CN101978798B - Re-releasable process film - Google Patents

Re-releasable process film Download PDF

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Publication number
CN101978798B
CN101978798B CN2009801095985A CN200980109598A CN101978798B CN 101978798 B CN101978798 B CN 101978798B CN 2009801095985 A CN2009801095985 A CN 2009801095985A CN 200980109598 A CN200980109598 A CN 200980109598A CN 101978798 B CN101978798 B CN 101978798B
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film
releasable
engineering
engineering film
nappe
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CN101978798A (en
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那须健司
山田晃史
仓田雄一
田畠浩司
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Lintec Corp
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Lintec Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4602—Manufacturing multilayer circuits characterized by a special circuit board as base or central core whereon additional circuit layers are built or additional circuit boards are laminated
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2425/00—Presence of styrenic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

A re-releasable process film which comprises a base film and, formed on one side thereof, a pressure-sensitive adhesive layer comprising: an acrylic copolymer (A) which comprises 40-80 mass% butyl acrylate units, 1-15 mass% styrene units, 1-30 mass% methyl methacrylate units, 1-30 mass% methyl acrylate units, 1-10 mass% hydroxylated vinyl monomer units, and 0.1-1 mass% carboxylated vinyl monomer units and has a weight-average molecular weight (Mw) of 300,000-1,000,000 and a molecular-weight distribution (Mw/Mn) of 3.0 or lower; and an isocyanate crosslinking agent (B). In the case where this process film is applied to a base sheet as an adhered element, the process film is inhibited from fouling the base sheet upon releasing therefrom. This base sheet has sufficient adhesion to an adhesive sheet to be applied after the releasing to the exposed surface. The process film is applicable even to an adhered element which is a glass part to be exposed to a high temperature of around 260 DEG C.

Description

Releasable engineering film
Technical field
The present invention relates to a kind of releasable engineering film, relate in more detail a kind of flexible printing wiring substrate for multi-layer printed circuit board make with the base material thin plate be suitable for metal material or the glass portion of in addition inorganic material such as charge coupled device or complementary mos device etc., have simultaneously releasable engineering film of the acrylic adhesives layer of upper setting of base film and its.
Background technology
Printed wiring board is that the conductor circuit pattern is waited surface or surface and the inner distributing board thereof be formed at insulated substrate by printing, and the circuit pattern of described conductor is necessary for connecting between carry thereon electric, electronic component.
Such printed wiring board sees from the shape face and roughly is divided into hard printed wiring board and flexible printing wiring substrate, is divided into individual layer, multilayer more than two-layer from structure.
In these printed wiring boards, the flexible printing wiring substrate is the goods that form the circuit pattern of conductor at the insulating properties base material thin plate that is rich in flexibility, at electronic instrument inner narrow and have three-dimensional high-density degree in labyrinth, the space install in indispensable substrate.Such flexible printing wiring substrate is the strongest electronic instrument one of the parts that require acquisition for the miniaturization and that adapts to electronic instrument class in recent years, densification, high precision int etc., and its demand is accelerated just rapidly.
In the above-mentioned flexible printing wiring substrate, because require to have pliability, base material thin plate as insulating properties uses sheet plastic, sheet plastics such as the good polyimides thin plate such as thermal endurance or insulating properties, polyphenylene sulfide thin plate, then on surface or the surface and inner of this base material thin plate, form circuit pattern by metal materials such as copper.As the formation method of circuit pattern, the known necessary part that the Copper Foil that for example only stays the laminated plate that spreads copper is arranged is removed outside the relief method of other parts by the etch processes dissolving, and known have an addition process etc.This addition process is only the necessary part of substrate to be used the method for electroplating processes formation circuit pattern, and semi-additive process or fully-additive process are arranged.
Performance as such flexible printing wiring substrate requirement, such as having beyond dimensional accuracy, low warpage twisting coefficient, thermal endurance, peel strength, bending strength, high specific insulation, resistance to chemical reagents, the thermal bending intensity etc., the processability of printed wiring board also is important.
In such flexible printing wiring substrate, in the formation of foregoing circuit or mounting electrical, electronic component process, sneak in order to suppress solvent contamination, foreign material to this wiring substrate, the generation of flaw etc., generally before carrying out these processing, on the base material thin plate of flexible printing distribution base material making usefulness, attach in advance releasable engineering film.This project film is the adhesive phase that can peel off again the one side setting of base film, after the base material thin plate that the flexible printing wiring substrate is used attaches, after the various steps such as punch process, solvent impregnated, hot pressing, peel off from the flexible printing wiring substrate of making.Thereby, can in above-mentioned steps, not produce floating or peel off etc., do not have glue residual on the nappe after peeling off (base material thin plate), and on nappe, do not produce crimping, it is very important having releasable.
So, the applicant at first carries out above-mentioned processing at the base material thin plate of flexible printing wiring substrate making usefulness, make in the flexible printing wiring substrate process, can not produce depart from, floating, peel off etc., can effectively suppress to solvent contamination, the foreign material on this wiring substrate surface sneak into, the generation of flaw etc., it is residual to be difficult to produce glue at nappe after peeling off simultaneously, nappe can not produce crimping, find such releasable engineering film, file an application (for example referring to patent documentation 1).
In recent years, along with high performance, the high speed of electronic instrument are followed and come printing distributing board also to require high-density installation, high density distribution, the multi-layer printed circuit board that satisfies this requirement gets most of the attention.And then, being accompanied by the recently miniaturization of electric, electronic instrument, multi-layer printed circuit board more and more requires slimming, densification, uses the multi-layer printed circuit board of adhesive thin plate (heat reactive resin thin plate) to be used.
In the manufacturing of such multi-layer printed circuit board, such as employing the adhesiveness thin plate that flexible printing wiring substrate that circuit pattern, electric, electronic unit installs inserts epoxylite thin plate etc. is set, with other flexible printing wiring substrate overlapping method repeatedly.
Particularly, form circuit pattern on the general base material thin plate that adopts releasable engineering film to attach, and then installing electronic elements, arrange thereon and cover thin plate (such as polyimides etc.) as a unit, peel off above-mentioned releasable engineering film, the base material thin plate that exposes is relative with the covering thin plate of other unit, inserts the adhesiveness thin plates such as epoxylite thin plate between it, is stacked in the method on the said units.In the method, the bonding enough height between unit and the unit.
On the other hand, in recent years, carry the solid photographic elements such as charge coupled device (CCD) or complementary mos device (CMOS) in digital camera, video camera, the camera cell phone etc.When making the product of these CCD or CMOS, for attaching on the glass portion that receives light usually as the releasable engineering film of protecting usefulness.Above-mentioned glass portion has in anti-flow step etc. and is exposed to high temperature (for example about 260 ℃), thereby, to being used for the releasable engineering film of this purposes, require the excellent heat resistance of this temperature of tolerance, for example distortion residual to the glue of nappe or base film is few.
[patent documentation 1] TOHKEMY 2005-281423 communique
Summary of the invention
The releasable engineering film of record as previously mentioned in the above-mentioned patent documentation 1, when the base material thin plate attaches as nappe, depart from although have can not produce, float, peel off etc., can effectively suppress the solvent contamination to this wiring substrate surface, foreign material are sneaked into, flaw generation etc., it is residual to be difficult to produce glue at nappe after peeling off simultaneously, be difficult to produce at nappe the good characteristic of crimping, but when using the wiring substrate unit that is used for multi-layer printed circuit board, when peeling off this releasable engineering film, the base material thin plate side of nappe is contaminated, the bonding force of the adhesiveness thin plate such as the epoxylite class thin plate that uses in the lamination of unit and unit and this base material thin plate is insufficient, wishes to improve this problem.
