CN109153239A - Mold release film - Google Patents

Mold release film Download PDF

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Publication number
CN109153239A
CN109153239A CN201780031010.3A CN201780031010A CN109153239A CN 109153239 A CN109153239 A CN 109153239A CN 201780031010 A CN201780031010 A CN 201780031010A CN 109153239 A CN109153239 A CN 109153239A
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CN
China
Prior art keywords
sticker
polymer
acrylic acid
electromagnetic wave
wave shielding
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Granted
Application number
CN201780031010.3A
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Chinese (zh)
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CN109153239B (en
Inventor
石岛英明
柳田裕贵
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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Publication of CN109153239A publication Critical patent/CN109153239A/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
    • 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
    • B32B15/09—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 polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/552—Protection against radiation, e.g. light or electromagnetic waves
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

A kind of mold release film, it includes supporter and electromagnetic wave shielding sheets, the supporter includes substrate and the adhesion coating being configured on the substrate, the electromagnetic wave shielding sheet is configured on the adhesion coating of the supporter, and the peeling force between the adhesion coating and the electromagnetic wave shielding sheet is 0.10N/50mm~2.00N/50mm.

Description

Mold release film
Technical field
The present invention relates to mold release films.
Background technique
In recent years, with the miniaturization of electronic equipment, it is desirable that the high density of semiconductor component surfaces carries technology It further increases.Therefore, in recent years, partly leading for multiple semiconductor elements, so-called storehouse encapsulation type is laminated with using multistage Body device.In the semiconductor device of such storehouse encapsulation type, semiconductor element is configured with integrated state, it is thus possible to be produced Raw the problem of being caused by external noise (electromagnetic wave obstacle).Digitlization of such noise problem with electronic equipment, high speed Develop with high frequency and becomes significant.Therefore, in order to inhibit to be influenced by noise bring, proposing will be used to shield electromagnetic wave Electromagnetic wave shielding sheet is formed in the technology in the sealing material being sealed to semiconductor element (for example, referring to patent document 1).
Manufacture as the semiconductor device recorded in the forming method of electromagnetic wave shielding sheet, such as known patent document 2 Method.In the manufacturing method, the transfer molding by using upper die and lower die and using sealing material to semiconductor element into In the process of row sealing, electromagnetism wave screen is used to form in release film (release film) (carrier film) coating for being configured at upper mold The material for covering piece in the material transferring to sealing material and will make its solidification, to form electromagnetic wave shielding sheet.
Existing technical literature
Patent document
Patent document 1: No. 4133637 bulletins of Japanese Patent No.
Patent document 2: Japanese Unexamined Patent Publication 2007-287937 bulletin
Summary of the invention
Subject to be solved by the invention
However, in the method documented by patent document 2, in the process being sealed using sealing material to semiconductor device When, need for the material for being used to form electromagnetic wave shielding sheet to be coated on the operation of carrier film every time, therefore from the sight of production efficiency Point considers there is room for improvement.
The present invention is invention completed to solve the above problems, and can be realized its purpose is to provide one kind has electricity Magnetic wave shields the mold release film of the raising of the production efficiency of the semiconductor device of piece.
The method used for solving the problem
It include the following embodiments and the accompanying drawings in method for solving the above subject.
A kind of mold release film of 1 > of <, it includes supporter and electromagnetic wave shielding sheet, above-mentioned supporter includes substrate and configuration Adhesion coating on above-mentioned substrate, above-mentioned electromagnetic wave shielding sheet are configured on the above-mentioned adhesion coating of above-mentioned supporter, and above-mentioned Peeling force between adhesion coating and above-mentioned electromagnetic wave shielding sheet is 0.10N/50mm~2.00N/50mm.
2 > of < mold release film according to 1 > of <, above-mentioned electromagnetic wave shielding sheet with a thickness of 0.01 μm~50 μm.
3 > of < mold release film according to 2 > of < 1 > or <, above-mentioned adhesion coating with a thickness of 1 μm~20 μm.
4 > of < mold release film according to any one of 1 > of <~<, 3 >, above-mentioned adhesion coating include selected from by organosilicon It is at least one of the group of sticker and acrylic acid series sticker composition.
5 > of < mold release film according to any one of claims 1 to 4 is used for the manufacture of semiconductor device, above-mentioned Work of the manufacture of semiconductor device comprising above-mentioned electromagnetic wave shielding sheet to be transferred to the sealing material being sealed to semiconductor element Sequence.
Invention effect
According to the present invention, it is possible to provide can be realized the raising of the production efficiency of the semiconductor device with electromagnetic wave shielding sheet Mold release film.
Detailed description of the invention
Fig. 1 is the summary sectional view for indicating an example of the structure of mold release film of present embodiment.
Fig. 2 is the general view for indicating an example of the structure of mold release film of present embodiment.
Specific embodiment
Hereinafter, being illustrated to mode for carrying out the present invention.But the present invention is not limited to embodiment party below Formula.In the following embodiments, constituent element (also including element step etc.) other than the case where especially expressing not It is necessary.It is also the same about numerical value and its range, it is not intended to limit the present invention.
In the present specification, " process " word is other than the process independently of other processes, though with other processes It also include the process as long as can be realized the purpose of the process in the case where can not clearly distinguishing.
In the present specification, the numberical range indicated using "~" include "~" front and back documented by numerical value respectively as Minimum value and maximum value.
In the numberical range recorded interim in the present specification, upper limit or lower limit documented by a numberical range It could alternatively be the upper limit or lower limit for the numberical range that other stages are recorded.In addition, the number recorded in the present specification It is worth in range, the upper limit or lower limit of numberical range also could alternatively be value shown in embodiment.
In the present specification, the containing ratio or content about each ingredient in composition, in composition there are it is a variety of quite In the case where the substance of each ingredient, unless otherwise specified, just refer to the total of many kinds of substance present in composition Containing ratio or content.
In the present specification, the partial size about each ingredient in composition is equivalent to each ingredient there are a variety of in composition Particle in the case where, unless otherwise specified, exactly refer to the mixture for a variety of particles present in composition Value.
In the present specification, about " layer " or " film " word, in addition in observation, there are be formed in when the region of this layer or film It also include the situation for being only formed in a part in the region other than the whole situation in the region.
In the present specification, " stacking " word expression layer heap is folded, can more than two layers combination, can also two with On layer can load and unload.
In this specification, " (methyl) acryloyl group " refers at least one of acryloyl group and methylacryloyl, " (first Base) acrylic acid " refer to acrylic acid and methacrylic acid at least one, " (methyl) acrylate " refers to acrylate and methyl At least one of acrylate.
The mold release film of present embodiment includes supporter and electromagnetic wave shielding sheet, and above-mentioned supporter includes substrate and configuration Adhesion coating on above-mentioned substrate, above-mentioned electromagnetic wave shielding sheet are configured on the above-mentioned adhesion coating of above-mentioned supporter, and above-mentioned Peeling force between adhesion coating and above-mentioned electromagnetic wave shielding sheet is 0.10N/50mm~2.00N/50mm.
The mold release film of present embodiment is by with above-mentioned composition, thus even if in advance by electromagnetism wave screen before sealing process It covers piece to be configured on supporter, also can remove well electromagnetic wave shielding sheet from supporter.It is therefore not necessary in sealing work every time Electromagnetic wave shielding sheet is configured in mold release film when sequence, in addition without forming electromagnetic wave shielding by other processes after sealing Layer, therefore be advantageous from the viewpoint of production efficiency.The mold release film of present embodiment can be suitably used for having electricity as a result, The manufacturing method of the semiconductor device of magnetic wave shielding piece is (more specifically, comprising above-mentioned electromagnetic wave shielding sheet to be transferred to half-and-half The manufacturing method of the semiconductor device of the process for the sealing material that conductor element is sealed) in.
In this specification, " peeling force between adhesion coating and electromagnetic wave shielding sheet " is under 170 DEG C of atmosphere, is removing The value (N/50mm) 180 ° of angle and measured under conditions of peeling rate 0.3m/ minutes.Peeling force can be used for example Tensilon universal testing machine (Co., Ltd.'s A&D system) is measured.
If the peeling force between adhesion coating and electromagnetic wave shielding sheet is greater than or equal to 0.10N/50mm, height can inhibit The tendency that electromagnetic wave shielding sheet when warm peels off.If the peeling force between adhesion coating and electromagnetic wave shielding sheet is less than or equal to 2.00N/50mm then has the tendency that fully obtaining the transferability that electromagnetic wave shielding sheet is transferred from adhesion coating.Adhesion coating and electricity Peeling force between magnetic wave shielding piece is preferably greater than or equal to 0.20N/50mm, it is additionally preferred to be less than or equal to 1.60N/50mm.
Hereinafter, being illustrated referring to mold release film of the attached drawing to present embodiment, but the present invention is not limited to this.In addition, Component size in each figure is notional size, and it's not limited to that for the relativeness of the size between component.
Fig. 1 is the summary sectional view for indicating an example of the structure of mold release film of present embodiment.Mold release film 10 includes: support Body 20 contains substrate 50 and the adhesion coating 40 being configured on substrate 50；And electromagnetic wave shielding sheet 30, it is configured at supporter On 20 adhesion coating 40.In supporter 2, adhesion coating can be configured at the entire surface of substrate 50, can also only be configured at a part, Its shape is not particularly limited.
In mold release film 10, as long as the position configured with electromagnetic wave shielding sheet 30 is not limit especially on adhesion coating 40 System.For example, electromagnetic wave shielding sheet 30 can be only configured in a part of supporter 20 as shown in the general view of Fig. 2, Electromagnetic wave shielding sheet 30 can also be configured in the entire surface of supporter 20.The shape of electromagnetic wave shielding sheet 30 does not limit especially System can be the desired shapes such as quadrangle, circle.Electromagnetic wave shielding sheet 30 can also at multiple regions hollow opening interval and Configuration, interregional interval in this case is also not particularly limited.
The method that electromagnetic wave shielding sheet 30 is configured on adhesion coating 40 is not particularly limited.Such as it can enumerate: sputtering method, Vapour deposition method, ion plating method, laminating method etc..From the viewpoint of the adaptation for adhesion coating 40, preferably vapour deposition method, ion plating method Or laminating method.The material of electromagnetic wave shielding sheet 30 is not particularly limited.Such as metal can be enumerated.From the viewpoint of price and processability Consider, preferably comprises selected from least one of the group being made of copper and aluminium metallic element.
