CN105623333A - Adhesive composition, adhesive sheet, manufacturing method thereof, and adhesive composition precursor - Google Patents
Adhesive composition, adhesive sheet, manufacturing method thereof, and adhesive composition precursor Download PDFInfo
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- CN105623333A CN105623333A CN201510835136.9A CN201510835136A CN105623333A CN 105623333 A CN105623333 A CN 105623333A CN 201510835136 A CN201510835136 A CN 201510835136A CN 105623333 A CN105623333 A CN 105623333A
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Abstract
The invention provides an adhesive sheet with high thermal conductivity, fire resistance and larger adhesive force than that in the prior art. The adhesive composition precursor is characterized by comprising (methyl) acrylic acid copolymer, (methyl) acrylic acid monomer, and plate-shaped or flaky aquo metallic compound. Compared with the total weight of the adhesive composition precursor, the content of the aquo metallic compound is over 30 but less than 70% by weight. The average grain diameter of the aquo metallic compound is more than 2[mu]m but less than 50[mu]m. The aspect ratio of the aquo metallic compound is more than 5. Compared with the aggregate weight of the (methyl) acrylic acid copolymer and (methyl) acrylic acid monomer, the content of the (methyl) acrylic acid monomer is more than 75% but less than 99% by weight.
Description
Technical field
The present invention relates to adhesion composition precursor, adhesion composition and manufacture method, adhesive sheet and manufacture method thereof and the electronic equipment comprising adhesive sheet.
Background technology
In recent years, with semiconductor light-emitting elements practical as light emitting diode (LED), electroluminescent (EL), tackle the hot countermeasure produced by these elements more and more important. This is because, there is caloric value to raise and the tendency that increases along with the brightness of light-emitting component, if the countermeasure of reply heating is insufficient, then the problem such as generating element service life reduction sometimes. Additionally, for other electronic equipments, also have the tendency that the internal temperature of equipment rises along with highly integrated, the high performance of parts, heating countermeasure is more and more important.
In the past, as the heating countermeasure of electronic equipment etc., carry out following measure: across the heat conductivity sheet that thermal conductivity is high, will engage between the heater such as element, parts with the radiating component such as chiller, fin. As to the characteristic required by this heat conductivity sheet, in most cases requiring cohesive, high-termal conductivity, additionally also have the anti-flammability required from safety aspect.
Therefore, in order to meet above-mentioned characteristic, carrying out various research, as one of its example, it is proposed that the scheme (patent documentation 1) containing inorganic filler and the adhesion zone of acrylic acid series copolymer. The program proposes, for needing the purposes of heat conductivity and anti-flammability, it is preferred to use have the heat conductive flame-retarding filler of heat conductivity and anti-flammability, as its example, uses metal hydroxides. Additionally, propose, for improving adhesion strength, to be used in molecule chain end and there is across the saturated hydrocarbyl that carbon number is more than 2 (methyl) acrylate monomer component as acrylic acid series copolymer of carboxyl. In patent documentation 1, it is proposed by being used in molecule chain end and there is across the saturated hydrocarbyl that carbon number is more than 2 (methyl) acrylate monomer component as acrylic acid series copolymer of carboxyl, even if thus in order to improve heat conductivity, anti-flammability and mix and join high amount of inorganic filler, it also is able to take into account the compendency of sticker and mobility, the adhesion physical property that display is excellent. So, in the past, about the adhesion zone with heat conduction function, for its heat conductivity and anti-flammability, it is adjusted by the kind of inorganic filler, and for its adhesive raising, is adjusted by sticker composition.
On the other hand, propose the conducting strip containing heat conductivity inorganic material and organic high molecular compound, the shape of inorganic particulate is set to flakey, ellipsoid shape, tabular or bar-shaped, makes inorganic particulate be oriented to the scheme (patent documentation 2) of thickness direction of conducting strip. In the program, it is achieved that the conducting strip of high heat conduction on film thickness direction.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2013-87214 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2010-114421 publication
Summary of the invention
Invent problem to be solved
Additionally, recently, for adhesive sheet, expectation fixes, for the interim of parts, the secondary member waited from electronic device field, develops into for not fixing with screw and using but the independent main fixing component engaged. In order to so make adhesive sheet become main fixing component, it is desirable to improve adhesion strength further.
The present invention completes in view of the foregoing, it is provided that a kind of heat conductivity is high, have anti-flammability and the adhesive sheet with bigger adhesion strength compared with the past.
For the method solving problem
The adhesion composition precursor of the present invention is characterised by, it is containing (methyl) acrylic copolymer, the adhesion composition precursor of (methyl) acrylic monomer and tabular or lepidiod moisture metallic compound, gross mass relative to described adhesion composition precursor, the content of described moisture metallic compound is below more than 30 mass % 70 mass %, the mean diameter of described moisture metallic compound is more than 2 ��m less than 50 ��m, the aspect ratio of described moisture metallic compound is more than 5, total quality relative to described (methyl) acrylic copolymer and described (methyl) acrylic monomer, the content of described (methyl) acrylic monomer is below more than 75 mass % 99 mass %.
Additionally, the adhesion composition of the present invention is characterised by, it it is the adhesion composition formed by making (methyl) acrylic monomer contained by the adhesion composition precursor of the invention described above be polymerized.
