CN105940299A - Reaction rate measurement method for acrylic adhesive, and acrylic adhesive - Google Patents

Reaction rate measurement method for acrylic adhesive, and acrylic adhesive Download PDF

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Publication number
CN105940299A
CN105940299A CN201580007074.0A CN201580007074A CN105940299A CN 105940299 A CN105940299 A CN 105940299A CN 201580007074 A CN201580007074 A CN 201580007074A CN 105940299 A CN105940299 A CN 105940299A
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acrylic adhesive
compound
response rate
carbon number
fluorene skeleton
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CN105940299B (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
    • 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
    • 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
    • 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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  • Physics & Mathematics (AREA)
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  • General Physics & Mathematics (AREA)
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  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided are a reaction rate measurement method by which the reaction rate of an acrylic adhesive can be measured accurately, even with a small quantity of a sample; and an acrylic adhesive. Using a compound having a fluorene skeleton as the internal standard substance, a sample solution containing an acrylic adhesive is separated by liquid chromatography, and an unreacted radical-polymerizable compound is detected by a UV detector. Because the compound having a fluorene skeleton exhibits high sensitivity to the UV detector, the reaction rate can be measured accurately, even with a small quantity of the sample. Moreover, as the compound having a fluorene skeleton does not participate in the acrylic adhesive curing reaction, it is possible to blend the compound into the acrylic adhesive in advance.

Description

The response rate assay method of acrylic adhesive and acrylic adhesive
Technical field
The present invention relates to the response rate assay method and third of the acrylic adhesive containing free-radical polymerised compound Olefin(e) acid system binding agent.The application in Japan to submit the Japanese Patent application number Japanese Patent Application applied on February 3rd, 2014 Based on 2014-18388, CLAIM OF PRIORITY, this application is quoted in addition the application in the way of reference.
Background technology
In the past, as circuit material, anisotropic conductive film (ACF:Anisotropic Conductive is widely used Film) etc..Bad reason is there is, thus it is speculated that have the inhomogeneities of curing degree in circuit electrode as ACF.It is believed that During anisotropic conductive connects, owing to making multiple electrode connect together and equably, therefore on the electrode that heat conductivity is relatively large The interelectrode position relatively low with heat conductivity, response rate produces difference.
But, in conventional analysis based on DSC, FT-IR etc., required sample size is many, it is difficult to good precision The response rate of the tiny area measured on electrode, between electrode etc..
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-251789 publication.
Summary of the invention
Invent problem to be solved
The present invention is the motion in view of such conventional situation, it is provided that even if the sample of use trace can also be with good Precision carries out the response rate assay method that the response rate of acrylic adhesive measures, and acrylic adhesive.
Solve the means of problem
The present inventor carries out the result of deep investigation, finds by the compound with fluorene skeleton is used as internal standard substance, even if making Response rate mensuration can also be carried out with good precision with the sample of trace.
In other words, the response rate assay method that the present invention relates to is characterised by, will have fluorene skeleton shown in following (1) formula Compound be used as internal standard substance, by liquid chromatograph, the sample solution containing acrylic adhesive is separated, passes through ultraviolet Detector detects unreacted free-radical polymerised compound.
[changing 1]
In formula, R1It is the group selected from the alkoxyl that the alkyl that hydrogen atom, carbon number are 1 ~ 3, carbon number are 1 ~ 3, R2It is Group selected from the hydroxy alkoxy base that the hydroxy alkyl that hydroxyl, carbon number are 1 ~ 3, carbon number are 1 ~ 3.
Additionally, the acrylic adhesive that the present invention relates to is characterised by, it contains and has fluorenes shown in described (1) formula The compound of skeleton, free-radical polymerised compound and reaction initiator.
Additionally, the anisotropic-electroconductive adhesive that the present invention relates to is characterised by, it is to bond at described acrylic acid series In agent, dispersed electro-conductive particle forms.
Invention effect
According to the present invention, UV-detector is demonstrated high sensitivity, even if therefore making owing to having the compound of fluorene skeleton Can also be with good precision determination response rate with the sample of trace.Additionally, there is the compound of fluorene skeleton owing to being not involved in third The curing reaction of olefin(e) acid system binding agent, therefore becomes to coordinate in advance in acrylic adhesive.
Brief Description Of Drawings
Fig. 1: Fig. 1 is the chromatogram of an example of the analysis result of the acrylic adhesive before representing solidification
Fig. 2: Fig. 2 is the chromatogram of an example of the analysis result of the acrylic adhesive after representing solidification.
