CN107267092A - Thermo-sensitive adhesive - Google Patents

Thermo-sensitive adhesive Download PDF

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Publication number
CN107267092A
CN107267092A CN201710195533.3A CN201710195533A CN107267092A CN 107267092 A CN107267092 A CN 107267092A CN 201710195533 A CN201710195533 A CN 201710195533A CN 107267092 A CN107267092 A CN 107267092A
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CN
China
Prior art keywords
thermo
sensitive adhesive
side chain
sensitive
crystalline polymer
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Pending
Application number
CN201710195533.3A
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Chinese (zh)
Inventor
加藤卓
南地实
河原伸郎
河原伸一郎
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Nitta Corp
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Nitta Corp
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Publication of CN107267092A publication Critical patent/CN107267092A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • 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
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides heat resistance and is heated to the excellent Thermo-sensitive adhesive of the fissility after high temperature.

Description

Thermo-sensitive adhesive
Technical field
The present invention relates to Thermo-sensitive adhesive.
Background technology
Thermo-sensitive adhesive is to contain side chain crystalline polymer as principal component, if be cooled to less than side chain crystallinity The temperature of the fusing point of polymer, then side chain crystalline polymer is crystallized, so that the adhesive that adhesion declines.Thermo-sensitive is glued Mixture is processed as sheet material, band etc., the substrate that will be made up of in the manufacturing process of flat-panel monitor (FPD) etc. glass, plastics etc. Used when interim fixed (referring for example to patent document 1).Thermo-sensitive adhesive used in such purposes sometimes due to Process and be heated to high temperature, it is desirable to excellent heat resistance.Additionally, it is desirable that it is also excellent to be heated to the fissility after high temperature.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-102212 publications
The content of the invention
The invention problem to be solved
The problem of the present invention is offer heat resistance and is heated to the excellent Thermo-sensitive adhesive of the fissility after high temperature.
Means for solving the problems
The Thermo-sensitive adhesive of the present invention is containing side chain crystalline polymer, less than above-mentioned side chain crystalline polymer Fusing point at a temperature of adhesion reduce Thermo-sensitive adhesive, also containing the tackifier comprising styrene resin.
The effect of invention
According to the present invention, with heat resistance and the excellent effect of the fissility after high temperature is heated to.
Brief description of the drawings
Fig. 1 is the coordinate diagram for the result for representing the thermogravimetric analysis in embodiment.
Embodiment
＜ Thermo-sensitive adhesives ＞
Explained below for the Thermo-sensitive adhesive that one embodiment of the present invention is related to.
(side chain crystalline polymer)
The Thermo-sensitive adhesive of present embodiment contains side chain crystalline polymer.Side chain crystalline polymer is with molten The polymer of point.Fusing point is to be turned into by the specific part of certain equilibrium process, the polymer for being initially integrated into Methodistic arrangement The temperature of disorder, it is meant that determined using differential heat scan calorimeter (DSC), under 10 DEG C/min of condition determination Obtained value.
Side chain crystalline polymer is crystallized at a temperature of less than above-mentioned fusing point, and more than the fusing point at a temperature of Phase transformation and show mobility.That is, side chain crystalline polymer have accordingly reversibly cause with temperature change crystalline state and The Thermo-sensitive of flow regime.
The Thermo-sensitive adhesive of present embodiment adhesion at a temperature of the fusing point less than side chain crystalline polymer drops It is low.In other words, when the Thermo-sensitive adhesive of present embodiment is crystallized with side chain crystalline polymer at a temperature of less than fusing point The ratio of adhesion reduction contains side chain crystalline polymer.That is, the Thermo-sensitive adhesive of present embodiment contains crystallizable side chain Property polymer is used as principal component.Therefore, when adherend is peeled off from Thermo-sensitive adhesive, if Thermo-sensitive adhesive cooled down The temperature of the fusing point for side chain crystalline polymer of arriving, then due to side chain crystalline polymer crystallization, adhesion is reduced. In addition, if Thermo-sensitive adhesive is heated into the temperature more than fusing point of side chain crystalline polymer, then due to crystallizable side chain Property polymer show that mobility and adhesion are replied, therefore, it is possible to Reusability.
