CN104380196B - Photocuring and compositions of thermosetting resin, the dry film solder mask prepared therefrom and circuit board for including the dry film solder mask - Google Patents

Photocuring and compositions of thermosetting resin, the dry film solder mask prepared therefrom and circuit board for including the dry film solder mask Download PDF

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Publication number
CN104380196B
CN104380196B CN201480001532.5A CN201480001532A CN104380196B CN 104380196 B CN104380196 B CN 104380196B CN 201480001532 A CN201480001532 A CN 201480001532A CN 104380196 B CN104380196 B CN 104380196B
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compound
weight
photocuring
compositions
thermosetting resin
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CN104380196A (en
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崔炳柱
郑遇载
崔宝允
李光珠
郑珉寿
具世真
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LG Corp
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LG Chemical Co Ltd
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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The present invention relates to a kind of photocuring and compositions of thermosetting resin, the photocuring and compositions of thermosetting resin include sour modified oligomer, photo polymerization monomer, thermosetting binder resins, photoinitiator, two or more Spherical alumina particles and organic solvent with different-grain diameter each other.The invention further relates to the dry film solder mask obtained by the resin combination and include the circuit board of the dry film solder mask.

Description

Photocuring and compositions of thermosetting resin, dry film solder mask prepared therefrom and include institute State the circuit board of dry film solder mask
Technical field
The present invention relates to photocuring and compositions of thermosetting resin, dry film solder mask (dry film solder resist) and Circuit board.
Background technology
Due to the micromation and lightweight of various electronic devices, minute opening pattern (minute opening can be formed Pattern protection against light sensitivity film) has been used for printed circuit board (PCB), conductor package substrate, flexible printed circuit board (FPCB) In.
Protective film (also referred to as solder resist) usually requires that developability, high-resolution, insulating properties, welds heat tolerance, is gold-plated Tolerance etc..Specifically, in addition to the performance, the solder resist for package substrate also requires, for example, to 55 DEG C to 125 DEG C Temperature cycling test (temperature cycle test, TCT) crack resistance or lametta between high accelerate to answer Power tests (highly accelerated stress test, HAST) performance.
Recently as solder resist, dry-film type solder resist (DFSR, dry film solder mask) has highly uniform film thickness, surface It is smooth and have film shaped property, caused to pay close attention to.
Using the dry film solder mask, the method to form welding resistance can be simplified, and can get reduction solvent row when forming welding resistance The effect of output.
Meanwhile semiconductor package product be with include non-conductor (such as epoxy resin mold object (epoxy molding) and Solder resist), the composite material configuration of semiconductor (such as chip), conductor (such as circuit board pattern) etc., it is this in order to prepare Product should carry out the various techniques for being related to severe thermal shock condition.
However, due to each component included in semiconductor package product, such as non-conductor, semiconductor or conductor, each other With different coefficient of thermal expansion (coefficients of thermal expansion CTE), therefore, dimensional stability can It can decline to a great extent, or the phenomenon that may be distorted.
When using soldered ball (solder ball) or gold thread connection chip with semiconductor substrate, the reduction of dimensional stability And twisted phenomena can lead to occur position deviation between chip and substrate, and product may be because shear stress and crack and Fracture, this can shorten the service life of product.
Further, since the reduction of substrate thickness, the reduction of the dimensional stability or twisted phenomena may be more serious. Therefore, in view of the micromation of various electronic devices and light-weighted trend, the substrate material with relatively low thermel expansion coefficient is more needed Material and solder resist.
Currently, as electronic device and component lighten, the thinning, trend that shortens and be miniaturized, the integrated journey of electronic component Degree just gradually increases, and is also being significantly increased using the calorific value of the operable electronic component of electricity.
Therefore, improve heat radiation with the demand for effectively disperseing and distributing the heat of inside of electronic component generation increasingly to increase.
Therefore, improve heat radiation widely to be ground with the measure for effectively disperseing and distributing the heat of electronic component generation Study carefully.
For example, to improve the heat-radiating properties of various electronic components, it has been suggested that as being equipped with the heat sink of heat conduction to release heat It puts to the method for silicone rubber plate extraneous or that outfit is with excellent thermal conductivity etc..However, being equipped with the heat sink, silicone rubber plate etc. Afterwards, it is difficult to it securely and be adhere closely on electronic component, and exist and can not show the limitations of heat-radiating properties completely.
Invention content
Technical goal
The present invention is intended to provide a kind of photocuring and compositions of thermosetting resin, the advantage is that and provide a kind of dry film solder mask (DFSR), the dry film solder mask not only has excellent light-cured performance, plating tolerance (plating resistance), machine Tool performance and heat resistance, additionally it is possible to so that dimensional stability is reduced phenomenon and twisted phenomena minimum, and there is high heat radiation Energy.
In addition, the present invention is intended to provide a kind of dry film solder mask obtained from the photocuring and compositions of thermosetting resin.
In addition, the present invention is intended to provide a kind of circuit board including the dry film solder mask.
Technical solution
The present invention provides a kind of photocuring and compositions of thermosetting resin, it includes sour modified oligomer, photo polymerization monomer, Thermosetting binder resins, photoinitiator, the Spherical alumina particles with different-grain diameter, surface are coated with each other for two or more The carbon compound and organic solvent of thermal conductive ceramic compound.
Also, the present invention provides a kind of dry film solder mask (DFSR) prepared by using the photosensitive resin composition.
In addition, the present invention provides a kind of circuit board including the dry film solder mask.
Hereinafter, the photocuring and heat is more fully described in specific exemplary implementation scheme according to the present invention Thermosetting resin composition, dry film solder mask and circuit board.
A kind of photocuring of exemplary implementation scheme offer and compositions of thermosetting resin of the present invention, it includes acid to change Property oligomer, photo polymerization monomer, thermosetting binder resins, photoinitiator, two or more each other with different-grain diameter ball Shape alumina particle, surface are coated with the carbon compound and organic solvent of thermal conductive ceramic compound.
To improve the various physical properties of the dry film solder mask, for example, physical property such as developability, PCT heat resistances, glass Change transition temperature and coefficient of thermal expansion, various fillers will be applied.However, if the content of filler is excessive, the filler may Precipitation is reunited, and physical property and quality to make the DFSR finally manufactured or circuit board deteriorate.
On the contrary, the photocuring and compositions of thermosetting resin of the exemplary implementation scheme of the present invention include two kinds or more The Spherical alumina particles with different-grain diameter, without reducing various physical properties, are shown kind simultaneously so as to improve heat resistance each other Write the content for increasing inorganic filler；The resin combination can reduce linear expansion coefficient, and heat-radiating properties can be greatly improved and The insulation performance of prepared dry film solder mask is not reduced.
In addition, the photocuring and compositions of thermosetting resin of an exemplary implementation scheme by using the present invention, it can A kind of dry-film type solder resist is provided, accordingly, it is possible to resolve it is as known in the art in liquid solder resist with the precipitation of filler or The problem of storage stability reunited and generated declines.
In addition, by using the photocuring and compositions of thermosetting resin, it is possible to provide a kind of dry film solder mask (DFSR), institute Stating dry film solder mask not only has excellent light-cured performance, plating tolerance, mechanical performance and heat resistance, also makes dimensional stability It reduces phenomenon and twisted phenomena minimizes, and there is low coefficient of thermal expansion.
As described above, the photocuring and compositions of thermosetting resin may include that two or more have different-grain diameter each other Spherical alumina particles.
