CN107075166A - Foaming body and foamed sheet - Google Patents

Abstract

The present invention provides a kind of foaming body, and its anticorrosive property to metal is excellent, even and if be not provided with adhesive linkage, the adaptation with adherend is also excellent.The foaming body of the present invention is formed by the thermoplastic resin composition containing thermoplastic resin (a) and the compound (b) of the ring containing azoles.The thermoplastic resin composition can also also contain at least one kind of surfactant.As the thermoplastic resin (a), at least one kind of polymer in acrylic acid series polymeric compounds, rubber, carbamate based polymer and EVAc is preferably selected from.

Description

Foaming body and foamed sheet

Technical field

The present invention relates to the foaming body and foamed sheet of the adaptation to metal and excellent corrosion resistance and the hair is used Steep the elec-tric-electronic equipment of piece.

Background technology

In the past, the image display devices such as liquid crystal display, electroluminescent display, plasma scope will be fixed on In image display member, the display structure that is installed in so-called " portable phone ", " smart mobile phone ", " portable information terminal " etc. When the optical components such as part, camera, lens are fixed on defined position (such as housing), expanded material has been used.It is used as this Kind of expanded material, except using low ratio foamed and the fine cellular carbamate system foaming body with separated foam structure, by height Foam beyond foaming body obtained by carbamate compression molding, be 30 times or so also using the expansion ratio with separated foam Polyethylene-based foaming body etc..Specifically, it is 0.3~0.5g/cm to use for example by density³Polyurethane series foaming body Pad (with reference to patent document 1), the elec-tric-electronic formed by the foamed structures that mean air bubble diameter is 1~500 μm of formation Equipment encapsulant (with reference to patent document 2) etc..In addition, it is also known that have and be laminated or infiltrated obtained by adhesive on foamed sheet It is bonded foamed sheet (with reference to patent document 3).

In recent years, with electricity such as PC (PC), tablet PC, PDA (personal portable information terminal), portable phones The multifunction of sub- equipment, others are being entered for the impact-absorbing sheet upper strata closed assembly for preventing the breakage of display member etc. and using Component, such as metal foil.Like this by impact-absorbing sheet with it is metal foil laminated in the case of, impact-absorbing sheet and metal foil The corrosivity of adaptation and metal foil just turns into problem.Further, since the further slimming of electronic equipment in recent years, because And wish that the components such as wherein used impact-absorbing sheet are further thin layer, it is desirable to the not impact-absorbing sheet and metal foil Adhesive linkage during stacking.

In addition, as the product for being provided with optical component (image display device, camera, lens etc.) is gradually slim Change, there is the trend significantly reduced using the space of the part of expanded material.As the reduction in the space is, it is necessary to reduce the foaming structure The thickness of part, but for conventional expanded material, once reduce thickness, can not just play sufficient impact absorbency.Cause This, it is desirable to there is a kind of foamed sheet, dropped such as the elec-tric-electronic equipment with display member by " smart mobile phone " on ground In the case of upper, impact during collision can be absorbed, the breakage of display member is prevented.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2001-100216 publications

Patent document 2：Japanese Unexamined Patent Publication 2002-309198 publications

Patent document 3：No. 2633714 publications of Japanese Patent No.

The content of the invention

Invent problem to be solved

Even if it is an object of the present invention to provide it is excellent to the anticorrosive property of metal and be not provided with adhesive linkage its with quilt The adaptation of viscous thing also excellent foaming body, the foamed sheet comprising the foaming body and used the foamed sheet layered product and Elec-tric-electronic equipment.

The other purpose of the present invention is that there is provided in addition to above-mentioned characteristic, thickness is very small also to be played even if making The foaming body of excellent impact absorbency, the foamed sheet comprising the foaming body and the layered product and electricity for having used the foamed sheet Gas-electronic equipment.

Method for solving problem

The present inventor etc. have made intensive studies to reach above-mentioned purpose, as a result find, by the chemical combination containing the ring containing azoles The foaming body that the thermoplastic resin composition of thing is formed is not only excellent to the anticorrosive property of metal, and when being pasted with adherend Dhering strength can be raised over time, so as to complete the present invention.

That is, the present invention provides a kind of foaming body, and it is by the heat containing thermoplastic resin (a) and the compound (b) of the ring containing azoles Thermoplastic resin composition is formed.

The thermoplastic resin composition can also also contain at least one kind of surfactant.

As the thermoplastic resin (a), acrylic acid series polymeric compounds, rubber, the polymerization of carbamate system are preferably selected from At least one kind of polymer in thing and vinyl-vinyl acetate copolymer.

The compound of the ring containing azoles is preferably selected from BTA based compound and benzothiazole based compound extremely Few a kind of compound.

The content of the compound (b) of the ring containing azoles in the thermoplastic resin composition is relative to the thermoplastic resin (a) 100 parts by weight are, for example, 0.2~5 parts by weight.

The thermoplastic resin composition is preferably water-dispersion type thermoplastic resin composition.

The foaming body can be following foaming body, i.e. density is 0.2~0.7g/cm³, mean cell diameter is 10 ~150 μm, the ratio of store elastic modulus and loss elastic modulus during angular frequency 1rad/s in Measurement of Dynamic Viscoelasticity Loss angle tangent (tan δ) has peak value more than -30 DEG C and in less than 30 DEG C of scope.In this case, the loss angle tangent Maximum in more than -30 DEG C of (tan δ) and less than 30 DEG C of scope is preferably more than 0.2.

The foaming body can be following foaming body, i.e. under 23 DEG C of environment and draw speed be 300mm/min drawing Stretch in experiment, initial elastic modulus is 5N/mm²Below.

In addition, the present invention also provides the foamed sheet for including the foaming body.

The thickness of the foamed sheet is, for example, 30~500 μm.

The foamed sheet is fitted with copper foil, 80 DEG C place 1 day after to copper foil bonding force (180 ° of peel angle, draw Stretch speed 300m/ minutes) it is preferably more than 2N/20mm.

The foamed sheet can be following foamed sheet, i.e. be formed via process A and process B, the process A is to make The thermoplastic resin composition of the water-dispersion type of compound (b) containing thermoplastic resin (a) and the ring containing azoles mechanically foams Process, the process B is will to be coated on base material and dry through water-dispersion type resin combination obtained by mechanically foaming Process.

The foamed sheet is for example used as elec-tric-electronic equipment with impact-absorbing sheet.

The present invention also provides the layered product of the foamed sheet and heat-conducting layer.

In addition, the present invention also provides the elec-tric-electronic equipment for having used the foamed sheet or the layered product.This electrically- Electronic equipment can be following elec-tric-electronic equipment, i.e. be the elec-tric-electronic equipment for possessing display member, with by described in Foamed sheet or the layered product are held on the structure electrically or electronically between the housing of equipment and the display member.

Invention effect

According to the present invention, because foaming body is formed by the thermoplastic resin composition of the compound containing the ring containing azoles, therefore It is not only excellent to the anticorrosive property of metal, even and if be not provided with adhesive linkage, it is closely sealed with adherend when being pasted with adherend Power (bonding force) can also be raised over time.Can speculate it is because of the chemical combination of the contained ring containing azoles in foaming body to this Thing is transferred to the interface with adherend, is interacted with adherend.Accordingly, it is possible to prevent position skew, from adherend In stripping, and adhesive linkage can not needed and realize thin layer, thus can ensure that the thickness of other building blocks of functions.

In addition, in foaming body there is specific density, specific mean cell diameter and loss angle tangent (tan δ) to exist In the case of there is peak value in specific temperature range, even if thickness of thin, impact absorbency is also excellent, even with including this The elec-tric-electronic equipment of the foamed sheet of the foaming body of invention earthward etc. drops, and is also possible to prevent the display caused by impact Deng breakage.

