CN1930228A

CN1930228A - Starch-blended resin composition, molding thereof and process for producing the same

Info

Publication number: CN1930228A
Application number: CNA2005800075219A
Authority: CN
Inventors: 上田实; 大野孝; 佐藤淳; 坂口和久
Original assignee: Joetsu Agriculture Future Co Ltd
Current assignee: Joetsu Agriculture Future Co Ltd; AGRI FUTURE JOETSU CO Ltd
Priority date: 2004-03-10
Filing date: 2005-02-24
Publication date: 2007-03-14
Anticipated expiration: 2025-02-24
Also published as: CN1930228B; JP2005255743A

Abstract

It is intended to attain effective utilization of starchy materials among surplus farm products, to realize a technology for blending such starchy materials with a thermoplastic resin, and to provide a starch-blended resin composition that can contain starch in high proportion without detriment to the properties of thermoplastic resin. There is provided a starch-blended resin composition characterized by containing, as main raw materials, 5 to 95 pts.wt. of thermoplastic resin (X), 95 to 5 pts.wt. of starchy material (Y) and, per 100 pts.wt. of the sum of components (X) and (Y), 0.2 to 20 pts.wt. of compatibilizer (Z) capable of enhancing the affinity at the interface of the thermoplastic resin (X) and the starchy material (Y). Further, there is provided relevant technology.

Description

Starch-blended resin composition, its molding and manufacture method thereof

Technical field

To utilize the superfluous farm crop that produce be purpose with effective in the present invention, relate to a kind of in thermoplastic resin the technology of mixing starch class material, relate in particular to the starch-blended resin composition and the relative technology of plasticity and mechanical characteristics excellence.

Background technology

As edible and excess electron excess fraction in the farm crop that produce can be during certain in deposit, but for the process material of valid period, have to it is abandoned.In order to reduce such stock who abandons or lay in, except edible purposes, groping effectively to utilize the purposes of farm crop.

All the time, the farm crop as starchy material being mixed to starch-blended resin composition in the thermoplastic resin forms processing and uses.And, in the technology of in the past manufacturing starch-blended resin composition,, must carry out following processing for the physical strength of the molding that suppresses to produce or reduction attractive in appearance owing to mixing starch class material.That is, institute's blended starchy material is in order to improve and the affinity of thermoplastic resin and dispersed and obtain the farm crop fine powder is broken, or is extracted the material (for example patent documentation 1) of starch component by farm crop.

Patent documentation 1: the Japanese Patent spy opens 2004-2613 communique (0046 section～0050 section)

Summary of the invention

The problem that invention will solve

But, in the prior art, because institute's blended starchy material needs above-mentioned such pre-treatment that bothers, so the manufacturing cost raising, can not in the superfluous farm crop of a large amount of processing, provide starch-blended resin composition at an easy rate.

In addition, for the molding that utilizes existing starch-blended resin composition to make, pointed out the problem of following quality aspect.

The first, starchy material has following point: common water absorbability height, and therefore be mixed in the thermoplastic resin and form after the molding, also can expand by moisture absorption, therefore, all character of this molding lacks permanent stability (dimensional stability etc.).In addition, also have following problem: if the molding of such starch-blended resin composition is immersed in the aqueous solution, starch component will stripping and produce mucus on the surface.

The second, if existing starch-blended resin composition is carried out stretch process and makes film like, will make the membrane thickness unevenness of film, be that starting point chaps easily with the starch small grain, destroy feel or attractive in appearance, the mechanical characteristics after perhaps being shaped obviously descends.Therefore, has following point: be difficult to obtain high-quality film shaped product,, obviously show above-mentioned unfavorable character if especially with the film thin layerization.

This is that perhaps its particle diameter is compared relatively large with the thickness of film owing to starch small grain in starch-blended resin composition disperses equably.But it is limited utilizing aforesaid method (pulverizing or the composition extraction) that starchy material is made thin starch small grain.In addition, affinity is poor usually for thermoplastic resin (for example polyolefin resin etc.) and starchy material (for example rice etc.), therefore, even become thin starch small grain by pre-treatment, after putting in the thermoplastic resin of heat flow, starch small grain still has the character of easy cohesion.Therefore, existing starch-blended resin composition is not looked after above-mentioned unfavorable character, thereby can not obtain the film shaped product of high-quality film.

The present invention is that problem is carried out to address the above problem, and its purpose is and can disperses imperceptibly and mixing starch class material in the matrix of thermoplastic resin, and then high-quality starch-blended resin composition and relevant therewith technology are provided.

Solve the means of problem

The present invention invents in order to achieve the above object.

The 1st invention is starch-blended resin composition, it is characterized in that, be main raw material with the following substances: the starchy material (Y) of 5～95 parts by weight of thermoplastic resin (X), 95～5 weight parts and with respect to (X) that amount to 100 weight parts (Y) composition be the compatilizer (Z) of the affinity at interface 0.2～20 weight part, that improve described thermoplastic resin (X) and described starchy material (Y).

The 2nd invention is a kind of manufacture method of starch-blended resin composition, it is characterized in that, comprise following operation: raw material drops into operation, to contain thermoplastic resin (X) at least and contain the starting raw material of the starchy material (Y) of moisture, put into the raw material throw-in part that temperature is adjusted into the mixing squeezing device below 140 ℃; The heat flow treatment process, pressure is higher than normal atmosphere and temperature is the pyritous High Temperature High Pressure portion of described thermoplastic resin (X) heat flow to being adjusted to input above-mentioned starting raw material conveyance, formation contains hydrothermal fluid, and at least a portion gelatinization of the above-mentioned starchy material (Y) that is contained and form pasted starch; The dispersion treatment operation, the mixing above-mentioned hydrothermal fluid that contains under identical high temperature, high pressure, make the nubbin gelatinization of described starchy material (Y), and the pasted starch that is generated is ground into starch small grain, and this starch small grain is scattered in and forms starch in the above-mentioned integral body that contains hydrothermal fluid and disperse hot-fluid; The processed operation, it is the pyritous degassing portion that described starch disperses the hot-fluid heat flow to being adjusted to the low pressure and the temperature of pressure below normal atmosphere that described starch is disperseed the hot-fluid conveyance, and described starch disperses contained moisture evaporation in the hot-fluid and forms no hydrothermal fluid; Discharge operation, discharge this no hydrothermal fluid from the relief outlet of described mixing squeezing device; Forming process, the above-mentioned no hydrothermal fluid of being discharged solidifies under the low temperature of forfeiture thermal fluidity and is formed.

