CN110300493A - Dry film, solidfied material and electronic component - Google Patents

Dry film, solidfied material and electronic component Download PDF

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Publication number
CN110300493A
CN110300493A CN201910098843.2A CN201910098843A CN110300493A CN 110300493 A CN110300493 A CN 110300493A CN 201910098843 A CN201910098843 A CN 201910098843A CN 110300493 A CN110300493 A CN 110300493A
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CN
China
Prior art keywords
resin
resin layer
inorganic filler
dry film
film
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Pending
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CN201910098843.2A
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Chinese (zh)
Inventor
远藤新
青山良朋
中居弘进
管众
播磨英司
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Publication of CN110300493A publication Critical patent/CN110300493A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The present invention relates to dry film, solidfied material and electronic components.There is provided: the adaptation of resin layer and protective film is good and resin layer contained in inorganic filler the few dry film and the dry film of sedimentation resin layer solidfied material and electronic component with the solidfied material.Dry film etc., the dry film are characterized in that having: carrier film, resin layer and protective film, and aforementioned protective film is biaxial stretch-formed polypropylene film, and aforementioned resin layer includes: inorganic filler；The macromolecule resin that glass transition point is 20 DEG C or less and weight average molecular weight is 30,000 or more；And epoxy resin, aforementioned resin layer include that at least wantonly a kind in semisolid epoxy resin and Cristalline epoxy resin is used as aforementioned epoxy resins.

Description

Dry film, solidfied material and electronic component
Technical field
The present invention relates to dry film, solidfied material and electronic components.
Background technique
In the past, it was protected as solder mask, interlayer insulating film being arranged on printed circuit board used in electronic equipment etc. etc. One of film, formation means of insulating layer utilize dry film (laminate film) (such as patent document 1).Dry film has and will have expectation Characteristic resin combination be coated in carrier film after by resin layer obtained from drying process, usually to be further laminated Have and circulates on the market for protecting with the state of the protective film in the face that carrier film is opposite side.The resin layer of dry film is attached (hereinafter also referred to " being laminated ") implements patterning, curing process after substrate, it is possible thereby to manufacture above-mentioned like that with protection The printed circuit board of film, insulating layer.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-010179 bulletin
Summary of the invention
Problems to be solved by the invention
When protective film being laminated in the manufacturing process of dry film, such as the compounding amount of the inorganic filler contained in resin layer is more The case where etc., when the viscosity of resin layer surface is lower, there are problems that being deteriorated with the adaptation of said protection film.
In addition, in the case that the compounding amount of inorganic filler contained in resin layer is more, when forming resin layer, by resin combination Object dilution carries out viscosity adjustment so that when with easy coatings such as solvents, and there are inorganic fillers contained in resin combination to become to hold Easily settled, dry film quality becomes unstable problem.
Therefore, contained in and resin layer good the object of the present invention is to provide: the adaptation of resin layer and protective film Inorganic filler the few dry film of sedimentation；With the solidfied material of the resin layer of the dry film；With the electronic component with the solidfied material.
The solution to the problem
Inventors etc. consider thin by using the low polyethylene of glass transition point (PE) first in face of realizing above-mentioned purpose Film is as protective film, so as to improve the adaptation of resin layer and protective film.Although being protected however, adaptation is improved When the cooling of film layer poststack, it was found that the new of constricted fold can be led to the problem of in resin layer surface by having.
On the other hand, high for glass transition point as polyethylene terephthalate (PET) and flexibility is low Protective film, it is difficult to adaptation is well laminated.
Therefore, inventor etc. be conceived to cooling meat it is few, i.e., glass transition temperature be higher than it is polyethylene (PE) and soft The good biaxial stretch-formed polypropylene film (OPP) of property, uses above-mentioned biaxial stretch-formed polypropylene film (OPP) to go forward side by side as protective film One step is studied.
In the studies above, for biaxial stretch-formed polypropylene film (OPP), although implementing embossing processing, sided corona treatment, It is still insufficient with the adaptation of resin layer.Although also can not eliminate to be formed moreover, being often stirred before coating Sedimentation when resin layer as the inorganic filler of problem.
Therefore, for inventor etc. in view of above-mentioned, the adaptation in face of resin layer and biaxial stretch-formed polypropylene film (OPP) is good The exploitation of the few dry film of the sedimentation of inorganic filler contained in good and resin layer, for constituting the resin combination of resin layer, into One step has made intensive studies.
The result found that in the resin combination for being used to form resin layer be compounded glass transition point be 20 DEG C or less and At least wantonly 1 in macromolecule resin and semisolid epoxy resin and Cristalline epoxy resin that weight average molecular weight is 30,000 or more Kind, so as to solve the above subject, so far complete the present invention.
That is, dry film of the invention is characterized in that having: carrier film, resin layer and protective film, aforementioned protective film are twin shaft Stretched polypropene film, aforementioned resin layer includes: inorganic filler；Glass transition point is 20 DEG C or less and weight average molecular weight is 3 Ten thousand or more macromolecule resin；And epoxy resin, aforementioned resin layer include in semisolid epoxy resin and Cristalline epoxy resin At least wantonly a kind be used as aforementioned epoxy resins.
Dry film of the invention is preferably, and aforementioned resin layer includes compound, active ester group with phenolic hydroxyl group Compound, at least wantonly a kind in the compound with cyanic acid ester group and the compound with dimaleoyl imino as solidification Agent.
Dry film of the invention is preferably, and is 0.1 comprising average grain diameter as aforementioned inorganic filler in aforementioned resin layer The mixture for the inorganic filler that~10 μm of inorganic filler and average grain diameter are 0.01~5 μm, and aforementioned average grain diameter be 0.1~ Peak-to-peak difference in the particle size distribution measuring for the inorganic filler that 10 μm of inorganic filler and aforementioned average grain diameter are 0.01~5 μm is 0.05 μm or more.
Dry film of the invention is preferably, comprising the solid component total amount benchmark with aforementioned resin layer be calculated as 50 mass % with On aforementioned inorganic filler.
Solidfied material of the invention is characterized in that, is obtained from solidifying the resin layer of aforementioned dry film.
Electronic component of the invention is characterized in that thering is said curing object.
The effect of invention
According to the present invention it is possible to provide: the adaptation of resin layer and protective film is good and resin layer contained in inorganic fill out The few dry film of the sedimentation of material；With the solidfied material of the resin layer of the dry film；With the electronic component with the solidfied material.
Detailed description of the invention
Fig. 1 is the perspective cross-sectional slice for schematically showing an embodiment of dry film of the invention.
Description of symbols
The dry film of 11 three-deckers
12 resin layers
13 carrier films
14 protective films
Specific embodiment
< dry film >
Dry film of the invention is characterized in that having: carrier film, resin layer and protective film, and aforementioned protective film is twin shaft drawing Polypropylene stretched film, aforementioned resin layer includes: inorganic filler；Glass transition point is 20 DEG C or less and weight average molecular weight is 30,000 Above macromolecule resin；And epoxy resin, aforementioned resin layer include in semisolid epoxy resin and Cristalline epoxy resin At least wantonly a kind is used as aforementioned epoxy resins.
In the present invention, especially with the weak biaxial stretch-formed polypropylene film conduct of the closing force of the resin layer low to viscosity In the case where protective film, the height that glass transition point is 20 DEG C or less and weight average molecular weight is 30,000 or more is compounded in resin layer Molecule resin and at least wantonly a kind in solid epoxy resin and Cristalline epoxy resin, thus resin layer and protective film Adaptation also becomes good.Detailed mechanism is unclear, but thinks: by being compounded above-mentioned macromolecule resin, the surface of resin layer becomes It is coarse, so that closing force is stablized, in addition, use semisolid epoxy resin or Cristalline epoxy resin as epoxy resin, thus At the closely sealed temperature of protective film softening or close to fusing point, as a result, the closely sealed stabilization of protective film.In addition, detailed mechanism is not It is clear, but by being compounded above-mentioned macromolecule resin in the resin combination for being used to form resin layer, so that inorganic filler is heavy Drop is reduced.
The problem of sedimentation of the adaptation and inorganic filler of resin layer and protective film is the content especially in inorganic filler It is obvious in the case where height, but according to the present invention, though in the case where the content of inorganic filler is high, can also manufacture resin layer with The adaptation of protective film is good and resin layer contained in inorganic filler the few dry film of sedimentation.
