WO2019128256A1 - 固化性树脂组合物、干膜、固化物、及印刷电路板 - Google Patents

固化性树脂组合物、干膜、固化物、及印刷电路板 Download PDF

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Publication number
WO2019128256A1
WO2019128256A1 PCT/CN2018/100646 CN2018100646W WO2019128256A1 WO 2019128256 A1 WO2019128256 A1 WO 2019128256A1 CN 2018100646 W CN2018100646 W CN 2018100646W WO 2019128256 A1 WO2019128256 A1 WO 2019128256A1
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Prior art keywords
resin composition
group
curable resin
component
epoxy resin
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PCT/CN2018/100646
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English (en)
French (fr)
Inventor
福田晋一朗
山本修一
董思原
王玉彬
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太阳油墨（苏州）有限公司
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Priority to JP2020535628A priority Critical patent/JP7184903B2/ja
Publication of WO2019128256A1 publication Critical patent/WO2019128256A1/zh
Priority to PH12020550990A priority patent/PH12020550990A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details

Definitions

  • the present invention relates to a curable resin composition, a dry film, a cured product, and a printed circuit board.
  • the solder is protected from adhesion to an unnecessary portion, and a protective layer called a cover layer or a solder resist layer is coated on the printed circuit board.
  • a protective layer called a cover layer or a solder resist layer is coated on the printed circuit board.
  • an epoxy-based carboxyl group-containing photosensitive resin is mainly used.
  • Japanese Laid-Open Patent Publication No. Hei 10-282665 proposes a photo solder resist composition using a carboxyl group having a resin having a radical polymerizable unsaturated acyl group and a carboxyl group and having one ring in one molecule.
  • An ultraviolet curable resin obtained by reacting an oxy group and a compound having one or more radical polymerizable unsaturated groups.
  • Japanese Patent No. 5556990 proposes a photosensitive resin composition containing a reaction product of an ester compound of a polyfunctional epoxy resin with an unsaturated monocarboxylic acid or an ester compound of a saturated or unsaturated polybasic acid.
  • a photosensitive prepolymer obtained by further adding a compound having one glycidyl group and at least one ethylenically unsaturated group in one molecule; at least one or more molecules in the molecule Photopolymerizable monomer of ethylenically unsaturated group; photopolymerization initiator; blocked isocyanate; bismaleimide compound.
  • the cured film obtained from the resin composition containing the carboxyl group-containing photosensitive resin as described above has a good heat resistance, but has a problem of low bendability or large warpage, and there is room for improvement.
  • An object of the present invention is to provide a curable resin composition capable of obtaining a cured product which is excellent in heat resistance and excellent in flexibility and low warpage, and a dry film, a cured product, and a printed wiring board using the same.
  • the present inventors have succeeded in obtaining not only heat resistance by combining a specific carboxyl group-containing photosensitive resin and compounding an ethylenically unsaturated group-containing compound having five or more alkylene oxide skeletons.
  • the present invention has been completed by a curable resin composition of a cured product which is excellent in the properties and excellent in flexibility and low warpage.
  • the present invention is as follows.
  • a curable resin composition comprising:
  • component (A) it comprises:
  • a carboxyl group-containing photosensitive resin obtained by reacting an epoxy resin with a carboxylic acid having an ethylenically unsaturated group to react a generated hydroxyl group with an acid anhydride.
  • the curable resin composition according to any one of the above-mentioned items (1), wherein the content of the component (A1) is from 10 to 30, based on 100 parts by weight of the component (A). Parts by weight.
  • the curable resin composition according to any one of the above aspects, further comprising (D) an epoxy resin having a structure of the following formula (1).
  • X represents an alicyclic skeleton or an aromatic skeleton having 7 or more carbon atoms
  • n represents a number of 0 or more.
  • component (A) further contains a carboxyl group-containing resin having a urethane skeleton.
  • the ninth aspect of the invention is the resin layer obtained from the curable resin composition according to any one of the items 1 to 8.
  • a curable resin composition capable of obtaining a cured product which is excellent in not only heat resistance but also excellent in flexibility and low warpage, and a dry film, a cured product, and a printed wiring board using the same.
  • the present invention is a curable resin composition
  • a curable resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated group having 5 or more alkylene oxide skeletons.
  • the group compound, as the component (A), comprises: (A1) reacting an epoxy resin with a carboxylic acid having an ethylenically unsaturated group, reacting the generated hydroxyl group with an acid anhydride, and adding the carboxyl group-containing resin thus formed a carboxyl group-containing photosensitive resin formed by a compound having a glycidyl group and an ethylenically unsaturated group; and (A2) reacting the epoxy resin with a carboxylic acid having an ethylenically unsaturated group to form a hydroxyl group formed A carboxyl group-containing photosensitive resin formed by an acid anhydride reaction.
  • (meth) acrylate means a term collectively referred to as acrylate, methacrylate, and a mixture thereof, and the same applies to the following other similar expressions.
  • (A) carboxyl group-containing resin As the (A) carboxyl group-containing resin, (A1) an epoxy resin is reacted with a carboxylic acid having an ethylenically unsaturated group, and the resulting hydroxyl group is reacted with an acid anhydride, thereby forming a carboxyl group-containing photosensitive resin formed by adding a compound having a glycidyl group and an ethylenically unsaturated group to a carboxyl group-containing resin (also referred to simply as "(A1) component”); and (A2) an epoxy resin having an olefinic group A carboxyl group-containing photosensitive resin (also simply referred to as "(A2) component”) formed by reacting a generated carboxylic acid with an acid anhydride to form an unsaturated group is an essential component.
  • (meth)acrylic acid or the like is preferably exemplified.
  • maleic anhydride succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic acid can be typically used.
  • Diacid anhydrides such as acid anhydride, endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chloric acid anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride, homobenzene
  • An aromatic polycarboxylic acid anhydride such as tetracarboxylic anhydride or benzophenone tetracarboxylic dianhydride; and an accompanying compound such as 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1
  • a polybasic acid anhydride derivative such as 2-dicarboxylic anhydride is preferably a dibasic acid anhydride.
  • epoxy resin a resin having an epoxy group can be arbitrarily used.
  • a bifunctional epoxy resin having two epoxy groups in the molecule, a polyfunctional epoxy resin having a plurality of epoxy groups in the molecule, and the like can be given.
  • epoxy resin examples include bisphenol A epoxy resin, brominated epoxy resin, novolac epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, and glycidylamine.
  • Type epoxy resin hydantoin type epoxy resin, alicyclic epoxy resin, trishydroxyphenylmethane type epoxy resin, bisphenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetrahydroxyphenylethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylene
  • Examples of the compound having a glycidyl group and an ethylenically unsaturated group include a glycidyl group in a molecule such as glycidyl (meth)acrylate or ⁇ -methylglycidyl (meth)acrylate.
  • One or more (meth)acryloyl groups and the like include a glycidyl group in a molecule such as glycidyl (meth)acrylate or ⁇ -methylglycidyl (meth)acrylate.
  • One or more (meth)acryloyl groups and the like are examples of the compound having a glycidyl group and an ethylenically unsaturated group.
  • the epoxy resin which is a raw material of the component (A1) is preferably a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, or a bisphenol S epoxy resin.
  • the epoxy resin which is a raw material of the component (A2) is preferably a bisphenol epoxy resin.
