CN105940299B - The reactivity assay method and acrylic adhesive of acrylic adhesive - Google Patents

The reactivity assay method and acrylic adhesive of acrylic adhesive Download PDF

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Publication number
CN105940299B
CN105940299B CN201580007074.0A CN201580007074A CN105940299B CN 105940299 B CN105940299 B CN 105940299B CN 201580007074 A CN201580007074 A CN 201580007074A CN 105940299 B CN105940299 B CN 105940299B
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compound
acrylic adhesive
reactivity
carbon number
fluorene skeleton
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CN105940299A (en
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上泽尚也
田中雄介
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Dexerials Corp
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Dexerials Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/74—Optical detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G01N2030/8854—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving hydrocarbons

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Abstract

The reactivity assay method and acrylic adhesive for the reactivity measure that acrylic adhesive can also be carried out with good precision even if using micro sample are provided.Compound with fluorene skeleton is used as internal standard compound, the sample solution containing acrylic adhesive is separated with liquid chromatogram, unreacted free-radical polymerised compound is detected by UV-detector.Because the compound with fluorene skeleton shows high sensitivity to UV-detector, therefore even if can also be with good precision determination reactivity using micro sample.In addition, the compound with fluorene skeleton is due to being not involved in the curing reaction of acrylic adhesive, therefore become in advance to coordinate in acrylic adhesive.

Description

The reactivity assay method and acrylic adhesive of acrylic adhesive
Technical field
The present invention relates to the reactivity assay method of the acrylic adhesive containing free-radical polymerised compound and third Olefin(e) acid system adhesive.The application is with Japan on 2 3rd, the 2014 Japanese Patent application number Japanese Patent Applications for submitting application Based on 2014-18388, CLAIM OF PRIORITY, this application is quoted in a manner of reference to be added in the application.
Background technology
In the past, as circuit material, widely use anisotropic conductive film (ACF：Anisotropic Conductive Film) etc..The reason for bad occurs as ACF, thus it is speculated that have the inhomogeneities of the curing degree in circuit electrode.It is believed that In anisotropic conductive connection, due to making multiple electrodes together and equably connect, therefore on the relatively large electrode of thermal conductivity The relatively low interelectrode position with thermal conductivity, reactivity produce difference.
But conventional based in DSC, FT-IR etc. analysis, required sample size is more, it is difficult to good precision Determine the reactivity of the tiny area on electrode, between electrode etc..
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-251789 publications.
The content of the invention
Invent problem to be solved
The present invention is in view of such conventional situation and motion, there is provided even if can also be with good using micro sample Good precision carries out the reactivity assay method of the reactivity measure of acrylic adhesive, and acrylic adhesive.
The means to solve the problem
The present inventor go deep into the result of investigation, finds by the way that the compound with fluorene skeleton is used as into internal standard compound, i.e., Reactivity measure can also be carried out with good precision using micro sample.
In other words, reactivity assay method of the present invention is characterised by, will have fluorenes shown in following (1) formulas The compound of skeleton is used as internal standard compound, and the sample solution containing acrylic adhesive is separated with liquid chromatogram, passed through UV-detector detects unreacted free-radical polymerised compound.
[changing 1]
In formula, R1It is selected from hydrogen atom, the alkyl that carbon number is 1 ~ 3, the group for the alkoxy that carbon number is 1 ~ 3, R2 It is selected from hydroxyl, the hydroxy alkyl that carbon number is 1 ~ 3, the group for the hydroxy alkoxy base that carbon number is 1 ~ 3.
In addition, acrylic adhesive of the present invention is characterised by, it, which contains shown in described (1) formula, has fluorenes Compound, free-radical polymerised compound and the reaction initiator of skeleton.
In addition, anisotropic-electroconductive adhesive of the present invention is characterised by, it is bonded in the acrylic acid series Dispersed electro-conductive particle forms in agent.
Invention effect
According to the present invention, because the compound with fluorene skeleton shows high sensitivity to UV-detector, therefore i.e. Can also be with good precision determination reactivity using micro sample.In addition, the compound with fluorene skeleton is not due to joining With the curing reaction of acrylic adhesive, therefore become in advance to coordinate in acrylic adhesive.