Brief description of the drawings

Fig. 1 is the schematic illustration of copper corrosion experiment.

Embodiment

[foaming body]

The foaming body of the present invention is by the combinations of thermoplastic resins containing thermoplastic resin (a) and the compound (b) of the ring containing azoles Thing is formed.

[thermoplastic resin (a)]

In the present invention, thermoplastic resin is used as the resin material (polymer) for constituting the foaming body.It is used as thermoplastic Property resin, is not particularly limited, can use can constitute the known or known thermoplastic resin of foaming body.It is used as the thermoplastic Property resin, for example, can enumerate acrylic acid series polymeric compounds, rubber, carbamate based polymer, ethylene-vinyl acetate c Thing etc..Among them, from the viewpoint of impact absorbency, preferably acrylic acid series polymeric compounds, rubber, the polymerization of carbamate system Thing.Constitute foaming body thermoplastic resin both can be independent a kind or two or more.

Aforesaid propylene acid based polymer contains (methyl) alkyl acrylate as principal component.It is used as above-mentioned (methyl) propylene Acid alkyl ester, is not particularly limited, but can for example enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) third The secondary butyl ester of olefin(e) acid, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) propylene The own ester of acid, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid Different monooctyl ester, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) Isodecyl Ester, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (first Base) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) propylene Sour heptadecane base ester, (methyl) octadecyl acrylate, (methyl) acrylic acid isooctadecane base ester, (methyl) acrylic acid 19 Arrcostab, (methyl) acrylic acid eicosane base ester etc. have (methyl) alkyl acrylate of carbon number for 1~20 alkyl. Above-mentioned (methyl) alkyl acrylate can be used alone or two or more is applied in combination.

(methyl) for the monomer component total amount (whole monomer components) for constituting the sour based polymer of aforesaid propylene The ratio of alkyl acrylate (such as with (methyl) alkyl acrylate of carbon number for 1~20 alkyl) is, for example, 50 More than weight %, preferably more than 60 weight %, more preferably more than 80 weight %, more preferably more than 85 weight %. The ratio of (methyl) alkyl acrylate for the monomer component total amount for constituting the sour based polymer of aforesaid propylene it is upper Limit for example, 100 weight %, more preferably preferably 98 weight %, 96 weight %.

Aforesaid propylene acid based polymer can be the monomer that only contains above-mentioned (methyl) alkyl acrylate as composition into Point polymer, but from can assign function as needed in terms of, more rightly control adhesion characteristic in terms of examine Consider, can be not only contain above-mentioned (methyl) alkyl acrylate, also contain can be with their copolymerization co-polymerized monomer conduct The polymer of the monomer component of composition.Co-polymerized monomer can be used alone or two or more is applied in combination.

As above-mentioned co-polymerized monomer, the monomer containing polar group can be enumerated.As the above-mentioned monomer containing polar group, do not have Be particularly limited to, however can for example enumerate the monomer of nitrogen atom, carboxylic monomer, the monomer of hydroxyl, containing sulfonic Monomer, monomer of phosphorous acidic group etc..Monomer containing polar group can be used alone or two or more is applied in combination.

As the monomer of above-mentioned nitrogen atom, as long as there is the monomer of nitrogen-atoms and ethylenic unsaturated bond in intramolecular (polymerizable compound), is just not particularly limited, the monomer of cyano-containing such as can enumerate (methyl) acrylonitrile；N- (2- hydroxyls Base ethyl) (methyl) acrylamide, N- (2- hydroxypropyls) (methyl) acrylamide, N- (1- hydroxypropyls) (methyl) acryloyl Amine, N- (3- hydroxypropyls) (methyl) acrylamide, N- (2- hydroxybutyls) (methyl) acrylamide, N- (3- hydroxybutyls) N- hydroxy alkyls (methyl) acrylamides such as (methyl) acrylamide, N- (4- hydroxybutyls) (methyl) acrylamide；N- (first Base) ring-type (methyl) acrylamide such as acryloyl morpholine, N- (methyl) acryloyl group pyrrolidines；(methyl) acrylamide, N- Replace non-annularity (methyl) acrylamides such as (methyl) acrylamide.Replace (methyl) acrylamide, Ke Yiju as above-mentioned N- Go out N- alkyl (methyl) acrylamides such as N- ethyls (methyl) acrylamide, N- normal-butyls (methyl) acrylamide；N, N- diformazan Base (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N, N- dipropyl (methyl) acrylamide, N, N- diisopropyls Base (methyl) acrylamide, N, N- di-n-butyls (methyl) acrylamide, N, the N, N- such as N- di-t-butyls (methyl) acrylamide Dialkyl group (methyl) acrylamide etc..

In addition, as the monomer of above-mentioned nitrogen atom, such as NVP (NVP), N- second can be enumerated Alkenyl -2- piperidones, N- vinyl -3- morpholones, N- vinyl -2- caprolactams, N- vinyl -1,3- oxazine -2- ketone, N- The N- vinyl cyclic acid amides such as vinyl -3,5- morpholine diketone；(methyl) acrylate, (methyl) acrylic acid N, N- bis- Methylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc. have the monomer of amino；N- cyclohexyl maleimides Amine, N-phenylmaleimide etc. have the monomer of maleimide skeleton；N- methyl clothing health acid imide, N- ethyl clothing health acyl are sub- Amine, N- butyl clothing health acid imide, N-2- ethylhexyl clothing health acid imide, N- lauryl clothing health acid imide, N- cyclohexyl clothing health acyls Clothing health imide series monomer such as imines etc..The monomer of nitrogen atom can be used alone or two or more is applied in combination.

Above-mentioned carboxylic monomer can also be acid anhydrides to have the monomer of the carboxyl of more than 1 in 1 molecule Form.As above-mentioned carboxylic monomer, be not particularly limited, however can for example enumerate (methyl) acrylic acid, itaconic acid, Maleic acid, fumaric acid, crotonic acid, iso-crotonic acid, maleic anhydride, itaconic anhydride etc..Carboxylic monomer can be used alone Or two or more is applied in combination.

As the monomer of above-mentioned hydroxyl, for example, it can enumerate (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 6- hydroxyls oneself Ester, (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid 10- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylaurics ester, (4- Hydroxymethyl-cyclo-hexyls) methylmethacylate etc..Wherein, preferably (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) third Olefin(e) acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls.The monomer of hydroxyl can be with It is used alone or in combination of two or more.

Contain sulfonic monomer as above-mentioned, for example, can enumerate styrene sulfonic acid, allyl sulphonic acid, (methyl) acrylic acid Sulfonic acid propyl ester, (methyl) propane sulfonic acid etc..2 kinds are can be used alone or are applied in combination containing sulfonic monomer More than.

As the monomer of above-mentioned phosphorous acidic group, such as can enumerate 2- hydroxyethyl acryloyl phosphates.Moreover, containing The monomer of phosphate can be used alone or two or more is applied in combination.

The mixing ratio of the above-mentioned monomer containing polar group in the monomer component of the sour based polymer of composition aforesaid propylene is (2 Toatl proportion in the case of more than kind) be not particularly limited, but relative to constitute the monomer of the sour based polymer of aforesaid propylene into Divide total amount, preferably 1~30 weight %, lower limit is more preferably 3 weight %, and the upper limit is more preferably 20 weight %.In addition, as upper The monomer containing polar group is stated, the monomer of at least nitrogen atom is preferably used.The mixing ratio of the monomer of the nitrogen atom is relative In the monomer component total amount for constituting the sour based polymer of aforesaid propylene, preferably 1~30 weight %, lower limit is more preferably 3 weight %, The upper limit is more preferably 20 weight %.If the mixing ratio of the monomer containing polar group is in above-mentioned scope, adhesive phase Cohesiveness appropriateness, can obtain high confining force and bonding force.

