CN1708382A - Wax composition and method for production thereof - Google Patents

Abstract

A method for producing a composition containing a wax as its primary component, characterized in that it comprises admixing said wax and a material to be mixed with said wax through applying an external force at a temperature at which the melting of said wax is not completed.

Description

Wax composition and manufacture method thereof

Technical field

The present invention relates to a kind of composition and manufacture method thereof based on wax.The invention still further relates to moistureproofness good, form the Biodegradable wax composition of multilayer film or coating easily.The invention still further relates to the Wax composition of good, the easy to implement melt molding of moistureproofness and other processing.

Background technology

At present, obtaining moisture-proof coating etc. mainly can adopt the method (for example with reference to Japanese kokai publication hei 7-278510 communique) of composition composition mechanically mixing under molten state, use wax emulsion and blended method (for example Japanese kokai publication sho 59-66598 communique) based on the technical scheme of the composition of wax.In addition, also adopted coating to use solvent and blended solution,, form the method (for example TOHKEMY 2002-266284 communique) of composition film, but aforesaid method has had following problems solvent seasoning.

Under molten state in the method for mechanically mixing, because the viscosity of the wax of molten state is low, so with wax and solid state or high-viscosity material mixing the time, owing to these mixtures are not applied sufficient shearing force, and be difficult to reach each uniform ingredients dispersive state.

In the method for using wax emulsion, because the composition that constitutes emulsion is distributed to below the granular size, so be difficult to obtain the composition of homogeneously dispersed state.

In using the method for solvent, in intermediate or end article because of residual solvent causes the problem of smell or security aspect, because use a large amount of solvents, so there is the problem that physical environment, work situation etc. is made a very bad impression.In recent years, fears are entertained that impacts human body from the residual solvent of lamination caking agent in the packaging material for food or printing-ink etc., therefore requires it is improved.Therefore, in manufacturing process, do not use the method for solvent just to become basic resolution policy.

Be insoluble in the solvent because have the wax of high melting point, so be difficult to obtain uniform composition.Be under the situation of the material (for example inorganic particle etc.) that is insoluble to solvent, at mixed thing because mixed thing is not applied sufficient power, so be difficult to abundant dispersion; Have under the situation of difference in specific gravity between wax and mixed thing, mixed thing precipitates and the generation density unevenness.

The present invention is exactly the invention of finishing in view of the above problems, its first purpose provide a kind of do not have residual solvent, composition finely dispersed based on wax Wax composition and can make the manufacture method of the Wax composition of this Wax composition with low cost.

On the other hand, wax is widely used as one of non-blushing thinner or hotmelt composition.In recent years, along with the raising day by day of people's Environmental awareness, the material that uses wax is also required to have biological degradability gradually.The wax that has biological degradability among the wax has a variety of.Because the melt viscosity of wax is extremely low, so usually mix use with resin etc.

It is known that to have for example be the biological degradability hot-melt adhesive composition (with reference to Japanese kokai publication hei 5-339557 communique) of major ingredient with thermoplastic resin and tackifier.In said composition, in thermoplastic resin and the tackifier one of them is made of poly(lactic acid) or lactic acid copolymer at least, contain the following wax of 50 weight %.Also known have a biological degradability hot-melt adhesive composition (with reference to Japanese kokai publication hei 7-278510 communique) that is made of natural rosin, natural rubber and wax.These compositions are not because have a sufficient moistureproofness, thus can not be with the said composition melt molding and film as for example needing the moistureproof wrapping material or the lining (liner) of container.And when these compositions are used as hotmelt, compare with the wax monomer in nature, its melt viscosity increases, but does not use forcing machine to make the high melt viscosity that T mould film or blown film etc. are implemented the melt molding degree.

The biological degradability composition of melting moulding is known to be had with Zein powder and natural rubber is the composition (spy opens the 2001-288295 communique) of major ingredient.The water tolerance of said composition, moistening intensity height.But to open the hot-melt adhesive composition that flat 5-339557 communique and the flat 7-278510 communique of Te Kai disclosed the same with the spy, do not possess sufficient moistureproofness.

The masking liquid (opening the 2002-266284 communique) that also known use solvent mixes natural rubber and carnauba wax or gama wax with reference to the spy.This masking liquid is used on paper-made vessel forming and has the coating of moistureproofness.But because the masking liquid that the document disclosed contains a large amount of solvents, viscosity is also very low, so can not use forcing machine to implement moulding.

Therefore, people also do not obtain melting moulding and the sufficiently high biological degradability composition of moistureproofness or cementability height and the abundant high biological degradability composition of moistureproofness.

Therefore, second purpose of the present invention is to provide a kind of Biodegradable wax composition that solves the existing various unfavorable conditions of above-mentioned prior biological degradation property Wax composition.

On the other hand, have in formation under the situation of the wrapping material of humidity resistance or container etc., on base materials such as paper, resin molding coating contain low-molecular-weight wax Wax composition or with the thermoplastic resin co-extrusion modling, form the multiwalled laminate.

These processing are many to be implemented more than the melting point of low-molecular-weight wax.But because low-molecular-weight wax viscosity is low, so contain the problem that the composition of these low-molecular-weight wax has poor in processability.Although a large amount of polymer substances are coupled in the Wax composition can increase the viscosity that adds man-hour, exist the problem that humidity resistance reduces this moment.

And, in the goods such as moisture-proof container that use Wax composition to make, when sterilization or conditioning etc. are at high temperature filled, at high temperature carried out to content, can occur peeling off between wax layer and the adjacent with it layer, or the wax laminar flow is moving and make Wax composition layer thickness forfeiture homogeneity, the situation that causes humidity resistance etc. to reduce.

Japanese kokai publication hei 8-209000 communique has been put down in writing the paper container Wax composition that is used to give paper container water tolerance etc., and it is that oil with 45～85 ℃ of melting points is that wax is the composition of major ingredient.But because the viscosity of said composition molten state is low, thus for example be difficult to utilize T modulus method or inflation method to implement to melt extrude moulding etc., and gained paper container can not be kept water resistance when at high temperature heat-treating.

Although and in TOHKEMY 2003-5431 communique, disclosed the electronic photo that contains two kinds of different waxes of melting point toning agent, it is compared with resin, the ratio of wax is extremely low, makes this toning agent can not be used for the formation of moisture-proof barrier.

Summary of the invention

Discoveries such as the inventor: under the temperature of the fusion end temp that is lower than wax, mix composition, can reach above-mentioned first purpose based on wax.

The invention that the present invention finishes with regard to being based on above-mentioned opinion, a kind of manufacture method of Wax composition is provided, this manufacture method is the manufacture method based on the composition of wax, it is characterized in that, under the temperature of the fusion end temp that is lower than this wax, give this wax and apply external force and also mix with the mixed thing of this wax blended.

The present invention also provide the above-mentioned Wax composition of the present invention of a kind of usefulness the manufacture method manufacturing contain the high molecular Biodegradable wax composition of biological degradability amorphous based on wax.

It is a kind of based on wax that the present invention also provides, and contains biodegradation high molecular, and residual solvent concentration is the following Biodegradable wax composition of 3ppm.

The present invention is by providing a kind of based on wax, and the Water Vapour Permeability under 40 ℃, 90%RH is 3g.mm/m ².24hr below, the melt flow rate (MFR) under 125 ℃, 1.2kgf load is the Biodegradable wax composition of 0.1～1000g/10min, thereby has reached above-mentioned second purpose.

The present invention also is provided at the long-pending Biodegradable resin layer in the upper strata of one side at least of the moisture-proof barrier that the Biodegradable wax composition by the invention described above forms and the Biodegradable films that forms.

The present invention also is provided at the Biodegradable wax composition that the invention described above is set on the paper material surface, and the Biodegradable resin layer is set and the biological degradability lamination body that forms on this.

The present invention also provides with above-mentioned Biodegradable films of the present invention and covers the whole or local of biodegradable container body, and the coverage mode of this Biodegradable films is to make the biodegradable container of described Biodegradable resin layer towards the opposition side of container body.

The present invention reaches above-mentioned the 3rd purpose by providing based on the Wax composition of two kinds of wax compositions, said composition contains: according to having the high-temperature digestion wax composition of endothermic peak more than 100 ℃ in the DSC calorimetric measurement, more than 40 ℃, be lower than the low temperature fusion wax composition and the polymer substance that have endothermic peak under 100 ℃ the temperature.

The damp-proof membranes that the invention provides the long-pending resin layer in the upper strata of one side at least of the moisture-proof barrier that forms at Wax composition and form by the invention described above.

The invention provides and a kind ofly use the Wax composition manufacturing of the invention described above to have the method for the moistureproofness article of the moisture-proof barrier that forms by this Wax composition, it is characterized in that, possess above-mentioned Wax composition is heated to more than 100 ℃, and the operation of processing, the Heating temperature of this operation is made as, make when measuring the heat of all wax compositions that the ratio (the former/latter) of caloric receptivity and the caloric receptivity of the low temperature side that is lower than this Heating temperature that is higher than the high temperature side of this Heating temperature is 0.1～5.0 temperature according to DSC.

Description of drawings

Fig. 1 is the synoptic diagram that concerns that Δ H, the Δ H ' in the DSC measurement result reaches mixing temperature.

Fig. 2 is for being tried to achieve the fusion end temp, fusing the explanatory view of the method for peak temperature by the DSC measurement result.

Fig. 3 is the calorimetric measurement result schematic diagram based on DSC of the used wax of embodiment 2-1.

Fig. 4 is the DSC curve synoptic diagram of an embodiment of Wax composition of the present invention.

Embodiment

Below, according to preferred implementation explanation the present invention.

The Wax composition of embodiment 1 at first, is described.

The Wax composition of embodiment 1 is the composition based on wax, can select polymer substances such as thermoplastic resin or elastomerics, organic and inorganic powder etc. as mixed thing.Particularly, compare with the melt viscosity of wax when having full-bodied thickness polymer substance, or when being distributed to solid matters such as powder in the wax, manufacture method of the present invention especially can be brought into play effect when mixing.Reason is, by using manufacture method of the present invention described later, utilizes the not high viscosity wax of molten state, can apply high shear force to mixed thing.

When above-mentioned Wax composition requires to have biological degradability, preferably use biological degradability (by JIS K6950 regulation) be 50% or more, more preferably use is that material more than 60% is as the composition of said composition.