Additionally, the adhesive sheet of the present invention is characterised by, it it is the adhesive sheet adhesion composition of the invention described above being shaped to lamellar and obtaining.
Additionally, the electronic equipment of the present invention is characterised by, comprise the adhesive sheet of the invention described above.
In addition, the manufacture method of the adhesion composition of the present invention is characterised by, including: the operation modulating the adhesion composition precursor of the invention described above and the operation making described (methyl) acrylic monomer contained by described adhesion composition precursor be polymerized.
In addition, the manufacture method of the adhesive sheet of the present invention is characterised by, including: modulate the operation of the adhesion composition precursor of the invention described above and make described (methyl) acrylic monomer contained by described adhesion composition precursor be polymerized and be shaped to the operation of lamellar.
The effect of invention
In accordance with the invention it is possible to provide a kind of heat conductivity high, there is anti-flammability and the adhesive sheet with bigger adhesion strength compared with the past.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section of an example of the adhesive sheet representing the present invention.
Description of reference numerals
10 adhesive sheets
11,13 stripping film
12 stickers
Detailed description of the invention
(the adhesion composition precursor of the present invention)
The adhesion strength of sticker is furtherd investigate by the present inventor, found that the shape of the inorganic filler contained by sticker affects adhesion strength, thus complete the present invention.
That is, the adhesion composition precursor of the present invention contains (methyl) acrylic copolymer, (methyl) acrylic monomer and tabular or lepidiod moisture metallic compound. In addition, gross mass relative to above-mentioned adhesion composition precursor, the content of above-mentioned moisture metallic compound is below more than 30 mass % 70 mass %, and the mean diameter of above-mentioned moisture metallic compound is more than 2 ��m less than 50 ��m, and the aspect ratio of above-mentioned moisture metallic compound is more than 5. Further, relative to the total quality of above-mentioned (methyl) acrylic copolymer and above-mentioned (methyl) acrylic monomer, the content of above-mentioned (methyl) acrylic monomer is below more than 75 mass % 99 mass %.
The adhesion composition precursor of the present invention, due to containing moisture metallic compound, therefore, it is possible to provide the sticker with high-termal conductivity. That is, above-mentioned moisture metallic compound is the inorganic filler with high-termal conductivity, by making sticker contain above-mentioned moisture metallic compound, it is possible to give high-termal conductivity to sticker. Additionally, in the present invention, moisture metallic compound is defined as, and releases the metallic compound of water by heating. Therefore, by making sticker contain above-mentioned moisture metallic compound, it is possible to give anti-flammability to sticker.
Relative to the total amount of above-mentioned adhesion composition precursor, the content of above-mentioned moisture metallic compound needs to be set to below more than 30 mass % 70 mass %, more preferably more than 35 mass % below 65 mass %. If the gross mass relative to above-mentioned adhesion composition precursor, the content of above-mentioned moisture metallic compound is lower than 30 mass %, then the heat conductivity of sticker and anti-flammability reduce, if the gross mass relative to above-mentioned adhesion composition precursor, the content of above-mentioned moisture metallic compound is more than 70 mass %, then the adhesion strength of sticker reduces, and the flexibility of sticker reduces. If the flexibility of sticker reduces, then the trackability of engagement member is reduced, therefore not preferred.
Additionally, above-mentioned moisture metallic compound has tabular or lepidiod shape, the mean diameter of above-mentioned moisture metallic compound is more than 2 ��m less than 50 ��m, and the aspect ratio of above-mentioned moisture metallic compound is more than 5. Therefore, compared with the conventional sticker employing particulate inorganic fillers, it is possible to obtain bigger adhesion strength.
Further, the adhesion composition precursor of the present invention contains (methyl) acrylic copolymer, (methyl) acrylic monomer, by making above-mentioned (methyl) acrylic monomer be polymerized, produces adhesion strength. Therefore, the adhesion composition precursor of the present invention itself does not have adhesion strength, or only has little adhesion strength.
In addition, relative to the total quality of above-mentioned (methyl) acrylic copolymer and above-mentioned (methyl) acrylic monomer, the content of above-mentioned (methyl) acrylic monomer needs to be set as below more than 75 mass % 99 mass %. If the content of above-mentioned (methyl) acrylic monomer is lower than 75 mass %, then the mobility of the adhesion composition precursor of the present invention reduces, if the content of above-mentioned (methyl) acrylic monomer is more than 99 mass %, then the mobility of the adhesion composition precursor of the present invention becomes too high, it is difficult to use the adhesion composition precursor of the present invention to form adhesive sheet.
Hereinafter, each composition of the adhesion composition precursor of the present invention is described in detail.
The moisture metallic compound > of <
As it has been described above, the tabular of the present invention or lepidiod moisture metallic compound are the metallic compounds that can be released water by heating, it is particularly preferred to aluminium hydroxide or boehmite. This is because, they have high-termal conductivity, anti-flammability and electrical insulating property. The adhesion composition precursor of the present invention can contain aluminium hydroxide and boehmite simultaneously. The adhesion composition precursor of the present invention is due to containing above-mentioned moisture metallic compound, therefore, it is possible to provide the sticker with high-termal conductivity and anti-flammability.
