CN1755524B - Phototonus thermosetting resin composition and printing plug board coating with resist and its manufacturing method - Google Patents
Phototonus thermosetting resin composition and printing plug board coating with resist and its manufacturing method Download PDFInfo
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- CN1755524B CN1755524B CN 200510107592 CN200510107592A CN1755524B CN 1755524 B CN1755524 B CN 1755524B CN 200510107592 CN200510107592 CN 200510107592 CN 200510107592 A CN200510107592 A CN 200510107592A CN 1755524 B CN1755524 B CN 1755524B
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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, andthe 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 bycomprising 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
Technical field
The present invention relates to for useful photosensitive heat curing resin combinations and the printing distributing board (particularly being coated with the smoothing printing distributing board of solder resist etc.) and the manufacture method thereof that are coated with resist such as etchingresistant printing materials (particularly solder mask ink).
Technical background
With resin against corrosion or seal feed composition, known use reacts the epoxy resin of ad hoc structure and (methyl) acrylic acid reactant and polybasic carboxylic acid (acid anhydrides) to the polycarboxylic acid resin that contains unsaturated group that obtains as the active energy ray-curable resin as the photosensitive printing distributing board.
For example, put down in writing the polycarboxylic acid resin that contains unsaturated group in the patent documentation 1～3 by ad hoc structure, thinning agent [trimethylolpropane tris (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate etc.], Photoepolymerizationinitiater initiater, epoxy compound [phenol-novolac epoxy resin, cresol-novolac epoxy resin, bisphenol-type epoxy resin, three (2, the 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, di-toluene phenol-type epoxy resin, bisphenol-type epoxy resin triglycidyl group isocyanuric acid ester etc.) and the printing distributing board that constitutes of epoxy curing agent (dicyandiamide etc.) with welding resistance resin combination or flexible printing distributing board etchingresistant printing material composition.
The purpose of patent documentation 1 is to provide the printing distributing board welding resistance resin combination of the solder resist of development property excellence and cohesive, welding rod thermotolerance, resistance to chemical reagents, anti-gold-plated attribute, electrical insulating property excellence.
The purpose of patent documentation 2 and patent documentation 3 is to provide and gives and can develop with dilute alkaline aqueous solution, and the flexible printing distributing board etchingresistant printing material composition of excellent resist such as pliability, folding resistance, cohesive, resistance to chemical reagents, thermotolerance.
But the resin against corrosion-Yin feed composition of patent documentation 1～3 has the not so good problem of dry to touch of filming.In addition, therefore the resin against corrosion-Yin feed composition of patent documentation 1～3 has the problem of storage stability (shelf life) difference owing to almost use the solvent soluble resin.In addition, there is HAST (Highly Accelerated Temperature and Humidity Stress Test: the unsaturated steam under pressure test) problem of patience (the particularly HAST patience in the electrical insulating property) and resistance to sudden heating deficiency by this resist that resin against corrosion-the Yin feed composition obtains.
With resin against corrosion-Yin feed composition, (or as side group) has the reactant-polymkeric substance-resin of acidic group (carboxyl), ester group and (methyl) acryloyl group etc. in the known use side chain as other photosensitive printing distributing boards.
For example, in patent documentation 4, put down in writing by the polycarboxylic acid resin that contains unsaturated group, epoxy (methyl) acrylate of other ad hoc structure, had carboxyl or acid anhydride's polymkeric substance and contain the alkali developable photosensitive heat curing solder mask ink composition that reactant, three (2, the 3-glycidyl) isocyanuric acid ester, thinning agent (dipentaerythritol polyacrylate etc.), Photoepolymerizationinitiater initiater and the epoxy curing agent (dicyandiamide etc.) of (methyl) acrylate of hydroxyl constitute.
The purpose of patent documentation 4 is to provide alkali developable photosensitive heat curing solder mask ink composition, it gives excellences such as storage-stable, the thermal stability when predrying, alkali-developable, photonasty, and excellent solder resists such as cohesive, electrical insulating property, welding rod thermotolerance, resistance to chemical reagents, anti-gold-plated attribute.
But by the resist that the etchingresistant printing material composition of patent documentation 4 obtains, its transparency of filming is low.Therefore, in printing distributing board, there is the problem that is difficult to directly the printing distributing board surface be carried out visualization and inspection from the outside with this resist lining.In addition, HAST patience of the resist of patent documentation 4 (the particularly HAST patience in the electrical insulating property) and resistance to sudden heating deficiency, and also the resistance to bend(ing) of filming etc. can not be fully satisfied.In addition, the etchingresistant printing material composition that has used liquid epoxy resin is also disclosed in the patent documentation 4, but when using liquid epoxy resin, compare, have the problem of storage stability (shelf life) difference of etchingresistant printing material composition with the situation of having used crystallinity epoxy resin.
Put down in writing Photocurable composition in the patent documentation 5; it is made of base polymer, photopolymerization monomer [2-hydroxyethyl (methyl) acrylate etc.], light trigger, and this base polymer is to import (methyl) acryloyl group with fatty alcohol after with a part of addition of the anhydride rings in the copolymer-maleic anhydride, open loop to obtain.
The purpose of patent documentation 5 is to provide the covering that can form fine pattern and positional precision excellence with photoetch method, and can develop by enough aqueous alkalis, and having the cohesive of abundant water-fast dissolubility flux, while thermotolerance, engineering properties and chemical property be the Photocurable composition of excellence also.
But the Photocurable composition of patent documentation 5 is identical with described patent documentation 4, has the not so good problem of storage stability.In addition, the resist that is obtained by the etchingresistant printing material composition of patent documentation 5 is identical with described patent documentation 1～4, and the transparency of filming, HAST patience (the particularly HAST patience in the electrical insulating property), resistance to sudden heating and the resistance to bend(ing) of filming etc. can not be fully satisfied.
Put down in writing in the patent documentation 6 by having carboxyl; the active energy ray-curable resin of ester group and (methyl) acryloyl group etc.; thinning agent (2-hydroxy ethyl methacrylate; pentaerythrite; dipentaerythritol; multicomponent methacrylate class of polyvalent alcohols such as tris(2-hydroxy ethyl)isocyanurate or their oxirane or propylene oxide adduct etc.); Photoepolymerizationinitiater initiater; the bonding imparting agent of curable (S-triaizine compounds etc.); compound (bisphenol-s epoxy resin with epoxy radicals; the o-phthalic acid diglycidyl ester resin; the heterocyclic ring epoxy resins; di-toluene phenol-type epoxy resin; four glycidyl group dimethylbenzene acyl group ethane resin etc.) the optical polymerism compositions of thermosetting resin of Gou Chenging.
The purpose of patent documentation 6 is to provide as operation (coating, drying property, stickability, photo-curable, development, Thermocurable, storage stability-shelf life) excellence, can make printing distributing board with the short time, the useful optical polymerism compositions of thermosetting resin of aqueous photoresist that can alkali develops that cured film characteristic (cohesive on the electrical specification under welding rod thermotolerance, solvent resistance, resistance to chemical reagents, cohesive, electrical insulating property, electric erosion resistance, the humidification, anti-plating, the antirust treatment substrate) is excellent.
But, the resist that obtains by the optical polymerism compositions of thermosetting resin of patent documentation 6, identical with described patent documentation 1～5, the transparency of filming, HAST patience (the particularly HAST patience in the electrical insulating property), resistance to sudden heating and the resistance to bend(ing) of filming etc. can not be fully satisfied.
The present patent application people in first to file in the cured film the remaining and surface grinding of no bubble be easy to compositions of thermosetting resin and thereby the recess that fills it on the substrate has the flat runner and the manufacture method (patent documentation 7) thereof of the surface smoothing of height.
Patent documentation 1: the spy opens flat 5-32746 communique.
Patent documentation 2: the spy opens flat 7-207211 communique.
Patent documentation 3: the spy opens flat 8-134390 communique.
Patent documentation 4: the spy opens flat 3-250012 communique.
Patent documentation 5: the spy opens clear 63-72710 communique.
Patent documentation 6: the spy opens flat 10-20493 communique.
Patent documentation 7: the spy opens the 2003-26765 communique.
Summary of the invention
In view of described situation, the object of the present invention is to provide the photosensitive heat curing resin combination, it can give excellent resist such as excellent storage stability and development, dry to touch, resistance to bend(ing), cohesive, the transparency of filming, HAST patience (the particularly HAST patience in the electrical insulating property) and resistance to sudden heating.
In addition, the present invention also aims to provide the printing distributing board (particularly smoothing printing distributing board) and the manufacture method thereof of resist with described excellence.
In order to reach described purpose, carried out research with keen determination, its result has finished the present invention.
That is, the invention provides the photosensitive heat curing resin combination, it contains:
[I]: contain the polycarboxylic acid resin of unsaturated group, it is the epoxy resin shown in the following formula (change I/E) and contains the monocarboxylic reactant of unsaturated group and the reactant of polybasic carboxylic acid or its acid anhydrides,
In the formula (changing I/E), G is a following formula
The group of expression, A
11, A
13And A
15Expression can be identical or different the aromatic residue or the hydrogenated aromatic residue of divalent, A
12And A
14Can be identical or different, represent H or G independently of one another, wherein A
12And A
14Both are not H simultaneously, a
11And a
12Expression can be identical or different the integer more than 0, but a
11And a
12Be not 0 simultaneously;
[III]: thinning agent;
[IV]: Photoepolymerizationinitiater initiater;
[V]: the crystallinity epoxy resin of following formula (changing V) expression,
In the formula (changing V), G and described synonym, E
11～E
13And E
15～E
17Expression can be identical or different H or C1～C5 alkyl, e
11And e
12Expression can be identical or different 0～3 integer, E
14Expression S, O ,-CH
2-,-C (CH
3)
2Or the divalent group of following formula (changing V/X) or (changing F) expression,
In the formula (changing V/X), E
21～E
24Can be identical or different, represent C1～C6 alkyl independently of one another; With
[VI]: solidify the cohesive imparting agent.
The invention provides described photosensitive heat curing resin combination, this photosensitive heat curing resin combination also contains [II]: have carboxyl and (methyl) acryloyl group, acid number (mgKOH/g) be 20～160 and mean molecular weight be 3000～70000 polymkeric substance.
The invention provides described photosensitive heat curing resin combination; wherein polymkeric substance [II] is [II-1]: polymkeric substance with carboxyl or acid anhydride and the reactant that contains (methyl) acrylate of hydroxyl, and/or [II-2]: thus at least a portion with the carboxyl in the polymkeric substance of carboxyl and the unsaturated monomer reaction that contains epoxy radicals have imported the reactant of (methyl) acryloyl group.
The invention provides described each photosensitive heat curing resin combination, the softening point of the epoxy resin shown in its Chinese style (changing I/E) is more than 50 ℃, and the fusing point of crystallinity epoxy resin [V] is 110～135 ℃.
The invention provides described each photosensitive heat curing resin combination, epoxy resin shown in its Chinese style (changing I/E) is more than one that choose from alternating polymerization type resin shown in the homopolymerization type resin shown in the following formula (changing I/E-1), the following formula (changing I/E-2) and the block polymerization type resin shown in the following formula (changing I/E-3)
In formula (changing I/E-1)～(the changing I/E-3), G and described synonym,
In the formula (changing I/E-1), A
31And A
33Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, in the formula (changing I/E-1), a
31The integer of expression more than 1, in the formula (changing I/E-1), A
32Expression H or G, at least one is G,
In the formula (changing I/E-2), A
41, A
43And A
45Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, in the formula (changing I/E-2), a
41The integer of expression more than 1, in the formula (changing I/E-2), A
42And A
44Can be identical or different, represent H or G independently of one another, but A
42And A
44Both are not H simultaneously,
In the formula (changing I/E-3), A
51, A
53And A
55Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, in the formula (changing I/E-3), a
51And a
52Represent the integer more than 1 independently of one another, in the formula (changing I/E-3), A
52And A
54Can be identical or different, represent H or G independently of one another, but A
52And A
54Both are not H simultaneously.
The invention provides described photosensitive heat curing resin combination, wherein resin (changing I/E-1) is the resin of following formula (changing I/E-1-1) and/or (changing I/E-1-2) expression, resin (change I/E-2) is for being selected from respectively by more than one of the resin of following formula (changing I/E-2-1)～(changing I/E-2-4) expression, resin (change I/E-3) is for being selected from respectively by more than one of the resin of following formula (changing I/E-3-1)～(changing I/E-3-4) expression
In the described formula, G and described synonym, A
611And A
621Respectively with described A
32Synonym, a
611And a
621Respectively with described a
31Synonym, A
631, A
641, A
651And A
661Respectively with described A
42Synonym, A
632, A
642, A
652And A
662Respectively with described A
44Synonym, a
631, a
641, a
651And a
661Respectively with described a
41Synonym, A
711, A
721, A
731And A
741Respectively with described A
52Synonym, A
712, A
722, A
732And A
742Respectively with described A
64Synonym, a
712, a
722, a
732And a
742Respectively with described a
52Synonym,
In the described formula, A
633, A
634, A
643, A
644, A
653, A
654, A
663, A
664, A
713, A
714, A
723, A
724, A
733, A
734, A
743And A
744Be H or CH independently of one another
3
The invention provides described each photosensitive heat curing resin combination, wherein crystallinity epoxy resin [V] is for being selected from respectively by more than one of the resin of following formula (changing V/1)～(changing V/9) expression,
In formula (changing V/1)～(the changing V/9), G and described synonym, in the formula (changing V/8), E
31～E
34Can be identical or different, represent H or C1～C6 alkyl independently of one another.
The invention provides described each photosensitive heat curing resin combination, it also contains and is selected from [VII-1]: the crystallinity epoxy resin that fusing point is 135～170 ℃, [VII-2]: the poly-carbodiimide of list shown in the following formula (changing VII-2), [VII-3]: more than one of compound that contain allylic compound and [VII-4]: Han oxazolinyl are as the thermosetting composition
In the formula (changing VII-2), G
21And G
23Aromatic residue, aliphatic residue or the ester ring type residue of representing 1 valency independently of one another, G
22Aromatic residue, aliphatic residue or the ester ring type residue of expression divalent, g
21The number of expression 0～30.
The invention provides described photosensitive heat curing resin combination, wherein crystallinity epoxy resin [VII-1] is for being selected from more than one of resin shown in following formula (change VII-1/1)～(the changing VII-1/3), contain allylic compound [VII-3] for being selected from containing of mean molecular weight 400～30000 of allylic prepolymer, diallyl 3 shown in (different) cyanogen urea acid three (first generation) allyl ester and the following formula (changing VII-3/1), the compound [VII-4] of more than one Han oxazolinyls of methylene tetrahydric phthalimide (bisallylnadiimide) compound is 2 in the 6-, 2-(1, the 3-phenylene) polymkeric substance of two-2-oxazoline and/or Han You oxazolinyl
In formula (changing VII-1/1)～(the changing VII-1/3), G and described synonym, in the formula (changing VII-1/1), g
11The number of expression 0～2,
In the formula (changing VII-3/1), G
71The divalent group of expression following formula (changing VII-3/1-R1), (changing VII-3/1-R2) or (changing VII-3/1-R3) expression,
In the formula (changing VII-3/1-R3), g
81The integer of expression 4～8.
The invention provides the printing distributing board that is coated with resist, wherein resist contains described each photosensitive heat curing resin combination.
The invention provides the described printing distributing board that is coated with resist, thereby wherein printing distributing board is that the recess on printing distributing board surface is filled the smoothing printing distributing board make surface smoothing with resin.
The invention provides described each the manufacture method of the printing distributing board that is coated with resist, wherein in the manufacture method of the printing distributing board that is coated with resist, use contain described each the photosensitive heat curing resin combination aqueous photosensitive resist agent or in photoresist, contain described each the dry film photoresist of photosensitive heat curing resin combination, on the printing distributing board surface, apply resist.