The invention effect

Starch-blended resin composition, its molding and manufacture method thereof by the present invention relates to can play excellent effect shown below.

That is, starch-blended resin composition is that starchy material (Y) is fine and be evenly dispersed in the thermoplastic resin (X) that forms matrix, thereby, mechanical characteristics and outward appearance excellence.Particularly, if make film shaped product, can make the film shaped product that have with the situation quality much at one of using 100% thermoplastic resin (X) by this starch-blended resin composition.

In addition, owing to utilize compatilizer (Z) that starchy material (Y) has been carried out chemical treatment, thermoplastic resin composition's molding demonstrates character steady in a long-term.Therefore, can improve the ratio of institute's blended starchy material (Y), thereby can effectively utilize the superfluous farm crop that produce in large quantities, and can reduce the consumption of the thermoplastic resin (X) that generates by fossil oil.In addition; carry out burning disposal even contain the molding of starch-blended resin composition, the generation of the combustion heat and carbonic acid gas also seldom, and owing to have a biological degradability; even thereby bury processing and also can be decomposed by 100%, help very much the protection of global environment.

Description of drawings

The overall perspective view of the prilling granulator of the starch-blended resin composition (particle) that [Fig. 1] expression manufacturing present embodiment relates to.

[Fig. 2] (a) represents the side cross-sectional views of the mixing squeezing device of twin shaft that uses in the present embodiment, (b) expression horizontal sectional view.

[Fig. 3] is the vertical view that the multilayer body that is arranged on the blade on the kneading screw is amplified demonstration (a), (b) is the figure that observes from the axle vertical direction of cylinder.

The figure that [Fig. 4] expression is installed in the running of a pair of blade on the adjacent kneading screw (a)～(e) represents the state of kneading screw when equidirectional respectively rotates 45 ° respectively.

The front view of the inflation building mortion of the film shaped product of [Fig. 5] expression manufacturing present embodiment.

Nomenclature

The mixing squeezing device of 20 twin shafts (mixing squeezing device)

28 relief outlets

30 kneading screws

40 hot-rollings

42 gaps

60 inflation building mortions

The A raw material drops into operation

B heat flow treatment process

B ₁Heating process

B ₂The gelatinization operation

C dispersion treatment operation

D, F processed operation

The E chemical reaction process

G discharges operation

H micronize operation

The I forming process

The mixing operation of J

The K stretching process

P contains hydrothermal fluid

Q starch disperses hot-fluid

R does not have hydrothermal fluid

Embodiment

The detailed hereafter embodiments of the present invention.

The thermoplastic resin (X) that uses as the raw material of the matrix that forms starch-blended resin composition of the present invention, can list new LDPE (film grade) (LDPE), high density polyethylene(HDPE) (HDPE) or polypropylene polyolefin resines such as (PP) typically, perhaps ethene-vinyl acetate copolymer (EVA) or ethylene-ethyl acrylate copolymer ethene copolymers such as (EEA).

In addition, can also use polycarbonate resin (PC), pet resin (PET), acronitrile-butadiene-styrene (ABS) etc., so long as have the resin of the character of heat flow, can use and do not have particular restriction by heating.In addition, these thermoplastic resins can also use mixing more than two kinds.

In addition; if use materials such as polyolefine, polyester, poly(lactic acid) (PLA), polybutylene succinate (PBS), polycaprolactone (PCL), poly butyric ester (PHB), polyvinyl alcohol (PVA) and the multipolymer thereof possess biological degradability, polyamide (PA), rhodia, poly-aspartic-acid, polysaccharide derivatives, can make to have and buriedly abandon that the back Restore All becomes the character of soil and suitable starch-blended resin composition aspect environment protection as thermoplastic resin (X).In addition; use is endowed the above-mentioned thermoplastic resin (X) that ECM マス one バ Star チ (trade(brand)name) of テグラノボ Application (trade mark) or マ Network ロテ Network リサ one チ company (U.S.) etc. provides the additive of biological degradability; from the viewpoint of environment protection, equally also be suitable.

The starchy material (Y) that uses as being mixed into the raw material in the starch-blended resin composition of the present invention can be enumerated rice, wheat, corn, potato, sweet potato, cassava etc., can use so long as contain the farm crop of starch, and without limits.In addition, these starchy materials (Y) can directly use under the common state in when deposit, or through washing, remove not amyloid part such as crust, cut under the state of simple pre-treatment such as appropriate size and use.

In addition, further preferred after having applied so simple pre-treatment as the starchy material (Y) of raw material, carry out the αization processing according to following main points.That is, the starch that constitutes starchy material (Y) originally has crystalline structure (beta structure), if but placing temperature in the presence of an amount of moisture is environment more than 70 ℃, this beta structure will be disintegrated and be become non-crystal structure (α structure).The starch of Shenging is by heating containing under the condition of moisture like this, thereby is called gelatinization by the phenomenon that beta structure becomes the α structure.This gelatinization the starch small grain of demonstration α structure of starchy material (Y) compare with the situation of the beta structure that originally is heated state (give birth to state), be in the thermoplastic resin (X) of heat flow homodisperse imperceptibly easily state with the starch molecule horizontal decomposition.

The starch that has a beta structure as such making becomes the concrete processing of α structure, can enumerate be immersed in boil in the water or the water steamed is such, usually for the heat-treating methods that applies that when edible, carries out.

Generally all know: if As time goes on the amorphous starch with α structure, observe the phenomenon (being called aging) of the crystal state that is back to original beta structure containing low temperature placement under the state of moisture.On the other hand, if knownly remove moisture from the amorphous starch with α structure, even then place for a long time at low temperatures thereafter, starch can still be kept the α structure and can reversibly not be transformed into beta structure (aging).

Therefore, the starchy material (Y) that uses as raw material of the present invention is the material of starch structure as α structure (non-crystal structure), thereby comprises the state that contains moisture and two states of state of moisture-free (dehydration).No matter which kind of state, as long as being mixed into the starch structure of the starchy material (Y) in the thermoplastic resin (X) is α structure (non-crystal structure), when carrying out mixing processing described later, the molecular chain of starch can be untied in the matrix of thermoplastic resin (X) and disperse imperceptibly easily.This is that the mixing starch structure is following effect that can not obtain of situation of starchy material (Y) of the non-heating of beta structure (crystalline structure).

Make the method for starchy material (Y) of the α structure of dehydration, specifically, be in the presence of moisture, heat make it gelatinization after, directly utilize vacuum unit that atmosphere is reduced pressure.If use the starchy material (Y) of the α structure of dehydration like this since be difficult for aging, thereby can be with monomer prolonged preservation starchy material (Y), help the shortening of manufacturing time of starch-blended resin composition and the reduction of manufacturing cost.

