CN104423165A - Photosensitive Resin Composition Of Excellent Reliability And Method For Manufacturing Same - Google Patents
Photosensitive Resin Composition Of Excellent Reliability And Method For Manufacturing Same Download PDFInfo
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- CN104423165A CN104423165A CN201410442819.3A CN201410442819A CN104423165A CN 104423165 A CN104423165 A CN 104423165A CN 201410442819 A CN201410442819 A CN 201410442819A CN 104423165 A CN104423165 A CN 104423165A
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- 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
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- 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
- H05K3/0002—Apparatus or processes for manufacturing printed circuits for manufacturing artworks for printed circuits
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- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
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Abstract
The present invention relates to a photosensitive resin composition of an excellent reliability and a method for manufacturing the same, in particular to a photocuring and thermocuring resin composition which can guarantee the important characteristics, such as the PCT resistance, the HAST resistance, the non-electrolytic gold plating resistance, the thermal shock resistance, etc., of a semiconductor package solder resist, and also can form a cured film having the excellent flexibility, a method for manufacturing the same, a dry film, a cured material, and a printed circuit board formed by the cured film forming the solder resist and the like.
Description
Technical field
The present invention relates to photosensitive polymer combination excellent in reliability and preparation method thereof, relate more specifically to guarantee as the PCT patience of semiconductor-sealing-purpose solder resist, HAST patience, without while the key properties such as the gold-plated patience of electrolyzing gold, thermal shock patience, light solidifying/heat solidifying resin composition of the cured film of pliability excellence and preparation method thereof can be formed, and dry film and solidfied material, and form the cured film of solder resist etc. and the printed-wiring board (PWB) that forms by this.
Background technology
The conductor package substrate solder resist of current use needs to have high resolving power, high resulting visualization, high reliability etc.Especially, in order to ensure high reliability, need the patience to high temperature, super-humid conditions, such as, at evaluation pressure cooker test (PCT, Pressure Cooker Test), high accelerated stress testing (HAST, Highly Accelerated Stress Test), thermal cycling test (TC, Thermal Cycle) must alleviate the technology of stress suffered by solder resist when evaluating.In addition, compactization according to semiconductor packages is inclined to, and solder resist also needs to possess stress relieve and pliability.Meanwhile, the technology of the corrosion (Cu migration) that can prevent copper pattern in circuit substrate under high temperature, super-humid conditions is also needed.
Have in traditional solder resist and as stress relieve agent, butadiene modified epoxy be used as elastic body and guarantee the example (No. 10-2012-0022820th, Korean Patent Publication, No. 10-2011-0102193 etc.) of reliability, but there is elastic body itself and participate in thermal response, the thermotolerance caused by glass transition temperature sensitivity may be caused low, and the degree of reaction of overall solder mask composition regulates the shortcoming of difficulty.
In addition, the Photosensitve resin composition that common printed circuit board (PCB) uses uses inorganic filler to improve thermotolerance and reliability, demonstrating thermotolerance and the weatherability of excellence, needing its homodisperse operation to make these inorganic fillers mix with raw material.
Roll crusher (Roll Mill) is used in order to inorganic filler be scattered in raw material time prepared by Photosensitve resin composition in the past, forming according to resin the physical characteristics applied in dispersion step is carried out can be different with degree of scatter, the characteristic of Photosensitve resin composition also can be different thus, therefore qualitative control and process management bring difficulty.
As mentioned above, when utilizing roll crusher to prepare Photosensitve resin composition according to conventional art, need long preparation time and output reduces, cause the problem that production efficiency reduces thus.In addition roll crusher has the product when dispersion step and is exposed to outside and the possibility polluted is high, and the shortcoming that the danger of handling safety accident is high.
Summary of the invention
(1) technical matters that will solve
The present invention is problem in order to solve above-mentioned conventional art and proposes, its object is to, applicable non-reacted elastic body is provided and improves resin dispersion, thus PCT patience, HAST patience can be guaranteed, without while the gold-plated patience of electrolyzing gold, thermal shock patience, light solidifying/heat solidifying resin composition of the cured film of pliability excellence and preparation method thereof can be formed, and dry film and solidfied material, and form the cured film of solder resist etc. and the printed-wiring board (PWB) that forms by this.
In addition, another object of the present invention is to, provide and shorten preparation time and while increase yield, improve stay in grade, also there is the desirable preparation method of the above-mentioned photosensitive polymer combination of cost-saving effect.
(2) technical scheme
In order to achieve the above object, the invention provides comprise (1) high-fire resistance resin containing unsaturated double-bond and carboxyl, (2) Photoepolymerizationinitiater initiater, (3) reactive diluent containing unsaturated double-bond, (4) Thermocurable composition, (5) filler, (6) ion adsorbent and (7) are selected from more than one elastomeric light solidifying/heat solidifying resin composition in core-shell particles type elastic body and silicone elastomer.
According to a further aspect in the invention, the described light solidifying/heat solidifying resin composition of coating is provided and dry and solder resist that is that obtain.
According to a further aspect in the invention, provide and described light solidifying/heat solidifying resin composition is coated on basement membrane and dry and solder resist dry film that is that obtain.
According to a further aspect in the invention, the solidfied material of the patterning of described light solidifying/heat solidifying resin composition is provided.
According to a further aspect in the invention, providing package is containing the printed-wiring board (PWB) of the solidification nitride layer of the patterning of described light solidifying/heat solidifying resin composition.。
According to a further aspect of the invention, there is provided the preparation method of described light solidifying/heat solidifying resin composition, it comprises the steps: (1) mixes 1 raw mixture of the high-fire resistance resin comprised containing unsaturated double-bond and carboxyl, Thermocurable composition and filler with organic solvent is moistening in stirring machine; (2) ball mill (Bead Mill) is utilized the moistening potpourri obtained in step (1) to be carried out dispersion mixing; And drop into 2 raw mixtures comprising Photoepolymerizationinitiater initiater in (3) dispersed mixture of obtaining in described step (2) and be uniformly mixed.
(3) invention effect
Use according to light solidifying/heat solidifying resin composition of the present invention, as semiconductor-sealing-purpose solder resist, PCT patience, HAST patience can be guaranteed, without while the key properties such as the gold-plated patience of electrolyzing gold, thermal shock patience, the cured film of pliability excellence can be formed.
In addition, prepare light solidifying/heat solidifying resin composition according to the preferred method of the present invention, preparation time can be shortened and while increase yield, improve stay in grade, also there is cost-saving effect, therefore highly beneficial.
Embodiment
The following detailed description of the present invention.
1, light solidifying/heat solidifying resin composition
Light solidifying/heat solidifying resin composition of the present invention comprises (1) high-fire resistance resin containing unsaturated double-bond and carboxyl, (2) Photoepolymerizationinitiater initiater, (3) reactive diluent containing unsaturated double-bond, (4) Thermocurable composition, (5) filler, (6) ion adsorbent and (7) are selected from more than one elastic body in core-shell particles type elastic body and silicone elastomer as required composition.