Adopt the present invention, the photosensitive heat curing resin combination of the resist that can give excellent storage stability and development, dry to touch, resistance to bend(ing), cohesive, the transparency of filming, HAST patience (the particularly HAST patience in the electrical insulating property) and resistance to sudden heating excellence can be provided.
In addition, adopt the present invention, the smoothing printing distributing board and the manufacture method thereof of the resist with described excellence can be provided.
Description of drawings
Fig. 1 is the sectional drawing that is coated with the smoothing printing distributing board of resist of the present invention.
Fig. 2 is for having the sectional drawing of the printing distributing board of recess between circuit.
Fig. 3 is the sectional drawing of smoothing printing distributing board.
Fig. 4 is the sectional drawing of dry film photoresist involved in the present invention.
Symbol description
1: resist
2: photoresist
3: recess
4: cured resin
5: insulated substrate
6: conductor circuit
7: antistatic layer
8: carrier film
9: the water soluble resin layer
10: diaphragm
Embodiment
Below the present invention is described in detail.
In photosensitive heat curing resin combination of the present invention, contain the polycarboxylic acid resin that [I] contains unsaturated group.By containing the polycarboxylic acid resin that [I] contains unsaturated group, can improve development, resistance to bend(ing) and the cohesive etc. of the storage stability and the resist of photosensitive heat curing resin combination.
The polycarboxylic acid resin that [I] contains unsaturated group is by making epoxy resin shown in the following formula (changing I/E) and the monocarboxylic acid reaction that contains unsaturated group, this reactant and polybasic carboxylic acid or its anhydride reaction being obtained.
In the formula (change I/E), G is a glycidyl, the group of representing for following formula.
In the formula (changing I/E), each repetitive putting in order in resin matrix shown in following formula (changing I/E-U1) and (the changing I/E-U2) do not carried out any regulation (qualification).
Therefore, when repetitive (change I/E-U1) and (change I/E-U2) are inequality, as resin (changing I/E), can enumerate resin that repetitive for example (changing I/E-U1) and (change I/E-U2) be arranged in the block polymerization type, be arranged in the resin of alternating polymerization type and be arranged in the resin etc. of atactic polymerization type, can use these more than one.
In the formula (changing I/E), A
11, A
13And A
15Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, preferred A
15Be A
11Or A
13
At A
11, A
13And A
15In, as the aromatic residue of divalent, can enumerate divalent group, phenylene or the naphthylene etc. shown in for example following formula (changing I/E-Ar1).
In the formula (changing I/E-Ar1), A
21Expression (ring) alkylidene ,-O-,-CO-,-COO-,-S-,-S-S-,-SO-,-SOO-or following formula (changing F)
The divalent group of expression, a
21 Be 0 or 1.
In aromatic residue,, can enumerate A as divalent group (changing I/E-Ar1)
21Group for (ring) alkylidene.As (ring) alkylidene, can enumerate for example group of C1～C8.(ring) alkylidene can have substituting group [for example C1～C6 (ring) alkyl, aryl ,-CF
3Base etc.].In addition, in formula (changing I/E-Ar1), on a side or two sides' phenyl ring, can also have the substituting group (for example C1～C6 alkyl, halogen atom etc.) more than 1.Specifically, as this aromatic residue, can enumerate the group shown in following formula (changing I/E-Ar1-1)～(the changing I/E-Ar1-5) etc.
In aromatic residue,, can enumerate A as other divalent group (changing I/E-Ar1)
21For-O-,-CO-,-COO-,-S-,-S-S-,-SO-or-group of SOO-.In addition, in formula (changing I/E-Ar1), on a side or two sides' phenyl ring, can have the substituting group (for example C1～C6 alkyl, halogen atom etc.) more than 1.Specifically, as this aromatic residue, can enumerate the group shown in following formula (changing I/E-Ar1-6) and (the changing I/E-Ar1-7) etc.
In aromatic residue,, can enumerate A as other divalent group (changing I/E-Ar1)
21Be following formula (changing F)
Shown group etc.In addition, in formula (change I/E-Ar1), on a side or two sides' phenyl ring, can have substituting group more than 1 (for example C1～C6 alkyl etc.).Specifically, as this aromatic residue, can enumerate the group shown in the following formula (changing I/E-Ar1-F) etc.
In aromatic residue,, can enumerate a as other divalent group (changing I/E-Ar1)
21It is 0 group.In addition, in formula (changing I/E-Ar1), on a side or two sides' phenyl ring, can have the substituting group (for example C1～C6 alkyl, halogen atom etc.) more than 1.Specifically, as this aromatic residue, can enumerate the group shown in following formula (changing I/E-Ar1-8) and (the changing I/E-Ar1-9) etc.
In aromatic residue, as phenylene, at the substituting group (for example C1～C6 alkyl, halogen atom etc.) that can have on the aromatic rings more than 1.Specifically, as phenylene, can enumerate the group shown in the following formula (changing I/E-Ar2-1) etc.
In aromatic residue,, can enumerate the group shown in the following formula (changing I/E-Ar3-1) etc. particularly as naphthylene.
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).
At A
11, A
13And A
15In, as the hydrogenated aromatic residue of divalent, can enumerate group with the aromatic rings hydrogenation (hydrogenation) in the described aromatic residue etc.Replace described aromatic residue, can make A
11, A
13And A
15In at least a portion be the hydrogenated aromatic residue.When being the hydrogenated aromatic residue when replacing aromatic residue, the compatibility that has with closing property of acrylic acid copolymer resin improves the advantage that weatherability also improves.
As the hydrogenated aromatic residue, can enumerate complete hydrogenation and partially hydrogenated aromatic residue.Specifically, as the hydrogenated aromatic residue, can enumerate with the unsaturated link in the aromatic residue (two keys etc.) fully hydrogenation and become the group of saturated bond and be hydrogenated to the stage in the middle of it group and with unsaturated links all in the aromatic rings all hydrogenation group and only with the group of the unsaturated link hydrogenation of a part in the aromatic rings etc.
When use has the epoxy resin (change I/E) of hydrogenated aromatic residue, can make weatherability and with the raisings such as compatibility of acrylic copolymer.
Hydrogenation conditions is suitably selected according to the degree (for example hydrogenation 40～100%) of hydrogenation, for example, can use the fixed bed flow through reactors of the preformed catalyst of having filled the appendix ruthenium, use with gas-liquid upwards and stream make the material solution that is dissolved in the ether solvent and hydrogen be passed to fluidized bed process in the reactor, under the scope of velocity of liquid assets (LHSV) 0.2～10/h of the scope of the scope of 10～150 ℃ of temperature of reaction, reaction pressure (hydrogen-pressure) 0.5～15MPa, material solution, carry out hydrogenation.
At A
11, A
13And A
15In, as the hydrogenated aromatic residue, part or all that specifically can enumerate group shown in following formula (change I/E-S-1)～(the changing I/E-S-12) and their cyclohexane ring becomes the group of cyclohexene ring etc.
In the formula (changing I/E), a
11And a
12Expression can be identical or different the integer more than 0, but a
11And a
12Be not 0 simultaneously.a
11And a
12Summation (a
11+ a
12) can be for example 1～30.Work as a
11And a
12Summation (a
11+ a
12) when big, the dry to touch excellence.
In the formula (changing I/E), A
12And A
14Can be identical or different, represent H or G independently of one another.Especially, a
11Individual A
12Can be identical or different, represent H or G independently of one another.Similarly, a
12Individual A
14Can be identical or different, represent H or G independently of one another.But, all A
12And A
14Be not H simultaneously.Preferred a
11Be not 0 o'clock, a
11Individual A
12In have 1 at least for G.Similarly, preferred a
12Be not 0 o'clock, a
12Individual A
14In have 1 at least for G.
In addition, the preferred softening point of epoxy resin (changing I/E) is more than 50 ℃ (preferred especially 60～100 ℃).By making softening point is more than 50 ℃, has the advantage that dry to touch raising and photonasty improve.
As epoxy resin (changing I/E), can enumerate homopolymerization resin and copolymer resins etc., can use these more than one.Kind as " resin ", for example novolac epoxy resin, triphenyl methane type epoxy resin, di-toluene phenol-type epoxy resin, dicyclopentadiene phenolic aldehyde type epoxy resin, naphthalene framework ring epoxy resins, fluorenes type epoxy resin, silicone-modified epoxy resin and the 6-caprolactone modified epoxy etc. of bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-A/F and the type of using epoxy resin, novolac epoxy resin, bisphenol-A (or F) can be enumerated, they more than one can be used.
As epoxy resin (changing I/E), block copolymerization type resins shown in alternating copolymerization type resin shown in homopolymerization type resin shown in the preferred following formula (change I/E-1), the following formula (changing I/E-2) and the following formula (changing I/E-3) etc. can use they more than one.
In formula (changing I/E-1)～(the changing I/E-3), G and described synonym.
In the formula (changing I/E-1), A
31And A
33Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, but preferred A
33Be A
31At A
31And A
33In, as the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, can be described A
11, A
13And A
15In cited group.In the formula (changing I/E-1), a
31Expression integer of (for example 1～30) more than 1.In the formula (changing I/E-1), A
32Represent H or G, but at least 1 is G.
In the formula (changing I/E-2), A
41, A
43And A
45Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, preferred A
45Be A
41Or A
43At A
41, A
43And A
45In, as the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, can be at described A
11, A
13And A
15The illustrative group of middle explanation.In the formula (changing I/E-2), a
41Expression integer of (for example 1～15) more than 1.In the formula (changing I/E-2), A
42And A
44Can be identical or different, represent H or G independently of one another.Especially, a
41Individual A
42Can be identical or different, represent H or G independently of one another.Similarly, a
41Individual A
44Can be identical or different, represent H or G independently of one another.But, all A
42And A
44Be not H simultaneously.Preferred a
41Individual A
42In have 1 at least for G.Similarly, preferred a
41Individual A
44In have 1 at least for G.
In the formula (changing I/E-3), A
51, A
53And A
55Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, preferred A
55Be A
51Or A
53At A
51, A
53And A
55In, as the aromatic residue of divalent or the hydrogenated aromatic residue of divalent, can be at described A
11, A
13And A
15The illustrative group of middle explanation.In the formula (changing I/E-3), a
51And a
52The integer of representing more than 1 (for example 1～15) independently of one another.In the formula (changing I/E-3), A
52And A
54Can be identical or different, represent H or G independently of one another.Especially, a
51Individual A
52Can be identical or different, represent H or G independently of one another.Similarly, a
52Individual A
54Can be identical or different, represent H or G independently of one another.But, all A
52And A
54Be not H simultaneously.Preferred a
51Individual A
52In have 1 at least for G.Similarly, preferred a
52Individual A
54In have 1 at least for 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, the resin properties-feature of resin (changing I/E-1) is because of basic framework A
31Difference and difference.Specifically, work as A
31In when importing the Bisphenol F type, have pliability, fusible resin properties-feature.Work as A
31During middle importing group (changing I/E-Ar1-9), has the resin properties-feature of crystallinity, low water absorption.Therefore, in order to obtain both features, can be with the epoxy blend of various homopolymerization types.On the other hand, by using the copoly type epoxy resin that in a part, has imported described skeleton respectively, also can synthesize the resin of the characteristic-feature that has two resins concurrently.Therefore, by using the epoxy resin of copoly type, can make the situation equilibrium that exists in the relation of cancelling out each other as resin properties and additional function.
In epoxy resin (changing I/E), as resin (changing I/E-1), specifically can enumerate the resin shown in following formula (changing I/E-1-1) and (the changing I/E-1-2). as resin (changing I/E-2), specifically can enumerate respectively by the following formula resin that (change I/E-2-1)～(changing I/E-2-4) represented. as resin (changing I/E-3), specifically can enumerate respectively by the following formula resin that (change I/E-3-1)～(changing I/E-3-4) represented. as epoxy resin (changing I/E), can use these more than one.
In described formula, G and described synonym.A
611And A
621Respectively with described A
32Synonym.a
611And a
621Respectively with described a
31Synonym.A
631, A
641, A
651And A
661Respectively with described A
42Synonym.A
632, A
642, A
652And A
662Respectively with described A
44Synonym.a
631, a
641, a
651And a
661Respectively with described a
41Synonym.A
711, A
721, A
731And A
741Respectively with described A
52Synonym.A
712, A
722, A
732And A
742Respectively with described A
64Synonym.a
712, a
722, a
732And a
742Respectively with described a
52Synonym,
In described formula, A
633, A
634, A
643, A
644, A
653, A
654, A
663, A
664, A
713, A
714, A
723, A
724, A
733, A
734, A
743And A
744Be H or CH independently of one another
3Preferred A respectively
633And A
634Identical, A
643And A
644Identical, A
653And A
654Identical, A
663And A
664Identical, A
713And A
714Identical, A
723And A
724Identical, A
733And A
734Identical, A
743And A
744Identical.
The epoxy resin of alternating copolymerization type, for example epoxy resin (change I/E-2-1) is at first to make bisphenol A type epoxy resin and 4, behind 4 '-dihydroxy diphenyl methane addition copolymerization, epoxidation modulates by remaining hydroxyl is carried out.
The epoxy resin of block copolymerization type, after for example epoxy resin (change I/E-3-1) was homopolymer (n is more than 1) the binding addition of the homopolymer (n is more than 1) that for example makes bisphenol A type epoxy resin and bisphenol f type epoxy resin, epoxidation modulated by remaining hydroxyl is carried out.
As with the monocarboxylic acid that contains unsaturated group of epoxy resin (change I/E) reaction, can enumerate and have ethylenic unsaturated link and carboxyl in the molecule (the monocarboxylic acid that comprises carboxylic acid group-COOH).In addition, ethylenic unsaturated link and carboxyl be conjugation (adjacency) mutually, also conjugation (adjacency) not.
Specifically, as the monocarboxylic acid that contains 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.
Epoxy resin (change I/E) with contain in the monocarboxylic reaction of unsaturated group, can make the epoxy radicals of per 1 equivalent epoxy resin (changing I/E) that 0.8～1.3 mole the monocarboxylic acid reaction that contains unsaturated group is arranged.
Then, make the epoxy resin that obtains like this (changing I/E) and the monocarboxylic reactant that contains unsaturated group (below be sometimes referred to as " initial reaction thing ") and polybasic carboxylic acid or its acid anhydrides (below be sometimes referred to as " polybasic carboxylic acid (acid anhydride) ") reaction, modulation contains the polycarboxylic acid resin [I] of unsaturated group.
As polybasic carboxylic acid (acid anhydride), can enumerate for example C1～C8 dicarboxylic acid (acid anhydride).Specifically can enumerate succinic acid (acid anhydride), maleic acid (acid anhydride), fumaric acid (acid anhydride), itaconic acid (acid anhydride), four or hexahydrophthalic acid (acid anhydride) etc.
In the reaction of reactant and polybasic carboxylic acid (acid anhydride), with respect to the hydroxyl in the initial reaction thing, preferred per 1 equivalent hydroxyl makes the reaction of 0.05～1.00 equivalent polybasic carboxylic acid in the early stage.In the reaction of reactant and polybasic carboxylic acid (acid anhydride), with respect to the hydroxyl in the initial reaction thing, preferred per 1 equivalent hydroxyl makes 0.1～0.9 equivalent polybasic carboxylic acid anhydride reactant in the early stage.
Polycarboxylic acid resin [I] preferred acid number (mgKOH/g) 40～150 (preferred especially 50～120) that contains unsaturated group.If acid number is low excessively, the development residue increases sometimes, if opposite too high, the moisture-proof of filming reduces sometimes.
