CA2191901C - Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof - Google Patents
Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereofInfo
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- CA2191901C CA2191901C CA002191901A CA2191901A CA2191901C CA 2191901 C CA2191901 C CA 2191901C CA 002191901 A CA002191901 A CA 002191901A CA 2191901 A CA2191901 A CA 2191901A CA 2191901 C CA2191901 C CA 2191901C
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Abstract
Disclosed is a laminate structure adapted for use as a retortable packaging material, comprising: (I) a layer of polyalkylene terephthalate or polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and (II) interposed therebetween, a layer of an adhesive resin composition. The adhesive resin composition comprises 100 wt. parts of a soft polymer and 1-30 wt. parts of polyethylene partially or wholly graft modified with unsaturated carboxylic acid or its derivative. The soft polymer may be styrene elastomer alone or in combination with ethylene/.alpha.-olefin copolymer and/or ethylene/vinyl acetate copolymer. Interlaminar peeling of the laminate rarely occurs even under a high temperature filling or retort treatment.
Description
2 1 9 1 90 1 ADHESIVE RESIN COMPOSITION, LAMINATE COMPRISING
~IS COMP08ITION AS ADHESIVE LAYER, AND PROCE8S
FOR PREPARATION THEREOF
~ackqround of the Inventlon This i8 a dlvislonal appllcatlon dlvlded out of parent appllcation Serlal No. 2,022,799 flied on August 7, 1990 .
(1) Fleld of the Inventlon The present lnventlon relates to an adhesive resin composltlon and a iamlnate comprlslng thls resln as an adheslve layer. More speclflcally, the subject matter of thls appllcatlon 18 dlrected to a lamlnate comprlslng the second adheslve resln mentloned hereinunder, while the sub~ect matter of the parent applicatlon 18 dlrected to the flrst adheslve resln composltlon mentloned herelnunder and a lamlnate formed by uslng the same.
It should be noted that the "present lnventlon" ln thls speclflcatlon lncludes the sub~ect matter of both parent and this dlvlslonal appllcations. The present lnventlon relates to an adhesive resin composltlon glving an excellent adheslveness between a metal and a thermoplastic resin, and a metal/resin sheath laminate to be used for a lamlnate sheath cable, which is formed by uslng thls resin composltlon.
Furthermore, the present lnventlon relates to an adheslve resln composltlon, of whlch the adheslve force is not reduced even under contact with hlgh-temperature water, and a lamlnate having an excellent gas-barrier property and being capable of resisting a retort treatment, which ls formed by '- :
- la -uslng thls adhesive resln compositlon.
(2) Descriptlon of the Related Art An adheslve resln composltlon comprlslng three ~~ts, that 18, Q styrene resln, an ethylene/vlnyl acetate copolymer resin and a polyethylene resln graft-modifled with an unsaturated car~oxyllc acld or a derlvative thereof has been publicly known. Thls adheslve resin composltlon has an excellent adheslveness between a metal and a thermoplastlc resln and also between a polyester resln and an ethylene/vlnyl acetate copolymer, whlch are used for a packaglng material or the llke to be sub~ected a retort treatment.
Thls adheslve resln composltlon ls used for laminate sheath cable havlng a resln sheath arranged on the outer slde of a barrler materlal for a cable and a cable core, and since this lamlnate sheath cable i9 excellent ln such characteristics as mechanical properties, corrosion resistance and moisture resistance, this cable is widely used at the present.
In this laminate sheath cable, the above-mentioned adhesive resin composition is used ror bonding a metal tape composed of aluminum, copper or the like, to be used as the barrier layer, to a sheath resin composed mainly of low-density polyethylene.
The lamlnate metal tape 19 generally prepared by extrusion lamination cr a metal and a Yheath resin or bonding a metal layer to a rusion-bonding resin layer rllm and a sheath resin layer rilm. In case Or conventlonal rusion-bondlng resins, streaks are orten formed on the laminated rusion-bonding resin layer.
These streaks are rormed because of local changes Or the thickness cr the fusion-bonding resin layer and the presence Or these streaks degrades the adhesion between the metal and sheath resLn and reduces the appearance characterigticg Or the product. Moreover, cracks are rormed in a thin portion of the rusion-bonding resin=layer and even the perrormances Or the product are reduced.
In Japanese UnPx~m~n~d Patent Publication No. 61-296044, we previougly proposed a thermoplastic resin compositlon capable Or preventlng formation Or streaks in the rusion-bonding resin layer, which comprises 97 to 45 parts by weight of an ethylene/vinyl acetate copolymer, 30 to 1 parts by weight of a styrene polymer resin, 15 to 1 parts by weight of polyethylene grart-modified with an unsaturated carboxylic acid or a derivative thereor and 30 to 1 parts by weight of a monovinyl aromatic hydrocarbon/olefin block copolymer.
~hen a laminate metal tape is prepared by using this thermoplastic resin composltion as the rusion-bonding ~ 2191901 resin, streaks are not formed in the rusion bonding resin layer, but the adhesiveness between the metal and a resin sheath layer is not completely satisractory.
Accordingly, development of an adhesive resin composition which can prevent rormation of streaks in the fusion-bonding (adhesive) resin layer and can give an excellent adhesiveness between a metal and a resin sheath layer iB eagerly desired.
Although the above-mentLoned adhesive resin composition is uced ror the production Or a laminate Or a polyester resin and a gas-barrier resin to be used ror a packaging vessel or the like and shows a good adhesiveness, lr a heat treatment such a high-temperature filling treatment or a retort treatment is carried out at the production of this laminate or at the time Or eating or drinking a content in the packaging vessel, the adhesive force iB sometimes reduced by heating, resulting in peeling of the layer and reduction Or the gas permeation resistance.
As the adhesive resin composition capable Or retaining a high adhesive rorce bet~een layers Or a laminate even after a high-temperature treatment such as a high-temperature filling treatment or a retort treatment, we previously proposed in Japanese Unexamined Patent Publication No. 64-45445 an adhesive resin composition comprising (a) 95 to 50 % by weight Or an ethylene/c~-olefin copolymer having a melt flow rate Or 0.1 to 50 g/10 min, a density of o.850 to 0.900 g/cm3, an ethylene content of 75 to 95 mole% and an X-ray crystallinity lower than 30%, tb) 5 to 50 % by weight cr an ethylene/vinyl acetate copolymer having a melt flow rate Or O . 1 to 50 g/10 min and a vinyl acetate content of 5 to 40~ by weight, and (c) 1.0 to 30 ~ by weight, based on the sum of components (a) and (b), Or partially or wholly grart-modified polyethylene having a grafting ~ 21ql~1 amount Or an unsaturated carboxylic acid or a derivative thereof of 0.05 to 15 % by weight, a melt rlow rate cr 0.1 to 50 g/10 mln, a density Or 0.900 to 0.980 g/cm3 and an X-ray crystallinity of at least 30%, wherein the grafting ratio cr the composition as a whole is 0.01 to
~IS COMP08ITION AS ADHESIVE LAYER, AND PROCE8S
FOR PREPARATION THEREOF
~ackqround of the Inventlon This i8 a dlvislonal appllcatlon dlvlded out of parent appllcation Serlal No. 2,022,799 flied on August 7, 1990 .
(1) Fleld of the Inventlon The present lnventlon relates to an adhesive resin composltlon and a iamlnate comprlslng thls resln as an adheslve layer. More speclflcally, the subject matter of thls appllcatlon 18 dlrected to a lamlnate comprlslng the second adheslve resln mentloned hereinunder, while the sub~ect matter of the parent applicatlon 18 dlrected to the flrst adheslve resln composltlon mentloned herelnunder and a lamlnate formed by uslng the same.
It should be noted that the "present lnventlon" ln thls speclflcatlon lncludes the sub~ect matter of both parent and this dlvlslonal appllcations. The present lnventlon relates to an adhesive resin composltlon glving an excellent adheslveness between a metal and a thermoplastic resin, and a metal/resin sheath laminate to be used for a lamlnate sheath cable, which is formed by uslng thls resin composltlon.
Furthermore, the present lnventlon relates to an adheslve resln composltlon, of whlch the adheslve force is not reduced even under contact with hlgh-temperature water, and a lamlnate having an excellent gas-barrier property and being capable of resisting a retort treatment, which ls formed by '- :
- la -uslng thls adhesive resln compositlon.
(2) Descriptlon of the Related Art An adheslve resln composltlon comprlslng three ~~ts, that 18, Q styrene resln, an ethylene/vlnyl acetate copolymer resin and a polyethylene resln graft-modifled with an unsaturated car~oxyllc acld or a derlvative thereof has been publicly known. Thls adheslve resin composltlon has an excellent adheslveness between a metal and a thermoplastlc resln and also between a polyester resln and an ethylene/vlnyl acetate copolymer, whlch are used for a packaglng material or the llke to be sub~ected a retort treatment.
Thls adheslve resln composltlon ls used for laminate sheath cable havlng a resln sheath arranged on the outer slde of a barrler materlal for a cable and a cable core, and since this lamlnate sheath cable i9 excellent ln such characteristics as mechanical properties, corrosion resistance and moisture resistance, this cable is widely used at the present.
In this laminate sheath cable, the above-mentioned adhesive resin composition is used ror bonding a metal tape composed of aluminum, copper or the like, to be used as the barrier layer, to a sheath resin composed mainly of low-density polyethylene.
The lamlnate metal tape 19 generally prepared by extrusion lamination cr a metal and a Yheath resin or bonding a metal layer to a rusion-bonding resin layer rllm and a sheath resin layer rilm. In case Or conventlonal rusion-bondlng resins, streaks are orten formed on the laminated rusion-bonding resin layer.
These streaks are rormed because of local changes Or the thickness cr the fusion-bonding resin layer and the presence Or these streaks degrades the adhesion between the metal and sheath resLn and reduces the appearance characterigticg Or the product. Moreover, cracks are rormed in a thin portion of the rusion-bonding resin=layer and even the perrormances Or the product are reduced.
In Japanese UnPx~m~n~d Patent Publication No. 61-296044, we previougly proposed a thermoplastic resin compositlon capable Or preventlng formation Or streaks in the rusion-bonding resin layer, which comprises 97 to 45 parts by weight of an ethylene/vinyl acetate copolymer, 30 to 1 parts by weight of a styrene polymer resin, 15 to 1 parts by weight of polyethylene grart-modified with an unsaturated carboxylic acid or a derivative thereor and 30 to 1 parts by weight of a monovinyl aromatic hydrocarbon/olefin block copolymer.
~hen a laminate metal tape is prepared by using this thermoplastic resin composltion as the rusion-bonding ~ 2191901 resin, streaks are not formed in the rusion bonding resin layer, but the adhesiveness between the metal and a resin sheath layer is not completely satisractory.
Accordingly, development of an adhesive resin composition which can prevent rormation of streaks in the fusion-bonding (adhesive) resin layer and can give an excellent adhesiveness between a metal and a resin sheath layer iB eagerly desired.
Although the above-mentLoned adhesive resin composition is uced ror the production Or a laminate Or a polyester resin and a gas-barrier resin to be used ror a packaging vessel or the like and shows a good adhesiveness, lr a heat treatment such a high-temperature filling treatment or a retort treatment is carried out at the production of this laminate or at the time Or eating or drinking a content in the packaging vessel, the adhesive force iB sometimes reduced by heating, resulting in peeling of the layer and reduction Or the gas permeation resistance.
As the adhesive resin composition capable Or retaining a high adhesive rorce bet~een layers Or a laminate even after a high-temperature treatment such as a high-temperature filling treatment or a retort treatment, we previously proposed in Japanese Unexamined Patent Publication No. 64-45445 an adhesive resin composition comprising (a) 95 to 50 % by weight Or an ethylene/c~-olefin copolymer having a melt flow rate Or 0.1 to 50 g/10 min, a density of o.850 to 0.900 g/cm3, an ethylene content of 75 to 95 mole% and an X-ray crystallinity lower than 30%, tb) 5 to 50 % by weight cr an ethylene/vinyl acetate copolymer having a melt flow rate Or O . 1 to 50 g/10 min and a vinyl acetate content of 5 to 40~ by weight, and (c) 1.0 to 30 ~ by weight, based on the sum of components (a) and (b), Or partially or wholly grart-modified polyethylene having a grafting ~ 21ql~1 amount Or an unsaturated carboxylic acid or a derivative thereof of 0.05 to 15 % by weight, a melt rlow rate cr 0.1 to 50 g/10 mln, a density Or 0.900 to 0.980 g/cm3 and an X-ray crystallinity of at least 30%, wherein the grafting ratio cr the composition as a whole is 0.01 to
3 % by weight, the melt rlow rate o~ the composition as a whole is 0.1 to 50 g/10 min and the crystallinity Or the composition as a whole is lower than 35 %. In this patent publication, we also proposed a laminate comprisin~ a polyester or polycarbonate layer, an intermediate layer composed Or this adhesive resin composition and a saponiried olerin/vinyl acetate copolymer layer.