  • component (A1) it is more preferred to further add a compound such as (1) to (2) to a molecule such as glycidyl (meth)acrylate or ⁇ -methylglycidyl (meth)acrylate.
  • a carboxyl group-containing photosensitive resin formed of a compound having one glycidyl group and one or more (meth)acryloyl groups.
  • the resin of the following (1) to (2) is preferable as the component (A2).
  • the component (A2) is contained, the flexibility of the cured product is further improved as compared with the carboxyl group-containing resin having a urethane skeleton, and the cured product is excellent in flexibility.
  • a carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or bifunctional or higher polyfunctional epoxy resin with (meth)acrylic acid to form a dibasic acid anhydride in a hydroxyl group present in a side chain.
  • a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid, and a dibasic acid anhydride is added to the produced hydroxyl group to obtain a dibasic acid anhydride.
  • a carboxyl group-containing photosensitive resin is added to the produced hydroxyl group to obtain a dibasic acid anhydride.
  • the carboxyl group-containing resin may be used alone or in combination of a plurality of carboxyl group-containing resins other than the above (A1) component and (A2) component in a range that does not impair the effects of the present invention.
  • the (A) carboxyl group-containing resin may further contain (A3) a carboxyl group-containing resin having a urethane skeleton. When the component (A3) is contained, the flexibility and heat resistance of the cured product can be improved.
  • any of the following resins (3) to (7) is preferable.
  • Diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate, and carboxyl group-containing diol such as dimethylolpropionic acid or dimethylolbutanoic acid a compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a phenolic hydroxyl group; A carboxyl group-containing photosensitive polyurethane resin obtained by a polyaddition reaction of a diol compound such as an alcoholic hydroxyl group compound.
  • a diol compound such as an alcoholic hydroxyl group compound.
  • a compound having one hydroxyl group and one or more (meth)acryloyl groups in a molecule such as a hydroxyalkyl (meth)acrylate is added to the synthesis of the resin of the above (4) or (5) to carry out the terminal ( A carboxyl group-containing photosensitive urethane resin obtained by acrylation with a methyl group.
  • the compounding amount of the (A) carboxyl group-containing resin is suitably 20 to 80% by mass in the curable resin composition. When it is 20% by mass or more and 80% by mass or less, the film strength is good, and the viscosity of the composition can be lowered, and the coating property and the like are excellent. More preferably, it is 20-60 mass %.
  • the content ratio of the component (A1) to the component (A2) is not particularly limited.
  • the content of the component (A1) is preferably 10 to 30 parts by weight, and more preferably 10 to 20 parts by weight based on 100 parts by weight of the component (A), from the viewpoint of the balance between heat resistance, flexibility, and low warpage. Parts by weight.
  • the photopolymerization initiator used as the component (B) is not particularly limited as long as it is a photopolymerization initiator which is generally used for the curable resin composition.
  • Specific examples thereof include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone, and 2-benzyl-2-dimethylamino-1-(4).
  • an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylphenone-based photopolymerization initiator, and an ⁇ -aminoacetophenone-based photopolymerization initiator can be suitably used.
  • oxime ester-based photopolymerization initiator For the oxime ester-based photopolymerization initiator, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like are exemplified. Further, a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used.
  • the oxime ester photopolymerization initiator is preferably an oxime ester compound having a carbazole structure.
  • the commercially available product of the alkyl phenyl ketone photopolymerization initiator may, for example, be an ⁇ -hydroxyalkyl phenyl ketone type such as IRGACURE 184, Dalocure 1173, IRGACURE 2959 or IRGACURE 127 manufactured by BASF Japan Ltd.
  • ⁇ -aminoacetophenone-based photopolymerization initiator examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1,2- Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- 1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like.
  • IRGACURE907, IRGACURE369, IRGACURE379, etc. by BASF Japan Ltd. are mentioned.
  • acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl).
  • LUCIRIN TPO by BASF Corporation, IRGACURE 819 by BASF Japan Ltd., etc. are mentioned.
  • a titanocene-based photopolymerization initiator such as IRGACURE 389 or IRGACURE 784 manufactured by BASF Japan Ltd. can be suitably used.
  • the compounding amount of the photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.
  • the compounding amount is from 0.1 to 25 parts by mass, a cured film having excellent photocurability and resolution, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance can be obtained.
  • the compounding amount is 25 parts by mass or less, the effect of reducing the exhaust gas can be obtained, and further, the light absorption on the surface of the coating film can be suppressed to be severe, and the deep curability can be lowered.
  • the component (C) is not particularly limited as long as it has five or more alkylene oxide skeletons and contains an ethylenically unsaturated group.
  • a compound having five or more EO or PO in the molecule and having two or more ethylenically unsaturated groups is preferred.
  • the component (C) preferably contains a structure having a (meth)acryloyl group at the terminal of the alkylene oxide skeleton.
  • the number of ethylenically unsaturated groups is more preferably 2 or more and 4 or less, and most preferably 2 or more and 3 or less.
  • EO means “ethylene oxide”
  • PO means “propylene oxide”.
  • EO modification means a block structure having an ethylene oxide unit (-CH 2 -CH 2 -O-)
  • PO modification means having a propylene oxide unit (-CH 2 - Block structure of CH 2 -CH 2 -O-, -CH(CH 3 )-CH 2 -O-, -CH 2 -CH(CH 3 )-O-).
  • the component (C) is exemplified by the EO-modified polyacrylate, and a compound represented by the following formula (1) or (2) is more preferable.
  • n represents the number of modifications, n ⁇ 5.
  • the "having five or more alkylene oxide skeletons" means that when two or more types of alkylene oxide skeletons are contained, all of the alkylene oxide skeletons have five or more. If it is less than 5, the excellent bendability and low warpage of the present invention cannot be achieved.
  • the component (C) preferably has 5 or more and 30 or less alkylene oxide skeletons, and more preferably has 5 or more and 20 or less alkylene oxide skeletons from the viewpoint of balance of properties.
  • the number of the alkylene oxide skeletons is 30 or less, the thickness of the cured film can be easily ensured without adjusting the viscosity of the composition.
  • the compounding amount of the component (C) is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, even more preferably 10 to 20 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.
  • an epoxy resin having a structure of the following formula (1) may be contained.
  • X represents an alicyclic skeleton or an aromatic skeleton having 7 or more carbon atoms
  • n represents a number of 0 or more.
  • X in the above formula (1) is a dicyclopentadiene skeleton, it is preferred to exhibit the effects of the present invention remarkably.
  • an epoxy resin other than the component (D), for example, the above bisphenol A epoxy resin may be contained.
  • (E) a diamine having an ether skeleton may be contained.
  • the component (E) include JEFFAMINE D-230 and JEFFAMINE D-2000 (manufactured by Huntsman Co., Ltd.).
  • the component (E) preferably contains a polyetheramine (also referred to as polyether diamine) having an ether skeleton of 15 or more, and is suitable for use.
  • a polyetheramine also referred to as polyether diamine
  • the number of diamines and ether skeletons having the number of ether skeletons of 1 or more and 10 or less is 20 or more and 40 or less.
  • the content of the diamine having a number of the ether skeleton of 1 or more and 10 or less is preferably 1 to 40 parts by weight based on 100 parts by weight of the total weight of the component (E), and the content of the polyetheramine having 15 or more ether skeletons is 15 or more. It is preferably 60 to 99 parts by weight based on 100 parts by weight of the total weight of the component (E).