The Wax composition of present embodiment is the composition based on wax, and the ratio of components of this wax is preferably more than the 40wt%, can reach higher efficacy; More preferably 50wt% is above, more preferably the above wax phase of 60wt% becomes the system of matrix, and can reach higher effect.Particularly when mixed thing was high inorganic powder of proportion etc., the volume fraction of wax was preferably more than 50%, more preferably the wax phase more than 60% becomes the system of matrix, can reach higher effect.

Above-mentioned wax can use department of botany's wax, animal be wax, mineral be wax, oil be wax, synthetic wax etc. (for example can use that the Fu Lai river strong is hidden, " character of wax and application ", good fortune study, 1993, change 2 editions first impressions, page 2, the described wax of table 1.0.1 (hereinafter referred to as document 1 described wax)).

This department of botany's wax can be enumerated a meter wax, carnauba wax, haze tallow, gama wax etc.; This animal is that wax can be enumerated beeswax, lanolin, spermaceti etc.; This oil is that wax can be enumerated Microcrystalline Wax, paraffin etc.; This synthetic wax can be enumerated polyethylene wax, fischer-tropsch wax (Fisher-Tropsch wax) etc.; This mineral wax can be enumerated montanin wax, ceresine, ceresin etc.These waxes can preferably use any.Because of the reduction of shearing the wax viscosity that heating causes, mixed thing is applied sufficient shearing force, preferably use the low few wax of melting point composition when suppress mixing.Based on same reason, preferably use the few wax of amorphous composition.But, according to the purposes of Wax composition, in the life temperature scope, need tackiness to a certain degree sometimes, so, also preferably contain the low melting point composition or the amorphous composition of appropriate amount sometimes not causing in the scope of big influence to mixing.According to this viewpoint, preferably the fusing point of measuring with the described method of JIS K2235-5.3.2 is the material more than 40 ℃, the more preferably material more than 60 ℃.

Above-mentioned polymer substance can be used for purposes such as the modification of the rerum natura of the solid state of above-mentioned wax or molten state or function are additional, for example, the cementability of the mechanical strength of raising solid state (anti-disconnected ultimate strength, shock strength, flexural strength, increasing tougheness etc.), raising and other material or the melt viscosity of raising under molten state etc.Above-mentioned polymer substance is 5～35%, is preferably 15～30% especially with respect to its content of weight of above-mentioned wax.When this polymer substance content is in this scope, can carry out modification or additional function etc. to the rerum natura of above-mentioned wax effectively.

Above-mentioned polymer substance can be enumerated non-polycrystalline macromolecule such as the multipolymer of crystallization polymers such as polyolefin-based resins, polyester based resin, polyamide-based resin, uncrosslinked rubber or polyester system, polyamide-based, polystyrene, poly-(methyl) acrylic acid series or low crystallization polymer etc.But being the polymer substance of dispersing and mixing imperceptibly, is under the high molecular situation of crystallization at above-mentioned polymer substance, is preferably fused material under the expection mixing temperature below the fusion end temp of wax; At above-mentioned polymer substance is under the situation of non-polycrystalline macromolecule, is preferably the material that has second-order transition temperature below the expection mixing temperature below the fusion end temp of wax.

Particularly, above-mentioned crystallization polymer can be enumerated low melting point polymers such as ethene-alpha-olefin copolymer, vinyl-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, polycaprolactone, polybutylene terephthalate-adipic acid ester, polybutylene succinate-adipic acid ester.Above-mentioned non-polycrystalline macromolecule can be enumerated synthetic polyisoprene, natural rubber, poly-d, l-lactic acid etc.These crystallization polymers and noncrystalline polymer can use separately, and also optional majority kind is used.

Requiring above-mentioned Wax composition to have under the situation of biological degradability, as the biodegradation high molecular that modification rerum natura aspect has very high effect, lift in the material above-mentioned, preferably use natural rubber or synthetic synthetic polyisoprene.When considering the aspects such as allergy that caused by smell, look, contained protein, synthetic synthetic polyisoprene than natural rubber more preferably.When wax and natural rubber or synthetic synthetic polyisoprene are mixed, in aftermentioned manufacture method of the present invention, do not use solvent etc. can obtain having the composition of the rerum natura modified effect that does not reach at present.When utilizing aftermentioned manufacture method blended wax of the present invention and natural rubber or synthetic synthetic polyisoprene, natural rubber or synthetic synthetic polyisoprene can be mixed in the wax extremely equably, the melt viscosity that obtains wax becomes very high or has significantly improved the effects such as fragility of the following wax of wax melting point.

Above-mentioned polymer substance both can use separately also can two or more and usefulness.

Above-mentioned organic powder can be enumerated organic powders such as W-Gum, starch, various polymer powders.Above-mentioned inorganic powder can be enumerated inorganic powders such as titanium oxide, talcum, mica, montmorillonite, silica.

Because the Wax composition of present embodiment does not contain solvent, so be the composition that does not contain residual solvent in fact.Therefore, the residual solvent amount is the following concentration of detectable 3ppm.Therefore, even in the manufacturing process of middle product that use the present embodiment Wax composition or goods, also do not pollute work situation, security is high.It is many fields of representative that the Wax composition of present embodiment can be used safely in the wrapping material of food and other material.

In the scope of not impact effect or manufacturing process, the Wax composition of present embodiment can contain antioxidant, tinting material, dispersing auxiliary and other suitable additives as required etc.

The preferred implementation of the manufacture method of Wax composition of the present invention then, is described based on the manufacture method of the Wax composition of above-mentioned embodiment 1.

The manufacture method of the Wax composition of present embodiment is: be lower than the fusion end temp of this wax, be preferably be not higher than utilize DSC (Differential Scanning Calorimeter: differential scanning calorimeter) measure heat and the temperature of the melt curve analysis fusion peak temperature of trying to achieve under, mechanical force by various mixing rolls, cooperation ratio with afore mentioned rules mixes above-mentioned wax and above-mentioned mixed thing, obtains composition.When having a plurality of fusion peak value, be preferably below the peak temperature of melting heat peak-peak and mix.When mixing this wax and this mixed thing under the temperature more than the melting point at this wax, owing to because of the fusion of wax sharply reduces wax viscosity, fail mixed thing is applied sufficient shearing force, so undercompounding, and be difficult to obtain uniform composition.When mixing under the temperature of the fusion end temp that is being lower than wax, because residual have a not wax crystallization of molten state, wax can be handled as apparent full-bodied liquid, so can utilize the method identical of common execution that wax and mixed thing are mixed with the plastic material mixture.

The method for selecting of preferred mixing temperature has following method.As shown in Figure 1, according to utilizing DSC to measure the melt curve analysis that heat gets, total caloric receptivity with fusion wax composition is Δ H, the integrated value Δ H ' of the heat (caloric receptivity from fusion beginning temperature to mixing temperature Tmix) that absorbs from low temperature side is preferably in the temperature range below 70% of Δ H, more preferably in the temperature range below 50%, more preferably in the temperature range below 30%, and can well blend.Although when the fusion that is being lower than wax begins to mix under the temperature of temperature, there is not obstacle, but preferably under sticking selection situation under the mixing temperature, it is more than 3%, more preferably more than 5% that selected lower limit temperature is preferably above-mentioned integrated value Δ H ' at high hard waxes of crystallinity etc.

Optimum mixing temperature can suitably be selected from above-mentioned mixing temperature according to the rerum natura of mixed thing.For example, when mixed thing is non-polycrystalline macromolecule, is preferably under the temperature more than the high molecular second-order transition temperature of amorphous and mixes.When mixed thing is the crystallization polymer, is preferably under the temperature more than the high molecular fusing point of crystallization and mixes.When mixed thing is above-mentioned inorganic or organic powder, be easy to homodisperse for making powder, preferably mix down in the temperature (for example the fusion than wax begins the also low temperature of temperature) of the fusion end temp that fully is lower than wax., dispersion state really up to the mark for fear of wax worsens, the mixing device overload, preferably mixes more than the second-order transition temperature of wax.Consider the temperature dependency of wax or mixed thing,, also preferably mixing temperature is adjusted into and makes both rerum naturas reach the suitableeest blended state even in above-mentioned preferable range.

The fusion end temp of the wax of present embodiment, fusion peak temperature, Δ H try to achieve with the available for example following method of the ratio of Δ H '.

Mensuration machine: the pattern DSC220 of Seiko electronic industry (strain)

Test portion container: model PN/50-020 (aluminum open-type test portion container, capacity 15 μ l) and model PN/50-021 (crimping of the open test portion container of aluminum is with covering)

Test portion weight: about 10mg

Heat-up rate, cooling rate: 5 ℃/min

Measure temperature range: select the suitableeest scope according to used wax.Fusion end temp and fusion peak temperature are to use after fusion once, with the speed crystallization of 5 ℃/min, and then try to achieve with the data after the speed intensification of 5 ℃/min.

For example, to [first temperature-rise period], 130 ℃ (keeping 5 minutes) of 30 ℃～130 ℃～one 30 ℃ [temperature-fall period], 30 ℃～130 ℃ [second temperature-rise period] measured, and uses the data of second temperature-rise period continuously.

Fusion end temp: as shown in Figure 2, serve as to fuse end temp with the intersection point place temperature of the tangent line of the baseline of fusion peak high temperature side and the tangent line of the point of peak value high temperature side parallax 1/5 peak height position.When having a plurality of peak, select to be positioned at the peak of highest temperature side, try to achieve the fusion end temp.

Main peak value temperature: the peak temperature of trying to achieve melt curve analysis by above-mentioned data.When having a plurality of peak, select the peak of fusing heat maximum, with this peak value as the fusion peak temperature.

Because the mixing of above-mentioned wax and above-mentioned mixed thing is to mix under the state of remaining wax crystallization, so preferred use mixing device used when mixing the high material of viscosity, and because for reaching uniform admixture, be necessary to be controlled at the following Optimal Temperature of wax fusion end temp, so be preferably the mixing vessel of temperature controllable, more preferably also can the refrigerative device to movable parts such as rotor, screw rods.Therefore, preferred pressurization kneading machine, open kneading machine, the roll mixing roll of using mixes.

Use the manufacture method of present embodiment, above-mentioned organic powder, inorganic powder can be evenly spread in the wax.Particularly when the powder that wetting ability is higher was distributed in the high wax of hydrophobicity, more than the melting point of wax, powder can condense, and powder can not homodisperse, but when utilizing the manufacture method of present embodiment, can obtain the polymolecularity of powder.

