CN1266194C - Film and clamping plate - Google Patents
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- CN1266194C CN1266194C CN 02122343 CN02122343A CN1266194C CN 1266194 C CN1266194 C CN 1266194C CN 02122343 CN02122343 CN 02122343 CN 02122343 A CN02122343 A CN 02122343A CN 1266194 C CN1266194 C CN 1266194C
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Abstract
There are provided: (I) a film having a layer which layer comprises a resin composition containing: (A) 100 parts by weight of at least one resin selected from the group consisting of a rubber modified polystyrene resin and a polystyrene resin, (B) 120 to 1700 parts by weight of an ethylene-unsaturated carboxylic acid ester copolymer, and (C) 10 to 250 parts by weight of at least one tackifier selected from the group consisting of an alicyclic hydrocarbon resin, a terpene resin, a rosin and an aliphatic hydrocarbon resin, the tackifier having a number average molecular weight of not more than 1500 measured by a gel permeation chromatography, provided that at least one outermost layer of the film is the layer comprising said resin composition, and (II) a laminate comprising: (1) a layer (1) comprising the above-mentioned film (I), and (2) a substrate layer (2), provided that at least one outermost layer of the laminate is the layer (1).
Description
Technical field
The invention relates to a kind of film, is the application that is used for as the protective membrane of container and packing bag, and is applied to a kind of overlapping layers, comprises one deck and contains the structural sheet of above-mentioned film and the overlapping layers of a stratum basale.
Background technology
The protective membrane that is used on the container need not only have the function of protection content, also wants and can open easily; A kind of known film that divests is easily arranged, it comprises a kind of resin composition that contains different resins, for instance, a kind of film that divests is easily just disclosed among the Japanese Patent JP-A11-92605, this film comprises a kind of resin composition, contain (i) a kind of styrene resin, (ii) a kind of solubility parameter is 8.45 to 8.70, and containing, and the (iii) another kind of alkene hydroxyl resin that is different from above-mentioned alkene hydroxyl resin from a kind of aromatic series acetyl group compound deriving unit unduplicated alkene hydroxyl resin (all being referred to as afterwards) with " aromatic series acetyl group compound unit ".
When the above-mentioned film that divests easily is used as a kind of protective cover of container, can presents excellent driving fit characteristic and open the characteristic that just divests easily easily.But this kind film has a problem, carries out driving fit exactly under the situation that contains the liquid existence on a driving fit surface, and the driving fit characteristic of film will disappear.
Summary of the invention
In view of this, one of purpose of the present invention is to provide a kind of film, under general driving fit situation, can present excellent driving fit characteristic and the characteristic that divests easily.
Another object of the present invention is to provide a kind of overlapping layers, comprise a structural sheet and a stratum basale with above-mentioned film.
In the present invention, when film is to contain under the situation that liquid exists on a driving fit surface to use, the driving fit characteristic that it presents can be called the surface and contain the driving fit characteristic of the film of liquid (afterwards all with " the driving fit characteristic when liquid exists ").
Families of the present invention are devoted to study to reach above-mentioned purpose always, found that above-mentioned purpose of the present invention can realize through using a kind of resin to form, this resin is formed and is comprised (i) a kind of styrene resin that contains discrete cell, (ii) a kind of polymkeric substance of ethene unsaturation carbonyl acid ester class, (iii) a kind of particular adhesive with the specific blend ratio (tackifier) is whereby to be accomplished the present invention.
The invention provides a kind of film, have an outermost structural layer, the outermost structural layer contains a resin to be formed, and this resin is formed and comprised:
(A) resin of at least one 100 weight parts, this resin be selected from group that a rubber modified polystyrene resin and a polystyrene resin form one of them;
(B) an ethene unsaturation carboxylate copolymer of 120-1700 weight part; And
(C) viscose glue of at least one 10 to 250 weight parts, this viscose glue be selected from contain group that an alicyclic hydrocarbon resin, a terpine resin and a rosin forms one of them, wherein can not surpass 1500 with the number-average molecular weight that a gel permeation chromatography measures this viscose glue.
The present invention also provides a kind of overlapping layers, comprising:
(1) one structural sheet (1);
(2) one stratum basalees (2);
Wherein structural sheet (1) comprises the have structural sheet film of (a), forms and comprise a kind of resin in the structural sheet (a), and it contains:
(A) resin of at least one 100 weight parts, this resin be selected from group that a rubber modified polystyrene resin and a polystyrene resin form one of them;
(B) an ethene unsaturation carboxylate copolymer of 120-1700 weight part; And
(C) viscose glue of at least one 10 to 250 weight parts, this viscose glue be selected from contain group that an alicyclic hydrocarbon resin, a terpine resin and a rosin forms one of them, wherein the number-average molecular weight that measures this viscose glue with a gel permeation chromatography can not surpass 1500, and an outermost structural layer of this film is to contain the structural sheet that this resin is formed.