In addition, if using OPP as protective film, being easy when cutting processing in the case that the content of inorganic filler is high Removing, the rupture/picking of OPP, but dry film according to the present invention are generated, removing when cutting processing can be inhibited, rupture/fall Powder.
For the solidfied material of the resin layer of dry film of the invention, in the case where there are bumps on pasted objects object, such as bury In the case where entering the components such as circuit, the flatness on solidfied material surface is also excellent.Therefore, electricity is further formed on the surface of solidfied material Whens road etc., it can be carried out fine pattern and formed, therefore, interlayer dielectic use can be suitable as.
In turn, the excellent adhesion of the solidfied material of the resin layer of dry film of the invention and pasted objects object, for low coarse Degree circuit board, the substrate etched, semiconductor can also be closely sealed well.
The resistance to warpage of the solidfied material of the resin layer of dry film of the invention is also excellent.
Fig. 1 is the perspective cross-sectional slice for showing an embodiment of dry film of the invention.It is formed in carrier for resin layer 12 On film 13 and be laminated with protective film 14 three-decker dry film 11.As needed, can be arranged between film and resin layer Other resin layers.It should be noted that the resin layer of dry film of the invention can be 1 layer or 2 layers or more.
[resin layer]
The resin layer of dry film of the invention is generally the state for being referred to as B scalariform state, is obtained by hardening resin composition It arrives.Specifically, the resin layer of dry film by film be coated with hardening resin composition after through drying process and obtain. Said curing property resin combination is not particularly limited the type of other compositions, compounding amount as long as comprising mentioned component.Tree The thickness of rouge layer is not particularly limited, such as with a thickness of 1~200 μm.In the case that thickness is big in the present invention, flatness is more It is excellent, it may be thus possible, for example, to be suitble to use with a thickness of 30 μm or more, further be 50 μm or more and also further be 100 μm with Upper person.It should be noted that the resin layer of multiple dry films of the invention can be overlapped and form the resin that thickness is more than 200 μm Layer.At this point, using layer of rolls press, vacuum laminator.
[macromolecule resin that glass transition point is 20 DEG C or less and weight average molecular weight is 30,000 or more]
The high score subtree that aforementioned resin layer is 20 DEG C or less containing glass transition point and weight average molecular weight is 30,000 or more Rouge.Preferably -40~20 DEG C, more preferably -15~15 DEG C of the glass transition point of aforementioned macromolecule resin, particularly preferably -5~15 ℃.When being -5~15 DEG C, the warpage of solidfied material can be inhibited well.
In addition, the weight average molecular weight of aforementioned macromolecule resin is higher, the anti-settling effect of inorganic filler is bigger, therefore, excellent Select 100,000 or more, more preferable 200,000 or more.As upper limit value, for example, 1,000,000 or less.
As macromolecule resin, can enumerate has selected from butadiene skeletal, amide backbone, acid imide skeleton, acetal bone One or more of frame, carbonic ester skeleton, ester skeleton, carbamate skeleton, acrylic compounds skeleton and siloxane backbone skeleton Macromolecule resin etc..For example: the macromolecule resin (Tso Tat Co., Ltd., Japan system " G- with butadiene skeletal 1000 ", " G-3000 ", " GI-1000 ", " GI-3000 ", Idemitsu Petrochemical Co., Ltd.'s system " R-45EPI ", Daicel Chemical Industries, Ltd., system " PB3600 ", " EPFD AT501 ", Clay Valley corporation " Ricon130 ", " Ricon142 ", " Ricon150 ", " Ricon657 ", " Ricon130MA "), with butadiene skeletal and polyimide backbone Macromolecule resin (substance that Japanese Unexamined Patent Publication 2006-37083 bulletin is recorded), the macromolecule resin with acrylic compounds skeleton (Nagase ChemteX Corporation system " SG-P3 ", " SG-600LB ", " SG-280 ", " SG-790 ", " SG-K2 ", root Upper Industrial Co., Ltd's system " SN-50 ", " AS-3000E ", " ME-2000 ") etc..
As aforementioned macromolecule resin, from the viewpoint of the flatness of solidfied material, preferred glass transition point is 20 DEG C Below and weight average molecular weight be 200,000 or more acrylate copolymer.In addition, from biaxial stretch-formed polypropylene film (OPP) Cementability and with low roughness substrate, circuit cementability from the perspective of, preferred glass transition point is -5~15 DEG C and again The acrylate copolymer that average molecular weight is 200,000~500,000.
Foregoing acrylates copolymer can have functional group, as functional group, for example, carboxyl, hydroxyl, ring Oxygroup, amide groups etc..
Foregoing acrylates copolymer preferably has epoxy group, further preferably has epoxy group and amide groups.Pass through tool There is epoxy group, the warpage of solidfied material can be inhibited.
As foregoing acrylates copolymer, it can enumerate Nagase ChemteX Corporation's TEISANRESIN SG-70L、SG-708-6、WS-023EK30、SG-P3、SG-80H、SG-280EK23、SG-600TEA、SG- 790.Foregoing acrylates copolymer, which may be synthesized, to be obtained, as synthetic method, for example, Japanese Unexamined Patent Publication The synthetic method that 2016-102200 bulletin is recorded.
Aforementioned macromolecule resin can be used alone or combine two or more use.The compounding amount of aforementioned macromolecule resin Preferably 0.5~10 mass % in terms of the solid component total amount benchmark of composition, more preferable 1.0~7.0 mass %, further preferably 2.0~7.0 mass %, particularly preferred 4.0~7.0 mass %.
It should be noted that the value of weight average molecular weight (Mw) can pass through gel permeation chromatography method in this specification (GPC) method (polystyrene standard), be measured with following measurement devices, determination condition.
Measurement device: Waters system " Waters 2695 "
Detector: Waters system " Waters2414 ", RI (differential refractometer)
Column: Waters system " HSPgel Column, HR MB-L, 3 μm, 6mm × 150mm " × 2+Waters system " HSPgel Column, HR1,3 μm, 6mm × 150mm " × 2
Determination condition:
Column temperature: 40 DEG C
RI detector set temperature: 35 DEG C
Developing solvent: tetrahydrofuran
Flow velocity: 0.5ml/ minutes
Sample size: 10 μ l
Sample concentration: 0.7wt%
[epoxy resin]
Aforementioned resin layer includes epoxy resin.Epoxy resin is the resin with epoxy group, be can be used any previous public The substance known.It can enumerate: there are 3 or more epoxies in the 2 functionality epoxy resin, molecule with 2 epoxy groups in molecule The polyfunctional epoxy resin etc. of base.It should be noted that or hydrogenated epoxy resin.Aforementioned resin layer includes half solid At least wantonly a kind in state epoxy resin and Cristalline epoxy resin is used as aforementioned epoxy resins.Semisolid epoxy resin and crystallization Property epoxy resin can use individually a kind or combine two or more use.In addition, aforementioned resin layer can contain solid-state ring Oxygen resin, liquid-state epoxy resin.In this specification, solid epoxy resin refers to, is the epoxy resin of solid-like at 40 DEG C, partly Solid epoxy resin refers to, be at 20 DEG C solid-like, at 40 DEG C be liquid epoxy resin, liquid-state epoxy resin refers to, It is the epoxy resin of liquid at 20 DEG C.The judgment basis of liquid enables (the Heisei first year about the test of danger and the province of character Autonomous province enables No. 1) the attached 2nd " confirmation method of liquid " and carry out.For example, with Japanese Unexamined Patent Publication 2016-079384's The method recorded in paragraph 23~25 carries out.In addition, Cristalline epoxy resin means the strong epoxy resin of crystallinity, refer to At fusing point temperature below, macromolecular chain is regularly arranged, although for solid resin, in melting when become with liquid resin etc. The epoxy resin of the Thermocurable of same low viscosity.
As semisolid epoxy resin, can enumerate Dainippon Ink Chemicals Epiclon 860, Epiclon 900-IM, Epiclon EXA-4816, Epiclon EXA-4822, Asahi Chiba Co. Ltd. system Araldite AER280, Dongdu At Co. Ltd. system Epototo YD-134, Mitsubishi chemical Co., Ltd jER834, jER872, Sumitomo Chemical strain formula meeting The bisphenol A type epoxy resins such as society ELA-134；The naphthalene type epoxy resins such as Dainippon Ink Chemicals Epiclon HP-4032；DIC plants Phenol novolak type epoxy resins such as formula commercial firm Epiclon N-740 etc..