Detailed description of the invention
Hereinafter, about embodiments of the present invention, it is described in detail in the following sequence referring to the drawings:
1. the response rate assay method of acrylic adhesive
2. acrylic adhesive
3. embodiment.
<the 1. response rate assay method of acrylic adhesive>
The response rate assay method of the acrylic adhesive involved by present embodiment is, by having shown in following (1) formula The compound of fluorene skeleton is used as internal standard substance, separates the sample solution containing acrylic adhesive by liquid chromatograph, logical Cross UV-detector and detect unreacted free-radical polymerised compound.
[changing 2]
In formula, R1It is selected from the alkyl (-C that hydrogen atom (-H), carbon number are 1 ~ 3nH2n+1, n=1 ~ 3), carbon number be 1 ~ 3 Alkoxyl (-OCnH2n+1, n=1 ~ 3) group, R2Be selected from hydroxy alkyl that hydroxyl (-OH), carbon number are 1 ~ 3 (- CnH2nOH, n=1 ~ 3), carbon number be 1 ~ 3 hydroxy alkoxy base (-OCnH2nOH, n=1 ~ 3) group.
As the object lesson of the compound with fluorene skeleton shown in (1) formula, double phenyl phenol fluorenes can be enumerated (BPEF:R1=H、R2=OC2H4OH), bisphenol fluorene (BPF:R1=H、R2=OH), double cresol fluorenes (BCF:R1=CH3、R2=OH) etc..(1) formula The shown compound with fluorene skeleton is high due to ultraviolet absorption ability, therefore demonstrates UV-detector high sensitive Degree, even if the sample of use trace can also be with good precision determination response rate.
Should illustrate, as can with UV-detector detection conventional internal standard substance, have dibenzylatiooluene (BHT), Benzotriazole (BTZ) etc., but its detection sensitivity is insufficient, it has to add in a large number.Additionally, due to BHT benzene double with acrylic acid Ethoxy-ethanol fluorenes ester (BPEFA), BTZ overlap with the blob detection position of acrylic acid 4-hydroxybutyl (4-HBA), therefore versatility Difference.
Liquid chromatography is high performance liquid chromatography (HPLC:High Performance liquid Chromatography), make sample solution by being filled with the detached dowel of separating medium, by relative to the distribution of separating medium, absorption The difference of complexity etc., be separated into Multiple components.
As separating medium (filler), can enumerate the particle diameter of HPLC be the silica gel about 2 ~ 30 μm, 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, if to sample solution irradiating ultraviolet light and measure absorbance based on sample solution i.e. Can, there is no particular limitation, it is possible to use UV absorbance detector general in analysis based on HPLC.
Then, the details measured response rate illustrates.This technology can be in advance in acrylic adhesive The compound with fluorene skeleton is coordinated, it is also possible to the sample solution of acrylic adhesive is added tool with ormal weight with ormal weight There is the compound of fluorene skeleton.As the solvent dissolving acrylic adhesive, it is possible to use acetonitrile, acetone etc..
Fig. 1 and Fig. 2 be respectively show solidification before and solidification after the example of analysis result of acrylic adhesive Chromatogram.The peak intensity of the chromatogram obtained by UV-detector is generally represented by peak area or peak heights, but Hereinafter, illustrate for response rate computational methods based on peak heights.
First, the chromatogram of the acrylic adhesive before solidifying and the acrylic adhesive after being fully cured obtain Internal standard substance and the strength ratio of unreacted monomer, such as, to solidify previous crops for response rate 0%, using after being fully cured as response rate 100%, make strength ratio and the relation line of response rate.It is then possible to obtained internal standard substance and unreacted by the chromatogram of unknown sample The strength ratio of monomer, is obtained response rate by the relation line made.
Like this by the compound with fluorene skeleton shown in (1) formula is used as internal standard substance, even if using the sample of trace Product can also be with good precision determination response rate.
2. acrylic adhesive
Acrylic adhesive of the present embodiment contains and has the compound of fluorene skeleton, freedom shown in following (1) formula Base polymerizable compound and reaction initiator.
[changing 3]
In formula, R1It is selected from the alkyl (-C that hydrogen atom (-H), carbon number are 1 ~ 3nH2n+1, n=1 ~ 3), carbon number be 1 ~ 3 Alkoxyl (-OCnH2n+1, n=1 ~ 3) group, R2Be selected from hydroxy alkyl that hydroxyl (-OH), carbon number are 1 ~ 3 (- CnH2nOH, n=1 ~ 3), carbon number be 1 ~ 3 hydroxy alkoxy base (-OCnH2nOH, n=1 ~ 3) group.
