in this way.

<modulation of photosensitive heat curing resin combination>

Examples 1 to 9 and comparative example 1~7

According to table E_XWith being combined into shown in/1, each gradation composition is kneaded with 3 roller kneading machines, is modulated photosensitive heat curing resin combination (each Examples 1 to 9 and comparative example 1~7).

Table Ex/1

Gradation composition (parts by weight)		Embodiment									Comparative example
																		1	2	3	4	5	6	7	8	9	1	2	3	4	5	6	7
		Ingredient [I]	Polycarboxylic acid resin [I] (synthesis example 6) containing unsaturated group	149	--	--	--	146	--	--	--	--	--	--	--	--	--																	--	--
Polycarboxylic acid resin [I] (synthesis example 7) containing unsaturated group	--																	--	--	--	--	--	--	154	154			154	--	--	--	--
			Polycarboxylic acid resin [I] (synthesis example 8) containing unsaturated group	--	123	--	--	--	--	--	--	--	--	--	--	--	--																146	--
Polycarboxylic acid resin [I] (synthesis example 9) containing unsaturated group	--																	--	139	--	--	--	--	--	--	--	--	--	--	--	--	--
			Polycarboxylic acid resin [I] (synthesis example 10) containing unsaturated group	--	--	--	146	--	146	--	--	--	--	--	--	--	--																--	154
Polycarboxylic acid resin [I] (synthesis example 8S) containing unsaturated group	--																	--	--	--	--	--	144	--	--	--	--	--	--	--	--	--
			Ingredient [II]	Reactant [II-1] (synthesis example 12)	--	--	15	--	--	7.7	10	--	--	--	154	--	--																--	7.7	--
Reactant [II-1] (synthesis example 13)	4.6	31																--	7.7	7.7	--	--	--	--	--	--	--	154	154	--	--
				Ingredient [III]	Carbitol acetate	10	10	10	10	10	10	10	10	10	10	10	10															10	20	10	10
Dipentaerythritol hexaacrylate (DPHA)	10	10	10															10	10	10	10	10	--	10	10	10	10	--	10	15
					Trimethylolpropane trimethacrylate (TMPTA)	10	10	10	10	10	10	10	10	20	10	10	10														10	20	10	5
Ingredient [IV]	2- dimethylamino -2- (4- methylbenzyl) -1- (4- morphlinophenyl)-butanone -1	12	--															--	--	12	12	12	--	12	12	--	12	12	12	--					6
				Bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides	--	12	12	12	--	--	--	12	--	--	12	--	--														--	12	6
	2,4- diethyl thioxanthones	1	1															1	1	1	1	1	1	1	1	1	1	1	1	1				1
				Ingredient [V]	Cristalline epoxy resin (changing V/1) (synthesis example 14)	36	--	--	36	--	26	--	20	--	--	--	--														--	--	--		--
Cristalline epoxy resin (changing V/2) (synthesis example 15)	--	--	--															--	--	--	--	--	32	--	--	--	--	--	--	--
					Cristalline epoxy resin (changing V/3) (synthesis example 16)	--	--	32	--	--	--	--	--	--	--	--	--														--	--	--	--
Cristalline epoxy resin (changing V/6) (synthesis example 18)	--	36	--															--	22	--	30	--	--	--	--	--	--	22	--	--
					Ingredient [VI]	Melamine	1	1	1	1	1	1	1	1	1	1	1														1	1	1	1	1
Dicyandiamide	--	--	--	--														--	--	0.5	0.5	--	--	--	--	--	--	--	1
						Ingredient [VII]	Cristalline epoxy resin (changes VII-1/1)1)	--	--	--	--	6	--	--	--	--	--													32	--	--	8	8	--
Cristalline epoxy resin (changes VII-1/2)	--	--	--	--	--													10	--	20	--	32	--	--	--	--	16	30
							Cristalline epoxy resin (changes VII-1/3)	--	--	--	--	4	--	--	--	--	--												--	--	--	--	8	--
Single poly- carbodiimide (changing VII-2)2)	--	4	--	--	--													--	--	--	--	--	--	--	--	--	--	--
							Triallyl isocyanurate prepolymer [VII-3]	4	--	--	--	--	--	--	--	--	--												--	--	--	--	--	--
Diallyl phthalate prepolymer [VII-3]	--	--	--	--	--													--	8	--	4	--	--	--	--	4	--	--
							Diallyl 3,6- methylene tetrahydric phthalimide compound (change VII-3/1)3)	--	--	--	--	--	--	--	--	--	--												--	--	--	--	4	--
Other ingredients	Silica	30	30	30	30													30	30	30	30	30	30	30	30	30	30	30							30
						Barium sulfate	70	70	70	70	70	70	70	70	70	70	70												70	70	70	70	70
	Dimethyl silicone polymer	1	1	1	1													1	1	1	1	1	1	1	1	1	1	1						1
						Polycarboxylic acid resin (synthesis example 11) containing unsaturated group	--	--	--	--	--	--	--	--	--	165	--												--	--	--	--	--
	Cresol-novolac epoxy resin (epoxide equivalent 220)	--	--	--	--													--	--	--	--	--	--	--	30	30	--	--						--