Wherein:
(i) making the outermost layer of film at least is exactly to comprise the structural sheet (a) that this resin is formed; And
The outermost layer that (ii) makes this overlapping layers at least is exactly this structural sheet (1).
When the resin that uses is in the present invention formed the composition (B) that contains less than 120 weight parts, or when the content of wherein composition (C) during less than 10 weight parts, the film that obtains can not have enough low temperature driving fit characteristics and the driving fit characteristic deficiency when liquid exists.When the content of the composition (B) in resin is formed surpasses 1700 weight parts, or when the content of the composition (C) in resin is formed surpassed 250 weight parts, the characteristic of its agglomeration resistance of film that obtains can reduce.
" rubber modified polystyrene resin " of Shi Yonging is a kind of polystyrene (HIPS) resin that is used as a kind of height extruding usually in the present invention, this resin can be by volume production, such as a kind of elastomeric polymer that will be selected from vinylbenzene at least and form with a kind of monomer polymerization in its derivative, the kenel of this resin is combined by (1) a kind of polymkeric substance and (2) a kind of elastomeric polymer with disperse phase with external phase, wherein continuous phase polymer contain a kind of be selected from least contain vinylbenzene with and a kind of monomeric unit of derivative; Elastomeric polymer content in above-mentioned resin is generally 5 to 25%, such as the styrenic that vinylbenzene and various alpha-alkyl replace, similarly is that alpha-methyl styrene etc. can be used as above-mentioned monomer; And can be used as above-mentioned elastomeric polymer such as polyhutadiene, styrene-butadiene copolymer, polyisobutylene and vinylbenzene-different propylene copolymer etc.
" polystyrene resin " of Shi Yonging is a kind of polystyrene (GPPS) that is used as general objects usually in the present invention, its contain be selected from least vinylbenzene with and one of them monomeric unit of derivative, this resin can utilize such as the mode of above-mentioned at least monomer polymerization is come volume production, such as the vinylbenzene that vinylbenzene and various alpha-alkyl replace, similarly be that alpha-methyl styrene etc. can be used as above-mentioned monomer.
When using the unsaturation carboxylicesters in the composition (B) that uses in the present invention, more suitable is esters of acrylic acid, and similarly is methyl acrylic esters such as methyl olefin(e) acid salt, ethyl acrylate, butylacrylate, methyl first acrylate, ethyl first acrylate and butyl first acrylate etc.Wherein, selected by the viewpoint that easily divests characteristic of film according to the present invention, more suitable is methacrylate and methyl first acrylate; According to the present invention by the viewpoint that easily divests characteristic of film, and the part that film divests after divesting has good aspects such as outward appearance, with whole composition (B) is 100 listed as parts by weight, unsaturation carboxylic ester units content in the composition (B) is preferably 25-50wt% (weight percent), and more suitable be 25-45wt%.
See through gel permeation chromatography and measure, the number-average molecular weight of the composition of Shi Yonging (C) can be above 1500 in the present invention, and have the viewpoint of enough driving fit characteristics by the film that obtains when liquid exists, and are preferably by 300-1000; Number-average molecular weight represents to convert to the later a kind of number-average molecular weight of polystyrene number-average molecular weight.
The alicyclic ring hydroxy resin example that uses in the composition in the present invention (C) comprise with go out from petroleum fractionating similarly be C4 oil fragment and the segmental cyclic dimer of the C5 oil resin that carries out polyreaction and produce later on, will such as for cyclopentadiene with and the resin that produces of cyclic diene compound polymerization such as hydrogenated products, make aromatic series hydroxyl resin aromatic nucleus hydrogenation generation resin and with the resin of one of alicyclic ring hydroxyl-aromatic series hydroxyl copolymer resin aromatic nucleus hydrogenation generation.
In the present invention the example of the terpine resin of the composition of Shi Yonging (C) such as for a kind of similarly be α-Dipentine, β-Dipentine and limonene, with and the multipolymer of the compound of hydrogenated products, and obedient alkene-phenol copolymer resin etc.
The rosin that uses composition (C) in the present invention such as rosin, rosin ester, hydrogenant rosin, hydrogenant rosin ester, with and the product of polyreaction.