In photosensitive heat curing resin combination of the present invention, as composition [II], can contain and have carboxyl and (methyl) acryloyl group, acid number be 20～160 and mean molecular weight be 3000～70000 polymkeric substance.If the acid number less than 20 of polymkeric substance [II], alkali-developable reduces sometimes, if opposite to 160, the moisture-proof of filming reduces sometimes.If the mean molecule quantity not sufficient 3000 of polymkeric substance [II], is reduced sometimes by film development dry to touch,, reduce sometimes with compatibility, the cohesive of resin if surpass 70000 on the contrary.
In addition, preferred respectively per 1000 molecular weight of the carboxyl number in the polymkeric substance [II] and (methyl) acryloyl radix are 0.2～5.0 and 0.2～4.0.
Especially, reactant described later [II-1] preferred acid number is 20～160, and mean molecular weight is 3000～30000, and carboxyl number is 0.2～5.0 of per 1000 molecular weight, and (methyl) acryloyl radix is 0.2～4.0 of per 1000 molecular weight.Reactant [II-2] preferred acid number is 20～160, and mean molecular weight is 3000～30000, and carboxyl number is 0.2～5.0 of per 1000 molecular weight, and (methyl) acryloyl radix is 0.2～4.0 of per 1000 molecular weight.
By containing polymkeric substance [II], can make the dry to touch raising of filming.When making the photosensitive dry film resist, can improve the fissility of diaphragm.
As polymkeric substance [II], from viewpoints such as the security used and acquired easily, synthetic simplicities, preferred [II-1]: have carboxyl or acid anhydride's polymkeric substance and contain the reactant of (methyl) acrylate of hydroxyl.
In reactant [II-1],, can enumerate for example making as ethylenic unsaturated acid homopolymerization that must monomer or (methyl) acrylic resin that copolymerization obtains as the polymkeric substance with carboxyl of brewable material.Preferably (methyl) acrylic resin is ethylenic unsaturated acid and the multipolymer that contains the monomer of ethylenic unsaturated link.
In (methyl) acrylic resin, as the ethylenic unsaturated acid, specifically can enumerate 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 use these more than one.
In (methyl) acrylic resin, as the monomer that contains the ethylenic unsaturated link, specifically can enumerate C1～C8 alkyl (methyl) acrylate [(methyl) methyl acrylate, (methyl) ethyl acrylate etc.], 2-hydroxyl C1～C18 alkyl (methyl) acrylate [2-methylol (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate etc.], ethylene glycol methacrylate, glycol monomethyl methyl acrylate, glycol monomethyl ethyl propylene acid esters, glycol monomethyl ethyl-methyl acrylate, the glycerine acrylate, the glycerine methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-EHA, methacrylic acid 2-Octyl Nitrite, benzyl acrylate, benzyl methacrylate, carbitol acrylate, the methacrylic acid carbitol ester, 6-caprolactone modified acroleic acid tetrahydrochysene chaff ester, 6-caprolactone modified methacrylic acid tetrahydrochysene chaff ester, diglycol ethoxy propylene acid esters, isodecyl acrylate, isodecyl methacrylate, 2-ethyl hexyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, methacrylic acid tridecyl ester, the stearyl acrylate ester, methacrylic acid stearyl esters etc. can use these more than one.
Specifically, (methyl) acrylic resin can be enumerated the multipolymer etc. of multipolymer, methacrylic acid and the methyl acrylate of methacrylic acid and isobutyl methacrylate, can use these more than one.
The preferred mean molecular weight of polymkeric substance with carboxyl is 3000～30000, and the carboxyl number in the resin is 0.2～5.0 of per 1000 molecular weight, and acid number is 20～160.
In reactant [II-1],, can enumerate the polymkeric substance shown in the following formula (changing II-1/An) as polymkeric substance with acid anhydride.
[in the formula (changing II-1/An), B
11And B
12Represent H, C independently of one another
1～C
3Alkyl or aromatic group (phenyl, phenol etc.).b
11And b
12The integer of all representing 10～500 (preferred 15～300)].
In formula (changing II-1/An), to the putting in order in the polymkeric substance that contains the acid anhydride base (changing II-1/An) skeleton of each repetitive shown in following formula (changing II-1/An-U1) and (the changing II-1/An-U2) without any regulation (qualification).
[in the formula (changing II-1/An-U2), B
11And B
12With described identical].
Therefore, when repetitive (change II-1/An-U1) and (change II-1/An-U2) not simultaneously, as the polymkeric substance that contains the acid anhydride base (changing II-1/An), can enumerate polymkeric substance that repetitive for example (changing II-1/An-U1) and (change II-1/An-U2) be arranged as the block polymerization type, be arranged as the polymkeric substance of alternating polymerization type and be arranged as the polymkeric substance etc. of atactic polymerization type, can use these more than one.
As the polymkeric substance that contains the acid anhydride base (changing II-1/An), the polymkeric substance of the alternating polymerization type shown in the preferred following formula (changing II-1/An-1).
[in the formula (changing II-1/An-1), B
21And B
22Respectively with described B
11And B
12Identical.b
21The integer of expression 5～400 (preferred 10～300)].
Specifically, as polymkeric substance with acid anhydride, the multipolymer of multipolymer, styrene and maleic anhydride of multipolymer, α-isobutylene and maleic anhydride of styrene and maleic anhydride and reactant of alkylol etc. can be enumerated, these more than one can be used.
The preferred mean molecular weight of polymkeric substance with acid anhydride is 3000～30000, and the acid anhydrides radix in the resin is 0.2～5.0 of per 1000 molecular weight, and acid number is 20～160.
In reaction equation [II-1],, can enumerate the material shown in the following formula (changing II-1/Ac) etc. as (methyl) acrylate that contains hydroxyl.
[in the formula (changing II-1/Ac), B
31Expression C1～C6 alkylidene].
Specifically, as (methyl) acrylate that contains hydroxyl (changing II-1/Ac), reactant, pentaerythrite three (methyl) acrylate of 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 4-hydroxyl butyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate and 6-caprolactone etc. can be enumerated, these more than one can be used.
In the reaction of polymkeric substance with carboxyl and (methyl) acrylate that contains hydroxyl (changing II-1/Ac), with respect to 1 equivalent of the carboxyl in the polymkeric substance, the hydroxyl that preferably contains (methyl) acrylate (changing II-1/Ac) of hydroxyl is 0.1～0.75 equivalent.
In the reaction of polymkeric substance with acid anhydride and (methyl) acrylate that contains hydroxyl (changing II-1/Ac), with respect to 1 equivalent of the acid anhydride in the polymkeric substance, the hydroxyl that preferably contains (methyl) acrylate (changing II-1/Ac) of hydroxyl is 0.4～0.6 equivalent.
As reactant [II-1], the material shown in the preferred following formula (changing II-1).
[in the formula (changing II-1), B
41, B
42And B
43Respectively with described B
31, B
11And B
12Synonym.b
41And b
42The integer of all representing 10～500 (preferred 15～300)].
In formula (changing II-1), to each repetitive the putting in order in polymer backbone shown in following formula (changing II-1/U1) and (the changing II-1/U2) without any regulation (qualification).
[in the described formula, B
41, B
42And B
43Respectively with described synonym].
Therefore, when repetitive (change II-1/U1) and (change II-1/U2) not simultaneously, as reactant (changing II-1), can enumerate polymkeric substance that repetitive for example (changing II-1/U1) and (change II-1/U2) be arranged as the block polymerization type, be arranged as the polymkeric substance of alternating polymerization type and be arranged as the polymkeric substance etc. of atactic polymerization type, can use these more than one.
As reactant (changing II-1), the material shown in the preferred following formula (changing II-1/1).
[in the formula (changing II-1/1), B
51, B
52And B
53Respectively with described B
31, B
11And B
12Synonym.b
51The integer of expression 5～400 (preferred 10～300)].
As other polymkeric substance [II]; from raw material obtain easily, synthetic viewpoint such as easy, preference is as [II-2]: make at least a portion of the carboxyl in the polymkeric substance with carboxyl and contain the unsaturated monomer reaction of epoxy radicals and import the reactant of (methyl) acryloyl group.Reactant [II-2] can surrogate response thing [II-1] or is used with reactant [II-1].
In reactant [II-2],, can be set forth in illustrative polymkeric substance in the described reactant [II-1] as the polymkeric substance with carboxyl of brewable material.
Reactant [II-2] obtains by at least a portion that makes the carboxyl in the described polymkeric substance with carboxyl and the unsaturated monomer reaction that contains epoxy radicals.Its result imports (methyl) acryloyl group in resin.
As the unsaturated monomer that contains epoxy radicals, specifically can enumerate (methyl) glycidyl acrylate, 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 type epoxy radicals, 4-epoxy cyclohexylmethyl (methyl) acrylate, 3,4-epoxycyclohexyl ethyl (methyl) acrylate, 3,4-epoxycyclohexyl butyl (methyl) acrylate, 3,4-epoxycyclohexyl methylamino acrylate etc.] etc., can use these more than one.
In addition, in the modulation of reactant [II-2],, can also make hydroxyl and acid anhydrides in the resin carry out addition reaction as required in order to obtain required acid number.As acid anhydrides, specifically can enumerate phthalic anhydride, two, four or hexahydrophthalic anhydride, maleic anhydride, succinic anhydride etc., can use these more than one.
In the polymkeric substance with carboxyl and the reaction of unsaturated monomer that contains epoxy radicals, with respect to 1 equivalent of the carboxyl in the polymkeric substance, the epoxy radicals that preferably contains the unsaturated monomer of epoxy radicals is 0.1～0.9 equivalent.
In photosensitive heat curing resin combination of the present invention, contain thinning agent as composition [III].By containing thinning agent [III], can improve cross-linking efficiency, improve thermotolerance, regulate the coating viscosity of composition.
As thinning agent [III], can be with an organic solvent and/or photopolymerization monomer.In thinning agent [III],, specifically can enumerate ketones such as ethyl methyl ketone, cyclohexanone as organic solvent; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; Dibasic alcohol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol list ether, triethylene glycol list ether; The ester classes such as carboxylate of ethyl acetate, butyl acetate and described dibasic alcohol ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc. can use these more than one.
In thinning agent [III],, specifically can enumerate hydroxyalkyl (methyl) esters of acrylic acids such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxyl butyl (methyl) acrylate as photopolymerization monomer; The list or the diacrylate class of dibasic alcohol such as ethylene glycol, methoxyl tetraethylene glycol, polyglycol, propylene glycol; N, (methyl) acrylic amides such as N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide; N, aminoalkyl (methyl) esters of acrylic acids such as N-dimethylaminoethyl (methyl) acrylate; The oxirane of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or its etc. or polynary (methyl) esters of acrylic acid of propylene oxide adduct; (methyl) esters of acrylic acid of the oxirane of the phenols of phenoxy group (methyl) acrylate, bisphenol-A two (methyl) acrylate and its etc. or propylene oxide adduct etc.; (methyl) esters of acrylic acid of glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; And melamine (methyl) acrylate etc., can use these more than one.
In photosensitive heat curing resin combination of the present invention, contain Photoepolymerizationinitiater initiater as composition [IV].As Photoepolymerizationinitiater initiater [IV], the storage-stable of resin combination is good after preferred each components matching, dissolubility is good, and does not produce the initiating agent of the mist of unreacted initiating agent in various heat treatment steps (predrying, heat curing, molding, real dress welding).
As this Photoepolymerizationinitiater initiater [IV], specifically can be used singly or two or more kinds in combination benzoin class and benzoin alkylether classes such as benzoin, benzoin benzylic ether, benzoin methylether, benzoin iso-propylether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methyl mercapto) phenyl)-2-morpholinyl-propane-1-ketone, N, acetophenones such as N-dimethylamino acetophenone; Anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-amino anthraquinones; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones; Ketals such as acetophenone dimethyl ketone acetal, benzyl dimethyl ketal; Benzophenone, methyldiphenyl ketone, 4,4 '-dichloro benzophenone, 4, benzophenone such as 4 '-lignocaine benzophenone and xanthene ketone etc.; And benzoates such as ethyl 4-dimethylaminobenzoic acid ester, 2-(dimethylamino) ethylamino benzonitrile acid esters; Or the various light sensitizers of tertiary amines such as triethylamine, triethanolamine.
As from the preferred Photoepolymerizationinitiater initiater of environmental problem; can enumerate 2; 4; 6-trimethylbenzoyl-diphenyl-phosphine oxide; two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1; 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino phenyl)-butanone-1; 2; the 4-diethyl thioxanthone; 4-benzoyl-4 '-dimethyl diphenyl sulfide; the 4-phenyl benzophenone; 2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl-propiono)-benzyl)-phenyl)-2-methyl-propane-1-ketone; poly-(oxygen (methyl isophthalic acid; 2-ethane two bases)); α-(4-(dimethylamino) benzoyl-ω-butoxy; the 9-phenylacridine; 1; 7-two (9-acridinyl) heptane; 1; 5-two (9-acridinyl) pentane; 1; 3-two (9-acridinyl) propane etc. can use these more than one.
In photosensitive heat curing resin combination of the present invention, contain the crystallinity epoxy resin shown in the following formula (changing V) as composition [V].By polycarboxylic acid resin [I] and the crystallinity epoxy resin [V] and the usefulness that will contain unsaturated group, the transparency of filming, HAST patience (the particularly HAST patience in the electrical insulating property) and the resistance to sudden heating of resist are embodied and raising.In addition, by polycarboxylic acid resin [I], polymkeric substance [II] and the crystallinity epoxy resin [V] and the usefulness that will contain unsaturated group, the HAST patience in the electrical insulating property is improved.
In the formula (changing V), G and described synonym.E
11～E
13And E
15～E
17Expression can be identical or different H or C1～C5 alkyl.e
11And e
12Expression can be identical or different 0～3 integer.If e
11And e
12Surpass 3, crystallinity, storage stability reduce sometimes.
E
14Expression S, O ,-CH
2-,-C (CH
3)
2-or the divalent group of following formula (change V/X) or (changing F) expression.
In the formula (changing V/X), E
21～E
24Can be identical or different, represent C1～C6 alkyl independently of one another.
The powder body of the preferred fusing point 40～140 of crystallinity epoxy resin [V] (particularly 110～135) ℃, maximum particle diameter 20 μ m following (particularly 0.5～15 μ m).If fusing point is low excessively, dry to touch reduces sometimes, and perhaps storage stability reduces sometimes, if it is opposite too high, sometimes the compatibility of light reactive resin and crystallinity epoxy resin descends, the transparent variation of filming, and perhaps the rerum natura of filming such as thermotolerance, moisture-proof reduces sometimes.If particle diameter is excessive, flatness, the thermotolerance of filming reduce sometimes.
Specifically, as crystallinity epoxy resin [V], can enumerate the resin and 2 shown in following formula (changing V/1)～(the changing V/9), 2 '-dimethyl-5,5 '-di-t-butyl-4, the diglycidyl ether of 4 '-dihydroxy diphenyl methane, 1, the diglycidyl ether, 1 of 4-two (3-methyl-4-hydroxyl cumyl) benzene, the diglycidyl ether of 4-two (3,5-dimethyl-4-hydroxyl cumyl) benzene etc. can be used these more than one.Wherein, the resin shown in preferred formula (changing V/1) and (the changing V/6), the most preferably resin shown in the formula (changing V/1).
In (changing V/1)～(the changing V/9), G and described synonym.In the formula (changing V/8), E
31～E
34Can be identical or different, represent H or C1～C6 alkyl (methyl, ethyl, isopropyl, the tert-butyl group etc.) independently of one another.
In photosensitive heat curing resin combination of the present invention, contain and solidify the cohesive imparting agent as composition [VI].Solidify cohesive imparting agent [VI] by containing, characteristics such as cohesive, resistance to chemical reagents, thermotolerance, moisture-proof are improved.