Brief Description Of Drawings
Fig. 1：Fig. 1 is the chromatogram of an example of the analysis result for representing the acrylic adhesive before solidifying
Fig. 2：Fig. 2 is the chromatogram of an example of the analysis result for representing the acrylic adhesive after solidifying.
Embodiment
Hereinafter, on embodiments of the present invention, it is described in detail in the following sequence referring to the drawings：
1. the reactivity assay method of acrylic adhesive
2. acrylic adhesive
3. embodiment.
<1. the reactivity assay method of acrylic adhesive>
The reactivity assay method of acrylic adhesive involved by present embodiment is, by shown in following (1) formulas Compound with fluorene skeleton is used as internal standard compound, and the sample solution containing acrylic adhesive is divided with liquid chromatogram From detecting unreacted free-radical polymerised compound by UV-detector.
[changing 2]
In formula, R1It is selected from hydrogen atom (- H), the alkyl (- C that carbon number is 1 ~ 3nH2n+1, n=1 ~ 3), carbon number 1 ~ 3 alkoxy (- OCnH2n+1, n=1 ~ 3) group, R2Be selected from hydroxyl (- OH), carbon number be 1 ~ 3 hydroxy alkyl (- CnH2nOH, n=1 ~ 3), carbon number be 1 ~ 3 hydroxy alkoxy base (- OCnH2nOH, n=1 ~ 3) group.
As the specific example of the compound with fluorene skeleton shown in (1) formula, double phenoxetol fluorenes can be enumerated (BPEF：R1=H、R2=OC2H4OH), bisphenol fluorene (BPF：R1=H、R2=OH), double cresols fluorenes (BCF：R1=CH3、R2=OH) etc..(1) formula The shown compound with fluorene skeleton is shown high sensitive because ultraviolet absorption ability is high to UV-detector Degree, even if can also be with good precision determination reactivity using micro sample.
Should illustrate, as can use UV-detector detect conventional internal standard compound, have dibutyl hydroxy toluene (BHT), BTA (BTZ) etc., but its detection sensitivity is insufficient, it has to a large amount of additions.Further, since BHT and the double benzene of acrylic acid Ethoxy-ethanol fluorenes ester (BPEFA), BTZ overlap with the blob detection position of acrylic acid 4- hydroxybutyls (4-HBA), therefore versatility Difference.
Liquid chromatography is high performance liquid chromatography (HPLC：High Performance liquid Chromatography), sample solution is made by the splitter filled with release agent, by the distribution relative to release agent, absorption Complexity etc. difference, be separated into Multiple components.
As release agent (filler), particle diameter that HPLC can be enumerated be 2 ~ 30 μm or so of silica gel, with octadecyl, The chemical bond mould assembly silica gel of the group bondings such as cyanopropyl, porous polymer, ion exchange resin etc..
As UV-detector, as long as the absorbance based on sample solution is to sample solution irradiating ultraviolet light and measure Can, there is no particular limitation, can use UV absorbance detector general in the analysis based on HPLC.
Then, the details of reactivity measure is illustrated.This technology can be in advance in acrylic adhesive Compound with fluorene skeleton is coordinated with ormal weight, the sample solution of acrylic adhesive can also be added with ormal weight and had There is the compound of fluorene skeleton.As the solvent of dissolving acrylic adhesive, acetonitrile, acetone etc. can be used.
Fig. 1 and Fig. 2 is an example of the analysis result for showing the preceding acrylic adhesive with after solidification of solidification respectively Chromatogram.The peak intensity of the chromatogram obtained by UV-detector generally represents with peak area or peak heights, but Hereinafter, illustrated for the reactivity computational methods based on peak heights.
First, obtained by the chromatogram of the acrylic adhesive before solidifying and the acrylic adhesive after being fully cured The intensity of internal standard compound and unreacted monomer ratio, for example, using before solidification as reactivity 0%, to be used as reactivity after being fully cured 100%, intensity is made than the relation line with reactivity.It is then possible to internal standard compound and unreacted are obtained by the chromatogram of unknown sample The intensity ratio of monomer, reactivity is obtained by the relation line made.
Like this by the way that the compound with fluorene skeleton shown in (1) formula is used as into internal standard compound, even if using micro sample Product can also be with good precision determination reactivity.