(1) the high-fire resistance resin containing unsaturated double-bond and carboxyl
High-fire resistance resin preferred source containing unsaturated double-bond and carboxyl is from guaranteeing the phenol of high-fire resistance or cresols or their derivant, and preferred softening point is 60 DEG C-120 DEG C, more preferably 70 DEG C-110 DEG C.The softening point of the high-fire resistance resin containing unsaturated double-bond and carboxyl is less than 60 DEG C, then the thermotolerance of composition dies down and causes bad in the thermotolerances such as scolding tin thermotolerance; If more than 120 DEG C, then in resin preparation process, operability is caused to lack due to too high viscosity and yield minimizing.
In described high-fire resistance resin, unsaturated double-bond preferred source is from acrylic or methacrylic acid or their derivant (such as, acrylate or methyl acrylate).And in order to the resulting visualization of excellence and formed and the reactive group of Thermocurable part, described high-fire resistance resin contains carboxyl, and described carboxyl preferred source is from the multi-anhydride such as phthalic anhydride, maleic anhydride.
After the instantiation in the present invention with the high-fire resistance resin of unsaturated double-bond and carboxyl has monocarboxylic acid that the product that the phenolic hydroxyl group of the phenolics of phenol or cresols or their derivant and chloropropylene oxide reaction obtained and methacrylic acid etc. contain unsaturated double-bond to react, the resin that the product of gained and the multi-anhydride such as maleic anhydride, phthalic anhydride react and obtain.
The acid value of described high-fire resistance resin is preferably 40-150mgKOH/g, is more preferably 50-130mgKOH/g.When the acid value of described high-fire resistance resin is less than 40mgKOH/g, the resulting visualization deficiency according to alkaline aqueous solution may be caused; If more than 150mgKOH/g, then can pattern lines be caused by the video picture of alkaline aqueous solution thinning, or during individual cases, exposed portion and unexposed portion be indistinguishably all dissolved by alkaline aqueous solution and peel off, thus being difficult to form normal pattern.
Although the weight-average molecular weight of described high-fire resistance resin is different according to basic resin skeleton, preferably 2,000-150,000, more preferably 5,000-100,000.Weight-average molecular quantity not sufficient 2, when 000, the moisture-proof of the cured film after exposure and reliability deficiency, may cause profile variation and the low resolution such as contraction during video picture.In addition, if weight-average molecular weight is more than 150, when 000, resulting visualization remarkable reduction, storage stability reduces, therefore not preferred.
With the general assembly (TW) of composition for benchmark, the use level of described high-fire resistance resin is 20-60 % by weight, preferred 30-50 % by weight.Composition total weight that the use level of described high-fire resistance resin is not enough 20 % by weight time, cause being coated with film strength and to reduce and not preferred; During more than 60 % by weight, because the operability that rises according to the viscosity of composition reduces and the problem such as operability reduction in coating operation and not preferred.
(2) Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater preferably use be selected from oxime ester class Photoepolymerizationinitiater initiater, α-acetophenones Photoepolymerizationinitiater initiater and acylphosphine oxide class Photoepolymerizationinitiater initiater 1 in more than.The example structure of these Photoepolymerizationinitiater initiaters is as follows.
In described structural formula (1), R
1the naphthenic base that the alkyl that expression hydrogen atom, phenyl, carbon number are 1-20, carbon number are 5-8, carbon number are alkanol or the benzoyl of 2-20; R
2the naphthenic base that the alkyl that expression phenyl, carbon number are 1-20, carbon number are 5-8, carbon number are alkanol or the benzoyl of 2-20.
In described structural formula (2), R
3and R
4represent that carbon number be the alkyl of 1-12 or carbon number is the aralkyl of 7-12 independently of one another; R
5and R
6represent that hydrogen atom, carbon number are alkyl or 2 cyclic alkyl ethers combined of 1-6 independently of one another.
In described structural formula (3), R
7and R
8represent that carbon number is straight chain type or the branch chain type alkyl of 1-10 independently of one another; Cyclohexyl; Cyclopentyl; Carbon number is the aryl of 6-12 or the aryl by the replacement of halogen atom, alkyl or alkoxy.
The compound of the preferred following structural of the representational oxime ester class Photoepolymerizationinitiater initiater (4) shown in described structural formula (1) and structural formula (5).
In described structural formula (5), R
9represent hydrogen atom, silane alcohol base or alkoxy that alkyl that halogen atom, carbon number are 1-12, cyclopentyl, cyclohexyl, phenyl, benzoyl, carbon number are 2-2; R
10the naphthenic base that the alkyl that expression phenyl, carbon number are 1-12, carbon number are 5-8, carbon number are alkanol or the benzoyl of 2-20; R
11the naphthenic base that the alkyl that expression hydrogen atom, phenyl, carbon number are 1-20, carbon number are 5-8, carbon number are alkanol or the benzoyl of 2-20; R
12the naphthenic base that the alkyl that expression phenyl, carbon number are 1-12, carbon number are 5-8, carbon number are alkanol or the benzoyl of 2-20.
The product of the oxime ester class Photoepolymerizationinitiater initiater of described structural formula (1) can exemplify BASF (
) IRGACURE OXE-01 or IRGACURE OXE-02 etc.These oxime ester class Photoepolymerizationinitiater initiaters can be used alone or two or more combinationally uses.
Representational α-acetophenones Photoepolymerizationinitiater initiater shown in described structural formula (2) has 2-methyl isophthalic acid-[(4-methyl thio) phenyl]-2-(4-morpholinyl)-1-propyl alcohol, 2-benzyl-2-(dimethylamino)-4-morpholinyl phenyl propyl ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl)-1-butanone etc.These α-acetophenones Photoepolymerizationinitiater initiater can exemplify IRGACURE 907, the IRGACURE 369 or IRGACURE 379 etc. of BASF.
The representational acylphosphine oxide class Photoepolymerizationinitiater initiater that described structural formula (3) represents has TMDPO, two-2; 4; 6-trimethylbenzoyl-phenyl phosphine oxide, two-2,4,4-trimethyl-phenyl phosphine oxides etc.The product of these acylphosphine oxide class Photoepolymerizationinitiater initiaters can exemplify IRGACURE TPO or IRGACURE819 etc. of BASF.
Relative to described (1) high-fire resistance resin 100 mass parts containing unsaturated double-bond and carboxyl, the use level of described Photoepolymerizationinitiater initiater is preferably 0.01-30 mass parts, more preferably position 0.5-15 mass parts.Relative to described (1) high-fire resistance resin 100 mass parts, when the use level of described Photoepolymerizationinitiater initiater is less than 0.01 mass parts, photocuring is not enough, and the coating characteristics such as film stripping or resistance to chemical reagents reduce, therefore not preferred; If during more than 30 mass parts, the light absorption of film coated surface becomes serious, causes the reduction of deep curability thus, therefore not preferred.