  • the curable resin composition of the present invention may contain (F) a trifunctional or higher ethylenically unsaturated group-containing compound for increasing the crosslinking density in a range that does not impair the effects of the present invention (excluding ( C) ingredients).
  • Examples of the component (F) include trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, and PO-modified trimethylolpropane III ( Methyl) acrylate, EO ⁇ PO modified trimethylolpropane tri(meth) acrylate, tetramethylol methane tri(meth) acrylate, tetramethylol methane tetra(meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
  • a known conventional filler such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, silica, bentonite, kaolin, glass fiber, carbon fiber or mica may be added depending on the desired physical properties.
  • Various additives such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, and the like which are conventionally used dyes, coloring pigments, antifoaming agents, flame retardants, adhesion imparting agents or leveling agents, or hydroquinone or hydroquinone
  • a known conventional polymerization inhibitor such as monomethyl ether, pyrogallol, t-butyl catechol, or phenothiazine.
  • the curable resin composition of the present invention may contain an organic solvent for preparing a composition and adjusting the viscosity.
  • an organic solvent for example, ketones such as methyl ethyl ketone or cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and A can be used.
  • Glycol ethers such as carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, lactic acid Butyl ester, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, An ester such as propylene carbonate; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, petroleum brain or solvent naphtha. These organic solvents may be used alone or in combination of two or more.
  • a cured product which is excellent in heat resistance and excellent in flexibility and low warpage can be obtained, and therefore it is preferably used for the production of a flexible printed circuit board.
  • Another aspect of the present invention provides a dry film having a resin layer obtained from the above curable resin composition.
  • the dry film of the present invention can be obtained by coating on a carrier film (support) and drying it.
  • the composition of the present invention is adjusted to an appropriate viscosity by diluting with the above organic solvent as needed, using a comma coater, a knife coater, a lip coater, a bar coater, and extrusion coating.
  • a cloth machine, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc. are coated on the carrier film with a uniform thickness, and are usually dried at a temperature of 50 to 130 ° C for 1 to 30 minutes.
  • a resin layer as a dry coating film can be produced.
  • the thickness of the resin layer is not particularly limited, and is usually appropriately selected in the range of 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m, in terms of the film thickness after drying.
  • a plastic film As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
  • the thickness of the carrier film is not particularly limited, and is usually appropriately selected in the range of 0.1 to 150 ⁇ m.
  • a peelable cover film on the surface of the resin layer for the purpose of preventing adhesion of dust or the like on the surface of the resin layer.
  • a peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when the cover film is peeled off, the adhesion between the resin layer and the cover film is smaller than that of the resin layer and the carrier. The adhesion of the film is sufficient.
  • Another aspect of the present invention provides a cured product obtained from the above curable resin composition.
  • the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method as needed, and is applied to, for example, a circuit formed by a screen printing method, a curtain coating method, a spray coating method, a roll coating method, or the like.
  • the organic solvent contained in the composition is volatilized and dried at a temperature of, for example, 60 to 100 ° C to form a non-tacky coating film.
  • the obtained coating film or the resin layer of the dry film is selectively exposed by an active energy ray through a photomask having a predetermined exposure pattern, and the unexposed portion is developed with a developing solution to form a resist pattern.
  • the film is heated to a temperature of, for example, 140 to 180 ° C to be thermally cured, whereby a cured product excellent in heat resistance, flexibility, and low warpage can be obtained as a resist film.
  • the volatilization drying after the application of the composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like using a heat source having a heat method using steam to dry the inside of the dryer.
  • a hot air circulation type drying furnace an IR furnace, a hot plate, a convection oven, or the like
  • a heat source having a heat method using steam to dry the inside of the dryer.
  • the method of hot air convection contact and the method of blowing the nozzle to the support body can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like using a heat source having a heat method using steam to dry the inside of the dryer.
  • a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, or the like may be mounted and irradiated with ultraviolet rays in a range of 350 to 450 nm, and further, it may be used.
  • a direct rendering device eg, a direct imaging device that directly illuminates an active energy ray to draw an image based on CAD data from a computer.
  • the light source of the direct drawing machine a light source having a maximum wavelength of light in the range of 350 to 410 nm may be used.
  • the amount of exposure for forming an image differs depending on the film thickness and the like, and can be usually in the range of 20 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .
  • a dipping method, a shower method, a spray method, a brushing method, or the like can be used.
  • potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, or ammonia can be used.
  • a dilute aqueous alkali solution such as an amine.
  • the present invention provides a printed circuit board having the above cured product.
  • An ortho-cresol novolak-type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6) 1070 g was placed in 700 g of diethylene glycol monoethyl ether acetate ( The glycidyl group (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid and 1.5 g of hydroquinone were stirred while heating to 100 ° C to be uniformly dissolved.
  • triphenylphosphine was added, and after heating to 110 ° C for 2 hours, 1.6 g of triphenylphosphine was further added, and the temperature was raised to 120 ° C to further carry out a reaction for 12 hours.
  • 562 g of an aromatic hydrocarbon (SOLVESSO 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were placed in the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours.
  • the solid content of the resin solution thus obtained was 65%, and the acid value of the solid content was 100 mgKOH/g.
  • a polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having a plurality of alcoholic hydroxyl groups is introduced into a reaction vessel equipped with a stirring device, a thermometer, and a condenser (Asahi Kasei Chemical Co., Ltd.) T5650J, number average molecular weight 800) 3600 g (4.5 mol), dimethylglycolic acid 814 g (5.5 mol), and n-butanol 118 g (1.6 mol) as a molecular weight modifier (reaction stop).
  • IRGACURE 784, IRGACURE 369, 4,4'-bis(diethylamino)benzophenone (EAB) manufactured by BASF Japan Ltd. was used as a photopolymerization initiator as a dicyclopentadiene type solid ring.
  • Oxygen resin is XD-1000 manufactured by Nippon Kayaku Co., Ltd., and NC-3000 manufactured by Nippon Kayaku Co., Ltd. is used as the biphenol novolak type epoxy resin, and Nakamura Chemical Co., Ltd. is used as the EO-modified acrylic monomer.
  • DPHA dipentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.
  • JEFFAMINE D-230 JEFFAMINE D-2000 (manufactured by Huntsman Co., Ltd.) were used.
  • the polyimide substrate having the cured coating film was cut into 5 cm ⁇ 5 cm to prepare an evaluation sample.
  • the surface on which the coating film was cured was used as the upper surface, and the warpage of each corner was measured with a ruler, and the average value of four points was evaluated.
  • ⁇ The average value of each corner warp is 2 mm or less
  • ⁇ The average value of each corner warp is 3 mm or less
  • the polyimide substrate having the cured coating film was cut into a width of 10 mm ⁇ a length of 70 mm to prepare an evaluation sample.
  • the surface having the cured coating film was folded into a mountain shape, and a weight of 1 kg was placed thereon. After being placed for 10 seconds, the bent portion was developed. Then, the weight was placed on the bending portion again for 10 seconds, and this was taken once. The bent portion was observed with a microscope, and the number of times until the copper was observed was evaluated.
  • the polyimide substrate having the cured coating film was cut into a length of 20 mm ⁇ a width of 20 mm to prepare an evaluation sample.