<2. acrylic adhesive>
Acrylic adhesive of the present embodiment contain the compound with fluorene skeleton shown in following (1) formulas, Free-radical polymerised compound and reaction initiator.
[changing 3]
In formula, R1It is selected from hydrogen atom (- H), the alkyl (- C that carbon number is 1 ~ 3nH2n+1, n=1 ~ 3), carbon number 1 ~ 3 alkoxy (- OCnH2n+1, n=1 ~ 3) group, R2Be selected from hydroxyl (- OH), carbon number be 1 ~ 3 hydroxy alkyl (- CnH2nOH, n=1 ~ 3), carbon number be 1 ~ 3 hydroxy alkoxy base (- OCnH2nOH, n=1 ~ 3) group.
As the specific example of the compound with fluorene skeleton shown in (1) formula, double phenoxetol fluorenes can be enumerated (BPEF：R1=H、R2=OC2H4OH), bisphenol fluorene (BPF：R1=H、R2=OH), double cresols fluorenes (BCF：R1=CH3、R2=OH) etc..
Hereinafter, enter for the anisotropic-electroconductive adhesive that dispersed electro-conductive particle forms in acrylic adhesive Row explanation.(1) even if the compound with fluorene skeleton shown in formula coordinates in anisotropic-electroconductive adhesive, in hot pressing Also do not decompose, further, since being not involved in curing reaction, therefore Gao Ling can be shown to UV-detector when determining reactivity Sensitivity.Therefore, can be with good precision determination electrode, between electrode etc. if using the anisotropic-electroconductive adhesive The reactivity of tiny area.
The use level of compound with fluorene skeleton is preferably more than 0.01wt% and below 5.0wt%, more preferably 0.2wt% Above and below 1.0wt%.If use level is very few, measure peak diminishes, it is impossible to the function as internal standard compound is played, if matched somebody with somebody Resultant is excessive, then the characteristic as anisotropic conductive film is deteriorated.
As free-radical polymerised compound, simple function (methyl) acrylate monomer, multifunctional (methyl) can be used Acrylate monomer or introducing epoxy radicals, carbamate groups, amino, oxyethylene group, oxypropylene group etc. in them The simple function of obtained modification or multifunctional (methyl) acrylate monomer.In addition, free-radical polymerised compound can be with list Any state uses in body, oligomer, can also use monomer and oligomer in the lump.
As (methyl) acrylate monomer, can enumerate at least has more than one (methyl) third in a molecule (methyl) acrylate of enoyl-, its modifier etc..In addition, as their modifier, acrylic acid four can be enumerated Hydrogen chaff ester, isobornyl acrylate, methacrylic acid methyl acrylate, methacrylic acid ethyl acrylate, tristane diformazan Alcohol diacrylate, Tricyclodecane Dimethanol dimethylacrylate, ethoxylated bisphenol a diacrylate, propoxylation are double Phenol A diacrylates, pentaerythritol triacrylate, ethoxylation cyamelide triacrylate etc..It can be with one kind Use, two or more uses can also be mixed.
As reaction initiator, organic peroxide, optical free radical polymerization initiator etc. can be used.As organic peroxy Compound, diacyl peroxide, dialkyl peroxide, peroxy dicarbonate, peroxyester, peroxidating can be used to contract It is more than one or two kinds of in ketone, hydroperoxides, silicyl peroxide etc..In addition, draw as optical free radical polymerization Agent is sent out, the benzyls such as benzoin ether, benzyl, the hydroxycyclohexylphenylketones such as styrax ethylether, isopropyl benzoin ether can be used It is one or two kinds of in the ketones such as base ketal, benzophenone, acetophenone or its derivative, thioxanthene ketone class, bisglyoxaline class etc. More than.
For electroconductive particle, the electroconductive particle used in conventional anisotropic conductive film can be used, such as The metallics such as gold particle, silver particles, nickel particles；By the surfaces of the resin particles such as benzoguanamine resin, styrene resin gold, Metallic cover resin particle that the metallic covers such as nickel, zinc obtain etc..As the average grain diameter of such electroconductive particle, it is usually 1 ~ 10 μm, more preferably 2 ~ 6 μm.