(methyl) acrylate that side chain crystalline polymer includes the straight-chain alkyl with carbon number more than 16 is used as list Body composition.For (methyl) acrylate of the straight-chain alkyl with carbon number more than 16, the straight-chain of its carbon number more than 16 Alkyl is used as the side chain crystallinity position function in side chain crystalline polymer.That is, side chain crystalline polymer is in side Chain has the polymer of the comb shape of the straight-chain alkyl of carbon number more than 16, and its side chain is integrated into orderly by molecular separating force etc. Arrangement and crystallize.It should illustrate, above-mentioned (methyl) acrylate means acrylate or methacrylate.
As (methyl) acrylate of the straight-chain alkyl with carbon number more than 16, for example, it can include (methyl) propylene Sour cetyl ester, (methyl) octadecyl acrylate, (methyl) acrylic acid eicosane base ester, (methyl) acrylic acid 22 Arrcostab etc. has (methyl) acrylate of the wire alkyl of carbon number 16~22.(methyl) acrylate illustrated can be used only 1 kind, also two or more may be used.Preferably with 10~99 weight %, more preferably with 20~99 weight % ratio in monomer component Example contains (methyl) acrylate of the straight-chain alkyl with carbon number more than 16.
Can be included in monomer component can be with (methyl) acrylic ester copolymer of the straight-chain alkyl with carbon number more than 16 Other monomers.As other monomers, for example, it can include (methyl) acrylate, the polar monomer of the alkyl with carbon number 1~6 Deng.
As (methyl) acrylate of the alkyl with carbon number 1~6, can for example include (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate etc..(methyl) acrylate illustrated can be only Using a kind, also two or more may be used.Preferably with below 70 weight %, more preferably with 1~70 weight % in monomer component Ratio contain (methyl) acrylate of the alkyl with carbon number 1~6.
As polar monomer, for example, it can include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, rich horse The ethylenically unsaturated monomer with carboxyl such as acid；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, Own ester of (methyl) acrylic acid 2- hydroxyls etc. has ethylenically unsaturated monomer of hydroxyl etc..The polar monomer of illustration can only use a kind, Also two or more may be used.Contain in monomer component preferably with below 10 weight %, more preferably with 1~10 weight % ratio Polarized monomer.
Reactive F compound is can further include in monomer component.Thus, if Thermo-sensitive adhesive be cooled to Less than the temperature of the fusing point of side chain crystalline polymer, then except side chain crystalline polymer crystallizes caused adhesion Beyond reduction, also release property caused by additional fluorinated compound, therefore, it is possible to which adhesion is greatly reduced.
Reactive F compound means the fluorine compounds of the functional group with display reactivity.It is used as display reactivity Functional group, for example, can include epoxy radicals (comprising glycidyl and epoxy cycloalkyl), sulfydryl, methanol-based (methylol), carboxylic Base, silanol group, phenolic group, amino, hydroxyl, group with ethylenical unsaturated double bonds etc..As with ethylenical unsaturated double bonds Group, can for example include vinyl, pi-allyl, (methyl) acrylic, (methyl) acryloyl group, (methyl) acryloyl-oxy Base etc..
As the concrete example of reactive F compound, compound for being represented by following logical formula (I)s etc. can be included.
R1-CF3 (I)
[in formula, R1The group of expression is：CH2=CHCOOR2- or CH2=C (CH3)COOR2- (in formula, R2Represent alkylene Base.).]
It is used as R2The alkylidene of expression, for example, can include methylene, ethylidene, trimethylene, propylidene, four methylenes The straight chain of the carbon numbers such as base, pentamethylene, hexa-methylene 1~6 or the alkylidene of branch etc..
As the concrete example by leading to the compound that formula (I) is represented, the acrylic acid 2 represented by following formula (Ia) can be included, 2,2- trifluoro ethyl esters, the methacrylic acid 2,2,2- trifluoro ethyl esters represented by formula (Ib) etc..