Specifically; as solidifying cohesive imparting agent [VI]; can enumerate S-triazines [melamine; ethyl diamido-S-triazine; 2; 4-diamido-S-triazine; 2; 4-diamido-6-tolyl-S-triazine; 2; 4-diamido-6-xylyl-S-triazine etc.]; guanamines class [guanamines; acetylguanamine; benzoguanamine; 3; [2-(3 for 9-two; 5-diamido-2; 4; 6-triazine base) ethyl]-2; 4; 8; 10-four oxaspiros [5; 5] hendecane etc.]; glyoxaline compound [2-ethyl-4-methylimidazole; 1-cyanoethyl-2-phenylimidazole; 2-phenyl-4; 5-dihydroxy methylimidazole; (four countries change into industry to the isocyanuric acid addition product of glyoxal ethyline; " 2MZ-OK " etc.); 1-(4; 5-diamido-2-triazinyl)-(four countries change into industry to ethane to 2-(2-methyl isophthalic acid-imidazole radicals); " 2MZ-AZINE " etc.)]; imidazolidine TMOS derivant [TMSIM N imidazole methyltrimethoxy silane; N-2-methylimidazole methyltrimethoxy silane; N-2-ethyl imidazol(e) methyltrimethoxy silane; N-2-isopropylimdazole methyltrimethoxy silane; N-2-ethyl-4-methylimidazole methyltrimethoxy silane; N-2-undecyl imidazole methyltrimethoxy silane; N-2-heptadecyl imidazoles methyltrimethoxy silane; the TMSIM N imidazole methyl triethoxysilane; N-2-methylimidazole ethyl trimethoxy silane; N-2-ethyl imidazol(e) methyl triethoxysilane; N-2-isopropylimdazole methyl triethoxysilane; N-2-ethyl-4-methylimidazole methyl triethoxysilane; N-2-undecyl imidazole methyl triethoxysilane; N-2-heptadecyl imidazoles methyl triethoxysilane; 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 imidazoles) 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 imidazoles) 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 imidazoles) propyl trimethoxy silicane; 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 imidazoles) propyl-triethoxysilicane etc.]; season imidazole salts derivant [1-ethyl-3-methylimidazole trifluoromethyl sulfate; N-methyl-N '-normal-butyl imidazoles hexafluorophosphate; (negative ion is from two (trifluoromethyl sulfonyl) imidic acid to N-alkyl-N '-alkoxyalkyl imidazole salts; perchloric acid; tetrafluoro boric acid; hexafluorophosphoric acid; three (trifluoromethyl sulfonyl) carbonic acid; trifluoromethanesulfonic acid; choose in trifluoroacetic acid or organic carboxyl acid or the halide ion at least a kind) etc.]; diaminodiphenyl-methane; m-phenylene diamine; diamino diphenyl sulfone; cyclohexylamine; m-xylene diamine; 4; 4 '-diamido-3; 3 '-diethyl diphenyl methane; diethylene triamine; tetren; the N-aminoethyl piperazine; isophorone diamine; dicyandiamide; urea class [urea self etc.]; polyamines class [polynary hydrazides etc.]; the acylate of these grades and/or epoxy adduct; the amine complex of boron trifluoride; tertiary amines [trimethylamine; triethanolamine; N; N-dimethyl octylame; N; accelerine; the N-benzyl dimethylamine; pyridine; the N-picoline; N-methylmorpholine; hexamethoxy methyl cyanuramide; 2; 4; 6-three (dimethylamino phenol); N-cyclohexyl dimethylamine; tetramethyl guanidine; m-aminophenol etc.]; organic phosphine class [tributylphosphine; triphenylphosphine; three-2-cyanoethyl phosphine etc.] phosphonium salt class [three normal-butyls (2; 5-dihydroxyphenyl) phosphonium bromide; cetyl tributyl phosphorus chloride etc.]; quaternary ammonium salt [benzyltrimethylammonium chloride; phenyl tributyl ammonium chloride; benzyltrimethylammonium bromide etc.]; tetrafluoro boric acid diphenyl iodine; the hexafluoro-antimonic acid triphenylsulfonium; 2; 4; 6-triphenyl sulfo-pyridine hexafluorophosphate; the light cationic polymerization catalyst; the styrene-maleic acid resin; silane coupling agents etc. can use these more than one.
Be to solidify cohesive imparting agent [VI],, can realize that the cohesive of resist improves, and can make raisings such as anti-gold-plated attribute, welding rod thermotolerance, moisture-proof, peel strength when using imidazolidine TMOS derivant and/or season during the imidazole salts derivant.
As solidifying cohesive imparting agent [VI], preferred dicyandiamide, S-pyrrolotriazine derivatives [being specially melamine, ethyl diamido-S-triazine, 2,4-diamido-S-triazine etc.], imidazolidine TMOS derivant [being specially TMSIM N imidazole methyltrimethoxy silane, 3-(N-2-methylimidazole) propyl trimethoxy silicane etc.], season imidazole salts derivant [1-ethyl-3-methylimidazole trifluoromethyl sulfate, N-methyl-N '-normal-butyl imidazoles hexafluorophosphate, N-alkyl-N '-alkoxyalkyl imidazoles phthalate] etc.
In photosensitive heat curing resin combination of the present invention, preferably also contain the thermosetting composition.As the thermosetting composition, for example can enumerate [VII-1]: the crystallinity epoxy resin that fusing point is 135～170 ℃ (but not comprising crystallinity epoxy resin [V]).By using crystallinity epoxy resin [VII-1], can further make storage stability stable.
Crystallinity epoxy resin [VII-1] preferably has the powder body of 135～170 ℃ of fusing points, preferred 140～170 ℃, maximum particle diameter 20 μ m following (particularly 0.5～15 μ m).If 135 ℃ of fusing point less thaies, storage stability reduces sometimes, if opposite to 170 ℃, causes the reduction of the compatibility of resin, the transparency of filming and thermotolerance etc. sometimes.
As crystallinity epoxy resin [VII-1], specifically can enumerate respectively by the resin shown in following formula (changing VII-1/1), (the changing VII-1/2) and (change VII-1/3), can use these more than one.
In formula (changing VII-1/1)～(the changing VII-1/3), G and described synonym.In the formula (changing VII-1/1), g
11The number of expression 0～2.If g
11Excessive, then do not show crystallinity, its as a result storage stability reduce sometimes.
As other thermosetting compositions, can enumerate [VII-2]: following formula (is changed the poly-carbodiimide (single carbodiimide and/or poly-carbodiimide) of the list shown in the VII-2.By containing single poly-carbodiimide [VII-2], can make hydrolytic resistance and cold-resistant thermal shock raising.
In the formula (changing VII-2), G
21And G
23Aromatic residue, aliphatic residue or the ester ring type residue of representing 1 valency independently of one another.G
22Aromatic residue, aliphatic residue or the ester ring type residue of expression divalent.g
21The number of expression 0～30 (preferred 2～15).
At G
21And G
23In, as the aromatic residue of 1 valency, can enumerate phenyl, a tolyl, o-tolyl, 3,5-xylyl, naphthyl etc. as aliphatic residue, can be enumerated cyclohexyl, butyl etc.
At G
22In, aromatic residue as divalent, can enumerate 4, the suitable group of the divalent of 4 '-diphenyl methane, to phenylene, 4, the suitable group of the divalent of 4 '-diphenyl ether, 3,3 '-dimethoxy-4 ', the suitable group of the divalent of 4 '-biphenyl, naphthylene etc. are as aliphatic residue, can enumerate 1,6-hexylidene, 2,2,4-trimethyl-1,6-hexylidene, 4, the suitable group of divalent of 4 '-two cyclohexylidenes, xylylene, tetramethyl xylylene, isophorone, the suitable group of the divalent of cyclohexylidene, lysine, the suitable group of divalent of methylcyclohexane etc.
Poly-carbodiimide [VII-2] is modulated this polymerization end-capped with end-capping reagent for example by with after the polymerizable monomer polymerization.
In the modulation of poly-carbodiimide [VII-2], as the polymerizable monomer of brewable material, can enumerate the organic diisocyanate shown in following formula (changing VII-2/D1) and (the changing VII-2/D2), can use these more than one.
In the formula (changing VII-2/D1), G
31Expression C1～C6 alkyl, halogen atom etc.In the formula (changing VII-2/D2), G
41And G
43Represent 1 valency group (for example C1～C6 alkyl, halogen atom etc.) independently of one another.G
42Expression divalent group (for example C1～C6 alkylidene, phenylene, naphthylene ,-O-,-S-,-Si-etc.).g
41The number of expression 0～6.If g
41Surpass 6, thermotolerance descends sometimes.
Specifically, as organic diisocyanate (changing VII-2/D1) and (changing VII-2/D2), can enumerate right-phenylene diisocyanate, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, 1-anisyl-2, the 4-diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 4,4 '-diphenyl ether diisocyanate, 3,3 '-dimethyl-4,4 '-diphenyl ether diisocyanate, the ortho-tolidine diisocyanate, 3,3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate etc., any or two or more (for example 4, the potpourri of 4 '-methyl diphenylene diisocyanate and toluene diisocyanate etc.) that can use these.
In the modulation of poly-carbodiimide [VII-2], as end-capping reagent, organic single-isocyanate [phenyl isocyanate, isocyanic acid (adjacent,, 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 [VI I-2], polymerization can be homopolymerization or copolymerization, can as described belowly carry out.Promptly, in polymer solvent [zellon etc.], under the inert atmosphere [nitrogen etc.], as required in the presence of carbodiimide catalyzer [3-methyl isophthalic acid-phenyl-2-phosphorane-1-oxide etc.], under 120～200 ℃ to organic diisocyanate [4, the potpourri of 4 '-methyl diphenylene diisocyanate and toluene diisocyanate etc.] and end-capping reagent [phenyl isocyanate etc.] heated and stirred, carry out condensation reaction, can obtain poly-carbodiimide with decarbonation.
From viewpoints such as the storage stability of resin combination, HAST patience, the powder body of the preferred softening point 100～150 of single poly-carbodiimide [VII-2] (particularly 105～140) ℃, maximum particle diameter 20 μ m following (particularly 1～15 μ m).If softening point is low excessively, even can cause also sometimes at low temperatures and the addition reaction that contains the polycarboxylic acid resin [I] of unsaturated group that storage stabilities such as the storage stability of resin combination worsen sometimes.If particle diameter is excessive, the flatness of filming descends sometimes, because the generation of pinprick etc. make thermotolerance reduce sometimes.
As other thermosetting compositions, can enumerate [VII-3]: contain allylic compound.Contain allylic compound by containing [VII-3], can make thermotolerance, resistance to chemical reagents etc. solidify rerum natura and improve.
Contain allylic prepolymer as containing allylic compound [VII-3], can enumerating.
In containing allylic compound [VII-3], contain the preferred mean molecular weight 400～30000 of allylic prepolymer, preferred especially 1000～20000.If mean molecule quantity not sufficient 400, dry to touch, thermotolerance reduce sometimes, if opposite to 30000, the viscosity of resin raises and is difficult to handle, and the compatibility of resin descends sometimes.
In containing allylic compound [VII-3], as containing allylic prepolymer, specifically can enumerate the diallyl phthalate prepolymer of triallyl isocyanurate prepolymer and repetitive following formula (changing VII-3/U1) expression and the diallyl isophthalate prepolymer of following formula (changing VII-3/U2) expression etc., can use these more than one.
In the formula (changing VII-3/U1), g
51The integer of expression 2～50.In the formula (changing VII-3/U2), g
61The integer of expression 2～50.If g
51Or g
61Too small, dry to touch, thermotolerance reduce sometimes, if opposite excessive, the viscosity of resin can raise, and handles the difficulty that becomes, and the compatibility of resin descends sometimes.
Contain allylic compound [VII-3] as other, specifically can enumerate triallyl isocyanurate, triallyl cyanurate, isocyanuric acid front three for allyl ester etc., can use these more than one (below be sometimes referred to as " (different) cyanogen urea acid three (first generation) allyl ester ").
In addition, contain allylic compound [VII-3], can enumerate the diallyl 3 shown in the following formula (changing VII-3/1), the interior methylene tetrahydric phthalimide compound of 6-etc. as other.
In the formula (changing VII-3/1), G
71Divalent group shown in expression following formula (changing VII-3/1-R1), (the changing VII-3/1-R2) or (changing VII-3/1-R3).
In the formula (changing VII-3/1-R3), g
81The integer of expression 4～8.If g
81Too small, handle the difficulty that becomes sometimes, if opposite excessive, thermotolerance descends sometimes.
As containing allylic compound [VII-3], can use described allylic prepolymer, (different) cyanogen urea acid three (first generation) allyl ester and diallyl 3, more than one of the interior methylene tetrahydric phthalimide compound (VII-3/1) of 6-of containing.These compounds all at high temperature carry out thermal response, but few to the influence of the storage stability of resin combination, development, and can make the raising such as thermotolerance, welding rod thermotolerance of cured film.
As other thermosetting compositions, can enumerate the compound of [VII-4]: Han You oxazolinyl etc.From the storage stability of resin combination, the viewpoint of HAST patience, the powder body of the preferred softening point 100～150 of the compound [VII-4] of Han You oxazolinyl (particularly 110～140) ℃, maximum particle diameter 20 μ m following (particularly 0.5～15 μ m).The compound [VII-4] of Han You oxazolinyl if softening point low excessively, even also can cause sometimes at low temperatures and contain the addition reaction of the polycarboxylic acid resin [I] of unsaturated group, storage stabilities such as the storage stability of resin combination worsen sometimes.If particle diameter is excessive, the flatness of filming descends sometimes, because the generation of pinprick etc. make thermotolerance reduce sometimes.By containing the compound that [VII-4] contains oxazolinyl, can make with the compatibility of resin and improve, and cohesive is improved.
In the thermosetting composition, as the compound [VII-4] of Han You oxazolinyl, specifically can enumerate 2, the polymkeric substance of 2-(1, the 3-phenylene) two-2-oxazoline and Han You oxazolinyl etc. can use these more than one.
In the compound [VII-4] of Han You oxazolinyl, the preferred mean molecular weight of polymkeric substance of Han You oxazolinyl is 1000～10000.If mean molecular weight is too small, dry to touch, thermotolerance reduce sometimes, if opposite excessive, the viscosity of resin can raise, and handles the difficulty that becomes, and the compatibility of resin descends sometimes.
Polymkeric substance as Han You oxazolinyl, can be set forth on the polymer chain Ju You oxazolinyl as the polymkeric substance of side group, specifically be included on the part of copoly types such as acryl resin, styrene/acrylic resin, polystyrene and have polymkeric substance of side group etc., can use these more than one.
In photosensitive heat curing resin combination of the present invention, can use more than one of described thermosetting composition [VII-1]～[VII-4].
In addition, in photosensitive heat curing resin combination of the present invention, can add silane coupling agent, organic/inorganic alkoxysilane polymer, defoamer, colorant (dyestuff, pigment, inorganic), filling agent etc. arbitrarily as adding ingredient.
In the composition of photosensitive heat curing resin combination of the present invention, with respect to the polycarboxylic acid resin that contains unsaturated group [I] 100 weight portions, polymkeric substance [II] preferred 0～60 (particularly 2～40) weight portion.If [II] is very few for polymkeric substance, dry to touch can variation sometimes, and the development of tunicle can variation, if too much opposite, reduces sometimes with the compatibility of resin, and cohesive can variation.
In the composition of photosensitive heat curing resin combination of the present invention, with respect to the polycarboxylic acid resin that contains unsaturated group [I] 100 weight portions, thinning agent [III] preferred 10～300 (particularly 30～200) is if weight portion. and [III] is very few for thinning agent, sometimes coating can worsen and be difficult to be coated with, optical polymerism can reduce, if too much opposite, dry to touch, resolution reduce sometimes.
In the composition of photosensitive heat curing resin combination of the present invention, with respect to the polycarboxylic acid resin that contains unsaturated group [I] 100 weight portions, Photoepolymerizationinitiater initiater (IV) preferred 0.5～40 (particularly 2～30) weight portion.