The above-mentioned adhesive resln composition has an excellent adhesiveness at normal temperature after a high-temperature treatment, but interlaminar peeling is sometimes caused in the above-mentioned laminate during a high-temperature rilling treatment or a retort treatment.
Accordingly, development Or an adhesive resin composition capable Or completely preventing occurrence Or interlaminar peeling in a laminate even under a high-temperature rilling treatment or a retort treatment is desired.
5ummary Or the Invention The present invention is to solve the above-mentioned problems of the conventional techniques, and it is a primary ob~ect Or the present invention to provide an adhesive resin composition capable cr preventing formation of streaks in a rusion-bonding resin layer and giving an excellent adhesiveness between a metal and a thermoplastic resin sheath layer, and a lamLnate rormed by using thLs adhesLve resLn composLtion.
Another ob~ect Or the present invention is to .....
: ~ ' 2191901 provide an adhesive resin composLtion having such an excellent heat-Fesistant adhesiveness at a high temperature that occurrence of interlaminar peeling in a laminate can be completely prevented even during a ~evere treatment such as a high-temperature rilling treatment or a retort treatment, while maintaining a practical adhesion strength at normal temperature arter a h~gh-temperature treatment.
Stlll another ob~ect of the present inventlon is to provide a laminate having an excellent gas permeation resistance and not causing interlamlnar peeling at a high-temperature rilling treatment or a retort treatment, which is formed by bonding a polycarbonate layer or polyalkylene terephthalate layer and a saponiried ethylene/vinyl acetate copolymer layer by using an adhesive resin composition as set forth above.
A rirst adhesive resin composition having an excellent adhesiveness between a metal and a thermoplastic resin sheath layer according to the present invention comprlses (a) 96 to ~5 parts by weight of an ethylene/vinyl acetate copolymer, (b) 30 to 1 parts by weight Or a styrene polymer resln, (c) 15 to 1 parts by welght cr polyethylene graft-modirled wlth an unsaturated carboxylic acld or a derivatlve thereof, (d) 20 to 1 parts by welght of a monovlnyl aromatlc hydrocarbon/olefin block copolymer elastomer and (e) an ethylene/~ -olefin copolymer, the total amount of components (a), (b), (c), (d) and (e) being 100 parts by welght.
1 A flrst laminate formed by using the above-mentioned first adhesive resin compositlon according to the presen~ invention comprises a layer Or a metal such as aluminum, copper or iron, a layer of a thermoplastic resin such as a polyamide, a saponiried ethylene/vinyl acetate copolymer, polyethylene or a polyester, and a layer of the flrst adheslve resln lnterposed between the two layars.
The second adheslve resln composltlon of the present lnventlon, whlch has e~cellent adheslveness between a polyester resln such as a polyalkylene terephthalate or a polycarbonate and a gas-barrler resln such as a saponlfled ethylene/vlnyl acetate copolymer, lncludes the followlng four ~-~ir-~ts-A flrst embodlment of the second adheslve composltlon comprlses 100 parts by welght of a soft polymerand 1 to 30 parts by welght of partlaliy or wholly graft-modlfled polyethylene ln whlch a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05 to 15 % by welghtl the soft polymer belng a styrene elastomer, A second : 1o~ of the second adheslve resln composltlon comprlses lbO parts by welght of a soft polymer and 1 to 30 parts by welght of partlally or wholly graft-modlfled polyethylene ln whlch a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof ls 0.05 to 15 ~ by welght, the soft polymer comprlslng (a) at least 20 ~ by welght, preferably 20 to 90 ~ by welght, of a styrene elastomer and (b) not more than 80 % by welght, preferably 80 to 10 % by weight of an ethylene/a-olefln copolymer havlng an ethylene content of 45 to 95 mole%.
A thlrd embodlment of the second adheslve resln composltlon comprlses 100 parts by welght of a soft polymer and 1 to 30 parts by welght of partlally or wholly graft-,_ ~
~ 21 91 901 modlfied polyethylene ln whlch a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05 to 15 % by welght, the soft polymer comprlslng ~a) at least 20 % by welght, preferably 20 to 90 ~ by welght, of a styrene elastomer and ~c) not more than 80 % by welght, preferably 80 to lO % by welght, of an ethylene/vlnyl acetate copolymer havlng a vlnyl acetate content of 5 tq 40 % by welght.
A fourth ~ ir-- L of the second adheslve resln composition comprlses 100 parts by welght of a soft polymer and 1 to 30 parts by welght of partlally or wholly graft-modlfled polyethylene ln Which a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05 to 15 ~ by welght, the soft polymer comprlslng ~a) at least 20 ~ by welght, preferably 20 to 80 % by welght, of a styrene elastomer, ~b) up to about 80 ~ by welght, preferably 10 to 70 ~ by welght, of an ethylene/~-olefln copolymer havlng an ethylene content of 45 to 95 mole~ and ~c) up to about 80 %
by welght, preferably 10 to 70 % by welght, of an ethylene/vlnyl acetate copolymer havlng a vlnyl acetate content of 5 to 40 ~ by welght.
The lamlnate of the present lnventlon f ormed by the second adheslve resln composltlon lncludes the followlng two embodlments.
A lamlnate of the flrst embodlment comprlses ~I) a polyalkylene terephthalate resln layer, ~II) an adheslve layer composed of a second adheslve resln composltlon as set forth above and ~III) a saponifled olefln/vlnyl acetate copolymer layer.
~ .
~ - 7a -A lamlnate of the second embodlment comprlses (I) a polycarbonate resln layer, (II) an adheslve layer composed of a aecond adheslve resln composltlon as set forth above and (III) a saponlfled olefln/vlnyl acetate copolymer layer.
Lamlnates of the flrst and second . '1-- ~8 are prepared by meltlng the respectlve reslns ~nd~r~ ,.lly ln dlfferent extruders, feedlng the melts to a dle havlng a three-layer atructure and co-extrudlng them BO that the adheslve realn composltlon 18 lnterposed between the two other resln layers, or by formlng layers of two reslns other than the adheslve resln composltlon ln advance and melt-extrudlng the adheslve resln composltlon between the two layers .
Petalled Descrlptlon of the Inventlon Adheslve resln composltlons of the present lnventlon, lamlnates formed by uslng these adhealve .
resin compositions and processes for the preparation Or these laminates will now be described.
(A) Adhesive Resin Compositions Ethylene/vinyl acetate copolymer The ethylene/vinyl acetate copolymer used in the present inventlon is a known ethylene/vinyl acetate copolymer (EVA). In general, there is used~an ethylene/vinyl acetate copolymer having a melt rlow rate ~MFR(E), ASTM D-1238, E~ Or 0.1 to 50 g/10 min, preferably 1 to 30 g~10 min, and a vinyl acetate conptent Or 5 to 40 ~ by weight, prererably 8 to 11 % by weight in case of the rirst adhesive resin composition or 10 to 35 % by welght in case Or the second adhesive resin composition. Ir an ethylene/vinyl acetate copolymer having MFR within the above-mentioned range is used, the melt viscosity is reduced, the moldability is improved and the adhesiveness is increased, and especially in the case of the second adhesive resin composition, the adhesiveness arter a retort treatment can be rurther improved.
Styrene resin The styrene polymer resin used ror the second adhesive resin composition of the present invention includes not only a homopolymer Or styrene but also polymers and copolymers Or styrene, nuclear substitution products thereor and substitution products Or styrene rormed by substitution at the ~-position Or the double bond, such as chlorostyrene, dichlorostyrene, methylstyrene, dimethylstyrene and ~-methylstyrene.
In general, in the present invention, a styrene polymer resin having a melt rlow rate ~MFR(G), ASTM D-1238, G~
Or 0.1 to 50 g/10 min, prererably 1 to 40 g/10 min, is used. Ir a styrene polymer resin having MFR (G) within the above-mentLoned range is used, an adhesive resin composition having an excellent extrusion moldability is , ~ 2 1 9 1 90 1 _ 9 _ obtained.
Grart-modified polyethylene The grart-modified polyethylene used in the present invention i8 characterized in that the grarting amount of an unsaturated carboxylic acid or a derivative thereor is 0.01 to 15 ~ by weight, preferably 0.1 to 5 by weight in case of the rirst adhesive resln composltion or 0.1 to 10 % by weight ln case Or the second adhesive resin composition, the melt flow rate (ASTM D-1238, conditlon E)ls 0.1 to 50 g/10 min, preferably 0.3 to 30 g/10 mln, the denslty is 0.900 to o.980 g/cm3, prererably 0.905 to 0.970 g/cm3, and the X-ray crystalinity 18 at least 30 %, preferably 35 to 75 %.
In thls graft polyethylene, the polyethylene i8 partially or wholly graft-modlfled. The graft-modified polyethylene can be a product formed by grart-modlrylng an ethylene/~ -olefin copolymer of ethylene wlth a mlnor amount, for example, up to 5 mole%, of at least one other ~-olefln selected from propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, l-octene and l-decene.
The graft-modifled polyethylene is obtaLned by partially or wholly graft-modifying polyethylene or an ethylene/~ -olerin copolymer with an unsaturated carboxylic acid or a derivative thereof. As the unsaturated carboxylic acid and its derivative, there can be mentioned, for example, unsaturated carboxylic acids such as acrylic acidt maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and Nadic acid~
(endocis-bicyclo~2,2,1~hept-5-ene-2,3-dicarboxylic acid), derivatives thereof such as acid halides, amides, imides, anhydrides and esters. As specific examples of the derivative, there can be mentioned malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate and glycidyl ~ 2 l 9 l 90 1 maleate. Among these compounds, an unsaturated dlcarboxyllc acld or lts anhydrlde ir preferably used, and malelc acld, Nadlc acld ~ and acld anhydrldes thereof are especlally preferably used.
For the production of a modlflcatlon product by graft copolymerizatlon of polyethylene wlth a graftlng monomer selected from the above-mentloned unsaturated carboxyllc aclds and derlvatlves, varlous known processes can be adopted. For example, there can be adopted a process ln whlch polyethylene ls melted, the graftlng monomer ls added to the melt and graft polymerlzatlon 1B carrled out, and a process ln whlch a solutlon of the graftlng monomer ln a solvent ls added and graft polymerlzatlon 18 carrled out. In each case, ln order to lncrease the graftlng efflclency of the graftlng monomer, the reactlon ls preferably carrled out ln the presence of a radlcal lnltlator. The graftlng reactlon 18 generally carrled out at a temperature of 60 to 350~C. The amount used of the radlcal lnltlator lr generally 0.001 to 1 part by welght per 100 parts by welght of polyethylene. As the radlcal lnltlator, there can be mentloned organlc peroxldes and organlc peresters such as benzoyl peroxlde, dlchlorobenzoyl peroxlde, dlcumyl peroxlde, dl-tert-butyl peroxlde, 2,5-dlmethyl-2,5-dl(pero~ob~n70ato)hexyne-3, 1-4-bls(tert-butylperoxy-lsopropyl)benzene, lauroyl peroxlde, tert-butyl peracetate, 2,5-dlmethyl-2,5-dl(tert-butylperoxy)hexyne-3, 2,5-dlmethyl-2,5-dl(tert-butylperoxyjhexane, tert-butylperbenzoate, tert-butylperphenyl acetate, tert-butyl perlsobutyrate, tert-butyl ~ , .
- lOa -per-sec-octoate, tert-butyl perplvalate and cumyl perpivalate, and other azo compounds such as azoblsisobutyrlnltrlle and dlmethyl azolsobutyrate. Among these compounds, there are preferably used dlalkyl peroxldes such as dl-tert-butyl peroxide, 2,5-dlmethyl-~ 67616-181D
.
2,5-di(tert-butylperoxy)-hexyne-3 and 1,4-bis(tert-butylperoxyisopropyl)benzene.
Monovinyl aromatic hydrocarbon/olerin black copolymer elastomer (styrene elastomer) The monovinyl aromatic hydrocarbon/olerln block copolymer elastomer (styrene elastomer) is a polymer having a linear or branched block structure having a monovinyl aromatic hydrocarbon polymer block on at least one termlnal thereof, which is represented by the general rormula of (A-B)n,(A-B ~ A' or (A-B ~ X wherein A and A' represent a monovinyl aromatic hydrocarbon polymer block, B represents an olefin polymer block, n is an integer of from 1 to 5, m is an integer Or from 2 to 7 and X represents a polyfunctional compound having a valency of m. Styrene and ~-methylstyrene are pre~erably used as the monovinyl aromatic hydrocarbon, and styrene is especially prererably used. As the olerin, there can be mentioned conjugated diolefins such as butadiene and isoprene, and ~-olerins such as ethylene, propylene and 1-butene. The polymer block formed by polymerizatlon of a con~ugated diolefln can be hydrogenated. The block B
may be composed Or a copolymer Or butadlene or lsoprene wlth styrene or ~ -methylstyrene, 80 far as olerln unlts are contalned ln a maJor amount. In the present lnvention, in the monovlnyl aromatic hydrocarbon/olefln block copolymer elastomer (d), the amount of the monovlnyl aromatic hydrocarbon polymer blocks is generally 8 to 55~ by welght and prererably 10 to 35% by weight. A block copolymer havlng monovinyl aromatic hydrocarbon polymer blocks on both of the termlnals la prererably used. These block copolymers are marketed, ror ex~mple, under tradenames of Carlflex~ TR and Krato ~ G (each being a registered trade mark for a product supplled by Shell Chemlcals~.