In addition, as above-mentioned co-polymerized monomer, in addition to the above, such as (methyl) acrylic acid ring penta can also be enumerated Ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid norbornene ester, (methyl) isobornyl acrylate etc. have alicyclic type hydrocarbon (methyl) acrylate；(methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, (first Base) acrylic acid phenoxy group binaryglycol ester etc. has (methyl) acrylate of aromatic hydrocarbyl；(methyl) acrylic acid 2- methoxies Base ethyl ester, (methyl) acrylic acid 3- methoxyl groups propyl ester, (methyl) methoxyethyl glycol ester, (methyl) methoxyethyl Polypropylene glycol ester etc. has the monomer of alkoxyalkyl；(methyl) glycidyl acrylate, allyl glycidyl ether etc. Monomer with epoxy radicals；The styrenic monomers such as styrene, α-methylstyrene；Ethene, propylene, isoprene, butadiene, The alpha-olefins such as isobutene；2- isocyanatoethyls acrylate, 2- isocyanatoethyl methacrylates etc. have different The monomer of cyanic acid ester group；The vinyl esters such as vinyl acetate, propionate system monomer；The vinyl ethers such as vinyl ethers system is single Body；(methyl) tetrahydrofurfuryl acrylate etc. has (methyl) acrylate of heterocycle；(methyl) acrylate with fluorine atom Deng the monomer with halogen atom；3- methacryloxypropyl trimethoxy silanes, vinyltrimethoxy silane etc. have There is the monomer of alkoxysilyl；Silicone (methyl) acrylate etc. has monomer of siloxanes key etc..

In addition, as above-mentioned co-polymerized monomer, polyfunctional monomer can be used.If, can be with using the polyfunctional monomer Cross-linked structure is imported into acrylic acid series polymeric compounds, the cohesiveness of adhesive phase can be adjusted.It is used as above-mentioned polyfunctional monomer, example Hexylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, (methyl) third of (poly-) ethylene glycol two can such as be enumerated Olefin(e) acid ester, (poly-) propane diols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) third Olefin(e) acid ester, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (first Base) acrylate, tetramethylol methane three (methyl) acrylate, (methyl) allyl acrylate, (methyl) vinyl Ester, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate etc..It is excellent as polyfunctional monomer Select multifunctional acrylic monomer.Moreover, above-mentioned polyfunctional monomer can be used alone or two or more is applied in combination.

Can be any one of natural rubber, synthetic rubber as the rubber., for example can be with as the rubber Enumerate nitrile rubber (NBR), methyl methacrylate butadiene rubber (MBR), butadiene-styrene rubber (SBR), acrylic rubber (ACM, ANM), polyurethane rubber (AU), silicon rubber etc..Among them, preferably nitrile rubber (NBR), methyl methacrylate- Butadiene rubber (MBR), silicon rubber.

As the carbamate based polymer, can for example enumerate polycarbonate-based polyurethane, Polyester polyurethane, Polyethers system polyurethane etc..

As the vinyl-vinyl acetate copolymer, known or known ethylene-vinyl acetate c can be used Thing.

In the present invention, surface has viscosity preferably at producing foamed body (foamed sheet).In the table of foaming body (foamed sheet) In the case of mask is sticking, can also well it be laminated with adherend adaptation even if adhesive linkage is not provided with.As to foaming The method that the surface of body (foamed sheet) assigns viscosity, for example, can enumerate following method, i.e. be used as composition foaming body The monomer of thermoplastic resin (a) (such as acrylic acid series polymeric compounds), relative to composition thermoplastic resin (a) (such as acrylic acid series Polymer) whole monomer components (monomer component total amount), for example using 70~98 weight % (lower limit is preferably 75 weight %, The upper limit is preferably 97 weight %) the Tg of homopolymer to be less than -10 DEG C (be such as preferably -70 DEG C -70 DEG C less than -10 DEG C ~-12 DEG C, more preferably -65 DEG C~-15 DEG C) monomer, and rightly selection uses other monomers.

In addition, in the present invention, as described later, being used as the Measurement of Dynamic Viscoelasticity of the thermoplastic resin, preferably foaming body In angular frequency 1rad/s when store elastic modulus and loss elastic modulus ratio be loss angle tangent (tan δ) peak value Thermoplastic resin in more than -30 DEG C and less than 30 DEG C of scope.By using such a thermoplastic resin, hair can be improved The impact absorbency of foam.In order that the peak value of the loss angle tangent (tan δ) is more than -30 DEG C and less than 30 DEG C of scope In, the Tg of the thermoplastic resin can be regard as index or reference value.For example, as the thermoplastic resin, preferably from Tg In -50 DEG C less than 50 DEG C (lower limit is preferably -40 DEG C, more preferably -30 DEG C, the upper limit is preferably 40 DEG C, more preferably 30 DEG C) scope polymer in select.

Consider from such a viewpoint, such as in the case where thermoplastic resin is acrylic acid series polymeric compounds, be used as the acrylic acid Based polymer, is preferably less than -10 DEG C of monomer as must by more than -10 DEG C of monomer and the Tg of homopolymer of the Tg of homopolymer The acrylic acid series polymeric compounds of the monomer component formation needed.By using such a acrylic acid series polymeric compounds, adjust the former monomer with The amount ratio of the monomer of the latter, it is possible to relatively easily obtain the energy storage bullet during angular frequency 1rad/s in Measurement of Dynamic Viscoelasticity Property modulus and the ratio of loss elastic modulus be that the peak value of loss angle tangent (tan δ) is in more than -30 DEG C and less than 30 DEG C of model Foaming body in enclosing.

Moreover, in the present invention, so-called " Tg " of homopolymer refers to the " glass transition temperature of the homopolymer of the monomer (Tg) ", specifically, exist《Polymer Handbook》It there are in (the 3rd edition, John Wiley＆Sons, Inc, 1987) Numerical value.Moreover, the Tg for not having the homopolymer for the monomer recorded in above-mentioned document for example refers to obtain using following assay method Value (with reference to Japanese Unexamined Patent Publication 2007-51271 publications).That is, to possessing thermometer, mixer, nitrogen ingress pipe and returned cold In the reactor of solidifying pipe, the parts by weight of monomer 100,2, the parts by weight of 2 '-azodiisobutyronitrile 0.2 and the second as polymer solvent are put into The parts by weight of acetoacetic ester 200, are stirred 1 hour while nitrogen is imported.After the oxygen in polymerization system is removed like this, it is warming up to 63 DEG C and it is allowed to react 10 hours.Then, room temperature is cooled to, the homopolymer solution that solid component concentration is 33 weight % is obtained. Then, the homopolymer solution curtain coating is coated on partition, dry and produce thickness about 2mm test specimen (sheet it is equal Polymers).Hereafter, it is the discoid of diameter 7.9mm the test specimen to be punched, and is sandwiched with parallel-plate, uses test for viscoelastic machine (ARES, Rheometrics company system) apply frequency 1Hz shear strain while, temperature province -70~150 DEG C, with 5 DEG C/min of programming rate determines viscoplasticity using shear mode, and tan δ peak temperature is set to the Tg of homopolymer.Moreover, The Tg of above-mentioned thermoplastic resin can also be determined using this method.

In the Tg of homopolymer is more than -10 DEG C of monomer, the Tg is, for example, -10 DEG C~250 DEG C, preferably 10~230 DEG C, more preferably 50~200 DEG C.