In addition, can dissolve trehalose in the water that when the above-mentioned starch that will have beta structure becomes the α structure, uses.Its effect is as follows: for example, when using Mi Zuowei starchy material (Y), give birth in the rice by aqueous trehalose solution being contained be dipped into, can access the effect that trehalose suppresses the lipid composition decomposition of rice, and can suppress rice mixed thermoplastic resin's composition deterioration in time of manufacturing.Its reason is considered to because trehalose covers Mi Chengfen, thereby has the effect of the not oxidized decomposition of protection lipid acid.

Such effect can both be brought into play in general starch class material (Y), and be not limited to rice, in addition, as material with such effect, except above-mentioned trehalose, can also enumerate salt, sucrose, antioxidant, protein decomposition accelerating agent, Mierocrystalline cellulose decomposition accelerating agent etc.In addition, add the starchy material (Y) that these materials convert the α structure to, can also obtain to prevent the distinctive foul smell of starch-blended resin composition, the coking of manufacturing, the effect of band look by being blended in the water.

Above, about as raw material blended starchy material (Y), the situation of using the material of having implemented the αization processing is illustrated, in manufacture method described later, can also use the starchy material with beta structure (Y) that contains moisture.

Specifically, will give birth to rice and in water, soak the specified time, control water, drop into mixing roll with thermoplastic resin (X) then, under the heat flow temperature of thermoplastic resin (X), carry out mixing.It is enough temperature that this heat flow temperature (normally 100～200 ℃) is transformed into the α structure for the starch structure that will give birth to rice by beta structure, therefore, gives birth to rice by the αization processing in mixing process.Like this, give birth to rice and be transformed into after the α structure, as mentioned above, the molecular chain of starch is untied, miniaturization and being distributed in the matrix of thermoplastic resin (X).In addition, about this manufacturing processed, will describe in detail with reference to accompanying drawing in the back.

At this, become the αization structure in order to heat the giving birth to rice of beta structure, the expectation moisture content is more than 17%, the time that for this reason is immersed in the water must be for more than 5 minutes.In addition, for example, about potato such self contain the starchy material (Y) that makes starch become the required enough moisture of α structure, can directly drop into mixing roll and need not as rice, to be immersed in processing in the water.

The compatilizer (Z) that uses as raw material of the present invention can use saturated carboxylic acid, unsaturated carboxylic acid or derivatives thereof, with the thermoplastic resin (X) of unsaturated carboxylic acid or derivatives thereof modification and with the starchy material (Y) of unsaturated carboxylic acid or derivatives thereof modification.In addition, can also use oil-modified alkyd resin or derivatives thereof, starch producing or derivatives thereof.

As saturated carboxylic acid, can enumerate succinyl oxide, succsinic acid, Tetra hydro Phthalic anhydride, phthalic acid, tetrahydronaphthalic anhydride, adipic anhydride etc.As unsaturated carboxylic acid, can enumerate maleic anhydride, toxilic acid, norbornene dicarboxylic anhydride, itaconic anhydride, methylene-succinic acid, citraconic anhydride, citraconic acid, Ba Dousuan, iso-crotonic acid, methylfumaric acid, angelicic acid, Sorbic Acid, vinylformic acid etc.As the derivative of saturated carboxylic acid or unsaturated carboxylic acid, can use metal-salt, acid amides, imide, ester of saturated carboxylic acid or unsaturated carboxylic acid etc.Can also use in addition with the thermoplastic resin (X) of unsaturated carboxylic acid or derivatives thereof modification and with the starchy material (Y) of unsaturated carboxylic acid or derivatives thereof modification.This can be by in the presence of the solvent or not, thermoplastic resin (X) or starchy material (Y), unsaturated carboxylic acid or derivatives thereof and free-radical generating agent is heated mix and make.The addition amount of unsaturated carboxylic acid or derivatives thereof is 0.1～15 weight %, is preferably 1～10 weight % especially.As the compatilizer that uses among the present invention (Z), preferably with the thermoplastic resin of no foul smell, acid little unsaturated carboxylic acid or derivatives thereof modification and with its derivative modified starchy material.

The compatilizer (Z) and mixed being incorporated under 100 ℃～200 ℃ of starchy material (Y) of using among the present invention are heated, then chemical bonding by the esterification shown in the following formula.By like this, in starchy material (Y), the hydroxyl that wetting ability is high is substituted by ester group, thereby plays the hygroscopic effect that suppresses starchy material (Y).Further, also bring following effect: make in the binding property at the interface of thermoplastic resin (X) and starchy material (Y) well, reduce melting temperature thermoplastic resin composition's down viscosity, the physical strength of the molding that raising obtains by various shapings.

[Chemical formula 1]

And with respect to amounting to 100 parts by weight of thermoplastic resin (X) and starchy material (Y), its upper limit of combined amount of starchy material (Y) is that 95 weight parts, lower limit are 5 weight parts.Why will on be defined as 95 weight parts, be that the matrix of rice mixed thermoplastic resin composition is formed the mechanical characteristics variation of the molding of manufacturing by starchy material (Y) because if the combined amount of starchy material (Y) is increased to more than 95 weight parts.Why will be defined as 5 mass parts down, this is owing to if below 5 weight parts, then can not handle superfluous farm crop in a large number.

In addition, the preferable combined amount of compatilizer (Z) is the value of trying to achieve by experiment, with respect to (X) that amount to 100 weight parts (Y) composition, is suitable in the scope of 0.2～20 weight part.

But, the present invention be with starch mixed thermoplastic resin composition and molding thereof keep as the desired character of product and in above-mentioned scope with the technology of high as far as possible mixed starchy material (Y).Thus, the farm crop of reluctant overstock can be handled effectively in a large number, the consumption of the thermoplastic resin of making by fossil oil (X) can be reduced simultaneously.In addition; with the starch mixed thermoplastic resin's of mixing starch class material (Y) molding at high proportion; even after use, carry out burning disposal also because carbon is residual as residue, thereby the generation of the combustion heat or carbonic acid gas is few, is very beneficial for the protection of global environment.In addition, even bury under the situation of processing, being reduced into the reduction ratio height of soil, also is favourable to environment.

Manufacture method

Below, on one side with reference to accompanying drawing, the manufacture method of the starch-blended resin composition that the present invention relates to is described on one side.The embodiment of the manufacture method of the particle (starch-blended resin composition) that is to use the raw material that thermoplastic resin (X), starchy material (Y) and compatilizer (Z) mix with above-mentioned combined amount given here.