The alicyclic hydrogenated resin that uses composition (C) in the present invention such as for the alkene hydroxyl unit that contains 4-5 carbon atom as the resin of formant and contain the resin of the diene unit of 4-5 carbon atom as formant.
In these above-mentioned examples, more suitable is the hydrogenant resin, and according to demand of the present invention, by the driving fit characteristic of film and the viewpoint that divests characteristic easily, more suitable is the hydrogenant terpine resin.
If the words that need are arranged, indivedual compositions (A) of Shi Yonging, (B) can be used in combination with a kind of thermoplastic resin with (C) in the present invention, and the example of thermoplastic resin is such as for similarly being polyethylene kinds such as new LDPE (film grade) and high density polyethylene(HDPE), ethene-α-alkene hydroxyl multipolymer, the ethylene unit repetition multipolymer different with composition (B) and similarly being the polyene hydroxyl resin of polypropylene and propylene-α-alkene hydroxyl multipolymer.
If having needs, indivedual compositions (A) of Shi Yonging, (B) can be further with (C) and uses such as stablizer (compatibilizers), static inhibitor, antioxidant, thermo-stabilizer, UV light absorber, pigment, dyestuff, antiseptic-germicide, anti-cloud agent, lubricant, anti-caking agent and moulding dose (plastisizers) (similarly being a kind of mineral oil) in the present invention.
The example of above-mentioned lubricant be contain 10-50 carbon atom than high fatty acid ammonium class, such as ammonium stearate, ammonium oleate, erucic acid ammonium and propylene two ammonium oleates; (A) is used as 100 weight parts composition, and the usage quantity of this lubricant is generally the 0.3-50 weight part.
Above-mentioned anti-caking agent contains inorganic or organic fine particle, such as similarly being inorganic particles such as aluminosilicate grain and diatom grogs, and similarly is organic granulars such as alkene hydroxyl resin particle and styrene resin particle, all can be used to make tiny particle; Is the weight of composition (A) that benchmark is used as 100 weight parts, and the amount that anti-caking agent uses is generally the 1-100 weight part.
The mode of production that the resin that uses among the present invention is formed is restriction not, and resin is formed and can be made in various manners, and such as (1) a kind of manufacture craft, its step comprises (i) with a predetermined blending ratio, dried mixing element (A), (B) with (C); And (ii) melt kneading mixture with the device of a kneading; And (2) a kind of manufacture craft, its step comprises direct composition (A) with the predetermined mix ratio, (B) and (C) joins to finish in the kneading device melts kneading.
The film that obtains through the present invention can be the film of (1) single structure layer, only forms the single structure layer that constitutes by contained resin and forms; Also can be (2) overlapping layers, form that each structural sheet comprises separately with the composition of specific blend mixed (A), (B) and forming with resin (C) by double-layer structure layer at least; It more can be (3) a kind of overlapping layers, by one deck at least to contain the structural sheet that composition (A), (B) and resin (C) are formed, and one deck is formed jointly with the structural sheet that other composition or material constitute at least, as mentioned herein other composition or material such as for contain composition (A), (B) forms different resins with resin (C) and forms; Containing composition (A) forms with resin (B); With composition (A) and (B) different resins; A kind of sheet metal is such as aluminium foil; And paper etc.
Being applied to other above-mentioned composition or the resin in the material can be to be selected from high density polyethylene(HDPE), new LDPE (film grade), polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, polystyrene, the polystyrene of modified rubber, polyester and poly-ammonium class, and the resin that comprises above-mentioned two kinds of compositions at least forms one of them, contains the structural sheet that above-mentioned these resins or resin form and can comprise the direction-free film of one deck, biax film, be coated with organic and/or inorganic materials or similarly be the film of this class organic materials of chloroethene diene, or has the film of a print surface.
The film that uses as the present invention is the film of above-mentioned single structure layer, and this single structure layer film can be selected a more suitable thickness, and preferred thickness is generally 10-100 μ m.
The production method of above-mentioned single structure layer film is not limit, and can make in various manners, makes sculpting method, tubular film sculpting method and opens cloth sculpting method etc. such as the casting of a kind of T-district.
When film of the present invention is a kind of overlapping layers, this overlapping layers can by two or multilayer form, each structural sheet is made up of the discrete resin, contain respectively composition (A), (B) with (C), composition (A) during each resin is formed, (B) can be identical or different with blending ratio (C).