(3) reactive diluent containing unsaturated double-bond
The reactive diluent containing unsaturated double-bond used in the present invention irradiates photocuring by energy of activation, and makes described (1) high-fire resistance resin containing unsaturated double-bond and carboxyl be insoluble to alkaline aqueous solution.In addition, also have and improve solidification film strength by photocuring and improve the effect of thermotolerance and reliability.As long as the compound containing such as 2-6 unsaturated double-bond in reactive diluent skeleton as above just can use, be not particularly limited, but according to the number of unsaturated double-bond, can difference be demonstrated in the pliability of cured film and the reliability of intensity and composition.
The instantiation of the reactive diluent containing unsaturated double-bond is as follows: caprolactone, double pentaerythritol methacrylate, double pentaerythritol C5 methacrylate, tetramethylol methane tetraacrylate, dimethylpropane tetraacrylate, trimethyl propanol triacrylate, tristane dimethyl alcohol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, bipentaerythrite caprolactone etc.
The product of described reactive diluent can exemplify M200, M300, M600 etc. of DPHA, DPCA-30 and miwon company of Japanese chemical drug.
Relative to described (1) high-fire resistance resin 100 mass parts containing unsaturated double-bond and carboxyl, the use level of described reactive diluent is preferably 5-100 mass parts, is more preferably 10-70 mass parts.The use level of reactive diluent relative to described (1) high-fire resistance resin 100 mass parts less than 5 mass parts time, photo-curable reduces, and is difficult to form pattern after energy of activation irradiates according to the video picture of alkaline aqueous solution, therefore not preferred; More than 100 mass parts, then the dissolubility of alkaline aqueous solution to be reduced and not preferred.
(4) Thermocurable composition
Thermocurable composition is used in order to give thermotolerance to light solidifying/heat solidifying resin composition in the present invention.Described Thermocurable composition can use block isocyanide ester compound, benzoxazine resin (
), Thermocurable composition that cyclic carbonate compound, multi-functional epoxy compound, multi-functional oxetane compound etc. are conventional.Described Thermocurable composition preferably uses in molecule has the cyclic ether group of more than 2 or the compound of thioether group.
The example in described molecule with the compound of the cyclic ether group of more than 2 can enumerate in molecule the compound with more than 2 epoxy radicals, that is, multi-functional epoxy compound; The example in described molecule with the compound of more than 2 thioether groups can enumerate multi-functional episulfide.
The example of described multi-functional epoxy compound has the multi-functional epoxy resin of bisphenol-A, the multi-functional epoxy resin of Bisphenol F, the multi-functional epoxy resin of hydrogenated bisphenol A, the multi-functional epoxy resin of bromination, non-halogen multi-functional epoxy resin, the multi-functional epoxy resin of phenolic aldehyde, the multi-functional epoxy resin of biphenyl etc.
The multi-functional epoxy resin product of bisphenol-A has JER828, JER834, JER1001 of japan epoxy resin; Epiclon840, Epiclon850, Epiclon1050 of large Japanese ink chemical industry; Dongdu changes into YD-011, YD-013, YD-127, YD-128 of company; DER317, DER331, DER661, DER664 of Dow Chemical; ESA-011, ESA-014, ESA-115, ESA-128 of BASF AG; AER330, AER331, AER661, AER664 etc. of Asahi Kasei Corporation.
The multi-functional epoxy resin product of bromination has the JERYL903 of japan epoxy resin company; Epiclon152, Epiclon165 of large Japanese ink chemical industry; Dongdu changes into company YDB-400, YDB-500; The DER542 of Dow Chemical; The Araldite8011 etc. of BASF AG.
The multi-functional epoxy resin product of phenol aldehyde type has JER152, JER154 of japan epoxy resin; Epiclon N-730, the Epiclon N-770 of large Japanese ink chemical industry, Epiclon N-865; Dongdu changes into YDCN-701, YDCN-704 of company; DEN431, DEN438 of DOW Chemical; Araldite ECN1235, AralditeECN1273, Araldite ECN1299 of BASF AG; EPPN-201, EOCN-1020, EOCN-104S, RE-306 etc. of Japan's chemical drug.But be not limited to above-mentioned mentioned multi-functional epoxy compound.These multi-functional epoxy resin can be used alone or two or more is used in combination.Preferred use phenol aldehyde type epoxy resin or its potpourri.
The episulfide compound products in described molecule with the cyclic thioether base of more than 2 has the YL7000 of japan epoxy resin; Dongdu changes into the YSLV-120TE etc. of company.And the oxygen atom in the epoxy radicals of phenol aldehyde type epoxy resin can also be used to replace with the episulfide resin of sulphur atom.
Relative to described (1) high-fire resistance resin 1 equivalent containing unsaturated double-bond and carboxyl, the use level of described Thermocurable composition is preferably 0.6-2.5 equivalent, is more preferably 0.8-2.0 equivalent.Relative to described (1) high-fire resistance resin 1 equivalent, when the use level of Thermocurable composition is less than 0.6 equivalent, residual carboxyl in composition film, the reductions such as thermotolerance, alkali resistance and electrical insulating property, therefore not preferred; When its use level is more than 2.5 equivalent, low-molecular-weight cyclic thioether base remains in dry coating, is coated with the reductions such as film strength, therefore not preferred.
(5) filler
Light solidifying/heat solidifying resin composition of the present invention in order to improve the physical strength of its film etc. containing filler.Described filler can use conventional inorganic or organic filler especially preferably to use the inorganic filler such as barium sulphate, nano silicon.In order to obtain white appearance and flame retardancy, metal hydroxides such as metal oxide, aluminium hydroxide such as titanium dioxide etc. can be used as filler.
Relative to described (1) high-fire resistance resin 100 mass parts containing unsaturated double-bond and carboxyl, the use level of described filler is preferably below 200 mass parts, such as, be 0.1-150 mass parts, be more preferably 1-100 mass parts.Relative to described (1) high-fire resistance resin 100 mass parts, the use level of filler is more than 200 mass parts, and the viscosity of composition uprises, thus causes operability shortage, printing reduction or solidfied material deliquescing, therefore not preferred.
(6) ion adsorbent
Light solidifying/heat solidifying resin composition of the present invention rises and tack to not hinder viscosity, and can suppress the generation of the Ion transfer (migration) in cured film under high-temperature humidifying condition for a long time, comprises ion adsorbent.This is considered to may be in acid condition as the character of anion exchanger effect owing to ion adsorbent (such as metal hydroxides).That is, the copper circuit be known as under common high-temperature humidifying condition becomes anode in acid, negative electrode due to the applying of voltage be alkalescence.And can think, because the negative ion such as chloride ion attracted near anode, the metal hydroxides with anion exchange effect can effectively by the reason material halide ion of Ion transfer, especially chlorion is accommodated in structure, can suppress the generation of Ion transfer thus for a long time.