In addition, anisotropic-electroconductive adhesive can also contain film-forming resin, silane coupler, phosphate, inorganic filler, Stress moderator etc..As film-forming resin, phenoxy resin, polyvinyl acetal resin, polyvinyl butyral resin can be enumerated It is resin, alkylated cellulose resin, polyester resin, acrylic resin, styrene resin, carbamate resins, poly- to benzene two Formic acid glycol ester resin etc..As silane coupler, γ-glycidylpropyl trimethoxy silane, γ-sulfydryl can be enumerated Propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-urea propyl-triethoxysilicane, N- beta-aminoethyls- Gamma-amino propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane etc..
, can be with good precision determination electrode, between electrode if anisotropic-electroconductive adhesive as use Deng the reactivity of tiny area, therefore become the engaging condition that can be stablized with the short time.
Embodiment
<3. embodiment>
Hereinafter, embodiments of the invention are illustrated.In the present embodiment, using bis-phenol ethanol fluorenes (BPEF) in Thing is marked, with HPLC (high performance liquid chromatographies：High performance liquid chromatography) measure acrylic acid The reactivity of the anisotropic-electroconductive adhesive of system, is evaluated for standard deviation.In addition, as comparative example, also to DSC (differential scanning calorimetry：Differential scanning calorimetry), FT-IR (Fourier transform infrared spectroscopies Method：Fourier Transform Infrared Spectroscopy) standard deviation of reactivity of measure evaluated.This Outside, using this technology, determine on the distribution of fixing body, the reactivity of wiring closet, be attached the evaluation of reliability.Further, BPEF addition is discussed.It should illustrate, the present invention is not limited to these embodiments.
Anisotropic conductive film and fixing body are prepared as described below.
[preparation of anisotropic conductive film]
Use the anisotropic-electroconductive adhesive of following cooperations.With being combined into：Phenoxy resin (trade name：YP50, Nippon Steel live Aurification (strain)) 40 mass parts, polyurethanes (trade name：N-5196, Japanese Port リ ウ レ タ Application are industrial (strain)) 40 mass Part, phosphate (trade name：PM-2, Japanese chemical drug (strain)) 2 mass parts, silane coupler (trade name：A-187, モ メ Application テ ィ Block パ フ ォ ー マ Application ス マ テ リ ア Le ズ (strain)) 2 mass parts, 2 functional acrylate's (trade names：DCP, Xin Zhong village chemistry Industrial (strain)) 3 mass parts, acrylate (trade name：SG-P3, (long rapids ケ system テ ッ Network ス (strain)) 5 mass parts, diacyl mistake Oxide (trade name：パ ー ロ イ Le L, Japanese grease (strain)) 5 mass parts and average grain diameter (D50) be 10 μm electric conductivity Particle (ponding chemistry (strain)) 3 mass parts, amount to 100 mass parts.The combination that the cooperation will be obtained with ormal weight addition BPEF Thing is coated on PET (polyethylene terephthalates：Polyethylene Terephthalate), done under 60 DEG C of hot blast Dry 4 minutes, thus obtain the membranaceous anisotropic-electroconductive adhesive that thickness is 16 μm.
[preparation of fixing body]
As evaluation base material, FPC (200 μm of P, L/S=1/1, PI/Cu=25/12 μm, plating Au) and glass substrate are used (ITO β-glass, 10 Ω/, 0.7mm t) prepares fixing body.Upper fitting anisotropic conductive film on the glass substrate, 45 DEG C, 1MPa, under conditions of 2 seconds heating pressurization after, peel off PET, carry out pre-pressing.FPC is configured in anisotropic conductive film, Defined temperature, 2MPa, pressurization is heated under conditions of 5 seconds, obtain fixing body.
<The standard deviation of 3.1 measured values>
After preparing fixing body using the obtained anisotropic conductive films of cooperation 0.5wt% BPEF as previously mentioned, use HPLC, DSC and FT-IR, carry out the measure of the reactivity of anisotropic conductive film.Peel FPC from fixing body, from 2.0mm × On 0.2mm distribution and 2.0mm × 0.2mm wiring closet is measured sampling with sample.
