JP3478299B2 - Degradable composite material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decomposable composite material.
You.further,For details, mainly use aliphatic polyester
Thermoplastic polymer composition and celluloseOrNature
It relates to composite materials that are degradable in the environment.
You. These are the sheetsorIs a moisture-proof packaging material as a film
Can be used for food, cosmetic boxes, milk and juice containers, etc.
Wear. In addition, these materials can be easily used in the natural environment after use.
Decomposed. [0002] 2. Description of the Related Art Conventionally, polyethylene, polypropylene, etc.
Polyolefin resin, paper and regenerated cellulose fill
(Cellophane) mixed with milk and juice
Widely used for water-resistant packaging containers. Also, the book table
In order to satisfy the aesthetic needs of consumers, paper and gift boxes etc.
Coated paper with smooth and glossy surfaces is frequently used
You. However, such polyolefin-based polymers are
It is hardly degradable in the natural environment and is discarded and buried.
The degradation rate of cellulose, which is naturally degradable,
Significantly lower. In addition, paper is collected and used as pulp resources.
The film is used in the process of disintegrating the pulp before reuse.
It gets in the way and reduces efficiency. Also, the polymer pieces
Because of the possibility of mixing in the pulp,
Techniques for separating polymers from inside are also needed. Japanese Patent Application Laid-Open No. 4-336246 discloses a natural
Laminate of polylactic acid and paper with degradability under environment
Materials are disclosed. In addition, Japanese Patent Application Laid-Open No. 4-38784
In the official gazette, there is a composite film of polylactic acid and regenerated cellulose film.
The film is shown. However, polylactic acid has low elongation
Because the polymer is hard and hard,
orWhen the regenerated cellulose film is folded,
-The film may be cracked and cracked. This
Composite films such as milk and juice storage containers
Liquids or gas to be used as storage containers for confectionery
And barrier properties against bacteria are important.
The generation of cracks and the like due to spalling is not preferable. [0004] In addition, thermoplastic and degradable polymers
Thus, aliphatic polyesters are known. But many
AlcoholAndPolybaseTo acidThe esterification reaction
The molecular weight increases with the reaction time.
The generated water reduces the molecular weight of the polycondensate by hydrolysis.
It has the effect of lowering, so it can be obtained by direct condensation
Aliphatic polyester has a molecular weight of at most about 10,000
WhenIHad been [0005] JP-A-4-189822 and JP-A-Hei-4
No. 189823 discloses that the number average molecular weight is 5,000 or less.
Above, the terminal group is substantially a hydroxyl group and the acid component
Is a compound having 3 or more carbon atomsorIs the mixture of saturated poly
In the molten state above its melting point,
Isocyanate groups equivalent to 1/10 to 2 equivalents of xyl groups
By adding a diisocyanate having
It describes how to make the molecular weight polyester.
However, as described above, isocyanate is contained in the polymer chain.
Toxic diamines are formed during the decomposition process and
When accumulated or used as packaging materials for food etc.
And partially decomposed diamine contaminates the contentsfearThere
You. [0006] Aliphatic polyesters are compared in the presence of water.
Easily hydrolyzed and degraded by microorganisms
Therefore, these polymers and cellulose
No composite materials of any kind are known. [0007] SUMMARY OF THE INVENTION The present invention provides strength and water resistance.
Excellent flexibility, flexibility and bending resistanceYoAnd at the same time under the natural environment
Biodegradable, toxic due to biodegradabilityfearof
Give rise to a substanceHatefulThermoplastic degradable polymer and cellulo
ーAndIt is an object of the present invention to provide a composite material. [0008] Means for Solving the Problems The present inventors have solved the above problems.
As a result of intensive studies to solve the problem, ethylene glycol
, Diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, zip
Propylene glycol, 1,3-butanediol, 1,4
-Butanediol, 3-methyl-1,5-pentanedio
, 1,6-hexanediol, 1,9-nonangio
, Neopentyl glycol, polytetramethylene glycol
Recall 1,4-cyclohexanedimethanol, 1,4
One or more aliphatics selected from benzene dimethanol
Polyhydric alcohol and succinic acid, oxalic acid, malon
Acid, glutaric acid, adipic acid, pimelic acid, suberin
Acid, azelaic acid, sebacic acid, undecandioic acid, dode
Candioic acid, 1,4-phenylenediacetic acid, phenyl succinate
One or more aliphatic polysaccharides selected from acids and their anhydrides
Basic acid, or even lactic acid, glycolic acid, 3-hydrid
Roxybutyric acid, 4-hydroxybutyric
Acid, 3-hydroxyvaleric acid, 5-hi
Droxyvaleric acid, 6-hydroxycapron
One or more hydroxycarboxylic acids selected from acids
The amount obtained by direct condensation reaction in a reaction mixture containing a solvent
Aliphatic polyester with 50,000 to 300,000 children
A thermoplastic polymer composition comprising
Fibers and nonwovens made from wood pulp
Regenerated cellulose except cellulose film
Cellulos selected from steal or cellulose ether
1) the cellulose and the aliphatic
Impregnated or coated with polyester or its solution
2) The aliphatic in fibrous or pulp form
Mix polyester and cellulose fiber or pulp
3) The cellulose and the fat
Glue the polyester film with heat or adhesive
ToBy the wayThe resulting degradable composite material for strength and water resistance
Excellent, flexible, good bending resistance, and at the same time under natural environment
The present invention was found to be a composite material having a decomposability of
Was completed. In addition, on the surface of a material made of cellulose
Forming a film of the aliphatic polyester of the present invention
As a result, a material with a good surface gloss and beautiful appearance can be obtained.