As the monomer that the Tg of above-mentioned homopolymer is more than -10 DEG C, for example, it can exemplify (methyl) acrylonitrile；(first Base) amide-containing such as acrylamide, N- hydroxyethyls (methyl) acrylamide monomer；(methyl) acrylic acid；Methacrylic acid The Tg of the homopolymers such as methyl esters, EMA is more than -10 DEG C (methyl) alkyl acrylate；(methyl) acrylic acid is different Norbornene ester etc. has (methyl) acrylate of alicyclic type hydrocarbon；The vinyl list containing heterocycle such as NVP Body (N- vinyl cyclic acid amides etc.)；Monomer of the hydroxyls such as 2- HEMAs etc..They can individually make With a kind or two or more is applied in combination.Among them, particularly preferred (methyl) acrylonitrile (especially acrylonitrile).If being used as homopolymerization The Tg of thing uses (methyl) acrylonitrile (especially acrylonitrile) for more than -10 DEG C of monomer, then is probably because intermolecular mutual Effect is strong, thus can increase the peak strength of the loss angle tangent (tan δ) of foaming body.

Be less than in the Tg of homopolymer in -10 DEG C of monomer, the Tg be, for example, -70 DEG C less than -10 DEG C, be preferably - 70 DEG C~-12 DEG C, more preferably -65 DEG C~-15 DEG C.

It is less than -10 DEG C of monomer as the Tg of above-mentioned homopolymer, for example, can enumerates ethyl acrylate, acrylic acid fourth The Tg of the homopolymers such as ester, 2-EHA is less than -10 DEG C (methyl) alkyl acrylate etc..They can individually make With a kind or two or more is applied in combination.Among them, particularly preferably there is the alkyl acrylate of the alkyl of carbon number 2~8.

The Tg of homopolymer for the monomer component total amount for constituting the sour based polymer of aforesaid propylene is more than -10 DEG C The content of monomer be preferably 2~30 weight %.Its lower limit is more preferably 3 weight %, more preferably 4 weight %, the upper limit More preferably 25 weight %, more preferably 20 weight %.In addition, relative to the monomer for constituting the sour based polymer of aforesaid propylene The content that the Tg of homopolymer for composition total amount is less than -10 DEG C of monomer is preferably 70~98 weight %.Its lower limit is more preferably For 75 weight %, more preferably 80 weight %, the upper limit is more preferably 97 weight %, more preferably 96 weight %.

[compound (b) of the ring containing azoles]

As the compound (b) of the ring containing azoles, as long as with the five-membered ring that the nitrogen-atoms of more than 1 is included in ring Compound, can for example enumerate with diazole (imidazoles, pyrazoles) ring, triazole ring, tetrazole ring, oxazole ring, isoxazole rings, Compound of thiazole ring or isothiazole ring etc..These rings can also with the fragrant cyclic condensation such as phenyl ring and form fused rings.It is used as tool There is the compound of such a fused rings, for example, can enumerate with benzimidazole ring, benzopyrazoles ring, BTA ring, Ben Bing Evil Azoles ring, benzoisoxazole ring, compound of benzothiazole ring or benzisothiazole ring etc..

The azoles ring, the fused rings (BTA ring, benzothiazole ring etc.) can also have substituent respectively.As The substituent, the carbon number 1~6 such as can enumerate methyl, ethyl, propyl group, isopropyl, butyl (is preferably carbon number 1 ~alkyl 3)；The carbon numbers such as methoxyl group, ethyoxyl, isopropoxy, butoxy 1~12 (being preferably carbon number 1~3) Alkoxy；The aryl of the carbon numbers such as phenyl, tolyl, naphthyl 6~10；Amino；Methylamino, dimethylamino etc. (it is single or Two) C_1-10Alkyl amino；Amino-the C such as amino methyl, 2- amino-ethyls_1-6Alkyl；N, N- diethylamino methyl, N, N- are double The list such as (2- ethylhexyls) amino methyl or two (C_1-10Alkyl) amino-C_1-6Alkyl；Sulfydryl；Methoxycarbonyl, ethoxy carbonyl Carboxyl-the C such as the alkoxy carbonyl carboxyl carboxymethyl group Deng carbon number 1~6_1-6Carboxyl-the C such as alkyl 2- carboxy ethyl sulfenyls_1-6 Alkylthio group；Double (hydroxyl-the C of the N such as double (hydroxymethyl) amino methyls of N, N-, N-_1-4Alkyl) amino-C_1-4Alkyl；Sulfo group etc..Separately Outside, the compound (b) of the ring containing azoles can also form the salt such as sodium salt, sylvite.

In the present invention, from the aspect of the anti-rust action to metal, the preferably aromatic rings such as azoles ring and phenyl ring formation is condensed The compound of ring, wherein, particularly preferred BTA based compound (compound with BTA ring), benzothiazole system Compound (compound with benzothiazole ring).

As above-mentioned BTA based compound, for example, it can enumerate 1,2,3- BTAs, methylbenzotrazole, carboxyl BTA, carboxymethyl group BTA, 1- [double (2- ethylhexyls) amino methyls of N, N-] BTA, the 1- [double (2- of N, N- Ethylhexyl) amino methyl] methylbenzotrazole, 2,2 '-[[(methyl isophthalic acid H- BTA -1- bases) methyl] imino group] double second Alcohol or their sodium salt etc..

As above-mentioned benzothiazole based compound, for example, it can enumerate 2-mercaptobenzothiazole, 3- (2- (benzothiazolyl) It is thio) propionic acid or their sodium salt etc..

The compound (b) of the ring containing azoles can be used singly or in combination of two or more.

Content for the compound (b) of the ring containing azoles in the thermoplastic resin composition for the foaming body for forming the present invention [solid constituent (nonvolatile component)] as long as do not damage the scope of the characteristic original with the adaptation of adherend, foaming body i.e. Can, for example, relative to thermoplastic resin (a) [solid constituent (nonvolatile component)] 100 parts by weight, preferably 0.2~5 weight Part.Its lower limit is more preferably 0.3 parts by weight, more preferably 0.4 parts by weight, and its upper limit is more preferably 3 parts by weight, further Preferably 2 parts by weight.If the content of the compound (b) of the ring containing azoles is above-mentioned scope, it can take into account at a high level to metal Anticorrosive property and adaptation with adherend.

[additive]

In the thermoplastic resin composition of the foaming body for forming the present invention, can also in thermoplastic resin (a) and Beyond the compound (b) of the ring containing azoles, always according to needs, contain surfactant, crosslinking agent, thickener, other additives.

For example, the thermoplastic resin composition is in order to realize the miniaturization of bubble diameter, the stabilization steeped obtained by foaming Property, arbitrary surfactant can also be contained.It is not particularly limited as surfactant, anion system surface can be used Any one of activating agent, cation system surfactant, nonionic surfactants, amphoteric surfactant etc., but From the viewpoint of the stability steeped obtained by miniaturization, foaming from bubble diameter, preferred anionic system surfactant, especially It is the more preferably aliphatic acid ammonium such as ammonium stearate system surfactant.Surfactant can be used alone, and can also combine makes Use two or more.Alternatively, it is also possible to and with surfactant not of the same race, for example, it is also possible to by anion system surfactant with Nonionic surfactants, anion system surfactant and amphoteric surfactant are used in combination.

The addition [solid constituent (nonvolatile component)] of surfactant is for example relative to thermoplastic resin (a) [solid Composition (nonvolatile component)] 100 parts by weight be 0~10 parts by weight, lower limit is preferably 0.5 parts by weight, more preferably 1 parts by weight, The upper limit is preferably 8 parts by weight, more preferably 6 parts by weight.

In addition, the thermoplastic resin composition can also contain to improve the intensity, heat resistance, moisture-proof of foaming body There is arbitrary crosslinking agent.Crosslinking agent is not particularly limited, can use oil-soluble, it is water miscible any one.As crosslinking agent, Such as can enumerate epoxy, oxazolines system, isocyanates system, carbodiimide system, melamine series, metal oxide system. Wherein, You Xuan oxazolines system crosslinking agent.