Above-mentioned reactive F compound can use commercially available product.As commercially available reactive F compound, for example, it can arrange Enumerate be Osaka Organic Chemical Industry Co., Ltd. manufacture " Viscoat 3F ", " Viscoat 3FM ", " Viscoat 4F ", " Viscoat 8F ", " Viscoat 8FM ", " LIGHT ESTER M-3F " etc. of Kyoeisha Chemical Co., Ltd.'s manufacture.
Reactive F compound can only use a kind, and also two or more may be used.In monomer component, preferably with 1~20 Weight %, reactive F compound is more preferably contained with 1~10 weight % ratio.
As the preferred composition of side chain crystalline polymer, for (methyl) of the straight-chain alkyl with carbon number more than 16 The weight % of acrylate 25~30, alkyl with carbon number 1~6 the weight % of (methyl) acrylate 50~65, polar monomer 5 ~the 10 weight % and weight % of reactive F compound 5~10.
As the polymerization of monomer component, can for example include solution polymerization process, mass polymerization, suspension polymerization, Emulsion polymerization etc..In the case of using solution polymerization process, monomer component and solvent can be mixed, be added as needed on polymerization and draw Agent, chain-transferring agent etc. are sent out, it is reacted at 40~90 DEG C or so while stirring 2~10 hours or so.
The weight average molecular weight of side chain crystalline polymer is preferably more than 100000, and more preferably 300000~900000, More preferably 400000~700000.Weight average molecular weight is using gel permeation chromatography (GPC) measure, the measure to obtaining Value has carried out the value of polystyrene conversion.
The fusing point of side chain crystalline polymer is preferably more than 0 DEG C, more preferably 10~60 DEG C.Fusing point can be by changing Composition of monomer component etc. and adjust.
(tackifier)
The Thermo-sensitive adhesive of present embodiment is in addition to above-mentioned side chain crystalline polymer, also containing including benzene second The tackifier of olefine resin.Thus, it is possible to suppress to be heated to heat deterioration during more than 200 DEG C of high temperature, as a result it can play excellent Heat resistance, also obtains and is heated to the excellent effect of the fissility after high temperature.Specifically, the Thermo-sensitive adhesive of present embodiment is adopted 180 ° for polyimide film at 200 DEG C and 250 DEG C obtained are determined with the assay method described in embodiment described later Peel strength is more than 2N/25mm, and the 180 ° of peel strengths for polyimide film that have passed through at 5 after 250 DEG C DEG C are Below 0.25N/25mm.Therefore, the Thermo-sensitive adhesive of present embodiment can be suitable as the substrate in FPD manufacturing process Interim fixation used with Thermo-sensitive adhesive.
Commercially available product can be used in above-mentioned tackifier.As commercially available tackifier, for example, it can include YASUHARA CHEMICAL CO., LTD. manufactures " YS Resin SX100 " etc..
Relative to the parts by weight of side chain crystalline polymer 100, preferably with more than 1 parts by weight, more preferably with 5~100 weight Part, tackifier are further preferably contained with the ratio of 20~60 parts by weight.
The softening point of tackifier is preferably 90~110 DEG C, more preferably 95~105 DEG C.Softening point is according to JIS K The value that ring and ball method specified in 5902 is determined.
(crosslinking agent)
The Thermo-sensitive adhesive of present embodiment can also contain crosslinking agent.As crosslinking agent, for example, it can include metal chelating Polymerisable compounds, aziridine cpd, isocyanate compound, epoxide etc..In these, on heat resistance is improved, preferably Metal chelate compound.
As metal chelate compound, for example, it can include acetylacetone,2,4-pentanedione complex, the polyvalent metal of polyvalent metal Acetoacetic ester complex etc..As polyvalent metal, for example, it can include aluminium, nickel, chromium, iron, titanium, zinc, cobalt, manganese, zirconium Deng.Metal chelate compound can only use a kind, and also two or more may be used.In these, the preferred acetylacetone,2,4-pentanedione coordinationization of aluminium Compound or acetoacetic ester complex, more preferably aluminium tris(acetylacetonate).
Relative to the parts by weight of side chain crystalline polymer 100, crosslinking agent is preferably contained with the ratio of 0.1~10 parts by weight.