Ethylene/~ -olerln copolymer 2 ~ q l 9o l The ethylene/~ -olefin copolymer u3ed in the present invention is an ethylene/ ~-olerin random copolymer which is characterized in that the melt rlow rate ~MFR(E), ASTM D-1238, condition E~ i9 0.1 to 50 g/10 min, preferably 0.3 to 30 g/10 min, the density is o.850 to 0.900 g,~cm3, preferably 0.850 to 0.890 g/cm3, the ethylene content is 75 to 95 mole%, prererably 75 to 90 mole%, in case Or the second adhesive resin composition,Jor 45 to 95 mole%, preferably 45 to 90 mole%, in case Or the second adhesive composltion, and the X-ray crystallinity is lower than 30 %, preferably lower than 25~.
Ir an ethylene/~ -olerin copolymer having the above-mentioned characteristics is used, an adhesive resin composition having an excellent adhesiveness can be obtalned. Especially, in the second adhesive resin composition, the adhesiveness after a retort treatment and the adhesiveness to a polyolerin are highly improved.
An ethylene ~-olerin having 3 to 20 carbon atoms is used ag the ~-olerin constituting this ethylene/~ -olefin copolymer. As speciric examples, there can be mentioned propylene, l-butene, l-hexene, 4-methyl-1-pentene, l-octene, l-decene, l-tetradecene and l-octadecene. These ~-olerin can be used alone or in the rorm Or a mixture Or two or more Or them.
The ethylene/~ -olerin copolymer generally has a melting point (ASTM D-3418) lower than 100 C.
Mixing ratios In the rirst adhesive resin composition of the pregent invention, the ethylene/vinyl acetate copolymer (a) is used in an amount Or 96 to 45 parts by weight, prererably 85 to 50 parts by weight, the styrene polymer resin (b) is used in an amount Or 30 to 1 parts by weight, preferably 25 to 5 parts by weight, the grart-modified polyethylene (c) is used in an amount Or 15 to - ~ 2191901 1 partE by welght, preferably 10 to 2 parts by welght, the monovlnyl aromatic hydrocarbon/olefin block copolymer elastomer (d) 18 used in an amount of 20 to 1 parts by welght, preferably 18 to 3 parts by welght, and the ethylene/a-olefin copolymer (e) is used in an amount of 20 to 1 parts by weight, 18 to 3 parts by weight, per 100 parts by weight of the total amount of components la) through (e).
In the second adheslve resln compositlon of the present inventlon, the graft-modified polyethylene ls used ln an amount of 1 to 30 parts by welght, preferably 2 to 28 parts by welght, per lO0 parts by weight of the soft polymer.
In the first embodiment of the seconq adhesive resin composition, the soft polymer is a styrene elastomer In the second ~ of the second adhesive resin composition, a styrene elastomer and an ethylene/a-olefln copolymer are used ln comblnatlon as the so~t polymer.
In thls case, the soit polymer comprlses at least 20 % by weight, preferably 20 to gO % by welght, of the styrene elastomer, and up to 80 % by welght, preferably 10 to 80 % by welght, of the ethylene/a-olefln copolymer, with the provlso that the total amount of the styrene elastomer and the styrene/a-olefln copolymer is lO0 ~ by welght.
In the thlrd ~ of the second adheslve resln composition, a styrene elastomer and an ethylene/vinyl acetate copolymer are used in combination as the soft polymer. In this case, the soft polymer comprises at least 20 % by weight, preferably 20 to 90 ~ by welght, of the styrene elastomer and up to 80 % by welght, preferably lO to -.
: ~ 2191901 80 % by welght, of the ethylene/vlnyl acetate copolymer, wlth the provlso that the total amount of the styrene elastomer and the ethylene/vlnyl acetate copolymer 18 100 ~ by welght.
In the fourth . '-~ir ~ of the second adheslve resln compositlon, an ethylene/a-olefln copolymer and an ethylene/vlnyl acetate copolymer can be used together wlth the styrene elastomer as the soft polymer. In thls case, the so~t polymer comprlses at least 20 % by welght, preferably 20 to 80 % by welght, of the styrene elastomer, up to about 80 %
by welght, preferably 10 to 70 % by welght of the ethylene/a-olefln copolymer, and up to about 80 % by welght, preferably 10 to 70 % by weight, of the ethylene/vlnyl acetate copolymer, wlth the provlso that the total amount of the styrene elastomer, the ethylene/a-olefln copolymer and the ethylene/vlnyl acetate copolymer 18 lO0 % by welght.
The second adheslve resln composltlon of the present lnventlon comprlses the styrene elastomer and the graft-modlfled polyethylene as lndlspensable components, and the graftlng ratlo of the entlre composltlon 18 0.01 to 3 %
by welght, preferably 0.05 to 2.5 % ~y welght, MFR of the total composltlon 18 0.1 to 50 g/10 mln, preferably 0.2 to 40 g/10 mln, and the crystalllnlty of the total compoBltlon 1B
lower than 35 ~.
The adheslve resln composltlon of the present lnventlon 18 prepared by mlxlng the above-mentloned amounts of the above-mentloned components by known mlxlng means such as a Henschel mlxer, a V-type blender, a rlbbon blender or a tumbllng blender, or by melt-kn~ ng the above mlxture by a .
- .14a -single-screw extruder, a twln-screw extruder, a kneader or a Banbury mlxer and granulatlng or pulverlzlng the melt-kneaded mlxturè.
Addltlves customarlly used ~or thermoplastlc reslns, ~or example, a heat-reslstant stablllzer, a weatherlng stablllzer, an antlstatic agent, a lubrlcant, a sllp agent, a nùcieatlng agent, a dye or plgment and a ' ~ 2191qOl plasticizer such as a hydrocarbon oll, can be added to the adhesive resin composition of the present lnvention, ao rar as the attainment of the ob~ects Or the present inventLon is not hindered.
(B) Laminates and Process ror Preparation Thereor In the laminate rorming by using the rirst adheslve resin composition, the adhesive resin composition is interposed between a metal such as aluminum, copper or iron and a thermoplastic resin such as a polyamide, a saponiried ethylene/vinyl acetate copolymer, polyethylene, a polycarbonate or a polyester.
This laminate can be prepared, for example, according to a process in which a film having a thickness Or 10 to 200 ~m is formed from the adhesive resin composition, the film is set between adherends, that is, the metal and thermoplastic resin, and rusion bonding is carried out to erfect lamination, or a process ln which the adhesive resin composition and the thermoplastic resin as the adhered are independently melted in dirferent extruders and the melts are extruded through a multi-layer dye to errect lamination.
The laminate rormed by using the second adhesive resin composition Or the present invention comprises (I) a polyalkylene terephthalate resin or polycarbonate 2S resin layer, (II) an adhesive layer composed Or the second adhesive resin composition and (III) a saponiried olerin/vinyl acetate copolymer layer.
The la~er (I) constituting the laminate of the present invention is composed of a member selected from a polyalkylene terephthalate resin and a polycarbonate resin.
The polyester resin used is a polyester comprising units of at least one dihydroxyl compound selected rrom aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and . .
.
hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol and aromatic duhydroxyl compounds such as bisphenol, and unit3 of at least one dicarboxylic acid compound selected from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalene-dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid and undecane-dicarboxylic acid and alicyclic dicarboxylic acids such as hexahydroterephthalic acid. The polyester can be modified with a small amount Or a polyhydroxyl compound or polycarboxylic acid having a valency cr at least 3, such as a triol or a tricarboxylic acid, 80 rar as the polyester shows thermoplastic properties. As the thermoplastic polyester, there can be mentioned polyethylene terephthalate, polybutylene terephthalate and a polyethylene isophthalate/terephthalate copolymer.
The polycarbonate resin used in the present invention includes various polycarbonates and copolycarbonates obtained by reacting dihydroxyl compounds with phosgene or diphenyl carbonate according to known processes, As speciric examples Or the dihydroxyl compound, there can be mentioned hydroquinone, resorcinol, 4,4'-dihydroxy-diphenylmethane, 4,4'-dihydroxydiphenylethane,
The above-mentioned adhesive resln composition has an excellent adhesiveness at normal temperature after a high-temperature treatment, but interlaminar peeling is sometimes caused in the above-mentioned laminate during a high-temperature rilling treatment or a retort treatment.
Accordingly, development Or an adhesive resin composition capable Or completely preventing occurrence Or interlaminar peeling in a laminate even under a high-temperature rilling treatment or a retort treatment is desired.
5ummary Or the Invention The present invention is to solve the above-mentioned problems of the conventional techniques, and it is a primary ob~ect Or the present invention to provide an adhesive resin composition capable cr preventing formation of streaks in a rusion-bonding resin layer and giving an excellent adhesiveness between a metal and a thermoplastic resin sheath layer, and a lamLnate rormed by using thLs adhesLve resLn composLtion.
Another ob~ect Or the present invention is to .....
: ~ ' 2191901 provide an adhesive resin composLtion having such an excellent heat-Fesistant adhesiveness at a high temperature that occurrence of interlaminar peeling in a laminate can be completely prevented even during a ~evere treatment such as a high-temperature rilling treatment or a retort treatment, while maintaining a practical adhesion strength at normal temperature arter a h~gh-temperature treatment.
Stlll another ob~ect of the present inventlon is to provide a laminate having an excellent gas permeation resistance and not causing interlamlnar peeling at a high-temperature rilling treatment or a retort treatment, which is formed by bonding a polycarbonate layer or polyalkylene terephthalate layer and a saponiried ethylene/vinyl acetate copolymer layer by using an adhesive resin composition as set forth above.
A rirst adhesive resin composition having an excellent adhesiveness between a metal and a thermoplastic resin sheath layer according to the present invention comprlses (a) 96 to ~5 parts by weight of an ethylene/vinyl acetate copolymer, (b) 30 to 1 parts by weight Or a styrene polymer resln, (c) 15 to 1 parts by welght cr polyethylene graft-modirled wlth an unsaturated carboxylic acld or a derivatlve thereof, (d) 20 to 1 parts by welght of a monovlnyl aromatlc hydrocarbon/olefin block copolymer elastomer and (e) an ethylene/~ -olefin copolymer, the total amount of components (a), (b), (c), (d) and (e) being 100 parts by welght.
1 A flrst laminate formed by using the above-mentioned first adhesive resin compositlon according to the presen~ invention comprises a layer Or a metal such as aluminum, copper or iron, a layer of a thermoplastic resin such as a polyamide, a saponiried ethylene/vinyl acetate copolymer, polyethylene or a polyester, and a layer of the flrst adheslve resln lnterposed between the two layars.
The second adheslve resln composltlon of the present lnventlon, whlch has e~cellent adheslveness between a polyester resln such as a polyalkylene terephthalate or a polycarbonate and a gas-barrler resln such as a saponlfled ethylene/vlnyl acetate copolymer, lncludes the followlng four ~-~ir-~ts-A flrst embodlment of the second adheslve composltlon comprlses 100 parts by welght of a soft polymerand 1 to 30 parts by welght of partlaliy or wholly graft-modlfled polyethylene ln whlch a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05 to 15 % by welghtl the soft polymer belng a styrene elastomer, A second : 1o~ of the second adheslve resln composltlon comprlses lbO parts by welght of a soft polymer and 1 to 30 parts by welght of partlally or wholly graft-modlfled polyethylene ln whlch a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof ls 0.05 to 15 ~ by welght, the soft polymer comprlslng (a) at least 20 ~ by welght, preferably 20 to 90 ~ by welght, of a styrene elastomer and (b) not more than 80 % by welght, preferably 80 to 10 % by weight of an ethylene/a-olefln copolymer havlng an ethylene content of 45 to 95 mole%.
A thlrd embodlment of the second adheslve resln composltlon comprlses 100 parts by welght of a soft polymer and 1 to 30 parts by welght of partlally or wholly graft-,_ ~
~ 21 91 901 modlfied polyethylene ln whlch a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05 to 15 % by welght, the soft polymer comprlslng ~a) at least 20 % by welght, preferably 20 to 90 ~ by welght, of a styrene elastomer and ~c) not more than 80 % by welght, preferably 80 to lO % by welght, of an ethylene/vlnyl acetate copolymer havlng a vlnyl acetate content of 5 tq 40 % by welght.
A fourth ~ ir-- L of the second adheslve resln composition comprlses 100 parts by welght of a soft polymer and 1 to 30 parts by welght of partlally or wholly graft-modlfled polyethylene ln Which a graftlng amount of an unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05 to 15 ~ by welght, the soft polymer comprlslng ~a) at least 20 ~ by welght, preferably 20 to 80 % by welght, of a styrene elastomer, ~b) up to about 80 ~ by welght, preferably 10 to 70 ~ by welght, of an ethylene/~-olefln copolymer havlng an ethylene content of 45 to 95 mole~ and ~c) up to about 80 %
by welght, preferably 10 to 70 % by welght, of an ethylene/vlnyl acetate copolymer havlng a vlnyl acetate content of 5 to 40 ~ by welght.