And, be applicable to require excellent heat resistance in the purposes of glass portion of CCD or CMOS, for example under 260 ℃, the releasable engineering film of several minutes anti-flow steps of tolerance.
The present invention is based on such situation, a kind of releasable engineering film of the acrylic adhesives layer that has base film and arrange in its one side is provided, when using the flexible printing wiring substrate that is used for multilayer printed wiring board to make with the base material thin plate, when peeling off this releasable engineering film, can suppress nappe is the pollution of base material thin plate side, abundant raising epoxylite thin plate etc. is the bonding force of adhesiveness thin plate and this base material thin plate, when perhaps being used for the glass portion of CCD or CMOS, even be exposed near the lower time of temperature 260 ℃, provide the distortion of or base film residual to the glue of nappe few, the releasable engineering film of excellent heat resistance.
The inventor studies intensively to achieve these goals repeatedly, found that when the flexible printing wiring substrate making that is used for multi-layer printed circuit board is used with the base material thin plate, when peeling off releasable engineering film, be the oligomer composition in the acrylic adhesives layer in the releasable engineering film to covering the polluter that shifts on the side.The inventor reduces the content of this oligomer composition in the acrylic adhesives layer; further again research; found that when making the acrylic adhesives that consists of above-mentioned adhesive phase; the resinous principle of control in the acrylic adhesives is that the molecular weight distribution of acrylic acid esters co-polymer is at certain below the value; the content of the remaining monomer of preferred control is in certain scope simultaneously; can reduce the content of oligomer composition in the adhesive; and the peeling agent layer of the release liner of the protection when using as adhesive phase; by using non-silicone class material; make the attaching usefulness of using the base material thin plate as above-mentioned flexible printing wiring substrate, obtain more suitably releasable engineering film.
Have again, when being used for the glass portion attaching of CCD or CMOS, below the value, can obtain the releasable engineering film of excellent heat resistance at certain by the rate of change that uses the dynamic elastic modulus ratio that is limited by specific formula as base film.The present invention is based on these knowledge and finishes.
That is, the invention provides:
[1] a kind of releasable engineering film, it is characterized in that the adhesive phase that has base film and arrange in one surface, above-mentioned adhesive phase contains the butyl acrylate units that (A) has 40～80 quality %, the styrene units of 1～15 quality %, the methyl methacrylate units of 1～30 quality %, the methyl acrylate unit of 1～30 quality %, the vinyl monomer unit that contains hydroxyl of 1～10 quality %, 0.1 the acrylic acid esters co-polymer of the vinyl monomer unit that contains carboxyl of～1 quality %, (B) isocyanates crosslinking agent, above-mentioned adhesive phase is that the weight average molecular weight Mw of use aforesaid propylene esters of gallic acid copolymer is 300,000～1,000,000 simultaneously, and molecular weight distribution (weight average molecular weight Mw/ number-average molecular weight Mn) is that the adhesive below 3.0 forms.
[2] above-mentioned [1] described releasable engineering film is characterized in that the content of the remaining monomer in (A) acrylic acid esters co-polymer is 5～20 quality % with respect to above-mentioned (A) acrylic acid esters co-polymer.
[3] a kind of releasable engineering film, it has the releasable engineering film of above-mentioned [1] or [2] record and the release liner of non-silicone class peeling agent layer, and the adhesive phase of above-mentioned releasable engineering film carries out lamination with respect to the peeling agent layer side of above-mentioned release liner.
[4] above-mentioned [3] described releasable engineering film, wherein non-silicone class peeling agent layer is acrylic resin.
[5] one of any described releasable engineering film of above-mentioned [1]～[4], wherein adhesive contains toluene di-isocyanate(TDI) class crosslinking agent and paraxylene diisocyanates crosslinking agent as the isocyanates crosslinking agent.
[6] one of any described releasable engineering film of above-mentioned [1]～[5], the sheet plastic of the flexible printing wiring substrate that wherein uses in multi-layer printed circuit board is suitable as nappe.
[7] above-mentioned [6] described releasable engineering film, wherein (a) is with respect to the confining force of the sheet plastic that uses in the flexible printing wiring substrate as nappe, assay method based on JIS Z0237, under 40 ℃ of temperature, be 70, more than 000 second, and 70, depart from not enough 0.1mm in the time of 000 second, (b) with respect to the bonding force of the sheet plastic that uses in the flexible printing wiring substrate as nappe, before hot pressing, assay method based on JIS Z 0237 is 0.01～0.5N/25mm, after the sheet plastic that (c) uses in the flexible printing wiring substrate as nappe attaches, 180 ℃ of temperature, pressure 4.3N/mm 2Condition under carry out bonding force after 60 minutes the hot pressing, be below the 2.0N/25mm based on the assay method of JIS Z 0237, and (d) the gel percentage of adhesive phase is more than 95%.
[8] above-mentioned [6] or [7] described releasable engineering film, wherein the plastic film of flexible printing wiring substrate is the film that uses polyimides thin plate or polyphenylene sulfide thin plate to obtain.
[9] one of any described releasable engineering film of above-mentioned [6]～[8], wherein base film is pet film.
[10] one of any described releasable engineering film of above-mentioned [1]～[4], wherein metal material or the inorganic material beyond it are suitable as nappe.
[11] the releasable engineering film described in above-mentioned [10], wherein nappe is the glass portion in charge coupled device or the complementary mos device.
[12] the releasable engineering film described in one of any or [10] or [11] of above-mentioned [1]～[4], wherein adhesive is as the isocyanates crosslinking agent, the goods that use paraxylene diisocyanates crosslinking agent to obtain.
[13] the releasable engineering film described in above-mentioned [1]～[4], [10]～[12] one of any, wherein the dynamic elastic modulus ratio of base film in the time of 23 ℃ is as G ' 23, the dynamic elastic modulus ratio in the time of 260 ℃ is as G ' 260The time, the rate of change X of the dynamic elastic modulus ratio that is expressed from the next is below 85%.
X(％)＝[(G’ 23-G’ 260)/G’ 23]×100
[14] one of any described releasable engineering film of above-mentioned [1]～[8], [10]～[13], wherein base film is polyimide film.
According to the present invention, a kind of releasable engineering film that has base film and the acrylic adhesives layer is set in its one side can be provided, (1) when the flexible printing wiring substrate that uses for multi-layer printed circuit board is made with the base material thin plate, when peeling off this releasable engineering film, can suppress nappe is the pollution of base material thin plate side, the reduction of the adhesiveness thin plate of inhibition epoxylite thin plate etc. and the bonding force of this base material thin plate.And when glass portion that a kind of (2) be applicable to metal material or inorganic material in addition such as CCD or CMOS etc. can be provided, even be exposed under near the temperature 260 ℃, distortion residual to the glue of nappe or base film is few, the releasable engineering film of excellent heat resistance.
Embodiment
Releasable engineering film of the present invention (following referred to as " engineering film ") is to have base film and the releasable engineering film of the adhesive phase that arranges in its one side, the acrylic acid esters co-polymer that it is characterized in that the specific monomeric unit with special ratios of above-mentioned adhesive phase shown in containing below (A), (B) isocyanates crosslinking agent, the weight average molecular weight Mw that uses simultaneously aforesaid propylene esters of gallic acid copolymer is 300,000～1,000,000, and molecular weight distribution (weight average molecular weight Mw/ number-average molecular weight Mn) is that the adhesive below 3.0 forms.