The thickness of substrate 50 is preferably 20 μm~200 μm, and more preferably 25 μm~100 μm, further preferably 25 μm~ 50μm.If the thickness of substrate 50 is greater than or equal to 20 μm, sufficient intensity can get, having, which can inhibit, occurs sticking up for lead frame The tendency of the problems such as bent, if it is less than or be equal to 200 μm, then have the tendency that excellent to the adaptability of semiconductor manufacturing apparatus.
The thickness of adhesion coating 40 is preferably 1 μm~20 μm, more preferably 2 μm~12 μm.If the thickness of adhesion coating 40 is big In or be equal to 1 μm, then electromagnetic wave shielding sheet 30 can be carried out well by having the tendency that transfers from adhesion coating 40 to adherend, if Less than or equal to 20 μm, then have the tendency that electromagnetic wave shielding sheet 30 is not easy to remove from adhesion coating 40 in sealing process.
The thickness of electromagnetic wave shielding sheet 30 is preferably 0.01 μm~50 μm, more preferably 0.05 μm~12 μm.If electromagnetism The thickness that wave screen covers piece 30 is greater than or equal to 0.01 μm, then has the tendency that can get sufficient electromagnetic wave shielding performance, if it is less than Or be equal to 50 μm, then have the tendency that excellent in workability.
In this specification, the thickness of substrate 50, adhesion coating 40 and electromagnetic wave shielding sheet 30 is set as being measured at 5 points and The number average value of the value of acquisition.The measuring method of thickness is not particularly limited, and carries out using well known method.
Mold release film 10 also can according to need with the structure in addition to substrate 50, adhesion coating 40 and electromagnetic wave shielding sheet 30 Part.For example, it is also possible to have the protective film for protecting the surface of stripping film 10.
< adhesion coating >
As long as the peeling force between adhesion coating and electromagnetic wave shielding sheet becomes in above range, it is not particularly limited.Example It can such as enumerate viscous comprising organic silicon-type sticker, acrylic acid series sticker, rubber series sticker, carbamate system sticker The layer of agent.Sticker contained in adhesion coating can be individually a kind of, or two or more.
In the present invention, sticker contained in adhesion coating can partially or even wholly be reacted, can also be with unreacted. Furthermore it is possible to have carried out cured state by heat etc., or uncured state.
(1) organic silicon-type sticker
In this specification, organic silicon-type sticker, which refers to, is set as base polymer (component of polymer for organosilicon polymer In principal component, i.e., the ingredient more than or equal to 50 mass % is accounted in component of polymer entirety) sticker.
Organic silicon-type sticker is advantageous from the consideration of following viewpoint, it may be assumed that peeling force can be made lower and make electromagnetism wave screen Piece is covered to be easy to remove from adhesion coating；It is able to suppress the viewpoints such as the residue glue (remaining of sticker) of electromagnetic wave shielding on piece.As having Machine silicon systems sticker can enumerate addition reaction-type organic silicon-type sticker, peroxide curing type silicone system sticker, condensation Type organic silicon-type sticker etc..From in curing reaction do not use peroxide, from the viewpoint of not generating decomposition product, preferably plus At response type organic silicon-type sticker.
(addition reaction-type organic silicon-type sticker)
Addition reaction-type organic silicon-type sticker is organic containing addition reaction type silicone resin and organic siliconresin Silicon systems sticker, above-mentioned addition reaction type silicone resin is included in a molecule, and there are at least two alkenyls (can enumerate ethylene The monovalent hydrocarbons such as base, allyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, wherein particularly preferred second Alkenyl) the 1st dimethyl silicone polymer and in a molecule at least two hydrosilyl groups (hydrosilyl) the 2 dimethyl silicone polymers.
Containing ratio (ratio of the number of alkenyl relative to the number of siloxanes key of alkenyl in 1st dimethyl silicone polymer Example) it is preferably 0.01%~10%, more preferably 0.1%~5%.Alkenyl is preferably at least present in two ends of strand, more It is preferably in two ends and side chain.The degree of polymerization (number of siloxanes key) of 1st dimethyl silicone polymer is preferably 200~5, 000, more preferably 500~3,000.
The weight average molecular weight of 1st dimethyl silicone polymer is preferably 20, and 000~1,300,000, more preferably 300,000 ~1,200,000.
The molecular weight (weight average molecular weight and number-average molecular weight) of polymer is to pass through gel permeation chromatography in this specification (GPC) value of the polystyrene conversion of method measurement.
The content of hydrosilyl groups in 2nd dimethyl silicone polymer is 2~300 preferably in a molecule, more excellent It is selected as 4~200.The degree of polymerization (number of siloxanes key) of 2nd dimethyl silicone polymer is preferably 50~2, and 000, it is more excellent It is selected as 100~1,500.
In addition reaction type silicone resin, the ratio of the 1st dimethyl silicone polymer and the 2nd dimethyl silicone polymer is for example It is preferred that the 2nd dimethyl silicone polymer is 0.01 mass parts~20 relative to the match ratio of 100 mass parts of the 1st dimethyl silicone polymer Mass parts, more preferably 0.1 mass parts~10 mass parts.
If hydrogenated contained in the content of alkenyl contained in the 1st dimethyl silicone polymer, the 2nd dimethyl silicone polymer The content of silylation and the 2nd dimethyl silicone polymer are respectively above range relative to the match ratio of the 1st dimethyl silicone polymer It is interior, then have the tendency that the 1st dimethyl silicone polymer and the addition reaction of the 2nd dimethyl silicone polymer carry out well.It needs Bright, the 1st dimethyl silicone polymer does not preferably have hydrosilyl groups, and the 2nd dimethyl silicone polymer does not preferably have alkenyl.
Organic siliconresin has the function of assigning adherence to organic silicon-type sticker.In this specification, organic siliconresin Refer to the organosilicon with three-dimensional mesh structure.
As organic siliconresin, such as can enumerate by as a functional silicone unit [(CH3)3SiO1/2] M unit and As 4 functional silicone unit [SiO4/2] Q unit constitute MQ resin.In MQ resin, the molar ratio (M of M unit and Q unit Unit/Q unit) it is preferably 0.6~1.7.
In addition reaction-type organic silicon-type sticker, organic siliconresin is relative to 100 matter of addition reaction type silicone resin The match ratio for measuring part is preferably 1 mass parts~30 mass parts, more preferably 3 mass parts~20 mass parts, further preferably 5 matter Measure part~15 mass parts.It is in above range by the match ratio of organic siliconresin, addition reaction-type organic silicon-type can be glued The fissility of agent be adjusted to ideal range.That is, there is following tendency: electromagnetic wave shielding sheet becomes easier to from using addition anti- The adhesion coating removing answering type organic silicon-type sticker and obtaining, becomes the residue glue being less also easy to produce on electromagnetic wave shielding sheet.
Addition reaction-type organic silicon-type sticker preferably comprises catalyst.It, being capable of higher efficiency by containing catalyst Carry out the curing reaction of addition reaction type silicone resin.As catalyst, as long as the 1st dimethyl silicone polymer and can be made 2 dimethyl silicone polymers carry out addition reaction, there is no particular limitation, wherein preferably comprise the compound of platinum group metal.As Compound comprising platinum group metal can be enumerated: microgranular platinum, the microgranular platinum, chloroplatinic acid, the alcohol that are adsorbed in carbon powder carrier change Property chloroplatinic acid, the alkene complex of chloroplatinic acid, palladium, rhodium etc..
In the case where addition reaction-type organic silicon-type sticker includes catalyst, catalyst has relative to addition reaction-type The use level of 100 mass parts of machine silicone resin is (in the case that catalyst is the compound comprising platinum group metal, to be equivalent to platinum family gold The amount of category) it is preferably 0.0001 mass parts~0.1 mass parts, more preferably 0.001 mass parts~0.01 mass parts.
(peroxide curing type silicone system sticker and condensed type organic silicon system sticker)
Peroxide curing type silicone system sticker generally hands over organopolysiloxane solidification (using peroxide Connection) and generate the sticker of organic silicon-type polymer.In addition, condensed type organic silicon system sticker in end generally by having Dehydration or dealcoholization between the polysiloxane of the hydrolyzable silyl groups such as silanol group or alkoxysilyl and give birth to At the sticker of organic silicon-type polymer.
In the case where peroxide curing type silicone system sticker, using at least with methyl organic silicon rubber, In the case where condensed type organic silicon system sticker, there is silanol group or water-disintegrable alkoxysilyl using in end Organic silicon rubber.It should be noted that the weight average molecular weight of the organopolysiloxane in organic silicon rubber will be generally greater than or equal to 150000, preferably 280,000~1,000,000, more preferably 500,000~900,000.
In addition to component of polymer, also may include that reaction suppressor, closely sealed enhancer etc. are various adds organic silicon-type sticker Add agent.
The method for being formed adhesion coating on substrate using organic silicon-type sticker is not particularly limited.For example, can pass through Organic silicon-type sticker is assigned to substrate, and is dried, is solidified to form as needed.Stick can be used for example in imparting The coating machines such as painting machine, die coating machine, gravure coater, roll coater, doctor knife coater carry out.
In the case where organic silicon-type sticker includes diluent, diluent is not particularly limited.Such as it can enumerate: first The hydrocarbon compounds such as benzene, hexane, heptane, acetone, ethyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc..Organic silicon-type sticker Contained in diluent can be individually a kind of, or it is two or more.
It is preferably that addition reaction-type is organic in the case where organic silicon-type sticker is addition reaction-type organosilicon sticker Silicon sticker is heated after assigning to substrate and makes its solidification.Heating temperature in this case is preferably 80 DEG C~180 DEG C, Heating time is preferably 10 seconds~90 seconds degree.
(2) acrylic acid series sticker
In this specification, acrylic acid series sticker refers to the sticker that acrylic acid series polymeric compounds are set as to base polymer. So-called acrylic acid series polymeric compounds refer to the monomer in a molecule at least one (methyl) acryloyl group (hereinafter, sometimes It is referred to as " acrylic monomer ") main composition monomer component is set as (in the monomer total amount for constituting acrylic acid series polymeric compounds In account for the ingredient more than or equal to 50 mass %) polymer.Acrylic acid series sticker is from the transparency, weatherability, heat resistance, resistance to Solvent borne etc. consideration is advantageous.