Wherein, thermoplastic resin (X) as starting raw material is general commercially available poly particle, starchy material (Y) is life rice (having beta structure) is soaked the specified time in tap water (15 ℃) after, utilizes separating centrifuge to control the material of water treatment (hereinafter referred to as the rice of giving birth to through aqueous treatment).

Fig. 1 is the overall perspective view of the prilling granulator that provides as an example making the starch-blended resin composition (particle 51) that present embodiment relates to.

Prilling granulator 10 is by constituting with lower device: behind the thermoplastic resin (X) and starchy material (Y) (through the rice of giving birth to of aqueous treatment) of input as the starting raw material of starch-blended resin composition, make it heat flowization and the mixing mixing squeezing device 20 of twin shaft, this mixing required motivating force is offered the driving part 22 of the mixing squeezing device 20 of twin shaft, make hot-fluid that mixing back extruded by relief outlet 28 by and the hot-rolling 40 that the starch small grain that is contained carried out miniaturization, the hot-fluid that will pass through this hot-rolling 40 chops up and makes its hardening to form particle 51,51...... side device for thermally cutting 50.

Utilize accompanying drawing 2 to describe the mixing squeezing device 20 of twin shaft.Wherein, the side cross-sectional views of the mixing squeezing device 20 of Fig. 2 (a) expression twin shaft, (b) expression horizontal sectional view.

The mixing squeezing device 20 of twin shaft constitutes peripheral part by the cylinder 21 with hollow shape, motivating force by driving part 22 is arranged to 2 kneading screws 30,30 of equidirectional interlock rotation in the hollow internal configuration of cylinder 21.And, be provided with in order to drop into the hopper 23 of starting raw material at the upstream end that is provided with driving part 22 of the mixing squeezing device 20 of twin shaft.In addition, above the opening of this hopper 23, be provided with the thermoplastic resin (X) of starting raw material send into hopper 23 charging stock tank 23a and will be equally as the charging stock tank 23b that rice (starchy material (Y)) is sent into hopper 23 that gives birth to through aqueous treatment of starting raw material.

So, send into hopper 23 by charging stock tank 23a and charging stock tank 23b respectively as the thermoplastic resin (X) and the starchy material (Y) (through the rice of giving birth to of aqueous treatment) of starting raw material, and make it become the blending ratio of afore mentioned rules.In addition, when mixing compatilizer (Z), can in the process that drops into to this hopper 23, mix, also can in subsequent process, mix.

As shown in Figure 1; in order to use prilling granulator 10 to make starch-blended resin composition (particle 51,51...); must be successively through dropping into operation A, heat flow treatment process B, dispersion treatment operation C, processed step D with raw material, a plurality of operations that F, chemical reaction process E, discharge operation G, micronize step H, forming process I represent.And as shown in Figure 2, the A～F in these operations carries out in a plurality of subregions of length direction with the prescribed distance setting of the mixing squeezing device 20 of twin shaft.

Wherein, it is in a subregion with the mixing squeezing device 20 of twin shaft of raw material throw-in part (low-temp. portion) a (with reference to Fig. 2) expression that raw material drops into operation A (with reference to Fig. 1), drops into the operation of the starting raw material (be thermoplastic resin (X) at least, through the mixture of giving birth to rice (starchy material (Y)) of aqueous treatment) of starch-blended resin compositions from hopper 23.These starting raw materials are to be transferred to the intensification portion b1 adjacent in the downstream side by be arranged to spiral helicine alar part 31 with the pitch of predetermined distance on the surface of the kneading

screw

30,30 that rotates to equidirectional.But this raw material throw-in part (low-temp. portion) a is adjusted to temperature T ₁Be the low temperature that (is preferably below 100 ℃) below 140 ℃, therefore, can not evaporate at once in input moisture its major part in raw material input operation A that contains in the rice (starchy material (Y)) of giving birth to.

Then, heat flow treatment process B (with reference to Fig. 1) is further divided into heating process B1 and gelatinization process B 2.Wherein, heating process B1 on one side transfers to the downstream with starting raw material (contain thermoplastic resin (X) at least, through the mixture of giving birth to rice (starchy material (Y)) of aqueous treatment) from a sectional upstream with the mixing squeezing device 20 of twin shaft of the b1 of intensification portion (with reference to Fig. 2) expression, on one side from temperature T ₁Be warming up to the heat flow temperature T of thermoplastic resin (X) heat flow ₂The operation of (being preferably 120 ℃～200 ℃).

In addition, below, (" heat flow temperature T has appearred in the temperature of a～f) for each subregion of representing the mixing squeezing device 20 of twin shaft ₂" this record, it is meant the temperature of raw material heat flow, is to have certain amplitude, as each subregion (temperature of a～f) and the heat flow temperature T that provides ₂It is not identical all temperature.Certainly, (a～design temperature f) should suitably be chosen to make the temperature of each process optimization to each subregion.

Gelatinization process B 2 (with reference to Fig. 1) is a subregion at the mixing squeezing device of representing with (weak kneading part) b2 of High Temperature High Pressure portion (with reference to Fig. 2) 20 of twin shaft, makes the operation of the Mi Fasheng gelatinization that drops into as raw material.The b2 of this High Temperature High Pressure portion (weak kneading part) is from upstream to the downstream and remains on the heat flow temperature T ₂Further, for the pitch of being arranged to spiral helicine alar part 32,32...... on the surface of corresponding kneading screw 30,30, it is arranged to narrower than the pitch of upstream side alar part 31,31.......By like this, at the b2 of High Temperature High Pressure portion, pitch narrows down, and the space that raw material occupied diminishes, and further raw material integral body is carried out heat flow, and therefore, raw material is by faintly mixing.And, medial surface in the cylinder 21 of the b2 of High Temperature High Pressure portion has been blocked extraneous gas fully, and be in the state that upstream, downstream side all by material sealing, and therefore can think that the inside of the b2 of High Temperature High Pressure portion is in air-tight state, form than normal atmosphere highly compressed atmosphere more.In the b2 of High Temperature High Pressure portion,, still can exist with the state of liquid even the water that is exposed under such high-pressure atmosphere can not gasify under high temperature (more than 100 ℃) yet.And, in such pyritous heat flow temperature T ₂Water in the rice of giving birth to that soaking at short notice gelatinization taking place and becomes the α structure from beta structure.

