CN106200266A - Hardening resin composition, dry film, solidfied material and printed circuit board (PCB) - Google Patents
Hardening resin composition, dry film, solidfied material and printed circuit board (PCB) Download PDFInfo
- Publication number
- CN106200266A CN106200266A CN201610576040.XA CN201610576040A CN106200266A CN 106200266 A CN106200266 A CN 106200266A CN 201610576040 A CN201610576040 A CN 201610576040A CN 106200266 A CN106200266 A CN 106200266A
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- Prior art keywords
- resin composition
- epoxy resin
- resin
- hardening resin
- film
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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
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Abstract
The present invention provides thermostability and the hardening resin composition of percentage elongation excellence of solidfied material, has the solidfied material of the resin bed of the dry film of the resin bed obtained by said composition, said composition or this dry film and have the printed circuit board (PCB) of this solidfied material.Hardening resin composition etc., it is characterised in that comprise (A) containing carboxy resin, (B) heat curable component and (C) boric acid ester compound.
Description
Technical field
The present invention relates to hardening resin composition, dry film, solidfied material and printed circuit board (PCB).
Background technology
In printed circuit board (PCB), the base material of conductor layer with circuit pattern forms solder resist.It is not limited to such resistance
Solder flux, as the interlayer dielectic of printed circuit board (PCB), the material of the permanent protecting film such as cover layer of flexible printed circuit board, with
Past, it is proposed that multiple hardening resin composition.
For example, Patent Document 1 discloses the photonasty hardening resin composition of permanent resist, it comprises and has
The polymer of carboxyl, the photopolymerizable compound with ethylenic unsaturated bond and Photoepolymerizationinitiater initiater.Additionally, protect as permanent
The material of cuticula, it is also known that compositions of thermosetting resin (such as patent documentation 2).
For above-mentioned such permanent protecting film, even if also requiring that in the environment of harsh and having for peeling, be full of cracks etc.
The patience of deterioration, i.e. requires reliability.As for one of characteristic realizing height reliability, thermostability can be enumerated.Such as,
For solder resist, need to weld thermostability.Additionally, at the printed circuit board (PCB) that can use in high temperature environments, such as car
In the printed circuit board (PCB) carried, also require that the permanent protecting film of high-fire resistance.Additionally, by Laser Processing cutting solidfied material from
And carry out in the case of the pattern formation of permanent protecting film, need to give thermostability so that will not deteriorate because of LASER HEAT.
As other characteristics for realizing height reliability, percentage elongation can be enumerated.If percentage elongation is low, then become to hold
Yi Yin impacts and cracks.Additionally, carrying out in the case of pattern formation by Laser Processing, exist owing to Laser Processing is led
The opening that causes and the risk that cracks.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-99647 publication (claims)
Patent documentation 2: Japanese Unexamined Patent Publication 2011-63653 publication (claims).
Summary of the invention
Invent problem to be solved
Therefore, it is an object of the invention to, it is provided that the thermostability of solidfied material and the hardening resin composition of percentage elongation excellence, tool
There is the solidfied material of the resin bed of the dry film of the resin bed obtained by said composition, said composition or this dry film and there is this admittedly
The printed circuit board (PCB) of compound.
Solve the means of problem
The present inventor conducts in-depth research in view of the foregoing, it was found that by coordinating boric acid ester compound, can solve
Certainly above-mentioned problem, thus complete the present invention.
That is, the hardening resin composition of the present invention is characterised by, comprises (A) containing carboxy resin, (B) thermosetting chemical conversion
Divide and (C) boric acid ester compound.
The preferably hardening resin composition of the present invention comprises liquid-state epoxy resin as described (B) heat curable component.
The preferably hardening resin composition of the present invention also comprises Photoepolymerizationinitiater initiater.
The preferably hardening resin composition of the present invention is used for forming solder resist, cover layer or interlayer dielectic.
The dry film of the present invention is characterised by, has and said curing property resin combination is applied on film and is dried
And the resin bed obtained.
The solidfied material of the present invention is characterised by, it is by said curing property resin combination or the resin bed of described dry film
Solidify and obtain.
The printed circuit board (PCB) of the present invention is characterised by, has said curing thing.
Invention effect
According to the present invention it is possible to provide thermostability and the hardening resin composition of percentage elongation excellence of solidfied material, have by this
The solidfied material of the resin bed of the dry film of the resin bed that compositions obtains, said composition or this dry film and there is this solidfied material
Printed circuit board (PCB).
Accompanying drawing explanation
Fig. 1: represent the schematic side elevation of 2 test tubes of the liquid judgement for heat curable component.
Detailed description of the invention
The hardening resin composition of the present invention is characterised by, comprise (A) containing carboxy resin, (B) heat curable component and
(C) boric acid ester compound.
For the hardening resin composition of the present invention, by coordinating (C) boric acid ester compound, not only increase resistance to
Hot and percentage elongation, when it is alkali-developable Photocurable resin composition, also improves the dry span of control.
It is dried the span of control (also referred to as developing the life-span) to refer to, alkali-developable Photocurable resin composition is being coated with
In the drying steps carried out after to base material, before development, there is not the amplitude of the drying condition of poor visualization.If be dried
The span of control is short, then at the baking temperature limited and must be dried under drying time.In actual manufacturing step, will be dry
Dry time management was not easy to the short period, and its result is to become to be difficult to carry out pattern formation with good developability.In the past,
Short for forming the dry span of control of alkali-developable Photocurable resin composition existence of the solder resist etc. of high-fire resistance
Problem.It is believed that the short reason of the dry span of control of such alkali-developable Photocurable resin composition is as composing
The heat curable component giving high-fire resistance and coordinate.Such as, as heat curable component, with use solid, the feelings of powder body epoxy resin
Condition is compared, if using liquid-state epoxy resin, then and reactive raising, high-fire resistance can be significantly increased, but owing to becoming appearance
It is easily generated hot photographic fog, is therefore dried the span of control and shortens.Additionally, containing the feelings of tripolycyanamide etc. to improve high-fire resistance
In condition, also become easily to produce hot photographic fog.But, as it has been described above, according to the present invention it is possible to obtain be dried the span of control the most excellent
Alkali-developable Photocurable resin composition.
When the hardening resin composition of the present invention is alkali-developable Photocurable resin composition, even if coordinating
Exist in the case of easily producing the liquid thermoset composition of problem of hot photographic fog, particularly liquid-state epoxy resin, be dried management
Amplitude is the most excellent.
Additionally, by coordinating (C) boric acid ester compound, it is also possible to raising solidfied material is close with the copper circuit of printed circuit board (PCB)
Conjunction property.
Hereinafter, the composition contained by the hardening resin composition of the present invention is described in detail.
[(A) contains carboxy resin]
By the carboxyl being had containing carboxy resin, so that be reacted to possibility with the heat cure of (B) heat curable component.This
Outward, by carboxyl, alkaline development is also possibly realized.From the viewpoint of photo-curable, resistance to developability, preferably except carboxyl it
Outward, in intramolecular, also there is ethylenic unsaturated bond but it also may only use do not have ethylenical unsaturated double bonds containing carboxy resin.
As ethylenical unsaturated double bonds, the olefinic preferably originating from acrylic or methacrylic acid or their derivant is unsaturated double
Key.
In the hardening resin composition of the present invention, from the viewpoint of thermostability, (A) preferably has benzene containing carboxy resin
At least any of in the structure of phenol novolaks (novolac) type, bis-phenol phenolic varnish type and cresol novolak type.This
Outward, in addition to welding thermostability, from the viewpoint of the adaptation of underfill, (A) more preferably has containing carboxy resin
There is the structure of phenol novolak type, can be suitably used for such as going between engaging and uses such as using, flip-chip installation is used is installed
The printed circuit board (PCB) of the installation of underfill.
As the concrete example containing carboxy resin, (oligomer or polymer are equal can to enumerate the compound as being set forth below
Can).
(1) make 2 officials can or above polyfunctional epoxy resin react with (methyl) acrylic acid, make to be present in the hydroxyl of side chain
With the dibasic acid anhydrides such as phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride carry out that addition obtains containing carboxylic
Base photoresist.Here, preferably 2 officials can or above polyfunctional epoxy resin be solid-state.