When film of the present invention or overlapping layers are used to protective coating as a container; this protective coating can be made of following manner; its step comprises the shape that film or overlapping layers is overlayed into protective coating; from the viewpoint that overlays easily; film or overlapping layers that suggestion is used are to contain a structural sheet; this structural sheet includes the composition (A) of 100 weight parts; the composition (C) of composition of 120-1700 weight part (B) and 10-250 weight part; and a kind of resin that the ethenoid resin of 200-900 weight part is formed as other above-mentioned material is formed; all represent this resin composition with " resin is formed (B) " afterwards, the composition of forming in (B) at resin (A) is different with not containing ethenoid resin as the composition (A) in the resin composition of other material.The example of ethenoid resin is such as being new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) and above-mentioned one or two kind combination, wherein by the viewpoint that overlays easily, LDPE and LLDPE are more suitable materials.
If the words that need are arranged, the composition that is used for resin composition (B) can combine with a thermoplastic resin respectively, the example of thermoplastic resin comprises the multipolymer that contains ethylene unit, similarly be ethylene-methyl methacrylate methyl terpolymer, ethene-first acrylate multipolymer and vinyl-vinyl acetate copolymers etc., also can be alkene hydroxyl resin, such as polypropylene and propylene-α-alkene hydroxyl multipolymer etc.
If the words that need are arranged, can be further and stablizer (compatibilizers) at indivedual compositions that resin is formed in (B), static inhibitor, antioxidant, thermo-stabilizer, UV light absorber, pigment, dyestuff, antiseptic-germicide, anti-cloud agent, lubricant, anti-caking agent, and moulding dose (plastisizers) (similarly being a kind of mineral oil) etc. used together, wherein the example of stablizer is the hydrogenated products of vinylbenzene-paired diene block copolymer, similarly be hydrogenant styrene-isoprene block copolymer (SEPS) and hydrogenant styrene butadiene block copolymer (SEBS), with composition (A) is 100 weight parts, and the usage quantity of this stablizer is generally the 20-100 weight part.
When the film of the present invention's use is overlapping layers, the thickness of overlapping layers can decide according to situation about using, the viewpoint that has the characteristic that divests easily by the overlapping layers of making, in such overlapping layers, do not comprise the structural sheet of ethenoid resin as other material, its thickness is preferably 5-50 μ m; By the viewpoint of the overlapping layers that obtains being easier to overlay, comprise resin form (B) a structural sheet be about 5-50 μ m than suitable thickness.
Make resin and form the not restriction of method of (B), this resin composition can utilize variety of way to make, and such as (1) a kind of manufacture craft, its step comprises (i) with a predetermined blending ratio, the various compositions of dried mixing; And (ii) melt kneading mixture with the device of a kneading; And its step of (2) a kind of manufacture craft comprises directly that various compositions with the predetermined mix ratio join to finish in the kneading device and melts kneading.
The film that uses as the present invention is to comprise that (i) contains the structural sheet that composition (A), (B) and resin (C) are formed, and when (ii) containing the overlapping layers of a structural sheet of above-mentioned resin other material beyond forming, such overlapping layers can be made in various manners, such as suppressing altogether that overlapping layers moulds that manufacture craft, compacting overlapping layers are moulded manufacture craft and the cramping manufacture craft done etc.
When overlapping layers is when making with the cramping manufacture craft of doing, wherein individual layers can be bonded together with other layer, this manufacture craft is fit to usually to comprise that it similarly is the surface that at least one structural sheet is handled in the surface treatment of corona treatment that step (i) is utilized a kind of, and (ii) utilizes tackiness agent that individual layers is bonded together.In this case, include in the structural sheet and be different from composition (A), (B) and comprise non-directional or biax film with (C) examples of material, wherein containing a kind of at least similarly is the multipolymer of polyethylene kind, polyester, poly-ammonium class and ethene-alkene hydroxyl alcohol; This film can see through a coating agent is coated on the film and prepare, and the preparation of film also can with vapour deposition such as a kind of material of metal on this film.
Importantly, it is the structural sheet (1) that comprises film of the present invention that overlapping layers of the present invention has an outermost layer at least, whereby so that the function that overlapping layers can effectively represent film provided by the invention to be possessed; And the stratum basale in the overlapping layers (2) can provide one similarly to be the same function of characteristic of strengthening film, and the structural sheet (1) and (2) two of the stratum basalees that comprise film can directly press together, or lumps together through another lamination.
The used material category of stratum basale (2) is restriction not, such as being the film that thermoplastic resin makes, similarly is biax polyethylene terephthalate film (PET film), such as being the sheet metal of aluminium foil and paper etc.
The material that the selection of the method that structural sheet (1), structural sheet (2) and other selective structure lamination are lumped together is used according to individual layers decide, the method for the pressing of carrying out such as pressing (joint) method of using tackiness agent and with the object that heats driving fit (joint).
