CN102277111A - Preparation method of substrate-free thermal pad based on acrylic acid - Google Patents
Preparation method of substrate-free thermal pad based on acrylic acid Download PDFInfo
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- CN102277111A CN102277111A CN 201110142530 CN201110142530A CN102277111A CN 102277111 A CN102277111 A CN 102277111A CN 201110142530 CN201110142530 CN 201110142530 CN 201110142530 A CN201110142530 A CN 201110142530A CN 102277111 A CN102277111 A CN 102277111A
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Abstract
The invention discloses a preparation method of a substrate-free thermal pad based on acrylic acid. The preparation method comprises the following steps: mixing and pre-polymerizing a 2-ethylhexyl (meth)acrylate monomer and terpene resin to obtain a first prepolymer; mixing and pre-polymerizing a butyl (meth)acrylate monomer and/or ethylhexyl (meth)acrylate monomer and partial (meth)acrylic acid monomer to obtain a second prepolymer; mixing an N-hydroxymethyl acrylamide monomer and/or N-hydroxymethyl methyl acrylamide monomer, a methyl (meth)acrylate monomer, a styrene-butadiene block copolymer, the residual (meth)acrylic acid monomer, thermal fillers and a volatile organic solvent to obtain a monomer and thermal filler premix; mixing the first prepolymer, the second prepolymer and the monomer and thermal filler premix under vacuum to obtain a mixture; and carrying out polymerization after preparing the mixture into a pad. The thermal pad prepared by the method has the advantages of low thermal resistance, strong adhesiveness, good elasticity and easiness in removal after use.
Description
Technical field
The present invention relates to a kind of based on acrylic acid heat conduction paster, especially a kind of preparation method based on acrylic acid no base material heat conduction paster.
Background technology
Along with electronics will be more strong functions be integrated in the littler assembly, the rising of temperature can cause that the equipment travelling speed slows down, device work is out of order midway, the problem of dimensional space restriction and other a lot of aspect of performances.Therefore, temperature control has become one of vital challenge in the design, under the situation about promptly tighten, the operating space is more and more littler, how to take away the more high-power more heats that produce effectively at framework, need be at electricity thermal component be installed on the heat generating components of equipment made heat diffusion.In order to make heat generating components, in the purposes of fixedly heat generating components and thermal component, adopt pressure sensitive adhesion sheet usually to thermal component heat conduction efficiently.Angle from engineering design, need to adopt high performance soft thermally conductive material to make with the irregular surface of device and be complementary, eliminate the clearance conveniently to carry out contoured design, and under working conditions, can closely fit, pass on ability thereby improve whole heat, the heat transmission of finishing between heat generating components and thermal component is worked device in lower temperature.Therefore thermally conductive material need have snappiness and to the adhesivity of heat generating components and thermal component, is difficult to remove after can causing again using but viscosity is too high.
This class conducting strip of using mainly contains two classes at present, silicone based and acrylic acid or the like, no matter be any, how to guarantee that existing good snappiness has good thermal conductivity again, not only had under the working temperature well pressure-sensitive-adhesive but also had the ability removed of using the back good, this balance often is difficult to accomplish.Adopt the little foaming method of acrylic ester polymer to improve snappiness such as some technology, though obtained product having shape-following-up performance preferably, thermal resistance has increased, and heat conductivility descends, and high-temperature bond strength also descends.Also have technology by in thermally conductive material, introducing acrylate copolymer, improved the ability removed after using, also obtained lower thermal resistance, but the conducting strip hardness that makes increases snappiness decline with long chain alkyl group.Also have technology to obtain good thermal conductivity, hardness and the fusible balance of material itself in addition, but elasticity is not enough, need be compounded on the base material with certain intensity and make conducting strip, this causes the increase of thermal resistance again.
Summary of the invention
The invention provides a kind of preparation method based on acrylic acid no base material heat conduction paster, the well balanced and thermal resistance that the heat conduction paster that adopts this preparation method to get has been obtained the ability removed after hardness, snappiness, thermal conductivity, binding property and the use is low.
The technical solution adopted in the present invention is: a kind of preparation method based on acrylic acid no base material heat conduction paster, described heat conduction paster comprises binder component and heat conductive filler, described binder ingredients is by comprising (methyl) 2-EHA monomer (a), (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b), N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c), (methyl) methacrylate monomer (d), styrene-butadiene block copolymer (K resin) (e), the mixture of (methyl) Acrylic Acid Monomer (f) and terpine resin (g) obtains through polyreaction, and described preparation method comprises the following steps:
B1, (methyl) 2-EHA monomer (a) and terpine resin (g) are mixed and prepolymerization, obtain the first prepolymer (P
1), its viscosity controller is 3000mPas～10000mPas;
B2, (methyl) Acrylic Acid Monomer (f) that (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b) and part are measured mix and prepolymerization, obtain the second prepolymer (P
2), its viscosity controller is 3000mPas～10000mPas;
B3, make N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c), (methyl) methacrylate monomer (d), styrene-butadiene block copolymer (K resin) (e), (methyl) Acrylic Acid Monomer (f), heat conductive filler and the volatile organic solvent of residual content mix, and obtains monomer heat conductive filler pre-composition (M
1);
B4, make the above-mentioned first prepolymer (P
1), the second prepolymer (P
2) and monomer heat conductive filler pre-composition (M
1) under vacuum condition, mix and obtain mixture (M);
B5, carry out polyreaction after mixture (M) made sheet.