As the object lesson of the compound with fluorene skeleton shown in (1) formula, double phenyl phenol fluorenes can be enumerated (BPEF:R1=H、R2=OC2H4OH), bisphenol fluorene (BPF:R1=H、R2=OH), double cresol fluorenes (BCF:R1=CH3、R2=OH) etc..
Hereinafter, enter for the anisotropic-electroconductive adhesive of dispersed electro-conductive particle in acrylic adhesive Row explanation.(1) even if the compound with fluorene skeleton shown in formula coordinates in anisotropic-electroconductive adhesive, when hot pressing Do not decompose, additionally, due to be not involved in curing reaction, therefore when measuring response rate, UV-detector can be demonstrated Gao Ling Sensitivity.Therefore, if using this anisotropic-electroconductive adhesive, then can be with on good precision determination electrode, between electrode etc. The response rate of tiny area.
The use level of the 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, then measuring peak and diminish, it is impossible to playing the function as internal standard substance, if joined Resultant is too much, then the characteristic as anisotropic conductive film is deteriorated.
As free-radical polymerised compound, it is possible to use simple function (methyl) acrylate monomer, multifunctional (methyl) Acrylate monomer or introduce epoxy radicals, carbamate groups, amino, oxyethylene group, oxypropylene group etc. in them The modified simple function obtained or multifunctional (methyl) acrylate monomer.Additionally, free-radical polymerised compound can be with list In body, oligomer, any one state uses, it is also possible to use monomer and oligomer in the lump.
As (methyl) acrylate monomer, can enumerate and at least there is in a molecule more than one (methyl) third (methyl) acrylate of enoyl-, its modifier etc..Additionally, as their modifier, acrylic acid four can be enumerated Hydrogen bran ester, isobornyl acrylate, methacrylic acid acrylic acid methyl ester., methacrylic acid ethyl acrylate, tristane diformazan Alcohol diacrylate, Tricyclodecane Dimethanol dimethylacrylate, ethoxylated bisphenol a diacrylate, propoxylation are double Phenol A diacrylate, pentaerythritol triacrylate, ethoxylation cyamelide triacrylate etc..It can be with one Use, it is also possible to mix two or more use.
As reaction initiator, it is possible to use organic peroxide, optical free radical polymerization initiator etc..As organic peroxy Compound, it is possible to use diacyl peroxide, dialkyl peroxide, peroxy dicarbonate, peroxyester, peroxidating contracting More than the one or two kinds of in ketone, hydroperoxides, silicyl peroxide etc..Additionally, draw as optical free radical polymerization Send out agent, it is possible to use the benzyls such as the benzoin ethers such as Benzoinum ethylether, isopropyl benzoin ether, benzyl, hydroxycyclohexylphenylketone One or two kinds of in the ketones such as base ketal, benzophenone, 1-Phenylethanone. or its derivant, thioxanthene ketone, bisglyoxaline class etc. Above.
For electroconductive particle, it is possible to use the electroconductive particle used in conventional anisotropic conductive film, such as The metallics such as gold particle, silver particles, nickel particles；By the surface of the resin particle such as benzoguanamine resin, styrene resin gold, The metallic cover resin particle etc. that the metallic cover such as nickel, zinc obtains.As the mean diameter of such electroconductive particle, usually 1 ~ 10 μm, more preferably 2 ~ 6 μm.
Additionally, anisotropic-electroconductive adhesive can also contain film-forming resin, silane coupler, phosphate ester, inorganic filler, Stress demulcent etc..As film-forming resin, phenoxy resin, polyvinyl acetal resin, polyvinyl butyral resin can be enumerated 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-aminoethyl- Gamma-amino propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane etc..
If using such anisotropic-electroconductive adhesive, then can be with on good precision determination electrode, between electrode Deng the response rate of tiny area, therefore become to obtain stable engaging condition with the short time.