(2) make with epoxychloropropane, the hydroxyl of 2 functional epoxy resins is carried out the multifunctional ring that epoxidation obtains further
Epoxy resins is reacted with (methyl) acrylic acid, and addition obtains containing carboxyl photonasty tree to make the hydroxyl of generation and dibasic acid anhydride carry out
Fat.Here, preferably 2 functional epoxy resins are solid-state.
(3) make the epoxide in 1 molecule with more than 2 epoxy radicals and at least there is in 1 molecule 1 alcohol hydroxyl
The monocarboxylic acid reaction containing unsaturated group such as base and the compound of 1 phenolic hydroxyl group and (methyl) acrylic acid etc., for the reaction obtained
The alcoholic extract hydroxyl group of product so that it is with maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic acid
The reaction of the multi-anhydride such as acid anhydride and obtain containing carboxyl photoresist.
(4) bisphenol-A, Bisphenol F, bisphenol S, novolak phenolics, poly(4-hydroxystyrene), naphthols and aldehydes are made
The condensation substance etc. of condensation substance, dihydroxy naphthlene and aldehydes have in 1 molecule the compound of more than 2 phenolic hydroxyl groups and oxirane,
The epoxyalkane reactions such as expoxy propane, make the described product obtained of reacting with epoxyalkane contain not with (methyl) acrylic acid etc.
The monocarboxylic acid reaction of saturated group, makes the described product obtained of reacting with monocarboxylic acid react with multi-anhydride and containing of obtaining
Carboxyl photoresist.
(5) make the compound in 1 molecule with more than 2 phenolic hydroxyl groups ring-type with ethylene carbonate, propylene carbonate etc.
Carbonate products reacts, and makes the described product and the list containing unsaturated group reacted with cyclic carbonate compound and obtain
Carboxylic acid reaction, make described react with monocarboxylic acid the product obtained react with multi-anhydride and obtain containing carboxyl photonasty tree
Fat.
(6) make by aliphatic diisocyanate, branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatics
The diisocyanate cpds such as diisocyanate and polycarbonate-based polyhydric alcohol, polyethers system polyhydric alcohol, polyester-based polyols, polyene
Hydrocarbon system polyhydric alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adducts dihydroxylic alcohols, there is the change of phenolic hydroxyl group and alcoholic extract hydroxyl group
The sudden reaction of the diatomic alcohol compounds such as compound and the end of carbamate resins that obtains and anhydride reaction containing end
The carbamate resins of end carboxyl.
(7) by carboxylic diol compound such as diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acid etc.,
With in the sudden reaction of diatomic alcohol compounds and the synthesis of carboxylic carbamate resins that obtains, add (methyl) propylene
Acid hydroxyalkyl acrylate etc. has the compound of (methyl) acryloyl group of 1 hydroxyl and more than 1 in the molecule, by end (first
Base) the carboxylic carbamate resins that obtains of acrylated.
(8) obtained by diisocyanate and carboxylic diol compound and the sudden reaction of diatomic alcohol compounds
To carboxylic carbamate resins synthesis in, add isophorone diisocyanate and pentaerythritol triacrylate
Reaction with same mole thing etc. there is the compound of (methyl) acryloyl group of 1 NCO and more than 1 in the molecule, will
The carboxylic carbamate resins that end (methyl) acrylated obtains.
(9) by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, (methyl) acrylic acid lower
The copolymerization of the compound containing unsaturated group such as Arrcostab, isobutene. and obtain containing carboxyl photoresist.
(10) dicarboxylic acids such as multifunctional oxetane resin and adipic acid, phthalic acid, hexahydrophthalic acid are made
Reaction, addition obtains containing carboxyl polyester resin to make the primary hydroxyl of generation and dibasic acid anhydride carry out.
(11) make in above-mentioned (1) ~ (10) any one containing carboxy resin with there is in 1 molecule cyclic ether groups and (first
Base) compound of acryloyl group carries out addition and obtains containing carboxyl photoresist.
Should illustrate, here, (methyl) acrylate is to be referred to as acrylate, methacrylate and their mixture
Term, for it is directed to similar statement hereinafter too.
(A) containing carboxy resin owing to having multiple carboxyl on the side chain of trunk polymer, therefore becoming can be by dilute
Alkaline aqueous solution develops.
Additionally, the acid number that (A) is containing carboxy resin is suitably for the scope of 30 ~ 200mg KOH/g, more preferably 30 ~ 150mg
The scope of KOH/g, particularly preferably 45 ~ 120mg KOH/g.If the acid number containing carboxy resin is more than 30mg KOH/g, then
Alkaline development becomes good, on the other hand, if below 200mg KOH/g, then can suppress the exposure caused by developer solution
The dissolving in portion, therefore can suppress line to exceed and attenuate necessarily, or according to circumstances, suppression exposure portion and unexposed portion indifference
Be dissolved by the developing stripping, such that it is able to the resist of depicting pattern shape well.
Additionally, weight average molecular weight Mw when such as measuring with gel permeation chromatography (GPC) that (A) is containing carboxy resin (is changed
Calculate the weight average molecular weight for polystyrene) different according to resin matrix, but preferably greater than 4,000 and 150, less than 000, enter one
Step is preferably in the range of 5,000 ~ 100,000.If weight average molecular weight is more than 4,000, then non-adhesion behavior is good, after exposure
The moisture-proof of film is good, can suppress film loss during development, can suppress the reduction of resolution.On the other hand, if weighed
Average molecular weight is 150, less than 000, then developability becomes good.
[(B) heat curable component]
As (B) heat curable component, as long as reacting containing carboxy resin with (A), epoxide, amino tree can be enumerated
Fat, oxetane compound, isocyanate compound etc..Wherein, preferred epoxide.As epoxide, permissible
The multi-functional epoxy that enumerate the 2 functionality epoxy resin in the molecule with 2 epoxy radicals, there is multiple epoxy radicals in the molecule
Resin etc..Additionally, from the viewpoint of thermostability, heat curable component is preferably liquid.
As described epoxide, epoxidized vegetable oil can be enumerated；Bisphenol A type epoxy resin；Hydroquinone type asphalt mixtures modified by epoxy resin
Fat, bisphenol-type epoxy resin, thioether-type epoxy resin；Brominated epoxy resin；Phenolic resin varnish type epoxy resin；Xenol phenolic aldehyde is clear
Paint shaped epoxy resin；Bisphenol f type epoxy resin；Bisphenol-A epoxy resin；Glycidyl amine type epoxy resin；In second
Uride type epoxy resin；Alicyclic epoxy resin；Trihydroxy benzene methylmethane type epoxy resin；Di-toluene phenolic or biphenyl phenolic
Epoxy resin or their mixture；Bisphenol-s epoxy resin；Bisphenol A novolac type epoxy resin；Four phenol ethane type rings
Epoxy resins；Hetero ring type epoxy resin；O-phthalic acid diglycidyl ester resin；Four glycidyl group xylenols ethane tree
Fat；Epoxy resin containing naphthyl；There is the epoxy resin of dicyclopentadiene skeleton；Glycidyl methacrylate copolymerization system ring
Epoxy resins；N-cyclohexylmaleimide and the copolymerization epoxy resin of glycidyl methacrylate；Epoxide modified polybutadiene
Alkene rubber derivative, CTBN modified epoxy etc., but it is not limited to these.From the viewpoint of reactivity, preferably 2 officials can more than
Epoxide.
Epoxide can be any one in solid epoxy resin, semisolid epoxy resin, liquid-state epoxy resin, but
Preferably liquid-state epoxy resin.In this specification, solid epoxy resin refers to the epoxy resin at 40 DEG C for solid, shaped, semisolid
Epoxy resin refers to be solid, shaped at 20 DEG C, is the epoxy resin of liquid at 40 DEG C, and liquid-state epoxy resin refers at 20 DEG C
It is down the epoxy resin of liquid.In this specification, about solid-state, semisolid, the definition of liquid, other heat curable component is also pressed
According to above-mentioned definition.
According to making about the test of danger and (Japanese) province of character, (Heisei autonomous province in the first year makes the 1st in the judgement of liquid
Number) " confirmation method of liquid " of another page 2 carry out.