Wherein step B1, B2, B3 do not have the branch of sequencing, and (methyl) Acrylic Acid Monomer (f) all will be used in step B2, B3, as long as divide two parts in work just passable (methyl) Acrylic Acid Monomer (f).
Preferably, the ratio of weight and number of described binder ingredients and heat conductive filler is 40～60:40～60, is 100% with whole binder ingredients weight, and described binder ingredients is obtained by the polymerization of mixtures of monomer that comprises following weight percentage and resin:
(methyl) 2-EHA monomer (a) of 20%～50%,
30%～50% (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b),
1%～5% N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c),
(methyl) methacrylate monomer (d) of 0.5%～5%,
3%～5% styrene-butadiene block copolymer (K resin) (e),
(methyl) Acrylic Acid Monomer (f) of 1%～10% and
3%～10% terpine resin (g).
Preferably, the consumption of (methyl) methacrylate monomer (d) is 30%～70% of the total consumption of this monomer in binder ingredients among the described step B2.
As further improvement, the described step B1 first prepolymer (P
1) preparation in, terpine resin (g) adds when (methyl) 2-EHA monomer (a) prepolymerization reaction system viscosity reaches 2000mPas～4500mPas.
As preferably, the volatile organic solvent consumption is 1.5～2.5 times of heat conductive filler weight among the described step B3.
As further improvement, after prepolymerization is finished among described step B1, the B2 with the first prepolymer (P
1), the second prepolymer (P
2) place to leave standstill under the room temperature to stablize and carried out step B4 in 20～30 hours again.
As preferably, the pre-polymerization of described step B1, B2 is combined into polyreaction under the ultraviolet light conditions, and described UV-light maximum wavelength is that 250～400nm, intensity are 1～2mW/cm
2
As further improvement, among the described step B3, earlier with heat conductive filler with mix with other monomers again after volatile organic solvent mixes.
As preferably, polyreaction is polymerization under the ultraviolet light conditions among the described step B5, and described UV-light maximum wavelength is that 250～400nm, intensity are 1～2mW/cm
2, polymerization time is 10～120 seconds.
As further improving, described step B5 finishes polyreaction and also comprises the following steps of carrying out immediately afterwards:
B6, with 5～10 ℃ cold wind cooling 30～120 seconds.
" (methyl) vinylformic acid " is meant a kind of in vinylformic acid, the methacrylic acid or their mixture among the present invention; Equally, (methyl) alkyl acrylate, as (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA etc., be meant a kind of in corresponding alkyl acrylate, the alkyl methacrylate or their mixture.
Kinetic viscosity when " viscosity " among the present invention is meant 23 ℃ is measured according to GB/T 2794-1995 " mensuration of tackiness agent viscosity " method.
Technique effect of the present invention: the heat conduction paster that adopts the inventive method to make, its shoreA hardness is between 60～90, and thermal resistance is 1.0～1.5cm
2K/W, but heatproof is more than 150 ℃, demonstrate good thermal conductivity and low thermal resistance during use, bond properties significantly promoted when temperature was increased to more than 50 ℃, can peel off with adherend safely and easily again after the use, reach the well balanced of the ability removed after hardness, snappiness, thermal conductivity, binding property and the use.Be very suitable for the heat radiation of electronic products such as display panel, chip, CPU and LED lamp at mobile phone, computer, notebook etc.Simultaneously, in connecting between the electronic product components and parts, between components and parts and machine plate, frame and the shell, adopt pressure sensitive adhesive composition of the present invention to carry out bonding mode, can replace a large amount of at present screws bolts fastening means of using, representing a kind of direction of environmental protection.The inventive method, the technology uniqueness, simple to operate, cost is low, is fit to large-scale production.
Embodiment
Below in conjunction with embodiment the present invention is elaborated, can further be well understood to the present invention by these embodiment.But they are not limitation of the invention.
The present invention is based on the preparation method of acrylic acid no base material heat conduction paster, preferred, described heat conduction paster comprises 40～60 parts binder component and 60～40 parts heat conductive filler in parts by weight; Binder ingredients is obtained through polyreaction by the mixture that comprises monomer and resin, in whole binder ingredients weight is 100%, monomer and resin comprise: (methyl) 2-EHA monomer (a) of 20%～50%, 30%～50% (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b), 1%～5% N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c), (methyl) methacrylate monomer (d) of 0.5%～5%, 3%～5% styrene-butadiene block copolymer (K resin) (e), 1%～10% (methyl) Acrylic Acid Monomer (f) and 3%～10% terpine resin (g).
Wherein the preferred consumption of (methyl) 2-EHA monomer (a) is that the whole binder ingredients weight of 35%～50%(are 100%).
The preferred consumption of (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b) is that the whole binder ingredients weight of 30%～40%(are 100%).