Embodiment
3. embodiment
Hereinafter, embodiments of the invention are illustrated.In the present embodiment, use bis-phenol ethanol fluorenes (BPEF) as internal standard Thing, measures acrylic acid series with HPLC (high performance liquid chromatography: High performance liquid chromatography) The response rate of anisotropic-electroconductive adhesive, be evaluated for standard deviation.Additionally, as comparative example, also to DSC (differential scanning calorimetry: Differential scanning calorimetry), FT-IR (Fourier transform infrared spectroscopy Method: Fourier Transform Infrared Spectroscopy) standard deviation of response rate that measures is evaluated.This Outward, use this technology, measure on the distribution of fixing body, the response rate of wiring closet, be attached the evaluation of reliability.Further, The addition of BPEF is discussed.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 cooperation.Cooperation is: (trade name: YP50, aurification is lived to phenoxy resin by Nippon Steel Learn (strain)) 40 mass parts, polyurethanes (trade name: N-5196, Japan Port リ ウ レ タ Application industry (strain)) 40 mass parts, Phosphate ester (trade name: PM-2, Japan's chemical medicine (strain)) 2 mass parts, silane coupler (trade name: A-187, モ メ Application テ ィ Block パ Off ォ マ Application ス マ テ リ ア Le ズ (strain)) 2 mass parts, 2 functional acrylates (trade name: DCP, Xin Zhong village chemical industry (strain)) 3 mass parts, acrylate (trade name: SG-P3, (long rapids ケ system テ ッ Network ス (strain)) 5 mass parts, diacyl peroxidating Thing (trade name: パ ロ イ Le L, Japan's oils and fats (strain)) 5 mass parts and the electroconductive particle that mean diameter (D50) is 10 μm (hydrops chemistry (strain)) 3 mass parts, amount to 100 mass parts.This cooperation will be added, with ormal weight, the compositions painting that BPEF obtains It is distributed in PET (polyethylene terephthalate: Polyethylene Terephthalate), under the hot blast of 60 DEG C, is dried 4 Minute, thus obtain the membranaceous anisotropic-electroconductive adhesive that thickness is 16 μm.
[preparation of fixing body]
As evaluate base material, use FPC (200 μm P, L/S=1/1, PI/Cu=25/12 μm, plating Au) and glass substrate (ITO β- Glass, 10 Ω/, 0.7mm t) prepare fixing body.Fit on the glass substrate anisotropic conductive film, 45 DEG C, 1MPa, Under conditions of 2 seconds after heating pressurization, peel off PET, carry out pre-pressing.Anisotropic conductive film configures FPC, in the temperature of regulation Degree, 2MPa, heating pressurization under conditions of 5 seconds, obtain fixing body.
<standard deviations of 3.1 measured values>
After the anisotropic conductive film using the BPEF coordinating 0.5wt% to obtain as previously mentioned prepares fixing body, use HPLC, DSC and FT-IR, carries out the mensuration of the response rate of anisotropic conductive film.FPC is peeled, from 2.0mm × 0.2mm's from fixing body On distribution, the wiring closet with 2.0mm × 0.2mm is measured with the sampling of sample.
HPLC]
As HPLC analytical equipment, use the UPLC (connecting UV detector) that Waters company produces.By test sample 0.005mg is dissolved in acetonitrile, is injected into detached dowel (10cm, 40 DEG C), obtains chromatogram.Analysis condition is as described below.
Acetonitrile room temperature extraction-HPLC/DAD method
Extraction: acetonitrile 30 μ L
Gradient condition: A60%, B40% (keeping 1 minute) → after 5 minutes A1%, B99% (keeping 6 minutes), A=H2O, B=ACN
Flow: 0.4mL/min
Injection rate: 5 μ L
Resolve wavelength: 210-400nm.
The mensuration strength ratio of BPEF and acrylic monomers is obtained, by the BPEF made in advance and propylene by the chromatogram obtained The mensuration strength ratio of acid monomers and the relation line of response rate obtain response rate.Repeat aforesaid operations totally 3 times.
As shown in table 1, when pressing-in temp is 130 DEG C, the measurement result of response rate is, for the first time 78.5%, for the second time 79.4%, and third time 79.2%, standard deviation is 0.4726.Additionally, the measurement result of response rate when pressing-in temp is 140 DEG C For, for the first time 86.3%, for the second time 86.8%, and third time 85.2%, standard deviation is 0.8185.When pressing-in temp is 150 DEG C The measurement result of response rate is, for the first time 91.1%, for the second time 92.0%, and third time 91.0%, standard deviation is 0.5508.
DSC]
Use differential thermometric analysis device (DSC6200, セ イ U イ Application ス Star Le メ Application ト (strain)), make test sample 5.0mg is warming up to 250 DEG C with the condition of 10 DEG C/min by 30 DEG C, obtains DSC curve figure.