On this point, by having the Spherical alumina particles of different-grain diameter each other comprising two or more, tree can be made Pore-size in aliphatic radical body between Spherical alumina particles minimizes, to greatly improve thermal radiation effect.
Due to the use of two or more Spherical alumina particles with different-grain diameter each other, and described two spherical shapes are used The quantitative summation acted on caused by each in alumina particle compares the synergistic effect or combination that bigger can be achieved.
Above-mentioned Spherical alumina particles are the alumina particle with spherical or 3D shape close to spherical shape.
Two or more have at least one of Spherical alumina particles of different-grain diameter Spherical alumina particles each other Grain size can be 0.1 μm or smaller, such as 0.01 μm to 0.1 μm.
In addition, two or more have at least one of Spherical alumina particles of different-grain diameter ball-aluminium oxide each other The grain size of particle can be 0.2 μm to 0.7 μm.
Therefore, there are the Spherical alumina particles of different-grain diameter may include that a kind of grain size is 0.1 μm each other for two or more Or the Spherical alumina particles that smaller Spherical alumina particles and another grain size are 0.2 μm to 0.7 μm.
The photocuring and compositions of thermosetting resin may include that two or more of 1 weight % to 75 weight % have each other There are the Spherical alumina particles of different-grain diameter.
If the content of Spherical alumina particles is too low, it may be difficult to heat-radiating properties are fully realized, if spherical oxidation The content of alumina particles is too high, and the uniformity of the photocuring and compositions of thermosetting resin can be made to deteriorate, or may be not easy Coating operation is carried out, so that be difficult to form film etc., and the adhesiveness reduced can prevent it from being easily adhered on PCB etc..
Meanwhile the photocuring and compositions of thermosetting resin may include that surface is coated with the carbon compound of thermal conductive ceramic compound Object, to greatly improve heat-radiating properties, the insulation performance without reducing prepared dry film solder mask.
The thermal conductive ceramic compound may include in the photocuring and compositions of thermosetting resin to be applied to On the surface of carbon compound so that the heat generated in electronic component etc. can be shifted promptly.
The specific example of the thermal conductive ceramic compound may include aluminium oxide (Al2O3), boron nitride (BN), aluminium nitride (AlN), silicon carbide (SiC), magnesia (MgO), zinc oxide (ZnO), aluminium hydroxide (Al (OH)3Or mixtures thereof), and can be excellent Choosing uses aluminium oxide or magnesia.
In addition, by the way that thermal conductive ceramic compound to be coated in the surface of carbon compound, it can be achieved that excellent dielectric strength is same When keep carbon compound high thermal conductivity, and also can be improved be included in photocuring and compositions of thermosetting resin in it is other The compatibility of component.
The carbon compound that surface is coated with thermal conductive ceramic compound may include 0.5 weight % to the thermal conductive ceramic of 20 weight % The carbon compound that conjunction object and 80 weight % are coated with thermal conductive ceramic compound to the carbon compound of 99.5 weight % or surface can wrap Thermal conductive ceramic compound and 90 weight % containing 1 weight % to 10 weight % to 99 weight % carbon compound.
If the content of thermal conductive ceramic compound is too low, the photocuring and thermosetting resin group of the exemplary implementation scheme Close object or product prepared therefrom ensures its physical property such as dielectric strength or electrical insulating property in which may be unable to fully, therefore uncomfortable Share the insulating film for making electronic material.
In addition, if the content of thermal conductive ceramic compound is too high, may occur in surface treatment process between filler Reunite, so that the resin is not suitable in dispersion method.
The specific example of the carbon compound may include or mixtures thereof carbon nanotube, graphene, graphite, and preferably make Use carbon nanotube.
The average grain diameter that the surface is coated with the carbon compound of thermal conductive ceramic compound can be 0.5 μm to 4 μm.
The photocuring and compositions of thermosetting resin may include 1.1 weight % or less, preferably 0.2 weight % to 1.0 The surface of weight % is coated with the carbon compound of thermal conductive ceramic compound.
If surface is coated with the carbon compound of thermal conductive ceramic compound, the content in resin combination is too low, improves thermal conductivity The effect of rate may be less apparent, if content is 1.1 weight % or more, insulation performance can be greatly reduced.
Meanwhile it as the sour modified oligomer being contained in the photocuring and compositions of thermosetting resin, can be used first Without any restrictions, described group is divided into light all components in the preceding known resin combination that can be used to form DFSR Curing functional groups (for example, acrylate group or intramolecular contain the photocurable functional group of unsaturated double-bond and carboxyl) it is oligomeric Object.
For example, the main chain of the additional sour modified oligomer can be novolac epoxy resin (novolac epoxy) or poly- The component that carboxyl, acrylate-based etc. are introduced on the main chain can be used as additional sour modified oligomer by urethane etc..
The photocurable functional group is preferably acrylate-based.Herein, the sour modified oligomer can be by containing The copolymerization of the polymerisable monomer of carboxyl and monomer containing acrylic ester compound etc. forms oligomer and obtains.
Specifically, the specific example that can be used for the additional sour modified oligomer of resin combination includes following components：
(1) carboxylic resin, by (a) unsaturated carboxylic acid (such as (methyl) acrylic acid) and (b) containing unsaturated double The compound (for example, styrene, α-methylstyrene, (methyl) lower alkyl acrylate and isobutene) of key is copolymerized and obtains ；
(2) carboxylic photosensitive resin, by making a part of (a) unsaturated carboxylic acid and the change of (b) containing unsaturated double-bond It closes the copolymer of object and contains ethylenically unsaturated groups (for example, vinyl, allyl and (methyl) acryloyl group) and reactive group The compound (for example, (methyl) glycidyl acrylate) of (for example, epoxy group and acid chlorine) is reacted, and introduces ethylenic bond not Saturated group is obtained as side group (pendent group)；
(3) carboxylic photosensitive resin, by make compound containing unsaturated double-bond of (a) unsaturated carboxylic acid and (b) and (c) compound containing epoxy group and unsaturated double-bond is (for example, (methyl) glycidyl acrylate and (methyl) acrylic acid α-first Base ethylene oxidic ester) copolymer reaction, then make gained secondary hydroxyl and (d) saturated or unsaturated multi-anhydride (for example, Anhydrous phthalic acid, anhydrous tetrahydrophthalic acid and anhydrous hexahydro-phthalic acid) it reacts and obtains；
(4) carboxylic photosensitive resin, by making the acid anhydrides of (e) containing unsaturated double-bond (for example, anhydrous maleic acid and nothing Water itaconic acid) and (b) copolymer Yu (f) of the compound containing unsaturated double-bond contain a hydroxyl and one or more ethylenic bonds not The compound (for example, (methyl) hydroxyalkyl acrylates) of saturation double bond is reacted and is obtained；
(5) carboxylic light-sensitive compound includes two or more epoxy groups (as disclosed below) by molecule The epoxy group of multi-functional epoxy compound (g), or by addition carrying out the hydroxyl of multi-functional epoxy compound with epichlorohydrin Epoxidation and the epoxy group of polyfunctional epoxy resin obtained, with (h) unsaturated monocarboxylic acid (for example, (methyl) acrylic acid) Carboxyl between implement esterification (all esterification or partial esterification, preferably all esterifications), and further make prepared hydroxyl Base is saturated with (d) or unsaturated multi-anhydride is reacted and obtained；