As semisolid shape epoxy resin, preferably comprise selected from by bisphenol A type epoxy resin, naphthalene type epoxy resin and phenol At least one of the group of phenolic resin varnish type epoxy resin composition.By the inclusion of semisolid shape epoxy resin, the glass of solidfied material Change transition temperature (Tg) to get higher, CTE is lower, resistance to anti-thread breakage excellent.
As Cristalline epoxy resin, can be used for example with biphenyl structural, sulfide based structural, phenylene structure, naphthalene knot The Cristalline epoxy resin of structure etc..The epoxy resin of biphenyl type is for example with Mitsubishi chemical Co., Ltd jER YX4000, jER The form offer of YX4000H, jER YL6121H, jER YL6640, jER YL6677, diphenylsulfide type epoxy resin is for example It is provided in the form of Dongdu is melted into Co. Ltd. system EPOTOTO YSLV-120TE, phenylene-type epoxy resin is for example with Dongdu It is provided at the form of Co. Ltd. system EPOTOTO YDC-1312, naphthalene type epoxy resin is for example with Dainippon Ink Chemicals EPICLON The form offer of HP-4032, EPICLON HP-4032D, EPICLON HP-4700.In addition, as Cristalline epoxy resin, Toto Kasei KK EPOTOTO YSLV-90C, Hitachi Chemical Co., Ltd.'s TEPIC-S (isocyanide can be used Urea acid three-glycidyl ester).
As solid epoxy resin, Dainippon Ink Chemicals HP-4700 (naphthalene type epoxy resin), DIC plants of formula meetings can be enumerated Society EXA4700 (4 function naphthalene type epoxy resin), Nippon Kayaku K. K NC-7000 (the multifunctional solid-state ring containing naphthalene skeleton Oxygen resin) etc. naphthalene type epoxy resins；The phenols such as Nippon Kayaku K. K EPPN-502H (triphenol epoxy resin) with have phenol The epoxides (tris phenol type epoxy) of the condensation product of the aromatic aldehyde of hydroxyl；Dainippon Ink Chemicals Epiclon HP- The dicyclopentadienes aralkyl-type epoxy resins such as 7200H (the multifunctional solid epoxy resin of skeleton containing dicyclopentadiene)；Japanization The biphenyl aralkyl-type epoxy resins such as medicine Co. Ltd. system NC-3000H (the multifunctional solid epoxy resin containing biphenyl backbone)；Japan Biphenyl/the phenol novolak type epoxy resins such as chemical drug Co. Ltd. system NC-3000L；Dainippon Ink Chemicals Epiclon The phenolic resin varnish type epoxy resins such as N660, Epiclon N690, N770, Nippon Kayaku K. K EOCN-104S；Nippon Steel The firmly phosphorous epoxy resins such as aurification Co. Ltd. system TX0712；(the 2,3- ring of Nissan Chemical Ind Ltd TEPIC etc. three Oxygroup propyl) isocyanuric acid ester etc..By the inclusion of solid epoxy resin, the glass transition temperature of solidfied material is got higher, heat resistance It is excellent.
As liquid-state epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type ring oxygen can be enumerated Resin, phenol novolak type epoxy resin, tert-butyl catechol type epoxy resin, glycidyl amine type epoxy resin, amino Phenol type epoxy resin, alicyclic epoxy resin etc..By the inclusion of liquid-state epoxy resin, the flexibility of dry film is excellent.
The compounding amount of semisolid epoxy resin and Cristalline epoxy resin is in terms of epoxy resin total amount benchmark, total preferably 5 ~40 mass %, more preferable 10~30 mass %.When in above range, the viscosity and flexibility of the resin layer of dry film are excellent.
Hot curing resin composition of the invention can contain (A) ring in the range of not impairing the effect of the present invention Isocyanate compound, blocked isocyanate compounds, amino tree can be used for example in heat-curing resin other than oxygen resin Rouge, benzoxazine resin, carbodiimide resin, cyclic carbonate compound, multifunctional oxetane compound, episulfide resin etc. Known usual heat-curing resin.
[inorganic filler]
Aforementioned resin layer contains inorganic filler.By compounding inorganic filler, the cure shrinkage of gained solidfied material can be inhibited, Improve adaptation, hardness, be consistent with the calorific intensity of the conductor layer for the copper etc. being located at around insulating layer it is generated resistance to anti-thread breakage etc. Thermal characteristics.As inorganic filler, known inorganic filler can be used, be not limited to specific substance, such as can lift The titanium dioxides such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silicon dioxide out Silicon, talcum, clay, noy fort silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminium oxide, aluminium hydroxide, nitridation The metal-powders such as the extender pigments such as silicon, aluminium nitride, calcium zirconate, copper, tin, zinc, nickel, silver, palladium, aluminium, iron, cobalt, gold, platinum.It is inorganic to fill out Expect preferred spherical particle.Wherein, preferred silica, inhibits the cure shrinkage of the solidfied material of solidification compound, becomes lower CTE, in addition, improving the characteristics such as adaptation, hardness.In addition, the heavy general sinking speed of inorganic filler as aluminium oxide It becomes faster, but is settled in the present invention due to that can inhibit, can be suitble to use.Inorganic filler average grain diameter (median particle diameter, D50) preferably 0.01~10 μm.As inorganic filler, from the viewpoint of cutting processability, preferably average grain diameter is 0.01~3 μ The silica of m.It should be noted that the average grain diameter of inorganic filler is the grain for not only including primary particle in this specification Diameter further includes the average grain diameter including the partial size of second particle (aggregation).Average grain diameter can pass through laser diffraction formula partial size point Cloth measurement device and find out.As the measurement device based on laser diffractometry, Nikkiso Company Limited's system can be enumerated Nanotrac wave etc..
Aforementioned inorganic filler can be surface-treated.As surface treatment, the surface using coupling agent can also be carried out Processing, alumina treatment etc. do not import the surface treatment of organic group.The surface treatment method of inorganic filler is not particularly limited, Using known customary way, with curability reactive group surface treating agent, for example with curability reactive group Coupling agent etc. of the group as organic group handles the surface of inorganic filler.
The surface treatment of inorganic filler preferably by coupling agent surface treatment.As coupling agent, can be used silane system, The coupling agents such as titanate esters system, aluminate-series and zircoaluminate system.Wherein, preferred silane series coupling agent.It is even as above-mentioned silane system The example for joining agent, can enumerate vinyltrimethoxysilane, vinyltriethoxysilane, N- (2- amino methyl) -3- ammonia Base hydroxypropyl methyl dimethoxysilane, N- (2- amino-ethyl) -3- TSL 8330, three ethoxy of 3- aminopropyl Base silane, 3- anilino- propyl trimethoxy silicane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group Methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- methacryloxypropyl front three Oxysilane, 3-mercaptopropyi trimethoxy silane etc., they can be used alone or be applied in combination and use.These silane systems Coupling agent preferably first passes through absorption or reaction in advance and is immobilized in the surface of inorganic filler.Herein, coupling agent is filled out relative to inorganic The treating capacity for expecting 100 mass parts is, for example, 0.5~10 mass parts.
As curability reactive group, preferably Thermocurable reactive group.As Thermocurable reactive group, can enumerate Hydroxyl, carboxyl, isocyanate group, amino, imino group, epoxy group, oxetanylmethoxy, sulfydryl, methoxy, methoxyl group second Base, ethoxyl methyl, ethoxyethyl group, oxazoline group etc..Wherein, at least wantonly a kind preferably in amino and epoxy group.It needs Bright, surface treated inorganic filler can also have photo-curable reaction on the basis of Thermocurable reactive group Group.