Releasable engineering film of the present invention with adhesive phase of such characteristic can be divided into releasable engineering film A (following referred to as " engineering film A ") and releasable engineering film B (following referred to as " engineering film B ") according to the purposes difference.
Engineering film A is the engineering film of nappe that is suitable as the sheet plastic of flexible printing wiring substrate, described sheet plastic forms the circuit pattern of conductor at the base material thin plate that is rich in flexibility, insulating properties that is used for multi-layer printed circuit board, and engineering film B is the engineering film that is suitable as the nappe that metal material or inorganic material such as the glass portion of CCD or CMOS beyond it use etc.
[engineering film A base film]
As the base film among the releasable engineering film A of the present invention, requirement is the film of excellent heat resistance, specifically can enumerate pet film, polycarbonate film, the amorphous polyolefins film, the aromatic polyamides film, the PEN film, PPS (polyphenylene sulfide) films, and then also has the aromatic series polysulphone film, the Polyetherimide film, the polyarylate film, poly (ether ether ketone) film, the Super Engineering plastic films such as various liquid crystal polymer films etc., in them, from taking into account good mechanical property, electrical insulating property, barrier, thermal endurance, resistance to chemical reagents, the considerations such as economy are fit to use pet film.The thickness of this base film is not particularly limited, but is generally 16～200 μ m, is preferably the scope of 25～100 μ m.
[engineering film B base film]
Engineering film B base film is that metal material or other inorganic material are used, and requires better thermal endurance than above-mentioned engineering film A with base film.For example, when engineering film B is applicable to the glass portion of CCD or CMOS, have situation under near the high temperature that is exposed to 260 ℃ by anti-flow step etc., thereby require the good thermal endurance (distortion residual to the glue of nappe or base film is few) of this temperature of tolerance.
In addition, as the applicable metal material of engineering film B, such as enumerating gold, platinum, silver, copper, iron, aluminium or its alloy, being used for the semiconductor alloy of wafer etc., as the inorganic material beyond the metal material, such as having enumerated glass plate, ceramic wafer etc.
As engineering film B base film, the dynamic elastic modulus ratio in the time of 23 ℃ is G ' 23, the dynamic elastic modulus ratio in the time of 260 ℃ is G ' 260The time, the rate of change X that preferably uses the dynamic elastic modulus ratio that following formula represents is the film below 85%.
X(％)＝[(G’ 23-G’ 260)/G’ 23]×100
As such base film, such as having enumerated polyimide film or aromatic polyamides film etc., be particularly suitable for using polyimide film.
In addition, above-mentioned dynamic elastic modulus ratio G ' 23With dynamic elastic modulus ratio be G ' 260It is the value of measuring with following method.
(TA イ Application ス Star Le メ Application Star company makes as 20mm is installed in the Measurement of Dynamic Viscoelasticity device take measured length (distance between chuck) with base film, trade name " DMA-Q800 ") in, under the condition of 5 ℃/minute of frequency 11Hz, amplitude 20 μ m, programming rates, measure the dynamic elastic modulus ratio G ' of 15～300 ℃ of temperature ranges, the dynamic elastic modulus ratio G ' when measuring 23 ℃ 23, the dynamic elastic modulus ratio G ' in the time of 260 ℃ 260
This project film B is not particularly limited with the thickness of base film, but is generally 16～200 μ m, preferably in the scope of 25～100 μ m.
For improve above-mentioned engineering film A with and B with the adhesiveness of base film and adhesive phase, at least to implementing as required the surface treatment such as oxidizing process or concavo-convexization method on the surface that adhesive phase one side is set.And, also can implement bottom layer treatment.As above-mentioned oxidizing process, process (wet type), flame treatment, hot blast processing, ozone-ultraviolet line treatment with irradiation etc. such as using Corona discharge Treatment, plasma treatment, chromic acid, as concavo-convexization method, such as using sand-blast, solvent treatment method etc.These surface preparations can suit according to the kind of base film to select, but the Corona discharge Treatment method is preferred from considerations such as effect and operability usually.
[engineering film A uses and the B adhesive phase]
Among releasable engineering film A of the present invention and the B, the adhesive phase that arranges in the one side of above-mentioned base film can use contain (A) have at least butyl acrylate units, styrene units, methyl methacrylate units, methyl acrylate unit, contain the vinyl monomer unit of hydroxyl and contain carboxyl the vinyl monomer unit acrylic acid esters co-polymer and (B) the isocyanates crosslinking agent adhesive and form.
((A) acrylic acid esters co-polymer)
In the adhesive that uses among the present invention, (A) methyl methacrylate units in the acrylic acid esters co-polymer of composition and styrene units have and improve cohesiveness and glass transition temperature, (after the hot pressing flexible printing wiring substrate are departed among the A or the rising of bonding force has inhibitory action at the engineering film.On the other hand, the methyl acrylate unit has the effect of stabilized polymeric, raising molecular weight in the manufacturing of this acrylic acid esters co-polymer.The vinyl monomer unit that contains hydroxyl in this acrylic acid esters co-polymer is to import in order to give the bridging property functional group (hydroxyl, carboxyl) that obtains with crosslinking agent reaction described later in this acrylic acid esters co-polymer with the vinyl monomer unit that contains carboxyl.
As forming the above-mentioned monomer that contains the vinyl monomer unit of hydroxyl, can enumerate (methyl) acrylic acid hydroxyalkyl acrylates such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 3-hydroxy butyl ester, (methyl) acrylic acid 4-hydroxy butyl ester etc.They can be used alone, and also can be used in combination.In them, be fit to use acrylic acid 2-hydroxyl ethyl ester and HEMA.
On the other hand, as forming the above-mentioned monomer that contains the vinyl monomer unit of carboxyl, such as the ethene unsaturated carboxylic acid that can enumerate acrylic acid, methacrylic acid, butenoic acid, maleic acid, itaconic acid, citraconic acid etc. etc.They can be used alone, and also can be used in combination.Be fit to use methacrylic acid and acrylic acid in them.
Among the present invention, by introduce simultaneously the above-mentioned vinyl monomer unit that contains the vinyl monomer unit of hydroxyl and contain carboxylic acid in this acrylic acid esters co-polymer, the reactivity of this acrylic acid esters co-polymer and crosslinking agent is good.
In the resinous principle acrylic acid esters co-polymer of above-mentioned adhesive, the content of butyl acrylate units is as described later as long as more than 40.0 quality %, engineering film A is attached to the manufacturing of flexible printing wiring substrate with on the base material thin plate, for example be difficult to produce departing between this base material thin plate and the engineering film during hot pressing.
The content ratio of above-mentioned each unit in this acrylic acid esters co-polymer, consider from the performance of adhesive, butyl acrylate units is 40～80 quality %, styrene units is 1～15 quality %, methyl methacrylate units is 1～30 quality %, the methyl acrylate unit is 1～30 quality %, the vinyl monomer unit that contains hydroxyl is 1～10 quality % and vinyl monomer unit 0.1～1 quality % that contains carboxyl, and preferred butyl acrylate units is 50～65 quality %, styrene units is 2～10 quality %, methyl methacrylate units 3～20 quality %, the methyl acrylate unit is 5～20 quality %, the vinyl monomer unit that contains hydroxyl is that 2～7 quality % and the vinyl monomer unit that contains carboxyl are 0.1～0.5 quality %.