In the inside of the b2 of High Temperature High Pressure portion, even the heat flow temperature T ₂The high temperature of (normally 120 ℃～200 ℃), water still exist in large quantities as liquid, thereby can make the starch structure of giving birth to rice convert the α structure to from beta structure at short notice.In this gelatinization process B 2, raw material contains a large amount of water and carry out heat flowization under high temperature, highly compressed atmosphere, forms to contain hydrothermal fluid P.This contains the living rice (starchy material (Y)) that is comprised among the hydrothermal fluid P can be at short notice by gelatinization in mixing process.

Then, dispersion treatment operation C (with reference to Fig. 1) is at a subregion with the mixing squeezing device 20 of twin shaft of the last 1 kneading part c (with reference to Fig. 2) expression, to contain gelatinization contained among the hydrothermal fluid P rice (pasted starch) pulverize and make it the dispersive operation.The last 1 kneading part c is from upstream to the downstream and remains on the heat flow temperature T ₂And the corresponding section of kneading

screw

30,30 is provided with a plurality of blades 33,33.......

Wherein, Fig. 3 (a) is the vertical view that amplify to show the multilayer body of the blade 33 that is arranged on the kneading screw 30,30 (with reference to Fig. 2), 33......, (b) is the figure from the axle vertical direction observation of cylinder 21.

Structure and the operation of blade 33,33...... are described below.

These blades 33,33...... are at adjacent kneading

screw

30,30 each other, and the rotatable phase 90 ° of ground that stagger are mutually fixed, and in addition, the 45 ° of ground that stagger successively on the length direction of kneading

screw

30,30 are fixed.

Fig. 4 is the figure that expression is installed in the operation of a pair of blade 33 on the adjacent kneading

screw

30,30,33......, (a)～(e) represents the state of kneading

screw

30,30 when equidirectional respectively rotates 45 ° respectively.

As shown in Figure 4: be positioned at of the rotation of the mixing thing in the zone of representing with A, B, C, around the inner periphery quilt mixing strongly (mixing by force) of cylinder 21 along with kneading screw 30,30.At this, the manufacturing process of getting back to starch-blended resin composition continues to describe, at the b2 of High Temperature High Pressure portion, give birth to rice gelatinization (becoming the α structure) and be transferred to the last 1 kneading part c from beta structure, the rice of gelatinization (starchy material (Y)) demonstrates gel state, and therefore by mixing by force, the molecular chain of starch can be untied, starch small grain is miniaturization on molecular level, thereby is scattered in (starch disperses hot-fluid Q) in the matrix of thermoplastic resin (X).

Like this gelatinization the easy miniaturization of (having the α structure) starch, this be since its molecular structure have non-crystal structure, on the molecular chain level, have the character of easy dismission.In addition, the internal pressure of the last 1 kneading part c remains on and is higher than atmospheric high pressure, therefore, in the b2 of High Temperature High Pressure portion not by the lingering section of giving birth to rice of gelatinization here fully by gelatinization, miniaturization similarly and disperseing.Like this, starch small grain miniaturization to molecular level being come the dispersive thing, is impossible realize according to the method for the starchy material of fine pulverizing beta structure described in the prior art.

Next processed step D (with reference to Fig. 1) is to remove moisture and form the operation of no hydrothermal fluid R from starch dispersion hot-fluid Q in as a subregion of the mixing squeezing device 20 of twin shaft of the 1st d of degassing portion (with reference to Fig. 2) expression.And the 1st d of degassing portion remains on the heat flow temperature T ₂The end face position of the cylinder 21 of the 1st d of degassing portion is provided with the

open type ventage

25,25 that communicates with atmosphere.Become the normal atmosphere level by the internal pressure that has this

open type ventage

25,25, the 1 d of degassing portion, the last the 1 kneading part c of one side shifts the environment that the starch dispersion hot-fluid Q that comes is exposed to the rapid decline of pressure from the upstream.Therefore, the contained moisture of raw material gasifies apace, is expelled to the outside from

open type ventage

25,25, thereby forms no hydrothermal fluid R.

Like this, in processed operation (D), the contained water that helps gelatinization of starchy material (Y) is finished its task and is discharged from.This is because moisture is useless composition for the starch-blended resin composition as the finished product.

Next chemical reaction process E (with reference to Fig. 1) is in a subregion of the mixing squeezing device of representing as the last 2 kneading part e (with reference to Fig. 2) 20 of twin shaft, make the compatilizer (Z) that drops into as raw material as required that chemical transformation take place, improve the affinity of thermoplastic resin (X) and starchy material (Y), improve the operation of dispersity.The last 2 kneading part e remains on the heat flow temperature T ₂, the no hydrothermal fluid R by herein is once more by mixing strongly (mixing by force), thereby further makes the starch small grain miniaturization of pasted starch.In addition, chemical reaction takes place in the compatilizer that is added (Z), to the hydrophilic starchy material of common demonstration (Y) with show that the low affinity at the interface of hydrophobic thermoplastic resin (X) improves, thereby improves dispersiveness.

Next processed operation F (with reference to Fig. 1) is in a subregion of the mixing squeezing device of representing as the 2nd f of degassing portion (with reference to Fig. 2) 20 of twin shaft, further removes the operation that residues in the moisture among the no hydrothermal fluid R by forced exhaust device 27.Top at the cylinder 21 of the 2nd f of degassing portion is provided with the vacuum venting mouth 26 that communicates with atmosphere, is provided with forced exhaust device 27 here.By driving this forced exhaust device 27, internal pressure becomes below the normal atmosphere, and the lingering section of the moisture that is not discharged from the processed step D is discharged from no hydrothermal fluid R.

Next, in discharging operation G (with reference to Fig. 1), no hydrothermal fluid R is from the relief outlet that has dwindled bore 28 discharges of the downstream end of cylinder 21.

Then, in the micronize step H, the no hydrothermal fluid R that is discharged is by hot-rolling 40, and starch small grain is by further miniaturization.The central shaft that pair of

rolls

41,41 is configured to length direction is parallel to each other, and is the center rotation with its central shaft.The gap 42 that the

roller

41,41 of these pair of cylinders shapes forms is suitably regulated according to the size of target starch small grain.In addition, determine the direction and the speed of the rotation of

roller

41,41, thereby make the micronized effect of bringing into play starch small grain to greatest extent by test.Further, these pair of

rolls

41,41 integral body are accommodated in the process furnace 43, make it can be with the temperature maintenance on surface in the heat flow temperature T ₂

In addition, in Fig. 1, hot-rolling 40 is made of pair of

rolls

41,41, but is not limited to such structure, for example, can also constitute by the roller and the smooth plate of a rotation.That is, hot-rolling 40 be in the gap 42 that the periphery of the roller 41 of a rotation and other body surfaces form by no hydrothermal fluid R, the starch contained therein grain is crushed or the power that is sheared is destroyed and further miniaturization by periphery.