The mean diameter of above-mentioned moisture metallic compound is preferably more than 2 ��m less than 50 ��m, more preferably more than 2 ��m less than 10 ��m. If the mean diameter of above-mentioned moisture metallic compound is less than 2 ��m, then the adhesion strength of sticker reduces, if the mean diameter of above-mentioned moisture metallic compound is more than 50 ��m, then the surface undulation of sticker becomes big, and the adhesion strength of sticker reduces. In the present invention, the mean diameter of above-mentioned moisture metallic compound is obtained as follows: observe the particle of above-mentioned moisture metallic compound with scanning electron microscope (SEM) or infiltration type ultramicroscope (TEM), measure the major axis footpath of 100 particles, calculate its arithmetic mean of instantaneous value.
The aspect ratio of above-mentioned moisture metallic compound is preferably more than 5, more preferably more than 8, and more preferably more than 10. If above-mentioned aspect ratio is less than 5, then the shape of particle being likely to be due to above-mentioned moisture metallic compound is similar to granular, and therefore the adhesion strength of sticker reduces. In the present invention, the aspect ratio of above-mentioned moisture metallic compound is obtained as follows: with the particle of the above-mentioned moisture metallic compound of SEM or tem observation, the length of the thickness direction of above-mentioned moisture metallic compound is set to t, the greatest length in its plate face is set to d, 100 particles are obtained respectively by the d/t value calculated, calculates its arithmetic mean of instantaneous value.
In the present invention, when above-mentioned aspect ratio is more than 5, it is believed that be the particle of tabular, and when above-mentioned aspect ratio is more than 15, it is believed that be lepidiod particle.
Gross mass relative to above-mentioned adhesion composition precursor, the content of above-mentioned moisture metallic compound needs to be set as below more than 30 mass % 70 mass %, it is preferable that be adjusted such that the anti-flammability of sticker reaches more than 21 in the oxygen index (OI) of JISK7201-2 defined.
The content of the moisture metallic compound contained by the adhesion composition precursor of the present invention can be measured by such as thermal analysis system. Namely, above-mentioned adhesion composition precursor can be heated near 500 DEG C, measure the quality of residue (metallic compound after water disengaging), obtained the quality of moisture metallic compound contained by above-mentioned adhesion composition precursor by the quality of this residue, the quality of this moisture metallic compound obtain the containing ratio of moisture metallic compound contained by adhesion composition precursor.
< (methyl) acrylic copolymer >
The polymer that (methyl) acrylic copolymer contained by the adhesion composition precursor of the present invention is is monomer component with (methyl) acrylic monomer. As (methyl) acrylic monomer becoming above-mentioned monomer component, (methyl) acrylic acid, (methyl) acrylate or this derivant can be enumerated such as. As above-mentioned (methyl) acrylate, (methyl) acrylate such as with the alkyl that carbon number is 1��18 can be used, specifically, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate, isobornyl acrylate, decyl acrylate, octadecyl acrylate etc. can be used. (methyl) acrylic monomer becoming above-mentioned monomer component can use one or more.
(methyl) acrylic copolymer contained by the adhesion composition precursor of the present invention preferably has functional group. This is because, by above-mentioned (methyl) acrylic copolymer, there is functional group, thus improving with the adhesion of above-mentioned moisture metallic compound, adhesion strength improves. As above-mentioned functional group, hydroxyl, carboxyl, amino, substituted-amino, epoxy radicals etc. can be enumerated. Wherein, more preferably the acidic functionalities such as carboxyl. This is because, the adhesion of (methyl) acrylic copolymer and above-mentioned moisture metallic compound with acidic functionalities such as carboxyls improves more.
In order to (methyl) acrylic copolymer contained by the adhesion composition precursor to the present invention gives functional group, as long as containing (methyl) acrylic monomer with functional group in above-mentioned (methyl) acrylic monomer become monomer whose composition. As above-mentioned (methyl) acrylic monomer with functional group, such as acrylic acid, methacrylic acid, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 2-hydroxybutyl, �� propyloic acrylic ester, acrylamide, N,N-DMAA etc. can be enumerated. Above-mentioned (methyl) acrylic monomer with functional group can use one or more.
Effect in order to ensure above-mentioned functional group, gross mass relative to above-mentioned (methyl) acrylic monomer becoming above-mentioned monomer component, the content of above-mentioned (methyl) acrylic monomer with functional group is preferably below more than 1 mass % 30 mass %, more preferably 1��15 mass %.
< (methyl) acrylic monomer >
As (methyl) acrylic monomer contained by the adhesion composition precursor of the present invention, known monomer can be used suitably, it is particularly preferred to use the monomer same with (methyl) acrylic monomer of the monomer component as (methyl) acrylic copolymer contained by aforementioned adhesion composition precursor of the present invention. As (methyl) acrylic monomer contained by the adhesion composition precursor of the present invention, it is also preferred that containing (methyl) acrylic monomer with functional group, particularly more preferably there is (methyl) acrylic monomer of acidic functionality. By above-mentioned (methyl) acrylic monomer, there is functional group, thus above-mentioned moisture metallic compound is combined with above-mentioned (methyl) acrylic monomer, the wettability of above-mentioned moisture metallic compound in above-mentioned adhesion composition precursor can be improved, it is achieved homogenizing of the composition of above-mentioned adhesion composition precursor.