After adding crosslinking agent in Thermo-sensitive adhesive, cross-linking reaction can be carried out by being heated.It is used as heating Condition, temperature is 90~110 DEG C or so, and the time is 1 minute~20 minutes or so.
Use form to above-mentioned Thermo-sensitive adhesive is not particularly limited, for example, can use as former state, can also As following middle explanations, used with the form of bonding sheet, adhesive tape etc..
＜ Thermo-sensitive bonding sheets ＞
The Thermo-sensitive bonding sheet of present embodiment includes above-mentioned Thermo-sensitive adhesive, is the sheet of no base material.Thermo-sensitive The thickness of bonding sheet is preferably 5~100 μm, more preferably 5~50 μm.
Mold release film can be laminated on the surface of Thermo-sensitive bonding sheet.As mold release film, for example, it can include by gathering to benzene two The surface of the film of the compositions such as formic acid glycol ester is coated with the mold release film of the releasing agents such as organosilicon.The thickness of mold release film is preferably 5 ~500 μm, more preferably 25~250 μm.Mold release film is peeled off in the use of Thermo-sensitive bonding sheet.
＜ Thermo-sensitive adhesive tapes ＞
The Thermo-sensitive adhesive tape of present embodiment has：Membranaceous base material and the bonding of at least one side stacking in base material Oxidant layer.It is so-called membranaceous, be not only defined in it is membranaceous, as long as not damaging the effect of present embodiment, be also include membranaceous or sheet Concept.
As the constituent material of base material, for example, it can include polyethylene, polyethylene terephthalate, polypropylene, poly- Ester, polyamide, polyimides, makrolon, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethene- The synthetic resin such as polypropylene copolymer, polyvinyl chloride.
The structure of base material can be any of single layer structure or sandwich construction.The thickness of base material is preferably 5~500 μm, More preferably 25~250 μm.To improve the adaptation for adhesive phase, base material can be implemented to be surface-treated.At surface Reason, such as can include Corona discharge Treatment, corona treatment, blasting treatment, chemical etching processing, prime treatment.
The adhesive phase being laminated at least one side of base material includes above-mentioned Thermo-sensitive adhesive.By adhesive phase in base material At least one side stacking when, for example can add solvent in Thermo-sensitive adhesive and prepare coating fluid, by obtained coating fluid use Coating machine etc. is coated on the one or both sides of base material and drying.As coating machine, for example, it can include knife type coater, roll-type and apply Cloth machine, calender courter, chipping wheel coater, heliogravure coating machine, rod coater etc..
The thickness of adhesive phase is preferably 5~100 μm, more preferably 5~50 μm.
In the case of the two sides laminate adhesive oxidant layer of base material, adhesive phase and the adhesive phase of another side simultaneously are each other Thickness, composition etc. can be with identical, can also be different.As long as in addition, the adhesive phase of one side is by above-mentioned Thermo-sensitive adhesive Constitute, then the adhesive phase of another side is not particularly limited.The adhesive phase of another side for example can be also bonded by pressure-sensitive Agent is constituted.As pressure-sensitive bonding agents, for example, it can include natural rubber bonding agent, synthetic rubber bonding agent, styrene-fourth two Alkene latex system bonding agent, acrylic acid series bonding agent etc..
Mold release film can be laminated on the surface of Thermo-sensitive adhesive tape.As mold release film, it can include and in above-mentioned Thermo-sensitive The mold release film identical mold release film illustrated in bonding sheet.Mold release film is peeled off in the use of Thermo-sensitive adhesive tape.
It is exemplified below synthesis example and embodiment is explained to the present invention, but the present invention is not only defined in following conjunction Into example and embodiment.
(synthesis example：Side chain crystalline polymer)
First, the monomer shown in table 1 is added in reaction vessel with the ratio shown in table 1.Monomer shown in table 1 As shown below.