When film provided by the invention is intended for wrapping material, the surface of this film (this surface be with desire to be heat-sealed in similarly be a apparent surface on the object as the container of desiring to pack) can similarly be corona treatment (corona treating) surface treatment, similarly be the coating of printing-ink or when specific demand was arranged, vapour deposition similarly was the material of metal etc.
Film provided by the invention and overlapping layers can be made into the shape of actual needs, similarly are to make to be used for the cup-like container or the protective cover of shallow discoid container; It similarly is bag-like containers such as three limit driving fit bags, four limit driving fit bags and the bag shape bag of standing that film provided by the invention and overlapping layers also can be used to.For instance, come the mode of package object to comprise the following steps: with three limit driving fit bags
(1) prepares one three limit driving fit bag, Yi Bian wherein open;
(2) object is put into this bag such as food by opening part;
(3) with the opening driving fit, whereby so that the innermost layer of sack, just have comprise composition (A), (B) can own driving fit with the structural sheet that resin (C) is formed.
According to the present invention, a kind of film and overlapping layers are provided, the object that object of making at least a styrene resin and acrylic resin make arbitraryly all has excellent driving fit characteristic, excellent divesting easily still has excellent driving fit characteristic when characteristic and liquid exist.
Specifically, when object that object that above-mentioned styrene resin is made or acrylic resin make carries out driving fit under the temperature of heating driving fit is the situation of 120-200 degree Celsius, no matter be to use film provided by the invention or overlapping layers, the dhering strength of this object can reach 0.3-2.0kg/cm
2(29-196kPa just).Mention along band, in general dhering strength is less than 0.3kg/cm
2The time can present poor driving fit characteristic; And intensity surpasses 2.0kg/cm
2Then can present the poor characteristic of opening easily.Above-mentioned dhering strength can measure with a kind of method, and the step of this method comprises:
(1) heating plastic containers of driving fit and a protective cover are tightly to be enclosed in container with protective cover;
(2) air is inserted in the container of driving fit to increase the gaseous tension in the container slowly;
Pressure (usually such situation can take place) when (3) measuring the driving fit skin breakage in the container can't driving fit and pressure when separating with protective cover when container or measure, and the pressure that measures at this moment is exactly dhering strength.
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, cited below particularly
Embodiment elaborates.
Embodiment
Below will describe the present invention in detail, but be not in order to limit the scope of the invention with embodiment.
1, the method for utilizing dry-pressing to close is made the overlapping layers structural sheet for assessment
The overlapping layers structural sheet that is used to assess can see through a method preparation, and the step of this method comprises:
(1) tackiness agent of a kind of alicyclic ester class of coating is on the white shape surface of the thick aluminium foil (stratum basale) of one 25 μ m, its white shape surface is by YASUI SEIKI., LTD. the multi-usage coating machine of Zhi Zuoing makes, wherein tackiness agent contains the matrix of (a) 10 weight parts, its trade mark is called A515, and by Takeda Chemical Industries, Ltd. makes, the solidifying agent of (b) 1 weight part, its trade mark is called A50, also is to be made and (c) vinyl acetic monomer of 18 weight parts by above-mentioned company;
(2) vinyl acetic monomer is removed fully;
(3) contact of above-mentioned aluminium foil surface and press seal are scribbled alicyclic ester class tackiness agent and did on the film on corona treatment surface to provided by the invention, whereby to obtain an overlapping layers, wherein corona treatment is carried out when forming film, whereby so that its surface tension of the surface of corona treatment can be less than 42dyne/cm; And
(4) under 40 degree Celsius, in a moisture eliminator, made the overlapping layers slaking 48 hours, to obtain an overlapping layers that can be used for assessing.
2. the measurement of the dhering strength when liquid being arranged
Dhering strength when having liquid to exist can utilize a kind of method to measure, and the step of this method comprises:
(1) preparing concentration is the sugar aqueous solution of 20% weight percent, and the sugar aqueous solution that will be about 0.05mg is coated on the surface of the cup edge section that rubber modified polystyrene makes (its opening diameter is 24mm, and border width is 2mm);
(2) overlapping layers provided by the invention is placed on the above-mentioned coating surface, whereby so that contain and comprise that composition (A), (B) and the structural sheet that resin (C) is formed place with ventricumbent direction, wherein overlapping layers makes the external form of protective cover;
(3) at 120 degree Celsius, 1.4kg/cm
2Pressure under, with NISSAN KOHKI CO., the table cup driving fit device that LTD. makes is sealed a second, to obtain a sample that is used for assessing;
(4) wear the hole of a 1mm φ in the bottom of the sample cup that is used for assessing;
(5) with NISSAN KOHKI CO., the puncture tstr that LTD. makes is measured lid is divested needed intensity from the cup edge, and the strength that measures is the intensity of liquid driving fit when existing.