The addition [solid constituent (nonvolatile component)] of crosslinking agent is for example relative to thermoplastic resin (a) [solid constituent (nonvolatile component)] 100 parts by weight be 0~10 parts by weight, lower limit is preferably 0.01 parts by weight, more preferably 0.1 parts by weight, on Limit is preferably 9 parts by weight, more preferably 8 parts by weight.

In addition, the thermoplastic resin composition can also contain to improve the stability steeped obtained by foaming, film forming There is arbitrary thickener.It is not particularly limited as thickener, acrylic acid series, carbamate system, polyvinyl alcohol can be enumerated System etc..Wherein, preferred polyacrylic thickener.

The addition [solid constituent (nonvolatile component)] of thickener is for example relative to thermoplastic resin (a) [solid constituent (nonvolatile component)] 100 parts by weight be 0~10 parts by weight, lower limit is preferably 0.1 parts by weight, more preferably 0.3 parts by weight, on Limit is preferably 6 parts by weight, more preferably 3 parts by weight.

In addition, the thermoplastic resin composition can also not damaging the anticorrosive property to metal, it is close with adherend In the range of the original characteristic of conjunction property, foaming body, contain arbitrary suitable other compositions.Such a other compositions both can only contain There is a kind, two or more can also be contained.As the other compositions, for example, it can enumerate the polymer beyond thermoplastic resin (a) Composition, softening agent, antioxidant, age resistor, antirust agent, gelating agent, curing agent, plasticizer, filler, reinforcing agent, foaming agent, Fire retardant, light stabilizer, ultra-violet absorber, colouring agent (pigment, dyestuff etc.), pH adjusting agent, thermal polymerization, photopolymerization Initiator etc..

As the filler, such as can include silica, clay (mica, talcum, montmorillonite), aluminum oxide, Titanium dioxide, zinc oxide, tin oxide, zeolite, graphite, CNT, inorfil (carbon fiber, glass fibre etc.), organic fibre Dimension, metal powder (silver, copper etc.) etc..In addition, as filler, can also add piezoelectric particles (titanium oxide etc.), electroconductive particle, lead Hot particle (boron nitride etc.), organic filler (silicone powder etc.) etc..

The thermoplastic resin composition can be water-dispersion type thermoplastic resin composition, solvent-based thermal plastic resin group Compound, do not contain water and solvent thermoplastic resin composition any one.

The foaming body of the present invention can be manufactured by the way that the thermoplastic resin composition is foamed.In addition, this hair Bright foamed sheet can be by carrying out foaming and molding by the thermoplastic resin composition, being allowed to flaking and manufacture.It is used as hair Bubble method (forming method of bubble), can be using commonly used approach in the foaming and moldings such as physical method, chemical method.One As for, physical method is the gas componants such as air, nitrogen is scattered in polymer solution and is formed by mechanical mixture The method of bubble.In addition, the gas that chemical method is produced being the thermal decomposition by the foaming agent because being added in polymer substrate Body is to form abscess, the method so as to obtain foaming body.Consider from viewpoints such as environmental problems, preferably physical method.Pass through physics The bubble of method formation is generally continuous air bubbles.

As the thermoplastic resin composition of (foaming and molding) of being foamed, the thermoplastic for not containing water and solvent can be used Property resin combination, the resin solution (solvent-based thermal thermoplastic resin composition) being dissolved in thermoplastic resin in solvent, but From the viewpoint of bubble, the emulsion (water-dispersion type thermoplastic resin composition) containing thermoplastic resin is preferably used.Make For emulsion, used after can emulsion of more than two kinds be mixed.

The higher the better from the viewpoint of film forming for the solid component concentration of emulsion.The solid component concentration of emulsion is preferably More than 30 weight %, more preferably more than 40 weight %, more preferably more than 50 weight %.

In the present invention, mechanically sent out preferably via water-dispersion type thermoplastic resin composition (emulsion resin composition) is made Bubble and method that the process (process A) of alveolation makes foaming body.As sparger, it is not particularly limited, for example can be with Enumerate the devices such as high speed shear mode, mode of vibration, the spray mode of gas-pressurized.Among them, from the fine of bubble diameter Change, from the viewpoint of Large Copacity makes, preferred high speed shear mode.

Bubble when being bubbled by mechanical agitation is the bubble introducing gas (gas) in emulsion.It is used as gas Body, as long as being inactive relative to emulsion, is just not particularly limited, can enumerate air, nitrogen, carbon dioxide etc..Wherein, From the viewpoint of economy, preferred air.

It is coated on base material and is dried via emulsion resin composition obtained by alveolation will be played using the above method Process (process B), and the foamed sheet of the present invention can be obtained.As above-mentioned base material, it is not particularly limited, but can for example lifts Go out it is release-treated after plastic foil (polyethylene terephthalate film after release-treated etc.), plastic foil it is (poly- to benzene Naphthalate film etc.), heat-conducting layer (heat-conducting layer described later) etc..

In the process B, as coating method, drying means, general method can be used.Process B is preferably included： By the emulsion resin composition for the bubbles being coated on base material 50 DEG C less than 125 DEG C at a temperature of be dried Preparation drying process B1 and after preparation drying process B1 further more than 125 DEG C and master that less than 200 DEG C are dried Drying process B2.

By setting preparation drying process B1 and trunk drying process B2, it is possible to prevent temperature drastically from rising caused gas The mergingization of bubble, the rupture of bubble.For the small foamed sheet of thickness, cause bubble because of steeply rising for temperature Merge or rupture, therefore, set preparation drying process B1's significant.Temperature in preparation drying process B1 is preferably 50 DEG C Above and less than 100 DEG C.Preparation drying process B1 time is, for example, 0.5 minute~30 minutes, preferably 1 minute~15 points Clock.In addition, the temperature in trunk drying process B2 is preferably more than 130 DEG C and less than 180 DEG C.Trunk drying process B2 time is for example For 0.5 minute~30 minutes, preferably 1 minute~15 minutes.

The foaming body preferred density of the present invention is 0.2~0.7g/cm³, mean cell diameter is 10~150 μm, and dynamic is viscous The ratio of store elastic modulus and loss elastic modulus during angular frequency 1rad/s in elasticity measurement is loss angle tangent (tan δ) there is peak value more than -30 DEG C and in less than 30 DEG C of scope.Such a foaming body has HI high impact absorbability.Moreover, at this In specification, the density of so-called foaming body refers to " apparent density ".

The lower limit of the density of the foaming body is more preferably 0.21g/cm³, more preferably 0.22g/cm³, the upper limit is more excellent Elect 0.6g/cm as³, more preferably 0.5g/cm³, particularly preferably 0.4g/cm³.By making the density of foaming body be 0.2g/ cm³More than, high intensity can be maintained, by being allowed to as 0.7g/cm³Hereinafter, HI high impact absorbability can be played.In addition, by making The density of foaming body is 0.2~0.4g/cm³Scope, higher impact absorbency can be played.The density of foaming body can lead to Gas (gas) component amount crossed in emulsion resin composition of adjustment when being incorporated into mechanical agitation and be set to 0.2~0.7g/cm³ Density.

The lower limit of the mean cell diameter of the foaming body is more preferably 15 μm, and more preferably 20 μm, the upper limit is more excellent Elect 140 μm, more preferably 130 μm as.By making mean cell diameter be more than 10 μm, excellent impact can be played and inhaled The property received.In addition, by making mean cell diameter be less than 150 μm, excellent compression recovery can be obtained.Foaming body is averaged Cell diameter can by adjust surfactant species or amount, adjustment mechanical agitation when mixing speed or mixing time and It is set to 10~150 μm of scope.