And then, in the aforesaid propylene esters of gallic acid copolymer, according to expectation, can use can with other monomers of above-mentioned monomer copolymerization as the combined polymerization composition.As other the example of monomer, can enumerate (methyl) ethyl acrylate, (methyl) propyl acrylate, butyl methacrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid myristyl ester, (methyl) aliphatic acrylate, the alkyl carbon atoms number of the ester moiety beyond the butyl acrylate of (methyl) acrylic acid stearyl etc. and (methyl) methyl acrylate is (methyl) acrylate of 2～20; The vinyl esters of vinylacetate, propionate etc.; The olefines such as ethene, propylene, isobutene; The haloalkene hydro carbons of vinyl chloride, vinylidene chloride etc.; The dienes monomer of butadiene, isoprene, chlorobutadiene etc.; The nitrile monomer such as acrylonitrile, methacrylonitrile; The acrylic amide of acrylamide, N methacrylamide, N,N-DMAA etc.; AMS etc.They can use separately, also can be used in combination.
Among the present invention, its combined polymerization form of aforesaid propylene esters of gallic acid copolymer is not particularly limited, and can be any of random, block, graft copolymer.And, molecular weight satisfy weight average molecular weight Mw be 300,000～1,000,000 and molecular weight distribution (weight average molecular weight Mw/ number-average molecular weight Mn) be below 3.0.
If above-mentioned number-average molecular weight Mw satisfies 300,000～1,000,000 scope, just the adhesive of acquisition can be brought into play good bond properties.And molecular weight distribution mw/mn is below 3.0, and weight average molecular weight is 1,000～30, and the content of about 000 oligomer is few, can realize purpose of the present invention.Preferred molecular weight distribution mw/mn is below 2.8.
In addition, above-mentioned weight average molecular weight Mw and number-average molecular weight Mn measure by the following condition that the present invention does not specify according to gel permeation chromatography (GPC) method mensuration, with the value of polystyrene conversion.
The GPC device: high speed GPC device (East ソ one (strain) made, trade name " HLC-8120GPC ")
Post: high speed post [East ソ one (strain) made, trade name " TSK guard column H XL-H ", " TSKGel GMH XL", " TSKGel GMH XL", " TSKGel G2000H XL"], measure in the device connection according to this order.
Eluting solvent: oxolane
Polymer concentration 10mg/ml)
Temperature: 40 ℃
Flow velocity: 1.0ml/ minute
Detector: ultraviolet visual detection device (detector wavelength; 254nm) with differential refractometer " Dou Shi East ソ one (strain) manufacturing "
In addition, monomer component adopts the value of getting rid of.
At present, resinous principle in the acrylic adhesives is in the manufacturing of acrylic acid esters co-polymer, usually use (methyl) acrylate, have the vinyl monomer of functional group of reactive hydrogen and other monomers that use according to expectation, till the monomer that consumes in the presence of radical polymerization initiator and the suitable solvent about 40%, carry out the radical polymerization of phase I, afterwards remaining unreacted monomer is eliminated as far as possible and consumed, carry out the radical polymerization of second stage, adopt the two-stage polymerization method.
But, the inventor is by research, find to adopt such two-stage polymerization method, in the second step polymerization, can produce more above-mentioned oligomer, this oligomer is when the base film of nappe is peeled off releasable engineering film A, shift to this nappe one side, can reduce the adhesive films of epoxylite film etc. and the bonding force of this nappe.Thus, the inventor is through further research, remaining quantity by the unreacted monomer of control in above-mentioned first step radical polymerization accounts for about 5～20 quality % of the acrylic acid esters co-polymer in the adhesive of generation, preferred 5～15 quality % just stop reaction, can reduce like this formation of oligomer.The weight average molecular weight Mw of the acrylic acid esters co-polymer that generates thus successfully is controlled in 300,000～1,000,000 scopes, and molecular weight distribution mw/mn is below 3.0.Diffusion when the remaining unreacted monomer that contains in adhesive heating when forming adhesive phase, the dry processing does not have in fact residual in adhesive phase.
((B) isocyanates crosslinking agent)
Among the present invention, as the crosslinking agent of this adhesive, the isocyanates crosslinking agent uses as neccessary composition.As the example of this isocyanates crosslinking agent, can enumerate the toluene di-isocyanate(TDI) class, the methyl diphenylene diisocyanate class, the aromatic poly-isocyanate class of paraxylene diisocyanates etc., the aliphatic polymeric isocyanate class of hexamethylene diisocyanate class etc., the IPDI class, the ester ring type PIC class of hydrogenation methyl diphenylene diisocyanate class etc. etc. and their biuret body, the isocyanuric acid ester body, and then and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, the reactant of the compound that contains low molecular activity hydrogen of castor-oil plant wet goods is adduction object etc.
In these isocyanates crosslinking agents, in engineering film A, the adhesiveness of considering reactivity or base material and adhesive is good, reduce the bonding force that obtains appropriateness after the residual and hot pressing of glue etc., expects to be combined with toluene di-isocyanate(TDI) class crosslinking agent and paraxylene diisocyanates crosslinking agent.At this moment, its use amount is with respect to the aforesaid propylene esters of gallic acid copolymer of 100 mass parts, the total amount of toluene di-isocyanate(TDI) class and paraxylene diisocyanates is generally the scope of 0.5～30 mass parts, preferred 1.0～20 mass parts, thus the selected adhesive phase that can obtain to have the aftermentioned proterties.
On the other hand, among the engineering film B, consider stable on heating words, preferred paraxylene diisocyanates.Its use amount is generally 0.5～30 mass parts with respect to the aforesaid propylene esters of gallic acid copolymer of 100 mass parts, is preferably the scope of 1.0～20 mass parts.
In this adhesive, in the scope of harmless the object of the invention, can suit to be added on normally used various additives in the acrylic adhesives, such as antioxidant, ultra-violet absorber, light stabilizer, softening agent, filler, crosslinking accelerator etc. according to expectation.In addition, can be combined with bonding imparting agent, but because bonding force is risen, not be preferred.
[character of releasable engineering film A]
Preferably has following character among the releasable engineering film A of the present invention that uses above-mentioned adhesive to form.
At first, being the manufacturing of flexible printing wiring substrate with respect to nappe is generally more than 70,000 seconds with the confining force of base material thin plate, and preferably has not been considered to the substantial generation that departs from the time of 70,000 seconds.This confining force less than 70,000 seconds attaches to the engineering film on the base material thin plate of nappe, through suppressing processing, be impregnated in the solvent, the operating procedure of hot pressing etc., have the possibility that generation departs between engineering film and the nappe.In addition, above-mentioned confining force is the value of measuring according to following method.And the generation that departs from " thinking does not in fact have " refers to depart from not enough 0.1mm in the time of 70,000 seconds.
(confining force)
Based on JIS Z 0237, to measure with in the engineering film attaching section of test film at the confining force that SUS makes, bonding conduct is used for the polyimides thin plate of the base film of flexible wiring substrate making, makes test film.Then, severing engineering film is made the test film of wide 25mm, long 150mm.Contact with the area of 25mm * 25mm at an end of test film this test film an end the adhesive aspect and attach, come back pressure 5 times with the roller of 2kg.Be arranged on after 15 minutes in the creep tester, under 40 ℃ condition, placed 15 minutes.Bear a heavy burden vertically downward with 9.807N, measure when falling or have or not the amount that produces and depart from that departs from 70,000 seconds the time.