(6) carboxylic resin, by making the compound of (b) containing unsaturated double-bond and (methyl) glycidyl The epoxy group of the copolymer of ester is with the organic acid containing a carboxyl and without ethylenic bond unsaturated bond in (i) molecule (for example, containing 2 To the alkyl carboxylic acid of 17 carbon atoms and containing the alkyl carboxylic acid of aryl) reaction, then make prepared secondary hydroxyl be saturated with (d) or Unsaturated multi-anhydride is reacted and is obtained；
(7) carboxylic polyurethane resin, by making (j) diisocyanate (for example, aliphatic vulcabond, branch Aliphatic vulcabond, alicyclic diisocyanate and aromatic diisocyanates), (k) carboxylic diol compound (for example, Dihydromethyl propionic acid and dimethylolpropionic acid) and (m) diol compound (for example, polycarbonate polyol, polyether-type are polynary Alcohol, polyester polyol, polyolefin polyols, acryloyl type polyalcohol, bisphenol type epoxy alkane addition product dihydric alcohol and contain The compound of phenolic hydroxyl group and alcoholic extract hydroxyl group) it carries out sudden reaction and obtains；
(8) carboxylic photosensitive polyurethane resin, by making (j) diisocyanate, (n) bifunctional epoxy resin (example Such as, bisphenol A type epoxy resin, hydrogen addition bisphenol A type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, Bisphenol-s epoxy resin, union II first phenol-type epoxy resin and united phenol-type epoxy resin or its be modified part acid anhydrides) (first Base) acrylate, (k) carboxylic diol compound and (m) diol compound carry out sudden reaction and obtain；
(9) its end is introduced into the carboxylic polyurethane resin of a unsaturated double-bond, by synthesizing above-mentioned (7) Or compound (the example of (f) containing a hydroxyl and one or more ethylenically unsaturated double bonds is added during the resin of (8) Such as, (methyl) hydroxyalkyl acrylates) and obtain；
(10) carboxylic polyurethane resin, by the way that molecule is added during synthesizing the resin of above-mentioned (7) or (8) In the compound containing isocyanate group and one or more (methyl) acryloyl groups (for example, isophorone diisocyanate With the reaction with same mole object of pentaerythritol triacrylate), and carry out end (methyl) acroleic acid esterification and obtain；
(11) carboxylic photosensitive resin contains two or more oxetanes (oxetane) ring by making in molecule Multifunctional oxetane compound (as disclosed below) reacted with (h) unsaturated monocarboxylic acid to prepare modified oxa- Then cyclobutane compound makes the primary hydroxyl in the oxetane compound of the modification and (d) saturation or unsaturated polyacid Anhydride reactant and obtain；
(12) carboxylic photosensitive resin reacts production by what unsaturated double-bond was introduced diepoxides and bis-phenol In object, and so that it is reacted with (d) saturation or unsaturated multi-anhydride and obtain；
(13) carboxylic photosensitive resin, by making (d) saturation or unsaturated multi-anhydride be reacted with what is obtained as follows Product is reacted and is obtained：By make novolac type phenol resin and epoxyalkane (for example, ethylene oxide, propylene oxide, epoxy butane, Oxetanes, tetrahydrofuran and oxinane) and/or cyclic carbonate (for example, ethylene carbonate, propene carbonate, carbonic acid Butene esters and methacrylic acid 2,3- propyl carbonates) reaction product reacted with (h) unsaturated monocarboxylic acid and the reaction that obtains Product；And
As the commercial components of above-mentioned additional sour modified oligomer, specifically, such as Nippon Kayaku Co., Ltd. ZAR-2000, CCR-1235, ZFR-1122 or CCR-1291H etc..
The more specific examples of the acid modified oligomer may include epoxy (methyl) acrylic ester compound.
Epoxy (methyl) acrylic ester compound is 1) epoxide or polyepoxides and 2) (methyl) Reaction product between acrylic ester compound or hydroxyl (methyl) acrylic ester compound.
Due to the use of epoxy (methyl) acrylic ester compound, the elasticity of DFSR is can be sufficiently ensured, and show relatively low Coefficient of thermal expansion and improvement resistance to thermal reliability, and the preferable package substrate material as semiconductor element etc. can be provided DFSR。
As epoxy (methyl) acrylic ester compound, can be used derived from cresol novolac (cresol novolac) Epoxy (methyl) acrylate compounds or epoxy (methyl) acrylate compounds derived from Bisphenol F.
In addition, it is 4 that epoxy (methyl) acrylic ester compound, which can contain weight ratio,:1 to 1:1 or 3:1 to 2:1 Epoxy (methyl) acrylate compounds derived from cresol novolac and epoxy (methyl) acrylate chemical combination derived from Bisphenol F Object.
The weight average molecular weight of epoxy (methyl) acrylic ester compound can be 5000 to 50,000 or 6000 to 20, 000.If the weight average molecular weight of epoxy (methyl) acrylic ester compound is too high, the ratio of light-cured acrylate can It relatively reduces, to reduce developability or reduce the intensity of DFSR.If epoxy (methyl) acrylic ester compound Weight average molecular weight it is too low, in precipitation or the reunion for disperseing that inorganic filler particle can occur when inorganic filler, an exemplary reality Applying the resin combination of scheme can excessively develop.
The content of above-mentioned acid modified oligomer can be about 5 weight % to 75 weight %, or about 20 weight % to 50 weight %, Or about 25 weight % to 45 weight %, the resin combination total weight based on an exemplary implementation scheme.If the acid The content of modified oligomer is too low, and the developability of resin combination may be not good enough, and the intensity of DFSR can reduce.On the contrary, if The content of the acid modified oligomer is too high, and resin combination may excessively develop, and the uniformity of coating may be not good enough.
The photo polymerization monomer may include one or more compounds selected from the following：Contain two or more ethylene in molecule Contain the multifunctional (methyl) acrylate chemical combination of two or more (methyl) acryloyl groups in the polyfunctional compound of base and molecule Object.
The photo polymerization monomer can be, for example, unsaturated functional group containing photocuring is (for example, two or more multifunctional second Alkenyl) compound, and formed and be crosslinked with the unsaturated functional group of above-mentioned sour modified oligomer, to solid by light in exposure Change forms cross-linked structure.
Therefore, it allows to be positioned corresponding to the resin combination on the exposure area for forming the parts DFSR being retained in substrate On without by alkali development.
The photo polymerization monomer can be liquid at room temperature, therefore can also be exemplary for adjusting one according to painting method The viscosity of the resin combination of embodiment, or further improve the alkali-developable of unexposed area.
As photo polymerization monomer, the esters of acrylic acid chemical combination containing two or more photocuring unsaturated functional groups can be used Object, it is one or more to be selected from following compound as its specific embodiment：The acrylic ester compound of hydroxyl, such as third Olefin(e) acid -2- hydroxyethyl esters, acrylic acid -2- hydroxypropyl esters, pentaerythritol triacrylate or five acrylate dipentaerythritols；Water Soluble acrylic ester type compound, such as polyethyleneglycol diacrylate or polypropyleneglycol diacrylate；Polyalcohol it is multifunctional Polyester acrylates compound, such as three acrylic acid trihydroxy methyl propyl ester, two season of pentaerythritol tetracrylate or six acrylic acid Doutrate；The ethylene oxide adduct of polyfunctional alcohol and/or the acrylic ester compound of propylene oxide adduct, such as three hydroxyls Methylpropane or hydrogenated bisphenol A or polyphenol (such as bisphenol-A or xenol (biphenol))；Multifunctional or simple function polyurethane Acrylic ester compound is the isocyanates of the modification of hydroxy acryl acid ester；Epoxy acrylate is Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolak type epoxy (phenol novolac Epoxy resin) (methyl) acrylic acid adduct；The acrylic ester compound of caprolactone modification, such as caprolactone modification The hydroxyl new penta of the double trihydroxy methyl propyl ester of tetrapropylene acid, the acrylic acid dipentaerythritol ester that 6-caprolactone is modified or caprolactone modification Sour neopentyl glycol ester diacrylate；And photosensitive (methacrylate) compound, such as correspond to above-mentioned esters of acrylic acid chemical combination The methyl acrylic ester compound of object, the compound can be used alone or can be by two or more groups in these compounds It closes and uses.