Table E_XIn/1,1)~3) indicate the following contents.

1): in formula (changing VII-1/1), g₁₁It is 0.1.

2): in formula (changing VII-2), G₂₁For phenyl, G₂₂It is 4,4 '-diphenyl methanes, G₂₃For phenyl, g₂₁It is 23.3.

3): in formula (changing VII-3/1), G₇₁For diphenyl methane.

<manufacture of the printing distributing board coated with solder resist>

Smooth the manufacture of printing distributing board

It will be used with a thickness of the printing distributing board of 0.8mm [copper circuit is 40 μm, L/S=75 μm/75 μm thick] as substrate.That is, the polyester screen using 250 mesh is masked printing to the compositions of thermosetting resin of following compositions, it is applied on the substrate.Then, the substrate is heated to 150 DEG C with heating furnace, carries out 60 minutes one-step solidifications at such a temperature.Then, 1 grinding is carried out to the surface comprising one-step solidification film side with No. 400 abrasive band polishing grinders first, then carries out 4 grindings with No. 600 emery wheels.90 minutes secondary curings are finally carried out at 180 DEG C with box like dryer, manufacture the printing distributing board for smoothing the recess portion between circuit (within 2 μm of concave-convex difference of height).Additionally distinguish that secondary curing can carry out after grinding, can also be carried out while solder resist solidifies.

Matching for compositions of thermosetting resin is combined into (parts by weight):

75% acrylic acid adduct (100), isobornyl acrylate (40), Tricyclodecane Dimethanol acrylate (100), trimethylolpropane trimethacrylate (10), t-butyl peroxybenzoate (10), tetramethyl biphenyl type epoxy resin (100), dicyandiamide (16), barium sulfate (120), the dimethyl silicone polymer (0.1) of phenol novolak epoxy resin.

Manufacture embodiment 1,4,5 and 7 and manufacture comparative example 2 and 6

The production of dry film photoresist

Photosensitive heat curing resin combination (each embodiment 1,4,5 and 7 and comparative example 2 and 6) layer is coated on the pet vector film of thick 0.03mm with applicator, dry film thickness is made to reach 20 μm.It is dried after twenty minutes at 80 DEG C, then coats the polyethylene protective film of 0.05mm above it, production obtains dry film photoresist.

By the protection film stripping of the dry film photoresist of the production, it is thermally laminated on the smoothing printing distributing board of the manufacture using laminating machine, then removes carrier film.