C18A：Stearyl acrylate ester
C1A：Methyl acrylate
AA：Acrylic acid
V3F：It is used as the Osaka Organic Chemical Industry strain of the acrylic acid 2,2,2- trifluoro ethyl esters by above-mentioned formula (Ia) expression Reactive F compound " the Viscoat 3F " of formula commercial firm manufacture
Next, in the way of solid component concentration turns into 30 weight %, by ethyl acetate：Toluene=75：25 (weight Than) mixed solvent add reaction vessel in, obtained mixed liquor.By the way that obtained mixed liquor is stirred 4 hours at 55 DEG C, So that each monomer copolymerization, has obtained side chain crystalline polymer.The weight average molecular weight of obtained side chain crystalline polymer is 553000, fusing point is 24 DEG C.Weight average molecular weight is obtained to carry out polystyrene conversion to the measured value obtained using GPC measure Value.Fusing point is the value determined using DSC under 10 DEG C/min of condition determination.
【Table 1】
1) C18A stearyl acrylates ester, C1A methyl acrylates, AA：Acrylic acid
V3F：Acrylic acid 2,2,2- trifluoro ethyl esters
[embodiment 1 and comparative example 1~8]
The making ＞ of ＜ Thermo-sensitive bonding sheets
First, it is mixed with the ratio of 20 parts by weight relative to the parts by weight of side chain crystalline polymer 100 obtained in synthesis example The tackifier shown in table 2 are closed.Tackifier shown in table 2 are as shown below.
A：Softening point is the styrene resin " YS of 95~105 DEG C of YASUHARA CHEMICAL CO., LTD. manufactures Resin SX100”
B：Softening point is the special rosin ester " A-100 " of 95~105 DEG C of Arakawa Chemical Industries, Ltd.'s manufacture
C：Softening point is the special rosin ester " A-125 " of 120~130 DEG C of Arakawa Chemical Industries, Ltd.'s manufacture
D：Softening point is 100~110 DEG C of YASUHARA CHEMICAL CO., the hydrogenated terpene resin that LTD. is manufactured “CLEARON M105”
E：Softening point is 95~105 DEG C of YASUHARACHEMICAL CO., the aromatic modified hydrogenation terpene that LTD. is manufactured Olefine resin " CLEARON K100 "
F：Softening point is 145~155 DEG C of YASUHARA CHEMICAL CO., the hydrogenated terpene resin that LTD. is manufactured “CLEARON P150”
G：Softening point is the terpene phenol resin " YS of 155~165 DEG C of YASUHARA CHEMICAL CO., LTD. manufactures POLYSTER T160”
H：Softening point is the special rosin ester " KT- of 180~190 DEG C of Harima Chemicals Group, Inc. manufactures 2”
I：Softening point is the rosin ester " D-160 " of 150~170 DEG C of Arakawa Chemical Industries, Ltd.'s manufacture
Next, relative to the parts by weight of side chain crystalline polymer 100, crosslinking is further mixed with the ratio of 3 parts by weight Agent, has obtained Thermo-sensitive adhesive.The crosslinking agent used is as described below.
Crosslinking agent：It is used as three (second of Kawaken Fine Chemicals Co., the Ltd. manufactures of metal chelate compound Acyl acetone) aluminium
Next, being adjusted with ethyl acetate to obtained Thermo-sensitive adhesive so that solid component concentration turns into 30 weights % is measured, coating fluid has been obtained.Then, obtained coating fluid is coated with mold release film, entered under conditions of 100 DEG C × 10 minutes Row cross-linking reaction, has obtained thick 25 μm Thermo-sensitive bonding sheet.It should illustrate, mold release film on surface using being coated with organosilicon 50 μm of thickness polyethylene terephthalate film.
＜ evaluates ＞
For each Thermo-sensitive bonding sheet obtained in embodiment 1 and comparative example 1~8,180 ° of peel strengths are commented Valency.In addition, for each Thermo-sensitive bonding sheet obtained in embodiment 1 and comparative example 8, having carried out thermogravimetric analysis (TGA).With shown below Go out each evaluation method, while the results are shown in table 2 and Fig. 1.
(180 ° of peel strengths)
180 ° of strippings for polyimide film at 50 DEG C, 200 DEG C, 250 DEG C and 5 DEG C are determined according to JIS Z0237 Intensity.Specifically, first, under 50 DEG C of environment temperature, Thermo-sensitive bonding sheet is pasted on glass using 2kg rubber rollers Plate.Next, having carried out degassing process to Thermo-sensitive bonding sheet under conditions of 200 DEG C × 10 minutes.