Example 1
Is the rubber modified polystyrene (HIPS) of JPSH550 with 100 weight parts by JAPAN POLYSTYRENE INC. producer entitling, 800 weight parts are by Sumitomo ChemicalCo., Ltd. producer's entitling is that (the unitary content of methacrylic methyl esters accounts for weight 31% for ethene-methacrylic methyl terpolymer of ACRYFT CG4002, the content of ethylene unit accounts for weight 69%), 100 weight parts are the hydrogenated terpene resin (number-average molecular weight of utilizing gel permeation chromatography to measure is 700) of CLEARON P125 by Yasuhara Chemical Co. producer entitling, the lubricant of 8 weight parts, the mixture of erucicamide and ethene two ammonium oleates, and the particle of the polymethylmethacrylate of 15 weight parts (average particulate diameter is 10 μ m), a right cylinder temperature is that Celsius 190 grades of spending are melted above-mentioned each composition of mixing in double-screw extrusion device, forms the bead of (1) to obtain a resin whereby.
On the other hand, is the rubber modified polystyrene (HIPS) of JPS H550 with 100 weight parts by JAPAN POLYSTYRENE INC. producer entitling, 350 weight parts are by Sumitomo Chemical Co., Ltd. producer's entitling is that (it melts flow velocity is 2g/10min, and density is 0.924g/cm for the new LDPE (film grade) (LDPE) of SUMIKATHENE
3), and 50 weight part by Kuraray Co., Ltd. producer's entitling is hydrogenated styrene-isoprene block copolymer of SEPTON 2104, a right cylinder temperature is that Celsius 190 grades of spending are melted above-mentioned each composition of mixing in double-screw extrusion device, forms the bead of (2) to obtain a resin whereby.
With CHUGAI TECH CO., LTD. the 3-kind of Zhi Zuoing-3-floor T-district casts machine, under the extrusion temperature of 230 degree Celsius, carry out the making of film, make film with the bead of above-mentioned resin being formed (1) and (2), this film has a thickness, that is to say and comprise that resin forms the thickness of the structural sheet of (1)/comprise resin and form the thickness of the structural sheet of (1)/comprise that it is 10/17/13 (μ m) that resin is formed the thickness of the structural sheet of (2), the outermost surface of film contains resin forms (2), this outermost surface can be made corona treatment one, to obtain the film that a corona treatment is crossed, the dhering strength the when liquid of the film that this corona treatment is crossed exists is 0.55kg/cm whereby
2(54kPa).
Example 2
In the making of the bead of forming (1) at resin, the amount of ethylene-methyl methacrylate methyl terpolymer, hydrogenant terpine resin and lubricant is made into respectively 700 weight parts, 200 weight parts and 12.5 weight parts, repeat the step of example 1, form the bead of (3) to obtain a resin whereby.
On the other hand, except the amount with ethylene-methyl methacrylate methyl terpolymer, hydrogenant terpine resin and lubricant changes over 125 weight parts, 25 weight parts and 3.8 weight parts respectively, repeat the step of example 1, form the bead of (4) to obtain a resin whereby.
This is external more on the other hand, except in the bead step of making resin composition (2), making into rubber modified polystyrene and new LDPE (film grade) by JAPANPOLYSTYRENE INC. producer entitling respectively is the rubber modified polystyrene of JPS H320, and by Sumitomo Chemical Co., Ltd. producer's entitling is that (it melts flow velocity is 9.5g/10min, and density is 0.930g/cm for the new LDPE (film grade) (LDPE) of SUMIKATHENEL5715
3) in addition, still repeat the step of example 1, form the bead of (5) to obtain resin whereby.
With with example 1 similar methods, above-mentioned resin is formed (3), (4) make a film with (5) with film producing process, that is to say the thickness of this film, resin is formed the thickness of the structural sheet of (3)/comprise resin and is formed the thickness of the structural sheet of (4)/comprise that it is 20/10/10 (μ m) that resin is formed the thickness of the structural sheet of (5), the outermost surface of this film contains resin forms (5), this outermost surface can be made corona treatment one, to obtain the film that a corona treatment is crossed, the dhering strength the when liquid of the film that this corona treatment is crossed exists is 1.07kg/cm whereby
2(105kPa).