Then, using ultraviolet exposure apparatus according (mono- Network of オ makes institute, pattern HMW-680C), ultraviolet light 500mj/cm is irradiated by solder resist negative film².Then spray developing is carried out with 1% aqueous sodium carbonate, the resin for not irradiating ultraviolet part is removed.

After washing and drying, it is made to be heating and curing reaction 60 minutes to obtain cured film in 150 DEG C of hot-air drier.Just manufacture obtains the printing distributing board (each manufacture embodiment 1,4,5 and 7 and manufacture comparative example 2 and 6) coated with solder resist in this way.

Manufacture comparative example 4

Instead of photosensitive heat curing resin combination (each embodiment 1, 4, 5 and 7 and comparative example 2 and 6) and use photonasty compositions of thermosetting resin (comparative example 4) make dry film photoresist, embossing distributing board (thick 0.8mm is used instead of smoothing printing distributing board, copper circuit is 25 μm thick, L/S=75 μm/75 μm), it is carried out outside screen printing instead of 100 mesh polyester using 250 mesh polyester, remaining and the manufacture embodiment 1, 4, 5 and 7 and manufacture comparative example 2 and 6 equally carry out, manufacture obtains the printing distributing board (manufacture comparative example 4) coated with solder resist.

Manufacture embodiment 2,3,6 and 8 and manufacture comparative example 1 and 5

Printing photosensitive heat curing resin combination (each embodiment 2,3,6 and 8 and comparative example 1 and 5) on the smoothed surfaces of the smoothing printing distributing board of the manufacture using mesh (100 mesh polyester) print process makes dry film thickness reach 20 μm, dried coating film is made in 80 DEG C of hot-air drier 20 minutes.

Then, using ultraviolet exposure apparatus according (mono- Network of オ makes institute, pattern HMW-680C), ultraviolet light 500mj/cm is irradiated by solder resist negative film².Then spray developing is carried out with 1% aqueous sodium carbonate, the resin for not irradiating ultraviolet part is removed.

After washing and drying, it is made to be heating and curing reaction 60 minutes to obtain cured film in 150 DEG C of hot-air drier.Just manufacture obtains the printing distributing board (each manufacture embodiment 2,3,6 and 8 and manufacture comparative example 1 and 5) coated with solder resist in this way.

Manufacture embodiment 9 and manufacture comparative example 3 and 7

Embossing distributing board (thick 0.8mm is used instead of smoothing printing distributing board, copper circuit is 25 μm thick, L/S=75 μm/75 μm), instead of photosensitive heat curing resin combination ( embodiment 2, 3, 6 and 8 and comparative example 1 and 5) and use photonasty compositions of thermosetting resin (each embodiment 9 and comparative example 3 and 7), it is carried out outside screen printing instead of 100 mesh polyester using 250 mesh polyester, remaining and the manufacture embodiment 2, 3, 6 and 8 and manufacture comparative example 1 and 5 equally carry out, manufacture obtains the printing distributing board (each manufacture embodiment 9 and manufacture comparative example 3 and 7) coated with solder resist.

<evaluation test of the printing distributing board coated with solder resist>

Following various evaluation tests are carried out to the respectively printing distributing board coated with solder resist (each manufacture Examples 1 to 9 and manufacture comparative example 1~7) of the manufacture.Test method and evaluation method is as follows described.

(storage stability)

Each print material composition is placed 5 days in 40 DEG C of thermostats, storage stability is evaluated by viscosity change.Judge that benchmark is as described below.

Zero: 1.5 times of viscosity change deficiency initial value.

△: viscosity change is 1.5 times or more of initial value, less than 3.0 times.

×: viscosity change is 3.0 times or more of initial value.

(developability after preservation)

The dry film photoresist placed 10 days in 25 DEG C of thermostats is laminated on printing distributing board, carries out spray developing with 1% aqueous sodium carbonate, judges whether to develop.

Zero: can develop.

×: produce development residue.