Then, be that the bonding force of the base material thin plate of flexible printing wiring substrate manufacturing usefulness is preferably 0.01～0.5N/25mm, 180 ℃ of temperature, pressure 4.3N/mm before hot pressing with respect to nappe 2Condition under, hot pressing was preferably below the 2.0N/25mm after 60 minutes.If the bonding force before the hot pressing is in above-mentioned scope, it is that the printed wiring board manufacturing is with on the base material thin plate that the engineering film is attached to nappe, even suppress processing or solvent impregnatedly wait the front mechanically actuated operation of hot pressing, just has sufficient bonding force, be difficult between engineering film and the nappe produce and depart from, the engineering film is peeled off easily, and can suppress to peel off the crimping of the residual or nappe of the glue of rear generation.Bonding force before the hot pressing is preferably 0.03～0.4N/25mm.And, if the bonding force after the hot pressing is below 2.0N/25mm, it is that printed wiring board is made of on the base material thin plate that the engineering film is attached to nappe, carries out after the hot press operation just than being easier to peel off the engineering film, and can suppress to peel off the crimping of the residual or nappe of the glue of rear generation.And, when carrying out hot press operation, because have sufficient bonding force, can suppress the generation that departs between engineering film and the nappe, the lower of bonding force is limited to about 0.08N/25mm after the hot pressing.Bonding force after the preferred hot pressing is 0.12～1.0N/25mm.In addition, before the hot pressing and the bonding force after the hot pressing be the value of measuring according to following method.
(bonding force before the hot pressing)
Based on JIS Z 0237, to measure with in the engineering film attaching section of test film at the bonding force that SUS makes, bonding conduct is made test film for the polyimides thin plate of wide 120mm, the long 150mm of the base film of flexible wiring substrate making.On the other hand, the engineering film is cut into the test film of wide 25mm, long 250mm.With the adhesive aspect of an end of this test film take area of attachment as wide 25mm * be about 90mm to attach on the test film, come back pressure 1 time with the roller of 2kg.With peel angle 180 degree, peeling rate 300mm/ minute disbonded test sheet, measure the bonding force of this moment after attach to 24 hours.Remove measure the beginning zone and stop the zone each 15%, with the mean value of middle body 70% bonding force before as hot pressing.
(bonding force after the hot pressing)
Prepare a flexible printing wiring substrate that has been cut into wide 120mm, long 150mm size and make the base material thin plate (polyimides thin plate) of usefulness, on the other hand, the engineering film is cut into the test film of wide 100mm, long 250mm.With the adhesive aspect of an end of this test film take area of attachment as wide 100mm * after being about 90mm and attaching on the base material thin plate, on the pressing plate under 180 ℃ of the temperature from the test film 4.3N/mm that exerts pressure 2, carry out hot pressing in 60 minutes.Then, the thin plate of the test film after the hot pressing and the applying of base material thin plate is cut into wide 25mm, long 250mm, bonding force mensuration test film in the bonding SUS manufacturing of base material thin plate side, based on JIS Z 0237, the bonding force when being determined at peel angle 180 degree, peeling rate 300mm/ minute lower disbonded test sheet.Remove measure the beginning zone and stop the zone each 15%, with the mean value of middle body 70% bonding force after as hot pressing.
And then the gel percentage of adhesive phase is usually more than 95% among releasable engineering film A of the present invention and the B.The words of this gel percentage less than 95%, among the engineering film A, be that printed wiring board is made the adhesive aspect that attaches the engineering film with base film at nappe, after carrying out various operations, it is residual to produce easily glue when peeling off the engineering film, is the reason of polluting nappe, and then, the engineering film produces easily and departs from during hot pressing, is the reason that causes the problem of circuit printing precision reduction.Preferred gel percentage is more than 96%.In addition, above-mentioned gel percentage is the value of measuring according to following method.
(assay method of gel percentage)
On the remover aspect of pet film coating as the stripping film of the polyorganosiloxane resin of remover of thickness 25 μ m, be coated with this adhesive, with releasable engineering thin film fabrication of the present invention the time under the identical condition behind the Cross-linked, strip adhesive (50mm * 100mm) from stripping film.Then, wrap into two above-mentioned Cross-linked adhesives (adding up to quality Ag) with woven wire on the woven wire of 200 meshes of 100 * 130mm size, it is arranged on the Soxhlet's extractor, extraction is 16 hours under the backflow of ethyl acetate.Then, after extraction is processed, with adhesive remaining on the woven wire 100 ℃ lower dry 24 hours, under 23 ℃, the environment of 50%RH, adjust humidity more than 3 hours, measure the quality (Bg) of this adhesive, come calculated for gel percentage based on following formula.
Gel percentage (%)=(B/A) * 100
[engineering film A and B release liner]
Can the lamination release liner on the adhesive phase of engineering film A and B.As this release liner, for example can enumerate glassine paper, coated paper, the paper base material of cast coated paper etc., the laminated paper of the thermoplastic resin such as laminated polyethylene on these paper base materials, perhaps at PETG, polybutylene terephthalate (PBT), the polyester film of PEN etc., be coated with olefine kind resin on the plastic film of the polyolefin film of polypropylene or polyethylene etc. etc., the isoprene resinoid, the rubber-like elastomer of butadiene type resin etc., the chain alkyl resinoid, alkyd based resin, the polysiloxanes resinoid, the goods of the remover of fluorine-type resin etc. etc.And, the laminate goods of shape of these remover former states.Particularly, when the flexible printing wiring substrate is made with base material thin plate use engineering film A of the present invention, use polysiloxane-based remover, trace is mobile from peeling agent layer to adhesive phase, this polysiloxanes composition is attached on this base material thin plate, has the situation of pollution.Thereby, engineering film A of the present invention is used for flexible wiring substrate makes the time spent, preferably use non-silicone class remover.Composition in the above-mentioned remover shifts few, and it is acrylic resin that the result preferably uses the large olefine kind resin of bonding force.Thickness as peeling agent layer is about 0.01～100 μ m.And the thickness of this release liner has no particular limits, and is generally about 20～150 μ m.
[making of releasable engineering film A and B]
Releasable engineering film A of the present invention and B can directly be coated with adhesive of the present invention by the one side at base film, with 100～130 ℃ of left and right sides heat dryings about 1～5 minute, form adhesive phase, on this adhesive aspect, prepare by release liner is set.And, coating adhesive on the lift-off processing face of release liner, such as above-mentioned heat drying, form adhesive phase after, attach adhesive phase in the one side of base film and prepare also passable.Consider the adhesiveness of adhesive phase and base film, preferred applicable front a kind of preparation method.
In addition, in the above-mentioned making operation, behind the coating adhesive, fully dry the processing carried out in expectation.Some dry insufficient, be after nappe attaches, to produce to depart from the reason that increases with residual solvent or residual monomer.And, dry inadequate words, among the engineering film A, adhesive phase and printed wiring board are made of producing easily between the base film and are departed from, bonding force after the hot pressing significantly rises, and printed wiring board is made of the base material thin plate and produced bending easily or glue is residual when peeling off.
The thickness of the adhesive phase among releasable engineering film A of the present invention and the B is generally 5～60 μ m, about preferred 5～30 μ m.
Releasable engineering film A of the present invention makes the engineering film of usefulness as the flexible printing wiring substrate that uses in the above-mentioned multi-layer printed circuit board.The flexible printing wiring substrate that uses in multi-layer printed circuit board is made in the base material thin plate of of, when using releasable engineering film A of the present invention, when peeling off this releasable engineering film, can suppress nappe is the pollution of base material thin plate side, suppress the reduction of the bonding force of the adhesiveness thin plate such as epoxylite thin plate and this base material thin plate, can make the multi-layer printed circuit board of quality better.The base material thin plate of the flexible printing wiring substrate of applicable releasable engineering film A of the present invention, its kind is not particularly limited, but usually uses the heat-resistant plastic thin plate of polyimides or polyphenylene sulfide etc. on this flexible printing wiring substrate.