In these compounds, as photo polymerization monomer, preferably uses and contain two or more (methyl) propylene in molecule The multifunctional (methyl) acrylate class compound of acyl group, can especially be suitably used pentaerythritol triacrylate, 3 third The double trihydroxy methyl propyl ester of tetrapropylene acid etc. of olefin(e) acid trihydroxy methyl propyl ester, six acrylic acid dipentaerythritol esters, caprolactone modification.
Commercially available photo polymerization monomer may include the DPEA-12 etc. of Kayarad.
The content of above-mentioned photo polymerization monomer can be about 1 weight % to 40 weight %, or about 5 weight % to 30 weight %, or About 7 weight % are to 15 weight %, the total weight based on resin combination.
If the content of photo polymerization monomer is too low, photocuring may be insufficient, if content is too high, the aridity of DFSR can Can be not good enough, and physical property may be decreased.
Photoinitiator may include one or more compounds selected from the following：Styrax class compound, acetophenones chemical combination Object, anthraquinone analog compound, thioxanthone compounds, ketal compound, benzophenone compound, alpha-aminoacetophenone compound, Acylphosphine oxide compound, oxime ester compound, double imidazole compounds and compound in triazine class.
Specifically, those of any known, such as styrax and its alkyl ether can be used as photoinitiator, such as pacify Breath perfume, benzoin methyl ether and benzoin ethyl ether；Acetophenones, such as acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 1, 1- dichloroacetophenones and 4- (two oxygroup -1- Methylethyls of 1- tertiary butyls) acetophenone；Anthraquinones, such as 2-methylanthraquinone, 2- penta Base anthraquinone, 2- tertiary butyls anthraquinone and 1- chloroanthraquinones；Thioxanthene ketone class, such as 2,4- dimethyl thioxanthones, 2,4- diisopropyl thioxanthenes Ketone and 2-chlorothioxanthone；Ketal class, such as acetophenone dimethyl ketal and benzyl dimethyl ketal；Benzophenone, such as two Benzophenone, 4- (two oxygroup -1- Methylethyls of 1- tertiary butyls) benzophenone and 3,3 ', 4,4 '-four (two Epoxide carbonyls of tertiary butyl) Benzophenone.
In addition, epsilon-amino acetophenones are can be mentioned that as preferred photoinitiator, such as 2- methyl-1s-[4- (methyl mercapto) benzene Base] -2- morpholinopropanone -1,2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butyl- 1- ketone, 2- (dimethylaminos Base) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone and N, N- dimethylamino benzoylformaldoxime (city Sell such as Ciba Specialty Chemicals Co., Ltd. (being now Ciba Japan K.K)907、 Irgacure 369 and Irgacure 379 etc.)；Or acylphosphine oxide, such as 2,4,6- trimethylbenzoyldiphenyl oxygen Compound, bis- (2,4,6- trimethylbenzoyls)-phenylphosphine oxides and bis- (2,6- Dimethoxybenzoyls) -2,4,4- three Methyl amyl phosphine oxide is (the commercially available Corporation such as BASFTPO and Ciba Specialty The Irgacure 819 etc. of Chemicals Co., Ltd.).
Furthermore it is preferred that photoinitiator may include oxime esters.The specific example of the oxime esters may include 2- (acetoxyl groups Iminomethyl) thioxanthene-9-one, (1,2- acetyl caproyls, 1- [4- (thiophenyl) phenyl]-, 2- (O- benzoyl oximes)), (ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -, 1- (O- acetyl group oxime)) etc..Commercial product may include GGI-325, Irgacure OXE01 and Irgacure OXE02 of Ciba Specialty Chemicals Co., Ltd.s, The Darocur TPO etc. of the N-1919 of ADEKA Corporation, Ciba Specialty Chemicals Co., Ltd.s.
The content of photoinitiator can be about 0.1 weight % to 20 weight %, or about 1 weight % to 10 weight %, or about 1 weight % is to 5 weight % for amount, the total weight based on resin combination.
If the content of photoinitiator is too low, possibly photocuring can not suitably occur, if content is too high, may be decreased The resolution ratio of resin combination or the reliability of DFSR may be insufficient.
The thermosetting binder resins can contain it is one or more selected from epoxy group, oxetanyl, cyclic ethers base and The functional group of epithio ether.
The resin combination of the exemplary implementation scheme of the present invention further includes being capable of heat cure with one or more Functional group resinoid, the functional group for capableing of heat cure be selected from epoxy group, oxetanyl, cyclic ethers base and Epithio ether.The resinoid can be formed by heat cure with sour modified oligomer etc. and is crosslinked, so that it is guaranteed that DFSR Heat resistance or mechanical performance.
The softening point of the resinoid can be about 70 to 100 DEG C, can be reduced in lamination by the softening point Inhomogeneities.If softening point is low, the viscosity of DFSR can be increased, if it is high, mobility possible deviation.
As resinoid, it can be used in molecule and contain two or more cyclic ethers bases and/or epithio ether (hereinafter Referred to as ring (sulphur) ether) resin and bifunctional epoxy resin.It can also be used other diisocyanate and di-functional block different Cyanate.
The resinoid containing two or more rings (sulphur) ether can be in molecule containing two or more in the molecule The compound of group, the group are either one or two of cyclic ethers base and epithio ether with 3,4 or 5 membered rings.
In addition, the resinoid can be the multi-functional epoxy compound for containing at least two epoxy groups in molecule, divide Containing two or more thioether groups in multifunctional oxetane compound, molecule in son containing at least two oxetanyls Episulfide resin etc..
The specific example of the multi-functional epoxy compound may include bisphenol A type epoxy resin, hydrogenated bisphenol A type asphalt mixtures modified by epoxy resin Fat, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin, phenol phenol It is aldehyde type epoxy resin, cresol novolak type epoxy resin, N- glycidyl type epoxy resins, phenol aldehyde type bisphenol A epoxide resin, double Dimethlbenzene (bixylenol) type epoxy resin, bisphenol-type epoxy resin, chelating type epoxy resin, glyoxal type epoxy resin, Amino-containing epoxy resin, the epoxy resin of modified rubber, dicyclopentadiene phenol epoxy resin, phthalic acid two shrink sweet Grease resin, the epoxy resin of heterocycle, four glycidyl group dimethylbenzene phenolic group ethane (tetraglycidyl Xylenoylethane) the epoxy resin etc. that resin, silicone modified epoxy resin, 6-caprolactone are modified.
In addition, in order to assign anti-flammability, can introduce phosphorus into the structure.
The epoxy resin can possess improved performance by heat cure, such as to the close adhesion of solidify coating, butt welding The heat resistance connect or the tolerance to electroless plating layer.