Example 3
Except making the amount of ethylene-methyl methacrylate methyl terpolymer and lubricant into 700 weight parts and 12.5 weight parts respectively in the making of the bead of forming (1) at resin, and change the hydrogenated terpene resin of 200 weight parts into 200 weight parts by Arakawa ChemicalIndustries, Ltd. producer's entitling be PINECRYSTAL KE100 rosin ester class (with the gel permeation chromatography amount to number-average molecular weight be 800) in addition, repeat the step of example 1, form the bead of (6) to obtain a resin whereby.
On the other hand, except in the bead step of making resin composition (2), making into rubber modified polystyrene and new LDPE (film grade) by JAPAN POLYSTYRENE INC. producer entitling respectively is the rubber modified polystyrene of JPS H320, and by SumitomoChemical Co., Ltd. producer's entitling be SUMIKATHENE L5715 new LDPE (film grade) (LDPE) (its fusing flow velocity be 9.5g/10min, density is 0.930g/cm
3) in addition, still repeat the step of example 1, form the bead of (7) to obtain resin whereby.
With with example 1 similar methods, above-mentioned resin is formed (6) and (7), and by Mitsui Chemicals, Inc. producer's entitling is the polyvinyl resin of ADMER NF550, make a film with film producing process, that is to say the thickness of this film, the thickness of the structural sheet of the thickness/ADMER NF550 of the structural sheet of resin composition (6)/comprise that it is 20/10/10 (μ m) that resin is formed the thickness of the structural sheet of (7), the outermost surface of this film contains resin forms (7), this outermost surface can be made corona treatment one, to obtain the film that a corona treatment is crossed, the dhering strength the when liquid of the film that this corona treatment is crossed exists is 0.89kg/cm whereby
2(87kPa).
Comparative example 1
Is the rubber modified polystyrene (HIPS) of JPSH550 with 100 weight parts by JAPAN POLYSTYRENE INC. producer entitling, and 150 weight part by SumitomoChemical Co., Ltd. producer's entitling is that (content of methyl methacrylate units accounts for weight 38% for the ethylene-methyl methacrylate methyl terpolymer of ACRYFT WM403, the content of ethylene unit accounts for weight 62%), a right cylinder temperature is that Celsius 190 grades of spending are melted above-mentioned each composition of mixing in double-screw extrusion device, forms the bead of (8) to obtain a resin whereby.
On the other hand, except in the bead step of making resin composition (2), change new LDPE (film grade) into Co. by Sumitomo Chemical, Ltd. producer's entitling be SUMIKATHENE-E FV202 linear low density polyethylene (LLDPE) (its fusing flow velocity be 2g/10min, density is 0.925g/cm
3) in addition, still repeat the step of example 1, form the bead of (9) to obtain resin whereby.
With with example 1 similar methods, above-mentioned resin is formed (8) and (9), and by Sumitomo Chemical Co., Ltd. producer's entitling is the linear low density polyethylene (LLDPE) of SUMIKATHENE-E FV202, make a film with film producing process, that is to say the thickness of this film, resin is formed the thickness of the structural sheet of (8)/comprise resin and is formed the thickness of the structural sheet of (9)/comprise that the thickness of the structural sheet of LLDPE is 20/10/10 (μ m), the outermost surface of this film contains LLDPE, this outermost surface can be made corona treatment one, to obtain the film that a corona treatment is crossed, the dhering strength the when liquid of the film that this corona treatment is crossed exists is 0.03kg/cm whereby
2(3kPa).
Comparative example 2
With the rubber modified polystyrene of 100 weight parts by the JPSH550 of JAPAN POLYSTYRENE company made, it is that (content of methyl methacrylate units accounts for weight 38% for the ethylene-methyl methacrylate methyl terpolymer (EMMA) of ACRYFT WM403 that 375 weight parts are made commodity by Sumitomo Chemical company, the content of ethylene unit accounts for weight 62%) and 150 weight parts are made the linear low density polyethylene (LLDPE) that commodity are SUMIKAATHENE-E FV403 by Sumitomo Chemical company, and (its fusing flow velocity is 2g/10min, and density is 0.925g/cm
3), be that Celsius 190 grades of spending are melt-blended in double-screw extrusion device a right cylinder temperature, form the bead of (10) to obtain a resin.
On the other hand, repeat example 1, but making that resin forms in the bead step of (10) is to change new LDPE (film grade) into by the commodity SUMIKATHENE-E FV202 by name of Sumitomo Chemical company manufacturing linear low density polyethylene (LLDPE) (its fusing flow velocity is 2g/10min, and density is 0.925g/cm
3), form the bead of (11) to obtain resin.