Effect in order to ensure above-mentioned functional group, gross mass relative to (methyl) acrylic monomer contained by above-mentioned adhesion composition precursor, the content of above-mentioned (methyl) acrylic monomer with functional group is preferably below more than 1 mass % 30 mass %, more preferably 1��15 mass %.
< acrylic syrup >
Above-mentioned (methyl) acrylic copolymer and above-mentioned (methyl) acrylic monomer contained by the adhesion composition precursor of the present invention can each prepare respectively, but it is easy from starting the just use commercially available acrylic syrup containing above-mentioned (methyl) acrylic copolymer and above-mentioned (methyl) acrylic monomer, thus preferably. Starch as aforesaid propylene acid resin, the UV curing type sticker " ARONTACUVA series " etc. of the non-solvent type acryl class sticker " SK-DyneSyrup series " of such as Soken Chemical Company, East Asia Synesis Company can be enumerated.
In aforesaid propylene acid resin slurry, in order to regulate viscosity or the characteristic of the adhesion composition precursor of the present invention, it is possible to add (methyl) acrylic monomer further. As additional (methyl) acrylic monomer, it is possible to use the monomer same with (methyl) acrylic monomer contained by the adhesion composition precursor of the aforementioned present invention.
< dispersant >
If above-mentioned moisture metallic compound being mixed with aforesaid propylene acid resin slurry, thickening sometimes. This interaction that may be considered (methyl) acrylic copolymer in being starched by above-mentioned moisture metallic compound and aforesaid propylene acid resin causes. Therefore, it can in the adhesion composition precursor of the present invention, add dispersant to suppress tackified phenomenon. As above-mentioned dispersant, it is preferable that the macromolecular dispersant good with the affinity of above-mentioned (methyl) acrylic copolymer and above-mentioned (methyl) acrylic monomer. As above-mentioned macromolecular dispersant, the macromolecular compounds such as such as acrylic acid series, ethylene base system, Polyester, polyurethane series, polyethers system, epoxy, polystyrene, ammonia system can be enumerated. Above-mentioned dispersant can be used alone one, it is also possible to mixing uses two or more.
Above-mentioned dispersant preferably has functional group to improve divergent function. As above-mentioned functional group, can enumerating carboxyl, phosphate, sulfonic group, carboxylic acid ester groups, phosphate-based, sulfonate group, hydroxyl, amino, quaternary ammonium salt base, amide groups etc., above-mentioned dispersant is preferably the amphoteric dispersant with both acidic functionality and basic functionality.
The acidity of above-mentioned dispersant is determined with its acid number for benchmark, and the basicity of above-mentioned dispersant is determined with its amine number for benchmark. It is the dispersant of more than 20mgKOH/g by using acid number, it is possible to prevent the tackified phenomenon of above-mentioned adhesion composition precursor. Additionally, be the dispersant of more than 5mgKOH/g by using amine number, it is possible to prevent the change of sticker adhesion strength when stored. It is believed that the basic activated site of the above-mentioned moisture metallic compound of the acid functional team knowledge of above-mentioned dispersant, suppress the interaction of above-mentioned moisture metallic compound and above-mentioned (methyl) acrylic copolymer, thus preventing the tackified phenomenon of above-mentioned adhesion composition precursor. In addition, it is believed that the basic functionality in above-mentioned dispersant interacts with the acidic functionality in above-mentioned (methyl) acrylic copolymer, suppress above-mentioned dispersant to the movement at above-mentioned adhesion composition interface, thus preventing the change of sticker adhesion strength when stored.
Relative to above-mentioned moisture metallic compound 100 mass parts, the content of above-mentioned dispersant is preferably 0.1��15 mass parts, more preferably 0.3��10 mass parts. If the content of above-mentioned dispersant is less than 0.1 mass parts, then cannot obtaining sufficient dispersibility, if the content of above-mentioned dispersant is more than 15 mass parts, then the cohesive under high temperature is easily reduced, and the impact of adhesion strength, retentivity is troubling.
< Photoepolymerizationinitiater initiater >
The adhesion composition precursor of the present invention preferably further contains Photoepolymerizationinitiater initiater. As above-mentioned Photoepolymerizationinitiater initiater, such as acetophenones, benzophenone class, ketal class, Anthraquinones, thioxanthene ketone, azo-compound, peroxide, 2,3-dialkyl group dione compounds, disulfide, thiuram compound, fluoroamine compounds etc. can be used. About these Photoepolymerizationinitiater initiaters, use at least one. The consumption that makes of above-mentioned Photoepolymerizationinitiater initiater is not particularly limited, relative to total 100 mass parts as (methyl) acrylic copolymer of resinous principle and (methyl) acrylic monomer, the consumption that makes of above-mentioned Photoepolymerizationinitiater initiater is 0.01��3 mass parts, it is preferred to 0.1��2 mass parts.
< cross-linking agent >
The adhesion composition precursor of the present invention can contain cross-linking agent further. As above-mentioned cross-linking agent, such as 1,6-hexanediyl ester, tetramethylolmethane three (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipentaerythritol acrylate etc. multifunctional (methyl) acrylate monomer can be enumerated. Relative to total 100 mass parts as (methyl) acrylic copolymer of resinous principle and (methyl) acrylic monomer, the addition of above-mentioned cross-linking agent is 0.05��5 mass parts.