Because the composition that is obtained by aforesaid method contains bubble sometimes in mixed processes, also to carry out deaeration sometimes.Deaeration can be adopted usual method.For example, keep the method more than the melting temperature (Tm) of wax in the decompression thermostatic bath down, or the mixing devices such as kneading machine that maintenance has a mechanism of decompressor under reduced pressure, in the above blended method of the melting temperature (Tm) of wax etc.

When using natural rubber or synthetic polyisoprene etc. as mixed thing, more even for the dispersion that makes wax and mixed thing, be preferably the gained above-mentioned composition is heated to more than the melting temperature (Tm) of above-mentioned wax.

Utilize the manufacture method of the Wax composition of present embodiment, can make the Wax composition of above-mentioned embodiment 1 at short notice with high yield, and mixed thing can be evenly spread in the wax.Particularly when blended wax and natural rubber or synthetic polyisoprene,, also can disperse mixed thing extremely equably even wax is molten state not.

Below, according to the Wax composition (Biodegradable wax composition) of its preferred implementation explanation embodiment 2.

Because the Wax composition of present embodiment is a major ingredient with wax, show sufficient moistureproofness.And can guarantee biological degradability.Consequently: it is 3gmm/m that the Wax composition of present embodiment has biological degradability and its Water Vapour Permeability under 40 ℃, 90%RH ²24hr is following, be preferably 2g.mm/m ²24hr is following, 1gmm/m more preferably ²Below the 24hr.The lower value of the Water Vapour Permeability of Wax composition does not have special restriction, and it is low more good more to be preferably.

The Water Vapour Permeability of the Wax composition of present embodiment is by being shaped to the film of specific thickness by this Wax composition, utilizing cylinder plate method (JIS Z0208 condition B) to measure the Water Vapour Permeability of this film, again it is scaled thickness 1mm film and value.The scaled value of this Water Vapour Permeability is that supposition Water Vapour Permeability and film thickness are inversely proportional to, and will multiply by film thickness with the Water Vapour Permeability that cylinder plate method is measured and calculate.But owing to make the film that only constitutes by Wax composition, it is relatively more difficult as a rule to measure its Water Vapour Permeability with aforesaid method, so, in the case, can obtain the Water Vapour Permeability of Wax composition by making the laminated film of known Biodegradable resin film and Wax composition.For example, make the trilamellar membrane that is made of Biodegradable resin layer (A)/Wax composition layer (B)/Biodegradable resin layer (C), with the Water Vapour Permeability of aforesaid method mensuration trilamellar membrane integral body, establishing this Water Vapour Permeability is d.In addition, measure the Water Vapour Permeability of Biodegradable resin layer (A) and Biodegradable resin layer (C) equally, its Water Vapour Permeability is established respectively make a and c.When the Water Vapour Permeability of Wax composition layer (B) was b, following relation was set up.Wherein, a, b, c, d are the Water Vapour Permeabilitys of actual (real) thickness, are not the Water Vapour Permeability that is scaled 1mm thickness.

1/d＝1/a+1/b+1/c

Can obtain Water Vapour Permeability b by following formula as the Wax composition layer (B) of unknown number.

As mentioned above, the Wax composition of present embodiment is major ingredient with wax, but for being easy to realize that above-mentioned Water Vapour Permeability, Wax composition preferably contain wax 65～95 weight %, are preferably 70～85 weight % especially.

Biological degradability for the Wax composition of guaranteeing present embodiment preferably uses the wax of biological degradability (JIS K6950 or JIS K6953) more than 30%, more preferably uses this value at the wax more than 50%, and further preferred this value of using is at the wax more than 60%.

Consider Wax composition or by the package stability of the formed body of this Wax composition melt molding, the melting point of wax is preferably more than 40 ℃, more preferably more than 60 ℃.The melting point of wax is measured according to JISK2235-5.3.

In above-mentioned wax with various characteristics, it is that wax, oil are wax etc. that the preferred in the present embodiment wax that uses has department of botany's wax, animal.For example, can use above-mentioned document 1 described wax.Particularly, department of botany's wax can be enumerated a meter wax, carnauba wax, gama wax etc.; Animal is that wax can be enumerated beeswax, lanolin, spermaceti etc.; Oil is that wax can be enumerated Microcrystalline Wax, paraffin etc., wherein is preferably Microcrystalline Wax.Even synthetic wax as long as have biological degradability, just can be used for the present invention.

For obtaining in the good bonding on other material time the and for obtaining the flexible of Wax composition with the Wax composition lamination, the contained wax of this Wax composition is preferably in the calorimetric measurement that utilizes DSC, under 50 ℃ environment, the caloric receptivity Δ H1 of low temperature side is more than 10% with respect to total caloric receptivity Δ H2, more preferably more than 20%, more preferably more than 30%.This means that Wax composition contains fused wax at a lower temperature.Value by making Δ H1/ Δ H2 is more than the above-mentioned value, can improve the bonding force of Wax composition and Biodegradable resin or paper material etc., and is difficult for producing because of defectives such as breaking of causing of distortion such as bending or be full of cracks.In order to obtain the thermotolerance of sufficient Wax composition, this Wax composition institute content of wax is preferably under 50 ℃ environment, and the caloric receptivity Δ H1 of low temperature side is below 90% with respect to total caloric receptivity Δ H2, more preferably below 80%, more preferably below 70%.Can suppress stable on heating reduction thus.Based on the calorimetric measurement of DSC adopt with above-mentioned embodiment 1 in same method.

The melt flow rate (MFR) (be also referred to as MFR) of the Wax composition of present embodiment under 125 ℃, 1.2kgf load is preferably 0.1～1000g/10min, more preferably 0.5～100g/10min, 1～30g/10min more preferably.That is, Wax composition of the present invention has the melt flow characteristics of the melt molding that is suitable for using forcing machine.Therefore, as long as use Wax composition of the present invention, just can easily utilize T modulus method or inflation method to implement film forming.

The melting point of Biodegradable wax is usually less than 100 ℃, so after the Wax composition fusion of present embodiment, viscosity is reduced and be difficult to melt molding.For improving the melt viscosity of such Wax composition, the contriver thinks, outside whole wax compositions, add polymer substance in composition, but the moistureproofness of the Wax composition of gained reduces easily at this moment.Therefore, distinguish after the further investigations such as the inventor: when adding in the composition as polymer substance polyisoprene (synthesizing) or natural rubber, the moistureproofness of the Wax composition that obtains does not reduce, and melt viscosity improves.And because utilizing the mushroom that is grown in the soil to produce usually, polyisoprene or natural rubber decompose, so, also do not damage its biological degradability even these compositions are coupled in the Wax composition of the present invention.That is, polyisoprene, natural rubber are the biological degradability polymer substance.And by cooperate polyisoprene or natural rubber, also have can give the Wax composition moulding and forming composition thermotolerance, intensity, flexible etc. effect.

For prevent allergy, prevent the Wax composition that causes because of cross linked gel ununiformity, prevent the qualities such as viscosity of the Wax composition that causes because of the molecular weight change fluctuation, prevent to produce stink or painted, according to the concrete purposes of Wax composition, compare with natural rubber and more preferably to use polyisoprene.

For fear of the reduction of Wax composition moistureproofness, obtain being suitable for the melt flow characteristics of melt molding, be coupled to polyisoprene in the Wax composition or natural rubber amount and be preferably 5～35 weight %, be preferably 15～30 weight % especially.

For the melt flow characteristics that makes Wax composition is suitable for melt molding, distinguish according to inventor's etc. research: the molecular weight of suitably controlling biodegradation high molecular materials such as polyisoprene or natural rubber helps the realization of purpose.When its weight-average molecular weight of control is more than 200000, particularly more than 40000, especially 700000 when above, can make the melt flow characteristics of Wax composition be suitable for melt molding.The upper limit of weight-average molecular weight is being not particularly limited aspect the melt viscosity improving, and considers and be preferably the produceability of Wax composition below 4000000, is preferably below 2000000 especially.Weight-average molecular weight is measured by GPC and is tried to achieve.Specifically be after making Wax composition be dissolved in chloroform, the solution of removing undissolved wax after filtration carried out GPC as determination object measure.The calibration curve that gets according to measurement result and the known polystyrene standard sample of determining molecular weight is tried to achieve the weight-average molecular weight of polyisoprene or natural rubber.

Molecular weight for control polyisoprene or natural rubber, for example following method is arranged, in the manufacturing processed of Wax composition of the present invention, mixing time, shearing force, temperature when adjusting mixing wax and polyisoprene or natural rubber manufacturing Wax composition, apply mechanical shear stress for polyisoprene or natural rubber, cut off molecular chain, or utilize the heat induced oxidizing reaction that produces when mixing to cut off molecular chain.Usually, the tendency that when mixing time is elongated, have the molecular weight of polyisoprene or natural rubber to reduce, the MFR of Wax composition rises.And when in the presence of oxygen, heating, obviously reduce molecular weight because of oxidizing reaction sometimes.Therefore, for keeping high melt viscosity, preferred (1) is not given by mixing thing and is applied over-drastic shearing force or the mixed thing of non-superheated quilt when mixing, carries out under inert gas environment during (2) heating, and (3) use suitable antioxidant.

Other method of the molecular weight of control polyisoprene or natural rubber has: make suitably crosslinked method of polyisoprene or natural rubber.This method be especially effectively improve above-mentioned mixing in the method for the molecular weight of polyisoprene or the natural rubber molecular weight when excessively reducing.The kind of linking agent does not have special restriction.For example can be by adding with respect to polyisoprene before crosslinked or the lauroyl peroxide about natural rubber 0.1～2 weight %, the molecular weight that makes polyisoprene or natural rubber is in above-mentioned scope.Easy make polyisoprene or the crosslinked scheme of natural rubber have, and for example when making the Wax composition melt molding of present embodiment with forcing machine, add linking agent in forcing machine.Certainly, the polyisoprene of mixing precrosslink or natural rubber and wax also can obtain Wax composition.

The Wax composition of present embodiment is processed into particulate state and supplies to common forcing machine, also can melt molding.But because of the kind of the kind of wax, biodegradation high molecular material etc. or the difference of ratio of components, particle easily sticks together, so preferably make antiblocking be processed into particulate state with powder under attached to lip-deep state.Be processed into granular method and can adopt the usual method that is used to make resin granular material.