This composite material is easily surfaced under alkaline conditions.
The limer film dissolves and recovers only the cellulose.
Found that it has the feature of being able to
Ming completed. [0009]In the present invention, the outline of the term "composite material" is used.
Just make sure that the resin is
Adhering to fiber, paper, film etc.
An embodiment of impregnation is included. In the present invention, "cellulo
The concept of the word “source” is described in paragraph numbers 0036 to 0037.
Also as described later, wood pulp, cotton linter, etc.
Cellophane, such as fibers, paper, non-woven fabric, etc.
Cellulose, nitrose, etc.
Nitric acid, sulfuric acid, acetic acid,
Esters with ropionic acid, butyric acid, other higher fatty acids, etc.
Cellulose esters or methyl cellulose
, Ethyl cellulose, benzyl cellulose, carboxyl
Cimethylcellulose, hydroxyethylcellulose,
Droxypropyl cellulose, ethyl hydroxyethyl
Cellulose, like carboxymethylethylcellulose
Cellulose A with etherified cellulose hydroxyl groups
And the like. Here, when the cellulose is paper,
As described later in paragraph 0037. Art paper (coated
Paper), kraft paper, roll paper, rice paper, etc.
Processing base paper, cloth paper, cardboard and the like are included. In the present invention
In a preferred embodiment for producing a composite material, a step
As described below in the drop number 0038, the cellulose
Fiber or paper impregnated with polymer or its solution or coated
Method of fibrous or pulp-like polymer
Combine cellulose fiber or pulp and press by heat
Method, cellulose film or paper and polymer fill
The method of bonding heat with heat or an adhesive
it can. In the present invention, it is particularly preferable to produce a composite material.
As a preferred embodiment, the latter is also described in paragraph number 0038.
As described above, it is continuously melted into a sheet of paper such as a roll.
Extrusion Coating Coated Polymer
Is preferred. When using an adhesive, glue,
Use degradable materials such as gelatin, casein, and starch.
Is preferred.Aliphatic polyester used in the present invention
Is an aliphatic polyhydric alcoholRumataIs the mixture and aliphatic polysalt
BaseAcid orIs a polyester of the mixture, and,Mo
Hydroxycarboxylic as nomerAcid orIs the mixture,or
Is,It contains those oligomers, and the organic solvent
Obtained by direct condensation reaction in a reaction mixture containing
You. The degree of polymerization of the aliphatic polyester is 100
20,000. If the polymerization degree is lower than this,
The strength at the time of doing it is not suitable for practical use. Also, the degree of polymerization
If it is too high, the viscosity in the hot molten state will be high,
Poor workability. The polymerization method is a polyvalent alcohol.AndPolybaseacid,
Or,further,HydroxycarboxylicAcidAdded
Water condensation reaction in an organic solventorIs over
Excess monomer is distilled out of the reaction system together with the organic solvent
And water dissolved in the distilled organic solventorIs a monomer
Less than the amount of waterorIs an organic solvent containing the amount of monomer
The reaction is performed while charging the reaction system as an additional solvent. The polyhydric alcohols include aliphatic hydroxyls
Having a group, for example,Ethylene glycol, di
Ethylene glycol, triethylene glycol, polyether
Tylene glycol, propylene glycol, dipropylene
Glycol, 1,3-butanediol, 1,4-butadiene
Diol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, 1,9-nonanediol,
Neopentyl glycol, polytetramethylene glycol
1,4-cyclohexanedimethanol, 1,4-ben
Sendi methanol etc.CeremonyI can do it. Also, polybasicWith acidAnd aliphatic carbo
It has a xyl group, for example,,Succinic acid, Shu
Acid, malonic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, undecane
Acid, dodecanedioic acid, 1,4-phenylenediacetic acid, phenyl
Succinic acid, etc., of course,,These anhydrides
Can be used. Hydroxycarboxylic acidTo acidAbout lactic acid,
Glycolic acid, 3-hydroxybutyric acid, 4
-Hydroxybutyric acid, 3-hydroxyvale
Rick acid, 5-hydroxyvaleric acid,
6-hydroxycaproic acid and the likeCeremonyI can do it. When the compound has an asymmetric carbon in the molecule, it is D-form, L-form