(1) device
Thermostatic water bath:
Use possesses blender, heater, thermometer, automatic temperature regulator (can carry out temperature control with ± 0.1 DEG C)
The degree of depth is that 150mm is with upper flume.
Should illustrate, in the judgement of the epoxy resin used in aftermentioned embodiment, all use Yamato Scientific
Co., Low Constant Temperature Water Baths (model BU300) that Ltd. produces and Constant Temperature Devices Thermomate (model BF500)
Combination, adds about 22 liters of tap waters in Low Constant Temperature Water Baths (model BU300), connects and be assembled in Thermomate thereon
The power supply of (model BF500), is set as design temperature (20 DEG C or 40 DEG C), with Thermomate (model BF500), water temperature is micro-
Being adjusted to design temperature ± 0.1 DEG C, but as long as being the device that can carry out same adjustment, the most all can use.
Test tube:
As test tube, as it is shown in figure 1, use liquid judgement test tube 30a and temperature measuring test tube 30b, described liquid judges
With test tube 30a be internal diameter be 30mm, height be the flat cylinder type clear glass test tube of 120mm, it is started at the bottom of with pipe
Indicating graticule 31,32 at the height of 55mm and 85mm respectively, with rubber stopper 33a by airtight for the mouth of test tube, described temperature measuring is used
Test tube 30b is same size and indicates graticule equally, is used in central authorities and offers the rubber by inserting the hole based on support temperature
Plug 33b, by airtight for the mouth of test tube, inserts thermometer 34 in rubber stopper 33b.Hereinafter, by the height to start at 55mm at the bottom of pipe
Graticule is referred to as " A line ", and the graticule of the height to start at 85mm at the bottom of pipe is referred to as " B line ".
As thermometer 34, use what JIS B7410 (1982) " petroleum-type test glass thermometer " specified to coagulate
Solid point measures with thermometer (SOP-58 scale range 20 ~ 50 DEG C), but as long as being the temperature of the temperature range that can measure 0 ~ 50 DEG C
Degree is counted.
(2) implementing procedure tested
The sample placing more than 24 hours under the atmospheric pressure that temperature is 20 ± 5 DEG C is added separately to the liquid shown in Fig. 1 (a)
Judge with in the temperature measuring test tube 30b shown in test tube 30a and Fig. 1 (b) until A line.2 test tubes 30a, 30b are made to reach with B line
Erectly it is statically placed in Low Constant Temperature Water Baths to undersurface mode.The lower end making thermometer reaches 30mm under A line.
After specimen temperature reaches design temperature ± 0.1 DEG C, keep this state 10 minutes.After 10 minutes, liquid is judged
Taking out from Low Constant Temperature Water Baths with test tube 30a, level was fallen on the testing stand of level immediately, measures with stopwatch and records examination
The time to B line is moved from A line in the front end of the liquid level in pipe.For sample, at a set temperature, it it is 90 seconds by the time of mensuration
Within sample be judged to liquid, the sample more than 90 seconds is judged to solid, shaped.
As solid epoxy resin, HP-4700 (naphthalene type epoxy resin), the life of DIC company that DIC company produces can be enumerated
NC-7000 (the multifunctional solid-state containing naphthalene skeleton that the EXA4700 (4 officials' energy naphthalene type epoxy resin) produced, Japanese chemical medicine company produce
Epoxy resin) etc. naphthalene type epoxy resin；Phenols and the tools such as the EPPN-502H (trisphenol epoxy resin) that chemical medicine company of Japan produces
There is the epoxide (triphen phenol-type epoxy resin) of the condensation substance of the aromatic aldehyde of phenolic hydroxyl group；The EPICLON HP-that DIC company produces
The dicyclopentadiene aralkyl-type epoxy resin such as 7200H (the multifunctional solid epoxy resin containing dicyclopentadiene skeleton)；Japan
The biphenyl aralkyl-type epoxy resin such as the NC-3000H (the multifunctional solid epoxy resin containing biphenyl backbone) that chemical medicine company produces；
Biphenyl/the phenol novolak type epoxy resin such as the NC-3000L that chemical medicine company of Japan produces；The EPICLON that DIC company produces
The phenolic resin varnish type epoxy resins such as the EOCN-104S that N660, EPICLON N690, chemical medicine company of Japan produce；Mitsubishi Chemical is public
The biphenyl type epoxy resins such as the YX-4000 that department produces；The phosphorous asphalt mixtures modified by epoxy resin such as the TX0712 that Zhu Jin chemical company of Nippon Steel produces
Fat；Three (2,3-glycidyl) isocyanuric acid esters etc. such as the TEPIC that Nissan Chemical Industries company produces.
As semisolid epoxy resin, can enumerate EPICLON 860 that DIC company produces, EPICLON 900-IM,
Araldite AER280 that EPICLON EXA-4816, EPICLON EXA-4822, rising sun チ バ company produce, Dongdu chemical conversion public affairs
The エ Port ト ト YD-134 of department's production, the jER834 of Mitsubishi Chemical Ind's production, jER872, Sumitomo Chemical Co. Ltd. produce
The bisphenol A type epoxy resins such as ELA-134；The naphthalene type epoxy resin such as the EPICLON HP-4032 that DIC company produces；DIC company is raw
The phenol novolak type epoxy resin etc. such as the EPICLON N-740 produced.
As liquid-state epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type epoxy can be enumerated
Resin, phenol novolak type epoxy resin, tert butyl-catechol type epoxy resin, glycidyl amine type epoxy resin, ammonia
Base phenol type epoxy resin, alicyclic epoxy resin etc..
When the hardening resin composition of the present invention is alkali-developable Photocurable resin composition, described epoxy compound
The use level of thing is preferably 1 ~ 100 mass parts relative to (A) of 100 mass parts containing carboxy resin.Reason is, if above-mentioned
Scope, then curable improves, and the general various characteristics of welding thermostability etc become better.Additionally, reason also resides in, can
To obtain sufficient obdurability, storage stability does not reduces.More preferably 2 ~ 70 mass parts.
During additionally, use liquid-state epoxy resin, contain carboxy resin relative to (A) of 100 mass parts, liquid-state epoxy resin
Ratio is preferably 5 ~ 50 mass parts, more preferably 5 ~ 40 mass parts.When the ratio of liquid-state epoxy resin is 5 ~ 50 mass parts, heat-resisting
Property more excellent, additionally, when for alkali-developable Photocurable resin composition, developability is excellent.
As amino resins, melmac, benzoguanamine resin etc. can be enumerated.Such as there is melamine methylol
Compound, methylolbenzoguanamine compound, methylol glycoluril compound and methylol urea compounds etc..Further, alkoxyl
Methylated melamine compound, aikoxymethytated benzoguanamine compound, aikoxymethytated glycolurils compound and alcoxyl
Ylmethyl carbamide compound respectively can be by by melamine methylol compound, methylolbenzoguanamine compound, hydroxyl first
The methylol of base glycoluril compounds and methylol urea compounds is converted into alkoxy methyl and obtains.For this alkoxy methyl
Kind is not particularly limited, such as, can be methoxy, ethoxyl methyl, propoxy methyl, butoxymethyl etc..Especially
It is preferably the melamine derivative of less than 0.2% to human body, eco-friendly formalin concentration.
As described oxetane compound, double [(3-methyl-3-oxetanylmethoxy methoxyl group) methyl] can be enumerated
Double [(3-methyl-3-oxetanylmethoxy methoxyl group) first of ether, double [(3-ethyl-3-oxetanylmethoxy methoxyl group) methyl] ether, 1,4-
Base] benzene, 1,4-double [(3-ethyl-3-oxetanylmethoxy methoxyl group) methyl] benzene, acrylic acid (3-methyl-3-oxetanylmethoxy) first
Ester, acrylic acid (3-ethyl-3-oxetanylmethoxy) methyl ester, methacrylic acid (3-methyl-3-oxetanylmethoxy) methyl ester, methyl-prop
The multifunctional oxetanes classes such as olefin(e) acid (3-ethyl-3-oxetanylmethoxy) methyl ester, their oligomer or copolymer, except this it
Can enumerate outward oxetanes alcohol and novolac resin, poly-(4-Vinyl phenol), Cardo type bisphenols, calixarene kind,
Resorcinol calixarene kind or silsesquioxane etc. have the etherate etc. of the resin of hydroxyl.Further, it is also possible to enumerate, there is oxygen
The unsaturated monomer of azetidine ring and the copolymer etc. of (methyl) alkyl acrylate.