The modulation that can in all sorts of ways of the Wax composition of present embodiment.For instance, can be by wax and polyisoprene or natural rubber being supplied in the mixing roll such as pressurization kneading machine, carry out mixing and obtain with high shear force.Another example is by polyisoprene or natural rubber are dissolved in the normal heptane equal solvent, again with after the wax dissolving, utilizes method such as solvent evaporates to remove normal heptane and obtain.In aforesaid method, because of the former does not have residual solvent, does not use solvent, so carrying capacity of environment is little, low cost of manufacture, so preferably use the former method.Because under the situation that adopts arbitrary method, when heating polyisoprene or natural rubber, can significantly reduce because of oxidation causes molecular weight, so, when heating, preferably shorten heat-up time as possible, consider under nitrogen environment, to heat etc.Particularly using solvent to adjust under the situation of Wax composition,, melt viscosity is easily taking place significantly reduce, so should be noted that because molecular weight can reduce during solvent evaporates.

The Wax composition of present embodiment can for example be heated on the biodegradable container surface of systems such as being coated in Biodegradable resin or paper under the fused state.

With the surface of the Wax composition covering paper material of present embodiment, the long-pending Biodegradable resin layer of surface layer thereon also can obtain biological degradability lamination body again.

The Wax composition of also available T modulus method or inflation method melt molding present embodiment obtains moisture-proof barrier, cover the one side at least of this moisture-proof barrier with the Biodegradable resin layer, obtain having the multi-layer biological degradative membrane (below be also referred to as " Biodegradable films of embodiment 2 ") of moistureproofness.In the preferred implementation of Biodegradable films, lamination Biodegradable resin layer on each face of moisture-proof barrier forms three-layer structure.Because there is moisture-proof barrier in this Biodegradable films, so have moistureproofness.Value when the moistureproofness of Biodegradable films is preferably the Water Vapour Permeability of utilizing cylinder plate method (JIS Z 0208 condition B) to measure and is scaled the film of thickness 1mm is 2gmm/m ²24hr, 1gmm/m more preferably ²The degree of 24hr.This Water Vapour Permeability value is relevant with the Water Vapour Permeability of Wax composition, and the same method of the available and described computing method of preamble is calculated.

For the Biodegradable films with present embodiment covers the biodegradable container body surface, this film preferably has hot formability.Hot formability is meant, Biodegradable films after heating under the preset temperature, is controlled the two ends of this film, when the single shaft direction is stretched to the length of twice in the opposite direction, and this Biodegradable films non-cracking.Heating temperature during the Biodegradable films thermoforming can suitably be selected according to used Biodegradable resin, the used wax of moisture-proof barrier, thermoforming process (vacuum/vacuum pressure moulding, compression molding etc.).Select this Heating temperature,, and obtain sufficient moistureproofness so that moulding Biodegradable films integral body has suitable thickness distribution.For obtaining sufficient moistureproofness, in that can to suppress to carry out thermoforming under the inhomogenous Heating temperature of film thickness very important.Those skilled in the art can utilize the condition optimizing method of common employing to try to achieve the Heating temperature that satisfies this condition.

When judgement has or not hot formability, also select to obtain Heating temperature with the same good result of actual moulding.In most cases, as the benchmark of Heating temperature, can obtain good result by selection condition in following temperature range.For example, when Biodegradable resin is crystalline resins, the fusion peak value temperature T m that the melt curve analysis that gets with respect to being measured by DSC is tried to achieve (℃), Heating temperature is the scope of (Tm-40 ℃)～(Tm+20 ℃).But when having a plurality of fusion peak temperature, then select the fusion peak value of fusing heat maximum.When Biodegradable resin was the amorphous resin, with respect to its glass transition temperature Tg, Heating temperature was Tg～Tg+50 ℃ a scope.

In can be during acceptable, decompose, compost etc. is decomposed in during 2～3 months, the biological degradability of the Biodegradable films of present embodiment (aerobic ultimate biodegradation degree: JIS K 6950 or JIS K6953) is preferably more than 30%, more preferably more than 50%, more preferably more than 60%.

The Biodegradable films of present embodiment is a raw material with the Biodegradable wax composition of the above-mentioned embodiment that constitutes moisture-proof barrier and the Biodegradable resin that constitutes the Biodegradable resin layer, and the fusion co-extrusion modling by for example many menifolds T mould obtains.The Biodegradable wax composition of present embodiment has the flow characteristics that is suitable for melt molding as mentioned above, so can implement this co-extrusion modling with starting well and ending well.The gained film can carry out single shaft or biaxial stretch-formed as required.

Consider film strength and film forming, the total thickness of the Biodegradable films of present embodiment is preferably 10～2000 μ m, more preferably 20～1000 μ m.In the present embodiment, can suitably select the thickness of the Biodegradable resin layer in the Biodegradable films as required.Consider the operability of film strength and film, be preferably 5～1000 μ m, more preferably 10～500 μ m.In addition, in order to obtain practical moistureproofness, can keep the biological degradation film strength under the high temperature again, the thickness of moisture-proof barrier is preferably 1～500 μ m, more preferably 10～100 μ m.

The Biodegradable films of present embodiment of many uses, except that the covering on the container body surface that is used for biodegradable container as mentioned above, also can be used for various wrapping material films or paperboard (biological degradation paper) and biological degradation film lamination and biological degradability building papers such as laminated paper, be the biodegradable container of forms such as cup or case through bending machining or forming process by this biological degradability building paper.

The Biodegradable resin layer of the Biodegradable films of present embodiment is preferably formed by the copolymer resins or the aliphatic polycarbonate resin of the aliphatic polyester resin that possesses biological degradability, aliphatic polyester and aromatic polyester.Specifically can enumerate polydiethylene glycol succinate (PES), polybutylene succinate (PBS), poly(lactic acid) (PLA), polyoxyethylene glycol acid (PGA), poly butyric ester (PHB), polycaprolactone (PCL), the mixture of polycaprolactone and polybutylene succinate or multipolymer (PCL/PBS), the multipolymer of poly butyric ester and poly-hydroxyl valerate (PHB/PHV), the mixture of polybutylene succinate and poly adipate succinic acid ester or multipolymer (PBS/PBA), the multipolymer of polyethylene terephthalate and polydiethylene glycol succinate (PET/PES), the multipolymer of polybutylene terephthalate and poly adipate succinic acid ester (PBT/PBA) etc.These resins can use separately or be used in combination.

In can be during acceptable, decompose, (aerobic ultimate biodegradation degree: JIS K 6950 or JIS K6953) is preferred more than 30% for the biological degradability of the Biodegradable resin layer in the Biodegradable films of present embodiment, more preferably more than 50%, more preferably more than 60%.

The Biodegradable films of present embodiment is covered the biodegradable container surface, obtain biodegradable container.When Biodegradable films was the two-layer structure of moisture-proof barrier and Biodegradable resin layer, this Biodegradable films became relative mode to cover with Biodegradable resin layer and vessel side.As long as the material of said vesse possesses biological degradability, remove this and do not have special restriction.The biological degradability of container (aerobic ultimate biodegradation degree: JIS K 6950 or JIS K6953) is preferably more than 30%, more preferably more than 50%, more preferably more than 60%.Container material can be enumerated for example fiber such as natural fiber, biological degradability synthon, natural polymer, and above-mentioned Biodegradable resin, and the mixture of above-mentioned materials etc.Natural fiber can be enumerated wood pulp cellulose, non-wood pulp cellulose, thin,tough silk, wool etc.The biological degradability synthon can be enumerated acid fiber by polylactic, vinylon, regenerated fiber etc.Natural polymer can be enumerated starch, protein etc.Container shapes does not have special restriction.For example can enumerate various container shapes such as cup, jorum, bottle, dish, alms bowl, case, tube.

The container position that covers with Biodegradable films can suitably be selected according to the purposes of container, shape etc.For example can cover container inner face, container outside etc.Particularly under the situation that is used for cup etc., be preferably the internal surface of using the Biodegradable films covering container at least.

Cover at vessel surface under the situation of Biodegradable films, both can engage between vessel surface and the Biodegradable films, also vessel surface and Biodegradable films directly can be engaged by caking agent.When using caking agent,, and it is formed the special restriction of nothing as long as this caking agent has biological degradability.Caking agent is the same with Biodegradable films, and its biological degradability (aerobic ultimate biodegradation degree: JIS K6950 or JIS K6953) is preferably more than 30%, more preferably more than 50%, more preferably more than 60%.Specifically can enumerate starch, polyvinyl alcohol, gelatin, gelatin, casein, not sulfurized natural rubber, do not vulcanize polyisoprene etc.For utilizing heating and melting to be bonded on the container, caking agent also can use melting point to be lower than the Biodegradable resin of vessel side Biodegradable resin layer or various natural resins etc.When use utilizes solvent evaporates to carry out bonding caking agent, the solution that contains bonding composition can be coated on Biodegradable films and container either party or two sides, by on Biodegradable films or container either party's surface, forming bonding composition and solvent being coated on the opposing party, also can realize bonding.The method that vessel surface and Biodegradable films are directly engaged for example can be enumerated at container inner face configuration Biodegradable films, heats this container from the container exterior side then, implements the method for vacuum forming or vacuum pressure moulding under this state.

The Wax composition of embodiment 3 then, is described based on its preferred implementation.

Have the high-temperature digestion wax composition of endotherm(ic)peak more than 100 ℃ when the Wax composition of present embodiment contains based on the DSC calorimetric measurement, and more than 40 ℃, be lower than 100 ℃ of low temperature fusion wax compositions with endotherm(ic)peak, based on these two kinds of wax compositions.With two kinds of wax compositions is that main body means that the total content of above-mentioned high-temperature digestion wax composition and above-mentioned low temperature fusion wax composition accounts for maximum volume fractions in all contained compositions.When being major ingredient, can show sufficient moistureproofness with the wax composition.In order to obtain better moistureproofness, two wax compositions are preferably in volume fraction and are higher than 40 weight %, more preferably are higher than 50 weight %.

In this embodiment, mean that heat-up rate is 5 ℃/min having the high-temperature digestion wax composition of endothermic peak (below be also referred to as " high-temperature digestion wax composition ") more than 100 ℃ during based on the calorimetric measurement of DSC, during based on the calorimetric measurement of DSC, the composition that in the zone of temperature more than 100 ℃, has endothermic peak; And more than 40 ℃, be lower than 100 ℃ of low temperature fusion wax compositions with endotherm(ic)peak (below be also referred to as " low temperature fusion wax composition ") and mean in the calorimetric measurement at the same terms, in temperature more than 40 ℃, be lower than the composition that has endothermic peak in 100 ℃ the zone.The endothermic peak of two kinds of wax compositions is accompanied by the crystalline fusion.