As mentioned above, coordinate ion adsorbent in light solidifying/heat solidifying resin composition, the halide ion such as chloride ions because heat or moisture produce can be trapped, remove and dysgenic foreign ion is produced to electrical insulating property, suppress Ion transfer, thus can electrical insulating property be improved.This ion adsorbent is have excellent ion exchange property and the ion getter agent (getter) of thermotolerance concurrently, the ionic impurity that can exist in trapping system, suppress the various problems caused by ion, mainly add in IC encapsulant or FPC bonding agent etc. and use, to the raising of the reliability of electronic material, there is help.
The kind of the particle impurities that ion adsorbent can trap as required is used alone or two or more combinationally uses.The commercially available prod of ion adsorbent can exemplify IXE-100, IXE-200, IXE-300, IXE-700F, IXE-770D, IXE-800, IXE-6107, IXEPLAS-A1, IXEPLAS-A2, IXEPLAS-A3, IXEPLAS-B1 etc. of East Asia synthesis (TOAGOSEI) company.Preferably use metal hydroxides to use as ion adsorbent in the present invention, and also preferably can carry out the ion adsorbent of bipolarity ion-exchange.More preferably the potpourri of hydrotalcite and basic zirconium phosphate is used.Its form is preferably microgranular, and preferred diameter of particle is less than 1 μm, is more preferably less than 0.5 μm.
Relative to light solidifying/heat solidifying resin composition 100 mass parts, the use level of described ion adsorbent is preferably 0.01-30 mass parts, is more preferably 0.2-30 mass parts, most preferably is 0.5-20 mass parts.If the use level of ion adsorbent is more too much than above-mentioned scope, the viscosity of composition and thixotropy (
) too high, thus there will be the situation that printing reduces or adhesion reduces, therefore not preferred; Very few on the contrary, the inhibition of Ion transfer is very micro-, therefore not preferred.
(7) elastic body of more than a kind in core-shell particles type elastic body and silicone elastomer is selected from
When light solidifying/heat solidifying resin composition of the present invention is not in order to hinder the degree of cure such as glass transition temperature and hardness, improves the pliability of its film, comprising the elastic body of more than a kind of being selected from core-shell particles type elastic body and silicone elastomer.Conventional elastic body polybutadiene-modified epoxy resin or nbr carboxyl terminal (CTBN, CARBOXYLTERMINATED BUTADIENE ACRYLONITRILE) are owing to reducing degree of cure such as glass transition temperature and not preferred.
The elastomeric core of described core-shell particles type (core) is preferably selected from polybutadiene, silicones, styrene butadiene ribber (SBR) and their potpourri, shell (shell) can use the polymkeric substance with core with intermiscibility, the epoxy resin such as preferred bisphenol A epoxide resin, bisphenol F epoxy resin.
Described core-shell particles type elastomer product can exemplify MX-153, MX-257, MX-960, MX-170, MX-136, MX-965, MX-217, MX-416, MX-551 etc. of KANEKA.These core-shell particles type elastomer products can be used alone or two or more combinationally uses.
Described silicone elastomer preferably uses particle diameter to be the microfine subtype epoxy functional silicone elastomer of 1 μm-10 μm.The product of this silicone elastomer can exemplify EP-5500, EP-5518, EP-2600, EP-2601, EP-2720 etc. of eastern beautiful DOW CORNING (Dow Corning Toray).These microfine subtype silicone elastomer products can be used alone or two or more combinationally uses.
Described core-shell particles type elastic body or silicone elastomer preferably use and disperse in the epoxy with high concentration.Epoxy resin for being disperseed by these elastic bodys can be used singly or two or more kinds in combination bisphenol A epoxide resin, bisphenol F epoxy resin, phenol novolak type epoxy, diglycidyl ammonia type epoxy resin, alicyclic type epoxy resin.Now, relative to epoxy resin 100 mass parts, the elastomeric content of dispersion is preferably 10-40 mass parts, is more preferably 20-40 mass parts.Relative to epoxy resin 100 mass parts, dispersion elastomeric containing quantity not sufficient 10 mass parts time, the flexible raising of cured film can not be obtained; During more than 40 mass parts, lack dispersing characteristic and remain as impurity in cured film, cause bad order (core-shell particles type elastic body) or reduce development latitude (DEVELOPMENT MARGIN), thus in PCB operational sequence, causing bad generation (silicone elastomer).
The use level of described core-shell particles type elastic body or silicone elastomer is preferably the 1-20 % by weight of composition total weight, is more preferably 5-15 % by weight.Composition total weight that described elastomeric use level is not enough 1 % by weight time, the pliability of cured film is not enough and cause by the painting membrane damage that causes etc. such as impacting bad, therefore not preferred; During more than 20 % by weight, bad order is there is due to the non-break-up shot gonosome in the surface of the cured film of film, and after drying process, be clamminess (tacky) (the core-shell particles type elastic body) on film surface is caused due to the epoxy resin be suitable for, or it is not video picture edge reduces and bad (silicone elastomer) occurs in PCB operational sequence, therefore preferred.
(8) colorant
Light solidifying/heat solidifying resin composition of the present invention preferably also contains toner except mentioned component.These colorants can use pigment, dyestuff, pigment or toner etc., to reduce and on preferred not halogen-containing during the affecting of human body from the viewpoint of carrying capacity of environment.
In the present invention, spendable yellow colorants has azo, bisdiazo class, azo condensation class, benzimidazole (benzoimidazol), isoindoline ketone, Anthraquinones etc., and instantiation is as follows:
Azo: pigment yellow (Pigment Yellow) 001,002,003,004,005,006,009,010,012,061,062,065,073,074,075,097,100,104,105,111,116,167,169
Bisdiazo class: pigment yellow 012,013,014,016,017,055,063,081,083,087,126,127,152,170,172,174,176,188,198
Azo condensation class: pigment yellow 093,094,095,128,155,166,180
Benzimidazole: pigment Yellow 12 0,151,154,156,175,181
Isoindolinone: pigment yellow 109,110,139,179,185
Anthraquinones: solvent yellow (Solvent Yellow) 163, pigment yellow 024,108,147,193,199,222
In the present invention, spendable blue colorant has phthalocyanines, Anthraquinones etc., and instantiation is as follows:
Pigment blue 15: 00,15:01,15:02,15:03,15:04,15:06,16:00,16:01,60:00
The substituted or unsubstituted phthalocyanine-like compound of metal can also be used apart from the above.
The use level of described colorant is had no particular limits, but relative to described (1) high-fire resistance resin 100 mass parts containing unsaturated double-bond and carboxyl, is preferably below 10 mass parts, is more preferably 0.1-0.5 mass parts.
Light solidifying/heat solidifying resin composition of the present invention, except mentioned component, can also comprise normally used composition (such as, defoamer) in curable resin composition as required.In addition, in order to suitable adjusting viscosity during composition coating, organic solvent can also be comprised.