The multifunctional oxetane compound may include multifunctional oxetane compound class, such as bis- [(3- first Base -3- oxetanylmethoxies) methyl] ether, bis- [(3- ethyl -3- oxetanylmethoxies) methyl] ethers, 1,4- Bis- [(3- methyl -3- oxetanylmethoxies) methyl] benzene, 1,4- bis- [(3- ethyl -3- oxetanylmethoxies) Methyl] benzene, acrylic acid (3- methyl -3- oxetanyls) methyl esters, acrylic acid (3- ethyl -3- oxetanyls) methyl esters, Methacrylic acid (3- methyl -3- oxetanyls) methyl esters, methacrylic acid (3- ethyl -3- oxetanyls) methyl esters or Resin (such as phenolic resin, poly- (the para hydroxybenzene second of its oligomer or copolymer and oxetanes alcohol and hydroxyl Alkene), ether ketone type bis-phenol (cardo-type bisphenol), calixarenes (calix arene), resorcinol calixarenes (calix Resorcinarene) or silsesquioxane) etherification product.
In addition, it may include the copolymer of the unsaturated monomer and (methyl) alkyl acrylate of oxygen heterocycle butane ring.
Compound containing two or more epithio ethers in the molecule may include, for example, being purchased from Japan Epoxy Bisphenol A-type episulfide resin YL7000 of Resin, Co., Ltd. etc..
In addition, the ring obtained by replacing the oxygen atom of the epoxy group in phenol aldehyde type epoxy resin with sulphur atom can be used Sulphur resin.
In addition, as commercial product, the YDCN-500-80P etc. purchased from Kukdo Chemical Co., Ltd.s can be used.
The photocuring and compositions of thermosetting resin may include 0.5 weight % to the resinoid of 40 weight %.
In addition, the content of the resinoid can be equivalent to about 0.8 to 2.0 equivalent, 1 based on sour modified oligomer Equivalent carboxyl meter.
If the content of resinoid is too low, after solidification, carboxyl may remain in DFSR, heat-resisting to reduce Property, alkali resistance, electrical insulating property etc..On the contrary, if content is too high, ring (sulphur) ether of low molecular weight can remain on dry coating In film, to reduce coating film strength etc., and this is undesirable.
In order to dissolve the photocuring and compositions of thermosetting resin or assign its concentration appropriate, can by its with it is a kind of or Multi-solvents are used in mixed way.
The solvent may include ketone, such as methyl ethyl ketone and cyclohexanone；Aromatic hydrocarbons, such as toluene, dimethylbenzene and tetramethyl Base benzene；Gylcol ether (cellosolve), such as ethylene glycol monoethyl ether, glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol list second Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monoethyl ether and three Ethylene glycol monoethyl ether；Acetate esters, such as ethyl acetate, butyl acetate, ethylene glycol monoethylether acetate, ethylene glycol monobutyl ether acetic acid Ester, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, propylene glycol methyl ether acetate and dipropylene glycol list first Ether acetic acid ester；Alcohols, such as ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol and carbitol (carbitol)；Aliphatic hydrocarbon, such as octane and the last of the ten Heavenly stems Alkane；Petroleum solvents, such as petroleum ether, naphtha, hydrotreated naphtha and solvent naphtha；And amides, such as dimethylacetamide Amine and dimethylformamide (DMF).
These solvents can be used alone or use as a mixture of two or more thereof.
The content of the solvent can be about 1 weight % to 90 weight % or 10 weight % to 50 weight %, be based on above-mentioned tree The total weight of oil/fat composition.
The photocuring and compositions of thermosetting resin also may include one or more inorganic fillers selected from the following：Sulfuric acid Barium, barium titanate, amorphous silica, crystalline silica, fused silica, preparing spherical SiO 2, talcum, clay, carbon Sour magnesium, calcium carbonate, aluminium oxide, aluminium hydroxide and mica.
The inorganic filler can be used for improving heat-resistant stability, dimensional stability and resin stickiness to heat.
In addition, the inorganic filler enhances color, to be used as extender pigment (extender pigment).
The dosage of inorganic filler can be adjusted according to the physical property or quality of the dry film solder mask finally prepared.
In the photocuring and compositions of thermosetting resin, two or more spherical oxidations with different-grain diameter each other The sum of alumina particles and the content of inorganic filler can be 30 weight % to 60 weight %, based on the solid content in addition to organic solvent Meter.
The solid content means the component in addition to organic solvent, example in the photocuring and compositions of thermosetting resin Such as, the component includes all sour modified oligomer, photo polymerization monomer, thermosetting binder resins, photoinitiator and two kinds Or a variety of Spherical alumina particles with different-grain diameter each other.
The photocuring and compositions of thermosetting resin also may include thermal curing agents, pigment, levelling agent (leveling ) or dispersant agent.
The thermal curing agents are used to promote the heat cure of resinoid.
The thermal curing agents may include, for example, imidazoles and imdazole derivatives such as 2-methylimidazole, 2- ethyl imidazol(e)s, 2- second Base -4-methylimidazole, 2- phenylimidazoles, 4- phenylimidazoles, 1-cyanoethyl-2-phenylimidazole and 1- (2- cyanoethyls) -2- ethyls - 4-methylimidazole；Amine compounds such as dicyandiamide, benzyl dimethylamine, 4- (dimethylamino)-N, N- dimethyl benzylamine, 4- methoxyl groups- N, N- dimethyl benzylamine and 4- methyl-N, N- dimethyl benzylamine；Hydrazine compound such as adipic dihydrazide and sebacic dihydrazide；With And phosphorus compound such as triphenylphosphine.
In addition, the thermal curing agents are commercially available, such as the 2MZ- purchased from Shikoku Chemicals Corporation A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of glyoxaline compound), purchased from San-Apro Limited U-CAT3503N, UCAT3502T (being the trade name of the block isocyanate compound of dimethyl amine), DBU, DBN, U-CATS A102, U-CAT5002 (being the trade name of bicyclic amidine compound and its salt) etc..
The thermal curing agents can promote the thermal curing catalyst of epoxy resin or oxetane compound, or promote epoxy Base and/or oxetanyl are reacted with carboxyl, but are not particularly limited as to this, can be used alone or with two or more Form of mixtures use.
In addition, S- pyrrolotriazine derivatives such as guanamines, acetylguanamine, benzoguanamine, melamine, 2,4- diamino-can be used 6- methacryloxyethyl-S- triazines, 2- vinyl -4,6- diamino-S- triazines, 2- vinyl -4,6- diamino-S- Triazine isocyanuric acid adduct and 2,4- diamino -6- methacryloxyethyl-S- triazine isocyanuric acid adducts, and it is excellent The compound that these are also played tackifier by choosing is used in combination with the thermal curing agents.
In view of thermosetting property appropriate, the content of the thermal curing agents can be about 0.3 weight % to 15 weight %, based on tree The total weight of oil/fat composition.
Pigment can be used for playing visual and masking power, to cover the scratch of defect such as circuit line.
Available pigment may include red, blue, green, yellow and black pigment etc..
As blue pigment, phthalocyanine blue, pigment blue 15 can be used:1, pigment blue 15:2, pigment blue 15:3, pigment blue 15: 4, pigment blue 15:6, pigment blue 60 etc..
As viridine green, it can be used that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 Deng.
Yellow uitramarine may include Anthraquinones, iso-indole ketone, condensation azo and benzimidazole ketone pigment etc., such as can Use pigment yellow 108, pigment yellow 147, pigment yellow 151, pigment yellow 166, pigment yellow 181, pigment yellow 193 etc..
The content of preferred pigments is about 0.5 weight % to 3 weight %, the total weight based on above-mentioned resin combination.
If content is less than 0.5 weight %, visual and masking power may deteriorate, heat-resisting if content is higher than 3 weight % Property may deteriorate.