In addition, in the present embodiment, use with the same method of above-mentioned embodiment 1 based on the calorimetric measurement of DSC and to carry out.And Wax composition (composition that contains high-temperature digestion wax composition, low temperature fusion wax composition and polymer substance) measured as test portion.

The Water Vapour Permeability of the Wax composition of present embodiment is according to the method calculating same with above-mentioned Water Vapour Permeability method of calculation.

As mentioned above, the Wax composition of present embodiment contains high-temperature digestion wax composition and low temperature fusion wax composition.Under the situation that only contains low temperature fusion wax composition, when making the Wax composition fusion, viscosity reduces, and is difficult to carry out processing such as melt molding sometimes; But by combination high-temperature digestion wax composition, can not only suppress moistureproofness and reduce, can also improve and utilize T modulus method, inflation method melt molding etc. other adds the processibility in man-hour.

High-temperature digestion wax composition and low temperature fusion wax composition are preferably different types of wax.

The temperature of the above-mentioned endothermic peak of high-temperature digestion wax composition is 120～250 ℃, is preferably 150～200 ℃ especially; The temperature of the above-mentioned endothermic peak of low temperature fusion wax composition is 40～90 ℃, is preferably 50～80 ℃ especially; The temperature head of the endothermic peak of two wax compositions is 20～200 ℃, more preferably 40～180 ℃, is preferably 50～160 ℃ especially.

In order to obtain the high melt viscosity that processibility is improved, the Wax composition of present embodiment with Wax composition as the calorimetric measurement based on DSC of test portion (in 5 ℃ of the heat-up rates/min), the caloric receptivity Δ H that is higher than 100 ℃ high temperature side is preferably 0.1～5.0 with the ratio (the former/latter) of caloric receptivity Δ H that is lower than 100 ℃ low temperature side, more preferably 0.2～4.0, be preferably 0.2～3.0 especially.In addition, in this calorimetric measurement, with Wax composition (composition that contains high-temperature digestion wax composition, low temperature fusion wax composition and polymer substance) as test portion.

The wax that is preferably used as high-temperature digestion wax composition can be enumerated N, N '-ethylene lauric amide, N, N '-ethylene bis-stearamide, N, N '-methylene radical distearyl acid acid amides, N, N '-ethylene-12-oxystearic acid acid amides, stearic acid monomethylol acid amides, N, N '-N-substituted fatty acid acid amides such as distearyl terephthalic acid acid amides, fatty acid amides such as 12-oxystearic acid acid amides, metallic soaps such as 12-hydroxy lithium stearate, 12-oxystearic acid calcium.Wherein,, be preferably the N-substituted fatty acid acid amides of the endothermic peak that has more than 130 ℃, be preferably the N of the lipid acid that uses carbonatoms 6～18 especially, N '-ethylene diamide etc. because of the temperature range widely that can guarantee that processibility is good.Also can preferably use the mixed fatty acid that will contain the different lipid acid of carbonatoms to be used as the fatty acid amide of raw material.Wherein, the preferred wax with biological degradability that uses also can use the wax that does not have biological degradability.When use had Biodegradable wax, biological degradability (aerobic ultimate biodegradation degree: JIS K 6950 or JIS K6953) was preferably more than 30%, more preferably more than 50%, more preferably more than 60%.

It is that wax, oil are wax etc. that the wax that low temperature fusion wax composition preferably uses has department of botany's wax, animal, for example can use above-mentioned document 1 described wax.

Department of botany's wax can be enumerated a meter wax, carnauba wax, gama wax etc.; Animal is that wax can be enumerated beeswax, lanolin, spermaceti etc.; Oil is that wax can be enumerated Microcrystalline Wax, paraffin etc., wherein is preferably Microcrystalline Wax.These waxes all are Biodegradable waxes, also can use the wax of nonbiodegradability.

The Wax composition of present embodiment also contains polymer substance except that all wax compositions that contain high-temperature digestion wax composition and low temperature fusion wax composition.When Wax composition only during content of wax composition, when making the Wax composition fusion of present embodiment, viscosity will be reduced, be difficult to carry out other processing such as melt molding sometimes.Therefore, also contain paraffin removal composition polymer substance in addition.

Same material in the Wax composition of above-mentioned polymer substance use and above-mentioned embodiment 1.

Wherein, be preferably amorphism and more than the melting point of wax, have polymer substance with the intermiscibility of wax, be preferably polyisoprene or natural rubber especially.

The contriver thinks: for improving the melt viscosity of Wax composition, polymer substance is added in the composition, but in the case, polymer substance might reduce the moistureproofness of Wax composition.Distinguish after the further investigations such as the inventor: when adding to polymer substances such as polyisoprene or natural rubber in the composition, the moistureproofness of gained Wax composition does not reduce, and melt viscosity is improved.As described later, can be combined to form Biodegradable wax composition with Biodegradable wax.And, by adding polyisoprene or natural rubber, give the moulding Wax composition in addition and the forming composition thermotolerance or the additional effect of intensity etc.

For avoiding the reduction of Wax composition moistureproofness, obtain melt flow characteristics that is suitable for melt molding etc., the use level of polymer substances such as polyisoprene in the Wax composition or natural rubber is preferably 5～35 weight %, is preferably 15～30 weight % especially.

The inventor etc. distinguish after after deliberation: for the melt flow characteristics that makes Wax composition is suitable for melt molding, the molecular weight of suitably controlling polyisoprene or natural rubber is favourable.For example the weight-average molecular weight when polyisoprene is controlled at more than 200000, is preferably more than 40000 especially, more preferably in the scope more than 700000 time, can make the melt flow characteristics of Wax composition be suitable for melt molding.For improving melt viscosity, the weight-average molecular weight upper limit is not had special restriction, but consider the difficulty or ease that Wax composition is made, be preferably below 4000000, be preferably below 2000000 especially.Weight-average molecular weight is measured by GPC and is tried to achieve.After Wax composition is dissolved in chloroform, removes by filter not the solution of the wax of fusion and measure with utilizing, by this measurement result and the known polystyrene standard sample of determining molecular weight and calibration curve try to achieve weight-average molecular weight.

For obtaining biological degradability moistureproofness article (comprising damp-proof membranes, moisture-proof container) etc., the Wax composition of present embodiment is preferably above-mentioned high-temperature digestion wax composition, above-mentioned low temperature fusion wax composition and above-mentioned polymer substance and all has biological degradability.

For guaranteeing the biological degradability of Biodegradable wax composition, as the wax of above-mentioned high-temperature digestion wax composition and as the wax of above-mentioned low temperature fusion wax composition preferred respectively use biological degradability (JIS K 6950 or JIS K6953) be 30% or more wax, more preferably use the wax more than 50%, the further wax that preferably uses more than 60%.

Above-mentioned polymer substance is preferably above-mentioned polyisoprene or natural rubber.Because polyisoprene or natural rubber can be decomposed by the bacterium that is grown in the soil usually, so, even these compositions are engaged in the Wax composition of the present invention, also harmless its biological degradability.

The Wax composition of present embodiment is suitable for melt moldings such as T mold forming or inflation moulding, usually the MFR that is preferably under 125 ℃, 1.2kgf load is 0.1～1000g/10min, but for improving the processibility of other processing such as melt molding, more preferably 0.5～100g/10min, the Wax composition of 1～30g/10min more preferably.

Be to improve the processibility of other processing such as melt molding under higher temperature, the MFR of the Wax composition of present embodiment under 150 ℃, 1.2kgf load is preferably 0.1～1000g/10min, more preferably 0.5～100g/10min, 1～30g/10min more preferably.

The modulation that can in all sorts of ways of the Wax composition of present embodiment.For instance, can be by will supplying to as the wax of high-temperature digestion wax composition with as the wax of low temperature fusion wax composition and polymer substance (polyisoprene, natural rubber etc.) in the mixing roll such as pressurization kneading machine, carry out mixing and obtain with high shear force.Another example is by polymer substance (polyisoprene, natural rubber etc.) is dissolved in the normal heptane equal solvent, again with the dissolving of wax composition, utilizes method such as solvent evaporates to remove normal heptane and obtain then.

As mentioned above, for example the Wax composition of present embodiment can be coated on the surface of Biodegradable resin or paper-made vessel etc. under the heating and melting state.Obtain moisture-proof barrier with T modulus method or inflation method melt molding Wax composition of the present invention, resin layer or ply of paper are amassed on the one side at least of this moisture-proof barrier, also can form multilayer damp-proof membranes or building paper thus with moistureproofness.

Then, the preferred implementation based on the manufacture method of moistureproofness article of the present invention illustrates its manufacture method.The moisture-proof container that utilizes the moistureproofness article of the manufacture method manufacturing of moistureproofness article of the present invention to comprise to obtain as mentioned above, damp-proof membranes, building paper etc.

The manufacture method of the moistureproofness article of present embodiment is the manufacture method with laminate of following operation, it is heated to fusion under the temperature more than 100 ℃ with the Wax composition of above-mentioned embodiment 3, this melts is coated in resin sheet or film, paper, on the surface of resin or paper-made vessel etc., form the Wax composition layer, the Heating temperature of above-mentioned Wax composition is, (during 5 ℃ of heat-up rates/min), making high temperature side caloric receptivity that is higher than this Heating temperature and the ratio that is lower than the low temperature side caloric receptivity of this Heating temperature (the former/latter) is 0.1～5.0 temperature as the calorimetric measurement based on DSC of test portion with Wax composition.

Another embodiment of the manufacture method of moistureproofness article of the present invention is the manufacture method with laminate of following operation, in this operation, use forcing machine the Wax composition melt molding of above-mentioned embodiment 3 to be film or thin slice with T modulus method or inflation method, the temperature of extruding Wax composition from forcing machine etc. is, (during 5 ℃ of heat-up rates/min), the ratio (the former/latter) that makes high temperature side caloric receptivity that is higher than this Heating temperature and the low temperature side caloric receptivity that is lower than this Heating temperature is 0.1～5.0 temperature as the calorimetric measurement based on DSC of test portion with Wax composition.

In arbitrary manufacture method, be higher than the high temperature side caloric receptivity of this Heating temperature and the ratio of the low temperature side caloric receptivity that is lower than this Heating temperature (the former/latter) and all be preferably 0.2～4.0, be preferably 0.2～3.0 especially.

Then, the preferred implementation based on damp-proof membranes of the present invention illustrates damp-proof membranes of the present invention.