(dry to touch)

After coating, it is put into heated air circulation type drying oven, it is dry at 80 DEG C to use finger force extrusion coated face after twenty minutes, adhesiveness is investigated, judges the state of film.

Zero: absolutely not finding tacky, fingerprint trace.

△: there is a small amount of tacky, fingerprint trace in discovery surface.

×: there is significant tacky, fingerprint trace in discovery surface.

(developability)

With ultraviolet exposure apparatus according (mono- Network of オ makes institute, pattern HMW-680C), ultraviolet light 500mj/cm is irradiated by solder resist negative film².Then with the developer solution of 1wt% aqueous sodium carbonate with 2.0 × 10⁵The jet pressure of Pa carries out development in 60 seconds, visually confirms the state for thereafter removing unexposed portion.

Zero: print material can be completely removed and be developed when development.

×: in the presence of the part that do not develop when development.

(photo sensitivity)

21 sections of step tablet (manufacture of mono- company of ス ト Off ア) are adhered on the film after drying, accumulative light quantity 500mJ/cm is irradiated²Ultraviolet light be exposed.Then with 1% aqueous sodium carbonate with 2.0 × 10⁵The jet pressure of Pa carries out development in 60 seconds, confirmation number of segment of remaining film without development.

(resistance to bend(ing): cylindrical mandrel method)

Each composition, which is printed on 35 μm of copper foils, makes the film thickness after solidifying reach 40 μm, and cured film is made wide 10mm × long 100mm test film after exposing, solidifying, according to JIS K5600, is tested using the diameter 2mm of axle.Test film is observed with following benchmark.

Zero: film surface does not find to rupture.

×: film surface rupture.

(pencil hardness)

It is evaluated according to JIS K5600.

(adhesiveness)

According to JIS K5600, the grid of 100 1mm is made on test film, carries out disbonded test with cord belt.The exfoliated state for observing grid, is evaluated with benchmark below.

Zero: not removing.

×: removing.

(transparency of film)

Whether printing is carried out on black substrate makes cured coating film reach 40 μm, evaluate after defined process and change in appearance.

Zero: appearance of film is without exception, transparent.

△: the transparency of appearance of film has certain decline.

×: appearance of film generates gonorrhoea, transparency decline.

(bubble between circuit)

The bubble the circuit of printing distributing board is observed using 30 times of magnifying glasses.

Zero: bubble-free.

×: there is bubble.

(solvent resistance)

Test film is impregnated 30 minutes in isopropanol at room temperature.Confirm that appearance with the presence or absence of after exception, carries out the disbonded test using cord belt (R), evaluated by benchmark below.

Zero: appearance of film is without exception, no swelling, removing.

×: there is swelling, removing on film.

(acid resistance)

Test film is impregnated 30 minutes in 10% aqueous hydrochloric acid solution at room temperature.Confirm that appearance with the presence or absence of after exception, carries out the disbonded test using cord belt, evaluated by benchmark below.

Zero: appearance of film is without exception, no swelling, removing.

×: there is swelling, removing on film.

(heat resistance)

Even paint is applied on test film with solder flux W-121 (メ ツク company manufactures), is impregnated 10 seconds in 288 DEG C of welding rod slot.It is recycled as 1,3 circulations is repeated.After letting cool room temperature, the disbonded test using cord belt (R) is carried out, is evaluated by benchmark below.

Zero: appearance of film is without exception, no swelling, removing.

×: there is swelling, removing on film.

(resistance to gold-plated attribute)

Substrate dipping 3 minutes in 30 DEG C of acidic degreasing liquid (the 20vol% aqueous solution of Japanese mono- ミ Star ト system of マ Network ダ, MetexL-5B) will be tested, are then washed.Then, it impregnates 3 minutes in 14.4wt% ammonium persulfate aqueous solution, is then washed at room temperature, then washed after at room temperature impregnating test substrate 1 minute in 10vol% aqueous sulfuric acid.