The lamlnate of the present lnventlon f ormed by the second adheslve resln composltlon lncludes the followlng two embodlments.
A lamlnate of the flrst embodlment comprlses ~I) a polyalkylene terephthalate resln layer, ~II) an adheslve layer composed of a second adheslve resln composltlon as set forth above and ~III) a saponifled olefln/vlnyl acetate copolymer layer.
~ .
~ - 7a -A lamlnate of the second embodlment comprlses (I) a polycarbonate resln layer, (II) an adheslve layer composed of a aecond adheslve resln composltlon as set forth above and (III) a saponlfled olefln/vlnyl acetate copolymer layer.
Lamlnates of the flrst and second . '1-- ~8 are prepared by meltlng the respectlve reslns ~nd~r~ ,.lly ln dlfferent extruders, feedlng the melts to a dle havlng a three-layer atructure and co-extrudlng them BO that the adheslve realn composltlon 18 lnterposed between the two other resln layers, or by formlng layers of two reslns other than the adheslve resln composltlon ln advance and melt-extrudlng the adheslve resln composltlon between the two layers .
Petalled Descrlptlon of the Inventlon Adheslve resln composltlons of the present lnventlon, lamlnates formed by uslng these adhealve .
resin compositions and processes for the preparation Or these laminates will now be described.
(A) Adhesive Resin Compositions Ethylene/vinyl acetate copolymer The ethylene/vinyl acetate copolymer used in the present inventlon is a known ethylene/vinyl acetate copolymer (EVA). In general, there is used~an ethylene/vinyl acetate copolymer having a melt rlow rate ~MFR(E), ASTM D-1238, E~ Or 0.1 to 50 g/10 min, preferably 1 to 30 g~10 min, and a vinyl acetate conptent Or 5 to 40 ~ by weight, prererably 8 to 11 % by weight in case of the rirst adhesive resin composition or 10 to 35 % by welght in case Or the second adhesive resin composition. Ir an ethylene/vinyl acetate copolymer having MFR within the above-mentioned range is used, the melt viscosity is reduced, the moldability is improved and the adhesiveness is increased, and especially in the case of the second adhesive resin composition, the adhesiveness arter a retort treatment can be rurther improved.
Styrene resin The styrene polymer resin used ror the second adhesive resin composition of the present invention includes not only a homopolymer Or styrene but also polymers and copolymers Or styrene, nuclear substitution products thereor and substitution products Or styrene rormed by substitution at the ~-position Or the double bond, such as chlorostyrene, dichlorostyrene, methylstyrene, dimethylstyrene and ~-methylstyrene.
In general, in the present invention, a styrene polymer resin having a melt rlow rate ~MFR(G), ASTM D-1238, G~
Or 0.1 to 50 g/10 min, prererably 1 to 40 g/10 min, is used. Ir a styrene polymer resin having MFR (G) within the above-mentLoned range is used, an adhesive resin composition having an excellent extrusion moldability is , ~ 2 1 9 1 90 1 _ 9 _ obtained.
Grart-modified polyethylene The grart-modified polyethylene used in the present invention i8 characterized in that the grarting amount of an unsaturated carboxylic acid or a derivative thereor is 0.01 to 15 ~ by weight, preferably 0.1 to 5 by weight in case of the rirst adhesive resln composltion or 0.1 to 10 % by weight ln case Or the second adhesive resin composition, the melt flow rate (ASTM D-1238, conditlon E)ls 0.1 to 50 g/10 min, preferably 0.3 to 30 g/10 mln, the denslty is 0.900 to o.980 g/cm3, prererably 0.905 to 0.970 g/cm3, and the X-ray crystalinity 18 at least 30 %, preferably 35 to 75 %.
In thls graft polyethylene, the polyethylene i8 partially or wholly graft-modlfled. The graft-modified polyethylene can be a product formed by grart-modlrylng an ethylene/~ -olefin copolymer of ethylene wlth a mlnor amount, for example, up to 5 mole%, of at least one other ~-olefln selected from propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, l-octene and l-decene.
The graft-modifled polyethylene is obtaLned by partially or wholly graft-modifying polyethylene or an ethylene/~ -olerin copolymer with an unsaturated carboxylic acid or a derivative thereof. As the unsaturated carboxylic acid and its derivative, there can be mentioned, for example, unsaturated carboxylic acids such as acrylic acidt maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and Nadic acid~
(endocis-bicyclo~2,2,1~hept-5-ene-2,3-dicarboxylic acid), derivatives thereof such as acid halides, amides, imides, anhydrides and esters. As specific examples of the derivative, there can be mentioned malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate and glycidyl ~ 2 l 9 l 90 1 maleate. Among these compounds, an unsaturated dlcarboxyllc acld or lts anhydrlde ir preferably used, and malelc acld, Nadlc acld ~ and acld anhydrldes thereof are especlally preferably used.
For the production of a modlflcatlon product by graft copolymerizatlon of polyethylene wlth a graftlng monomer selected from the above-mentloned unsaturated carboxyllc aclds and derlvatlves, varlous known processes can be adopted. For example, there can be adopted a process ln whlch polyethylene ls melted, the graftlng monomer ls added to the melt and graft polymerlzatlon 1B carrled out, and a process ln whlch a solutlon of the graftlng monomer ln a solvent ls added and graft polymerlzatlon 18 carrled out. In each case, ln order to lncrease the graftlng efflclency of the graftlng monomer, the reactlon ls preferably carrled out ln the presence of a radlcal lnltlator. The graftlng reactlon 18 generally carrled out at a temperature of 60 to 350~C. The amount used of the radlcal lnltlator lr generally 0.001 to 1 part by welght per 100 parts by welght of polyethylene. As the radlcal lnltlator, there can be mentloned organlc peroxldes and organlc peresters such as benzoyl peroxlde, dlchlorobenzoyl peroxlde, dlcumyl peroxlde, dl-tert-butyl peroxlde, 2,5-dlmethyl-2,5-dl(pero~ob~n70ato)hexyne-3, 1-4-bls(tert-butylperoxy-lsopropyl)benzene, lauroyl peroxlde, tert-butyl peracetate, 2,5-dlmethyl-2,5-dl(tert-butylperoxy)hexyne-3, 2,5-dlmethyl-2,5-dl(tert-butylperoxyjhexane, tert-butylperbenzoate, tert-butylperphenyl acetate, tert-butyl perlsobutyrate, tert-butyl ~ , .
- lOa -per-sec-octoate, tert-butyl perplvalate and cumyl perpivalate, and other azo compounds such as azoblsisobutyrlnltrlle and dlmethyl azolsobutyrate. Among these compounds, there are preferably used dlalkyl peroxldes such as dl-tert-butyl peroxide, 2,5-dlmethyl-~ 67616-181D
.
2,5-di(tert-butylperoxy)-hexyne-3 and 1,4-bis(tert-butylperoxyisopropyl)benzene.
Monovinyl aromatic hydrocarbon/olerin black copolymer elastomer (styrene elastomer) The monovinyl aromatic hydrocarbon/olerln block copolymer elastomer (styrene elastomer) is a polymer having a linear or branched block structure having a monovinyl aromatic hydrocarbon polymer block on at least one termlnal thereof, which is represented by the general rormula of (A-B)n,(A-B ~ A' or (A-B ~ X wherein A and A' represent a monovinyl aromatic hydrocarbon polymer block, B represents an olefin polymer block, n is an integer of from 1 to 5, m is an integer Or from 2 to 7 and X represents a polyfunctional compound having a valency of m. Styrene and ~-methylstyrene are pre~erably used as the monovinyl aromatic hydrocarbon, and styrene is especially prererably used. As the olerin, there can be mentioned conjugated diolefins such as butadiene and isoprene, and ~-olerins such as ethylene, propylene and 1-butene. The polymer block formed by polymerizatlon of a con~ugated diolefln can be hydrogenated. The block B
may be composed Or a copolymer Or butadlene or lsoprene wlth styrene or ~ -methylstyrene, 80 far as olerln unlts are contalned ln a maJor amount. In the present lnvention, in the monovlnyl aromatic hydrocarbon/olefln block copolymer elastomer (d), the amount of the monovlnyl aromatic hydrocarbon polymer blocks is generally 8 to 55~ by welght and prererably 10 to 35% by weight. A block copolymer havlng monovinyl aromatic hydrocarbon polymer blocks on both of the termlnals la prererably used. These block copolymers are marketed, ror ex~mple, under tradenames of Carlflex~ TR and Krato ~ G (each being a registered trade mark for a product supplled by Shell Chemlcals~.
Ethylene/~ -olerln copolymer 2 ~ q l 9o l The ethylene/~ -olefin copolymer u3ed in the present invention is an ethylene/ ~-olerin random copolymer which is characterized in that the melt rlow rate ~MFR(E), ASTM D-1238, condition E~ i9 0.1 to 50 g/10 min, preferably 0.3 to 30 g/10 min, the density is o.850 to 0.900 g,~cm3, preferably 0.850 to 0.890 g/cm3, the ethylene content is 75 to 95 mole%, prererably 75 to 90 mole%, in case Or the second adhesive resin composition,Jor 45 to 95 mole%, preferably 45 to 90 mole%, in case Or the second adhesive composltion, and the X-ray crystallinity is lower than 30 %, preferably lower than 25~.
Ir an ethylene/~ -olerin copolymer having the above-mentioned characteristics is used, an adhesive resin composition having an excellent adhesiveness can be obtalned. Especially, in the second adhesive resin composition, the adhesiveness after a retort treatment and the adhesiveness to a polyolerin are highly improved.
An ethylene ~-olerin having 3 to 20 carbon atoms is used ag the ~-olerin constituting this ethylene/~ -olefin copolymer. As speciric examples, there can be mentioned propylene, l-butene, l-hexene, 4-methyl-1-pentene, l-octene, l-decene, l-tetradecene and l-octadecene. These ~-olerin can be used alone or in the rorm Or a mixture Or two or more Or them.
The ethylene/~ -olerin copolymer generally has a melting point (ASTM D-3418) lower than 100 C.
Mixing ratios In the rirst adhesive resin composition of the pregent invention, the ethylene/vinyl acetate copolymer (a) is used in an amount Or 96 to 45 parts by weight, prererably 85 to 50 parts by weight, the styrene polymer resin (b) is used in an amount Or 30 to 1 parts by weight, preferably 25 to 5 parts by weight, the grart-modified polyethylene (c) is used in an amount Or 15 to - ~ 2191901 1 partE by welght, preferably 10 to 2 parts by welght, the monovlnyl aromatic hydrocarbon/olefin block copolymer elastomer (d) 18 used in an amount of 20 to 1 parts by welght, preferably 18 to 3 parts by welght, and the ethylene/a-olefin copolymer (e) is used in an amount of 20 to 1 parts by weight, 18 to 3 parts by weight, per 100 parts by weight of the total amount of components la) through (e).
In the second adheslve resln compositlon of the present inventlon, the graft-modified polyethylene ls used ln an amount of 1 to 30 parts by welght, preferably 2 to 28 parts by welght, per lO0 parts by weight of the soft polymer.
In the first embodiment of the seconq adhesive resin composition, the soft polymer is a styrene elastomer In the second ~ of the second adhesive resin composition, a styrene elastomer and an ethylene/a-olefln copolymer are used ln comblnatlon as the so~t polymer.
In thls case, the soit polymer comprlses at least 20 % by weight, preferably 20 to gO % by welght, of the styrene elastomer, and up to 80 % by welght, preferably 10 to 80 % by welght, of the ethylene/a-olefln copolymer, with the provlso that the total amount of the styrene elastomer and the styrene/a-olefln copolymer is lO0 ~ by welght.
In the thlrd ~ of the second adheslve resln composition, a styrene elastomer and an ethylene/vinyl acetate copolymer are used in combination as the soft polymer. In this case, the soft polymer comprises at least 20 % by weight, preferably 20 to 90 ~ by welght, of the styrene elastomer and up to 80 % by welght, preferably lO to -.
: ~ 2191901 80 % by welght, of the ethylene/vlnyl acetate copolymer, wlth the provlso that the total amount of the styrene elastomer and the ethylene/vlnyl acetate copolymer 18 100 ~ by welght.
In the fourth . '-~ir ~ of the second adheslve resln compositlon, an ethylene/a-olefln copolymer and an ethylene/vlnyl acetate copolymer can be used together wlth the styrene elastomer as the soft polymer. In thls case, the so~t polymer comprlses at least 20 % by welght, preferably 20 to 80 % by welght, of the styrene elastomer, up to about 80 %
by welght, preferably 10 to 70 % by welght of the ethylene/a-olefln copolymer, and up to about 80 % by welght, preferably 10 to 70 % by weight, of the ethylene/vlnyl acetate copolymer, wlth the provlso that the total amount of the styrene elastomer, the ethylene/a-olefln copolymer and the ethylene/vlnyl acetate copolymer 18 lO0 % by welght.