The damp-proof membranes of present embodiment is that Biodegradable resin amasss layer by layer that above-mentioned two wax compositions in the Wax composition of the above-mentioned embodiment 3 of melt molding and above-mentioned polymer substance all have Biodegradable wax composition and on each face of the moisture-proof barrier that obtains and the biological degradability damp-proof membranes of the three-layer structure that forms.Damp-proof membranes has moistureproofness because of the existence of moisture-proof barrier.The moistureproofness degree of film be preferably will utilize the value of the Water Vapour Permeability measured of cylinder plate method (JIS Z 0208 condition B) when being converted into the film of thickness 1mm be 3gmm/m ²24hr is following, 2gmm/m more preferably ²24hr is following, 1gmm/m more preferably ²Below the 24hr.The method that this Water Vapour Permeability value adopts and aforementioned algorithm is same is calculated.

The following describes this biological degradability damp-proof membranes (being designated hereinafter simply as " Biodegradable films "), except that special repugnance, be equally applicable to not possess the damp-proof membranes of biological degradability in the following explanation.

For the Biodegradable films with present embodiment covers on the biodegradable container surface, the Biodegradable films that this film is preferably with above-mentioned embodiment 1 has hot formability equally.Hot formability is meant, Biodegradable films after heating under the preset temperature, is controlled the two ends of this film, when the single shaft direction is stretched to the length of twice in the opposite direction, and this Biodegradable films non-cracking.Heating temperature during the Biodegradable films thermoforming can suitably be selected according to used Biodegradable resin, the used wax of moisture-proof barrier, thermoforming process (vacuum/vacuum pressure moulding, compression molding etc.).Select this Heating temperature,, and obtain sufficient moistureproofness so that moulding Biodegradable films integral body has suitable thickness distribution.For obtaining sufficient moistureproofness, in that can to suppress to carry out thermoforming under the inhomogenous Heating temperature of film thickness very important.Those skilled in the art can utilize the condition optimizing method of common employing to try to achieve the Heating temperature that satisfies this condition.

When judgement has or not hot formability, also select to obtain Heating temperature with the same good result of actual moulding.In most cases, as the benchmark of Heating temperature, can obtain good result by selection condition in following temperature range.For example, when Biodegradable resin is crystalline resins, the fusion peak value temperature T m that the melt curve analysis that gets with respect to being measured by DSC is tried to achieve (℃), Heating temperature is the scope of (Tm-40 ℃)～(Tm+20 ℃).But when having a plurality of fusion peak temperature, then select the fusion peak value of fusing heat maximum.When Biodegradable resin was the amorphous resin, with respect to its glass transition temperature Tg, Heating temperature was Tg～Tg+50 ℃ a scope.

The preferred biological degradability of the Biodegradable films of present embodiment is the same with the Biodegradable films of above-mentioned embodiment 2.

The Biodegradable films of present embodiment can be with obtaining with the same forming method of the Biodegradable films of above-mentioned embodiment 2.Its preferred thickness and the purposes also Biodegradable films with above-mentioned embodiment 2 are the same.

Biodegradable resin layer in the Biodegradable films of present embodiment is preferably by forming with the same Biodegradable resin of the Biodegradable films of above-mentioned embodiment, and biological degradability too.

The Biodegradable films of present embodiment is covered the biodegradable container surface, can obtain biodegradable container.When Biodegradable films was the two-layer structure of moisture-proof barrier and Biodegradable resin layer, this Biodegradable films became relative mode to cover with Biodegradable resin layer and vessel side.As long as the said vesse bulk material possesses biological degradability, remove this and do not have special restriction.The biological degradability of container (aerobic ultimate biodegradation degree: JIS K 6950 or JIS K6953) is preferably more than 30%, more preferably more than 50%, more preferably more than 60%.Container material can be enumerated for example fiber such as natural fiber, biological degradability synthon, natural polymer, and above-mentioned Biodegradable resin, and the mixture of above-mentioned materials etc.Natural fiber can be enumerated wood pulp cellulose, non-wood pulp cellulose, thin,tough silk, wool etc.The biological degradability synthon can be enumerated acid fiber by polylactic, vinylon, regenerated fiber etc.Natural polymer can be enumerated starch, protein etc.Container shapes does not have special restriction.For example can enumerate various container shapes such as cup, jorum, bottle, dish, alms bowl, case, tube.

The container position that covers with Biodegradable films can suitably be selected according to the purposes of container, shape etc.For example can cover container inner face, container outside etc.Particularly under the situation that is used for cup etc., be preferably the internal surface of using the Biodegradable films covering container at least.

The Biodegradable films of present embodiment is the same with the Biodegradable films of above-mentioned embodiment, can cover vessel surface.

Below, be described more specifically the present invention by embodiment.And the present invention is not subjected to any restriction of following embodiment.

As making Wax composition as described in following embodiment 1-1～embodiment 1-3 and comparative example 1-1 and the comparative example 1-2.Then, the dispersing uniformity of evaluation said composition as described below.When doing dispersed the evaluation, said composition is heated to more than the melting point of wax and deaeration, being stretched to thickness then under molten state is about 5mm, and naked eyes confirm whether to exist granular mixed thing.In addition, above-mentioned saccharoid is judged to not dispersion state.

Embodiment 1-1

With Microcrystalline Wax (Japanese smart wax (strain) system, model " Hi-Mic-1070 ", fusion 86 ℃ of end temps, 44 ℃ of main peak value temperature) 44g and add the smart mechanism of Japan through not sulfurized natural rubber (being designated hereinafter simply as " the natural rubber ") 11g of mastication and do in the mixing container of the system Laboplastomill (30C150 type) of institute's (strain), with the revolution of 30rpm mixing 10 minutes.The thermometer displays temperature is 22 ℃ in the mixing container before feeding intake.Well heater at mixing roll is to be mixed to mixing end under the complete shut-down state.The thermometer displays temperature is 37 ℃ in mixing container during mixing the end.Δ H ' under 37 ℃ is 12% of Δ H.At this moment, it is mixing not use any solvent to carry out.

Can confirm: resulting composition is the white mass that contains bubble, and each composition is uniformly dispersed.110 ℃, stream of nitrogen gas ,-drying machine of 500mmHg in, resulting composition is implemented deaeration handles, after confirming to become dispersion state once more under the molten state, form the transparent and uniform composition, but can not confirm the not existence of dispersive natural rubber.

Embodiment 1-2

Replace the natural rubber among the embodiment 1-1 with synthetic polyisoprene (Japanese Zeon (strain) system, model " Nipol-IR2200 "), use method similarly to Example 1 to obtain Wax composition.The thermometer displays temperature is 39 ℃ in mixing container during mixing the end.39 ℃ Δ H ' is 16% of Δ H.Be mixing under the state of complete shut-down at well heater, directly the well heater of mixing vessel brought up to 85 ℃, mixing again 7.5 minutes then.After confirming the dispersion state under the molten state, mixing under 85 ℃, remove the bubble in the composition, form the transparent and uniform composition, but can not confirm the not existence of dispersive synthetic polyisoprene.

Embodiment 1-3

Use (strain) gloomy mountain to make made pressurization kneading machine (DS0.3-3 type), Microcrystalline Wax (Japanese smart wax (strain) system, model " Hi-Mic-1070 ") 1800g and synthetic polyisoprene (Japanese Zeon (strain) system, model " Nipol-IR2200 ") 600g are added in the mixing container of pressurization kneading machine, with the revolution of 20rpm mixing 5 minutes, the same wax 600g of additional input and mixing 10 minutes again.Mixing water coolant at 10 ℃ flows in mixing vessel and the kneading machine and well heater is to carry out under the state of complete shut-down.The top temperature of mixture is 37 ℃ (thermometer displays temperatures in the mixing vessel) in mixing, directly measures composition temperature after the mixing end with contact thermometer, is 36～42 ℃.36 ℃ Δ H ' is that 10%, 42 ℃ the Δ H ' of Δ H is 22% of Δ H.

Confirm: resulting composition is the white mass that contains bubble, and is homogeneously dispersed state.With with the same method of embodiment 1-1 to the resulting composition deaeration, under molten state, reaffirm dispersion state, form the transparent and uniform composition then, but can not confirm the not existence of dispersive synthetic polyisoprene.

Embodiment 1-4

With the method same, replace Microcrystalline Wax (Japanese smart wax (strain) system, model " Hi-Mic-1070 ") to carry out mixing with Microcrystalline Wax (Japanese smart wax (strain) system, model " Hi-Mic-1080 ", 86 ℃ of end temps of fusion, 59 ℃ of main peak value temperature) with embodiment 1-3.The mixture top temperature is 45 ℃ (displays temperatures of thermometer in the mixing vessel) in mixing, directly measures mixing end back composition temperature with contact thermometer, is 37～50 ℃.37 ℃ Δ H ' is that 0%, 50 ℃ the Δ H ' of Δ H is 5% of Δ H.

Confirm: resulting composition is the white mass that contains bubble, and is homogeneously dispersed state.With with the same method of embodiment 1-1 to the resulting composition deaeration, under molten state, reaffirm dispersion state, form the transparent and uniform composition, but can not confirm the not existence of dispersive synthetic polyisoprene.

Embodiment 1-5

In embodiment 1-1,, use with the same method of embodiment 1-1 and obtain Wax composition except that using mineral filler lipophilicity montmorillonite (Co-Op Chemical (strain) system, model " Lucentite SAN ") to replace the natural rubber.The thermometer displays temperature is 35 ℃ in mixing container during mixing the end.35 ℃ Δ H ' is 9% of Δ H.Confirm: resulting composition is the homogeneously dispersed state of whole white.With with the same method of embodiment 1-1 to the resulting composition deaeration, under molten state, reaffirm dispersion state, be the oyster white homogeneous compositions.

Comparative example 1-1

Except that the well heater of mixing vessel is made as 90 ℃, uses with the same method of embodiment 1-1 and mix.Owing to wax fusion significantly reduces viscosity, so the dispersive natural rubber is not the state that directly is bonded on kneading machine and the mixing vessel, even continue mixingly, its state is no change also.

Comparative example 1-2

Make the coating liquid of hexanaphthene 80wt%, gama wax 16wt%, natural rubber 4wt% of following method.In three days, will be dissolved in hexanaphthene while stirring, add the gama wax (64 ℃ of the wild field system of (strain) Cerarica, melting points) of fine pulverizing then,, form coating liquid 70 ℃ of dissolvings down through the natural rubber (sumitomo rubber industry (strain) system) that deproteinization is handled.At room temperature, with the scraper of #40 gained is applied liquid (solid composition 20wt%) and be coated in paper (coated cardboard) and go up air-dryly, after the drying, be coated with air-dry drying again with same scraper.After coating finishes for the second time, measure the middle hexanaphthene residual quantity of filming with following method.Cut 1g from paper and film, be dissolved into 10ml, then with it as test portion, measure the hexanaphthene residual quantity with the gas-chromatography (Agilent-6890) of having equipped hydrogen ion flame detector.The result is shown in table 1-1.As show shown in the 1-1, even the filming of composition that obtains with this method passed through seven days, also residual have a 0.1wt% hexanaphthene.