Other available additives can be to be removed on surface for eliminating the foam of resin combination, in thin film coated Protrusion and recess assign anti-flammability or control viscosity or the component as catalyst.
Specifically, in combination with known conventional additives, for example, as it is known that Conventional thickeners such as fine particle silica (pulverizing silica), organobentonite and montmorillonite；Antifoaming agent and/or levelling agent such as silicone, fluorine class and polymerization The antifoaming agent and/or levelling agent of species；The silane coupling agent of silane coupling agent such as imidazoles, thiazoles and triazole type；And resistance Fire agent such as Phosphorus and antimony based flame retardant.
Among them, levelling agent can be used and for example purchase for removing protrusion and recess on surface in thin film coated From BYK-380N, BYK-307, BYK-378 and BYK-350 etc. of BYK-Chemie GmbH.
The content of other additives is preferably from about 0.01 weight % to 10 weight %, the total weight based on resin combination Meter.
Can by photocuring and compositions of thermosetting resin of the following method using an exemplary implementation scheme shape At DFSR.
First, film is formed with the resin combination, and the film layer is pressed on preset substrate, then selectively exposed Light will form the resin combination part of DFSR.
When carrying out the exposure, be included in the unsaturated functional group in sour modified oligomer with included in photo polymerization monomer Unsaturated functional group cause photocuring to each other formed crosslinking, and can therefore by photocuring exposure area formed be crosslinked Structure.
Hereafter, when being developed with alkaline-based developer, the resin combination positioned at the exposure area for forming cross-linked structure It is retained on substrate as former state, remaining is dissolved in developer solution positioned at the resin combination of unexposed area and is removed.
Then, heat cure is carried out by being heat-treated the resin combination left on substrate.Included in sour modified oligomer Carboxyl in (such as iminocarbonic acid esters compound) can be capable of in resinoid the functional group reactions of heat cure from And crosslinking is formed, and cross-linked structure is therefore formed by heat cure, to form DFSR on the desired part of substrate.
In other words, in the case where forming DFSR using resin combination, the cured resin combination for forming DFSR contains There is basic cross-linked structure, therefore, the thermalexpansioncoefficientα 1 of DFSR can be down to 40 or smaller, and α 2 can be down to 150 or smaller.
This is improved by the difference of reduction DFSR and the package substrate storeroom coefficient of thermal expansion of semiconductor element The resistance to thermal reliability of DFSR simultaneously makes distortion problem minimize.
In addition, another exemplary implementation scheme according to the present invention, it is possible to provide a kind of oligomeric by using modification containing acid Object, photo polymerization monomer, thermosetting binder resins, photoinitiator, two or more spherical oxidations with different-grain diameter each other Alumina particles, surface be coated with the carbon compound of thermal conductive ceramic compound and the photocuring of organic solvent and compositions of thermosetting resin and The dry film solder mask (DFSR) of manufacture.
The required various physics of package substrate material that the dry film solder mask (DFSR) can not only meet semiconductor element HAST tolerances between performance such as PCT tolerances, TCT heat resistances and lametta, can also reduce distortion, to reduce failure simultaneously Extend the service life of product.
In addition, the content of inorganic filler can be significantly increased in the dry film solder mask (DFSR), it is each without making to improve heat resistance Kind physical property deteriorates, and reduces linear expansion coefficient and simultaneously greatly improves heat-radiating properties without reducing the exhausted of manufactured dry film solder mask Edge performance.
The dry film solder mask may include the cured of the photosensitive resin composition or dry product.
It is described comprising sour modified oligomer, photo polymerization monomer, thermosetting binder resins, photoinitiator, two or more The photocuring and compositions of thermosetting resin of the Spherical alumina particles and organic solvent each other with different-grain diameter are specifically Bright includes the explanation above with respect to the exemplary implementation scheme of the present invention.
The thickness of the dry film solder mask can be 10 μm to 150 μm.
It will be outlined below preparing welding resistance using the photocuring and compositions of thermosetting resin of exemplary implementation scheme dry The method of film (DFSR).
First, with unfilled corner wheel coating machine (comma coater), blade coater, lip coating machine (lip coater), Rod coaters, squash type coating machine (squeeze coater), reversed coating machine (reverse coater), transfer roll-type apply Cover machine (transfer roll coater), rotogravure application machine (gravure coater), spray application machine (spraying ) etc. coater coated the resin combination of an exemplary implementation scheme as photosensitive coating material on a carrier film, then It makes it through 50 to 130 DEG C of baking oven and comes within 1 to 30 minute drying, and lamination release film (release film) on it, to Prepare the dry film being made of carrier film, photosensitive film and release film from bottom.
The thickness of the photosensitive film can be about 5 to 100 μm.
Herein, plastic foil such as polyethylene terephthalate (PET) can be used, polyester film, polyimide film, gather Amide imide film, polypropylene screen and polystyrene film are as carrier film；Polyethylene (PE) can be used, polytetrafluoroethylene film, gather Propylene film, surface treated paper etc. are used as release film.When removing the release film, preferably between photosensitive film and release film Adhesiveness is less than the adhesiveness between photosensitive film and carrier film.
Then, after removing the release film, vacuum laminator, hot roll laminator, vacuum pressing-combining machine (vacuum are used ) etc. press photosensitive film is made to be attached on the substrate to form circuit.
Later, substrate is exposed under the light with fixed wave length range (UV etc.).
It is selectively exposed using hood, or is directly exposed using the direct exposure device of laser, to be formed Pattern.
The carrier film is removed after exposure.
Light exposure depends on the thickness of the film of coating, however, it is preferably 0 to 1000mJ/cm2。
When being exposed, for example, photocuring can occur in sour modified oligomer, photo polymerization monomer etc. in exposure area Contained in crosslinking is formed between unsaturated functional group, therefore, the exposure area can not be removed in subsequent developing process.
In contrast, the unexposed area formed wherein can be free of cross-linked structure crosslinking and being consequently formed, and protect Carboxyl is stayed, so as to by alkali development.
Later, developed using alkaline solution etc..
As alkaline solution, alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, phosphoric acid can be used Sodium, sodium metasilicate, ammonia, amine.
By the development, it can only retain the film positioned at exposure area.
Finally, by heat cure (rear solidification), the printed circuit board for including the solder resist formed by the photosensitive film is completed.
The heat curing temperature is about 100 DEG C or more.
Pass through above method etc., it is possible to provide DFSR and the printed circuit board for including the DFSR.
Since the DFSR undergoes photocuring and heat cure, it may include sour modified oligomer, there are two or more light Cure the photo polymerization monomer of unsaturated functional group and the cured resinoid with the functional group for capableing of heat cure.
The dry film solder mask can be used as the protective film of printed circuit board.
The dry film solder mask can be used for preparing the package substrate of semiconductor element.
In addition, another exemplary implementation scheme according to the present invention, it is possible to provide include the circuit board of the dry film solder mask.
The preparation method of circuit board uses the preparation method of printed circuit board of dry film solder mask identical with as described above, described Dry film solder mask can be used as the protective film of printed circuit board.
Beneficial effects of the present invention
According to the present invention, it is possible to provide a kind of photocuring and compositions of thermosetting resin not only have excellent photocuring Performance, plating tolerance, mechanical performance and heat resistance, additionally it is possible to dimensional stability be reduced into phenomenon and twisted phenomena minimizes simultaneously It is capable of providing the dry film solder mask (DFSR) with high-heating radiation performance.
In addition, by using the photocuring and compositions of thermosetting resin, it is possible to provide a kind of resistance with above-mentioned performance Weld dry film and a kind of circuit board including the dry film solder mask.