With method similar in appearance to example 1, above-mentioned resin is formed (10) and (11), and to make trade(brand)name by Sumitomo Chemical company be the linear low density polyethylene (LLDPE) of SUMIKATHENE-E FV403, utilizes a thin-film technique to make a film.The thickness of the thickness of the structural sheet of the thickness of the structural sheet of resinous composition (10)/resinous composition (11)/the contain structural sheet of LLDPE is 20/10/10 (μ m), the outermost surface of this film contains LLDPE, and this outermost surface can be made corona treatment one, carried out the film that corona treatment is crossed to receive one, the dhering strength the when liquid of the film that this corona treatment is crossed exists is 0.26kgf/cm
2(25kPa).
With example 1-3 and comparative example 2 can find after relatively viscose glue of the present invention liquid is arranged the time dhering strength (0.55-1.07kgf/cm
2, 54-87kPa) much larger than known technology with alicyclic ring bunch hydrocarbon resin as viscose glue liquid is arranged the time dhering strength (0.26kgf/cm
2, 25kPa).
Though the present invention with a preferred embodiment openly as above; right its is not in order to limiting the present invention, anyly is familiar with this operator, without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention defines and is as the criterion when looking claims.
Claims (8)
1, a kind of film has an outermost structural layer, and this outermost structural layer contains a resin to be formed, and it is characterized in that: this resin is formed and comprised:
(A) resin of at least one 100 weight parts, this resin be selected from group that a rubber modified polystyrene resin and a polystyrene resin form one of them;
(B) an ethene unsaturation carboxylate copolymer of 120-1700 weight part; And
(C) viscose glue of at least one 10 to 250 weight parts, this viscose glue be selected from contain group that an alicyclic hydrocarbon resin, a terpine resin and a rosin forms one of them, wherein can not surpass 1500 with the number-average molecular weight that a gel permeation chromatography measures this viscose glue.
2, film as claimed in claim 1 is characterized in that: wherein the gross weight with composition (B) is 100% calculating, and the content of the unsaturation carboxylic ester units in this composition (B) is between 25-50 weight %.
3, film as claimed in claim 1 is characterized in that: wherein utilize a gel permeation chromatography to measure, the number-average molecular weight of composition (C) is between 300-1000.
4, film as claimed in claim 1 is characterized in that: wherein this composition (C) comprises a hydrogenant terpine resin.
5, a kind of overlapping layers is characterized in that: comprising:
(1) one structural sheet (1); And
(2) one stratum basalees (2),
Wherein this structural sheet (1) comprises a film that contains a structural sheet (a), and wherein this structural sheet (a) comprises resin composition, and this resin is formed and comprised:
(A) resin of at least one 100 weight parts, this resin be selected from group that a rubber modified polystyrene resin and a polystyrene resin form one of them;
(B) an ethene unsaturation carboxylate copolymer of 120-1700 weight part; And
(C) viscose glue of at least one 10 to 250 weight parts, this viscose glue be selected from contain group that an alicyclic hydrocarbon resin, a terpine resin and a rosin forms one of them, wherein measure with a gel permeation chromatography, the number-average molecular weight of this viscose glue can not surpass 1500, wherein:
(i) an outermost structural layer of this film is to contain this structural sheet (a) that this resin is formed at least; And
(ii) an outermost layer of this overlapping layers is this structural sheet (1) at least.
6, overlapping layers as claimed in claim 5 is characterized in that: wherein the gross weight with composition (B) is 100% calculating, and the content of the unsaturation carboxylic ester units in this composition (B) is between 25-50 weight %.
7, overlapping layers as claimed in claim 5 is characterized in that: wherein utilize a gel permeation chromatography to measure, the number-average molecular weight of composition (C) is between 300-1000.
8, overlapping layers as claimed in claim 5 is characterized in that: wherein this composition (C) comprises a hydrogenant terpine resin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001019864 | 2001-06-29 | ||
| JP2001-19864 | 2001-06-29 | ||
| JP2001198642 | 2001-06-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1393381A CN1393381A (en) | 2003-01-29 |
| CN1266194C true CN1266194C (en) | 2006-07-26 |
Family
ID=18885665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02122343 Expired - Fee Related CN1266194C (en) | 2001-06-29 | 2002-06-14 | Film and clamping plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1266194C (en) |
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2002
- 2002-06-14 CN CN 02122343 patent/CN1266194C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1393381A (en) | 2003-01-29 |
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