Table 1-1

Coating back experience (my god)	The contained hexanaphthene amount (wt%) of filming
		??1	??14
??2	??2
		??3	??0.5
??7	??0.1

Comparative example 1-3

Except that the well heater of mixing vessel is made as 90 ℃, uses with the same method of embodiment 1-5 and mix.The weighting material cohesion can not evenly spread in the wax.

Embodiment 2-1

Wax uses Japanese smart wax (strain) system Microcrystalline Wax " Hi-Mic-1070 " (trade(brand)name).The biodegradation high molecular material uses polyisoprene (IR2200 of Japanese Zeon (strain) system).Wax and polyisoprene mix with 7: 3 weight ratio, and using has mixing 15 minutes of 10 ℃ cooling water circulation pressurization kneading machine, obtains Wax composition.The gained Wax composition contains bubble, so in vacuum drying oven, deaeration is 24 hours under 100 ℃, nitrogen gas stream environment.Wax composition based on the calorimetric measurement result of DSC as shown in Figure 3.

Again the Wax composition layer is clipped between the film that the Biodegradable resin that polycaprolactone and polybutylene succinate polymer blending form (Daicel chemical industry (strain) system PHB05) forms, utilize the compression molding forming machine moulding, make the Biodegradable films of three-layer structure.Gained Biodegradable films total thickness is 400 μ m, and the Wax composition layer thickness is 200 μ m, and each Biodegradable resin film thickness is 100 μ m.

Embodiment 2-2

Weight ratio blended wax and polyisoprene with 8: 2.The same with the embodiment 2-1 in addition Wax composition of making obtains the Biodegradable films of three-layer structure.

Embodiment 2-3

1 weight % adds in the Wax composition of embodiment 2-2 with the linking agent lauroyl peroxide, with Laboplastomill mixing after, under nitrogen environment,, obtain crosslinked polyisoprene Wax composition 100 ℃ baking oven internal heating 40 hours.Use this Wax composition to obtain the Biodegradable films of three-layer structure.

Comparative example 2-1

Except that mixing time is 60 minutes, other is the same with embodiment 2-1, makes Wax composition, obtains the Biodegradable films of three-layer structure.

Embodiment 2-4

With embodiment 2-1 gained Wax composition and Biodegradable resin (Biodegradable resin that polycaprolactone and polybutylene succinate polymer blending form (Daicel chemical industry (strain) system PHB05)) is raw material, utilize T modulus method fusion coextrusion, obtain the Biodegradable films of moisture-proof barrier and the three-layer structure of the Biodegradable resin layer of lamination on its each face.Used T mould is three kinds of menifold types more than three layers.In this example, with pulverizer with the deaeration of embodiment 2-1 after the Wax composition freezing and pulverizing, obtain the particle about particle diameter 3mm, with respect to gained particulate 100 weight parts, make anhydrous silica granule (Japanese Aerosil (strain) makes R927, median size 12 μ m) 1 weight part attached on the particle as antiblocking agent.Moisture-proof barrier in the gained Biodegradable films is made of Wax composition, and each Biodegradable resin layer is made of Biodegradable resin.Gained Biodegradable films total thickness is 400 μ m, and moisture-proof barrier thickness is 200 μ m, and each Biodegradable resin film thickness is 100 μ m.

Embodiment 2-5

Except that replace the embodiment 2-1 gained Wax composition the same Biodegradable films that obtains three-layer structure with embodiment 2-2 gained Wax composition with embodiment 2-4.

Comparative example 2-2

Remove in order to weight ratio 9: 1 with Hi-Mic-1070 with after the natural rubber (sumitomo rubber industry (strain) system) that deproteinization is handled is dissolved in normal heptane and thorough mixing, heating the Wax composition that made the normal heptane volatilization in 72 hours and get down at 120 ℃ replaces outside the embodiment 2-1 gained Wax composition, other is the same with embodiment 2-4, attempts the Biodegradable films of moulding three-layer structure.But extrude at the both ends of the central part of Wax composition deflection mould, Biodegradable resin deflection mould, can not be shaped to three-layer thin-film.The MFR of the Wax composition that this example is used is 2000g/10min.

Embodiment 2-6

Use embodiment 2-1 gained Wax composition and Biodegradable resin (Biodegradable resin that polycaprolactone and polybutylene succinate polymer blending form (Daicel chemical industry (strain) system PHB05)), utilize compression molding forming machine to obtain the double-layer structural Biodegradable films of moisture-proof barrier and Biodegradable resin layer.Gained Biodegradable resin film is made of Biodegradable resin.Gained Biodegradable films total thickness is 200 μ m, and moisture-proof barrier thickness is 100 μ m, and each Biodegradable resin film thickness is 100 μ m.Utilize compression molding forming machine with this film and paper (quantitative 370g/m ²Coated cardboard) lamination, obtain laminate by paper/moisture-proof barrier/the Biodegradable resin layer constitutes.The Wax composition of gained laminate is few to the infiltration of paper, has the moisture-proof barrier of uniform thickness.

Embodiment 2-7

Utilize vacuum forming that embodiment 2-4 gained Biodegradable films is engaged and covers with pulp mold container body inner face, obtain the cup-shaped biodegradable container.The container body size shape is upper end open internal diameter 90mm, bottom internal diameter 60mm, high 100mm, the about 300cm of internal surface area ²

Performance evaluation

Measure the Water Vapour Permeability and the MFR of the Wax composition of embodiment 2-1～2-3 and comparative example 2-1 with aforesaid method.And the weight-average molecular weight of mensuration polyisoprene.The result is shown in table 2-1.Estimate the cementability of Biodegradable films of embodiment 2-1～2-3 and comparative example 2-1 and flexible with following method.The result is shown in table 2-1.And measure with aforesaid method embodiment 2-4,2-5 and comparative example 2-2 Biodegradable films Water Vapour Permeability and estimate its formability.The result is shown in table 2-2.At this, by the measured value of the Water Vapour Permeability of three-layer thin-film and the Water Vapour Permeability measured value 132g/m of Biodegradable resin rete (PHB05,100 μ m) ²24hr tries to achieve the Water Vapour Permeability of Wax composition.By the do not convert value of thickness of the Water Vapour Permeability of the laminate (embodiment 2-6) that paper/moisture-proof barrier/the Biodegradable resin layer constitutes is 10g/m ²24hr, the average Water Vapour Permeability of the biodegradable container (embodiment 2-7) of calculating with following method is 0.8g/m ²24hr.

The evaluation of the cementability of Biodegradable films

The gained three-layer thin-film is cut into the wide band of 20mm, and when bending its end with hand, the situation that the surface of Wax composition layer and Biodegradable resin layer is not peeled off is designated as zero, and the situation of sur-face peeling is designated as *.

The Wax composition layer flexible of Biodegradable films estimated

The gained three-layer thin-film is cut into the wide band of 20mm, and when it was curved 90 °, the situation that the Wax composition layer is not cracked was designated as zero, and situation about cracking is designated as *.

The mensuration of the average Water Vapour Permeability of biodegradable container

Calcium chloride 50g is added biodegradable container, then sheet glass is placed on the opening, with the gap of wax fixing seal opening and sheet glass.Container is placed on a week in the constant temperature and humidity cabinet of 40 ℃ of temperature, 90RH%, tries to achieve the poor of gross weights (container, calcium chloride, wax, sheet glass) before and after placing.Film unit elongation when then, establishing vacuum forming is that 400% (area), cup inner area are 0.03m ², utilize following formula to try to achieve average Water Vapour Permeability.

By table 2-1 as can be known: the Wax composition Water Vapour Permeability of embodiment 2-1 and 2-3 is low, MFR is low and the melt viscosity height.And as can be known the Wax composition of embodiment 2-2 moistureproofness height, MFR height but melt viscosity is low.By table 2-2 as can be known: when using the high Wax composition of MFR, utilize co-extrusion modling can make evenly and the low multilayer film of Water Vapour Permeability.

Table 2-1

	Wax composition						Biodegradable films
									Water Vapour Permeability gmm/m 2·24hr	??MFR ??g/10min	Wax wt%	Polyisoprene wt%	The polyisoprene weight-average molecular weight	ΔH1/ΔH2％	Cementability	Flexible
	Embodiment 2-1	??1.5	??40	??70	??30	??490000	49	??○									??○
Embodiment 2-2									??1.2	??790	??80	??20	??520000	49	??○	??○
	Embodiment 2-3	??1.2	??14	??80	??20	??560000	49	??○									??○
Comparative example 2-1									??1.2	More than 2000	??70	??30	??190000	-	??-	??-

Table 2

	Biodegradable films
			Formability	Water Vapour Permeability gmm/m 2·24hr
	Embodiment 2-4	??○			??3
Embodiment 2-5			??○	??2.4
	Comparative example 2-2	??×			Can not measure

By table 2-1 as can be known: when using the Wax composition of embodiment, can improve the cementability of Biodegradable films and flexible.Though do not show in the table, but still as can be known, even the Biodegradable films of embodiment is also no problem on performances such as moistureproofness under 40 ℃ environment, Wax composition has sufficient thermotolerance.Also as can be known, can obtain with the low paper of Water Vapour Permeability is the laminate or the biodegradable container of base material.In addition, though do not show in the table, but still can confirm that the Wax composition of each embodiment, Biodegradable films and biodegradable container all have biological degradability.Also can confirm: when utilizing co-extrusion modling to form three-layer thin-film, antiblocking agent is used for particle to carry out moulding and compares with the situation of not using antiblocking agent, in the pellet supply part of shaper, have prevent attached on the Wax composition, prevent the effect of adhesion between the particle.

Embodiment 3-1

(1) manufacturing of Wax composition

Under 150 ℃, will spend king's (strain) system ethene-difatty acid acid amides " flower king wax EB-FF " (trade(brand)name) and Japanese smart wax (strain) system Microcrystalline Wax " Hi-Mic-1045 " (trade(brand)name) to mix with 50: 50 weight ratios.And separately to " EB-FF " carry out based on DSC calorimetric measurement (heat-up rate be 5 ℃/min), the temperature of its endothermic peak (melting point) is 146 ℃.With 8: 2 weight ratios this blended wax and polyisoprene are mixed, use the pressurization kneading machine mixing, obtain masterbatch (master batch).