Polyreaction can be thermopolymerization or uv photopolymerization.Can use polymerization starter during thermopolymerization, what can exemplify has benzoyl peroxide, tertbutyl peroxide, cyclohexanone peroxide, a Diisopropyl azodicarboxylate etc.Photopolymerization can be used light trigger, and what can exemplify has Benzoin ethyl ether, benzoin isobutyl ether, an Alpha-hydroxy sec.-propyl benzophenone etc.With respect to the monomer of per 100 weight parts, the consumption of thermal polymerization or light trigger is generally 0.01～5 weight part.
What can be used as heat conductive filler has pottery, metal oxide, a metal hydroxides etc., preferably chooses from following material: Al
2O
3, Al (OH)
3, MgO, ZnO, Fe
2O
3, CaO, BeO, ZrO
2, TiO
2, SiO
2, AlN, Si
3N
4, ZrN, BN, SiC, BC, graphite, more preferably Al
2O
3, MgO, Al (OH)
3, TiO
2, SiO
2, AlN, SiC.The selected average particle size range of heat conductive filler is preferably 0.1～80 micron, and more preferably 0.1～40 micron, " median size " herein is meant 50% by particle diameter (D
50).The shape of heat conductive filler powder can be a spheric or unbodied.The preferable situation of heat conductive filler is to carry out pre-treatment before the adapted, and the pre-treatment preferable methods is to use coupling agent, and for example hexamethyldisilazane, methyltrimethoxy silane, vinyltrimethoxy silane, dimethyldimethoxysil,ne or 3-glycidoxy trimethoxy siloxane are carried out surface treatment to powder.
The preparation method of heat conduction paster of the present invention also can be added with known various additives such as tinting material, fire retardant, toughener, molecular weight regulator as required.
Tinting material such as carbon black or titanium dioxide etc. can be given the pressure sensitive adhesive composition distinct colors.Fire retardant can be organophosphorus based compound, zinc borate, aluminium hydroxide, nano-sized magnesium hydroxide etc.Toughener can be glass fibre, carbon fiber, calcium titanium fiber etc.Molecular weight regulator can be selected dodecyl mercaptans, 2 for use, 4-phenylbenzene-4-methyl-1-pentene, 2-ethylhexyl mercaptoacetate etc.
Preparation method based on acrylic acid no base material heat conduction paster of the present invention may further comprise the steps:
B1, (methyl) 2-EHA monomer (a) and terpine resin (g) are mixed and prepolymerization, obtain the first prepolymer (P
1), its viscosity controller is 3000mPas～10000mPas;
B2, (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b) and part (methyl) Acrylic Acid Monomer (f) are mixed and prepolymerization, obtain the second prepolymer (P
2), its viscosity controller is 3000mPas～10000mPas; Preferably, wherein the consumption of (methyl) Acrylic Acid Monomer (f) is 30%～70% of a formula ratio;
B3, make N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c), (methyl) methacrylate monomer (d), styrene-butadiene block copolymer (K resin) (e), (methyl) Acrylic Acid Monomer (f), heat conductive filler and the volatile organic solvent of residual content mix, and obtains monomer heat conductive filler pre-composition (M
1); Preferably, wherein the volatile organic solvent consumption is 1.5～2.5 times of heat conductive filler weight;
B4, make the above-mentioned first prepolymer (P
1), the second prepolymer (P
2) and monomer heat conductive filler pre-composition (M
1) under vacuum condition, mix and obtain mixture (M);
B5, carry out polyreaction after mixture (M) made sheet.
In the above-mentioned steps " prepolymerization " be meant the partially polymerized meaning.The viscosity of prepolymer can be by adding molecular weight regulator, regulate the thermopolymerization temperature, changing polymerizing condition controls such as ultraviolet lighting intensity and time among step B1, the B2, and these all can adopt conventional method.The common consumption of molecular weight regulator is 0.01～1 weight part based on per 100 weight parts monomers.
Among the step B1, it is optimum that terpine resin (g) adds when (methyl) 2-EHA monomer (a) prepolymerization reaction system viscosity reaches 2000mPas～4500mPas.
Step B1, B2, B3 do not have the sequencing requirement, because of (methyl) Acrylic Acid Monomer (f) all will be used in step B2 and B3, " formula ratio " among the step B2 is meant the total consumption of (methyl) Acrylic Acid Monomer (f) in binder ingredients, if the consumption that step B3 during prior to B2, then only needs the amount according to (methyl) Acrylic Acid Monomer (f) of stipulating among the step B2 calculate in step B3 adds polymerization system.
The mixture of one or more among the step B3 in volatile organic solvent particular methanol, Virahol, acetone, ethyl acetate, methylene dichloride, hexanaphthene, the ethanol, most preferred ethanol.Preferred working method be earlier with heat conductive filler with mix with each monomer again after volatile organic solvent is fully mixed thoroughly, can avoid heat conductive filler and high polymer to be agglomerated into spheroid like this, influence homodisperse, and then the thermal resistance of increase composition.The preferred consumption of volatile organic solvent is 1.8～2.2 times of heat conductive filler weight.
Among the step B4, mixing is meant and vacuumizes in the mixing process under the vacuum condition, vacuum tightness is preferably 0.05 ~ 0.095MPa, mixes the preferred high-viscosity material blended intensive mixer that is suitable for, and for example can be planetary mixer, twin-screw mixer machine, single screw extrusion machine etc.