The second adheslve resln composltlon of the present lnventlon comprlses the styrene elastomer and the graft-modlfled polyethylene as lndlspensable components, and the graftlng ratlo of the entlre composltlon 18 0.01 to 3 %
by welght, preferably 0.05 to 2.5 % ~y welght, MFR of the total composltlon 18 0.1 to 50 g/10 mln, preferably 0.2 to 40 g/10 mln, and the crystalllnlty of the total compoBltlon 1B
lower than 35 ~.
The adheslve resln composltlon of the present lnventlon 18 prepared by mlxlng the above-mentloned amounts of the above-mentloned components by known mlxlng means such as a Henschel mlxer, a V-type blender, a rlbbon blender or a tumbllng blender, or by melt-kn~ ng the above mlxture by a .
- .14a -single-screw extruder, a twln-screw extruder, a kneader or a Banbury mlxer and granulatlng or pulverlzlng the melt-kneaded mlxturè.
Addltlves customarlly used ~or thermoplastlc reslns, ~or example, a heat-reslstant stablllzer, a weatherlng stablllzer, an antlstatic agent, a lubrlcant, a sllp agent, a nùcieatlng agent, a dye or plgment and a ' ~ 2191qOl plasticizer such as a hydrocarbon oll, can be added to the adhesive resin composition of the present lnvention, ao rar as the attainment of the ob~ects Or the present inventLon is not hindered.
(B) Laminates and Process ror Preparation Thereor In the laminate rorming by using the rirst adheslve resin composition, the adhesive resin composition is interposed between a metal such as aluminum, copper or iron and a thermoplastic resin such as a polyamide, a saponiried ethylene/vinyl acetate copolymer, polyethylene, a polycarbonate or a polyester.
This laminate can be prepared, for example, according to a process in which a film having a thickness Or 10 to 200 ~m is formed from the adhesive resin composition, the film is set between adherends, that is, the metal and thermoplastic resin, and rusion bonding is carried out to erfect lamination, or a process ln which the adhesive resin composition and the thermoplastic resin as the adhered are independently melted in dirferent extruders and the melts are extruded through a multi-layer dye to errect lamination.
The laminate rormed by using the second adhesive resin composition Or the present invention comprises (I) a polyalkylene terephthalate resin or polycarbonate 2S resin layer, (II) an adhesive layer composed Or the second adhesive resin composition and (III) a saponiried olerin/vinyl acetate copolymer layer.
The la~er (I) constituting the laminate of the present invention is composed of a member selected from a polyalkylene terephthalate resin and a polycarbonate resin.
The polyester resin used is a polyester comprising units of at least one dihydroxyl compound selected rrom aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and . .
.
hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol and aromatic duhydroxyl compounds such as bisphenol, and unit3 of at least one dicarboxylic acid compound selected from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalene-dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid and undecane-dicarboxylic acid and alicyclic dicarboxylic acids such as hexahydroterephthalic acid. The polyester can be modified with a small amount Or a polyhydroxyl compound or polycarboxylic acid having a valency cr at least 3, such as a triol or a tricarboxylic acid, 80 rar as the polyester shows thermoplastic properties. As the thermoplastic polyester, there can be mentioned polyethylene terephthalate, polybutylene terephthalate and a polyethylene isophthalate/terephthalate copolymer.
The polycarbonate resin used in the present invention includes various polycarbonates and copolycarbonates obtained by reacting dihydroxyl compounds with phosgene or diphenyl carbonate according to known processes, As speciric examples Or the dihydroxyl compound, there can be mentioned hydroquinone, resorcinol, 4,4'-dihydroxy-diphenylmethane, 4,4'-dihydroxydiphenylethane,
4,4'-dihydroxydiphenyl-n-butane, 4,4'-dihydroxydiphenyl-heptane, 4,4'-dihydroxydiphenylphenylmethane, 4,4'-dihydroxy-diphenyl-2,2-propane (bisphenol A), 4,4'-dihydroxy-3,3'-dimethyldiphenyl-2,2'-propane, 4,4'-dihydroxy-3,3'-dlphenyldiphenyl-2,2-propane, 4,4'-dihydroxydichlorophenyl-2,2-propane, 4,4'-dihydroxydiphenyl-1,1-cyclopentane, 4,4'-dihydroxydLphenyl-1,1-cyclohexane, 4,4'-dihydroxy-., :
' 2 1 9 1 901 diphenylmethylphenylmethsne, 4,4'-diphydroxydiphenylethyl-phenylmethane, 4,4'-dihydroxydlphenyl-Z,2,Z-trichlorol,l-ethane, 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-diethoxyphenyl ether. Among these compounds, 4,4'-dihydroxy-diphenyl-2,2-propane (bisphenol) is preferably used, because the formed polycarbonate has excellent mechanical properties and transparency.
The above-mentioned adhesive resin composition is used ror the adhesive layer (II) Or the laminate Or the present invention.
The layer (III) constituting the laminate of the present invention is composed of a saponiried olefin/vinyl acetate copolymer. A saponiried olerin/vinyl acetate copolymer prepared by saponirying an olerin/vinyl acetate copolymer having an olefin content Or 15 to 60 mole%, preferably 25 to 50 moleS, to a saponiricatLon degree Or at ieast 50 %, prererably at least 90 S. Ir the olefin content is wlthin the above-mentioned range, thermal decompositlon is hardly caused and melt rormlng can be easily performed, and the drawability, water resistance and gas permeation resiatance are highly improved. Ir the saponirication degree is higher than 50 %, the gas permeation resistance is highly improved.
As the olefin to be copolymerized with vinyl acetate, there can be mentioned ethylene, propylene, 1-butene, l-hexane, 4-methyl-1-pentene, l-octane, 1-decene, 1 tetradecene and l-octadecene. Among them, ethylene is especially prererably used in view Or the mechanical stability and moldability.
For the preparation Or the laminate of the present inventlon, there can be adopted, for example, a ~ 21 ql ~01 co-extrusion process in whlch the polyalkylene terephthalate resin or polycarbonate resln, the adheslve resln composltlon and the saponlfled olefln/vlnyl acetate copolymer are melted ln dlfferent extruders, the melts are supplled to a dle havlng a multl-layer structure and the melts are co-extruded 80 that the adheslve resln composltlon forms an lntermedlate layer, or a sandwlch lamlnatlon process ln whlch the polyalkylene terephthalate resln or polycarbonate resln and the saponlfled oleflntvlnyl acetate copolymer are formed lnto layers ln advance and the adheslve resln composltlon ls melt-extruded between the two layers. In vlew of the lnterlamlner bondlng force, the co-extruslon process ls preferably adopted. The co-extruslon process includes a T-die method uslng a flat dle and an lnflatlon method uslng a clrcular dle. ~lther a slngle manlfold type uslng a black box or a multlple-manlfold type can be used as the flat dle.
Rnown dles can also be used ln the lnflatlon method.
The th1ckn~QQ of each layer of the lamlnates can be approprlately determlned accordlng to the lntended use. In general, when the lamlnate 18 used as a sheet of fllm, lt ls preferred that the thlckness of the polyalkyl terephthalate resln or polycarbonate resln layer be 0.02 to 5 mm, the thlckness of the adheslve layer be 0.01 to 1 mm and the saponlfled olefln~vlnyl acetate copolymer layer be 0.01 to 1 mm.
The lamlnate of the present lnventlon can further have a structure of (I)~II~/(III)/~II)/(I) ln whlch layers (I) are arranged on both the sldes, or a structure further : .
' - 2191901 ~ .
comprislng a polyolefin layer, for example, a structure of polypropylene/ (II)t(III)/(IIj/(I) or polyethylene/
(II)/(III)/(II)/(I).
The present invention will now be described in detail with re~erence to the ~ollowlng examples that by no means limit the scope of the invention.
Exam~le 1 ~igh-density polyethylene (Hizex* supplied by Mitsui Petrochemical Industrles, Ltd.; MFR (E) - 5.5 g/10 min) was reacted with maleic anhydride to obtaln graft-modified polyethylene having a maleic anhydrlde content of 0.5 % by welght, MFR (E) of 3.0 g/10 min and a gel content lower than 0.1%.
To 5 parts by weight of the graft-modified polyethylene were added 60 parts by weight of an ethylene/vinyl acetate copolymer (vinyl acetate content = 10%
by welght, MFR (E) - 9.0 g/10 mln~ hereinafter referred to as "EVA"), 20 parts by weight of polystyrene (supplied under trademark "Denka Styrol GP200) by Denki Kagàku Kogyo, MFR (G) - 25 g/10 min~ hereinafter referred to as "PS"), 10 parts by weight of a polybutadiene block-hyd-ou~na~ed polystyrene/polybutadiene/polystyrene block copolymer (supplied under trademark "Krayton G1652" by 8hell Chemicala, styrene content ~ 29% by weight) and 5 parts by weight of an ethylene/propylene copolymer [MFR (E) - 1.0 g/10 min, ethylene content - 80 mole%, X-ray crystallinity = 5%, denslty = 0.870 g/cm ], and the mixture was melt-kneaded and ~Trade-mark -' ~ 219l~01 - l9a -granulated by using an extruder provlded wlth a Dulmage screw havlng a diameter of 40 mm to obtaln a composltlon (1).
The nht~lnPd composltlon (1) was melted at 200~ and formed lnto a press sheet havlng a thlckness of 3 mm by uslng a composltlon moldlng machlne. The physlcal propertles (MFR
and the denslty) of the press sheet were determlned. The nht~1n~ results are shown ln Table 1.
h fuslon-bondlng fllm havlng a thlckness of 50 ~m was formed from the composltlon (1) by uslng a moldlng machlne provlded wlth a T-dle havlng a dlameter of 30 mm, ' 67616-181D
.: . ~ ,.; ~.. .
21 q 1 901 . . .
and the presence or absence of streaks on the formed film was checked. By using this fusion-bonding film, an aluminum foil was bonded to a polyethylene sheet under conditions described below to obtain a laminate.
(Structure) A foil/film of composition (l)/polyethylene sheet A foil: 200 ~m in thickness, 10 mm in width and 15 cm in length Composition (1) film: 50 ,um in thickness, 25 mm in width and 15 cm in length Polyethylene sheet: 2 mm in thickness, 25 mm in width and 15 cm in length (Bonding Conditions) Temperature: 200~C
Pressure: 6 kg/cm2 Time: 3 minutes A test piece having a width of 10 mm and a length of 15 cm for measuring the bonding strength was cut out from the laminate by using a knife, and the 180~ peel strength was measured at a pulling speed of 200 mm/min.
The obtained results are shown in Table 2.
Example 2 To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 70 parts by weight of EVA, 10 parts by weight of PS, 10 parts by weight of ICrayton G and 5 parts by weight of the ethylene/propylene copolymer, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (2), The physical properties (MFR and the density~ of a press sheet of the obtained composition (2) are shown in Table 1.
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50 ,um was ., ~ .,-.
2 1 ~ 1 ~0 1 formed from the composition (2) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180 peel strength was measured.
The obtained results are shown in Table 2.
Example 3 To 10 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 60 parts by weight of EVA, 15 parts by weight of PS, 5 parts by weight of Krayton G and 10 parts by weight of an ethylene/propylene copolymer, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (3).
The physical properties (MFR and the density) of a press sheet of the obtained composition (3) are shown in Table 1.
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50,um was formed from the composition (3) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180 peel strength was measured.
The obtained results are shown in Table 2.
Example 4 To 5 parts by weight of the maLeic anhydride-grafted high-density polyethylene used in Example 1 were added 65 parts by weight of EVA, lS parts by weight of PS, 10 parts by weight of Krayton G and 5 parts by weight of an ethylene/butene copolymer ~MFR (E) = 3.5 g/10 min, ethylene content = 85 mole%, crystallinity = 15%, density = 0.885 g/cm ~, and the mixture wa5 melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (4).
The physical properties (MFR and the density) of a press sheet Qf the obtained composition (4) are shown in ..:
21 q 1 qOl .
Table 1.
In the same manner as described ln Example 1, a fusion-bonding film having a thickness of 50 ~m was formed'from the composition (4) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative Example 1 =
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 80 parts by weight of EVA, 15 parts by weight of PS and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition
' 2 1 9 1 901 diphenylmethylphenylmethsne, 4,4'-diphydroxydiphenylethyl-phenylmethane, 4,4'-dihydroxydlphenyl-Z,2,Z-trichlorol,l-ethane, 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-diethoxyphenyl ether. Among these compounds, 4,4'-dihydroxy-diphenyl-2,2-propane (bisphenol) is preferably used, because the formed polycarbonate has excellent mechanical properties and transparency.
The above-mentioned adhesive resin composition is used ror the adhesive layer (II) Or the laminate Or the present invention.