  • the temperature of the solder bath was set to 320 ° C, and the sample substrate was placed therein, and after 10 seconds, the substrate was taken out, and the swelling of the cured coating film on the surface of the substrate was confirmed, and the number of times until the bulging occurred was evaluated.
  • Examples 1 to 7 containing a combination of the component (A1) and the component (A2) as a carboxyl group-containing resin and an ethylenically unsaturated group-containing compound having 5 or more alkylene oxide skeletons were used. Excellent results were obtained in the evaluation of low warpage, bendability, and heat resistance of the cured product. On the other hand, in Comparative Example 1 using an ethylenically unsaturated group-containing compound having less than 5 alkylene oxide skeletons, the cured product was slightly inferior in warpage and bendability.
  • Comparative Example 2 In Comparative Example 2 in which the ethylenically unsaturated group-containing compound having an alkylene oxide skeleton was not used, the cured product was inferior in low warpage and bendability. In Comparative Example 3 which did not contain the component (A1), the cured product was slightly inferior in warpage and bendability, and was inferior in soldering heat resistance.
  • the curable resin composition of the present invention can form a cured product which is excellent not only in heat resistance but also in flexibility and low warpage. From the results of excellent bendability and low warpage, it is also suitable for flexible printed circuit boards.

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Abstract

一种不仅耐热性优异而且弯曲性、翘曲性也优异的固化物的固化性树脂组合物、干膜、固化物、及印刷电路板。固化性树脂组合物包含(A)含羧基树脂、(B)光聚合引发剂、以及(C)具有5个以上环氧烷骨架的含烯属不饱和基团化合物，作为(A)成分，包含(A1)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应，对由此形成的含羧基树脂加成具有缩水甘油基和烯属不饱和基团的化合物而形成的含羧基感光性树脂；以及(A2)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应而形成的含羧基感光性树脂。

Description

固化性树脂组合物、干膜、固化物、及印刷电路板 技术领域
本发明涉及固化性树脂组合物、干膜、固化物、及印刷电路板。
背景技术
近年来，智能手机、平板终端的普及和性能的提高正在急速推进。对于以它们为代表的信息设备终端，消费者对小型化、薄型化的要求高，为了响应该要求，产品内部的电路基板的高密度化、节省空间化成为必需。因此，能弯曲地收纳且能提高电路配置自由度的柔性印刷电路板的用途正在扩大，对于柔性印刷电路板的可靠性也要求比以往更高。
印刷电路板的制造工序中，为了保护在基板上通过丝网印刷等方法形成的布线(电路)图案不受外部环境的影响，或者为了在将电子部件在印刷电路板进行表面安装时进行的焊接工序中以焊料不会附着在不需要的部分的方式进行保护，将被称为覆盖层或阻焊层的保护层覆盖在印刷电路板上。以往，上述用途中使用的阻焊层用的固化性树脂组合物中，主要使用环氧系的含羧基感光性树脂。
例如，日本特开平10-282665号公报中提出了一种光致阻焊墨组合物，其使用了通过使具有自由基聚合性不饱和酰基和羧基的树脂的羧基与1分子中具有1个环氧基和1个以上自由基聚合性不饱和基团的化合物进行反应而得到的紫外线固化性树脂。
另外，日本特许5556990号公报中提出了一种感光性树脂组合物，其含有：使多官能环氧树脂与不饱和一元羧酸的酯化合物或者饱和或不饱和多元酸的酯化合物的反应产物与饱和或不饱和多元酸酐进行反应后，进一步加成1分子中具有1个缩水甘油基和至少1个烯属不饱和基团的化合物而得到的感 光性预聚物；分子中具有至少1个以上烯属不饱和基团的光聚合性单体；光聚合引发剂；封端化异氰酸酯；双马来酰亚胺化合物。
发明内容
发明要解决的问题
然而，由使用了上述那样的含羧基感光性树脂的树脂组合物得到的固化膜虽然耐热性良好，但存在弯曲性低或翘曲大的问题，有改善的余地。
本发明的目的在于，提供能得到不仅耐热性优异而且弯曲性、低翘曲性也优异的固化物的固化性树脂组合物、及使用其的干膜、固化物、及印刷电路板。
用于解决问题的方案
本发明人等进行了深入研究，结果通过组合特定的含羧基感光性树脂，并配混具有5个以上环氧烷骨架的含烯属不饱和基团化合物，从而成功地获得能得到不仅耐热性优异而且弯曲性、低翘曲性也优异的固化物的固化性树脂组合物，由此完成了本发明。
即，本发明如下所述。
【第1项】一种固化性树脂组合物，其特征在于，包含：
(A)含羧基树脂、
(B)光聚合引发剂、以及
(C)具有5个以上环氧烷骨架的含烯属不饱和基团化合物，
作为前述(A)成分，包含：
(A1)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应，对由此形成的含羧基树脂加成具有缩水甘油基和烯属不饱和基团的化合物而形成的含羧基感光性树脂；以及