It should be noted that as long as surface treated inorganic filler is contained with surface treated state in aforementioned resin Layer can be compounded inorganic filler and surface treating agent in the hardening resin composition for forming aforementioned resin layer respectively, Inorganic filler is surface-treated in the composition, but the inorganic filler that preferred compounding is surface-treated in advance.Pass through The inorganic filler that compounding is surface-treated in advance, can prevent may be remaining not by surface in the case where being compounded respectively Manage the resistance to anti-thread breakage reduction waited caused by the surface treating agent of consumption.In the case where being surface-treated in advance, preferably it is compounded The pre-dispersed pre-dispersed liquid for having inorganic filler in solvent, curable resin, it is even more preferred that inorganic being filled out surface treated Expect pre-dispersed in solvent, is compounded the pre-dispersed liquid in the composition；Or keep the untreated inorganic filler in surface pre-dispersed in solvent When be sufficiently surface-treated after, be compounded the pre-dispersed liquid in the composition.
Inorganic filler can be compounded with powder or solid state and epoxy resin etc., can also be with solvent, dispersant It is compounded after forming slurry with epoxy resin etc..
Inorganic filler can be used alone, and can also be used in the form of mixture of more than two kinds.Inorganic filler Compounding amount in terms of the solid component total amount benchmark of the resin layer of dry film, preferably 10~90 mass %, more preferable 50~90 mass %, Even more preferably 60~90 mass %.When the compounding amount of inorganic filler is 10 mass % or more, inhibit thermal expansion, heat resistance mentions On the other hand height when being 90 mass % or less, can inhibit the generation of crackle.
In addition, as above-mentioned, especially inorganic the problem of the sedimentation of the adaptation and inorganic filler of resin layer and protective film It is obvious in the case that the content of filler is high.In the case that the compounding amount of inorganic filler in the present invention is more, such as with the resin of dry film In the case that the solid component total amount benchmark of layer is calculated as 50 mass % or more, available particularly excellent effect.In turn, it is In the case where 70 mass % or more, the sedimentation of especially inorganic filler is obvious, but according to the present invention, the sedimentation of inorganic filler Inhibit excellent.
In turn, from the viewpoint of the sedimentation for inhibiting inorganic filler, it is preferred that aforementioned resin layer is comprising average grain diameter The inorganic filler that 0.1~10 μm of inorganic filler (hereinafter also referred to as " major diameter inorganic filler ") and average grain diameter are 0.01~5 μm The mixture of (hereinafter also referred to as " path inorganic filler "), and aforementioned average grain diameter be 0.1~10 μm inorganic filler with it is aforementioned The peak-to-peak difference of partial size in the particle size distribution measuring for the inorganic filler that average grain diameter is 0.01~5 μm is 0.05 μm or more.It is logical It crosses and is compounded the different inorganic filler of such average grain diameter, and be 20 DEG C or less with glass transition point and weight average molecular weight is 3 Ten thousand or more macromolecule resin combination can inhibit sedimentation when coating so as to further prevent the sedimentation of inorganic filler. In addition, the flatness on the solidfied material surface of resin layer is also excellent, the thickness of resin layer can also be maintained after embedment component.In turn, It is easy to carry out high filling to inorganic filler, be filled by height, the high solidfied material of available elasticity modulus.The peak value of partial size can be with It is found out by laser diffraction formula particle size distribution analyzer.As the measurement device based on laser diffractometry, can enumerate day Machine fills Co. Ltd. system Nanotrac wave etc..It should be noted that will be averaged in the case where comprising 3 kinds or more inorganic fillers The inorganic filler of most path in the range of partial size is 0.01~5 μm is set as aforementioned path inorganic filler, in addition to this inorganic In filler average grain diameter be in 0.1~10 μm in the range of and in the particle size distribution measuring of the inorganic filler of aforementioned most path Peak-to-peak difference be 0.05 μm or more person, be all equivalent to aforementioned major diameter inorganic filler.
The preferred average grain diameter of the inorganic filler that aforementioned average grain diameter is 0.1~10 μm is 0.1~8 μm.Aforementioned average grain diameter More become smaller, the low roughening on the solidfied material surface after de-smear is more excellent, can inhibit sedimentation, the aggregation of silica.
The preferred average grain diameter of the inorganic filler that aforementioned average grain diameter is 0.01~5 μm is 0.03~3 μm.Aforementioned average grain diameter More become smaller, the low roughening on the solidfied material surface after de-smear is more excellent, can inhibit sedimentation, the aggregation of silica.
The inorganic filler that the inorganic filler and aforementioned average grain diameter that aforementioned average grain diameter is 0.1~10 μm are 0.01~5 μm Particle size distribution measuring in the maximum value of peak-to-peak difference be, for example, 5 μm.
The compounding amount for the inorganic filler that aforementioned average grain diameter is 0.1~10 μm is with the solid component total amount benchmark of composition Meter, preferably 5~80 mass %.
The compounding amount for the inorganic filler that aforementioned average grain diameter is 0.01~5 μm is with the solid component total amount benchmark of composition Meter, preferably 5~15 mass %.
[curing agent]
Aforementioned resin layer preferably comprises curing agent.As curing agent, compound, poly- carboxylic with phenolic hydroxyl group can be enumerated Acid and its acid anhydrides, the compound with cyanic acid ester group, the compound of active ester group, the chemical combination with dimaleoyl imino Object, ester ring type olefin polymer etc..Curing agent can be used alone or combine two or more use.
In the present invention, aforementioned resin layer preferably comprise compound with phenolic hydroxyl group, active ester group compound, At least wantonly a kind in compound with cyanic acid ester group and the compound with dimaleoyl imino.By using with phenol The compound of the compound of hydroxyl and active ester group, it is available with low roughness substrate, circuit it is excellent in adhesion Solidfied material.In addition, the Tg of solidfied material is got higher by using cyanate, heat resistance is improved, by using with dimaleoyl imino Compound, the Tg of solidfied material gets higher, and heat resistance improves, and can reduce CTE.
As the aforementioned compound with phenolic hydroxyl group, can be used: phenol resol resins, alkylphenol phenolic aldehyde are clear Coating resins, bisphenol A novolac resin, dicyclopentadiene type phenolic resin, Xylok type phenolic resin, terpene modified phenolic aldehyde tree Rouge, cresols/naphthol resin, polyvinylphenol class, phenol/naphthol resin, the phenolic resin of skeleton containing alpha-Naphthol, skeleton containing triazine The known objects such as cresol novolac resin, biphenyl aralkyl-type phenol resin, Xylok type phenol resol resins Matter.
In the aforementioned compound with phenolic hydroxyl group, preferably hydroxyl equivalent is 100g/eq. or more person.As hydroxyl equivalent For the compound with phenolic hydroxyl group of 100g/eq. or more, for example: dicyclopentadiene skeleton phenol novolacs Resin (GDP series, group's honor Chemical Co., Ltd. system), Xylok type phenol resol resins (MEH-7800, bright and chemical conversion strain Formula commercial firm system), biphenyl aralkyl type phenol varnish gum (MEH-7851, it is bright and chemical conversion Co. Ltd. system), naphthols aralkyl-type Curing agent (SN series, Nippon Steel & Sumitomo Metal Corporation's system), the cresol novolac resin of skeleton containing triazine (LA-3018-50P, Dainippon Ink Chemicals's system), phenol resol resins of skeleton containing triazine (LA-705N, Dainippon Ink Chemicals's system) etc..
With the chemical combination of 2 or more cyanic acid ester groups (- OCN) in the aforementioned compound with a cyanic acid ester group preferably molecule Object.Any conventionally known substance can be used in compound with cyanic acid ester group.As the compound with cyanic acid ester group, example Phenol novolak type cyanate ester resin, alkylphenol phenolic varnish type cyanate ester resin, dicyclopentadiene type can such as be enumerated Cyanate ester resin, bisphenol A cyanate ester resin, bisphenol-f type cyanate ester resin, bisphenol S type cyanate ester resin.Furthermore it is possible to be Prepolymer made of a part of triazine.
It as the commercially available compound with cyanic acid ester group, can enumerate: phenol novolak type multifunctional cyanate ester tree Part or all of rouge (Lonza Japan Ltd system, PT30S), bisphenol A dicyanate become tripolymer through triazine Prepolymer (Lonza Japan Ltd system, BA230S75), (the Lonza Japan Ltd of cyanate ester resin containing dicyclopentadiene structure System, DT-4000, DT-7000) etc..