With the heat-up rate of 5 ℃/min, after use DSC measured the heat of this Wax composition, the former wax had very big endotherm(ic)peak at about 140 ℃, and the latter's wax demonstrates very big endotherm(ic)peak (main peak value) at about 42 ℃.When measuring this Wax composition heat, be higher than MFR under 100 ℃ high temperature side caloric receptivity Δ H and the ratio that is lower than 100 ℃ low temperature side caloric receptivity Δ H (the former/latter), the MFR under 125 ℃, 1.2kgf load and 150 ℃, the 1.2kgf load shown in table 3-2.

Fig. 4 is the DSC graphic representation of this Wax composition.H is a high-temperature digestion wax composition, and L is a low temperature fusion wax composition.And when calculating the ratio of caloric receptivity, when a peak value is crossed over 100 ℃ of lines, with 100 ℃ be the boundary, be divided into high-temperature digestion wax composition side and low temperature and fuse wax composition side and calculate.

Embodiment 3-2～3-4, comparative example 3-1,3-2

The same with embodiment 3-1, use the blended wax shown in the table 3-1 to make the Wax composition of embodiment 3-1～3-4, comparative example 3-1 and 3-2.

When measuring each Wax composition heat, be higher than MFR under 100 ℃ high temperature side caloric receptivity Δ H and the ratio that is lower than 100 ℃ low temperature side caloric receptivity Δ H (the former/latter), the MFR under 125 ℃, 1.2kgf load and 150 ℃, the 1.2kgf load shown in table 3-2.

Embodiment 3-5

The Wax composition of use embodiment 3-1 gained and Biodegradable resin utilize compression molding to obtain the film of moisture-proof barrier and the three-layer structure of the Biodegradable resin layer of lamination on its each face as raw material.The moisture-proof barrier of gained damp-proof membranes is formed by Wax composition, and each Biodegradable resin layer is formed by Biodegradable resin.Biodegradable resin is the polymer blend of polycaprolactone and polydiethylene glycol succinate.Biaxial stretch-formed gained film obtains damp-proof membranes.The total thickness of gained damp-proof membranes is 100 μ m, and moisture-proof barrier thickness is 50 μ m, and each Biodegradable resin film thickness is 25 μ m.Water Vapour Permeability with cylinder plate method (JIS Z 0208 condition B) mensuration gained film is 13g/m ²24hr.By the measured value of the Water Vapour Permeability of three-layer thin-film and the Water Vapour Permeability 530g/m of Biodegradable resin thin film layer (PHB05,25 μ m) ²24hr tries to achieve the Water Vapour Permeability of Wax composition, is 0.7gmm/m ²24hr.

Embodiment 3-6

Except that using embodiment 3-2 gained Wax composition to replace implementing the Wax composition of 3-1, the same with embodiment 3-5, obtain damp-proof membranes.The same Water Vapour Permeability of measuring the gained film is 31g/m ²24hr.Equally, the Water Vapour Permeability of Wax composition is 1.8gmm/m ²24hr.

Table 3-1

	Low temperature fusion wax			High-temperature digestion wax			Polymer substance
								??Hi-Mic-1045 ??wt％	??Hi-Mic-1070 ??wt％	Endothermic peak ℃	??EB-FF ??wt％	??EB-WAX(C8) ??wt％	Endothermic peak ℃	Polyisoprene wt%
	Embodiment 3-1	??40	??---	??42	??40	??---	??140								??20
Embodiment 3-2								??---	??64	??45	??16	??---	??138	??20
	Embodiment 3-3	??40	??---	??42	??---	??40	??166								??20
Embodiment 3-4								??---	??64	??44	??---	??16	??168	??20
	Comparative example 3-1	??---	??80	??44	??---	??---	??---								??20
Comparative example 3-2								??40	??---	??43	??40	??---	??---	??0

Table 3-2

	The ratio of caloric receptivity	??????????????MFR
				??125℃ ??g/10min	??150℃ ??g/10min
		Embodiment 3-1	??1.11			??1	Greater than 1000
Embodiment 3-2	??0.33			??101	Greater than 1000
		Embodiment 3-3	??0.77			??4	??49
Embodiment 3-4	??0.33			??207	??303
		Comparative example 3-1	??0			??790	Greater than 1000
Comparative example 3-2	??0.3			Can not measure	Can not measure

By table 3-2 as can be known, the MFR of each embodiment Wax composition is in being suitable for the scope of melt molding.By embodiment 3-5 and 3-6 as can be known: the Water Vapour Permeability of the damp-proof membranes of each embodiment is low.

Utilizability on the industry

Wax composition of the present invention is particularly preferably as damp proof composition or the bonding composition of using take wax as main body. Because Wax composition organic solvent of the present invention etc. need not just can be made without exception, so but extremely safe ground is used for packaging material take food etc. in each field of representative.

The moisture resistance of Wax composition of the present invention is excellent and be easy to melt molding. Moisture resistance excellence and the zygosity of Wax composition of the present invention are good. By using these Wax compositions, can obtain the good Biodegradable films of moisture resistance, biodegradation laminate and biodegradable container.

The processing such as the good and melt molding easy to implement of the moisture resistance of Wax composition of the present invention. Use hot water resistance and the hot formability of the damp-proof membrane that this Wax composition obtains good. Utilize the manufacture method of moisture resistance article of the present invention, can not only keep the sufficient viscosity of Wax composition, can also add hot-working, can effectively make the excellent moisture resistance article such as moisture resistance, heat endurance. Wax composition of the present invention be preferred for damp-proof membrane damp-proof layer, have the moistureproof article of this damp-proof layer.

Claims (25)

1. the manufacture method of a Wax composition, described Wax composition is characterized in that based on wax, under the temperature of the fusion end temp that is lower than described wax, applies external force to described wax and with the mixed thing of described wax blended and mix.

2. the manufacture method of Wax composition according to claim 1 is characterized in that, under the temperature of the fusion end temp that is lower than described wax, described wax is mixed with described mixed thing, then, with described mixture heating up to more than the fusion end temp of described wax.

3. the manufacture method of Wax composition according to claim 1 is characterized in that described mixed thing contains polymer substance.

4. the manufacture method of Wax composition according to claim 1 is characterized in that described polymer substance is non-polycrystalline macromolecule, and the temperature during mixing is more than the high molecular second-order transition temperature of described amorphous.

5. as the manufacture method of Wax composition as described in claim 3 or 4, it is characterized in that described polymer substance is synthetic polyisoprene or natural rubber.

6. a Biodegradable wax composition is characterized in that, based on wax, contains biodegradation high molecular, and residual solvent concentration is below the 3ppm.

7. a Biodegradable wax composition is characterized in that, the wax based on the manufacture method manufacturing of the described Wax composition of claim 1 contains the non-polycrystalline macromolecule of biological degradability.

8. as claim 6 or 7 described Biodegradable wax compositions, it is characterized in that described polymer is synthetic polyisoprene or natural rubber.

9. a Biodegradable wax composition is characterized in that, based on wax, the Water Vapour Permeability under 40 ℃, 90%RH is 3gmm/m ²Below the 24hr, the melt flow rate (MFR) under 125 ℃, 1.2kgf load is 0.1～1000g/10min.

10. as Biodegradable wax composition as described in the claim 9, it is characterized in that the content of described wax is 65～95 weight %.

11. as Biodegradable wax composition as described in the claim 9, it is characterized in that, also contain polyisoprene or natural rubber 5～35 weight % as the biodegradation high molecular material.

12. Biodegradable wax composition as claimed in claim 11 is characterized in that, the weight-average molecular weight of described biodegradation high molecular material is more than 200000.

13. Biodegradable wax composition as claimed in claim 11 is characterized in that, it is crosslinked that described biodegradation high molecular material is crosslinked agent.

14. a Biodegradable films is characterized in that, on the one side at least of the moisture-proof barrier that the described Biodegradable wax composition of claim 9 constitutes, and lamination Biodegradable resin layer and obtaining.

15. a biological degradability lamination body is characterized in that, on the surface of paper material, and the described Biodegradable wax composition of lamination claim 1, and lamination Biodegradable resin layer more in the above.

16. biodegradable container, it is characterized in that, whole or the part of described biodegradable container body is coated with the described Biodegradable films of claim 14, and the coverage mode of this Biodegradable films is to make the opposition side of described Biodegradable resin layer towards container body.

17. Wax composition, it is characterized in that, contain: in calorimetric measurement based on DSC, the high-temperature digestion wax composition that has endothermic peak more than 100 ℃ and more than 40 ℃ less than 100 ℃ of low temperature fusion wax compositions with endothermic peak, and the dfrtgy polymer substance, and based on described two kinds of wax compositions.

18. as Wax composition as described in the claim 17, it is characterized in that, in with the calorimetric measurement based on DSC of Wax composition as test portion, high temperature side caloric receptivity Δ H and the ratio that is lower than 100 ℃ low temperature side caloric receptivity Δ H (the former/latter) that are higher than 100 ℃ are 0.1～5.0.

19., it is characterized in that the melt flow rate (MFR) under 25 ℃, 1.2kgf load is 0.1～1000g/10min as Wax composition as described in the claim 17.

20., it is characterized in that described high-temperature digestion wax composition is an acid amide type wax as Wax composition as described in the claim 17.

21., it is characterized in that described high-temperature digestion wax composition, described low temperature fusion wax composition and described polymer substance all have biological degradability as Wax composition as described in the claim 17.

22., it is characterized in that described polymer substance is polyisoprene or natural rubber as Wax composition as described in the claim 17.

23. a damp-proof membranes is characterized in that, long-pending resin layer forms on the upper strata of one side at least of the moisture-proof barrier that is formed by the described Wax composition of claim 17.

24. the manufacture method of a laminate, it uses the described Wax composition manufacturing of claim 17 to have the cambial laminate of this Wax composition, it is characterized in that,

Possess described Wax composition is followed the manufacturing procedure that is heated to more than 100 ℃, and the Heating temperature of this operation is set at, in with the calorimetric measurement based on DSC of Wax composition as test portion, the ratio (the former/latter) that makes high temperature side caloric receptivity that is higher than described Heating temperature and the low temperature side caloric receptivity that is lower than described Heating temperature is 0.1～5.0 temperature.

25. the manufacture method as laminate as described in the claim 24 is characterized in that, follows being processed as of described heating to melt extrude moulding.

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