Next forming process I can take various embodiments, and the normally used side device for thermally cutting 50 that utilizes shown in Figure 1 is to as the particle 51 of starch-blended resin composition, the operation that 51...... carries out granulation.

In addition, in Fig. 1, after hot-rolling 40, utilize side device for thermally cutting 50 to fritter and cut processing, still, also can be not directly directly do not draw no hydrothermal fluid R and fritter and cut processing from the relief outlet 28 of the mixing squeezing device 20 of twin shaft by this hot-rolling 40.

In the manufacture method of above starch-blended resin composition, institute's blended compatilizer (Z) can also drop among the operation A at raw material shown in Figure 1 and mix, and in addition, also can mix by never illustrated dispensing port in arbitrary operation of other process B～E process.In addition, even do not mix compatilizer (Z), also can bring into play the intrinsic effect of the manufacture method of starch-blended resin composition.

Foregoing description is to be the manufacture method of the preferred starch-blended resin composition of beta structure and aqueous situation by listing the rice of giving birth to through aqueous treatment, explaining raw starch class material (Y).Therefore, adaptable starchy material (Y) is not limited to the rice of giving birth to through aqueous treatment in above-mentioned manufacture method, for example, can also directly use initial corn that just contains the required enough moisture of αization processing or potato etc.

In addition, starch-blended resin composition of the present invention is not limited to the mixing squeezing device of twin shaft shown in Figure 1 and just can makes.Especially when the starchy material (Y) of the starch that uses prior αization processing, when being main raw material, adding hot milling and make with general device (for example stirrer, kneader, mixing roller, Banbury, single shaft or double-shafted extruder) with thermoplastic resin (X) and compatilizer (Z).

The hot milling that adds of this moment is to carry out under general condition, specifically, with above-mentioned suitable combined amount mixed thermoplastic resin (X), starchy material (Y), compatilizer (Z) and other compositions (biological degradability imparting agent etc.) of adding as required, mixing to this mixture heating up under 130～200 ℃, 20 seconds～30 minutes conditions.By carrying out chemical reaction, can make the starch-blended resin composition that possesses required character through such hot milling operation that adds.

That is, in the matrix of thermoplastic resin (X), show that the molecular chain of the starchy material (Y) of α structure can be untied, and improve its interface, thereby be spread in the matrix by chemical reaction with compatilizer (Z).Its result, starchy material (Y) miniaturization and disperseing equably in as the matrix of the thermoplastic resin (X) of hot-fluid.Then, this hot-fluid for example is configured as particulate state and is cooled to room temperature, just can make the starch-blended resin composition that the present invention relates to.

Fig. 5 represents other embodiment of forming process, and the operation of utilizing inflation building mortion 60 to make the film shaped product of thin layer cylindraceous is shown.In addition, in Fig. 5,, add same-sign and omit explanation for the textural element of having mentioned.

Inflation is shaped and is meant that utilization is equipped with mixing squeezing device 20 compounding raw materials of twin shaft (mixing operation J) of the metal pattern with ring-type joint (mould) 61, hot-fluid is squeezed into tubular (discharging operation G), be blown into air S therein and the back (stretching process K) that stretches, utilize air ring 66 to cool off, be configured as the film cylindraceous (forming process I) of thin layer, utilize balancing plate 65 channeling conducts, bore pinch roll 64 and extracted inner air out, through deflector roll 63, the method for utilizing wind2 62 to reel.

Be shaped by this inflation, utilize biaxial stretch-formed formation resin film, therefore, each mechanical properties excellence such as tensile strength, shock resistance.In addition, inflation is shaped can form the film shaped product of successive tubular, therefore can be widely used in the preservative film or the bag of thermoplastic resins such as making polyethylene or polypropylene.

The manufacture method of the film shaped product by the starch-blended resin composition that the present invention relates to, even be blown into air S in the inside of the resin of heat flow and sharply expand, also owing to starch small grain is disperseed equably by miniaturization, and the granulous defect part that does not have this starch small grain cohesion and form therefore can be with even and same thickness oriented film.Therefore, after the cooling, resulting film shaped product are just as being formed by 100% thermoplastic resin (X), even thickness equates, beautiful appearance improves degree of drawing defective such as be full of cracks or pin hole and mechanical characteristics (tensile strength etc.) are unexcellent yet yet.

Above in the description of Fig. 5, the situation of the mixing squeezing device 20 of twin shaft that imagination utilization describes in detail in Fig. 2, but use general mixing squeezing device 20 ' to substitute it, also can bring into play the specific characteristic of above-mentioned film shaped product by the existence of hot-rolling 40.In addition, even the inflation building mortion 60 of general mixing squeezing device 20 ' is installed, if utilization with particle 51, the 51...... of prilling granulator 10 granulations of Fig. 1, also can obtain the film shaped product of the characteristic of above-mentioned same excellence.

The molding that contains starch-blended resin composition of the present invention and make described above, in matrix, be dispersed with the starchy material (Y) of miniaturization equably as the thermoplastic resin (X) of constituent, therefore, physical strength, for example excellence such as tensile strength, flexural strength.These all are based on effect by compatilizer (Z) and have improved the effect of interfacial adhesion of thermoplastic resin (X) and starchy material (Y) and fine and disperse the effect of starch to produce equably in matrix by the starchy material (Y) of mixed display α structure.

In addition, starch-blended resin composition of the present invention adds hot milling and carries out chemical reaction after mixing each component substances under the melt temperature of thermoplastic resin (X), therefore, can directly be transferred to the forming process of molding.Therefore, can produce the operation of starch-blended resin composition and the operation of manufacturing molding continuously, thereby can reduce manufacturing cost.

In addition, can also in the starch-blended resin composition of the present invention of 5～80 weight parts, mix 95～20 parts by weight of thermoplastic resin (X) and add hot milling, and in above-mentioned scope, change arbitrarily the blending ratio of starchy material (Y), thereby make the molding of starch-blended resin composition.

Owing to can carry out such change, therefore, if make the starch-blended resin composition of mixing starch class material (Y) at high proportion in advance and lay in, even, also can not improve manufacturing cost at the small serial production of the different separately multiple molding of the blending ratio of starchy material (Y).