< other compositions >
In the adhesion composition precursor of the present invention, adhesion imparting agent can be added as needed on. As above-mentioned adhesion imparting agent, such as terpenic series resin, terpene phenol resin, rosin series resin, petroleum line resin (C5 through-stone oleoresin, C9 through-stone oleoresin), benzene phenol resin, coumarone-indene resin, alicyclic through-stone oleoresin, alicyclic ring family hydrogenated petroleum resin, phenylethylene resin series, dcpd resin etc. can be enumerated. Relative to total 100 mass parts as above-mentioned (methyl) acrylic copolymer of resinous principle and above-mentioned (methyl) acrylic monomer, the use level of above-mentioned adhesion imparting agent is preferably 2��200 mass parts.
The manufacture method of the adhesion composition precursor of the present invention is not particularly limited, for instance mix above-mentioned each composition, makes each solid constituent fully dispersed. Above-mentioned mixed method is not particularly limited, and such as disperser, homogeneous mixer, ribbon stirrer, paddle type mixer, planetary-type mixer, roller mill, kneader, ball mill, sand mill, ultrasonic dispersing machine etc. can be used to mix.
(adhesion composition of the present invention)
The adhesion composition of the present invention is to make the polymerization of (methyl) acrylic monomer contained by adhesion composition precursor of the invention described above be formed. By making above-mentioned (methyl) acrylic monomer be polymerized, above-mentioned adhesion composition precursor becomes the adhesion composition with adhesion strength, i.e. sticker. Owing to the adhesion composition of the present invention is that therefore heat conductivity is high, have anti-flammability by making (methyl) acrylic monomer polymerization contained by the adhesion composition precursor of the invention described above be formed, and compared with the past there is bigger adhesion strength.
Therefore, the adhesion composition of the present invention can be manufactured by following manufacture method, and described manufacture method possesses: the operation modulating the adhesion composition precursor of the invention described above and the operation making above-mentioned (methyl) acrylic monomer contained by above-mentioned adhesion composition precursor be polymerized. Make the method that above-mentioned (methyl) acrylic monomer is polymerized be not particularly limited, the method to ionizing radiation such as above-mentioned adhesion composition precursor irradiation ultraviolet radiations can be used.
As above-mentioned ionizing radiation, such as ultraviolet, electron ray, �� line etc. can be used, from can the easy angle utilized, commonly used ultraviolet. As ultraviolet light source, high-pressure mercury-vapor lamp, metal halide lamp, ultraviolet LED etc. can be used. When using ultraviolet as above-mentioned ionizing radiation, it is preferable that containing Photoepolymerizationinitiater initiater in above-mentioned adhesion composition precursor.
(adhesive sheet of the present invention)
The adhesive sheet of the present invention is to obtain by the adhesion composition of the invention described above is shaped to lamellar. Owing to the adhesive sheet of the present invention is to be obtained by the adhesion composition molding by the invention described above, thus heat conductivity is high, have anti-flammability, and compared with the past has bigger adhesion strength.
The thickness of the adhesive sheet of the present invention is not particularly limited, and can be set to such as 10��800 ��m.
The adhesive sheet of the present invention can possess peeling base on two sides further. By possessing above-mentioned peeling base so that the adhesive sheet of the present invention becomes prone to operation.
In addition, the adhesive sheet of the present invention can be manufactured by following manufacture method, and described manufacture method possesses: modulates the operation of the adhesion composition precursor of the invention described above and makes above-mentioned (methyl) acrylic monomer contained by above-mentioned adhesion composition precursor be polymerized and be shaped to the operation of lamellar.
Make above-mentioned (methyl) acrylic monomer be polymerized and be shaped to the method for lamellar to be not particularly limited, such as can use following method: on base material, be coated with above-mentioned adhesion composition precursor and after forming film, base material is configured further, then across above-mentioned base material to ionizing radiation such as the above-mentioned film aforementioned ultraviolet of irradiation on this film. Now, if using peeling base as above-mentioned base material, then the adhesive sheet with peeling base can be obtained easily. Additionally, when using ultraviolet as ionizing radiation, it is preferable that the ultraviolet irradiation side as above-mentioned base material at least one party is used transparent base.
In addition, about the method being coated with above-mentioned adhesion composition precursor, as long as the coating process of smooth film can be formed, just it is not particularly limited, such as gravure roll method, micro-gravure roll method, micro-gravure coating process, slot-form die rubbing method, spraying process, spin-coating method, doctor blade method, kiss formula method, squeezing and pressing method, reversible type rolling method, infusion process, bar rubbing method etc. can be enumerated.
As above-mentioned base material, it is not particularly limited, the thin film or sheet that comprise materials described below can be used, described material is the such as polyester based resin such as polyethylene terephthalate, PEN, TPO, the cellulose-based resin such as cellulosic triacetate, the amide such as nylon, aramid fiber system resin, the polyethers system resin such as polyphenylene oxide, polysulfones ether, polycarbonate-based resin, polyamide series resin, polyimides system resin, polyamidoimide system resin, aromatic polyamide system resin, cyclic olefin polymer class, paper etc.