(A2)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基 与酸酐反应而形成的含羧基感光性树脂。
【第2项】根据第1项所述的固化性树脂组合物，其特征在于，前述(A2)成分的环氧树脂为双酚型环氧树脂。
【第3项】根据第1项或第2项所述的固化性树脂组合物，其特征在于，前述(C)成分具有5个以上且30个以下的环氧烷骨架。
【第4项】根据第1～3项中任一项所述的固化性树脂组合物，其特征在于，相对于前述(A)成分100重量份，前述(A1)成分的含量为10～30重量份。
【第5项】根据第1～4项中任一项所述的固化性树脂组合物，其特征在于，还包含(D)具有下述通式(1)的结构的环氧树脂。
Figure PCTCN2018100646-appb-000001
(式(1)中，X表示碳数7以上的脂环式骨架或芳香族骨架，n表示0以上的数。)
【第6项】根据第5项所述的固化性树脂组合物，其特征在于，作为前述(D)成分，包含通式(1)中的X为双环戊二烯骨架的环氧树脂。
【第7项】根据第1～6项中任一项所述的固化性树脂组合物，其特征在于，作为前述(A)成分，还包含具有氨基甲酸酯骨架的含羧基树脂。
【第8项】根据第1～7项中任一项所述的固化性树脂组合物，其特征在于，用于柔性印刷电路板的制造。
【第9项】一种干膜，其特征在于，具有由第1～8项中任一项所述的固化性树脂组合物得到的树脂层。
【第10项】一种固化物，其特征在于，使第1～8项中任一项所述的固化性树脂组合物或第9项所述的干膜的树脂层固化而得到。
【第11项】一种印刷电路板，其特征在于，具有第10项所述的固化物。
发明的效果
根据本发明，能够提供能得到不仅耐热性优异而且弯曲性、低翘曲性也优异的固化物的固化性树脂组合物、及使用其的干膜、固化物、及印刷电路板。
具体实施方式
本发明为一种固化性树脂组合物，其特征在于，包含(A)含羧基树脂、(B)光聚合引发剂、以及(C)具有5个以上环氧烷骨架的含烯属不饱和基团化合物，作为前述(A)成分，包含：(A1)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应，对由此形成的含羧基树脂加成具有缩水甘油基和烯属不饱和基团的化合物而形成的含羧基感光性树脂；以及(A2)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应而形成的含羧基感光性树脂。
以下，分别说明本发明的固化性树脂组合物的各成分。需要说明的是，(甲基)丙烯酸酯是指，统称丙烯酸酯、甲基丙烯酸酯和它们的混合物的术语，对于以下其它类似的表达也是同样的。
(A)含羧基树脂
本发明的组合物中，作为(A)含羧基树脂，包含(A1)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应，对由此形成的含羧基树脂加成具有缩水甘油基和烯属不饱和基团的化合物而形成的含羧基感光性树脂(也简称为“(A1)成分”)；以及(A2)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应而形成的含羧基感光性树脂(也简称为“(A2)成分”)作为必需成分。
作为前述具有烯属不饱和基团的羧酸，可优选地列举出(甲基)丙烯酸等。
作为前述酸酐，代表性地可以使用马来酸酐、琥珀酸酐、衣康酸酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、甲基内亚甲基四氢邻苯二甲酸酐、氯菌酸酐、甲基四氢邻苯二甲酸酐等二元酸酐；偏苯三酸酐、均苯四甲酸酐、二苯甲酮四羧酸二酐等芳香族多元羧酸酐；以及它们附带的例如5-(2，5-二氧四氢呋喃)-3-甲基-3-环己烯-1，2-二羧酸酐那样的多元羧酸酐衍生物等，优选二元酸酐。
作为前述环氧树脂，为具有环氧基的树脂，可以任意地使用公知的物质。可列举出分子中具有2个环氧基的2官能性环氧树脂、分子中具有多个环氧基的多官能环氧树脂等。
作为上述环氧树脂，可列举出双酚A型环氧树脂、溴化环氧树脂、酚醛清漆型环氧树脂、双酚F型环氧树脂、氢化双酚A型环氧树脂、缩水甘油胺型环氧树脂、乙内酰脲型环氧树脂、脂环式环氧树脂、三羟苯基甲烷型环氧树脂、联二甲酚型或联苯酚型环氧树脂或它们的混合物；双酚S型环氧树脂、双酚A酚醛清漆型环氧树脂、四羟苯基乙烷型环氧树脂、杂环式环氧树脂、邻苯二甲酸二缩水甘油酯树脂、四缩水甘油基二甲苯酰基乙烷树脂、含萘基环氧树脂、具有双环戊二烯骨架的环氧树脂等。
作为前述具有缩水甘油基和烯属不饱和基团的化合物，可列举出(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸α-甲基缩水甘油酯等分子中具有1个缩水甘油基和1个以上(甲基)丙烯酰基的化合物等。
作为成为前述(A1)成分的原料的环氧树脂，优选双酚A型环氧树脂、氢化双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂等双酚型环氧树脂、联二甲酚型环氧树脂和联苯酚型环氧树脂。
作为成为前述(A2)成分的原料的环氧树脂，优选双酚型环氧树脂。
作为(A1)成分，进一步优选的是，对下述(1)～(2)的树脂进一步 加成(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸α-甲基缩水甘油酯等分子中具有1个缩水甘油基和1个以上(甲基)丙烯酰基的化合物而形成的含羧基感光性树脂。
作为(A2)成分，进一步优选下述(1)～(2)的树脂等。包含(A2)成分时，与具有氨基甲酸酯骨架的含羧基树脂相比进一步提高固化物的柔软性，使固化物的弯曲性优异。
(1)使2官能或2官能以上的多官能环氧树脂与(甲基)丙烯酸反应，对存在于侧链的羟基加成二元酸酐而得到的含羧基感光性树脂。
(2)使将2官能环氧树脂的羟基进一步用环氧氯丙烷进行环氧化而成的多官能环氧树脂与(甲基)丙烯酸反应，对所生成的羟基加成二元酸酐而得到的含羧基感光性树脂。
(A)含羧基树脂可以在不妨碍本发明的效果的范围内使用1种或组合使用多种除上述(A1)成分和(A2)成分以外的含羧基树脂。作为(A)含羧基树脂，还可以包含(A3)具有氨基甲酸酯骨架的含羧基树脂。包含(A3)成分时，能够提高固化物的弯曲性和耐热性。
作为(A3)成分，优选下述(3)～(7)中任意种树脂。
(3)通过二异氰酸酯与含羧基二元醇化合物的加聚反应得到的含羧基聚氨酯树脂。
(4)通过脂肪族二异氰酸酯、支链脂肪族二异氰酸酯、脂环式二异氰酸酯、芳香族二异氰酸酯等二异氰酸酯与二羟甲基丙酸、二羟甲基丁酸等含有羧基的二元醇化合物、聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烃系多元醇、丙烯酸类多元醇、双酚A系环氧烷加成物二醇、具有酚性羟基和醇性羟基的化合物等二醇化合物的加聚反应得到的含羧基感光性聚氨酯树脂。
(5)通过二异氰酸酯、与双酚A型环氧树脂、氢化双酚A型环氧树脂、 双酚F型环氧树脂、双酚S型环氧树脂、联二甲酚型环氧树脂、双酚型环氧树脂等2官能环氧树脂的(甲基)丙烯酸酯或其部分酸酐改性物和含羧基二元醇化合物的加聚反应得到的含羧基感光性聚氨酯树脂。
(6)在上述(4)或(5)的树脂的合成中加入(甲基)丙烯酸羟基烷基酯等分子内具有1个羟基和1个以上(甲基)丙烯酰基的化合物来进行末端(甲基)丙烯酰基化而得到的含羧基感光性聚氨酯树脂。