Among the step B5, mixture (M) promptly obtains thermal conductivity acrylic pressure sensitive glue composition through photopolymerization or heat polymerization.Afterwards carry out polyreaction more preferably with the polyester film surface of mixture (M) paint, and by calendering or mold pressing formation sheet, promptly make vinylformic acid heat conduction paster after polymerization is finished like this through the Organosilicon Release Agent processing.
Embodiment 1
The benzoin isobutyl ether of 35 parts by weight of acrylic 2-ethylhexyls and 0.02 weight part is mixed, be heated to 75 ℃, using maximum wavelength is the ultraviolet light source of 250～400nm, and it is 1～2mW/cm that mixture is exposed to intensity
2Ultraviolet ray in carry out polyreaction, the terpine resin and the stirring that when mixture viscosity reaches 3500～4500mPas, add 9.5 weight parts, continue polymerization 2～4 hours, at room temperature leave standstill and stablize 20～30 hours, obtaining partially polymerized viscosity is the first prepolymer (P of 8000～8200mPas
1).
The benzoin isobutyl ether of the butyl methacrylate of 19 weight parts, the own ester of 20 parts by weight of acrylic, 2 parts by weight of acrylic, 0.02 weight part is mixed, be heated to 75 ℃, using maximum wavelength is the ultraviolet light source of 250～400nm, and it is 1～2mW/cm that mixture is exposed to intensity
2Ultraviolet ray in carried out polyreaction 3～4 hours, at room temperature leave standstill again and stablize 20～30 hours, obtaining partially polymerized viscosity is 6000～6200mPas, the second prepolymer (P
2).
With the aluminium nitride of 60 weight parts, the aluminium hydroxide of 20 weight parts and the ethanol mixing and stirring of 160 weight parts, mix with the N hydroxymethyl acrylamide of 4 weight parts, 3.4 parts by weight of acrylic methyl esters, the K resin of 4.6 weight parts, the methacrylic acid of 1.5 weight parts, the benzoin isobutyl ether of 0.1 weight part again, obtain monomer heat conductive filler pre-composition (M
1).
With the first prepolymer (P for preparing
1), the second prepolymer (P
2) and monomer heat conductive filler pre-composition (M
1) place planetary mixer to mix, and vacuumize, keeping more than the vacuum tightness 0.07MPa, emptying alcohol solvent (reclaim and use) wherein obtains mixture (M).
Mixture (M) at room temperature is applied over the polyester film surface of handling through Organosilicon Release Agent down and covers the polyester film of handling through Organosilicon Release Agent, the calendering slabbing, carry out thermopolymerization 20～40 minutes then under 80 ℃, perhaps at room temperature being exposed to intensity is 1～2mW/cm
2UV-light under solidified 10～120 seconds, through 5～10 ℃ cold wind cooling 30～120 seconds, promptly obtain the two-sided fusible vinylformic acid heat conduction paster that has then.
The performance evaluation of heat conduction paster:
Shao Er hardness adopts the method test of GB/T 531.1-2008 " vulcanized rubber or thermoplastic elastomer penetration hardness test method first part: Shore durometer method (Shao Er hardness) " regulation, and shoreA hardness is 65.
Thermo-resistance measurement method: get 10 * 10mm heat conduction paster (area is S), be sandwiched between the copper coin that is respectively arranged with Heating element, heat dissipation element after removing polyester film, apply the electric power (η) of constant load and the 15W of 1kg, measure the temperature head (△ T) between two copper coins, be calculated as follows thermal resistance: △ T (K) * S (cm2)/η (W).Recording thermal resistance is 1.2cm2K/W.
Thermal conductivity adopts ASTM D5470-06 standard method test, and thermal conductivity is 1.0 w/mk.
Bounding force adopts the method test of GB/T 4851-1998 " pressure-sensitive adhesive tape is held the adhesive test method " regulation.23 ℃ of bounding forces: load 1kg tries hard to keep to hold and did not come off in 10000 minutes; 60 ℃ of following bounding forces: load 3kg tries hard to keep to hold and did not come off in 10000 minutes.
Can remove ability after the use: get 10 50mm * 50mm test film and be attached between the unidimensional aluminium sheet and sheet glass, with the roll-in three times back and forth of 2kg pressure roller, placed then 1 hour, place again in 150 ℃ of thermostatic baths and placed 1 hour, taking-up is cooled to room temperature, slightly twisting aluminium flake and glass are to apply shearing force to test film in the other direction with two hands respectively, and 10 all do not need too big power peelable.
As seen, this thermal conductivity acrylic pressure sensitive composition and heat conduction paster thereof have reached the well balanced of the ability removed after hardness, snappiness, thermal conductivity, binding property and the use.