In the composition of photosensitive heat curing resin combination of the present invention, with respect to the polycarboxylic acid resin that contains unsaturated group [I] 100 weight portions, crystallinity epoxy resin [V] preferred 1～100 (particularly 4～70) weight portion.Crystallinity epoxy resin [V] is if very few, and the rerum naturas of filming such as thermotolerance, resistance to chemical reagents, cohesive, moisture-proof reduce sometimes, if too much opposite, alkali-developable descends sometimes.
In the composition of photosensitive heat curing resin combination of the present invention,, solidify cohesive imparting agent [VI] preferred 0.1～20 (particularly 0.5～10) weight portion with respect to the polycarboxylic acid resin that contains unsaturated group [I] 100 weight portions.If it is very few to solidify cohesive imparting agent [VI], cohesive, anti-gold-plated attribute reduce sometimes, if too much opposite, storage stability descends sometimes.
In the composition of photosensitive heat curing resin combination of the present invention, with respect to the polycarboxylic acid resin that contains unsaturated group [I] 100 weight portions, crystallinity epoxy resin [VII-1] preferred 0.1～50 (particularly 2～40) weight portion, single poly-carbodiimide [VII-2] preferred 0.1～50 (particularly 2～40) weight portion, contain allylic compound [VII-3] preferred 0.1～50 (particularly 2～30) weight portion, the compound [VII-4] of Han You oxazolinyl preferred 0.1～50 (particularly 2～30) weight portion.
But, the total amount of crystallinity epoxy resin [V] and described thermosetting composition [VII-1]～[VII-4] (i.e. [V]+[VII-1]+[VII-2]+[VII-3]+[VII-4]) is with respect to the polycarboxylic acid resin that contains unsaturated group [I] 100 weight portions, preferred 2～100 (particularly 5～80) weight portion.
If described thermosetting composition is very few, the rerum naturas of filming such as thermotolerance, resistance to chemical reagents, cohesive, moisture-proof reduce sometimes, if too much opposite, alkali-developable, storage stability descend sometimes.
In addition, with respect to crystallinity epoxy resin [V] 100 weight portions, crystallinity epoxy resin [VII-1] preferred 0～200 (particularly 5～150) weight portion.[VII-1] if too much, the transparency of filming descends sometimes with respect to crystallinity epoxy resin [V].
Photosensitive heat curing resin combination of the present invention has acid number 40～120 usually.If acid number is low excessively, alkali-developable reduces sometimes, if opposite too high, the moisture-proof of filming reduces sometimes.
As mentioned above, can modulate the transparency, cohesive, electrical insulating property, welding rod resistance to sudden heating, resistance to chemical reagents, anti-gold-plated attribute, resistance to bend(ing), long-term reliability (resistance to migration, the HAST patience) excellence that are applicable to storage stability, pre-dried thermal stability, dry to touch, the development in aqueous alkali, photonasty and cured film, be difficult for vapour discharge and take into account the photosensitive heat curing resin combination of the present invention of the solder resist of environment.This photosensitive heat curing resin combination of the present invention expects that with seal for example the aqueous photic solder mask ink of alkali developable, alkali developable dry film solder resist etc. are particularly useful for various resists (solder resist, interlayer dielectic etc.).
Below the printing distributing board that is coated with resist that the resist-coating that will be obtained by described photosensitive heat curing resin combination of the present invention is obtained to the surface of printing distributing board describe.As printing distributing board, preferred smoothing printing distributing board.As the smoothing printing distributing board, the through-hole section of preferred especially printing distributing board, the recess on printing distributing board surface make the smoothing printing distributing board of printing distributing board surface smoothing with the resin filling.Certainly also can use other any printing distributing boards [for example having concavo-convex printing distributing board in the past (below be sometimes referred to as " embossing distributing board ") etc. on the printing distributing board surface] in the present invention, the printing distributing board that is coated with resist of Huo Deing also belongs to technology category of the present invention like this.
As described " recess ", be not particularly limited, can enumerate for example recess of the recess between the lip-deep circuit of distributing board, through hole and the recess that the landfill part is used etc.
Resin for filling as the recess on printing distributing board surface, preference is the compositions of thermosetting resin of record in the patent documentation 7 as described, but also can use other thermoset resin in the present invention, any printing distributing board that is coated with resist that obtains so also belongs to technical scope of the present invention.
This smoothing printing distributing board adopts the method for record in for example described patent documentation 7 to obtain.That is, at first compositions of thermosetting resin is applied on the recess on printing distributing board surface, carries out one-step solidification at low temperatures, carry out surface grinding, make the smoothing printing distributing board thereby at high temperature carry out regelate then.
Below the manufacture method of smoothing printing distributing board when just " recess " be recess between the lip-deep circuit of distributing board, the use accompanying drawing describes.At first, compositions of thermosetting resin is filled, is coated with to the recess 3 (Fig. 2) that forms between the conductor circuit on the printing distributing board of being made of insulated substrate 5 (Fig. 2) and conductor circuit 6 (Fig. 2).
As compositions of thermosetting resin, the composition of record in the preferred described patent documentation 7.That is the compositions of thermosetting resin that, preferably contains addition product, [B] (methyl) esters of acrylic acid, [C] radical polymerization initiator, [D] crystallinity epoxy resin and [E] potentiality hardening agent of [A] epoxy resin and unsaturated fatty acid.
As composition [A], specifically, addition product [specifically for preferred novolac epoxy resin and (methyl) acrylic acid 20～80% (particularly 40～60%), cresol-novolac epoxy resin and acrylic acid 20～80% (particularly 40～60%) addition product etc.], bisphenol A type epoxy resin and (methyl) acrylic acid 20～80% (particularly 40～60%) addition product etc., in thermoset composition, can contain these more than one.
As composition [B], specifically, hydroxyalkyl acrylates classes such as preferred acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxyl butyl ester; The list or the diacrylate class of dibasic alcohol such as ethylene glycol, methoxyl tetraethylene glycol, polyglycol, propylene glycol; Acrylic amide such as N,N-DMAA, N hydroxymethyl acrylamide; N, aminoalkyl esters of acrylic acids such as N-dimethylaminoethyl acrylate; The oxirane of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or its etc. or the multicomponent methacrylate class of propylene oxide adduct; The esters of acrylic acid of the oxirane of the phenols of acrylic acid benzene oxygen ester, bisphenol a diacrylate and its etc. or propylene oxide adduct etc.; The esters of acrylic acid of glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl isocyanurate; With melamine acrylate, isobornyl acrylate, methacrylic acid two ring pentyl esters and/or the methyl acrylic ester corresponding etc. with described esters of acrylic acid, in thermoset composition, can contain these more than a kind.
As composition [C], specifically, preferred t-butyl peroxybenzoate, the peroxide-2-ethyl acid tert-butyl ester, dicumyl peroxide etc., can contain in the thermoset composition these more than a kind.
As composition [D], specifically, preferred Japanese chemical drug corporate system is made BPS-200, エ one シ one ア one Le company makes bisphenol-s epoxy resins such as EPX-30, the big manufacturing エ ピ of Japanese ink chemical industrial company Network ロ Application EXA-1514; Nof Corp. makes o-phthalic acid diglycidyl ester resins such as Block レ Application マ one DGT; Daily output chemical company makes TEPIC, チ バ one ガ イ ギ one company makes heterocyclic ring epoxy resins such as ア ラ Le ダ イ ト PT810; Oiling シ エ Le company makes di-toluene phenol-type epoxy resins such as YX-4000; Oiling シ エ Le company makes bisphenol-type epoxy resins such as YL-6056; Dongdu company that changes into makes four glycidyl group dimethylbenzene acyl group ethane resin such as ZX-1063 etc., can contain in the thermoset composition these more than a kind.
As composition [E], preference such as dicyandiamide (DICY) class, imidazoles, BF
3-amine complex, amine add-on type hardening agent, amine-acid anhydrides (polyamide) add-on type hardening agent, hydrazides are that hardening agent, amine are carboxylate, salt of hardening agent etc., can contain in the thermoset composition these more than a kind.
In the composition of described compositions of thermosetting resin, with respect to composition [A] 100 weight portions, preferred 50～300 weight portions of composition [B] (particularly 150～250 weight portions), preferred 5～20 weight portions of composition [C] (particularly 8～15 weight portions), preferred 50～200 weight portions of composition [D] (particularly 60～120 weight portions), preferred 5～30 weight portions of composition [E] (particularly 10～20 weight portions).
As the coating process of described compositions of thermosetting resin, can enumerate for example screen printing method, rolling method etc.
Then, carry out one-step solidification at low temperatures.So-called " low temperature " is meant than the low temperature of regelate temperature described later.Specifically, as the one-step solidification temperature, can be for example 100～150 ℃.
Then, the surface of the one-step solidification film that contains described formation is ground make it level and smooth.As Ginding process, can enumerate mechanical lapping (abrasive band polishing grinding, emery wheel grinding, sandblast, brush are wiped grinding etc.), chemical grinding (using the grinding of persulfate, hydrogen peroxide-sulfuric acid mixture, inorganic-organic acid etc. etc.) etc.
Then, at high temperature carry out regelate.So-called " high temperature " is meant than the high temperature of described one-step solidification temperature.As the regelate temperature, can be for example 150～200 ℃.
Use the cured resin 4 (Fig. 3) of described compositions of thermosetting resin that the recess between the lip-deep circuit of distributing board is filled like this, thereby obtain the smoothing printing distributing board (Fig. 3) of surface smoothing.
Then, on the smooth surface of the smoothing printing distributing board that obtains as mentioned above, apply resist 1 (Fig. 1).As painting method, can enumerate the method for for example using aqueous photosensitive resist agent.Specifically, at first, aqueous photosensitive resist agent is applied on the smooth surface of described smoothing printing distributing board.Then, optionally adopt active ray exposure by the photomask that is formed with predetermined pattern after, form corrosion-resisting pattern thereby unexposed portion is developed with developer solution.Then, make the heat curing of described heat curing composition, can make the smoothing printing distributing board that is coated with resist of the present invention by heating.
As aqueous photosensitive resist agent, contain photosensitive heat curing resin combination of the present invention.In addition, [ketones such as ethyl methyl ketone, cyclohexanone with an organic solvent; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; Dibasic alcohol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol list ether, triethylene glycol list ether; The ester classes such as acetic acid carboxylate of ethyl acetate, butyl acetate and described dibasic alcohol ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.], known habitual inorganic filler, can contain so known habitual additive kind of cohesive imparting agents such as known habitual colorant, known habitual heat polymerization inhibitors, known habitual tackifier, defoamer, silane coupling agent etc. in addition.
Coating can adopt for example screen printing, the coating of curtain formula, print roll coating, spraying etc. to carry out.
As active ray, can enumerate ultraviolet ray (300～450nm etc.).Exposure for example can be adopted, and Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, arc lamp, xenon lamp etc. carry out.In addition, also can expose by the excimer laser outside the irradiation ultraviolet radiation, X ray, electron ray etc.
As developer solution, can enumerate lithium, sodium, alkali-metal oxyhydroxide such as potassium, carbonate, supercarbonate, phosphate, pyrophosphate, benzylamine, butylamine, primary amine such as monoethanolamine, dimethylamine, dibenzylamine, secondary amine such as diethanolamine, trimethylamine, triethylamine, tertiary amines such as triethanolamine, morpholine, piperazine, cyclic amine such as pyridine, ethylenediamine, polyamines such as hexamethylene diamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium, benzyltrimethyl ammonium hydroxide, ammonium hydroxide classes such as hydroxide trimethylphenyl hexadecyldimethyl benzyl ammonium, the hydroxide trimethylsulfonium, hydroxide diethylmethyl sulfonium, hydroxide sulfonium classes such as hydroxide dimethyl benzyl sulfonium, and choline, contain the damping fluid of silicate etc.
In addition, also can use alcohols solvent (butyl cellosolve, butyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propyl alcohol, propylene glycol), surfactant (amphoteric surfactant, non-ionic surfactant etc.) as required.
Heat curing can for example carried out 0.1～3 hour under 120～180 ℃.
As other coating methods, can enumerate the method for for example using the dry film photoresist.As the dry film photoresist, can enumerate the dry film photoresist that constitutes by carrier film, photoresist (photographic layer) and diaphragm at least.
As carrier film, specifically can enumerate synthetic resin films such as polyester film, polyethylene terephthalate film, poly (ethylene naphthalate) film, tygon, polypropylene, polycarbonate, Polyvinylchloride etc.
Photoresist can be by being diluted in photosensitive heat curing resin combination of the present invention in the organic solvents such as ethyl acetate, methyl ethyl ketone, adopts applicator, metering bar coater, roll coater, curtain formula coating machine, flow coater etc. to be coated with to make dry film thickness reach 10～100 μ m and form.In addition, in photoresist, can use known habitual inorganic filler, can contain so known habitual additive kind of cohesive imparting agents such as known habitual colorant, known habitual heat polymerization inhibitors, known habitual tackifier, defoamer, silane coupling agent etc. in addition.In addition, photoresist can make the difference stratification more than 2 kinds of photosensitive heat curing resin combination of the present invention, becomes the sandwich construction more than 2 layers.
As diaphragm, specifically can enumerate synthetic resin films such as polyethylene film, polypropylene, Polyvinylchloride etc.
In addition, can in the dry film photoresist, have water soluble resin layer, antistatic layer etc. as required.
By the water soluble resin layer is set, can easily carrier film be peeled off.In the water soluble resin layer, as water soluble resin, can enumerate from natural starch, gelatin, semisynthetic carboxymethyl cellulose (CMC), methylcellulose cellulose derivatives such as (MC) water soluble polymer of polyvinyl alcohol (PVA) (PVA), partly-hydrolysed polyvinyl alcohol resin, polyacrylic polymer, polyacrylamide (PAM), polyethylene oxide synthetic systems such as (PEO) etc.
As antistatic layer, specifically can enumerate and adopt vapour deposition method or sputtering method to form the layer of metal or metal oxide, be that the transparent conductivity polymeric layer or the aniline of monomer component is electric conductive polymer layer etc. with the acrylic acid series ester that contains quaternary ammonium base at least.
In addition, can add to more than one of conductive materials such as lewis acid, carbon, metal particle, metal oxide and/or cationic, anionic and amphoteric surfactant etc. in carrier film and/or the antistatic layer or form it, thereby give anti-static function.
As antistatic layer or anti-static function, consider the problem of the static obstacle generation when making etc., surperficial intrinsic resistance value preferred 10
11(particularly 10
9) Ω/cm
2Below.
As the dry film photoresist, specifically, preferred antistatic layer 7, carrier film 8, water soluble resin layer 9, photoresist 2 and the stacked in order structure of diaphragm 10 shown in Figure 4.
Described dry film photoresist is laminated on the smooth surface of described smoothing printing distributing board.At this moment, use that dry film-laminating machine is equilateral peels off diaphragm, the limit is laminated to the dry film photoresist on the smooth surface.
In this application, when using in the past embossing distributing board as printing distributing board, the generation of the bad and bubble of the lamination that produces for fear of concavo-convex influence etc., and for the smoothing on distributing board surface etc., preferably carry out lamination with vacuum furnace laminating machine, vacuum pressing laminating machine etc.
On the other hand, in this application, when using the smoothing printing distributing board as printing distributing board, even adopt the normal pressure laminating machine that the dry film photoresist is handled, the generation of, bubble bad for described lamination and smoothing etc. also all can the manufacturings of no problem ground.As the normal pressure lamination, can be for example preheating: 60～70 ℃, roll temperature: 80～110 ℃, roller speed: 0.5～2.0m/ branch, roller pressure: 2 * 10
5Pa (2kgf/cm
2) more than.
In addition, described aqueous photosensitive resist agent can further be set between smooth surface and dry film.