HPLC]
As HPLC analytical equipments, the UPLC produced using Waters companies (connection UV detectors).By test sample 0.005mg is dissolved in acetonitrile, is injected into splitter (10cm, 40 DEG C), obtains chromatogram.Analysis condition is as described below.
Acetonitrile normal temperature extraction-HPLC/DAD methods
Extraction：The μ L of acetonitrile 30
Gradient condition：A60%, B40% (keep 1 minute) → after 5 minutes A1%, B99% (being kept for 6 minutes), A=H2O, B=ACN
Flow：0.4mL/min
Injection rate：5μL
Parse wavelength：210-400nm.
The measure intensity ratio of BPEF and acrylic monomers is obtained by obtained chromatogram, by the BPEF and propylene of pre-production The measure intensity of acid monomers obtains reactivity than the relation line with reactivity.Repeat aforesaid operations totally 3 times.
As shown in table 1, the measurement result of reactivity is when pressing-in temp is 130 DEG C, first time 78.5%, second 79.4%, and third time 79.2%, standard deviation 0.4726.In addition, pressing-in temp be 140 DEG C when reactivity measurement result For, first time 86.3%, second 86.8%, and third time 85.2%, standard deviation 0.8185.When pressing-in temp is 150 DEG C The measurement result of reactivity is first time 91.1%, second 92.0%, and third time 91.0%, standard deviation 0.5508.
DSC]
Using differential thermometric analysis device (DSC6200, セ イ コ ー イ Application ス Star Le メ Application ト (strain)), make measure sample Product 5.0mg is warming up to 250 DEG C with 10 DEG C/min condition by 30 DEG C, obtains DSC curve figure.
Reference is used as using the sample of uncured (before pressing).Obtain uncured sample caloric value and pressing after it is unknown The difference of the caloric value of sample, using the caloric value of uncured sample as 1, calculate the reactivity of unknown sample.Unknown sample Measure carries out 3 times (N=3).It should illustrate, caloric value is obtained by the area of DSC curve figure.
As shown in table 1, the measurement result of reactivity is when pressing-in temp is 130 DEG C, first time 72.0%, second 83.2%, and third time 75.7%, standard deviation 5.7064.In addition, pressing-in temp be 140 DEG C when reactivity measurement result For, first time 82.6%, second 78.9%, and third time 88.1%, standard deviation 4.6293.When pressing-in temp is 150 DEG C The measurement result of reactivity is first time 94.2%, second 86.8%, and third time 90.2%, standard deviation 3.7041.
FT-IR]
Using Fourier transform infrared spectrophotometer (FT/IR-4100, Japanese light splitting company production), with penetrant method pair Test sample 0.02mg is measured.
By unknown sample after the measure intensity of the acrylic monomers (unsaturated group) of uncured (before pressing) sample and pressing The measure intensity ratio of the acrylic monomers (unsaturated group) of product, calculate the reactivity of unknown sample.The measure of unknown sample Carry out 3 times (N=3).
As shown in table 1, the measurement result of reactivity is when pressing-in temp is 130 DEG C, first time 68.7%, second 79.6%, and third time 74.2%, standard deviation 5.4501.In addition, pressing-in temp be 140 DEG C when reactivity measurement result For, first time 77.8%, second 82.0%, and third time 89.7%, standard deviation 6.0352.When pressing-in temp is 150 DEG C The measurement result of reactivity is first time 88.8%, second 87.3%, and third time 93.8%, standard deviation 3.4034.
[table 1]
。
As shown in table 1, in the measure using DSC, FT-IR, the standard deviation of measured value becomes big, and precision is low.In addition, sample Product amount needs much, it is difficult to carries out on distribution as described later, the measure of the reactivity of wiring closet.On the other hand, using In the measure of HPLC-UV detections, by the BPEF high to UV detection sensitivities, it is good that precision can be carried out with a small amount of sample Reactivity determines.
<On the distribution of 3.2 fixing bodies, the measure of the reactivity of wiring closet>
After preparing fixing body using the obtained anisotropic conductive films of cooperation 0.5wt% BPEF as previously mentioned, use HPLC carries out the measure of the reactivity of anisotropic conductive film.FPC is peeled from fixing body, on the distribution for carrying out 2.0mm × 0.2mm Test sample, 2.0mm × 0.2mm wiring closet test sample and distribution on the test sample of wiring closet Sampling.