As described isocyanate compound, it is possible to use have the polyisocyanates of multiple NCO in the molecule
Compound.As polyisocyanate compound, it is possible to use such as aromatic polyisocyanate, aliphatic polyisocyante or alicyclic ring
Formula polyisocyanates.As the concrete example of aromatic polyisocyanate, 4 can be enumerated, 4'-methyl diphenylene diisocyanate, 2,
4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), naphthalene-1,5-diisocyanate, adjacent eylylene diisocyanate,
Between eylylene diisocyanate and 2,4 tolylene diisoeyanate dimer.Concrete as aliphatic polyisocyante
Example, can enumerate tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl six Asia
Methyl diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate.As ester ring type polyisocyanate
The concrete example of cyanate, can enumerate norbornane triisocyanate.And, the isocyanates hereinbefore enumerated can be enumerated
Compound add zoarium, biuret body and isocyanuric acid ester body.Described isocyanate compound can be that NCO is sealed
The blocked isocyanate compounds that end agent is protected and is temporarily passivated.
For (B) heat curable component, it is possible to use public heat curable component other than the above, it is possible to use Malaysia
Imide compound, benzoxazine resins, carbodiimide resin, cyclic carbonate compound, episulfide resin etc..Additionally, as (B)
Heat curable component, it is possible to use imidazoles, 2-methylimidazole, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-
The imdazole derivatives such as phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole；
Dicyanodiamine, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl-benzyl amine, 4-methoxyl group-N, N-dimethyl benzene
Methylamine, 4-methyl-N, the hydrazine compounds such as amines, adipic dihydrazide, sebacic dihydrazide such as N-dimethyl-benzyl amine；Three
The phosphorus compounds etc. such as Phenylphosphine, as commercially available product, can enumerate 2MZ-A that such as four countries' chemical conversion industrial group produces, 2MZ-OK,
U-CAT3503N, U-that 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound), San-Apro Ltd. produce
CAT3502T (being the trade name of the blocked isocyanate compounds of dimethyl amine), DBU, DBN, U-CATSA102, U-
CAT5002 (being two ring type amidine compound and salt thereof) etc..Further, it is also possible to by guanamines, acetylguanamine, benzoguanamine, trimerization
Cyanamide, 2,4-diaminourea-6-methylacryloyl epoxide ethyl-s-triazine, 2-vinyl-4,6-diaminourea-s-triazine, 2-second
Thiazolinyl-4,6-diaminourea-s-triazine isocyanuric acid adduct, 2,4-diaminourea-6-methylacryloyl epoxide ethyl-equal three
The Striazine derivatives such as piperazine isocyanuric acid adduct etc. also serve as adaptation imparting agent and the compound of function is used as (B)
Heat curable component.(B) heat curable component can be used singly or in combination of two or more.
As (B) heat curable component, preferably comprise tripolycyanamide.Owing to tripolycyanamide is bonded with (C) boric acid ester compound,
Therefore tripolycyanamide and the combination of (C) boric acid ester compound are more effective for extending the dry span of control.
(B) use level of heat curable component is preferably 5 ~ 250 mass parts relative to (A) of 100 mass parts containing carboxy resin,
More preferably 10 ~ 230 mass parts.If the use level of heat curable component is above-mentioned scope, then thermostability is better, additionally, solid
Change painting film strength the best.
[(C) boric acid ester compound]
As (C) boric acid ester compound, it is possible to use known boric acid ester compound.For example, it is possible to enumerate the boron that volatility is low
Triphenyl phosphate ester, cycliborate etc..It is preferably cyclic boronate ester compounds.Cyclic boronate ester compounds refers to wrap in ring structures
The compound of boracic, particularly preferred 2,2'-epoxide is double (5,5'-dimethyl-1,3,2-dioxoborinane).As boric acid
Ester compounds, in addition to triphenyl borate, cyclic boronate ester compounds, can enumerate such as methyl borate., boron triethylenetetraminehexaacetic acid
Ester, triproylborate, butyl borate etc., but these boric acid ester compounds are high due to volatility, therefore for particularly high temperature
Time compositions storage stability for, there is also the situation that its effect is insufficient.Boric acid ester compound can be used alone 1
Kind, it is also possible to it is applied in combination two or more.
As the commercially available product of (C) boric acid ester compound, can enumerate such as Ha イ ボ ロ Application BC1, Ha イ ボ ロ Application BC2,
Ha イ ボ ロ Application BC3, Ha イ ボ ロ Application BCN (they are Boron International Co., Ltd. and produce),
CUREDUCT L-07N (chemical conversion industrial group of four countries produces) etc..
(C) use level of boric acid ester compound is preferably 0.01 ~ 5 mass relative to (A) of 100 mass parts containing carboxy resin
Part, more preferably 0.05 ~ 3 mass parts.
(Photoepolymerizationinitiater initiater)
The hardening resin composition of the present invention can contain Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater is not particularly limited, can
To use public Photoepolymerizationinitiater initiater.Such as benzoin, benzil, benzoin methyl ether, benzoin second can be enumerated
The benzoin classes such as base ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether；Benzoin alkyl ethers；Two
Benzophenone, to methyl benzophenone, Michler's keton (Michler's ketone), methyl benzophenone, 4,4'-dichloro first
The benzophenones such as the double diethylamino benzophenone of ketone, 4,4'-；1-Phenylethanone., 2,2-dimethoxy-2-phenyl acetophenone, 2,
2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-[4-(first sulfur
Base) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, N, N-bis-
The acetophenones such as methylamino 1-Phenylethanone.；Thiaxanthone, 2-ethyl thiaxanthone, ITX, 2,4-dimethyl thioxanthone,
The thioxanthene ketones such as 2,4-diethyl thioxanthone, CTX, 2,4-diisopropylthioxanthone；Anthraquinone, chloroanthraquinone, 2-methyl anthracene
The Anthraquinones such as quinone, 2-ethyl-anthraquinone, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-amino anthraquinones；1-Phenylethanone. diformazan
The ketal classes such as base ketal, benzil dimethyl ketal；EDMAB, benzoic acid 2-(dimethylamino) second
The benzoates such as ester, ethyl p-methyl benzoate；1-[4-(thiophenyl) phenyl]-1,2-octanedione 2-(O-benzoyl
Oxime), the oxime esters such as 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethyl ketone 1-(O-acetyl oxime)；Double (η
5-2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles's-1-base) phenyl) titanium, double (cyclopentadienyl groups)-bis-[2,
The fluoro-3-of 6-bis-(2-(1H-pyrroles's-1-base) ethyl) phenyl] the titanocenes class such as titanium；2,4,6-trimethyl benzoyl diphenyl base oxygen
Change the acylphosphine oxide class such as phosphine, double (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide；Diphenyl disulfide, 2-nitrofluorene, fourth
Acyloin, anisoin ethyl ether, azobis isobutyronitrile, tetramethylthiuram disulfide etc..Wherein, preferably acetophenones, thioxanthene
Ketone, oxime esters (hereinafter also referred to as " oxime ester system Photoepolymerizationinitiater initiater ").Photoepolymerizationinitiater initiater can be used alone a kind, it is possible to group
Close and use two or more.
The use level of Photoepolymerizationinitiater initiater is preferably 0.01 ~ 20 mass relative to (A) of 100 mass parts containing carboxy resin
Part.Reason is, if above-mentioned scope, then the photo-curable on copper is abundant, and the curable of film becomes good, chemically-resistant
The coating characteristics such as medicine improve, additionally, deep curable also improves.More preferably relative to (A) tree Han carboxyl of 100 mass parts
Fat is 0.5 ~ 15 mass parts.