Then, identical with described in the described aqueous photosensitive resist agent, after optionally adopting active ray exposure by the photomask that is formed with predetermined pattern, thereby with developer solution unexposed portion is developed and form corrosion-resisting pattern. then, make the heat curing of described heat curing composition by heating, can make the smoothing printing distributing board that is coated with resist of the present invention.
The thickness of the described resist that is made of photosensitive heat curing resin combination of the present invention that obtains as mentioned above can be 7～35 μ m.
By the described resist that photosensitive heat curing resin combination of the present invention constitutes, excellences such as its development, dry to touch, resistance to bend(ing), cohesive, the transparency of filming, HAST patience (the particularly HAST patience in the electrical insulating property) and resistance to sudden heating.In addition, by the described resist-coating that will constitute by photosensitive heat curing resin combination of the present invention to the smoothing printing distributing board, can also obtain underfill (underfill) is difficult for soaking into, be difficult for producing dislocation, be difficult for to produce the effect of cracking, thus the variety of issue can solve actual installation the time.
Below the present invention is specifically described.
Embodiment
Synthesizing of＜epoxy resin (changing I/E) 〉
Synthesis example 1: epoxy resin (change I/E-1-1) synthesizes
With the raw material bisphenol A type epoxy resin [h shown in the following formula
11Mean value (being average degree of polymerization) 3.3, epoxide equivalent 650,81.1 ℃ of softening points, melt viscosity (150 ℃) 12.5 pools] 371 weight portions, chloropropylene oxide 925 weight portions and dimethyl sulfoxide (DMSO) 462.5 weight portion uniform dissolution.70 ℃ of following NaOH then, under agitation, with 100 minutes interpolation 52.8 weight portions 98.5% in this uniform dissolution thing.
[in the formula, h
11The expression degree of polymerization].
After the interpolation, under 70 ℃, carry out reaction in 3 hours again.Then, under reduced pressure with the unreacted chloropropylene oxide of surplus and most distilling of dimethyl sulfoxide (DMSO).Then, make the resultant of reaction that contains secondary living salt and dimethyl sulfoxide (DMSO) be dissolved in methyl isobutyl ketone 750 weight portions after, add 30%NaOH aqueous solution 10 weight portions again, 70 ℃ of down reactions 1 hour.
After reaction finished, water 200 weight portions carried out 2 washings.Reclaim methyl isobutyl ketone from the oil reservoir distillation after the oil and water separation, obtain epoxy resin (synthesis example 1) 340 weight portions shown in the formula (changing I/E-1-1).
This epoxy resin (synthesis example 1) is epoxide equivalent 287,64.2 ℃ of softening points, melt viscosity (150 ℃) 7.1 pools.In addition, if calculate, can judge that this epoxy resin (synthesis example 1) is to have an appointment 3.1 by epoxidised resin in 3.3 of the alcohol hydroxyl groups in the bisphenol A type epoxy resin of described raw material by epoxide equivalent.
Synthesis example 2: epoxy resin (change I/E-1-2) synthesizes
With the solid type epoxy resin [h of the raw material Bisphenol F type shown in the following formula
2179 ℃ of mean value 5.8, epoxide equivalent 800, softening points] 400 weight portions, chloropropylene oxide 925 weight portions and dimethyl sulfoxide (DMSO) 462.5 weight portion uniform dissolution.70 ℃ of following NaOH then, under agitation, with 100 minutes interpolation 81.2 weight portions 98.5% in this uniform dissolution thing.
[in the formula, h
21The expression degree of polymerization].
After the interpolation, under 70 ℃, carry out reaction in 3 hours again.Then, under reduced pressure with the unreacted chloropropylene oxide of surplus and most distilling of dimethyl sulfoxide (DMSO).Then, make the resultant of reaction that contains secondary living salt and dimethyl sulfoxide (DMSO) be dissolved in methyl isobutyl ketone 750 weight portions after, add 30%NaOH aqueous solution 10 weight portions again, 70 ℃ of down reactions 1 hour.
After reaction finished, water 200 weight portions carried out 2 washings.Reclaim methyl isobutyl ketone from the oil reservoir distillation after the oil and water separation, obtain epoxy resin (synthesis example 2) 370 weight portions shown in the formula (changing I/E-1-2).
This epoxy resin (synthesis example 2) is 62 ℃ of epoxide equivalent 290, softening points.In addition, if calculate, can judge that this epoxy resin (synthesis example 2) is to have an appointment 5.2 by epoxidised resin in 5.8 of the alcohol hydroxyl groups in the solid type epoxy resin of Bisphenol F type of raw material by epoxide equivalent.
Synthesis example 3: epoxy resin (change I/E-2-1) synthesizes
Then, add triphenyl phasphine 0.084 weight portion, continue down to stir 4 hours, finish addition reaction, obtain the raw material bisphenol-A/F shown in the following formula also with type epoxy resin [h at 150 ℃
31Mean value 1.6, epoxide equivalent 600].
[in the formula, h
31The expression degree of polymerization].
Then, with this raw material bisphenol-A/F and with after type epoxy resin 308 weight portions, chloropropylene oxide 925 weight portions and the dissolving of dimethyl sulfoxide (DMSO) 462.5 weight portions, under agitation, 70 ℃ down with the NaOH of 100 minutes interpolation 52.8 weight portions 98.5%.After the interpolation, under 70 ℃, carry out reaction in 3 hours again.
Then, under reduced pressure with the unreacted chloropropylene oxide of surplus and most distilling of dimethyl sulfoxide (DMSO).Then, the resultant of reaction that contains secondary living salt and dimethyl sulfoxide (DMSO) is dissolved in methyl isobutyl ketone 750 weight portions, adds 30%NaOH aqueous solution 10 weight portions again, reacted 1 hour down at 70 ℃.
After reaction finished, water 200 weight portions carried out 2 washings.Reclaim methyl isobutyl ketone from the oil reservoir distillation after the oil and water separation, obtain epoxy resin (synthesis example 3) 312 weight portions shown in the formula (changing I/E-2-1).
This epoxy resin (synthesis example 3) is 64 ℃ of epoxide equivalent 290, softening points.In addition, if calculate, can judge that this epoxy resin (synthesis example 3) is raw material bisphenol-A/F and has an appointment 3.0 by epoxidised resin with in 3.3 of the alcohol hydroxyl groups in the type epoxy resin by epoxide equivalent.
Synthesis example 3S: hydrogenated epoxy resin synthetic
Then, add triphenyl phasphine 0.084 weight portion, continue down to stir 4 hours at 150 ℃, finish addition reaction, the raw material hydrogenation bisphenol A-type/F type shown in the following formula that obtains is also with epoxy resin [h
32Mean value 1.6, epoxide equivalent 580].
[in the formula, h
32The expression degree of polymerization].
Then, with this raw material hydrogenation bisphenol A-type/F type and with after epoxy resin 308 weight portions, chloropropylene oxide 925 weight portions and the dissolving of dimethyl sulfoxide (DMSO) 462.5 weight portions, under agitation, 70 ℃ down with the NaOH of 100 minutes interpolation 52.8 weight portions 98.5%.After the interpolation, under 70 ℃, carry out reaction in 3 hours again.
Then, under reduced pressure with the unreacted chloropropylene oxide of surplus and most distilling of dimethyl sulfoxide (DMSO).Then, the resultant of reaction that contains secondary living salt and dimethyl sulfoxide (DMSO) is dissolved in methyl isobutyl ketone 750 weight portions, adds 30%NaOH aqueous solution 10 weight portions again, reacted 1 hour down at 70 ℃.
After reaction finished, water 200 weight portions carried out 2 washings.Reclaim methyl isobutyl ketone from the oil reservoir distillation after the oil and water separation, obtain epoxy resin (synthesis example 3S) 312 weight portions.
This epoxy resin (synthesis example 3S) is 61 ℃ of epoxide equivalent 280, softening points.In addition, if calculate, can judge that this epoxy resin (synthesis example 3S) is raw material hydrogenation bisphenol A-type/F type and has an appointment 3.0 by epoxidised resin with in 3.3 of the alcohol hydroxyl groups in the epoxy resin by epoxide equivalent.
Synthesis example 4: epoxy resin (change I/E-2-2) synthesizes
9,9 '-two (4-hydroxy phenyl) fluorenes 168 weight portions and bisphenol A-type liquid epoxy resin [Dongdu change into company make " YD-128 ", epoxide equivalent 186g/eq] 332 weight portions of packing in flask carry out melting mixing under 150 ℃.The phenol hydroxyl of this moment and the mol ratio of epoxy radicals are 0.53: 1.
Then, add triphenyl phasphine 0.084 weight portion, continue to stir 4 hours down, finish addition reaction, obtain the epoxy resin [mean value 1.6 of h41, epoxide equivalent 720] that the raw material shown in the following formula contains fluorene skeleton at 150 ℃.
[in the formula, G is with described identical, h
41The expression degree of polymerization].
Then, this raw material is contained epoxy resin 371 weight portions, chloropropylene oxide 925 weight portions and the dissolving of dimethyl sulfoxide (DMSO) 462.5 weight portions of fluorene skeleton after, under agitation, 70 ℃ down with the NaOH of 100 minutes interpolation 52.8 weight portions 98.5%.After the interpolation, under 70 ℃, carry out reaction in 3 hours again.
Then, under reduced pressure with the unreacted chloropropylene oxide of surplus and most distilling of dimethyl sulfoxide (DMSO).Then, the resultant of reaction that contains secondary living salt and dimethyl sulfoxide (DMSO) is dissolved in methyl isobutyl ketone 750 weight portions, adds 30%NaOH aqueous solution 10 weight portions again, reacted 1 hour down at 70 ℃.
After reaction finished, water 200 weight portions carried out 2 washings.Reclaim methyl isobutyl ketone from the oil reservoir distillation after the oil and water separation, obtain epoxy resin (synthesis example 4) 368 weight portions shown in the formula (changing I/E-2-2).
This epoxy resin (synthesis example 4) is 68 ℃ of epoxide equivalent 350, softening points.In addition, if calculate, can judge that this epoxy resin (synthesis example 4) is that raw material contains in the epoxy resin of fluorene skeleton in 3.3 of the alcohol hydroxyl groups and has an appointment 3.0 by epoxidised resin by epoxide equivalent.
Synthesis example 5: epoxy resin (change I/E-2-3) synthesizes
In flask, pack 3,3 ', 5 into, 5 '-tetramethyl-4,4 '-dihydroxybiphenyl, 116 weight portions and bisphenol A-type liquid epoxy resin [Dongdu changes into company and makes " YDF-170 ", epoxide equivalent 172g/eq] 301 weight portions carry out melting mixing under 150 ℃.The phenol hydroxyl of this moment and the mol ratio of epoxy radicals are 0.53: 1.
Then, add triphenyl phasphine 0.084 weight portion, continue to stir 4 hours down, finish addition reaction, obtain the epoxy resin [h that the raw material shown in the following formula contains bisphenol-A/di-cresols skeleton at 150 ℃
51Mean value 1.6, epoxide equivalent 600].
[in the formula, G is with described identical, h
51The expression degree of polymerization].
Then, this raw material is contained epoxy resin 310 weight portions, chloropropylene oxide 925 weight portions and the dissolving of dimethyl sulfoxide (DMSO) 462.5 weight portions of bisphenol-A/di-cresols skeleton after, under agitation, 70 ℃ down with the NaOH of 100 minutes interpolation 52.8 weight portions 98.5%.After the interpolation, under 70 ℃, carry out reaction in 3 hours again.
Then, under reduced pressure with the unreacted chloropropylene oxide of surplus and most distilling of dimethyl sulfoxide (DMSO).Then, the resultant of reaction that contains secondary living salt and dimethyl sulfoxide (DMSO) is dissolved in methyl isobutyl ketone 750 weight portions, adds 30%NaOH aqueous solution 10 weight portions again, reacted 1 hour down at 70 ℃.
After reaction finished, water 200 weight portions carried out 2 washings.Reclaim methyl isobutyl ketone from the oil reservoir distillation after the oil and water separation, obtain epoxy resin (synthesis example 5) 368 weight portions shown in the formula (changing I/E-2-3).
This epoxy resin (synthesis example 5) is 66 ℃ of epoxide equivalent 295, softening points.In addition, if calculate, can judge that this epoxy resin (synthesis example 5) is that raw material contains in the epoxy resin of bisphenol-A/di-cresols skeleton in 3.3 of the alcohol hydroxyl groups and has an appointment 3.0 by epoxidised resin by epoxide equivalent.
＜contain polycarboxylic acid resin [I] synthetic of unsaturated group 〉
Synthesis example 6
Pack into described epoxy resin (synthesis example 1) 2870 weight portions (10 equivalent), acrylic acid 720 weight portions (10 equivalent), methylnaphthohydroquinone 2.8 weight portions, carbitol acetic acid esters 1943.5 weight portions are heated to 90 ℃, stir reaction mixture is dissolved.Then, reactant liquor is cooled to 60 ℃, triphenyl phasphine 16.6 weight portions of packing into are heated to 100 ℃, react about 32 hours, obtain the reactant of acid number 1.0.Then, add succinic anhydride 783 weight portions (7.83 equivalent), carbitol acetic acid esters 421.6 weight portions, be heated to 95 ℃, react after about 6 hours and cool off, obtain containing the polycarboxylic acid resin [I] (synthesis example 6) of unsaturated group to it.
This polycarboxylic acid resin [I] (synthesis example 6) that contains unsaturated group is the acid number 100 of solid constituent, solid component concentration 65%, viscosity (25 ℃) 25Pas.
Synthesis example 7
Pack into described epoxy resin (synthesis example 2) 2900 weight portions (10 equivalent), acrylic acid 720 weight portions (10 equivalent), methylnaphthohydroquinone 2.8 weight portions, carbitol acetic acid esters 1950 weight portions are heated to 90 ℃, stir reaction mixture is dissolved.Then, reactant liquor is cooled to 60 ℃, triphenyl phasphine 16.7 weight portions of packing into are heated to 100 ℃, react about 32 hours, obtain the reactant of acid number 1.0.Then, add tetrabydrophthalic anhydride 1845 weight portions and carbitol acetic acid esters 993.5 weight portions, and hexahydrophthalic anhydride 1810 weight portions and carbitol acetic acid esters 974.7 weight portions, react, obtain containing the polycarboxylic acid resin [I] (synthesis example 7) of unsaturated group.
This polycarboxylic acid resin [I] (synthesis example 7) that contains unsaturated group is the acid number 90 of solid constituent, solid component concentration 65%, viscosity (25 ℃) 72Pas.
Synthesis example 8
Described epoxy resin (synthesis example 3) 2900 weight portions (10 equivalent) of packing into, acrylic acid 720 weight portions (10 equivalent), methylnaphthohydroquinone 2.8 weight portions, carbitol acetic acid esters 1950 weight portions, be heated to 90 ℃, stir reaction mixture is dissolved. then, reactant liquor is cooled to 60 ℃, triphenyl phasphine 16.7 weight portions of packing into, be heated to 100 ℃, reacted about 32 hours, obtain the reactant of acid number 1.0. then, add tetrabydrophthalic anhydride 1845 weight portions and carbitol acetic acid esters 993.5 weight portions, react, obtain containing the polycarboxylic acid resin [I] (synthesis example 8) of unsaturated group.
This polycarboxylic acid resin [I] (synthesis example 8) that contains unsaturated group is the acid number 98 of solid constituent, solid component concentration 65%, viscosity (25 ℃) 30Pas.
Synthesis example 8S
Pack into described epoxy resin (synthesis example 3S) 2800 weight portions (10 equivalent), acrylic acid 720 weight portions (10 equivalent), methylnaphthohydroquinone 2.8 weight portions, carbitol acetic acid esters 1950 weight portions are heated to 90 ℃, stir reaction mixture is dissolved.Then, reactant liquor is cooled to 60 ℃, triphenyl phasphine 16.7 weight portions of packing into are heated to 100 ℃, react about 32 hours, obtain the reactant of acid number 1.0.Then, add tetrabydrophthalic anhydride 1845 weight portions and carbitol acetic acid esters 993.5 weight portions, react, obtain containing the polycarboxylic acid resin [I] (synthesis example 8S) of unsaturated group.