When designing acrylic acid series polymeric compounds contained in acrylic acid series sticker, it is important to consider that glass transition point (to adherence, the temperature that can be applied etc. of adherend), the importing (durability, heat resistance etc.) of crosslinking points, acrylic acid series Copolymerizable (uniformities of molecular structure, crosslinking points of acrylic acid series polymeric compounds etc.) of monomer etc. and adjust monomer type, point Son amount etc..In order to import crosslinking points in the molecule, using containing can with the monomer (third of functional group that reacts of crosslinking agent Olefin(e) acid, Hydroxyethyl Acrylate etc.) carry out acrylic acid synthesizing based polymer.
As acrylic acid series polymeric compounds, it can enumerate and (methyl) alkyl acrylate is set as main composition monomer component Polymer.As (methyl) alkyl acrylate, such as it can suitably use compound represented by following formula (1).
CH2=C (R1)COOR2(1)
Herein, the R in above-mentioned formula (1)1Indicate hydrogen atom or methyl, R2Indicating the alkyl of carbon atom number 1~20 (can be Any one of chain-like alkyl or ester ring type alkyl).
From the viewpoint of obtaining the excellent sticker of adhesive performance, R2Preferably carbon atom number 2~14 (C2~14) Chain-like alkyl (can be any one of straight-chain alkyl or branched-chain alkyl).As the chain-like alkyl of C2~14, can enumerate: Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, just Heptyl, n-octyl, iso-octyl, 2- ethylhexyl, n-nonyl, isononyl, positive decyl, isodecyl, n-undecane base, n-dodecane Base, n-tridecane base, n-tetradecane base etc..As R2Ester ring type alkyl in the case where for ester ring type alkyl, can enumerate hexamethylene Base, isobornyl etc..
From the viewpoint of obtaining the superior acrylic acid series polymeric compounds of adhesive performance, the synthesis institute of acrylic acid series polymeric compounds In the monomer total amount used be greater than or equal to 50 mass % (for example, 50 mass % of mass %~99.9), more preferably greater than or Equal to 70 mass % (for example, 70 mass % of mass %~99.9), further preferably greater than or equal to 85 mass % (for example, 85 The mass % of quality %~99.9) it is preferably R in above-mentioned formula (1)2It is more excellent for (methyl) acrylate of the chain-like alkyl of C2~14 Select R2For the acrylic acid chain-like alkyl ester of C4~10, it is further preferably selected from n-butyl acrylate and 2-EHA At least one of.
Acrylic acid series polymeric compounds preferably have hydroxyl as crosslinking points.It, can as the acrylic acid series polymeric compounds with hydroxyl It is preferably employed in the substance in polymeric composition comprising the acrylic monomer containing hydroxyl.
It as the concrete example of the acrylic monomer containing hydroxyl, can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate, (first Base) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) propylene Sour 4- hydroxybutyl, the own ester of (methyl) acrylic acid 2- hydroxyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl Monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester, acrylic acid (4- hydroxymethyl hexamethylene Base) methyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyethyl (methyl) acrylamide, N- hydroxypropyl (methyl) third Acrylamide etc..Acrylic monomer containing hydroxyl can be used alone one kind, also can be used in combination two or more.
In acrylic monomer containing hydroxyl, (methyl) acrylate of hydroxyl is preferably comprised.As containing hydroxyl (methyl) acrylate, preferably (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) propylene Sour 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl etc..
About the acrylic acid series polymeric compounds with hydroxyl, the acrylic acid containing hydroxyl in used monomer total amount is synthesized The ratio for being monomer can be for example the range of 0.01 mass of mass %~20 %, preferably 0.05 mass of mass %~15 %'s Range, the more preferably range of 0.1 mass of mass %~10 %.
Acrylic acid series polymeric compounds also may include with hydroxyl-removal other than functional group acrylic monomer and except propylene Monomer (hereinafter also referred to as other monomers) other than acid system monomer is used as polymeric composition.Other monomers for example can be for adjusting The purpose of Tg, the adhesive performance of acrylic acid series polymeric compounds etc. and use.For example, as cohesiveness that sticker can be improved and heat-resisting The monomer of property, can enumerate: containing sulfonic monomer, the monomer of phosphorous acidic group, the monomer of cyano-containing, vinyl esters, aromatic series second Alkenyl compound etc..In addition, as importing the monomer that can become the functional group of crosslinking basic point into acrylic acid series polymeric compounds or having The monomer for helping improve bonding force, can enumerate: carboxylic monomer, the monomer containing anhydride group, the monomer of amide-containing, containing amino Monomer, the monomer containing imide, the monomer containing epoxy group, (methyl) acryloyl morpholine, vinyl ethers etc..Other lists Body can be used alone one kind, also can be used in combination two or more.
As sulfonic monomer is contained, can enumerate: styrene sulfonic acid, allyl sulphonic acid, 2- (methyl) acrylamide -2- first Base propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester, (methyl) propane sulfonic acid, ethylene Base sodium sulfonate etc..
As the monomer of phosphorous acidic group, 2- hydroxyethyl acryloyl phosphate etc. can be enumerated.
As the monomer of cyano-containing, acrylonitrile, methacrylonitrile etc. can be enumerated.
It as vinyl esters, can enumerate: vinyl acetate, vinyl propionate, vinyl laurate etc..
It as aromatic ethenyl compound, can enumerate: styrene, substituted phenylethylene (chlorostyrene, chloromethylbenzene second Alkene, α-methylstyrene etc.) etc..
It as carboxylic monomer, can enumerate: acrylic acid, methacrylic acid, (methyl) carboxyethyl acrylates, (methyl) Acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid, crotonic acid, iso-crotonic acid etc..
It as the monomer containing anhydride group, can enumerate: maleic anhydride, itaconic anhydride, acid anhydrides of above-mentioned carboxylic monomer etc..
It as the monomer of amide-containing, can enumerate: acrylamide, Methacrylamide, acrylamide, N- ethylene Base pyrrolidones, N, N- dimethacrylamide, N, N- dimethylmethacryl amide, N, N- acrylamide, N, N- Diethyhnethacrylamide, N, N'- methylene-bisacrylamide, N, N- dimethylaminopropylacryl amide, N, N- diformazan Base propyl methacrylamide, diacetone acrylamide etc..
It as amino-containing monomer, can enumerate: (methyl) acrylate, (methyl) acrylic acid N, N- dimethylamino Base ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc..
It as the monomer containing imide, can enumerate: N-cyclohexylmaleimide, isopropylmaleimide, N- hexamethylene Base maleimide, clothing health acid imide etc..
It as the monomer containing epoxy group, can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid methylglycidyl Glyceride, allyl glycidyl ether etc..
It as vinyl ethers, can enumerate: methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether etc..
Acrylic acid series polymeric compounds include other monomers as polymeric composition in the case where, the containing ratio of other monomers is preferred Being aggregated in monomer total amount used in the synthesis of acrylic acid series polymeric compounds for other monomers is less than or equal to 40 mass %, more excellent Choosing is less than or equal to 30 mass %.Additionally, it is preferred that being aggregated in for other monomers is single used in the synthesis of acrylic acid series polymeric compounds It is greater than or equal to 0.001 mass % in body total amount.
Acrylic monomer only can also be set as polymeric composition by acrylic acid series polymeric compounds.As only by acrylic monomer The acrylic acid series polymeric compounds of polymeric composition are set as, such as can be enumerated: (methyl) acrylic acid alkyl for being only 6~14 by carbon atom number Ester be set as polymeric composition acrylic acid series polymeric compounds, only by carbon atom number be 6~14 (methyl) alkyl acrylate and containing hydroxyl (methyl) acrylate of base is set as the acrylic acid series polymeric compounds etc. of polymeric composition.
The standard polystyren conversion of acrylic acid series polymeric compounds obtained by gel permeation chromatography (GPC) is divided equally again Son amount (Mw) can for example be greater than or equal to 20 × 104, preferably greater than or equal to 30 × 104.In addition, such as can be less than or In 90 × 104, preferably lower than or equal to 80 × 104.If the weight average molecular weight of acrylic acid series polymeric compounds be above range in, Have the tendency that can get the sticker for showing good adhesive performance.
Acrylic acid series polymeric compounds can be random copolymer, can be block copolymer, or graft copolymer etc.. Consider from viewpoints such as productivities, it is often preferred that random copolymer.
The glass transition temperature (Tg) of acrylic acid series polymeric compounds is preferably lower than or equal to -15 DEG C, more preferably less than or waits In -25 DEG C, it is further preferably no larger than or equal to -40 DEG C.In addition, glass transition temperature (Tg) is preferably greater than or equal to -70 DEG C. If the glass transition temperature (Tg) of acrylic acid series polymeric compounds is above range, has to be formed and show good adherence The tendency of the sticker of energy.
In this specification, the Tg of acrylic acid series polymeric compounds refers to the homopolymerization based on each monomer for constituting acrylic acid series polymeric compounds The Tg of body (homopolymer) and the mass fraction (copolymerization ratios of quality criteria) of the monomer, according to the formula of Fox (Off ォ ッ Network ス) The value found out.Therefore, the Tg of acrylic acid series polymeric compounds can be by being suitable for changing monomer composition (that is, acrylic acid series polymeric compounds Type, the usage amount ratio etc. of monomer used in synthesizing) it adjusts.Herein, as the Tg of homopolymer, using remembering in known data Carry the value of (" polymer handbook (Polymer Handbook) " (the 3rd edition, John Wiley&Sons, Inc 1989)).As The Tg of above-mentioned homopolymer specifically uses the following value.
The homopolymer of 2-EHA: -70 DEG C
The homopolymer of n-butyl acrylate: -55 DEG C
The homopolymer of ethyl acrylate: -22 DEG C
The homopolymer of methyl acrylate: 8 DEG C
The homopolymer of methyl methacrylate: 105 DEG C
The homopolymer of cyclohexyl methacrylate: 66 DEG C
The homopolymer of vinyl acetate: 32 DEG C
The homopolymer of styrene: 100 DEG C
The homopolymer of acrylic acid: 106 DEG C
The homopolymer of methacrylic acid: 130 DEG C
As the Tg for the homopolymer that do not recorded in " polymer handbook (Polymer Handbook) ", using passing through following sides The value of method measurement.