(7)在上述(5)或(6)的树脂的合成中加入异佛尔酮二异氰酸酯与季戊四醇三丙烯酸酯的等摩尔反应物等分子内具有1个异氰酸酯基和1个以上(甲基)丙烯酰基的化合物来进行末端(甲基)丙烯酰基化而得到的含羧基感光性聚氨酯树脂。
(A)含羧基树脂的配混量在固化性树脂组合物中为20～80质量％是适当的。为20质量％以上且80质量％以下时，皮膜强度良好，能够降低组合物的粘性，涂布性等优异。更优选为20～60质量％。
前述(A)含羧基树脂中，对(A1)成分与(A2)成分的含有比例没有特别限定。若(A1)成分的含量过低，则存在由(A1)成分带来的提高耐热性的效果变得不充分的担心，若过高，则存在弯曲性差、翘曲变大的担心。从耐热性与弯曲性、低翘曲性的平衡的观点出发，相对于前述(A)成分100重量份，前述(A1)成分的含量优选为10～30重量份、进一步优选为10～20重量份。
(B)光聚合引发剂
本发明中，作为用作(B)成分的光聚合引发剂，只要是通常用于固化性树脂组合物的光聚合引发剂，就没有特别限制。具体而言，例如可列举出二苯甲酮、N，N’-四烷基-4，4’-二氨基二苯甲酮、2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)-丁酮-1、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基-丙酮-1等芳香族酮、4，4’-双(二甲基氨基)二苯甲酮(米氏酮)、4，4’-双(二乙基氨基) 二苯甲酮、4-甲氧基-4’-二甲基氨基二苯甲酮、2-苄基-2-二甲基氨基-1-(吗啉基苯基)-丁酮-1、2-乙基蒽醌、菲醌等芳香族酮、苯偶姻甲醚、苯偶姻乙醚、苯偶姻苯醚等苯偶姻醚、甲基苯偶姻、乙基苯偶姻等苯偶姻、苯偶酰二甲基缩酮等苯偶酰衍生物、2-(邻氯苯基)-4，5-二苯基咪唑二聚体、2-(邻氯苯基)-4，5-二(间甲氧基苯基)咪唑二聚体、2-(邻氟苯基)-4，5-二苯基咪唑二聚体、2-(邻甲氧基苯基)-4，5-二苯基咪唑二聚体、2，4-二(对甲氧基苯基)-5-苯基咪唑二聚体、2-(2，4-二甲氧基苯基)-4，5-二苯基咪唑二聚体等2，4，5-三芳基咪唑二聚体、9-苯基吖啶、1，7-双(9，9’-吖啶基)庚烷等吖啶衍生物、N-苯基甘氨酸、N-苯基甘氨酸衍生物、香豆素系化合物等。它们可以单独使用1种，也可以组合使用2种以上。
作为(B)成分，可以适宜地使用选自由具有肟酯基的肟酯系光聚合引发剂、烷基苯基酮(alkylphenone)系光聚合引发剂、α-氨基苯乙酮系光聚合引发剂、酰基氧化膦系光聚合引发剂、二茂钛系光聚合引发剂组成的组中的1种以上光聚合引发剂。
对于肟酯系光聚合引发剂，作为市售品，可列举出BASF Japan Ltd.制造的CGI-325、IRGACURE OXE01、IRGACURE OXE02、ADEKA株式会社制造的N-1919、NCI-831等。另外，也可以适宜地使用分子内具有2个肟酯基的光聚合引发剂。作为肟酯系光聚合引发剂，优选为具有咔唑结构的肟酯化合物。
作为烷基苯基酮系光聚合引发剂的市售品，可列举出BASF Japan Ltd.制造的IRGACURE184、Dalocure1173、IRGACURE2959、IRGACURE127等α-羟基烷基苯基酮型。
作为α-氨基苯乙酮系光聚合引发剂，具体而言，可列举出2-甲基-1-[4-(甲硫基)苯基]-2-吗啉代丙酮-1、2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)-丁烷-1-酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-吗啉基)苯基]-1-丁酮、N，N- 二甲基氨基苯乙酮等。作为市售品，可列举出BASF Japan Ltd.制造的IRGACURE907、IRGACURE369、IRGACURE379等。
作为酰基氧化膦系光聚合引发剂，具体而言，可列举出2，4，6-三甲基苯甲酰二苯基氧化膦、双(2，4，6-三甲基苯甲酰)-苯基氧化膦、双(2，6-二甲氧基苯甲酰)-2，4，4-三甲基-戊基氧化膦等。作为市售品，可列举出BASF公司制造的LUCIRIN TPO、BASF Japan Ltd.制造的IRGACURE819等。
另外，作为光聚合引发剂，也可以适宜地使用BASF Japan Ltd.制造的IRGACURE389、IRGACURE784等二茂钛系光聚合引发剂。
(B)光聚合引发剂的配混量相对于100质量份(A)含羧基树脂，优选为0.1～25质量份、更优选为1～20质量份。通过其配混量为0.1～25质量份，可以得到光固化性和分辨率优异，密合性、PCT耐性也提高，进而化学镀金耐性等耐化学药品性也优异的固化膜。特别是其配混量为25质量份以下时，可得到减少排气的效果，进而能够抑制在涂膜表面的光吸收变得剧烈而使深部固化性降低。
(C)具有5个以上环氧烷骨架的含烯属不饱和基团化合物
本发明中，作为(C)成分，只要具有5个以上环氧烷骨架，并且含有烯属不饱和基团，就没有特别限定。优选分子中具有5个以上EO或PO、且具有2个以上烯属不饱和基团的化合物。另外，(C)成分优选包含在环氧烷骨架的末端具有(甲基)丙烯酰基的结构。烯属不饱和基团的个数更优选为2以上且4以下、最优选为2以上且3以下。
需要说明的是，“EO”是指“环氧乙烷”，“PO”是指“环氧丙烷”。另外，以下，“EO改性”意味着具有环氧乙烷单元(-CH 2-CH 2-O-)的嵌段结构，“PO改性”意味着具有环氧丙烷单元(-CH 2-CH 2-CH 2-O-、-CH(CH 3)-CH 2-O-、-CH 2-CH(CH 3)-O-)的嵌段结构。
作为(C)成分，以EO改性的多元丙烯酸酯为例，进一步优选下述通式 (1)或(2)所示的化合物。
Figure PCTCN2018100646-appb-000002
(式中，l+m+n的总和表示改性数，l+m+n≥5。)
CH 2＝CH-CO-O(CH 2-CH 2O) nOC-CH＝CH 2    式(2)
(式中，n表示改性数，n≥5。)
“具有5个以上环氧烷骨架”是指，在含有两种以上环氧烷骨架时，所有种类的环氧烷骨架总计具有5个以上。若少于5个，则变得无法实现本发明的优异的弯曲性和低翘曲性。
从各性能的平衡的观点出发，前述(C)成分优选具有5个以上且30个以下的环氧烷骨架、更优选具有5个以上且20个以下的环氧烷骨架。环氧烷骨架的个数为30个以下时，能够在不调节组合物的粘度的条件下容易地确保固化膜的厚度。
(C)成分的配混量相对于(A)含羧基树脂100质量份优选为1～30质量份、更优选为5～25质量份、进一步优选为10～20质量份。
其它成分
本发明中，除了上述(A)～(C)成分之外，还可以包含(D)具有下述通式(1)的结构的环氧树脂。
Figure PCTCN2018100646-appb-000003
(式(1)中，X表示碳数7以上的脂环式骨架或芳香族骨架，n表示0以上的数。)
前述通式(1)中的X为双环戊二烯骨架时，从显著发挥本发明的效果出 发是优选的。
需要说明的是，本发明中，也可以包含除(D)成分以外的环氧树脂、例如上述双酚A型环氧树脂等。
本发明中，除了上述(A)～(C)成分之外，还可以包含(E)具有醚骨架的二胺。作为(E)成分，例如可列举出JEFFAMINE D-230、JEFFAMINE D-2000(Huntsman公司制造)。