Additionally, in order to give fissility to above-mentioned base material, at least one side of above-mentioned base material forms the release layer comprising organic siliconresin etc.
Then, the adhesive sheet of the present invention is described based on accompanying drawing. Fig. 1 is the schematic cross-section of an example of the adhesive sheet representing the present invention. In Fig. 1, the adhesive sheet 10 of the present invention possesses the sticker 12 of lamellar between stripping film 11 and 13. When using adhesive sheet 10, remove stripping film 11 and 13, the sticker 12 of lamellar is arranged between engagement member, carries out pressurization etc. and engage.
About the adhesion strength of the adhesive sheet of the present invention, the adhesion strength based on 90 �� of disbonded tests is preferably more than 5N/10mm. If above-mentioned adhesion strength is less than 5N/10mm, worry such as can be peeling between the electronic unit of heating etc. and the radiating component such as chiller, fin.
About the thermal conductivity of the adhesive sheet of the present invention, in order to show Heat transmission fully, it is preferred to more than 0.5W/m K. Additionally, about the anti-flammability of above-mentioned adhesive sheet, in order to suppress burning in an atmosphere, the oxygen index (OI) of JISK7201-2 defined be preferably more than 21.
(electronic equipment of the present invention)
The electronic equipment of the present invention possesses the adhesive sheet of the invention described above, by above-mentioned adhesive sheet, is engaged with the radiating component such as chiller, fin by the electronic unit etc. of heating. Owing to generating component is engaged by the adhesive sheet of electronic equipment the application of the invention of the present invention with radiating component, it is thus possible to suppress the heating of above-mentioned electronic equipment.
Embodiment
Hereinafter, the present invention is explained by embodiment. But the invention is not restricted to following example. Additionally, in following example, " part " is meant to " mass parts ".
(embodiment 1)
The modulation > of < adhesion composition precursor (sticker precursor)
First, following component (1)��(6) are put into the beaker of stainless steel, when water-cooled, use disperser to be stirred, mix to modulate mixed liquor.
(1) acrylic syrup (Soken Chemical Company system, trade name " SKDyneSyrupB ", be comprise 90 mass parts 2-ethylhexyl acrylate, the acrylic acid of 9 mass parts, 1 mass parts the copolymer segment of 2-hydroxyethylmethacry,ate): 58.39 parts
(2) 2-ethylhexyl acrylate: 52.55 parts
(3) acrylic acid: 5.84 parts
(4) cross-linking agent (trimethylolpropane trimethacrylate): 0.29 part
(5) dispersant (Bi Ke chemical company system, trade name " DISPERBYK145 ", amphoteric dispersant): 2.34 parts
(6) Photoepolymerizationinitiater initiater (double; two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide): 0.58 part
Then, coordinating following compositions (7) in above-mentioned mixed liquor, stirring 15 minutes, obtain sticker precursor (adhesion composition precursor) further.
(7) moisture metallic compound (tabular boehmite, mean diameter is 4 ��m, and aspect ratio is 10): 100 parts
The making > of < adhesive sheet
Thickness 38 ��m demoulding polyethylene terephthalate (PET) thin film (in this Packs company system, trade name " NS-38+A ") on, it is coated with above-mentioned sticker precursor, after forming film, on this film superposition thickness 50 ��m demoulding PET film (in this Packs company system, trade name " NS-50-ZW ") after, take turns coating machine by unfilled corner and regulate the thickness of film, then carry out ultraviolet radiation and carry out the cured of above-mentioned film, make the adhesive sheet with demoulding PET film. Take turns, about by above-mentioned unfilled corner, the thickness adjusted that coating machine carries out, be carried out as follows: the clearance gap of adjustable supporting roll and rotor, make the thickness of the adhesive sheet after cured become 250 ��m. It is carried out as follows about above-mentioned ultraviolet radiation: be used in wavelength 365nm place and there is the black light lamp of peak value and to make accumulated light be 300mJ/cm2, use further high-pressure mercury-vapor lamp and to make accumulated light be 250mJ/cm2��
(embodiment 2)
Except moisture metallic compound being changed to tabular boehmite (mean diameter be 2 ��m, aspect ratio be 10): except 100 parts, operate similarly to Example 1, make the adhesive sheet with demoulding PET film.
(embodiment 3)
The modulation > of < adhesion composition precursor (sticker precursor)
First, following component (1)��(6) are put into the beaker of stainless steel, when water-cooled, use disperser to be stirred, mix to modulate mixed liquor.
(1) acrylic syrup (Soken Chemical Company system, trade name " SKDyneSyrupB "): 32.53 parts
(2) 2-ethylhexyl acrylate: 19.52 parts
(3) acrylic acid: 2.17 parts
(4) cross-linking agent (trimethylolpropane trimethacrylate): 0.14 part
(5) dispersant (Bi Ke chemical company system, trade name " DISPERBYK145 "): 1.08 parts
(6) Photoepolymerizationinitiater initiater (double; two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide): 0.27 part
Then, coordinating following compositions (7) in above-mentioned mixed liquor, stirring 15 minutes, obtain sticker precursor (adhesion composition precursor) further.