100 mass of monomer is put into the reactor for having thermometer, blender, nitrogen ingress pipe and the cooling tube that flows back Part, 0.2 mass parts of azodiisobutyronitrile and 200 mass parts of ethyl acetate as polymer solvent. while making nitrogen circulate It is stirred 1 hour at (25 DEG C) of room temperature.It operates after removing the oxygen in polymerization system in this way, is warming up to 63 DEG C and reacts 10 hours. Then, it is cooled to room temperature (25 DEG C), obtains the homopolymer solution that solid component concentration is 33 mass %.Then, by the homopolymer Solution curtain coating is coated on release liner, is dried and makes the test specimen (sheet homopolymer) of thickness about 2mm.By the examination Test sample and strike out the discoid of diameter 7.9mm, sandwiched using parallel-plate, using test for viscoelastic machine (ARES, Rheometrics company) shear strain of frequency 1Hz is assigned, and with -70 DEG C~150 DEG C of temperature region, 5 DEG C/min of heating Speed measures viscoplasticity using shear mode, and the summit temperature of tan δ is set as to the Tg of homopolymer.
The method of acrylic acid synthesizing based polymer is not particularly limited, can solution application polymerization, emulsion polymerization, ontology The method that polymerization, suspension polymerization etc. generally use.From the solvent type adhesion agent composition comprising acrylic acid series polymeric compounds From the viewpoint of modulating easness, preferred solution polymerization process.Organic solvent used in solution polymerization process (polymer solvent) does not have Especially limitation, can enumerate: toluene, ethyl acetate, hexane, hexamethylene etc..Used organic solvent can be individually one kind, It can be two or more.
In this specification, solvent type adhesion agent composition refers to the combination of the form in organic solvent comprising adhesion ingredient Object.Organic solvent is not particularly limited.Such as it can enumerate: toluene, dimethylbenzene, ethyl acetate, hexane, hexamethylene, methyl cyclohexane Alkane, isopropanol etc..Organic solvent can be individually a kind of, or two or more.Solvent type adhesion agent composition preferably its NV (non-volatile component) is the whole 30 mass % of mass %~60, more preferably 30 mass of mass %~50 %.Solvent type is viscous The viscosity of agent composition be preferably 3Pas~25Pas, more preferably 5Pas~15Pas.On it should be noted that It states viscosity and refers to the value for using rotary viscosity design determining in the environment of 23 DEG C.
Acrylic acid series sticker can be designed in such a way that acrylic acid series polymeric compounds are crosslinked.As making propylene The specific method of sour based polymer crosslinking, can be listed below method, it may be assumed that by wrapping in the polymeric composition of acrylic acid series polymeric compounds Functional group is directed into acrylic acid series polymeric compounds containing the monomer with the functional group's (hydroxyl, carboxyl etc.) that can become crosslinking points In, and by the compound (crosslinking agent) that cross-linked structure can be formed with the functional group reactions be added in acrylic acid series polymeric compounds into Row reaction.
Crosslinking agent is not particularly limited, and can be selected from the general compound being crosslinked for acrylic acid series polymeric compounds.Such as it can arrange It lifts: epoxy crosslinking agent, isocyanates system crosslinking agent, melamine series crosslinking agent, peroxide system crosslinking agent, metal alkoxide system Crosslinking agent, metallo-chelate system crosslinking agent, metal salt system crosslinking agent, carbodiimide system crosslinking agent,Oxazoline system crosslinking agent, nitrogen Third pyridine system crosslinking agent, amine system crosslinking agent etc., wherein it is preferred that epoxy crosslinking agent and isocyanates system crosslinking agent.Used crosslinking Agent can be individually a kind of, or two or more.
As epoxy crosslinking agent, can enumerate: N, N, N', N'- four glycidyl group-m-xylene diamine, two shrinks are sweet Bis- (N, the N- diglycidyl amino methyl) hexamethylenes of oil base aniline, 1,3-, 1,6 hexanediol diglycidylether, new penta 2 Alcohol diglycidyl ether, propylene glycol diglycidylether, polyethyleneglycol diglycidylether, gathers ethylene glycol diglycidylether Propylene glycol diglycidylether, d-sorbite polyglycidyl ether, glycerine polyglycidyl ether, pentaerythrite poly epihydric alcohol Ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, oneself two Sour 2-glycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl group-three (2- hydroxyethyl) isocyanuric acid ester, Resorcinolformaldehyde resin, bis-phenol-S- diglycidyl ether, intramolecular have the epoxy resin of more than two epoxy groups Deng.
It as isocyanates system crosslinking agent, can enumerate: 1,2- ethylidene diisocyanate, Isosorbide-5-Nitrae-butylidene diisocyanate The lower aliphatics polyisocyanate compounds such as ester, 1,6- hexamethylene diisocyanate；Cyclopentylene diisocyanate, sub- ring The rouge such as hexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate Fat adoption isocyanate compound；2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI), 4,4'- diphenyl methane two Aromatic poly-isocyanates compound such as isocyanates, benzene dimethylene diisocyanate etc..
The usage amount of crosslinking agent for example relative to 100 mass parts of acrylic acid series polymeric compounds can be set to about 0.01 mass parts~ 15 mass parts are preferably set to 0.1 mass parts~10 mass parts (for example, 0.2 mass parts~2 mass parts).With above-mentioned usage amount packet In the case where containing crosslinking agent, have the tendency that can get the sticker for showing good adhesive performance.
Acrylic acid series sticker also can according to need comprising various additives.As additive, can enumerate: surface lubrication Agent, levelling agent, antioxidant, preservative, light stabilizer, ultraviolet absorbing agent, polymerization inhibitor, silane coupling agent etc..
Acrylic acid series sticker also can according to need comprising tackifying resin.The type of tackifying resin is not particularly limited, It can enumerate: rosin series tackifying resin, terpenic series tackifying resin, hydrocarbon system tackifying resin, epoxy tackifying resin, polyamide-based thickening Resin, elastic system tackifying resin, phenol system tackifying resin, ketone system tackifying resin etc..It is viscosified contained in acrylic acid series sticker Resin can be individually a kind of, or two or more.
It as rosin series tackifying resin, can enumerate: the unmodified rosins such as gum rosin, wood rosin, Starex (pine gum)； Modified rosin made of being modified unmodified rosin by hydrogenation, disproportionation, polymerization etc. (hydrogenated rosin, disproportionated rosin, polymerization pine Perfume, the rosin modified through other chemical modes etc.)；Other various rosin derivatives etc..
It as rosin derivative, can enumerate: object made of being esterified unmodified rosin or modified rosin using alcohols Matter (rosin ester)；Substance (unsaturated lipid made of being modified unmodified rosin or modified rosin using unsaturated fatty acid Fat acid modified rosin)；(the unsaturated fatty acid modified rosin of substance made of being modified rosin ester using unsaturated fatty acid Ester)；To the carboxylic in unmodified rosin, modified rosin, unsaturated fatty acid modified rosin or unsaturated fatty acid modified rosin ester Base carries out substance (abienol) made of reduction treatment；Unmodified rosin, modified rosin and above-mentioned rosin derivative are (especially loose Fragrant ester) metal salt；By utilizing acid catalyst addition phenol on unmodified rosin, modified rosin and above-mentioned rosin derivative And carry out thermal polymerization and the rosin phenolic resin etc. that obtains.
It as terpenic series tackifying resin, can enumerate: the terpenes such as australene alkene polymer, beta-pinene polymer, diamyl alkene polymer Alkene system resin；These terpenic series resins are modified made of (phenol is modified, aromatic modified, hydrogenation modification, hydrocarbon are modified etc.) Modified terpene system resin etc..It as modified terpene system resin, can enumerate: terpenes-phenol resin, styrenated terpene system tree Rouge, aromatic modified terpenic series resin, hydriding terpene system resin etc..
It as hydrocarbon system tackifying resin, can enumerate: fatty family hydrocarbon resin, aromatic system hydrocarbon resin, fatty family cyclic hydrocarbon Resin, aliphatic/aromatic through-stone oleoresin (styrene-olefin based copolymer etc.), aliphatic/alicyclic ring family Petropols, Hydrogenated hydrocarbon resins, coumarone system resin, coumarone-indenes system resin etc..
As fatty family hydrocarbon resin, can enumerate selected from alkene and one of diene that carbon atom number is 4~5 degree or The polymer etc. of two or more aliphatic hydrocarbons.It as alkene, can enumerate: 1- butylene, isobutene, 1- amylene etc..As diene, It can enumerate: butadiene, 1,3- pentadiene, isoprene etc..
As the example of aromatic system hydrocarbon resin, the aromatic system containing vinyl of 8~10 degree of carbon atom number can be enumerated The polymer etc. of hydrocarbon (styrene, vinyltoluene, α-methylstyrene, indenes, methyl indenes etc.).
It as fatty family ring-type hydrocarbon resin, can enumerate: so-called " C4 petroleum distillate " or " C5 petroleum distillate " is cyclized The ester ring type hydrocarbon system resin being polymerized after Dimerized；Cyclic diene compound (cyclopentadiene, bicyclopentadiene, Asia Ethyl norbornene, cinene etc.) polymer or its hydride；To aromatic system hydrocarbon resin or aliphatic/aromatic through-stone Ester ring type hydrocarbon system resin etc. made of the aromatic rings of oleoresin is hydrogenated.
The preferred softening point of tackifying resin (softening temperature) is greater than or equal to 80 DEG C (preferably greater than or equal to 100 DEG C).Pass through Using such tackifying resin, has the tendency that (for example, cementability is high) sticker of available higher performance.Tackifying resin The upper limit of softening point is not particularly limited, such as can be set as being less than or equal to 200 DEG C (preferably lower than or equal to 180 DEG C).It needs Illustrate, the softening point of tackifying resin described herein is set as through JIS K 5902:2006 and JIS K 2207:2006's Softening point test method (ring and ball method) specified in any one and measure value.
The usage amount of tackifying resin is not particularly limited, and can be suitable for setting according to target adhesive performance (bonding force etc.).Example Such as, it is preferably counted on the basis of solid component, relative to 100 mass parts of acrylic acid series polymeric compounds, with 10 mass parts~100 mass parts The ratio of (preferably 15 mass parts~80 mass parts, more preferably 20 mass parts~60 mass parts) uses tackifying resin.