The using method of light solidifying/heat solidifying resin composition of the present invention is such as follows:
First, after composition organic solvent is adjusted to the viscosity of applicable painting method, applied on base material by the method such as dip-coating, flow coat, roller coat, rod painting, serigraphy, curtain showering, the organic solvent volatile dry will contained in composition at the temperature of about 60-120 DEG C.Then by contact or contactless and form the photomask of pattern, optionally with the directly exposing patterns such as energy of activation exposure or the direct exposure machine of laser, unexposed portion utilizes alkaline aqueous solution (aqueous sodium carbonate of 0.1-3.0%) video picture to form pattern.Composition of the present invention contains Thermocurable composition, when heating at the temperature of 130-160 DEG C, there is in the carboxyl of the described high-fire resistance resin containing unsaturated double-bond and carboxyl and molecule the Thermocurable composition reaction of the cyclic thioether base of more than 2, thus form the cured coating film of the excellences such as thermotolerance, resistance to chemical reagents, resistance to hydroscopicity, adherence, electrology characteristic.
Described base material can use the printed-wiring board (PWB) that is pre-formed circuit or flexibility printed circuit board, impregnation phenol resin glass fibre, containing the glass fibre of epoxy resin dipping, the glass fibre, copper-clad laminate, polyamide film, PET film, glass substrate, ceramic substrate, wafer substrate etc. of impregnation bismaleimide-triazine resin.
The solvent volatile dry implemented after light solidifying/heat solidifying resin composition coating of the present invention can use heated air circulation type drying oven, infrared drying stove, electric hot plate etc.
Energy of activation exposure is implemented to applying the film obtained after light solidifying/heat solidifying resin composition of the present invention carries out volatile dry.Film is solidified by the exposure of energy of activation.The exposure machine that energy of activation uses in irradiating can be direct exposure device (such as, directly being used the laser direct imaging device swashing light forming pattern by computer according to cad data), carry the direct exposure device of the exposure machine of metal halide lamp, the UV-lamp such as exposure machine, use (surpassing) high-pressure mercury-vapor lamp of lift-launch (surpassing) high-pressure mercury-vapor lamp.The scope of energy of activation is use laser and ultraviolet light in the scope that maximum wavelength is 340-420nm, and gas laser or solid state laser all can use.
Developing method can use dip-coating, showering, spraying, brushing etc., and imaging liquid can use the alkaline aqueous solution of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammoniacal liquor, amine etc.
Light solidifying/heat solidifying resin composition of the present invention, can also and the dry film form use with solder mask layer that obtain dry with application composition on the films such as polyethylene terephthalate except with except the aqueous method being directly coated to base material.The instantiation that light solidifying/heat solidifying resin composition of the present invention is used as dry film is as follows:
Dry film is basement membrane and solder mask layer, and the structure of the strippable diaphragm used as required lamination successively.Solder mask layer is the layer that can apply drying by the light solidifying/heat solidifying resin composition of alkaline aqueous solution video picture on basement membrane or diaphragm and obtain.Basement membrane is formed lamination diaphragm after solder mask layer, or on diaphragm, forms laminated base film after solder mask layer, just can obtain dry film.Basement membrane uses the thermoplastic films such as the mylar of 1-200 μm of thickness range.Solder mask layer is formed with dry after the thickness even spread of 5-200 μm on basement membrane or diaphragm by being utilized by light solidifying/heat solidifying resin composition knife type coater, lip type coating machine (LIP COATER), unfilled corner to take turns coating machine, film coating machine etc.When using dry film to make diaphragm on a printed-wiring board, peel off diaphragm, then make the base material of formation solder mask layer and circuit superpose, use film laminator to make them mutually paste, then on base material, form solder mask layer.According to the method described above to formed solder resist carries out exposure process, video picture operation, be heating and curing operation, then can obtain cured coating film.As long as basement membrane with exposure before or independently peel off after exposing.
Thus according to a further aspect in the invention, provide by dry for the coating of described light solidifying/heat solidifying resin composition and obtain solder resist, by described light solidifying/heat solidifying resin composition in coating on base films drying the solidfied material of the solder resist dry film obtained, described light solidifying/heat solidifying resin composition patterning and comprise the printed-wiring board (PWB) of solidification nitride layer of described light solidifying/heat solidifying resin composition patterning.
2, the preparation method of light solidifying/heat solidifying resin composition
The preparation method of light solidifying/heat solidifying resin composition of the present invention can be prepared according to common preparation method.Such as, can by dropping into above-mentioned raw materials composition in the reactor with stirring apparatus, after being uniformly mixed, prepared by the method using 3 roll crushers (3 Roll Mill) to disperse.Now, material composition can all drop into simultaneously, also can drop into successively.According to a specific example of the present invention, can first under the low speed (such as except the composition of elastic body and filler, after 500rpm) being uniformly mixed, elastic body and filler is dropped into further at this, at high speeds (such as, after 700rpm) being uniformly mixed, with 3 roll crusher dispersions at the end of stirring.After having disperseed, confirm granular level, when granularity is more than 10 μm, re-start dispersion.
Preferably, prepare light solidifying/heat solidifying resin composition of the present invention by the following method, it comprises the following steps: 1 raw mixture of the high-fire resistance resin comprised containing unsaturated double-bond and carboxyl, Thermocurable composition and filler mixes with organic solvent is moistening in stirring machine by (1); (2) ball mill (Bead Mill) is utilized the moistening potpourri obtained in step (1) to be carried out dispersion mixing; And drop into 2 raw mixtures comprising Photoepolymerizationinitiater initiater in (3) dispersed mixture of obtaining in described step (2) and be uniformly mixed.
In the preparation method of described light solidifying/heat solidifying resin composition, reactive diluent, ion adsorbent, elastic body and as colorants such as pigment etc. arbitrarily composition can be contained in as described in 1 feedstock composition, in 2 feedstock compositions or they both, be preferably contained in 1 feedstock composition.According to of the present invention one preferred concrete example, except all material compositions of Photoepolymerizationinitiater initiater all can be contained in 1 raw mixture.
In the preparation method of described light solidifying/heat solidifying resin composition, spendable ball mill decollator is rotatably connecting inner container in external container, makes the filler put between external container and internal container be rotated by internal container along with moistening potpourri and disperse.In the process, roll into a ball the filler granulated and be dispersed into homogeneous size.
In described step (1), the moistening mixing of the filler of stirring machine (such as, homogeneous stirring machine) is utilized preferably to implement more than 20 minutes (such as, 20 minutes-4 hours).Moistening incorporation time is less than 20 minutes, then particle is uneven, and can remain huge particle.The viscosity of the moistening potpourri obtained in described step (1) is preferably less than 10,000cPs (10rpm ,@25 DEG C).The viscosity of moistening potpourri is greater than this, in subsequent step (2), be then difficult to the smooth circulation of the potpourri realized in ball mill dispersion machine, filler may be produced not disperse and with original particle shape Problems existing, jitter time also can be caused to postpone and productivity reduction, therefore not preferred.