On the other hand, releasable engineering film B of the present invention is suitable as the inorganic material beyond metal material or its, such as the protective film of the glass portion of CCD or CMOS etc.At this moment, even be exposed under near 260 ℃ the high temperature, also can suppress residual with respect to the glue of the glass portion of nappe, the distortion of base film is few simultaneously.
Embodiment
Below, illustrate in greater detail the present invention according to embodiment, but the invention is not restricted to these examples.
In addition, estimate for the following method of every characteristic of the engineering film of making among each embodiment.
(1) bonding force
The base material thin plate (polyimides thin plate) that to make be used to the flexible printing wiring substrate that has been cut into 22cm * 22cm size is as test film (nappe), not with bubble attach on the adhesive aspect of the engineering film that has been cut into 20cm * 20cm size, at 180 ℃ of temperature, pressure 4.3N/mm 2Condition under hot pressing after 1 hour, peel off the engineering film.([Du Pont's (strain) makes パ イ ラ ラ ッ Network ス " LF0100 " to insert adhesive film between the base material thin plate (polyimides thin plate) of the honorable and new printed wiring board manufacturing usefulness of the covering of having peeled off the engineering film, registered trade mark " Pyralux ", acrylic acid modified epoxies adhesive film], wide 20mm, long 150mm), at 180 ℃ of temperature, pressure 4.3N/mm 2Condition under hot pressing after 30 minutes, the base material thin plate of bonding nappe on the bonding force of SUS system is measured with test film, based on JIS Z 0237, minute measure the bonding force of polyimides thin plate and another polyimides thin plate with peel angle 180 degree, peeling rate 300mm/, with it as bonding force.
In addition, bonding force is qualified more than 30N/20mm.
(2) skew after the hot pressing
The base material thin plate (polyimides thin plate) that to make be used to the flexible printing wiring substrate that has been cut into 22cm * 22cm size is as test film (nappe), not with bubble attach on the adhesive aspect of the engineering film that has been cut into 20cm * 20cm size, open the through hole that diameter is 6mm at four jiaos.With it at 180 ℃ of temperature, pressure 4.3N/mm 2Condition under hot pressing after 60 minutes, measure the skew of engineering film and nappe on four jiaos the through hole, average as deviant.
(3) adhesiveness of adhesive phase and base film
Based on JIS K 5600-5-6, on the adhesive phase of engineering film, be cut into tessellated 100 grids at 1mm angle with rotary knife cutter, ([ニ チ バ Application company makes hinge to stick with glue band, registered trade mark]) pressing after, within 0.5 second～1.0 second time, peeled off adhesive tape with about 60 ° angle, calculate remaining film number in 100 grids, carry out thus the adhesion test of base film and adhesive phase in the engineering film.The evaluation of adhesion test is carried out based on following judgment standard.
More than 90/100: 5
80/100～not enough 90/100:4
70/100～not enough 80/100:3
60/100～not enough 70/100:2
Less than 60/100: 1
(4) glue residual evaluation test-1
The base material thin plate (polyimides thin plate) that to make be used to the flexible printing wiring substrate that has been cut into 22cm * 22cm size is as test film (nappe), not with bubble attach on the adhesive aspect of the engineering film that has been cut into 20cm * 20cm size, at 180 ℃ of temperature, pressure 4.3N/mm 2Condition under hot pressing after 60 minutes, peel off the engineering film, FT-IR (Fourier Tranform infrared absorption spectra analysis is used on surface to test film, the ATR method) carrying out IR measures, according to having or not of the absworption peak that comes Autoadhesive check have glue-free residual, as evaluation, not having the residual situation of glue is zero, have the residual situation of glue for *.
(5) glue residual evaluation test-2
With the float glass of 7cm * 15cm, thickness 2mm as test film (nappe), not with bubble attach on the adhesive aspect of the engineering film that has been cut into 3cm * 5cm size, carry out maximum temperature and be 260 ℃, the anti-stream of IR (the anti-stoves that flows: the WL-15-20DNX type that phase mould science and engineering is made) of 3 minutes heating times.Then after at room temperature placing 1 hour, peel off the engineering film, with the surface of digital micro-analysis sem observation nappe, inspection has glue-free residual.The residual evaluation of glue is carried out based on following criterion.
1cm 2The ratio that middle glue is residual
Less than 5%: zero
5%～less than 30%: △
More than 30%: *
(6) residual polysiloxanes
The base material thin plate (polyimides thin plate) that to make be used to the flexible printing wiring substrate that has been cut into 22cm * 22cm size is as test film (nappe), not with bubble attach on the adhesive aspect of the engineering film that has been cut into 20cm * 20cm size, at 180 ℃ of temperature, pressure 4.3N/mm 2Condition under hot pressing after 1 hour, peel off the engineering film.Carry out under the following conditions the surface-element analysis of test film according to x-ray photoelectron optical spectroscopy (XPS).
Determinator: the Quantera SXM that ア Le バ ッ Network Off ァ イ makes
X-ray source: AlK α (1486.6eV)
Take out angle: 45 degree
Measure element: silicon (Si), carbon (C) and nitrogen (N)
In addition, the Si amount is on duty with 100 with Si/'s (Si+C+N), represents with " atom % ".
Detected Si amount is converted into polysiloxanes.
(7) mensuration of weight average molecular weight and number-average molecular weight (GPC method)
The adhesive that obtains among each embodiment etc. is dissolved in (polymer concentration: 10mg/ml), measure weight average molecular weight and the number-average molecular weight that is converted by polystyrene standard according to gel permeation chromatography (GPC) in the oxolane.Mensuration use GPC device [high speed GPC device " HLC-8120GPC ", (and strain) East ソ one (strain) manufacturing], according to high speed post TSK guard column H XL-H, TSKGel GMH XL, TSKGel GMH XL, TSKGel G2000H XLMeasure on the auto levelizer that is linked in sequence of (above all make for East ソ one (strain) (strain)).40 ℃ of column temperatures, transfusion speed 1.0ml/ minute use UV-vis detector (detector wavelength as detector; 254nm) make with differential refractometer (Jun Shi East ソ one (strain)).
Molecular weight distribution is according to the weight average molecular weight (Mw) of GPC method mensuration and the ratio (Mw/Mn) of number-average molecular weight (Mn).In addition, monomer component is the value of getting rid of.
(8) rate of change of dynamic elastic modulus ratio
Dynamic elastic modulus ratio G ' when measuring 23 ℃ according to following method 23With the dynamic elastic modulus ratio G ' 260 ℃ the time 260, again according to formula X (%)=[(G ' 23-G ' 260)/G ' 23The rate of change X of dynamic elastic modulus ratio is tried to achieve in] * 100.
＜G ' 23And G ' 260Mensuration
(TA イ Application ス Star Le メ Application Star company makes as 20mm is installed in the Measurement of Dynamic Viscoelasticity device take measured length (distance between chuck) with base film, trade name " DMA-Q800 ") in, under the condition of 5 ℃/minute of frequency 11Hz, amplitude 20 μ m, programming rates, measure the dynamic elastic modulus ratio G ' of 15～300 ℃ of temperature ranges, the dynamic elastic modulus ratio G ' when measuring 23 ℃ 23, the dynamic elastic modulus ratio G ' in the time of 260 ℃ 260
And, before the confining force of adhesive phase, hot pressing and the bonding force after the hot pressing, gel percentage measure according to the method for specification text record.