(3) rubber series sticker
Rubber series sticker refers to the sticker that rubber-based polymeric object is set as to base polymer in this specification.Rubber series Polymer is not particularly limited, and can be natural rubber based polymer (including modified natural rubber based polymer), or Synthetic rubber based polymer.As synthetic rubber based polymer, ABA type or AB block copolymer (A expression thermoplasticity can be enumerated Block, B indicate diblock rubber.Styrene-isoprene-styrene copolymer (SIS), styrene-butadiene-benzene second can be enumerated Alkene copolymer (SBS) etc.).Rubber-based polymeric object may be the group of natural rubber based polymer Yu synthetic rubber based polymer It closes.
In the case that rubber series sticker includes synthetic rubber based polymer, as synthetic rubber based polymer, it can enumerate: Polybutadiene, polyisoprene, butyl rubber, polyisobutene, styrene butadiene ribber (SBR), styrene-butadiene-benzene Ethylene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene- Styrene block copolymer (SIS) etc..
In the case that rubber series sticker includes modified natural rubber based polymer, it polymerize as modified natural rubber system Object, it is the structure division from natural rubber that preferably it, which is greater than or equal to 50 mass % (being greater than or be equal to 60 mass %),. As modified natural rubber based polymer, can enumerate makes other monomers graft on graft modification made of natural rubber based polymer Natural rubber based polymer etc..As the monomer for grafting on natural rubber based polymer, can enumerate acrylic monomer (has third The monomer of enoyl- or methylacryloyl), styrene etc..The monomer for grafting on natural rubber based polymer can be independent one Kind, or it is two or more.
As the acrylic monomer for grafting on natural rubber based polymer, can enumerate: alkyl acrylate is (for example, third The acrylic acid that the carbon atom number of the alkyl such as e pioic acid methyl ester, ethyl acrylate, isopropyl acrylate, tert-butyl acrylate is 1~16 Arrcostab), alkyl methacrylate is (for example, methyl methacrylate (MMA), ethyl methacrylate, methacrylic acid are different The carbon atom number of the alkyl such as propyl ester, Tert-butyl Methacrylate be 1~16 alkyl methacrylate), acrylic acid, methyl-prop Olefin(e) acid etc..
As modified natural rubber based polymer, preferably grafts on being greater than in the monomer of natural rubber based polymer or wait In 50 mass % be acrylic monomer (acrylic acid modified natural rubber based polymer).
In the case that the base polymer of rubber series sticker is natural rubber based polymer, it polymerize as natural rubber system Object, for example, 100 DEG C of preferred MS (1+4) (use L-type rotor, preheat 1 minute, the viscosimetric analysis time 4 minutes, test temperature 100 DEG C) determination condition under Mooney viscosity be 10~60 degree.
In another mode, preferably methyl methacrylate (MMA) is grafted on made of natural rubber based polymer Acrylic acid modified natural rubber based polymer (NR-MMA graft copolymer).Above-mentioned graft copolymer can be made by conventional method It makes, can also be used as commercially available product acquisition.The grafting rate of MMA in NR-MMA graft copolymer is (by the MMA for being incorporated into natural rubber Quality/for grafting natural rubber quality × 100 (%) indicate, usually and according to for manufacture NR-MMA grafting altogether The natural rubber of polymers and the mass ratio of MMA and the value that calculates is same) can for example be set as 1%~120%, preferably 5%~ 100%, more preferably 10%~90%, further preferably 30%~80%.Being grafted rate is preferably 50%~90%, more excellent It is selected as 60%~80%.If being grafted rate is greater than or equal to 1%, can inhibit adhesion strength becomes excessively high, if grafting rate Less than or equal to 120%, then can inhibit becomes too low for the adhesion strength of the adherend such as SUS plate.It is connect for manufacturing NR-MMA The MMA of graft copolymer a part (for example, the monomer for grafting on natural rubber it is whole be less than or equal to 5 mass %, it is typical and Speech is less than or equal to 3 mass %) other monomers can be replaced into.
Rubber series sticker also may include other polymers in addition to base polymer (hereinafter also referred to as secondary polymerization Object).It as secondary polymer, can enumerate: it is viscous well known acrylic acid series sticker, Polyester sticker, polyurethane series can be become The acrylic acid series polymeric compounds of the base polymer of agent, organic silicon-type sticker etc., polyester based polymer, polyurethane series polymerization Object, organosilicon polymer etc..It or may be substance in addition to base polymer in above-mentioned rubber-based polymeric object.Rubber series Secondary polymer contained in sticker can be individually a kind of, or two or more.As basic polymer with it is secondary The combination of polymer can be enumerated: natural rubber based polymer and the NR-MMA as secondary polymer as basic polymer The combination of graft copolymer, the NR-MMA graft copolymer as basic polymer and the natural rubber system as secondary polymer The combination etc. of polymer.
In the case that rubber series sticker includes base polymer and secondary polymer, secondary polymer can be relative to basis 100 mass parts of polymer and be less than or equal to 100 mass parts usage amount (secondary polymer be it is two or more in the case where, It is total for it) it uses.In general, appropriately usage amount of the secondary polymer phase for 100 mass parts of base polymer is set as Less than or equal to 70 mass parts, it is preferably set to be less than or equal to 50 mass parts.Rubber series sticker can also be substantially free of secondary Polymer (that is, the substantial 100 mass % of component of polymer is basic polymer).Alternatively, it is also possible to be removed to be substantially free of The rubber series sticker of component of polymer other than rubber-based polymeric object is (for example, be substantially free of except natural rubber and modified day The rubber series sticker of component of polymer other than right rubber).
Rubber series sticker also may include tackifier in addition to component of polymer.Especially in the adherence comprising its own It, can be for a variety of glued by the inclusion of tackifier in the case that low natural rubber based polymer is as component of polymer Body shows high adhesion.In the case that rubber series sticker includes tackifier, as tackifier, such as it can enumerate as can wrap It is contained in substance illustrated by the tackifying resin in acrylic acid series sticker.
In the case that rubber series sticker includes component of polymer and tackifier, the usage amount (tackifier two of tackifier Kind or more in the case where, it is total for it) for example can be set as 20 mass parts~150 mass relative to 100 mass parts of component of polymer Part (preferably 30 mass parts~100 mass parts).If the usage amount of tackifier is greater than or equal to 20 mass parts, having can be abundant Ground obtains the tendency of the adhesion strength for adherend such as lead frames.On the other hand, if the usage amount of tackifier is less than or waits In 150 mass parts, then there is adhesion strength (the gluing especially under low temperature environment that can fully obtain for adherend such as lead frames Put forth effort) tendency.
Rubber series sticker is assigned to the method to substrate to be not particularly limited.It such as can be suitable for using: rubber will be become The ingredient of glue system sticker is dissolved or dispersed in medium appropriate and obtains adhesion agent composition, combines resulting sticker Object is coated on substrate and makes it dry the method to form adhering agent layer directly on substrate；It will be formed in that there is fissility Method well known to method that adhering agent layer on surface is transferred to substrate etc..Adhesion agent composition for example can by conventional method by Component of polymer, typical tackifier, other compositions used as needed and above-mentioned medium are mixed and are modulated.
Rubber series sticker also can according to need comprising vulcanization accelerator.As vulcanization accelerator, two sulphur can be used For carbamic acid class, (sodium dimethyl dithiocarbamate, sodium diethyldithiocarbamate, dimethyl disulfide are for amino first Sour zinc, zinc diethyl dithiocarbamate etc.), thiazoles (2-mercaptobenzothiazole, dibenzothiazyl disulfide etc.), guanidine (diphenylguanidine, di-o-tolylguanidine etc.), sulfenamide (benzothiazolyl -2- diethyl sulfenamide, N- cyclohexyl -2- benzo Thiazolyl sulfenamide etc.), thiurams (tetramethylthiuram monosulfide, tetramethylthiuram disulfide etc.), xanthan acids (sodium isopropyl xanthate, zinc isopropyl xanthate etc.), aldehyde ammonia class (acetaldehyde ammonia, hexa etc.), acetal amine are (just Butyraldehyde aniline condensation object, butyraldehyde dibutyl amine condensation product etc.), Thiourea (diethyl thiourea, trimethyl thiourea etc.) etc..Rubber series are viscous Vulcanization accelerator contained in agent can be individually a kind of, or it is two or more.For example, can also and dithiocarbamates be used Formic acid class and thiurams.The usage amount of vulcanization accelerator for example can be set as 0.1 mass relative to 100 mass parts of component of polymer Part~10 mass parts (preferably 0.5 mass parts~5 mass parts).
Rubber series sticker also can according to need comprising crosslinking agent.It as crosslinking agent, can enumerate: isocyanates chemical combination Object, sulphur, sulfur-containing compound, phenolic resin, organo-metallic compound etc..As crosslinking agent, preferred isocyanate compound is more excellent Select the isocyanate compound of 2 functions or more.It as isocyanate compounds more than 2 functions, can enumerate: two isocyanide of butylidene The lower aliphatics Polyisocyanate esters such as acid esters, hexamethylene diisocyanate；Cyclopentylene diisocyanate, cyclohexylidene two The alicyclic isocyanates class such as isocyanates, isophorone diisocyanate；2,4 toluene diisocyanate, 4,4'- diphenyl The aromatic diisocyanates class such as methane diisocyanate, benzene dimethylene diisocyanate；Trimethylolpropane/toluene two is different Cyanate tripolymer addition product (Nippon Polyurethane Industry Co., Ltd.'s system, trade name " Coronate L "), trimethylolpropane/ Hexamethylene diisocyanate trimer addition product (Nippon Polyurethane Industry Co., Ltd.'s system, trade name Coronate HL), six The isocyanuric acid ester body (Nippon Polyurethane Industry Co., Ltd.'s system, trade name " Coronate HX ") of methylene diisocyanate Equal isocyanate addition products etc..Crosslinking agent contained in rubber series sticker can be individually a kind of, or two or more. The usage amount (the case where isocyanate compound) of crosslinking agent is set as 0.3 mass preferably with respect to 100 mass parts of component of polymer Part~10 mass parts (such as 0.5 mass parts~5 mass parts).