Body, each aloneYoMixing of D and L isomers
object,Ie,Even if it ’s racemicYoNo. In order to obtain a soft non-woven fabric, economical efficiency
Considering, ethylene glycol as polyhydric alcohol,
PolybaseWith acidAnd a polymer using succinic acid is preferable,
Lactic acidPassingIf it contains glycerol and glycolic acid, the ratio is 50% or less
Is preferable, and 20% or less is more preferable. In this heat condensation reaction,,Use catalyst
With or withoutYoHowever, when a catalyst is used,
Speed upthingCan be. The catalyst used is
Metals of Groups II, III, IV, V of the Periodic Tables and Their Oxides,
Or,Such as saltCeremonyI can do it. Specifically, zinc
Powder, tin powder, aluminum, magnesium, titanium, gel
Metals such as manium, tin oxide, antimony oxide, zinc chloride
Lead, aluminum oxide, magnesium oxide, titanium oxide
Etc., metal oxides, stannous chloride, stannic chloride, first bromide
Tin, stannic bromide, antimony fluoride, zinc chloride,
Metal halides such as gnesium and aluminum chloride,
Sulfates such as tin sulfate, zinc sulfate, and aluminum sulfate, and carbonic acid
Carbonates such as magnesium and zinc carbonate, tin acetate, octane
Organic acids such as tin acid, tin lactate, zinc acetate and aluminum acetate
Rubonates, tin trifluoromethanesulfonate, trif
Zinc fluoromethanesulfonate, trifluoromethanesulfur
Magnesium phonate, tin methanesulfonate, p-tolue
Organic sulfonates such as tin sulfonateCeremonyI can do it. So
And other organic metals such as dibutyltin oxide
Oxides,orAbove, such as titanium isopropoxide
Metal alkoxide, metalorIs above diethyl zinc
Alkyl metal of the above metal,orThe Dowex, Amber
Ion exchange resins such as light; The amount of the aliphatic polyhydric alcohol used
Tools, aliphatic polybasic acids,PassingAnd,Aliphatic hydroxycarbo
Acid,orIs 0.0001 to 10 times those oligomers
Amount%YoEconomical and consider in vivo use
And 0.001 to 2% by weight. Further, according to the present invention,PertainFor polyester production
The solvent used in this step is, for example, toluene,
, Hydrocarbon solvents such as mesitylene, chlorobenzene,
Bromobenzene, iodobenzene, dichlorobenzene,
1,1,2,2-tetrachloroethane, p-chlorotol
Halogen solvents such as ene, 3-hexanone, acetophen
Ketone solvents such as non- and benzophenone;
Ter, anisole, phenetole, o-dimethoxyben
Zen, p-dimethoxybenzene, 3-methoxytolue
, Dibenzyl ether, benzyl phenyl ether,
Ether solvents such as methoxynaphthalene, phenyl sulf
Thioether solvents such as fido and thioanisole, repose
S, such as methyl fragrance, methyl phthalate and ethyl phthalate
Ter solvent, diphenyl ether,orIs 4-methylfe
Nyl ether, 3-methylphenyl ether, 3-Fe
Alkyl-substituted diphenyl ethers such as nonoxytoluene,
orIs 4-bromophenyl ether, 4-chlorophenyl
Ether, 4-bromophenyl ether, 4-methyl
Halogen substituted di such as -4'-bromodiphenyl ether
Phenyl ether,orIs 4-methoxydiphenylate
Ter, 4-methoxyphenyl ether, 3-methoxyphenyl
Phenyl ether, 4-methyl-4'-methoxydiphenyl
Alkoxy-substituted diphenyl ethers such asor
Is a cyclic diphenyl ether such as dibenzofuran or xanthene
Diphenyl ether solvents such as
Can be mixed and usedYoNo. And easy as solvent
What can be separated from water is preferable, especially,Average molecule
To obtain a high amount of polyester, an ether solvent,
Alkyl-aryl ether solventPassingBiphenyl A
Ter-based solvents are more preferred, but alkyl-aryl
Ter solventas well asDiphenyl ether solvents are particularly preferred.
No. The amount of these solvents used depends on the polymer to be obtained.
Is preferably 10 to 80%. In the production of aliphatic polyesters,
WaterorIs necessary to distill excess monomer out of the reaction system.
Is the organic solvent used and waterorIs due to azeotropy with the monomer
Is preferred. The organic solvent distilled by azeotropic distillation contains
WaterorIs the amount of monomer,Water for the organic solventorIs
If the solubility is higher than the,Water by separationorIs a thing
After removing the polymer, return it to the reaction system.,Further use
Water dissolved in organic solventorIs removed to remove the monomer.
Treat with water or a demonomer, or distillorIs
After reducing the nomer content, it may be returned to the reaction system.