Embodiment 2
With respect to embodiment 1, present embodiment has changed the amount of material, and the consumption of all materials is specific as follows:
Prepare first prepolymer (P1): the benzoin isobutyl ether of 50 parts by weight of acrylic 2-ethylhexyls, 0.02 weight part, the terpine resin of 3.5 weight parts;
Prepare second prepolymer (P2): the benzoin isobutyl ether of the own ester of 31.7 parts by weight of acrylic, 4 parts by weight of acrylic, 0.02 weight part;
Preparation monomer heat conductive filler pre-composition (M1): the aluminium hydroxide of the aluminium nitride of 80 weight parts, 25 weight parts, the ethanol of 210 weight parts, the benzoin isobutyl ether of the K resin of the N hydroxymethyl acrylamide of 2 weight parts, 0.6 parts by weight of acrylic methyl esters, 3.2 weight parts, 6 parts by weight of acrylic, 0.1 weight part.
The performance evaluation of heat conduction paster:
Shao Er hardness adopts the method test of GB/T 531.1-2008 " vulcanized rubber or thermoplastic elastomer penetration hardness test method first part: Shore durometer method (Shao Er hardness) " regulation, and shoreA hardness is 76.
Thermo-resistance measurement method: get 10 * 10mm heat conduction paster (area is S), be sandwiched between the copper coin that is respectively arranged with Heating element, heat dissipation element after removing polyester film, apply the electric power (η) of constant load and the 15W of 1kg, measure the temperature head (△ T) between two copper coins, be calculated as follows thermal resistance: △ T (K) * S (cm2)/η (W).Recording thermal resistance is 1.3cm2K/W.
Thermal conductivity adopts ASTM D5470-06 standard method test, and thermal conductivity is 1.2 w/mk.
Bounding force adopts the method test of GB/T 4851-1998 " pressure-sensitive adhesive tape is held the adhesive test method " regulation.23 ℃ of bounding forces: load 1kg tries hard to keep to hold and did not come off in 10000 minutes; 60 ℃ of following bounding forces: load 3kg tries hard to keep to hold and did not come off in 10000 minutes.
Can remove ability after the use: get 10 50mm * 50mm test film and be attached between the unidimensional aluminium sheet and sheet glass, with the roll-in three times back and forth of 2kg pressure roller, placed then 1 hour, place again in 150 ℃ of thermostatic baths and placed 1 hour, taking-up is cooled to room temperature, slightly twisting aluminium flake and glass are to apply shearing force to test film in the other direction with two hands respectively, and 10 all do not need too big power peelable.
As seen, this thermal conductivity acrylic pressure sensitive composition and heat conduction paster thereof have reached the well balanced of the ability removed after hardness, snappiness, thermal conductivity, binding property and the use.
Embodiment 3
With respect to embodiment 1, present embodiment has changed the viscosity of amount, first prepolymer of material and the opportunity that terpine resin adds, the amount of all materials and, the viscosity of first prepolymer and viscosity that terpine resin adds fashionable system is specific as follows:
Prepare first prepolymer (P1): the benzoin isobutyl ether of 43 parts by weight of acrylic 2-ethylhexyls, 0.015 weight part, the terpine resin of 4 weight parts; The viscosity of first prepolymer (P1) is 3000～3200mPas; It is 2000～2500mPas that terpine resin adds fashionable mixture system viscosity;
Prepare second prepolymer (P2): the benzoin isobutyl ether of the own ester of 35 parts by weight of acrylic, 3.5 parts by weight of acrylic, 0.02 weight part;
Preparation monomer heat conductive filler pre-composition (M1): the aluminium hydroxide of the aluminium nitride of 70 weight parts, 20 weight parts, the ethanol of 180 weight parts, the benzoin isobutyl ether of the K resin of the N hydroxymethyl acrylamide of 5 weight parts, 5 parts by weight of acrylic methyl esters, 4 weight parts, 1.5 parts by weight of acrylic, 0.1 weight part.
The performance evaluation of heat conduction paster:
Shao Er hardness adopts the method test of GB/T 531.1-2008 " vulcanized rubber or thermoplastic elastomer penetration hardness test method first part: Shore durometer method (Shao Er hardness) " regulation, and shoreA hardness is 71.
Thermo-resistance measurement method: get 10 * 10mm heat conduction paster (area is S), be sandwiched between the copper coin that is respectively arranged with Heating element, heat dissipation element after removing polyester film, apply the electric power (η) of constant load and the 15W of 1kg, measure the temperature head (△ T) between two copper coins, be calculated as follows thermal resistance: △ T (K) * S (cm2)/η (W).Recording thermal resistance is 1.1cm2K/W.
Thermal conductivity adopts ASTM D5470-06 standard method test, and thermal conductivity is 1.1 w/mk.
Bounding force adopts the method test of GB/T 4851-1998 " pressure-sensitive adhesive tape is held the adhesive test method " regulation.23 ℃ of bounding forces: load 1kg tries hard to keep to hold and did not come off in 10000 minutes; 60 ℃ of following bounding forces: load 3kg tries hard to keep to hold and did not come off in 10000 minutes.
Can remove ability after the use: get 10 50mm * 50mm test film and be attached between the unidimensional aluminium sheet and sheet glass, with the roll-in three times back and forth of 2kg pressure roller, placed then 1 hour, place again in 150 ℃ of thermostatic baths and placed 1 hour, taking-up is cooled to room temperature, slightly twisting aluminium flake and glass are to apply shearing force to test film in the other direction with two hands respectively, and 10 all do not need too big power peelable.