从本发明的固化性树脂组合物的显影性、适用期的观点出发，前述(E)成分优选包含醚骨架的个数为15以上的聚醚胺(也称为聚醚二胺)，从适用期和耐热性的观点出发，更优选包含醚骨架的个数为1以上且10以下的二胺和醚骨架的个数为20以上且40以下的聚醚胺这两者。醚骨架的个数为1以上且10以下的二胺的含量相对于(E)成分的总重量100重量份优选为1～40重量份，醚骨架的个数为15以上的聚醚胺的含量相对于(E)成分的总重量100重量份优选为60～99重量份。
另外，本发明的固化性树脂组合物中也可以在不妨碍本发明的效果的范围内含有(F)用于提高交联密度的3官能以上的含烯属不饱和基团化合物(不包括(C)成分)。作为该(F)成分，例如可列举出三羟甲基丙烷三(甲基)丙烯酸酯、EO改性三羟甲基丙烷三(甲基)丙烯酸酯、PO改性三羟甲基丙烷三(甲基)丙烯酸酯、EO·PO改性三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等。
进而，本发明的固化性树脂组合物中也可以根据期望物性而添加硫酸钡、氧化硅、滑石、粘土、碳酸钙、硅石、膨润土、高岭土、玻璃纤维、碳纤维、云母等公知惯用的填充剂、酞菁蓝、酞菁绿、氧化钛、炭黑等公知惯用的染料、着色颜料、消泡剂、阻燃剂、密合性赋予剂或流平剂等各种添加剂、或氢醌、氢醌单甲醚、邻苯三酚、叔丁基儿茶酚、吩噻嗪等公知惯用的 阻聚剂等。
进而，本发明的固化性树脂组合物也可以含有用于制备组合物、调节粘度的有机溶剂。作为有机溶剂，例如可以使用甲乙酮、环己酮等酮类；甲苯、二甲苯、四甲基苯等芳香族烃类；溶纤剂、甲基溶纤剂、丁基溶纤剂、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇单甲醚、二丙二醇单甲醚(DPM)、二丙二醇二乙醚、三丙二醇单甲醚等二醇醚类；乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纤剂乙酸酯、丁基溶纤剂乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇单甲醚乙酸酯、二丙二醇单甲醚乙酸酯、碳酸亚丙酯等酯类；辛烷、癸烷等脂肪族烃类；石油醚、石油脑、溶剂石脑油等石油系溶剂等。这些有机溶剂可以单独使用或组合使用2种以上。
根据本发明的固化性树脂组合物，能得到不仅耐热性优异而且弯曲性、低翘曲性也优异的固化物，因此优选地用于柔性印刷电路板的制造。
本发明的另一个方式提供具有由上述固化性树脂组合物得到的树脂层的干膜。
本发明的干膜可以通过涂布在载体膜(支撑体)上并使其干燥而得到。干膜化时，将本发明的组合物根据需要用上述有机溶剂稀释来调节至适当的粘度，用逗点涂布机、刮刀涂布机、唇口涂布机、棒涂机、挤压涂布机、反向涂布机、转印辊涂布机、凹版涂布机、喷涂机等以均匀的厚度涂布在载体膜上，通常在50～130℃的温度下干燥1～30分钟，能够制成作为干燥涂膜的树脂层。对树脂层的厚度没有特别限制，通常以干燥后的膜厚计在0.1～100μm、适宜地在0.5～50μm的范围内适当选择。
作为载体膜，使用塑料薄膜，优选使用聚对苯二甲酸乙二醇酯等聚酯薄膜、聚酰亚胺薄膜、聚酰胺酰亚胺薄膜、聚丙烯薄膜、聚苯乙烯薄膜等塑料薄膜。对于载体膜的厚度没有特别限制，通常在0.1～150μm的范围内适当选择。
此时，在载体膜上形成树脂层后，为了防止树脂层的表面上附着灰尘等的目的，优选在树脂层的表面上进一步层叠能剥离的覆盖膜。作为能剥离的覆盖膜，例如可以使用聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、经表面处理的纸等，剥离覆盖膜时，树脂层与覆盖膜的粘接力小于树脂层与载体膜的粘接力即可。
本发明的另一个方式提供由上述固化性树脂组合物得到的固化物。
本发明的固化性树脂组合物根据需要调节至适合于涂布方法的粘度，将其通过丝网印刷法、帘式涂布法、喷涂法、辊涂法等方法涂布在例如形成有电路的印刷电路板上，根据需要在例如60～100℃的温度下使组合物中所含的有机溶剂挥发干燥，从而能够形成不粘性的涂膜。然后，对于所得的涂膜或上述干膜的树脂层，用活性能量射线通过形成有规定曝光图案的光掩模进行选择性曝光，用显影液将未曝光部显影，能够形成抗蚀图案，进而加热至例如140～180℃的温度使其热固化，从而能够得到耐热性、弯曲性、低翘曲性优异的固化物作为抗蚀膜。
涂布本发明的组合物后进行的挥发干燥可以使用如下方法进行：使用热风循环式干燥炉、IR炉、热板、对流烘箱等使用具备利用蒸汽的空气加热方式的热源的设备使干燥机内的热风对流接触的方法、及利用喷嘴吹附到支撑体的方法。
作为活性能量射线照射中使用的曝光机，搭载高压汞灯、超高压汞灯、金属卤化物灯、汞短弧灯等并以350～450nm的范围照射紫外线的装置即可，进而，也可以使用直接描绘装置(例如根据来自计算机的CAD数据直接照射活性能量射线来描绘图像的直接成像装置)。作为直描机的光源，使用最大波长处于350～410nm的范围的光的光源即可。用于形成图像的曝光量根据膜厚等而不同，通常可以设为20～1000mJ/cm 2、优选为20～800mJ/cm 2的范围内。
作为前述显影方法，可以利用浸渍法、冲淋法、喷雾法、刷涂法等，作 为显影液，可以使用氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、磷酸钠、硅酸钠、氨、胺类等的稀碱水溶液。
另外，本发明提供具有上述固化物的印刷电路板。
【实施例】
以下示出实施例和比较例来具体说明本发明，但本发明当然不限定于下述实施例。需要说明的是，以下，“份”及“％”在没有特别说明的情况下均为质量基准。
将表1所示的各成分按照其示出的固体成分的配混比(质量基准)混合，从而得到固化性树脂组合物。
[(A1)成分的合成例]
在二乙二醇单乙醚乙酸酯700g中投入邻甲酚酚醛清漆型环氧树脂(DIC株式会社制造、EPICLON N-695、软化点95℃、环氧当量214、平均官能团数7.6)1070g(缩水甘油基数(芳香环总数)：5.0摩尔)、丙烯酸360g(5.0摩尔)和氢醌1.5g，加热搅拌至100℃，均匀溶解。
接着，投入三苯基膦4.3g，加热至110℃进行2小时反应后，进一步追加三苯基膦1.6g，升温至120℃进一步进行12小时反应。向所得的反应液中投入芳香族系烃(SOLVESSO150)562g、四氢邻苯二甲酸酐684g(4.5摩尔)，在110℃下进行4小时反应。进而，向所得的反应液中投入甲基丙烯酸缩水甘油酯142.0g(1.0摩尔)，在115℃下进行4小时反应，得到成为(A1)成分的含羧基感光性树脂溶液。由此得到的树脂溶液的固体成分为65％，固体成分的酸值为87mgKOH/g。
[(A2)成分的合成例]
使环氧当量800、软化点79℃的双酚F型固型环氧树脂400份溶解于环氧氯丙烷925份和二甲基亚砜462.5份后，在搅拌下在70℃下用100分钟添加98.5％NaOH 81.2份。添加后，进一步在70℃下进行3小时反应。
接着，在减压下蒸馏去除过剩的未反应环氧氯丙烷和二甲基亚砜的大半部分，使包含副产盐和二甲基亚砜的反应产物溶解于甲基异丁基酮750份，进一步添加30％NaOH 10份，在70℃下使其反应1小时。反应结束后，用水200份进行2次水洗。油水分离后，从油层蒸馏回收甲基异丁基酮，得到环氧当量290、软化点62℃的环氧树脂(a-1)370份。