Embodiment 1
Use is with blender, reflux condenser, dropping funel, the reaction unit of nitrogen ingress pipe and thermometer, the butyl acrylate (BA) that adds 61.0 mass parts, 18.0 the methyl methacrylate of mass parts (MMA), 3.5 mass parts styrene (St), 12.0 the methyl acrylate of mass parts (MA), 5.0 the HEMA of mass parts (HEMA), 0.15 the acrylic acid of mass parts (AAc), 0.01 the azodiisobutyronitrile as polymerization initiator of mass parts (AIBN), adding is as the toluene of solvent, under nitrogen environment, by polymerisation in solution, make solid and divide concentration 40.0 quality %, weight average molecular weight about 450,000, the acrylic acid esters co-polymer of molecular weight distribution (Mw/Mn) 2.60.
In addition, remaining content of monomer is measured according to following determination method, is 10.0 quality % with respect to acrylic acid esters co-polymer.
The mensuration of the content of＜remaining monomer 〉
The content of remaining monomer is to measure with gas chromatography quantitatively to calculate.
In this acrylic acid esters co-polymer of 100 mass parts, mix toluene di-isocyanate(TDI) class (TDI class) crosslinking agent [(strain) East ocean イ Application キ manufacturing (strain) manufacturing of 8.0 mass parts, trade name " オ リ バ イ Application BHS8515 " (solid constituent 37.5 quality %)], 3.0 mass parts paraxylene diisocyanates (XDI class) crosslinking agent [make by military field pharmaceutical industries (strain) (strain), trade name " D-110N " (solid constituent is 75 quality %)], 30.0 mass parts toluene, 1.0 the mass parts ethyl acetate, the preparation adhesive.
Then, be take dried coating weight as 10g/m on the one side of PETG (PET) film [ユ ニ チ power (strain) make, commodity are called " エ Application Block レ ッ ト TA-50 "] of 50 μ m at thickness 2The amount of (thickness 10 μ m) directly is coated with this adhesive, after 1 minute, lamination has the release liner [Oji Paper company makes, trade name " 40RL-01Z "] of polysiloxane-based peeling agent layer thereon 120 ℃ of lower dryings, the manufacturing engineering film is estimated every characteristic.In addition, as test film (nappe), use the polyimides thin plate.And, the residual employing glue residual evaluation test-1 of glue.The results are shown in the table 1.
Embodiment 2
Except monomer composition change as shown in table 1, the same with embodiment 1, make that solid component concentration 40.0 quality %, weight average molecular weight are about 460,000, the acrylic acid esters co-polymer of molecular weight distribution (Mw/Mn) 2.70, remaining monomer 12.0 quality %.
Below, the same with embodiment 1, the manufacturing engineering film is estimated every characteristic.The results are shown in the table 1.
Comparative example 1
In embodiment 1, carry out polymerisation in solution after, and then carry out again beyond the polymerization, the same with embodiment 1, make acrylic acid esters co-polymer.The weight average molecular weight of the acrylic acid esters co-polymer that obtains is that about 470,000, molecular weight distribution is (Mw/Mn) 3.29.
And the content of remaining monomer and embodiment 1 the same mensuration are 3.4 quality % with respect to acrylic acid esters co-polymer.
Below, the same with embodiment 1, the manufacturing engineering film is estimated every characteristic.The results are shown in the table 1.
Table 1
Figure BPA00001228603500241
As can be seen from Table 1, embodiment 1 compares with comparative example 1 with 2 engineering film, has very high bonding force in bonding experiment.
Embodiment 3
Use is with blender, reflux condenser, dropping funel, the reaction unit of nitrogen ingress pipe and thermometer, the butyl acrylate (BA) that adds 60.0 mass parts, 18.0 the methyl methacrylate of mass parts (MMA), 3.5 mass parts styrene (St), 13.0 the methyl acrylate of mass parts (MA), 5.0 the HEMA of mass parts (HEMA), 0.15 the acrylic acid of mass parts (AAc), 0.01 the azodiisobutyronitrile as polymerization initiator of mass parts (AIBN), adding is as the toluene of solvent, under nitrogen environment, by polymerisation in solution, make solid component concentration 40.0 quality %, weight average molecular weight about 470,000, the acrylic acid esters co-polymer of molecular weight distribution (Mw/Mn) 2.4.
In addition, remaining content of monomer and embodiment 1 measure equally, are 11.0 quality % with respect to acrylic acid esters co-polymer.
Toluene di-isocyanate(TDI) class (TDI class) the crosslinking agent [East ocean イ Application キ that mixes 8.0 mass parts in this acrylic acid esters co-polymer solution of 100 mass parts (solid constituent is 40.0 quality %) makes (strain) and makes, trade name " オ リ バ イ Application BHS8515 " (solid constituent 37.5 quality %)], 3.0 mass parts paraxylene diisocyanates (XDI class) crosslinking agents [make by military field pharmaceutical industries (strain), trade name " D-110N " (solid constituent is 75 quality %)], 40.0 mass parts ethyl acetates, the preparation adhesive.
Then, be take dried coating weight as 10g/m on the one side of PETG (PET) film [ユ ニ チ カ (strain) make, commodity are called " エ Application Block レ ッ ト TA-50 "] of 50 μ m at thickness 2The amount of (thickness 10 μ m) directly is coated with this adhesive, at 120 ℃ after lower dry 1 minute, the release liner [Oji Paper company makes, trade name " ア Le Off ァ Application PP40SD-001 "] that made by acrylic resin of lamination thereon, the manufacturing engineering film is estimated every characteristic.In addition, the residual employing glue residual evaluation test-1 of glue.The results are shown in the table 2.
Embodiment 4
Except monomer composition such as table 2 change, equally with embodiment 3 make that solid component concentration 40.0 quality %, weight average molecular weight are about 500,000, the acrylic acid esters co-polymer of molecular weight distribution (Mw/Mn) 2.7, remaining monomer 8.3 quality %.
Below, the same with embodiment 3, the manufacturing engineering film is estimated every characteristic.The results are shown in the table 2.
Embodiment 5
Except release liner is changed into [リ Application テ ッ Network (strain) manufacturing of the one side pet film of the thickness 50 μ m of alkyd resins demoulding processing, trade name " PET50 AL-5 "] in addition, with embodiment 3 the same manufacturing engineering films, estimate every characteristic.The results are shown in the table 2.
Embodiment 6
Except using polysiloxane-based peeling agent layer as release liner [リ Application テ ッ Network (strain) is made, trade name " SP-PET3811 "] in addition, with embodiment 3 the same manufacturing engineering films.The results are shown in the table 2.
Comparative example 2
In embodiment 3, carry out polymerisation in solution after, carry out again beyond the polymerization, with the embodiment 3 the same acrylic acid esters co-polymers of making.The weight average molecular weight of the acrylic acid esters co-polymer that obtains is about 550,000, and molecular weight distribution (Mw/Mn) is 3.4.
And the content of remaining monomer and embodiment 1 the same mensuration are 3.5 quality % with respect to acrylic acid esters co-polymer.
Below with embodiment 3 the same preparation engineering films, estimate every characteristic.The results are shown in the table 2.
Table 2
Figure BPA00001228603500271
As can be seen from Table 2, the engineering film of embodiment 3～6 is compared with comparative example 2, has high bonding force in adhesive test.And embodiment 3～5th, use the goods of the release liner with non-silicone class peeling agent layer, and embodiment 6 is the goods that use the release liner with polysiloxane-based peeling agent layer, and the bonding force in adhesive test is poorer than embodiment 3～5.