With the compound of 2 or more active ester groups in the compound of an aforementioned active ester group preferably molecule.Have The compound of active ester groups can usually be obtained by the condensation reaction of carboxylic acid compound and hydroxy compounds.Wherein, preferably Use oxybenzene compound or naphthol compound as the compound of active ester group obtained from hydroxy compounds.As phenol Compound or naphthol compound can enumerate hydroquinone, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalein, methylation pair Phenol A, methylation Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxy two Benzophenone, phloroglucin, benzenetriol, dicyclopentadienyl biphenol, phenol novolacs etc..In addition, as active ester The compound of base can be naphthalene glycol alkyl/benzoic acid type.
As the compound of commercially available active ester group, bisphenol compounds, the example of dicyclopentadiene type can be enumerated Such as, HPC8000-65T (Dainippon Ink Chemicals's system), HPC8100-65T (Dainippon Ink Chemicals's system), HPC8150-65T (DIC plants of formulas Commercial firm's system).
The aforementioned compound with dimaleoyl imino is the compound with maleimide skeleton, be can be used any Conventionally known substance.Compound with dimaleoyl imino preferably has 2 or more maleimide skeletons, more preferably N, N ' -1,3- phenylene dimaleimide, N, N ' -1,4- phenylene dimaleimide, N, N ' -4,4- diphenyl methane are double Bis- (maleimide) ethane of maleimide, 1,2-, 1,6- bisinaleimidohexane, 1,6- bismaleimide-(2,2, 4- trimethyl) hexane, 2,2 '-bis--[4- (4- maleimidephenoxy) phenyl] propane, 3,3 '-dimethyl -5,5 '-diethyl Base -4,4 '-diphenyl methane bismaleimide, 4- methyl-1,3- phenylene bismaleimide, bis- (3- ethyl -5- first Base -4- maleimide phenyl) methane, bisphenol-A diphenyl ether bismaleimide, polyphenyl methylmethane maleimide and it Oligomer and diamines condensation product with maleimide skeleton among at least any one.Aforementioned oligomer is logical Cross make among the above-mentioned compound with dimaleoyl imino as the compound condensation with dimaleoyl imino of monomer and Obtained oligomer.
As the commercially available compound with dimaleoyl imino, can enumerating BMI-1000, (4,4 '-diphenyl methanes are double Maleimide, Daiwa Kasei Industry Co., Ltd.'s system), BMI-2300 (phenylmethane bismaleimide, big and chemical conversion industry Co. Ltd. system), BMI-3000 (meta-phenylene bismaleimide, Daiwa Kasei Industry Co., Ltd.'s system), BMI-5100 (3, 3 '-dimethyl -5,5 '-dimethyl -4,4 '-diphenyl methane bismaleimide, Daiwa Kasei Industry Co., Ltd.'s system), BMI-7000 (4- methyl-1,3- phenylene bismaleimide, Daiwa Kasei Industry Co., Ltd.'s system), BMI-TMH ((1,6- Bismaleimide -2,2,4- trimethyl) hexane, Daiwa Kasei Industry Co., Ltd.'s system) etc..
The compounding amount of curing agent is relative to 100 mass parts of epoxy resin, preferably 20~100 mass parts, more preferable 25~90 Mass parts.
As the concrete example for the hardening resin composition for forming aforementioned resin layer, heat-curing resin combination can be enumerated Object, the light solidifying/heat solidifying resin composition containing Photoepolymerizationinitiater initiater, contains light solidifying/heat solidifying resin composition There are the light solidifying/heat solidifying resin composition of Photobase generator, the Photosetting and thermosetting resin combination containing photoacid generator Object, minus light solidifying/heat solidifying resin composition and positive light sensitivity hot curing resin composition, alkali developable light are solid The property changed hot curing resin composition, solvent development type light solidifying/heat solidifying resin composition, the exfoliated heat cure of swelling Property resin combination, the exfoliated hot curing resin composition of dissolution, but be not limited to these.
In below, as an example, for forming resin layer by the hot curing resin composition without photo-curable ingredient The case where, the ingredient that may include in addition to mentioned component is illustrated.
Aforementioned resin layer can be used for example: isocyanates containing the heat-curing resin in addition to epoxy resin Compound, blocked isocyanate compounds, amino resins, benzoxazine resin, carbodiimide resin, cyclic carbonate compound, Usual heat-curing resin known in multifunctional oxetane compound, episulfide resin etc..
In order to improve the mechanical strength of gained cured film, aforementioned resin layer can further contain thermoplastic resin.Thermoplastic Property resin is preferably soluble in solvent.When dissolving in solvent, the flexibility of dry film is improved, and is able to suppress generation, the picking of crackle.Make For thermoplastic resin, thermoplasticity polyhydroxy polyether resin can be enumerated, as epoxychloropropane and various 2 function phenolic compounds The hydroxyl in hydroxy ether portion present on its skeleton is esterified by the phenoxy resin of condensation product with various acid anhydrides and/or carboxylic acid halides Made of phenoxy resin, polyvinyl acetal resin, polyamide, polyamide-imide resin, block copolymer etc..Heat Plastic resin can be used alone or two or more is applied in combination.
The compounding amount of thermoplastic resin in terms of the solid component total amount benchmark of resin layer, it is preferably 0.5~20 mass %, more excellent Select 0.5~10 mass %.When the compounding amount of thermoplastic resin is in above range, it is easy to get uniform coarse surface state.
In turn, aforementioned resin layer can according to need containing rubber-like particles.As this rubber-like particles, can enumerate Polybutadiene rubber, polyisobutylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, third Alkene nitrile modified polybutadiene rubber, carboxy-modified polybutadiene rubber, with the acrylonitrile butadiene rubber of carboxyl or hydroxyl modification, With their cross-linked rubbery particle, nucleocapsid type rubber particle etc., it can be used alone or two or more is applied in combination.These rubbers Colloidal particle is the flexibility of cured film in order to improve or improves resistance to anti-thread breakage or make thick using the surface of oxidant Roughening is treated as the dhering strength of possibility, raising and copper foil etc. and adds.
The average grain diameter of rubber-like particles is preferably 0.005~1 μm of range, more preferably 0.2~1 μm of range.This The average grain diameter of the rubber-like particles of invention can be found out by laser diffraction formula particle size distribution analyzer.For example, using super Sound wave etc. keeps rubber-like particles evenly dispersed in a suitable organic solvent, uses Nikkiso Company Limited Nanotrac Wave, with the size distribution of quality criteria production rubber-like particles, using its median particle diameter as average grain diameter, thus, it is possible to survey It is fixed.
The compounding amount of rubber-like particles is in terms of the solid component total amount benchmark of resin layer, preferably 0.5~10 mass %, more Preferably 1~5 mass %.In the case where 0.5 mass % or more, anti-cracking line can be obtained, can be improved with conductive pattern etc. Dhering strength.In 10 mass % situations below, thermal expansion coefficient (CTE) is reduced, and glass transition temperature (Tg) rises, Gu Change characteristic to improve.
Aforementioned resin layer can contain curing accelerator.Curing accelerator be promote heat cure reaction substance, for into One step improves the characteristics such as adaptation, chemical resistance, heat resistance.As the concrete example of this curing accelerator, can enumerate Imidazole and its derivants；The guanamines such as acetylguanamine, benzoguanamine；Diaminodiphenyl-methane, m-phenylenediamine, diformazan The polyamines classes such as phenylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivative, melamine, polynary hydrazides；Their organic acid Salt and/or epoxy adduct；The amine complex of boron trifluoride；Ethyl diamino-s-triazine, 2,4- diamino-s-triazine, 2,4- The triazine derivatives species such as diamino -6- xylyl-s-triazine；Trimethylamine, triethanolamine, N, N- dimethyl octyl amine, N- Benzyldimethylamine, 2,4, pyridine, N-methylmorpholine, six (N- methyl) melamines, 2,4,6- tri- (Dimethylaminophenol), tetramethyl The amines such as base guanidine, m-aminophenol；Polyvinylphenol, polyvinylphenol bromide, phenol novolacs, alkylphenol phenol The Polyphenols such as Novolac；Organic phosphines such as tributylphosphine, triphenylphosphine, three -2- cyano ethyl phosphines；Three-normal-butyls (2,5- dihydroxy Base phenyl) phosphonium bromide, phosphonium hexadecanyl-3-butyl chloride Deng phosphonium salts class；Benzyltrimethylammonium chloride, phenyl tributyl ammonium chloride Equal quaternary ammonium salts；Aforementioned polybasic acids acid anhydride；Diphenyl iodine tetrafluoroborate, triphenylsulfonium hexafluoro antimonate, 2,4,6- triphenyl The light cationic polymerization catalyst such as thio-pyrylium hexafluorophosphate；Phenylethylene-maleic anhydride resin；Phenyl isocyanate and two Organic multiple isocyanates and the diformazans such as the reaction with same mole object of methyl amine, toluene di-isocyanate(TDI), isophorone diisocyanate The conventionally known curing accelerators such as the reaction with same mole object of base amine, metallic catalyst.In curing accelerator, from can obtain It sets out in terms of BHAST patience, You Xuan phosphonium salt class.