No. Also,Instead of organic solvent distilled by azeotropic distillation, new
WaterorIs charged with an organic solvent with low monomer content
Is also good. Also,Water at the beginning of the reactionorIs excess monomer
Is removed under reduced pressure, and then an organic solvent is added.
Removal of some organic solvents from reaction mixtures containing solvents
And by the reaction mixture waterorIs the specified value of the monomer
You can also. That is, at least at a certain stage of the reaction, the solvent
Using waterorAdvances condensation reaction while removing monomer
In this embodiment, the solvent is water.orIs a thing
May or may not azeotrope with theorIs
Something that separates with Nomer,It may not be. Ma
In another embodiment, the excess solvent is charged in advance.
Dehydration and demonomerization by simply extracting the solvent
Dehydration and demonomerization of the reaction solvent using another solvent
Method is also included. Also,further,As a variant, the reaction solution
Water with the medium itself liquidorMay remove the monomer.
As for the reaction temperature, the solvent is waterorIs the same as the monomer
Because of boiling, even if the boiling point is lowered,
Just do it. The average molecular weight of the aliphatic polyester
Organic solvent water charged to the systemorDepends on the amount of monomer,
Depending on the type of solvent, the solvent is 400 to 500 ppm
High waterorHas the amount of monomer,
The weight average molecular weight of the ester is 15,000 to 50,
000. Even with the above high moisture and high monomer content,Jife
When using a nyl ether solvent,40,000-50,
Aliphatic polyester having a weight average molecular weight of 2,000
That is surprising. In addition, high average molecular weight
In order to obtain aliphatic polyester, it is charged to the reaction system
Organic solvent waterorPreferably have a low monomer content,
Dehydration of organic solvent distilled by boiling, treatment with demonomerizing agent
And waterorRemoves monomerorIs reduced and returned to the reaction system.
WaterorUses a new organic solvent with low monomer content in the reactor
Water to be charged by chargingorIs 50
ppm or less, the weight average molecular weight is 50,000.
0-300,000 aliphatic polyesters can be obtained
it can. The high average molecular weight used in the composite material of the present invention
Dehydration and demonomerization agent used to obtain a new polyester
As molecular sieve 3A, molecular sieve 4
A, molecular sieve 5A, molecular sieve 13X, etc.
Molecular sieves, alumina, silica gel, potassium chloride
Lucium, calcium sulfate, diphosphorus pentoxide, concentrated sulfuric acid,
Magnesium chlorate, barium oxide, calcium oxide,
Potassium hydroxide, sodium hydroxide or hydrogenation
Calcium, sodium hydride, lithium aluminum hydride
Metal hydrides such asorIs an alkali such as sodium
Metal and the like. Among them, handlingPassingAnd regeneration
Sakare molecularityIspreferable. In the present inventionPertainOne of the manufacturing methods of polyester
The following is an exampleStreetIt is. That is, the separator (example
For example, a reactor equipped with a Dean Stark trap)
And the solventPassingAnd predetermined amounts of ethylene glycol and succinic acid
Lactic acid and a predetermined amount of catalyst are charged, and the reactor is heated to azeotropic
More solvent and waterorDistills excess monomer and feeds it to the separator.
Good. Water above the solubility of the solventorSeparates monomers with a separator
And remove it out of the system.orContains monomers
The solvent is returned to the reaction system. Weight average molecular weight at this stage
Is from 500 to 1,000, and the weight average molecular weight is 5,
Even if it reaches about 000YoNo. The reaction time during this time is approximately
0.5 hours to several hours. This oligomerization reaction
Beforehand in a separate reactor with no solvent, no catalyst,
Even if you goYoAnd even when using a solvent without a catalystYoNo.
Produced as the reaction proceeds at the solvent distillation temperature
waterorRemoves monomers and removes waterorIs the solution saturated with the monomer
Even if the reaction is continued while returning the medium to the reaction system,YoBut several tens of o'clock
Although the reaction may take place depending on the type of the solvent, the weight average molecular weight is 1
5,000-50,000 are obtained. In order to obtain a polymer having a higher molecular weight,
Water in the chargeorAfter the excess monomer is almost distilled off, the separator
And fill the tube filled with a desiccant such as molecular sieve.
So that the distilling solvent refluxes through this tube
Or process the distilled solvent in a separate reactor containing a desiccant.
Or return it to the reactororIs new waterorIs
A solvent having a low nomer content is charged to the reactor. these
By the way,Water in which the solvent dissolvesorMeans 50
ppm and keep the reaction for several tens of hours.
Weight average molecular weight of 50,000, depending on the type of solvent.
Obtain 0-300,000 copolymerthingCan be.
After completion of the reaction, what is the treatment method to obtain the desired copolymer?
Even in a wayYoHowever, for example, chloroform was added to the reaction solution.