(7) moisture metallic compound (tabular boehmite, mean diameter is 2 ��m, and aspect ratio is 10): 100 parts
The making > of < adhesive sheet
Beyond above-mentioned sticker precursor, operate similarly to Example 1, make the adhesive sheet with demoulding PET film.
(embodiment 4)
The modulation > of < adhesion composition precursor (sticker precursor)
First, following component (1)��(6) are put into the beaker of stainless steel, when water-cooled, be stirred with disperser, mix and modulate mixed liquor.
(1) acrylic syrup (Soken Chemical Company system, trade name " SKDyneSyrupB "): 40.33 parts
(2) 2-ethylhexyl acrylate: 24.20 parts
(3) acrylic acid: 2.69 parts
(4) cross-linking agent (trimethylolpropane trimethacrylate): 0.17 part
(5) dispersant (Bi Ke chemical company system, trade name " DISPERBYK145 "): 1.34 parts
(6) Photoepolymerizationinitiater initiater (double; two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide): 0.34 part
Then, coordinating following compositions (7) in above-mentioned mixed liquor, stirring 15 minutes, obtain sticker precursor (adhesion composition precursor) further.
(7) moisture metallic compound (flakey aluminium hydroxide, mean diameter is 8 ��m, and aspect ratio is 15): 100 parts
The making > of < adhesive sheet
Beyond above-mentioned sticker precursor, operate similarly to Example 1, make the adhesive sheet with demoulding PET film.
(comparative example 1)
Except moisture metallic compound being changed to granular boehmite (mean diameter is 1 ��m, and aspect ratio is 1.2): beyond 100 parts, operate similarly to Example 1, make the adhesive sheet with demoulding PET film.
(comparative example 2)
Except moisture metallic compound being changed to tabular boehmite (mean diameter is 1 ��m, and aspect ratio is 10): beyond 100 parts, operate similarly to Example 3, make the adhesive sheet with film PET film.
(comparative example 3)
Except moisture metallic compound being changed to particulate aluminum hydroxide (mean diameter is 5 ��m, and aspect ratio is 1.4): beyond 100 parts, operate similarly to Example 4, make the adhesive sheet with demoulding PET film.
(comparative example 4)
The modulation > of < adhesion composition precursor (sticker precursor)
First, following component (1)��(6) are put into the beaker of stainless steel, when water-cooled, use disperser to be stirred, mix to modulate mixed liquor.
(1) acrylic syrup (Soken Chemical Company system, trade name " SKDyneSyrupB "): 195.45 parts
(2) 2-ethylhexyl acrylate: 117.27 parts
(3) acrylic acid: 13.03 parts
(4) cross-linking agent (trimethylolpropane trimethacrylate): 0.81 part
(5) dispersant (Bi Ke chemical company system, trade name " DISPERBYK145 "): 6.52 parts
(6) Photoepolymerizationinitiater initiater (double; two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide): 1.63 parts
Then, coordinating following compositions (7) in above-mentioned mixed liquor, stirring 15 minutes, obtain sticker precursor (adhesion composition precursor) further.
(7) moisture metallic compound (flakey aluminium hydroxide, mean diameter is 8 ��m, and aspect ratio is 15): 100 parts
The making > of < adhesive sheet
Beyond above-mentioned sticker precursor, operate similarly to Example 1, make the adhesive sheet with demoulding PET film.
The evaluation > of < adhesive sheet
Adhesion strength and thermal conductivity to the adhesive sheet with demoulding PET film made in embodiment 1��4 and comparative example 1��4, is evaluated according to as follows.
< adhesion strength >
Whole PET film is peeled off from the made adhesive sheet with demoulding PET film, adhesive sheet after stripping PET film is attached at the common PET film processed without the demoulding of thickness 50 ��m, this is cut into width 25mm, length 250mm with the adhesive sheet of PET film, make evaluation sample, the adhesive sheet side of this evaluation sample is attached at corrosion resistant plate, the roller making quality 2kg with the 300mm/ speed divided is evaluating round trip on sample, sample will be evaluated crimp on stainless steel, place 24 hours. Then, carry out evaluating from stainless steel sheet peeling off 90 �� of disbonded tests of sample with the 300mm/ peeling rate divided, the peeling load recorded is converted into the value wide by 10mm, as the measured value of adhesion strength.
< thermal conductivity >
Whole PET film is peeled off from the made adhesive sheet with demoulding PET film, adhesive sheet after peeling off PET film is cut into width 50mm, length 150mm to make evaluation sample, using this evaluation sample superposition 5 as duplexer, combination uses the rapid thermal conductivity meter " QTM-500 " of capital of a country Electronics Industry Company and thin film to measure software, measures the thermal conductivity of above-mentioned duplexer. As the reference value of this mensuration, employ silicones, quartz, zirconium oxide.
Result above is shown in Table 1. Additionally, in table 1, it is also shown that the kind of moisture metallic compound, mean diameter, aspect ratio and the containing ratio used.