As seen, this thermal conductivity acrylic pressure sensitive composition and heat conduction paster thereof have reached the well balanced of the ability removed after hardness, snappiness, thermal conductivity, binding property and the use.
Embodiment 4
With respect to embodiment 1, present embodiment has changed the amount of material and the viscosity of second prepolymer, and the viscosity of the amount of all materials and second prepolymer is specific as follows:
Prepare first prepolymer (P1): the benzoin isobutyl ether of 25 parts by weight of acrylic 2-ethylhexyls, 0.02 weight part, the terpine resin of 8 weight parts;
Prepare second prepolymer (P2): the benzoin isobutyl ether of the own ester of 50 parts by weight of acrylic, 3 parts by weight of acrylic, 0.025 weight part; The viscosity of second prepolymer (P2) is 9700～9900mPas;
Preparation monomer heat conductive filler pre-composition (M1): the aluminium hydroxide of the aluminium nitride of 70 weight parts, 25 weight parts, the ethanol of 190 weight parts, the benzoin isobutyl ether of the K resin of the N hydroxymethyl acrylamide of 1.5 weight parts, 2 parts by weight of acrylic methyl esters, 5 weight parts, 6 parts by weight of acrylic, 0.1 weight part.
The performance evaluation of heat conduction paster:
Shao Er hardness adopts the method test of GB/T 531.1-2008 " vulcanized rubber or thermoplastic elastomer penetration hardness test method first part: Shore durometer method (Shao Er hardness) " regulation, and shoreA hardness is 73.
Thermo-resistance measurement method: get 10 * 10mm heat conduction paster (area is S), be sandwiched between the copper coin that is respectively arranged with Heating element, heat dissipation element after removing polyester film, apply the electric power (η) of constant load and the 15W of 1kg, measure the temperature head (△ T) between two copper coins, be calculated as follows thermal resistance: △ T (K) * S (cm2)/η (W).Recording thermal resistance is 1.5cm2K/W.
Thermal conductivity adopts ASTM D5470-06 standard method test, and thermal conductivity is 1.1 w/mk.
Bounding force adopts the method test of GB/T 4851-1998 " pressure-sensitive adhesive tape is held the adhesive test method " regulation.23 ℃ of bounding forces: load 1kg tries hard to keep to hold and did not come off in 10000 minutes; 60 ℃ of following bounding forces: load 3kg tries hard to keep to hold and did not come off in 10000 minutes.
Can remove ability after the use: get 10 50mm * 50mm test film and be attached between the unidimensional aluminium sheet and sheet glass, with the roll-in three times back and forth of 2kg pressure roller, placed then 1 hour, place again in 150 ℃ of thermostatic baths and placed 1 hour, taking-up is cooled to room temperature, slightly twisting aluminium flake and glass are to apply shearing force to test film in the other direction with two hands respectively, and 10 all do not need too big power peelable.
As seen, this thermal conductivity acrylic pressure sensitive composition and heat conduction paster thereof have reached the well balanced of the ability removed after hardness, snappiness, thermal conductivity, binding property and the use.
Embodiment 5
With respect to embodiment 1, present embodiment has changed the viscosity of amount, first, second prepolymer of material and the opportunity that terpine resin adds, and it is specific as follows that the amount of all materials, the viscosity of first, second prepolymer and terpine resin add the viscosity of fashionable system:
Prepare first prepolymer (P1): the benzoin isobutyl ether of 35 parts by weight of acrylic 2-ethylhexyls, 0.015 weight part, the terpine resin of 7.5 weight parts; The viscosity of first prepolymer (P1) is 4100～4300mPas; It is 2500～3500mPas that terpine resin adds fashionable mixture system viscosity;
Prepare second prepolymer (P2): the benzoin isobutyl ether of the own ester of 45 parts by weight of acrylic, 1 parts by weight of acrylic, 0.025 weight part; The viscosity of second prepolymer (P2) is 3000～3200mPas;
Preparation monomer heat conductive filler pre-composition (M1): the aluminium hydroxide of the aluminium nitride of 80 weight parts, 30 weight parts, the ethanol of 220 weight parts, the benzoin isobutyl ether of the K resin of the N hydroxymethyl acrylamide of 1 weight part, 4.5 parts by weight of acrylic methyl esters, 3 weight parts, 1 parts by weight of acrylic, 0.1 weight part.
The performance evaluation of heat conduction paster:
Shao Er hardness adopts the method test of GB/T 531.1-2008 " vulcanized rubber or thermoplastic elastomer penetration hardness test method first part: Shore durometer method (Shao Er hardness) " regulation, and shoreA hardness is 81.
Thermo-resistance measurement method: get 10 * 10mm heat conduction paster (area is S), be sandwiched between the copper coin that is respectively arranged with Heating element, heat dissipation element after removing polyester film, apply the electric power (η) of constant load and the 15W of 1kg, measure the temperature head (△ T) between two copper coins, be calculated as follows thermal resistance: △ T (K) * S (cm2)/η (W).Recording thermal resistance is 1.4cm2K/W.
Thermal conductivity adopts ASTM D5470-06 standard method test, and thermal conductivity is 1.3 w/mk.