Using the sample of uncured (before pressing) as reference.Obtain the unknown after the caloric value of uncured sample and pressing The difference of the caloric value of sample, using the caloric value of uncured sample as 1, calculates the response rate of unknown sample.Unknown sample Mensuration carries out 3 times (N=3).Should illustrate, caloric value is obtained by the area of DSC curve figure.
As shown in table 1, when pressing-in temp is 130 DEG C, the measurement result of response rate is, for the first time 72.0%, for the second time 83.2%, and third time 75.7%, standard deviation is 5.7064.Additionally, the measurement result of response rate when pressing-in temp is 140 DEG C For, for the first time 82.6%, for the second time 78.9%, and third time 88.1%, standard deviation is 4.6293.When pressing-in temp is 150 DEG C The measurement result of response rate is, for the first time 94.2%, for the second time 86.8%, and third time 90.2%, standard deviation is 3.7041.
FT-IR]
Use Fourier transform infrared spectrophotometer (FT/IR-4100, light splitting company of Japan produces), by penetrant method to mensuration It is measured with sample 0.02mg.
By sample unknown after the mensuration intensity of the acrylic monomers (unsaturated group) of uncured (before pressing) sample and pressing The mensuration intensity ratio of the acrylic monomers (unsaturated group) of product, calculates the response rate of unknown sample.The mensuration of unknown sample Carry out 3 times (N=3).
As shown in table 1, when pressing-in temp is 130 DEG C, the measurement result of response rate is, for the first time 68.7%, for the second time 79.6%, and third time 74.2%, standard deviation is 5.4501.Additionally, the measurement result of response rate when pressing-in temp is 140 DEG C For, for the first time 77.8%, for the second time 82.0%, and third time 89.7%, standard deviation is 6.0352.When pressing-in temp is 150 DEG C The measurement result of response rate is, for the first time 88.8%, for the second time 87.3%, and third time 93.8%, standard deviation is 3.4034.
[table 1]
。
As shown in table 1, in the mensuration using DSC, FT-IR, the standard deviation of measured value becomes big, and precision is low.Additionally, sample Product amount needs much, it is difficult to carry out on distribution as described later, the mensuration of the response rate of wiring closet.On the other hand, using In the mensuration of HPLC-UV detection, by the BPEF high to UV detection sensitivity, precision can be carried out with a small amount of sample good Response rate measures.
<on the distribution of 3.2 fixing bodies, the mensuration of the response rate of wiring closet>
After the anisotropic conductive film using the BPEF coordinating 0.5wt% to obtain as previously mentioned prepares fixing body, HPLC is used to enter The mensuration of the response rate of row anisotropic conductive film.Peel FPC from fixing body, carry out the mensuration on the distribution of 2.0mm × 0.2mm With sampling with the test sample of wiring closet on sample, the test sample of the wiring closet of 2.0mm × 0.2mm and distribution.
HPLC]
As HPLC analytical equipment, use the UPLC (connecting UV detector) that Waters company produces.By test sample 0.005mg is dissolved in acetonitrile, is injected into detached dowel (10cm, 40 DEG C), obtains chromatogram.Analysis condition is as described below.
Acetonitrile room temperature extraction-HPLC/DAD method
Extraction: acetonitrile 30 μ L
Gradient condition: A60%, B40% (keeping 1 minute) → after 5 minutes A1%, B99% (keeping 6 minutes), A=H2O, B=ACN
Flow: 0.4mL/min
Injection rate: 5 μ L
Resolve wavelength: 210-400nm.
The mensuration strength ratio of BPEF and acrylic monomers is obtained, by the BPEF made in advance and propylene by the chromatogram obtained The mensuration strength ratio of acid monomers and the relation line of response rate obtain response rate.Repeat aforesaid operations totally 3 times, obtain meansigma methods.
Additionally, the fixing body prepared for the anisotropic conductive film using the BPEF coordinating 0.5wt% to obtain, carry out ring Border test (60 DEG C, 95%, 500hr), measures conducting resistance.Conducting resistance is to use digital multimeter (デ ジ タ Le マ Le チ メ タ 7561, Yokogawa Motor company produces), it is measured with 4 terminal methods.The evaluation of reliability test with conducting resistance for 3 More than Ω is " NG ", with less than 3 Ω for " OK ".
As shown in table 2, when pressing-in temp is 130 DEG C, the response rate on distribution is 75%, and the response rate of wiring closet is 82%, On distribution and the response rate of wiring closet is 80%, reliability test be evaluated as NG.During additionally, pressing-in temp is 140 DEG C, distribution On response rate be 83%, the response rate of wiring closet is 89%, on distribution and the response rate of wiring closet is 86%, reliability test It is evaluated as OK.During additionally, pressing-in temp is 150 DEG C, the response rate on distribution is 88%, and the response rate of wiring closet is 93%, distribution Upper and wiring closet response rate is 90%, reliability test be evaluated as OK.