Curing accelerator can be used alone or be mixed with two or more.The use of curing accelerator is not required , but can be to be preferably 0.01~5 mass relative to 100 mass parts of epoxy resin in the case where particularling hope to promote cured situation The range of part uses.In the case where metallic catalyst, relative to 100 mass parts of compound with cyanic acid ester group, changed with metal Calculate preferably 10~550ppm, more preferably 25~200ppm.
It as organic solvent, is not particularly limited, such as ketone, aromatic hydrocarbon, glycol ethers, glycol ethers can be enumerated Acetate esters, esters, alcohols, aliphatic hydrocarbon, petroleum series solvent etc..Specifically, can enumerate methyl ethyl ketone, cyclohexanone, The ketones such as methyl butyl ketone, methyl iso-butyl ketone (MIBK)；Toluene, dimethylbenzene, durol etc. are aromatic hydrocarbon；Cellosolve, methyl are molten Fine agent, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol The glycol ethers such as monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether；Second Acetoacetic ester, butyl acetate, isobutyl acetate, ethylene glycol monoethylether acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol monomethyl ether second The esters such as acid esters, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters；It is ethyl alcohol, propyl alcohol, 2- methoxypropanol, n-butanol, different The alcohols such as butanol, isoamyl alcohol, ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, naphtha, hydrogenated naphtha, Petroleum series solvent such as solvent naphtha etc. and N,N-dimethylformamide (DMF), tetrachloro-ethylene, turpentine oil etc..In addition, Maruzen Petrochemical Co., Ltd. SWASOL1000, SWASOL1500, Standard Sekiyu Osaka can be used Hatsubaisyo CO., LTD SOLVESSO100, SOLVESSO150, three altogether Chemical Co., Ltd. Solvent#100, Solvent#150, Japanese firm, Shell Chemical SHELLSOL A100, SHELLSOL A150, Idemitsu Kosen Co., Ltd.'s system The organic solvents such as No. IPSOL100, No. IPSOL150.Organic solvent can be used alone, can also be with mixing of more than two kinds The form of object uses.
Residual solvent amount preferably 0.5~7.0 mass % in aforementioned resin layer.When residual solvent is 7.0 mass % or less, Inhibit bumping when heat cure, the flatness on surface becomes better.It is additionally possible to suppress melt viscosity excessively reduces and resin It can flow, flatness becomes good.When residual solvent is 0.5 mass % or more, good fluidity when lamination, flatness and embedment Property become better.
Aforementioned resin layer can further as needed using phthalocyanine blue, phthalocyanine green, iodine is green, dual-azo yellow, crystal violet, oxygen Change the conventionally known increasings such as conventionally known colorant, asbestos, ORBEN, BENTON, the fine particle silicas such as titanium, carbon black, naphthalene be black Thick dose, organic silicon-type, fluorine system, the defoaming agent of macromolecular etc. and/or levelling agent, thiazole system, triazole system, silane coupling agent etc. it is close Close property imparting agent, fire retardant, titanate esters system, aluminium system conventionally known additive kind.
As the manufacturing method for the printed circuit board for using dry film of the invention, conventionally known method is used.Example In the case where being formed such as resin layer by hot curing resin composition, pressed from both sides between carrier film and protective film as shown in Figure 1 In the case where the dry film for holding resin layer, printed circuit board can be manufactured by following such methods.Carrier is removed from dry film Any one of film or protective film, heated lamination carry out heat cure after being formed with the circuit substrate of circuit pattern.Heat cure can Make its solidification to solidify in an oven or by hot plate compacting.By be formed with circuit substrate and dry film lamination of the invention or When hot plate is suppressed, by copper foil or the substrate of circuit can also be formed with while being laminated.Be formed with circuit pattern substrate on The corresponding position in specified position, pattern, through-hole are formed by laser irradiation or drill bit, expose wiring, so as to Enough manufacture printed circuit board.It is not completely removed and remaining ingredient (glue at this point, existing on the wiring in pattern, through-hole Slag) processing of Shi Jinhang de-smear.Residual person in carrier film or protective film after laminating, after heat cure, after laser processing or remove Glue residue treated any opportunity removing.It should be noted that the connection method of interlayer circuit can be to utilize copper post Connection.
[carrier film]
Carrier film refers to have the function of supporting the film of the resin layer of dry film, solid to be coated with when forming the resin layer The film of the property changed resin combination.As carrier film, polyethylene terephthalate, poly- naphthalenedicarboxylic acid second two can be used for example The polyester films such as alcohol ester, Kapton, polyamidoimide film, polyethylene film, polytetrafluoroethylene film, polypropylene Film and surface-treated paper that film, polystyrene film etc. are formed by thermoplastic resin etc..From heat-resisting among them From the perspective of property, mechanical strength, treatability etc., polyester film can be properly used.The thickness of carrier film does not limit especially System, the appropriate selection depending on the application in the range of substantially 10~150 μm.The face that resin layer is arranged of carrier film can also be implemented Demoulding processing.In addition, also could be formed with sputtering or extra thin copper foil on the face of the setting resin layer of carrier film.
[protective film]
For protective film, for surface adhesive dust for the resin layer for preventing dry film etc. and the mesh of treatability is improved , the face opposite with carrier film of resin layer is set.In the present invention, as protective film, biaxial stretch-formed polypropylene film is used. By for biaxial stretch-formed polypropylene film, it is possible to reduce the cooling meat to after resin layer stackup.The thickness of protective film is without spy It does not limit, the appropriate selection depending on the application in the range of substantially 10~100 μm.It is excellent for the face of the setting resin layer of protective film Choosing implements embossing processing, sided corona treatment, micro- adhesion process etc. for improving processing, the demoulding processing of adaptation.
Dry film of the invention can be preferably used for the shape of the permanent protective film of electronic component, particularly printed circuit board At, more particularly to be preferably used for solder mask, interlayer insulating film, flexible printed circuit board coating formation.In particular, this The dry film of invention can be preferably used to form the purposes of the solidfied material more than inorganic filler content.Dry film of the invention can be used, glue Patch line is to form wiring plate.Furthermore it is also possible to which the sealing material as semiconductor chip uses.
Embodiment
Hereinafter, showing examples and comparative examples of the present invention, the present invention is specifically described, the present invention does not limit certainly In following embodiments.It should be noted that hereinafter, so-called " part " and " % " are quality base in case of no particular description It is quasi-.
The Production Example 1 for the high-molecular compound that < glass transition point is 20 DEG C or less and weight average molecular weight is 30,000 or more > (manufacture of macromolecule resin A, macromolecule resin B)
In the reaction vessel, by 2 functional hydroxyl groups end polybutadiene G-3000 (hydroxyl equivalents=1800g/eq., solid Ingredient 100wt%: Tso Tat Co., Ltd., Japan's system) 50g, IPSOL150 (aromatic series hydrocarbon system mixed solvent: light petrochemistry strain out Formula commercial firm system) 100g and dibutyl tin laurate 0.005g mixing, make its uniform dissolution.As uniformly after be warming up to 50 DEG C, side It stirs side and adds isophorone diisocyanate (IPDI, Mw=222, isocyanate group equivalent=111g/eq.) 3.08g, with about 3 hours and about 12 hours 2 kinds of modes are reacted.Reaction solution obtained by being added dropwise respectively in hexane solution, makes white precipitate Object is precipitated.Later, white depositions are recovered by filtration, it is 2 hours dry with 100 DEG C, obtain the polybutadiene of ratio about 1:1 with The polymer of IPDI.