Store elastic modulus and loss elasticity during angular frequency 1rad/s in the Measurement of Dynamic Viscoelasticity of the foaming body The ratio of modulus is the peak value of loss angle tangent (tan δ) as described above, it is preferred to the scope in more than -30 DEG C and less than 30 DEG C In.The lower limit of temperature range present in the peak value of the loss angle tangent is more preferably -25 DEG C, more preferably -20 DEG C, The upper limit is more preferably 20 DEG C, more preferably 10 DEG C.In the material of the peak value with more than 2 loss angle tangents Under, best at least one therein is fallen into above range.By making peak temperature be more than -30 DEG C, excellent pressure can be played Contracting restoration.In addition, by making peak temperature be less than 30 DEG C, high flexibility can be shown, excellent impact absorbing is played Property.

The peak strength (maximum) of more than -30 DEG C and the loss angle tangent (tan δ) in less than 30 DEG C of scope is from impact The higher the better from the viewpoint of absorbability, for example, more than 0.2, preferably more than 0.3.The peak strength (maximum) it is upper Limit value is, for example, 2.0.

Said, the peak temperature of the loss angle tangent (tan δ), peak strength largely contribute to hair The impact absorbency of foam.If store elastic modulus and damage during angular frequency 1rad/s in the Measurement of Dynamic Viscoelasticity of foaming body The ratio of consumption modulus of elasticity is that the peak value of loss angle tangent (tan δ) is present in more than -30 DEG C and less than 30 DEG C of scope, then The impact absorbency of foamed sheet is improved, although unclear the reasons why for this point, however can speculate be because, it is described to damage The peak value of consumption angle tangent (tan δ) is present in the scope matched with the frequency impacted.That is, due to the loss angle tangent (tan Temperature-time conversion rule that δ) can be in determination of viscoelasticity for more than -30 DEG C and less than 30 DEG C of scope, be scaled and The scope of the suitable frequency of the drop impact of works, therefore there is described damage more than -30 DEG C and in less than 30 DEG C of scope The foamed sheet of the peak temperature of angle tangent (tan δ) is consumed, its impact absorbency is improved.In addition, store elastic modulus is with putting on The repulsion that the impact energy of foamed sheet is mutually resisted, if store elastic modulus is high, impact of directly rebounding.On the other hand, bullet is lost Property modulus be the physical property that the impact energy for putting on foamed sheet is converted to heat, loss elastic modulus is higher, then more will punching Hit energy and be converted to heat, therefore absorb impact, deformation is diminished.It thereby it is assumed that, impact is converted into heat and reprimand in large quantities The small foamed sheet of power, the ratio of namely store elastic modulus and loss elastic modulus are the big foaming of loss angle tangent (tan δ) Piece, its impact absorbing rate is high.

The initial elastic modulus of the foaming body is more low better from the viewpoint of impact absorbency.The initial elastic modulus (value that slope when being strained according to 10% under 23 DEG C of environment, in the tension test that draw speed is 300mm/min is calculated) is excellent Elect 5N/mm as²Hereinafter, more preferably 3N/mm²Below.Moreover, the lower limit of the initial elastic modulus is, for example, 0.1N/mm²。

The foaming body can be formed by the way that the thermoplastic resin composition is foamed, but unexpanded state The dynamic viscoelastic of resin combination (solid content) [material for not making the thermoplastic resin composition foam and shaping] survey The ratio of store elastic modulus and loss elastic modulus during angular frequency 1rad/s in fixed is loss angle tangent (tan δ) peak Value is it is also preferred that in more than -30 DEG C and less than 30 DEG C of scope.Temperature range present in the peak value of the loss angle tangent Lower limit be more preferably -20 DEG C, more preferably -10 DEG C, the upper limit is more preferably 20 DEG C, more preferably 10 DEG C.In tool In the case of the material of peak value for having more than 2 loss angle tangents, best at least one therein is fallen into above range.The tree More than -30 DEG C of oil/fat composition (solid content) and peak strength (this of the loss angle tangent (tan δ) in less than 30 DEG C of scope Value is equivalent to by the peak strength of the loss angle tangent (tan δ) in -30 DEG C of the foaming body scopes less than 30 DEG C Divided by density (the g/cm of foaming body³) obtained by be worth) the higher the better from the viewpoint of impact absorbency.In addition, unexpanded shape The initial elastic modulus (23 DEG C, draw speed 300mm/min) of the resin combination (solid content) of state is more low better, is preferably 50N/mm²Hereinafter, more preferably 30N/mm²Below.Moreover, the lower limit of the initial elastic modulus is, for example, 0.3N/mm²。

Can be continuous air bubbles structure, separated foam structure, semicontinuous semi-independent as the bubble structure of the foaming body Any one of bubble structure.From the viewpoint of impact absorbency, preferably continuous air bubbles structure, semicontinuous semi-independent bubble knot Structure.

[foamed sheet]

The thickness of the foamed sheet of the present invention is not particularly limited, and can be selected according to purposes.For example, the thickness of foamed sheet is 30~2000 μm or so.Moreover, from being suitable for from the viewpoint of slight void, the thickness of foamed sheet is preferably 30~500 μm Scope.Its lower limit is more preferably 40 μm, and more preferably 50 μm, the upper limit is more preferably 400 μm, more preferably 300 μm. It is more than 30 μm by making the thickness of foamed sheet, can equably contains bubble, excellent impact absorbency can be played.Separately Outside, it is less than 500 μm by the thickness for making foamed sheet, can also be easily followed even for slight void.

Store elastic modulus during with regard to angular frequency 1rad/s in the Measurement of Dynamic Viscoelasticity of foregoing foaming body with The ratio of loss elastic modulus is that the peak value of loss angle tangent (tan δ) is in foaming in more than -30 DEG C and less than 30 DEG C of scope For piece, even if thickness is 30~500 μm so thin, it may have HI high impact absorbability.

Foamed sheet thickness it is big to a certain extent in the case of, impact absorbency can be by selecting Average Cell straight Footpath, density etc. are adjusted, and in the case where the thickness of foamed sheet is very small (for example, 30~200 μm of thickness), simply adjust this A little characteristics can not fully absorb impact.Because, in the case where the thickness of foamed sheet is very thin, the bubble in foaming body It can immediately crush, be disappeared by the impact buffer function of bubble because of impact.Angle in the Measurement of Dynamic Viscoelasticity of foaming body The ratio of store elastic modulus and loss elastic modulus during frequency 1rad/s is that the peak value of loss angle tangent (tan δ) is in -30 In the case of more than DEG C and in less than 30 DEG C of scope, after bubble breaking, the constituent material of foaming body can also play slow The function of hitting in a state of excitement.

In the present invention, from the viewpoint of impact absorbency, mean cell diameter (μm) and the thickness (μm) of foamed sheet Than (the former/the latter) it is preferably in 0.2~0.9 scope.Above-mentioned mean cell diameter (μm) and the thickness (μm) of foamed sheet The lower limit of ratio be preferably 0.25, more preferably 0.3, the upper limit is preferably 0.85, more preferably 0.8.

If the foamed sheet of the present invention is pasted onto on the adherend of metal foil etc., the bonding force to adherend will be with the time Passage is raised at leisure.Thus, it is possible to obtain high bonding reliability.For example, the foamed sheet of the present invention is fitted with copper foil, 80 DEG C place 1 day after to copper foil bonding force (180 ° of peel angle, draw speed 300m/ minute) be more than 2.0N/20mm, preferably For more than 2.5N/20mm, more preferably more preferably more than 3.0N/20mm, more than 3.5N/20mm.Moreover, the present invention Foamed sheet can also be bonded on plastic foil, paper, non-woven fabrics etc. in addition to copper foil (metal foil).