Owing to the light sensitivitys to light during exposure can be improved, the most preferably by thioxanthene ketone (hereinafter also referred to as " thioxanthene
Ketone system Photoepolymerizationinitiater initiater ") with other Photoepolymerizationinitiater initiaters using.As thiaxanthone system Photoepolymerizationinitiater initiater, above-mentioned central, more
2,4-diethyl thioxanthone is preferably used.The use level of thiaxanthone system Photoepolymerizationinitiater initiater contains carboxylic relative to (A) of 100 mass parts
Base resin is preferably 0.05 ~ 2 mass parts, more preferably 0.1 ~ 1 mass parts.Reason is, if the model of 0.05 ~ 2 mass parts
Enclose, then the effect that light sensitivitys improves is big, and its result is to become easily to suppress lateral erosion (undercut), additionally becomes to be not likely to produce
Aerofluxus.
Use level during oxime ester system's Photoepolymerizationinitiater initiater is used to be preferably containing carboxy resin relative to (A) of 100 mass parts
0.01 ~ 5 mass parts.Reason is, if above-mentioned scope, then the photo-curable on copper is abundant, and the curable of film becomes
Well, the coating characteristic such as chemical proofing improves, additionally, deep curable also improves.Additionally, oxime ester system Photoepolymerizationinitiater initiater
Being irradiated by light and produce alkali, therefore thermosetting improves, after can further improve the heat cure such as gold-plated patience, welding thermostability
The characteristic of solidfied material.The use level of oxime ester system Photoepolymerizationinitiater initiater is more preferably containing carboxy resin relative to (A) of 100 mass parts
0.5 ~ 3 mass parts.
(photocuring composition)
The hardening resin composition of the present invention can contain photocuring composition.As photocuring composition, photoreaction is preferably used
Property monomer.Photoreactivity monomer is the compound in the molecule with more than 1 ethylenically unsaturated group.Photoreactivity monomer has
Help the photocuring containing carboxy resin caused because active energy beam irradiates.
As can serve as the compound of described photoreactivity monomer, the most public polyester (methyl) can be enumerated
Acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, ring
Oxygen (methyl) acrylate etc..Specifically, the acrylic acid such as acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester can be enumerated
Hydroxy alkyl esters；The diacrylate esters of the dihydroxylic alcohols such as ethylene glycol, methoxyl group TEG, Polyethylene Glycol, propylene glycol；N,N-
DMAA, N hydroxymethyl acrylamide, N, the acrylic amide such as N-dimethylaminopropylacryl amide；Acrylic acid
N, N-dimethylamino ethyl ester, acrylic acid N, the acrylate class such as N-dimethylamino propyl ester；Hexanediol, three hydroxyl first
The polyhydric alcohol such as base propane, tetramethylolmethane, dipentaerythritol, tris-hydroxyethylisocyanuande or their ethylene oxide adduct,
The multicomponent methacrylate class of propylene oxide adduct or 6-caprolactone addition product etc.；Phenoxy group acrylate, bisphenol-A two propylene
Acid esters and the multicomponent methacrylate class of the ethylene oxide adduct of these phenols or propylene oxide adduct etc.；Glycerol two contracts
Water glyceryl ether, glycerol triglycidyl group ether, trimethylolpropane tris glycidyl ether, triglycidyl group isocyanuric acid
The multicomponent methacrylate class of the glycidyl ethers such as ester；It is not limited to above-mentioned substance, it is also possible to enumerate polyether polyol, poly-carbonic acid
The polyhydric alcohol such as esterdiol, the polybutadiene of C-terminal, PEPA directly carry out acroleic acid esterification or via two Carbimide .s
Esters of acrylic acid that ester carries out urethane acrylate and obtains and melamine acrylate and with described propylene
Each methyl acrylic ester etc. that acid esters is corresponding.
Obtain further, it is possible to the polyfunctional epoxy resins such as cresol novolak type epoxy resin will be made to react with acrylic acid
Epocryl, make the hydroxyls such as the hydroxyl of this Epocryl and pentaerythritol triacrylate further
The epoxy that half carbamate compounds of the diisocyanate such as acrylate and isophorone diisocyanate reacts and obtains
Urethane acrylate compounds etc. are as photoreactivity monomer.Such epoxy acrylate system resin can not reduce
Photo-curable is improved in the case of dry to touch.
Photocuring composition can be used alone a kind, it is possible to is applied in combination two or more.The use level of photocuring composition relative to
(A) of 100 mass parts is preferably 1 ~ 15 mass parts containing carboxy resin.Reason is, if above-mentioned scope, then photo-curable carries
Height, the alkaline development after being irradiated by active energy beam, pattern is formed and becomes easy, additionally, coating strength improves.More preferably
It it is 1 ~ 10 mass parts.
(inorganic filling material)
For improving the purpose of the characteristics such as adaptation, hardness, thermostability, the hardening resin composition of the present invention can contain with or without
Machine filler.As inorganic filler, can enumerate calcium carbonate, magnesium carbonate, flyash (fly ash), dewatered sludge, natural two
Silicon oxide, synthetic silica, Kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide,
Aluminium hydroxide, aluminium oxide, magnesium hydroxide, Talcum, Muscovitum, brucite, aluminium silicate, magnesium silicate, calcium silicates, calcination of talc, silicon ash
Stone, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, meerschaum, Vermiculitum (Zonolite), boron nitride, Alborex M 12, silica spheres
Capsule, sheet glass, glass sacculus, silicon dioxide, iron blast furnace slag processed, copper, ferrum, ferrum oxide, white carbon black, ferrum sial (Sendust), aluminum nickel cobalt
The magnetic powder such as Magnetitum, various ferrites, cement, glass powder, Nuo Yibao (Neuburg) tripoli, kieselguhr, antimony trioxide, alkali
Formula magnesium sulfate, hydrated aluminum, hydrated gypsum, bright sail etc..Additionally, as inorganic filler, can enumerate organobentonite, cover de-
The fiber-reinforced materials etc. such as stone, glass fibre, carbon fiber, boron nitride fiber.Inorganic filler can be used alone a kind, it is possible to
To be applied in combination two or more.
Preferably the mean diameter (D50) of inorganic filler is below 25 μm, below more preferably 10 μm, more preferably
Below 3 μm.Here, D50 refers to utilize laser diffraction and scattering formula particle size distribution method based on Michaelis (Mie) scattering theory to obtain
The particle diameter during volume-cumulative 50% arrived.More specifically, can be measured in the following manner: pass through laser diffraction and scattering
Formula particle size distribution device, makes the particle size distribution of microgranule, using its median particle diameter as mean diameter in terms of volume reference.Right
In measuring sample, it may be preferred to use the sample obtained by ultrasonic being dispersed in water by microgranule.As laser diffraction formula grain
Degree distribution measurement device, it is possible to use the LA-500 etc. that Ku Chang manufacturing company produces.
From the viewpoint of the film forming hardening resin composition, the use level of inorganic filler is relative to 100 matter
(A) of amount part is preferably 50 ~ 400 mass parts, more preferably 80 ~ 350 mass parts containing carboxy resin.
(organic solvent)
In the hardening resin composition of the present invention, in order to regulate the viscosity of compositions, in order to carry out being applied on substrate, film
For the purpose of viscosity adjust, public organic solvent can be comprised.Can enumerate such as toluene, dimethylbenzene, ethyl acetate,
Butyl acetate, methanol, ethanol, isopropanol, isobutanol, n-butyl alcohol, DAA, ethylene glycol monobutyl ether, propylene glycol list ethyl
Ether, propylene glycol monomethyl ether, terpinol, butanone, carbitol, carbitol acetate, butyl carbitol, butyl card must
Alcohol acetic ester etc..Organic solvent can be used singly or in combination of two or more.
(other optional members)
In the hardening resin composition of the present invention, additive public in field of electronic materials can be coordinated.As adding
Add agent, thermal polymerization inhibitor, UV absorbent, silane coupler, plasticizer, fire retardant, antistatic agent can be enumerated, prevent always
Agent, antibacterial mildew inhibitor, defoamer, levelling agent, organic filler, thickening agent, adaptation imparting agent, thixotropy conferring agents,
Toner, light-initiated auxiliary agent, sensitizer etc..