Bounding force adopts the method test of GB/T 4851-1998 " pressure-sensitive adhesive tape is held the adhesive test method " regulation.23 ℃ of bounding forces: load 1kg tries hard to keep to hold and did not come off in 10000 minutes; 60 ℃ of following bounding forces: load 3kg tries hard to keep to hold and did not come off in 10000 minutes.
Can remove ability after the use: get 10 50mm * 50mm test film and be attached between the unidimensional aluminium sheet and sheet glass, with the roll-in three times back and forth of 2kg pressure roller, placed then 1 hour, place again in 150 ℃ of thermostatic baths and placed 1 hour, taking-up is cooled to room temperature, slightly twisting aluminium flake and glass are to apply shearing force to test film in the other direction with two hands respectively, and 10 all do not need too big power peelable.
As seen, this thermal conductivity acrylic pressure sensitive composition and heat conduction paster thereof have reached the well balanced of the ability removed after hardness, snappiness, thermal conductivity, binding property and the use.
Employing the present invention is based on the heat conduction paster that the preparation method of acrylic acid no base material heat conduction paster makes, its shoreA hardness is between 60～90, thermal resistance is 1.0～1.5cm2K/W, but heatproof is more than 150 ℃, demonstrate good thermal conductivity and low thermal resistance during use, bond properties significantly promoted when temperature was increased to more than 50 ℃, can peel off with adherend safely and easily again after the use.The heat conduction paster that the inventive method makes is very suitable for the heat radiation of the electronic products such as display panel, chip, CPU and LED lamp at mobile phone, computer, notebook etc.Simultaneously, in connecting between the electronic product components and parts, between components and parts and machine plate, frame and the shell, adopt pressure sensitive adhesive composition of the present invention to carry out bonding mode, can replace a large amount of at present screws bolts fastening means of using, representing a kind of direction of environmental protection.The inventive method, the technology uniqueness, simple to operate, cost is low, is fit to large-scale production.
Claims (10)
1. plant preparation method based on acrylic acid no base material heat conduction paster, described heat conduction paster comprises binder component and heat conductive filler, it is characterized in that: described binder ingredients is by comprising (methyl) 2-EHA monomer (a), (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b), N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c), (methyl) methacrylate monomer (d), styrene-butadiene block copolymer (e), the mixture of (methyl) Acrylic Acid Monomer (f) and terpine resin (g) obtains through polyreaction, and described preparation method comprises the following steps:
B1, (methyl) 2-EHA monomer (a) and terpine resin (g) are mixed and prepolymerization, obtain the first prepolymer (P
1), its viscosity controller is 3000mPas～10000mPas;
B2, (methyl) Acrylic Acid Monomer (f) that (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b) and part are measured mix and prepolymerization, obtain the second prepolymer (P
2), its viscosity controller is 3000mPas～10000mPas;
B3, (methyl) Acrylic Acid Monomer (f) that makes N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c), (methyl) methacrylate monomer (d), styrene-butadiene block copolymer (e), residual content, heat conductive filler and volatile organic solvent mix, and obtain monomer heat conductive filler pre-composition (M
1);
B4, make the above-mentioned first prepolymer (P
1), the second prepolymer (P
2) and monomer heat conductive filler pre-composition (M
1) under vacuum condition, mix and obtain mixture (M);
B5, carry out polyreaction after mixture (M) made sheet.
2. the preparation method based on acrylic acid no base material heat conduction paster according to claim 1, it is characterized in that: the ratio of weight and number of described binder ingredients and heat conductive filler is 40～60:40～60, with whole binder ingredients weight is 100%, and described binder ingredients is obtained by the polymerization of mixtures of monomer that comprises following weight percentage and resin:
(methyl) 2-EHA monomer (a) of 20%～50%,
30%～50% (methyl) Butyl Acrylate Monomer and/or (methyl) Ethyl acrylate monomer (b),
1%～5% N hydroxymethyl acrylamide monomer and/or N-methylol methacrylamide monomer (c),
(methyl) methacrylate monomer (d) of 0.5%～5%,
3%～5% styrene-butadiene block copolymer (e),
(methyl) Acrylic Acid Monomer (f) of 1%～10% and
3%～10% terpine resin (g).
3. the preparation method based on acrylic acid no base material heat conduction paster according to claim 1 and 2 is characterized in that: the consumption of (methyl) methacrylate monomer (d) is 30%～70% of the total consumption of this monomer in binder ingredients among the described step B2.
4. the preparation method based on acrylic acid no base material heat conduction paster according to claim 1 and 2 is characterized in that: the described step B1 first prepolymer (P
1) preparation in, terpine resin (g) adds when (methyl) 2-EHA monomer (a) prepolymerization reaction system viscosity reaches 2000mPas～4500mPas.
5. the preparation method based on acrylic acid no base material heat conduction paster according to claim 1 and 2 is characterized in that: the volatile organic solvent consumption is 1.5～2.5 times of heat conductive filler weight among the described step B3.
6. the preparation method based on acrylic acid no base material heat conduction paster according to claim 1 and 2 is characterized in that: after prepolymerization is finished among described step B1, the B2 with the first prepolymer (P
1), the second prepolymer (P
2) place to leave standstill under the room temperature to stablize and carried out step B4 in 20～30 hours again.