Specific implementation mode
The present invention will be more fully described in the examples below.However, following embodiment is to illustrate the present invention, this hair Bright range is not limited to following embodiment.
Embodiment and comparative example：The preparation of resin combination, dry film and printed circuit board
Examples 1 and 2 and comparative example 1
Resin combination is prepared by mixing component shown in the following table 1.Herein, the use of weight ratio is 3:1 Epoxy (methyl) acrylate compounds derived from cresol novolac and epoxy (methyl) acrylate chemical combination derived from Bisphenol F The mixture of object is as sour modified oligomer.
Resin combination produced above is applied on the PET as carrier film, and by it by 75 DEG C of baking oven It is dry, PE is then laminated as release film, to prepare from bottom by carrier film, photosensitive film (thickness is 20 μm) and release film The dry film of composition.
After the cover film of the prepared dry film of stripping, by photosensitive film layer vacuum lamination on the substrate for forming circuit, and Hood corresponding with circuit pattern is placed in photosensitive film layer, and is exposed to ultraviolet light.The ultraviolet light for being 365nm with wavelength exists 350mJ/cm2Light exposure under be exposed.
Hereafter, PET film is removed, and at 31 DEG C with 1 weight %Na2CO3Alkaline solution carry out development a period of time to remove Undesired part, to form desired pattern.
Then, in 1000mJ/cm2Light exposure under carry out photocuring, finally at 160 to 170 DEG C carry out heat cure 1 it is small When, to complete to include the printed circuit board of the protective film (welding resistance) formed by photosensitive film.
Composite material (the unit of 1 embodiment 1 to 2 of table and comparative example 1：g)
Comparative example 2 and 3
Resin combination is prepared by mixing component shown in the following table 2.
Herein, the use of weight ratio is 3:1 epoxy (methyl) acrylate compounds derived from cresol novolac and The mixture of epoxy (methyl) acrylate compounds derived from bisphenol-A is as sour modified oligomer.
By method identical with the method in embodiment 1, it is prepared for dry film using resin combination prepared above, and The printed circuit for including protective film (welding resistance) is completed using the dry film by method identical with the method in embodiment 1 Plate.
Composite material (the unit of 2 embodiment 2 and 3 of table：g)
Test example
Dry film and printed circuit board prepared in above embodiment and comparative example are measured in the following manner Physical property.
Test example 1：The assessment of developability (sensitivity)
It will be cut into 5cm x 5cm's purchased from 12 μm of copper-clad laminates of Mitsui Mining＆Smelting Co., Ltd. Square, and slight roughness is formed in copper foil surface by chemical etching.
In removal above embodiment and comparative example after the release film of each prepared dry film, vacuum lamination is used Machine (MVLP-500 of Meiki Co., Ltd.) is by film layer vacuum lamination on the copper-clad laminate (substrate) for forming roughness.
Then, female (negative-type) hood (shape with a diameter of 80 μm of hole) is closely adhered to Thereon, it is used in combination the ultraviolet light that wavelength is 365nm in 350mJ/cm2Light exposure under be exposed.
Then, PET film is removed, and at 31 DEG C with 1 weight %Na2CO3Alkaline solution carry out development a period of time, to Form pattern.
Then, the shape that the pattern of above-mentioned formation is observed with SEM, to be assessed according to following standard.
1：Cross section is linear and does not have film residual in bottom.
2：Cross section is non-linear, and has undercut (undercut) or protrusion (overhang) in the shape in hole.
3：Observe undeveloped situation.
4：Due to excessively developing without forming pattern.
Test example 2：Acid proof measurement
By copper-clad laminate (thickness：0.1mm, copper thickness：12 μm, the LG-T-500GA of LG Chem Ltd.) it is cut into The square of 5cmx5cm, and slight roughness is formed in copper foil surface by chemical etching.
In removal above embodiment and comparative example after the release film of each prepared dry film, vacuum lamination is used Machine (MVLP-500 of Meiki Co., Ltd.) is by film layer vacuum lamination on the copper-clad laminate (substrate) for forming roughness.
Then, thereon, it is used in combination the wavelength to be female hood (shape with a diameter of 80 μm of hole) tight adhesion The ultraviolet light of 365nm is in 350mJ/cm2Light exposure under be exposed.
Then, PET film is removed, at 31 DEG C with 1 weight %Na2CO3Alkaline solution carry out development a period of time, and about 1000mJ/cm2Light exposure under carry out photocuring.
Hereafter, heat cure is carried out at 170 DEG C 1 hour to prepare sample.
By the above-mentioned sample sulfuric acid solution (H of 10 weight %2SO4) handled 30 minutes at 25 DEG C, and observe the shape of coating film State, to be assessed according to following standard.
1：DSFR is not removed and discoloration.
2：DSFR starts to generate visible stripping/discoloration.
3：DSFR generates serious stripping/discoloration.
Test example 3：The measurement of absorptivity
The ICS-25um copper foils of IIjin Material Industries Co., Ltd. are cut into the pros of 11cmx11cm Shape, and measure its quality.Then each dry film prepared in embodiment and comparative example is cut into the pros of 10cmx10cm Shape, and remove release film.Then sample is prepared in a manner of identical with the sample for measuring PCT heat resistances, and measures its matter Amount.
Wait wet equipment (SH-941 of ESPEC Corp.) in 85 DEG C of temperature and 85% damp condition using isothermal- The lower processing sample 24 hours, and measure its quality.
1) hydroscopicity (%)=(quality of quality/sample of the moisture of absorption) x100
2) absorb moisture quality=(isothermal-waits the quality of sample after wet process)-(isothermal-waits sample before wet process Quality)
3) quality of sample=(isothermal-waits the quality of sample before wet process)-(quality of copper foil)
Test example 4：The measurement of pencil hardness
Sample is prepared in a manner of identical with experiment above embodiment 2 [acid proof measurement], and is cut into The square of 11cmx11cm.
Use a set of pencil (Mitsubishi) and pencil hardness measuring instrument (CKTrading for measuring hardness Co.), the scratch grade of sample is measured under the load of constant speed and 100g.
Using hardness be B to 9H hardness one it is pencil encased in a pencil, identification will not remove the lead of the coating film The hardness of pen.
Test example 5：The measurement of insulation resistance
Using vacuum laminator (MVLP-500 for being purchased from Meiki Co., Ltd.s), by institute in embodiment and comparative example Each dry film vacuum lamination prepared is formed with the combed of the pattern B of IPC standards on FR-4 substrates on the FR-4 substrates (comb-type) electrode.
Then, female hood (shape with a diameter of 80 μm of hole) is closely adhered on substrate, wavelength is used in combination For 365nm ultraviolet light in 350mJ/cm2Light exposure under be exposed.
Hereafter, PET film is removed, at 31 DEG C with 1 weight %Na2CO3Alkaline solution carry out development a period of time, and about 1000mJ/cm2Light exposure under carry out photocuring.
Hereafter, heat cure is carried out at 170 DEG C 1 hour to prepare sample.
The insulation resistance numerical value of the electrode of obtained sample is measured under the application voltage of 500V.
Test example 6：The measurement of thermal conductivity
12 μm of copper-clad laminates (3EC-M3-VLP for being purchased from Mitsui Mining＆Smelting Co., Ltd.) are cut into The square of 15cmx15cm, and using vacuum laminator the MVLP-500 of Meiki Co., Ltd.s (be purchased from), by embodiment and right Than in embodiment each prepared dry film on the copper-clad laminate prepared with predetermined size vacuum lamination for several times, to obtain About 100 μm of thickness.