And heated, then discharged into acetone and the precipitated crystalsFiltration
After drying, the desired copolymer is obtained. The aliphatic polyester obtained by this method
Weight average molecular weight depends on the type of solvent and catalystPassing
Volume, reaction rate, reaction time,
Various things can be obtained by changing the processing method etc.
Is about 15,000 to 300,000. In the method of the present invention, the condensation reaction is carried out using a catalyst.
When performed in the presence, if the catalyst remains in the polymer
Because it affects the thermal stability and weather resistance of the polymer,
It is preferable to remove the catalyst therein. The preferred removal method
The condensation reaction solution under stirring.orCan be cooled as it is
Powdered polymer in the presence of a hydrophilic organic solvent
This is a method of contacting with an acidic substance. As the hydrophilic organic solvent used in this method,
Methanol, ethanol, isopropanol,
Alcohols such as ethanol, acetone, methyl ethyl ketone
Ketones such as tons, tetrahydrofuran, dioxane, etc.
Ethers, carboxylic acids such as acetic acid and butyric acid, acetonitrile
Nitriles such as tolyl, N, N-dimethylformamid
, N, N-dimethylacetamide, 1,3-dimethyl
Such as imidazolidinone and hexamethylphosphoramide
Mids etc.CeremonyCan be Especially cheap,Moreover,The polymer
Alcohols that do not dissolve the acid are preferred. The acidic substances include hydrochloric acid, sulfuric acid, nitric acid,
Inorganic acids such as acid,orIs acetic acid, paratoluenesulfonic acid
And especially inexpensive hydrochloric acid, sulfuric acid, nitric acid
Are preferred. The amount of the acidic substance used is based on the amount of the polymer.
0.0001 to 5.0 mol / 100 parts by weight.
Or 0.001 to 1 mol / 100 parts by weight. 0.
If the amount is less than 0001 mol, the effect of removing the catalyst becomes worse,
Also,If the amount is more than 5.0 mol, the polymer may deteriorate.
Problem may occur. The polymer used in this method is a solid
Powder, granule, granule, flake, block
In general, as a method for obtaining the polymer,
After dissolving the polymer in a good solvent once by the usual method, drop the poor solvent.
Method of dropping under or in poor solvent,orIs a specific solvent
There is a method of cooling and crystallizing after heating and dissolving. The properties of the polymer are preferably bulky
The degree is 0.60 g / ml or less, more preferably
0.05-0.5g / mlYoNo. Bulk density is 0.60g
/ Ml, the contact with acidic substances becomes insufficient
May not be able to completely remove the catalyst in the polymer.
When the bulk density is less than 0.05 g / ml,
There is no problem, but operation becomes difficult due to poor filterability after treatment.
Problems may occur. The conditions for contacting the polymer with the acidic substance are as follows:
Preferably, the solid concentration in the hydrophilic organic solvent is 3 to 40.
Weight%, contact temperature is 0 to 100 ° C., particularly preferably
0-60 ° C, contact time about 0.1-24 hours, particularly preferred
About 0.5 to 8 hours. The aliphatic polyester of the present invention is generally known
Thermoplastic polymerorIs a plasticizer,further,Various modifiers
To form a thermoplastic polymer composition. Thermoplastic resin
The proportion occupied by the aliphatic polyester in the limmer composition,
Any ratio is used depending on the desired degradability
However, 50% or more is generally preferred. Also thermoplastic poly
All known kneading techniques can be applied to the production of the mer composition.
The composition is used in the form of pellets, rods, powders, etc.
You. Cellulose used in the composite material of the present inventionS
IsNaturally produced from wood pulp, cotton linter, etc.
Fiber, paper, non-woven fabric, etc.
Regenerated cells for processed products, cellophane, viscose rayon, etc.
Low,Or,Nitrocellulose, cellulose acetate
Such as nitric, sulfuric, acetic, propionic, butyric,
Other higher fatty acidsorIs esterified by their mixture
Cellulose esters, or methylcellulose,
Ethyl cellulose, benzyl cellulose, carboxyme
Chill cellulose, hydroxyethyl cellulose, hydro
Xypropylcellulose, ethyl hydroxyethyl cell
Loose, such as carboxymethyl ethyl cellulose
Cellulose ether obtained by etherifying the hydroxyl group of lurose
And so on. Cellulose derivatives are converted to ordinary cellulose
Heat resistance and water resistance are high compared to such materials and the present invention.
Even when made into a composite material of aliphatic polyester,
It is preferable because the property is improved. CelluloseIsFor paper, art paper (coated
Paper), kraft paper, roll paper, rice paper, etc.
Processing base paper, cloth paper, cardboard and the like are used. this
These papers may be papers containing recycled pulp. As a method of compounding, cellulose fibers may be used.