HPLC]
As HPLC analytical equipments, the UPLC produced using Waters companies (connection UV detectors).By test sample 0.005mg is dissolved in acetonitrile, is injected into splitter (10cm, 40 DEG C), obtains chromatogram.Analysis condition is as described below.
Acetonitrile normal temperature extraction-HPLC/DAD methods
Extraction：The μ L of acetonitrile 30
Gradient condition：A60%, B40% (keep 1 minute) → after 5 minutes A1%, B99% (being kept for 6 minutes), A=H2O, B=ACN
Flow：0.4mL/min
Injection rate：5μL
Parse wavelength：210-400nm.
The measure intensity ratio of BPEF and acrylic monomers is obtained by obtained chromatogram, by the BPEF and propylene of pre-production The measure intensity of acid monomers obtains reactivity than the relation line with reactivity.Repeat aforesaid operations totally 3 times, obtain average value.
In addition, for the fixing body prepared using the anisotropic conductive film for coordinating 0.5wt% BPEF to obtain, ring is carried out (60 DEG C, 95%, 500hr) are tested in border, determine conducting resistance.Conducting resistance is to use digital multimeter (デ ジ タ Le マ Le チ メ ー タ 7561, the production of Yokogawa Motor company), it is measured with 4 terminal methods.The evaluation of reliability test is using conducting resistance as 3 More than Ω is " NG ", using less than 3 Ω as " OK ".
As shown in table 2, when pressing-in temp is 130 DEG C, the reactivity on distribution is 75%, and the reactivity of wiring closet is 82%, Reactivity on distribution with wiring closet is 80%, and reliability test is evaluated as NG.In addition, when pressing-in temp is 140 DEG C, distribution On reactivity be 83%, the reactivity of wiring closet is 89%, and on distribution and the reactivity of wiring closet is 86%, reliability test It is evaluated as OK.In addition, when pressing-in temp is 150 DEG C, the reactivity on distribution is 88%, and the reactivity of wiring closet is 93%, distribution Upper and wiring closet reactivity is 90%, and reliability test is evaluated as OK.
[table 2]
。
As shown in table 2, it is known that cause big, not accumulation of heat of radiating on distribution due to the influence of the high thermal conductivity of the metals such as copper, Therefore compared with wiring closet, the tendency that ACF is difficult to solidify be present.Like this, in this technique, because sample is a small amount of, because This can with good precision determination distribution, the local reaction rate of wiring closet etc..
<3.3 BPEF addition>
Below, the influence of the addition for coordinating the BPEF in anisotropic conductive film is discussed.Anisotropy Conducting film and fixing body use material as hereinbefore, change the addition of the BPEF in anisotropic conductive film, for peace Fill the outward appearance of anisotropic conductive film part, peel strength, embeddability (Ya Write body of body) and measure easiness progress Evaluation.
Evaluation for the outward appearance of the anisotropic conductive film part of fixing body, does not have the alveolate situation to be by visual observation " ◎ ", minute bubbles be present is "○", and air pocket be present is " △ ", and the situation that generation floats (floating I) is “×”.In addition, the evaluation of the peel strength (JIS K6854) for fixing body, the feelings that 90 ° of peel strengths are more than 10N/25mm Condition is " ◎ ", and 90 ° of peel strengths are that 8N/25mm less than 10N/25mm situation is "○", and 90 ° of peel strengths are 6N/ 25mm is " △ " less than 8N/25mm situation, and 90 ° of peel strengths are "×" for the situation less than 6N/25mm.In addition, Evaluation for embeddability, the conducting resistance of fixing body are that 1 below Ω is " ◎ ", and 1 Ω is "○" less than 2 Ω, 2 Ω is " △ " less than 5 Ω's, 5 more than Ω for "×".Conducting resistance is to use digital multimeter (デ ジ タ Le マ Le チ メ ー タ 7561, the production of Yokogawa Motor company), it is measured with 4 terminal methods.In addition, the evaluation of the easiness for measure, By visual observation it is readily seen that the situation at the peak of chromatogram is " ◎ ", the typically visible situation in peak is "○", it is difficult to sees the feelings at peak Condition is " △ ", it is impossible to which situation about seeing is "×".