The layer (III) constituting the laminate of the present invention is composed of a saponiried olefin/vinyl acetate copolymer. A saponiried olerin/vinyl acetate copolymer prepared by saponirying an olerin/vinyl acetate copolymer having an olefin content Or 15 to 60 mole%, preferably 25 to 50 moleS, to a saponiricatLon degree Or at ieast 50 %, prererably at least 90 S. Ir the olefin content is wlthin the above-mentioned range, thermal decompositlon is hardly caused and melt rormlng can be easily performed, and the drawability, water resistance and gas permeation resiatance are highly improved. Ir the saponirication degree is higher than 50 %, the gas permeation resistance is highly improved.
As the olefin to be copolymerized with vinyl acetate, there can be mentioned ethylene, propylene, 1-butene, l-hexane, 4-methyl-1-pentene, l-octane, 1-decene, 1 tetradecene and l-octadecene. Among them, ethylene is especially prererably used in view Or the mechanical stability and moldability.
For the preparation Or the laminate of the present inventlon, there can be adopted, for example, a ~ 21 ql ~01 co-extrusion process in whlch the polyalkylene terephthalate resin or polycarbonate resln, the adheslve resln composltlon and the saponlfled olefln/vlnyl acetate copolymer are melted ln dlfferent extruders, the melts are supplled to a dle havlng a multl-layer structure and the melts are co-extruded 80 that the adheslve resln composltlon forms an lntermedlate layer, or a sandwlch lamlnatlon process ln whlch the polyalkylene terephthalate resln or polycarbonate resln and the saponlfled oleflntvlnyl acetate copolymer are formed lnto layers ln advance and the adheslve resln composltlon ls melt-extruded between the two layers. In vlew of the lnterlamlner bondlng force, the co-extruslon process ls preferably adopted. The co-extruslon process includes a T-die method uslng a flat dle and an lnflatlon method uslng a clrcular dle. ~lther a slngle manlfold type uslng a black box or a multlple-manlfold type can be used as the flat dle.
Rnown dles can also be used ln the lnflatlon method.
The th1ckn~QQ of each layer of the lamlnates can be approprlately determlned accordlng to the lntended use. In general, when the lamlnate 18 used as a sheet of fllm, lt ls preferred that the thlckness of the polyalkyl terephthalate resln or polycarbonate resln layer be 0.02 to 5 mm, the thlckness of the adheslve layer be 0.01 to 1 mm and the saponlfled olefln~vlnyl acetate copolymer layer be 0.01 to 1 mm.
The lamlnate of the present lnventlon can further have a structure of (I)~II~/(III)/~II)/(I) ln whlch layers (I) are arranged on both the sldes, or a structure further : .
' - 2191901 ~ .
comprislng a polyolefin layer, for example, a structure of polypropylene/ (II)t(III)/(IIj/(I) or polyethylene/
(II)/(III)/(II)/(I).
The present invention will now be described in detail with re~erence to the ~ollowlng examples that by no means limit the scope of the invention.
Exam~le 1 ~igh-density polyethylene (Hizex* supplied by Mitsui Petrochemical Industrles, Ltd.; MFR (E) - 5.5 g/10 min) was reacted with maleic anhydride to obtaln graft-modified polyethylene having a maleic anhydrlde content of 0.5 % by welght, MFR (E) of 3.0 g/10 min and a gel content lower than 0.1%.
To 5 parts by weight of the graft-modified polyethylene were added 60 parts by weight of an ethylene/vinyl acetate copolymer (vinyl acetate content = 10%
by welght, MFR (E) - 9.0 g/10 mln~ hereinafter referred to as "EVA"), 20 parts by weight of polystyrene (supplied under trademark "Denka Styrol GP200) by Denki Kagàku Kogyo, MFR (G) - 25 g/10 min~ hereinafter referred to as "PS"), 10 parts by weight of a polybutadiene block-hyd-ou~na~ed polystyrene/polybutadiene/polystyrene block copolymer (supplied under trademark "Krayton G1652" by 8hell Chemicala, styrene content ~ 29% by weight) and 5 parts by weight of an ethylene/propylene copolymer [MFR (E) - 1.0 g/10 min, ethylene content - 80 mole%, X-ray crystallinity = 5%, denslty = 0.870 g/cm ], and the mixture was melt-kneaded and ~Trade-mark -' ~ 219l~01 - l9a -granulated by using an extruder provlded wlth a Dulmage screw havlng a diameter of 40 mm to obtaln a composltlon (1).
The nht~lnPd composltlon (1) was melted at 200~ and formed lnto a press sheet havlng a thlckness of 3 mm by uslng a composltlon moldlng machlne. The physlcal propertles (MFR
and the denslty) of the press sheet were determlned. The nht~1n~ results are shown ln Table 1.
h fuslon-bondlng fllm havlng a thlckness of 50 ~m was formed from the composltlon (1) by uslng a moldlng machlne provlded wlth a T-dle havlng a dlameter of 30 mm, ' 67616-181D
.: . ~ ,.; ~.. .
21 q 1 901 . . .
and the presence or absence of streaks on the formed film was checked. By using this fusion-bonding film, an aluminum foil was bonded to a polyethylene sheet under conditions described below to obtain a laminate.
(Structure) A foil/film of composition (l)/polyethylene sheet A foil: 200 ~m in thickness, 10 mm in width and 15 cm in length Composition (1) film: 50 ,um in thickness, 25 mm in width and 15 cm in length Polyethylene sheet: 2 mm in thickness, 25 mm in width and 15 cm in length (Bonding Conditions) Temperature: 200~C
Pressure: 6 kg/cm2 Time: 3 minutes A test piece having a width of 10 mm and a length of 15 cm for measuring the bonding strength was cut out from the laminate by using a knife, and the 180~ peel strength was measured at a pulling speed of 200 mm/min.
The obtained results are shown in Table 2.
Example 2 To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 70 parts by weight of EVA, 10 parts by weight of PS, 10 parts by weight of ICrayton G and 5 parts by weight of the ethylene/propylene copolymer, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (2), The physical properties (MFR and the density~ of a press sheet of the obtained composition (2) are shown in Table 1.
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50 ,um was ., ~ .,-.
2 1 ~ 1 ~0 1 formed from the composition (2) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180 peel strength was measured.
The obtained results are shown in Table 2.
Example 3 To 10 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 60 parts by weight of EVA, 15 parts by weight of PS, 5 parts by weight of Krayton G and 10 parts by weight of an ethylene/propylene copolymer, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (3).
The physical properties (MFR and the density) of a press sheet of the obtained composition (3) are shown in Table 1.
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50,um was formed from the composition (3) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180 peel strength was measured.
The obtained results are shown in Table 2.
Example 4 To 5 parts by weight of the maLeic anhydride-grafted high-density polyethylene used in Example 1 were added 65 parts by weight of EVA, lS parts by weight of PS, 10 parts by weight of Krayton G and 5 parts by weight of an ethylene/butene copolymer ~MFR (E) = 3.5 g/10 min, ethylene content = 85 mole%, crystallinity = 15%, density = 0.885 g/cm ~, and the mixture wa5 melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (4).
The physical properties (MFR and the density) of a press sheet Qf the obtained composition (4) are shown in ..:
21 q 1 qOl .
Table 1.
In the same manner as described ln Example 1, a fusion-bonding film having a thickness of 50 ~m was formed'from the composition (4) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative Example 1 =
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 80 parts by weight of EVA, 15 parts by weight of PS and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition
(5)-The physical properties (MFR and the density) of apress sheet of the obtained composition (5) are shown in Table 1.
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50 ~m was formed from the composition (5) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained resultg are shown in Table 2.
Comparative Example 2 ~ . . .
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 70 parts by weight of EVA, 15 parts by weight of PS and 10 parts by weight of Krayton G, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (6).
The physical properties (MFR and the density) of a press sheet of the obtained composition (6) are shown in Table L.
21 9 l 901 In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50,um was formed from the composition (6) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative E~a~ple 3 _ .. .
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in ExampLe 1 were added 70 parts by weight of EVA, 15 parts by weight of PS and 10 parts by weight of the ethylene/propylene copolymer, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (7)-The physical properties (MFR and the density) of a press sheet oi' the obtained composition (7) are shown in Table 1.
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50,um was formed from the composition (7) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative Example 4 ~ .
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 60 parts by weight of EVA, lS parts by weight of PS, 10 parts by weight of high-density polyethylene ~MFR (E) =
8.2 g/10 min, density = 0.965 g/cm3, crystallinity =
81~ J and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (8).
The physical properties (MFR and the density) of a ~ - 24 -press sheet of the obtained composition (8) are shown in Table l.
In the same manner as described in Example l, a fusion-bonding film having a thickness of SO~um was formed from the composition (8) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
1 0 = = =~
Table 1 MOa~Ut Example Example Example Example Compara- Compara- Compara- Compara-Method 1 2 3 4 tive tive tive tive . Example Example Example ~xample ., 1 2 3 4 MFR(E) (g/lOmin) ASTM D 1238 5.2 4.5 6.8 6.4 7.4 5.2 5.9 6.5 Density (g/cm3) ASTM D 1505 0.94 0.94 0.94 0.94 0.95 0.94 0-94 ~-95 't Strain at Yield Point (kg/cm2) ASTM D 638 ~ 74 - - 86 Tensile Force at Break Point (kg/cm2) ASTM D 638 97 110 100 99 64 130 96 103 Elongation O
(between bench marks) (%) ASTM D 638490 500 490 530 190 500 510 430 Shore Hardness(D) ASTM D 2240 48 45 46 49 48 44 43 48 Vicat Softening Point ( C) ASTM D 1525 64 62 63 65 72 69 64 72 2 1 9 ~ 90 1 .
Table 2 .
Formation 180 Peel Strength (kg/10 mm) Or streaks (bondin~ temperature = 200 C) Example 1 O 5.2 Example Z O 4 9 Example 3 O 5.2 Example 4 O 5.1 Comparative Example 1 X 5.1 Comparative Example 2 O 3.0 Comparative Example 3 X 4.0 Comperative Example 4 O 2.5 Note O : not observed X : observed . .
21 91 9~1 ~xamPle 5 A 5-layer sheet was formed unde} conditions described below by uslng a compo~ition (1) comprising 100 parts by welght of a ~tyrene elastomer (Rrayton* G 1652 supplied by 6hell Chemical~; hereinafter referred to as "6EBS") and 10 parts by welght of maleic anhydride-~rafted modified polyethylene (MFR = 1.0 g/10 min, density ~ 0.925 g/cm , crystallinity - 52%, butene content 3.6 mole~, maleic anhydride grafting amount ~ 1.0 g/100 g of polymer~
hereinafter referred to as "MAH-PE-l"), polycarbonate (Panlite* L-1250 supplied by Tei~in Kasei~ hereinafter referred to as "PC"), a saponified ethylene/vlnyl acetate copolymer (Kuraray Eval* EP-F supplled by Kuraray, MFR - 1.3 g/10 min, density ~ 1.19 g/cm3, ethylene content 32 mole~, herelnafter referred to as "EVOH"), and polypropylene (Hipol*
F 401 supplied by Mitsui Petrochemical Industries, Ltd.
herelnafter referred to as "PP").
6heet structure-PC/ ( 1 ) /eVOH/ ( 1 ) /PP20 Layer thickness (~m):
Extruders.
40-mm screw dlameter extruder, 260OC ~for PC) 30-mm screw diameter extruder, 250~C [for (1)]
30-mm screw dlameter extruder, 210~C (for EVOH) 40-mm screw dlameter extruder, 230~C (for PP) Wlth respect to the obtalned 5-layer sheet, the *Trade-mark ~ 2 l q l 901 - 27a -interfaclal bonding strength (FPC, g~l5 mm) between the layer ~f 11) and the EVOH layer and the lnterfacial bondlng strength ~FEVOH, g/15 mm~ between the FVOH layer and the layer o~ (1) were measured at a peeling atmosphere temperature of 23 or 80~C and a peeling speed oi 300 mm/min according to the T-peel test.
me sheet was su~iected to a retort treatment at .
, ~ - 28 -131~C for 30 minutes. Then, the T-peel test was carried out under the same conditions as described above.
The obtained results are shown in Table 3.
Example 6 ==
A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~2) comprising 75 parts by weight of SEBS, 25 parts by weight of an ethylene/propylene random copolymer (MFR = 1.0 g/10 min, ethylene content = 80 mole%, density = 0.865 g/cm3, crystallinity = 4~; hereinafter referred to as "EPR-l") and 10 parts by weight of MAH-PE-l was used instead of the composition (l) used in Example 5.
The obtained results are shown in Table 3.
Then, a 5-layer sheet was formed by using the composition (2), the above-mentioned EVOH, polyethylene terephthalate (formed by adding a crystallization promoter to Jl35 supplied by Mitsui Pet; hereinafter referred to as "PET") and PP under conditions described below.
Sheet structure:
PET/(2)/EVOH/(2)/PP
Layer thicknesses (,um):
Extruders:
40-mm screw diameter extruder, 280~C (for PET) 30-mm screw diameter extruder, 250~C (for (2)) 30-mm screw diameter extruder, 210~C (for EVOH) 40-mm screw diameter extruder, 230~C (for PP) With respect to the obtained sheet, the interfacial bonding strength (FPET, g/15 mm) between the PET layer and the layer of (2) and the interfacial bonding strength (FEVOH, g/15 mm) between the EVOH layer and the layer of (2) were measured under the same conditions as described above with respect to PC.