WeiTo aliphatic polyester orImpregnate the solution or
Coating method, fibrous or pulpedFat
Aliphatic polyesterAnd cellulose fibers or pulp
Method of mixing and pressing by heat, with cellulosesAliphatic
polyesterAdhesive film with heat or adhesive
Methodis there. ContactWhen using an adhesive, glue, gelatin
It is preferable to use degradable substances such as carbohydrate, casein, starch, etc.
New The aliphatic polyester thus obtained is
-Based thermoplastic polymer composition and celluloseS
WhenThe composite material is a biodegradable polyhydric
Higher flexibility compared to composite materials using roxycarboxylic acid
It has flexibility. For example, as apparent from the following examples
In addition, the composite material of the present invention is a composite material obtained using polylactic acid.
High bending resistance compared to composite material, sufficient softness
Has the same properties as composite materials obtained from polyethylene
Indicates that it can be suitably used in the field of packaging materials and food containers.
You. [0040] The method of the present invention will be described below with reference to Examples and Comparative Examples.
Will be specifically described, but the present invention is not limited to these.
Not. The weight average molecular weight in the examples is
Chromatography (column temperature 40
° C, chloroform solvent).
It was determined by comparison with pull. Production Example 1 To 20.0 g of ethylene glycol and 38.1 g of succinic acid
207.0 g of diphenyl ether, 0.931 g of metal tin
At 130 ° C / 140 mmHg for 7 hours.
Was heated and stirred while flowing to oligomerize. this
Attach Dean Stark trap to 14
Perform azeotropic dehydration at 0 ° C./30 mmHg for 8 hours, and then
Attach a tube filled with 20 g of molecular sieve 3A and flow out
Solvent returns to the reactor through the molecular sieve layer
And stirred at 130 ° C / 17 mmHg for 49 hours.
Was. Dissolve the reaction mass in 400 ml of chloroform
And added to 3 liters of acetone for reprecipitation.
0.5 hour sludge with solution (HCl 0.7wt%)
(3 times), washed with IPA, and then at 60 ° C. under reduced pressure for 6 hours
While drying. The tin content of the catalyst in the polymer is 10 pp
m or less. The weight average molecular weight of this polymer is
124,000. Production Example 2 50.5 g of 1,4-butanediol and 66.5 succinic acid
g to 293.0 g of diphenyl ether and 2.02 to tin metal
g at 130 ° C / 140mmHg for 7 hours.
The mixture was heated and stirred while the water was flowing out to form oligomers. this
Attach Dean Stark trap to 140
Azeotropic dehydration at 80 ° C / 30 mmHg for 8 hours.
Attach a tube filled with 40 g of Recursive Sieve 3A
Solvent returns to the reactor through the molecular sieve layer
The mixture was stirred at 130 ° C./17 mmHg for 49 hours.
The reaction mass was dissolved in 600 ml of chloroform,
l of acetone and reprecipitated, then IPA solution of HCl
(HCl 0.7wt%) for 0.5 hours
(3 times), after washing with IPA, 6 hours at 60 ° C under reduced pressure
Dried. Tin content of the catalyst contained in this polymer
Was 10 ppm or less. Weight average of this polymer
The average molecular weight was 118,000. Production Example 3 trans-1,4-cyclohexanedimethanol 8
0.8 g and 66.5 g of succinic acid in diphenyl ether 2
93.0 g and 2.02 g of metallic tin were added, and 130 ° C./14
Heating at 0 mmHg for 7 hours while allowing water to flow out of the system
Oligomerization occurred. To this, Dean Stark
  Attach trap, 140 ° C / 30mmHg at 8:00
Intermediate azeotropic dehydration, followed by molecular sieve 3A40
g filled tube, and the eluted solvent is molecular
130 ° C./17
Stirred at mmHg for 40 hours. The reaction mass is 600m
dissolved in 1 l of chloroform, added to 4 l of acetone and reprecipitated.
After that, with HCl IPA solution (HCl 0.7wt%)
Sludge for 0.5 hour (3 times), wash with IPA
And dried at 60 ° C. for 6 hours under reduced pressure. Catalyst in polymer
Had a tin content of 10 ppm or less. This poly
The weight average molecular weight of the mer was 122,000. Production Example 4 20.2 g of ethylene glycol and 38.5 g of succinic acid
7.3 g of lactic acid, 123.0 g of diphenyl ether, metal
Add 0.66g of tin, 9 hours at 125 ° C / 140mmHg
During the heating, it is heated and stirred while water is flowing out of the system to oligomerize.
did. Take the Dean Stark trap
Azeotropic dehydration at 140 ° C / 15mmHg for 3 hours
Then, a tube filled with 30 g of molecular sieve 3A
And the escaping solvent passes through the molecular sieve layer
Return to the reactor and add 33 ° C at 130 ° C / 13 mmHg.
Time-stirred. The reaction mass was added to 720 ml of acetonitrile.