As shown in table 3, when BPEF addition is 0.01wt%, outward appearance is evaluated as ◎, and peel strength is evaluated as ◎, Embeddability is evaluated as ◎, and the easiness of measure is △.In addition, when BPEF addition is 0.1wt%, outward appearance is evaluated as ◎, Peel strength is evaluated as ◎, and embeddability is evaluated as ◎, and the easy degree of measure is zero.In addition, BPEF addition is During 0.2wt%, outward appearance is evaluated as ◎, and peel strength is evaluated as ◎, and embeddability is evaluated as ◎, and the easy degree of measure is ◎.In addition, when BPEF addition is 0.5wt%, outward appearance is evaluated as ◎, and peel strength is evaluated as ◎, the evaluation of embeddability For ◎, the easy degree of measure is ◎.In addition, when BPEF addition is 1.0wt%, outward appearance is evaluated as ◎, peel strength ◎ is evaluated as, embeddability is evaluated as zero, and the easy degree of measure is ◎.In addition, when BPEF addition is 5.0wt%, outward appearance Be evaluated as zero, peel strength is evaluated as △, and embeddability is evaluated as △, and the easy degree of measure is ◎.In addition, BPEF When addition is 10.0wt%, outward appearance is evaluated as △, and being evaluated as of peel strength ×, being evaluated as of embeddability ×, the appearance of measure Easy degree is ◎.In addition, when BPEF addition is 30.0wt%, being evaluated as of outward appearance ×, being evaluated as of peel strength ×, it is embedding Being evaluated as of entering property ×, the easy degree of measure is ◎.
[table 3]
。
As shown in table 3, it is known that coordinate BPEF in anisotropic conductive film in use, its use level is preferably More than 0.01wt% and below 5.0wt%, more preferably more than 0.2wt% and below 1.0wt%.Understand, if BPEF cooperation quantitative change Greatly, then the easy degree determined improves, but produces bubble during pressing in ACF, and peel strength and embeddability are deteriorated.

Claims (8)

1. reactivity assay method, the compound with fluorene skeleton shown in following (1) formulas is used as internal standard compound, uses liquid chromatogram Sample solution containing acrylic adhesive is separated, detected by UV-detector unreacted free-radical polymerised Compound,
[changing 1]
In formula, R1It is selected from hydrogen atom, the alkyl that carbon number is 1 ~ 3, the group for the alkoxy that carbon number is 1 ~ 3, R2It is choosing From hydroxyl, the hydroxy alkyl that carbon number is 1 ~ 3, the hydroxy alkoxy base that carbon number is 1 ~ 3 group.
2. reactivity assay method according to claim 1, wherein, the compound with fluorene skeleton is selected from double benzene One or more of ethoxy-ethanol fluorenes (BPEF), bisphenol fluorene (BPFL), double cresols fluorenes (BCF).
3. reactivity assay method according to claim 1 or 2, wherein, the acrylic adhesive contains the tool There is the compound of fluorene skeleton.
4. reactivity assay method according to claim 3, wherein, the use level of the compound with fluorene skeleton is More than 0.01wt% and below 5.0wt%.
5. acrylic adhesive, it contains the compound with fluorene skeleton shown in following (1) formulas, free-radical polymerised chemical combination Thing and reaction initiator,
[changing 2]
In formula, R1It is selected from hydrogen atom, the alkyl that carbon number is 1 ~ 3, the group for the alkoxy that carbon number is 1 ~ 3, R2It is choosing From hydroxyl, the hydroxy alkyl that carbon number is 1 ~ 3, the hydroxy alkoxy base that carbon number is 1 ~ 3 group.
6. acrylic adhesive according to claim 5, wherein, the compound with fluorene skeleton is selected from double benzene One or more of ethoxy-ethanol fluorenes (BPEF), bisphenol fluorene (BPFL), double cresols fluorenes (BCF).
7. the acrylic adhesive according to claim 5 or 6, wherein, the cooperation of the compound with fluorene skeleton Measure as more than 0.01wt% and below 5.0wt%.
8. anisotropic-electroconductive adhesive, it divides in the acrylic adhesive according to any one of claim 5 to 7 Scattered electroconductive particle forms.
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