Moreover, (being peeled off to copper foil bonding force (initial bonding force) after the foamed sheet of the present invention is just fitted with copper foil 180 ° of angle, draw speed 300m/ minutes) for example it is preferably more than 0.03N/20mm or 0.03~1N/20mm or so (or 0.05~0.5N/20mm or so).

The foamed sheet of the present invention can also set adhesive phase (adhesive layer) in the one or both sides of foamed sheet as needed. As constitute adhesive phase adhesive, be not particularly limited, for example can be acrylic adhesive, elastomeric adhesive, Any one of silicone-based adhesive etc..In addition, in the case where setting adhesive phase, peeling liner can also be laminated on its surface Pad, the release liner protects adhesive phase in the past when in use.Due to the foamed sheet and adherend (hardware etc.) of the present invention Excellent adhesion, even if therefore be not provided with adhesive phase, can also be fixed by component etc..

The foamed sheet of the present invention can also in the market circulate as the coiling body (roll) for being wound into a roll tubular.

The foamed sheet of the present invention as it was previously stated, the compound containing the ring containing azoles, therefore with the hardware such as metal foil In the case that the state of contact is set, the corrosion of metal can be prevented for a long time.Additionally, it is possible to be due to contained in foamed sheet The compound of the ring containing azoles be transferred to interface with adjacent component (adherend), occur phase interaction with the adjacent component With, therefore bonding force raises over time.Therefore, it can not need adhesive linkage and realize it is thin layer, can be with adhesive linkage The degree of thickness ensure the thickness of other materials.Thus, for example in elec-tric-electronic equipment, as by various components or Part (such as optical component) assembles (installation) elec-tric-electronic equipment used when defined position (such as housing) and used It is useful for component, especially impact-absorbing sheet.Component (adherend) particularly at least one surface side of foamed sheet is gold It is useful in the case of metal elements (metal foil etc. such as copper foil, aluminium foil, goldleaf, silver foil).

As the optical component of (installation) can be assembled using the foamed sheet of the present invention, for example, it can enumerate and be installed on liquid Image display member in the image display devices such as crystal display, electroluminescent display, plasma scope is (particularly small The image display member of type), be installed on moving bodys such as so-called " portable phones ", " smart mobile phone " or " portable information terminal " lead to The display members such as the touch panel in the device of letter, camera or lens (especially small-sized camera or lens) etc..

[layered product]

The layered product of the present invention is the layered product (sheet layered product) of foamed sheet (foaming lamella) and heat-conducting layer.The heat conduction The thermal conductivity of layer is preferably more than 200W/mK.The thermal conductivity is the value determined according to steady state method.The thermal conductivity of heat-conducting layer is excellent Elect more than 300W/mK, more preferably more than 400W/mK as.By making the thermal conductivity of heat-conducting layer be more than 200W/mK, Excellent heat diffusivity (thermal diffusivity) can be played.The practical upper limit of thermal conductivity is, for example, 1500W/mK.

The thickness of above-mentioned heat-conducting layer can be adjusted to arbitrary suitable thickness according to purpose.The thickness of heat-conducting layer is preferably More than 5 μm, more preferably more than 7 μm.The upper limit of the thickness of heat-conducting layer is, for example, 130 μm, preferably 120 μm, further preferably For 110 μm.

As heat-conducting layer, for example, it can enumerate graphite flake, metal foil.As the material of metal foil, can for example enumerate aluminium, Gold, silver, copper etc..It is used as metal foil, preferably aluminium foil, copper foil with high far infrared reflectivity and low processing cost Deng.

As the method for making the layered product, method, the guide that (stickup) foamed sheet is transferred to heat-conducting layer can be enumerated Thermosphere has been coated with the emulsion resin composition of alveolation and drying and the method etc. for forming foaming lamella.Utilize the side of the latter The layered product that method makes embodies the bonding force of the method higher than the former.

According to the layered product of the present invention, due to foamed sheet and heat-conducting layer, therefore impact absorbency and heat diffusivity (dissipate It is hot) it is excellent.Further, since adjacent structure when bonding force and the layered product using the present invention of foamed sheet and heat conduction interlayer Bonding force between part and foamed sheet is raised over time, therefore bonding reliability is excellent.In addition, being metal in heat-conducting layer In the case of can prevent the corrosion of metal for a long time, using the present invention layered product when adjacent members be metal situation Under can prevent the corrosion of metal for a long time.Thus, for example in elec-tric-electronic equipment, as by various components or part (such as optical component) assembling (installation) the elec-tric-electronic equipment structure used at defined position (such as housing) Part, especially as useful for thermal diffusion impact-absorbing sheet.

Can be using the optical component of the layered product assembling (installation) of the present invention with the foaming of the invention can be utilized The optical component of piece assembling is identical.

[elec-tric-electronic equipment]

The elec-tric-electronic equipment of the present invention has used the foamed sheet or layered product of the invention.Such a elec-tric-electronic is set In standby, including following elec-tric-electronic equipment, for example, possesses the elec-tric-electronic equipment of display member, with by above-mentioned hair Bubble sheet or layer stack is held on the structure between the housing of the elec-tric-electronic equipment and the display member.It is used as the electrically-electricity Sub- equipment, the dress of mobile communicating such as can enumerate so-called " portable phone ", " smart mobile phone ", " portable information terminal " Put.

Embodiment

Embodiment is enumerated below to illustrate the present invention in more detail, but the present invention is not appointed by these embodiments What is limited.Moreover, unless otherwise specified, representing that " % " of content refers to weight %.Moreover, coordinating number (parts by weight) complete Portion is the value of solid constituent (nonvolatile component) conversion.

Embodiment 1

By acrylic emulsions solution (solid constituent amount 55%, ethyl acrylate-acrylic acid butyl ester-acrylonitrile copolymer (weight is than 45: 48: 7)) 100 parts by weight, aliphatic acid ammonium system surfactant (aqueous dispersions of ammonium stearate, solid constituent amount 33%) 3 parts by weight, oxazolines crosslinking agents (" EPOCROSS WS-500 " Japan catalyst company system, solid constituent amount 39%) 0.35 Parts by weight, the parts by weight of BTA sodium salt (solid constituent 40%) 1, (ethyl acrylate-acrylic acid is common for polyacrylic thickener Polymers (the weight % of acrylic acid 20), solid constituent amount 28.7%) 0.8 parts by weight disperser (" RoboMix " PRIMIX companies System) stir mixing and be allowed to alveolation.The composition, foam is coated on to the PET (poly terephthalic acids for having carried out lift-off processing Glycol ester) film (thickness：38 μm, Resins Corporation of trade name " MRF#38 " Mitsubishi system) on, dried 4.5 minutes at 70 DEG C, 140 DEG C dry 4.5 minutes, obtain thickness 130 μm, density 0.29g/cm³, 85 μm of mean cell diameter continuous air bubbles structure foaming Body (foamed sheet).

Embodiment 2

In addition to the usage amount of BTA sodium salt (solid constituent 40%) is set into 1.5 parts by weight, carry out with implementing The identical of example 1 is operated, and obtains the foaming body (foamed sheet) of thick 130 μm continuous air bubbles structure.The density of the foaming body is 0.3g/ cm³, mean cell diameter is 80 μm.

Embodiment 3

In addition to the usage amount of BTA sodium salt (solid constituent 40%) is set into 0.5 parts by weight, carry out with implementing The identical of example 1 is operated, and obtains the foaming body (foamed sheet) of thick 130 μm continuous air bubbles structure.The density of the foaming body is 0.38g/cm³, mean cell diameter is 70 μm.