Rubber series sticker also can according to need comprising vulcanization accelerator additive.As vulcanization accelerator additive, can enumerate hard Resin acid zinc etc..By using vulcanization accelerator additive, activity of accelerator can be made and promote curing efficiency.Promote comprising vulcanization In the case where auxiliary agent, usage amount for example can be set as 0.1 mass parts~10 mass parts relative to 100 mass parts of component of polymer (preferably 0.5 mass parts~5 mass parts).
Rubber series sticker also can according to need comprising additive.As additive, can enumerate: softening agent, fire retardant, Antistatic agent, light stabilizer (free radical scavenger, ultraviolet absorbing agent etc.), antioxidant etc..
(4) carbamate system sticker
In this specification, carbamate system sticker, which refers to, is set as the viscous of base polymer for urethane polymer Agent.As urethane polymer, the polymer for reacting polyalcohol with polyisocyanate compounds and obtaining can be enumerated, The carbamic acid containing terminal isocyanate group for reacting polyalcohol with excessive polyisocyanate compounds and obtaining Ester prepolymer (hereinafter referred to as " end NCO prepolymer ").End NCO prepolymer can be by gathering various polyalcohols with excessive Isocyanate compound for example carries out in such a way that the equivalent proportion of OH and NCO (number/NCO number of OH) is 1/1.2~3.5 Reaction is to synthesize.Reaction can according to need in the catalysts appropriate (organotins such as dibutyl tin dilaurate system catalysis Tertiary amines series catalysts such as the bismuths such as agent, Bismuth Octoate series catalysts, Isosorbide-5-Nitrae-diaza [2.2.2] double-octane etc.) in the presence of, such as It is carried out under conditions of 20 DEG C~90 DEG C (preferably 60 DEG C~90 DEG C) and 1 hour~7 hours.
End from the viewpoint of the storage stability of prepolymer and the flexibility of solidfied material, in the NCO prepolymer of end The content of isocyanate group (NCO) is preferably the 0.2 mass % of mass %~15.0, more preferably 0.5 matter of mass %~3.5 Measure %.The number-average molecular weight of end NCO prepolymer is usually 3,000~50,000, from the viewpoint of operation, preferably 4, 000~30,000.
It as polyalcohol, can enumerate: make the epoxyalkane such as propylene oxide or propylene oxide and ethylene oxide and second two The polyalcohols such as alcohol, propylene glycol, glycerol, trimethylolpropane, pentaerythrite, D-sorbite, sucrose carry out made of addition polymerization Polyether polyols alcohols；Ethylene glycol, propylene glycol and their oligomeric diol class；Butanediol, hexylene glycol and polytetramethylene ether two Alcohol；Polycaprolactone polyol；The polyester polyols alcohols such as polyethylene glycol adipate；Polybutadiene polyol class；The tool such as castor oil There are the higher fatty acids esters of hydroxyl；Make vinyl monomer carry out grafting with polyether polyols alcohols or polyester polyols alcohols to form Polymer polyol alcohols etc..Polyalcohol for synthesis of carbamates polymer can be individually a kind of, or two Kind or more.
Polyalcohol may be polymer.In the case that polyalcohol is polymer, examined from the viewpoint of reactivity, operability Consider, number-average molecular weight is preferably 500~20,000, more preferably 1,000~20,000.
From the viewpoint of inhibiting foaming, operability, the stability of curability and physical property, especially from it is aftermentioned specific Curing catalysts obtain the excellent balance of these characteristics when combining from the viewpoint of, polyalcohol is preferably to be used as adding for propylene oxide At the polyoxy sub alkyl polylol of object, or as the polyoxy sub alkyl polylol of propylene oxide and the addition product of ethylene oxide.From From the viewpoint of practicability, more preferably as the polyoxy sub alkyl polylol of the addition product of propylene oxide, (i.e. polytrimethylene is polynary Alcohol), further preferred polypropylene glycol.
Polyalcohol may be rosin diol.By using rosin diol, the adhesion strength of sticker becomes more excellent.Rosin Glycol is the glycol for being respectively provided with two rosin skeletons and two hydroxyls in the molecule.
As rosin diol, can enumerate: rosin ester, rosin and the bisphenol-A two for making rosin and polyol reaction and obtaining contract The reactant etc. of water glycerin ether etc..These rosin diols can be manufactured by previously known method.
In rosin diol, from from the viewpoint of the intermiscibility of the end NCO prepolymer, preferably there is polyoxy alkylidene skeleton Rosin diol.It as the commercially available product of the rosin diol with polyoxy alkylidene skeleton, can enumerate: Pinecrystal D- 6011, KE-615-3, D-6250 (being Arakawa Chemical Industries, Ltd.) etc..
Rosin diol is preferably used in combination with other polyalcohols.As other polyalcohols, preferably polypropylene glycol.And use rosin diol In the case where other polyalcohols, from the viewpoint of the character after solidification, the usage amount of rosin diol is preferably lower than or equal to 50 mass % of polyalcohol total amount, the more preferably 2 mass % of mass %~30, further preferably 3 mass of mass %~15 %.
Polyalcohol may be multi-functional polyol.For example, by using more than 4 functions (preferably 4 functions~8 functions) Multi-functional polyol, the adhesion strength (peel strength (peel strength)) after the solidification of sticker becomes more excellent.
It as multi-functional polyol, can enumerate: tetrol (pentaerythrite, two glycerol etc.), pentol (triglycerin, galactolipin Deng), it is six alcohol (dipentaerythritol, D-sorbite etc.), seven alcohol, eight alcohol (tripentaerythritol, sucrose etc.), multifunctional polynary at these Substance made of addition of ethylene oxide, propylene oxide etc. etc. on alcohol.From the viewpoint of from versatility and effect, preferred pentaerythrite Alkoxide addition product.These multi-functional polyols can be manufactured by previously known method, also be can be used as commercially available product and obtained. It as the commercially available product of multi-functional polyol, can enumerate: EL-410NE (Asahi Glass Co., Ltd), 4525 (Perstorp of POLYPL Specialty Chemicals AB company) etc..
Multi-functional polyol may be polymer.In the case that multi-functional polyol is polymer, number-average molecular weight Usually 100~2,000, from the viewpoint of character and reactivity, preferably 300~700.
Multi-functional polyol is preferably used in combination with other polyalcohols.As other polyalcohols, preferably polypropylene glycol, more preferably For the combination of polypropylene glycol and rosin diol.In the case where multi-functional polyol and other polyalcohols to be used in combination, from solidfied material From the viewpoint of the flexibility of (convered structure), the usage amount of multi-functional polyol is preferably to make of the hydroxyl of multi-functional polyol Number is less than or equal to 60% amount of the number of the hydroxyl of polyalcohol entirety, more preferably becomes 5%~20% amount.
Polyisocyanate compounds are not particularly limited, or belong to aromatic series, aliphatic or alicyclic any Compound.Specifically, can enumerate: toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), 3,3'- bis- Methyl -4,4'- biphenyl diisocyanate, 1,4- phenylene diisocyanate, benzene dimethylene diisocyanate, two methylene of durol Group diisocyanate, naphthalene diisocyanate, dicyclohexyl methyl hydride -4,4'- diisocyanate, thick (crude) TDI, polymethylene/ Polphenyl isocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate, hydrogenation phenylenedimethylidyne two are different Cyanate etc..Alternatively, it is also possible to be the isocyanuric acid carboxylate of these polyisocyanate compounds, carbodiimide compound, contracting two Urea compound etc..Polyisocyanate compounds for synthesis of carbamates polymer can be individually a kind of, or two Kind or more.Wherein, from the viewpoint of flexibility, non-xanthochromia and the safety after the character of prepolymer, solidification, preferably IPDI。
Polyisocyanate compounds preferably comprise the multifunctional poly- isocyanide of 3 functions or more (suitable is 3 functions~6 functions) Acid esters.By using multifunctional polyisocyanate more than 3 functions, the adhesion strength (peel strength) after the solidification of sticker becomes It is more excellent.
It as the commercially available product of multifunctional polyisocyanate, can enumerate: Coronate HX (alicyclic polymeric isocyanate, Japan Polyurethane industrial Co., Ltd.), Takenate D-170N (alicyclic polymeric isocyanate, Wu Tian drug Co., Ltd.), Sumidur N-3500 (aliphatic polymeric isocyanate firmly changes Bayer polyurethane Co., Ltd.), Sumidur N-3200 (aliphatic Polyisocyanate, firmly change Bayer polyurethane Co., Ltd.), Duranate 24A-100 and the Duranate E-405-80T (rising sun At Chemical Co., Ltd.) etc..
Multifunctional polyisocyanate compounds are preferably used in combination with other polyisocyanate compounds.As other polyisocyanates Ester compounds, preferably IPDI.And with multifunctional polyisocyanate compounds and other polyisocyanate compounds in the case where, from From the viewpoint of character after reaction, the usage amount of multifunctional polyisocyanate compounds preferably makes multifunctional polyisocyanate The number of the NCO base of compound is less than or equal to 60% amount of the number of the NCO base of polyisocyanate compounds entirety, more excellent Hank the amount for 5%~20%.
End NCO prepolymer can make as needed polyalcohol, excessive polyisocyanate compounds and monohydric alcohol reaction and It obtains.In this case, the adhesion strength (peel strength) after the solidification of sticker becomes more excellent.
It as monohydric alcohol, can enumerate: poly (oxyalkylene) base system monohydric alcohol, polyester monohydric alcohol, polyethers/ester monohydric alcohol, advanced full With monohydric alcohol, the monohydric alcohol with ethylene unsaturated double-bond etc..It can be individually one kind in the case where using monohydric alcohol, It can be two or more.
As poly (oxyalkylene) base system monohydric alcohol, can enumerate alkyl compound containing a reactive hydrogen etc. as initiation Agent makes the epoxyalkane such as ethylene oxide, propylene oxide, epoxy butane, tetrahydrofuran carry out made of ring opening polyaddition, divide The poly (oxyalkylene) base system monohydric alcohol etc. of high molecular weight containing a hydroxyl in sub.
It as polyester monohydric alcohol, such as can enumerate: the alkylation modification object of the terminal hydroxyl of known polyester polyol；It will Monohydroxy compound makes annular lactone compound carry out the reaction of open loop addition copolymerization or esterification and obtain as initiator Lactone system polyester monohydric alcohol；It is big with saturated fatty acid or (methyl) acrylic acid, cinnamic acid or as carbon atom number by polyalcohol In or equal to 10 the carboxylic acid with ethylene unsaturated double-bond such as oleic acid, linoleic acid, the linolenic acid of higher unsaturated fatty acid And the ester monohydric alcohol etc. obtained.