In addition, the molding that utilizes thermoplastic resin composition of the present invention to make is not limited to above-mentioned film shaped product, in the many fields or product that can be applied to be suitable for or made with thermoplastic resin in the past.Specifically, can suit to be applied to the field of electrically insulating material, industrial component materials, structure material, wherein suitable raw material as dwelling house material, material of construction, household appliances.

In addition, object lesson as this molding, except above-mentioned film, can enumerate dish, tableware class, loud speaker, bathroom facilities floor at the bottom of, the main leaf of spring of bucket, toilet seat, kitchen cabinet, three-dimensional kitchen cabinet, wall dunnage, door material, sales counter, window frame, insulating board, shelf, civil engineering timber, column, structured material, kitchen material, bed, bathroom, floor, piano organ, ceiling material etc.

Embodiment

Embodiments of the invention are described below.Wherein, illustration goes out to use the situation through the living Mi Zuowei starchy material (Y) of aqueous treatment.In addition, at using the situation of giving birth to rice of not carrying out such aqueous treatment to provide data as a comparative example.

Table 1 expression changes the moisture containing ratio when giving birth to the time that rice soaks in water and the outward appearance of the film shaped product that made by the starch-blended resin composition of giving birth to rice that has mixed such processing and the result of mechanical characteristics (tension test data).In addition, in table, also put down in writing in water, not soak and given birth to rice and the direct comparative example of blended situation.Can know: compare with this comparative example, the embodiment that is soaked in the tap water demonstrates excellent result.And the soak time of living rice in water is long more, and the result who obtains is good more.

In addition, though not shown data are boiled Sheng Mi and starch is become under the situation of α structure in use, also can access and 120 minutes identical results of immersion data.

Theing contents are as follows of the starting material that use in the test shown in the table 1 etc. is described.At first, use new LDPE (film grade) (エボリユ one SP2520: Mitsui Chemicals production) give birth to rice (put down into 8 produce the Nigata counties per year produce road early rice more) as the toxilic acid MODIFIED PP (ユ one メ Star Network ス 2000: Sanyo changes into production) of starchy material (Y), 2.2 weight % biological degradability imparting agent (MB particle: マ Network ロテ Network リサ one チ company (U.S.)) of 77 weight % as compatilizer (Z), 0.8 weight % as the purified of thermoplastic resin (X), 20 weight %.

In addition, the aqueous treatment of giving birth to rice is soak the specified time described in the table in tap water (15 ℃) after, to carry out about 3 minutes centrifuge dehydration.Mixing condition is as follows: utilize the mixing squeezing device 20 of twin shaft shown in Figure 2, screw speed 40rpm makes the cylinder temperature T of raw material throw-in part a ₁Be 90 ℃, operation afterwards is with temperature T ₂Being made as 150 ℃ carries out.The manufacturing conditions of film shaped product is: utilize thermocompressor, 150 ℃ of temperature, pressure 15MPa, 2 minutes time.

Table 1

	Comparative example	Embodiment
	Comparative example	Embodiment						Soak solvent	Do not have	Tap water (15 ℃)
Polished rice soak time (branch)	0	5	10	20	40	60	120	Soak solvent	Do not have	Tap water (15 ℃)
Polished rice soak time (branch)	0	5	10	20	40	60	120	Moisture containing ratio (%) after polished rice soaks	12.9	17.0	20.1	22.6	27.7	30.7	30.5
Appearance of films (residue what) is many-*, in-▲, little by-zero, nothing-◎	×	▲	▲	▲	○	○	◎	Moisture containing ratio (%) after polished rice soaks	12.9	17.0	20.1	22.6	27.7	30.7	30.5
	×	▲	▲	▲	○	○	◎	Tension test intensity (MPa)	10.0	11.0	11.3	11.2	10.7	10.9	11.2
Tension test elongation (%)	13.4	20.0	26.5	30.6	35.2	39.9	72.4	Tension test intensity (MPa)	10.0	11.0	11.3	11.2	10.7	10.9	11.2
Tension test elongation (%)	13.4	20.0	26.5	30.6	35.2	39.9	72.4	(sorrel) such as particulate band looks strong-*, in-▲, weak-zero, nothing-◎	×	▲	▲	△	△	○	○

Table 2 expression will be given birth to rice and is immersed in the water or be immersed in and dissolved 1% trehalose (non-reducing saccharide in the water, the woods original production) in the solvent or be immersed in and dissolved 1% protin P in the water (protein decomposes yeast preparation, big and change into production) solvent in, the overall picture of the film shaped product that make by the starch-resin composition that has mixed these meters and the result of mechanical characteristics (tension test data).In addition, also put down in writing the result of the situation of adding 0 weight %, 2.5 weight %, 5.5 weight % compatilizers in the table.Can know: compare with the comparative example that does not add compatilizer, add the situation of compatilizer and in the immersion treatment of giving birth to rice, use the embodiment of the solvent that is dissolved with 1% trehalose or protin all to demonstrate excellent result.And the addition of compatilizer is many more, and the result who obtains is good more.The example of the addition 5.5% of compatilizer can obtain and utilize 100% polyolefin resin (X) to be configured as the roughly the same result of situation (omitted data is represented) of film.

In addition, can find: use the solvent that is dissolved with trehalose and protin P to giving birth to the embodiment of Mi Jinhang immersion treatment, very little by the foul smell of its film shaped product that make.

Table 2

	Comparative example	Embodiment
	Comparative example	Embodiment				Soak solvent	Tap water (15 ℃)	Tap water (15 ℃)	Tap water (15 ℃)	Tap water (15 ℃) trehaloses (1%)	Tap water (15 ℃) protins (1%)
Polished rice soak time (branch)	120	120	120	120	120	Soak solvent	Tap water (15 ℃)	Tap water (15 ℃)	Tap water (15 ℃)	Tap water (15 ℃) trehaloses (1%)	Tap water (15 ℃) protins (1%)
Polished rice soak time (branch)	120	120	120	120	120	Moisture containing ratio (%) after polished rice soaks	30.7	30.5	30.4	31.8	32.0
The addition of compatilizer (weight %)	0	2.5	5.5	2.5	2.5	Moisture containing ratio (%) after polished rice soaks	30.7	30.5	30.4	31.8	32.0
The addition of compatilizer (weight %)	0	2.5	5.5	2.5	2.5	Appearance of films (residue what) is many-*, in-▲, little by-zero, nothing-◎	×	◎	◎	◎	◎
Tension test intensity (MPa)	7.2	11.7	12.3	12.1	11.5		×	◎	◎	◎	◎
Tension test intensity (MPa)	7.2	11.7	12.3	12.1	11.5	Tension test elongation (%)	18.5	199.7	224.3	210.5	187.8
(sorrel) such as particulate band looks strong-*, in-▲, weak-zero, nothing-◎	×	○	○	◎	◎	Tension test elongation (%)	18.5	199.7	224.3	210.5	187.8

Theing contents are as follows of the raw material that uses in the test shown in the table 2 etc. is described.