The hardening resin composition of the present invention can be 1 liquid, it is also possible to be more than 2 liquid.When being more than 2 liquid, such as, can
To coordinate (C) boric acid in comprising (A) host containing carboxy resin and any one in the firming agent comprising (B) heat curable component
Ester compounds.
The hardening resin composition of the present invention can also as possess film and on this film formed by above-mentioned curable
The form of the dry film of the resin bed that resin combination is constituted.When carrying out dry film, film can be obtained in the following manner: use institute
State the hardening resin composition of the organic solvent diluting present invention, regulate to suitable viscosity, take turns coating machine, scraper painting by unfilled corner
Cloth machine, lip type coating machine, rod coater, extrusion coating machine, reverse coating machine, transfer roll coater, gravure coater, spraying
Machines etc. are coated into uniform thickness in carrier film (support), generally, carry out 1 ~ 30 minute doing at a temperature of 50 ~ 130 DEG C
Dry, thus obtain film.Coating film thickness is not particularly limited, but with dried film thickness gauge, generally in 10 ~ 150 μm, preferably
Suitably select in the range of 20 ~ 60 μm.
As carrier film, it is possible to use plastic foil, the polyester films such as polyethylene terephthalate, polyamides Asia are preferably used
The plastic foils such as amine film, polyamidoimide film, polypropylene screen, polystyrene film.Thickness for carrier film is not particularly limited,
But generally suitably select in the range of 10 ~ 150 μm.
After the hardening resin composition using the present invention forms resin bed on a carrier film, further for preventing dust and dirt
It is attached to the first-class purpose in surface of film, the strippable coverlay of stacking the most on the surface of the film.As strippable coverlay,
Such as polyethylene film, poly tetrafluoroethylene, polypropylene screen, surface treated paper etc. can be used, as long as cover peeling off
The coverlay that during film, film is less than the bonding force of film Yu carrier film with the bonding force of coverlay.
For the hardening resin composition of the present invention, such as, regulate to being suitable to coating side with aforementioned organic solvents
The viscosity of method, is applied on base material by methods such as dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain coatings,
At a temperature of about 60 ~ 100 DEG C, make the organic solvent volatile dry (predrying) contained in compositions, thus can be formed not
The film of viscosity.Additionally, being applied in carrier film by foregoing, make it be dried form that film being wound obtains dry
In the case of film, by the laminating resin bed such as laminating machine so that it contacts with base material, then peel off carrier film, thus can be
Resin bed is formed on base material.
As described base material, in addition to being pre-formed with the printed circuit board (PCB) of circuit, flexible printed circuit board, Ke Yiju
Go out to employ the coating foil laminated board of whole grades (FR-4 etc.) of following material: employ paper phenolic resin, paper epoxy resin,
Glass cloth epoxy resin, glass polyimides, glass cloth/non-woven fabrics epoxy resin, glass cloth/paper epoxy resin, synthetic fibers
Epoxy resin, fluorine polyethylene polyphenylene oxide, the high-frequency circuit material of coating foil laminated board etc. of polyoxygenated phenylenecyanate etc.
Matter；Additionally can enumerate polyimide film, PET film, glass substrate, ceramic substrate, wafer board etc..
After the hardening resin composition of the coating present invention volatile dry that carries out can use heated air circulation type drying oven,
IR stove, heating plate, convection oven etc. (use the device of the thermal source being equipped with air mode of heating based on steam, in making exsiccator
Hot air convection contact method, and the mode purged to support by nozzle) carry out.
Its thermosetting is made for the hardening resin composition of the present invention, the such as temperature by being heated to about 140 ~ 180 DEG C
Change, thus (A) react with (B) heat curable component containing carboxy resin, can be formed thermostability, chemical proofing, resistance to hygroscopicity,
The cured coating film of the various excellent such as adaptation, electrical characteristic.
When the hardening resin composition of the present invention is alkali-developable, to being coated with hardening resin composition and making solvent
The film obtained after volatile dry is exposed (irradiation of active energy beam), and thus exposure portion (is shone by active energy beam
The part penetrated) solidification.Additionally, by contact (or cordless), optionally lead to via forming figuratum photomask
Cross active energy beam be exposed or carry out direct pattern exposure by the direct exposure machine of laser, unexposed portion is passed through
Dilute alkali aqueous solution (such as 0.3 ~ 3wt% aqueous sodium carbonate) develops, and forms Resist patterns.
As the exposure machine irradiated for described active energy beam, as long as carry high voltage mercury lamp, ultrahigh pressure mercury lamp, gold
Belong to halide lamp, mercury short arc lamp etc. the device of the range illumination ultraviolet with 350 ~ 450nm, further, it is also possible to
Use direct drawing apparatus (such as by the cad data from computer directly with the laser direct imaging of laser scanning drawing picture
Device).As directly retouching the LASER Light Source of machine, as long as using maximum wavelength at the laser of the scope of 350 ~ 410nm, then gas laser
Device, solid state laser.For formed the light exposure of image according to thickness etc. and different, but generally can be at 20 ~ 800mJ/
cm2, preferably at 20 ~ 600mJ/cm2In the range of.
As described developing method, can be based on infusion process, spray process, nebulization, spread coating etc., as developer solution, can
To use the alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amine etc..
The hardening resin composition of the present invention is applicable to printed circuit board (PCB), the solder resist of flexible printed circuit board, covering
The formation of the permanent cured film that insulate such as layer and interlayer insulating film.
Embodiment
Hereinafter, use embodiment that the present invention is described in further detail, but the present invention is not limited by following embodiment.Should
Give explanation, hereinafter, for " part " and " % ", unless otherwise specified, all on the basis of quality.
[synthesis containing carboxy resin and adjustment]
(A-1: there is the synthesis containing carboxy resin of the structure of phenol novolak type)
By 190 parts of (1 equivalent) phenol novolak type epoxy resin, (chemical medicine company of Japan produces, P-201, epoxide equivalent 190g/
Eq), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphthas be encased in flask, be heated to 90 DEG C and be stirred,
Make it dissolve.The solution obtained first is cooled to 60 DEG C, adds 72 parts of (1 mole) acrylic acid, 0.5 part of methylnaphthohydroquinone, 2 parts of triphens
Base phosphine, is heated to 100 DEG C so that it is reacts about 12 hours, obtains the reactant that acid number is 0.2mg KOH/g.It is added to 80.6
Part (0.53 mole) tetrabydrophthalic anhydride, is heated to 90 DEG C so that it is reacting about 6 hours, obtaining solid state component acid number is
60mg KOH/g, solid component concentration are the resin solution of 65.8%.Hereinafter referred to as varnish A-1.
(A-2: there is the synthesis containing carboxy resin of the structure of cresol novolak type)
By 220 parts of (1 equivalent) cresol novolak type epoxy resins, (chemical medicine company of Japan produces, EOCN-104S, epoxide equivalent
220g/eq), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphthas be encased in flask, be heated to 90 DEG C and carry out
Stirring so that it is dissolve.The solution obtained first is cooled to 60 DEG C, add 72 parts of (1 mole) acrylic acid, 0.5 part of methylnaphthohydroquinone, 2
Part triphenylphosphine, is heated to 100 DEG C so that it is react about 12 hours, obtain the reactant that acid number is 0.2mg KOH/g.Xiang Qitian
Add 80.6 parts of (0.53 mole) tetrabydrophthalic anhydrides, be heated to 90 DEG C so that it is react about 6 hours, obtain solid state component acid
Value is 85mg KOH/g, solid component concentration is the resin solution of 65.8%.Hereinafter referred to as varnish A-2.
(A-3: the adjustment of the copolymer resins containing carboxyl)
(acid number is 70.0mg KOH/g to Cyclomer P (ACA) Z250 using Daicel chemical industrial company to produce, solid-state
Constituent concentration is 45%).Hereinafter referred to as varnish A-3.
[embodiment 1 ~ 14, comparative example 1,2]
Above-mentioned resin solution (varnish) is together carried out with the ratio (mass parts) shown in table 1 with the various compositions shown in table 1
Coordinate, after carrying out premixing with blender, carry out mixing with three-high mill, prepare hardening resin composition.