As polyethers/ester monohydric alcohol, can enumerate, which makes above-mentioned (list) epoxyalkane and aliphatic ester monohydric alcohol carry out addition, gathers Polyoxyalkylene fatty acid esters monohydric alcohol etc. made of conjunction.
As advanced saturated monohydroxy alcohol, can enumerate: the carbon atom numbers such as laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol are greater than Or equal to 10 straight-chain and the advanced saturated alcohols etc. of unitary.
It as the monohydric alcohol with ethylene unsaturated double-bond, can enumerate: the carbon atoms such as oleyl alcohol, linolenyl alcohol, secondary linolenyl alcohol The advanced unsaturated alcohol of straight-chain of the number more than or equal to 10 and unitary, allyl alcohol etc..
Wherein, from the viewpoint of general and safety, preferred poly (oxyalkylene) base system monohydric alcohol, more preferable polyoxypropylene Alkyl ether.
Monohydric alcohol may be polymer.In the case that monohydric alcohol is polymer, number-average molecular weight for example can be 100 ~10,000, from the viewpoint of versatility and operation, preferably 500~10,000.
For the commercially available product as the monohydric alcohol of polymer, PML-S1004F (Asahi Glass Co., Ltd) etc. can be enumerated.
In the case where monohydric alcohol used as polymer, from the viewpoint of the performance after solidification, usage amount is opposite In polyalcohol total amount be preferably the 5 mass % of mass %~50, more preferably 5 mass of mass %~30 %.
Carbamate system sticker also can according to need comprising tackifier.As long as tackifier can be to carbamate It is that sticker assigns adherence or can be improved adherence, is just not particularly limited.As tackifier, such as conduct can be enumerated It may include the tackifying resin in acrylic acid series sticker and the substance being described above.
In the case that carbamate system sticker includes tackifier, from the viewpoint of the balance of physical property and performance after solidification Consider, the content of tackifier is preferably the 10 mass % of mass %~60 of adhesion agent composition total amount, more preferably 10 mass % ~50 mass %.
Carbamate system sticker also can according to need comprising reactive monofunctional compound.By the inclusion of reactivity Monofunctional compound, so that the adhesion strength (peel strength) after the solidification of sticker becomes more excellent.
As long as reactive monofunctional compound is to have reactivity in urethane reaction and can be improved sticker Solidification after adhesion strength (peel strength) monofunctional compound, be just not particularly limited.Specifically, can enumerate: as Can the monohydric alcohol used in the synthesis of end NCO prepolymer and be described above monohydric alcohol, monofunctional isocyanates Close object (monohydric alcohol and the reactant of diisocyanate etc.), other simple function compositions for being able to carry out urethane reaction (amine, amide, mercaptan, carboxylic acid etc.) etc..Used reactivity monofunctional compound can be individually a kind of, or two kinds More than.From the viewpoint of safety and versatility, preferred monofunctional isocyanates compound, more preferable monohydric alcohol and two isocyanides The reactant of acid esters.As the reactant of monohydric alcohol and diisocyanate, the trade name " Additive of Beyer Co., Ltd can be enumerated TI " etc..
In the case that carbamate system sticker includes reactive monofunctional compound, from the viewpoint of the performance after solidification Considering, the usage amount of reactive monofunctional compound is preferably 5 mass %~50 mass % of sticker total amount, and more preferably 5 The mass of quality %~30 %.
Carbamate system sticker also can according to need comprising additive.As additive, can enumerate: carbamic acid Ester catalyst, plasticizer (acrylic ester plasticizer, phthalate esters, two esters of epoxidation hexahydrophthalic acid, Two esters of alkylene dicarboxylic acids, alkyl benzene etc.), filler (powdered whiting, fatty acid treatment calcium carbonate, gas phase titanium dioxide Silicon, settleability silica, carbon black, talcum, titanium oxide, sphere (balloon), bead etc.), antioxidant (Hinered phenols Deng), fire retardant, thixotropy conferring agents (colloidal silicon dioxide, organobentonite, fatty acid amide, polyamide wax, hydrogenated castor Oil etc.), ultraviolet absorbing agent (benzotriazole, hindered amines etc.), antiaging agent (Hinered phenols, thio-alcohol, thioether class, two Thiocarboxylic acid salt, Thiourea, thiophosphoric acid salt, thioaldehydes class etc.), closely sealed dose (epoxide, silane coupling agent etc.), it is de- Aqua etc..
It as urethane catalyst, can enumerate: DBU series catalysts, amine system catalyst, metal salt of organic carboxylic acid, miaow Azoles series catalysts etc..It as DBU series catalysts, can enumerate: DBU [1,8- diazabicyclo [5.4.0] hendecene -7], DBU benzene Phenates, DBU caprylate, DBU formates etc..As amine system catalyst, can enumerate: monoamine (triethylamine etc.), diamines (N, N, N', N'- tetramethylethylenediamine etc.), triamine (tetramethylguanidine etc.), cyclic amine (triethylenediamine etc.), hydramine (dimethylaminomethanol Deng), ether amines (bis- (2- dimethyl aminoethyl) ethers etc.) etc..It as metal salt of organic carboxylic acid, can enumerate: Sn system (tin dilaurate Dibutyl tin, tin octoate etc.), Pb system (lead octoate etc.), Zn system (zinc octoate etc.) etc..As imidazoles series catalysts, can enumerate: 2- Methylimidazole, DMIZ 1,2 dimethylimidazole etc..
The production method of carbamate system sticker is not particularly limited.For example, can be by the way that carbamate system be glued Component of polymer contained in agent and the other compositions for including as needed mixing and the carbamate system as a liquid type Sticker makes.Carbamate system sticker may be the no-solvent type sticker for not including solvent substantially.If Carbamate system sticker does not include solvent substantially, then when solidifying sticker by heat, is able to suppress smelly because generating Environmental pollution caused by gas, volatile organic compounds (VOC) etc..
(filler)
Adhesion coating also may include filler.It include filler by adhesion coating, can get makes the outer surface of adhesion coating (with substrate side Opposite face) roughening and other effects.
The material of filler is not particularly limited, and can be the organic substances such as resin, or metal, metal oxide etc. Inorganic substances can also be the combination of organic substance and inorganic substances.In addition, filler contained in adhesion coating can be independent one Kind, or it is two or more.
The volume average particle size of filler is not particularly limited.Such as it can be selected from 1 μm~20 μm of range.In this specification, The volume average particle size of filler is tired from path side in the size distribution of the volume reference measured by laser diffractometry Product becomes the partial size (D50) when 50%.
From with from the viewpoint of the compatibility of sticker contained in adhesion coating, filler is preferably resin particle.As structure It at the resin of resin particle, can enumerate: acrylic resin, olefin resin, styrene resin, acrylonitrile resin, organic siliconresin Deng.From the viewpoint of inhibiting the residue in encapsulation after molding, preferred acrylic resins.
< substrate >
The material of substrate is not particularly limited.From the viewpoint of the tracing ability to mold, preferably resin.As tree Rouge can be enumerated: the polyester such as polyethylene terephthalate (PET), polyimides, polyamide, polyester ether, polyamide acyl are sub- Amine, fluorine resin etc..In the case where using resin, preferably there is sufficient heat resistance to the heating temperature in sealing process Resin.
Also implement for improving between substrate and adhesion coating in the face that can according to need the setting adhesion coating side to substrate Closing force processing.It as the method for processing, can enumerate: the surface treatment such as sided corona treatment, corona treatment, silane coupling agent The coating etc. of (priming paint).
Also it can according to need and the back side (face opposite with adhesion coating side) of substrate assigned for adjusting adhesive film from roller The back side process agent of the rolling out property rolled out.As back side process agent, can enumerate: organic siliconresin, fluorine resin, polyvinyl alcohol, The monomers such as the resin with alkyl, modified body, mixture etc..
As needed, electrostatic is generated in order to inhibit when adhesive film rolls out, when removing from adherend etc., it can also be to substrate The back side or be arranged adhesion coating side face assign antistatic agent.It as antistatic agent, can enumerate: quaternary ammonium salt, pyridineSalt, tool There is the cationic antistatic agent of the cationic groups such as primary amino group~tertiary amino；With sulfonate group, sulfuric ester alkali, phosphoric acid The anionic system antistatic agent of the anionic groups such as ester alkali；The both sexes antistatic agents such as amino acid system, amino acid sulfuric ester system； Amino alcohol system, glycerol system, polyethylene glycol system etc. have the nonionic system antistatic agent of nonionic group；To these antistatic agents Carry out Polymer Antistatic Agent made of molecular weight etc..These antistatic agents from the transparency it is good from the aspect of also fit It closes.
Embodiment
Hereinafter, being illustrated based on mold release film of the embodiment to present embodiment.But present embodiment is not limited to Embodiment below.
1 > of < embodiment
By 100 mass parts of sticker A, 0.5 mass parts of catalyst and the solvent (mixing of toluene and methyl iso-butyl ketone (MIBK) Object, mass ratio 1:1) cooperation of 275 mass parts, it is stirred by disperser and modulates adhesion coating formation composition.With adhesion Layer thickness as 3 μm mode by the adhesion coating formation with composition be coated on substrate (PET film with a thickness of 50 μm) its The whole face of middle one side heats 1 minute at 120 DEG C and forms adhesion coating, to make supporter.Then, pass through layer as shown in Figure 2 Length is 232mm by platen press, width 67mm, with a thickness of 9 μm of copper foils (" F2-WS ", The Furakawa Electric Co., Ltd.) patch Together in the adhesion coating of supporter, to form electromagnetic wave shielding sheet, strikes out predetermined shape and make mold release film.
2 > of < embodiment
By 100 mass parts of sticker B, 10 mass parts of crosslinking agent A and the solvent (mixing of toluene and methyl ethyl ketone Object, mass ratio 8:2) cooperation of 227 mass parts, it is stirred by disperser and modulates adhesion coating formation composition.With adhesion Layer thickness as 3 μm mode by the adhesion coating formation with composition be coated on substrate (PET film with a thickness of 38 μm) its The whole face of middle one side heats 1 minute at 100 DEG C and forms adhesion coating, to make supporter.Then, in the whole face of adhesion coating On, aluminium layer is formed in such a way that thickness becomes 1 μm ion plating method, to form electromagnetic wave shielding sheet, and is struck out predetermined Shape and make mold release film.