This polycarboxylic acid resin [I] (synthesis example 8S) that contains unsaturated group is the acid number 103 of solid constituent, solid component concentration 65%, viscosity (25 ℃) 26Pas.
Synthesis example 9
Pack into described epoxy resin (synthesis example 4) 3500 weight portions (10 equivalent), acrylic acid 720 weight portions (10 equivalent), methylnaphthohydroquinone 2.8 weight portions, carbitol acetic acid esters 1950 weight portions are heated to 90 ℃, stir reaction mixture is dissolved.Then, reactant liquor is cooled to 60 ℃, triphenyl phasphine 16.7 weight portions of packing into are heated to 100 ℃, react about 32 hours, obtain the reactant of acid number 1.0.Then, add succinic anhydride 953 weight portions (9.5 equivalent), carbitol acetic acid esters 513 weight portions, be heated to 95 ℃, react cooling after about 6 hours, obtain containing the polycarboxylic acid resin [I] (synthesis example 9) of unsaturated group.
This polycarboxylic acid resin [I] (synthesis example 9) that contains unsaturated group is the acid number 100 of solid constituent, solid component concentration 65%, viscosity (25 ℃) 45Pas.
Synthesis example 10
Pack into described epoxy resin (synthesis example 5) 2950 weight portions (10 equivalent), acrylic acid 720 weight portions (10 equivalent), methylnaphthohydroquinone 2.8 weight portions, carbitol acetic acid esters 1950 weight portions are heated to 90 ℃, stir reaction mixture is dissolved.Then, reactant liquor is cooled to 60 ℃, triphenyl phasphine 16.7 weight portions of packing into are heated to 100 ℃, react about 32 hours, obtain the reactant of acid number 1.00.Then, add tetrabydrophthalic anhydride 1845 weight portions and carbitol acetic acid esters 993.5 weight portions, react, obtain containing the polycarboxylic acid resin [I] (synthesis example 10) of unsaturated group.
This polycarboxylic acid resin [I] (synthesis example 10) that contains unsaturated group is the acid number 96 of solid constituent, solid component concentration 65%, viscosity (25 ℃) 35Pas.
Synthesis example 11
Cresol-novolac epoxy resin (epoxide equivalent 220) 3300 weight portions are packed into have in the flask of gas introduction tube, stirring apparatus, cooling tube and thermometer, add carbitol acetic acid esters 4000 weight portions, after the heating for dissolving, add quinhydrones 4.6 weight portions, triphenyl phasphine 13.8 weight portions.With this mixture heated to 95～105 ℃, slowly splash into acrylic acid 1080 weight portions, reacted 16 hours.Then this resultant of reaction is cooled to 80～90 ℃, adds tetrabydrophthalic anhydride 1630 weight portions, reacted 8 hours, obtain containing the polycarboxylic acid resin [I] (synthesis example 11) of unsaturated group.
This polycarboxylic acid resin [I] (synthesis example 11) that contains unsaturated group is the acid number 100 of solid constituent, solid component concentration 60%.
Synthesizing of＜polymkeric substance [II] 〉
Synthesis example 12
Pack into multipolymer (manufacturing of ATOCHEM company, SMA-1000, acid number 480) 434 weight portions, acrylic acid 2-hydroxy methacrylate 216 weight portions, diethylene glycol dimethyl ether 350 weight portions, metoquinone 0.5 weight portion of styrene and maleic anhydride, reacted about 20 hours down at 90 ℃, obtain reactant [II-1] (synthesis example 12).
This reactant [II-1] (synthesis example 12) is solid constituent 65%, resinous acid value 142, number-average molecular weight about 4500.
Synthesis example 13
Under nitrogen atmosphere, to splash in normal butyl alcohol 500 weight portions and methyl isobutyl ketone 400 weight portions that drop into the reaction vessel that remains on 110 ℃ by the mixed liquor that styrene 300 weight portions, butyl acrylate 350 weight portions, acrylic acid 350 weight portions and azoisobutyronitrile 30 weight portions are formed with 3 hours, splashed into post curing 1 hour, with splashing into the mixed liquor of forming by azo two (methyl pentane nitrile) 10 weight portions and methyl isobutyl ketone 100 weight portions in 1 hour.Then, slaking is 5 hours again, obtains high acid value acryl resin (acid number 260) solution.
Then, in this solution, add methacrylic acid 3,4-epoxycyclohexyl methyl esters 780 weight portions and hydroquinone monomethyl ether 1.4 weight portions, the limit is blown into air, and reacted 5 hours down at 80 ℃ on the limit, obtains reactant [II-2] (synthesis example 13).
This reactant [II-2] (synthesis example 13) is solid constituent 65%, resinous acid value 50, number-average molecular weight about 16000.
Synthesizing of＜crystallinity epoxy resin [V] 〉
Synthesis example 14
With 2,2 '-dimethyl-5,5 '-di-t-butyl-4,4 '-dihydroxy diphenylsulfide 120g is dissolved among the chloropropylene oxide 720g, add benzyltriethylammoinium chloride 0.3g again, under reduced pressure (about 150mmHg), 70 ℃ down with splashing into 48% sodium hydrate aqueous solution 55.7g in 4 hours.The water of Sheng Chenging is discharged to outside the system by the azeotropic with chloropropylene oxide therebetween, and the chloropropylene oxide that distillates turns back in the system.After splashing into end, continue reaction 1 hour again.Then, by filtering the salt that generates is removed, and then after the washing chloropropylene oxide is distilled, obtain faint yellow aqueous epoxy resin 165g.
In the liquid epoxy resin that obtains, add micropowder epoxy resin (changing V/1) [2,2 '-dimethyl-5,5 '-di-t-butyl-4, the diglycidyl ether of 4 '-dihydroxy diphenylsulfide] 3g as the other modulation of crystallization kind.Under 30 ℃, leave standstill then and carry out crystallization.
Its result obtains white crystals shape epoxy resin (changing V/1) (synthesis example 14) 149g.This crystalloid epoxy resin (changing V/1) (synthesis example 14) is 121 ℃ of epoxide equivalent 239, fusing points.
Synthesis example 15
In flask, pack 3 into, 3 '-dimethyl-4,4 '-dihydroxy diphenylsulfide 147.6g (0.6 mole), chloropropylene oxide 666g, under reduced pressure (about 140mmHg), 60 ℃ down with splashing into 48% sodium hydrate aqueous solution 97.0g in 4 hours.Therebetween, water is discharged to outside the system by the azeotropic with chloropropylene oxide, and the chloropropylene oxide that distillates turns back in the system.After splashing into end, continue reaction 1 hour.Then, the chloropropylene oxide decompression distillation of surplus remaining in the system is fallen, be dissolved among the methyl isobutyl ketone 501.2ml, by filtering the salt that generates is removed then.Then, add 24% sodium hydrate aqueous solution 39.3g, reacted 2 hours down at 80 ℃.And then after washing, neutralizing methyl isobutyl ketone is distilled, obtain epoxy resin (changing V/2) (synthesis example 15) 202g.Epoxide equivalent is 183, and fusing point is 47～51 ℃.
Synthesis example 16
In flask, pack 4 into, 4 '-dihydroxy diphenylsulfide 130.8g (0.6 mole), chloropropylene oxide 666g, under reduced pressure (about 140mmHg), 60 ℃ splashed into 48% sodium hydrate aqueous solution 97.0g. therebetween with 4 hours down, water is discharged to outside the system by the azeotropic with chloropropylene oxide, the chloropropylene oxide that distillates turns back in the system. after splashing into end, continue reaction 1 hour again. then, the chloropropylene oxide decompression distillation of surplus remaining in the system is fallen, be dissolved among the methyl isobutyl ketone 462ml, by filtering the salt that generates is removed then. then, add 24% sodium hydrate aqueous solution 55.8g, reacted 2 hours down at 80 ℃. and then washing, after the neutralization methyl isobutyl ketone is distilled, obtaining epoxy resin (changing V/3) (synthesis example 16) 184g. epoxide equivalent is 172, and fusing point is 43～47 ℃.
Synthesis example 17
Synthesis example 18
With 2,2 ', 3,3 ', 5,5 '-hexamethyl-4,4 '-dihydroxy diphenyl methane 120g is dissolved among the chloropropylene oxide 960g, adds benzyltriethylammoinium chloride 0.3g again, under reduced pressure (about 150mmHg), 70 ℃ down with splashing into 48% sodium hydrate aqueous solution 81.3g in 4 hours.The water of Sheng Chenging is discharged to outside the system by the azeotropic with chloropropylene oxide therebetween, and the chloropropylene oxide that distillates turns back in the system.After splashing into end, continue reaction 1 hour again.Then, by filtering the salt that generates is removed, and then after the washing chloropropylene oxide is distilled, obtain faint yellow aqueous epoxy resin 165g.
In the liquid epoxy resin that obtains, add micropowder crystallization (changing V/6) [2,2 ', 3,3 ', 5,5 '-hexamethyl-4, the diglycidyl ether of 4 '-dihydroxy diphenyl methane] 3g, under 30 ℃, leave standstill then and carry out crystallization as the other modulation of crystallization kind.
So just, obtain 160g epoxy resin (changing V/6) (synthesis example 18) [115 ℃ of epoxide equivalent 210, fusing points].
The modulation of＜photosensitive heat curing resin combination 〉
According to table E
XCooperation shown in/1 is formed, and with 3 roller mixing rolls each gradation composition is carried out mixingly, modulates photosensitive heat curing resin combination (each embodiment 1～9 and comparative example 1～7).
Table E
XIn/1,1)～3) represents following content.
1): in the formula (changing VII-1/1), g
11Be 0.1.
2): in the formula (changing VII-2), G
21Be phenyl, G
22Be 4,4 '-diphenyl methane, G
23Be phenyl, g
21Be 23.3.
3): in the formula (changing VII-3/1), G
71Be diphenyl methane.
＜be coated with the manufacturing of the printing distributing board of solder resist 〉
The manufacturing of smoothing printing distributing board
With thickness is that the printing distributing board [the thick 40 μ m of copper circuit, L/S=75 μ m/75 μ m] of 0.8mm uses as substrate.That is, use 250 purpose polyester screen that the compositions of thermosetting resin of following composition is carried out the mask printing, be applied on the described substrate.Then, this substrate is heated to 150 ℃, under this temperature, carries out 60 minutes one-step solidification with heating furnace.Then, at first the surface that comprises one-step solidification film side is carried out 1 time and grind, carry out 4 grindings with No. 600 emery wheels then with No. 400 abrasive band polishing muller.Under 180 ℃, carry out 90 minutes regelate at last with the box dryer, make the printing distributing board (in the concavo-convex difference of height 2 μ m) that makes the recess smoothing between circuit.Distinguish that in addition regelate can carry out after grinding, also can when solder resist solidifies, carry out.
(weight portion) formed in the cooperation of compositions of thermosetting resin:
75% acrylic acid addition product (100) of phenol-novolac epoxy resin, isobornyl acrylate (40), tristane dimethanol acrylate (100), trimethylolpropane triacrylate (10), t-butyl peroxybenzoate (10), tetramethyl biphenyl type epoxy resin (100), dicyandiamide (16), barium sulphate (120), dimethyl silicone polymer (0.1).
Make embodiment 1,4,5 and 7 and make comparative example 2 and 6
The making of dry film photoresist
On the pet vector film of thick 0.03mm, be coated with photosensitive heat curing resin combination (each embodiment 1,4,5 and 7 and comparative example 2 and 6) layer with applicator, make dry film thickness reach 20 μ m.After under 80 ℃ dry 20 minutes, apply the polyethylene protective film of 0.05mm more in the above, make obtaining the dry film photoresist.
The diaphragm of the dry film photoresist of described making is peeled off, used laminating machine that its thermosphere is pressed onto on the smoothing printing distributing board of described manufacturing, peel off carrier film then.
Then, use ultraviolet exposure apparatus according (オ one Network is made institute, pattern HMW-680C), by solder resist negative film irradiation ultraviolet radiation 500mj/cm
2Carry out spray developing with 1% aqueous sodium carbonate then, the resin of the part of irradiation ultraviolet radiation is not removed.
Behind the washing and drying, thereby in 150 ℃ hot-air drier, make its reaction that is heating and curing obtain cured film in 60 minutes.So just make the printing distributing board obtain being coated with solder resist (respectively make embodiment 1,4,5 and 7 and make comparative example 2 and 6).
Make comparative example 4
Replace photosensitive heat curing resin combination (each embodiment 1,4,5 and 7 and comparative example 2 and 6) and usability photosensitiveness compositions of thermosetting resin (comparative example 4) is made the dry film photoresist, replace the smoothing printing distributing board and use embossing distributing board (thick 0.8mm, the thick 25 μ m of copper circuit, L/S=75 μ m/75 μ m), replace 100 order polyester and use 250 order polyester to carry out outside the screen printing, all the other and described manufacturing embodiment 1,4,5 and 7 and make comparative example 2 and 6 and carry out equally, make the printing distributing board (making comparative example 4) that obtains being coated with solder resist.
Make embodiment 2,3,6 and 8 and make comparative example 1 and 5
Adopt mesh (100 order polyester) print process on the smoothing surface of the smoothing printing distributing board of described manufacturing, to print photosensitive heat curing resin combination (each embodiment 2,3,6 and 8 and comparative example 1 and 5) and make dry film thickness reach 20 μ m, in 80 ℃ hot-air drier, made dried coating film 20 minutes.
Then, use ultraviolet exposure apparatus according (オ one Network is made institute, pattern HMW-680C), by solder resist negative film irradiation ultraviolet radiation 500mj/cm
2Carry out spray developing with 1% aqueous sodium carbonate then, the resin of the part of irradiation ultraviolet radiation is not removed.
Behind the washing and drying, thereby in 150 ℃ hot-air drier, make its reaction that is heating and curing obtain cured film in 60 minutes.So just make the printing distributing board obtain being coated with solder resist (respectively make embodiment 2,3,6 and 8 and make comparative example 1 and 5).
Make embodiment 9 and make comparative example 3 and 7
Replace the smoothing printing distributing board and use embossing distributing board (thick 0.8mm, the thick 25 μ m of copper circuit, L/S=75 μ m/75 μ m), (embodiment 2 to replace the photosensitive heat curing resin combination, 3,6 and 8 and comparative example 1 and 5) and usability photosensitiveness compositions of thermosetting resin (each embodiment 9 and comparative example 3 and 7), replace 100 order polyester and use 250 order polyester to carry out outside the screen printing, all the other and described manufacturing embodiment 2,3,6 and 8 and make comparative example 1 and 5 and carry out equally, make the printing distributing board (respectively make embodiment 9 and make comparative example 3 and 7) that obtains being coated with solder resist.
＜be coated with the evaluation test of the printing distributing board of solder resist 〉
The printing distributing board that respectively is coated with solder resist (respectively make embodiment 1～9 and make comparative example 1～7) to described manufacturing carries out following various evaluation test.Test method and evaluation method are as described below.
(storage stability)
Each seal feed composition was placed 5 days in 40 ℃ of calibration cells, changed by viscosity storage stability is estimated.Judgment standard is as described below.
Zero: 1.5 times of viscosity deficient change initial value.
△: viscosity is changed to 3.0 times of more than 1.5 times of initial value, less thaies.
*: viscosity is changed to more than 3.0 times of initial value.
(preserving the back development)
The dry film photoresist that to place 10 days in 25 ℃ of calibration cells is laminated on the printing distributing board, carries out spray developing with 1% aqueous sodium carbonate, judges whether and can develop.
Zero: can develop.