7. the preparation method based on acrylic acid no base material heat conduction paster according to claim 1 and 2, it is characterized in that: the pre-polymerization of described step B1, B2 is combined into polyreaction under the ultraviolet light conditions, and described UV-light maximum wavelength is that 250～400nm, intensity are 1～2mW/cm
2
8. the preparation method based on acrylic acid no base material heat conduction paster according to claim 1 and 2 is characterized in that: among the described step B3, earlier with heat conductive filler with mix with other monomers again after volatile organic solvent mixes.
9. according to claim 1,2 or 3 described preparation methods based on acrylic acid no base material heat conduction paster, it is characterized in that: polyreaction is polymerization under the ultraviolet light conditions among the described step B5, and described UV-light maximum wavelength is that 250～400nm, intensity are 1～2mW/cm
2, polymerization time is 10～120 seconds.
10. according to claim 1,2 or 3 described preparation methods based on acrylic acid no base material heat conduction paster, it is characterized in that: described step B5 finishes polyreaction and also comprises the following steps of carrying out immediately afterwards:
B6, with 5～10 ℃ cold wind cooling 30～120 seconds.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868095A (en) * | 2019-03-28 | 2019-06-11 | 上海西怡新材料科技有限公司 | In-situ polymerization type has organic silicon-acrylate adhesive preparation method of light diffusion function and products thereof and application |
| CN111019567A (en) * | 2019-12-24 | 2020-04-17 | 李智远 | Water-based environment-friendly acrylic emulsion adhesive and preparation method thereof |
| CN113214744A (en) * | 2021-04-29 | 2021-08-06 | 宁波启合新材料科技有限公司 | Substrate-free heat conduction adhesive tape |
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| US5908881A (en) * | 1996-11-29 | 1999-06-01 | Sumitomo Bakelite Company Limited | Heat-conductive paste |
| CN101407706A (en) * | 2007-10-12 | 2009-04-15 | 比亚迪股份有限公司 | Adhesive compositions |
| CN102002346A (en) * | 2010-10-15 | 2011-04-06 | 深圳市安品有机硅材料有限公司 | Organic silicon heat conduction composition and organic silicon heat conduction patch |
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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908881A (en) * | 1996-11-29 | 1999-06-01 | Sumitomo Bakelite Company Limited | Heat-conductive paste |
| CN101407706A (en) * | 2007-10-12 | 2009-04-15 | 比亚迪股份有限公司 | Adhesive compositions |
| CN102002346A (en) * | 2010-10-15 | 2011-04-06 | 深圳市安品有机硅材料有限公司 | Organic silicon heat conduction composition and organic silicon heat conduction patch |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868095A (en) * | 2019-03-28 | 2019-06-11 | 上海西怡新材料科技有限公司 | In-situ polymerization type has organic silicon-acrylate adhesive preparation method of light diffusion function and products thereof and application |
| CN109868095B (en) * | 2019-03-28 | 2021-04-27 | 上海西怡新材料科技有限公司 | Preparation method of in-situ polymerization type organic silicon-acrylate adhesive with light diffusion function, product and application thereof |
| CN111019567A (en) * | 2019-12-24 | 2020-04-17 | 李智远 | Water-based environment-friendly acrylic emulsion adhesive and preparation method thereof |
| CN111019567B (en) * | 2019-12-24 | 2021-12-07 | 浙江安益新材料有限公司 | Water-based environment-friendly acrylic emulsion adhesive and preparation method thereof |
| CN113214744A (en) * | 2021-04-29 | 2021-08-06 | 宁波启合新材料科技有限公司 | Substrate-free heat conduction adhesive tape |
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|---|---|
| CN102277111B (en) | 2012-11-07 |
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Address after: 300384 Tianjin City, Rong Yuan Road Binhai high tech Zone Huayuan Industrial Park No. 15 -4-D-501 Patentee after: TIANJIN WAERMTIMO NEW MATERIAL TECHNOLOGY Corp.,Ltd. Address before: 300384 Tianjin Nankai District City, Rong Yuan Road No. 15 -4-D-501 Patentee before: WAERMTIMO TIANJIN NEW MATERIALS TECHNOLOGY Co.,Ltd. Address after: 300384 Tianjin Nankai District City, Rong Yuan Road No. 15 -4-D-501 Patentee after: WAERMTIMO TIANJIN NEW MATERIALS TECHNOLOGY Co.,Ltd. Address before: Rong Yuan Road 300384 Tianjin city Nankai District Huayuan Industrial Park No. 15 Xinmao science and Technology Park 2 4-D-501 Patentee before: TIANJIN ANPIN SILICONE MATERIAL Co.,Ltd. |
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Effective date of registration: 20211215 Address after: 518122 workshop 303, No. 2, Qixin science and Technology Park, No. 18, Jinxiu Middle Road, Laokeng community, Longtian street, Pingshan District, Shenzhen City, Guangdong Province Patentee after: Shenzhen voltimo Electronic Material Co.,Ltd. Address before: No.15-4-d-501, Rongyuan Road, Huayuan Industrial Park, hi tech Zone, Binhai New Area, Tianjin 300384 Patentee before: TIANJIN WAERMTIMO NEW MATERIAL TECHNOLOGY Corp.,Ltd. |