At first, use new LDPE (film grade) (エボリユ one SP2150: Mitsui Chemicals production) give birth to rice (put down into 8 produce the Nigata counties per year produce road early rice more) as the toxilic acid MODIFIED PP (ユ one メ Star Network ス 1001: Sanyo changes into production) of starchy material (Y), 0～5.5 weight % biological degradability imparting agent (MB particle: マ Network ロテ Network リサ one チ company (U.S.)) of 79.2～73.7 weight % as compatilizer (Z), 0.8 weight % as the purified of thermoplastic resin (X), 20 weight %.

In addition, the manufacturing conditions of aqueous treatment, mixing condition and the film shaped product of living rice is identical with the condition that table 1 carries out.

Claims

1. a starch-blended resin composition is characterized in that, said composition is main raw material with the following substances:

5～95 parts by weight of thermoplastic resin (X),

The starchy material of 95～5 weight parts (Y) and

With respect to (X) that amount to 100 weight parts (Y) composition be the compatilizer (Z) of the affinity at interface 0.2～20 weight part, that improve described thermoplastic resin (X) and described starchy material (Y).

2. starch-blended resin composition according to claim 1 is characterized in that, described compatilizer (Z) is saturated carboxylic acid, unsaturated carboxylic acid or their derivative.

3. starch-blended resin composition according to claim 1 is characterized in that, described compatilizer (Z) is the above-mentioned thermoplastic resin (X) with the modification of unsaturated carboxylic acid or derivatives thereof.

4. starch-blended resin composition according to claim 1 is characterized in that, described compatilizer (Z) is the above-mentioned starchy material (Y) with the modification of unsaturated carboxylic acid or derivatives thereof.

5. according to any described starch-blended resin composition in the claim 1～4, it is characterized in that described starchy material (Y) is made of the a kind of material that is selected from the following substances group at least: rice, wheat, corn, potato, sweet potato, cassava.

6. according to any described starch-blended resin composition in the claim 1～4, it is characterized in that described starchy material (Y) is the rice of giving birth to that soaks more than 5 minutes in water.

7. starch-blended resin composition according to claim 6 is characterized in that, is dissolved with at least a kind in salt, sucrose, trehalose, antioxidant, protein decomposition accelerating agent, the Mierocrystalline cellulose decomposition accelerating agent in above-mentioned water.

8. according to any described starch-blended resin composition in the claim 1～7, it is characterized in that by gelatinization, starch demonstrates the α structure to described starchy material (Y) by heating in the presence of moisture.

9. according to any described starch-blended resin composition in the claim 1～7, it is characterized in that described starchy material (Y) dewaters after by gelatinization by heating in the presence of moisture, starch demonstrates the α structure.

10. according to any described starch-blended resin composition in the claim 1～9, it is characterized in that described thermoplastic resin (X) is made of the a kind of compound that is selected from the following compound group at least: biological degradability polyolefine, Biodegradable polyester, biological degradability polyvinyl alcohol copolymer, biological degradability polysaccharide derivatives, biological degradability polymeric amide.

11., it is characterized in that adding has the additive of giving biological degradability according to any described starch-blended resin composition in the claim 1～9 in described thermoplastic resin (X).

12. the molding of a starch-blended resin composition is characterized in that, contains any described starch-blended resin composition in the claim 1～11.

13. the molding of a starch based blended resin composition, it is characterized in that, form as main raw material with any described starch-blended resin composition and the above-mentioned thermoplastic resin of 95～20 weight parts (X) in 5～80 weight part claims 1～11 and process.

14. the manufacture method of a starch-blended resin composition is characterized in that, comprises following operation:

Raw material drops into operation: will contain thermoplastic resin (X) at least and contain the starting raw material of the starchy material (Y) of moisture, and put into the raw material throw-in part that temperature is adjusted into the mixing squeezing device below 140 ℃;

The heat flow treatment process: pressure is higher than normal atmosphere and temperature is the pyritous High Temperature High Pressure portion of described thermoplastic resin (X) heat flow to being adjusted to input above-mentioned starting raw material conveyance, formation contains hydrothermal fluid, and at least a portion gelatinization of the above-mentioned starchy material (Y) that is contained and form pasted starch;

Dispersion treatment operation: the mixing above-mentioned hydrothermal fluid that contains under identical high temperature, high pressure, make the nubbin gelatinization of described starchy material (Y), and the pasted starch that is generated is ground into starch small grain, and this starch small grain is scattered in and forms starch in the above-mentioned integral body that contains hydrothermal fluid and disperse hot-fluid;

The processed operation: it is the pyritous degassing portion that described starch disperses the hot-fluid heat flow to being adjusted to the low pressure and the temperature of pressure below normal atmosphere that described starch is disperseed the hot-fluid conveyance, and described starch disperses contained moisture evaporation in the hot-fluid and forms no hydrothermal fluid;

Discharge operation: discharge this no hydrothermal fluid from the relief outlet of described mixing squeezing device;

Forming process: the above-mentioned no hydrothermal fluid of being discharged solidifies under the low temperature of forfeiture thermal fluidity and is formed.

15. the manufacture method of starch-blended resin composition according to claim 14 is characterized in that, also is included in after the described discharge operation, makes described no hydrothermal fluid make the micronize operation of described starch small grain miniaturization by the gap of hot-rolling.

16. the manufacture method of a starch-blended resin composition is characterized in that, comprises following operation:

Mixing operation: the starting raw material that comprises thermoplastic resin (X) and starchy material (Y) at least becomes at described thermoplastic resin (X) under the temperature of hot-fluid by mixing, and the starch small grain that the above-mentioned starchy material (Y) that contained or its pulverizing are formed disperses;

Discharge operation: discharge through mixing above-mentioned hot-fluid from the relief outlet of described mixing squeezing device;

Micronize operation: make the above-mentioned hot-fluid of being discharged gap, thereby make described starchy material or the further miniaturization of described starch small grain after the dispersion by hot-rolling;

Forming process: the described hot-fluid that has passed through this micronize operation solidifies under the low temperature of forfeiture thermal fluidity and is formed.

17. the manufacture method according to any described starch-blended resin composition in the claim 14～16 is characterized in that, comprising also that described no hydrothermal fluid or described hot-fluid stretched before solidifying becomes the stretching process of film like.