3 > of < embodiment
By 100 mass parts of sticker C, 17.4 mass parts of crosslinking agent B, 10 mass parts of filler and solvent (toluene and first The mixture of base ethyl ketone, mass ratio 8:2) cooperation of 87 mass parts, it is stirred by disperser and modulates adhesion coating formation use Composition.It in addition to using the adhesion coating formation composition, operates similarly to Example 2, makes mold release film.
1 > of < comparative example
Using the adhesion coating formation composition for operating and modulating similarly to Example 2, grasp similarly to Example 2 Make, forms adhesion coating on substrate and make supporter.Then, it operates similarly with example 1, forms electromagnetism on adhesion coating Wave screen covers piece, to make mold release film.
The details of each material used in the production of mold release film is as described below.
(sticker)
Sticker A: addition reaction-type organic silicon-type sticker, trade name " LTC755 ", 30 mass % of solid component, east Beautiful DOW CORNING Co., Ltd.
Sticker B: acrylic acid series sticker, trade name " S-43 ", solid component 24 mass % are comprehensive to grind chemical strain formula meeting Society is made of butyl acrylate (BA) and the mix monomer of acrylic acid 4- hydroxybutyl (4HBA)
Sticker C: acrylic acid series sticker, trade name " FS-1208 ", 45 mass % of solid component, lion king refine strain Formula commercial firm is made of the mix monomer of a variety of methacrylates
(catalyst)
Platinum catalyst (trade name " NC-25 ", Dong Li DOW CORNING Co., Ltd.)
(crosslinking agent)
Crosslinking agent A: trade name " Coronate HL ", 75 mass % of solid component, TOSOH Co., Ltd, trihydroxy methyl 75% ethyl acetate solution of propane/hexamethylene diisocyanate trimer addition product, the isocyanates radix in a molecule: 3
Crosslinking agent B: trade name " Duranate E405-80T ", 80 mass % of solid component, Asahi Chemical Industry's chemistry strain formula meeting Society, polyisocyanate system crosslinking agent (hexamethylene diisocyanate crosslinking agent (HMDI)), the isocyanates radix in a molecule: 2
Filler: dispersed particle in cross-linked acrylic acid, trade name " MZ-10HN " are 10 μm of volume average particle size, comprehensive to grind chemistry Co., Ltd.
< evaluation test >
Test is conducted the following evaluation using made mold release film.
(1) peeling force between adhesion coating-electromagnetic wave shielding sheet
In the embodiment 1 and comparative example 1 for foring electromagnetic wave shielding sheet by laminating method, made mold release film is thrown Enter to 170 DEG C of atmosphere, after the scheduled time, is existed using Tensilon universal testing machine (Co., Ltd.'s A&D system) Peeling force (N/50mm) is measured under 0.3m/ minutes 180 ° of peel angle, peeling rate stripping conditions.Show the result in table 1.
In the embodiment 2 and embodiment 3 for foring electromagnetic wave shielding sheet by ion plating method, by made mold release film Be cut into scheduled size, by adhesion coating above in a manner of be placed in 170 DEG C heating plate on, by the sealing material of predetermined amount (trade name " CEL-9750 ", Hitachi Chemical Co., Ltd.) intersperses among on adhesion coating, and the PET film loaded with a thickness of 100 μm.It connects , the counterweight of 4kg is loaded on a pet film, places 3 minutes until sealing material solidification.Then, mold release film is cut into 50mm Width, and put into 170 DEG C of atmosphere.After 1 minute, Tensilon universal testing machine (Co., Ltd. A&D is utilized Make) peeling force is measured under 0.3m/ minutes 180 ° of peel angle, peeling rate stripping conditions.Show the result in table 1.
(2) transferability of electromagnetic wave shielding sheet
The mold release film made in embodiment 1 and comparative example 1 is cut into predefined size, by adhesion coating above in a manner of put It is placed in 170 DEG C of heating plate, the sealing material (trade name " CEL-9750 ", Hitachi Chemical Co., Ltd.) of predetermined amount is interspersed among On adhesion coating, and the PET film loaded with a thickness of 100 μm.Then, the counterweight of 4kg is loaded on a pet film, is placed 3 minutes until close Until sealing material solidification.Then, electromagnetic wave shielding sheet is removed from supporter (substrate and adhesion coating), confirms electromagnetic wave by visual observation Shield the transferability of piece.
In embodiment 2 and embodiment 3, make to seal in the same manner as the evaluation of peeling force between adhesion coating-electromagnetic wave shielding sheet In the state of material solidification, electromagnetic wave shielding sheet is removed from supporter (substrate and adhesion coating), confirms electromagnetic wave shielding by visual observation The transferability of piece.
About the transferability of electromagnetic wave shielding sheet, do not generate fold, bending, breakage etc. in electromagnetic wave shielding sheet and can be from Supporter is evaluated as " good " in the case where removing, and produces fold, bending, breakage etc. in electromagnetic wave shielding sheet or can not be from support Body is evaluated as " bad " in the case where removing.Show the result in table 1.
[table 1]
As shown in the result of table 1, the peeling force between adhesion coating and electromagnetic wave shielding sheet is 0.10N/50mm~2.00N/ In the release sheet of the embodiment of 50mm, the transferability of electromagnetic wave shielding sheet is good.On the other hand, adhesion coating and electromagnetic wave shielding sheet Between peeling force less than 0.10N/50mm comparative example release sheet in, the electromagnetic wave shielding sheet after removing produces fold, The transferability of electromagnetic wave shielding sheet is poorer than embodiment.
The disclosure that Japanese patent application the 2016-091947th is introduced into this specification entirely through reference In.Documented whole document, patent application and technical standard in this specification, with it is specific and respectively describe by referring to And the case where introducing each document, patent application and technical standard, is to same extent, by referring to and be introduced into this specification.

Claims (5)

1. a kind of mold release film, it includes supporter and electromagnetic wave shielding sheet, the supporter includes substrate and is configured at described Adhesion coating on substrate, the electromagnetic wave shielding sheet are configured on the adhesion coating of the supporter, and the adhesion coating Peeling force between the electromagnetic wave shielding sheet is 0.10N/50mm~2.00N/50mm.
2. mold release film according to claim 1, the electromagnetic wave shielding sheet with a thickness of 0.01 μm~50 μm.
3. mold release film according to claim 1 or 2, the adhesion coating with a thickness of 1 μm~20 μm.
4. mold release film described in any one of claim 1 to 3, the adhesion coating includes selected from by organic silicon-type sticker With at least one of the group of acrylic acid series sticker composition.
5. mold release film according to any one of claims 1 to 4 is used for the manufacture of semiconductor device, the semiconductor Process of the manufacture comprising the electromagnetic wave shielding sheet is transferred to the sealing material being sealed to semiconductor element of device.
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI802657B (en) * 2018-02-27 2023-05-21 日商三菱化學股份有限公司 polyester film
CN111936283A (en) * 2018-06-08 2020-11-13 仓敷纺绩株式会社 Mold release film and method for producing mold release film

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0817855A (en) * 1994-06-29 1996-01-19 Nitto Denko Corp Manufacture of semiconductor device and laminate used therefor
WO2010114300A2 (en) * 2009-03-31 2010-10-07 주식회사 잉크테크 Method for manufacturing thin metal laminated film
CN102132391A (en) * 2008-08-28 2011-07-20 三井化学株式会社 Mold release film for manufacturing semiconductor resin package and semiconductor resin package manufacturing method using same
CN102468185A (en) * 2010-11-18 2012-05-23 日东电工株式会社 Die bond film, dicing die bond film, method of manufacturing die bond film, and semiconductor device having die bond film
JP2013021270A (en) * 2011-07-14 2013-01-31 Nitto Denko Corp Film for manufacturing semiconductor device
CN104520978A (en) * 2012-06-08 2015-04-15 日立化成株式会社 Method for manufacturing semiconductor device
CN104937712A (en) * 2013-03-22 2015-09-23 琳得科株式会社 Protective film-forming film and protective film-forming composite sheet
CN105407624A (en) * 2014-09-04 2016-03-16 信越聚合物株式会社 Electromagnetic wave shielding film and method for manufacturing flexibility printing distribution board with the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08288686A (en) * 1995-04-20 1996-11-01 Nec Corp Semiconductor device
JP4133637B2 (en) 2003-07-11 2008-08-13 三井化学株式会社 Electromagnetic wave shielding sheet for semiconductor element adhesion and semiconductor device
JP2007287937A (en) 2006-04-17 2007-11-01 Kyocera Chemical Corp Resin-sealed semiconductor device and its manufacturing method
CN101617400A (en) * 2007-01-31 2009-12-30 富士通微电子株式会社 Semiconductor device and manufacture method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0817855A (en) * 1994-06-29 1996-01-19 Nitto Denko Corp Manufacture of semiconductor device and laminate used therefor
CN102132391A (en) * 2008-08-28 2011-07-20 三井化学株式会社 Mold release film for manufacturing semiconductor resin package and semiconductor resin package manufacturing method using same
WO2010114300A2 (en) * 2009-03-31 2010-10-07 주식회사 잉크테크 Method for manufacturing thin metal laminated film
CN102468185A (en) * 2010-11-18 2012-05-23 日东电工株式会社 Die bond film, dicing die bond film, method of manufacturing die bond film, and semiconductor device having die bond film
US20120126379A1 (en) * 2010-11-18 2012-05-24 Daisuke Uenda Die bond film, dicing die bond film, method of manufacturing die bond film, and semiconductor device having die bond film
JP2013021270A (en) * 2011-07-14 2013-01-31 Nitto Denko Corp Film for manufacturing semiconductor device
CN104520978A (en) * 2012-06-08 2015-04-15 日立化成株式会社 Method for manufacturing semiconductor device
CN104937712A (en) * 2013-03-22 2015-09-23 琳得科株式会社 Protective film-forming film and protective film-forming composite sheet
CN105407624A (en) * 2014-09-04 2016-03-16 信越聚合物株式会社 Electromagnetic wave shielding film and method for manufacturing flexibility printing distribution board with the same

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