<development life-span>
By silk screen printing, each hardening resin composition of embodiment 1 ~ 11 and comparative example 1,2 is applied to by entire surface through pattern
On the copper clad laminate formed, the accumulation light that will produce via photomask, use ORC MANUFACTURING CO., LTD. respectively
Gauge irradiates 750mJ/cm2The object that obtains of the ultraviolet irradiation light quantity of 365nm wavelength as test film, dry at 80 DEG C
Dry 30 minutes, to respective developer solution with 2kg/cm2The develop removing state in the unexposed portion after 60 seconds of atomisation pressure enter
Row visually confirms.
Zero: develop completely
×: fail to develop.
<gold-plated patience>
By silk screen printing, each hardening resin composition of embodiment 1 ~ 11 and comparative example 1,2 is applied to by entire surface through pattern
On the copper clad laminate formed, carry out 30 minutes being dried at 80 DEG C, place and be cooled to room temperature.To this substrate, use and be equipped with height
Solder resist pattern is exposed by the exposure device of pressure mercury lamp (short-arc lamp) with optimal light exposure, at the 1wt% making 30 DEG C
Na2CO3The atomisation pressure of aqueous solution is 2kg/cm2Under conditions of develop 60 seconds, obtain Resist patterns.By defeated for this substrate UV
Send formula stove with cumulative exposure amount as 1000mJ/cm2Condition carry out ultraviolet irradiation, then heat to enter for 60 minutes at 150 DEG C
Row solidification.For the printed base plate (evaluation substrate) obtained, the electroless nickel plating bath of commercially available product and electroless gold plating is used to bathe, with
Nickel 0.5 μm, the condition of golden 0.03 μm carry out plating, are peeled off by adhesive tape, to resist layer with or without peeling off, penetrating into or without plating
Row is evaluated, and is then peeled off by adhesive tape, is evaluated resist layer with or without peeling.
For each hardening resin composition of embodiment 12 ~ 14, it is being applied to Copper Foil base by entire surface by silk screen printing
After on plate, heat at 150 DEG C and solidify for 60 minutes.Except using printed base plate (evaluation substrate) obtained as indicated above
Outside, in the way of similarly to Example 1, resist layer is evaluated with or without peeling.
Determinating reference is as described below.
◎: without peeling off
Zero: exist part peel off, but be at 3 within
△: there is the peeling centered by marginal portion
×: there is expansion, peel off.
<welding thermostability>
By silk screen printing, in the way of dried thickness reaches 20 μm, by embodiment 1 ~ 11 and each solidification of comparative example 1,2
Property resin combination is applied on substrate by entire surface, makes it be dried 30 minutes, then in the heated air circulation type drying oven of 80 DEG C
Placement is cooled to room temperature.This substrate (is carried the ORC of mercury short arc lamp with the exposure device carrying high voltage mercury lamp
The exposure machine that MANUFACTURING CO., LTD. company produces) it is exposed with optimal light exposure, it is 30 in temperature
DEG C, atomisation pressure be 0.2MPa, developer solution be to develop 60 seconds under conditions of 1 mass % aqueous sodium carbonate, obtain pattern.Enter one
Step, by this substrate UV conveyor furnace with cumulative exposure amount as 1000mJ/cm2Condition carry out ultraviolet irradiation, then 160
At DEG C, heating solidifies for 60 minutes.For optimal light exposure, when exposure via stage actinometer (step
Tablet) (T4105C that Stouffer company produces) is exposed, and is 8 by the hop count of the stage actinometer of remaining after development
As optimal light exposure during section.For the printed base plate (evaluation substrate) obtained, it is coated with rosin scaling powder, is setting
Impregnate 30 seconds to the solder baths of 260 DEG C.Clean this test substrate with organic solvent, then carry out based on adhesive tape
The disbonded test of (cellophane adhesive tape), uses following benchmark to be evaluated.
For each hardening resin composition of embodiment 12 ~ 14, it is being applied to Copper Foil base by entire surface by silk screen printing
After on plate, heat at 150 DEG C and solidify for 60 minutes.Except using printed base plate (evaluation substrate) obtained as indicated above
Outside, in the way of similarly to Example 1, carry out disbonded test.
◎: without peeling off
Zero: exist part peel off, but at 3 within
△: there is the peeling centered by marginal portion
×: there is expansion, peel off.
<insulation resistance>
Each hardening resin composition of embodiment 1 ~ 14 and comparative example 1,2 is coated into IPC combed B pattern, with above-mentioned plating
When gold patience is evaluated, same mode solidifies, 90%RH, 25 ~ 65 DEG C, apply DC100V under conditions of humidify 7 days, then
Insulating resistance value after observing 1 minute with DC500V.
Zero: 1012More than Ω
△: 1011Ω is less than 1012Ω
×: less than 1011Ω。
<hot strength, percentage elongation>
Each hardening resin composition of embodiment 1 ~ 11 and comparative example 1,2 is applied to by entire surface the glassy surface of Copper Foil, 80
It is dried 30 minutes at DEG C, places and be cooled to room temperature.(short with being equipped with high voltage mercury lamp to the hardening resin composition on this Copper Foil
Arc lamp) exposure device carry out whole exposure with optimal light exposure.Then, by the hardening resin composition on this Copper Foil
With UV conveyor furnace with cumulative exposure amount as 1000mJ/cm2Condition carry out ultraviolet irradiation, at 150 DEG C, then heat 60
Minute make it solidify, obtain solidfied material.
On the other hand, each hardening resin composition of embodiment 12 ~ 14 is applied to by entire surface the glassy surface of Copper Foil,
Make it carry out solidification in 90 minutes at 180 DEG C, obtain solidfied material.
Remove Copper Foil from each solidfied material obtained as indicated above, be cut to that width is about 5mm, length is about 80mm
Test film, use cupping machine (company of Shimadzu Seisakusho Ltd. produce, Autograph AGS-100N) to measure breakaway poing elongation
Rate.
Condition determination is: Sample Width is about 10mm, and distance between the fulcrum is about 40mm, and draw speed is 1.0 mm/ minute,
Percentage elongation till near fracture is as breakaway poing percentage elongation.
By following benchmark evaluation hot strength.
◎: more than 7%
Zero: more than 5% and less than 7%
△: more than 3% and less than 5%.
<peel strength>
Each hardening resin composition of embodiment 1 ~ 11 and comparative example 1,2 is applied to carry out in advance surface process by entire surface
The glassy surface of the Copper Foil of (MEC Co., Ltd. produces, CZ-8101, and etch quantity is about 1.0 μm), is dried 30 minutes at 80 DEG C,
Placement is cooled to room temperature.Hardening resin composition on this Copper Foil is used the exposure device carrying high voltage mercury lamp (short-arc lamp)
Whole exposure is carried out with optimal light exposure.Then, by the hardening resin composition on this Copper Foil with UV conveyor furnace with
Cumulative exposure amount is 1000mJ/cm2Condition carry out ultraviolet irradiation, then at 150 DEG C, heating makes it solidify in 60 minutes,
To solidfied material.
On the other hand, each hardening resin composition of embodiment 12 ~ 14 is applied to carry out in advance surface by entire surface
Process the Copper Foil of (etch quantity is about 1.0 μm for MEC Co., Ltd., CZ-8101), make it carry out 60 minutes admittedly at 180 DEG C
Change, make the Copper Foil with cured film.
After the cured film coating adhesive (Araldite) on each Copper Foil obtained as indicated above, existed by forcing press
Make deposited copper under pressure is 0.5MPa and temperature is 60 DEG C pressurization and warm-up mode and evaluate substrate.
Evaluate substrate for the deposited copper that obtains, cut out with the size of about 10mm × about 80mm, reaching the degree of depth of cured film
Otch, slightly stripped end are so that it is guaranteed that after clamping part, with clamping holder, use cupping machine (Shimadzu Seisakusho Ltd.
Company produces, Autograph AGS-100N) measure peel strength.Condition determination is: at room temperature, and making draw speed is 50
Mm/ minute, measure average load when peeling off 35mm.By following benchmark evaluation peel strength.
◎: more than 10N
Zero: more than 7N and below 10N
△: more than 5N and below 7N.