:. , . ,~ .
2l q 1 ~0 1 .
The obtained results are shown in Table 4.
Example 7 _ _. ......................... .. . -A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 6 except that a composition (3) comprlsing 80 parts by weight of SEBS, 20 parts by weight of an ethylene/vinyl acetate copolymer (MFR = 2.5 g/10 min, vinyl acetate content = 25% by weight; hereinafter referred to as "EVA-1") and 10 parts by weight of MAH-PE-l was used instead of the composition (2) used in Example 6.
The obtained results are shown in Tables 3 and 4.
Example 8 ~
A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 6 except that a composition (4) comprising 40 parts by weight of SEBS, 45 parts by weight of an ethylene/l-butene random copolymer (MFR = 3.5 g/10 min, ethylene content = 89 moLe~, density = 0.885 g/cm3, crystallinity = 15~ hereinafter referred to as "EBR-l"), 15 parts by weight of EVA-l and 20 parts by weight of MAH-PE-l was used instead of the composition (2) used in Example 6.
The obtained results are shown in Tables 3 and 4.
Example 9 , . . .~-----=~-= - -A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition (5) comprising 20 parts by weight of SEBS, 60 parts by weight of EBR-l, 20 parts by weight of EVA-l and 10 partg by weight of MAH-PE-l was used instead of the composition (1) used in Example 5.
The obtained results are 3hown in Table 3.
Example 10 _r:- ' ' ' ' ' '' ~ ' A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as descrlbed in Example 5 except that a composition (6) comprising 60 parts by weight of SEBS, 20 parts by weight of E8R-1, 20 parts by ,. ..
weight of EVA-l and 10 parts by weight of MAH-PE-l was used instead of the composition (1) used in Example 5.
The obtained results are shown in Table 3.
Comparative Example 5 A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~7) comprising 100 parts by weight of EBR-l and 10 parts by weight of MAH-PE-l was used instead of the composition ~1) used in Example 5.
The obtained results are shown in Table 3.
Comparat~ve Example 6 . --A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~8) comprising 85 parts by weight of EBR-l, 15 parts by weight of EVA-l and 10 parts by weight of MAH-PE-l was used instead of the composition ~1) used in Example 5.
The obtained results are shown in Table 3.
Comparative Example 7 A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~9) comprising 40 parts by weight of SEBS, 45 parts by weight of EBR-l and 15 parts by weight of EVA-l was used instead of the composition ~1) used in Example 5.
The obtained results are shown in Table 3.
Table 3 Recipe (parts hy PC/EVOH Multi-Layer Sheet weight) of FPC (g/15 mmwidth) FEVOH (g/15 mmwidth) Composition 23 C 80 C Z3 C atmos- 23 C 80 C 23 C atmos-atmosphere atmosphere phere after atmosphere atmosphere phere after retort retort treatment treatment Example 5 SEBS 100 940 920 390 690 630 350 MAH-PE-1 10 Example 6 SEBS 75 1250 930 860 830 720 790 EPR-1 25 Example 7 EvAS1 20 1190 1010 750 45~ 410 440 MAH-PE-1 lC
Example 8 SEBS 40 860 440 590 450 400 440 EBR-1 45 MAH-PE-1 20 ~
Example 9 SEBS 20 690 350 810 520 370 500 ~
Example 10 SEBS 60 830 670 570 39~ 320 410 Comparative EBR-1 100 910 180 110 1300 210 1030 Example 5 MAH-PE-l 10 Comparctive EBR-1 ô5 1600 120 1390 460 170 450 Example 6 EVA-1 1~
Comparative SEBS 40 750 610 430 90 50 10 Example 7 EBR-1 45 Table 4 Recipe (parts by PET/EVOH Multi-Layer Sheet weight) of FPET (g/15mm w1dth) FEVOH (g/15mm width) Composition 23 C 80 C 23 C atmos- 23 C 80 C 23 C atmos-atmosphere atmosphere phere after atmosphere atmosphere phere after retort retort treatment trea~ment Example SEBS 75 960 890 880 810 700 800
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50 ~m was formed from the composition (5) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained resultg are shown in Table 2.
Comparative Example 2 ~ . . .
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 70 parts by weight of EVA, 15 parts by weight of PS and 10 parts by weight of Krayton G, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (6).
The physical properties (MFR and the density) of a press sheet of the obtained composition (6) are shown in Table L.
21 9 l 901 In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50,um was formed from the composition (6) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative E~a~ple 3 _ .. .
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in ExampLe 1 were added 70 parts by weight of EVA, 15 parts by weight of PS and 10 parts by weight of the ethylene/propylene copolymer, and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (7)-The physical properties (MFR and the density) of a press sheet oi' the obtained composition (7) are shown in Table 1.
In the same manner as described in Example 1, a fusion-bonding film having a thickness of 50,um was formed from the composition (7) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative Example 4 ~ .
To 5 parts by weight of the maleic anhydride-grafted high-density polyethylene used in Example 1 were added 60 parts by weight of EVA, lS parts by weight of PS, 10 parts by weight of high-density polyethylene ~MFR (E) =
8.2 g/10 min, density = 0.965 g/cm3, crystallinity =
81~ J and the mixture was melt-kneaded and granulated in the same manner as described in Example 1 to obtain a composition (8).
The physical properties (MFR and the density) of a ~ - 24 -press sheet of the obtained composition (8) are shown in Table l.
In the same manner as described in Example l, a fusion-bonding film having a thickness of SO~um was formed from the composition (8) and the presence or absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
1 0 = = =~
Table 1 MOa~Ut Example Example Example Example Compara- Compara- Compara- Compara-Method 1 2 3 4 tive tive tive tive . Example Example Example ~xample ., 1 2 3 4 MFR(E) (g/lOmin) ASTM D 1238 5.2 4.5 6.8 6.4 7.4 5.2 5.9 6.5 Density (g/cm3) ASTM D 1505 0.94 0.94 0.94 0.94 0.95 0.94 0-94 ~-95 't Strain at Yield Point (kg/cm2) ASTM D 638 ~ 74 - - 86 Tensile Force at Break Point (kg/cm2) ASTM D 638 97 110 100 99 64 130 96 103 Elongation O
(between bench marks) (%) ASTM D 638490 500 490 530 190 500 510 430 Shore Hardness(D) ASTM D 2240 48 45 46 49 48 44 43 48 Vicat Softening Point ( C) ASTM D 1525 64 62 63 65 72 69 64 72 2 1 9 ~ 90 1 .
Table 2 .
Formation 180 Peel Strength (kg/10 mm) Or streaks (bondin~ temperature = 200 C) Example 1 O 5.2 Example Z O 4 9 Example 3 O 5.2 Example 4 O 5.1 Comparative Example 1 X 5.1 Comparative Example 2 O 3.0 Comparative Example 3 X 4.0 Comperative Example 4 O 2.5 Note O : not observed X : observed . .
21 91 9~1 ~xamPle 5 A 5-layer sheet was formed unde} conditions described below by uslng a compo~ition (1) comprising 100 parts by welght of a ~tyrene elastomer (Rrayton* G 1652 supplied by 6hell Chemical~; hereinafter referred to as "6EBS") and 10 parts by welght of maleic anhydride-~rafted modified polyethylene (MFR = 1.0 g/10 min, density ~ 0.925 g/cm , crystallinity - 52%, butene content 3.6 mole~, maleic anhydride grafting amount ~ 1.0 g/100 g of polymer~
hereinafter referred to as "MAH-PE-l"), polycarbonate (Panlite* L-1250 supplied by Tei~in Kasei~ hereinafter referred to as "PC"), a saponified ethylene/vlnyl acetate copolymer (Kuraray Eval* EP-F supplled by Kuraray, MFR - 1.3 g/10 min, density ~ 1.19 g/cm3, ethylene content 32 mole~, herelnafter referred to as "EVOH"), and polypropylene (Hipol*
F 401 supplied by Mitsui Petrochemical Industries, Ltd.
herelnafter referred to as "PP").
6heet structure-PC/ ( 1 ) /eVOH/ ( 1 ) /PP20 Layer thickness (~m):
Extruders.
40-mm screw dlameter extruder, 260OC ~for PC) 30-mm screw diameter extruder, 250~C [for (1)]
30-mm screw dlameter extruder, 210~C (for EVOH) 40-mm screw dlameter extruder, 230~C (for PP) Wlth respect to the obtalned 5-layer sheet, the *Trade-mark ~ 2 l q l 901 - 27a -interfaclal bonding strength (FPC, g~l5 mm) between the layer ~f 11) and the EVOH layer and the lnterfacial bondlng strength ~FEVOH, g/15 mm~ between the FVOH layer and the layer o~ (1) were measured at a peeling atmosphere temperature of 23 or 80~C and a peeling speed oi 300 mm/min according to the T-peel test.
me sheet was su~iected to a retort treatment at .
, ~ - 28 -131~C for 30 minutes. Then, the T-peel test was carried out under the same conditions as described above.
The obtained results are shown in Table 3.
Example 6 ==
A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~2) comprising 75 parts by weight of SEBS, 25 parts by weight of an ethylene/propylene random copolymer (MFR = 1.0 g/10 min, ethylene content = 80 mole%, density = 0.865 g/cm3, crystallinity = 4~; hereinafter referred to as "EPR-l") and 10 parts by weight of MAH-PE-l was used instead of the composition (l) used in Example 5.
The obtained results are shown in Table 3.
Then, a 5-layer sheet was formed by using the composition (2), the above-mentioned EVOH, polyethylene terephthalate (formed by adding a crystallization promoter to Jl35 supplied by Mitsui Pet; hereinafter referred to as "PET") and PP under conditions described below.
Sheet structure:
PET/(2)/EVOH/(2)/PP
Layer thicknesses (,um):
Extruders:
40-mm screw diameter extruder, 280~C (for PET) 30-mm screw diameter extruder, 250~C (for (2)) 30-mm screw diameter extruder, 210~C (for EVOH) 40-mm screw diameter extruder, 230~C (for PP) With respect to the obtained sheet, the interfacial bonding strength (FPET, g/15 mm) between the PET layer and the layer of (2) and the interfacial bonding strength (FEVOH, g/15 mm) between the EVOH layer and the layer of (2) were measured under the same conditions as described above with respect to PC.
:. , . ,~ .
2l q 1 ~0 1 .
The obtained results are shown in Table 4.
Example 7 _ _. ......................... .. . -A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 6 except that a composition (3) comprlsing 80 parts by weight of SEBS, 20 parts by weight of an ethylene/vinyl acetate copolymer (MFR = 2.5 g/10 min, vinyl acetate content = 25% by weight; hereinafter referred to as "EVA-1") and 10 parts by weight of MAH-PE-l was used instead of the composition (2) used in Example 6.
The obtained results are shown in Tables 3 and 4.
Example 8 ~
A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 6 except that a composition (4) comprising 40 parts by weight of SEBS, 45 parts by weight of an ethylene/l-butene random copolymer (MFR = 3.5 g/10 min, ethylene content = 89 moLe~, density = 0.885 g/cm3, crystallinity = 15~ hereinafter referred to as "EBR-l"), 15 parts by weight of EVA-l and 20 parts by weight of MAH-PE-l was used instead of the composition (2) used in Example 6.
The obtained results are shown in Tables 3 and 4.
Example 9 , . . .~-----=~-= - -A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition (5) comprising 20 parts by weight of SEBS, 60 parts by weight of EBR-l, 20 parts by weight of EVA-l and 10 partg by weight of MAH-PE-l was used instead of the composition (1) used in Example 5.
The obtained results are 3hown in Table 3.
Example 10 _r:- ' ' ' ' ' '' ~ ' A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as descrlbed in Example 5 except that a composition (6) comprising 60 parts by weight of SEBS, 20 parts by weight of E8R-1, 20 parts by ,. ..
weight of EVA-l and 10 parts by weight of MAH-PE-l was used instead of the composition (1) used in Example 5.
The obtained results are shown in Table 3.
Comparative Example 5 A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~7) comprising 100 parts by weight of EBR-l and 10 parts by weight of MAH-PE-l was used instead of the composition ~1) used in Example 5.
The obtained results are shown in Table 3.
Comparat~ve Example 6 . --A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~8) comprising 85 parts by weight of EBR-l, 15 parts by weight of EVA-l and 10 parts by weight of MAH-PE-l was used instead of the composition ~1) used in Example 5.
The obtained results are shown in Table 3.
Comparative Example 7 A 5-layer sheet was obtained and the T-peel test was carried out in the same manner as described in Example 5 except that a composition ~9) comprising 40 parts by weight of SEBS, 45 parts by weight of EBR-l and 15 parts by weight of EVA-l was used instead of the composition ~1) used in Example 5.
The obtained results are shown in Table 3.