Dissolve in rill and add 300 ml of 1N HCl aqueous solution
After stirring for 0.5 hour, add 320 ml of IPA,
Released and reprecipitated in 4.5 l of methanol. Normal Heki
After washing with 3 l of sun, it was dried under reduced pressure. Catalyst in polymer
Had a tin content of 10 ppm or less. This poly
The weight average molecular weight of the mer was 147,000. Production Example 5 35.0 g of 1,4 butanediol and 30.4 succinic acid
g, adipic acid 9.4 g and diphenyl ether 176
g, 0.66 g of metallic tin, 130 ° C / 140 mmH
g for 10 hours while heating and stirring while flowing water out of the system.
Gommered. In addition, Dean Stark tra
azeotropic removal at 140 ° C / 15 mmHg for 5 hours
Water, and then add 30 g of molecular sieve 3A
Attach the filled tube and distill off the solvent into the molecular sieve layer.
130 ℃ / 13mm
Stirred with Hg for 30 hours. The reaction mass was reduced to 720 ml
Dissolve in acetonitrile, 1N HCl aqueous solution 300m
After stirring for 0.5 hour, 320 ml of IPA was added.
Then, it was released into 4.5 l of methanol and reprecipitated. Nor
After washing with 3 l of malhexane, the product was dried under reduced pressure. This poly
The weight average molecular weight of the mer was 137,000. Poly
The tin content of the catalyst in the mer was less than 10 ppm. Embodiment 1 The weight average molecular weight of 124,000 obtained in Production Example 1
The rimer is pressed with a press molding machine at 170 ° C. for 5 minutes.
Then, by cooling at 40 ° C. for 5 minutes, a thickness of 100 μm
m was obtained. This film and basis weight 6
5.5 g / m^Two Of high quality paper, and press
30kg / cm for 5 minutes at 70 ° C^Two By crimping with
A coated paper with good surface gloss was obtained. This coating
Paper is flexible and made by folding coated paper
Cracks of polymer film out of 20 folds found
It did not fit. The cracks in the film were
To check the area where the color has soaked.
Confirmed. This coated paper is treated with 5N sodium hydroxide
When heated to 60 ° C. in an aqueous solution of
The polymer layer on the surface dissolved and disappeared. Also,This film
When buried in a 40 ° C compost, there is no shape in 2 weeks
became. Embodiment 2 The weight average molecular weight of 118,000 obtained in Production Example 2
Using a reamer, set the film forming temperature and the pressure
A film and a film were prepared in the same manner as in Example 1 except that the temperature was changed to 50 ° C.
And coated paper. Good surface gloss,Shinaya
Kana coated paper was obtained. Further, the same as in the first embodiment
According to the bending test of the polymer film,
No cracks were observed. This coated paper,
Heated to 60 ° C in 5N sodium hydroxide aqueous solution
After 5 hours, the polymer layer on the surface dissolved and disappeared. Ma
Was,When this film was buried in a compost at 40 ° C,
The shape disappeared in two weeks. Embodiment 3 The weight average molecular weight of 122,000 obtained in Production Example 3
A film was prepared in the same manner as in Example 1 except that a limer was used.
And coated paper. Good surface gloss,Shina
A soft coated paper was obtained. further,Example 1 and
A similar bending test revealed that the polymer fill
No cracks were found. This coated paper
Was heated to 60 ° C. in a 5N aqueous sodium hydroxide solution.
At this time, the polymer layer on the surface dissolved and disappeared after 5 hours.
Also,This film was buried in a 40 ° C compost
Of course, the shape disappeared in two weeks. Embodiment 4 The polystyrene having a weight average molecular weight of 147,000 obtained in Production Example 4
A film was prepared in the same manner as in Example 1 except that a limer was used.
And coated paper. Good surface gloss,Shina
A soft coated paper was obtained. further,Example 1 and
A similar bending test revealed that the polymer fill
No cracks were found. This coated paper
Was heated to 60 ° C. in a 5N aqueous sodium hydroxide solution.
At this time, the polymer layer on the surface dissolved and disappeared after 5 hours.
Also,This film was buried in a 40 ° C compost
Of course, the shape disappeared in two weeks. Embodiment 5 The weight average molecular weight of 137,000 obtained in Production Example 5
A film was prepared in the same manner as in Example 1 except that a limer was used.
And coated paper. Good surface gloss,Shina
A soft coated paper was obtained. further,Example 1 and
A similar bending test revealed that the polymer fill
No cracks were found. This coated paper
Was heated to 60 ° C. in a 5N aqueous sodium hydroxide solution.
At this time, the polymer layer on the surface dissolved and disappeared after 5 hours.
Also,This film was buried in a 40 ° C compost
Of course, the shape disappeared in two weeks. Comparative Example 1 Using poly L-lactic acid having a weight average molecular weight of 130,000,
After setting the film forming temperature and the pressing pressure to paper to 200 ° C
Outside, film and coating in the same manner as in Example 1.