In described step (2), pearl (bead) preferable particle size used during ball mill dispersion is 0.5mm-2mm, the more preferably from about zirconium oxide bead of 1mm.In described step (2), during ball mill dispersion, the rotational speed of rotor is preferably 5Hz (400rpm)-20Hz (1600rpm), is more preferably 10Hz (800rpm)-15Hz (1200rpm).When the rotational speed of rotor is less than 5Hz, may has and not disperse and with the original state Problems existing of particle; If more than 20Hz, even if filler dispersion, also can temperature be made due to the friction of pearl to increase, thus cause resin characteristics to change.In addition, ball mill jitter time is preferably 20 minutes-2 hours, more preferably 50-80 minute.When ball mill jitter time was less than 20 minutes, may has and not disperse and with the original state Problems existing of particle; Constantly little more than 2, have the problem of solvent volatilization problems and resin properties change, thus cause productivity to reduce.
In described step (3), be uniformly mixed and preferably carry out more than 20 minutes (such as, 20 minutes-3 hours).If mixing time is shorter than above-mentioned scope, then Photoepolymerizationinitiater initiater cannot fully be dissolved in resin, and adjuvant and raw material dispersion cannot Homogeneous phase mixing, therefore the function reductions of adjuvant.If mixing time is long can reduce productivity.The final Photosensitve resin composition obtained after described step (3) preferably has 20,000-25, the viscosity of 000cPs (10rpm ,@25 DEG C) scope.
Below, by embodiment and comparative example, the present invention is described in more detail.But scope of the present invention is not limited thereto.
Embodiment
Embodiment 1
High-fire resistance resin (the SR90-B3T4 containing unsaturated double-bond and carboxyl is dropped in the reactor with stirring apparatus, solid constituent=65%, acid number=57mgKOH/g, KCC) 400g, bisphenol A-type Thermocurable composition (YD-012, bisphenol A epoxide resin, softening point=80 DEG C, equivalent=650, national capital chemistry) 100g, stirs 10 minutes with 500rpm.Reactive diluent dipentaerythritol acrylate (DPHA) (Japanese chemical drug) 10g containing unsaturated double-bond and Photoepolymerizationinitiater initiater (Irgacure 369 is dropped into after stirring, oxime ester class Photoepolymerizationinitiater initiater, BASF) after 30g, drop into yellow colorants (pigment yellow 147 successively, BASF) 2g, blue colorant (pigment blue 1 6:00, BASF) 6g and ion adsorbent (IXEPLAS, the potpourri of hydrotalcite and basic zirconium phosphate, East Asia is synthesized) 5g, stirs 10 minutes with 500rpm.After stirring completes, drop into core-shell particles type elastic body (MX-170, core: silicones, core content: 25%, dispersion medium: bisphenol A epoxide resin, KANEKA) 100g, 10 minutes are stirred, then by filler (B-30, the surface-treated barium sulphate of 250g with 500rpm, D (50)=0.3 μm, SAKAI) drop into 3-6 gradation.After input completes, with 700rpm high-speed stirred 20 minutes.Now, the heating produced according to high-speed stirred, controls internal temperature and is no more than 45 DEG C.Use 3 roll crusher dispersion after stirring completes.After having disperseed, confirm the level of granularity, when granularity is more than 10 μm, repeating dispersion.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 75%, and viscosity is 13000mPa.s.
Embodiment 2
Light solidifying/heat solidifying resin composition is prepared according to the method identical with embodiment 1, unlike using core-shell particles type elastic body (MX-170, core: silicones, core content: 25% as elastic body, dispersion medium: bisphenol A epoxide resin, KANEKA) 50g.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 73%, and viscosity is 12500mPa.s.
Embodiment 3
Light solidifying/heat solidifying resin composition is prepared according to the method identical with embodiment 1, unlike using core-shell particles type elastic body (MX-136, core: polybutadiene, core content: 25% as elastic body, dispersion medium: bisphenol F epoxy resin, KANEKA) 100g.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 75%, and viscosity is 12500mPa.s.
Embodiment 4
Prepare light solidifying/heat solidifying resin composition according to the method identical with embodiment 1, use silicone elastomer (EP-2600, eastern beautiful DOW CORNING) 100g unlike as elastic body.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 73%, and viscosity is 13000mPa.s.
Embodiment 5
Prepare light solidifying/heat solidifying resin composition according to the method identical with embodiment 1, use silicone elastomer (EP-2600, eastern beautiful DOW CORNING) 50g unlike as elastic body.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 73%, and viscosity is 12500mPa.s.
Embodiment 6
Light solidifying/heat solidifying resin composition is prepared according to the method identical with embodiment 1, silicone elastomer (EP-2601 is used unlike as elastic body, (the Epoxy Functional) of epoxy resin effect, eastern beautiful DOW CORNING) 100g.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 75%, and viscosity is 12500mPa.s.
Comparative example 1
Light solidifying/heat solidifying resin composition is prepared, unlike not using elastic body according to the method identical with embodiment 1.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 74%, and viscosity is 15000mPa.s.
Comparative example 2
Light solidifying/heat solidifying resin composition is prepared, unlike employing epoxidized polybutadiene (EPOLEAD PB-3600, molecular weight: 5900, acid number: less than 1, DAICEL) 50g as elastic body according to the method identical with embodiment 1.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 75%, and viscosity is 13500mPa.s.
Comparative example 3
Light solidifying/heat solidifying resin composition is prepared, unlike employing butyronitrile (CTBN 1300X8, acrylonitrile content: 17%, CVC) 50g as elastic body according to the method identical with embodiment 1.The solid constituent of the light solidifying/heat solidifying resin composition of preparation is 75%, and viscosity is 13500mPa.s.
To light solidifying/heat solidifying resin composition prepared by above-described embodiment and comparative example, based on standard specification JPCA standard, Dynamic Mechanical Analysis (DMA, DYNAMICMECHANICAL ANALYSIS) is used to measure glass transition temperature and modulus.In addition, the dispersion degree of the light solidifying/heat solidifying resin composition of preparation is less than 10 μm by the result that grind meter is evaluated.The mixing ratio of embodiment and comparative example and glass transition temperature and modulus measurements result are shown in following table 1.
Table 1 (use level unit: g)
Can know from the result of above-mentioned table 1, relative to the composition of the embodiment 4-6 of the composition and use silicone elastomer that use the elastomeric embodiment 1-3 of core-shell particles type, although do not use the glass transition temperature of elastomeric comparative example 1 equal, modulus is significantly high.During modulus height like this, tunicle becomes frangible, therefore occurs by membrane damage etc. bad in manufacturing process.In addition, use the comparative example 2 and 3 of conventional elastomers equal relative to embodiment modulus, but glass transition temperature is low about about 10 DEG C.This low glass transition temperature can hinder degree of cure and cause reliability low.
In addition, following evaluating characteristics is carried out to the composition of embodiment and comparative example.