Table 3 Recipe (parts hy PC/EVOH Multi-Layer Sheet weight) of FPC (g/15 mmwidth) FEVOH (g/15 mmwidth) Composition 23 C 80 C Z3 C atmos- 23 C 80 C 23 C atmos-atmosphere atmosphere phere after atmosphere atmosphere phere after retort retort treatment treatment Example 5 SEBS 100 940 920 390 690 630 350 MAH-PE-1 10 Example 6 SEBS 75 1250 930 860 830 720 790 EPR-1 25 Example 7 EvAS1 20 1190 1010 750 45~ 410 440 MAH-PE-1 lC
Example 8 SEBS 40 860 440 590 450 400 440 EBR-1 45 MAH-PE-1 20 ~
Example 9 SEBS 20 690 350 810 520 370 500 ~
Example 10 SEBS 60 830 670 570 39~ 320 410 Comparative EBR-1 100 910 180 110 1300 210 1030 Example 5 MAH-PE-l 10 Comparctive EBR-1 ô5 1600 120 1390 460 170 450 Example 6 EVA-1 1~
Comparative SEBS 40 750 610 430 90 50 10 Example 7 EBR-1 45 Table 4 Recipe (parts by PET/EVOH Multi-Layer Sheet weight) of FPET (g/15mm w1dth) FEVOH (g/15mm width) Composition 23 C 80 C 23 C atmos- 23 C 80 C 23 C atmos-atmosphere atmosphere phere after atmosphere atmosphere phere after retort retort treatment trea~ment Example SEBS 75 960 890 880 810 700 800
6 EPR-l 25 MAH-PE-l 10 Example SEBS 80 840 320 730 460 420 410
7 EVA-l 20 MAH-PE-l 10 o Example SEBS 40 520 380 510 460 390 430
8 EBR-l 45 EVA-l 15 MAH-PE-l 20 21 91 90l In Examples 5 through lO and Comparative Examples 5 through 7, the crystallinity and density were measured according to the following procedures.
(l) Preparation of Sample The sheet was heated at 180~C by a hot press for lO
minutes and was rapidly cooled by a cooling press ~water cooling) to prepare a sample.
(2) Crystallinity The crystallinity of the sample obtained in (l) above was determined by the X-ray diffractometry.
~3) Density The density of the sample was measured at 23~C
according to the density gradient tube method.
As is apparent from the results of the foregoing examples, since the first adhesive resin composition comprises ~a) an ethylene/vinyl acetate copolymer, (b) a styrene polymer resin, (c) graft-modified polyethylene, (d) a monovinyl aromatic hydrocarbon/olefin block copolymer elastomer and (e) an ethylene/d-olefin copolymer at a specific ratio, streaks are not formed at the extrusion molding, and a fusion-bonding (adhesive) film having a good appearance is obtained. Eurthermore, the adhesive resin composition of the present invention can give an excellent adhesiveness between a metal and a thermoplastic resin sheath layer.
Accordingly, the adhesive resln composition of the present invention can be suitably used as a melt adhesive for laminates of laminate sheath cables and films of various packaging materials.
When the second adhesive composition of the present invention is USed for bonding (I) a layer of a polyalkylene terephthalate resin or polycarbonate resin and (III) a layer of a saponified olefin/vinyl acetate copolymer, the layers (I) and (III) can be so tightly bonded that peeling of the layers (I) and (III) is not caused even under high-temperature conditions as adopted for a high-temperature filling treatment or a retort treatment, and a practicalLy sufficient bonding strength can be maintained at normaL temperature after this high-temperature treatment.
AccordingLy, a laminate comprising the layers (I) and (III) bonded by using the adhesive~resin composition of the present invention has a high resistance to permeation of gases such as oxygen and therefore, the Laminate has excelLent properties as a retortabLe food packaying materiaL.
~:
_.
(l) Preparation of Sample The sheet was heated at 180~C by a hot press for lO
minutes and was rapidly cooled by a cooling press ~water cooling) to prepare a sample.
(2) Crystallinity The crystallinity of the sample obtained in (l) above was determined by the X-ray diffractometry.
~3) Density The density of the sample was measured at 23~C
according to the density gradient tube method.
As is apparent from the results of the foregoing examples, since the first adhesive resin composition comprises ~a) an ethylene/vinyl acetate copolymer, (b) a styrene polymer resin, (c) graft-modified polyethylene, (d) a monovinyl aromatic hydrocarbon/olefin block copolymer elastomer and (e) an ethylene/d-olefin copolymer at a specific ratio, streaks are not formed at the extrusion molding, and a fusion-bonding (adhesive) film having a good appearance is obtained. Eurthermore, the adhesive resin composition of the present invention can give an excellent adhesiveness between a metal and a thermoplastic resin sheath layer.
Accordingly, the adhesive resln composition of the present invention can be suitably used as a melt adhesive for laminates of laminate sheath cables and films of various packaging materials.
When the second adhesive composition of the present invention is USed for bonding (I) a layer of a polyalkylene terephthalate resin or polycarbonate resin and (III) a layer of a saponified olefin/vinyl acetate copolymer, the layers (I) and (III) can be so tightly bonded that peeling of the layers (I) and (III) is not caused even under high-temperature conditions as adopted for a high-temperature filling treatment or a retort treatment, and a practicalLy sufficient bonding strength can be maintained at normaL temperature after this high-temperature treatment.
AccordingLy, a laminate comprising the layers (I) and (III) bonded by using the adhesive~resin composition of the present invention has a high resistance to permeation of gases such as oxygen and therefore, the Laminate has excelLent properties as a retortabLe food packaying materiaL.
~:
_.
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A laminate structure adapted for use as a retortable packaging material, comprising:
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially or wholly graft modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or derivative thereof is 0.05 to 15% by weight, and the soft polymer comprises [1] a styrene elastomer alone, [2] at least 20% by weight of the styrene elastomer and not more than 80% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole%, [3]
at least 20% by weight of the styrene elastomer and not more than 80% by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight or [4]
at least 20% by weight of the styrene elastomer, up to 80% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole% and up to 80% by weight of an ethylene/vinyl acetate copolymer having an ethylene content of 5 to 40% by weight.
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially or wholly graft modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or derivative thereof is 0.05 to 15% by weight, and the soft polymer comprises [1] a styrene elastomer alone, [2] at least 20% by weight of the styrene elastomer and not more than 80% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole%, [3]
at least 20% by weight of the styrene elastomer and not more than 80% by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight or [4]
at least 20% by weight of the styrene elastomer, up to 80% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole% and up to 80% by weight of an ethylene/vinyl acetate copolymer having an ethylene content of 5 to 40% by weight.
2. A laminate structure adapted for use as a retortable packing material comprising, (I) a layer of a polvalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially or wholly graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or a derivative thereof is 0.05 to 15% by weight, the soft polymer being a styrene elastomer.
3. A laminate structure adapted for use as a retortable packing material comprising:
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially of wholly graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or a derivative thereof is 0.05 to 15% by weight, the soft polymer comprising (a) 20 to 90% by weight of a styrene elastomer and (b) 80 to 10% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole% and a X-ray crystallinity of lower than 30%.
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially of wholly graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or a derivative thereof is 0.05 to 15% by weight, the soft polymer comprising (a) 20 to 90% by weight of a styrene elastomer and (b) 80 to 10% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole% and a X-ray crystallinity of lower than 30%.
4. A laminate structure adapted for use as a retortable packing material comprising:
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially or wholly graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or a derivative thereof is 0.05 to 15% by weight, the soft polymer comprising (a) 20 to 90% by weight of a styrene elastomer and (c) 80 to 10% by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40%
by weight.
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially or wholly graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or a derivative thereof is 0.05 to 15% by weight, the soft polymer comprising (a) 20 to 90% by weight of a styrene elastomer and (c) 80 to 10% by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40%
by weight.
5. A laminate structure adapted for use as a retortable packing material comprising:
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially or wholly graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or a derivative thereof is 0.05 to 15% by weight, the soft polymer comprising (a) 20 to 80% by weight of a styrene elastomer, (b) 10 to 70% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole% and a X-ray crystallinity of lower than 30% and (c) 10 to 70% by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight.
(I) a layer of a polyalkylene terephthalate resin or a polycarbonate resin, (III) a saponified olefin/vinyl acetate copolymer layer, and interposed therebetween, (II) a layer of an adhesive resin composition, wherein the adhesive resin composition comprises 100 parts by weight of a soft polymer and 1 to 30 parts by weight of partially or wholly graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or a derivative thereof is 0.05 to 15% by weight, the soft polymer comprising (a) 20 to 80% by weight of a styrene elastomer, (b) 10 to 70% by weight of an ethylene/.alpha.-olefin copolymer having an ethylene content of 45 to 95 mole% and a X-ray crystallinity of lower than 30% and (c) 10 to 70% by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight.
6. A laminate structure according to claim 3, wherein the .alpha.-olefin in the ethylene/.alpha.-olefin copolymer is propylene.
7. A laminate structure according to claim 5, wherein the .alpha.-olefin in the ethylene/.alpha.-olefin copolymer is propylene.
8. A laminate structure according to claim 4, wherein the ethylene/vinyl acetate copolymer has a melt flow rate of 0.1 to 50 g/10 min.
9. A laminate structure according to claim 5, wherein the ethylene/vinyl acetate copolymer has a melt flow rate of 0.1 to 50 g/10 min.
10. A laminate structure according to any one of claims 2 through 9, wherein:
the adhesive composition has a grafting ratio of the unsaturated carboxylic acid or derivative thereof of 0.01 to 3% by weight based on the entire composition, a melt flow rate of 0.1 to 50 g/10 min and a crystallinity of lower than 35%;
the styrene elastomer is a homopolymer of styrene or a copolymer of styrene and chlorostyrene, dichlorostyrene, methylstyrene or .alpha.-methylstyrene and has a melt flow rate of 0.1 to 50 g/10 min; and the saponified olefin/vinyl acetate copolymer is saponified ethylene/vinyl acetate copolymer having an ethylene content of 15 to 60 mole%.
the adhesive composition has a grafting ratio of the unsaturated carboxylic acid or derivative thereof of 0.01 to 3% by weight based on the entire composition, a melt flow rate of 0.1 to 50 g/10 min and a crystallinity of lower than 35%;
the styrene elastomer is a homopolymer of styrene or a copolymer of styrene and chlorostyrene, dichlorostyrene, methylstyrene or .alpha.-methylstyrene and has a melt flow rate of 0.1 to 50 g/10 min; and the saponified olefin/vinyl acetate copolymer is saponified ethylene/vinyl acetate copolymer having an ethylene content of 15 to 60 mole%.
11. A laminate structure according to any one of claims 2 through 10, which further comprises a layer of polyolefin bonded to the saponified olefin/vinyl acetate copolymer layer (III) by a further layer of the adhesive resin (II).
12. A laminate structure according to claim 11, wherein the polyolefin is polypropylene or polyethylene and has the structure: polypropylene/(II)/(III)/(II)/(I) or polyethylene/(II)/(III)/(II)/(I).
13. A method of producing the laminate structure as defined in any one of claims 2 through 10, which comprises:
melting in different extruders, (I) the polyalkylene terephthalate resin or the polycarbonate resin, (II) the adhesive resin composition and (III) the saponified product of the ethylene/vinyl acetate copolymer, feeding them into a die having a multi-layer structure, and co-extruding them so that the adhesive resin composition is interposed between layers of (I) and (II).
melting in different extruders, (I) the polyalkylene terephthalate resin or the polycarbonate resin, (II) the adhesive resin composition and (III) the saponified product of the ethylene/vinyl acetate copolymer, feeding them into a die having a multi-layer structure, and co-extruding them so that the adhesive resin composition is interposed between layers of (I) and (II).
14. A method of producing the laminate structure as defined in any one of claims 2 through 8, which comprises:
forming (I) a layer of the polyalkylene terephthalate resin or the polycarbonate resin, and (III) the olefin/vinyl acetate copolymer saponified product resin layer, and then melt-extruding (II) the adhesive resin composition between the two layers (I) and (III).
forming (I) a layer of the polyalkylene terephthalate resin or the polycarbonate resin, and (III) the olefin/vinyl acetate copolymer saponified product resin layer, and then melt-extruding (II) the adhesive resin composition between the two layers (I) and (III).
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP204508/89 | 1989-08-07 | ||
| JP1204508A JP2820242B2 (en) | 1989-08-07 | 1989-08-07 | Adhesive resin composition |
| JP242775/89 | 1989-09-19 | ||
| JP1242775A JP2760595B2 (en) | 1989-09-19 | 1989-09-19 | Laminate |
| CA002022799A CA2022799C (en) | 1989-08-07 | 1990-08-07 | Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002022799A Division CA2022799C (en) | 1989-08-07 | 1990-08-07 | Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2191901A1 CA2191901A1 (en) | 1991-02-08 |
| CA2191901C true CA2191901C (en) | 1999-02-16 |
Family
ID=27168787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002191901A Expired - Fee Related CA2191901C (en) | 1989-08-07 | 1990-08-07 | Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2191901C (en) |
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1990
- 1990-08-07 CA CA002191901A patent/CA2191901C/en not_active Expired - Fee Related
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| CA2191901A1 (en) | 1991-02-08 |
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