Table 1
As shown in Table 1, for the adhesive sheet of embodiments of the invention 1��4, adhesion strength is more than 5N/10mm, and thermal conductivity also becomes more than 0.5W/m K, and adhesion strength and thermal conductivity are all high. And on the other hand, it is known that, in the comparative example 1 that the mean diameter of moisture metallic compound is less than 2 ��m, its aspect ratio is less than 5, adhesion strength and thermal conductivity inequality; In the mean diameter of the moisture metallic compound comparative example 2 less than 2 ��m, adhesion strength is poor; In the aspect ratio of the moisture metallic compound comparative example 3 less than 5, adhesion strength is poor; In the containing ratio of the moisture metallic compound comparative example 4 less than 30 mass %, thermal conductivity is far smaller than 0.5W/m K.
Industrial applicability
The present invention can provide the adhesive sheet that adhesion strength and heat conductivity are all excellent, can while there is high-termal conductivity, to engage between generating component and radiating component with very big adhesion strength, it is possible to increase possess the heat dispersion of the electronic equipment of generating component and radiating component.
Claims (11)
1. an adhesion composition precursor, it is characterised in that be the adhesion composition precursor containing (methyl) acrylic copolymer, (methyl) acrylic monomer and tabular or lepidiod moisture metallic compound,
Relative to the gross mass of described adhesion composition precursor, the content of described moisture metallic compound is below more than 30 mass % 70 mass %,
The mean diameter of described moisture metallic compound is more than 2 ��m less than 50 ��m,
The aspect ratio of described moisture metallic compound is more than 5,
Relative to the total quality of described (methyl) acrylic copolymer and described (methyl) acrylic monomer, the content of described (methyl) acrylic monomer is below more than 75 mass % 99 mass %.
2. adhesion composition precursor according to claim 1, wherein, described moisture metallic compound is aluminium hydroxide or boehmite.
3. adhesion composition precursor according to claim 1 and 2, wherein, described (methyl) acrylic copolymer has acidic functionality.
4. the adhesion composition precursor according to any one of claims 1 to 3, wherein, as described (methyl) acrylic monomer, containing (methyl) acrylic monomer with acidic functionality.
5. the adhesion composition precursor according to any one of Claims 1 to 4, wherein, contains Photoepolymerizationinitiater initiater further.
6. an adhesion composition, it is characterised in that be the adhesion composition making (methyl) acrylic monomer contained by the adhesion composition precursor according to any one of Claims 1 to 5 be polymerized and being formed.
7. an adhesive sheet, it is characterised in that be the adhesive sheet adhesion composition described in claim 6 being shaped to lamellar and obtaining.
8. adhesive sheet according to claim 7, wherein, possesses peeling base on two sides further.
9. an electronic equipment, it is characterised in that comprise the adhesive sheet described in claim 7.
10. the manufacture method of an adhesion composition, it is characterised in that including:
The operation of modulation adhesion composition precursor according to any one of Claims 1 to 5 and
Make the operation that described (methyl) acrylic monomer contained by described adhesion composition precursor is polymerized.
11. the manufacture method of an adhesive sheet, it is characterised in that including:
The operation of modulation adhesion composition precursor according to any one of Claims 1 to 5 and
Described (methyl) acrylic monomer contained by described adhesion composition precursor is made to be polymerized and be shaped to the operation of lamellar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014239212A JP6454139B2 (en) | 2014-11-26 | 2014-11-26 | Adhesive composition precursor, adhesive composition and method for producing the same, adhesive sheet and method for producing the same, and electronic device including the adhesive sheet |
| JP2014-239212 | 2014-11-26 |
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| Publication Number | Publication Date |
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| CN105623333A true CN105623333A (en) | 2016-06-01 |
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| CN201510835136.9A Pending CN105623333A (en) | 2014-11-26 | 2015-11-26 | Adhesive composition, adhesive sheet, manufacturing method thereof, and adhesive composition precursor |
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| Country | Link |
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| JP (1) | JP6454139B2 (en) |
| KR (1) | KR20160063269A (en) |
| CN (1) | CN105623333A (en) |
| TW (1) | TWI674305B (en) |
Cited By (2)
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| CN111788273A (en) * | 2018-03-01 | 2020-10-16 | Dic株式会社 | Adhesive tape |
| CN114981376A (en) * | 2020-01-31 | 2022-08-30 | 日东电工株式会社 | Double-sided adhesive tape |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109749511B (en) * | 2019-01-22 | 2022-09-20 | 苏州世华新材料科技股份有限公司 | Halogen-free insulating flame-retardant ink and flame-retardant adhesive tape using same |
| JP2021080384A (en) * | 2019-11-20 | 2021-05-27 | 日東電工株式会社 | Double-sided adhesive tape |
| JP2021080383A (en) * | 2019-11-20 | 2021-05-27 | 日東電工株式会社 | Double-sided adhesive tape |
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| CN102741372A (en) * | 2010-02-19 | 2012-10-17 | 日本瑞翁株式会社 | Thermally conductive pressure-sensitive adhesive composition,thermally conductive pressure-sensitive adhesive sheet,and electronic component |
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Also Published As
| Publication number | Publication date |
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| JP2016098366A (en) | 2016-05-30 |
| JP6454139B2 (en) | 2019-01-16 |
| KR20160063269A (en) | 2016-06-03 |
| TWI674305B (en) | 2019-10-11 |
| TW201634646A (en) | 2016-10-01 |
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Application publication date: 20160601 |