Then, the substrate is impregnated 7 minutes in 30 DEG C of catalytic liquid (the 10vol% aqueous solution of メ Le テ Star Network ス system, plating metal promotor 350), it is washed, dipping 20 minutes in 85 DEG C of nickel-plating liquids (メ Le テ Star Network ス system, the 20vol% aqueous solution of mono- ト Ni-865M of メ Le プ レ, pH4.6), after carrying out nickel plating, it impregnates 1 minute, is washed in 10vol% aqueous sulfuric acid at room temperature.

Then, substrate dipping 10 minutes in 95 DEG C of gold plating liquid (aqueous solution, the pH6 of メ Le テ Star Network ス system, オ ウ ロ レ Network ト ロ レ ス UP15vol% and potassium auricyanide 3vol%) will be tested, it is washed after carrying out electroless plating gold, it is impregnated 3 minutes in 60 DEG C of warm water again, is washed, dried.Celluloid adhesive tape is attached on the electroless plating gold evaluation substrate of preparation, state when observation is removed.

Zero: completely without exception.

×: observe several removings.

(HAST patience)

In 130 DEG C, 85% unsaturated pressurizing vessel, the applied voltage of additional DC5V between the line/gap=50 μm/50 μm comb-type electrode for having granted each solder resist, will be after test substrate placement 168 hours, whether confirmation appearance is abnormal, while measuring insulation resistance before and after the test.

Insulation resistance is using " R8340A " (ア De バ Application テ ス ト system, digital ultra-high resistance/pettiness galvanometer), according to the insulation resistance test specification of JPCA-HD01, behind DC voltage 1 minute of additional 10V, insulation resistance is measured under the outer plus state.

Zero: appearance of film is without exception.

△: discoloration, no swelling, removing are found on electrode.

×: there is swelling, removing on film.

(thermal shock resistance)

It is 1 circulation with -40 DEG C/30 points, 125 DEG C/30 points, the additional Thermal Cycling of test film, with micro- sem observation test film, is evaluated after 1000 circulations according to benchmark below.

Zero: without generating cracking on film.

×: cracking is produced on film.

(concave-convex difference of height)

With the surface shape of surface roughness meter measurement test piece, Rmax is marked.

(peel strength)

Each composition is printed on 35 μm of copper foils, after predrying, heat lamination is carried out to composition and printing distributing board with 80 DEG C on the FR4 of the 0.4mm thickness of no copper foil using laminating machine, from the back side with 1000mJ/cm²Ultraviolet exposure is irradiated, is solidified.It after solidification, is cut off with copper foil 10mm wide, the measurement load that copper foil and composition removing is required.

Table Ex/2

		Manufacture embodiment									Manufacture comparative example
																		1	2	3	4	5	6	7	8	9	1	2	3	4	5	6	7
		The photosensitive heat curing resin combination used		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5																	Comparative example 6	Comparative example 7
Evaluation test project	Storage stability																	○	○	△	○	○	○	○	○	△	○	×	×	×	×	○	○
		Developability after preservation	○	-	-	○	○	-	○	-	-	-	×	-	×	-	○																	-
	Dry to touch																	△	○	○	○	○	○	○	○	×	○	○	△	○	○	○	○
		Developability	○	○	○	○	○	○	○	○	○	○	○	×	×	×	○																	○
	Photo sensitivity																	12	11	12	11	11	11	11	11	11	11	9	11	11	12	11	11
		Resistance to bend(ing)	○	○	○	○	○	○	○	○	○	×	×	×	×	×	△																	△
	Pencil hardness (H)																	6	6	6	6	6	6	6	6	6	6	6	6	6	7	6	7
		Adhesiveness	○	○	○	○	○	○	○	○	○	×	×	△	×	×	△																	△
	The film transparency																	○	○	○	○	△	△	○	○	○	×	×	○	○	×	×	×
		Bubble between circuit	○	○	○	○	○	○	○	○	×	○	○	×	×	○	○																	○
	Solvent resistance																	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○
		Acid resistance	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○																	○
	Heat resistance																	○	○	○	○	○	○	○	○	○	×	○	×	×	○	○	○
		Resistance to gold-plated property	○	○	○	○	○	○	○	○	○	○	×	○	×	○	△																	○
	Resistance to HAST																	○	○	○	○	○	○	○	○	○	×	×	×	×	×	×	×
		Initial stage insulation resistance (× 1013Ω)	1.30	1.50	1.70	1.60	1.40	1.30	1.80	1.80	1.50	1.40	1.50	1.30	1.50	1.30	1.40																	1.20
	Insulation resistance (× 10 after 168 hours10  Ω)																	888	225	358	805	308	151	160	110	40.7	15.9	29.6	4.06	3.28	13	45	15
		Thermal shock resistance	○	○	○	○	○	○	○	○	○	×	×	×	×	×	×																	×
	Concave-convex maximum difference of height (μm)																	1	2	2	1	1	2	1	2	10	2	1	12	6	2	1	10
		Peel strength (g/cm)	500	400	500	450	400	450	400	400	400	250	200	300	300	200	300																	300