Comparative example 1

In addition to not using BTA sodium salt (solid constituent 40%) completely, behaviour same as Example 1 is carried out Make, obtain the foaming body (foamed sheet) of thick 130 μm continuous air bubbles structure.The density of the foaming body is 0.43g/cm³, average bubble Bore dia is 72 μm.

<Evaluate>

To the foaming body (foamed sheet) obtained in embodiment and comparative example, following evaluation has been carried out.It the results are shown in In table 1.In table 1, the numerical value of each composition is the parts by weight that solid constituent (nonvolatile component) converts.

(mean cell diameter)

Utilize low vacuum SEM mirror (" S-3400N types SEM " Hitachi Hightech Science Systems company systems) obtain foaming body section enlarged drawing, obtain Average Cell by carrying out graphical analysis Diameter (μm).Moreover, the number of bubbles analyzed is 10~20 or so.

(density)

Foaming body (foamed sheet) is punched using 100mm × 100mm punching blade mould, the examination being punched out is determined The size of sample.In addition, determining thickness using the diameter (φ) of terminal is determined for 20mm 1/100 amesdial.Calculated according to these values Go out the volume of foaming body.

Then, the weight of foaming body is determined using more than minimum scale 0.01g counter scale.Calculated according to these values Density (the g/cm of foaming body³)。

(dynamic viscoelastic)

Drawn using the film of determination of viscoelasticity device (" ARES2KFRTN1-FCO " TA Instruments Japan company systems) Mode determination is stretched, temperature dispersion experiment is carried out when angular frequency is 1rad/s.To store elastic modulus E ' now and loss The ratio of elastic modulus E " is that the temperature (DEG C) and intensity (maximum) of the peak value of loss angle tangent (tan δ) are measured.

The temperature (DEG C) of the peak value of the loss angle tangent (tan δ) of foaming body has been recorded in " tan δ temperature " column of table 1, The intensity (maximum) of the peak value has been recorded in " tan δ maximums " column.

(initial elastic modulus)

Under 23 DEG C of environment and draw speed for 300mm/min tension test in, by 10% strain when slope calculate Initial elastic modulus (N/mm²), the initial elastic modulus is evaluated.

(bonding force)

Foaming body (the foamed sheet obtained in each embodiment and each comparative example；One side be laminated with stripping film) one Face, adhesive tape of having fitted (No.31B, day eastern electrician's company system).20mm × 100mm size is cut into, evaluation sample is used as Product.Stripping film is peeled, another face of foaming body is pasted onto as on the copper foil of adherend at 25 DEG C, makes 5Kg rollers reciprocal Once crimped.It is placed after the stipulated time under each temperature environment, taken out, after room temperature is placed 2 hours, is being peeled off 180 ° of angle, draw speed implement disbonded test under conditions of 300mm/ minutes, determine bonding force (to copper foil bonding force) (N/ 20mm)。

(copper corrosion performance experiment)

The foaming body (foamed sheet) obtained in each embodiment and each comparative example is cut into 52mm × 52mm, hand roller is used 50mm × 50mm copper foil surface is fitted in, both sides are clamped with acrylic compounds plate (67mm × 67mm × 2mm (thickness)), with folder Son is fixed (reference picture 1).Placed under (i) room temperature, 85 DEG C of (ii), (iii) 60 DEG C/95%RH each environment.Taken after 125 hours Go out, visually confirm the pollution level of the contact surface with foaming body of copper foil, evaluated according to following benchmark.And And, as reference, only copper foil is placed under above-mentioned each environment, is taken out after 125 hours, visually observes copper foil surface, Evaluated according to following benchmark.Even if, can also practical application according to purposes difference moreover, be evaluated as " △ ".

○：Do not change in copper foil

△：Copper slightly corrodes

×：Acutely, copper foil surface changes colour for the corrosion of copper

[table 1]

Table 1

In to the column of copper foil bonding force one, * destroys for foam, is in addition interfacial failure.

Industrial applicability

The foaming body and foamed sheet of the present invention is in elec-tric-electronic equipment, as by various components or part (such as optics Component etc.) assemble (installation) elec-tric-electronic equipment piece used at defined position (such as housing), especially impact It is useful for absorbing sheet.The foaming body and foamed sheet of the present invention is due to the adaptation and excellent corrosion resistance for metal, therefore Component (adherend) at least one surface side of foamed sheet is the hardware (metal such as copper foil, aluminium foil, goldleaf, silver foil Paper tinsel etc.) in the case of it is particularly useful.

The explanation of symbol

1 test film (foamed sheet), 2 copper foils, 3 acrylic compounds plates, 4 clips.

Claims (17)

1. a kind of foaming body, it is by thermoplastic resin composition's shape containing thermoplastic resin (a) and the compound (b) of the ring containing azoles Into.

2. foaming body according to claim 1, wherein, the thermoplastic resin composition also lives containing at least one kind of surface Property agent.

3. foaming body according to claim 1 or 2, wherein, the thermoplastic resin (a) is selected from acrylic polymeric At least one kind of polymer in thing, rubber, carbamate based polymer and Ethylene vinyl accetate copolymer.

4. according to foaming body according to any one of claims 1 to 3, wherein, the compound of the ring containing azoles is selected from benzo At least one kind of compound in three azole compounds and benzothiazole based compound.

5. according to foaming body according to any one of claims 1 to 4, wherein, contain azoles in the thermoplastic resin composition The content of the compound (b) of ring is 0.2~5 parts by weight relative to the parts by weight of thermoplastic resin (a) 100.

6. according to foaming body according to any one of claims 1 to 5, wherein, the thermoplastic resin composition dissipates for moisture Type thermoplastic resin composition.

7. according to foaming body according to any one of claims 1 to 6, its density is 0.2~0.7g/cm³, mean cell diameter For 10~150 μm, store elastic modulus and loss elastic modulus during angular frequency lrad/s in Measurement of Dynamic Viscoelasticity Ratio is that losstangenttanδ has peak value more than -30 DEG C and in less than 30 DEG C of scope.

8. foaming body according to claim 7, wherein, the losstangenttanδ is more than -30 DEG C and less than 30 DEG C Scope in maximum be more than 0.2.

9. according to foaming body according to any one of claims 1 to 8, wherein, under 23 DEG C of environment and draw speed is In 300mm/min tension test, initial elastic modulus is 5N/mm²Below.

10. a kind of foamed sheet, it includes foaming body according to any one of claims 1 to 9.

11. foamed sheet according to claim 10, its thickness is 30~500 μm.

12. the foamed sheet according to claim 10 or 11, wherein, fitted with copper foil and after 80 DEG C are placed 1 day, it is right Copper foil bonding force is more than 2N/20mm in the case of 180 ° of peel angle, draw speed 300m/ minutes.

13. the foamed sheet according to any one of claim 10~12, its to be formed via process A and process B, its In, the process A is the thermoplastic resin group for the water-dispersion type for making the compound (b) containing thermoplastic resin (a) and the ring containing azoles The process that compound mechanically foams, the process B is will to be applied through water-dispersion type resin combination obtained by mechanically foaming It is distributed in the process on base material and dried.

14. the foamed sheet according to any one of claim 10~13, it is used as elec-tric-electronic equipment impact absorbing Piece is used.

15. a kind of layered product, it is the layered product of foamed sheet any one of claim 10~14 and heat-conducting layer.

16. a kind of elec-tric-electronic equipment, it uses the foamed sheet or claim any one of claim 10~14 Layered product described in 15.

17. elec-tric-electronic equipment according to claim 16, it is the elec-tric-electronic equipment for possessing display member, is had Layered product described in foamed sheet or claim 15 any one of claim 10~14 is held on the elec-tric-electronic Structure between the housing of equipment and the display member.