<PCBT patience>
Each curable resin composition of embodiment 1 ~ 14 and comparative example 1,2 is coated into L/S:100 μm/100 μ that copper thickness is 18 μm
The combed pattern of m, puts into temperature in groove by carrying out solidifying the substrate obtained with above-mentioned gold-plated patience in the way of as in time evaluating
In the environment of degree is retained as 121 DEG C, humidity is retained as 97%, applies DC30V, be 10 by resistance value6Below Ω is as measuring
Terminal, mensuration can the Connection Time.
More than ◎: 200 hours
: 150 hours less than 200 hours
△: 100 hours less than 150 hours
×: less than 100 hours.
<adaptation of underfill>
Use plasma (gas Ar/O2, output: 350W, vacuum: 300 mTorr), in evaluating in above-mentioned gold-plated patience
The evaluation substrate obtained through electroless gold plating carries out 60 seconds processing, coating underfill (DENA TITE R3003iEX,
Nagase ChemteX company produces), carry out 160 DEG C, the solidification of 1h, carry out the Reflow Soldering at 3 260 DEG C of peaks further, then enter
One step 121 DEG C, 2 atmospheric pressure, 100% humidity under carry out 100h pressure cooking, then by thrust meter (push gauge)
Measure the adaptation of underfill and resist layer, be evaluated by following benchmark.
◎: more than 100N
: 80N is less than 100N
△: 60N less than 80N
×: less than 60N.
[table 1]
* 1: have phenol novolak type skeleton photonasty containing carboxy resin (PN (phenol novolak type epoxy resin)/
AA (acrylic acid)/THPA (tetrabydrophthalic anhydride))
* 2: have cresol novolak type skeleton photonasty containing carboxy resin (CN (cresol novolak type epoxy resin)/
AA (acrylic acid)/THPA (tetrabydrophthalic anhydride))
* 3: containing carboxyl copolymer resins (Cyclomer P (ACA) Z250 that Daicel chemical industrial company produces)
* Irgacure 907 (2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl acrylate-that 4:BASF Japan company produces
1-ketone)
* 5: the DETX-S (2,4-diethyl thioxanthone) that chemical medicine company of Japan produces
* Irgacure OXE02 (1-[9-ethyl-6-(2-the methyl benzoyl)-9H-click that 6:BASF Japan company produces
Azoles-3-base]-ethyl ketone 1-(O-acetyl oxime))
* 7: the B-30 that chemical company produces
* the SO-E2 that 8:Admatechs produces
* 9:2,2'-epoxide is double (5,5'-dimethyl-1,3,2-dioxoborinane)
* 10: TC acetas
* 11: aromatic hydrocarbon (Solvesso 150)
* the N-730A (phenol novolak type epoxy resin, liquid-state epoxy resin) that 12:DIC company produces
* 13: the jER828 (bisphenol A type epoxy resin, liquid-state epoxy resin) that Mitsubishi Chemical Ind produces
* the N-770 (phenol novolak type epoxy resin, solid epoxy resin) that 14:DIC company produces
* 15: the 2PHZ (2-phenyl-4,5-bishydroxymethyl imidazoles) that chemical conversion company of four countries produces
* 16: dipentaerythritol acrylate (production of chemical company of common prosperity society)
* 17: trimethylolpropane trimethacrylate (chemical medicine company of Japan produces).
From the result shown in above-mentioned table 1, the thermostability of the solidfied material of the hardening resin composition of embodiment 1 ~ 14
And percentage elongation is excellent.In addition understand, in the compositions of the embodiment 1 ~ 11 as alkali-developable Photocurable resin composition
In the case of, even if evaluating the development life-span under above-mentioned drying condition, it is also possible to obtain good developability, be therefore dried management
Amplitude is excellent.On the other hand, the solidfied material of the hardening resin composition of the comparative example 1,2 of (C) boric acid ester compound is not contained
Thermostability and elongation rate variance.
Claims (7)
1. hardening resin composition, it is characterised in that comprise:
(A) containing carboxy resin；
(B) heat curable component；With
(C) boric acid ester compound.
2. hardening resin composition as claimed in claim 1, it is characterised in that comprise liquid-state epoxy resin as described
(B) heat curable component.
3. hardening resin composition as claimed in claim 1 or 2, it is characterised in that also comprise Photoepolymerizationinitiater initiater.
4. the hardening resin composition as according to any one of claim 1 ~ 3, it is characterised in that be used for being formed solder resist,
Cover layer or interlayer dielectic.
5. dry film, it is characterised in that have and the hardening resin composition according to any one of claim 1 ~ 4 is applied to film
The resin bed gone up and be dried and obtain.
6. solidfied material, it is characterised in that it is by the hardening resin composition according to any one of claim 1 ~ 4 or right
Require that the resin bed solidification of the dry film described in 5 obtains.
7. printed circuit board (PCB), it is characterised in that there is the solidfied material described in claim 6.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-144277 | 2015-07-21 | ||
| JP2015144277 | 2015-07-21 | ||
| JP2016090155A JP6742796B2 (en) | 2015-07-21 | 2016-04-28 | Curable resin composition, dry film, cured product and printed wiring board |
| JP2016-090155 | 2016-04-28 |
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| CN106200266A true CN106200266A (en) | 2016-12-07 |
| CN106200266B CN106200266B (en) | 2020-01-24 |
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| CN201610576040.XA Active CN106200266B (en) | 2015-07-21 | 2016-07-21 | Curable resin composition, dry film, cured product, and printed wiring board |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110520475A (en) * | 2017-03-31 | 2019-11-29 | 太阳控股株式会社 | Hardening resin composition, dry film, solidfied material, electronic component and printed circuit board |
| CN111270412A (en) * | 2020-02-21 | 2020-06-12 | 稳健医疗（黄冈）有限公司 | Preparation method of super-soft moisturizing cotton soft towel and super-soft moisturizing cotton soft towel |
| WO2021036538A1 (en) * | 2019-08-29 | 2021-03-04 | 浙江福斯特新材料研究院有限公司 | Photosensitive resin composition and application thereof |
| CN113126430A (en) * | 2019-12-31 | 2021-07-16 | 太阳油墨（苏州）有限公司 | Solder resist composition and printed wiring board having cured product thereof |
| CN115639723A (en) * | 2022-11-15 | 2023-01-24 | 珠海市能动科技光学产业有限公司 | Photosensitive dry film photoresist for printed circuit board and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012062386A (en) * | 2010-09-15 | 2012-03-29 | Dic Corp | Thermosetting resin composition and interlayer adhesive film for printed wiring board |
| CN103370371A (en) * | 2011-02-01 | 2013-10-23 | Dic株式会社 | Thermosetting resin composition, cured product thereof, and interlayer adhesive film for printed wiring board |
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2016
- 2016-07-21 CN CN201610576040.XA patent/CN106200266B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012062386A (en) * | 2010-09-15 | 2012-03-29 | Dic Corp | Thermosetting resin composition and interlayer adhesive film for printed wiring board |
| CN103370371A (en) * | 2011-02-01 | 2013-10-23 | Dic株式会社 | Thermosetting resin composition, cured product thereof, and interlayer adhesive film for printed wiring board |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110520475A (en) * | 2017-03-31 | 2019-11-29 | 太阳控股株式会社 | Hardening resin composition, dry film, solidfied material, electronic component and printed circuit board |
| CN110520475B (en) * | 2017-03-31 | 2023-02-28 | 太阳控股株式会社 | Curable resin composition, dry film, cured product, electronic component, and printed wiring board |
| WO2021036538A1 (en) * | 2019-08-29 | 2021-03-04 | 浙江福斯特新材料研究院有限公司 | Photosensitive resin composition and application thereof |
| CN113126430A (en) * | 2019-12-31 | 2021-07-16 | 太阳油墨（苏州）有限公司 | Solder resist composition and printed wiring board having cured product thereof |
| CN111270412A (en) * | 2020-02-21 | 2020-06-12 | 稳健医疗（黄冈）有限公司 | Preparation method of super-soft moisturizing cotton soft towel and super-soft moisturizing cotton soft towel |
| CN115639723A (en) * | 2022-11-15 | 2023-01-24 | 珠海市能动科技光学产业有限公司 | Photosensitive dry film photoresist for printed circuit board and preparation method thereof |
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|---|---|
| CN106200266B (en) | 2020-01-24 |
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