For resulting polymers, GPC measurement (Waters corporation, the conversion of 2695 polystyrene) and DSC measurement are carried out ((DSC-6100, Seiko Instruments Inc. system, 5 DEG C of heating rate), has carried out molecular weight Mw respectively and vitrifying turns The confirmation of temperature Tg.As a result, confirmed that reaction time short person (following title is denoted as macromolecule resin A) is Weight-average molecular Measure Mw=50000, Tg=-10 DEG C.On the other hand, it is thus identified that reaction time elder (following title is denoted as macromolecule resin B) is Weight average molecular weight Mw=250000, Tg=-12 DEG C.
The preparation > of < hardening resin composition
Be put into the solvent recorded in embodiment and comparative example in a reservoir, stirred when being heated up to 50 DEG C, then, respectively plus Enter each ingredient in addition to filler.After confirmed the dissolution of these ingredients, filler is added, is sufficiently stirred.Later, triple-roller mill is used It is kneaded, prepares hardening resin composition.It should be noted that the numerical value in table indicates mass parts, in addition, except solvent is with appearance Show solid content.
Precipitating > after < stirring standing
It is put into the hardening resin composition prepared in transparent glass thread pipe, is being set as 23 DEG C of thermostat 12 hours progress maturation process of middle keeping.It is that 50mm puts into hardening resin composition from the bottom apart from screwed pipe.After curing, Hardening resin composition is taken out, is observed by visual observation by side, confirms the settling phase of hardening resin composition.Sentence Disconnected benchmark is as described below.
◎ ◎: sedimentation is had no.
◎: confirming the top apart from composition is the transparent supernatant lower than 1mm.
〇: confirming the top apart from composition is transparent supernatant of the 1mm more than or lower than 3mm.
△: confirming the top apart from composition is transparent supernatant of the 3mm more than or lower than 5mm.
×: confirm the transparent supernatant that the top apart from composition is 5mm or more.Confirmed with grind meter and is settled As a result object confirms aggregated particle.
The production of < dry film and the evaluation > of appearance
The amount of adjustment solvent makes viscosity become 0.5~20dPas (rotational viscometer 5rpm, 25 DEG C), is applied respectively using stick The hardening resin composition prepared is coated on carrier film in a manner of becoming 40 μm after the thickness of resin layer is dry by machine (PET film；Dongli Ltd. Lumirror 38R75,38 μm of thickness, size 30cm × 30cm).Then, it is followed in hot wind In ring drying furnace, in such a way that the residual solvent of resin layer becomes 0.5~2.5 mass %, with 70~120 DEG C (average 100 DEG C) 5~10 minutes dry, resin layer is formed on a carrier film.Based on white light source, with visual, by the surface state of resin layer It is divided into following 3 kinds of situations.
It is matt: under white light source, the reflection also not light-exposed on resin surface.
Semi-glossy: the slightly reflection of visible white light source.
Gloss: the reflection of visible white light source.
The adaptation > of < and biaxial stretch-formed polypropylene film (OPP)
Using layer of rolls press, keep OPP (ALPHAN FG-201, without flake, prince F-TEX) closely sealed in the dry film made Resin layer surface.The condition of layer of rolls press are as follows: 80 DEG C or 110 DEG C this 2 kinds of surface temperature, in line pressure 0.3MPa, conveying It is carried out under speed 5cm/sec.For the dry film of gained 3-tier architecture, the item of width 1cm, long 10cm are made, according in JIS-C-6481 The removing weight of measuring method (90 ° of directions, tensile speed 50mm/min) the measurement OPP of the peel strength of record.Evaluation criteria As described below.
◎: maximum peeling strength 3N/cm or more.
〇: maximum peeling strength 1N/cm is more than or lower than 3N/cm.
△: maximum peeling strength is lower than 1N/cm.
×: it is not closely sealed.
< cutting processing >
For the dry film of the 3-tier architecture of the closely sealed 30 × 30cm of size for having OPP, it is thus identified that be cut to end using cutter The state of 25 × 25cm size.Evaluation criteria is as described below.
◎: the floating of OPP, the rupture of resin do not occur.
〇: confirm the floating of OPP in cutting portion (largest portion is lower than 1mm).
△: floating and the rupture of resin end for OPP has occurred in cutting portion (largest portion 1mm is more than or lower than 5mm).
×: floating and the rupture of resin end (largest portion 5mm or more) for OPP has occurred in cutting portion.
< glass transition point (Tg) >
After the OPP of the dry film for the 3-tier architecture made is removed, with vacuum laminator MVLP-500, (name mechanism makees institute System), make the resin layer of dry film be pasted onto electrolytic copper foil glassy surface (GTS-MP-18, Furukawa Circuit Foil Co., Ltd. on).It is carried out in the case where condition is 80~110 DEG C of temperature, pressure 0.5MPa.Later, by carrier film stripping, in heated air circulation type Make material solidification in drying oven.It is carried out in the case where condition is 100 DEG C × 30min+180 DEG C × 30min+200 DEG C × 60min.Then, Gained solidfied material is removed from copper foil, obtains solidfied material.Later, sample is cut into measurement size (size of 3mm × 10mm), used The TMA6100 of Seiko Instruments Inc., is measured.TMA measurement is following to be carried out: to test counterweight 5g, 10 DEG C/ The heating rate of minute is by sample from room temperature to 280 DEG C, and later, air is cooled to room temperature, and METHOD FOR CONTINUOUS DETERMINATION 2 times.By the 2nd time In, the inflection point of the 2nd heating process evaluated as Tg.Evaluation criteria is as described below.
◎: Tg=190 DEG C or more.
〇: Tg=is lower than 190 DEG C.
< CTE >
In method same as the measuring method of Tg, implement TMA measurement.It will be flat between 30 DEG C in the 2nd time~100 DEG C Equal coefficient of thermal expansion is as CTE (unit ppm).
Warpage > on < copper foil
For the dry film made, after OPP is removed, with vacuum laminator MVLP-500 (Co., Ltd. Mingji Koito System), make dry film pasting in electrolytic copper foil (GTS-MP-18 μm, society, Furukawa Circuit Foil Co., Ltd. system, size 20 × 20cm) glassy surface on.It is carried out in the case where condition is 80~110 DEG C of temperature, pressure 0.5MPa.Later, by carrier film stripping, In heated air circulation type drying oven, make material solidification.Condition be 100 DEG C × 30min+180 DEG C × 30min+200 DEG C × It is carried out under 60min.After being cooled to room temperature, with the warped state at the 4 of vernier caliper measurement copper foil, (warped shapes are all immediately Smile-shaped).Evaluation criteria is as described below.
◎: without warpage.
In at 〇: 4, the amount of warpage of the big part of warpage the 1st is lower than 3mm.
In at △: 4, the amount of warpage of the big part of warpage the 1st is 3mm more than or lower than 10mm.
×: at 4, the amount of warpage of the big part of warpage the 1st is 10mm or more.
Closely sealed (low roughness cathode copper) > of < and substrate
12 μm thick to copper, the solid copper base (MCL-E-770G, Hitachi Chemical Co., Ltd.'s system) of plate thickness 0.2mm into Row electro-coppering (the surface roughness 100nm or less after Atotek corporation, plating) processing, makes copper thickness add up to 20 μm.Then, Carry out the flat bond processing (treated surface roughness 100nm hereinafter, Mecrk corporation) as pre-treatment.Later, With 2 cell-type vacuum laminator CVP-600 (Nichigo-Morton Co., Ltd. system), make the dry film pasting for having removed OPP in base Surface back side on plate.Lamination, pressurization are carried out in the case where condition is 80~110 DEG C of temperature, pressure 0.5MPa respectively.Then, it removes Carrier film solidifies resin layer in heated air circulation type drying oven.It is 100 DEG C × 30min+180 DEG C × 30min+200 in condition DEG C × 60min under carry out.Later, on the surface of gained cured film, 100 grids are made with size 1mm × 1mm with cutter Draw lattice (JIS-K5400, foundation cross cut test).Later, make polyester belt ((1) product number 8422B: bonding force 5.1N/cm and (2) product number 879: bonding force 15N/cm is 3M corporation) it is adhered to the surface of cut cured film, lift band immediately One end, with solidification film surface be held vertically throughout, moment release band.State according to the film after benchmark below judgement removing.