Created paper. Good surface gloss,Supple coating
Paper was obtained. Further, the same bending test as in Example 1 was performed.
Investigation revealed that 2 out of 20 folds had polymer
Cracks in the film were observed. This coated paper
Was heated to 60 ° C. in a 5N aqueous sodium hydroxide solution.
At this time, the polymer layer on the surface dissolved and disappeared after 5 hours.
Also,This film was buried in a 40 ° C compost
Of course, the shape disappeared in two weeks. Comparative Example 2 Polyethylene (Mirason-11) as raw material polymer
A film and a coat were prepared in the same manner as in Example 1 except that they were used.
I made a toting paper. Good surface gloss,Supple ko
Printing paper was obtained. Further, the same bending as in the first embodiment
Inspection of the polymer film
Was not found. Also,This film is
When buried in compost, there was no change even after 2 weeks. Embodiment 6 The weight average molecular weight of 124,000 obtained in Production Example 1
The limer is dissolved in chloroform at a concentration of 5%, and the basis weight is 65.
5g / m^Two Coated on high quality paper, dried and supple
I got the printing paper. This coated paper is
Heated to 60 ° C in aqueous thorium solution, surface after 5 hours
No change was observed in the polymer layer. Also,This film
When buried in a 40 ° C compost, there is no shape in 2 weeks
became. Embodiment 7 100 μm thick film obtained in Example 1 and thickness
Stack 50μm regenerated cellulose film (cellophane)
30kg / cm at 170 ° C for 5 minutes^Two so
Good surface gloss by pressure bonding,Flexible compound
A film was obtained. Also,Compost the film at 40 ° C
When buried inside, it lost its shape in two weeks. Embodiment 8 100 μm thick film obtained in Example 2 and acetylation
40% cellulose acetate film (50μm thick)
Overlap and press at 150 ° C for 5 minutes 30kg / cm
^Two Composite film with good surface gloss by crimping with
I got Also,Bury this film in a 40 ° C compost
After two weeks, the shape disappeared. Embodiment 9 100 μm thick film obtained in Example 2
Methylcellulose film with a xy group content of 29% (thickness
50 μm), and 150 ° C. for 5 minutes 3
0kg / cm^Two Good surface gloss by pressure bonding
A composite film was obtained. This composite film is 5N hydroxylated
After heating to 60 ° C in sodium aqueous solution, after 5 hours
Dissolved and disappeared. Also,Compost the film at 40 ° C
When buried inside, it lost its shape in two weeks. [0057] According to the present invention, excellent strength and water resistance,
Flexible and durable against bending, while at the same time in the natural environment
A composite material having a decomposable property can be obtained. In addition, the cell
LowOrOf the aliphatic polyester of the present invention
The gloss of the surface is improved by forming
Ku,A material with a beautiful appearance is obtained, and this composite material
Easily dissolves the polymer film on the surface under luke-like conditions
And celluloOfOnly parts can be recovered.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 1/00 C08L 1/00 67/02 ZBP 67/02 ZBP // C08L 101/16 101/16 C08L 67:02 67:02 (56) References JP-A-4-146953 (JP, A) JP-A-4-334448 (JP, A) JP-A-4-336246 (JP, A) JP-A-5-38784 (JP, A) JP-A-5-311600 (JP, A) JP-A-5-170885 (JP, A) JP-A-5-170886 (JP, A) JP-A-5-310898 (JP, A) JP-A-6-172624 ( JP, A) JP-A-7-119098 (JP, A) JP-A-7-228675 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 5/00-5/24 B32B 23/00-23/22 B32B 27/00-27/42 C08L 1/00 C08L 67/02

Claims (1)

(57) [Claim 1] Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
1,3-butanediol, 1,4-butanediol, 3
-Methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol One or more aliphatic polyhydric alcohols, and succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, 1,4 -One or more aliphatic polybasic acids selected from phenylenediacetic acid, phenylsuccinic acid and anhydrides thereof, or lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvale Ric acid, 5-hydroxyvaleric acid, 6-hydroxy Molecule obtained by direct condensation reaction of one or more hydroxycarboxylic acids selected from caproic acid in a reaction mixture comprising an organic solvent content 50,000～30
A thermoplastic polymer composition comprising 000 aliphatic polyesters; and a cellulose selected from wood pulp, fibers made from wood pulp, and nonwoven fabrics, regenerated cellulose, cellulose esters, or cellulose ethers excluding regenerated cellulose films. Comprising
1) a method of impregnating or coating the cellulose with the aliphatic polyester or a solution thereof; 2) a method of mixing the fibrous or pulp-like aliphatic polyester with the cellulose fiber or pulp and pressing the mixture by heat; ) the cellulose and by Ri resulting degradable composite material in the method of the film of the aliphatic polyester to adhere by heat or an adhesive.