Embodiment 7
With the embodiment 3 the same acrylic acid esters co-polymer solution of making.
In this acrylic acid esters co-polymer solution (solid constituent 40.0 quality %) of 100 mass parts, mix paraxylene diisocyanates (XDI class) crosslinking agent [military field pharmaceutical industries (strain) manufacturing of 9.0 mass parts, trade name " D-110N " (solid constituent is 75 quality %)], 40.0 mass parts ethyl acetates, the preparation adhesive.
Then, be that the rate of change of 50 μ m, dynamic elastic modulus ratio is that 40% polyimide film [East レ デ ュ Port Application (strain) is made at thickness, registered trade mark is " カ プ ト Application "] one side on take dried coating weight as 10g/m 2Amount directly be coated with this adhesive, at 120 ℃ after lower dry 1 minute, the release liner [Oji Paper company makes, trade name " ア Le Off ァ Application PP40SD-001 "] that made by acrylic resin of lamination thereon, the manufacturing engineering film, the residual employing glue residual evaluation test-2 of glue is estimated.The results are shown in the table 3.
Embodiment 8
With the embodiment 1 the same acrylic acid esters co-polymer of making.
In this acrylic acid esters co-polymer solution (solid constituent 40.0 quality %) of 100 mass parts, mix paraxylene diisocyanates (XDI class) crosslinking agent [military field pharmaceutical industries (strain) manufacturing of 7.0 mass parts, trade name " D-110N " (solid constituent is 75 quality %)], 40.0 mass parts ethyl acetates, the preparation adhesive.
Then, be that the rate of change of 50 μ m, dynamic elastic modulus ratio is take dried coating weight as 10g/m on the one side of 40% polyimide film [East レ デ ュ Port Application (strain) is made, and commodity are called " カ プ ト Application " (registered trade mark)] at thickness 2Amount directly be coated with this adhesive, at 120 ℃ after lower dry 1 minute, the release liner [Oji Paper company makes, trade name " ア Le Off ァ Application PP40SD-001 "] that made by acrylic resin of lamination thereon, the manufacturing engineering film, the residual employing glue residual evaluation test-2 of glue is estimated.The results are shown in the table 3.
Comparative example 3
The binder solution of making in usage comparison example 1, with embodiment 7 the same manufacturing engineering films, the residual employing glue residual evaluation test-2 of glue is estimated.The results are shown in the table 3.
Table 3
Figure BPA00001228603500291
Industrial applicibility
Releasable engineering film of the present invention is made in the situation of using the base material thin plate at the flexible printing wiring substrate that uses for multi-layer printed circuit board, can suppress the pollution of nappe base material thin plate side when peeling off this releasable engineering film, the reduction of the adhesiveness thin plate of inhibition epoxylite thin plate etc. and the bonding force of this base material thin plate.And as the nappe of the glass portion of CCD or CMOS etc. the time, even be exposed under near 260 ℃ the temperature, distortion residual to the glue of nappe or base film is also few, excellent heat resistance.

Claims (16)

1. releasable engineering film, it is characterized in that the adhesive phase that has base film and arrange in one surface, above-mentioned adhesive phase contains the butyl acrylate units that (A) has 40～80 quality %, the styrene units of 1～15 quality %, the methyl methacrylate units of 1～30 quality %, the methyl acrylate unit of 1～30 quality %, the vinyl monomer unit that contains hydroxyl of 1～10 quality %, 0.1 the acrylic acid esters co-polymer of the vinyl monomer unit that contains carboxyl of～1 quality %, (B) isocyanates crosslinking agent, above-mentioned adhesive phase is that the weight average molecular weight Mw of use above-mentioned (A) acrylic acid esters co-polymer is 300,000～1,000,000 simultaneously, molecular weight distribution (weight average molecular weight Mw/ number-average molecular weight Mn) is that the adhesive below 3.0 forms, and the content that is somebody's turn to do the remaining monomer in (A) acrylic acid esters co-polymer is 5～20 quality % with respect to above-mentioned (A) acrylic acid esters co-polymer.
2. releasable engineering film as claimed in claim 1, it has the release liner that contains non-silicone class peeling agent layer, and the adhesive phase of above-mentioned releasable engineering film carries out lamination with respect to the peeling agent layer side of above-mentioned release liner.
3. releasable engineering film as claimed in claim 2, wherein non-silicone class peeling agent layer is acrylic resin.
4. releasable engineering film as claimed in claim 1 or 2 is characterized in that the isocyanates crosslinking agent contains toluene di-isocyanate(TDI) class crosslinking agent and paraxylene diisocyanates crosslinking agent.
5. releasable engineering film as claimed in claim 1 or 2, the sheet plastic of the flexible printing wiring substrate that wherein uses in multi-layer printed circuit board is suitable as nappe.
6. releasable engineering film as claimed in claim 5, wherein (a) is with respect to the confining force of the sheet plastic that uses in the flexible printing wiring substrate as nappe, assay method based on JIS Z 0237, under 40 ℃ of temperature, be 70, more than 000 second, and 70, depart from not enough 0.1mm in the time of 000 second, (b) with respect to the bonding force of the sheet plastic that uses in the flexible printing wiring substrate as nappe before hot pressing, assay method based on JIS Z 0237 is 0.01～0.5N/25mm, (c) after the sheet plastic that uses in the flexible printing wiring substrate as nappe attaches, 180 ℃ of temperature, pressure 4.3N/mm 2Condition under carry out bonding force after 60 minutes the hot pressing, be below the 2.0N/25mm based on the assay method of JIS Z 0237, and (d) the gel percentage of adhesive phase is more than 95%.
7. releasable engineering film as claimed in claim 5, wherein the plastic film of flexible printing wiring substrate is the film that uses polyimides thin plate or polyphenylene sulfide thin plate to obtain.
8. releasable engineering film as claimed in claim 5, wherein base film is pet film.
9. releasable engineering film as claimed in claim 1 or 2, wherein metal material or the inorganic material beyond it are suitable as nappe.
10. releasable engineering film as described in claim 9, wherein nappe is the glass portion in charge coupled device or the complementary mos device.
11. releasable engineering film as claimed in claim 1 or 2 is characterized in that the isocyanates crosslinking agent is paraxylene diisocyanates crosslinking agent.
12. releasable engineering film as claimed in claim 9 is characterized in that the isocyanates crosslinking agent is paraxylene diisocyanates crosslinking agent.
13. releasable engineering film as claimed in claim 1 or 2, wherein the dynamic elastic modulus ratio of base film in the time of 23 ℃ is as G ' 23, the dynamic elastic modulus ratio in the time of 260 ℃ is as G ' 260The time, the rate of change X of the dynamic elastic modulus ratio that is expressed from the next is below 85%,
X(％)＝[(G’ 23-G’ 260)/G’ 23]×100。
14. releasable engineering film as claimed in claim 9, wherein the dynamic elastic modulus ratio of base film in the time of 23 ℃ is as G ' 23, the dynamic elastic modulus ratio in the time of 260 ℃ is as G ' 260The time, the rate of change X of the dynamic elastic modulus ratio that is expressed from the next is below 85%,
X(％)＝[(G’ 23-G’ 260)/G’ 23]×100。
15. releasable engineering film as claimed in claim 1 or 2, wherein base film is polyimide film.
16. releasable engineering film as claimed in claim 9, wherein base film is polyimide film.
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