The following contents can be known from table Ex/2.

As manufactured shown in comparative example 5, if the polycarboxylic acid resin [I] containing unsaturated group is insufficient, storage stability, developability, resistance to bend(ing) and adhesiveness are significantly reduced.

It is found that by addition polymer [II] from manufacture embodiment 8 and 9 is compared with manufacturing Examples 1 to 7, dry to touch can be made to improve.

As manufactured shown in comparative example 5 and 6, if any one of polycarboxylic acid resin [I] or Cristalline epoxy resin [V] containing unsaturated group are insufficient, the film transparency, HAST patience (insulating properties after especially 168 hours) and thermal shock resistance are significantly reduced.Therefore, the film transparency, HAST patience (insulating properties after especially 168 hours) and thermal shock resistance are only by the new effects for generating the polycarboxylic acid resin [I] containing unsaturated group and Cristalline epoxy resin [V] and use.

As manufactured shown in embodiment 9 and manufacture comparative example 3 and 4, when replacing smoothing printing distributing board and use previous embossing distributing board, bubble is generated sometimes between the circuit of the printing distributing board coated with solder resist of manufacture.

Claims (12)

1. photosensitive heat curing resin combination, it is characterised in that contain:

[I]: the polycarboxylic acid resin containing unsaturated group is the reactant of epoxy resin and monocarboxylic reactant and polybasic carboxylic acid or its acid anhydrides containing unsaturated group shown in following formula (changing I/E),

(changing I/E)

In formula (changing I/E), G is following formula

The group of expression, A₁₁、A₁₃And A₁₅Indicate the aromatic residue or hydrogenated aromatic residue of divalent that can be identical or different, A₁₂And A₁₄Can be identical or different, H or G is each independently represented, wherein A₁₂And A₁₄The two is not H, a simultaneously₁₁And a₁₂Indicate 0 or more integer that can be identical or different, but a₁₁And a₁₂It is not simultaneously 0；

[III]: diluent；

[IV]: Photoepolymerizationinitiater initiater；

[V]: the Cristalline epoxy resin that following formula (changing V) indicates,

(changing V)

In formula (changing V), G and described synonymous, E₁₁~E₁₃And E₁₅~E₁₇Indicate H or C1~C5 alkyl that can be identical or different, e₁₁And e₁₂Indicate 0~3 integer that can be identical or different, E₁₄Indicate S, O ,-CH₂-、-C(CH₃)₂Or the divalent group that following formula (changing V/X) or (changing F) indicate,

(changing V/X)

(changing F)

In formula (changing V/X), E₂₁~E₂₄Can be identical or different, each independently represent C1~C6 alkyl；With

[VI]: solidification adhesiveness imparting agent.