投入所得到的环氧树脂(a-1)2900份(10当量(以环氧基计10摩尔))、丙烯酸720份(10当量(以羧基计10摩尔))、甲基氢醌2.8份、卡必醇乙酸酯1950份，加热至90℃并搅拌，使反应混合物溶解。接着，将反应液冷却至60℃，投入三苯基膦16.7份，加热至100℃，进行约32小时反应，得到酸值为1.0mgKOH/g的反应物。接着，向其中投入马来酸酐786份(以酸酐结构计7.86摩尔)、卡必醇乙酸酯423份，加热至95℃，进行约6小时反应，得到感光性的含羧基树脂溶液。
由此得到的树脂溶液的固体成分为65％，固体成分的酸值为100mgKOH/g。
[(A3)成分的合成例]
在具备搅拌装置、温度计、冷凝器的反应容器中投入作为具有多个醇性羟基的化合物的衍生自1，5-戊二醇和1，6-己二醇的聚碳酸酯二醇(旭化成化学株式会社制造的T5650J、数均分子量800)3600g(4.5摩尔)、二羟甲基丁酸814g(5.5摩尔)、及作为分子量调节剂(反应停止剂)的正丁醇118g(1.6摩尔)。接着，投入作为不具有芳香环的异氰酸酯化合物的三甲基六亚甲基二异氰酸酯2009g(10.8摩尔)，边搅拌边加热至60℃，停止，在反应容器内的温度开始降低的时刻再次加热，在80℃下继续搅拌，用红外吸收光谱确认异氰酸酯基的吸收光谱(2280cm -1)消失并终止反应。接着，以固体成分成为60wt％的方式添加卡必醇乙酸酯，得到含有稀释剂的粘稠液体的含羧基树脂。所得到的(A3)具有氨基甲酸酯骨架的含羧基树脂的固体成分的酸值为 49.8mgKOH/g。
作为市售的材料，作为光聚合引发剂使用BASF Japan Ltd.制造的IRGACURE784、IRGACURE369、4，4’-双(二乙基氨基)二苯甲酮(EAB)，作为双环戊二烯型固体环氧树脂使用日本化药株式会社制造的XD-1000，作为联苯酚醛清漆型环氧树脂使用日本化药株式会社制造的NC-3000，作为EO改性丙烯酸类单体使用新中村化学工业株式会社制造的A-600、A-400、A-200、A-GLY-20E。此外，使用DPHA(二季戊四醇三丙烯酸酯、日本化药株式会社制造)、JEFFAMINE D-230、JEFFAMINE D-2000(Huntsman公司制造)。
在进行了清洗的具有铜电路的聚酰亚胺基板(聚酰亚胺薄膜的厚度：25μm、铜电路：1/3盎司)上通过丝网印刷以干燥后成为10μm的方式整面涂布实施例1～7和比较例1～3的各组合物，在热风循环式干燥炉中以160℃30分钟进行干燥，形成干燥涂膜，接着，利用ORC Manufacturing Co.，Ltd制造的搭载有金属卤化物灯的曝光机以达到灵敏度7级的曝光量进行曝光。然后，用1wt％Na 2CO 3水溶液以喷压0.1MPa进行1分钟显影，接着，使用热风循环式干燥炉在150℃下实施60分钟热固化处理，从而在聚酰亚胺基板上制作厚度10μm的固化涂膜。
将所得的各固化性树脂组合物的固化涂膜的评价结果示于表1。需要说明的是，评价方法及评价基准如下所述。
(固化物-低翘曲性评价)
将具有固化涂膜的聚酰亚胺基板切成5cm×5cm，制作评价样品。以固化涂膜的面作为上表面，用直尺测定各角的翘曲，评价4点的平均值。
○：各角翘曲的平均值2mm以下
△：各角翘曲的平均值3mm以下
×：各角翘曲的平均值4mm以下
(弯曲性)
将具有固化涂膜的聚酰亚胺基板切成宽度10mm×长度70mm，制作评价样品。将具有固化涂膜的面折成山形，载置砝码1Kg，载置10秒后将弯曲部展开。然后，再次在弯曲部将砝码载置10秒，将其作为1次。用显微镜观察弯曲部，评价直至能看到铜为止的次数。
○：弯曲次数-2次
△：弯曲次数-1次
×：弯曲次数-0次
(耐热性试验)
将具有固化涂膜的聚酰亚胺基板切成纵20mm×横20mm，制作评价样品。将焊料槽温度设为320℃，在其中放入样品基板，在10秒后取出基板，确认基板表面上的固化涂膜的鼓起，评价至出现鼓起为止的次数。
○：320℃×10秒3次以上
△：320℃×10秒2次
×：320℃×10秒1次
【表1】
Figure PCTCN2018100646-appb-000004
由表1明显可见，含有(A1)成分与(A2)成分的组合作为含羧基树脂、使用了具有5个以上环氧烷骨架的含烯属不饱和基团化合物的实施例1～7均在固化物的低翘曲性、弯曲性、及耐热性的评价中得到了优异的结果。另一方面，使用了具有少于5个环氧烷骨架的含烯属不饱和基团化合物的比较例1中，固化物的低翘曲性、弯曲性稍差。不使用具有环氧烷骨架的含烯属不饱和基团化合物的比较例2中，固化物的低翘曲性、弯曲性差。不含有(A1)成分的比较例3中，固化物的低翘曲性、弯曲性稍差，耐焊接热性能不良。
由这些结果判明了，本发明的固化性树脂组合物能够形成不仅耐热性优异而且弯曲性、低翘曲性也优异的固化物。从优异的弯曲性、低翘曲性的结果来看，也适用于柔性印刷电路板。

Claims (11)

  1. 一种固化性树脂组合物，其特征在于，包含：
    (A)含羧基树脂、
    (B)光聚合引发剂、以及
    (C)具有5个以上环氧烷骨架的含烯属不饱和基团化合物，
    作为所述(A)成分，包含：
    (A1)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应，对由此形成的含羧基树脂加成具有缩水甘油基和烯属不饱和基团的化合物而形成的含羧基感光性树脂；以及
    (A2)使环氧树脂与具有烯属不饱和基团的羧酸反应，使所生成的羟基与酸酐反应而形成的含羧基感光性树脂。
  2. 根据权利要求1所述的固化性树脂组合物，其特征在于，所述(A2)成分的环氧树脂为双酚型环氧树脂。
  3. 根据权利要求1或2所述的固化性树脂组合物，其特征在于，所述(C)成分具有5个以上且30个以下的环氧烷骨架。
  4. 根据权利要求1或2所述的固化性树脂组合物，其特征在于，相对于所述(A)成分100重量份，所述(A1)成分的含量为10～30重量份。
  5. 根据权利要求1或2所述的固化性树脂组合物，其特征在于，还包含(D)具有下述通式(1)的结构的环氧树脂，
    Figure PCTCN2018100646-appb-100001
    式(1)中，X表示碳数7以上的脂环式骨架或芳香族骨架，n表示0以上的数。
  6. 根据权利要求5所述的固化性树脂组合物，其特征在于，作为所述(D)成分，包含通式(1)中的X为双环戊二烯骨架的环氧树脂。
  7. 根据权利要求1或2所述的固化性树脂组合物，其特征在于，作为所述(A)成分，还包含具有氨基甲酸酯骨架的含羧基树脂。
  8. 根据权利要求1或2所述的固化性树脂组合物，其特征在于，用于柔性印刷电路板的制造。
  9. 一种干膜，其特征在于，具有由权利要求1～8中任一项所述的固化性树脂组合物得到的树脂层。
  10. 一种固化物，其特征在于，使权利要求1～8中任一项所述的固化性树脂组合物或权利要求9所述的干膜的树脂层固化而得到。
  11. 一种印刷电路板，其特征在于，具有权利要求10所述的固化物。
PCT/CN2018/100646 2017-12-27 2018-08-15 固化性树脂组合物、干膜、固化物、及印刷电路板 WO2019128256A1 (zh)

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