◎ ◎: using band (2), the grid removed is 0.
◎: using band (2), the grid removed be 1 at more than or lower than 5 at.Using band (1), the grid removed is 0。
〇: using band (1), the grid removed be 1 at more than or lower than 5 at.
△: using band (1), the grid removed be 5 at more than or lower than 20 at.
×: using band (1), the grid removed be 20 at more than.
< flatness >
Chip joint fastener FH-900 (10 μm of thickness, Hitachi Chemical Co., Ltd.'s system) is heated up to 60 DEG C and is pasted onto 150 μm of thickness, 10 × 10mm of size silicon analog chip the back side.Later, with vacuum laminator MVLP-500 (Co., Ltd.'s name Mechanism is made made；Condition is 100 DEG C, 0.5MPa, 1 minute time), soda-lime glass (thickness 1.1mm, size are pasted into 5mm spacing 60 × 60mm, Hiraoka Special Glass Company system) on.Later, with 2 cell-type vacuum laminator CVP-600 (Nichigo-Morton Co., Ltd. system), under conditions of the surface of resin becomes flat, with the total of the thickness of resin layer As 200 μm of mode, make the dry film pasting for having removed OPP on the glass substrate for being arranged with analog chip.Lamination, pressurization point It is not carried out in the case where condition is 80~110 DEG C of temperature, pressure 0.5MPa.Then, carrier film is removed, in heated air circulation type drying oven Make material solidification.It is carried out in the case where condition is 100 DEG C × 30min+180 DEG C × 30min+200 DEG C × 60min.As gained substrate Analog chip on flatness evaluation evaluated on chip and only solid with surface roughness measurement device Surfcorder SE-600 The bumps of the part of compound.Judge that benchmark is for example following.
◎: no concave-convex.
〇: bumps are lower than 5 μm.
△: concave-convex 5 μm more than or lower than 10 μm.
×: it is 10 μm concave-convex or more.
[table 1]
* 1: Mitsubishi chemical Co., Ltd jER828, bisphenol A type epoxy resin, epoxide equivalent 189g/eq, liquid
* 2:DIC Co. Ltd. system Epiclon N-740, phenol novolak type epoxy resin, epoxide equivalent 182g/eq, Semisolid
* 3: Mitsubishi chemical Co., Ltd Epikote YX4000H, 3,3 ' 5,5 '-tetramethyl -4,4- xenols two shrink Glycerin ether, epoxide equivalent 192g/eq, crystallinity
* 4: Nippon Kayaku K. K NC-3000H, biphenyl novolak type epoxy compounds, epoxide equivalent 290g/ eq、
* 5:Lonza Japan Ltd PRIMASET PT-30, phenolic varnish type cyanate ester resin, cyanate equivalent 124g/eq, solid-state
* 6:DIC Co. Ltd. system Epiclon HPC-8000, active ester resin, active equivalents 223g/eq, solid-state
* 7:DIC Co. Ltd. system LA-3018, the cresol novolac resin containing ATN, hydroxyl equivalent 151g/eq, solid-state
* 8: it is bright and chemical conversion Co. Ltd. system HF-1M, phenol resol resins, hydroxyl equivalent 106g/eq,
* 9: big and chemical conversion industry BMI-2300, phenylmethane bismaleimide, maleimide amine equivalent 187g/eq, Solid-state
* 10: four countries are melted into Co. Ltd. system 2E4MZ, 2-ethyl-4-methylimidazole
* 11: Tokyo Chemical Industry Co., Ltd CO (II) cobalt (II) acetylacetone,2,4-pentanedione, powder
* 12:Nagase ChemteX Corporation TEISANRESIN SG-80H MEK dissolves product, solid component 18 mass %, acrylate copolymer (functional group: epoxy group, amide groups)
* 13:Nagase ChemteX Corporation TEISANRESIN SG-P3MEK dissolves product, solid component 15 Quality %, acrylate copolymer (functional group: epoxy group)
* 14:Nagase ChemteX Corporation TEISANRESIN SG-280MEK dissolves product, solid component 23 mass %, acrylate copolymer (functional group: carboxyl)
* 15:Nagase ChemteX Corporation TEISANRESIN WS-023MEK dissolves product, solid component 30 mass %, acrylate copolymer (functional group: carboxyl, hydroxyl)
* 16: the polymer (macromolecule resin A) of the polybutadiene and IPDI that synthesize among the above
* 17: the polymer (macromolecule resin B) of the polybutadiene and IPDI that synthesize among the above
* 18: Mitsubishi chemical Co., Ltd YX6954, phenoxy resin, Mw=38000, Tg=130 DEG C
* 19:ADMATECHS COMPANY SO-C2, spherical silicon dioxide, average grain diameter (D50)=0.5 μm are (with partial size Peak value in measure of spread is identical)
* 20:ADMATECHS COMPANY SO-C1, spherical silicon dioxide, average grain diameter (D50)=200nm are (with partial size Peak value in measure of spread is identical)
* 21:ADMATECHS COMPANY YA050SV2, carry out with vinyl silanes KBM-1003, with 1 mass % The spherical silicon dioxide of processing, average grain diameter (D50)=50nm (identical as the peak value in particle size distribution measuring)
* 22: the gloomy Co. Ltd. system MUF-1BV of dragon, spherical silicon dioxide, average grain diameter (D50)=3 μm are (with particle diameter distribution Peak value in measurement is identical)
* 23: the gloomy Co. Ltd. system MSS-T72 of dragon, spherical silicon dioxide, average grain diameter (D50)=5 μm are (with particle diameter distribution Peak value in measurement is identical)
* 24:ADMATECHS COMPANY SO-C5, spherical silicon dioxide, average grain diameter (D50)=1.5 μm are (with partial size Peak value in measure of spread is identical)
* 25:Denka Company ASFP-20, aluminium oxide, average grain diameter (D50)=0.3 μm are (with particle size distribution measuring In peak value it is identical)
* 26:Shin-Etsu Silicone Company KBM-403, epoxy silane coupling agent
* 27: methyl ethyl ketone
[table 2]
[table 3]
For the result as shown in above-mentioned table it is found that in the case where the dry film of embodiment, the adaptation of resin layer and protective film is good It is good, and the sedimentation of inorganic filler contained in resin layer is few.In addition we know, in the case where the dry film of embodiment, when cutting is processed Removing, rupture picking inhibition, resistance to warpage, also excellent with the flatness of the adaptation of substrate, solidfied material surface.

Claims (7)

1. a kind of dry film, which is characterized in that have: carrier film, resin layer and protective film,
The protective film is biaxial stretch-formed polypropylene film,
The resin layer includes: inorganic filler；The high score that glass transition point is 20 DEG C or less and weight average molecular weight is 30,000 or more Subtree rouge；And epoxy resin,
The resin layer includes that at least wantonly a kind in semisolid epoxy resin and Cristalline epoxy resin is used as the asphalt mixtures modified by epoxy resin Rouge.
2. dry film according to claim 1, which is characterized in that the resin layer include with phenolic hydroxyl group compound, At least appointing in the compound of active ester group, the compound with cyanic acid ester group and the compound with dimaleoyl imino 1 kind is used as curing agent.
3. dry film according to claim 1 or 2, which is characterized in that the resin layer includes that average grain diameter is 0.1~10 μm Inorganic filler and average grain diameter be 0.01~5 μm inorganic filler mixture, and the average grain diameter is 0.1~10 μm Peak-to-peak difference in the particle size distribution measuring for the inorganic filler that inorganic filler and the average grain diameter are 0.01~5 μm is 0.05 μm More than.
4. dry film according to claim 1 or 2, which is characterized in that comprising with the solid component total amount base of the resin layer Standard is calculated as the inorganic filler of 50 mass % or more.
5. dry film according to claim 3, which is characterized in that comprising in terms of the solid component total amount benchmark of the resin layer For the inorganic filler of 50 mass % or more.
6. a kind of solidfied material, which is characterized in that it is to consolidate the resin layer of dry film described in any one of Claims 1 to 5 Obtained from change.
7. a kind of electronic component, which is characterized in that have solidfied material as claimed in claim 6.
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