2. photosensitive heat curing resin combination described in claim 1; it is characterized in that photosensitive heat curing resin combination also contains [II]: having carboxyl and (methyl) acryloyl group, the polymer that acid value (mgKOH/g) is 20~160 and average molecular weight is 3000~70000.

3. photosensitive heat curing resin combination as claimed in claim 2; it is characterized in that polymer [II] is [II-1]: the reactant of the polymer with carboxyl or acid anhydride and (methyl) acrylate containing hydroxyl, and/or [II-2]: at least part of the carboxyl in the polymer with carboxyl reacts to import the reactant of (methyl) acryloyl group with the unsaturated monomer containing epoxy group.

4. photosensitive heat curing resin combination according to any one of claims 1 to 3, it is characterised in that the softening point of epoxy resin shown in formula (changing I/E) is 50 DEG C or more, and the fusing point of Cristalline epoxy resin [V] is 110~135 DEG C.

5. photosensitive heat curing resin combination according to any one of claims 1 to 4, it is characterized in that epoxy resin shown in formula (changing I/E) is more than one chosen from block polymerization type resin shown in alternating polymerization type resin shown in homopolymerization type resin shown in following formula (changing I/E-1), following formula (changing I/E-2) and following formula (changing I/E-3)

(changing I/E-1)

(changing I/E-2)

(changing I/E-3)

In formula (change I/E-1)~(changing I/E-3), G with it is described synonymous,

In formula (changing I/E-1), A₃₁And A₃₃Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, in formula (changing I/E-1), a₃₁Indicate 1 or more integer, in formula (change I/E-1), A₃₂Indicating H or G, at least one is G,

In formula (changing I/E-2), A₄₁、A₄₃And A₄₅Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, in formula (changing I/E-2), a₄₁Indicate 1 or more integer, in formula (change I/E-2), A₄₂And A₄₄Can be identical or different, each independently represent H or G, but A₄₂And A₄₄The two is not H simultaneously,

In formula (changing I/E-3), A₅₁、A₅₃And A₅₅Each independently represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, in formula (changing I/E-3), a₅₁And a₅₂Each independently represent 1 or more integer, in formula (changing I/E-3), A₅₂And A₅₄Can be identical or different, each independently represent H or G, but A₅₂And A₅₄The two is not H simultaneously.

6. photosensitive heat curing resin combination described in claim 5, it is characterized in that resin (changing I/E-1) is following formula (changing I/E-1-1) and/or the resin that (changing I/E-1-2) indicates, resin (changing I/E-2) is more than one selected from the resin indicated respectively by following formula (changing I/E-2-1)~(changing I/E-2-4), resin (changing I/E-3) is more than one selected from the resin indicated respectively by following formula (changing I/E-3-1)~(changing I/E-3-4)

(changing I/E-1-1)

(changing I/E-1-2)

(changing I/E-2-1)

(changing I/E-2-2)

(changing I/E-2-3)

(changing I/E-2-4)

(changing I/E-3-1)

(changing I/E-3-2)

(changing I/E-3-3)

(changing I/E-3-4)

In the formula, G and described synonymous, A₆₁₁And A₆₂₁Respectively with the A₃₂It is synonymous, a₆₁₁And a₆₂₁Respectively with a₃₁It is synonymous, A₆₃₁、A₆₄₁、A₆₅₁And A₆₆₁Respectively with the A₄₂It is synonymous, A₆₃₂、A₆₄₂、A₆₅₂And A₆₆₂Respectively with the A₄₄It is synonymous, a₆₃₁、a₆₄₁、a₆₅₁And a₆₆₁Respectively with a₄₁It is synonymous, A₇₁₁、A₇₂₁、A₇₃₁And A₇₄₁Respectively with the A₅₂It is synonymous, A₇₁₂、A₇₂₂、A₇₃₂And A₇₄₂Respectively with the A₆₄It is synonymous, a₇₁₂、a₇₂₂、a₇₃₂And a₇₄₂Respectively with a₅₂It is synonymous,