*: produced the development residue.
(dry to touch)
After the coating, put into the heated air circulation type drying oven, after under 80 ℃ dry 20 minutes,, investigate adhesiveness, judge the state of filming with pointing firmly extrusion coated face.
Zero: not be not clamminess fully, fingerprint trace.
△: find that the surface existence is clamminess on a small quantity, fingerprint trace.
*: find that the surface existence significantly is clamminess, fingerprint trace.
(development)
With ultraviolet exposure apparatus according (オ one Network is made institute, pattern HMW-680C), by solder resist negative film irradiation ultraviolet radiation 500mj/cm
2The developer solution of using the 1wt% aqueous sodium carbonate then is with 2.0 * 10
5The row development in 60 seconds, the state that visual judgement is removed unexposed portion are thereafter compressed in the injection of Pa.
Zero: the seal material can be removed fully and developed during development.
*: there is the part that does not have development during development.
(photo sensitivity)
21 sections of step tablet (manufacturing of ス ト Off ア one company) are adhered on the dried coating irradiation accumulative total light quantity 500mJ/cm
2Ultraviolet ray expose.Use 1% aqueous sodium carbonate with 2.0 * 10 then
5The row development in 60 seconds is compressed in the injection of Pa, confirms not develop and the residual hop count of filming.
(resistance to bend(ing): cylindrical shape axle method)
Each composition is printed onto the thickness that makes on the 35 μ m Copper Foils after the curing reaches 40 μ m, exposure, cured film is made the test film of wide 10mm * long 100mm after solidifying,, the diameter 2mm of Yojimbo is tested according to JIS K5600.With following benchmark viewing test sheet.
Zero: face is not found to break.
*: face breaks.
(pencil hardness)
Estimate according to JIS K5600.
(cohesive)
According to JIS K5600, on test film, make the grid of 100 1mm, carry out disbonded test with cord belt.Observe the state of peeling off of grid, estimate with following benchmark.
Zero: do not peel off.
*: peel off.
(transparency of filming)
On black substrate, print and make cured coating film reach 40 μ m, whether change in appearance through the operation postevaluation of regulation.
Zero: appearance of film is no abnormal, transparent.
△: the transparency of appearance of film has certain decline.
*: appearance of film produces gonorrhoea, and transparency descends.
(bubble between circuit)
Use 30 times magnifier that the bubble between the circuit of printing distributing board is observed.
Zero: no bubble.
*: bubble is arranged.
(solvent resistance)
At room temperature test film was flooded in isopropyl alcohol 30 minutes.After confirming whether outward appearance exists unusually, adopt the disbonded test of cord belt (R), estimate by following benchmark.
Zero: appearance of film is no abnormal, no swelling, peels off.
*: there is swelling on filming, peels off.
(acid resistance)
At room temperature test film was flooded 30 minutes in 10% aqueous hydrochloric acid solution.After confirming whether outward appearance exists unusually, adopt the disbonded test of cord belt, estimate by following benchmark.
Zero: appearance of film is no abnormal, no swelling, peels off.
*: there is swelling on filming, peels off.
(thermotolerance)
To spare paint and be applied on the test film, in 288 ℃ welding rod groove, flood for 10 seconds with solder flux W-121 (manufacturing of メ Star Network company).It as 1 circulation, is carried out 3 circulations repeatedly.Put be as cold as room temperature after, adopt the disbonded test of cord belt (R), estimate by following benchmark.
Zero: appearance of film is no abnormal, no swelling, peels off.
*: there is swelling on filming, peels off.
(anti-gold-plated attribute)
The test substrate was flooded 3 minutes in 30 ℃ acid degreaser (the 20vol% aqueous solution of Japanese マ Network ダ one ミ Star ト system, MetexL-5B), wash then.Then, at room temperature in the 14.4wt% ammonium persulfate aqueous solution, flooded 3 minutes, wash then, at room temperature will test substrate again and in the 10vol% aqueous sulfuric acid, flood 1 minute after washing.
Then, this substrate was flooded 7 minutes in 30 ℃ catalytic liquid (the 10vol% aqueous solution of メ Le テ Star Network ス system, plating promoter 350), wash, dipping is 20 minutes in 85 ℃ nickel-plating liquids (20vol% aqueous solution, the pH4.6 of メ Le テ Star Network ス system, メ Le プ レ one ト Ni-865M), after carrying out nickel plating, at room temperature in the 10vol% aqueous sulfuric acid, flooded 1 minute, wash.
Then, the test substrate was flooded 10 minutes in 95 ℃ 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%), carry out washing behind the electroless plating gold, dipping 3 minutes in 60 ℃ warm water is washed, drying again.The electroless plating gold that the xylonite adhesion zone is attached to preparation is estimated on the substrate, observes the state when peeling off.
Zero: no abnormal fully.
*: observe some peeling off.
(HAST patience)
In 130 ℃, 85% unsaturated pressurizing vessel, between the comb-type electrode of the line/gap of having granted each solder resist=50 μ m/50 μ m, add the impressed voltage of DC5V, to test substrate and place after 168 hours, confirm whether outward appearance is unusual, before and after test, measure insulation resistance simultaneously.
Insulation resistance is to use " R8340A " (ア De バ Application テ ス ト system, digital ultra-high resistance/pettiness galvanometer), and according to the insulation resistance test specification of JPCA-HD01, the DC voltage that adds 10V was measured insulation resistance after 1 minute under this adds state.
Zero: appearance of film is no abnormal.
△: find variable color on the electrode, no swelling, peel off.
*: there is swelling on filming, peels off.
(resistance to sudden heating)
Be divided into 1 with-40 ℃/30 minutes, 125 ℃/30 and circulate,, after 1000 circulations, use the microscopic examination test film, estimate according to following benchmark to the outer heat cycles process of test film.
Zero: do not produce cracking on filming.
*: produced cracking on filming.
(concavo-convex difference of height)
With the surface configuration that the surfaceness instrumentation is decided test film, mark Rmax.
(peel strength)
Each composition is printed onto on the 35 μ m Copper Foils, predrying after, use laminating machine on the thick FR4 of the 0.4mm of no Copper Foil, composition and printing distributing board to be carried out heat lamination with 80 ℃, from the back side with 1000mJ/cm
2The irradiation ultraviolet radiation exposure is cured.After the curing, cut off, measure Copper Foil and composition are peeled off required load so that Copper Foil 10mm is wide.
From table Ex/2, can know following content.
As make shown in the comparative example 5, if contain polycarboxylic acid resin [I] deficiency of unsaturated group, then storage stability, development, resistance to bend(ing) and cohesive significantly reduce.
From make embodiment 8 and 9 with the comparison of making embodiment 1～7 as can be known, by interpolation polymkeric substance [II], can make the dry to touch raising.
As make shown in comparative example 5 and 6, if contain any one deficiency of the polycarboxylic acid resin [I] or the crystallinity epoxy resin [V] of unsaturated group, the transparency of then filming, HAST patience (particularly insulativity after 168 hours) and resistance to sudden heating significantly reduce.Therefore, the film transparency, HAST patience (particularly insulativity after 168 hours) and resistance to sudden heating is the only polycarboxylic acid resin [I] by will containing unsaturated group and crystallinity epoxy resin [V] and with the new effect that produces.
As make shown in embodiment 9 and the manufacturing comparative example 3 and 4, when using embossing distributing board in the past when replacing the smoothing printing distributing board, between the circuit of the printing distributing board of making that is coated with solder resist, produce bubble sometimes.
Claims (12)
1. photosensitive heat curing resin combination is characterized in that containing:
[I]: contain the polycarboxylic acid resin of unsaturated group, it is the epoxy resin shown in the following formula (change I/E) and contains the monocarboxylic reactant of unsaturated group and the reactant of polybasic carboxylic acid or its acid anhydrides,
In the formula (changing I/E), G is a following formula
The group of expression, A
11, A
13And A
15Aromatic residue or the hydrogenated aromatic residue of representing identical or different divalent, A
12And A
14Identical or different, represent H or G independently of one another, wherein A
12And A
14Both are not H simultaneously, a
11And a
12Represent the identical or different integer more than 0, but a
11And a
12Be not 0 simultaneously;
[III]: thinning agent;
[IV]: Photoepolymerizationinitiater initiater;
[V]: the crystallinity epoxy resin of following formula (changing V) expression,
In the formula (changing V), the G synonym in G and above-mentioned (the changing I/E), E
11～E
13And E
15～E
17Represent identical or different H or C1～C5 alkyl, e
11And e
12Represent identical or different 0～3 integer, E
14Expression S, O, CH
2, C (CH
3)
2Or the divalent group of following formula (changing V/X) or (changing F) expression,
(changing F)
In the formula (changing V/X), E
21～E
24Identical or different, represent C1～C6 alkyl independently of one another; With
[VI]: solidify the cohesive imparting agent;
Epoxy resin shown in the formula (changing I/E) is more than one that choose from the block polymerization type resin shown in homopolymerization type resin shown in the following formula (changing I/E-1) and the following formula (changing I/E-3),
(changing I/E-1)
(changing I/E-3)
In formula (changing I/E-1)～(the changing I/E-3), the G synonym in G and above-mentioned (the changing I/E),
In the formula (changing I/E-1), A
31And A
33Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, in the formula (changing I/E-1), a
31The integer of expression more than 1, in the formula (changing I/E-1), A
32Expression H or G, at least one is G,
In the formula (changing I/E-3), A
51, A
53And A
55Represent the aromatic residue of divalent or the hydrogenated aromatic residue of divalent independently of one another, in the formula (changing I/E-3), a
51And a
52Represent the integer more than 1 independently of one another, in the formula (changing I/E-3), A
52And A
54Identical or different, represent H or G independently of one another, but A
52And A
54Both are not H simultaneously.
2. the described photosensitive heat curing resin combination of claim 1 is characterized in that epoxy resin [V] is with above-mentioned formula (changing V) expression, wherein E
14The divalent group of expression S, O or above-mentioned formula (changing V/X) or (changing F) expression.
3. the described photosensitive heat curing resin combination of claim 1; it is characterized in that the photosensitive heat curing resin combination also contains [II]: have carboxyl and (methyl) acryloyl group, acid number is that 20～160mgKOH/g and mean molecular weight are 3000～70000 polymkeric substance.
4. the described photosensitive heat curing resin combination of claim 3; it is characterized in that polymkeric substance [II] is for [II-1]: have carboxyl or acid anhydride's polymkeric substance and the reactant that contains (methyl) acrylate of hydroxyl, and/or [II-2]: thus at least a portion with the carboxyl in the polymkeric substance of carboxyl and the unsaturated monomer reaction that contains epoxy radicals import the reactant of (methyl) acryloyl group.
5. each described photosensitive heat curing resin combination in the claim 1～4 is characterized in that the softening point of the epoxy resin shown in the formula (changing I/E) is more than 50 ℃, and the fusing point of crystallinity epoxy resin [V] is 110～135 ℃.
6. each described photosensitive heat curing resin combination in the claim 1～4, it is characterized in that the resin of resin (changing I/E-1) for following formula (changing I/E-1-1) and/or (changing I/E-1-2) expression, resin (change I/E-3) is for being selected from respectively by more than one of the resin of following formula (changing I/E-3-1)～(changing I/E-3-4) expression
(changing I/E-1-1)
(changing I/E-3-1)
(changing I/E-3-2)
(changing I/E-3-3)
(changing I/E-3-4)
In the described formula, the G synonym in G and above-mentioned (the changing I/E), A
611And A
621Respectively with described A
32Synonym, a
611And a
621Respectively with described a
31Synonym, A
711, A
721, A
731And A
741Respectively with described A
52Synonym, A
712, A
722, A
732And A
742Respectively with described A
54Synonym, a
712, a
722, a
732And a
742Respectively with described a
52Synonym,
In the described formula, A
713, A
714, A
723, A
724, A
733, A
734, A
743And A
744Be H or CH independently of one another
3
7. each described photosensitive heat curing resin combination in the claim 1～4 is characterized in that crystallinity epoxy resin [V] for being selected from respectively by more than one of the resin of following formula (changing V/1)～(changing V/9) expression,
(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 (changing V/1)～(the changing V/9), the G synonym in G and above-mentioned (the changing I/E), in the formula (changing V/8), E
31～E
34Identical or different, represent H or C1～C6 alkyl independently of one another.
8. each described photosensitive heat curing resin combination in the claim 1～4, it is characterized in that the photosensitive heat curing resin combination also contains is selected from [VII-1]: the crystallinity epoxy resin that fusing point is 135～170 ℃, wherein get rid of crystallinity epoxy resin (V), [VII-2]: single carbodiimide shown in the following formula (change VII-2) and/or poly-carbodiimide, [VII-3]: more than one of compound that contain allylic compound and [VII-4]: Han oxazolinyl are as the thermosetting composition
(changing VII-2)
In the formula (changing VII-2), G
21And G
23Aromatic residue, aliphatic residue or the ester ring type residue of representing 1 valency independently of one another, G
22Aromatic residue, aliphatic residue or the ester ring type residue of expression divalent, g
21The number of expression 0～30.
9. the described photosensitive heat curing resin combination of claim 8, it is characterized in that crystallinity epoxy resin [VII-1] is for being selected from more than one of resin shown in following formula (change VII-1/1)～(the changing VII-1/3), contain allylic compound [VII-3] for being selected from containing of mean molecular weight 400～30000 of allylic prepolymer, diallyl 3 shown in (different) cyanogen urea acid three (methyl) allyl esters and the following formula (changing VII-3/1), the compound [VII-4] of more than one Han oxazolinyls of methylene tetrahydric phthalimide compound is 2 in the 6-, 2-(1, the 3-phenylene) polymkeric substance of two-2-oxazoline and/or Han You oxazolinyl
(changing VII-1/1)
(changing VII-1/2)
(changing VII-1/3)
In formula (changing VII-1/1)～(the changing VII-1/3), the G synonym in G and above-mentioned (the changing I/E), in the formula (changing VII-1/1), g
11The number of expression 0～2,
In the formula (changing VII-3/1), G
71The divalent group of expression following formula (changing VII-3/1-R1), (changing VII-3/1-R2) or (changing VII-3/1-R3) expression,
(changing VII-3/1-R1)
In the formula (changing VII-3/1-R3), g
81The integer of expression 4～8.
10. be coated with the printing distributing board of resist, it is characterized in that resist contains each described photosensitive heat curing resin combination in the claim 1～9.
11. the described printing distributing board that is coated with resist of claim 10, thereby wherein printing distributing board is that the recess on printing distributing board surface is filled the smoothing printing distributing board make surface smoothing with resin.
12. claim 10 or the 11 described manufacture methods that are coated with the printing distributing board of resist, it is characterized in that in the manufacture method of the printing distributing board that is coated with resist, contain the aqueous photosensitive resist agent of each described photosensitive heat curing resin combination in the claim 1～9 or in photoresist, contain the dry film photoresist of each described photosensitive heat curing resin combination in the claim 1～9 by use, on the printing distributing board surface, apply resist.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004311541 | 2004-09-28 | ||
| JP2004-311541 | 2004-09-28 | ||
| JP2004311541A JP4683182B2 (en) | 2004-09-28 | 2004-09-28 | Photosensitive thermosetting resin composition, resist-coated printed wiring board and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| CN1755524A CN1755524A (en) | 2006-04-05 |
| CN1755524B true CN1755524B (en) | 2010-05-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200510107592 Active CN1755524B (en) | 2004-09-28 | 2005-09-28 | Phototonus thermosetting resin composition and printing plug board coating with resist and its manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP4683182B2 (en) |
| CN (1) | CN1755524B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI319411B (en) | 2010-01-11 |
| JP4683182B2 (en) | 2011-05-11 |
| JP2006096962A (en) | 2006-04-13 |
| CN1755524A (en) | 2006-04-05 |
| TW200610791A (en) | 2006-04-01 |
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