Surface treatment is carried out to circuit pattern substrate and through washing and drying process after, be coated with before substrate by the light solidifying/heat solidifying resin composition of serigraphy by embodiment and comparative example, dried film thickness is made to reach about 25 μm, drying 30 minutes at 80 DEG C.In order to exposure process employs the exposure device of lift-launch high-pressure mercury-vapor lamp as exposure sources after dry, sensitivity evaluation uses 41 sections of staged metraster (manufacturer: Hitachi changes into).Use this device to carry out exposure process, use the aqueous sodium carbonate of 1% to carry out video picture in 90 seconds at 30 DEG C.Optimum exposure condition is selected by the sensitivity results (sensitivity=6 section) of staged metraster.
Development latitude is evaluated
By serigraphy, composition is coated on substrate, dry at 80 DEG C, start after 30 minutes to 100 minutes, with every 10 minutes for interval taking-up at room temperature cools.Then, use the aqueous sodium carbonate of 1% to carry out video picture in 90 seconds at 30 DEG C, now there is no maximum permission drying time of remaining residue as development latitude.
Tackiness (TACKY) evaluates
By serigraphy, composition is coated on substrate, 80 DEG C of dryings 30 minutes, then at room temperature cools.Press against the pattern mask film 1 minute of polyester material on the substrate, and whether be clamminess on film when peeling off pattern mask film according to following standard evaluation.
Zero: during stripping film without transcribing (
)
△: during stripping film, existence part is transcribed, needs small dynamics during stripping
X: exist during stripping film and transcribe, need dynamics during stripping
By serigraphy, composition is coated on substrate, 80 DEG C of dryings 30 minutes, then at room temperature cools.Press against pattern mask film on the substrate, by carrying the exposure machine of high temperature mercury vapor lamp with after 600mJ/cm2 exposure, use the aqueous sodium carbonate of 1% to carry out video picture in 90 seconds at 30 DEG C, then washing forms pattern.Measure formed pattern size as resolution (
).
Scolding tin thermotolerance
By serigraphy, composition is coated on substrate, 80 DEG C of dryings 30 minutes, then at room temperature cools.After this substrate is exposed with 600mJ/cm2 by the exposure machine carrying high-pressure mercury-vapor lamp, further with 1100mJ/cm
2exposure.After this at 150 DEG C, heating completes final solidification in 60 minutes.Thus obtained substrate is immersed in 10 seconds in the solder bath being set to 260 DEG C.Repeat above-mentioned dipping process 3 times.Now by the profile variation of visual inspection solder mask layer and whether to peel off and according to following standard evaluation.
Zero: profile variation and peel off equal nothing
△: have fine profile variation and fine stripping
X: have serious profile variation and film to peel off
Pliability
By serigraphy, composition is coated on substrate, 80 DEG C of dryings 30 minutes, then at room temperature cools.After this substrate is exposed with 600mJ/cm2 by the exposure machine carrying high-pressure mercury-vapor lamp, further with 1100mJ/cm
2exposure.After this at 150 DEG C, heating completes final solidification in 60 minutes.The substrate obtained thus repeatedly carries out 3 folding and expansion under 90 °.Now by the profile variation of visual inspection solder mask layer and whether to peel off and according to following standard evaluation.
Zero: profile variation and peel off equal nothing
△: have fine profile variation and fine stripping
X: have serious profile variation and film to peel off
PCT
The substrate prepared by described operation uses PCT equipment (manufacturer: Yi Lai science and technology (ireatech), trade name: PCT-80), in temperature 121 DEG C, humidity 100%, pressure 2 air pressure, process under the condition of 168 hours time, according to the state of following standard evaluation film.
Zero: the equal nothing of profile variation, variable color and stripping
△: have fine profile variation, part variable color and stripping
X: have serious profile variation, cross color variable and stripping
HAST
Use the BT substrate forming electrode (linear interval (line space): 30 μm), based on above-mentioned operation, prepare evaluation substrate.This substrate applies 5V voltage under the hot and humid condition of temperature 130 DEG C, humidity 85%, carries out HAST evaluation through 168 hours.After 168 hours, by insulating resistance value according to following standard evaluation.
Zero: 108 more than Ω
△:106-108Ω
Below X:106 Ω
Evaluating characteristics result is shown in following table 2.
Table 2 (evaluating characteristics result: aqueous type)
The preparation of dry film and evaluation
After using methyl ethyl ketone to dilute respectively the light solidifying/heat solidifying resin composition of embodiment and comparative example, be applied in the PET film of polyester material, within 30 minutes, form the solder mask layer of thickness 25 μm 80 DEG C of dryings.Dry film prepared by lamination diaphragm thereon.Peel off diaphragm from the dry film of above-mentioned preparation, thin layer is pressed on substrate, after then being exposed with 600mJ/cm2 by the exposure machine carrying high-pressure mercury-vapor lamp according to above-mentioned operation, further with 1100mJ/cm
2exposure.After this at 150 DEG C, heating completes final solidification in 60 minutes.The substrate obtained thus is carried out to the evaluation of above-mentioned characteristic project, and show the result in following table 3.
Table 3 (evaluating characteristics result: dry-film type)
Can know from the result of described table 2 and table 3, light solidifying/heat solidifying resin composition of the present invention does not hinder the elastic body of the degree of cure such as glass transition temperature by using, improve PCT patience and HAST patience and pliability, while result improves the reliability such as PCT patience and HAST patience, improve in manufacturing process bad by membrane damage etc.Namely, light solidifying/heat solidifying resin composition of the present invention has possessed beyond PCT patience required in semiconductor-sealing-purpose solder resist, thermotolerance, HAST patience, also have pliability concurrently further, be therefore very suitable for the solder resist and the thin-film package solder resist that require high reliability.
In addition, in order to compare the productivity of the resin combination preparation method using ball mill and the preparation method using 3 roll crushers, following operation has been carried out.
The order of ball mill operation and required time
(1) 1 time raw mixture (high-fire resistance resin, Thermocurable composition, filler and solvent) is dropped into and moistening mixing: 4 hours
(2) ball mill dispersion: 2 hours
(3) 2 times raw mixture (surplus stock composition is whole) is dropped into and is uniformly mixed: 3 hours
(4) mix after the additional input of correction solvent: 1 hour
-total preparation time (taking 400kg as benchmark): 10 hours
-ultimate yield: 85%
-unit interval productivity: 34.0 kg/hr
The order of 3 roll crusher operations and required time
(1) material composition all drops into and moistening mixing: 4 hours
(2) 3 roll crushers dispersion (implementing 2 times (Pass), 1 time=400kg/4 hour): 8 hours
(3) mix after the additional input of correction solvent: 1 hour
-total preparation time (taking 400kg as benchmark): 13 hours
-ultimate yield: 85%
-unit interval productivity: 26.1kg/hr
In addition, for the light solidifying/heat solidifying resin composition using the method for ball mill and use the method for 3 roll crushers to prepare respectively, according to method evaluation development latitude same as described above, sensitivity, resolution, whether be clamminess, scolding tin thermotolerance and PCT characteristic, and to show the result in following table 4.