Next, environment temperature is reduced into 50 DEG C, polyimide film is pasted on into Thermo-sensitive at this ambient temperature glues Piece is closed, test film has been obtained.Then, so as to get test film become after following condition, using load sensor with Polyimide film is peeled off (n=3) for 180 ° by the speed of 300mm/ minutes from Thermo-sensitive bonding sheet.It the results are shown in table 2.
[50℃]
Test film 180 ° of strippings after 20 minutes have been stood into 50 DEG C of environment temperature.
[200℃]
Test film 180 ° of strippings after 20 minutes have been loaded on 200 DEG C of hot plate.
[250℃]
Test film 180 ° of strippings after 20 minutes have been loaded on 250 DEG C of hot plate.
[5℃]
Test film was loaded on 250 DEG C of hot plate after 1 hour and then loaded on 5 DEG C of buck after 20 minutes 180 ° of strippings.
(thermogravimetric analysis)
For each Thermo-sensitive bonding sheet obtained in embodiment 1 and comparative example 8, the weight associated with temperature change is determined Change.It the results are shown in Fig. 1.Condition determination is as described below.
Sensing equipment：" TG/DTA6200 " of high and new technology company of Hitachi manufacture
Heat scope：30~300 DEG C
Heating rate：10 DEG C/min
Other：Under the blanket of nitrogen of 250ml/ minutes
【Table 2】
As shown in Table 2, the value of 180 ° of peel strengths at 50~250 DEG C of embodiment 1 is high, have passed through 5 DEG C after 250 DEG C Under 180 ° of peel strengths value it is low.In addition, as shown in Figure 1, when embodiment 1 can suppress to be heated to more than 200 DEG C of high temperature Heat deterioration.
[embodiment 2~7]
Except relative to the parts by weight of side chain crystalline polymer 100 obtained in synthesis example, being incited somebody to action with the ratio shown in table 3 Beyond tackifier, i.e. styrene resin (YS Resin SX100) mixing same as Example 1, similarly to Example 1 Thick 25 μm Thermo-sensitive bonding sheet is arrived.Then, for obtained Thermo-sensitive bonding sheet, it have rated similarly to Example 1 180 ° of peel strengths.It the results are shown in table 3.In addition, in order to compare, the above embodiments 1 are also depicted in table 3.
【Table 3】
1) styrene resin " the YS Resin of YASUHARA CHEMICAL CO., the LTD. manufactures of 95-105 DEG C of softening point SX100”
As shown in Table 3, embodiment 2~7 be all 180 ° of peel strengths at 50~250 DEG C value it is high, have passed through after 250 DEG C 5 DEG C at 180 ° of peel strengths value it is low.Especially, the content of styrene resin is the embodiment 1,3 of 20~60 parts by weight Excellent result is shown in~6 180 ° of peel strengths at each temperature.

Claims (6)

1. a kind of Thermo-sensitive adhesive, the Thermo-sensitive adhesive contains side chain crystalline polymer, less than the crystallizable side chain Property polymer fusing point at a temperature of adhesion reduce, also containing the tackifier comprising styrene resin.
2. Thermo-sensitive adhesive according to claim 1, wherein, the softening point of the tackifier is 90~110 DEG C.
3. Thermo-sensitive adhesive according to claim 1, wherein, at 200 DEG C and 250 DEG C for polyimide film 180 ° of peel strengths are that 180 ° of peel strengths for polyimide film at more than 2N/25mm, 5 DEG C after 250 DEG C are Below 0.25N/25mm.
4. Thermo-sensitive adhesive according to claim 1, its substrate being used in the manufacturing process of flat-panel monitor faces When fix.
5. a kind of Thermo-sensitive bonding sheet, it includes the Thermo-sensitive adhesive described in claim 1.
6. a kind of Thermo-sensitive adhesive tape, it has：Membranaceous base material and the base material at least one side stacking and include right It is required that the adhesive phase of the Thermo-sensitive adhesive described in 1.
CN201710195533.3A 2016-04-01 2017-03-28 Thermo-sensitive adhesive Pending CN107267092A (en)

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Application publication date: 20171020