In the formula, A₆₃₃、A₆₃₄、A₆₄₃、A₆₄₄、A₆₅₃、A₆₅₄、A₆₆₃、A₆₆₄、A₇₁₃、A₇₁₄、A₇₂₃、A₇₂₄、A₇₃₃、A₇₃₄、A₇₄₃And A₇₄₄It is each independently H or CH₃。

7. photosensitive heat curing resin combination according to any one of claims 1 to 6, it is characterised in that Cristalline epoxy resin [V] is more than one selected from the resin indicated respectively by following formula (changing V/1)~(changing V/9),

(changing V/1)

(changing V/2)

(changing V/3)

(changing V/4)

(changing V/5)

(changing V/6)

(changing V/7)

(changing V/8)

(changing V/9)

In formula (change V/1)~(changing V/9), G and described synonymous, in formula (change V/8), E₃₁~E₃₄Can be identical or different, each independently represent H or C1~C6 alkyl.

8. photosensitive heat curing resin combination according to any one of claims 1 to 7, it is characterized in that photosensitive heat curing resin combination also contains selected from [VII-1]: the Cristalline epoxy resin that 135~170 DEG C of fusing point, [VII-2]: single poly- carbodiimide, [VII-3] shown in following formula (changing VII-2): compound and [VII-4] containing allyl: more than one of the compound containing oxazoline group are as thermosetting component

(changing VII-2)

In formula (changing VII-2), G₂₁And G₂₃Each independently represent the aromatic residue, aliphatic residue or ester ring type residue of 1 valence, G₂₂Indicate aromatic residue, aliphatic residue or the ester ring type residue of divalent, g₂₁Indicate 0~30 number.

9. photosensitive heat curing resin combination according to any one of claims 8, it is characterized in that Cristalline epoxy resin [VII-1] is more than one selected from resin shown in following formula (changing VII-1/1)~(changing VII-1/3), compound [VII-3] containing allyl is the prepolymer containing allyl selected from average molecular weight 400~30000, diallyl 3 shown in (different) cyanurate three (first generation) allyl ester and following formula (changing VII-3/1), 6- methylene tetrahydric phthalimide compound more than one, compound [VII-4] containing oxazoline group is 2, 2- (1, 3- phenylene) two -2- oxazolines and/or the polymer containing oxazoline group,

(changing VII-1/1)

(changing VII-1/2)

(changing VII-1/3)

In formula (change VII-1/1)~(changing VII-1/3), G and described synonymous, in formula (change VII-1/1), g₁₁Indicate 0~2 number,

(changing VII-3/1)

In formula (changing VII-3/1), G₇₁Indicate the divalent group that following formula (changing VII-3/1-R1), (changing VII-3/1-R2) or (changing VII-3/1-R3) indicates,

(changing VII-3/1-R1)

(changing VII-3/1-R2)

(changing VII-3/1-R3)

In formula (changing VII-3/1-R3), g₈₁Indicate 4~8 integer.

10. being coated with the printing distributing board of resist, it is characterised in that resist contains photosensitive heat curing resin combination according to any one of claims 1 to 9.

11. the printing distributing board described in any one of claim 10 coated with resist, wherein printing distributing board is the recess portion resin filling of printed wiring plate surface to make the smoothing printing distributing board of smooth surface.

12. the manufacturing method of the printing distributing board described in claim 10 or 11 coated with resist, it is characterized in that in the manufacturing method of printing distributing board for being coated with resist, the dry film photoresist for containing photosensitive heat curing resin combination according to any one of claims 1 to 9 using the liquid photosensitive resist agent containing photosensitive heat curing resin combination according to any one of claims 1 to 9 or in photoresist, coats resist in printed wiring plate surface.

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