Table 4
| Assessment item | Ball mill operation | 3 roll crushers |
| Development latitude | 90 minutes | 90 minutes |
| Sensitivity | 6 sections | 6 sections |
| Resolution (μm) | 78 | 79 |
| Whether be clamminess | ○ | ○ |
| Scolding tin thermotolerance | ○ | ○ |
| PCT | ○ | ○ |
Can know from the result of upper table 4, when using ball mill to prepare Photosensitve resin composition of the present invention, the composition with the composition similar characteristics using the method for 3 roll crushers to prepare can be obtained, can preparation time be shortened simultaneously, significantly mention productivity.
Claims (17)
1. a light solidifying/heat solidifying resin composition, it is characterized in that, the high-fire resistance resin that said composition comprises (1) containing unsaturated double-bond and carboxyl, (2) Photoepolymerizationinitiater initiater, (3) reactive diluent containing unsaturated double-bond, (4) Thermocurable composition, (5) filler, (6) ion adsorbent and (7) are selected from more than one the elastic body in core-shell particles type elastic body and silicone elastomer.
2. light solidifying/heat solidifying resin composition according to claim 1, it is characterized in that, described containing in the high-fire resistance resin of unsaturated double-bond and carboxyl, unsaturated double-bond is derived from acrylic or methacrylic acid or their derivant, and described carboxyl is derived from multi-anhydride.
3. light solidifying/heat solidifying resin composition according to claim 1; it is characterized in that, described Photoepolymerizationinitiater initiater is be selected from more than a kind in oxime ester class Photoepolymerizationinitiater initiater, α-acetophenones Photoepolymerizationinitiater initiater and acylphosphine oxide class Photoepolymerizationinitiater initiater.
4. light solidifying/heat solidifying resin composition according to claim 1, is characterized in that, the described reactive diluent containing unsaturated double-bond contains 2-6 unsaturated double-bond.
5. light solidifying/heat solidifying resin composition according to claim 1, is characterized in that, described Thermocurable composition is have the cyclic ether group of more than 2 or the compound of thioether group in molecule.
6. light solidifying/heat solidifying resin composition according to claim 1, is characterized in that, described ion adsorbent is the potpourri of hydrotalcite and basic zirconium phosphate.
7. light solidifying/heat solidifying resin composition according to claim 1, is characterized in that, the elastomeric core of described core-shell particles type is selected from polybutadiene, silicones, styrene butadiene ribber and their potpourri; Shell is epoxy resin.
8. light solidifying/heat solidifying resin composition according to claim 1, it, be characterised in that, described silicone elastomer to be particle diameter the be microfine subtype epoxy functional silicone elastomer of 1-10 μm.
9. light solidifying/heat solidifying resin composition according to claim 1, is characterized in that, it is also containing colorant.
10. the solder resist that the light solidifying/heat solidifying resin composition in coating claim 1-9 described in any one is also dry and obtain.
Light solidifying/heat solidifying resin composition described in any one in claim 1-9 to be coated on basement membrane and dry and solder resist dry film that is that obtain by 11..
The solidfied material of the patterning of the light solidifying/heat solidifying resin composition in 12. claim 1-9 described in any one.
13. printed-wiring board (PWB)s comprising the solidification nitride layer of the patterning of the light solidifying/heat solidifying resin composition in claim 1-9 described in any one.
The preparation method of the light solidifying/heat solidifying resin composition in 14. 1 kinds of claim 1-9 described in any one, it is characterized in that, described preparation method comprises the steps: that 1 raw mixture of the high-fire resistance resin comprised containing unsaturated double-bond and carboxyl, Thermocurable composition and filler mixes with organic solvent is moistening in stirring machine by (1); (2) ball mill is utilized the moistening potpourri obtained in step (1) to be carried out dispersion mixing; And drop into 2 raw mixtures comprising Photoepolymerizationinitiater initiater in (3) dispersed mixture of obtaining in described step (2) and be uniformly mixed.
The preparation method of 15. light solidifying/heat solidifying resin compositions according to claim 14, is characterized in that, the moistening mixing enforcement more than 20 minutes of described step (1).
The preparation method of 16. light solidifying/heat solidifying resin compositions according to claim 14, is characterized in that, the bowl mill dispersion enforcement of described step (2) 20 minutes to 2 hours.
The preparation method of 17. light solidifying/heat solidifying resin compositions according to claim 14, is characterized in that, described step (3) be uniformly mixed enforcement more than 20 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020130104675A KR101562964B1 (en) | 2013-09-02 | 2013-09-02 | Photosensitive resin composition with good reliability and method for preparing the same |
| KR10-2013-0104675 | 2013-09-02 |
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| CN104423165A true CN104423165A (en) | 2015-03-18 |
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| JP (1) | JP6092165B2 (en) |
| KR (1) | KR101562964B1 (en) |
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| JP7363182B2 (en) * | 2019-08-09 | 2023-10-18 | 味の素株式会社 | Photosensitive resin compositions, cured products of photosensitive resin compositions, resin sheets, printed wiring boards, and semiconductor devices |
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| CN108137791A (en) * | 2015-09-30 | 2018-06-08 | 太阳油墨制造株式会社 | Hardening resin composition, dry film and use its printed circuit board |
| US10795259B2 (en) | 2016-02-05 | 2020-10-06 | Lg Chem, Ltd. | Photo-curable and heat-curable resin composition and dry film solder resist |
| CN107226983A (en) * | 2016-03-25 | 2017-10-03 | 鹏鼎控股(深圳)股份有限公司 | The film and circuit board of resin combination and the application resin combination |
| CN108884180A (en) * | 2016-03-31 | 2018-11-23 | 电化株式会社 | Composition |
| CN108884180B (en) * | 2016-03-31 | 2021-06-29 | 电化株式会社 | Composition comprising a metal oxide and a metal oxide |
| CN109212899A (en) * | 2017-06-30 | 2019-01-15 | 住友化学株式会社 | Colored curable resin composition, colour filter and display device |
| CN109212899B (en) * | 2017-06-30 | 2024-06-07 | 住友化学株式会社 | Colored curable resin composition, color filter and display device |
| WO2019037491A1 (en) * | 2017-08-25 | 2019-02-28 | 京东方科技集团股份有限公司 | Preparation methods for photoresist composition, metal pattern and array substrate |
| US11592742B2 (en) | 2017-08-25 | 2023-02-28 | Hefei Xinsheng Optoelectronics Technology Co., Ltd. | Photoresist composition, its manufacturing method, and manufacturing methods of metal pattern and array substrate |
| CN110412831A (en) * | 2018-04-27 | 2019-11-05 | 株式会社田村制作所 | Photosensitive polymer combination |
| CN112638028A (en) * | 2020-12-02 | 2021-04-09 | 昆山国显光电有限公司 | Antioxidant mixture, circuit board and display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201523148A (en) | 2015-06-16 |
| JP2015049517A (en) | 2015-03-16 |
| KR20150027381A (en) | 2015-03-12 |
| TWI531861B (en) | 2016-05-01 |
| KR101562964B1 (en) | 2015-10-26 |
| JP6092165B2 (en) | 2017-03-08 |
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