[table 2]
。
As shown in table 2, it is known that cause dispelling the heat greatly due to the impact of high thermal conductivity of the metals such as copper on distribution, not accumulation of heat, Therefore, compared with wiring closet, there is the tendency that ACF is difficult to solidify.Like this, in this technique, due to sample on a small quantity, because of This can with on good precision determination distribution, the local response rate of wiring closet etc..
<additions of 3.3 BPEF>
Below, the impact for the addition of the BPEF coordinated in anisotropic conductive film is discussed.Anisotropic conductive Film and fixing body use material as hereinbefore, and the addition of the BPEF in change anisotropic conductive film, for fixing body The easiness of the outward appearance of anisotropic conductive film part, peel strength, embeddability (give as security body) and mensuration be evaluated.
For the evaluation of outward appearance of the anisotropic conductive film part of fixing body, by visually not having alveolate situation to be " ◎ ", the situation that there are minute bubbles is "○", and the situation that there is air pocket is " △ ", and generation floats the situation of (floating I) and is “×”.Additionally, the evaluation of the peel strength (JIS K6854) for fixing body, 90 ° of peel strengths are the feelings of more than 10N/25mm Condition is " ◎ ", and 90 ° of peel strengths are 8N/25mm less than the situation of 10N/25mm is "○", and 90 ° of peel strengths are 6N/ 25mm is " △ " less than the situation of 8N/25mm, 90 ° of peel strengths be the situation less than 6N/25mm be "×".Additionally, For the evaluation of embeddability, the conducting resistance of fixing body be 1 below Ω for " ◎ ", 1 Ω less than 2 Ω for "○", 2 Ω is " △ " less than 5 Ω, 5 more than Ω for "×".Conducting resistance is to use digital multimeter (デ ジ タ Le マ Le チ メ タ 7561, Yokogawa Motor company produces), it is measured with 4 terminal methods.Additionally, the evaluation of the easiness for measuring, Being " ◎ " by visually it is readily seen that the situation at the peak of chromatogram, the general visible situation in peak is "○", it is difficult to see the feelings at peak Condition is " △ ", it is impossible to situation about seeing is "×".
As shown in table 3, when the addition of BPEF is 0.01wt%, outward appearance be evaluated as ◎, peel strength be evaluated as ◎, Embeddability be evaluated as ◎, the easiness of mensuration is △.During additionally, the addition of BPEF is 0.1wt%, outward appearance be evaluated as ◎, Peel strength be evaluated as ◎, embeddability be evaluated as ◎, the easy degree of mensuration is zero.Additionally, the addition of BPEF is During 0.2wt%, outward appearance be evaluated as ◎, peel strength be evaluated as ◎, embeddability be evaluated as ◎, the easy degree of mensuration is ◎.During additionally, the addition of BPEF is 0.5wt%, outward appearance be evaluated as ◎, peel strength be evaluated as ◎, the evaluation of embeddability For ◎, the easy degree of mensuration is ◎.During additionally, the addition of BPEF is 1.0wt%, outward appearance be evaluated as ◎, peel strength Be evaluated as ◎, embeddability be evaluated as zero, the easy degree of mensuration is ◎.During additionally, the addition of BPEF is 5.0wt%, outward appearance Be evaluated as zero, peel strength be evaluated as △, embeddability be evaluated as △, the easy degree of mensuration is ◎.Additionally, BPEF When addition is 10.0wt%, outward appearance be evaluated as △, being evaluated as of peel strength ×, being evaluated as of embeddability ×, the appearance of mensuration Easily degree is ◎.During additionally, the addition of BPEF is 30.0wt%, being evaluated as of outward appearance ×, being evaluated as of peel strength ×, embedding Being evaluated as of entering property ×, the easy degree of mensuration is ◎.
[table 3]
。
As shown in table 3, it is known that by BPEF coordinate in anisotropic conductive film use time, its use level be preferably 0.01wt% with Go up and below 5.0wt%, more preferably more than 0.2wt% and below 1.0wt%.Understand, if the cooperation quantitative change of BPEF is big, then measure Easy degree improve, but ACF produces during pressing bubble, peel strength and embeddability are deteriorated.

Claims (8)

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