Then, female hood (shape with a diameter of 12.7 μm of hole) is closely adhered on substrate, wave is used in combination The ultraviolet light of a length of 365nm is in 350mJ/cm2Light exposure under be exposed.
Hereafter, PET film is removed, at 31 DEG C with 1 weight %Na2CO3Alkaline solution carry out development a period of time, and about 1000mJ/cm2Light exposure under carry out photocuring.
Hereafter, heat cure is carried out at 170 DEG C 1 hour to prepare sample, and copper foil is removed using etching solution, to prepare Sample for measuring thermal conductivity.
Thermal conductivity is calculated by formula [density x specific heat x thermal diffusion coefficients], wherein being surveyed using MettlerToledo equipment Metric density, and use the 447 device measuring specific heats of LFA and thermal diffusion coefficient purchased from Netzch.
The measurement result of above-mentioned test example 1 to 6 is as shown in table 3 below.
The measurement result of 3 test example 1 to 6 of table
Shown in measurement and assessment result such as upper table 3, it was confirmed that the DFSR of embodiment has excellent developability, photocuring Performance and physical property, and improved heat-radiating properties are without reducing insulation performance.
Especially in the case of using the sample of the dry film of comparative example 1, the content of inorganic filler is 57.7 weight %, It is about 0.5W/mK by the thermal conductivities of Bruggeman equation calculations and the thermal conductivity actually measured, and the sample of Examples 1 and 2 With with the comparable inorganic filler content of comparative example, but realize 1.00W/mK or higher thermal conductivities.
According to Bruggeman equations the dry film of comparative example 1 is used to realize the thermal conductivity of 1.00W/mK or more Sample used in the content of alumina packing should be 70 weight % or higher.However, in Examples 1 and 2, it can be little Amount realizes high thermal conductivity in the case of increasing inorganic filler content.
In other words, the DFSR of embodiment can ensure that electrical isolation, to be led with height in the case where not reducing dielectric strength Hot property and electromagnetic wave absorption performance, and excellent heat conductivility, electromagnetic wave absorption performance can be realized under relatively small thickness And dielectric strength.
[reference] Bruggeman equations
* in the case of the sample of comparative example 1 above, the proportion for the aluminium oxide applied is 4 and resin is 1.1.

Claims (21)

1. a kind of photocuring and compositions of thermosetting resin, it includes sour modified oligomer, photo polymerization monomer, resinoids Resin, photoinitiator, two kinds of carbon for being coated with thermal conductive ceramic compound with the Spherical alumina particles of different-grain diameter, surface each other Compound and organic solvent,
The carbon compound that the wherein described surface is coated with thermal conductive ceramic compound contains 0.5 weight % to the thermal conductive ceramic of 20 weight % The carbon compound of compound and 80 weight % to 99.5 weight %,
The grain size of one of which Spherical alumina particles is 0.1 μm or smaller, and the grain size of another Spherical alumina particles is 0.2 μm to 0.7 μm.
2. the photocuring and compositions of thermosetting resin of claim 1, wherein the surface is coated with the carbon of thermal conductive ceramic compound Compound is in the range of 1.1 weight % or smaller.
3. the photocuring and compositions of thermosetting resin of claim 1, wherein the thermal conductive ceramic compound includes a kind of or more Kind substance selected from the following：Aluminium oxide (Al2O3), boron nitride (BN), aluminium nitride (AlN), silicon carbide (SiC), magnesia (MgO), Zinc oxide (ZnO) and aluminium hydroxide (Al (OH)3)。
4. the photocuring and compositions of thermosetting resin of claim 1, wherein the carbon compound includes selected from graphite, graphene With it is one or more in carbon nanotube.
5. the photocuring and compositions of thermosetting resin of claim 1, wherein the surface is coated with the carbon of thermal conductive ceramic compound The average grain diameter of compound is 0.5 μm to 4 μm.
6. the photocuring and compositions of thermosetting resin of claim 1, wherein the acid modified oligomer includes epoxy (methyl) Acrylic ester compound.
7. the photocuring and compositions of thermosetting resin of claim 6, wherein the epoxy (methyl) acrylic ester compound Weight average molecular weight be 5000 to 50,000.
8. the photocuring and compositions of thermosetting resin of claim 1, wherein the photo polymerization monomer includes one or more choosings From compound below：Contain two or more (first in polyfunctional compound and molecule containing two or more vinyl in molecule Base) acryloyl group multifunctional (methyl) acrylate compounds.
9. the photocuring and compositions of thermosetting resin of claim 1, wherein the photoinitiator includes one or more is selected from Compound below：Styrax class compound, acetophenone compounds, anthraquinone analog compound, thioxanthone compounds, ketal chemical combination Object, benzophenone compound, alpha-aminoacetophenone compound, acylphosphine oxide, oxime ester compound, double glyoxaline compounds And compound in triazine class.
10. the photocuring and compositions of thermosetting resin of claim 1, wherein the thermosetting binder resins include it is a kind of or A variety of functional groups selected from epoxy group, oxetanyl, cyclic ethers base and epithio ether.
11. the photocuring and compositions of thermosetting resin of claim 1, wherein the thermosetting binder resins include it is a kind of or A variety of resins selected from the following：Polyfunctional epoxy resin containing two or more epoxy groups contains two or more oxetanes The multifunctional oxetane resin of base and the episulfide resin containing two or more thioether groups.
12. the photocuring and compositions of thermosetting resin of claim 1, it includes:
The sour modified oligomer of 5 weight % to 75 weight %,
The photo polymerization monomer of 1 weight % to 40 weight %,
The thermosetting binder resins of 0.5 weight % to 40 weight %,
The photoinitiator of 0.1 weight % to 20 weight,
Two kinds of 1 weight % to 75 weight % have the Spherical alumina particles of different-grain diameter each other,
The surface of 0.2 weight % to 1.0 weight % are coated with the carbon compound of thermal conductive ceramic compound, and
The organic solvent of 1 weight % to 90 weight %.
Also include one or more selected from the following inorganic fill out 13. the photocuring and compositions of thermosetting resin of claim 1 Material：Barium sulfate, barium titanate, amorphous silica, crystalline silica, talcum, clay, magnesium carbonate, calcium carbonate, aluminium hydroxide And mica.
Also include one or more selected from the following inorganic fill out 14. the photocuring and compositions of thermosetting resin of claim 1 Material：Fused silica, preparing spherical SiO 2.
15. the photocuring and compositions of thermosetting resin of claim 13 or 14, wherein described two have different-grain diameter each other Spherical alumina particles and the sum of the content of inorganic filler be 30 weight % to 60 in the solid content in addition to organic solvent Weight %.
16. a kind of dry film solder mask is prepared by using the photosensitive resin composition of claim 1.
17. the dry film solder mask of claim 16, including the cured of the photosensitive resin composition or dry product.
18. the dry film solder mask of claim 16, wherein the dry film solder mask is used as the protective film of printed circuit board.
19. the dry film solder mask of claim 16, wherein the thickness of the dry film solder mask is 10 μm to 150 μm, thermal conductivity is 1.10W/mK or higher.
20. the dry film solder mask of claim 19, wherein the insulation resistance of the dry film solder mask is 10.0*1011Ω or smaller.
21. a kind of circuit board, it includes the dry film solder masks of claim 16.
CN201480001532.5A 2013-06-17 2014-06-17 Photocuring and compositions of thermosetting resin, the dry film solder mask prepared therefrom and circuit board for including the dry film solder mask Active CN104380196B (en)

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